WO2011093331A1 - 海島複合繊維、極細繊維ならびに複合口金 - Google Patents
海島複合繊維、極細繊維ならびに複合口金 Download PDFInfo
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- WO2011093331A1 WO2011093331A1 PCT/JP2011/051482 JP2011051482W WO2011093331A1 WO 2011093331 A1 WO2011093331 A1 WO 2011093331A1 JP 2011051482 W JP2011051482 W JP 2011051482W WO 2011093331 A1 WO2011093331 A1 WO 2011093331A1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D4/00—Spinnerette packs; Cleaning thereof
- D01D4/06—Distributing spinning solution or melt to spinning nozzles
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/36—Matrix structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres 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]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
- Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2973—Particular cross section
- Y10T428/2976—Longitudinally varying
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
- Y10T442/614—Strand or fiber material specified as having microdimensions [i.e., microfiber]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
- Y10T442/614—Strand or fiber material specified as having microdimensions [i.e., microfiber]
- Y10T442/622—Microfiber is a composite fiber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
- Y10T442/614—Strand or fiber material specified as having microdimensions [i.e., microfiber]
- Y10T442/626—Microfiber is synthetic polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
- Y10T442/64—Islands-in-sea multicomponent strand or fiber material
Definitions
- the present invention relates to a sea-island composite fiber, and the cross-sectional shape of the ultrafine fiber generated from the sea-island composite fiber is irregular, but the shape homogeneity is excellent.
- Fibers using thermoplastic polymers such as polyester and polyamide are excellent in mechanical properties and dimensional stability, so they are widely used not only in clothing but also in interiors, vehicle interiors, and industrial applications. .
- the required properties are also various, and existing polymers often cannot be used.
- molecular design of a polymer from the beginning has problems in terms of cost and time. For this reason, the development of a composite fiber having the characteristics of a plurality of polymers may be selected.
- the main component is coated with the other component, so that a sensory effect such as a texture and bulkiness that cannot be achieved with a single fiber, and a mechanical property such as strength, elastic modulus, and wear resistance.
- a typical example of the use of sea-island composite fibers is ultrafine fiber.
- the island component of the hardly soluble component is arranged in the sea component of the easily soluble component, and after making the fiber or the fiber product, the ultrafine fiber made of the island component can be collected by removing the easily soluble component. it can.
- an ultrafine fiber having a single fiber diameter of several hundreds of nanometers is used, it is developed as, for example, artificial leather or a new tactile textile using a soft touch and fineness that cannot be obtained with ordinary fibers.
- the ultrafine fiber enters a fine groove, and dirt is trapped in an increase in specific surface area and in fine interfiber spaces. For this reason, high adsorptivity and dust collection property are expressed. Utilizing this characteristic, it is used as a wiping cloth for precision equipment and precision polishing cloth in industrial materials.
- sea-island composite fibers used as starting materials for ultrafine fibers.
- One is a polymer alloy type that melts and kneads polymers together, and the other is a composite spinning type that uses a composite die.
- the composite spinning die is an excellent method in that the composite cross section can be precisely controlled because a base is used.
- Patent Literature 1 and Patent Literature 2 disclose a technique characterized by a composite die.
- Patent Document 1 a polymer reservoir of an easily soluble component expanded in a cross-sectional direction is placed under the hole of the hardly soluble component, and the difficultly soluble component is inserted therein to temporarily form a core-sheath composite flow. After merging the sheath composite flows, they are compressed and discharged from the final hole.
- both the hardly soluble component and the easily soluble component are discharged from the introduction hole by controlling the pressure by the width of the flow path installed between the diversion flow path and the introduction hole and making the insertion pressure uniform. The amount of polymer produced is controlled. Thus, making each introduction hole uniform pressure is excellent in terms of controlling the polymer flow.
- the ultrafine yarn generated from the sea-island composite fibers obtained in the examples is about 0.07 to 0.08 d (about 2700 nm), and nanoscale ultrafine fibers have not been obtained.
- Sea-island composite fibers can be obtained. Further, it is described that an ultrafine fiber having a uniform fiber diameter can be obtained by dissolving an easily soluble component in a subsequent step.
- a sea-island composite fiber is obtained by once converting a hardly soluble component finely divided by a pipe group into a core-sheath composite formation hole, and then reducing the resultant after confluence.
- the formed core-sheath composite flow tends to become a perfect circle in cross section due to surface tension after discharging the formation hole. For this reason, it becomes very difficult to actively control the shape. Therefore, there is a limit to the cross-sectional shape control of the island component, and a perfect circle or an ellipse similar to it is mixed.
- the island component is a perfect circle or a cross-sectional shape similar to it, simply weaving and seawater removal makes it possible to connect the ultrafine fibers with a circular cross section tangentially.
- the flexibility simply increases according to the fiber diameter. For this reason, in the case of sports clothing, water permeates from here, so there is a limit to waterproof performance.
- the fabric becomes flexible, there are cases in which problems such as an unpleasant stickiness and heavy clothing are caused.
- the ultrafine fiber is a perfect circle or an ellipse similar thereto, dirt and abrasive may slide on the fiber surface.
- the ultrafine fibers that are raised by buffing on the surface layer are soft, so there is a limit to wiping performance and polishing performance, and dirt and abrasives caught under the ultrafine fibers are pressed with a line (tangent to the circle). In some cases, the non-polished material may be unnecessarily damaged.
- Patent Document 4 proposes a distribution-type die that forms a complex cross section by forming a polymer flow path using fine grooves and holes and combining them immediately before and / or immediately after discharge.
- this type of mouthpiece two or more types of polymer streams can be arbitrarily arranged at points on the fiber cross section by arrangement of the holes of the final distribution plate. Further, by joining island components together, there is a possibility that island components having irregular cross-sections on the order of microns or various composite cross-sections composed of them can be formed.
- the island component has an irregularity and the cross-sectional shape is uniform. Was anxious.
- JP-A-8-158144 (Claims) JP 2007-39858 A (pages 1 and 2) Japanese Unexamined Patent Publication No. 2007-10023 (pages 1 and 2) International Publication No. 89/02938 Pamphlet
- the present invention aims to solve the above-mentioned problems with respect to the sea-island composite fiber. Further, the ultrafine fiber generated by the sea-island composite fiber has a degree of irregularity, and has a homogeneity of shape such that variation in the degree of irregularity is extremely small.
- the circumscribed circle diameter of the island component is in the range of 10 to 1000 nm, the circumscribed circle diameter variation is 1 to 20%, the irregularity is 1.2 to 5.0, and the irregularity variation is 1 to A sea-island composite fiber characterized by being 10%.
- n is the number of intersections (n is an integer of 2 or more).
- (4) The sea-island composite fiber according to any one of (1) to (3), wherein there are three or more intersections of the straight portions.
- (6) A multifilament composed of a single fiber having a fiber diameter of 10 to 1000 nm, having a fiber diameter variation of 1 to 20%, an irregularity of 1.2 to 5.0, and an irregularity variation of 1 to 10%.
- the ultrafine fiber according to (5) or (6) having a breaking strength of 1 to 10 cN / dtex and an elastic modulus of 10 to 150 cN / dtex.
- a composite base for discharging a composite polymer flow composed of at least two or more polymers the composite base including a measuring plate having a plurality of measuring holes for measuring each polymer component, from a measuring hole
- a composite base comprising: a distribution plate in which a plurality of distribution holes are formed in a distribution groove for joining the discharge polymer flow; and a discharge plate.
- the distribution plate immediately above the discharge plate of the composite die is provided with a plurality of distribution holes for at least one component polymer so as to surround the outermost layer of the composite polymer flow (11) to (13) A composite die according to any one of the above.
- a discharge hole and an introduction hole are formed in the discharge plate of the composite die so that a plurality of polymer flows discharged from the distribution plate are introduced in a direction perpendicular to the distribution plate (11) to (14) A composite die according to any one of the above.
- the distribution plate directly above the discharge plate is characterized in that sea component polymer distribution holes are formed on the circumference centering on the island component polymer distribution holes so as to satisfy the following expression (11): To (15).
- p is the number of vertices of island components (p is an integer of 3 or more), and hs is the number of distribution holes for sea components.
- p is the number of vertices of island components (p is an integer of 3 or more), and hs is the number of distribution holes for sea components.
- (17) A sea-island composite fiber obtained by using the composite base according to any one of (11) to (16).
- (19) A method for producing a sea-island composite fiber according to (1), wherein the composite cap according to any one of (11) to (16) is used.
- the sea-island composite fiber of the present invention has an island component with a deformed cross-section that is extremely reduced to the nano order, and the island component has a uniform diameter and cross-sectional shape.
- the first feature of the sea-island composite fiber of the present invention is that the diameter and shape of nano-order island components are very homogeneous. For this reason, when tension is applied, all the island components bear the same tension in the fiber cross section, and the stress distribution in the fiber cross section can be suppressed.
- This effect means that the thread breakage of the composite fiber is unlikely to occur in post-processing that requires a relatively high tension such as a drawing step, a weaving step, and a sea removal treatment step. For this reason, in the conjugate fiber of the present invention, it becomes possible to obtain a fiber product with high productivity. Furthermore, since the shape of the island component is uniform, the effect that the processing speed in the sea removal treatment process is the same regardless of the island component is achieved.
- the second feature of the sea-island composite fiber of the present invention is that the island component in the nano order has a degree of irregularity.
- the ultrafine fiber generated from the sea-island composite fiber has a deformed cross section that is uniformly controlled in addition to the nano-order fiber diameter. Therefore, the textile product using the ultrafine fiber can freely control the fabric characteristics such as resilience and friction coefficient by the cross-sectional shape of the ultrafine fiber, while having a unique touch produced by nano-order fibers. Needless to say, this effect is used as a new sense of textiles in apparel use, and also exhibits excellent effects in sports apparel under harsh use conditions.
- the ultrafine fiber generated from the sea-island composite fiber of the present invention has excellent waterproof and moisture-permeable performance due to the close-packed structure. Furthermore, as long as the cross-sectional shape of the ultrafine fibers is changed depending on the part, the waterproof performance remains the same, and the fabric is prevented from adhering to the skin even in places where there is a lot of sweat. It will be possible.
- ultrafine fibers generated from the sea-island composite fiber of the present invention are suitable for wiper cloths, precision polishing cloths for IT, and the like. This is because the edge part of the cross section by the unusual cross section of this microfiber can be utilized. For this reason, in the ultrafine fiber of this invention, it becomes possible to improve a wiping performance, dust collection performance, and a grinding
- FIG.2 (a) is a front sectional view of the principal part which comprises a composite nozzle
- FIG. b) is a partial cross-sectional view of the distribution plate
- FIG. 2C is a cross-sectional view of the discharge plate.
- 2 is a part of an example of a distribution plate. It is an example of the distribution groove
- the sea-island composite fiber referred to in the present invention is one in which two or more types of polymers form a fiber cross section perpendicular to the fiber axis.
- the composite fiber has a cross-sectional structure in which island components made of one polymer are scattered in sea components made of the other polymer.
- the circumscribed circle diameter of the island component is 10 to 1000 nm and the circumscribed circle diameter variation is 1 to 20%.
- the circumscribed circle diameter referred to here is obtained as follows. That is, multifilaments composed of sea-island composite fibers are embedded with an embedding agent such as an epoxy resin, and this cross section is photographed with 10 images or more as a magnification at which 150 or more island components can be observed with a transmission electron microscope (TEM). To do. At this time, if the metal is dyed, the contrast of the island component can be made clear. The circumscribed circle diameter of 150 island components extracted at random in the same image from each image in which the fiber cross section is photographed is measured.
- an embedding agent such as an epoxy resin
- the circumscribed circle diameter referred to here means the diameter of a perfect circle circumscribing the cut surface, with a cross section perpendicular to the fiber axis taken as a cut surface from an image photographed two-dimensionally.
- FIG. 1 shows a schematic diagram of the island component of the present invention. A circle indicated by a broken line in FIG. 1 (2 in FIG. 1) corresponds to a circumscribed circle. In addition, the value of the circumscribed circle diameter is measured to the first decimal place in nm unit and rounded off after the decimal point.
- the circumscribed circle diameter of the island component can be less than 10 nm, but by setting it to 10 nm or more, the island component is prevented from being partially broken in the manufacturing process. . Moreover, it can prevent that the very fine fiber to generate becomes too thin.
- the circumscribed circle diameter of the island component needs to be 1000 nm or less.
- the circumscribed circle diameter of the island component is preferably 100 to 700 nm, and within such a range, the fiber does not fall off during pressing, and The effect of scraping off the dirt on the surface of the non-wiping object can be obtained.
- the particle diameter of the abrasive grains is about 100 to 300 nm, so that the circumscribed circle diameter of the island component is more preferably 100 to 500 nm. Within such a range, it can be suitably used for precision polishing for IT applications. Moreover, if it is in such a range, when used as a wiper, it goes without saying that excellent wiping performance and dust collection performance are exhibited.
- the circumscribed circle diameter variation of the island component must be 1-20%. Within such a range, it means that there are no locally coarse island components. For this reason, the stress distribution in the fiber cross section in the post-processing step is suppressed, and the process passability is good. In particular, the effect on the passability of the drawing process and weaving process, and further the sea removal process with a relatively high tension is great. Further, the ultrafine fiber after the sea removal treatment is similarly homogeneous. For this reason, there is no partial change in the surface characteristics and wiping performance of the fiber product made of ultrafine fibers, which can be utilized for high-performance wipers and polishing cloths.
