WO2017114313A1 - Core-sheath type composite fibre, false-twist yarns and fibrous structure - Google Patents

Core-sheath type composite fibre, false-twist yarns and fibrous structure Download PDF

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Publication number
WO2017114313A1
WO2017114313A1 PCT/CN2016/111763 CN2016111763W WO2017114313A1 WO 2017114313 A1 WO2017114313 A1 WO 2017114313A1 CN 2016111763 W CN2016111763 W CN 2016111763W WO 2017114313 A1 WO2017114313 A1 WO 2017114313A1
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WIPO (PCT)
Prior art keywords
core
type composite
sheath type
sheath
composite fiber
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PCT/CN2016/111763
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French (fr)
Chinese (zh)
Inventor
成娟
旦浩一
鹿野秀和
望月克彦
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东丽纤维研究所（中国）有限公司
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Priority to CN201680057381.4A priority Critical patent/CN108138377A/en
Priority to JP2018534054A priority patent/JP2019502036A/en
Priority to KR1020187021318A priority patent/KR20180097712A/en
Publication of WO2017114313A1 publication Critical patent/WO2017114313A1/en

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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
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/02—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist
    • D02G1/0206—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting
    • D02G1/022—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting while simultaneously drawing the yarn
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/36—Cored or coated yarns or threads

Definitions

  • the present invention relates to a core-sheath type composite fiber in which a core component and a sheath component are both crystalline polymers, and a core component is a hygroscopic polymer, and at least a part of core components on a fiber cross section are exposed on a surface. Specifically, it relates to a kind of smear and hairiness which are generated when a fiber structure such as a woven fabric or a knitted fabric is formed in order to suppress the occurrence of the elongation and the occurrence of the false twisting project, the occurrence of broken wires and hairiness is small, and the engineering passability is good.
  • polyester fiber Due to its low price and excellent mechanical properties, polyester fiber is extremely versatile. However, due to the lack of hygroscopicity, it is easy to generate a stuffy feeling in high humidity in summer, and it is easy to generate static electricity in low humidity in winter, and there are problems to be solved from the viewpoint of wearing comfort.
  • a general method for imparting hygroscopicity to a polyester fiber such as copolymerizing a hydrophilic compound or adding a hydrophilic compound to a polyester, wherein the hydrophilic compound may be polyethylene glycol.
  • Patent Document 1 a proposal has been made for a polyester to produce a fiber using a polyester copolymerized with polyethylene glycol as a hygroscopic polymer.
  • the hygroscopic polymer is separately fibrillated to make the polyester fiber hygroscopic.
  • Patent Document 2 proposes an eccentric core-sheath type composite fiber in which a sheath component is a hygroscopic polymer and a core component is a hydrophobic polymer.
  • a sheath component is a hygroscopic polymer
  • a core component is a hydrophobic polymer.
  • Patent Document 3 proposes a core-sheath type composite fiber in which a core component is a polyester in which polyethylene glycol is copolymerized and a sheath component is polyethylene terephthalate.
  • a core component is a polyester in which polyethylene glycol is copolymerized and a sheath component is polyethylene terephthalate.
  • the polyester fiber is hygroscopic.
  • Patent Documents 4 and 5 a core-sheath type composite fiber in which a core component is a polymer in which polyethylene glycol is copolymerized, a sheath component is polyethylene terephthalate, and a part of a sheath is opened is proposed.
  • the core component is hygroscopic, in these proposals, the hollow fiber is formed into a C-shaped hollow fiber by the elution of the core component, and the polyester fiber is imparted with lightness.
  • Patent Document 4 discloses that a polyparaphenylene group of polyethylene glycol having a weight average molecular weight of 500 to 8000 g/mol, that is, a number average molecular weight of 8000 g/mol or less is copolymerized in an amount of 8 to 70% by weight.
  • Patent Document 5 discloses polyethylene terephthalate copolymerized with 17 wt% of polyethylene glycol having a molecular weight of 3000 g/mol.
  • the core component is a hydrophobic polymer, it has morphological stability against reversible change in moisture absorption and drying, but at least half of the fiber surface is exposed by the hygroscopic polymer, and is described in Patent Document 1. In the same way, the swelling and shedding of the hygroscopic polymer occurs, and there are problems in engineering passability and quality.
  • An object of the present invention is to solve the above-mentioned problems and to provide a fiber structure in which a fiber structure such as a woven fabric or a knitted fabric is formed in order to suppress the occurrence of the elongation and the occurrence of the false twisting process, the occurrence of broken yarn and hairiness is small, and the engineering passability is good. It is possible to suppress the cracking of the sheath component and the elution of the hygroscopic polymer and the hygroscopicity after the hot water treatment by the volume expansion of the core component hygroscopic polymer during hot water treatment such as dyeing, and the like. A core-sheath type composite fiber that is still excellent and suitable for use in clothing.
  • the above object of the present invention can be solved by a core-sheath composite fiber having the following characteristics.
  • the core component and the sheath component of the core-sheath type composite fiber are both crystalline polymers, and the core component is a hygroscopic polymer; at least a part of the core component in the cross section of the core-sheath type composite fiber is exposed on the surface, and cross-section with an outer perimeter of the sum of the length r S R is exposed on the surface portion of the core component ratio r S / R of 0.05 to 0.40; outside of the core-sheath type composite fiber push melting start temperature of at least 150 °C, and the heat
  • the moisture absorption rate difference ⁇ MR after the water treatment was 2.0 to 10.0%.
  • the ratio r M /R of the outer peripheral length R of the cross section to the maximum value r M of the length of the core component exposed at the surface portion is 0.01 to 0.20, and the composite weight ratio of the core component to the sheath component is preferably 10/. 90 to 70/30.
  • the value of the color tone change value ⁇ b of the composite fiber before and after the hot water treatment is preferably 3.0 or less, and the composite fiber preferably contains a semi-hindered phenol antioxidant having a structure represented by Formula 1.
  • R1 is a semi-hindered phenolic antioxidant formed by combining any one of hydrocarbon, oxygen and nitrogen
  • R2 is a semi-hindered phenolic antioxidant formed by combining any one of hydrogen, hydrocarbon, oxygen and nitrogen.
  • the hygroscopic polymer of the core component is preferably at least one of a polyether ester, a polyether amide, and a polyether amide ester having a polyether as a copolymer component.
  • the polyether is preferably polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
  • the polyether ester preferably contains an aromatic dicarboxylic acid and an aliphatic diol as main constituent components, and the polyether is a copolymer component.
  • the aliphatic diol is preferably ethylene glycol
  • the number average molecular weight of the polyether is preferably from 4,000 to 30,000 g/mol
  • the copolymerization ratio of the polyether is preferably from 10 to 35 wt%.
  • the aliphatic diol is preferably 1,4-butanediol
  • the number average molecular weight of the polyether is preferably from 2,000 to 30,000 g/mol
  • the copolymerization ratio of the polyether is preferably from 10 to 60% by weight.
  • sheath component of the core-sheath type composite fiber is preferably a cationic dyeable polyester.
  • the false twist yarn of the present invention is formed by combining two or more core-sheath type composite fibers, and at least a part of the fiber structure is preferably a core-sheath type composite fiber and/or a false twist yarn.
  • the present invention it is possible to suppress the occurrence of the fusion and the occurrence of the false twisting project, and the occurrence of the broken yarn and the hairiness is small, and the engineering passability is good.
  • a fiber structure such as a woven fabric or a knitted fabric is formed, stains and hairiness are small, and the quality is excellent.
  • Type composite fiber is possible to suppress cracking of the sheath component due to volume expansion of the core component hygroscopic polymer during hot water treatment such as dyeing, and elution of the hygroscopic polymer, and excellent moisture absorption after hot water treatment, and the core sheath suitable for clothing use.
  • Fig. 1 (a) to (m) are schematic views showing the cross-sectional shape of the core-sheath composite fiber of the present invention.
  • 1 indicates a core component
  • 2 indicates a sheath component.
  • FIG. 2 is a schematic view showing the cross-sectional shape of a core-sheath composite fiber prepared in Comparative Example 1.
  • the core component and the sheath component are both crystalline polymers, and the core component is a hygroscopic polymer, at least a part of the core component on the cross section of the fiber is exposed on the surface, and the outer circumference R of the cross section is
  • the ratio r S /R of the total length r S of the core component exposed at the surface portion is 0.05 to 0.40;
  • the extrapolated melting initiation temperature of the core-sheath type composite fiber is 150 ° C or more, and the moisture absorption rate after hot water treatment
  • the difference ⁇ MR is 2.0 to 10.0%.
  • the hygroscopic polymer is likely to swell due to the presence of the spinning oil agent, rubbing against the roller or the yarn guide to cause detachment and formation of accumulated dirt, causing broken yarn and hairiness, and thus poor engineering passability, and due to formation
  • a fiber structure such as a woven fabric or a knitted fabric
  • staining and hairiness occur, and there is a problem of low quality.
  • the result of the intensive review conducted by the present inventors is that the core component and the sheath component are simultaneously crystallized, and the core component is hygroscopic, the cross-sectional outer circumference R of the fiber, and the length of the core component exposed at the surface portion.
  • the ratio r S /R of the sum r S is 0.05 to 0.40, and the extrapolated melting onset temperature of the core-sheath type composite fiber is 150 ° C or more.
  • the core component of the core-sheath type composite fiber of the present invention is a crystalline polymer.
  • the core component has crystallinity
  • the extrapolation melting onset temperature is measured by the method described in the examples, a melting peak can be observed with melting of the crystal.
  • the core component has crystallinity, the fusion between the fibers due to the extension and the contact with the heating roller and the heater in the false twisting process can be suppressed, and the deposit on the heating roller, the heater, and the yarn guide is reduced.
  • the silk and hairiness are less and the engineering passability is good.
  • a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent.
  • the elution of the hygroscopic polymer of the core component during hot water treatment such as dyeing can be suppressed, and the hygroscopicity after the hot water treatment can be maintained.
  • the core component of the core-sheath type composite fiber of the present invention is a hygroscopic polymer.
  • the hygroscopic polymer is a polymer having a moisture absorption rate difference (?MR) of 2.0% or more.
  • the moisture absorption rate difference (?MR) according to the present invention means a value measured by the method described in the examples.
  • the core component of the core-sheath type composite fiber of the present invention may specifically be a hygroscopic polymerization such as a polyether ester, a polyether amide, a polyether amide ester, a polyamide, a thermoplastic cellulose derivative or a polyvinylpyrrolidone.
  • a polyether ester, a polyether amide, or a polyether amide ester having a polyether as a copolymer component is preferable, and in particular, since the polyether ester is excellent in heat resistance, the obtained core-sheath type composite fiber has better mechanical properties and color tone. Therefore, it is more preferable.
  • hygroscopic polymers may be used alone or in combination of two or more. At the same time, those obtained by kneading these hygroscopic polymers with polyester, polyamide, and polyolefin can also be used as hygroscopic polymers.
  • the polyether of the copolymerizable component of the hygroscopic polymer may, for example, be a single polymer such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol, a polyethylene glycol-polypropylene glycol copolymer, polyethylene glycol- A copolymer or the like such as polytetramethylene glycol, but is not limited to the above.
  • polyethylene glycol, polypropylene glycol, and polytetramethylene glycol are preferred because they are excellent in recyclability during production and use, and polyethylene glycol is particularly preferred because it is excellent in hygroscopicity.
  • the polyether ester has an aromatic dicarboxylic acid and an aliphatic diol as main recurring units from the viewpoint of heat resistance and mechanical properties, and preferably a polyether as a copolymer component.
  • aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, sodium isophthalate-5-sulfonate, and lithium isophthalate-5-sulfonate.
  • 5-(tetraalkyl)-isophthalic acid sulfonate The acid phosphorus compound, 4,4'-biphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and the like are, but not limited to, the above.
  • the aliphatic diol may specifically be exemplified by ethylene glycol, 1,3-propanediol, 1,4-butanediol, hexanediol, cyclohexane hexanediol, diethylene glycol, and hexamethylene Ethylene glycol, neopentyl glycol, etc., but not limited to the above.
  • ethylene glycol, propylene glycol, and 1,4-butanediol are preferred because they are excellent in handleability and use. From the viewpoint of heat resistance and mechanical properties, ethylene glycol is more preferable; from the viewpoint of crystallinity, 1,4-butanediol is more preferable.
  • the number average molecular weight and the copolymerization ratio of the polyether ester copolymerization component polyether can be appropriately selected within the range in which the polyether ester has crystallinity, and the preferred range differs depending on the composition of the polyether ester. For example, when the aliphatic diol of the composition of the polyether ester is ethylene glycol, if the copolymerization ratio of the polyether is too high, the polyether ester will be eluted in hot water during hot water treatment such as dyeing. Hygroscopicity after water treatment is low.
  • the aliphatic diol which is a constituent of the polyether ester is 1,4-butanediol
  • the crystallinity of the polymer is high, even if it is a polyether compound, compared with the case where ethylene glycol is used as described above.
  • the polymerization rate is high, the elution of the polyether ester in hot water can also be suppressed. That is, when 1,4-butanediol is used as the aliphatic diol, since the copolymerization ratio of the polyether can be increased, the hygroscopicity of the polyether ester, and even the hygroscopicity of the obtained core-sheath type composite fiber can be Improved.
  • the number average molecular weight of the polyether is preferably 4,000 to 30,000 g/mol, and the copolymerization ratio of the polyether is preferably 10 to 35 wt%.
  • the number average molecular weight of the polyether is 4,000 g/mol or more, the polyether ester has high hygroscopicity, and when used as a core component, a core-sheath type composite fiber excellent in hygroscopicity can be obtained.
  • the number average molecular weight of the polyether is 30,000 g/mol or less, the polycondensation reactivity is high, and the unreacted polyether is reduced, and dissolution in hot water during hot water treatment such as dyeing can be suppressed, and moisture absorption after hot water treatment can be suppressed. Sex can be maintained.
  • the number average molecular weight of the polyether is preferably 25,000 g/mol or less, and more preferably 20,000 g/mol or less.
  • the copolymerization ratio of the polyether when the copolymerization ratio of the polyether is 10% by weight or more, the polyether ester has high hygroscopicity, and when used as a core component, a core-sheath type composite fiber excellent in hygroscopicity can be obtained.
  • the copolymerization ratio of the polyether is more preferably 15% by weight or more, and most preferably 20% by weight or more.
  • the copolymerization ratio of the polyether is 35 wt% or less, the fusion between the fibers due to the contact with the heating roller and the heater in the extension and the false twisting process can be suppressed, and the heating roller, the heater, and the guide rail are suppressed.
  • the occurrence of deposits, broken wires, and hairiness is reduced, and the engineering passability is good.
  • a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent.
  • the copolymerization ratio of the polyether is more preferably 32% by weight or less, and most preferably 30% by weight or less.
  • the number average molecular weight of the polyether is preferably 2,000 to 30,000 g/mol, and the copolymerization ratio of the polyether is preferably 10 to 60% by weight.
  • the number average molecular weight of the polyether is 2000 g/mol or more, the polyether ester has high hygroscopicity, and when used as a core component, a core-sheath type composite fiber excellent in hygroscopicity can be obtained. At the same time, it is possible to suppress a decrease in crystallinity of the polyether ester.
  • the number average molecular weight of the polyether is more preferably 3,000 g/mol or more, and most preferably 5,000 g/mol or more.
  • the number average molecular weight of the polyether is 8000 g/mol or more, the decrease in the crystallinity of the polyether ester and the decrease in the extrapolation melting initiation temperature can be suppressed, due to the extension and the false-twisting process due to the heating roller and the heater.
