WO2012090538A1 - Filière composite et procédé de fabrication de fibres composites - Google Patents

Filière composite et procédé de fabrication de fibres composites Download PDF

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Publication number
WO2012090538A1
WO2012090538A1 PCT/JP2011/066697 JP2011066697W WO2012090538A1 WO 2012090538 A1 WO2012090538 A1 WO 2012090538A1 JP 2011066697 W JP2011066697 W JP 2011066697W WO 2012090538 A1 WO2012090538 A1 WO 2012090538A1
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Prior art keywords
polymer
island component
component discharge
discharge holes
hole
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PCT/JP2011/066697
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English (en)
Japanese (ja)
Inventor
船越祥二
水上誠二
増田正人
Original Assignee
東レ株式会社
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Priority claimed from JP2010289980A external-priority patent/JP5728936B2/ja
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to EP11853367.8A priority Critical patent/EP2660369B1/fr
Priority to CN201180063082.9A priority patent/CN103261494B/zh
Publication of WO2012090538A1 publication Critical patent/WO2012090538A1/fr

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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
    • 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

Definitions

  • the present invention relates to a composite die and a method for producing a composite fiber.
  • thermoplastic polymers such as polyester and polyamide are excellent in mechanical properties and dimensional stability, so their uses have diversified and many fibers with various functionalities have been developed.
  • the composite fiber includes a core-sheath type, a side-by-side type, and a sea-island type fiber obtained by using a composite die, and an alloy type obtained by melt-kneading polymers.
  • the sheath component coats the core component, so that it is possible to impart sensibility effects such as texture and bulkiness that cannot be achieved with a single fiber, and mechanical properties such as strength, elastic modulus, and wear resistance. Become.
  • the side-by-side type it is possible to express crimpability, which is impossible with a single fiber, and to impart stretchability and the like.
  • the core-sheath type has a core component covered with a sheath component, so that it can provide a sensory effect such as a texture and bulkiness that cannot be achieved with a single fiber, and mechanical properties such as strength, elastic modulus, and wear resistance. It becomes possible. Further, in the side-by-side type, it is possible to express crimpability, which is impossible with a single fiber, and to impart stretchability and the like.
  • the method of manufacturing a composite fiber with a composite die is generally called a composite spinning method, and the method of manufacturing by melt-kneading polymers is called a polymer alloy method.
  • the polymer alloy method can be used to produce the ultrafine fibers as described above, the control of the fiber diameter is limited, and it is difficult to obtain uniform and homogeneous ultrafine fibers.
  • the composite spinning method precisely controls the composite polymer flow with a composite die, and in particular, it can form a highly accurate yarn cross-sectional form uniformly and homogeneously in the running direction of the yarn, compared with the polymer alloy method. The superiority is considered high.
  • the composite die technique in this composite spinning method is extremely important for stably determining the cross-sectional shape of the yarn, and various proposals have been made conventionally.
  • FIG. 12 a composite base as shown in FIG. 12 is disclosed.
  • (B) of FIG. 12 is a plan view of the composite base of Patent Document 1
  • (a) of FIG. 12 is a partially enlarged plan view of (b).
  • black circle 1 indicates an island component discharge hole for discharging an island component polymer
  • white circle 4 indicates a sea component discharge hole for discharging a sea component polymer
  • 5 indicates a lowermost layer distribution plate
  • 8 indicates a distribution groove.
  • Patent Document 1 a plurality of distribution plates are stacked, and a lowermost layer distribution plate 5 provided with distribution grooves 8, island component discharge holes 1, and sea component discharge holes 4 is disposed in the lowermost layer of the distribution plate.
  • a sea-island type composite fiber can be manufactured by combining immediately after discharge. Further, it is described that by using this composite die, 61 uniformly distributed composite fibers having an island shape of a hexagonal cross section (honeycomb shape) can be manufactured.
  • This composite base is generally called a distribution plate type base.
  • the obtained fiber is 0.06 denier (trial calculation of fiber diameter: about ⁇ 2.5 ⁇ m), the fiber diameter is micron size, and it has not reached the nano order.
  • the composite die becomes large, and there are cases where productivity and operability are unfavorable in a multi-spindle spinning facility in the fiber field.
  • the sea component discharge holes 4 so as to form hexagons around the island component discharge holes 1 as a hole group arrangement pattern, the island shape is six. Although it has a square cross section, no other hole group arrangement pattern is presented, and there may be cases where sea-island type composite fibers having various island shapes cannot be obtained.
  • FIG. 9, FIG. 10, and FIG. 23 are disclosed as hole arrangement patterns different from Patent Document 1.
  • 9 and 10 are partially enlarged plan views of the composite base of Patent Document 5 and FIG.
  • the lowermost layer distribution plate 5 shown in FIGS. 9 and 10 and the upper layer plate 29 of FIG. 23 have the same role, although the names are different.
  • Patent Document 5 and Patent Document 8 are patterns in which sea component discharge holes 4 are arranged in three or four equal arrangements (staggered arrangement) around the island component discharge holes 1.
  • sea-island type composite fiber in which the island components are polygonal is likely to be obtained, but according to the knowledge of the present inventors, the island component polymers may actually merge.
  • the polymer discharge rate ratio is preferably less sea component polymer to be eluted and more island component polymers.
  • the confluence of the island component polymers becomes more prominent.
  • the problem may not be resolved even if the spinning conditions such as the discharge amount of each component polymer and the discharge amount ratio are changed. If the value is not changed, production becomes impossible and productivity may deteriorate.
  • a staggered arrangement is adopted as an arrangement pattern, and a polymer is supplied to the island component discharge holes 1 and the sea component discharge holes 4 in order to arrange the island component discharge holes 1 and the sea component discharge holes 4 on the same surface of the upper layer plate 29. Due to the relationship between the distances between the wall surfaces of the distribution grooves 8 of the distribution plate 6, there are cases where many island component discharge holes 1 cannot be arranged and the hole filling density cannot be increased. Thus, when the hole packing density cannot be increased, the composite die becomes large, and there may be a problem that productivity and operability are not preferable in a multi-spindle type spinning facility in the fiber field.
  • FIG. 13 is a schematic cross-sectional view of the composite base of Patent Document 2.
  • 10 is a discharge plate
  • 11 is a discharge introduction hole
  • 43 is a multilayer plate
  • 44 is a divided plate
  • 45 is an array plate.
  • Patent Document 2 is configured by laminating a multilayer plate 43, a division plate 44, an array plate 45, and a discharge plate 10 in order.
  • the sea component polymer and the island component polymer that flowed in from the upstream side are multilayered and partially divided.
  • the island shape of the ultrafine fiber obtained by using the composite die of Patent Document 2 is limited to a circular shape or an elliptical shape similar to the circular shape, an ultrafine fiber having a complex shape, for example, a polygonal island shape, is used. You may not get it. Further, in Patent Document 2, the actual number of islands ((maximum number of islands ⁇ minimum number of islands) / average number of islands ⁇ 100 [%]) is within ⁇ 20% of the theoretical number of islands. In some cases, it is not possible to control the number of islands with high precision.
  • sea component polymers that can be used are limited to polyethylene and polystyrene, and there are cases where a wide variety of polymers (polymers having different molecular structures such as polyester, polyamide, polyphenylene sulfide, and polyolefin) cannot be used.
  • FIG. 14 is a schematic cross-sectional view of the composite die of Patent Document 3 and Patent Document 7.
  • 30 is a pipe
  • 31 is a sea component polymer introduction flow path
  • 32 is an island component polymer introduction flow path
  • 33 is an upper base plate
  • 34 is a middle base plate
  • 35 is a lower base plate
  • 40 is a sea component polymer distribution chamber.
  • 41 is a pipe insertion hole
  • 42 is a base discharge hole.
  • Patent Document 3 is generally known as a pipe-type base, and includes an upper base plate 33 provided with a sea component polymer introduction channel 31, an island component polymer introduction channel 32, and a pipe 30, and an outer diameter of the pipe 30. And a lower base plate 35 provided with a base discharge hole 42 and a middle base plate 34 provided with a pipe insertion hole 41 having the same or larger diameter.
  • the easily eluted component sea component polymer is guided from the ocean component polymer introduction channel 31 to the ocean component polymer distribution chamber 40 and fills the outer periphery of the pipe 30, whereas the hardly eluted component island component polymer is:
  • the polymers of both components merge to form a sea-island composite cross section, and then through the pipe insertion hole 41 and from the die discharge hole 42. It is described that a composite polymer can be discharged to produce a sea-island type composite fiber.
  • the major problem of the pipe-type base of Patent Document 3 is that the pipe thickness is added to produce one island, so that the area per pipe increases.
  • the pipe 30 is press-fitted into the upper base plate 33 and fixed by welding for manufacturing the base, a welding allowance is required, and further, a hole for inserting the pipe 30 is provided.
  • the gap between pipes cannot be reduced due to problems. Therefore, the pipes 30 cannot be densely arranged per unit area, the hole filling density cannot be increased, and it may be difficult to manufacture ultrafine fibers having a fiber diameter of nano-order.
  • the cylindrical pipe 30 is used, the island shape obtained is limited to a circular shape or an elliptical shape similar to the circular shape.
  • a sea-island type composite fiber having a complex shape for example, a polygonal island shape. May not be able to get. This is because the degree of freedom of arrangement of the pipes 30 is low, and there is a limit to the cross-sectional shape of the fiber that can be controlled, and it may be difficult to manufacture a fiber having a complex cross-section in multiple layers.
  • FIG. 18 is a schematic cross-sectional view of the composite die of Patent Document 6.
  • 25 is a discharge hole
  • 55 is an upper plate
  • 56 is a protrusion.
  • the discharge holes 25 and the island component discharge holes 1 have protrusions 56 around the periphery, the lower surface of the upper base plate 33, and the discharge
  • the gap between the upper surface of the protrusion 56 formed around the hole 25 and the gap between the lower surface of the upper plate 29 and the upper surface of the protrusion 56 formed around the island component discharge hole 1 are narrowed to reduce pressure loss.
  • the flow path pressure loss becomes large and the uniform distribution of both component polymers is possible, but the composite die of the present invention is targeted.
  • the channel pressure loss cannot be increased, and thus the above-described effects may not be obtained.
  • FIG. 15 is a schematic cross-sectional view of the composite die of Patent Document 4.
  • 27 is a radial groove and 28 is a concentric groove.
  • Patent Document 4 discloses that the distribution of the sea component polymer is improved by forming the radial grooves 27 around the island component discharge holes 1 and the concentric grooves 28 around the discharge holes 25, and the sea component polymer ratio is small. Even so, it is described that a sea-island type composite fiber that suppresses merging of island components can be obtained.
  • the grooves are formed around the island component discharge holes 1 and the discharge holes 25, the pitch between the holes is increased, the hole filling density cannot be sufficiently increased, and the fiber diameter is ultrafine with nano order. It may be difficult to produce the fiber. As described in the examples, the minimum diameter of the obtained fiber is 1 ⁇ m, so that it cannot reach the nano-order.
  • complicated grooving is performed on the base, it takes time, labor, and expense to manufacture the base, and there is a problem that the equipment cost is excessive in this respect as well.
  • JP-A-7-26420 JP 2000-110028 A Japanese Patent Laid-Open No. 2007-100343 JP 2006-183153 A JP 2008-38275 A JP-A-7-118913 JP 2009-91680 A International Publication No. 1989-02938 Pamphlet
  • the purpose of the present invention is to prevent the island component polymer from joining together while expanding the hole packing density of the discharge holes of the island component polymer in the distribution plate type die for producing the sea-island type composite fiber.
  • Various fiber cross-sectional forms in particular, irregular shaped cross-sections can be formed with high accuracy, and a composite base capable of maintaining high dimensional stability of the cross-sectional form, and a composite fiber manufacturing method for performing melt spinning by a composite spinning machine using the composite base Is to provide.
  • the composite base of the present invention has the following configuration. That is, according to the present invention, a composite base for discharging a composite polymer flow composed of an island component polymer and a sea component polymer, wherein distribution holes and distribution grooves for distributing each polymer component are formed. Consists of one or more distribution plates and a lowermost layer distribution plate that is located downstream of the distribution plate in the polymer spinning path direction and has a plurality of island component discharge holes and a plurality of sea component discharge holes The sea component discharge hole disposed on a virtual circumference line C1 having a radius R1 centered on the island component discharge hole, and the sea component discharge hole disposed on a virtual circumference line C2 having a radius R2.