- the third and fourth important requirements for the sea-island composite fiber of the present invention are that the island component has an irregularity of 1.2 to 5.0 and the variation is as small as 1 to 10%.
- the inscribed circle referred to here indicates a one-dot chain line (3 in FIG. 1) in FIG. This irregularity is measured for 150 island components randomly extracted in the same image.
- Deformation degree is less than 1.1 when the cut surface of the island component is a perfect circle or an ellipse similar to it. Further, when spinning with a conventional pipe-type sea-island composite die, the island component of the outermost layer of the cross section becomes a distorted ellipse, and the deformity may be 1.2 or more. However, in this case, variation in the degree of irregularity increases, so that the ultrafine fiber of the present invention is not satisfied. Furthermore, in this case, the circumscribed circle diameter variation is similarly increased.
- the major feature of the sea-island composite fiber of the present invention is that it has a nano-order island component diameter but has a deformity, that is, a cross-sectional shape different from a perfect circle, and each island component is almost It is characterized by having the same cross-sectional shape.
- the irregularity is 1.2 to 5.0.
- the ultrafine fibers contact each other at the tangent of the circle when the sea is removed. For this reason, in the fiber bundle, voids depending on the fiber diameter are formed between the single fibers. Therefore, the sea component residue may be caught in the gap during the sea removal treatment. Due to this influence, when nano-order ultrafine fibers are generated, the specific surface area of the ultrafine fibers is also increased, and the openability of the ultrafine fibers is often deteriorated.
- the island component has an irregularity of 1.2 or more. For this reason, it becomes possible for a single fiber to contact on a surface.
- the island component of the sea-island composite fiber of the present invention has an irregularity, in addition to improving the bending characteristics of the ultrafine fiber itself, it also has a convex portion as described later, Nano-order ultrafine fibers are fully opened. From the viewpoint of improving the spreadability, it is preferable that the degree of irregularity is 1.5 to 5.0.
- the surface properties and mechanical properties of the fabric change as the degree of deformity of the ultrafine fiber increases as compared with the conventional perfect ultrafine fiber.
- the degree of irregularity is more preferably 2.0 to 5.0.
- the degree of modification that can be substantially manufactured is 5.0.
- the island component of the sea-island composite fiber of the present invention preferably has at least two straight portions in the cross-sectional profile.
- the performance of scraping off dirt is improved. This is because if the straight portion exists in the cross section of the ultrafine fiber in the surface layer portion, the ultrafine fiber comes into close contact with the surface of the object to be polished.
- an external force such as pressing is applied to the fiber structure, in the case of a round cross section, the ultrafine fibers are likely to roll, but in the ultrafine fibers having a straight portion, the ultrafine fibers are easily fixed. For this reason, spreading
- the straight portion in the cross-sectional shape means a portion where the line segment having two end points is a straight line in the outline of the cross section in the direction perpendicular to the fiber axis of the single fiber.
- the straight line portion referred to here is a line segment having a length of 10% or more of the circumscribed circle diameter, and is evaluated as follows.
- the angle ⁇ of the intersection formed by the lines extending from the two adjacent straight portions satisfy the following formula.
- n is the number of intersections (n is an integer of 2 or more).
- ⁇ is 25 (5n-9) / n or more from the viewpoint that the shape of the convex portion can be maintained.
- ⁇ being 25 (5n-9) / n or more means that the island component is substantially a regular polygon. Within such a range, the length of the straight portion of the island component is substantially the same.
- ⁇ is particularly preferably in the range of 50 ° to 150 °.
- ⁇ is the angle of the intersection 4 of two adjacent extension lines by drawing an extension line as shown in 5 of FIG. 1 from the straight line portion existing in the contour of the cross section of 150 island components by the method described above. Measure. Record the intersection with the most acute angle among the intersections of each island component. The sum of the recorded angles was divided by the number of islands, and the value rounded to the nearest decimal point was the angle of intersection. A similar operation was performed on 10 images, and a simple number average was defined as ⁇ .
- the intersection mentioned above has many numbers, ie, there are many convex parts. Specifically, it is a preferable range to exist at three or more locations. That is, when there are three or more convex portions, island components repel each other during sea removal treatment, and are hardly affected by adhesion due to residues. For this reason, even if it is a nano order extra fine fiber, favorable fiber opening property can be provided.
- the fiber product of the ultrafine fiber obtained from the sea-island composite fiber of the present invention a convex portion is likely to exist on the surface layer. For this reason, it becomes easy to exhibit scraping performance. Furthermore, the fact that there are three or more intersections means that the island component is substantially a polygon. That is, since the single fibers contact each other at the side surfaces, the fibers are suppressed from rolling on the surface layer of the fiber product.
- the number of intersections is particularly preferably 10 or less.
- the sea-island composite fiber of the present invention can exhibit the above-mentioned effects for the first time because of its unprecedented cross-sectional shape. For this reason, when the variation in shape between island components is large as in the prior art, the effects of the present invention may be greatly impaired. This is due to the variation in the shape of the island components, which changes the seawater removal speed for each island component, and in addition to the variation in the original shape of the island components, this variation is promoted in the Nicolling process. is there. Further, the mechanical properties of the ultrafine fibers that have excessively advanced sea removal due to a small fiber diameter or the like are deteriorated, and dropping off of the ultrafine fibers may be a problem. Even when the ultrafine fiber is used as a fiber product, there are problems such as the formation of voids described above, a change in the partial touch of the fiber product, waterproof performance, polishing performance, and other various performances.
- the irregularity variation of the island component is 1 to 10%. If it exists in such a range, it represents that an island component has the substantially same shape.
- This homogenization of the cross-sectional shape means that the cross-section of the sea-island composite fiber equally bears the stress applied in the post-processing step. That is, it is possible to impart high mechanical properties by stretching at a high magnification in the stretching process, and to prevent process troubles such as yarn breakage and fabric wobbling in post-processing. Further, the surface characteristics of the fiber product made of the generated ultrafine fibers are uniform. Therefore, improvement in waterproof performance, wiping performance, polishing performance and dust collection performance due to the close-packed structure is achieved. Particularly preferably, the variation in the degree of irregularity is in the range of 1 to 7%, and the above-described performance can be remarkably improved.
- the sea-island composite fiber of the present invention preferably has a breaking strength of 0.5 to 10 cN / dtex and an elongation of 5 to 700%.
- the strength is a value obtained by calculating a load-elongation curve of a multifilament under the conditions shown in JIS L1013 (1999), and dividing the load value at the time of breaking by the initial fineness. It is a value obtained by dividing the elongation at break by the initial test length.
- the initial fineness is a value calculated from the obtained fiber diameter, the number of filaments and the density, or a value calculated from a simple average value obtained by measuring the weight of the unit length of the fiber a plurality of times per 10,000 m. Means.
- the breaking strength of the sea-island composite fiber of the present invention is preferably 0.5 cN / dtex or more in order to be able to withstand the processability and actual use in the post-processing step, and the upper limit that can be implemented is 10 cN. / Dtex. Further, the elongation is preferably 5% or more in consideration of the processability of the post-processing process, and the upper limit that can be implemented is 700%.
- the breaking strength and elongation can be adjusted by controlling the conditions in the production process according to the intended application.
- the sea-island composite fiber of the present invention generates various fine intermediates such as fiber winding packages, tows, cut fibers, cotton, fiber balls, cords, piles, knitted fabrics, and non-woven fabrics. It is possible to make various textile products. Moreover, it goes without saying that the sea-island composite fiber of the present invention can be made into a fiber product by partially removing sea components or performing a de-islanding process while leaving untreated. Textile products here include general clothing such as jackets, skirts, pants, and underwear, sports clothing, clothing materials, interior products such as carpets, sofas, and curtains, vehicle interiors such as car seats, cosmetics, cosmetic masks, and wiping. Used for daily use such as cloth and health supplies, environment and industrial materials such as abrasive cloth, filters, hazardous substance removal products, battery separators, and medical applications such as sutures, scaffolds, artificial blood vessels, blood filters, etc. Can do.
- the ultrafine fiber generated from the sea-island composite fiber of the present invention has an extremely fine fiber diameter of 10 to 1000 nm on average, but the fiber diameter variation is 1 to 20%. Is preferred.
- the fiber diameter of the ultrafine fiber referred to here is determined as follows. That is, multifilaments composed of ultrafine fibers generated by seawater-dissipating sea-island composite fibers are embedded with an embedding agent such as an epoxy resin, and this cross section is measured with a transmission electron microscope (TEM) of 150 or more. Taken as a magnification that allows observation of ultrafine fibers. At this time, when the outline of the ultrafine fiber is unclear, metal staining may be performed. The fiber diameters of 150 ultrafine fibers randomly extracted from the image within the same image are measured. At this time, the fiber diameter of each ultrafine fiber means a circumscribed circle of the cross section of the ultrafine fiber, and a circle indicated by a broken line in FIG. 1 (2 in FIG.
- the fiber diameter of the present invention is to determine the simple number average value by measuring the fiber diameter of each ultrafine fiber.
- the ultrafine fiber of the present invention preferably has a fiber diameter of 10 nm or more from the viewpoint of preventing the ultrafine fiber from being excessively thin, and 1000 nm or less from the viewpoint of imparting performance such as a unique touch possessed by the ultrafine fiber. .
- the fiber diameter variation is preferably 1.0 to 20.0%. If it is in such a range, it means that there are no locally coarse fibers, so there is very little partial change in the surface characteristics and wiping performance of the fiber product. This variation is preferably as small as possible, and more preferably 1.0 to 10.0% for use in high-performance sports clothing and precision polishing for IT.
- the degree of irregularity of the ultrafine fiber is 1.2 to 5 and the variation in degree of irregularity is 1.0 to 10.0%.
- the irregularity mentioned here is the same method as the fiber diameter and fiber diameter variation described above, and the cross section of the ultrafine fiber is photographed two-dimensionally, and from the image, the diameter of the perfect circle circumscribing the cut surface is circumscribed.
- the inscribed circle referred to here indicates a one-dot chain line (3 in FIG. 1) in FIG.
- This irregularity was measured with respect to 150 ultrafine fibers randomly extracted in the same image, and the irregularity referred to in the present invention is an irregularity variation (variantity CV%) from the average value and standard deviation. It is a value calculated as (standard deviation of irregularity / average value of irregularity) ⁇ 100 (%), and the second decimal place is rounded off.
- the feature of the ultrafine fiber of the present invention is that it has a degree of deformity while having a nano-order fiber diameter. That is, the cross-sectional shape is different from that of a perfect circle, and each ultrafine fiber has substantially the same cross-sectional shape. For this reason, it is preferable that the ultrafine fiber after sea removal has a deformity of 1.2 to 5.0. If the degree of irregularity is 1.2 or more, it becomes possible for single fibers to come into contact with each other, and when a multifilament or fiber product made of ultrafine fibers is used, a close-packed structure is obtained. From the viewpoint of suppressing variation in the degree of irregularity, the degree of irregularity that can be substantially produced by the ultrafine fiber of the present invention is 5.0.
- the ultrafine fiber of the present invention preferably has at least two straight portions in the cross-sectional profile. When there are two or more straight portions, the wiping performance and the like are greatly improved.
- the straight portion referred to here is a portion where the line segment having two end points is a straight line in the outline of the cross section perpendicular to the fiber axis of the single fiber, and has a length of 10% or more of the fiber diameter. Means the part.
- This straight line portion is evaluated as follows.
- the cross section of the ultrafine fiber is photographed two-dimensionally in the same manner as the fiber diameter and the fiber diameter variation described above, and the cross sections of 150 ultrafine fibers randomly extracted from the image within the same image are evaluated.
- the cross section of each ultrafine fiber is a cut surface perpendicular to the fiber axis from an image photographed two-dimensionally, and the contour of the cut surface is evaluated.
- For 150 ultrafine fibers count the number of straight line parts, calculate the number of straight line parts per ultrafine fiber by dividing the total by the number of ultrafine fibers, and round off to one decimal place. It is shown.
- the angle of the intersection formed by a line extending from two adjacent straight portions is 20 ° to 150 °.
- the convex portion present in the cross section of the ultrafine fiber of the present invention is sharp, and if the angle is 150 ° or less, the single fiber can easily scrape off dirt. For this reason, wiping performance and polishing performance are improved.
- the angle is preferably set to 20 ° or more from the viewpoint that the convex portion can maintain the shape and exhibit excellent wiping performance and the like.
- the angle of intersection mentioned here is a two-dimensional image of the cross section of 150 ultrafine fibers by the method described above, and an extension line is drawn as shown in FIG. It is calculated by measuring the angle of the intersection of two adjacent extra wars and dividing the sum of the angles by the number of intersections. The value calculated by rounding off the decimal point of this value was the angle of intersection of one ultrafine fiber. The same operation was performed on 150 ultrafine fibers, and the simple number average was taken as the angle of intersection.
- the irregularity variation is preferably 1.0 to 10.0%. That is, if the variation is within such a range, it indicates that the ultrafine fibers have substantially the same shape, and is uniform from the viewpoint of the surface characteristics of the fiber product.
- the variation in irregularity is more preferably in the range of 1.0 to 6.0%. In such a range, the effect of homogenizing the cross section is remarkable, and improvement of waterproof performance, wiping performance, polishing performance and dust collection performance by the close-packed structure is expected.