  • the fusion between the fibers caused by the contact can also be suppressed, and the occurrence of deposits on the heating roller, the heater, the guide rail, the broken wire, and the hairiness is reduced, and the engineering passability is good, and the fiber structure such as the woven fabric and the knitted fabric is dyed.
  • the number average molecular weight of the polyether is 30,000 g/mol or less, the polycondensation reactivity is high, and the unreacted polyether is reduced, and dissolution in hot water during hot water treatment such as dyeing can be suppressed, and moisture absorption after hot water treatment can be suppressed. Sex can be maintained.
  • the number average molecular weight of the polyether is more preferably 27,000 g/mol or less, most preferably 25,000 g/mol or less, and particularly preferably 20,000 g/mol or less.
  • the copolymerization ratio of the polyether is 10% by weight or more, the polyether ester has high hygroscopicity, and when used as a core component, a core-sheath type composite fiber excellent in hygroscopicity can be obtained.
  • the copolymerization ratio of the polyether is more preferably 15% by weight or more, and most preferably 20% by weight or more.
  • the copolymerization ratio of the polyether is 60% by weight or less, the fusion between the fibers due to the contact with the heating roller and the heater in the elongation and false twisting process can be suppressed, and the heating roller, the heater, and the guide rail are suppressed.
  • the occurrence of deposits, broken wires, and hairiness is reduced, and the engineering passability is good.
  • a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent.
  • the copolymerization ratio of the polyether is more preferably 55 wt% or less, and most preferably 50 wt%. Hereinafter, it is particularly preferably 45 wt% or less.
  • a fiber obtained by adding a polyether ester obtained by copolymerizing a large amount of a polyether to a polyester causes a drastic decrease in the moisture absorption rate of the fiber due to oxidative decomposition of the polyether group. Therefore, in the polymerization process of polyether esters, hindered phenolic antioxidants are added in most cases, and most of the hindered phenolic antioxidants are tetra[ ⁇ -(3,5-di-tert-butyl-4-hydroxyl). Phenyl)propionic acid]pentaerythritol ester (IR1010 manufactured by BASF).
  • the ether radical formed by oxidative decomposition attacks the para-position of the phenolic hydroxyl group of the hindered phenolic antioxidant to form an anthraquinone which causes yellowing.
  • the yellow matter is formed by the reaction with NO 2 , that is, the NOx (nitrogen oxide) fastness is low, which affects the quality of the fiber.
  • the copolymerization ratio of the polyether is 25 wt% or less, the yellowing phenomenon is less due to the small amount of the hindered phenol antioxidant added, but the yellowing phenomenon remarkably occurs when the copolymerization ratio of the polyether is 25 wt% or more.
  • the semi-hindered phenolic antioxidant having the structure of the formula 1 of the present invention even if it is oxidatively decomposed to form an ether radical, since the phenolic hydroxyl group is a methyl group on the one side of the phenolic hydroxyl group, the steric hindrance is small, and thus half.
  • the ortho position of the phenolic hydroxyl group of the hindered phenolic antioxidant is attacked, no quinone species are formed, and yellow becomes suppressed.
  • R1 is a semi-hindered phenolic antioxidant formed by combining any one of hydrocarbon, oxygen and nitrogen
  • R2 is a semi-hindered phenolic antioxidant formed by combining any one of hydrogen, hydrocarbon, oxygen and nitrogen.
  • the amount of the antioxidant to be added can be appropriately selected depending on the copolymerization ratio of the polyether, and is preferably from 0.5 to 8.0% by weight.
  • the amount of the antioxidant added is more preferably 1.0% by weight or more, and most preferably 1.5% by weight or more.
  • the amount of the antioxidant added is 8.0% by weight or less, the decomposition of the antioxidant itself causes the yellowing of the fiber to be suppressed, which is preferable.
  • the amount of the antioxidant added is more preferably 7.0% by weight or less, and most preferably 6.0% by weight or less.
  • the sheath component of the core-sheath type composite fiber of the present invention has crystallinity.
  • the sheath component has crystallinity, when the extrapolation melting onset temperature is measured by the method described in the examples, a melting peak can be observed with melting of the crystal.
  • the sheath component has crystallinity, it is possible to suppress the fusion between the fibers due to the contact with the heating roller and the heater during the extension and false twisting, and the deposit on the heating roller, the heater, and the yarn guide is reduced, and the yarn is broken.
  • the hairiness is reduced, and the engineering passability is good.
  • a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent.
  • sheath component of the core-sheath type composite fiber of the present invention include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyamides such as nylon 6, nylon 66, and the like.
  • Polyolefins such as polyethylene and polypropylene are not limited to the above.
  • polyester is preferred because of its excellent mechanical properties and durability.
  • the sheath component is a hydrophobic polymer such as polyester or polyolefin, the hygroscopicity of the core component hygroscopic polymer exposed on the surface can be coexisted with the dry touch of the sheath component hydrophobic polymer, and the wearing comfort can be obtained. Fiber structure.
  • the polyester of the sheath component of the core-sheath type composite fiber of the present invention may specifically be exemplified by polyethylene terephthalate, polytrimethylene terephthalate or polybutylene terephthalate.
  • the family polyester, an aliphatic polyester such as polylactic acid or polyglycolic acid, etc. but is not limited to the above.
  • polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate have excellent mechanical properties and durability, and are preferable because they are excellent in handleability at the time of production and use. Meanwhile, polyethylene terephthalate has a peculiar feeling of polyester fiber, and polybutylene terephthalate has high crystallinity and is preferable.
  • the sheath component of the core-sheath type composite fiber of the present invention is preferably a cationic dyeable polyester.
  • the polyester has an anionic moiety such as a sulfonic acid group, it can interact with a cationic dye having a cationic moiety, and thus has cationic dyeability.
  • the sheath component is a cationic dyeable polyester, it has a clear color developability and is preferably used in combination with a polyurethane fiber to prevent contamination of the dye.
  • the copolymerization component of the cationic dyeable polyester is specifically a 5-isophthalic acid sulfonate, and examples thereof include a lithium salt, a sodium salt, a potassium salt, a phosphonium salt, a phosphonium salt, and the like, but are not limited thereto. It is particularly preferable that the lithium salt and the sodium salt are particularly excellent in crystallinity of the sodium salt.
  • the core-sheath type composite fiber of the present invention at least a part of the core component on the fiber cross section is exposed on the surface. Unlike the core-sheath type composite fiber in which the core component is completely wrapped, at least a part of the core component is exposed on the surface of the fiber cross-section, and it is possible to suppress the damage of the sheath after the volume expansion of the core component hygroscopic polymer during hot water treatment such as dyeing. At the same time, since the core component hygroscopic polymer was exposed on the surface, it was found to have higher hygroscopicity than the core-sheath type composite fiber in which the core component was completely wrapped.
  • Core-sheath type composite fiber of the present invention the sum of the length of the fiber cross-section r S R and the outer perimeter of the surface of the exposed portion of the core component ratio r S / R of 0.05 to 0.40.
  • the ratio r S /R of the outer peripheral length R of the cross-sectional area of the fiber of the present invention to the total length r S of the core component exposed on the surface portion means a value calculated by the method described in the examples.
  • the r S /R of the core-sheath type composite fiber is preferably 0.07 or more, and more preferably 0.10 or more.
  • the r S /R of the core-sheath type composite fiber is 0.40 or less, the fusion between the fibers due to the contact with the heating roller and the heater in the false twisting process can be suppressed, and the heating roller and the heater are heated. The occurrence of deposits, broken wires, and hairiness on the yarn guide is reduced, and the engineering passability is good.
  • the r S /R of the core-sheath type composite fiber is more preferably 0.35 or less, and most preferably 0.30 or less.
  • the ratio r M /R of the outer peripheral length R of the cross section of the fiber to the maximum value r M of the length of the core component exposed on the surface portion is preferably 0.01 to 0.20.
  • the ratio r M /R of the outer peripheral length R of the cross-sectional area of the fiber of the present invention to the maximum value r M of the core component length exposed on the surface portion means a value calculated by the method described in the examples.
  • the core-sheath type composite fiber in which the core component is completely exposed is more hygroscopic than the core component hygroscopic polymer, and is preferable.
  • the core component hygroscopic polymer expands in volume, and it is possible to suppress the destruction of the sheath, which is preferable.
  • the r M /R of the core-sheath type composite fiber is more preferably 0.03 or more, and most preferably 0.05 or more.
  • the r M /R of the core-sheath type composite fiber is 0.20 or less, the fusion between the fibers due to the contact with the heating roller and the heater in the false twisting process can be suppressed, and the heating roller and the heater are heated. The occurrence of deposits, broken wires, and hairiness on the yarn guide is reduced, and the engineering passability is good. When a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent. At the same time, it is possible to suppress the elution of the core component hygroscopic polymer in hot water during hot water treatment such as dyeing, and to maintain hygroscopicity after hot water treatment.
  • the r M /R of the core-sheath type composite fiber is more preferably 0.17 or less, and most preferably 0.15 or less.
  • auxiliary modifiers may be added to the core component and/or the sheath component.
  • the auxiliary modifier may specifically be a phase solvent, a plasticizer, an acidification inhibitor, an ultraviolet absorber, an infrared absorber, an optical brightener, a mold release agent, an antibacterial agent, a nucleating agent, a heat stabilizer, and an acidification.
  • the above auxiliary additives may be used singly or in combination.
  • the core-sheath type composite fiber of the present invention has an extrapolated melting onset temperature of 150 ° C or more.
  • the extrapolated melting onset temperature of the core-sheath type composite fiber of the present invention means a value calculated by the method described in the examples. Further, when a plurality of melting peaks are observed, the melting peak from the lowest temperature side is calculated.
  • the extrapolation melting initiation temperature of the core-sheath type composite fiber is 150 ° C or more, the fusion between the fibers due to the contact with the heating roller and the heater in the extension and the false twisting process can be suppressed, and the heating roller, the heater, and the heating roller are heated.
  • the extrapolated melting initiation temperature of the core-sheath type composite fiber is more preferably 170 ° C or more, most preferably 190 ° C or more, and particularly preferably 200 ° C or more.
  • the composite ratio (weight ratio) of the core component/sheath component of the core-sheath type composite fiber of the present invention is preferably 10/90 to 70/30.
  • the composite ratio (weight ratio) of the core component/sheath component of the core-sheath type composite fiber of the present invention means a value calculated by the method described in the examples.
  • the composite ratio of the core component of the core-sheath type composite fiber is 10% by weight or more, a core-sheath type composite fiber having excellent hygroscopicity can be obtained.
  • the composite ratio of the core component of the core-sheath type composite fiber of the present invention is more preferably 20% by weight or more, and most preferably 30% by weight or more.
  • the core component composite fiber has a core component composite ratio of 70% by weight or less, that is, when the composite ratio of the sheath component is 30% by weight or more, the sheath component can have a firm and dry touch.
  • the composite ratio of the core component of the core-sheath type composite fiber of the present invention is more preferably 60% by weight or less, and most preferably 50% by weight or less.
  • the fineness of the multifilament of the core-sheath type composite fiber of the present invention is not particularly limited, and may be appropriately selected depending on the use and characteristics, and is preferably from 10 to 500 dtex.
  • the fineness of the present invention means a value measured by the method described in the examples.
  • the fineness of the core-sheath type composite fiber is 10 dtex or more, the number of broken wires is relatively small, the engineering passability is good, the occurrence of hairiness is small during use, and the durability is excellent.
  • the fineness of the core-sheath type composite fiber is more preferably 30 dtex or more, and most preferably 50 dtex or more.
  • the fineness of the core-sheath type composite fiber is 500 dtex or less, the flexibility of the fiber and the fiber structure is not impaired.
  • the fineness of the core-sheath type composite fiber is more preferably 400 dtex or less, and most preferably 300 dtex or less.
  • the single-filament fineness of the core-sheath type composite fiber of the present invention is not particularly limited, and may be appropriately selected depending on the use and characteristics, and is preferably 0.5 to 4.0 dtex.
  • the single yarn fineness of the present invention means a value obtained by dividing the fineness measured by the method described in the examples by the number of filaments.
  • the monofilament fineness of the core-sheath type composite fiber is more preferably 0.6 dtex or more, and most preferably 0.8 dtex or more.
  • the single-filament fineness of the core-sheath type composite fiber is 4.0 dtex or less, the flexibility of the fiber and the fiber structure is not impaired.
  • the monofilament fineness of the core-sheath type composite fiber is more preferably 2.0 dtex or less, and most preferably 1.5 dtex or less.
  • the strength of the core-sheath type composite fiber of the present invention is not particularly limited, and may be appropriately selected depending on the use and characteristics, and is preferably 2.0 to 5.0 cN/dtex in accordance with the requirements of mechanical properties.
  • the strength of the present invention means a value measured by the method described in the examples.
  • the strength of the core-sheath type composite fiber is more preferably 2.5 cN/dtex or more, and most preferably 3.0 cN/dtex or more.
  • the strength of the core-sheath type composite fiber is 5.0 cN/dtex or less, the flexibility of the fiber and the fiber structure is not impaired.
  • the elongation of the core-sheath type composite fiber of the present invention is not particularly limited, and may be appropriately selected depending on the use and characteristics, and is preferably from 10 to 60% from the viewpoint of durability.
  • the elongation of the present invention means a value measured by the method described in the examples.
  • the elongation of the core-sheath type composite fiber is 10% or more, the fiber and the fiber structure are excellent in abrasion resistance, and the occurrence of hairiness is small during use, and the durability is good.
  • the elongation of the core-sheath type composite fiber is more preferably 15% or more, and most preferably 20% or more.
  • the elongation of the core-sheath type composite fiber is 60% or less, the dimensional stability of the fiber and the fiber structure is good.
  • the elongation of the core-sheath type composite fiber is more preferably 55% or less, and most preferably 50% or less.
  • the core-sheath type composite fiber of the present invention has a moisture absorption rate difference ( ⁇ MR) after hot water treatment of 2.0 to 10.0%.
  • the moisture absorption rate difference (?MR) after the hot water treatment of the present invention means a value measured by the method described in the examples.
  • ⁇ MR is a difference between the moisture absorption rate at a temperature of 30 ° C and a humidity of 90% RH after a slight exercise, and the moisture absorption rate at an external temperature of 20 ° C and a humidity of 65% RH. That is, ⁇ MR is an indicator of hygroscopicity, and the higher the ⁇ MR, the better the wearing comfort.
  • the moisture absorption rate difference (?MR) of the present invention means a value after hot water treatment, and it is very important to exhibit hygroscopicity even after hot water treatment such as dyeing.
  • the ⁇ MR of the core-sheath type composite fiber after hot water treatment is 2.0% or more, the stuffing feeling in the clothes is lowered, and the wearing comfort is obtained.
  • the ⁇ MR of the core-sheath type composite fiber after hot water treatment is preferably 3.0% or more, more preferably 3.5% or more, and most preferably 4.0% or more.
  • the ⁇ MR of the core-sheath type composite fiber after hot water treatment is 10% or less, the workability and the usability are good, and the durability at the time of use is excellent.
  • the color fiber change value ⁇ b of the composite fiber after the hot water treatment is preferably 3.0 or less.
  • the change value ⁇ b of the color tone of the composite fiber before and after the hot water treatment according to the present invention is a value measured by the method described in the examples.
  • the change value ⁇ b of the color tone of the composite fiber before and after the hot water treatment is 3.0 or less, the yellowing of the fiber after the hot water treatment is small, and a fiber of good quality can be obtained.