  • C1 Three sea component discharge holes equally divided at a central angle of 120 degrees
  • C2 Three sea component discharge holes equally divided at a central angle of 120 degrees
  • C4 Three island component discharge holes at a central angle of 120 degrees
  • ⁇ 3 The phase angle between the discharge holes arranged in C1 and C2 is 60 degrees.
  • ⁇ 5 The phase angle between the discharge holes arranged in C1 and C4 is 0 degrees.
  • C1 Six sea component discharge holes equally divided at a central angle of 60 degrees
  • C2 Six sea component discharge holes equally divided at a central angle of 60 degrees
  • C4 Six island component discharge holes at a central angle of 60 degrees ⁇ 3: The phase angle between the discharge holes arranged at C1 and C2 is 0 degree.
  • ⁇ 5 The phase angle between the discharge holes arranged at C1 and C4 is 30 degrees.
  • C1 Four sea component discharge holes are equally divided at a central angle of 90 degrees
  • C2 Eight sea component discharge holes are equally distributed at a central angle of 90 degrees
  • C4 Four sea component discharge holes are equally divided at a central angle of 90 degrees
  • the phase angle between the discharge holes arranged in C2 is 26.6 degrees.
  • ⁇ 5 The phase angle between the discharge holes arranged in C1 and C4 is 0 degree. According to a preferred embodiment of the present invention, a plurality of the distribution plates are provided.
  • the distribution plate has an increased number of holes in the distribution hole toward the downstream side in the spinning path direction of the polymer, and the distribution hole located on the upstream side in the spinning path direction of the polymer;
  • the distribution groove is formed so as to communicate with the distribution hole located on the downstream side in the spinning path direction, and there is provided a composite base that constitutes a plurality of distribution holes communicating with the end of the distribution groove. .
  • a composite base in which the diameter of the distribution hole in the path having a relatively long polymer flow path is larger than the diameter of the distribution hole in the relatively short path.
  • a composite base in which at least a part of the sea component discharge hole is present in a region surrounded by two common circumscribed lines of two adjacent island component discharge holes. Is provided.
  • At least a part of each of the at least two sea component discharge holes in a region surrounded by two common outer tangent lines of the two adjacent island component discharge holes.
  • a composite base in which the two sea component discharge holes are arranged across a line segment connecting the centers of the two island component discharge holes.
  • a composite die having a thicker distribution plate constituting the distribution groove toward the upstream side in the polymer spinning path direction.
  • the diameter DMIN of the minimum hole formed in the distribution plate or the lowermost layer distribution plate and the plate thickness BT where the minimum hole is formed are expressed by the following equations: A composite base to fill is provided. BT / DMIN ⁇ 2 DMIN: diameter of the smallest hole formed in the distribution plate or the lowermost layer distribution plate (mm), BT: thickness of the distribution plate in which the smallest hole is formed, or the lowermost layer distribution plate (mm).
  • a composite base in which the thickness of the distribution plate or the lowermost distribution plate is in the range of 0.1 to 0.5 mm.
  • a composite die having a hole filling density of the island component discharge holes of 0.5 holes / mm 2 or more.
  • flow path pressure loss in each flow path from the distribution plate to the island component discharge hole of the lowermost layer distribution plate is equal
  • the distribution plate Provided is a method for producing a composite fiber, in which melt spinning is performed by a composite spinning machine using a composite base in which the flow path pressure loss in each flow path to the sea component discharge hole of the lowermost layer distribution plate is equal.
  • a method for producing a composite fiber in which melt spinning is performed with an island component polymer ratio of 50% or more by a composite spinning machine using the composite base.
  • the “distribution hole” means a hole that is formed by a combination of a plurality of distribution plates and plays a role of distributing the polymer in the direction of the polymer spinning path.
  • the “distribution groove” means a groove in which a groove is formed by a combination of a plurality of distribution plates and plays a role of distributing the polymer in a direction perpendicular to the polymer spinning path direction.
  • the distribution groove may be an elongated hole (slit), or an elongated groove may be dug.
  • the “polymer spinning path direction” refers to the main direction in which each polymer component flows from the measuring plate to the die discharge hole of the discharge plate.
  • the “direction perpendicular to the direction of polymer spinning path” refers to the direction perpendicular to the main direction in which each polymer component flows from the metering plate to the die discharge hole of the discharge plate.
  • the “virtual circumferential line C1 having a radius R1” refers to a virtual circumferential line C1 having a radius R1 as the distance between the center points of the sea component discharge hole closest to the reference island component discharge hole. .
  • the “virtual circumferential line C2 having a radius R2” means a virtual circumferential line C2 having a radius R2 as the distance between the center points of the sea component ejection hole that is second closest to the reference island component ejection hole.
  • the “virtual circumferential line C4 having a radius R4” refers to a virtual circumferential line C4 having a radius R4 as the distance between the center points of the island component ejection holes closest to the reference island component ejection hole. .
  • the “center angle” means the center point of the reference island component discharge hole and the center point of two sea component discharge holes adjacent to each other in the circumferential direction arranged on the virtual circumferential lines C1 and C2. Or the angle which the line segment which connects the center point of two island component discharge holes adjacent to the circumferential direction arrange
  • the “phase angle” means a line segment connecting the center point of the reference island component discharge hole and the center point of the sea component discharge hole arranged on the virtual circumferential line C1, and the reference island component.
  • the angle at which the line connecting the center point of the discharge hole and the center point of the sea component discharge hole arranged on the virtual circumference C2 intersects, or the center point of the reference island component discharge hole and the virtual circumference C1 A line segment connecting the center point of the sea component discharge hole disposed above, and a line segment connecting the center point of the reference island component discharge hole and the center point of the sea component discharge hole disposed on the virtual circumferential line C2. The angle at which crosses.
  • the “polymer flow path” refers to a path formed by communication between a distribution hole and a distribution groove formed inside the distribution plate.
  • the “hole filling density” refers to a value obtained by dividing the number of island component discharge holes for discharging the island component polymer by the cross-sectional area of the discharge introduction holes. The larger the pore packing density, the more the composite fiber is composed of a larger number of island component polymer components.
  • the island component polymers are uniformly distributed, and the island component polymers are prevented from merging with each other.
  • the irregular cross section can be formed with high accuracy, and the dimensional stability of the cross section can be maintained high.
  • FIG. 6 is a view taken in the direction of arrows XX in FIG. 5.
  • FIG. 27 is a view on arrow XX in FIG. 26.
  • FIG. 25 is a view on arrow YY in FIG. 24. It is a ZZ arrow line view of FIG.
  • FIG. 5 is a schematic cross-sectional view of a composite base used in the embodiment of the present invention
  • FIG. 7 is a view taken along the line XX of FIG. 5
  • FIG. 1 is a partially enlarged plan view of FIG. 2, 3, 4, and 16 are partially enlarged plan views of a lowermost layer distribution plate used in another embodiment of the present invention
  • FIG. 6 is a composite die and a spin pack used in the embodiment of the present invention
  • FIG. 17, FIG. 20, FIG. 21, FIG. 22, FIG. 31, and FIG. 38 are schematic partial sectional views of the distribution plate and the lowermost layer distribution plate used in the embodiment of the present invention.
  • These are conceptual diagrams for accurately transmitting the main points of the present invention, which are simplified, and the composite base of the present invention is not particularly limited, and the number of holes and grooves and the size ratio thereof are not limited. These can be changed according to the embodiment.
  • the composite base 18 used in the embodiment of the present invention is mounted on the spinning pack 15 and fixed in the spin block 16, and a cooling device 17 is configured immediately below the composite base 18. Therefore, after the polymer of two or more components led to the composite base 18 passes through the measuring plate 9, the distribution plate 6, and the lowermost layer distribution plate 5 and is discharged from the base discharge hole 42 of the discharge plate 10, After being cooled by the air flow blown out by the cooling device 17 and given an oil agent, it is wound up as a sea-island type composite fiber.
  • adopted you may use the cooling device which blows off airflow from one direction.
  • the composite base 18 used in the embodiment of the present invention is configured by laminating a measuring plate 9, at least one distribution plate 6, a lowermost layer distribution plate 5, and a discharge plate 10 in order.
  • the distribution plate 6 and the lowermost layer distribution plate 5 are preferably formed of thin plates.
  • the measuring plate 9 and the distribution plate 6, and the lowermost layer distribution plate 5 and the discharge plate 10 are positioned by the positioning pins so that the center position (core) of the spinning pack 18 is aligned, You may fix with a volt
  • the distribution plates 6 and the distribution plate 6 and the lowermost layer distribution plate 5 use thin plates, it is preferable to perform metal bonding (diffusion bonding) by thermocompression bonding.
  • the thickness of the thin plate is preferably in the range of 0.01 to 1 mm, and more preferably in the range of 0.1 to 0.5 mm.
  • the thickness of the distribution plate 6 and the lowermost distribution plate 5 is too thin, the strength of the thin plate is reduced and bending is likely to occur, so that the types of polymers that can be used may be limited (high viscosity) The pressure loss increases with the polymer, and bending occurs.)
  • a plurality of thin plates may be stacked and metal-bonded to increase the overall thickness and improve the strength.
  • the strength per sheet is improved, so that there is an advantage that the types of polymers that can be used increase.
  • the thickness of the distribution plate having a large number of holes may be reduced, and the thickness may be increased as the number of holes is reduced.
  • the polymer of each component supplied from the measuring plate 9 passes through the distribution groove 8 and the distribution hole 7 of the distribution plate 6 laminated at least one, and then discharges the island component polymer of the lowermost distribution plate 5.
  • the polymers of the respective components merge to form a composite polymer flow.
  • the composite polymer flow passes through the discharge introduction hole 11 and the reduction hole 12 of the discharge plate 10 and is discharged from the base discharge hole 42.
  • the hole diameters of the island component discharge holes 1 provided in the lowermost layer distribution plate 5 are preferably all equal, and the hole diameters of the sea component discharge holes 4 are preferably all equal.
  • the hole diameters of the island component discharge hole 1 and the sea component discharge hole 4 are preferably in the range of 0.03 to 0.8 mm, and more preferably in the range of 0.05 to 0.5 mm. .
  • the hole packing density of the composite die 18 which is the most important point of the present invention, it is possible to prevent merging of polymers of island components with each other and to form various fiber cross-sectional forms, particularly deformed cross-sections with high accuracy.
  • the principle will be described.
  • the interval between the island component discharge holes 1 must be as close as possible, but in this case, the island component polymers merge between adjacent island component discharge holes. . Therefore, in order to prevent the island component polymers from joining each other, for example, as shown in FIG. 12, the island component discharge hole 1 is surrounded by a sea component discharge hole 4 for discharging the sea component polymer.
  • the merging of the island component polymers when the cross-sectional shape of the island component is round is mainly generated on the line connecting the centers of the adjacent island component discharge holes 1, but the irregular shape having a plurality of edge (corner) portions. In some cases, it occurs not only on the line connecting the gravity centers of the island component discharge holes 1 but also between adjacent edge portions.
  • the sea component polymer since the sea component polymer is eluted after melt spinning, it is preferable to increase the island component polymer ratio as much as possible and reduce the sea component polymer ratio. Occurrence becomes more prominent.
  • the lowermost layer distribution plate 5 has a sea component discharge hole 4 and a virtual circumference C2 having a radius R2 on a virtual circumference C1 having a radius R1 with the island component discharge hole 1 as a center.
  • the sea component discharge hole 4 and the island component discharge hole 1 are arranged on a virtual circumferential line C4 having a radius R4, satisfying the formula (1) and any one of the conditions (1) to (2) in (2) It is arranged to be.
  • conditions (a) and (b) are the arrangement patterns of the island component discharge holes 1 and the sea component discharge holes 4 in which the island component is a triangular cross section, the condition c is a hexagonal cross section, and the condition D is a quadrilateral cross section. Show.
  • a virtual circumferential line having a radius R1 as a line segment connecting the reference island component discharge hole 1 and the center point of the sea component discharge hole 4a is defined as C1, and the sea component discharge hole 4 is disposed on the virtual circumferential line C1.
  • a virtual circumferential line having a radius R2 as a line segment connecting the reference island component discharge hole 1 and the center of the sea component discharge hole 4b is used.