- the cross-sectional shapes of the fibers are uniform. For example, when an external force in the fiber axis direction is applied, all the ultrafine fibers equally bear this external force. For this reason, it is suppressed that stress concentrates on a specific single fiber unnecessarily. Moreover, partial loosening of the single fiber is also suppressed by the close-packed structure where it is possible to have an irregularity. Therefore, the multifilament made of ultrafine fibers bears external force as one aggregate. For this reason, the homogeneity of the cross section and the close-packed structure can greatly contribute to the improvement of mechanical properties, particularly the breaking strength.
- the effect of homogenizing the cross-sectional shape and improving the mechanical properties (inhibition of breakage) by the close-packed structure is great.
- the homogenization of the cross-sectional shape means that the ultrafine fibers are equally responsible for the spinning stress and the drawing stress in the spinning process. Therefore, the fiber structure of the ultrafine fibers is highly oriented by high-stretching or the like, and a high elastic modulus is imparted.
- the effects of the homogenization of the cross section and the close-packed structure described above are also effective from the viewpoint of elastic modulus, and the ultrafine fiber of the present invention realizes high mechanical properties.
- the ultrafine fiber of the present invention preferably has a breaking strength of 1 to 10 cN / dtex and an elastic modulus of 10 to 150 cN / dtex.
- the strength is a value obtained by obtaining a multifilament load-elongation curve under the conditions shown in JIS L1013 (1999), and dividing the load value at break by the initial fineness. This is a value obtained by linearly approximating the initial rising portion of the load-elongation curve of the multifilament and calculating the slope.
- the initial fineness is a value calculated from the obtained fiber diameter, the number of filaments and the density, or a simple average value obtained by measuring the weight of the unit length of the multifilament made of ultrafine fibers a plurality of times per 10,000 m. It means the value calculated by weight.
- the breaking strength of the ultrafine fiber of the present invention is preferably 1 cN / dtex or more in order to be able to withstand the processability of the post-processing step and the actual use.
- the upper limit that can be implemented is 10 cN / dtex.
- the elastic modulus here means a stress that the material can withstand without plastic deformation. That is, a high elastic modulus indicates that the fiber product is not sticky even when an external force is repeatedly applied. For this reason, it is preferable that the elasticity modulus of the ultrafine fiber of this invention is 10 cN / dtex or more, and the upper limit which can be implemented is 150 cN / dtex.
- breaking strength and elastic modulus can be adjusted by controlling the conditions in the manufacturing process according to the intended application.
- the breaking strength is 1 to 4 cN / dtex and the elastic modulus is 10 to 30 cN / dtex.
- the breaking strength is preferably 3 to 5 cN / dtex and the elastic modulus is preferably 10 to 50 cN / dtex.
- use as a wiping cloth or an abrasive cloth can be considered.
- the breaking strength is 1 cN / dtex or more and the elastic modulus is 10 cN / dtex or more.
- the breaking strength is preferably in the range of 1 to 5 cN / dtex and the elastic modulus of 10 to 50 cN / dtex.
- the ultrafine fiber of the present invention can be imparted with high mechanical properties. For this reason, it becomes applicable also to the use called industrial material by making breaking strength 5cN / dtex or more and elastic modulus 30cN / dtex or more.
- a high-density fabric can be made into a thin fabric, it has good folding properties and can be suitably used for fabrics for airbags, tents or curing sheets.
- the sea-island composite fiber of the present invention can be produced by spinning a sea-island composite fiber composed of two or more types of polymers.
- sea-island composite spinning by melt spinning is preferable from the viewpoint of improving productivity.
- the method for producing the sea-island composite spinning of the present invention is preferably a method using a sea-island composite die from the viewpoint of excellent control of the fiber diameter and cross-sectional shape.
- the sea-island composite fiber of the present invention may be manufactured using a conventionally known pipe-type sea-island composite base.
- a conventionally known pipe-type sea-island composite base it is very difficult to control the cross-sectional shape of the island component with the pipe-type base and to design the base itself. It is also necessary to control sea components in order to control island component irregularities and variations in irregularities. For this reason, a method using a sea-island composite base as illustrated in FIG. 2 is preferable.
- the composite base shown in FIG. 2 is assembled into a spinning pack in a state where three kinds of members, ie, a metering plate 6, a distribution plate 7 and a discharge plate 8 are stacked from above, and is used for spinning.
- FIG. 2 is an example using two types of polymers such as an island component polymer (polymer A) and a sea component polymer (polymer B).
- the island component may be a hardly soluble component and the sea component may be an easily soluble component.
- the yarn may be produced using three or more kinds of polymers including polymers other than the hardly soluble component and the easily soluble component.
- the measuring plate 6 measures and flows in each discharge hole 14 and the amount of polymer per distribution hole of both the sea and island components, and the distribution plate 7 allows the single (sea-island composite) fiber to flow.
- the sea-island composite cross section and the cross-sectional shape of the island components in the cross section are controlled, and the composite polymer flow formed on the distribution plate 7 is compressed by the discharge plate 8 and discharged.
- a member having a flow path may be used in accordance with the spinning machine and the spinning pack. In this flow path, it is preferable to form a throttle hole step by step so as to have meterability.
- the existing spinning pack and its members can be utilized as they are by designing the measuring plate according to the existing flow path member.
- the composite polymer flow discharged from the discharge plate 8 is a conventional melt spinning.
- an oil agent is applied, and it is taken up by a roller having a prescribed peripheral speed to form a sea-island composite fiber.
- FIG. 2 (a) to 2 (c) are explanatory views for schematically explaining an example of the sea-island composite base used in the present invention.
- FIG. 2 (a) is a schematic diagram of main parts constituting the sea-island composite base.
- FIG. 2B is a cross-sectional view of a part of the distribution plate
- FIG. 2C is a cross-sectional view of a part of the discharge plate.
- 2B and 2C are a distribution plate and a discharge plate constituting FIG. 2A
- FIG. 3 is a plan view of the distribution plate
- FIG. 4 is one of the distribution plates according to the present invention.
- FIG. 2 is an enlarged view of a portion, and each is described as a groove and a hole related to one discharge hole.
- the composite base illustrated in FIG. 2 is made into a composite polymer flow through the measuring plate and the distribution plate, and the flow of the polymer from the upstream to the downstream of the composite base until the composite polymer flow is discharged from the discharge hole of the discharge plate. A description will be made sequentially along the flow.
- polymer A and polymer B flowed into the polymer A measuring hole (9- (a)) and polymer B measuring hole (9- (b)) of the measuring plate, and were drilled at the lower end. After being weighed by the aperture stop, it flows into the distribution plate.
- the polymer A and the polymer B are weighed by the pressure loss caused by the restriction provided in each metering hole.
- a guideline for the design of this diaphragm is that the pressure loss is 0.1 MPa or more.
- melt spinning with a viscosity of 100 to 200 Pa ⁇ s at a temperature of 280 ° C., a strain rate of 1000 s ⁇ 1 , a spinning temperature of 280 to 290 ° C., and a discharge rate of 0.1 to 5 g / min per metering hole.
- the aperture of the measurement hole is 0.01 to 1.0 mm in hole diameter and 0.1 to 5.0 L / D (hole length / hole diameter). In such a range, it is possible to discharge with good meterability.
- the pore diameter is reduced so as to approach the lower limit of the above range and / or the pore length is approached to the upper limit of the above range. You can extend it. Conversely, when the viscosity is high or the discharge rate increases, the hole diameter and the hole length may be reversed.
- the measuring plate provided with the above-described throttle holes (measuring holes) is composed of two to ten layers. It is preferable.
- each measuring hole 9 (9- (a) and 9- (b)) flows into the distribution groove 10 of the distribution plate 7.
- the same number of grooves as the measuring holes 9 are arranged, and a flow path that gradually extends the groove length in the cross-sectional direction along the downstream is provided.
- the stability of the sea-island composite cross section is improved.
- one groove for temporarily storing the polymer of each component is provided in at least two members of the member constituting the upstream of the discharge plate that joins the polymer and discharges the composite polymer flow.
- a plurality of holes are provided per member, a plurality of holes are provided per groove along the cross-sectional direction of the grooves, and a polymer derived from the plurality of independent grooves is joined to the downstream side of the holes temporarily. It is preferable to use a composite base characterized in that a plurality of grooves are further provided for each member.
- the polymer is allowed to flow downstream in the distribution groove 10 (10- (a) and 10- (b)) for joining the polymer flowing in from the measuring hole 9 and the lower surface of the distribution groove.
- Distributing holes 11 11- (a) and 11- (b)) are formed.
- the number of distribution grooves 10 be at least two per discharge hole at the most upstream portion of the distribution plate.
- the number of distribution grooves gradually increases toward the final distribution plate, and each of the holes formed in the distribution plate directly above is provided. Design is easy when the number of component distribution holes is taken as a guide.
- the distribution groove 10 is preferably provided with a plurality of two or more distribution holes.
- a plurality of distribution plates 7 are laminated so that each polymer is partially joined and distributed individually. If the flow path design is repeated such as a plurality of distribution holes-distribution grooves-a plurality of distribution holes, the polymer flow can flow into other distribution holes even if the distribution holes are partially blocked. . For this reason, even if the distribution hole is blocked, the missing portion is filled in the downstream distribution groove.
- a plurality of distribution holes are formed in the same distribution groove, and when this is repeated, even if the polymer of the closed distribution hole flows into another hole, the influence is virtually eliminated.
- the effect of providing the distribution groove is great in that the polymer that has passed through various flow paths, that is, the heat history is merged a plurality of times and viscosity variation is suppressed.
- the downstream distribution groove is arranged at an angle of 1 to 179 ° in the circumferential direction with respect to the upstream distribution groove, so that different distribution grooves are provided.
- the structure in which the polymers flowing in from the sea are merged is preferable in that the polymers that have received different thermal histories and the like are merged multiple times, and is effective in controlling the sea-island composite cross section.
- this merging and distributing mechanism is preferably employed from the upstream side for the above-mentioned purpose, and is preferably applied to the measuring plate and the upstream member. Further, a mechanism that repeats distribution-merging-distribution a plurality of times is preferable from the viewpoint of the stability of the discharge amount, and the distribution plate is preferably configured in the range of 2 to 15 layers.
- the composite die having such a structure is one in which the flow of the polymer is always stabilized as described above, so that it becomes possible to manufacture a highly accurate sea-island composite fiber required for the present invention. is there.
- the distribution hole 11- (a) (the number of islands) of the polymer A can theoretically be produced infinitely from 2 to the space allowed.
- 2 to 10,000 islands is a preferred range.
- 100 to 10,000 islands is a more preferable range
- the island packing density may be within a range of 0.1 to 20 islands / mm 2 . From the viewpoint of the island packing density, 1 to 20 islands / mm 2 is a preferable range.
- the island-filling density mentioned here represents the number of islands per unit area, and the larger this value is, the more the island-island composite fiber can be produced.
- the island filling density referred to here is a value obtained by dividing the number of islands discharged from one discharge hole by the area of the discharge introduction hole. This island filling density can be changed by each discharge hole.
- the cross-sectional shape of the composite fiber and the cross-sectional shape of the island component can be controlled by the arrangement of the distribution holes 11 of the polymer A and the polymer B in the distribution plate 7 immediately above the discharge plate 8. Specifically, a so-called staggered arrangement in which the distribution holes 11- (a) of the polymer A and the distribution holes 11- (b) of the polymer B are alternately arranged in the cross-sectional direction is preferable. Furthermore, from the viewpoint of suppressing the adhesion between island components, it is more preferable that sea component distribution holes are formed on the circumference centering on the island component distribution holes. Specifically, it is preferable that the sea component distribution hole is formed by 1/3 or more of the island component distribution hole.
- the island components can be satisfactorily enclosed, and adhesion between the island components can be suppressed.
- the manufacturing method of the present invention by using such enclosure, it is possible to make the island component polygonal that was very difficult to achieve with the prior art.
- the number of distribution holes for the sea component (polymer B) satisfy the following formula with respect to one distribution hole for the island component (polymer A).
- hs is the number of distribution holes for sea components
- p is the number of vertices of the polygon (p is an integer of 3 or more).
- p is an integer of 3 or more.
- the polymer discharged from the island component distribution holes can be satisfactorily enclosed. For this reason, a polygonal island component having a sharp edge can be formed.
- an increase in the number of sea component distribution holes is preferable from the viewpoint of enclosing the polymer, but the number of island component holes that can be drilled may be limited. For this reason, it is preferable to set it as 3p or less of a sea component hole.
- hs As a more preferable range of hs, p / 2-1 ⁇ hs ⁇ 2p is a more preferable range from the viewpoint that a large number of distribution holes for island components can be formed.
- the distribution grooves (10- (a) and 10- (b)) of the polymer A and the polymer B are alternately arranged in the cross-sectional direction, and the polymer A arranged at equal intervals. If the polymer B distribution holes are designed to be formed between the distribution holes, the polymer A and the polymer B are arranged in a rectangular lattice shape or a triangular lattice as shown in FIGS. 5 (a) and 5 (b). become.
- both the polymer A and the polymer B are arranged in dots (points), and the sea component that has not been performed in the conventional base is directly arranged. It is suitable for obtaining a composite fiber.
- the sea-island composite cross section constituted by the distribution plate is similarly compressed and discharged. At this time, if the arrangement illustrated in FIG. 5 is adopted, the amount of polymer discharged from each distribution hole becomes the occupation ratio with respect to the sea-island composite section with respect to the amount of polymer for each discharge hole, and the expansion range of the polymer A is as shown in FIG. It is limited to the range of the dotted line shown in the inside.