  • the change value ⁇ b of the color tone of the composite fiber before and after the hot water treatment is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.0 or less.
  • the ratio r S /R of the outer circumferential length R of the fiber cross section and the total length r S of the core component exposed at the surface portion is satisfied.
  • the viscosity is 0.05 to 0.40
  • the shape of the fiber cross-section there is no particular limitation on the shape of the fiber cross-section, and the corresponding selection can be made according to the use and characteristics.
  • the number of core components exposed on the surface portion for example, one position shown in Figs. 1(a) to (c) and two places shown in Figs. 1(d) and (e). In the three places shown in FIGS.
  • the four portions shown in FIGS. 1(h) to (j) have a cross-sectional shape of a portion exposed on the surface, but are not limited to the above.
  • the core component portion exposed on the surface is preferably as small as possible. It is preferable that the portion of the core component exposed on the surface shown in FIGS. 1(a) to 1(c) has a cross-sectional shape of one. More specifically, it is preferable that the eccentric core sheath type shown in Figs.
  • the sheath component shown in Fig. 1(c) have a C-shaped core-sheath cross-sectional shape.
  • the lengths of the core component portions exposed on the surface shown in Fig. 1(j) may not coincide.
  • the outer shape of the cross section shown in Figs. 1(k) to (m) may be a flat shape, a meander shape, or a trilobal shape.
  • the form of the fiber is not particularly limited, and various forms such as a monofilament, a multifilament, and a staple fiber may be used.
  • the core-sheath type composite fiber of the present invention can be subjected to the same false twisting and twisting processing as a general fiber, and the weaving and knitting can be carried out in the same manner as in the case of a general fiber.
  • the form of the core-sheath type composite fiber of the present invention and/or the fiber structure formed of the false twisted wire is not particularly limited, and according to a known method, a woven fabric, a knitted fabric, a terry cloth, a non-woven fabric, a spinning, and a filling are used. Cotton can be used. Meanwhile, the core-sheath type composite fiber of the present invention and/or the fiber structure formed of the false twisted silk may be any woven fabric, plain weave, twill weave, woven fabric, or a woven weave, warp knitting, weft knitting, Circular knitting, lace knitting, or variations of these can be used.
  • the core-sheath type composite fiber of the present invention may be combined with other fibers, or may be formed into a blended yarn with other fibers, and then formed into a fiber structure by interlacing or interlacing.
  • the method for producing the core-sheath type composite fiber of the present invention is as follows.
  • the core component and the sheath component it is preferred to dry the core component and the sheath component to a water content of 300 ppm or less before melt spinning.
  • the water content is 300 ppm or less, it is possible to suppress a decrease in molecular weight due to hydrolysis by desorption during melt spinning and foaming by moisture, and it is possible to perform stable spinning.
  • the water content is more preferably 100 ppm or less, and most preferably 50 ppm or less.
  • the previously dried chips are supplied to a screw type or hot plate type melt spinning machine, and the core component and the sheath component are separately melted and metered by a metering pump. Then, it is introduced into a spinning assembly heated in a spinning box, and after the molten polymer is filtered in the spinning assembly, the core component and the sheath component are combined by a core-sheath type composite spinning spinneret.
  • the core sheath structure is spun from a spinneret to form a fiber strand.
  • the fiber yarn spun from the spinning spinneret is cooled and solidified by a cooling device, taken up by the first roller, and wound up on the winder by the second roller to obtain a wound wire.
  • the fiber strands can be supplied with oil by means of an oil supply device, or the fiber strands can be entangled by means of an interlacing device.
  • the spinning temperature of the melt spinning can be appropriately selected depending on the core component, the melting point of the sheath component, and the heat resistance, and is preferably 240 to 320 °C.
  • the spinning temperature is more preferably 250 ° C or higher, and most preferably 260 ° C or higher.
  • the spinning temperature is 320 ° C or lower, thermal decomposition at the time of spinning, reduction in fiber mechanical properties, and coloring can be suppressed.
  • the spinning temperature is more preferably 310 ° C or lower, and most preferably 300 ° C or lower.
  • the spinning speed at the time of melt spinning can be appropriately selected depending on the composition of the core component and the sheath component, the spinning temperature, and the like.
  • the spinning speed in the case of melt-spinning and coiling, and then performing the extension or false twist two-stage engineering method is preferably 500 to 6000 m/min.
  • the spinning speed in the case of the two-stage engineering method is more preferably 1000 m/min or more, and most preferably 1500 m/min or more.
  • the spinning speed is 6,000 m/min or less, stable spinning can be performed by suppressing the spinning tension without breaking the yarn.
  • the spinning speed in the case of the two engineering methods is more preferably 4,500 m/min or less, and most preferably 4,000 m/min or less.
  • the spinning speed in the case of the one-stage engineering method in which the winding and the stretching are performed at the same time is preferably 500 to 5000 m/min for the low speed roller and 2500 to 6000 m/min for the high speed roller.
  • the spinning speed in the case of one-stage engineering method is more preferably a low-speed roller of 1000 to 4,500 m/min, a high-speed roller of 3,500 to 5,500 m/min, and most preferably a low-speed roller of 1,500 to 4,000 m/min and a high-speed roller of 4000 to 5,000 m/min.
  • a one-stage extension method or a multi-stage extension method of two or more stages may be used.
  • the heating method at the time of extension and the means for directly or indirectly heating the running yarn are not specifically limited.
  • Specific examples of the heating method include a liquid bath such as a heating roller, a hot needle, a hot plate, warm water, and hot water, a gas bath such as hot air or steam, a laser, or the like, but the invention is not limited thereto. These heating methods can be used singly or in combination.
  • the heating method preferably takes contact with the heating roller, the contact of the hot needle, the contact with the hot plate, and the immersion of the liquid bath from the viewpoints of the control of the heating temperature, the uniform heating of the running yarn, and the avoidance of the complexity of the apparatus.
  • the elongation temperature in the case of stretching may be appropriately selected depending on the core component, the extrapolated melting initiation temperature of the polymer of the sheath component, and the strength and elongation of the fiber after stretching, and is preferably 50 to 150 °C.
  • the stretching temperature is 50° C. or higher, the yarn to be stretched can be sufficiently preheated, and the thermal deformation during stretching is uniform, and generation of fine spots can be suppressed.
  • the stretching temperature is more preferably 60 ° C or higher, and most preferably 70 ° C or higher.
  • the stretching temperature is 150° C. or less, it is possible to suppress the fusion between the fibers and the thermal decomposition due to the contact with the heating roller, and the engineering passability and quality are good.
  • the stretching temperature is more preferably 145 ° C or lower, and most preferably 140 ° C or lower. At the same time, heat setting at 60 to 150 ° C can be performed if necessary.
  • the stretching ratio at the time of stretching can be appropriately selected depending on the elongation of the fiber before stretching, the strength and elongation of the fiber after stretching, and the like, and is preferably 1.02 to 7.0 times.
  • the stretching ratio is more preferably 1.2 times or more, and most preferably 1.5 times or more.
  • the stretching ratio is 7.0 or less, it is possible to suppress breakage during stretching and to perform stable extension.
  • the stretching ratio is more preferably 6.0 times or less, and most preferably 5.0 times or less.
  • the extension speed at the time of extension can be selected according to whether the extension method is one of the engineering method or the second-stage engineering method. In the case of a section of engineering, the speed of the high speed roller of the above spinning speed is equivalent to the speed of extension.
  • the extension speed in the case where the two-stage engineering method is extended is preferably 30 to 1000 m/min. When the extension speed is 30 m/min or more, the running yarn is stable and the yarn breakage can be suppressed.
  • the elongation speed in the case where the two-stage engineering method is extended is more preferably 50 m/min or more, and most preferably 100 m/min or more. On the other hand, when the stretching speed is 1000 m/min or less, it is possible to suppress breakage during stretching and to perform stable extension.
  • the elongation speed in the case where the two-stage engineering method is extended is more preferably 900 m/min or less, and most preferably 800 m/min or less.
  • a one-stage heater and a two-stage heater in addition to the so-called high-elastic processing using only one-stage heater, a one-stage heater and a two-stage heater, so-called low-elastic processing, can be selected.
  • the heating method of the heater can be contactless or non-contact.
  • Specific examples of the false twisting machine include a friction disk type, a pulley type, a pin type, and the like, but are not limited to the above examples.
  • the temperature of the heater in the case where the false twist processing is performed can be appropriately selected depending on the core component and the extrapolated melting onset temperature of the sheath component polymer, and is preferably 120 to 210 °C.
  • the heater temperature is 120 ° C or more, the yarn for the false twist processing can be sufficiently preheated, and the thermal deformation accompanying the extension is uniform, and the occurrence of the fineness can be suppressed.
  • the temperature of the heater is more preferably 140 ° C The above is most preferably 160 ° C or higher.
  • the temperature of the heater is 210 ° C or less, it is possible to suppress the fusion between the fibers and the thermal decomposition caused by the contact with the heater, and the wire breakage and the contamination of the heater are reduced, and the engineering passability and quality are good.
  • the temperature of the heater is more preferably 200 ° C or lower, and most preferably 190 ° C or lower.
  • the stretching ratio in the case of the false twisting processing can be appropriately selected depending on the elongation of the fiber before the false twist processing, the strength and the elongation of the fiber after the false twist processing, and is preferably 1.01 to 2.5 times.
  • the stretching ratio is more preferably 1.2 times or more, and most preferably 1.5 times or more.
  • the stretching ratio is 2.5 or less, the yarn breakage during the false twist processing can be suppressed, and the stable false twist processing can be performed.
  • the stretching ratio is more preferably 2.2 times or less, and most preferably 2.0 times or less.
  • the processing speed in the case of performing the false twist processing can be appropriately selected, and is preferably 200 to 1000 m/min.
  • the processing speed is more preferably 300 m/min or more, and most preferably 400 m/min or more.
  • the processing speed is 1000 m/min or less, the yarn breakage during the false twist processing can be suppressed, and the stable false twist processing can be performed.
  • the processing speed is more preferably 900 m/min or less, and most preferably 800 m/min or less.
  • the dye is preferably a disperse dye.
  • the dyeing method of the present invention is not particularly limited, and according to a known method, liquid flow dyeing, drum dyeing, shaft dyeing, and dyeing can be employed.
  • the concentration of the fuel and the dyeing temperature are not particularly limited, and a known method can be employed. At the same time, if necessary, it can be refined before the dyeing process, or after the dyeing process.
  • the core-sheath type composite spun fiber of the present invention and the pseudofilament yarn and the fiber structure formed therefrom are excellent in hygroscopicity. Therefore, it can be used for applications requiring comfort and quality. For example, general clothing use, sports clothing use, bedding use, interior decoration use, and use of materials, etc., are not limited to the above list.
  • the polymer of the core component or the sheath component was sampled by hot air drying at 60 ° C for 30 minutes, and then allowed to stand in a constant temperature and humidity machine LHU-123 manufactured by ESPEC at a temperature of 20 ° C and a humidity of 65% RH for 24 hours.
  • the weight of the polymer (W1) was followed by standing in a constant temperature and humidity machine at a temperature of 30 ° C and a humidity of 90% RH for 24 hours, and the weight of the polymer was determined to be (W2). Then, it was dried by hot air at 105 ° C for 2 hours, and the weight of the polymer after absolute drying was measured as (W3).
  • the moisture absorption rate MR1 (%) after standing for 24 hours from the dry state to 20 ° C and a humidity of 65% RH was calculated from the weights W1 and W3 of the polymer, and the weight of the polymer was used according to the following formula.
  • W2 and W3 calculated the moisture absorption rate MR2 (%) after leaving the dry state to 30 ° C and a humidity of 90% RH for 24 hours, and then calculated the moisture absorption rate difference ( ⁇ MR) according to the following formula. Further, one sample was measured five times, and the average value was taken as the moisture absorption rate difference ( ⁇ MR).
  • Hygroscopic rate difference ( ⁇ MR) (%) MR2-MR1.
  • the core component, the sheath component polymer, and the fiber obtained in the example were used as a sample, and the extrapolation melting onset temperature was measured using a Q2000 type differential scanning calorimeter (DSC) manufactured by TA Instruments.
  • DSC differential scanning calorimeter
  • the temperature change range was ⁇ 1 ° C, and the temperature was changed for 60 seconds, and then the temperature was raised to measure TMDSC.
  • the extrapolated melting onset temperature was calculated from the melting peak observed during the second temperature rise in accordance with the standard of JISK7121:1987 (method of measuring the transition temperature of plastic). One sample was measured three times, and the average value was used as the extrapolation melting onset temperature. Further, when a plurality of melting peaks are observed, the extrapolated melting onset temperature is calculated from the melting peak on the lowest temperature side.
  • the core/sheath composite ratio was calculated from the weight of the core component as the core-sheath type composite fiber raw material and the weight of the sheath component.
  • the number of broken wires during the 10-hour processing was counted as the number of broken wires.
  • the heater, the cooling plate, the friction disk, and the yarn guide of the extended false twisting machine after 10 hours of processing were observed, and [the deposit was substantially absent] was counted as ⁇ , [the deposit was A little is counted as ⁇ , [more deposits] is counted as ⁇ , [very much deposit] is counted as ⁇ , and ⁇ and ⁇ are qualified.
  • the fiber obtained in the examples was taken in an environment of a temperature of 20 ° C and a humidity of 65% RH using an electric scale machine manufactured by INTEC.
  • the obtained weight was measured, and the fineness (dtex) was calculated by the following formula. Further, one sample was measured five times, and an average value was taken as the fineness.
  • Denier (dtex) weight (g) of the fiber 100 m ⁇ 100.
  • the strength and the elongation are calculated by the fiber obtained in the examples as a sample, and are calculated in accordance with JIS L1013:2010 (Chemical Fiber Filament Test Method) 8.5.1.
  • the tensile test was carried out under the conditions of a temperature of 20 ° C and a humidity of 65% RH using a ⁇ UTM-III-100 instrument manufactured by Orientec, under the condition of an initial sample field of 20 cm and an extension speed of 20 cm/min.
  • the stress (cN) at the point indicated by the maximum load is divided by the fineness (dtex) to calculate the strength (cN/dtex), and the elongation (L1) at the point indicated by the maximum load and the initial sample length (L0) are passed through the following formula. Calculated the degree of stretch (%). Also, one sample was tested 10 times, and the average value was taken as the strength and the elongation.
  • the elongation (%) ⁇ (L1 - L0) / L0 ⁇ ⁇ 100.
  • the fiber obtained in the example was embedded in an epoxy resin, frozen by a FC ⁇ 4E Cryo sectioning system manufactured by Reichert Co., Ltd., and cut under a Reichert-Nissei ultracut N (concave-convex microscope) equipped with a masonry knife. Then, the cutting surface, that is, the fiber cross section, was plated under a platinum-palladium-gold alloy, and observed at 1000 times using an S-4000 electron microscope (SEM) manufactured by Hitachi, and a micrograph of the fiber cross section was taken.
  • SEM S-4000 electron microscope
  • the length of this portion is the maximum value r M of the length of the core component exposed at the surface portion and the length of the core component exposed at the surface portion.
  • the sum r S .
  • the maximum value of the core component length exposed on the surface portion of each fiber cross section and the core component exposed on the surface portion are obtained. After the sum of the lengths, 30 average values are taken as the maximum value r M of the length of the core component exposed on the surface portion, and the sum of the lengths of the core components exposed at the surface portion r S .