  • a virtual circumferential line C4 is arranged in a region sandwiched between the virtual circumferential line C1 and the virtual circumferential line C2, and satisfies the formula (1), and each virtual circumferential line C1, C2, and On C4, it arrange
  • Equation (1) is calculated by rounding off the fourth decimal place.
  • C1 Three sea component discharge holes equally divided at a central angle of 120 degrees
  • C2 Three sea component discharge holes equally divided at a central angle of 120 degrees
  • C4 Three island component discharge holes at a central angle of 120 degrees
  • ⁇ 3 The phase angle between the discharge holes arranged at C1 and C2 is 60 degrees.
  • ⁇ 5 The phase angle between the discharge holes arranged at C1 and C4 is 30 degrees.
  • C1 Six sea component discharge holes equally divided at a central angle of 60 degrees
  • C2 Six sea component discharge holes equally divided at a central angle of 60 degrees
  • C4 Six island component discharge holes at a central angle of 60 degrees ⁇ 3: The phase angle between the discharge holes arranged at C1 and C2 is 0 degree.
  • ⁇ 5 The phase angle between the discharge holes arranged at C1 and C4 is 30 degrees.
  • C1 Four sea component discharge holes are equally divided at a central angle of 90 degrees
  • C2 Eight sea component discharge holes are equally distributed at a central angle of 90 degrees
  • C4 Four sea component discharge holes are equally divided at a central angle of 90 degrees
  • the phase angle between the discharge holes arranged at C2 is 26.6 degrees.
  • ⁇ 5 The phase angle between the discharge holes arranged at C1 and C4 is 0 degree. 1 and the island component discharge hole 1a are prevented from joining each other, and the sea part discharge hole 4a on the virtual circumferential line C1 is arranged to form a straight section having an irregular cross section (triangular cross section). Then, by forming the edge portion by the arrangement of the sea component discharge holes 4b on the virtual circumferential line C2, it is possible to obtain a fiber having a uniform island component and a highly accurate cross section (triangular cross section).
  • both the island component polymer and the sea component polymer are simultaneously discharged toward the discharge introduction hole 11 on the downstream side of the lowermost layer distribution plate 5, As each polymer widens in a direction perpendicular to the direction of the polymer spinning path, the polymer flows along the direction of the polymer spinning path, and the two polymers merge to form a composite polymer stream. At that time, in order to prevent the island component polymers discharged from the reference island component discharge hole 1 and the island component discharge hole 1a from joining together, a sea component polymer that physically divides the island component polymer is interposed. The sea component polymer discharged from the sea component discharge hole 4a on the virtual circumference C1 plays this role.
  • the sea component discharge hole 4a on the virtual circumferential line C1 is to form a form in which the island component has an irregular cross section. This partially suppresses the widening of the island component polymer discharged from the reference island component discharge hole 1, that is, in order to obtain a form in which the island component has a triangular cross section, the three sea component discharge holes 4a are provided. By equally dividing at a central angle of 120 degrees, widening of the island component polymer is suppressed from three locations. And the island component which flows out from between the holes of the sea component discharge hole 4a by arranging the sea component discharge holes 4b on the virtual circumference C2 equally at a central angle of 120 degrees with a phase angle of 60 degrees.
  • the polymer is suppressed by the sea component polymer discharged from the sea component discharge hole 4b. Since the sea component discharge hole 4a and the sea component discharge hole 4b have a phase difference and are disposed on the virtual circumferential line C1 and the virtual circumferential line C2 having different radii, the sea disposed on the inner peripheral side
  • the component discharge hole 4a forms a side of a triangular cross section
  • the sea component discharge hole 4b arranged on the outer peripheral side has a role of forming an edge (corner) portion of the triangular cross section.
  • the island component polymer discharged from the reference island component discharge hole 1 and the island component polymer discharged from the island component discharge hole 1a on the virtual circumferential line C4 also have a role of suppressing merging. ing.
  • the radius R4 of the virtual circumferential line C4 is decreased, and the reference island component discharge hole 1 and the island component discharge hole 1a are formed.
  • the present inventors have found that there is a distance at which the island component polymers discharged from the respective holes widen and the island component polymers join together. This is because the space between the virtual circumference line C1 and the virtual circumference line C2 forms a space that sufficiently widens the island component polymer discharged from the island component discharge hole 1, and allows the island component polymers to merge.
  • the key is the arrangement of holes that can be suppressed. That is, it suffices to determine that the radius R4 that is the distance between the center points of the island component discharge holes 1a adjacent to the reference island component discharge hole 1 satisfies Expression (1).
  • the island component discharge hole 1 serving as a reference and the island component discharge holes 1a arranged on the virtual circumferential line C4 cannot be brought close to each other. As a result, the island packing density cannot be increased.
  • the feature of this arrangement is that the number of islands can be increased and the island packing density can be increased, but the island component polymer ratio cannot be increased to 50% or more. It is suitable to obtain a composite fiber.
  • the island component has a triangular cross section
  • three sea component discharge holes 4 are equally arranged at a central angle of 120 degrees on the virtual circumference C1 around the reference island component discharge hole 1, and on the outer circumference of the virtual circumference C4.
  • Three island component discharge holes 1 are equally divided at a central angle of 120 degrees with a phase angle of 0 degrees, and a phase angle of 60 degrees on a virtual circumferential line C2 on the outer periphery of the three island component discharge holes 1
  • the component discharge holes 4 are equally arranged at a central angle of 120 degrees.
  • the arrangement pattern in which the island component has a hexagonal cross section is arranged under the condition (2).
  • six sea component discharge holes 4 are equally arranged at a central angle of 60 degrees on a virtual circumferential line C1 around the reference island component discharge hole 1, and the outer periphery of the sea component discharge hole 1 is virtual.
  • Six island component discharge holes 1 are equally distributed at a central angle of 60 degrees with a phase angle of 30 degrees on the circumferential line C4, and a phase angle of 30 degrees on the virtual circumferential line C2 on the outer periphery thereof. Then, the six sea component discharge holes 4 are equally arranged at a central angle of 60 degrees.
  • the four sea component discharge holes 4 are equally divided at a central angle of 90 degrees on the virtual circumference C1 around the reference island component discharge hole 1, and Four island component discharge holes 1 are equally arranged at a central angle of 90 degrees on the virtual circumferential line C4 with a phase angle of 0 degree, and a phase angle of 22.5 is placed on the virtual circumferential line C2 on the outer periphery thereof.
  • the eight sea component discharge holes 4 are arranged at a certain degree.
  • a plurality of distribution plates 6 are provided.
  • the number of distribution holes 7 formed in the distribution plate 6 is in the direction of the polymer spinning path.
  • a distribution plate 6 configured to increase toward the downstream side and formed with distribution holes 7 for guiding the polymer in the direction of the polymer spinning path, and a distribution groove 8 for guiding the polymer in a direction perpendicular to the direction of the polymer spinning path.
  • the distribution holes 6 are alternately stacked, and the distribution holes 7 located on the upstream side in the direction of the polymer spinning path communicate with the distribution holes 7 located on the downstream side in the direction of the polymer spinning path.
  • a distribution groove 8 is formed.
  • a distribution hole 7 may be formed on one surface of one distribution plate 6 and a distribution groove 8 may be formed on the other surface, and the distribution hole 7 and the distribution groove 8 may communicate with each other. Further, as described above, the distribution hole 7 may be formed through the distribution plate 6, and the distribution groove 8 may be formed through the distribution plate 7.
  • a single distribution groove 8 that communicates with a single distribution hole 7 at a position downstream in the polymer spinning path direction is formed, and a plurality of distribution grooves 8 that communicate with the end of the distribution groove 8 (in FIG. 17).
  • a flow path for a tournament-type polymer constituting the two distribution holes 7 is formed.
  • the path length from the distribution hole 7 of the distribution plate 6 located at the uppermost end in the polymer spinning path direction or from the distribution groove 8 to the island component discharge hole 1 of the lowermost distribution plate 5 Are equal.
  • each distribution plate 6 has a structure in which the hole diameter of the distribution hole 7, the groove width, the groove depth, and the groove length of the distribution groove 8 are equal.
  • the distribution groove 8 communicates with two or more distribution holes 7 (in the case of a tournament type flow path having two or more branches), the distribution holes 7 on the downstream side are distributed from the distribution holes 7 on the upstream side in the polymer spinning path direction. It is preferable that the flow path pressure loss of the flow path of each polymer is equalized by equalizing the groove length, groove width, and groove depth of the distribution groove 8 that reaches the center. Further, disposing the distribution hole 7 at the end of the distribution groove 8 eliminates the abnormal retention of the polymer, has the advantage of high polymer distribution and precise control.
  • a plurality of polymer flow paths inside the distribution plate 6 formed by the distribution holes 7 and the distribution grooves 8 can be used. It is mentioned that the diameter of the distribution hole 6 in the path having a relatively long polymer flow path from the upper end to the lowermost layer distribution plate 5 is larger than the diameter of the distribution hole 6 in the relatively short path. This makes it possible to equalize the flow path pressure loss.
  • the hole diameter of the island component discharge hole 1 of the lowermost layer distribution plate 5 is set to the flow path in each flow path of the distribution plate 6 on the upstream side.
  • a structure for adjusting the pressure loss difference to be equal can be mentioned. Specifically, by increasing the diameter of the island component discharge hole 1 communicating with the flow path having a large flow path pressure loss and reducing the island component discharge hole 1 communicating with the upstream flow path having a small flow path pressure loss, It is possible to equalize the flow path pressure loss.
  • one distribution groove 8 communicates with the plurality of distribution holes 7 with respect to the downstream side in the polymer spinning path direction, and also with respect to the upstream side in the polymer spinning path direction.
  • the structure in which the flow path pressure loss of each polymer flow path is made equal is the distribution hole 7 communicating with the central portion of the distribution groove 8 and the end portion.
  • the diameter of the distribution hole 7 located at the end portion is made larger than that of the central portion, so that the flow path pressure loss can be made uniform. It becomes possible.
  • the distribution holes 7 provided in the distribution plate 6 distribute the polymer mainly in the direction of the polymer spinning path
  • the distribution groove 8 distributes the polymer mainly in the direction perpendicular to the direction of the polymer spinning path.
  • the polymer can be distributed freely and easily in the fiber cross-sectional direction, and by using this, the sea component discharge holes 4 can be arranged in a very narrow area between the adjacent island component discharge holes 1.
  • a distribution hole 6 and a distribution groove 8 are provided in the distribution plate 6 immediately above the lowermost layer distribution plate 5.
  • the island component discharge hole 1 is communicated with the distribution hole 7, and the sea component discharge hole 4 is communicated with the distribution groove 8.
  • the distribution groove 8 can be disposed at a position closer to the distribution hole 7, and the sea component discharge hole 4 communicating therewith can be disposed closer to the island component discharge hole 1.
  • the hole packing density can be increased.
  • the distribution plate 6 immediately above the lowermost layer distribution plate 5 may have a distribution hole 7 communicating with the downstream side of the distribution groove 8 in the polymer spinning path direction.
  • the distribution groove 8 communicates with the distribution hole 7 on the downstream side in the polymer spinning path direction, the same effect as described above can be obtained. Furthermore, the hole packing density of the island component discharge holes 1 of the lowermost layer distribution plate 5 is increased, that is, the sea component discharge holes 4 on the reference island component discharge holes 1 and the virtual circumferential line C1, or the virtual circumferential line.
  • the distribution plate 6 and the lowermost layer distribution plate 5 of the present invention have a laminated structure of thin plates. It has become.
  • the composite base 18 in the present invention is not limited to a circular shape, and may be a square or a polygon. Further, the arrangement of the base discharge holes 42 in the composite base 18 may be appropriately determined according to the number of sea-island composite fibers, the number of yarns, and the cooling device 17. As the cooling device 17, in the case of an annular cooling device, the base discharge holes 42 may be arranged in a ring or in a row over a plurality of rows. In the case of a one-way cooling device, the base discharge holes 42 are arranged in a staggered manner. Is good.
  • the cross section in the direction perpendicular to the polymer spinning path direction of the nozzle discharge hole 42 is not limited to a round shape, and may be a cross section other than a round shape or a hollow cross section. However, in the case of a cross-sectional shape other than a round shape, it is preferable to increase the length of the die discharge hole 42 in order to ensure the meterability of the polymer.
  • the island component discharge hole 1 in the present invention is not limited to a round shape in a cross section perpendicular to the polymer spinning path direction, and may have an irregular cross section other than a round shape or a hollow cross section.
