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JP7645984B2 - Core-sheath composite fiber, its manufacturing method, and fiber structure - Google Patents
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JP7645984B2 - Core-sheath composite fiber, its manufacturing method, and fiber structure - Google Patents

Core-sheath composite fiber, its manufacturing method, and fiber structure Download PDF

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JP7645984B2
JP7645984B2 JP2023503834A JP2023503834A JP7645984B2 JP 7645984 B2 JP7645984 B2 JP 7645984B2 JP 2023503834 A JP2023503834 A JP 2023503834A JP 2023503834 A JP2023503834 A JP 2023503834A JP 7645984 B2 JP7645984 B2 JP 7645984B2
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sheath
core
component
polymer
island
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JPWO2022186150A1 (en
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孝太 研井
俊一 長谷川
祐二 荻野
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Kuraray Co Ltd
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • D01D5/082Melt spinning methods of mixed yarn
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • D01D5/084Heating filaments, threads or the like, leaving the spinnerettes
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • D01D5/098Melt spinning methods with simultaneous stretching
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/28Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30Conjugate filaments; Spinnerette packs therefor
    • D01D5/34Core-skin structure; Spinnerette packs therefor
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D7/00Collecting the newly-spun products
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02JFINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J13/00Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D10B2331/042Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET] aromatic polyesters, e.g. vectran
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/06Load-responsive characteristics
    • D10B2401/063Load-responsive characteristics high strength

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Multicomponent Fibers (AREA)

Description

関連出願Related Applications

本願は、日本国で2021年3月4日に出願した特願2021-34707の優先権を主張するものであり、その全体を参照により本出願の一部をなすものとして引用する。 This application claims priority to Patent Application No. 2021-34707, filed in Japan on March 4, 2021, the entire contents of which are incorporated by reference into this application.

本発明は、芯成分として溶融異方性芳香族ポリエステルを有し、耐フィブリル性を向上させ耐摩耗性に優れる芯鞘複合繊維およびその製造方法、ならびに繊維構造体に関する。The present invention relates to a core-sheath composite fiber having a melt-anisotropic aromatic polyester as the core component, which has improved fibrillation resistance and excellent abrasion resistance, a method for producing the same, and a fiber structure.

溶融異方性芳香族ポリエステル繊維は高強力高弾性率となることが知られているが、これらの繊維は、分子鎖が繊維軸方向に高度に配向しているため摩耗により容易にフィブリル化するという問題があった。そこで、溶融異方性芳香族ポリエステルを芯成分とする一方で、周囲を鞘成分で被覆することによりフィブリル化を抑制した複合繊維が提案されている。 Melt-formed anisotropic aromatic polyester fibers are known to have high strength and high elastic modulus, but these fibers have the problem that they easily fibrillate due to wear because the molecular chains are highly oriented in the fiber axis direction. Therefore, composite fibers have been proposed that use melt-formed anisotropic aromatic polyester as the core component while suppressing fibrillation by covering the surrounding area with a sheath component.

例えば、特許文献1(特開2002-20932号公報)には、芯成分が溶融異方性芳香族ポリエステル(A)、鞘成分がポリマー(A)を0~10%含有する屈曲性ポリエステル(B)からなり、ポリエステル(B)の固有粘度[η]が、0.65dl/g以上であることを特徴とする複合繊維が開示されている。For example, Patent Document 1 (JP Patent Publication No. 2002-20932) discloses a composite fiber characterized in that the core component is made of a melt-anisotropic aromatic polyester (A) and the sheath component is made of a flexible polyester (B) containing 0 to 10% of polymer (A), and the intrinsic viscosity [η] of the polyester (B) is 0.65 dl/g or more.

特許文献1には、鞘成分に芯成分と同じポリマーをブレンドすることで、鞘成分の強力を高めると同時に芯成分との接着性を高めることが記載されている。Patent Document 1 describes how blending the sheath component with the same polymer as the core component increases the strength of the sheath component while also increasing its adhesion to the core component.

特許文献2(特開2008-255535号公報)には、芯成分が溶融異方性芳香族ポリエステル(Aポリマー)からなり、鞘成分が海島構造を有し、かつ鞘成分比が0.2~0.7であること、および該鞘成分を構成する海成分は屈曲性熱可塑性ポリマー(Bポリマー)からなり、島成分は溶融異方性芳香族ポリエステル(Cポリマー)からなり、鞘成分における島成分比が0~0.25であることを満足する芯鞘複合繊維において、繊維表面にケイ酸塩化合物を主成分とする無機微粒子を0.03~2.5質量%付着させてなる複合繊維が開示されている。Patent Document 2 (JP 2008-255535 A) discloses a core-sheath composite fiber in which the core component is made of a melt-dispersed anisotropic aromatic polyester (A polymer), the sheath component has a sea-island structure with a sheath component ratio of 0.2 to 0.7, and the sea component constituting the sheath component is made of a flexible thermoplastic polymer (B polymer), the island components are made of a melt-dispersed anisotropic aromatic polyester (C polymer), and the island component ratio in the sheath component is 0 to 0.25. The composite fiber has 0.03 to 2.5 mass % of inorganic fine particles mainly composed of a silicate compound attached to the fiber surface.

特許文献2では、溶融異方性を有しないポリマーは溶融異方性ポリエステルとの接着性が低く、剥離しやすいため、鞘成分を溶融異方性ポリエステルと溶融異方性を有しないポリマーからなるブレンドで形成することが記載されている。Patent document 2 describes that since polymers without melt anisotropy have low adhesion to melt anisotropic polyesters and are prone to peeling, the sheath component is formed from a blend of melt anisotropic polyesters and polymers without melt anisotropy.

特開2002-20932号公報JP 2002-20932 A 特開2008-255535号公報JP 2008-255535 A

しかしながら、特許文献1では、鞘成分中における溶融異方性芳香族ポリエステルの割合が10%を超える場合、繊維表面に凹凸が発生し、紡糸性が悪化するため、鞘成分中における溶融異方性芳香族ポリエステルの割合を高めることを否定している。However, Patent Document 1 denies increasing the proportion of molten anisotropic aromatic polyester in the sheath component because if the proportion of molten anisotropic aromatic polyester in the sheath component exceeds 10%, unevenness will occur on the fiber surface and spinnability will deteriorate.

また、特許文献2に記載の複合繊維は、繊維表面にケイ酸塩化合物を主成分とする無機微粒子を0.03~2.5質量%付着させることにより、繊維間の膠着を抑制し、解舒性を向上できることは記載されているものの、繊維のフィブリル化抑制については、屈曲性熱可塑性ポリマーを海成分として用いることにより、耐フィブリル性、耐摩耗性は大きく改善されることしか言及されていない。In addition, Patent Document 2 describes that the composite fiber described in the above can suppress adhesion between fibers and improve reeling properties by attaching 0.03 to 2.5 mass % of inorganic microparticles, the main component of which is a silicate compound, to the fiber surface. However, with regard to suppressing fiber fibrillation, the only thing mentioned is that fibrillation resistance and abrasion resistance are greatly improved by using a flexible thermoplastic polymer as the sea component.

溶融異方性芳香族ポリエステルを芯成分とし、周囲を鞘成分で被覆した芯鞘複合繊維の鞘成分中に、紡糸性を損なわずに溶融異方性芳香族ポリエステルを多く混和することができれば、芯と鞘の接着性をより強固にでき鞘剥がれを抑制し、従来以上に高い摩耗性を実現することができる。また、同様の理由により鞘を薄くすることもでき、その結果、芯側の溶融異方性芳香族ポリエステルに由来して強度を高めることができて好ましい。If it were possible to incorporate a large amount of molten anisotropic aromatic polyester into the sheath component of a core-sheath composite fiber, which has a core component made of molten anisotropic aromatic polyester and is surrounded by a sheath component, without impairing spinnability, it would be possible to strengthen the adhesion between the core and sheath, suppress sheath peeling, and achieve higher abrasion resistance than ever before. For the same reason, it would also be possible to make the sheath thinner, which would result in increased strength due to the molten anisotropic aromatic polyester on the core side, which is preferable.

したがって、本発明の目的は、芯鞘複合繊維の鞘成分中における溶融異方性芳香族ポリエステルの割合を高めつつ、一方でフィブリル化や紡糸性悪化を抑制し、耐摩耗性に優れた芯鞘複合繊維を提供することにある。Therefore, the object of the present invention is to provide a core-sheath composite fiber that has excellent abrasion resistance while increasing the proportion of melt-anisotropic aromatic polyester in the sheath component of the core-sheath composite fiber and at the same time suppressing fibrillation and deterioration of spinnability.

本発明の発明者らは、上記目的を達成するために鋭意検討した結果、芯成分として溶融異方性芳香族ポリエステルを有する芯鞘複合繊維において、(I)鞘成分を、溶融異方性芳香族ポリエステルからなる島部を有する海島構造とし、海島構造中の溶融異方性芳香族ポリエステルの割合を高めると、芯と鞘の接着性の改善により鞘剥がれを防止し、摩耗性をより高めつつ、鞘を薄くすることができ芯成分の溶融異方性芳香族ポリエステルに由来して強度を高めることができるが、(II)その一方で、溶融異方性芳香族ポリエステルの高い割合に由来して紡糸調子が著しく悪くなること、鞘成分がフィブリル化することに気づき、紡糸調子の改善と鞘成分のフィブリル化を抑制することを新たな課題とした。そして、(III)鞘成分中の溶融異方性芳香族ポリエステルの割合を高めつつ、特定の温度において鞘成分の混練を行って吐出された放流糸を、特定のドラフト値で引取ることにより、海部に対して、溶融異方性芳香族ポリエステルからなる島部を微分散させて島部の形状を制御することができ、その結果、鞘成分中の溶融異方性芳香族ポリエステルの割合が高い場合であっても、良好な紡糸調子を保ちつつ芯鞘複合繊維のフィブリル化を抑制し、かつ鞘を薄くした場合でも耐摩耗性を向上できることを見出し、本発明を完成した。As a result of intensive research into achieving the above-mentioned object, the inventors of the present invention have discovered that in a core-sheath composite fiber having a melt-anisotropic aromatic polyester as a core component, (I) when the sheath component has a sea-island structure with islands made of melt-anisotropic aromatic polyester and the proportion of melt-anisotropic aromatic polyester in the sea-island structure is increased, peeling of the sheath is prevented by improving the adhesion between the core and sheath, and abrasion resistance is improved while the sheath can be made thinner, and strength can be increased due to the melt-anisotropic aromatic polyester of the core component. However, (II) on the other hand, due to the high proportion of melt-anisotropic aromatic polyester, spinning conditions are significantly deteriorated and the sheath component is fibrillated. Thus, they have made it their new task to improve spinning conditions and suppress fibrillation of the sheath component. Then, (III) it was discovered that by increasing the proportion of molten anisotropic aromatic polyester in the sheath component, kneading the sheath component at a specific temperature, and drawing up the discharged yarn at a specific draft value, it is possible to finely disperse island portions made of molten anisotropic aromatic polyester in the sea portion and control the shape of the island portions, and as a result, even when the proportion of molten anisotropic aromatic polyester in the sheath component is high, it is possible to suppress fibrillation of the core-sheath composite fiber while maintaining good spinning condition, and to improve abrasion resistance even when the sheath is made thin, thereby completing the present invention.