  • r M /R and r S /R are the outer peripheral length R of the fiber cross section calculated by the above formula, the maximum value r M of the core component length exposed on the surface portion, and the length of the core component exposed on the surface portion. The sum r S is calculated.
  • the ratio r S /R r S /R of the total length R S of the cross-sectional outer perimeter R to the core component exposed at the surface portion.
  • the fiber obtained in the example was used as a sample, and 2 g of a cylinder was produced by a NCR-BL (3 inch and a half (8.9 cm), 27 needles) of the Incheon Industrial Co., Ltd., and then contained in sodium carbonate 1 g/L. After refining for 20 minutes at 80 ° C in an aqueous solution of BK-80 surfactant, it was dried in a hot air dryer at 60 ° C for 60 minutes to obtain a cylinder after refining.
  • the moisture absorption rate (%) is calculated from the water content of JIS L1096:2010 (the fabric test method of the woven fabric and the woven fabric) 8.10 based on the cylinder knitted fabric after the refining and the hot water treatment.
  • JIS L1096:2010 the fabric test method of the woven fabric and the woven fabric
  • W1 the weight of the package
  • the moisture absorption rate MR1 (%) after standing for 24 hours from the dry state to 20 ° C and humidity 65% RH atmosphere was calculated from the weights W1 and W3 of the polymer, and the tube was knitted according to the following formula.
  • the weights W2 and W3 were calculated from the absolute dry state to a moisture absorption rate MR2 (%) after standing for 24 hours in an atmosphere of 30 ° C and a humidity of 90% RH, and then the moisture absorption rate difference ( ⁇ MR) was calculated according to the following formula. Further, one sample was measured five times, and the average value was taken as the moisture absorption rate difference ( ⁇ MR).
  • Hygroscopic rate difference ( ⁇ MR) (%) MR2-MR1.
  • the hot-water treated tubular package obtained by the above I was gas-plated with a platinum-palladium-gold alloy, and was observed under a 1000-fold condition by a Hitachi electronic microscope (SEM) S-4000 model, and 5 fields of view were randomly taken. Microscope photo. Among the five photographs obtained, the total of the melted parts was melted.
  • the hot-water treated tubular package obtained by the above I was gas-plated with a platinum-palladium-gold alloy, and was observed under a 1000-fold condition by a Hitachi electronic microscope (SEM) S-4000 model, and 5 fields of view were randomly taken. Microscope photo. Among the five photographs obtained, the total number of sites where the sheath was broken was used as a sheath rupture.
  • the refining cylinder was prepared in the same manner as in the above I, and heat-set at 160 ° C for 2 minutes. After the dry heat setting, the dispersion was added with 1.3 wt% of the disperse dye Kayalon Polyester made by Nippon Kayaku. Blue UT-YA was adjusted in a dyeing solution having a pH of 5.0 at a bath ratio of 1:100, a dyeing temperature of 130 ° C, and a dyeing time of 60 minutes.
  • the bath ratio is 1:100, dyeing in a dyeing solution adjusted to a pH of 4.0 with a cationic dye Kayacrtyl Blue 2RL-ED prepared by adding 1.0 wt% of a Japanese chemical.
  • the dyeing was carried out under the conditions of a temperature of 130 ° C and a dyeing time of 60 minutes.
  • the dyed tube-shaped fabric was judged by the inspectors of five people who had more than 5 years of quality judgment experience.
  • the dyeing was very uniform, there was no staining at all, it was judged as ⁇ , [staining was basically uniform, basically no staining] ⁇ , [Cannot say that the uniform dyeing, slightly faint staining] was judged as ⁇ , [no uniform dyeing, and there was significant staining], and it was judged as ⁇ , and ⁇ and ⁇ were judged as pass.
  • the dyed cylinders obtained by the above-mentioned L are judged by the inspectors who have 5 years of experience in quality judgment, and [when there is no hairiness and excellent quality], it is judged as ⁇ , [there is basically no hairiness, and the quality is excellent]
  • ⁇ [there is basically no hairiness, and the quality is excellent]
  • the tubular product prepared in the same manner as in the above item I was subjected to hot water treatment at a bath ratio of 1:100, a treatment temperature of 130 ° C, and a treatment time of 20 minutes, and then dried in a hot air dryer at 60 ° C for 60 minutes. Forming a tubular braid after hot water treatment.
  • the cylinders before and after the hot water treatment were respectively measured by a color difference meter (USTC-datacolor), the b value of the cylinder before the hot water treatment was b1, and the value of the drum after the hot water treatment was b value.
  • polyethylene glycol manufactured by Sanyo Chemical Industries, Ltd. PEG 6000S
  • IV polyethylene terephthalate
  • the sheath-type composite spinneret (number of holes: 36, sectional shape: Fig. 1 (a)) was discharged, and the yarn was spun.
  • the spun yarn is cooled under cold air with a wind temperature of 20 ° C and a wind speed of 20 m / min.
  • the oil feed device is subjected to oil-contracting, and the first section of the roller is rotated at 2,500 m/min, and the first section of the roller is passed.
  • the second stage roller of the same turning speed is taken up to obtain an unstretched yarn of 144 dtex-36f.
  • extension false twisting machine tilting section: friction disk type, heater part: contact type
  • the obtained unstretched yarn was subjected to extension false twisting at a heater temperature of 170 ° C and a magnification of 1.7 times to obtain 84 dtex. -36f fake silk.
  • the evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 1.
  • the number of broken wires at the time of false twist is 0, and the deposits on the heater and the guide rail are hardly found after the false twist, and the engineering passability is extremely good.
  • the hygroscopicity after the hot water treatment is not substantially lowered, and the hygroscopicity after the hot water treatment is also good.
  • the fusion between the fibers was not found, and although the sheath was slightly broken, the level of dyeing and quality reached an acceptable level.
  • the false twist yarn was obtained in the same manner as in Example 1 except that the core/sheath composite ratio was changed as shown in Table 1.
  • a false twist yarn was obtained in the same manner as in Example 1 except that the cross-sectional shape was changed as shown in Table 1.
  • Example 1 In the same manner as in Example 1, the false twist yarn was obtained in the same manner as in Example 1 except that the number of the orifices of the spinneret of Example 11 was 72, the discharge amount of Example 12 was 28 g/min, and the number of the orifices of the spinneret was changed to 72.
  • the number average molecular weight, the copolymerization ratio, and the core/sheath recombination ratio of the polyethylene glycol copolymerization component of the core component are shown in Table 2, respectively.
  • Comparative Example 3 except that the heater temperature of the extension false twister was 150 ° C, In the same manner as in Example 1, a false twist yarn was obtained.
  • the evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 2.
  • Examples 13 to 19 when the number average molecular weight, the copolymerization ratio, and the core/sheath recombination ratio of the polyethylene glycol were changed, the properties of the workability and the fabric were good.
  • Comparative Example 1 the hygroscopicity after refining was lowered, and as a result, the hygroscopicity after hot water treatment was extremely poor.
  • Comparative Example 2 Although the hygroscopicity after refining was relatively high, the hygroscopicity after the hot water treatment was greatly lowered, the hygroscopicity after the hot water treatment was low, and the engineering passability was poor, and the leveling property and the quality did not reach the acceptable level.
  • the extrapolation melting onset temperature of the core component was low, and the extrapolation melting onset temperature of the core component of Comparative Example 4 was not detected, because there was no crystallinity, the filaments and deposits were extremely large, and the engineering passability was extremely high. bad. At the same time, it was found that there were many fusions and sheath ruptures, and the level of dyeing and quality did not reach the qualified level.
  • the composition, the spinning temperature was 255 ° C, and the core/sheath composite ratio was as shown in Table 3.
  • the temperature of the heater of the extension false twisting machine was changed to 150 ° C, and the same procedure as in Example 7 was carried out. The method produces a false twist.
  • Comparative Example 7 Although the hygroscopicity after refining was high, the hygroscopicity after hot water treatment was largely lowered, the hygroscopicity after hot water treatment was low, and the engineering passability was poor, and the leveling property and quality were not at a satisfactory level. Since the extrapolation melting initiation temperature of the core component of Comparative Example 8 was low, there were many broken wires and deposits, and the engineering passability was extremely poor. Further, the hygroscopicity after refining is low, and as a result, the hygroscopicity after hot water treatment is extremely poor.
  • the core component was nylon 6 obtained by copolymerization of polyethylene glycol having a number average molecular weight of 3,400 g/mol (PEG4000S manufactured by Sanyo Chemical Industries Co., Ltd.), and Example 31 was changed except for the "PEBAX MH1657” manufactured by ARKEMA. 1 The same method was used to make false silk.
  • the core component was "PAS-40N” manufactured by Toray Industries, and the false twist yarn was obtained in the same manner as in Example 1 except that the temperature of the heater of the extension false twisting machine was changed to 150 °C.
  • a false twist yarn was obtained in the same manner as in Example 1 except that the cross-sectional shape was changed as shown in Fig. 2 .
  • Table 4 shows the results of fiber properties, fabric properties, and engineering passability of the obtained fibers. There is no broken wire, almost no deposits are found, and the engineering passability is good. However, although there was no fusion, since the core component hygroscopic polymer was completely covered by the sheath component, and the volume of the hygroscopic polymer was expanded during hot water treatment, it was found that a plurality of sheath portions were broken. As a result, the level of dyeing and quality did not reach the acceptable level.
  • the core component of the comparative example 10 is polyethylene terephthalate copolymerized with polyethylene glycol having an average molecular weight of 3000 g/mol of 17 wt%.
  • the core component of Comparative Example 11 was polyethylene terephthalate copolymerized with 17 wt% polyethylene glycol having an average molecular weight of 3000 g/mol.
  • the sheath component was nylon 6, and a false twist yarn was obtained in the same manner as in Example 7 except that the core/sheath composite ratio was changed as shown in Table 4.
  • the sheath component was nylon 6 in which 8 wt% of an average molecular weight of 20,000 g/mol of polyethylene glycol was copolymerized, and a pseudofilament yarn was obtained in the same manner as in Example 1 except that the core/sheath recombination ratio was changed as shown in Table 4.
  • the evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 4. Because the sheath component is sucking The wet polymer has a large amount of hygroscopic polymer exposed on the surface, a large number of broken wires and deposits, and poor engineering passability. At the same time, it was found that the fusion and sheath rupture did not reach the acceptable level of dyeing and quality. Moreover, the hygroscopicity after the hot water treatment is low.
  • the core component was polyethylene terephthalate copolymerized with 30 wt% of an average molecular weight of 5000 g/mol of polyethylene glycol, and the sheath component was copolymerized by 1.5.
  • the sheath component is copolymerized with 1.5 mol% sodium isophthalate-5-sulfonate, 1.0 wt% number average molecular weight 1000 g/mol.
  • a false twist yarn was obtained in the same manner as in Example 7 except that the fiber cross-section r M /R and r S /R were changed as shown in Table 4.
  • a false twist yarn was obtained in the same manner as in Example 1 except that the core-sheath composite ratio was changed as shown in Table 4, for example.
  • a false twist yarn was obtained in the same manner as in Example 1 except that a single-component spinneret (pore number: 36, round hole) was used.

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Abstract

Provided is a core-sheath type composite fibre, wherein a core component and a sheath component of the fibre are both crystalline polymers, and the core component is a hygroscopic polymer; in a cross section of the core-sheath type composite fibre, at least part of the core component is exposed to the surface, with the ratio rS/R of the outer perimeter R of the cross section to the sum of length rS of the core component exposed to the surface being 0.05 to 0.40; and the extrapolated melting starting temperature of the core-sheath type composite fibre is not less than 150°C, and the hygroscopic rate difference ΔMR after a hot water treatment is 2.0% to 10.0%. The extension and false twisting engineering of the fibre can inhibit fusion, and rarely has yarn breakages and yarn hairiness but a good engineering passing property, and less specking and hairiness when forming a braided fabric and other fibrous structures; moreover, fracturing in the sheath portion when the hygroscopic polymer expands in volume during dyeing and other hot water treatments can be inhibited while providing an excellent quality, and the dissolution of the hygroscopic polymer can be inhibited; furthermore, there is an excellent hygroscopic property after a hot water treatment.

Description

芯鞘型复合纤维、假捻丝和纤维构造体Core-sheath type composite fiber, false twisted silk and fiber structure 技术领域Technical field
本发明涉及一种芯成分和鞘成分均为结晶性聚合物，且芯成分为吸湿性聚合物，纤维横截面上至少有一部分芯成分露出在表面的芯鞘型复合纤维。具体的，涉及一种为了抑制延伸以及假捻工程发生的融着，断丝和毛羽的发生少、工程通过性良好、形成织物和编物等纤维构造体时产生的染斑以及毛羽少、品质优异的同时，能够抑制经过染色等热水处理时芯成分吸湿性聚合物体积膨胀带来的鞘成分的破裂以及吸湿性聚合物的溶出、热水处理后吸湿性仍优异、适用于衣料用途的芯鞘型复合纤维。The present invention relates to a core-sheath type composite fiber in which a core component and a sheath component are both crystalline polymers, and a core component is a hygroscopic polymer, and at least a part of core components on a fiber cross section are exposed on a surface. Specifically, it relates to a kind of smear and hairiness which are generated when a fiber structure such as a woven fabric or a knitted fabric is formed in order to suppress the occurrence of the elongation and the occurrence of the false twisting project, the occurrence of broken wires and hairiness is small, and the engineering passability is good. In addition, it is possible to suppress cracking of the sheath component due to volume expansion of the core component hygroscopic polymer during hot water treatment such as dyeing, and elution of the hygroscopic polymer, and excellent moisture absorption after hot water treatment, and is suitable for use in clothing. Core-sheath type composite fiber.
背景技术Background technique
由于聚酯纤维价格低、机械特性优异，用途极为广泛。但是，由于缺乏吸湿性，在夏季高湿度时容易产生闷热感，冬季低湿度时容易产生静电，从穿着舒适性的观点来说，存在有待解决的问题。Due to its low price and excellent mechanical properties, polyester fiber is extremely versatile. However, due to the lack of hygroscopicity, it is easy to generate a stuffy feeling in high humidity in summer, and it is easy to generate static electricity in low humidity in winter, and there are problems to be solved from the viewpoint of wearing comfort.
为了改善上述缺点，在赋予聚酯纤维吸湿性的方法方面，目前为止有各种各样的提案。赋予聚酯纤维吸湿性的一般方法，比如在聚酯中共聚合亲水性化合物或者添加亲水性化合物，其中亲水性化合物举一例可以是聚乙二醇。In order to improve the above disadvantages, various proposals have been made so far for the method of imparting hygroscopicity to polyester fibers. A general method for imparting hygroscopicity to a polyester fiber, such as copolymerizing a hydrophilic compound or adding a hydrophilic compound to a polyester, wherein the hydrophilic compound may be polyethylene glycol.
例如，专利文献1中，对于聚酯，提出了使用共聚合了聚乙二醇的聚酯作为吸湿性聚合物制作纤维的提案。该提案中吸湿性聚合物单独进行纤维化，使聚酯纤维具有吸湿性。For example, in Patent Document 1, a proposal has been made for a polyester to produce a fiber using a polyester copolymerized with polyethylene glycol as a hygroscopic polymer. In the proposal, the hygroscopic polymer is separately fibrillated to make the polyester fiber hygroscopic.