  • the shape of the island component discharge holes 1 arranged in the lowermost layer distribution plate 5 is the same.
  • a shape other than the round cross section it is easy to obtain a fiber having a deformed cross section by making the island component discharge holes 1 similar in advance so that the island component has a desired shape.
  • the irregular cross-section fiber of the island component it becomes easier to form corners more sharply.
  • the island component discharge hole 1 has a cross-sectional shape other than a round shape
  • a round cross-sectional distribution hole 7 is arranged in communication with the island component discharge hole 1 to provide a round top right. It is preferable to discharge the polymer through the island component discharge holes 1 having a cross-sectional shape other than the round shape after ensuring the polymer meterability through the cross-sectional distribution holes 7.
  • the sea component discharge hole 4 in the present invention is not limited to a round shape in the direction perpendicular to the polymer spinning path direction, like the island component discharge hole 1, and has a cross-sectional shape other than a round shape. Also good. In this case, it is preferable that all the sea component discharge holes 4 arranged in the lowermost layer distribution plate 5 have the same shape.
  • the discharge introduction hole 11 in the present invention is provided with a constant running section from the lower surface of the lowermost layer distribution plate 5 in the polymer spinning path direction, so that the flow velocity difference immediately after the island component polymer and the sea component polymer merge. Can be relaxed and the composite polymer stream can be stabilized.
  • the hole diameter of the discharge introduction hole 11 is larger than the outer diameter of the virtual circle 52 of each discharge hole group of the island component discharge hole 1 and the sea component discharge hole 4 disposed in the lowermost layer distribution plate 5 and is virtual. It is preferable that the cross-sectional area ratio of the circle 52 and the cross-sectional area ratio of the discharge introduction hole 11 be as small as possible. Thereby, the widening of each polymer discharged from the lowermost layer distribution plate 5 is suppressed, and the composite polymer flow can be stabilized.
  • the reduction hole 12 in the present invention is unstable such as draw resonance of the composite polymer flow by setting the reduction angle ⁇ of the flow path from the discharge introduction hole 11 to the die discharge hole 42 in the range of 50 to 90 °. It is possible to suppress the phenomenon and supply the composite polymer stream stably.
  • the reduction angle ⁇ is smaller than 50 °, the instability phenomenon of the composite polymer flow can be suppressed, but the composite base 18 itself is enlarged, and when the reduction angle ⁇ is larger than 90 °, the composite polymer flow is reduced. Instability phenomenon may become more prominent.
  • the island component discharge hole 1, sea component discharge hole 4 and distribution hole 7 in the present invention preferably have a constant hole cross-sectional area in the polymer spinning path direction, but the cross-sectional area gradually decreases or increases, Alternatively, it may be gradually decreased and gradually increased. This is because, in the distribution plate 6 and the lowermost layer distribution plate 5 in the present invention, holes are cut mainly using an etching process, so that when the minute holes are processed, the holes are cut in the direction of the polymer spinning path. This is because the area may not be constant. In that case, the processing conditions and the like may be appropriately optimized.
  • the lowermost layer distribution plate 5 in the present invention may be one, or a plurality of layers may be laminated.
  • the single lowermost layer distribution plate 5 when the polymer meterability of the island component discharge hole 1 and the sea component discharge hole 4 cannot be obtained and the fiber form changes with time, a plurality of sheets are laminated. Thus, the meterability of the polymer can be ensured.
  • one distribution plate 6 of the present invention may be provided with a distribution hole 7 on the upstream side of the distribution plate 6 and a distribution groove 8 (downstream side) in communication therewith.
  • the distribution groove 8 may be disposed on the upstream side of the distribution plate 6, and the distribution hole 7 (downstream side) may be disposed in communication therewith. In this way, the polymer can be distributed by communicating the distribution hole 7 and the distribution groove 8 and repeating this one or more times.
  • the tournament method is most preferable as a method for distributing the polymer of one component on the distribution plate 6, but as shown in FIG. 38, one distribution groove 8 or a plurality of distribution holes 7 is provided.
  • a slit method in which a plurality of distribution grooves 8 are formed for a plurality of distribution holes 7 may be used, or a combined method in which a tournament method and a slit method are combined.
  • the polymer of the other components also adopts the same distribution method as described above, but only one component polymer will be described for the sake of simplicity.
  • the tournament method has the advantage that the distribution hole 7 is disposed at the end of the distribution groove 8 to eliminate abnormal retention of the polymer, the polymer distribution property is high, and the control can be precisely performed.
  • the polymer is not distributed downstream, and as a result, a desired composite cross-section fiber may not be obtained. is there.
  • the slit method has a plurality of distribution holes 7 for one distribution groove 8, it is highly compatible with problems such as blockage of the holes and grooves, and one distribution plate. 6 allows a large amount of polymer to be distributed in a direction perpendicular to the direction of the polymer spinning path. Therefore, the number of distribution plates 6 can be reduced, which has the advantage of reducing the manufacturing cost of the composite die 18. However, on the other hand, abnormal retention of the polymer is likely to occur, and the precise control of the polymer distribution may be inferior to the tournament method.
  • the polymer is uniformly distributed on the downstream side by improving the meterability of the polymer.
  • the distribution on the inflow side is performed.
  • the diameter of the distribution hole 7 on the outflow side is smaller than the diameter of the distribution hole 7 on the inflow side with respect to the hole 7, and the diameter of the far side is increased.
  • the hole diameter is adjusted so that the flow path pressure loss is equal between the distribution hole 7 (outflow side) closer to the inflow side distribution hole 7 and the distant distribution hole 7 (outflow side).
  • the flow path pressure loss may be adjusted by the groove width of the flow path groove 8.
  • the dimensions of the distribution holes 7 and the distribution grooves 8 may be adjusted, but the distribution plate in contact with the lowermost layer distribution plate 5. Only the six distribution holes 7 may be adjusted in diameter so that all the flow path pressure losses on the upstream side are equal.
  • the tournament method as a method for suppressing the blockage of the holes and grooves, it is preferable to increase the hole diameter of the distribution holes 7, the groove width and the groove depth of the distribution grooves 8, and particularly in the direction of the polymer spinning path. It is better to increase the thickness of the distribution plate 6 constituting the distribution groove 8 and to increase the depth of the distribution groove 8 on the upstream side (the measuring plate 9 side), and to the upstream side in the polymer spinning path direction. It is better to increase the groove width of the distribution groove 8 and to increase the hole diameter of the distribution hole 7 toward the measuring plate 9 side. Further, regarding the polymer distribution method on the distribution plate 6, the distribution groove 8 and the distribution hole 7 of the distribution plate 6 may be appropriately arranged according to the desired fiber cross-sectional shape, and the method is not particularly limited to the above method. Absent.
  • the method for producing the composite fiber of the present invention may be a known composite spinning machine using the composite base 18 of the present invention.
  • the spinning temperature is set to 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 spinning speed varies depending on the physical properties of the polymer and the purpose of the composite fiber, but can be about 500 to 6000 m / min.
  • a high molecular weight polymer set to 500 to 2000 m / min, and then stretch at a high magnification.
  • the upper limit of the preheating temperature is preferably a temperature at which yarn path disturbance does not occur due to spontaneous elongation of the fiber during the preheating process. For example, in the case of PET having a glass transition temperature around 70 ° C., this preheating temperature is usually set at about 80 to 95 ° C.
  • the discharge rate ratio of the polymer of each component discharged from the island component discharge hole 1 and the sea component discharge hole 4 of the present invention is controlled by the discharge amount, the hole diameter, and the number of holes.
  • the discharge speed is a value obtained by dividing the discharge flow rate by the cross-sectional area of the island component discharge hole 1 or the sea component discharge hole 4.
  • the discharge speed range is the discharge speed of the island component polymer per single hole.
  • the ratio (Va / Vb or Vb / Va) is preferably 0.05 to 20, more preferably 0.1 to 10. In this range, since the polymer discharged from the lowermost distribution plate 5 is led as a laminar flow through the discharge introduction hole 11 to the reduction hole 12, the cross-sectional shape is remarkably stabilized and the shape is maintained with high accuracy. be able to.
  • the composite polymer flow can be stably formed by setting the melt viscosity ratio of the polymer used in the present invention to less than 2.0.
  • the melt viscosity ratio is 2.0 or more, the island component polymer and the sea component polymer become unstable when they merge, and there are cases where uneven thickness of the yarn occurs in the traveling direction of the obtained fiber cross section.
  • a pattern is transferred to a thin plate, which is usually used for processing of electric / electronic parts, and fine processing is performed by chemical processing.
  • Etching is preferred.
  • etching is a processing method that applies a chemical reaction and corrosive action of chemicals such as an etchant to etch a thin plate (dissolution processing / chemical cutting), and masks the required processing shape (necessary)
  • the target processed shape can be obtained with very high accuracy by removing the unnecessary portion with a corrosive agent such as an etching solution.
  • this processing method does not require consideration to the thermal strain of the workpiece, there is no restriction on the lower limit of the thickness of the workpiece compared to the other processing methods described above, and the present invention can be applied to an extremely thin metal plate.
  • the junction grooves 8, the distribution holes 7, and the island component discharge holes 1 can be formed.
  • the distribution plate 6 and the lowermost layer distribution plate 5 manufactured by etching can be reduced in thickness per sheet, the effect on the total thickness of the composite base 18 even if a plurality of sheets are stacked. There is almost no need to newly install another pack member in accordance with the composite fiber having a desired cross-sectional shape. In other words, if only the distribution plate 6 and the lowermost layer distribution plate 5 are exchanged, the cross-sectional shape can be changed. Further, as another manufacturing method, it is possible to use a lathe, machining, press, laser processing, or the like, which is a drill processing or metal precision processing used in conventional base manufacturing.
  • the thickness of the distribution plate 6 is applicable to the composite die of the present invention in which a plurality of distribution plates are laminated. Need to be considered.
  • the fiber obtained by the composite base of the present invention means a fiber in which two or more kinds of polymers are combined, and two or more kinds of polymers are present in the form of a sea island or the like in the fiber cross section.
  • the two or more types of polymers referred to in the present invention include the use of two or more types of polymers having different molecular structures such as polyester, polyamide, polyphenylene sulfide, polyolefin, polyethylene, and polypropylene.
  • matting agents such as titanium dioxide, silicon oxide, kaolin, anti-coloring agents, stabilizers, antioxidants, deodorants, flame retardants, yarn friction reducing agents, coloring, as long as the yarn-making stability is not impaired.
  • examples include various functional particles such as pigments and surface modifiers, additives such as organic compounds, and different amounts of particles added, different molecular weights, and copolymerization.
  • the cross section of the single yarn of the fiber obtained by the composite base 18 of the present invention may be not only a round shape but also a shape other than a round shape such as a triangle or a flat shape or a hollow shape.
  • the present invention is an extremely versatile invention, and is not particularly limited by the single yarn fineness of the composite fiber, is not particularly limited by the number of single yarns of the composite fiber, and further, the number of yarns of the composite fiber Is not particularly limited, and may be a single yarn or a multi-yarn of two or more yarns.
  • sea-island type composite fibers obtained by the composite die of the present invention are shown in (a), (b), (c) of FIG. 8 and (a), (b), (c), (d) of FIG.
  • a sea-island structure (the sea-island structure referred to here is an island portion composed of the island component polymer 13 is composed of the sea component polymer 20).
  • the cross-sectional shape of the island portion is not limited, and the cross-sectional shape of the island portion may be configured by one island component discharge hole 1 as shown in FIG. 1 or FIG.
  • the cross-sectional shape may be configured by an island component discharge portion 21 in which a plurality of island component discharge holes 1 are gathered.
  • a sea-island type composite fiber having a triangular cross section as shown in FIG. 8A can be obtained.
  • a hexagonal cross section as shown in FIG. 8 (b) is obtained, and as shown in FIG.
  • a sea-island type composite fiber having a square cross section as shown in FIG. 8C can be obtained.
  • a sea-island structure (the sea-island structure referred to here is an island portion composed of the island component polymer 13).
  • the cross-sectional shape of the island portion is not limited, the cross-sectional shape of the island portion is controlled by the cross-sectional shape of the island component discharge hole 1, and the island portion is determined by the combination of the cross-sectional shapes of the island component discharge hole 1 and the discharge hole 25. The cross-sectional shape is controlled.