- FIG. 5 (c) has a hexagonal cross section.
- the island components are very rare as shown in FIGS. 5 (b) and 5 (c). It becomes a triangular cross section and a hexagonal cross section with a high edge interface.
- a plurality of polymer B distribution holes surround the plurality of polymer A distribution holes, or a small-diameter polymer B distribution hole is added between the polymer B distribution holes.
- the distribution holes of the polymer B are not only circular, but may be oval or rectangular depending on the location, which is a preferable means from the viewpoint of manufacturing the sea-island composite fiber having a highly deformed island component of the present invention.
- the cross-sectional shape of the island component can be adjusted to the application by changing the viscosity ratio of polymer A and polymer B (polymer A / polymer B) from 0.5 to 10.0, including the arrangement of the distribution holes described above. The degree of profile and the cross-sectional shape can be controlled.
- the expansion range of the island component is basically controlled by the arrangement of the distribution holes, the melt viscosity of the polymer A and the polymer B at that time is merged and reduced in the cross-sectional direction by the reduction holes 13 of the discharge plate.
- the ratio that is, the rigidity ratio at the time of melting affects the formation of the cross section.
- the polymer A / polymer B 0.5 to 1.3, and an elliptical shape having a high degree of irregularity. In order to achieve this, 3.0 to 10.0 is preferable.
- the composite polymer flow constituted by the polymer A and the polymer B discharged from the distribution plate flows into the discharge plate 8 from the discharge introduction hole 12.
- the discharge plate 8 is preferably provided with a discharge introduction hole 12.
- the discharge introduction hole 12 is for flowing the composite polymer flow discharged from the distribution plate 7 perpendicularly to the discharge surface for a certain distance. This is intended to alleviate the flow rate difference between the polymer A and the polymer B and reduce the flow rate distribution in the cross-sectional direction of the composite polymer flow.
- the composite polymer flow is reduced in the cross-sectional direction along the polymer flow by the reduction holes 13 while being introduced into the discharge holes having a desired diameter.
- the streamline of the middle layer of the composite polymer flow is substantially linear, but as it approaches the outer layer, it is greatly bent.
- the angle of the hole wall of the reduced hole is preferably set in a range of 30 ° to 90 ° with respect to the ejection surface.
- the distribution plate immediately above the discharge plate of the composite die is provided with a plurality of distribution holes for at least one component polymer to surround the outermost layer of the composite polymer flow. It is preferable. It is preferable that the distribution hole is provided with a flow path from the uppermost distribution plate at the time of designing the distribution plate, and constitutes a flow path in which at least one component polymer can be arranged in the outermost layer. Further, an annular groove 15 having a distribution hole formed in the bottom surface as shown in FIG. 3 may be provided on the distribution plate immediately above the discharge plate.
- the composite polymer flow discharged from the distribution plate is greatly reduced in the cross-sectional direction by the reduction hole without being subjected to mechanical control.
- the outer layer portion of the composite polymer flow in addition to being largely bent, it is subjected to shearing with the hole wall.
- the flow velocity distribution may be inclined such that the flow velocity at the contact surface with the pore wall is slow due to shear stress and the flow velocity increases toward the inner layer. For this reason, it is preferable to provide a distribution hole for discharging the sea component polymer. This is due to the formation of a layer composed of sea component polymer that will later dissolve in the outermost layer of the composite polymer stream.
- the shear stress with the above-described hole wall can be applied to the layer made of the sea component polymer, the flow velocity distribution in the outermost layer portion becomes uniform in the circumferential direction, and the composite polymer flow is stabilized.
- the homogeneity of the fiber diameter and fiber shape of the island component when it becomes a composite fiber is remarkably improved.
- the distribution hole formed in the bottom surface of the annular groove 15 consider the number of distribution grooves and the discharge amount of the distribution plate.
- the distribution groove of one of the polymers in the upstream distribution plate is extended in the cross-sectional direction, and a distribution hole is drilled at both ends. A polymer can flow into the annular groove 15.
- FIG. 3 shows an example of a distribution plate in which one annular groove is arranged, but this annular groove may have two or more rings, and different polymers may flow between the annular grooves.
- the composite polymer flow in which the layer composed of the sea component polymer is formed in the outermost layer is discharged while maintaining the cross-sectional shape formed by the distribution plate by taking into consideration the introduction hole length and the angle of the reduced hole wall. It is discharged from the hole 14 to the spinning line.
- the hole diameter and hole length of the discharge holes 14 are preferably determined in consideration of the viscosity of the polymer and the discharge amount.
- the discharge hole diameter in the range of 0.1 to 2.0 mm and the discharge hole length / discharge hole diameter in the range of 0.1 to 5.0.
- a drilling method or a metal precision processing method employed in conventional metal processing is applied. That is, it is possible to manufacture by adopting a processing method such as Numerical Control lathe processing, machining processing, press processing, laser processing, or the like.
- these processing methods have restrictions on the lower limit of the thickness of the processed plate from the viewpoint of suppressing distortion of the workpiece.
- the weighing plate, the distribution plate, and a part of them according to the present invention are laminated by thin plate processing from the viewpoint of applying the composite base to existing equipment.
- an etching method usually used for processing electric / electronic parts is preferably used.
- the etching processing method mentioned here is a technique for transferring a created pattern to a thin plate and chemically processing the transferred portion and / or the non-transferred portion, and is a technique for performing fine processing on a metal plate. . Since this processing method does not require consideration for distortion of the workpiece, the lower limit of the thickness of the workpiece is not limited as compared with the other processing methods described above, and the present invention is applied to an extremely thin metal plate.
- the metering hole, the distribution groove and the distribution hole can be formed. Since it is possible to reduce the thickness of each plate produced by etching, there is almost no influence on the total thickness of the composite die even if a plurality of these plates are laminated.
- the composite base of the present invention may increase the number of plates (members) to be stacked as compared with the conventional composite base. For this reason, when assembling the spinning pack, it is preferable to integrate the respective plates from the viewpoint of preventing misassembly and the like. In this case, it is also effective from the viewpoint of preventing polymer leakage from between the plates.
- the sea-island composite fiber of the present invention can be produced using the composite base as described above. Incidentally, it goes without saying that if this composite die is used, this sea-island composite fiber can be produced by a spinning method using a solvent such as solution spinning.
- melt spinning for example, polyethylene terephthalate or copolymers thereof, polyethylene naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, polypropylene, polyolefin, polycarbonate, polyacrylate, polyamide, polylactic acid And melt-moldable polymers such as thermoplastic polyurethane.
- a polycondensation polymer represented by polyester or polyamide has a high melting point and is more preferable.
- the melting point of the polymer is preferably 165 ° C. or higher because the heat resistance is good.
- the polymer contains various additives such as inorganic materials such as titanium oxide, silica and barium oxide, colorants such as carbon black, dyes and pigments, flame retardants, optical brighteners, antioxidants, and UV absorbers. You may go out.
- inorganic materials such as titanium oxide, silica and barium oxide
- colorants such as carbon black, dyes and pigments, flame retardants, optical brighteners, antioxidants, and UV absorbers.
- melt molding of polyester and its copolymer, polylactic acid, polyamide, polystyrene and its copolymer, polyethylene, polyvinyl alcohol, etc. is possible.
- copolymer polyester, polylactic acid, polyvinyl alcohol, etc. which are easily soluble in an aqueous solvent or hot water, are preferable.
- polyethylene glycol and sodium sulfoisophthalic acid are copolymerized singly or in combination.
- Use of polyester or polylactic acid is preferred from the viewpoint of spinnability and easy dissolution in a low concentration aqueous solvent.
- a polyester obtained by copolymerizing sodium sulfoisophthalic acid alone is particularly preferable.
- the difficultly soluble component is selected according to the intended use, and the easily soluble component that can be spun at the same spinning temperature is selected based on the melting point of the hardly soluble component, good.
- the easily soluble component that can be spun at the same spinning temperature is selected based on the melting point of the hardly soluble component, good.
- ultrafine fibers from the sea-island composite fiber of the present invention when generating ultrafine fibers from the sea-island composite fiber of the present invention, from the viewpoint of stability of the cross-sectional shape of the ultrafine fibers and maintenance of mechanical properties, dissolution of hardly soluble components and easily soluble components in the solvent used for sea removal A larger speed difference is preferable, and a combination may be selected from the polymers described above with a range up to 3000 times as a guide.
- the polymer combination suitable for collecting ultrafine fibers from the sea-island composite fiber of the present invention includes polyethylene terephthalate copolymerized with 1 to 10 mol% of 5-sodium sulfoisophthalic acid from the relationship of the melting point, and the island component.
- Polyethylene terephthalate, polyethylene naphthalate, polylactic acid as the sea component, nylon 6 as the island component, polytrimethylene terephthalate, and polybutylene terephthalate are preferable examples.
- the island component is preferably polyethylene terephthalate, polyethylene naphthalate, nylon 6, and the melt viscosity of the sea component. From the relationship, the molecular weight may be adjusted so that the melt viscosity ratio is 0.3 to 1.3.
- the spinning temperature in the present invention is a temperature at which a high melting point or high viscosity polymer mainly exhibits fluidity among two or more types of polymers.
- the temperature indicating the fluidity varies depending on the molecular weight, but the melting point of the polymer is a guideline and may be set at a melting point + 60 ° C. or lower. If it is less than this, the polymer is not thermally decomposed in the spinning head or the spinning pack, and the molecular weight reduction is suppressed, which is preferable.
- the discharge amount in the present invention may be 0.1 g / min / hole to 20 g / min / hole per discharge hole as a stable and dischargeable range. At this time, it is preferable to consider the pressure loss in the discharge hole that can ensure the stability of discharge.
- the pressure loss mentioned here is preferably determined from the range of the discharge amount based on the relationship between the melt viscosity of the polymer, the discharge hole diameter, and the discharge hole length with 0.1 MPa to 40 MPa as a guide.
- the ratio of the hardly soluble component and the easily soluble component when spinning the sea-island composite fiber used in the present invention can be selected in the range of 5/95 to 95/5 in terms of the sea / island ratio based on the discharge amount.
- this sea / island ratio it is preferable to increase the island ratio from the viewpoint of productivity of ultrafine fibers.
- the sea-island ratio is more preferably 10/90 to 50/50 as a range for producing the ultrafine fiber of the present invention efficiently and while maintaining stability. .
- the sea-island composite polymer flow discharged in this way is cooled and solidified, and is taken up by a roller to which an oil agent is applied and whose peripheral speed is defined, thereby forming sea-island composite fibers.
- the take-up speed may be determined from the discharge amount and the target fiber diameter.
- the take-up speed is preferably in the range of 100 to 7000 m / min. .
- This sea-island composite fiber may be stretched after being wound once, or may be continuously stretched without being wound once, from the viewpoint of improving the mechanical properties with high orientation.
- the drawing conditions for example, in a drawing machine composed of a pair of rollers or more, if the fiber is made of a polymer showing thermoplasticity that can generally be melt-spun, the first roller set to a temperature not lower than the glass transition temperature and not higher than the melting point; By the peripheral speed ratio of the second roller corresponding to the crystallization temperature, the second roller is stretched in the fiber axis direction without difficulty, and is heat set and wound.
- dynamic viscoelasticity measurement (tan ⁇ ) of the composite fiber is performed, and a temperature equal to or higher than the peak temperature on the high temperature side of the obtained tan ⁇ may be selected as the preheating temperature.
- an ultrafine fiber composed of a hardly soluble component can be obtained by immersing the sea-island composite fiber in a solvent or the like in which the easily soluble component can be dissolved to remove the easily soluble component.
- the easily eluting component is copolymerized PET or polylactic acid (PLA) in which 5-sodium sulfoisophthalic acid or the like is copolymerized
- an aqueous alkali solution such as an aqueous sodium hydroxide solution can be used.
- the composite fiber may be immersed in an alkaline aqueous solution.
- processing is performed using a fluid dyeing machine or the like, a large amount of processing can be performed at a time, so that productivity is good and it is preferable from an industrial viewpoint.
- the method for producing the ultrafine fiber of the present invention has been described based on a general melt spinning method. Needless to say, it can also be produced by a melt blow method and a spun bond method. It is also possible to manufacture by the solution spinning method.
- the melt viscosity of the polymer was adjusted to a moisture content of 200 ppm or less using a vacuum dryer, and the melt viscosity was measured by changing the strain rate stepwise using a Capillograph 1B manufactured by Toyo Seiki.
- the measurement temperature is the same as the spinning temperature, and the melt viscosity of 1216 s -1 is described in the examples or comparative examples. By the way, it took 5 minutes from putting the sample into the heating furnace to starting the measurement, and the measurement was performed in a nitrogen atmosphere.
- the number of intersections of two adjacent lines is counted, the angle is measured, and the angle of the most acute intersection of each island component or ultrafine fiber is recorded.
- the sum of the recorded angles was divided by the number, and the value rounded to the nearest decimal point was taken as the angle of intersection.
- the same operation is performed for 10 images, and 10 simple number average values are shown as the angles of intersections.