专利文献2中，提出了鞘成分为吸湿性聚合物、芯成分为疏水性聚合物的偏芯芯鞘型复合纤维的提案。该提案中，由于芯成分是疏水性聚合物，赋予了纤维对于吸湿与干燥的可逆变化时的形态稳定性。 Patent Document 2 proposes an eccentric core-sheath type composite fiber in which a sheath component is a hygroscopic polymer and a core component is a hydrophobic polymer. In this proposal, since the core component is a hydrophobic polymer, the morphological stability of the fiber when it is reversibly changed to moisture absorption and drying is imparted.
专利文献3中，提出了芯成分是共聚合了聚乙二醇的聚酯、鞘成分为聚对苯二甲酸乙二醇酯的芯鞘型复合纤维。该提案中，由于芯成分是吸湿性聚合物，使得聚酯纤维具有吸湿性。Patent Document 3 proposes a core-sheath type composite fiber in which a core component is a polyester in which polyethylene glycol is copolymerized and a sheath component is polyethylene terephthalate. In this proposal, since the core component is a hygroscopic polymer, the polyester fiber is hygroscopic.
专利文献4、5中，提出了芯成分为共聚合了聚乙二醇的聚合物、鞘成分为聚对苯二甲酸乙二醇酯，且鞘的一部分开口的芯鞘型复合纤维。虽然芯成分具有吸湿性，这些提案中，由于芯成分的溶出，形成C字形的中空纤维，赋予聚酯纤维轻量性。作为易溶出的芯成分的具体例，专利文献4中公开了共聚合了8～70wt％的重均分子量500～8000g/mol、即数均分子量8000g/mol以下的聚乙二醇的聚对苯二甲酸乙二醇酯；专利文献5中公开了共聚合了17wt％的分子量为3000g/mol的聚乙二醇的聚对苯二甲酸乙二醇酯。In Patent Documents 4 and 5, a core-sheath type composite fiber in which a core component is a polymer in which polyethylene glycol is copolymerized, a sheath component is polyethylene terephthalate, and a part of a sheath is opened is proposed. Although the core component is hygroscopic, in these proposals, the hollow fiber is formed into a C-shaped hollow fiber by the elution of the core component, and the polyester fiber is imparted with lightness. As a specific example of the core component which is easily eluted, Patent Document 4 discloses that a polyparaphenylene group of polyethylene glycol having a weight average molecular weight of 500 to 8000 g/mol, that is, a number average molecular weight of 8000 g/mol or less is copolymerized in an amount of 8 to 70% by weight. Ethylene glycol dicarboxylate; Patent Document 5 discloses polyethylene terephthalate copolymerized with 17 wt% of polyethylene glycol having a molecular weight of 3000 g/mol.
但是，上述专利文献1记载的方法中，全部露出在纤维表面的吸湿聚合物由于纺丝油剂的存在而发生膨胀，在纺丝、延伸、假捻工程以及制编、织造过程中，因与罗拉或导丝器发生摩擦而导致脱落、堆积在罗拉及导丝器上，其后果就是容易产生断丝及毛羽，工程通过性及品质都存在问题。并且染色等热水处理时，吸湿聚合物的共聚合成分聚乙二醇溶出，存在热水处理后吸湿性低下的问题。However, in the method described in Patent Document 1, all of the hygroscopic polymer exposed on the surface of the fiber is swollen by the presence of the spinning oil agent, and in the spinning, stretching, false twisting, and weaving and weaving processes, The roller or the yarn guide rubs and causes it to fall off and accumulate on the roller and the yarn guide. The consequence is that it is easy to produce broken yarn and hairiness, and there are problems in engineering passability and quality. Further, in the hot water treatment such as dyeing, the copolymerization component of the hygroscopic polymer is eluted with polyethylene glycol, and there is a problem that the hygroscopicity is lowered after the hot water treatment.
专利文献2记载的方法，由于芯成分为疏水性聚合物，虽然对于吸湿及干燥的可逆变化具有形态稳定性，但是由于至少有一半以上的纤维表面有吸湿聚合物露出，与专利文献1所述方法一样，会发生吸湿聚合物的膨胀与脱落，工程通过性及品质都存在问题。In the method described in Patent Document 2, since the core component is a hydrophobic polymer, it has morphological stability against reversible change in moisture absorption and drying, but at least half of the fiber surface is exposed by the hygroscopic polymer, and is described in Patent Document 1. In the same way, the swelling and shedding of the hygroscopic polymer occurs, and there are problems in engineering passability and quality.
专利文献3记载的方法，由于芯成分的吸湿性聚合物被鞘成分完全包裹，因此能够抑制吸湿性聚合物因纺丝油剂引起的膨胀，以及因与罗拉及导丝器摩擦引起的脱落，虽然工程通过性能得到改善，但是染色等热水处理时芯成分的吸湿聚合物发生体积膨胀，鞘成分被破坏，品质低下的问题仍然存在。尤其是，以鞘成分的破裂口为起点芯成分的吸湿性聚酯溶出，存在热水处理后吸湿性低下的问题。According to the method described in Patent Document 3, since the hygroscopic polymer of the core component is completely encapsulated by the sheath component, it is possible to suppress the swelling of the hygroscopic polymer due to the spinning oil agent and the peeling due to friction with the roller and the yarn guide. Although the performance of the project is improved, the moisture-absorbing polymer of the core component undergoes volume expansion during hot water treatment such as dyeing, and the sheath component is destroyed, and the problem of low quality still exists. In particular, the hygroscopic polyester having the core component of the rupture port of the sheath component is eluted, and there is a problem that the hygroscopicity is lowered after the hot water treatment.
专利文献4、5记载的方法，由于芯成分的吸湿性聚合物仅有一部分露出在纤维表面，因此能 够抑制吸湿性聚合物因纺丝油剂引起的膨胀，以及因与罗拉及导丝器摩擦引起的脱落，工程通过性能得到改善。但是，其目的是使芯成分溶出，由于经过染色等热水处理使得芯成分完全溶出，得到的C字形聚酯中空纤维不具有吸湿性。In the methods described in Patent Documents 4 and 5, since only a part of the hygroscopic polymer of the core component is exposed on the surface of the fiber, It is possible to suppress the expansion of the hygroscopic polymer due to the spinning oil agent, and the peeling due to friction with the roller and the yarn guide, and the engineering pass performance is improved. However, the purpose is to dissolve the core component, and the core component is completely eluted by hot water treatment such as dyeing, and the obtained C-shaped polyester hollow fiber is not hygroscopic.
[现有技术文献][Prior Art Literature]
[专利文献][Patent Literature]
[专利文献1]特开2006-104379号公报[Patent Document 1] JP-A-2006-104379
[专利文献2]特开平9-13257号公报[Patent Document 2] JP-A-9-13257
[专利文献3]特开2001-172374号公报[Patent Document 3] JP-A-2001-172374
[专利文献4]特开平6-200473号公报[Patent Document 4] JP-A-6-200473
[专利文献5]特开2007-131980号公报[Patent Document 5] JP-A-2007-131980
发明内容Summary of the invention
本发明的课题在于解决上述技术问题点，提供一种为了抑制延伸以及假捻工程发生的融着，断丝和毛羽的发生少、工程通过性良好、形成织物和编物等纤维构造体时产生的染斑以及毛羽少、品质优异的同时、能够抑制经过染色等热水处理时芯成分吸湿性聚合物体积膨胀带来的鞘成分的破裂以及吸湿性聚合物的溶出、热水处理后吸湿性仍优异、适用于衣料用途的芯鞘型复合纤维。An object of the present invention is to solve the above-mentioned problems and to provide a fiber structure in which a fiber structure such as a woven fabric or a knitted fabric is formed in order to suppress the occurrence of the elongation and the occurrence of the false twisting process, the occurrence of broken yarn and hairiness is small, and the engineering passability is good. It is possible to suppress the cracking of the sheath component and the elution of the hygroscopic polymer and the hygroscopicity after the hot water treatment by the volume expansion of the core component hygroscopic polymer during hot water treatment such as dyeing, and the like. A core-sheath type composite fiber that is still excellent and suitable for use in clothing.
上述本发明的课题通过具有下述特征的芯鞘复合纤维可以得到解决。所述芯鞘型复合纤维的芯成分和鞘成分均为结晶性聚合物，且芯成分为吸湿性聚合物；所述芯鞘型复合纤维的横截面上至少有一部分芯成分露出在表面，且横截面外周长R与露出在表面部分的芯成分的长度总和rS的比rS/R为0.05～0.40；所述芯鞘型复合纤维的外推熔融起始温度在150℃以上，且热水处理后的吸湿率差△MR为2.0～10.0％。The above object of the present invention can be solved by a core-sheath composite fiber having the following characteristics. The core component and the sheath component of the core-sheath type composite fiber are both crystalline polymers, and the core component is a hygroscopic polymer; at least a part of the core component in the cross section of the core-sheath type composite fiber is exposed on the surface, and cross-section with an outer perimeter of the sum of the length r S R is exposed on the surface portion of the core component ratio r S / R of 0.05 to 0.40; outside of the core-sheath type composite fiber push melting start temperature of at least 150 ℃, and the heat The moisture absorption rate difference ΔMR after the water treatment was 2.0 to 10.0%.
同时，纤维的横截面中，横截面外周长R与露出在表面部分的芯成分长度的最大值rM的比rM/R为0.01～0.20，芯成分与鞘成分的复合重量比优选10/90～70/30。Meanwhile, in the cross section of the fiber, the ratio r M /R of the outer peripheral length R of the cross section to the maximum value r M of the length of the core component exposed at the surface portion is 0.01 to 0.20, and the composite weight ratio of the core component to the sheath component is preferably 10/. 90 to 70/30.
并且，热水处理前后复合纤维的色调变化值△b值优选为3.0以下，复合纤维中优选含有为如式1所示结构的半受阻酚类抗氧化剂。Further, the value of the color tone change value Δb of the composite fiber before and after the hot water treatment is preferably 3.0 or less, and the composite fiber preferably contains a semi-hindered phenol antioxidant having a structure represented by Formula 1.
Figure PCTCN2016111763-appb-000001
Figure PCTCN2016111763-appb-000001
其中，R1为碳氢、氧、氮元素中任何一种结合形成的半受阻酚类抗氧化剂，R2为氢、碳氢、氧、氮元素中任何一种结合形成的半受阻酚类抗氧化剂。Wherein R1 is a semi-hindered phenolic antioxidant formed by combining any one of hydrocarbon, oxygen and nitrogen, and R2 is a semi-hindered phenolic antioxidant formed by combining any one of hydrogen, hydrocarbon, oxygen and nitrogen.
前述芯成分的吸湿性聚合物优选以聚醚为共聚合成分的聚醚酯、聚醚酰胺、聚醚酰胺酯中的至少一种。同时，聚醚优选聚乙二醇、聚丙二醇、聚丁二醇。The hygroscopic polymer of the core component is preferably at least one of a polyether ester, a polyether amide, and a polyether amide ester having a polyether as a copolymer component. Meanwhile, the polyether is preferably polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
前述聚醚酯优选以芳香族二元羧酸与脂肪族二元醇为主要构成成分，聚醚为共聚合成分。所述脂肪族二元醇优选乙二醇时，聚醚的数均分子量优选4000～30000g/mol，聚醚的共聚合率优选10～35wt％。同时，所述脂肪族二元醇优选1，4-丁二醇时，聚醚的数均分子量优选2000～30000g/mol，聚醚的共聚合率优选10～60wt％。The polyether ester preferably contains an aromatic dicarboxylic acid and an aliphatic diol as main constituent components, and the polyether is a copolymer component. When the aliphatic diol is preferably ethylene glycol, the number average molecular weight of the polyether is preferably from 4,000 to 30,000 g/mol, and the copolymerization ratio of the polyether is preferably from 10 to 35 wt%. Meanwhile, when the aliphatic diol is preferably 1,4-butanediol, the number average molecular weight of the polyether is preferably from 2,000 to 30,000 g/mol, and the copolymerization ratio of the polyether is preferably from 10 to 60% by weight.
并且，前述芯鞘型复合纤维的鞘成分优选阳离子可染性聚酯。Further, the sheath component of the core-sheath type composite fiber is preferably a cationic dyeable polyester.
本发明的假捻丝由2根以上前述芯鞘型复合纤维合捻形成，纤维构造体的至少一部分优先采用前述芯鞘型复合纤维和/或假捻丝。The false twist yarn of the present invention is formed by combining two or more core-sheath type composite fibers, and at least a part of the fiber structure is preferably a core-sheath type composite fiber and/or a false twist yarn.
通过本发明，能够抑制延伸以及假捻工程发生的融着，断丝和毛羽的发生少，工程通过性良好。同时，形成织物和编物等纤维构造体时产生的染斑以及毛羽少，品质优异。并且，能够抑制经过染色等热水处理时芯成分吸湿性聚合物体积膨胀带来的鞘成分的破裂以及吸湿性聚合物的溶出、热水处理后吸湿性仍优异、适用于衣料用途的芯鞘型复合纤维。According to the present invention, it is possible to suppress the occurrence of the fusion and the occurrence of the false twisting project, and the occurrence of the broken yarn and the hairiness is small, and the engineering passability is good. At the same time, when a fiber structure such as a woven fabric or a knitted fabric is formed, stains and hairiness are small, and the quality is excellent. In addition, it is possible to suppress cracking of the sheath component due to volume expansion of the core component hygroscopic polymer during hot water treatment such as dyeing, and elution of the hygroscopic polymer, and excellent moisture absorption after hot water treatment, and the core sheath suitable for clothing use. Type composite fiber.
附图说明 DRAWINGS
图1的(a)～(m)为列举的本发明芯鞘复合纤维的断面形状的示意图，图中，1表示芯成分，2表示鞘成分。Fig. 1 (a) to (m) are schematic views showing the cross-sectional shape of the core-sheath composite fiber of the present invention. In the figure, 1 indicates a core component, and 2 indicates a sheath component.
图2为比较例1制备的芯鞘复合纤维的断面形状的示意图。2 is a schematic view showing the cross-sectional shape of a core-sheath composite fiber prepared in Comparative Example 1.
具体实施方式Detailed ways
本发明的芯鞘型复合纤维，芯成分和鞘成分均为结晶性聚合物，且芯成分为吸湿性聚合物，纤维横截面上至少有一部分芯成分露出在表面，且横截面外周长R与露出在表面部分的芯成分的长度总和rS的比rS/R为0.05～0.40；所述芯鞘型复合纤维的外推熔融起始温度在150℃以上，且热水处理后的吸湿率差△MR为2.0～10.0％。In the core-sheath type composite fiber of the present invention, the core component and the sheath component are both crystalline polymers, and the core component is a hygroscopic polymer, at least a part of the core component on the cross section of the fiber is exposed on the surface, and the outer circumference R of the cross section is The ratio r S /R of the total length r S of the core component exposed at the surface portion is 0.05 to 0.40; the extrapolated melting initiation temperature of the core-sheath type composite fiber is 150 ° C or more, and the moisture absorption rate after hot water treatment The difference ΔMR is 2.0 to 10.0%.