  • the island component discharge hole 1 has a round shape and the discharge hole 25 has a star shape, or the island component discharge hole 1 has a star shape and the discharge hole 25 has a round shape.
  • the shape of the island portion can be changed to a star shape.
  • a core-sheath composite fiber is obtained by comprising the island part of sea-island composite fiber by two types of island component polymer 13 (c) and island component polymer 13 (d). Can do.
  • the core-sheath composite fiber is configured such that the sheath component covers the core component in a cross section perpendicular to the fiber axis direction of two or more different polymers.
  • a third component polymer surrounding the composite core-sheath component polymer flow obtained at the discharge hole 25 of the lower layer plate 37 is used.
  • a multi-core sheath fiber can be formed by laminating the distribution plates to be discharged.
  • this core-sheath composite fiber is not limited to being excellent in quality and sensitivity when used for clothing, but also from the standpoint of mechanical properties, chemical resistance, and heat resistance. Since it becomes the fiber which has the characteristic which cannot be taken out with a polymer, it can be used effectively also for an industrial material use. In particular, bending fatigue and wear characteristics are improved as compared with conventional products, and it can be suitably used not only for rubber reinforcement applications such as tire cords and tire cap layer materials, but also for fishing nets and agricultural materials, as well as screen rods.
  • side-by-side composite fibers can be obtained by configuring the island portion of the sea-island composite fibers with two types of island component polymers.
  • a side-by-side composite fiber is a structure in which two or more different polymers are bonded to each other in a cross section perpendicular to the fiber axis direction, and the cross-sectional form is regularly arranged with one or two kinds of intervals. Say fiber.
  • the island component discharge hole 1 for discharging the island component polymer (A) 13 and the island component polymer (A) 13 different from the island component polymer (A) 13 in the upper layer plate 29 of the composite base 18 are used.
  • the island component discharge holes 4 for discharging 14 may be collected as discharge hole groups, and the discharge hole groups may be arranged adjacent to each other and arranged symmetrically or asymmetrically.
  • a side-by-side composite fiber can be obtained by eluting the sea component polymer.
  • two or more types of polymers may be laminated together, and it is also preferable to impart three or more types of properties by bonding three or more types of polymers.
  • this side-by-side composite fiber a fiber having shrinkage characteristics and dyeing characteristics changed in the cross-sectional direction in the fiber cross-sectional direction can be obtained.
  • a polymer that exhibits shrinkage due to moisture absorption is placed on one side, the mesh of the fabric changes due to moisture absorption, so that the fabric has a breathable self-adjusting function and a moisture-permeable waterproof function for clothing.
  • the number of islands obtained using the composite base of the present invention it is theoretically possible to make an infinite range from two islands within the space allowed, but as a practically feasible range, 2 to 10,000 islands is a preferred range. As a range for obtaining the superiority of the composite die of the present invention, 100 to 10,000 islands is a more preferable range.
  • a hole filling density is 0.5 hole / mm ⁇ 2 > or more. If the hole filling density is 0.5 hole / mm 2 or more, the difference from the conventional composite die technology becomes more clear. In the range examined by the present inventors, the hole packing density was 0.5 to 20 holes / mm 2 . From the viewpoint of the hole packing density, the range in which the superiority of the composite die of the present invention is obtained is preferably 1 to 20 holes / mm 2 .
  • the sea-island type composite fiber according to the present invention is a very fine deformed fiber that cannot be obtained by single spinning by eluting the sea component polymer 20, and has a circumscribed fiber diameter of 10 to 1000 nm and a fiber diameter variation. It is possible to produce a long-fiber nanofiber having excellent uniformity with a fiber diameter CV% representing 0 to 30%.
  • the long fiber type nanofibers can be suitably used for finishing the aluminum alloy substrate or the glass substrate used for a magnetic recording disk or the like with ultrahigh precision.
  • the composite form that can be manufactured by the composite base 18 of the present invention has been described by exemplifying a conventionally known cross-sectional form.
  • the cross-sectional form can be arbitrarily controlled. Therefore, a free form can be produced without being restricted by the above form.
  • the strength of the composite fiber of the present invention is preferably 2 cN / dtex or more, and is preferably 5 cN / dtex or more in view of mechanical properties required for industrial materials.
  • a practical upper limit is 20 cN / dtex.
  • the elongation is preferably 2 to 60% for drawn yarn, particularly 2 to 25% in the industrial material field where high strength is required, and 25 to 60% for clothing.
  • the conjugate fiber of the present invention can be used in various fiber products such as fiber winding packages, tows, cut fibers, cotton, fiber balls, cords, piles, woven and knitted fabrics, non-woven fabrics, paper, and liquid dispersions.
  • FIG. 33 is a schematic cross-sectional view of the composite base used in the first embodiment
  • FIG. 34 is a schematic cross-sectional view around the composite base used in the first embodiment, the spin pack, and the cooling device.
  • 24 is a partial enlarged cross-sectional view of FIG. 33
  • FIG. 29 is a view taken in the direction of arrows YY of FIG. 24
  • FIG. 27 is a partial enlarged cross-sectional view of the composite base used in the first embodiment.
  • FIG. 25 is a partially enlarged cross-sectional view of the composite base used in the second embodiment
  • FIG. 26 is a partially enlarged cross-sectional view of the composite base used in the third embodiment
  • FIG. FIG. 30 is a view taken along the line XX
  • FIG. 30 is a view taken along the line ZZ in FIG.
  • 36 is an intermediate layer plate
  • 37 is a lower layer plate
  • 38 is an upper layer protruding portion
  • 39 is a virtual circumscribed circle
  • 46 is a lower surface of the upper layer protruding portion
  • 47 is an upper surface of the lower layer plate
  • 48 is a merge chamber
  • 49 is a virtual inscribed plate.
  • Circles and 50 indicate outer peripheral end holes, respectively.
  • the composite base 18 used in the first embodiment is mounted on the spin pack 15, is fixed in the spin block 16, and a cooling device 17 is configured immediately below the composite base 18. Therefore, the two or more polymers introduced to the composite base 18 pass through the measuring plate 9, the distribution plate 6, the upper layer plate 29, the middle layer plate 36, and the lower layer plate 37, respectively, and then the base discharge hole 42 of the discharge plate 10. After being discharged from the air, it is cooled by an air flow blown out by the cooling device 17 and applied with an oil agent, and then wound as a multifilament yarn.
  • the composite base 18 used in the first embodiment includes a measuring plate 9, a plurality of distribution plates 6, an upper layer plate 29, an intermediate layer plate 36, a lower layer plate 37, and a discharge plate 10 that are sequentially stacked.
  • the distribution plate 6, the upper layer plate 29, the middle layer plate 36, and the lower layer plate 37 are preferably formed of thin plates.
  • the measuring plate 9 and the distribution plate 6, the upper layer plate 29, the middle layer plate 36, the lower layer plate 37, and the discharge plate 10 are positioned by the positioning pins so that the center position (core) of the spinning pack 18 is aligned, After the lamination, it may be fixed with screws, bolts, etc., or may be metal bonded (diffusion bonded) by thermocompression bonding.
  • the distribution plates 6, the distribution plate 6 and the upper layer plate 29, the upper layer plate 29 and the middle layer plate 36, and the middle layer plate 36 and the lower layer plate 37 use thin plates, metal bonding (diffusion bonding) is performed by thermocompression bonding. Is preferred.
  • the polymer of each component supplied from the measuring plate 9 passes through the distribution grooves 8 and the distribution holes 7 of the plurality of stacked distribution plates 6, and then is the upper layer plate.
  • the outer periphery of the island component polymer is discharged from the island component discharge hole 1 for discharging 29 island component polymers and the sea component discharge hole 4 for discharging the sea component polymer into the joining chamber 48 of the intermediate layer plate 36.
  • the sea component polymer surrounds, and a core-sheath sea-island composite polymer flow is formed. Thereafter, the core-sheath sea-island composite polymer flow passes through the discharge holes 25 of the lower layer plate 37, passes through the discharge introduction holes 11 and the reduction holes 12 of the discharge plate 10, and is discharged from the base discharge holes 42.
  • the sea component discharge holes 4 are necessary. For example, as shown in FIG. 41, an array that surrounds the six sea component discharge holes 4 from six directions on the basis of one island component discharge hole 1 In this case, three times as many sea component discharge holes 4 as island component discharge holes 1 are required.
  • the island component polymers are merged with each other.
  • the hole filling density cannot be increased. There is a trade-off between the packing density and the merging of the island component polymers.
  • the island component polymer in order to uniformly discharge the island component polymer from all the island component discharge holes 1 arranged in the upper layer plate 29, the island component polymer is formed at the island component discharge hole 1 or upstream thereof. It is necessary to provide a mechanism for uniformly supplying, distributing, and weighing the liquid. Therefore, for example, as shown in FIG. 18, as the measuring mechanism, there is a protrusion 43 around the island component discharge hole 1, and by narrowing the gap, the flow path pressure loss is increased. In this case, the island component discharge holes 1 cannot be disposed closely, and the number of island component discharge holes 1 that can be disposed in the upper layer plate 29 is restricted, so that the hole filling density cannot be increased.
  • a radial groove 27 is disposed around the discharge hole 1 and a concentric groove 28 is disposed around the discharge hole 25.
  • the island component discharge hole 1 and the discharge hole 25 opposed thereto are provided. Cannot be disposed closely, and the number of island component discharge holes 1 that can be disposed on the upper layer plate 29 is limited, and the hole filling density cannot be increased.
  • the plurality of stacked distribution plates 6 have distribution holes 7 and / or for distributing the island component polymer and the sea component polymer, respectively.
  • the distribution groove 8 is formed, and the upper layer plate 29 is arranged with one or more sea component discharge holes 4 communicating with the distribution holes 7 or the distribution grooves 8 and more islands than the number of the sea component discharge holes 4.
  • the component discharge hole 1 is formed, the middle plate 36 is formed with a merge chamber 48 communicating with the island component discharge hole 1 and the sea component discharge hole 4, and the lower layer plate 37 is discharged with the merge chamber 48.
  • a hole 25 is formed at a position facing the island component discharge hole 1.
  • the island component polymer is discharged into the merge chamber 48 where the sea component polymer is filled around all the island component discharge holes 1, so that the outer periphery of the island component polymer is immediately after the discharge.
  • the sea component polymer surrounds and forms a core-sheath type sea-island composite polymer flow, it is guided to the discharge hole 25, so that it is difficult for the island component polymers to merge.
  • the flow path pressure loss of a plurality of polymer flow paths from the distribution plate 6 at the upper end in the polymer spinning path direction to the island component discharge holes 1 of the upper layer board 29 is made equal to be arranged on the upper layer board 29. It is possible to uniformly discharge the island component polymer from all the island component discharge holes 1 and suppress the merging of the island component polymers. As a result, a uniform core-sheath sea-island composite polymer flow can be formed, and a highly accurate fiber cross-sectional form can be formed.
  • an etching process that is usually used for processing electric / electronic parts is suitable.
  • the distance between the adjacent island component discharge holes 1 can be made closer, and also in the lower layer plate 37, the distance between the adjacent discharge holes 25 can be made closer. It is possible to increase the packing density.
  • the upper layer plate 29 is provided with sea component discharge holes 4 around the island component discharge holes 1 in which hole groups are formed.
  • the island component discharge holes 1 can be arranged densely, and the hole filling density can be increased.
  • the island component discharge holes 1 forming the hole group are preferably arranged with periodicity, but may be arranged non-periodically.
  • the sea component discharge holes 4 disposed around the island component discharge holes 1 are preferably disposed so as to surround the entire circumference of the hole group, but this is not a limitation.
  • the sea component discharge holes 4 may be provided only on two opposing side surfaces.
  • the sea component discharge is performed in the region where the island component discharge holes 1 arranged in the upper layer plate 29 form a hole group (in FIG. 30, a hole group region of 5 rows ⁇ 4 columns).
  • the holes 4 may be provided.
  • the hole filling density is slightly lower than the hole arrangement of the island component discharge holes 1 as shown in FIG. 29, but the sea component discharge holes 4 are provided, so that the sea area is formed in the center of the hole group region.