すなわち、本発明は、以下の態様で構成されうる。
〔態様1〕
芯成分が溶融異方性芳香族ポリエステル(Aポリマー)を含み、鞘成分が屈曲性熱可塑性ポリマー(Bポリマー)および溶融異方性芳香族ポリエステル(Cポリマー)を含み、前記Bポリマーが海成分を形成し、前記Cポリマーが島成分を形成し、前記海成分からなる海部中に前記島成分からなる複数の島部が分散する海島構造を有する芯鞘複合繊維であって、
前記鞘成分における島成分の割合は、10重量%を超えており、かつ、
この芯鞘複合繊維を繊維長手方向に切断した断面で、繊維垂直方向に最も大きな幅を有する島部の最大幅Wが0.65μm以下(好ましくは0.60μm以下、より好ましくは0.55μm以下、さらに好ましくは0.50μm以下)であり、
前記最大幅Wを有する島部において、繊維長手方向一端から他端に向かうに従って、前記繊維長手方向に対し定められた角度10°で延びる前記鞘成分中における斜線に接する島部のうち、前記斜線と重なる長さの斜め長の最大長さL1と、前記島部の最大幅Wとの比L1/Wが5.0以上(好ましくは5.1以上、より好ましくは5.2以上、さらに好ましくは5.3以上、さらにより好ましくは5.5以上)である、芯鞘複合繊維。
〔態様2〕
態様1に記載の芯鞘複合繊維であって、前記斜め長の最大長さL1が1.0μm以上(好ましくは1.3μm以上、より好ましくは1.5μm以上、さらに好ましくは1.7μm以上)である、芯鞘複合繊維。
〔態様3〕
態様1または2に記載の芯鞘複合繊維であって、前記芯鞘複合繊維を繊維長手方向に切断した断面で、前記鞘成分中における前記島部の繊維長手方向の長さL2が450~1000μm(好ましくは500~800μm、より好ましくは550~650μm)である芯鞘複合繊維。
〔態様4〕
態様1~3のいずれか一態様に記載の芯鞘複合繊維であって、前記鞘成分の厚みが0.8~5.0μm(好ましくは0.9~4.0μm、より好ましくは0.9~3.8μm)である芯鞘複合繊維。
〔態様5〕
態様1~4のいずれか一態様に記載の芯鞘複合繊維であって、前記Aポリマーと前記Cポリマーが同種の溶融異方性芳香族ポリエステルである芯鞘複合繊維。
〔態様6〕
態様1~5のいずれか一態様に記載の芯鞘複合繊維であって、前記芯成分と前記鞘成分の重量比である芯成分/鞘成分が20/80~97/3(好ましくは50/50~96/4、より好ましくは60/40~95/5、さらに好ましくは70/30~94/6、さらにより好ましくは75/25~93/7、特に好ましくは80/20~92/8、最も好ましくは82.5/17.5~90/10)である芯鞘複合繊維。
〔態様7〕
態様1~6のいずれか一態様に記載の芯鞘複合繊維であって、この芯鞘複合繊維の単糸繊度が1~120dtex(好ましくは2~60dtex、より好ましくは2.5~30dtex、さらに好ましくは3~15dtex)である芯鞘複合繊維。
〔態様8〕
芯成分が溶融異方性芳香族ポリエステル(Aポリマー)を含み、鞘成分が屈曲性熱可塑性ポリマー(Bポリマー)および溶融異方性芳香族ポリエステル(Cポリマー)を含み、前記Bポリマーが海成分を形成し、前記Cポリマーが島成分を形成し、前記海成分からなる海部中に前記島成分からなる複数の島部が分散する海島構造を有する芯鞘複合繊維の製造方法であって、
前記鞘成分に用いるBポリマーおよびCポリマーを、Bポリマーの融点(Mb)に対して(Mb)℃以上であって、Cポリマーの融点(Mc)℃に対して(Mc-20)℃以上、(Mc)℃未満で二軸押出機を用いて混練すると共に、前記芯成分に用いるAポリマーを、前記鞘成分に用いる前記二軸押出機とは異なる押出機を用いて溶融し混練する混練工程と、この混練工程でそれぞれ混練させた鞘成分および芯成分を複合して吐出して放流糸を得る吐出工程と、
吐出された放流糸を、吐出速度に対する巻取速度の比であるドラフト値として13~50(好ましくは15~45、より好ましくは16~40、さらに好ましくは19~38、特に好ましくは20~35)で引取る工程と、
を少なくとも備える芯鞘複合繊維の製造方法。
〔態様9〕
態様8に記載の芯鞘複合繊維の製造方法であって、前記吐出工程で得られた繊維に熱処理を施す熱処理工程を有する芯鞘複合繊維の製造方法。
〔態様11〕
様態1~7のいずれか一様態に記載の芯鞘複合繊維を少なくとも一部に含む、繊維構造体。
That is, the present invention can be configured in the following manner.
[Aspect 1]
A core-sheath composite fiber having a sea-island structure in which a core component contains a melt-type anisotropic aromatic polyester (A polymer), a sheath component contains a flexible thermoplastic polymer (B polymer) and a melt-type anisotropic aromatic polyester (C polymer), the B polymer forms a sea component, the C polymer forms island components, and a plurality of island components made of the island components are dispersed in a sea part made of the sea component,
The ratio of the island component in the sheath component is more than 10% by weight, and
In a cross section of the sheath-core composite fiber cut in the longitudinal direction of the fiber, the maximum width W of an island portion having the largest width in a direction perpendicular to the fiber is 0.65 μm or less (preferably 0.60 μm or less, more preferably 0.55 μm or less, and even more preferably 0.50 μm or less),
a sheath-core composite fiber, wherein in an island portion having the maximum width W, among the island portions that are in contact with an oblique line in the sheath component extending at a predetermined angle of 10° with respect to the longitudinal direction of the fiber from one end to the other end in the longitudinal direction of the fiber, the ratio L1/W of a maximum length L1 of a diagonal length that overlaps with the oblique line to a maximum width W of the island portion is 5.0 or more (preferably 5.1 or more, more preferably 5.2 or more, even more preferably 5.3 or more, and still more preferably 5.5 or more).
[Aspect 2]
A sheath-core composite fiber according to aspect 1, wherein the maximum length L1 of the oblique length is 1.0 μm or more (preferably 1.3 μm or more, more preferably 1.5 μm or more, and even more preferably 1.7 μm or more).
[Aspect 3]
A sheath-core composite fiber according to Aspect 1 or 2, wherein in a cross section of the sheath-core composite fiber cut in the fiber longitudinal direction, the length L2 of the island portion in the sheath component in the fiber longitudinal direction is 450 to 1000 μm (preferably 500 to 800 μm, more preferably 550 to 650 μm).
[Aspect 4]
A sheath-core composite fiber according to any one of Aspects 1 to 3, wherein the thickness of the sheath component is 0.8 to 5.0 μm (preferably 0.9 to 4.0 μm, more preferably 0.9 to 3.8 μm).
[Aspect 5]
A sheath-core conjugate fiber according to any one of aspects 1 to 4, wherein the A polymer and the C polymer are the same type of melt-anisotropic aromatic polyester.
[Aspect 6]
A sheath/core composite fiber according to any one of Aspects 1 to 5, wherein the weight ratio of the core component to the sheath component, that is, core component/sheath component, is 20/80 to 97/3 (preferably 50/50 to 96/4, more preferably 60/40 to 95/5, even more preferably 70/30 to 94/6, still more preferably 75/25 to 93/7, particularly preferably 80/20 to 92/8, and most preferably 82.5/17.5 to 90/10).
[Aspect 7]
A sheath-core conjugate fiber according to any one of Aspects 1 to 6, wherein the single filament fineness of the sheath-core conjugate fiber is 1 to 120 dtex (preferably 2 to 60 dtex, more preferably 2.5 to 30 dtex, and even more preferably 3 to 15 dtex).
[Aspect 8]
A method for producing a core-sheath composite fiber having a sea-island structure in which a core component contains a melt-type anisotropic aromatic polyester (A polymer), a sheath component contains a flexible thermoplastic polymer (B polymer) and a melt-type anisotropic aromatic polyester (C polymer), the B polymer forms a sea component, the C polymer forms island components, and a plurality of island components made of the island components are dispersed in a sea part made of the sea component, the method comprising the steps of:
a kneading step in which the B polymer and the C polymer used for the sheath component are kneaded using a twin-screw extruder at a temperature of (Mb)°C or higher relative to the melting point (Mb) of the B polymer and at a temperature of (Mc-20)°C or higher but lower than (Mc)°C relative to the melting point (Mc)°C of the C polymer, and the A polymer used for the core component is melted and kneaded using an extruder different from the twin-screw extruder used for the sheath component; and a discharge step in which the sheath component and the core component respectively kneaded in the kneading step are combined and discharged to obtain a discharged yarn.
A step of taking up the discharged discharged yarn at a draft value, which is the ratio of the winding speed to the discharge speed, of 13 to 50 (preferably 15 to 45, more preferably 16 to 40, even more preferably 19 to 38, and particularly preferably 20 to 35);
A method for producing a core-sheath composite fiber comprising at least the steps of:
[Aspect 9]
A method for producing a sheath-core composite fiber according to aspect 8, comprising a heat treatment step of subjecting the fiber obtained in the discharge step to a heat treatment.
[Aspect 11]
A fiber structure comprising at least a part of the core-sheath composite fiber according to any one of aspects 1 to 7.

本明細書中、「芯鞘複合繊維を繊維長手方向に切断した断面」とは、芯鞘複合繊維をこの繊維長手方向を含む平面で切断して見た断面と同義であり、以下、「繊維縦断面」と称す場合がある。また、繊維垂直方向とは、繊維縦断面において、繊維長手方向に対して直交する方向(または繊維長手方向に垂直な方向)を意味する。In this specification, the term "cross section of a sheath-core composite fiber cut in the fiber longitudinal direction" is synonymous with the cross section of a sheath-core composite fiber cut in a plane including the fiber longitudinal direction, and may be referred to as the "fiber longitudinal section" below. The fiber perpendicular direction means the direction perpendicular to the fiber longitudinal direction (or the direction perpendicular to the fiber longitudinal direction) in the fiber longitudinal section.

なお、請求の範囲および/または明細書および/または図面に開示された少なくとも2つの構成要素のどのような組み合わせも、本発明に含まれる。特に、請求の範囲に記載された請求項の2つ以上のどのような組み合わせも本発明に含まれる。It should be noted that any combination of at least two elements disclosed in the claims and/or the specification and/or the drawings is included in the present invention. In particular, any combination of two or more of the claims described in the claims is included in the present invention.

本発明の芯鞘複合繊維によれば、芯成分として溶融異方性芳香族ポリエステルを有し、鞘成分が海島構造である芯鞘複合繊維において、鞘成分の島部を溶融異方性芳香族ポリエステルとしてその割合を高めた場合であっても、島部を微分散させることにより紡糸中の島成分の凝集が抑制され、芯鞘複合繊維の耐フィブリル性を向上することができ、耐摩耗性に優れた繊維が得られる。According to the sheath-core composite fiber of the present invention, in a core-sheath composite fiber having a melt-anisotropic aromatic polyester as the core component and a sheath component having an island-sea structure, even if the island portions of the sheath component are made of melt-anisotropic aromatic polyester and the proportion of the polyester is increased, the aggregation of the island portions during spinning is suppressed by finely dispersing the island portions, and the fibrillation resistance of the core-sheath composite fiber can be improved, resulting in a fiber with excellent abrasion resistance.

この発明は、添付の図面を参考にした以下の好適な実施例の説明から、より明瞭に理解されるであろう。しかしながら、実施例および図面は単なる図示および説明のためのものであり、この発明の範囲を定めるために利用されるべきものではない。この発明の範囲は添付の請求の範囲によって定まる。添付図面において、複数の図面における同一の部品番号は、同一部分を示す。
本発明の一実施形態に係る芯鞘複合繊維の概略斜視図である。 同芯鞘複合繊維を繊維長手方向に切断して見た概略断面図である。 同芯鞘複合繊維の鞘成分を部分的に拡大して示す拡大概略断面図である。 同芯鞘複合繊維を繊維長手方向に垂直な平面で切断して見た概略断面図である。 同芯鞘複合繊維の紡糸に用いられる口金の構造を概略断面図である。
The present invention will be more clearly understood from the following description of preferred embodiments with reference to the accompanying drawings. However, the embodiments and drawings are merely for illustration and explanation, and should not be used to define the scope of the present invention. The scope of the present invention is defined by the appended claims. In the accompanying drawings, the same part numbers in multiple drawings indicate the same parts.
FIG. 1 is a schematic perspective view of a core-sheath composite fiber according to one embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of a concentric sheath composite fiber cut in the fiber longitudinal direction. FIG. 2 is an enlarged schematic cross-sectional view showing a part of a sheath component of a concentric sheath composite fiber. FIG. 2 is a schematic cross-sectional view of a concentric sheath composite fiber cut along a plane perpendicular to the longitudinal direction of the fiber. FIG. 1 is a schematic cross-sectional view showing the structure of a spinneret used in spinning concentric sheath composite fibers.

以下、本発明を例示に基づいて詳細に説明する。本発明の一態様は、芯成分と、この芯成分を覆う鞘成分とを備える芯鞘複合繊維であり、鞘成分が海成分および島成分を含む海島構造を有する。芯成分は溶融異方性芳香族ポリエステル(Aポリマー)を含み、鞘成分は屈曲性熱可塑性ポリマー(Bポリマー)および溶融異方性芳香族ポリエステル(Cポリマー)を含み、Bポリマーが海成分を形成し、Cポリマーが島成分を形成する。The present invention will be described in detail below with reference to examples. One aspect of the present invention is a core-sheath composite fiber having a core component and a sheath component covering the core component, and the sheath component has a sea-island structure containing a sea component and an island component. The core component contains a molten anisotropic aromatic polyester (A polymer), and the sheath component contains a flexible thermoplastic polymer (B polymer) and a molten anisotropic aromatic polyester (C polymer), with the B polymer forming the sea component and the C polymer forming the island component.