一般情况下，吸湿性聚合物因纺丝油剂的存在容易发生膨胀，与罗拉或导丝器发生摩擦导致脱落并形成堆积的污垢，引起断丝及毛羽，因而工程通过性不良，并且由于形成织物和编物等纤维构造体时会发生染斑和毛羽，存在品质低的问题。同时，因延伸以及假捻工程中与加热罗拉和加热器的接触，还存在纤维间的融着的问题。为了改善工程通过性及纤维品质，提出了芯成分吸湿性聚合物被完全被包裹的芯鞘型复合纤维的提案，但是染色等热水处理时芯成分的积膨胀，吸湿性聚合物从被破坏的鞘成分部分溶出，存在热水处理后吸湿性消失的问题。因此，提出了纤维横截面上一部分芯成分露出在表面的芯鞘型复合纤维的提案，但是不能同时抑制假捻时的融着、热水处理时鞘部分的破裂以及芯成分的溶出这些问题，其结果是，仍然不能得到工程通过性良好且具有高品质、并且热水处理后仍具有吸湿性的纤维。In general, the hygroscopic polymer is likely to swell due to the presence of the spinning oil agent, rubbing against the roller or the yarn guide to cause detachment and formation of accumulated dirt, causing broken yarn and hairiness, and thus poor engineering passability, and due to formation In the case of a fiber structure such as a woven fabric or a knitted fabric, staining and hairiness occur, and there is a problem of low quality. At the same time, there is a problem of fusion between fibers due to the contact with the heating roller and the heater in the extension and false twisting works. In order to improve the passability and fiber quality of the project, a proposal has been made for a core-sheath type composite fiber in which a core-component hygroscopic polymer is completely encapsulated, but the expansion of the core component during hot water treatment such as dyeing causes the hygroscopic polymer to be destroyed. The sheath component is partially dissolved, and there is a problem that hygroscopicity disappears after hot water treatment. Therefore, there has been proposed a core-sheath type composite fiber in which a part of the core component is exposed on the surface of the fiber cross-section, but it is not possible to simultaneously suppress the fusion at the time of false twisting, the cracking of the sheath portion during hot water treatment, and the elution of the core component. As a result, fibers having good engineering passability and high quality and having hygroscopicity after hot water treatment are still not obtained.
鉴于上述问题，本发明人进行的锐意检讨的结果是，满足芯成分和鞘成分同时具有结晶性、并且芯成分具有吸湿性、纤维的横截面外周长R与露出在表面部分的芯成分的长度总和rS的比rS/R为0.05～0.40、芯鞘型复合纤维的外推熔融起始温度在150℃以上之后，上述问题得以全部解决，成功得到工程通过性良好且品质高、热水处理后仍具有吸湿性的芯鞘型复合纤维。In view of the above problems, the result of the intensive review conducted by the present inventors is that the core component and the sheath component are simultaneously crystallized, and the core component is hygroscopic, the cross-sectional outer circumference R of the fiber, and the length of the core component exposed at the surface portion. The ratio r S /R of the sum r S is 0.05 to 0.40, and the extrapolated melting onset temperature of the core-sheath type composite fiber is 150 ° C or more. The above problems are all solved, and the engineering passability is good and the quality is high. The core-sheath type composite fiber which is still hygroscopic after the treatment.
本发明的芯鞘型复合纤维的芯成分为结晶性聚合物。芯成分具有结晶性的话，通过实施例中记载的方法测定外推熔融起始温度时，伴随着结晶的融解能观测到融解峰。芯成分具有结晶性的话，因延伸以及假捻工程中与加热罗拉以及加热器的接触引起的纤维间的融着能够被抑制，加热罗拉、加热器和导丝器上的堆积物变少，断丝以及毛羽发生变少，工程通过性良好。同时，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。并且，在具有结晶性的场合，染色等热水处理时芯成分的吸湿性聚合物的溶出能够被抑制，热水处理后吸湿性能够被保持。The core component of the core-sheath type composite fiber of the present invention is a crystalline polymer. When the core component has crystallinity, when the extrapolation melting onset temperature is measured by the method described in the examples, a melting peak can be observed with melting of the crystal. When the core component has crystallinity, the fusion between the fibers due to the extension and the contact with the heating roller and the heater in the false twisting process can be suppressed, and the deposit on the heating roller, the heater, and the yarn guide is reduced. The silk and hairiness are less and the engineering passability is good. At the same time, when a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent. Further, in the case of having crystallinity, the elution of the hygroscopic polymer of the core component during hot water treatment such as dyeing can be suppressed, and the hygroscopicity after the hot water treatment can be maintained.
本发明的芯鞘型复合纤维的芯成分为吸湿性聚合物。本发明中，所述吸湿性聚合物为吸湿率差(△MR)2.0％以上的聚合物。本发明所述的吸湿率差(△MR)是指实施例所记载的方法所测定的值。芯成分如果具有吸湿性的话，通过与鞘成分进行复合，能得到吸湿性优异的芯鞘型复合纤维。The core component of the core-sheath type composite fiber of the present invention is a hygroscopic polymer. In the present invention, the hygroscopic polymer is a polymer having a moisture absorption rate difference (?MR) of 2.0% or more. The moisture absorption rate difference (?MR) according to the present invention means a value measured by the method described in the examples. When the core component is hygroscopic, it can be obtained by compounding with the sheath component to obtain a core-sheath type composite fiber excellent in hygroscopicity.
本发明的芯鞘型复合纤维的芯成分，具体地可以列举的有聚醚酯、聚醚酰胺、聚醚酰胺酯、聚酰胺、热可塑性纤维素衍生物、聚乙烯吡咯烷酮等具有吸湿性的聚合物，但不限于以上聚合物。尤其，优选以聚醚为共聚合成分的聚醚酯、聚醚酰胺、聚醚酰胺酯，特别是由于聚醚酯耐热性优异、得到的芯鞘型复合纤维的机械特性以及色调都比较好因而更优选。上述吸湿性聚合物可以单独使用一种，也可以两种以上并用。同时，这些吸湿性聚合物和聚酯、聚酰胺、聚烯烃进行混炼后的物质也可以作为吸湿性聚合物使用。The core component of the core-sheath type composite fiber of the present invention may specifically be a hygroscopic polymerization such as a polyether ester, a polyether amide, a polyether amide ester, a polyamide, a thermoplastic cellulose derivative or a polyvinylpyrrolidone. But not limited to the above polymers. In particular, a polyether ester, a polyether amide, or a polyether amide ester having a polyether as a copolymer component is preferable, and in particular, since the polyether ester is excellent in heat resistance, the obtained core-sheath type composite fiber has better mechanical properties and color tone. Therefore, it is more preferable. These hygroscopic polymers may be used alone or in combination of two or more. At the same time, those obtained by kneading these hygroscopic polymers with polyester, polyamide, and polyolefin can also be used as hygroscopic polymers.
前述吸湿性聚合物的共聚合成分聚醚，具体地可以列举的有聚乙二醇、聚丙二醇、聚丁二醇等单独聚合体，聚乙二醇-聚丙二醇共聚合体，聚乙二醇-聚丁二醇等共聚合体等，但不限于以上物质。尤其，由于聚乙二醇、聚丙二醇、聚丁二醇制造以及使用时取用性良好而优选，特别是聚乙二醇吸湿性优异而更优选。The polyether of the copolymerizable component of the hygroscopic polymer may, for example, be a single polymer such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol, a polyethylene glycol-polypropylene glycol copolymer, polyethylene glycol- A copolymer or the like such as polytetramethylene glycol, but is not limited to the above. In particular, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol are preferred because they are excellent in recyclability during production and use, and polyethylene glycol is particularly preferred because it is excellent in hygroscopicity.
前述聚醚酯，从耐热性及机械特性的观点考虑，以芳香族二元羧酸与脂肪族二元醇为主要重复单元，优选以聚醚为共聚合成分。芳香族二元羧酸，具体地可以列举的有对苯二甲酸、间苯二甲酸、邻苯二甲酸、间苯二甲酸-5-磺酸钠、间苯二甲酸-5-磺酸锂、5-(四烷基)-间苯二甲酸磺 酸磷化合物、4，4’-联苯二元羧酸、2，6-奈二甲酸等，但不限于以上物质。同时，脂肪族二元醇具体地可以列举的有乙二醇、1，3-丙二醇、1，4-丁二醇、己二醇、环己烷己二醇、二乙二醇、六亚甲基乙二醇、新戊二醇等，但不限于以上物质。尤其，乙二醇、丙二醇、1，4-丁二醇制造以及使用时取用性良好因而优选。从耐热性以及机械特性的角度来看，更优选乙二醇；从结晶性的角度来看，更优选1，4-丁二醇。The polyether ester has an aromatic dicarboxylic acid and an aliphatic diol as main recurring units from the viewpoint of heat resistance and mechanical properties, and preferably a polyether as a copolymer component. Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, sodium isophthalate-5-sulfonate, and lithium isophthalate-5-sulfonate. 5-(tetraalkyl)-isophthalic acid sulfonate The acid phosphorus compound, 4,4'-biphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and the like are, but not limited to, the above. Meanwhile, the aliphatic diol may specifically be exemplified by ethylene glycol, 1,3-propanediol, 1,4-butanediol, hexanediol, cyclohexane hexanediol, diethylene glycol, and hexamethylene Ethylene glycol, neopentyl glycol, etc., but not limited to the above. In particular, ethylene glycol, propylene glycol, and 1,4-butanediol are preferred because they are excellent in handleability and use. From the viewpoint of heat resistance and mechanical properties, ethylene glycol is more preferable; from the viewpoint of crystallinity, 1,4-butanediol is more preferable.
前述聚醚酯的共聚合成分聚醚的数均分子量以及共聚合率，可以在聚醚酯具有结晶性的范围内进行适当选择，优选的范围根据聚醚酯的组成成分不同而不同。例如，在聚醚酯的组成成分脂肪族二元醇为乙二醇的场合下，聚醚的共聚合率过高的话，染色等热水处理时聚醚酯在热水中将被溶出，热水处理后吸湿性低下。同时，当聚醚酯的构成成分脂肪族二元醇为1，4-丁二醇时，与上述使用乙二醇的场合相比，由于聚合物的结晶性高，即便是聚醚化合物的共聚合率较高的情况下，也可以抑制热水中聚醚酯的溶出。也就是说，当脂肪族二元醇使用1，4-丁二醇时，由于可以提高聚醚的共聚合率，聚醚酯的吸湿性、甚至得到的芯鞘型复合纤维的吸湿性也能得到提高。The number average molecular weight and the copolymerization ratio of the polyether ester copolymerization component polyether can be appropriately selected within the range in which the polyether ester has crystallinity, and the preferred range differs depending on the composition of the polyether ester. For example, when the aliphatic diol of the composition of the polyether ester is ethylene glycol, if the copolymerization ratio of the polyether is too high, the polyether ester will be eluted in hot water during hot water treatment such as dyeing. Hygroscopicity after water treatment is low. Meanwhile, when the aliphatic diol which is a constituent of the polyether ester is 1,4-butanediol, the crystallinity of the polymer is high, even if it is a polyether compound, compared with the case where ethylene glycol is used as described above. When the polymerization rate is high, the elution of the polyether ester in hot water can also be suppressed. That is, when 1,4-butanediol is used as the aliphatic diol, since the copolymerization ratio of the polyether can be increased, the hygroscopicity of the polyether ester, and even the hygroscopicity of the obtained core-sheath type composite fiber can be Improved.
聚醚酯的构成成分脂肪族二元醇为乙二醇的场合，聚醚的数均分子量优选4000～30000g/mol，聚醚的共聚合率优选10～35wt％。聚醚的数均分子量在4000g/mol以上的话，聚醚酯的吸湿性高，作为芯成分使用时能得到吸湿性优异的芯鞘型复合纤维。同时，能够抑制聚醚酯的结晶性的下降及外推熔融起始温度的降低，由于延伸以及假捻工程中因与加热罗拉以及加热器的接触引起的纤维间的融着也能够被抑制，加热罗拉、加热器、导丝器上的堆积物、断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。另一方面，聚醚的数均分子量在30000g/mol以下的话，缩聚反应性高，未反应的聚醚减少，能够抑制染色等热水处理时在热水中的溶出，热水处理后的吸湿性能够被维持。聚醚的数均分子量优选25000g/mol以下，更优选为20000g/mol以下。同时，聚醚的共聚合率在10wt％以上的话，聚醚酯的吸湿性高，作为芯成分使用时能得到吸湿性优异的芯鞘型复合纤维。聚醚的共聚合率更优选15wt％以上，最优选20wt％以上。另一方面，聚醚的共聚合率在35wt％以下的话，由于延伸以及假捻工程中因与加热罗拉以及加热器的接触引起的纤维间的融着能够被抑制，加热罗拉、加热器、导轨上的堆积物、断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。同时，能够抑制染色等热水处理时热水中芯成分聚醚酯的溶出，热水处理后能够维持吸湿性。聚醚的共聚合率更优选32wt％以下，最优选为30wt％以下。When the aliphatic diol of the polyether ester is ethylene glycol, the number average molecular weight of the polyether is preferably 4,000 to 30,000 g/mol, and the copolymerization ratio of the polyether is preferably 10 to 35 wt%. When the number average molecular weight of the polyether is 4,000 g/mol or more, the polyether ester has high hygroscopicity, and when used as a core component, a core-sheath type composite fiber excellent in hygroscopicity can be obtained. At the same time, it is possible to suppress the decrease in the crystallinity of the polyether ester and the decrease in the extrapolation melting initiation temperature, and the fusion between the fibers due to the contact with the heating roller and the heater in the elongation and false twisting process can be suppressed. The occurrence of deposits, broken wires, and hairiness on the heating roller, the heater, and the yarn guide is reduced, and the engineering passability is good. When a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent. On the other hand, when the number average molecular weight of the polyether is 30,000 g/mol or less, the polycondensation reactivity is high, and the unreacted polyether is reduced, and dissolution in hot water during hot water treatment such as dyeing can be suppressed, and moisture absorption after hot water treatment can be suppressed. Sex can be maintained. The number average molecular weight of the polyether is preferably 25,000 g/mol or less, and more preferably 20,000 g/mol or less. In addition, when the copolymerization ratio of the polyether is 10% by weight or more, the polyether ester has high hygroscopicity, and when used as a core component, a core-sheath type composite fiber excellent in hygroscopicity can be obtained. The copolymerization ratio of the polyether is more preferably 15% by weight or more, and most preferably 20% by weight or more. On the other hand, when the copolymerization ratio of the polyether is 35 wt% or less, the fusion between the fibers due to the contact with the heating roller and the heater in the extension and the false twisting process can be suppressed, and the heating roller, the heater, and the guide rail are suppressed. The occurrence of deposits, broken wires, and hairiness is reduced, and the engineering passability is good. When a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent. At the same time, it is possible to suppress the elution of the polyether ester of the core component in the hot water during hot water treatment such as dyeing, and to maintain the hygroscopicity after the hot water treatment. The copolymerization ratio of the polyether is more preferably 32% by weight or less, and most preferably 30% by weight or less.