  • the distribution hole 6 and the distribution plate 6 in which the distribution groove 8 is formed are provided. This is possible by stacking and forming a flow path communicating with the sea component discharge hole 4 in the region of the island component discharge hole 1. Since the composite base uses a plurality of distribution plates 6 to form the flow path, the degree of freedom of the flow path is high, and the necessary number of island component discharge holes 1 and sea component discharge holes 4 are arranged at necessary positions. Can be set. Therefore, as described above, the arrangement of the island component discharge holes 1 and the sea component discharge holes 4 may be appropriately determined according to the polymer physical properties, the spinning conditions, and the like.
  • the upper layer plate 29 and the middle layer plate 36 are formed of the same thin plate. Therefore, by previously forming the merge chamber 48, the island component discharge holes 1, and the sea component discharge holes 4 in one thin plate by etching, the number of thin plates to be stacked is reduced, and as a result, the composite base is manufactured. Costs can be reduced. However, since the processing accuracy of the holes and grooves formed in the thin plate may deteriorate during the etching processing, it is preferable to confirm the processing accuracy in advance and determine the plate thickness, hole diameter, groove width, and the like. Although omitted in the specification, the middle layer plate 36 and the lower layer plate 37 may be composed of the same thin plate, and in this case, has the same characteristics as described above.
  • the third embodiment shown in FIGS. 26 and 28 will be described.
  • the third embodiment has an upper layer protruding portion 38 that protrudes downstream from the lower surface of the upper layer plate 29 in the polymer spinning path direction around the island component discharge hole 1.
  • a discharge hole 25 having a virtual circumscribed circle 39 larger than the outer peripheral shape of the portion 38 and a virtual inscribed circle 49 smaller than the outer peripheral shape of the upper layer protruding portion 38 is formed, and the lower surface 46 of the upper layer protruding portion 38 is formed as a lower layer plate
  • An outer end hole 50 is formed around the end of the upper layer protrusion 38 and is disposed on the same surface as or below the upper surface 47 of 37 and in the direction of the polymer spinning path.
  • the island component polymer is discharged from the discharge hole 25 toward the downstream side in the polymer spinning path direction, and the sea component polymer is spun from the outer end hole 50 around the end of the upper layer protruding portion 38. It is discharged toward the downstream side in the exit path direction, and then merges so that the sea component polymer surrounds the outer periphery of the island component polymer, forming a core-sheath composite polymer stream, and downstream in the polymer spinning path direction. Led.
  • a highly accurate cross-sectional shape of the island component polymer can be formed, but further, by adopting the third embodiment, the island component polymer, the sea component polymer, and the core-sheath composite polymer flow Forming all in the same direction, avoiding unnecessary collision of polymer flow and suppressing polymer turbulence, form a more accurate island component polymer cross-sectional shape and maintain this cross-sectional shape with high dimensional stability can do.
  • the strength of the distribution plate can be improved by configuring the thin plate in multiple layers and crimping.
  • the lower surface 46 of the upper layer protrusion 38 and the lower layer plate By joining the upper surface 47 of 37 on the same surface, the strength of the thin plate can be further improved, bending and the like can be suppressed, and poor polymer distribution due to bending can be suppressed.
  • the cross section of the island component discharge hole 1 in the direction perpendicular to the polymer spinning path direction is round, and the cross section in the direction perpendicular to the polymer spinning path direction of the discharge hole 25 is different.
  • An island component cross section can be made into an irregular shape. For example, as shown in FIG.
  • the obtained island component cross section has a cross shape.
  • the cross-sectional shapes of the island component discharge holes 1 and the discharge holes 25 may be appropriately determined in accordance with the desired island component cross-sectional shape. Although omitted in the specification, the island component discharge holes 1 may be formed in a cross shape and the discharge holes 25 may be formed in a round shape. In this case, the same features as described above are provided.
  • the manufacturing method of the conjugate fiber in the first, second, and third embodiments includes the measuring plate 9, the distribution plate 6, the upper layer plate 29, the middle layer plate 36, the lower layer plate 37, and the discharge.
  • a core-sheath composite fiber can be obtained by performing melt spinning using the composite base 18 composed of the plate 10.
  • FIG. 19 is a partially enlarged plan view of a composite base used in another embodiment of the present invention.
  • the composite base 18 used in another embodiment of the present invention is configured by laminating a measuring plate 9, at least one distribution plate 6, a lowermost layer distribution plate 5, and a discharge plate 10 in order.
  • the distribution plate 6 and the lowermost layer distribution plate 5 are preferably formed of thin plates. Therefore, as shown in FIG. 19, the polymer of each component supplied from the measuring plate 9 passes through the distribution groove 8 and the distribution hole 7 of the distribution plate 6 laminated at least one, and then the lowermost layer distribution plate.
  • the polymers of the respective components merge to form a composite polymer flow.
  • the composite polymer flow passes through the discharge introduction hole 11 and the reduction hole 12 of the discharge plate 10 and is discharged from the base discharge hole 42.
  • the interval between the island component discharge holes 1 must be as close as possible, but in this case, the island component polymers merge between adjacent island component discharge holes. .
  • the island component discharge hole 1 is surrounded by the sea component discharge hole 4 for discharging the sea component polymer.
  • the distance between the island component discharge holes becomes too large to increase the hole filling density. In other words, there is a trade-off relationship between the hole packing density and the prevention of merging of the island component polymers.
  • the lowermost layer distribution plate 5 includes two island component discharge holes that are adjacent to each other at the shortest center point distance, and two common outer tangent lines of the two island component discharge holes.
  • Each discharge hole is arranged so that at least a part of the sea component discharge hole exists in the enclosed region.
  • the island component discharge hole 1 adjacent to the reference island component discharge hole 1 at the shortest center distance is referred to as an island component discharge hole 53a.
  • the sea component discharge hole 1 is located in a region surrounded by the reference island component discharge hole 1, the island component discharge hole 53a, and the two common circumscribed lines 54 of the two island component discharge holes 1 and 53a.
  • Each discharge hole is arranged so that at least a part of 4 is present.
  • both the island component polymer and the sea component polymer are simultaneously discharged toward the discharge introduction hole 11 on the downstream side of the lowermost layer distribution plate 5, As each polymer widens in a direction perpendicular to the direction of the polymer spinning path, the polymer flows along the direction of the polymer spinning path, and the two polymers merge to form a composite polymer stream. At that time, in order to prevent the island component polymer discharged from the reference island component discharge hole 1 and the island component discharge hole 53a from joining, a sea component polymer that physically divides the island component polymer is interposed. Is effective.
  • a channel space connecting the reference island component discharge hole 1 and the island component discharge hole 53a (in this case, the reference island component discharge hole 1, the island component discharge hole 53a, and the two island component discharge holes 1, 53a).
  • the reference island component discharge hole 1 and the island component discharge hole 53a in this case, the reference island component discharge hole 1, the island component discharge hole 53a, and the two island component discharge holes 1, 53a.
  • the island component discharge holes 1 are often formed with one or two periods.
  • the island component discharge holes 1 are formed in two types of cycles. One is the distance between the center points of the reference island component discharge hole 1 and the island component discharge hole 53a, which is the shorter cycle. This shorter cycle is the aforementioned “shortest distance between center points”. The other is the distance between the center points of the reference island component discharge hole 1 and the island component discharge hole 53b, which is the longer cycle.
  • the distance between the center points of the reference island component discharge holes 1 and the island component discharge holes 53a, the reference island component discharge holes 1 and the island component discharge holes is the same.
  • the repetition directions of the two types of cycles are orthogonal, but they may not be orthogonal.
  • the island component discharge holes 1 are formed with two types of cycles, (i) a reference island component discharge hole 1 and an island component discharge hole 53a adjacent to each other with a shorter cycle, and the two island component discharge holes 1 , 53a and at least a part of the sea component discharge hole 4 in the region surrounded by the two common outer tangent lines 54, and (ii) a reference island component discharge hole adjacent in a longer cycle 1. Arranged so that at least a part of the sea component discharge hole 4 exists in a region surrounded by the island component discharge holes 53b and the two common outer tangent lines 54 of the two island component discharge holes 1 and 53b. It is preferable to do.
  • the shortest distance between the center points that is, the shortest distance between the center points, that is, the longer one, so that the island component polymers discharged from the two adjacent island component discharge holes 1 and 53a in the shorter cycle can be easily merged.
  • the island component polymers discharged from the two adjacent island component discharge holes 1 and 53b with a period of are easily joined together. Therefore, the island component is arranged by disposing at least part of the sea component discharge hole 4 for supplying the sea component polymer also in the channel space connecting the reference island component discharge hole 1 and the island component discharge hole 53b. Merge of polymers can be prevented.
  • the lowermost layer distribution plate 5 has at least a region surrounded by two adjacent island component discharge holes and two common circumscribing lines of the two island component discharge holes. It is preferable that at least a part of each of the two sea component discharge holes is present, and the two sea component discharge holes are arranged across a line segment connecting the centers of the two adjacent island component discharge holes. Specifically, as shown in FIG. 19, two adjacent island component discharge holes 1 (reference island component discharge hole 1 and island component discharge hole 53a, or reference island component discharge hole 1 and island component discharge hole 53b).
  • each of the at least two sea component discharge holes 4 and two adjacent island component discharge holes 1 (reference island component discharge hole 1 and island component discharge hole 53a, and The two sea component discharge holes 4 are arranged across a line segment A connecting the centers of the reference island component discharge hole 1 and the island component discharge hole 53b).
  • the two sea component discharge holes 4 can be arranged at the closest positions, so that the hole filling density is increased to the limit.
  • positioning of the two sea component discharge holes 4 is not specifically limited, It is preferable to arrange
  • the island component polymer discharged and widened from the island component discharge hole 1 is rejected to widen by the sea component polymer discharged from the two sea component discharge holes 4 and has a certain shape. It is preferable that the discharge holes 4 are arranged so that the line segment A is an axis of line symmetry, because the shape of the island component polymer after widening becomes a clean target shape having the line segment A as an axis of line symmetry.
  • the lowermost layer distribution plate 5 according to another embodiment of the present invention shown in FIG. 40 has a plurality of island component discharge holes 1 for discharging the island component polymers to be merged in order to intentionally merge the island component polymers. May be collected to form a hole group (aggregate). Further, in order to intentionally join the sea component polymers, a plurality of sea component discharge holes 4 for discharging the sea component polymers to be joined may be collected to form a hole group (aggregate). In this case, among the island component discharge holes 1 constituting one hole group, an area surrounded by a line connecting the outermost island component discharge holes 1 so as to be in contact with each other in sequence is an island component discharge unit.
  • sea component discharge holes 4 constituting one hole group
  • a region surrounded by a line connecting the outermost sea component discharge holes 4 so as to be in contact with each other sequentially is defined as a sea component discharge portion.
  • the hole group of the island component discharge holes 1 is the island component discharge hole portion 21
  • the hole group of the island component discharge holes 53 a is the island component discharge hole portion 22 a
  • the hole group of the island component discharge holes 53 b is the island component discharge hole portion 22 b
  • a group of sea component discharge holes 4 is defined as a sea component discharge hole portion 24.
  • the island component discharge hole 1, the island component discharge hole 53a, the island component discharge hole 53b, and the sea component discharge hole 4 in the description so far are designated as islands. What is necessary is just to read as the component discharge part 21, the island component discharge part 22a, the island component discharge part 22b, and the sea component discharge part 24.
  • the island component discharge part is constituted by one island component discharge hole, and the inside of the sea component discharge part is one sea component discharge. It is a lowermost layer distribution plate composed of holes.
  • FIG. 19 the island component discharge part is constituted by one island component discharge hole, and the inside of the sea component discharge part is one sea component discharge. It is a lowermost layer distribution plate composed of holes.
  • the island component polymer discharged from the island component discharge hole 1 (2a, 2b) in the island component discharge portion 21 (22a, 22b) or the sea component discharge hole in the sea component discharge portion 24 is used.
  • the sea component polymers discharged from No. 4 are merged immediately after the discharge, but are originally intended to be merged, so there is no problem even if they merge.
  • the minimum gap DA between the two adjacent island component discharge holes 1 and the minimum gap DB between the two sea component discharge holes 4 are DB / DA ⁇ 0.7.
  • the merging of the island component polymers can be stably prevented.
  • DB / DA> 0.7 merging of island component polymers may occur.
  • the lower limit of DB / DA is not particularly defined, and the smaller the smaller, the more the island component polymers can be prevented from joining, but the minimum gap DA becomes larger and the hole filling density becomes smaller. And the lower limit can be set.