(芯成分)
芯成分に用いられる溶融異方性芳香族ポリエステル(Aポリマー)とは、溶融相において光学異方性(液晶性)を示すポリマーである。例えば試料をホットステージに載せ、窒素雰囲気下で昇温加熱し、試料の透過光を観察することにより溶融異方性芳香族ポリエステルであるか否かを認定し得る。本発明の溶融異方性芳香族ポリエステルとしては、例えば芳香族ジオール、芳香族ジカルボン酸、芳香族ヒドロキシカルボン酸などに由来する反復構成単位からなり、本発明の効果を損なわない限り、芳香族ジオール、芳香族ジカルボン酸、芳香族ヒドロキシカルボン酸に由来する構成単位は、その化学的構成については特に限定されるものではない。また、本発明の効果を阻害しない範囲で、溶融異方性芳香族ポリエステルは、芳香族ジアミン、芳香族ヒドロキシアミンまたは芳香族アミノカルボン酸に由来する構成単位を含んでいてもよい。例えば、好ましい構成単位としては、表1に示す例が挙げられる。
(Core component)
The melt anisotropic aromatic polyester (A polymer) used for the core component is a polymer that exhibits optical anisotropy (liquid crystallinity) in the molten phase. For example, a sample is placed on a hot stage, heated under a nitrogen atmosphere, and the transmitted light of the sample is observed to determine whether it is a melt anisotropic aromatic polyester. The melt anisotropic aromatic polyester of the present invention is composed of repeating structural units derived from, for example, aromatic diols, aromatic dicarboxylic acids, aromatic hydroxycarboxylic acids, etc., and the structural units derived from aromatic diols, aromatic dicarboxylic acids, and aromatic hydroxycarboxylic acids are not particularly limited in terms of their chemical structure, so long as they do not impair the effects of the present invention. In addition, the melt anisotropic aromatic polyester may contain structural units derived from aromatic diamines, aromatic hydroxyamines, or aromatic aminocarboxylic acids, as long as they do not impair the effects of the present invention. For example, examples of preferred structural units are shown in Table 1.

Figure 0007645984000001
Figure 0007645984000001

表1の構成単位において、mは0~2の整数であり、式中のYは、1~置換可能な最大数の範囲において、それぞれ独立して、水素原子、ハロゲン原子(例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子など)、アルキル基(例えば、メチル基、エチル基、イソプロピル基、t-ブチル基などの炭素数1から4のアルキル基など)、アルコキシ基(例えば、メトキシ基、エトキシ基、イソプロポキシ基、n-ブトキシ基など)、アリール基(例えば、フェニル基、ナフチル基など)、アラルキル基[ベンジル基(フェニルメチル基)、フェネチル基(フェニルエチル基)など]、アリールオキシ基(例えば、フェノキシ基など)、アラルキルオキシ基(例えば、ベンジルオキシ基など)などが挙げられる。In the structural units in Table 1, m is an integer from 0 to 2, and Y in the formula, in the range of 1 to the maximum number that can be substituted, each independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (e.g., an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, a isopropoxy group, a n-butoxy group, etc.), an aryl group (e.g., a phenyl group, a naphthyl group, etc.), an aralkyl group [benzyl group (phenylmethyl group), phenethyl group (phenylethyl group), etc.], an aryloxy group (e.g., a phenoxy group), an aralkyloxy group (e.g., a benzyloxy group), etc.).

より好ましい構成単位としては、下記表2、表3および表4に示す例(1)~(18)に記載される構成単位が挙げられる。なお、式中の構成単位が、複数の構造を示しうる構成単位である場合、そのような構成単位を二種以上組み合わせて、ポリマーを構成する構成単位として使用してもよい。More preferred structural units include the structural units described in examples (1) to (18) in Tables 2, 3, and 4 below. When a structural unit in the formula is a structural unit that can exhibit multiple structures, two or more of such structural units may be combined and used as structural units that constitute the polymer.

Figure 0007645984000002
Figure 0007645984000002

Figure 0007645984000003
Figure 0007645984000003

Figure 0007645984000004
Figure 0007645984000004

表2、表3および表4の構成単位において、nは1または2の整数で、それぞれの構成単位n=1、n=2は、単独でまたは組み合わせて存在してもよく、YおよびYは、それぞれ独立して、水素原子、ハロゲン原子(例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子など)、アルキル基(例えば、メチル基、エチル基、イソプロピル基、t-ブチル基などの炭素数1から4のアルキル基など)、アルコキシ基(例えば、メトキシ基、エトキシ基、イソプロポキシ基、n-ブトキシ基など)、アリール基(例えば、フェニル基、ナフチル基など)、アラルキル基[ベンジル基(フェニルメチル基)、フェネチル基(フェニルエチル基)など]、アリールオキシ基(例えば、フェノキシ基など)、アラルキルオキシ基(例えば、ベンジルオキシ基など)などであってもよい。これらのうち、水素原子、塩素原子、臭素原子、またはメチル基が好ましい。 In the structural units of Tables 2, 3 and 4, n is an integer of 1 or 2, and each structural unit n=1, n=2 may exist alone or in combination, and Y 1 and Y 2 may each independently be a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (e.g., an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, etc.), an aryl group (e.g., a phenyl group, a naphthyl group, etc.), an aralkyl group [benzyl group (phenylmethyl group), phenethyl group (phenylethyl group), etc.], an aryloxy group (e.g., a phenoxy group, etc.), an aralkyloxy group (e.g., a benzyloxy group, etc.), etc. Of these, a hydrogen atom, a chlorine atom, a bromine atom, or a methyl group is preferred.

また、Zとしては、下記式で表される置換基が挙げられる。 Z can also be a substituent represented by the following formula:

Figure 0007645984000005
Figure 0007645984000005

溶融異方性芳香族ポリエステルは、好ましくは、ナフタレン骨格を構成単位として有する組み合わせであってもよい。なお、ヒドロキシ安息香酸(略称:HBA)由来の構成単位(A)と、ヒドロキシナフトエ酸(略称:HNA)由来の構成単位(B)の両方を含むことが、特に好ましい。例えば、構成単位(A)としては下記式(A)が挙げられ、構成単位(B)としては下記式(B)が挙げられ、溶融成形性を向上する観点から、構成単位(A)と構成単位(B)の比率は、好ましくは9/1~1/1、より好ましくは7/1~1/1、さらに好ましくは5/1~1/1の範囲であってもよい。The melt-anisotropic aromatic polyester may preferably be a combination having a naphthalene skeleton as a structural unit. It is particularly preferable to include both a structural unit (A) derived from hydroxybenzoic acid (abbreviation: HBA) and a structural unit (B) derived from hydroxynaphthoic acid (abbreviation: HNA). For example, the structural unit (A) may be represented by the following formula (A), and the structural unit (B) may be represented by the following formula (B). From the viewpoint of improving melt moldability, the ratio of the structural unit (A) to the structural unit (B) may be preferably in the range of 9/1 to 1/1, more preferably 7/1 to 1/1, and even more preferably 5/1 to 1/1.

Figure 0007645984000006
Figure 0007645984000006

Figure 0007645984000007
Figure 0007645984000007

また、(A)の構成単位と(B)の構成単位の合計は、例えば、全構成単位に対して65モル%以上であってもよく、より好ましくは70モル%以上、さらに好ましくは80モル%以上であってもよい。ポリマー中、特に(B)の構成単位が4~45モル%である溶融異方性芳香族ポリエステルが好ましい。The sum of the constituent units (A) and (B) may be, for example, 65 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, based on the total constituent units. In particular, a melt-type anisotropic aromatic polyester in which the constituent units (B) account for 4 to 45 mol% of the polymer is preferred.

本発明で好適に用いられる溶融異方性芳香族ポリエステルの融点は250~360℃の範囲であることが好ましく、より好ましくは260~320℃である。ここでいう融点とは、JIS K 7121に準拠した試験方法により測定されるものであり、示差走査熱量計(例えば(株)島津製作所DSC:Differential scanning calorimetry)で観察される主吸熱ピークのピーク温度である。The melting point of the melt anisotropic aromatic polyester preferably used in the present invention is preferably in the range of 250 to 360° C., more preferably 260 to 320° C. The melting point here is measured by a test method conforming to JIS K 7121, and is the peak temperature of the main endothermic peak observed with a differential scanning calorimeter (for example, Shimadzu Corporation DSC: Differential scanning calorimetry).

なお、上記溶融異方性芳香族ポリエステルには、本発明の効果を損なわない範囲で、ポリエチレンテレフタレート、変性ポリエチレンテレフタレート、ポリオレフィン、ポリカーボネート、ポリアミド、ポリフェニレンサルファイド、ポリエーテルエーテルケトン、フッ素樹脂などの熱可塑性ポリマーを添加してもよい。また酸化チタン、カオリン、シリカ、酸化バリウムなどの無機物、カーボンブラック、染料や顔料などの着色剤、酸化防止剤、紫外線吸収剤、光安定剤などの各種添加剤を含んでいてもよい。The melt-anisotropic aromatic polyester may contain thermoplastic polymers such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyamide, polyphenylene sulfide, polyether ether ketone, and fluororesin, as long as the effects of the present invention are not impaired. It may also contain various additives such as inorganic substances such as titanium oxide, kaolin, silica, and barium oxide, colorants such as carbon black, dyes, and pigments, antioxidants, ultraviolet absorbers, and light stabilizers.

(鞘成分)
鞘成分は海島構造を有しており、屈曲性熱可塑性ポリマー(Bポリマー)が海成分を形成し、溶融異方性芳香族ポリエステル(Cポリマー)が島成分を形成している。
海成分を形成する屈曲性熱可塑性ポリマー(Bポリマー)としては、主鎖上に芳香環を有さないポリマー、あるいは主鎖上に芳香環を有し、かつ芳香環間の主鎖上に原子が4個以上存在するポリマーが挙げられ、具体的には、例えば、ポリオレフィン;ポリアミド;ポリカーボネート;ポリフェニレンサルファイド(略称:PPS);ポリエチレンテレフタレート、変性ポリエチレンテレフタレート、非晶性ポリアリレート、ポリエチレンナフタレート(略称:PEN)などのポリエステル;ポリエーテルエーテルケトン;フッ素樹脂などが挙げられる。これらの屈曲性熱可塑性ポリマーは、単独でまたは二種以上組み合わせて使用してもよく、一方を主たる(例えば、80重量%以上を占める)熱可塑性ポリマーとし、それ以外を添加する熱可塑性ポリマーとしてもよい。この中でもPPS、PENが主たる熱可塑性ポリマーであるのが好ましい。
また屈曲性熱可塑性ポリマーは、酸化チタン、シリカ、酸化バリウムなどの無機物、カーボンブラック、染料または顔料などの着色剤、酸化防止剤、紫外線吸収剤、光安定剤、造核剤などの各種添加剤を含んでいてもよい。
(Sheath component)
The sheath component has a sea-island structure, with the flexible thermoplastic polymer (B polymer) forming the sea component and the melt-dispersible anisotropic aromatic polyester (C polymer) forming the island component.
The flexible thermoplastic polymer (B polymer) forming the sea component may be a polymer having no aromatic ring on the main chain, or a polymer having an aromatic ring on the main chain and having 4 or more atoms on the main chain between the aromatic rings, and specifically, for example, polyolefin; polyamide; polycarbonate; polyphenylene sulfide (abbreviation: PPS); polyesters such as polyethylene terephthalate, modified polyethylene terephthalate, amorphous polyarylate, and polyethylene naphthalate (abbreviation: PEN); polyether ether ketone; fluororesin, etc. These flexible thermoplastic polymers may be used alone or in combination of two or more, and one may be the main thermoplastic polymer (e.g., occupying 80% by weight or more) and the other may be added as a thermoplastic polymer. Among these, PPS and PEN are preferably the main thermoplastic polymers.
The flexible thermoplastic polymer may also contain various additives such as inorganic substances such as titanium oxide, silica, barium oxide, etc., colorants such as carbon black, dyes or pigments, antioxidants, ultraviolet absorbers, light stabilizers, nucleating agents, etc.

島成分を形成する溶融異方性芳香族ポリエステル(Cポリマー)は、前記Aポリマーにおいて記載した溶融異方性芳香族ポリエステルを挙げることができ、Aポリマーと同一であっても異なっていてもよいが、親和性の観点から、主たる構成単位が同一の溶融異方性芳香族ポリエステルであるのが好ましい。また、AポリマーとCポリマーとは、主たる構成単位が同一で、かつ、例えば添加する熱可塑性ポリマーまたは添加剤のみが異なる同種類のポリマーであってもよい。The melt-type anisotropic aromatic polyester (C polymer) forming the island component may be the melt-type anisotropic aromatic polyester described above for the A polymer, and may be the same as or different from the A polymer. From the viewpoint of affinity, however, it is preferable that the main structural unit of the melt-type anisotropic aromatic polyester is the same. The A polymer and the C polymer may be the same type of polymer, with the main structural unit being the same and, for example, only the thermoplastic polymer or additive added is different.

またCポリマーの融点(Mc)は、CポリマーをBポリマーに対して微分散することができる範囲で適宜選択することができ、例えば、Cポリマーの融点(Mc)は、Bポリマーの融点(Mb)に対して、(Mb-10)~(Mb+80)℃の範囲であってもよく、Mb~(Mb+70)℃の範囲であってもよい。 The melting point (Mc) of the C polymer can be appropriately selected within a range in which the C polymer can be finely dispersed in the B polymer. For example, the melting point (Mc) of the C polymer may be in the range of (Mb-10) to (Mb+80)°C relative to the melting point (Mb) of the B polymer, or in the range of Mb to (Mb+70)°C.