聚醚酯的组成成分脂肪族二元醇为1，4-丁二醇的场合，聚醚的数均分子量优选2000～30000g/mol，聚醚的共聚合率优选10～60wt％。聚醚的数均分子量在2000g/mol以上的话，聚醚酯的吸湿性高，作为芯成分使用时能得到吸湿性优异的芯鞘型复合纤维。同时，能够抑制聚醚酯的结晶性下降。聚醚的数均分子量更优选3000g/mol以上，最优选5000g/mol以上。同时，聚醚的数均分子量在8000g/mol以上的话，能够抑制聚醚酯的结晶性的下降以及外推熔融起始温度的降低，由于延伸以及假捻工程中因与加热罗拉以及加热器的接触引起的纤维间的融着也能够被抑制，加热罗拉、加热器、导轨上的堆积物、断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异，因而成为特别优选。另一方面，聚醚的数均分子量在30000g/mol以下的话，缩聚反应性高，未反应的聚醚减少，能够抑制染色等热水处理时在热水中的溶出，热水处理后的吸湿性能够维持。聚醚的数均分子量更优选27000g/mol以下，最优选25000g/mol以下，特别优选20000g/mol以下。同时，聚醚的共聚合率在10wt％以上的话，聚醚酯的吸湿性高，作为芯成分使用的时能得到吸湿性优异的芯鞘型复合纤维。聚醚的共聚合率更优选15wt％以上，最优选20wt％以上。另一方面，聚醚的共聚合率在60wt％以下时，由于延伸以及假捻工程中因与加热罗拉以及加热器的接触引起的纤维间的融着能够被抑制，加热罗拉、加热器、导轨上的堆积物、断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。同时，能够抑制染色等热水处理时在热水中的溶出，热水处理后的吸湿性能够维持。聚醚的共聚合率更优选55wt％以下，最优选50wt％ 以下，特别优选45wt％以下。When the aliphatic diol of the polyether ester is 1,4-butanediol, the number average molecular weight of the polyether is preferably 2,000 to 30,000 g/mol, and the copolymerization ratio of the polyether is preferably 10 to 60% by weight. When the number average molecular weight of the polyether is 2000 g/mol or more, the polyether ester has high hygroscopicity, and when used as a core component, a core-sheath type composite fiber excellent in hygroscopicity can be obtained. At the same time, it is possible to suppress a decrease in crystallinity of the polyether ester. The number average molecular weight of the polyether is more preferably 3,000 g/mol or more, and most preferably 5,000 g/mol or more. At the same time, when the number average molecular weight of the polyether is 8000 g/mol or more, the decrease in the crystallinity of the polyether ester and the decrease in the extrapolation melting initiation temperature can be suppressed, due to the extension and the false-twisting process due to the heating roller and the heater. The fusion between the fibers caused by the contact can also be suppressed, and the occurrence of deposits on the heating roller, the heater, the guide rail, the broken wire, and the hairiness is reduced, and the engineering passability is good, and the fiber structure such as the woven fabric and the knitted fabric is dyed. It is particularly preferable because the occurrence of spots and hairiness is small and the quality is excellent. On the other hand, when the number average molecular weight of the polyether is 30,000 g/mol or less, the polycondensation reactivity is high, and the unreacted polyether is reduced, and dissolution in hot water during hot water treatment such as dyeing can be suppressed, and moisture absorption after hot water treatment can be suppressed. Sex can be maintained. The number average molecular weight of the polyether is more preferably 27,000 g/mol or less, most preferably 25,000 g/mol or less, and particularly preferably 20,000 g/mol or less. When the copolymerization ratio of the polyether is 10% by weight or more, the polyether ester has high hygroscopicity, and when used as a core component, a core-sheath type composite fiber excellent in hygroscopicity can be obtained. The copolymerization ratio of the polyether is more preferably 15% by weight or more, and most preferably 20% by weight or more. On the other hand, when the copolymerization ratio of the polyether is 60% by weight or less, the fusion between the fibers due to the contact with the heating roller and the heater in the elongation and false twisting process can be suppressed, and the heating roller, the heater, and the guide rail are suppressed. The occurrence of deposits, broken wires, and hairiness is reduced, and the engineering passability is good. When a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent. At the same time, it is possible to suppress elution in hot water during hot water treatment such as dyeing, and the hygroscopicity after hot water treatment can be maintained. The copolymerization ratio of the polyether is more preferably 55 wt% or less, and most preferably 50 wt%. Hereinafter, it is particularly preferably 45 wt% or less.
一般情况下，由聚酯中加入大量聚醚共聚合而成的聚醚酯所得到的纤维，会因聚醚基团的氧化分解而导致纤维吸湿率大幅度下降。所以，在聚醚酯的聚合过程中，大多数情况下会添加受阻酚类抗氧剂，受阻酚类抗氧化剂大多数是用四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(BASF制的IR1010)。但是，氧化分解形成的醚自由基会进攻受阻酚类抗氧剂酚羟基的对位，形成黄变成因的醌类物质。另外同样的道理，由于与NO2反应也会生成黄色物质，即NOx(氮氧)坚牢度低下，对纤维的品质造成影响。聚醚的共聚合率在25wt％以下时，由于受阻酚类抗氧化剂的添加量少，黄变现象比较少，但是聚醚的共聚合率在25wt％以上时，黄变现象显著发生。然而，即使是氧化分解形成醚自由基，使用本发明式1所示结构的半受阻酚类抗氧化剂的情况下，由于酚羟基的一侧邻位上是甲基，空间位阻小，因而半受阻酚类抗氧化剂的酚羟基的邻位被进攻，不会生成醌类物质，黄变得到抑制。In general, a fiber obtained by adding a polyether ester obtained by copolymerizing a large amount of a polyether to a polyester causes a drastic decrease in the moisture absorption rate of the fiber due to oxidative decomposition of the polyether group. Therefore, in the polymerization process of polyether esters, hindered phenolic antioxidants are added in most cases, and most of the hindered phenolic antioxidants are tetra[β-(3,5-di-tert-butyl-4-hydroxyl). Phenyl)propionic acid]pentaerythritol ester (IR1010 manufactured by BASF). However, the ether radical formed by oxidative decomposition attacks the para-position of the phenolic hydroxyl group of the hindered phenolic antioxidant to form an anthraquinone which causes yellowing. In addition, the yellow matter is formed by the reaction with NO 2 , that is, the NOx (nitrogen oxide) fastness is low, which affects the quality of the fiber. When the copolymerization ratio of the polyether is 25 wt% or less, the yellowing phenomenon is less due to the small amount of the hindered phenol antioxidant added, but the yellowing phenomenon remarkably occurs when the copolymerization ratio of the polyether is 25 wt% or more. However, even in the case of the semi-hindered phenolic antioxidant having the structure of the formula 1 of the present invention, even if it is oxidatively decomposed to form an ether radical, since the phenolic hydroxyl group is a methyl group on the one side of the phenolic hydroxyl group, the steric hindrance is small, and thus half. The ortho position of the phenolic hydroxyl group of the hindered phenolic antioxidant is attacked, no quinone species are formed, and yellow becomes suppressed.
Figure PCTCN2016111763-appb-000002
Figure PCTCN2016111763-appb-000002
其中，R1为碳氢、氧、氮元素中任何一种结合形成的半受阻酚类抗氧化剂，R2为氢、碳氢、氧、氮元素中任何一种结合形成的半受阻酚类抗氧化剂。Wherein R1 is a semi-hindered phenolic antioxidant formed by combining any one of hydrocarbon, oxygen and nitrogen, and R2 is a semi-hindered phenolic antioxidant formed by combining any one of hydrogen, hydrocarbon, oxygen and nitrogen.
作为半受阻酚类抗氧化剂，优选如下式2所示结构的3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5.5]十一烷(ADEKA社制的AO-80)和下式3所示结构的1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮(CYTEC社制的CN1790)中的至少一种。As the semi-hindered phenolic antioxidant, 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) having the structure represented by the following formula 2 is preferable. Propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (AO-80 manufactured by ADEKA Co., Ltd.) and 1,3,5 of the structure shown in the following formula 3 -Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione ( At least one of CN1790 manufactured by CYTEC.
Figure PCTCN2016111763-appb-000003
Figure PCTCN2016111763-appb-000003
Figure PCTCN2016111763-appb-000004
Figure PCTCN2016111763-appb-000004
抗氧化剂的添加量可根据聚醚的共聚合率作适当的选择，优选为0.5～8.0wt％。抗氧化剂的添加量在0.5wt％以上时，聚醚酯的氧化分解被抑制，纤维的吸湿性低下也能被抑制，因而成为优选。抗氧化剂的添加量更优选为1.0wt％以上，最优选为1.5wt％以上。另一方面，抗氧化剂的添加量在8.0wt％以下时，抗氧化剂自身分解导致纤维的黄变被抑制，因而成为优选。抗氧化剂的添加量更优选为7.0wt％以下，最优选为6.0wt％以下。The amount of the antioxidant to be added can be appropriately selected depending on the copolymerization ratio of the polyether, and is preferably from 0.5 to 8.0% by weight. When the amount of the antioxidant added is 0.5% by weight or more, the oxidative decomposition of the polyether ester is suppressed, and the hygroscopicity of the fiber can be suppressed, which is preferable. The amount of the antioxidant added is more preferably 1.0% by weight or more, and most preferably 1.5% by weight or more. On the other hand, when the amount of the antioxidant added is 8.0% by weight or less, the decomposition of the antioxidant itself causes the yellowing of the fiber to be suppressed, which is preferable. The amount of the antioxidant added is more preferably 7.0% by weight or less, and most preferably 6.0% by weight or less.
本发明的芯鞘型复合纤维的鞘成分具有结晶性。鞘成分有结晶性的话，通过实施例中记载的方法测定外推熔融起始温度时，伴随着结晶的融解能观测到融解峰。鞘成分具有结晶性的话，能够抑制延伸以及假捻工程中因与加热罗拉以及加热器的接触引起的纤维间的融着，加热罗拉、加热器和导丝器上的堆积物变少，断丝以及毛羽发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。同时，能抑制染色等热水处理时鞘成分的溶出。The sheath component of the core-sheath type composite fiber of the present invention has crystallinity. When the sheath component has crystallinity, when the extrapolation melting onset temperature is measured by the method described in the examples, a melting peak can be observed with melting of the crystal. When the sheath component has crystallinity, it is possible to suppress the fusion between the fibers due to the contact with the heating roller and the heater during the extension and false twisting, and the deposit on the heating roller, the heater, and the yarn guide is reduced, and the yarn is broken. In addition, the hairiness is reduced, and the engineering passability is good. When a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent. At the same time, it is possible to suppress the elution of the sheath component during hot water treatment such as dyeing.
本发明的芯鞘型复合纤维的鞘成分，具体地可以列举的有聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等聚酯，尼龙6、尼龙66等聚酰胺，聚乙烯、聚丙烯等聚烯烃，但不限于以上物质。 尤其，由于聚酯具有优异的机械特性与耐久性而优选。同时，鞘成分为聚酯或聚烯烃等疏水性聚合物的场合，表面上露出的芯成分吸湿性聚合物的吸湿性，与鞘成分疏水性聚合物的干燥的触感可以并存，能够得到穿着舒适的纤维构造体。Specific examples of the sheath component of the core-sheath type composite fiber of the present invention include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyamides such as nylon 6, nylon 66, and the like. Polyolefins such as polyethylene and polypropylene are not limited to the above. In particular, polyester is preferred because of its excellent mechanical properties and durability. When the sheath component is a hydrophobic polymer such as polyester or polyolefin, the hygroscopicity of the core component hygroscopic polymer exposed on the surface can be coexisted with the dry touch of the sheath component hydrophobic polymer, and the wearing comfort can be obtained. Fiber structure.
关于本发明芯鞘型复合纤维的鞘成分的聚酯，具体地可以列举的有聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸丁二醇酯等芳香族聚酯，聚乳酸、聚乙二醇酸等脂肪族聚酯等，但不限于以上物质。尤其，聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸丁二醇酯具有优异的机械特性以及耐久性，制造时以及使用时取用性良好而优选。同时，聚对苯二甲酸乙二醇酯具有聚酯纤维特有的挺括感而优选，聚对苯二甲酸丁二醇酯具有高的结晶性而优选。The polyester of the sheath component of the core-sheath type composite fiber of the present invention may specifically be exemplified by polyethylene terephthalate, polytrimethylene terephthalate or polybutylene terephthalate. The family polyester, an aliphatic polyester such as polylactic acid or polyglycolic acid, etc., but is not limited to the above. In particular, polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate have excellent mechanical properties and durability, and are preferable because they are excellent in handleability at the time of production and use. Meanwhile, polyethylene terephthalate has a peculiar feeling of polyester fiber, and polybutylene terephthalate has high crystallinity and is preferable.
本发明的芯鞘型复合纤维的鞘成分，优选为阳离子可染聚酯。聚酯具有磺酸基等阴离子部位的话，可与具有阳离子部位的阳离子染料相互作用，因而具有阳离子可染性。鞘成分为阳离子可染聚酯的话，具有鲜明的发色性的同时，与聚氨酯纤维混合使用时能防止染料的污染因而优选。阳离子可染聚酯的共聚合成分具体地有5-间苯二甲酸磺酸盐，可以列举的有锂盐、钠盐、钾盐、铷盐、铯盐等，但不限于以上物质。尤其优选锂盐与钠盐，特别是钠盐的结晶性优异因而更优选。The sheath component of the core-sheath type composite fiber of the present invention is preferably a cationic dyeable polyester. When the polyester has an anionic moiety such as a sulfonic acid group, it can interact with a cationic dye having a cationic moiety, and thus has cationic dyeability. When the sheath component is a cationic dyeable polyester, it has a clear color developability and is preferably used in combination with a polyurethane fiber to prevent contamination of the dye. The copolymerization component of the cationic dyeable polyester is specifically a 5-isophthalic acid sulfonate, and examples thereof include a lithium salt, a sodium salt, a potassium salt, a phosphonium salt, a phosphonium salt, and the like, but are not limited thereto. It is particularly preferable that the lithium salt and the sodium salt are particularly excellent in crystallinity of the sodium salt.
本发明的芯鞘型复合纤维，纤维横截面上至少有一部分芯成分露出在表面。与芯成分完全被包裹的芯鞘型复合纤维不同，由于纤维横截面上至少有一部分芯成分露出在表面，能够抑制染色等热水处理时芯成分吸湿性聚合物发生体积膨胀后的鞘破损。同时，由于芯成分吸湿性聚合物露出在表面，发现其比芯成分完全被包裹的芯鞘型复合纤维具有更高的吸湿性。In the core-sheath type composite fiber of the present invention, at least a part of the core component on the fiber cross section is exposed on the surface. Unlike the core-sheath type composite fiber in which the core component is completely wrapped, at least a part of the core component is exposed on the surface of the fiber cross-section, and it is possible to suppress the damage of the sheath after the volume expansion of the core component hygroscopic polymer during hot water treatment such as dyeing. At the same time, since the core component hygroscopic polymer was exposed on the surface, it was found to have higher hygroscopicity than the core-sheath type composite fiber in which the core component was completely wrapped.
本发明的芯鞘型复合纤维，纤维横截面外周长R与露出在表面部分的芯成分的长度总和rS的比rS/R为0.05～0.40。本发明的纤维横截面外周长R与露出在表面部分的芯成分的长度总和rS的比rS/R，指通过实施例记载的方法算出的值。当芯鞘型复合纤维的rS/R在0.05以上时，发现因为芯成分吸湿性聚合物露出在表面所以比芯成分完全被包裹的芯鞘型复合纤维的吸湿性更高。同时，染色等热水处理时芯成分吸湿性聚合物发生体积膨胀，能够抑制鞘被破坏。芯鞘型复合纤维的rS/R优选在0.07以上，更优选在0.10以上。另一方面，芯鞘型复合纤维的rS/R在0.40以下时，延伸以及假捻工程中因与加热罗拉以及加热器的接触引起的纤维间的融着能够被抑制，加热罗拉、加热器、导丝器上的堆积物、断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。同时，能够抑制染色等热水处理时芯成分吸湿性聚合物在热水中的溶出，热水处理后能保持吸湿性。芯鞘型复合纤维的rS/R更优选0.35以下，最优选0.30以下。Core-sheath type composite fiber of the present invention, the sum of the length of the fiber cross-section r S R and the outer perimeter of the surface of the exposed portion of the core component ratio r S / R of 0.05 to 0.40. The ratio r S /R of the outer peripheral length R of the cross-sectional area of the fiber of the present invention to the total length r S of the core component exposed on the surface portion means a value calculated by the method described in the examples. When the r S /R of the core-sheath type composite fiber is 0.05 or more, it is found that the core-sheath type composite fiber which is completely wrapped than the core component is more hygroscopic because the core component hygroscopic polymer is exposed on the surface. At the same time, in the hot water treatment such as dyeing, the core component hygroscopic polymer expands in volume, and the sheath can be prevented from being destroyed. The r S /R of the core-sheath type composite fiber is preferably 0.07 or more, and more preferably 0.10 or more. On the other hand, when the r S /R of the core-sheath type composite fiber is 0.40 or less, the fusion between the fibers due to the contact with the heating roller and the heater in the false twisting process can be suppressed, and the heating roller and the heater are heated. The occurrence of deposits, broken wires, and hairiness on the yarn guide is reduced, and the engineering passability is good. When a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent. At the same time, it is possible to suppress the elution of the core component hygroscopic polymer in hot water during hot water treatment such as dyeing, and to maintain hygroscopicity after hot water treatment. The r S /R of the core-sheath type composite fiber is more preferably 0.35 or less, and most preferably 0.30 or less.