  • the island component discharge holes 1 and the sea component discharge holes 4 may be disposed on the entire surface, or as shown in FIG.
  • the discharge holes 1 and the sea component discharge holes 4 may be densely arranged (portion surrounded by a virtual circle 52 in FIG. 39).
  • the island component discharge in the virtual circle 52 is performed.
  • the arrangement of the holes 1 and the sea component discharge holes 4 may be the same for all virtual circles 52 or may be different for each virtual circle 52. Furthermore, as shown in FIG.
  • the arrangement of the island component discharge holes 1 and the sea component discharge holes 4 may be partially different in one virtual circle 52 (the right side in the virtual circle 52 in FIG. 39). Half and left half). Also in this case, the island component discharge holes 1 and the sea component discharge holes 4 in the individual portions may be arranged as described so far.
  • the composite base 18 of another embodiment of the present invention can easily distribute the sea component polymer in the fiber cross-sectional direction by using the lowermost distribution plate 5 and the distribution groove 8 of the distribution plate 6 immediately above the lower distribution plate 5. Therefore, the sea component discharge part 24 or the sea component discharge hole 4 can be easily arranged in a very narrow region between the two adjacent island component discharge parts 21 or the island component discharge holes 1. As a result, the hole filling density can be increased by bringing two adjacent island component discharge portions 21 or island component discharge holes 1 close to each other. Moreover, since the arrangement pattern of the island component discharge holes 1 can be easily changed by adding and overlapping the distribution plate 6 directly below the lowermost layer distribution plate 5, the time and cost associated with the design change are reduced. There are also advantages.
  • FIG. 35 is a fifth embodiment
  • FIG. 36 is a partially enlarged plan view of a composite base used in the sixth embodiment
  • FIG. 37 is a schematic partial sectional view of the lowermost layer distribution plate. .
  • the fifth embodiment shown in FIG. 35 includes two adjacent island component discharge holes 1 (reference island component discharge hole 1 and island component discharge hole 53a, and reference island component discharge hole 1 and island component discharge hole 53b).
  • the sea component discharge hole 4 is disposed so as to completely block the flow path space connected by the.
  • the sea component polymer since the sea component polymer is present in a path space where the island component polymers are expected to merge with each other, the island component polymers can be further prevented from joining.
  • the distance between the adjacent island component discharge holes 1 cannot be made smaller than the size of the sea component discharge holes 4.
  • the cross-sectional shape of the sea component discharge hole 4 is different from the round shape.
  • the sea component discharge hole 4 can be arranged even in a place where the hole shape cannot be arranged unless the hole diameter is reduced in the round shape, the sea component polymer can be locally discharged, and the merging of the island component polymers can be further prevented.
  • the adjacent island component discharge holes 1 can be brought close to the limit, and the hole filling density can be increased.
  • a distribution hole 7 having a round cross-sectional shape is connected to the upstream side of the sea component discharge hole 4 so as to communicate with the distribution hole 7 directly above.
  • the sea component polymer It is preferable to discharge the sea component polymer through the sea component discharge hole 4 after ensuring the meterability of the sea component polymer. Moreover, by controlling the cross-sectional shape of the sea component discharge hole 4, the island component polymer discharged from the island component discharge hole 1 and widened can be controlled to have an arbitrary cross-sectional shape.
  • the sea component discharge hole 4 is a circumferential slit surrounding the island component discharge hole 1.
  • the sea component polymers can be further prevented from joining.
  • a distribution hole 7 having a round cross-sectional shape is arranged in communication with the upstream side of the sea component discharge hole 4 so that the sea component polymer is disposed in the distribution hole 7 directly above. It is preferable to discharge the sea component polymer through the sea component discharge hole 4 after securing the measurement property.
  • the island-component composite fiber is formed by using the lowermost layer distribution plate in which the island component discharge portion is composed of one island component discharge hole and the sea component discharge portion is composed of one sea component discharge hole. Spinning was performed, and whether or not the island component polymers were merged was determined as described below.
  • the fiber diameter CV% coefficient of variation
  • Fiber diameter variation (CV%) (fiber diameter standard deviation / average fiber diameter) ⁇ 100 (3) Deformity and irregularity variation (CV%) The cross section of the multifilament is photographed by the same method as the fiber diameter and fiber diameter variation described above, and the diameter of the perfect circle circumscribing the cut surface is defined as the circumscribed circle diameter (fiber diameter) from the image.
  • the degree of irregularity the circumscribed circle diameter ⁇ the inscribed circle diameter was obtained up to the third decimal point, and the figure rounded to the third decimal place was obtained as the irregularity.
  • the inscribed circle refers to the broken line 19 in FIG.
  • Variation in irregularities (standard deviation of irregularities / average value of irregularities) x 100 (%) (4) Evaluation of cross-sectional shape of ultrafine fiber Using the same method as the fiber diameter and fiber diameter variation described above, a cross section of a multifilament is photographed, and a line segment having two end points in the cross-sectional outline is straight from the image. The number of parts that are The cross section of 150 multifilaments randomly extracted from the target image in the same image was evaluated. About 150 multifilaments, the number of straight portions was counted, and the total sum was divided by the number of multifilaments to calculate the number of straight portions per multifilament, and rounded off to the second decimal place. Further, a line extended as 22 in FIG.
  • 8A is drawn from the straight line portion existing in the outline of the cross section.
  • the number of intersections of two adjacent lines is counted, the angle is measured, the total of the angles is calculated by dividing by the number of intersections, and the value rounded to the nearest decimal point is 1
  • the angle of book intersection was performed on 150 multifilaments, and the simple number average was taken as the angle of intersection.
  • Fineness Sea-island type composite fibers are made into a circular knitting, and 99% or more of the readily soluble components are dissolved and removed by immersing them in a 3% by weight aqueous solution of sodium hydroxide (80 ° C. bath ratio 1: 100), and then the knitting is unwound. Then, a multifilament made of ultrafine fibers was extracted, the weight of 1 m was measured, and the fineness was calculated by multiplying by 10,000. This was repeated 10 times, and the value obtained by rounding off the second decimal place of the simple average value was defined as the fineness.
  • Insulation of polymer of island component Multifilament made of ultrafine fiber is embedded in epoxy resin, frozen with Reichert FC-4E cryosectioning system, and Reichert-Nissei ultracut N equipped with diamond knife (ultramicrotome) Then, the cut surface was photographed with a VE-7800 scanning electron microscope (SEM) manufactured by Keyence Corporation at a magnification of 5000 times.
  • SEM scanning electron microscope
  • WINROOF image processing software
  • a sea-island composite polymer stream was discharged from the hole.
  • 1000 island component discharge holes are perforated at regular intervals for one discharge introduction hole for the island component polymer.
  • the sea-island ratio was 50/50, 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 unstretched with 150 dtex-15 filament (single hole discharge rate 2.25 g / min) Fiber was collected.
  • the wound unstretched fiber is stretched 3.0 times between rollers heated to 90 ° C and 130 ° C to form a sea-island composite fiber of 50 dtex-15 filaments, and 99% or more of sea components are dissolved by the method described above. 15,000 multifilaments were collected.
  • the distribution plate in which the distribution holes are perforated and the distribution plate in which the distribution grooves are perforated are alternately laminated, and the lowermost layer as shown in FIG. Distribution plates are stacked.
  • the distribution plate is perforated with a thickness of 0.1 mm, a hole diameter of 0.2 mm, a groove width of 0.3 mm, a groove depth of 0.1 mm, and a minimum hole pitch of 0.4 mm.
  • the radius R2 is 0.8 mm
  • the radius R4 of the virtual circumference C4 is 0.693 mm
  • the holes are drilled so as to satisfy the condition (2).
  • the island component has a triangular cross-section (three straight portions at an intersection angle of 60 °), the island component polymers do not merge with each other, the fiber diameter variation is 4.6%, the degree of deformity is 1.9, and the shape is irregular. The variation was 4.5%, and the fiber diameter of this multifilament was 537 nm.
  • Example 2 As shown in FIG. 2, the island component polymer is formed using the same composite die as in Example 1 except that the arrangement of the island component discharge holes and the sea component discharge holes of the lowermost layer distribution plate is changed to the condition (2). The ratio was larger than that of Example 1 (sea / island ratio was 20/80). Otherwise, spinning was performed under the same polymer, equivalent fineness and spinning conditions as in Example 1, and 13,500 multifilaments were collected.
  • the composite base used in Example 2 has an island component discharge hole and a sea component discharge hole having a hole diameter of 0.2 mm, a radius R1 of the virtual circumferential line C1 of 0.4 mm, and a virtual circumferential line.
  • a hole is drilled with a radius R2 of C2 of 0.8 mm and a radius R4 of the virtual circumferential line C4 of 0.8 mm.
  • the island component has a triangular cross-section (three straight portions at an intersection angle of 60 °), the island component polymers do not merge with each other, the fiber diameter variation is 5.9%, the degree of deformity is 1.84, and the shape is irregular.
  • Example 3 As shown in FIG. 3, the same composite base as in Example 1 was used except that the arrangement of the island component discharge holes and the sea component discharge holes of the lowermost layer distribution plate was changed to the condition (2), and the sea island ratio 15000 multifilaments were collected by spinning under the same polymer, the same fineness, and the same spinning conditions as in Example 1 except that the ratio was 20/80.
  • the composite base used in Example 3 has an island component discharge hole and a sea component discharge hole with a hole diameter of 0.2 mm, a radius R1 of the virtual circumferential line C1 of 0.4 mm, and a virtual circumferential line.
  • the C2 radius R2 is 0.8 mm
  • the virtual circumference C4 has a radius R4 of 0.693 mm.
  • the island component has a hexagonal cross section (six straight-line portions at an intersection angle of 120 °), there is no merging of the island component polymers, the fiber diameter variation is 5.9%, the degree of deformity is 1.23, The irregularity variation was 3.9%, and the fiber diameter of this multifilament was 488 nm.
  • Example 4 As shown in FIG.
  • Example 4 the same composite base as in Example 1 was used except that the arrangement of the island component discharge holes and the sea component discharge holes in the lowermost layer distribution plate was changed to the condition (2).
  • the sample was spun under the same polymer, the same fineness, and the same spinning conditions as in Example 1 except that the ratio was changed to 30/70, and 13,000 multifilaments were collected.
  • the composite base used in Example 4 has an island component discharge hole and a sea component discharge hole with a hole diameter of 0.2 mm, a radius R1 of the virtual circumferential line C1 of 0.4 mm, and a virtual circumferential line.
  • the C2 has a radius R2 of 0.894 mm
  • the imaginary circumferential line C4 has a radius R4 of 0.8 mm.
  • the island component has a square cross section (angle of 90 ° at the four straight portions), there is no merging of the island component polymers, the fiber diameter variation is 5.3%, the degree of deformity is 1.71, and the shape is irregular. The degree of variation was 5.6%, and the fiber diameter of this multifilament was 868 nm.
  • Example 1 As shown in FIG. 9, except that the arrangement of the island component discharge holes and the sea component discharge holes of the lowermost layer distribution plate was changed, the same composite base as in Example 1 was used, and the same polymer, sea island ratio, Multifilaments were collected by spinning at the same fineness and spinning conditions.
  • three sea component discharge holes are equally arranged at a central angle of 120 degrees on the virtual circumferential line C1, and three sea component discharges are performed on the virtual circumferential line C2.
  • the holes are equally divided at a central angle of 120 degrees
  • the three island component discharge holes are equally divided at a central angle of 120 degrees on the virtual circumference C4
  • the phase angle between the discharge holes disposed at C1 and C2 Is arranged at 60 degrees and the phase angle between the discharge holes arranged at C1 and C4 is 30 degrees.
  • the diameter of the island component discharge hole and the sea component discharge hole is 0.2 mm
  • the radius R1 of the virtual circumferential line C1 is 0.4 mm
  • the radius R2 of the virtual circumferential line C2 is 0.8 mm
  • the radius R4 of C4 is perforated at 0.4 mm
  • R4 is out of the range of the formula (1).
  • Table 1 the island component polymer merged, and a multifilament having a triangular cross section could not be obtained.
  • Example 10 the same composite base as in Example 2 was used except that the arrangement pattern of the island component discharge holes and the sea component discharge holes in the lowermost layer distribution plate was changed, and the same polymer and sea island ratio as in Example 2 were used. Multifilaments were collected by spinning at the same fineness and spinning conditions.