さらにCポリマーの溶融粘度ηは、紡糸性の観点から、例えば、10~60Pa・sであってもよく、好ましくは20~50Pa・s、より好ましくは25~45Pa・sであってもよい。
なお、本発明にいう溶融粘度ηとは、温度T(Cポリマーの融点(Mc)が290℃以上の場合T=(Mc+10)℃、融点Mcが290℃未満の場合T=300℃)、せん断速度1000sec-1で測定した溶融粘度である。
Furthermore, the melt viscosity η of the C polymer may be, for example, from the viewpoint of spinnability, 10 to 60 Pa·s, preferably 20 to 50 Pa·s, and more preferably 25 to 45 Pa·s.
The melt viscosity η in the present invention is a melt viscosity measured at a temperature T (T=(Mc+10)° C. when the melting point (Mc) of the C polymer is 290° C. or higher, and T=300° C. when the melting point Mc is less than 290° C.) and a shear rate of 1000 sec -1 .

(芯鞘複合繊維の製造方法)
本発明の芯鞘複合繊維は、混練工程と、吐出工程と、を少なくとも備える製造方法により製造することができる。製造工程は、さらに熱処理工程を備えていてもよい。
(Method of manufacturing core-sheath composite fiber)
The core-sheath composite fiber of the present invention can be produced by a production method including at least a kneading step and a discharging step. The production process may further include a heat treatment step.

混練工程では、鞘成分に用いる前記Bポリマーおよび前記Cポリマーを、二軸押出機を用いて溶融し混練すると共に、芯成分に用いるAポリマーを、前記鞘成分に用いる前記二軸押出機とは別の押出機を用いて溶融し混練する。In the kneading process, the B polymer and the C polymer used for the sheath component are melted and kneaded using a twin-screw extruder, and the A polymer used for the core component is melted and kneaded using an extruder other than the twin-screw extruder used for the sheath component.

特に、BポリマーおよびCポリマーの混練に用いる二軸押出機において、この二軸押出機中の混練部の設定温度を、Bポリマーの融点(Mb)に対して(Mb)℃以上であって、Cポリマーの融点(Mc)に対して(Mc-20)℃以上、(Mc)℃未満に設定すると共に、混練部で回転自在に支持された平行二軸のスクリュの回転により、鞘成分中における複数の島部の微分散化を図ることが可能となる。
なお、芯成分に用いる前記Aポリマーを溶融し混練する押出機は、単軸押出機でもよく二軸押出機であってもよい。また、事前にBポリマーとCポリマーを上記の条件でコンパウンド化した原料を使用する場合には、すでに鞘成分中における複数の島部の微分散化を図ることができているため、鞘成分の溶融混練に使用する押出機は、単軸押出機でもよく二軸押出機であってもよい。
In particular, in a twin-screw extruder used for kneading the B polymer and the C polymer, the set temperature of the kneading section in this twin-screw extruder is set to (Mb)°C or higher with respect to the melting point (Mb) of the B polymer and to (Mc-20)°C or higher and lower than (Mc)°C with respect to the melting point (Mc) of the C polymer, and it becomes possible to finely disperse a plurality of island parts in the sheath component by the rotation of the parallel twin-screw screws rotatably supported in the kneading section.
The extruder for melting and kneading the A polymer used for the core component may be a single screw extruder or a twin screw extruder. When using a raw material in which the B polymer and the C polymer are compounded in advance under the above conditions, the multiple island portions in the sheath component are already finely dispersed, so the extruder for melt-kneading the sheath component may be a single screw extruder or a twin screw extruder.

混練工程において、芯成分と鞘成分の割合は、耐フィブリル化の向上を図ると共に芯成分の露出を抑制する観点から、芯成分/鞘成分の重量比(以下、単に芯鞘比と称する場合がある)として、例えば、20/80~97/3であってもよく、好ましくは50/50~96/4、より好ましくは60/40~95/5、さらに好ましくは70/30~94/6、さらにより好ましくは75/25~93/7、特に好ましくは80/20~92/8、最も好ましくは82.5/17.5~90/10であってもよい。特に、芯成分が50%以上の場合、複合繊維の強度を向上することができて好ましい。芯成分と鞘成分の重量比は、例えば、製造時において後述する各押出機にそれぞれ投入される芯成分と鞘成分の重量比などにより求め得る。In the kneading process, the ratio of the core component to the sheath component may be, for example, 20/80 to 97/3 as the weight ratio of the core component/sheath component (hereinafter, sometimes simply referred to as the core-sheath ratio) from the viewpoint of improving the resistance to fibrillation and suppressing the exposure of the core component, and may be preferably 50/50 to 96/4, more preferably 60/40 to 95/5, even more preferably 70/30 to 94/6, even more preferably 75/25 to 93/7, particularly preferably 80/20 to 92/8, and most preferably 82.5/17.5 to 90/10. In particular, when the core component is 50% or more, it is preferable because the strength of the composite fiber can be improved. The weight ratio of the core component to the sheath component can be determined, for example, by the weight ratio of the core component and the sheath component respectively fed into each extruder described later during production.

鞘成分における島成分の割合は、10重量%を超えており、好ましくは15重量%以上、より好ましくは20重量%以上であってもよい。島成分の割合を高めることにより、島成分による芯成分と鞘成分のアンカー効果を強固にすることができる。一方、島成分の割合が高すぎると、島成分が凝集する可能性が高まるため、島成分は、40重量%以下であってもよく、好ましくは35重量%以下であってもよい。The proportion of island components in the sheath component may be more than 10% by weight, preferably 15% by weight or more, and more preferably 20% by weight or more. By increasing the proportion of island components, the anchoring effect of the island components between the core component and the sheath component can be strengthened. On the other hand, if the proportion of island components is too high, the possibility of the island components agglomerating increases, so the island components may be 40% by weight or less, and preferably 35% by weight or less.

吐出工程では、前記混練工程でそれぞれ混練させた鞘成分および芯成分を、例えば、図4に示される構造の口金から複合して吐出することで断面(繊維横断面)円形状の芯鞘複合繊維を紡糸することができる。In the extrusion process, the sheath component and the core component kneaded in the kneading process are combined and extruded, for example, from a nozzle having a structure shown in Figure 4, to spin a core-sheath composite fiber having a circular cross section (fiber cross section).

吐出の際の口金温度(紡糸温度)は、例えば、Aポリマーの融点(Ma)に対して、(Ma+10)~(Ma+60)℃であってもよく、好ましくは(Ma+15)~(Ma+40)℃、より好ましくは(Ma+20)~(Ma+35)℃であってもよい。
微分散された島部の形状は、ドラフト値により制御され、吐出された放流糸は、ドラフト値13~50で引取られ、好ましくは15~45、より好ましくは16~40、さらに好ましくは19~38、特に好ましくは20~35で引き取られてもよい。なお、放流糸とは、ノズル孔から吐出され延伸がかかっていない糸、すなわちノズル孔径と略同等の繊維径を有する糸を意味し、また、ドラフト値とは、紡糸の際の吐出速度に対する巻取速度の比を意味している。
The die temperature (spinning temperature) during extrusion may be, for example, (Ma+10) to (Ma+60)°C, preferably (Ma+15) to (Ma+40)°C, and more preferably (Ma+20) to (Ma+35)°C, relative to the melting point (Ma) of the A polymer.
The shape of the finely dispersed island parts is controlled by the draft value, and the discharged discharged yarn may be drawn at a draft value of 13 to 50, preferably 15 to 45, more preferably 16 to 40, even more preferably 19 to 38, and particularly preferably 20 to 35. The discharged yarn means a yarn discharged from a nozzle hole and not stretched, that is, a yarn having a fiber diameter approximately equal to the nozzle hole diameter, and the draft value means the ratio of the take-up speed to the discharge speed during spinning.

さらに紡糸された繊維に対して熱処理を行ってもよい。熱処理により、鞘成分中のBポリマーの配向結晶化度を高めるだけでなく、溶融異方性芳香族ポリエステルを固相重合することができ、芯鞘複合繊維の強度を向上することができる。The spun fibers may be further subjected to a heat treatment. This heat treatment not only increases the oriented crystallinity of the B polymer in the sheath component, but also allows the molten anisotropic aromatic polyester to undergo solid-state polymerization, improving the strength of the core-sheath composite fiber.

熱処理では、紡糸された繊維を、窒素などの不活性ガス雰囲気下、または酸素含有の活性ガス(例えば、空気)雰囲気下において、常圧または減圧下で熱処理を行ってもよい。
熱処理を行う場合、熱処理雰囲気は露点が-50℃以下、好ましくは-60℃以下、より好ましくは-70℃以下の低湿気体が好ましい。熱処理条件としては、Aポリマーの融点(Ma)に対して、(Ma-20)℃以下、好ましくは(Ma-30)℃以下、より好ましくは(Ma-40)℃以下から鞘成分の融点以下まで順次昇温していく温度パターンが挙げられる。
熱の供給方法としては、気体の媒体を用いる方法、加熱板、赤外線ヒーターなどにより輻射を利用する方法、高周波などを利用した内部加熱方法などがある。処理形状は、ロールトゥロールの連続生産であってもよく、カセ状、トウ状、熱処理用ボビンに紡糸原糸を巻き返すことによるバッチ生産であってもよい。
In the heat treatment, the spun fiber may be heat-treated under an atmosphere of an inert gas such as nitrogen, or under an atmosphere of an oxygen-containing active gas (for example, air) at normal pressure or reduced pressure.
When the heat treatment is carried out, the heat treatment atmosphere is preferably a low-humidity atmosphere with a dew point of −50° C. or less, preferably −60° C. or less, more preferably −70° C. or less. The heat treatment conditions include a temperature pattern in which the temperature is gradually increased from (Ma-20)° C. or less, preferably (Ma-30)° C. or less, more preferably (Ma-40)° C. or less, relative to the melting point (Ma) of the A polymer, to the melting point of the sheath component or less.
Methods for supplying heat include a method using a gas medium, a method using radiation from a heating plate, an infrared heater, etc., an internal heating method using high frequency, etc. The treatment form may be roll-to-roll continuous production, or batch production by reeling or towing the raw spun yarn around a bobbin for heat treatment.

熱処理後の糸の膠着による鞘剥がれなどを防止する観点から、必要に応じて、繊維の紡糸中または紡糸後、熱処理前に繊維の表面に無機微粒子を塗布してもよい。前記無機微粒子としては、タルク、雲母を始めとするケイ酸塩化合物を主成分とするものが好ましい。 In order to prevent sheath peeling due to adhesion of the yarn after heat treatment, inorganic fine particles may be applied to the surface of the fiber during or after spinning, as necessary, before heat treatment. As the inorganic fine particles, those mainly composed of silicate compounds such as talc and mica are preferable.

特許文献2と異なり、本発明では、無機微粒子を付着させなくても良好な解舒性を有するが、解舒性をさらに向上させる観点から、無機微粒子の付着を行ってもよい。
繊維の紡糸中または紡糸後、熱処理前に繊維の表面に無機微粒子を均一に付着させることで、糸同士が直接接触することを防止し、糸の膠着を回避することができる。なお、ケイ酸塩化合物を主成分とする無機微粒子はその多くが不活性であり、繊維に付着させても繊維の物性低下は見られない。
Unlike Patent Document 2, the present invention has good releasability even without adhering inorganic fine particles, but from the viewpoint of further improving the releasability, inorganic fine particles may be adhered.
By uniformly attaching inorganic fine particles to the surface of the fiber during or after spinning and before heat treatment, it is possible to prevent the yarns from coming into direct contact with each other and to prevent the yarns from sticking together. Note that most of the inorganic fine particles mainly composed of silicate compounds are inactive, and there is no deterioration in the physical properties of the fiber even when they are attached to the fiber.

前記無機微粒子の繊維の表面への付着方法は、均一に繊維に付着させられる方法であれば何ら限定されるものではない。例えば、紡糸油剤に無機微粒子を攪拌分散させたものをオイリングローラーまたはカラス口を用いて付着させる方法が簡便であり好ましい。The method of attaching the inorganic fine particles to the surface of the fibers is not limited in any way as long as the inorganic fine particles can be attached uniformly to the fibers. For example, a method in which inorganic fine particles are stirred and dispersed in a spinning oil agent and then attached using an oiling roller or a glass nozzle is simple and preferable.