- Example 1 As the island component, polyethylene terephthalate (PET1 melt viscosity: 120 Pa ⁇ s T301T manufactured by Toray Industries, Inc.) and as the sea component, PET copolymerized with 5.0 mol% of 5-sodium sulfoisophthalic acid (copolymerized PET1 melt viscosity: 140 Pa ⁇ s A260 manufactured by Toray Industries, Inc. was melted separately at 290 ° C., weighed, and flowed into a spinning pack incorporating the composite die shown in FIG. 2, and a composite polymer flow was discharged from the discharge holes.
- PET1 melt viscosity: 120 Pa ⁇ s T301T manufactured by Toray Industries, Inc. PET copolymerized with 5.0 mol% of 5-sodium sulfoisophthalic acid
- the component polymers were weighed in stages. Further, ten distribution plates were laminated, and a flow path for distributing a fine polymer flow in the fiber cross-sectional direction was provided.
- the distribution plate directly above the discharge plate is provided with 1000 distribution holes for island components, and the hole arrangement pattern is the arrangement shown in FIG.
- An annular groove for sea component shown at 15 in FIG. 3 was used in which a distribution hole was formed every 1 ° in the circumferential direction.
- the discharge introduction hole length is 5 mm
- the angle of the reduction hole is 60 °
- the discharge hole diameter is 0.5 mm
- the discharge hole length / discharge hole diameter is 1.5.
- the composite ratio of the sea / island component was 30/70, and the discharged composite polymer stream was cooled and solidified and then applied with oil, wound at a spinning speed of 1500 m / min, and 150 dtex-15 filament (total discharge 22.5 g / min) ) Undrawn fibers were collected.
- the wound unstretched fiber was stretched at a stretching speed of 800 m / min between rollers heated to 90 ° C. and 130 ° C., and stretched 3.0 times.
- the obtained sea-island composite fiber was 50 dtex-15 filament.
- the drawn fiber was sampled for 4.5 hours with a 10 spindle, but the thread breakage was 0 spindle.
- the mechanical properties of the sea-island composite fiber were a breaking strength of 4.2 cN / dtex and an elongation of 35%. Further, when the cross section of the sea-island composite fiber was observed, it was confirmed that the island component had a regular hexagonal cross section with 6 straight portions and an intersection angle of 120 °.
- the circumscribed circle diameter (D 0 ) of the island component is 465 nm, the circumscribed circle diameter variation is 5.9%, the irregularity (S 0 ) is 1.23, the irregularity variation is 3.9%, and the island component is Both the diameter and shape were homogeneous.
- the circumscribed circle diameter (D 72 ) of the island component after 72 hours is 469 nm
- the circumscribed circle diameter variation is 5.9%
- the irregularity (S 72 ) is 1.23
- the irregularity variation is 4.0%. It was found that a highly accurate sea-island cross section was maintained even after spinning for a long time.
- the variation rate (D 72 / D 0 ) of the circumscribed circle diameter of the island component was 1.01
- the variation rate of the irregularity (S 72 / S 0 ) was 1.00
- Table 1 The results are shown in Table 1.
- Examples 2-4 From the method described in Example 1, the sea / island component ratio was changed stepwise to 20/80 (Example 2), 50/50 (Example 3), and 70/30 (Example 4). Except that, the procedure was performed according to Example 1. The evaluation results of these sea-island composite fibers are as shown in Table 1. As in Example 1, the circumscribed circle diameter and the shape of the island component are excellent in homogeneity, and there is no change even after 72 hours ( ⁇ ). there were. The results are shown in Table 1.
- Comparative Example 1 A conventionally known pipe-type sea-island composite base (number of islands 1000) described in JP-A-2001-192924 was used, and yarn was produced under the conditions described in Example 1. Although there was no problem with respect to spinnability, in the drawing process, there was yarn breakage with two spindles.
- the evaluation results of the sea-island composite fiber obtained in Comparative Example 1 are as shown in Table 2. Although the fiber diameter is relatively small, it is a perfect circle (degree of irregularity 1.05) and has a uniform cross-sectional shape. The property was inferior to the sea-island composite fiber of the present invention. Incidentally, there was no straight portion in the cross section of the island component.
- the circumscribed circle diameter (D 72 ) of the island component after 72 hours is 583 nm
- the fiber diameter variation is 23%
- the irregularity (S 72 ) is 1.08
- the irregularity variation is 18.0%, which is a long time.
- the variation rate (D 72 / D 0 ) of the circumscribed circle diameter of the island component was 1.23
- the variation rate of the irregularity (S 72 / S 0 ) was 1.02, both of which were varied ( ⁇ ). .
- Table 2 The results are shown in Table 2.
- Comparative Example 2 All the operations were performed in accordance with Example 1 except that a sea-island composite base was used which repeatedly reduced the size of the flow path described in JP-A-2007-39858. In order to match the number of islands with Example 1, the flow path reduction was required four times. During spinning, a single yarn flow (cut), and in the drawing process, there were four spindle weights. The evaluation results of the sea-island composite fiber obtained in Comparative Example 2 are as shown in Table 2.
- the circumscribed circle diameter of the island component is reduced, the island component located in the outer layer portion of the cross-section of the sea-island composite fiber is It was greatly distorted from a perfect circle, and was inferior to the sea-island composite fiber of the present invention in terms of circumscribed circle diameter variation and irregularity variation. Further, the spinning stability was also variable (x). Moreover, in the cross section of the island component, there was no straight portion. The results are shown in Table 2.
- the distribution composite base has 1024 islands, and the sea component and the island component are arranged in a staggered pattern. Note that no annular distribution hole is provided in the outermost periphery of the final distribution plate.
- the collected conjugate fiber was greatly reduced in accuracy as compared with the sea-island conjugate fiber of the present invention, and the island component was in the shape of a distorted ellipse (degree of irregularity: 1.16). Further, after 72 hours of continuous spinning, there were some places where a plurality of island components joined together in the outer layer part, and the circumscribed circle diameter and the degree of deformation were both varied (x). The results are shown in Table 2.
- Example 5 Polyethylene terephthalate (PET2 melt viscosity: 110 Pa ⁇ s T900F manufactured by Toray Industries, Inc.) as the island component, and PET copolymerized with 8.0 mol% of 5-sodium sulfoisophthalic acid (copolymerized PET2 melt viscosity: 110 Pa ⁇ s) as the sea component All of the steps were performed according to Example 1 except that the stretching ratio was 4.0 times. Since this sea-island composite fiber could be stretched at a high magnification, the strength could be relatively increased.
- the other evaluation results are as shown in Table 3.
- the island component was excellent in circumscribed circle diameter and shape uniformity.
- the manufacturing method of copolymerization PET2 used as a sea component in Example 5 is as follows.
- the reaction system was depressurized to start the reaction, the inside of the reactor was gradually heated from 250 ° C. to 290 ° C., and the pressure was reduced to 40 Pa. Thereafter, nitrogen purge was performed to return to normal pressure, and the polycondensation reaction was stopped to obtain copolymerized PET2.
- Example 6 All the operations were performed according to Example 5 except that the total discharge amount was 90 g / min, the number of discharge holes of the die was increased, and the number of filaments was 75.
- the evaluation results of this sea-island composite fiber are as shown in Table 3.
- the island component was excellent in the circumscribed circle diameter and the homogeneity of the shape.
- Example 7 The same procedure as in Example 5 was performed except that the spinning speed was 3000 m / min and the draw ratio was 2.5 times. As described above, even when the yarn making speed was increased, good sampling was possible without breaking the yarn.
- the evaluation results of the obtained sea-island composite fibers are as shown in Table 3.
- Example 8 The arrangement pattern of the holes of the distribution plate immediately above the discharge plate was the arrangement shown in FIG. 5B, and everything was carried out according to Example 1 except that the number of islands was 2000.
- the island component had a circumscribed circle diameter of 325 nm and had a shape of an equilateral triangle (an irregularity of 2.46, three straight portions at an intersection angle of 60 °).
- the post-processability was good and the spreadability was excellent.
- Table 4 The results are shown in Table 4.
- Example 9 All were performed according to Example 8 except that the number of islands was 1000.
- Table 4 shows the evaluation results of the sea-island composite fibers.
- Example 10 All the operations were performed according to Example 8 except that the number of islands was 450 and the total discharge amount was 45 g / min. Table 4 shows the evaluation results of the sea-island composite fibers.
- Example 11 The same procedure as in Example 1 was performed except that the arrangement pattern of the holes in the distribution plate immediately above the discharge plate was changed to the arrangement shown in FIG.
- the circumscribed circle diameter of the island component was 460 nm, and it was found that a cross section of a regular tetragon (an irregularity of 1.71 and four straight portions at an intersection angle of 90 °) was formed. It could be confirmed.
- the post-processability was also satisfactory.
- the evaluation results are shown in Table 4.
- Example 12 The arrangement pattern of the holes of the distribution plate immediately above the discharge plate is shown in FIG. 5A.
- the number of the distribution holes 1 is 1000, and the interval between the four adjacent distribution holes 1-distribution holes 1 is compared with Example 11.
- the total discharge amount was carried out according to Example 1 except that the total discharge amount was 50/50.
- the island component of the obtained sea-island composite fiber had a significantly increased irregularity of 4.85.
- Four island components were formed as one body, and an island component having a flat cross section having 250 sharp edge protrusions per sea-island composite fiber could be confirmed. As shown in Table 4, the variation in circumscribed circle diameter and irregularity was uniform.
- Example 13 Nylon 6 (N6 melt viscosity 145 Pa ⁇ s T100 manufactured by Toray Industries, Inc.), island component polylactic acid (PLA melt viscosity 100 Pa ⁇ s NatureWorks, Inc. “6201D”), spinning temperature 240 ° C. Except for the above, all were carried out according to Example 9.
- the sea-island composite fiber obtained in Example 13 had a triangular cross section, and the deformity was 1.20. As shown in Table 5, the circumscribed circle diameter and the irregularity of the island component were uniform.
- Example 14 The sea component was copolymerized PET2 used in Example 5 as well, except that the spinning temperature was 260 ° C. and the draw ratio was 4.0 times. Table 5 shows the evaluation results of the obtained sea-island composite fibers.
- Examples 15 and 16 Polytrimethylene terephthalate as an island component (Example 15 3GT melt viscosity 180 Pa ⁇ s “SORONA” J2241 manufactured by DuPont), polybutylene terephthalate (Example 16 PBT melt viscosity 120 Pa ⁇ s 1100S manufactured by Toray Industries, Inc.)
- the spinning temperature was 255 ° C. and the draw ratio was as shown in Table 5, and all the steps were performed according to Example 14.
- the evaluation results of the obtained sea-island composite fiber are shown in Table 5.
- Example 17 Using a distribution plate in which the number of filaments is 200 filaments and 500 island component distribution holes are formed in the arrangement of FIG. 5B, the island ratio is 20% (total discharge amount 22.5 g / min), The same procedure as in Example 5 was performed except that the spinning speed was 3000 m / min and the draw ratio was 2.3 times.
- the island component had a circumscribed circle diameter of 80 nm, and an extremely thin island component was obtained.
- the cross-sectional shape of the island component has a shape of an equilateral triangle (anomaly degree 2.25, three straight portions at an intersection angle of 62 °). It was. The results are shown in Table 6.
- Example 18 Using a distribution plate with 150 filaments, 600 island component distribution holes per filament, island ratio 50% (total discharge rate 22.5 g / min), spinning speed 2000 m / min, draw ratio All the steps were performed according to Example 17 except that the ratio was 2.5 times. When the cross section of the obtained sea-island composite fiber was observed, the island component had a circumscribed circle diameter of 161 nm. The results are shown in Table 6.
- Example 19 The arrangement pattern of the holes of the distribution plate immediately above the discharge plate is shown in FIG. 5B.
- the number of the distribution holes 1 is 1000, and the distance between the adjacent four distribution holes 1 to 1 is compared with Example 8.
- Example 19 a distribution plate of 1/3 was used.
- the island component and the sea component were the same as PET 2 and copolymerized PET 2 used in Example 5, and the spinning temperature and discharge conditions were carried out according to Example 5.
- island components were regularly joined together, and 200 island components having a flat shape in which triangles having a circumscribed circle diameter of 990 nm were connected could be observed per filament. It was 88 degrees when the intersection of the straight part of the obtained flat cross section was measured. The results are shown in Table 6.
- Example 20 All were carried out in accordance with Example 19 except that the sea / island ratio was 80/20 and the draw ratio was 4.2 times. A flat island component having a circumscribed circle diameter of 481 nm could be observed in the obtained sea-island composite fiber. The results are shown in Table 6.
- Example 21 The island component is high molecular weight PET (PET3 melt viscosity 285 Pa ⁇ s, T704T manufactured by Toray Industries, Inc.), and the sea component is copolymer PET 1 used in Example 1 preliminarily dried at 120 ° C. in a hot air dryer and then vacuumed.
- the undrawn yarn was drawn 4.2 times with two pairs of heating rollers heated to 90 ° C.-140 ° C.-230 ° C. to obtain a sea-island composite fiber.
- the mechanical properties of the obtained sea-island composite fiber were very excellent with a breaking strength of 8.6 cN / dtex and an elongation of 15%.
- a regular hexagonal island component having a circumscribed circle diameter of 639 nm was present in the cross section of the sea-island composite fiber, and the shape was very stable. The results are shown in Table 7.
- Example 22 The spinning speed was 1200 m / min, and everything was carried out according to Example 21 except that the drawing was not performed.
- a regular hexagonal island component having a circumscribed circle diameter of 922 nm was present. The results are shown in Table 7.