  • each sea component discharge hole is equally arranged at a central angle of 90 degrees on the virtual circumferential line C1, and eight sea component discharges are performed on the virtual circumferential line C2.
  • the four island component discharge holes are equally divided at a central angle of 90 degrees on the virtual circumferential line C4, and the phase angle between the discharge holes arranged at C1 and C2 is 26.6 degrees.
  • the phase angle between the ejection holes arranged at C4 is arranged at 45 degrees.
  • the diameter of the island component discharge hole and the sea component discharge hole is 0.2 mm
  • the radius R1 of the virtual circumferential line C1 is 0.4 mm
  • the radius R2 of the virtual circumferential line C2 is 0.894 mm
  • the virtual circumferential line C4 has a radius R4 of 0.566 mm
  • R4 is out of the range of equation (1).
  • Table 1 the island component polymer was merged, the fiber diameter variation was 26%, and the irregularity variation was 27%, and a multifilament having a uniform square cross section could not be obtained.
  • the hole arrangement in FIG. 11 is devised by the present inventors so that the island component has a parallelogram-shaped cross section as a deformation pattern of a square cross section.
  • the diameter of the island component discharge hole and the sea component discharge hole is 0.2 mm
  • the radius R1 of the virtual circumferential line C1 is 0.4 mm
  • the radius R2 of the virtual circumferential line C2 is 0.566 mm
  • the virtual circumferential line C4 A radius R4 is drilled at 0.8 mm, and R4 is out of the range of the formula (1).
  • Table 1 the island component polymer merged, and a multifilament having a parallelogram cross section could not be obtained.
  • [Comparative Example 4] As shown in FIG. 12, the same composite base as in Example 3 was used except that the arrangement pattern of the island component discharge holes and the sea component discharge holes in the lowermost layer distribution plate was changed, and the same polymer and sea island ratio as in Example 3 were used. Multifilaments were collected by spinning at the same fineness and spinning conditions.
  • the diameter of the island component discharge hole and the sea component discharge hole is 0.2 mm
  • the radius R1 of the virtual circumferential line C1 is 0.4 mm
  • the radius R2 of the virtual circumferential line C2 is 0.693 mm
  • the virtual circumferential line C4 has a radius R4 of 0.8 mm
  • R4 is out of the range of equation (1).
  • the island component has a hexagonal cross section (six straight-line portions at an intersection angle of 120 °), there is no merging of the island component polymers, the fiber diameter variation is 5.9%, the degree of deformity is 1.22, Although the irregularity variation was 4.2%, the fiber diameter was 1.4 ⁇ m, and nano-order multifilaments could not be obtained.
  • PET Polyethylene terephthalate
  • PET copolymerized as 5.0 mol% 5-sodium sulfoisophthalic acid having an intrinsic viscosity [ ⁇ ] 0.58 as a sea component polymer
  • Copolymerized PET was melted separately at 285 ° C., weighed, and poured into a spin pack incorporating the composite die shown in FIG. 33, and a core-sheath sea-island composite polymer flow was discharged from the die discharge hole.
  • 1800 island component discharge holes are formed at equal intervals for one discharge introduction hole for the island component polymer.
  • 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 (single hole discharge amount 2.25 g / min) undrawn fiber was collected.
  • the wound unstretched fiber is stretched 3.0 times between rollers heated to 90 ° C. and 130 ° C. to obtain a stretched fiber of 50 dtex-15 filaments. Multifilaments made of ultrafine fibers were collected.
  • the composite base used in Reference Example 1 is bifurcated by alternately stacking a distribution plate with a distribution hole and a distribution plate with a distribution groove.
  • a tournament type flow path is formed, and an upper layer plate, a middle layer plate, and a lower layer plate are sequentially laminated on the downstream side thereof.
  • These plates are perforated with a thickness of 0.1 mm, a hole diameter of 0.2 mm, a groove width of 0.3 mm, a groove depth of 0.1 mm, and a minimum inter-hole pitch of 0.4 mm.
  • the distribution groove perforated in one distribution plate is made equal in length so that the pressure loss of the polymer flow path from the distribution hole at the upper end to the island component discharge hole becomes uniform. .
  • an upper layer protrusion is formed on the upper layer plate, and a composite base having an outer end hole for supplying a sea component polymer around the end of the upper layer protrusion is used.
  • Sea-island type composite fibers were produced by spinning under the same polymer, discharge ratio, equivalent fineness, and spinning conditions.
  • the composite base used in Reference Example 3 has the island component discharge holes drilled in a round shape and the discharge holes in a cross shape.
  • a part of the upper surface of the plate is crimped and fixed by diffusion bonding, and the sea component polymer is supplied from the outer end hole of the non-crimped part.
  • Table 2 at the start of spinning and after 72 hours had passed, there was no merging of island component polymers, and the resulting island component cross-section became a cross shape.
  • the fiber diameter variation was 7.2% at the start of spinning and 7.3% after 72 hours.
  • the lowermost layer distribution plate of the composite base was configured as shown in FIG.
  • the island component discharge holes 1 had 1200 holes, a hole packing density of 2.0 holes / mm 2 , a diameter of 0.2 mm, a longer period of 0.6 mm, and a shorter period of 0.45 mm.
  • Two adjacent island component discharge holes 1 reference island component discharge hole 1 and island component discharge hole 53a in FIG.
  • the island component polymer did not merge at the start of spinning and after 72 hours had passed.
  • the lowermost distribution plate of the composite base was configured as shown in FIG.
  • the island component discharge holes 1 had 1020 holes, a hole filling density of 1.7 holes / mm 2 , a diameter ⁇ of 0.2 mm, a longer period of 0.6 mm, and a shorter period of 0.5 mm.
  • Two adjacent island component discharge holes 1 reference island component discharge hole 1 and island component discharge hole 53a, reference island component discharge hole 1 and island component discharge hole 53b in FIG. 35
  • One sea component discharge hole 4 is provided so as to completely block the region surrounded by the two common outer tangents 54 of the hole 1.
  • the diameter of the sea component discharge hole was ⁇ 0.2 mm.
  • the lowermost distribution plate of the composite base was configured as shown in FIG.
  • the island component discharge holes 1 had 900 holes, a hole filling density of 1.5 holes / mm 2 , a diameter of 0.2 mm, a longer period of 0.6 mm, and a shorter period of 0.55 mm.
  • the diameter of the sea component discharge hole was ⁇ 0.2 mm. A part of the sea component discharge hole 4 did not exist in a region surrounded by the two adjacent island component discharge holes 1 and the two common outer tangent lines 54 of the two island component discharge holes.
  • the present invention is not limited to a composite die used for a general solution spinning method, but can be applied to a melt blow method and a spun bond method, and also to a die used for a wet spinning method and a dry and wet spinning method.
  • the application range is not limited to these.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Multicomponent Fibers (AREA)

Abstract

L'invention concerne une filière composite pour la fabrication de fibres composites de type îlots-dans-la-mer, par laquelle les courants de polymère de composant îlot peuvent être empêchés de converger alors que la densité de tassement de trous des trous d'extrusion pour le polymère composant îlot est accrue, et par laquelle diverses sections transversales de fibre, et en particulier des sections transversales hétéromorphiques, peuvent être formées à précision élevée, tout en maintenant une stabilité dimensionnelle élevée de la section transversale. La présente invention concerne une filière composite pour extruder des courants de polymères composites composés d'un polymère composants îlot et d'un polymère de composant mer, la filière composite étant caractérisée en ce qu'elle est composée d'au moins une plaque de distribution dans laquelle sont formés des trous de distribution et des rainures de distribution pour distribuer les composants polymères; et d'une plaque de distribution de la couche la plus inférieure qui est positionnée sur le côté aval de la plaque de distribution dans la direction du trajet de filage de polymère et dans laquelle sont formées une pluralité de trous d'extrusion de composant îlot et une pluralité de trous d'extrusion de composant mer. La présente invention est également caractérisée en ce que certains des trous d'extrusion de composant mer sont disposés sur une ligne circulaire virtuelle (C1) de rayon (R1) centrée sur les trous d'extrusion de composant îlot, en ce que certains des trous d'extrusion de composant mer sont disposés sur une ligne circulaire virtuelle (C2) de rayon (R2), et en ce que certains des trous d'extrusion de composant îlot sont disposés sur une ligne circulaire virtuelle (C4) de rayon (R4) selon une disposition prédéterminée tout en satisfaisant l'expression (1) R2 ≥ R4 ≥ √3 × R1.
PCT/JP2011/066697 2010-12-27 2011-07-22 Filière composite et procédé de fabrication de fibres composites WO2012090538A1 (fr)

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CN201180063082.9A CN103261494B (zh) 2010-12-27 2011-07-22 复合喷丝头及复合纤维的制造方法

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JP2010289980A JP5728936B2 (ja) 2010-12-27 2010-12-27 複合口金および複合繊維の製造方法
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JP2011129780 2011-06-10
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WO2013133056A1 (fr) * 2012-03-09 2013-09-12 東レ株式会社 Embout composite, et procédé de fabrication de fibres synthétiques
JPWO2014077359A1 (ja) * 2012-11-19 2017-01-05 東レ株式会社 複合口金および複合繊維、複合繊維の製造方法
CN109306532A (zh) * 2018-12-07 2019-02-05 常州纺兴精密机械有限公司 一种复合导电纤维及其纺制组件
CN111763998A (zh) * 2020-07-16 2020-10-13 常州纺兴精密机械有限公司 三组份并列复合纤维及其纺丝组件
CN112725912A (zh) * 2020-12-04 2021-04-30 江苏立新化纤科技有限公司 一种在直径104mm内制备144孔的涤锦复合喷丝组件
CN114917686A (zh) * 2022-05-17 2022-08-19 苏州工业园区拓朴环保净化有限公司 长纤维复合滤芯的制备方法、滤芯及其模具
US11525191B2 (en) 2017-06-28 2022-12-13 Toray Industries, Inc. Pack for spinning and method for producing fiber
WO2023171363A1 (fr) * 2022-03-11 2023-09-14 東レ株式会社 Procédé de fabrication d'une fibre bicomposée, et filière bicomposante

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BE1024623B1 (nl) * 2016-09-30 2018-05-24 Nv Michel Van De Wiele Spinplaat
CN109112651A (zh) * 2018-10-19 2019-01-01 江苏尚科聚合新材料有限公司 一种海岛复合纺丝组件及一种复合纤维

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013133056A1 (fr) * 2012-03-09 2013-09-12 東レ株式会社 Embout composite, et procédé de fabrication de fibres synthétiques
EP2824225B1 (fr) * 2012-03-09 2019-07-03 Toray Industries, Inc. Filière composite, et procédé de fabrication de fibres synthétiques composites
JPWO2014077359A1 (ja) * 2012-11-19 2017-01-05 東レ株式会社 複合口金および複合繊維、複合繊維の製造方法
US11525191B2 (en) 2017-06-28 2022-12-13 Toray Industries, Inc. Pack for spinning and method for producing fiber
CN109306532A (zh) * 2018-12-07 2019-02-05 常州纺兴精密机械有限公司 一种复合导电纤维及其纺制组件
CN111763998A (zh) * 2020-07-16 2020-10-13 常州纺兴精密机械有限公司 三组份并列复合纤维及其纺丝组件
CN112725912A (zh) * 2020-12-04 2021-04-30 江苏立新化纤科技有限公司 一种在直径104mm内制备144孔的涤锦复合喷丝组件
CN112725912B (zh) * 2020-12-04 2022-05-10 江苏立新化纤科技有限公司 一种在直径104mm内制备144孔的涤锦复合喷丝组件
WO2023171363A1 (fr) * 2022-03-11 2023-09-14 東レ株式会社 Procédé de fabrication d'une fibre bicomposée, et filière bicomposante
CN114917686A (zh) * 2022-05-17 2022-08-19 苏州工业园区拓朴环保净化有限公司 长纤维复合滤芯的制备方法、滤芯及其模具
CN114917686B (zh) * 2022-05-17 2024-04-02 苏州工业园区拓朴环保净化有限公司 长纤维复合滤芯的制备方法、滤芯及其模具

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EP2660369A4 (fr) 2015-01-07
EP2660369B1 (fr) 2016-05-18
TW201226643A (en) 2012-07-01
CN103261494B (zh) 2015-08-12
CN103261494A (zh) 2013-08-21

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