芯鞘複合繊維の表面に付着させる無機微粒子の平均粒径は繊維表面に均一に付着する観点から、例えば、0.01~10μm、好ましくは0.02~5μmの範囲であってもよい。芯鞘複合繊維の表面に付着させる無機微粒子の付着量は、0.03~2.5質量%、好ましくは0.1~2.3質量%の範囲であってもよい。The average particle size of the inorganic fine particles attached to the surface of the core-sheath composite fiber may be, for example, in the range of 0.01 to 10 μm, preferably 0.02 to 5 μm, from the viewpoint of uniform attachment to the fiber surface. The amount of the inorganic fine particles attached to the surface of the core-sheath composite fiber may be in the range of 0.03 to 2.5 mass%, preferably 0.1 to 2.3 mass%.

(芯鞘複合繊維)
図1Aは、本発明の一実施形態に係る芯鞘複合繊維の概略斜視図であり、図1Bは、同芯鞘複合繊維を繊維長手方向に切断して見た概略断面図である。芯鞘複合繊維10は、芯成分で形成された芯部12と鞘成分で形成された鞘部14とを有している。
(Sheath-core composite fiber)
Fig. 1A is a schematic perspective view of a sheath-core composite fiber according to one embodiment of the present invention, and Fig. 1B is a schematic cross-sectional view of the sheath-core composite fiber cut in the longitudinal direction of the fiber. The sheath-core composite fiber 10 has a core portion 12 formed of a core component and a sheath portion 14 formed of a sheath component.

図2は、図1BのII部を部分的に拡大して示す拡大断面図である。図1Bおよび図2に示すように、芯鞘複合繊維をその繊維中心軸を含むように繊維長手方向に切断した断面(繊維縦断面)で、鞘部14は海島構造を形成し、海部16中に複数の島部18を形成している。島部は海部中で微分散し、島部の形状が制御されている。
本発明の芯鞘複合繊維では、海成分中の島成分の割合を高めつつ、島部を微分散させているため、多数の島部により芯部に対する鞘部のアンカー性を強固にして、鞘剥がれを抑制することができるだけでなく、鞘部のフィブリル化を抑制することができる。
Fig. 2 is an enlarged cross-sectional view partially enlarging part II in Fig. 1B. As shown in Fig. 1B and Fig. 2, in a cross section (longitudinal cross section) of the sheath-core composite fiber cut in the longitudinal direction of the fiber so as to include the central axis of the fiber, the sheath portion 14 forms a sea-island structure, and a plurality of island portions 18 are formed in the sea portion 16. The island portions are finely dispersed in the sea portion, and the shapes of the island portions are controlled.
In the sheath-core composite fiber of the present invention, the ratio of island parts in the sea part is increased while the island parts are finely dispersed. Therefore, the numerous island parts strengthen the anchoring ability of the sheath part to the core part, which not only prevents the sheath from peeling off but also prevents the sheath part from fibrillating.

島部は、微分散する中で、基本的に略楕円形状で繊維長手方向に延びている。島部の径が大きいと繊維表面への島成分由来の凹凸がより大きくなる。フィブリルが発生するのはこの繊維表面の凹凸の大きさに由来するため、島部の最大径は小さいことが好ましい。また、島部が繊維長手方向に長く延びる形状であるとアンカー効果を発揮できて好ましい。すなわち、一つの繊維横断面での島部の径を単に測定するだけでは、島部の長さによって発生するアンカー効果による寄与を加味できないが、鞘部の顕微鏡写真において、長手方向に島部の形状を観察し、最も大きな幅を有する島部について、当該島部の幅のみならず、その長さも加味して島部の形状を評価することにより、島部のアンカー効果による貢献度を加味しつつ、フィブリル性を評価することができる。そのためには、最大幅Wを有する島部を選択した後、この島部について、図2に示すように、繊維長手方向一端から他端に向かって、前記繊維長手方向に対し定められた角度α(10°)で延びる斜線と重なる長さの斜め長の最大長さL1を測定し、L1/Wを算出することにより、繊維長手方向の延びを加味した島部の形状を評価することが可能となる。 The islands are basically elliptical and extend in the longitudinal direction of the fiber while being finely dispersed. If the diameter of the island is large, the unevenness of the fiber surface due to the island components will become larger. Since the generation of fibrils is due to the size of the unevenness of the fiber surface, it is preferable that the maximum diameter of the island is small. In addition, it is preferable that the island has a shape that extends long in the longitudinal direction of the fiber, since it can exert an anchoring effect. In other words, simply measuring the diameter of the island in one fiber cross section does not take into account the contribution of the anchoring effect caused by the length of the island, but by observing the shape of the island in the longitudinal direction in a micrograph of the sheath and evaluating the shape of the island with the widest width by taking into account not only the width but also the length of the island, it is possible to evaluate the fibrillation while taking into account the contribution of the anchoring effect of the island. To this end, an island portion having a maximum width W is selected, and then, as shown in FIG. 2 , a maximum length L1 of the island portion that overlaps with a diagonal line extending from one end to the other end in the longitudinal direction of the fibers at a predetermined angle α (10°) with respect to the longitudinal direction of the fibers is measured, and L1/W is calculated, which makes it possible to evaluate the shape of the island portion taking into account the elongation in the longitudinal direction of the fibers.

まず、前記最大幅Wを有する島部は、繊維縦断面の拡大画像から選択し得る。具体的には、後述する走査型プローブ顕微鏡(Scanning Probe Microscope:SPM)にて、繊維縦断面を繊維長手方向に100μm以上1000μm以下で観察し、その観察範囲のうち、島部の繊維長手方向に垂直な方向(繊維垂直方向)の長さが最大となる箇所の数値を測定値としたものである。ただし、観察範囲は連続である必要は無く、ランダムに抽出された複数視野分の合計でよい。例えば、繊維縦断面の観察範囲において、繊維長手方向に延びる多数の島部のうち、繊維垂直方向の長さが相対的に大きい島部を複数個抽出し、抽出した島部の繊維垂直方向長さを島部の幅として比較することで最大幅を有する島部を決定することができる。この例では、繊維縦断面において、鞘成分の上側および下側部分のいずれか一方のみ(例えば図1Bの下側部分)を観察範囲とすればよい。またこの例では、繊維縦断面を走査型プローブ顕微鏡にて観察し島部の最大幅を求めているが、島部の最大幅を求め得るものであれば、走査型プローブ顕微鏡以外の手段を用いてもよい。なお、繊維切断時には、応力による影響を最小限にするため、樹脂包埋して繊維を固定した上で切断することが好ましい。First, the island portion having the maximum width W can be selected from an enlarged image of the fiber longitudinal section. Specifically, the fiber longitudinal section is observed in the fiber longitudinal direction at a range of 100 μm to 1000 μm using a scanning probe microscope (SPM) described later, and the numerical value of the portion in the observation range where the length of the island portion in the direction perpendicular to the fiber longitudinal direction (fiber perpendicular direction) is maximum is taken as the measured value. However, the observation range does not need to be continuous, and may be the sum of multiple randomly extracted fields of view. For example, in the observation range of the fiber longitudinal section, multiple island portions having relatively large lengths in the fiber perpendicular direction are extracted from among the many island portions extending in the fiber longitudinal direction, and the island portion having the maximum width can be determined by comparing the fiber perpendicular direction lengths of the extracted island portions as the widths of the island portions. In this example, only one of the upper and lower portions of the sheath component (for example, the lower portion of FIG. 1B) in the fiber longitudinal section may be taken as the observation range. In this example, the longitudinal cross section of the fiber is observed with a scanning probe microscope to determine the maximum width of the island portion, but any means other than a scanning probe microscope may be used as long as it can determine the maximum width of the island portion. Note that, when cutting the fiber, it is preferable to fix the fiber by embedding it in resin before cutting in order to minimize the effect of stress.

島部の最大幅Wは、0.65μm以下であり、好ましくは0.60μm以下、より好ましくは0.55μm、さらに好ましくは0.50μm以下であってもよい。島部の最大幅が上記上限値を超えると、耐フィブリル性が不十分となるおそれがある。また、島部の最大幅Wは、0.07μm以上であってもよく、0.1μm以上であってもよい。The maximum width W of the island portion is 0.65 μm or less, preferably 0.60 μm or less, more preferably 0.55 μm or less, and even more preferably 0.50 μm or less. If the maximum width of the island portion exceeds the above upper limit, there is a risk that the fibrillation resistance will be insufficient. In addition, the maximum width W of the island portion may be 0.07 μm or more, or 0.1 μm or more.

最大幅Wを有する島部を選択した後、この島部について連続的に長手方向に観察し、図2に示すように、繊維長手方向一端から他端に向かって、前記繊維長手方向に対し定められた角度α(10°)で延びる斜線と重なる長さの斜め長の最大長さL1を測定する。前記斜め長の最大長さL1と最大幅Wの比L1/Wが5.0以上である場合、芯鞘複合繊維は、フィブリル化を抑制しつつ、島部によるアンカー効果を向上させることが可能である。前記L1/Wは、好ましくは5.1以上であり、より好ましくは5.2以上、さらに好ましくは5.3以上、さらにより好ましくは5.5以上であってもよい。L1/Wの上限値に特に制限はないが、10以下であってもよい。After selecting an island having a maximum width W, the island is continuously observed in the longitudinal direction, and the maximum length L1 of the oblique length that overlaps with the oblique line extending from one end of the fiber longitudinal direction to the other end at a predetermined angle α (10°) with respect to the fiber longitudinal direction is measured as shown in FIG. 2. When the ratio L1/W of the maximum length L1 of the oblique length to the maximum width W is 5.0 or more, the core-sheath composite fiber can improve the anchoring effect of the island while suppressing fibrillation. The L1/W is preferably 5.1 or more, more preferably 5.2 or more, even more preferably 5.3 or more, and even more preferably 5.5 or more. There is no particular limit to the upper limit of L1/W, but it may be 10 or less.

前記斜め長の最大長さL1は、最大幅Wの値に応じて変化する値であるが、例えば、1.0μm以上であってもよく、好ましくは1.3μm以上、より好ましくは1.5μm以上、さらに好ましくは1.7μm以上であってもよい。斜め長の最大長さL1が上記下限値以上である場合、芯成分に対するアンカー効果が高まる傾向にある。また、前記斜め長の最大長さL1は、3.3μm以下であってもよく、好ましくは3.1μm以下、より好ましくは2.9μm以下であってもよい。斜め長の最大長さL1が上記上限値以下である場合、フィブリル化が抑制される傾向にある。The maximum length L1 of the oblique length is a value that varies depending on the value of the maximum width W, and may be, for example, 1.0 μm or more, preferably 1.3 μm or more, more preferably 1.5 μm or more, and even more preferably 1.7 μm or more. When the maximum length L1 of the oblique length is equal to or greater than the lower limit, the anchor effect on the core component tends to be enhanced. In addition, the maximum length L1 of the oblique length may be equal to or less than 3.3 μm, preferably equal to or less than 3.1 μm, and more preferably equal to or less than 2.9 μm. When the maximum length L1 of the oblique length is equal to or less than the upper limit, fibrillation tends to be suppressed.

前記繊維縦断面で、鞘成分中における最も大きな幅を有する島部の繊維長手方向の長さL2は、例えば、450~1000μmであってもよく、好ましくは500~800μm、より好ましくは550~650μmであってもよい。L2が長いほど、芯成分に対するアンカー効果を高めることができる。この島部の繊維長手方向の長さは、繊維縦断面の拡大画像から求め得る。また、放流糸にて島部の繊維長手方向の長さを求め、その値にドラフト値を掛けた計算値として算出してもよい。In the longitudinal fiber cross section, the length L2 of the island portion having the widest width in the sheath component in the longitudinal fiber direction may be, for example, 450 to 1000 μm, preferably 500 to 800 μm, and more preferably 550 to 650 μm. The longer L2 is, the greater the anchoring effect on the core component can be. The longitudinal fiber length of this island portion can be obtained from an enlarged image of the longitudinal fiber cross section. Alternatively, the longitudinal fiber length of the island portion may be obtained using the discharged yarn, and this value may be multiplied by the draft value to calculate the calculated value.

鞘成分の厚みは、芯成分の露出を防止し繊維の強度を確保する観点から、例えば、0.8~5.0μmであってもよく、好ましくは0.9~4.0μm、より好ましくは0.9~3.8μmであってもよい。 From the viewpoint of preventing exposure of the core component and ensuring the strength of the fiber, the thickness of the sheath component may be, for example, 0.8 to 5.0 μm, preferably 0.9 to 4.0 μm, and more preferably 0.9 to 3.8 μm.