- the sea-island composite fiber obtained by the production method of the present invention has a nano-order extremely reduced fiber diameter (circumferential circle diameter) and has a degree of irregularity.
- the variation was extremely small. Furthermore, even after spinning for a long time, not only the island components, which were problems in the prior art (comparative example), do not occur, but also the sea-island composite section itself is maintained with high accuracy.
- Example 23 The sea-island composite fiber collected in Example 1 was formed into a tubular knitting, and the sea component was reduced by 99% or more with a 3 wt% aqueous sodium hydroxide solution (bath ratio 1: 100) heated to 100 ° C. There was no dropout of ultrafine fibers at the time of sea removal (dropout judgment: ⁇ ), and the openability was also good (openness judgment: ⁇ ). Thereafter, the tubular knitting was unwound and the characteristics of the ultrafine fibers were examined. As shown in Table 8, it was found that very homogeneous ultrafine fibers having nano-order fiber diameters and irregularities were generated. The cross section of the ultrafine fiber was a regular hexagon, and the angle of the intersection was 123 ° on average. The results are shown in Table 8.
- Example 24 and 25 All the operations were performed in accordance with Example 23 except that the sea-island composite fibers collected in Example 2 (Example 24) and Example 4 (Example 25) were used as starting materials.
- the post-processability (detachment of ultrafine fibers, spreadability) was also good. Further, the properties of the ultrafine fiber were as good as in Example 22, and had a regular hexagonal cross section. The results are shown in Table 8.
- Comparative Example 5 All the operations were performed in accordance with Example 23 except that the sea-island composite fiber collected in Comparative Example 1 was used as the starting material. In the post-processability, although the ultrafine fibers did not fall off, the perfect circle had a distorted cross section, and many portions where the ultrafine fibers were in a bundle state were observed (opening property: x). . The results are shown in Table 9.
- Comparative Example 6 All the operations were performed in accordance with Example 23 except that the sea-island composite fiber collected in Comparative Example 2 was used as the starting material. In the post-processability, the openability was ⁇ , and there was a dropout of ultrafine fibers that was considered to be caused by variations in island components (dropout judgment: x). The results are shown in Table 9.
- Comparative Example 7 All the operations were performed according to Example 23 except that the sea-island composite fiber collected in Comparative Example 3 was used as the starting material.
- the cross section of the ultrafine fiber was a distorted circle, and the variation in shape was large.
- the openability was ⁇ , and there was a dropout of ultrafine fibers that was considered to be caused by variations in island components (dropout judgment: x). The results are shown in Table 9.
- Example 26 and 27 The whole procedure was performed according to Example 23, except that the sea-island composite fiber collected in Example 5 (Example 26) and Example 7 (Example 27) was used as a starting material and a 1% by weight sodium hydroxide aqueous solution was used. .
- the ultrafine fibers of Example 26 and Example 27 had a hexagonal cross section, and the post-processability was very good. In particular, in the openability, because of the hexagonal cross section, there are many protrusions and the influence of the residue between the ultrafine fibers has become very small, so that the ultrafine fibers are in a very dispersed state, compared with Example 23 Even it was excellent. The results are shown in Table 10.
- Example 28 The same procedure as in Example 23 was performed except that sea-island composite fibers collected in Example 8 (Example 28), Example 9 (Example 29), and Example 10 (Example 30) were used as starting materials. All of the ultrafine fibers had a triangular cross section, and the ultrafine fibers did not fall off, and the openability was good. The results are shown in Table 11.
- Example 31 Except that the sea-island composite fiber collected in Example 12 was used, the same procedure was performed as in Example 26. The results are shown in Table 11.
- Example 32 and 33 The same procedures as in Example 26 were performed except that the sea-island composite fibers collected in Example 14 (Example 32) and Example 16 (Example 33) were used. Each of them had a triangular cross section, and the island component had high alkali resistance. Therefore, the island component had little influence during sea removal, and the strength and elastic modulus of the ultrafine fiber were high. The results are shown in Table 12.
- Comparative Example 8 All were carried out in accordance with Example 23 except that the sea-island composite fiber collected in Comparative Example 4 was used. In Comparative Example 8, it took a long time to complete the sea removal treatment, and the dropping of the ultrafine fibers was conspicuous in the post-processability. The results are shown in Table 12.
- Example 34 and 35 All the operations were performed in accordance with Example 26 except that the sea-island composite fibers collected in Example 17 (Example 34) and Example 18 (Example 35) were used as starting materials. The results are shown in Table 13.
- Example 36 All were carried out in accordance with Example 22 except that the sea-island composite fiber collected in Example 21 and the starting material were used. The results are shown in Table 13.
- the ultrafine fiber generated from the sea-island composite fiber of the present invention had a highly uniform cross-sectional shape and had a deformity. In addition, there was almost no drop of the ultrafine fiber during sea removal, the fiber opening property was good, and the post-processability was excellent. In addition, since the cross-sectional shape is highly uniform, the multifilament made of ultrafine fibers has high strength and elastic modulus. On the other hand, in the comparative example that is not the present invention, the extra fine fibers dropped out during sea removal, and the post-processability was inferior to the extra fine fibers of the present invention.
- the wiping performance test was performed using the tubular braids of Example 23, Example 26, Example 29, Example 32, Example 34, Comparative Example 5, Comparative Example 7, and Comparative Example 8.
- the slide glass after wiping was photographed with a stereomicroscope at a magnification of 50x. If the liquid paraffin was not confirmed, it was good ( ⁇ ). If the liquid paraffin remained partially ( ⁇ ), it flowed over the entire screen.
- the evaluation was performed in a three-step evaluation in which paraffin was confirmed to be unacceptable (x).
- the ultrafine fibers of the present invention exhibited good wiping performance, and the wiping evaluation was good ( ⁇ ).
- the wiping performance was excellent and without reciprocation
- the liquid paraffin was completely wiped off.
- the comparative example that is not the present invention liquid paraffin was partially confirmed even after performing one reciprocal wiping ( ⁇ ), or liquid paraffin spread and adhered to the slide glass ( ⁇ ). .
- the knitted fabric was torn by the pressing pressure and there existed the part from which the ultrafine fiber fell off. The results are shown in Tables 8 to 13.
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Abstract
Description
特許文献3においては、口金技術としては、従来公知のパイプ型海島複合口金を用いているものの、易溶解成分と難溶解成分の溶融粘度比を規定することで、断面形状が比較的制御された海島複合繊維を得ることが可能となる。また、易溶解成分を後工程で溶解させることにより、均質な繊維径を有した極細繊維を得ることができると記載されている。しかしながら、この技術においては、パイプ群によって微細に分割された難溶解成分を一旦芯鞘複合形成孔にて、芯鞘複合流とし、合流後縮小させることによって海島複合繊維を得ている。形成された芯鞘複合流は、形成孔吐出後に表面張力によって断面が真円になろうとする。このため、形状を積極的に制御することは非常に困難なこととなる。よって、島成分の断面形状制御には限界があり、真円かそれに類似した楕円が混在したものとなる。これは、パイプの中空部分の形状を変更したとしても、ポリマー流の表面張力の影響から、その効果は非常に小さい。特許文献3の技術においては、島成分の外接円のバラツキとしては、比較的均質なものとなるものの、異形度を有し、かつこの断面形状を均質化することは、至極困難なことである。このため、用途に合わせた極細繊維ならびにそれからなる繊維製品の設計には大きな制限があるものであった。
(1)海島複合繊維において、島成分の外接円径が10~1000nmの範囲であり、外接円径バラツキが1~20%、異形度が1.2~5.0および異形度バラツキが1~10%であることを特徴とする海島複合繊維。
(2)島成分の繊維軸と垂直方向の断面において、断面の輪郭が少なくとも2箇所以上の直線部を有している(1)に記載の海島複合繊維。
(3)直線部の交点の角度θが下記式を満たす(1)または(2)に記載の海島複合繊維。
(4)直線部の交点が3箇所以上存在する(1)から(3)のいずれか1項に記載の海島複合繊維。
(5)(1)から(4)のいずれかに1項に記載の海島複合繊維を脱海処理することによって得られた極細繊維。
(6)繊維径10~1000nmの単繊維からなるマルチフィラメントであって、繊維径のバラツキが1~20%、異形度が1.2~5.0および異形度バラツキが1~10%である(5)記載の極細繊維。
(7)破断強度が1~10cN/dtexであり、弾性率が10~150cN/dtexである(5)または(6)に記載の極細繊維。
(8)単繊維の繊維軸と垂直方向の断面において、繊維断面の輪郭が少なくとも2箇所以上の直線部を有している(5)から(7)のいずれか1項に記載の極細繊維。
(9)隣り合う2箇所の直線部を延長した線がなす交点が3箇所以上存在する(5)から(8)のいずれか1項に記載の極細繊維。
(10)(1)から(9)のいずれか1項に記載の繊維が少なくとも一部を構成する繊維製品。
(11)少なくとも2成分以上のポリマーによって構成される複合ポリマー流を吐出するための複合口金であって、該複合口金は、各ポリマー成分を計量する複数の計量孔を有する計量プレート、計量孔からの吐出ポリマー流を合流する分配溝に複数の分配孔が穿設されている分配プレート、および、吐出プレートとで構成されるものであることを特徴とする複合口金。
(12)複合口金の計量プレートが2枚積層から10枚積層した(11)に記載の複合口金。
(13)複合口金の分配プレートが2枚積層から15枚積層した(11)または(12)記載の複合口金。
(14)複合口金の吐出プレート直上の分配プレートには、複合ポリマー流の最外層を取り囲むように少なくとも1成分のポリマーのための複数の分配孔が穿設されている(11)から(13)のいずれか1項記載の複合口金。
(15)複合口金の吐出プレートに、分配プレートから吐出された複数のポリマー流が分配プレートと垂直方向に導入されるように吐出孔および導入孔が穿設されている(11)から(14)のいずれか1項記載の複合口金。
(16)吐出プレート直上の分配プレートにおいて、島成分ポリマー用分配孔を中心とした円周上に海成分ポリマー用分配孔が下記式を満たすように穿設されたことを特徴とする(11)から(15)のいずれか1項記載の複合口金。
(17)(11)から(16)のいずれか1項に記載の複合口金を用いて得られる海島複合繊維。
(18)(11)から(16)のいずれか1項に記載の複合口金を用いて得られる(1)記載の海島複合繊維。
(19)(1)記載の海島複合繊維の製造方法であって、(11)から(16)のいずれか1項に記載の複合口金を用いることを特徴とする海島複合繊維の製造方法。
本発明の海島複合繊維は、第一および第二の要素として、島成分の外接円径が10~1000nmであり、該外接円径バラツキが1~20%であることが重要である。
本発明の極細繊維は、断面形状の輪郭が、少なくとも2箇所以上の直線部を有していることが好ましい。該直線部が2箇所以上存在すると、払拭性能等が大きく向上する。
本発明の海島複合繊維は、2種類以上のポリマーからなる海島複合繊維を製糸することにより製造可能である。ここで、海島複合繊維を製糸する方法としては、溶融紡糸による海島複合紡糸が生産性を高めるという観点から好適である。当然、溶液紡糸などして、本発明の海島複合繊維を得ることも可能である。ただし、本発明の海島複合紡糸を製糸する方法としては、繊維径および断面形状の制御に優れるという観点で、海島複合口金を用いる方法とすることが好ましい。
図2(a)~(c)は、本発明に用いる海島複合口金の一例を模式的に説明するための説明図であって、図2(a)は海島複合口金を構成する主要部分の正断面図であり、図2(b)は分配プレートの一部の横断面図、図2(c)は吐出プレートの一部の横断面図である。図2(b)および図2(c)は図2(a)を構成する分配プレート、および吐出プレートであって、図3は分配プレートの平面図、図4は本発明に係る分配プレートの一部の拡大図であり、それぞれが一つの吐出孔に関わる溝および孔として記載したものである。
該島成分の断面形状は、前述した分配孔の配置を含めて、ポリマーAおよびポリマーBの粘度比(ポリマーA/ポリマーB)を0.5~10.0と変化させることで、用途に合わせた異形度および断面形状を制御することができる。基本的には分配孔の配置によって、島成分の拡張範囲は制御されるものの、吐出プレートの縮小孔13によって、合流し、断面方向に縮小されるため、その時のポリマーAおよびポリマーBの溶融粘度比、すなわち、溶融時の剛性比が断面の形成に影響を与える。このため、島成分の断面形状が直線的な辺を持った多角形とするためには、ポリマーA/ポリマーB=0.5~1.3とすることが良く、高異形度をもった楕円とするためには、3.0~10.0とするのが良い。
本発明の複合口金の計量プレート、分配プレートおよび吐出プレートの作製方法は、従来の金属加工で採用されるドリル加工や金属精密加工方法が適用される。すなわち、NumericalControl旋盤加工、マニシング加工、プレス加工、レーザー加工等の加工方法を採用することで作製が可能となる。
但し、これらの加工方法は被加工物の歪抑制という観点から、加工板の厚みの下限に制約がある。このため、複数枚積層させる本発明の計量プレート、分配プレートおよびそれらの一部については、当該複合口金を既存の設備に適用するという観点から、薄板加工で作製することが好ましい。この場合、通常電気・電子部品の加工に用いられるエッチング加工方法が好適に用いられる。
エッチング加工で作製したプレートは1枚当たりの厚みを薄くすることが可能になるため、これらのプレートを複数枚積層させても、複合口金の総厚みに与える影響はほとんどない。このため、各断面形態用の分配プレートに合わせて、他のパック部材を新設する必要がない。すなわち、これらのプレートのみを交換すれば、断面形態を変更することが可能となるため、繊維製品の高性能多品種化が進む昨今では、好ましい特徴と言える。また、エッチング加工は、比較的安価で作製可能である。このため、これらのプレートを使い捨てすることも可能であり、分配孔等の詰まりを確認する必要がなく、生産工程管理という観点で、好適である。生産工程管理という観点においては、積層される各プレートを拡散接合等により圧着することも好ましい。これは、本発明の複合口金は、従来の複合口金と比較して、積層するプレート(部材)の枚数が増加する場合もある。このため、紡糸パックを組み立てる際に、組み違い等の防止という観点から、各プレートを一体化しておくことが好適である。また、この場合プレート間からのポリマー漏れ等の予防という観点でも有効である。
実施例および比較例については、下記の評価を行った。
チップ状のポリマーを真空乾燥機によって、水分率200ppm以下とし、東洋精機製キャピログラフ1Bによって、歪速度を段階的に変更して、溶融粘度を測定した。なお、測定温度は紡糸温度と同様にし、実施例あるいは比較例には、1216s-1の溶融粘度を記載している。ちなみに、加熱炉にサンプルを投入してから測定開始までを5分とし、窒素雰囲気下で測定を行った。
海島複合繊維の場合は、100m当りの重量、極細繊維の場合は1mの重量を測定し、この値から10000m当りの重量を算出した。これを10回繰り返し、その単純平均値の小数点第2位を四捨五入した値を繊度とした。
海島複合繊維をオリエンテック社製引張試験機 テンシロン UCT-100型を用い、試料長20cm、引張速度100%/分条件で応力-歪曲線を測定する。破断時の荷重を読みとり、その荷重を初期繊度で除することで破断強度を算出し、破断時の歪を読みとり、試料長で除した値を100倍することで、破断伸度を算出した。いずれの値も、この操作を水準毎に5回繰り返し、得られた結果の単純平均値を求め、小数点第2位を四捨五入した値である。
海島複合繊維あるいは極細繊維をエポキシ樹脂で包埋し、Reichert社製FC・4E型クライオセクショニングシステムで凍結し、ダイヤモンドナイフを具備したReichert-Nissei ultracut N(ウルトラミクロトーム)で切削した後、その切削面を(株)日立製作所製 H-7100FA型透過型電子顕微鏡(TEM)にて倍率5000倍で撮影した。得られた写真から無作為に選定した150本の島成分あるいは極細繊維を抽出し、写真について画像処理ソフト(WINROOF)を用いて全ての外接円径を測定し、平均値および標準偏差を求めた。これらの結果から下記式を基づき外接円径(繊維径)CV%を算出した。
外接円径バラツキ(CV%)=(標準偏差/平均値)×100
以上の値は全て10ヶ所の各写真について測定を行い、10ヶ所の平均値とし、nm単位で小数点1桁目まで測定し、小数点以下を四捨五入するものである。
前述した外接円径および外接円径バラツキと同様の方法で、島成分の断面を撮影し、その画像から、切断面に外接する真円の径を外接円径とし、さらに、内接する真円の径を内接円径として、異形度=外接円径÷内接円径から、小数点3桁目までを求め、小数点3桁目以下を四捨五入したものを異形度として求めた。この異形度を同一画像内で無作為に抽出した150本の島成分あるいは極細繊維について測定し、その平均値および標準偏差から、下記式に基づき異形度バラツキ(CV%)を算出した。
異形度バラツキ(CV%)=(異形度の標準偏差/異形度の平均値)×100(%)
この異形度バラツキについては、10ヶ所の各写真について測定を行い、10ヶ所の平均値とし、小数点2桁目以下は四捨五入するものである。
前述した外接円径および外接円径バラツキと同様の方法で、島成分あるいは極細繊維の断面を撮影し、その画像から、断面の輪郭にある2つの端点を持った線分が直線である部分の数をカウントした。対象該画像から同一画像内で無作為に抽出した150本の断面について評価した。150本の島成分あるいは極細繊維について、直線部の数をカウントし、その総和を本数で割り返すことで1本当たりの直線部の数を算出し、小数点第2位以下は四捨五入して示すものである。
また、断面の輪郭に存在する直線部から図1の5のように延長した線を引く。隣り合った2本の線の交点の数をカウントするとともに、その角度を測定し、各島成分あるいは極細繊維で最も鋭角な交点の角度を記録していく。記録した角度の総和を本数で割り返し、小数点以下を四捨五入した値を交点の角度とした。同様の操作を10画像について測定を行い、10ヶ所の単純な数平均値を交点の角度として示すものである。
各紡糸条件で採取した海島複合繊維からなる編地を海成分が溶解可能な溶媒によって満たされた脱海浴(浴比100)にて海成分を99%以上溶解除去した。
極細繊維の脱落の有無を確認するため、下記の評価を行った。
脱海後の溶媒を100ml採取し、この水溶液を保留粒子径0.5μmのガラス繊維ろ紙に通す。ろ紙の処理前後の乾燥重量差から極細繊維の脱落の有無を判断した。重量差が10mg以上の場合には、脱海有りとして「×」、10mg未満の場合には、脱落なし「○」とした。
前述した脱海条件で海島複合繊維からなる編地を脱海し、その編地の断面を(株)キーエンス製 VE-7800型走査型電子顕微鏡(SEM)にて倍率1000倍で撮影した。編地の断面を10ヶ所撮影し、その画像から極細繊維の状態を観察した。極細繊維同士が単独で存在し、バラケタ状態にある場合を開繊性良好「○」とし、画像あたりバンドル(束)が5本未満の場合は「△」、バンドルが5本以上の場合は開繊性が悪い「×」とした。
島成分として、ポリエチレンテレフタレート(PET1 溶融粘度:120Pa・s 東レ(株)社製T301T)と、海成分として、5-ナトリウムスルホイソフタル酸5.0モル%共重合したPET(共重合PET1 溶融粘度:140Pa・s 東レ(株)社製A260)を290℃で別々に溶融後、計量し、図2に示した複合口金が組み込まれた紡糸パックに流入させ、吐出孔から複合ポリマー流を吐出した。なお、計量プレートは4枚積層されており、下流に向けて拡張するように流路を設け、かつ各計量プレートには絞り孔(φ0.4 L/D=1.5)によって海成分および島成分のポリマーを段階的に計量した。また、分配プレートは10枚積層されており、微細なポリマー流を繊維断面方向に分配するような流路を設けた。吐出プレート直上の分配プレートには、島成分用として、1000の分配孔が穿設されており、孔の配列パターンとしては、図5(c)の配列とした。図3の15に示している海成分用の環状溝には円周方向1°毎に分配孔が穿設されたものを使用した。また、吐出導入孔長は5mm、縮小孔の角度は60°、吐出孔径0.5mm、吐出孔長/吐出孔径は1.5のものである。海/島成分の複合比は、30/70とし、吐出された複合ポリマー流を冷却固化後油剤付与し、紡糸速度1500m/minで巻き取り、150dtex-15フィラメント(総吐出量22.5g/min)の未延伸繊維を採取した。巻き取った未延伸繊維を90℃と130℃に加熱したローラ間で延伸速度800m/minにとし、3.0倍延伸を行った。得られた海島複合繊維は、50dtex-15フィラメントであった。なお、この延伸繊維の採取は、10錘の延伸機で4.5時間サンプリングをおこなったが、糸切れ錘は0錘であった。
該海島複合繊維の力学特性は、破断強度4.2cN/dtex、伸度35%であった。
また、該海島複合繊維の断面を観察したところ、直線部が6箇所、交点の角度が120°の正六角断面の島成分をしていることが確認できた。島成分の外接円径(D0)は465nm、外接円径バラツキは5.9%、異形度(S0)は、1.23、異形度バラツキは、3.9%であり、島成分は径および形状がいずれも均質性なものであった。
実施例1に記載される方法から、海/島成分の複合比を20/80(実施例2)、50/50(実施例3)、70/30(実施例4)と段階的に変更したこと以外は、実施例1に従い実施した。これらの海島複合繊維の評価結果は、表1に示す通りであるが、実施例1と同様に島成分の外接円径および形状の均質性に優れ、かつ72時間後でも変動なし(○)であった。結果を表1に示す。
特開2001-192924号公報で記載される従来公知のパイプ型海島複合口金(島数1000)を使用し、実施例1に記載の条件で、製糸を行った。紡糸性に関しては、問題がなかったものの、延伸工程では、2錘で糸切れがあった。
比較例1で得られた海島複合繊維の評価結果は、表2に示すとおりであるが、繊維径は比較的バラツキが小さいものの、真円(異形度1.05)であり、断面形状の均質性においては、本発明の海島複合繊維と比較して、劣るものであった。ちなみに、島成分の断面においては、直線部は存在しなかった。72時間後の島成分の外接円径(D72)は583nm、繊維径バラツキは23%、異形度(S72)は、1.08、異形度バラツキは、18.0%であり、長時間紡糸後には、部分的に粗大な島成分が確認されるようになり、海島断面の精度が大きく低下することがわかった。島成分の外接円径の変動率(D72/D0)は1.23、異形度の変動率(S72/S0)は1.02であり、いずれも変動あり(×)であった。結果を表2に示す。
特開2007-39858号公報に記載される流路の縮小を複数回繰り返す海島複合口金を用いたこと以外は、全て実施例1に従い実施した。実施例1と島数を合わせるためには、流路縮小が4回必要であった。紡糸中1回の単糸流れ(切れ)、延伸工程においては、4錘の糸切れ錘があった。
比較例2で得られた海島複合繊維の評価結果は、表2に示すとおりであるが、島成分の外接円径は縮小されるものの、海島複合繊維の断面の外層部に位置する島成分は真円から大きく歪んだものであり、外接円径バラツキおよび異形度バラツキの点で、本発明の海島複合繊維と比較して、劣るものであった。また、紡糸安定性に関しても、変動あり(×)であった。また、島成分の断面においては、直線部は存在しなかった。結果を表2に示す。