図3に示すように、鞘成分の厚みは、例えば、芯鞘複合繊維を繊維長手方向に垂直な平面で切断して見た断面(以下、「繊維横断面」と称す場合がある)において、その繊維横断面の拡大画像などから求め得る。具体的には、走査型顕微鏡等で繊維横断面を撮像し、繊維外周を3等分する任意の3点にて、芯成分の外周面から鞘成分の外周面までの径方向距離を測定し、その平均値から鞘成分の厚みを求めることが可能である。なお、繊維切断時には、応力による影響を最小限にするため、樹脂包埋して繊維を固定した上で切断することが好ましい。As shown in Figure 3, the thickness of the sheath component can be determined, for example, from an enlarged image of a cross section of a core-sheath composite fiber cut along a plane perpendicular to the longitudinal direction of the fiber (hereinafter sometimes referred to as the "fiber cross section"). Specifically, the fiber cross section is imaged with a scanning microscope or the like, and the radial distance from the outer surface of the core component to the outer surface of the sheath component is measured at any three points that divide the fiber circumference into thirds, and the thickness of the sheath component can be determined from the average value. Note that when cutting the fibers, it is preferable to fix the fibers by embedding them in resin before cutting in order to minimize the effects of stress.

芯鞘複合繊維の単糸繊度は、例えば1~120dtexであってもよく、好ましくは2~60dtex、より好ましくは2.5~30dtex、さらに好ましくは3~15dtexである。この単糸繊度は、例えば、JIS L 1013「化学繊維フィラメント糸試験方法」に準じて測定し得る。また芯鞘複合繊維は、モノフィラメントであってもよく、2本以上のモノフィラメントを含むマルチフィラメントであってもよい。The single yarn fineness of the core-sheath composite fiber may be, for example, 1 to 120 dtex, preferably 2 to 60 dtex, more preferably 2.5 to 30 dtex, and even more preferably 3 to 15 dtex. This single yarn fineness can be measured, for example, in accordance with JIS L 1013 "Testing Method for Chemical Fiber Filament Yarns." The core-sheath composite fiber may be a monofilament or a multifilament containing two or more monofilaments.

芯鞘複合繊維は、25℃雰囲気下における引張強度が、例えば、10cN/dtex以上であってもよく、好ましくは13cN/dtex以上、より好ましくは15cN/dtex以上、さらに好ましくは18cN/dtex以上、さらにより好ましくは20cN/dtex以上であってもよい。引張強度の上限値に特に制限はないが、30cN/dtex以下であってもよい。ここで引張強度は、JIS L 1013試験法を参考にして測定される値である。なお、芯鞘複合繊維がマルチフィラメントの場合、繊維の引き揃えによる強度の変化を考慮し、マルチフィラメントから1本取り出して単糸引張強度として測定してもよい。The tensile strength of the core-sheath composite fiber in an atmosphere of 25°C may be, for example, 10 cN/dtex or more, preferably 13 cN/dtex or more, more preferably 15 cN/dtex or more, even more preferably 18 cN/dtex or more, and even more preferably 20 cN/dtex or more. There is no particular upper limit to the tensile strength, but it may be 30 cN/dtex or less. Here, the tensile strength is a value measured with reference to the JIS L 1013 test method. In addition, when the core-sheath composite fiber is a multifilament, taking into account the change in strength due to the alignment of the fibers, one fiber may be taken out of the multifilament and measured as the single yarn tensile strength.

芯鞘複合繊維は耐フィブリル性に優れており、この芯鞘複合繊維に対して、120°の角度で互違いに配置された3本の櫛ガイドに試験対象の繊維をそれぞれ通し、各繊維に1g/dtexの荷重をかけ、ストローク長3cm、速度95回/分で30000回の往復運動を与えた場合に、繊維の長さ3cm当たりに発生した、平均毛羽数(5回平均)が、例えば1以下であってもよく、好ましくは0.5以下であってもよい。ここで、毛羽は、芯鞘複合繊維をカメラにて20倍に拡大した際に、1mm以下の小さな毛羽(フィブリル)や、1mmより大きい毛羽や鞘剥がれとして観察することができる。 Sheath-core composite fibers have excellent fibrillation resistance, and when a test fiber is passed through three comb guides arranged alternately at an angle of 120° with respect to this sheath-core composite fiber, and a load of 1 g/dtex is applied to each fiber, and the fiber is subjected to 30,000 reciprocating motions at a stroke length of 3 cm and a speed of 95 revolutions/min, the average number of fluffs (average of 5 times) generated per 3 cm of fiber length may be, for example, 1 or less, and preferably 0.5 or less. Here, fluff can be observed as small fluff (fibril) of 1 mm or less, fluff or sheath peeling of more than 1 mm, when the sheath-core composite fiber is magnified 20 times with a camera.

本発明の芯鞘複合繊維は、通常の方法で製織、編成することができ、また、屈曲性熱可塑性ポリマーの種類に応じて、通常の方法により染色することができる。例えば屈曲性高分子がポリエステル系ポリマーである場合、分散染料を用いた従来のポリエステル繊維の染色方法で染色することができる。The core-sheath composite fiber of the present invention can be woven and knitted by conventional methods, and can be dyed by conventional methods depending on the type of flexible thermoplastic polymer. For example, if the flexible polymer is a polyester polymer, it can be dyed by conventional polyester fiber dyeing methods using disperse dyes.

本発明の芯鞘複合繊維は、各種繊維構造体として好適に用いることができ、本発明の繊維構造体は、本発明の芯鞘複合繊維を少なくとも一部に含んでいる。繊維構造体としては、ロープ、混繊糸等の一次元構造体、織物、編物、不織布等の二次元構造体等の高次加工品が挙げられる。繊維構造体は、芯鞘複合繊維単独で構成されていてもよいし、他の構成部材を本発明の効果が阻害されない範囲で含んでいてもよい。繊維構造体を一旦形成した後に、上述の染色方法で繊維構造体を染色してもよい。The sheath-core composite fiber of the present invention can be suitably used as various fiber structures, and the fiber structure of the present invention contains at least a part of the sheath-core composite fiber of the present invention. Examples of fiber structures include one-dimensional structures such as ropes and mixed yarns, and highly processed products such as two-dimensional structures such as woven fabrics, knitted fabrics, and nonwoven fabrics. The fiber structure may be composed of sheath-core composite fibers alone, or may contain other components to the extent that the effects of the present invention are not impaired. Once the fiber structure is formed, it may be dyed by the dyeing method described above.

繊維構造体が織物である場合、織組織としては特に限定されず、例えば平織、斜文織、朱子織、変化平織、変化斜文織、変化朱子織、変わり織、紋織、片重ね織、二重組織、多重組織、経パイル織、緯パイル織、絡み織などが挙げられる。また、繊維構造体が編物である場合、編組織としては特に限定されず、例えば丸編、緯編、経編(トリコット編、ラッセル編を含む)、パイル編、平編、天竺編、リブ編、スムース編(両面編)、ゴム編、パール編、デンビー組織、コード組織、アトラス組織、鎖組織、挿入組織などが挙げられる。When the fiber structure is a woven fabric, the weave structure is not particularly limited, and examples thereof include plain weave, twill weave, satin weave, variable plain weave, variable twill weave, variable satin weave, variegated weave, patterned weave, single layer weave, double weave, multiple weave, warp pile weave, weft pile weave, entwined weave, etc. When the fiber structure is a knitted fabric, the knit structure is not particularly limited, and examples thereof include circular knit, weft knit, warp knit (including tricot knit and raschel knit), pile knit, plain knit, jersey knit, rib knit, smooth knit (double-sided knit), elastic knit, pearl knit, Denbigh weave, cord weave, atlas weave, chain weave, insertion weave, etc.

以下、実施例により本発明をより詳細に説明するが、本発明は本実施例により何ら限定されるものではない。なお、以下の実施例及び比較例においては、下記の方法により各種物性を測定した。The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, various physical properties were measured by the following methods.

[繊度]
JIS L 1013:2010 8.3.1 A法に基づき、大栄科学精器製作所製検尺器を用いて芯鞘複合繊維を100mカセ取りし、その重量(g)を100倍して1水準当たり3回の測定を行い、前記3回の測定値の平均値を得られた繊度(dtex)とした。
[Fineness]
Based on JIS L 1013:2010 8.3.1 A method, a 100 m skein of core-sheath composite fiber was taken using a measuring instrument manufactured by Daiei Scientific Instruments Manufacturing Co., Ltd., and the weight (g) was multiplied by 100 and measured three times per level, and the average value of the three measured values was taken as the obtained fineness (dtex).

[引張強度]
JIS L 1013に準じ、USTER社製強伸度測定機「TENSORAPID5」を用いて、試験長20cm、引張速度10cm/分、初荷重を0.33g/dtexとした条件で、1サンプルにつき5回の測定を行い、前記5回の測定値の平均値を強度(cN/dtex)とした。なお、芯鞘複合繊維がマルチフィラメントの場合、マルチフィラメントから1本取り出して単糸引張強度を測定した。
[Tensile strength]
In accordance with JIS L 1013, a tenacity and elongation tester "TENSORAPID5" manufactured by USTER was used to perform five measurements for each sample under conditions of a test length of 20 cm, a tensile speed of 10 cm/min, and an initial load of 0.33 g/dtex, and the average of the five measurements was taken as the strength (cN/dtex). When the core-sheath composite fiber was a multifilament, one fiber was taken out of the multifilament to measure the single yarn tensile strength.

[鞘成分の厚み]
芯鞘複合繊維をエポキシ樹脂に包埋し、この包埋したものを繊維長手方向に垂直な平面で切断することで繊維横断面の断面出しを行った。この繊維横断面において、マイクロスコープにて、繊維外周を3等分する任意の3点において、芯部の外周面から鞘部の外周面までの径方向距離を測定し、その平均値を算出し、鞘成分の厚みとした。
[Sheath component thickness]
The core-sheath composite fiber was embedded in epoxy resin, and the embedded fiber was cut in a plane perpendicular to the longitudinal direction of the fiber to expose the fiber cross section. In the fiber cross section, the radial distance from the outer periphery of the core to the outer periphery of the sheath was measured using a microscope at three arbitrary points dividing the fiber periphery into three equal parts, and the average value was calculated to be the thickness of the sheath component.

[島部長さ、島部最大幅]
芯鞘複合繊維をエポキシ樹脂に包埋し、この包埋したものをクロスセクションポリッシャ(CP)にて繊維長手方向に切断することで繊維縦断面の断面出しを行った。この繊維縦断面において、走査型プローブ顕微鏡(SPM)にて、繊維長手方向に100μm以上1000μm以下で観察した。観察範囲にて、繊維長手方向に延びる多数の島部のうち、繊維垂直方向の長さが相対的に大きい島部を複数個抽出し、抽出した島部の繊維垂直方向の長さを島部の幅として比較し、最も大きな幅を有する島部について、島部の最大幅Wを決定した。また、最大幅Wを有する島部について、繊維長手方向の長さL2を測定した。
[Island length, maximum island width]
The core-sheath composite fiber was embedded in epoxy resin, and the embedded fiber was cut in the fiber longitudinal direction with a cross-section polisher (CP) to expose the fiber longitudinal section. The fiber longitudinal section was observed in the fiber longitudinal direction at 100 μm to 1000 μm with a scanning probe microscope (SPM). Among the many islands extending in the fiber longitudinal direction within the observation range, a number of islands having a relatively large length in the fiber perpendicular direction were extracted, and the lengths of the extracted islands in the fiber perpendicular direction were compared as the island widths, and the maximum island width W of the island having the largest width was determined. In addition, the length L2 in the fiber longitudinal direction of the island having the maximum width W was measured.

[島部斜め長の最大長さ]
次に、最大幅Wを有する島部について、繊維長手方向一端から他端に向かって、前記繊維長手方向に対し定められた角度α(10°)で延びる斜線と重なる長さの中で、最も長い線分を島部の斜め長の最大長さL1として測定した。
[Maximum island diagonal length]
Next, for the island portion having the maximum width W, the longest line segment among the lengths overlapping with an oblique line extending from one end to the other end in the longitudinal direction of the fibers at a predetermined angle α (10°) with respect to the longitudinal direction of the fibers was measured as the maximum oblique length L1 of the island portion.

[耐摩耗性]
大栄科学精器製作所製のTM型抱合力試験機(型式 TM-200)を用い、120°の角度で互違いに配置された3本の櫛ガイドに試験対象の繊維をそれぞれ通し、各繊維に1g/dtexの荷重をかけ、ストローク長3cm、速度95回/分で30000回の往復運動を与え、カメラにて20倍に拡大して毛羽の状態を確認した。上記試験を5回行い、繊維の長さ3cm当たりについて、それぞれ毛羽の発生の有無を観察した。なお、発生した毛羽については、長さ1mm以下の微小な毛羽と、長さ1mmより大きい毛羽を区別し、以下の基準で評価した。
(毛羽の発生有無)
◎:5回の試験で1回も毛羽が観察されなかった
○:5回の試験で1回以上毛羽が観察されたが、長さ1mmより大きい毛羽は1回も観察されなかった
×:5回の試験で1回以上毛羽が観察され、長さ1mmより大きい毛羽が1回以上観察された
さらに、5回の試験で1回以上毛羽の発生が見られたものについては、発生した毛羽の個数を測定し、上記試験を5回行った平均値として算出した。
[Wear resistance]
Using a TM-type embracing force tester (model TM-200) manufactured by Daiei Kagaku Seiki Seisakusho, the fibers to be tested were passed through three comb guides arranged alternately at an angle of 120°, a load of 1 g/dtex was applied to each fiber, and 30,000 reciprocating motions were given at a stroke length of 3 cm and a speed of 95 times/min, and the state of fluff was confirmed by magnifying it 20 times with a camera. The above test was performed five times, and the presence or absence of fluff generation was observed for each 3 cm length of the fiber. The generated fluff was distinguished between minute fluff with a length of 1 mm or less and fluff with a length of more than 1 mm, and was evaluated according to the following criteria.
(Whether or not fluff occurs)
⊚: No fluff was observed in any of the five tests. ◯: Fuzz was observed once or more in any of the five tests, but no fluff greater than 1 mm in length was observed. ×: Fuzz was observed once or more in any of the five tests, and fluff greater than 1 mm in length was observed once or more. Furthermore, for samples in which fluff was observed once or more in any of the five tests, the number of fluffs that occurred was measured, and the average value of the five tests was calculated.