実施例1で使用した共重合PET1およびPET1をそれぞれ海成分および島成分とし、絞り孔(φ0.4 L/D=1.5)が穿設された計量プレートを1枚だけとし、海成分および島成分のポリマー各分配孔に対して、8孔に分配する分配板を25枚組み合わせた分配型口金を用いて、実施例1に記載の紡糸条件で紡糸を行った。なお、この分配複合口金は、島数が1024であり、海成分と島成分を千鳥格子状の配置とした。なお、最終分配板最外周には、環状に分配孔を設けていない。採取した複合繊維は表2に示す通り本発明の海島複合繊維と比較すると、大きく精度が低下しており、さらに島成分は歪んだ楕円の形状であった(異形度:1.16)。また、72時間連続紡糸後では、外層部にところどころ複数の島成分が合流している箇所が見られ、外接円径および異形度は、いずれも変動あり(×)であった。結果を表2に示す。
島成分としてポリエチレンテレフタレート(PET2 溶融粘度:110Pa・s 東レ(株)社製T900F)、海成分として、5-ナトリウムスルホイソフタル酸8.0モル%共重合したPET(共重合PET2 溶融粘度:110Pa・s)を用い、延伸倍率を4.0倍としたこと以外は、全て実施例1に従い実施した。この海島複合繊維は高倍率延伸が可能であったため、比較的強度を高くすることができた。他の評価結果は、表3に示す通りであるが、実施例1と同様に島成分の外接円径および形状の均質性に優れたものであった。
なお実施例5で海成分として使用した共重合PET2の製造方法は以下の通りである。
総吐出量を90g/minとし、口金の吐出孔数を増やしてフィラメント数を75本としたこと以外は全て実施例5に従い、実施した。
この海島複合繊維の評価結果は、表3に示す通りであるが、実施例5と同様に島成分の外接円径および形状の均質性に優れたものであった。
紡糸速度を3000m/min、延伸倍率を2.5倍としたこと以外は全て実施例5に従い実施した。前述のように、製糸速度を高めた場合でも、糸切れすることなく良好にサンプリングすることができた。得られた海島複合繊維の評価結果は、表3に示す通りである。
吐出プレート直上の分配プレートの孔の配列パターンを図5(b)の配列とし、島数を2000本としたこと以外は全て実施例1に従い実施した。
得られた海島複合繊維の断面を観察したところ、島成分は325nmの外接円径であり、正三角形(異形度2.46 直線部3箇所 交点の角度60°)の形状を有していた。後加工性においては、良好なものであり、開繊性にも優れていた。結果を表4に示す。
島数を1000本としたこと以外は、全て実施例8に従い実施した。海島複合繊維の評価結果を表4に示す。
島数を450本、総吐出量を45g/minとしたこと以外は全て実施例8に従い、実施した。海島複合繊維の評価結果を表4に示す。
吐出プレート直上の分配プレートの孔の配列パターンを図5(a)の配列としたこと以外は全て実施例1に従い実施した。
得られた海島複合繊維の断面を観察したところ、島成分の外接円径は460nmで、正四角形(異形度1.71 直線部4箇所 交点の角度90°)の断面を形成していることが確認できた。後加工性についても、問題のないものであった。評価結果を表4に示す。
吐出プレート直上の分配プレートの孔の配列パターンを図5(a)とし、分配孔1の数は1000孔としたまま、隣り合う4孔の分配孔1-分配孔1の間隔を実施例11比較して1/2とし、総吐出量を海/島複合比を50/50としたこと以外は全て実施例1に従い実施した。
得られた海島複合繊維の島成分は、異形度が4.85と大幅に増加したものであった。島成分は4個が1体になっており、海島複合繊維1本当たり250個のシャープエッジの凸を有した扁平断面の島成分を確認することができた。外接円径および異形度のバラツキは表4に示したように均質なものであった。
島成分をナイロン6(N6 溶融粘度145Pa・s 東レ(株)社製T100)、海成分をポリ乳酸(PLA 溶融粘度100Pa・s ネイチャーワークス(株)社製“6201D”)、紡糸温度を240℃としたこと以外は全て実施例9に従い実施した。実施例13で得られた海島複合繊維では三角断面であり、異形度が1.20であった。島成分の外接円径および異形度のバラツキは表5に示したように均質なものであった。
海成分を実施例5でも使用した共重合PET2とし、紡糸温度260℃、延伸倍率4.0倍としたこと以外は全て実施例13に従い実施した。得られた海島複合繊維の評価結果を表5に示す。
特開2001-192924号公報に記載された従来公知のパイプ型海島複合口金(島数1000)を使用し、海成分を実施例13で使用したナイロン6(N6 溶融粘度55Pa・s)、島成分を実施例1で使用したポリエチレンテレフタレート(PET1 溶融粘度:135Pa・s)、紡糸温度を285℃、延伸倍率2.3倍としたこと以外は実施例1に従い実施した。
比較例4では、N6の融点(225℃)に対して、紡糸温度が高すぎたため、複合流とした際の海成分の流動が不安定になり、島成分は、部分的には、ナノオーダーの極細繊維が存在するものの、断面形状がランダムに歪んだものが多く、かつ部分的に融着した粗大なものが存在した。また、長時間紡糸の結果では、島成分の部分的な融着がさらに進行するものであった。結果を表5に示す。
島成分としてポリトリメチレンテレフタレート(実施例15 3GT 溶融粘度180Pa・s デュポン(株)社製“SORONA”J2241)、ポリブチレンテレフタレート(実施例16 PBT 溶融粘度120Pa・s 東レ(株)社製1100S)をとし、紡糸温度を255℃、延伸倍率は表5に示した通りとしたこと以外は、全て実施例14に従い実施した。得られた海島複合繊維の評価結果は表5に示す。
フィラメント数が200フィラメント、1フィラメント当たり500の島成分用分配孔が図5(b)の配置で穿設された分配プレートを用いて、島比率20%(総吐出量22.5g/min)、紡糸速度3000m/min、延伸倍率2.3倍としたこと以外は全て実施例5に従い実施した。
得られた海島複合繊維の断面を観察したところ、島成分は80nmの外接円径であり、極めて細い島成分が得られた。実施例17で得られた海島複合繊維では、島成分が極めて細いものの、島成分の断面形状は、正三角形(異形度2.25 直線部3箇所 交点の角度62°)の形状を有していた。結果を表6に示す。
フィラメント数が150フィラメント、1フィラメント当たり600の島成分用分配孔が穿設された分配プレートを用いて、島比率50%(総吐出量22.5g/min)、紡糸速度2000m/min、延伸倍率2.5倍としたこと以外は全て実施例17に従い実施した。得られた海島複合繊維の断面を観察したところ、島成分は161nmの外接円径であった。結果を表6に示す。
吐出プレート直上の分配プレートの孔の配列パターンを図5(b)とし、分配孔1の数は1000孔としたまま、隣り合う4孔の分配孔1-分配孔1の間隔を実施例8比較して1/3とした分配プレートを実施例19では用いた。島成分および海成分は実施例5で用いたPET2および共重合PET2とし、紡糸温度や吐出条件に関しては実施例5に従い実施した。
得られた海島複合繊維の断面では、島成分同士が規則正しく合流しており、外接円径が990nmの三角形が連結した扁平状になった島成分が1フィラメント当たり200個観察することができた。得られた扁平断面の直線部の交点を測定すると、88°であった。結果を表6に示す。
海/島比率を80/20とし、延伸倍率を4.2倍としたこと以外は全て実施例19に従い実施した。
得られた海島複合繊維には外接円径が481nmの扁平状の島成分を観察することができた。結果を表6に示す。
島成分として高分子量PET(PET3 溶融粘度285Pa・s 東レ(株)社製T704T)とし、海成分として、実施例1で使用した共重合PET1を熱風乾燥機にて120℃で予備乾燥後、真空雰囲気下200℃で72時間固相重合した5-ナトリウムスルホイソフタル酸5.0モル%共重合PET(共重合PET3 溶融粘度:270Pa・s)を紡糸温度300℃、紡糸速度600m/minとしたこと以外は全て実施例1に従い紡糸した。未延伸糸を90℃-140℃-230℃に加熱された2対の加熱ローラにて4.2倍延伸し、海島複合繊維を得た。
得られた海島複合繊維の力学特性は破断強度が8.6cN/dtex、伸度15%であり、非常に優れたものであった。また、海島複合繊維の断面には、外接円径が639nmの正六角形の島成分が存在しており、形状は非常に安定したものであった。結果を表7に示す。
紡糸速度を1200m/minとし、延伸を行わないこと以外は全て実施例21に従い実施した。得られた海島複合繊維の断面には、外接円径が922nmの正六角形の島成分が存在していた。結果を表7に示す。
実施例1で採取した海島複合繊維を筒編みとし、100℃に加熱した3重量%の水酸化ナトリウム水溶液(浴比1:100)にて海成分を99%以上減量した。脱海時の極細繊維の脱落はなく(脱落判定:○)、開繊性に関しても良好なものであった(開繊性判定:○)。
その後筒編みを解き、極細繊維の特性を調べたところ、表8に示す通りナノオーダーの繊維径および異形度を有した非常に均質な極細繊維が発生していることがわかった。極細繊維の断面は正六角形であり、交点の角度は平均して123°であった。結果を表8に示す。
実施例2(実施例24)および実施例4(実施例25)で採取した海島複合繊維を出発原料としたこと以外は、全て実施例23に従い実施した。後加工性(極細繊維の脱落、開繊性)についても良好なものであった。また、極細繊維の特性に関しても、実施例22同様に良好なものでり、正六角形の断面を有していた。結果を表8に示す。
比較例1で採取した海島複合繊維を出発原料としたこと以外は全て実施例23に従い実施した。後加工性においては、極細繊維の脱落はなかったものの、真円が歪んだ断面を有しており、極細繊維同士がバンドル状態になっている部分が多く見られた(開繊性:×)。結果を表9に示す。
比較例2で採取した海島複合繊維を出発原料としたこと以外は全て実施例23に従い実施した。後加工性においては、開繊性については△であり、島成分のバラツキに起因すると考えられる極細繊維の脱落があった(脱落判定:×)。結果を表9に示す。
比較例3で採取した海島複合繊維を出発原料としたこと以外は全て実施例23に従い実施した。極細繊維の断面は歪んだ円形であり、形状のバラツキは大きいものであった。後加工性においては、開繊性については△であり、島成分のバラツキに起因すると考えられる極細繊維の脱落があった(脱落判定:×)。結果を表9に示す。
実施例5(実施例26)および実施例7(実施例27)で採取した海島複合繊維を出発原料とし、1重量%の水酸化ナトリウム水溶液を使用したこと以外は、全て実施例23に従い実施した。実施例26および実施例27の極細繊維は六角形の断面を有しており、後加工性は、非常に良好なものであった。特に開繊性においては、六角断面のため、凸部が多いことと、極細繊維間の残渣の影響が非常に小さくなったため、極細繊維同士が非常にばらけた状態にあり、実施例23と比較しても優れたものであった。結果を表10に示す。
実施例8(実施例28)、実施例9(実施例29)および実施例10(実施例30)で採取した海島複合繊維を出発原料としたこと以外は全て実施例23に従い実施した。いずれの極細繊維も三角形の断面を有しており、極細繊維の脱落もなく、開繊性が良好なものであった。結果を表11に示す。
実施例12で採取した海島複合繊維を用いたこと以外は全て実施例26に従い実施した。結果を表11に示す。
実施例14(実施例32)および実施例16(実施例33)で採取した海島複合繊維を用いたこと以外は全て実施例26に従い実施した。いずれも三角形の断面を有しており、島成分の耐アルカリ性が高いため、島成分に脱海時の影響が少なく、極細繊維の強度および弾性率は高いものであった。結果を表12に示す。
比較例4で採取した海島複合繊維を用いたこと以外は全て実施例23に従い実施した。比較例8では、脱海処理完了までに長時間を要し、かつ、後加工性においても、極細繊維の脱落が目立った。結果を表12に示す。
実施例17(実施例34)および実施例18(実施例35)で採取した海島複合繊維を出発原料としたこと以外は、全て実施例26に従い実施した。結果を表13に示す。
実施例21で採取した海島複合繊維と出発原料としたこと以外は、全て実施例22に従い実施した。結果を表13に示す。
2 外接円
3 内接円
4 交点
5 延長線
6 計量プレート
7 分配プレート
8 吐出プレート
9 計量孔
9-(a) 計量孔1
9-(b) 計量孔2
10 分配溝
10-(a)分配溝1
10-(b)分配溝2
11 分配孔
11-(a)分配孔1
11-(b)分配孔2
12 吐出導入孔
13 縮小孔
14 吐出孔
15 環状溝
16 海島複合繊維の島成分の例1
17 海島複合繊維の島成分の例2
Claims (19)
- 海島複合繊維において、島成分の外接円径が10~1000nmの範囲であり、外接円径バラツキが1~20%、異形度が1.2~5.0および異形度バラツキが1~10%であることを特徴とする海島複合繊維。
- 島成分の繊維軸と垂直方向の断面において、断面の輪郭が少なくとも2箇所以上の直線部を有している請求項1に記載の海島複合繊維。
- 直線部の交点が3箇所以上存在する請求項1から請求項3のいずれか1項に記載の海島複合繊維。
- 請求項1から請求項4のいずれか1項に記載の海島複合繊維を脱海処理することによって得られた極細繊維。
- 繊維径10~1000nmの単繊維からなるマルチフィラメントであって、繊維径のバラツキが1~20%、異形度が1.2~5.0および異形度バラツキが1~10%である請求項5に記載の極細繊維。
- 破断強度が1~10cN/dtexであり、弾性率が10~150cN/dtexである請求項5または請求項6に記載の極細繊維。
- 単繊維の繊維軸と垂直方向の断面において、繊維断面の輪郭が少なくとも2箇所以上の直線部を有している請求項5から請求項7のいずれか1項に記載の極細繊維。
- 隣り合う2箇所の直線部を延長した線がなす交点が3箇所以上存在する請求項5から請求項8のいずれか1項に記載の極細繊維。
- 請求項1から請求項9のいずれか1項に記載の繊維が少なくとも一部を構成する繊維製品。
- 少なくとも2成分以上のポリマーによって構成される複合ポリマー流を吐出するための複合口金であって、該複合口金は、各ポリマー成分を計量する複数の計量孔を有する計量プレート、計量孔からの吐出ポリマー流を合流する分配溝に複数の分配孔が穿設されている分配プレート、および、吐出プレートとで構成されるものであることを特徴とする複合口金。
- 複合口金の計量プレートが2枚積層~10枚積層である請求項11に記載の複合口金。
- 複合口金の分配プレートが2枚積層~15枚積層である請求項11または請求項12に記載の複合口金。
- 複合口金の吐出プレート直上の分配プレートには、複合ポリマー流の最外層を取り囲むための少なくとも1成分のポリマーのための複数の分配孔が穿設されている請求項11から請求項13のいずれか1項に記載の複合口金。
- 複合口金の吐出プレートに、分配プレートから吐出された複数のポリマー流が分配プレートと垂直方向に導入されるように吐出孔および導入孔が穿設されている請求項11から請求項14のいずれか1項に記載の複合口金。
- 請求項11から請求項16のいずれか1項に記載の複合口金を用いて得られる海島複合繊維。
- 請求項11から請求項16のいずれか1項に記載の複合口金を用いて得られる請求項1記載の海島複合繊維。
- 請求項1記載の海島複合繊維の製造方法であって、請求項11から請求項16のいずれか1項に記載の複合口金を用いることを特徴とする海島複合繊維の製造方法。
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Cited By (11)
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JP2012127022A (ja) * | 2010-12-15 | 2012-07-05 | Toray Ind Inc | 複合繊維 |
WO2012173116A1 (ja) * | 2011-06-15 | 2012-12-20 | 東レ株式会社 | 複合繊維 |
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Also Published As
Publication number | Publication date |
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EP2530188A1 (en) | 2012-12-05 |
CN102713034A (zh) | 2012-10-03 |
TWI551738B (zh) | 2016-10-01 |
US20150132428A1 (en) | 2015-05-14 |
KR20120128617A (ko) | 2012-11-27 |
US9758904B2 (en) | 2017-09-12 |
US20120288703A1 (en) | 2012-11-15 |
EP2530188B1 (en) | 2018-11-21 |
US8969224B2 (en) | 2015-03-03 |
TW201144497A (en) | 2011-12-16 |
KR101605933B1 (ko) | 2016-03-23 |
US20150184315A1 (en) | 2015-07-02 |
EP2530188A4 (en) | 2014-01-01 |
CN102713034B (zh) | 2016-07-06 |
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