[実施例1]
以下の方法に従い、芯鞘複合繊維を製造した。
芯成分では、ポリマーAとして構成単位(P:HBA)と(Q:HNA)のモル比が73/27である溶融異方性芳香族ポリエステル[融点(Ma):278℃、溶融粘度(MVa):32.1Pa・s]を用いた。また、鞘成分では、海成分を形成するBポリマーとしてPEN[融点(Mb):266.3℃、溶融粘度(MVb):100Pa・s]を用い、島成分を形成するCポリマーとして上記ポリマーAと同様の溶融異方性芳香族ポリエステル[融点(Mc):278℃、溶融粘度(MVc):32.1Pa・s]を用いた。
[Example 1]
Core-sheath composite fibers were produced according to the following method.
For the core component, a melt-anisotropic aromatic polyester having a molar ratio of constituent units (P:HBA) and (Q:HNA) of 73/27 [melting point (Ma): 278°C, melt viscosity (MVa): 32.1 Pa s] was used as polymer A. For the sheath component, PEN [melting point (Mb): 266.3°C, melt viscosity (MVb): 100 Pa s] was used as polymer B forming the sea component, and the same melt-anisotropic aromatic polyester as polymer A [melting point (Mc): 278°C, melt viscosity (MVc): 32.1 Pa s] was used as polymer C forming the island components.

混練工程では、芯成分と鞘成分を別々の押出機により溶融混練させた。鞘成分の混練工程では、BポリマーおよびCポリマーを鞘成分中の島成分の割合が30重量%となるように混合し、混練押出スタート後に二軸押出機の混練部の設定温度を266℃((Mc-12)℃)に設定して十分混練した後(低温混練工程)、吐出工程において、鞘成分比が0.35(芯鞘比(重量比)として65/35)となるように制御した図4の構造を有する口金より、紡糸温度310℃、ドラフト値22.3倍で紡糸し、10.3dtexのモノフィラメントの芯鞘複合繊維を得た。紡糸性は良好であり、断糸することなく採取が可能であった。In the kneading process, the core component and the sheath component were melt-kneaded in separate extruders. In the kneading process for the sheath component, the B polymer and the C polymer were mixed so that the ratio of the island component in the sheath component was 30% by weight, and after the start of kneading and extrusion, the set temperature of the kneading section of the twin-screw extruder was set to 266°C ((Mc-12)°C) and kneaded thoroughly (low-temperature kneading process). In the discharge process, the sheath component ratio was controlled to 0.35 (core-sheath ratio (weight ratio) 65/35), and the mixture was spun at a spinning temperature of 310°C and a draft value of 22.3 times from a spinneret having the structure shown in Figure 4, at which the spinnability was good and it was possible to collect the monofilament core-sheath composite fiber of 10.3 dtex.

ついで、熱処理工程として、得られた繊維を熱処理ボビンに巻き返し、段階的に処理温度を上げ、最高温度260℃として窒素ガス雰囲気中で18時間行った。熱処理ボビンからの解舒性には問題なく、得られた熱処理糸は表5に示す性能を有していた。Next, in the heat treatment process, the obtained fiber was rewound onto a heat treatment bobbin, and the treatment temperature was gradually increased to a maximum temperature of 260°C, and the treatment was carried out in a nitrogen gas atmosphere for 18 hours. There were no problems with the unwinding property from the heat treatment bobbin, and the obtained heat-treated yarn had the properties shown in Table 5.

[実施例2~8]
芯鞘比、鞘成分中の島成分の割合、フィラメント数、単糸繊度、ドラフト値を表5に示すごとく変更したこと以外は、実施例1と同様に芯鞘複合繊維を製造した。結果を表5に示す。いずれも紡糸性は良好であり、断糸することなく採取が可能であった。
[Examples 2 to 8]
Core-sheath composite fibers were produced in the same manner as in Example 1, except that the core-sheath ratio, the ratio of island components in the sheath component, the number of filaments, the single yarn fineness, and the draft value were changed as shown in Table 5. The results are shown in Table 5. In all cases, the spinnability was good, and the fibers could be harvested without any yarn breakage.

[比較例1]
鞘成分のBポリマーとCポリマーのチップを手混ぜによりブレンドしたチップブレンドを用い、BポリマーおよびCポリマーを、鞘成分中の島成分の割合が30重量%となるように混合して、低温混練工程において単軸押出機を用いて310℃で溶融混練し、鞘成分比が0.35(芯鞘比(重量比)として65/35)となるように制御した図4の構造を有する口金より、紡糸温度310℃、ドラフト値9.9倍で紡糸した以外は実施例1と同様に紡糸、熱処理を実施し、芯鞘複合繊維を製造した。紡糸性は劣っており、断糸する場合があった。結果を表5に示す。
[Comparative Example 1]
A chip blend prepared by manually blending chips of the B polymer and C polymer as the sheath component was used, and the B polymer and C polymer were mixed so that the ratio of island components in the sheath component was 30% by weight. The mixture was melt-kneaded at 310°C using a single-screw extruder in a low-temperature kneading process, and spun at a spinning temperature of 310°C and a draft value of 9.9 times using a spinneret having the structure shown in FIG. 4, which was controlled so that the sheath component ratio was 0.35 (core-sheath ratio (weight ratio) was 65/35). Spinning and heat treatment were carried out in the same manner as in Example 1 to produce a core-sheath composite fiber. The spinnability was poor, and there were cases where the yarn was broken. The results are shown in Table 5.

[比較例2]
鞘成分中の島成分の割合を20重量%となるように混合した以外は、比較例1と同様に芯鞘複合繊維を製造した。紡糸性は劣っており、断糸する場合があった。結果を表5に示す。
[Comparative Example 2]
A core-sheath composite fiber was produced in the same manner as in Comparative Example 1, except that the ratio of island components in the sheath component was 20% by weight. The spinnability was poor, and there were cases of yarn breakage. The results are shown in Table 5.

[比較例3]
鞘成分中の島成分の割合を5重量%となるように混合した以外は、比較例1と同様に紡糸、熱処理を実施し、芯鞘複合繊維を製造した。特許文献1に記載されているように、鞘成分中の島成分の割合が10重量%以下であるため、紡糸性は良好であり、断糸することなく採取が可能であった。結果を表5に示す。
[Comparative Example 3]
A core-sheath composite fiber was produced by spinning and heat treatment in the same manner as in Comparative Example 1, except that the ratio of island components in the sheath component was 5% by weight. As described in Patent Document 1, since the ratio of island components in the sheath component was 10% by weight or less, the spinnability was good and it was possible to collect the fiber without breaking the yarn. The results are shown in Table 5.

[比較例4]
鞘成分比が0.15(芯鞘比(重量比)として85/15)、ドラフト値15.5で紡糸した以外は、比較例1と同様に芯鞘複合繊維を製造した。紡糸性は劣っており、断糸する場合があった。結果を表5に示す。
[Comparative Example 4]
A core-sheath composite fiber was produced in the same manner as in Comparative Example 1, except that the sheath component ratio was 0.15 (core-sheath ratio (weight ratio) was 85/15) and spinning was performed at a draft value of 15.5. The spinnability was poor, and there were cases of yarn breakage. The results are shown in Table 5.

[比較例5]
鞘成分の混練工程において、実施例1と同様の低温混練工程を行った以外は、比較例1と同様に紡糸、熱処理を実施し、芯鞘複合繊維を製造した。紡糸性は良好であり、断糸することなく採取が可能であった。結果を表5に示す。
[Comparative Example 5]
A core-sheath composite fiber was produced by spinning and heat treatment in the same manner as in Comparative Example 1, except that in the kneading step of the sheath component, a low-temperature kneading step was carried out in the same manner as in Example 1. The spinnability was good, and it was possible to collect the fiber without any breakage. The results are shown in Table 5.

Figure 0007645984000008
Figure 0007645984000008

表5に示すように、実施例1~8では、いずれも、鞘成分中の溶融異方性芳香族ポリエステルの割合を高くしても、鞘成分の海島構造の島部の形状を制御することにより、高い耐摩耗性と紡糸性を両立することができている。As shown in Table 5, in all of Examples 1 to 8, even when the proportion of melt-dispersed anisotropic aromatic polyester in the sheath component was increased, it was possible to achieve both high abrasion resistance and spinnability by controlling the shape of the islands in the sea-island structure of the sheath component.

実施例1~8はいずれも、30000回の往復運動による摩耗試験において1mmより大きい毛羽の発生が見られなかったことから、鞘剥がれも発生せず、耐摩耗性に優れている。特に実施例2~3では、島部の最大幅が小さいためか、1mm以下の微小なフィブリルすらも観察されていない。さらに、実施例1および4~5では、島部の最大幅は実施例2~3より大きいものの、島部の幅を小さく、島部の長さを長くすることにより島部の斜め長の最大長さL1/最大幅Wを大きくすることができるためか、1mm以下の微小なフィブリルすらも観察されていないか、または、5回の測定のうちわずか1回観察されたにすぎない。In all of Examples 1 to 8, no fuzz larger than 1 mm was observed in the abrasion test involving 30,000 reciprocating movements, and no sheath peeling occurred, showing excellent abrasion resistance. In particular, in Examples 2 and 3, perhaps because the maximum width of the island is small, not even tiny fibrils smaller than 1 mm were observed. Furthermore, in Examples 1 and 4 to 5, although the maximum width of the island is larger than in Examples 2 and 3, not even tiny fibrils smaller than 1 mm were observed, or were observed only once out of five measurements, perhaps because the maximum length L1 of the diagonal length of the island can be increased by making the island width smaller and the island length longer.

特に、実施例4~5では、鞘成分中の島部形状を制御することにより、鞘を薄くしても耐摩耗性を維持しており、また、芯成分比が高いことに由来して強度も高くなっている。In particular, in Examples 4 and 5, by controlling the shape of the islands in the sheath component, wear resistance is maintained even when the sheath is made thin, and strength is also high due to the high core component ratio.

また、単糸繊度が小さい実施例6であっても、単糸繊度が大きい実施例7~8であっても、鞘成分中の島部形状を制御することにより、比較例1~3より良好な耐摩耗性を示している。 Furthermore, even in Example 6, which has a small single yarn fineness, and Examples 7 to 8, which have a large single yarn fineness, better abrasion resistance is shown than in Comparative Examples 1 to 3 by controlling the island shape in the sheath component.

一方、比較例1は、鞘成分について特定の溶融混練工程を行わないため、紡糸性が不良であり、紡糸中に断糸が発生した。また、比較例1では、実施例1と同様の芯鞘比および鞘成分における島成分の割合を有しているが、得られた芯鞘複合繊維の鞘部では、島部の最大幅が実施例1より大きく、大きな島部を有することが示されている。さらに、島部の斜め長の最大長さ/最大幅が小さいためか、鞘成分のアンカー効果が発揮できず、耐摩耗試験での毛羽の評価に際して、1mm以下の小さな毛羽(フィブリル)が発生するだけでなく、毛羽数も実施例1より多く発生し、さらに1mmより大きい毛羽、鞘剥がれも発生している。また、繊維強度についても、実施例1より低い値を示している。On the other hand, in Comparative Example 1, since a specific melt-kneading process was not performed on the sheath component, the spinnability was poor and yarn breakage occurred during spinning. In addition, in Comparative Example 1, the core-sheath ratio and the ratio of island components in the sheath component are the same as in Example 1, but the maximum width of the island part in the sheath part of the obtained core-sheath composite fiber is larger than that of Example 1, indicating that the sheath part has a large island part. Furthermore, perhaps because the maximum length/maximum width of the diagonal length of the island part is small, the anchor effect of the sheath component cannot be exerted, and when evaluating the fluff in the abrasion resistance test, not only small fluff (fibrils) of 1 mm or less is generated, but the number of fluffs is also greater than in Example 1, and fluff larger than 1 mm and sheath peeling also occur. In addition, the fiber strength is also lower than that of Example 1.

比較例2では、実施例2と同様の芯鞘比および鞘成分における島成分の割合を有しているが、鞘成分について特定の溶融混練工程を行わないため、実施例2と比べて島部の最大幅が大きく、大きな島部を有することが示されている。耐摩耗試験での毛羽の評価に際して、毛羽数も実施例2より多く発生し、さらに1mmより大きい毛羽、鞘剥がれも発生している。また、繊維強度についても、実施例2より低い値を示している。 Comparative Example 2 has the same core-sheath ratio and island component ratio in the sheath component as Example 2, but since no specific melt-kneading process is performed on the sheath component, the maximum width of the island portion is larger than that of Example 2, indicating that the island portion is larger. When evaluating fluff in the abrasion resistance test, the number of fluffs generated is greater than that of Example 2, and fluff larger than 1 mm and sheath peeling also occurred. In addition, the fiber strength is also lower than that of Example 2.

比較例3では、鞘成分中の溶融異方性芳香族ポリエステルの割合が実施例1および2より低いにもかかわらず、実施例1および2と比べて島部最大幅が大きく、大きな島部を有することが示されている。耐摩耗試験での毛羽の評価に際して、毛羽数も実施例1および2より多く発生し、さらに1mmより大きい毛羽、鞘剥がれが発生している。また、繊維強度についても、実施例1および2より低い値を示している。In Comparative Example 3, although the proportion of the melt-anisotropic aromatic polyester in the sheath component is lower than in Examples 1 and 2, the maximum island width is larger than in Examples 1 and 2, indicating that the island has a large island. When evaluating fluff in the abrasion resistance test, the number of fluffs generated is greater than in Examples 1 and 2, and fluff larger than 1 mm and sheath peeling occurred. In addition, the fiber strength is lower than in Examples 1 and 2.

比較例4では、実施例5と同様の芯鞘比および鞘成分における島成分の割合を有しているが、鞘成分について特定の溶融混練工程を行わないため、島部の斜め長の最大長さ/最大幅が小さく、1mmより大きい毛羽、鞘剥がれが発生している。In Comparative Example 4, the core-sheath ratio and the proportion of island components in the sheath components are similar to those in Example 5, but since a specific melt-kneading process is not performed on the sheath components, the maximum length/maximum width of the diagonal length of the island portions is small, and fuzz and sheath peeling of more than 1 mm occurs.

比較例5では、実施例1と同様の芯鞘比および鞘成分における島成分の割合を有しており、鞘成分について特定の溶融混練工程を行っているため、島成分の最大幅は小さいが、紡糸時のドラフト値が小さいため、島部の斜め長の最大長さ/最大幅が小さく、1mmより大きい毛羽、鞘剥がれが発生している。In Comparative Example 5, the core-sheath ratio and the proportion of island components in the sheath components are the same as in Example 1, and since a specific melt-kneading process is performed on the sheath components, the maximum width of the island components is small. However, since the draft value during spinning is small, the maximum length/maximum width of the diagonal length of the island portion is small, and fuzz and sheath peeling of more than 1 mm occurs.

本発明の芯鞘複合繊維は、鞘成分中の溶融異方性芳香族ポリエステルの割合を高めることで高強度・高弾性率を維持しつつフィブリル化を抑制できるため、テンションメンバー(電線、光ファイバー、アンビリカルケーブル、ヒーター線芯糸、イヤホンコード等の各種電気製品のコード等)、セールクロス、ロープ(海洋、登山、クレーン、ヨット、タグ等)、ザイル、陸上ネット、スリング、命綱、釣糸、縫い糸、網戸コード、漁網、延縄、ジオグリッド、防護手袋、防護衣・アウトドア衣料のリップストップ、ライダースーツ、スポーツ用ラケット、ガット、医療用カテーテル補強材、縫合糸、スクリーン紗、フィルター、プリント基板用基布、メッシュ状搬送ベルト、抄紙用ベルト、ドライヤーカンバス、飛行船、気球、エアーバッグ、スピーカーコーン、各種ホース・パイプ用の補強材、タイヤ・コンベアベルト等のゴム・プラスチック等の補強材等の高次加工製品等に活用される。また、一般的な手法で染色可能であるため、特にセールクロス、ザイル、陸上ネット、釣糸、漁網、延縄、防護衣・アウトドア衣料のリップストップ、ゴム・プラスチック等の補強材、一般衣料等の高次加工製品などにおいて、良好に活用される。The core-sheath composite fiber of the present invention can suppress fibrillation while maintaining high strength and high elasticity by increasing the proportion of molten anisotropic aromatic polyester in the sheath component, and is therefore useful in advanced processed products such as tension members (electric wires, optical fibers, umbilical cables, heater wire core threads, cords for various electrical products such as earphone cords, etc.), sailcloth, ropes (marine, mountain climbing, cranes, yachts, tugs, etc.), ropes, land nets, slings, lifelines, fishing lines, sewing threads, screen cords, fishing nets, longlines, geogrids, protective gloves, ripstop protective clothing and outdoor clothing, rider suits, sports rackets, guts, reinforcing materials for medical catheters, suture threads, screen gauze, filters, base fabrics for printed circuit boards, mesh conveyor belts, papermaking belts, dryer canvases, airships, balloons, airbags, speaker cones, reinforcing materials for various hoses and pipes, and reinforcing materials for rubber and plastic materials such as tires and conveyor belts. In addition, because it can be dyed using standard methods, it is particularly well suited for use in sailcloth, ropes, land nets, fishing lines, fishing nets, longlines, ripstop protective clothing and outdoor clothing, reinforcing materials for rubber and plastics, and advanced processed products such as general clothing.

以上のとおり、図面を参照しながら本発明の好適な実施形態を説明したが、当業者であれば、本件明細書を見て、自明な範囲内で種々の変更および修正を容易に想定するであろう。したがって、そのような変更および修正は、請求の範囲から定まる発明の範囲内のものと解釈される。As described above, a preferred embodiment of the present invention has been described with reference to the drawings. However, a person skilled in the art would easily imagine various changes and modifications within the obvious scope upon reading this specification. Therefore, such changes and modifications are interpreted as being within the scope of the invention as determined by the scope of the claims.

Claims (10)

芯成分が溶融異方性芳香族ポリエステル(Aポリマー)を含み、鞘成分が屈曲性熱可塑性ポリマー(Bポリマー)および溶融異方性芳香族ポリエステル(Cポリマー)を含み、前記Bポリマーが海成分を形成し、前記Cポリマーが島成分を形成し、前記海成分からなる海部中に前記島成分からなる複数の島部が分散する海島構造を有する芯鞘複合繊維であって、
前記鞘成分における島成分の割合は、10重量%を超えており、かつ、
この芯鞘複合繊維を繊維長手方向に切断した断面で、島部の最大幅Wが0.65μm以下であり、
前記最大幅Wを有する島部において、繊維長手方向一端から他端に向かうに従って、前記繊維長手方向に対し定められた角度10°で延びる前記鞘成分中における斜線に接する島部のうち、前記斜線と重なる長さの斜め長の最大長さL1と、前記島部の最大幅Wとの比L1/Wが5.0以上である、芯鞘複合繊維。
A core-sheath composite fiber having a sea-island structure in which a core component contains a melt-type anisotropic aromatic polyester (A polymer), a sheath component contains a flexible thermoplastic polymer (B polymer) and a melt-type anisotropic aromatic polyester (C polymer), the B polymer forms a sea component, the C polymer forms island components, and a plurality of island components made of the island components are dispersed in a sea part made of the sea component,
The ratio of the island component in the sheath component is more than 10% by weight, and
In a cross section of the sheath-core composite fiber cut in the longitudinal direction of the fiber, the maximum width W of the island portion is 0.65 μm or less,
a sheath-core composite fiber, wherein, in an island portion having the maximum width W, among the island portions that are in contact with an oblique line in the sheath component extending at a predetermined angle of 10° with respect to the longitudinal direction of the fiber from one end to the other end in the longitudinal direction of the fiber, a ratio L1/W of a maximum length L1 of a diagonal length that overlaps with the oblique line to a maximum width W of the island portion is 5.0 or more.
請求項1に記載の芯鞘複合繊維であって、前記斜め長の最大長さL1が1.0μm以上である、芯鞘複合繊維。 The sheath-core composite fiber according to claim 1, wherein the maximum length L1 of the oblique length is 1.0 μm or more. 請求項1または2に記載の芯鞘複合繊維であって、前記芯鞘複合繊維を繊維長手方向に切断した断面で、前記鞘成分中における前記島部の繊維長手方向の長さL2が450~1000μmである芯鞘複合繊維。 The sheath-core composite fiber according to claim 1 or 2, wherein in a cross section of the sheath-core composite fiber cut in the longitudinal direction of the fiber, the length L2 of the island portion in the sheath component in the longitudinal direction of the fiber is 450 to 1000 μm. 請求項1~3のいずれか一項に記載の芯鞘複合繊維であって、前記鞘成分の厚みが0.8~5.0μmである芯鞘複合繊維。 A sheath-core composite fiber according to any one of claims 1 to 3, wherein the thickness of the sheath component is 0.8 to 5.0 μm. 請求項1~4のいずれか一項に記載の芯鞘複合繊維であって、前記Aポリマーおよび前記Cポリマーが、主たる構成単位が同一の溶融異方性芳香族ポリエステルで構成される芯鞘複合繊維。 A sheath-core composite fiber according to any one of claims 1 to 4, wherein the A polymer and the C polymer are composed of the same melt-dispersed anisotropic aromatic polyester as main structural units. 請求項1~5のいずれか一項に記載の芯鞘複合繊維であって、前記芯成分と前記鞘成分の重量比である芯成分/鞘成分が20/80~97/3である芯鞘複合繊維。 A core-sheath composite fiber according to any one of claims 1 to 5, wherein the weight ratio of the core component to the sheath component, that is, core component/sheath component, is 20/80 to 97/3. 請求項1~6のいずれか一項に記載の芯鞘複合繊維であって、この芯鞘複合繊維の単糸繊度が1~120dtexである芯鞘複合繊維。 A sheath-core composite fiber according to any one of claims 1 to 6, the single filament fineness of which is 1 to 120 dtex. 芯成分が溶融異方性芳香族ポリエステル(Aポリマー)を含み、鞘成分が屈曲性熱可塑性ポリマー(Bポリマー)および溶融異方性芳香族ポリエステル(Cポリマー)を含み、前記Bポリマーが海成分を形成し、前記Cポリマーが島成分を形成し、前記海成分からなる海部中に前記島成分からなる複数の島部が分散する海島構造を有する芯鞘複合繊維の製造方法であって、
前記鞘成分に用いるBポリマーおよびCポリマーを、Bポリマーの融点(Mb)に対して(Mb)℃以上であって、Cポリマーの融点(Mc)℃に対して(Mc-20)℃以上、(Mc)℃未満で二軸押出機を用いて混練すると共に、前記芯成分に用いるAポリマーを、前記鞘成分に用いる前記二軸押出機とは異なる押出機を用いて溶融し混練する混練工程と、この混練工程でそれぞれ混練させた鞘成分および芯成分を複合して吐出して放流糸を得る吐出工程と、
吐出された放流糸を、吐出速度に対する巻取速度の比であるドラフト値として13~50で引取る工程と、
を少なくとも備える芯鞘複合繊維の製造方法。
A method for producing a core-sheath composite fiber having a sea-island structure in which a core component contains a melt-type anisotropic aromatic polyester (A polymer), a sheath component contains a flexible thermoplastic polymer (B polymer) and a melt-type anisotropic aromatic polyester (C polymer), the B polymer forms a sea component, the C polymer forms island components, and a plurality of island components made of the island components are dispersed in a sea part made of the sea component, the method comprising the steps of:
a kneading step in which the B polymer and the C polymer used for the sheath component are kneaded using a twin-screw extruder at a temperature of (Mb)°C or higher relative to the melting point (Mb) of the B polymer and at a temperature of (Mc-20)°C or higher but lower than (Mc)°C relative to the melting point (Mc)°C of the C polymer, and the A polymer used for the core component is melted and kneaded using an extruder different from the twin-screw extruder used for the sheath component; and a discharge step in which the sheath component and the core component respectively kneaded in the kneading step are combined and discharged to obtain a discharged yarn.
A step of taking up the discharged discharged yarn at a draft value of 13 to 50, which is the ratio of the winding speed to the discharge speed;
A method for producing a core-sheath composite fiber comprising at least the steps of:
請求項8に記載の芯鞘複合繊維の製造方法であって、前記吐出工程で得られた繊維に熱処理を施す熱処理工程を有する芯鞘複合繊維の製造方法。 The method for producing the sheath-core composite fiber according to claim 8, further comprising a heat treatment step of subjecting the fiber obtained in the extrusion step to a heat treatment. 請求項1~7のいずれか一項に記載の芯鞘複合繊維を少なくとも一部に含む、繊維構造体。A fiber structure comprising at least a portion of the core-sheath composite fiber according to any one of claims 1 to 7.
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