本发明的芯鞘型复合纤维，纤维横截面的外周长R与露出在表面部分的芯成分长度的最大值rM的比rM/R优选0.01～0.20。本发明的纤维横截面外周长R与露出在表面部分的芯成分长度的最大值rM的比rM/R，指通过实施例记载的方法算出的值。芯鞘型复合纤维的rM/R在0.01以上时，发现因为芯成分吸湿性聚合物露出在表面所以比芯成分完全被包裹的芯鞘型复合纤维的吸湿性更高，成为优选；同时，染色等热水处理时芯成分吸湿性聚合物发生体积膨胀，能够抑制鞘被破坏，成为优选。芯鞘型复合纤维的rM/R更优选在0.03以上，最优选在0.05以上。另一方面，芯鞘型复合纤维的rM/R在0.20以下时，延伸以及假捻工程中因与加热罗拉以及加热器的接触引起的纤维间的融着能够被抑制，加热罗拉、加热器、导丝器上的堆积物、断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。同时，能够抑制染色等热水处理时芯成分吸湿性聚合物在热水中的溶出，热水处理后能保持吸湿性。芯鞘型复合纤维的rM/R更优选在0.17以下，最优选在0.15以下。In the core-sheath type composite fiber of the present invention, the ratio r M /R of the outer peripheral length R of the cross section of the fiber to the maximum value r M of the length of the core component exposed on the surface portion is preferably 0.01 to 0.20. The ratio r M /R of the outer peripheral length R of the cross-sectional area of the fiber of the present invention to the maximum value r M of the core component length exposed on the surface portion means a value calculated by the method described in the examples. When the r M /R of the core-sheath type composite fiber is 0.01 or more, it is found that the core-sheath type composite fiber in which the core component is completely exposed is more hygroscopic than the core component hygroscopic polymer, and is preferable. In the hot water treatment such as dyeing, the core component hygroscopic polymer expands in volume, and it is possible to suppress the destruction of the sheath, which is preferable. The r M /R of the core-sheath type composite fiber is more preferably 0.03 or more, and most preferably 0.05 or more. On the other hand, when the r M /R of the core-sheath type composite fiber is 0.20 or less, the fusion between the fibers due to the contact with the heating roller and the heater in the false twisting process can be suppressed, and the heating roller and the heater are heated. The occurrence of deposits, broken wires, and hairiness on the yarn guide is reduced, and the engineering passability is good. When a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent. At the same time, it is possible to suppress the elution of the core component hygroscopic polymer in hot water during hot water treatment such as dyeing, and to maintain hygroscopicity after hot water treatment. The r M /R of the core-sheath type composite fiber is more preferably 0.17 or less, and most preferably 0.15 or less.
本发明的芯鞘型复合纤维，芯成分和/或鞘成分中还可以添加各种各样的辅助改性剂。辅助改性剂，具体地可以列举的有相溶剂、可塑剂、酸化防止剂、紫外线吸收剂、红外线吸收剂、荧光增白剂、脱模剂、抗菌剂、成核剂、热稳定剂、酸化防止剂、带电防止剂、着色防止剂、调整剂、消光剂、消泡剂、防腐剂、凝胶化剂、乳胶、填料、墨水、着色料、染料、颜料、香料等，但不 限于上述物质。上述辅助添加剂可以单独使用，也可以混合使用。In the core-sheath type composite fiber of the present invention, various auxiliary modifiers may be added to the core component and/or the sheath component. The auxiliary modifier may specifically be a phase solvent, a plasticizer, an acidification inhibitor, an ultraviolet absorber, an infrared absorber, an optical brightener, a mold release agent, an antibacterial agent, a nucleating agent, a heat stabilizer, and an acidification. Preventing agent, antistatic agent, coloring preventive agent, adjusting agent, matting agent, antifoaming agent, preservative, gelling agent, latex, filler, ink, coloring matter, dye, pigment, perfume, etc., but not Limited to the above substances. The above auxiliary additives may be used singly or in combination.
本发明的芯鞘型复合纤维的外推熔融起始温度在150℃以上。本发明的芯鞘型复合纤维的外推熔融起始温度，指通过实施例记载的方法算出的值。并且，观测到多个融解峰的场合，从温度最低侧的融解峰开始算出。芯鞘型复合纤维的外推熔融起始温度在150℃以上的话，延伸以及假捻工程中因与加热罗拉以及加热器的接触引起的纤维间的融着能够被抑制，加热罗拉、加热器、导丝器上的堆积物、断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。芯鞘型复合纤维的外推熔融起始温度更优选170℃以上，最优选190℃以上，特别优选200℃以上。The core-sheath type composite fiber of the present invention has an extrapolated melting onset temperature of 150 ° C or more. The extrapolated melting onset temperature of the core-sheath type composite fiber of the present invention means a value calculated by the method described in the examples. Further, when a plurality of melting peaks are observed, the melting peak from the lowest temperature side is calculated. When the extrapolation melting initiation temperature of the core-sheath type composite fiber is 150 ° C or more, the fusion between the fibers due to the contact with the heating roller and the heater in the extension and the false twisting process can be suppressed, and the heating roller, the heater, and the heating roller are heated. The occurrence of deposits, broken wires, and hairiness on the yarn guide is reduced, and the engineering passability is good. When a fiber structure such as a woven fabric or a knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent. The extrapolated melting initiation temperature of the core-sheath type composite fiber is more preferably 170 ° C or more, most preferably 190 ° C or more, and particularly preferably 200 ° C or more.
本发明的芯鞘型复合纤维的芯成分/鞘成分的复合比(重量比)优选10/90～70/30。本发明的芯鞘型复合纤维的芯成分/鞘成分的复合比(重量比)，指通过实施例记载的方法算出的值。芯鞘型复合纤维的芯成分的复合比例在10wt％以上时，能得到具有优异吸湿性的芯鞘型复合纤维。本发明的芯鞘型复合纤维的芯成分的复合比更优选20wt％以上，最优选30wt％以上。另一方面，芯鞘型复合纤维的芯成分复合比在70wt％以下，即鞘成分的复合比在30wt％以上时，鞘成分能得到挺括、干燥的触感。同时，能够抑制延伸时以及假捻时外力导致的鞘的破裂、吸湿时芯成分的体积膨胀导致的鞘的破裂，毛羽的产生导致的品质低下、染色等热水处理时芯成分吸湿性聚合物在热水中的溶出导致的吸湿性下降诸多问题。本发明的芯鞘型复合纤维的芯成分的复合比更优选60wt％以下，最优选50wt％以下。The composite ratio (weight ratio) of the core component/sheath component of the core-sheath type composite fiber of the present invention is preferably 10/90 to 70/30. The composite ratio (weight ratio) of the core component/sheath component of the core-sheath type composite fiber of the present invention means a value calculated by the method described in the examples. When the composite ratio of the core component of the core-sheath type composite fiber is 10% by weight or more, a core-sheath type composite fiber having excellent hygroscopicity can be obtained. The composite ratio of the core component of the core-sheath type composite fiber of the present invention is more preferably 20% by weight or more, and most preferably 30% by weight or more. On the other hand, when the core component composite fiber has a core component composite ratio of 70% by weight or less, that is, when the composite ratio of the sheath component is 30% by weight or more, the sheath component can have a firm and dry touch. At the same time, it is possible to suppress cracking of the sheath due to external force during extension and false twisting, cracking of the sheath due to volume expansion of the core component during moisture absorption, deterioration of quality due to hairiness, and heat-sensitive polymer of the core component during hot water treatment such as dyeing The hygroscopicity caused by dissolution in hot water has many problems. The composite ratio of the core component of the core-sheath type composite fiber of the present invention is more preferably 60% by weight or less, and most preferably 50% by weight or less.
本发明的芯鞘型的复合纤维的复丝的纤度，没有进行特定的限制，根据用途、特性要求可以进行适当的选择，优选为10～500dtex。本发明的纤度，指通过实施例记载的方法测定的值。芯鞘型复合纤维的纤度在10dtex以上时，断丝比较少，工程通过性良好，使用时毛羽的发生少，耐久性优异。芯鞘型复合纤维的纤度更优选30dtex以上，最优选50dtex以上。另一方面，芯鞘型复合纤维的纤度在500dtex以下时，纤维以及纤维构造体的柔软性不会受损。芯鞘型复合纤维的纤度更优选400dtex以下，最优选300dtex以下。The fineness of the multifilament of the core-sheath type composite fiber of the present invention is not particularly limited, and may be appropriately selected depending on the use and characteristics, and is preferably from 10 to 500 dtex. The fineness of the present invention means a value measured by the method described in the examples. When the fineness of the core-sheath type composite fiber is 10 dtex or more, the number of broken wires is relatively small, the engineering passability is good, the occurrence of hairiness is small during use, and the durability is excellent. The fineness of the core-sheath type composite fiber is more preferably 30 dtex or more, and most preferably 50 dtex or more. On the other hand, when the fineness of the core-sheath type composite fiber is 500 dtex or less, the flexibility of the fiber and the fiber structure is not impaired. The fineness of the core-sheath type composite fiber is more preferably 400 dtex or less, and most preferably 300 dtex or less.
本发明的芯鞘型复合纤维的单丝纤度，并没有进行特定的限制，根据用途、特性要求可以进行适当的选择，优选为0.5～4.0dtex。本发明的单丝纤度，指根据实施例所记载的方法测定的纤度除以单丝数所得的值。芯鞘型复合纤维的单丝纤度在0.5dtex以上时，断丝比较少，工程通过性良好，使用时毛羽的发生少，耐久性优异。芯鞘型复合纤维的单丝纤度更优选0.6dtex以上，最优选0.8dtex以上。另一方面，芯鞘型复合纤维的单丝纤度在4.0dtex以下时，纤维以及纤维构造体的柔软性不会受损。芯鞘型复合纤维的单丝纤度更优选2.0dtex以下，最优选1.5dtex以下。The single-filament fineness of the core-sheath type composite fiber of the present invention is not particularly limited, and may be appropriately selected depending on the use and characteristics, and is preferably 0.5 to 4.0 dtex. The single yarn fineness of the present invention means a value obtained by dividing the fineness measured by the method described in the examples by the number of filaments. When the single-filament fineness of the core-sheath type composite fiber is 0.5 dtex or more, the number of broken wires is relatively small, the engineering passability is good, the occurrence of hairiness is small during use, and the durability is excellent. The monofilament fineness of the core-sheath type composite fiber is more preferably 0.6 dtex or more, and most preferably 0.8 dtex or more. On the other hand, when the single-filament fineness of the core-sheath type composite fiber is 4.0 dtex or less, the flexibility of the fiber and the fiber structure is not impaired. The monofilament fineness of the core-sheath type composite fiber is more preferably 2.0 dtex or less, and most preferably 1.5 dtex or less.
本发明的芯鞘型复合纤维的强度，并没有进行特定的限制，根据用途及特性要求可以进行适当的选择，根据机械特性的要求优选2.0～5.0cN/dtex。本发明的强度，指通过实施例记载的方法测定的值。芯鞘型复合纤维的强度在2.0cN/dtex以上时，使用时毛羽的发生少，耐久性优异。芯鞘型复合纤维的强度更优选2.5cN/dtex以上，最优选3.0cN/dtex以上。另一方面，芯鞘型复合纤维的强度在5.0cN/dtex以下时，纤维以及纤维构造体的柔软性不会受损。The strength of the core-sheath type composite fiber of the present invention is not particularly limited, and may be appropriately selected depending on the use and characteristics, and is preferably 2.0 to 5.0 cN/dtex in accordance with the requirements of mechanical properties. The strength of the present invention means a value measured by the method described in the examples. When the strength of the core-sheath type composite fiber is 2.0 cN/dtex or more, the occurrence of hairiness is small during use, and the durability is excellent. The strength of the core-sheath type composite fiber is more preferably 2.5 cN/dtex or more, and most preferably 3.0 cN/dtex or more. On the other hand, when the strength of the core-sheath type composite fiber is 5.0 cN/dtex or less, the flexibility of the fiber and the fiber structure is not impaired.
本发明的芯鞘型复合纤维的伸度，并未进行特定的限制，根据用途及特性要求可以进行适当的选择，从耐久性的观点优选10～60％。本发明的伸度，指通过实施例记载的方法测定的值。芯鞘型复合纤维的伸度在10％以上时，纤维及纤维构造体的耐磨耗性良好，使用时毛羽的发生少，耐久性良好。芯鞘型复合纤维的伸度更优选15％以上，最优选20％以上。另一方面，芯鞘型复合纤维的伸度在60％以下时，纤维及纤维构造体的尺寸安定性良好。芯鞘型复合纤维的伸度更优选55％以下，最优选50％以下。The elongation of the core-sheath type composite fiber of the present invention is not particularly limited, and may be appropriately selected depending on the use and characteristics, and is preferably from 10 to 60% from the viewpoint of durability. The elongation of the present invention means a value measured by the method described in the examples. When the elongation of the core-sheath type composite fiber is 10% or more, the fiber and the fiber structure are excellent in abrasion resistance, and the occurrence of hairiness is small during use, and the durability is good. The elongation of the core-sheath type composite fiber is more preferably 15% or more, and most preferably 20% or more. On the other hand, when the elongation of the core-sheath type composite fiber is 60% or less, the dimensional stability of the fiber and the fiber structure is good. The elongation of the core-sheath type composite fiber is more preferably 55% or less, and most preferably 50% or less.
本发明的芯鞘型复合纤维的热水处理后的吸湿率差(△MR)为2.0～10.0％。本发明热水处理后的吸湿率差(△MR)，指通过实施例记载的方法测定的值。△MR是指，假定轻度运动后衣服内温度30℃、湿度90％RH时的吸湿率，与外界温度20℃、湿度65％RH时的吸湿率的差。也就是说， △MR是吸湿性的指标，△MR越高穿着舒适性越好。本发明的吸湿率差(△MR)是指热水处理后的值，表示在染色等热水处理后仍具有吸湿性是非常重要的。芯鞘型复合纤维热水处理后的△MR在2.0％以上时，衣服内的闷热感降低，具有穿着舒适性。芯鞘型复合纤维热水处理后的△MR优选在3.0％以上，更优选在3.5％以上，最优选在4.0％以上。另一方面，芯鞘型复合纤维热水处理后的△MR在10％以下时，工程通过性及取用性良好，使用时耐久性优异。The core-sheath type composite fiber of the present invention has a moisture absorption rate difference (ΔMR) after hot water treatment of 2.0 to 10.0%. The moisture absorption rate difference (?MR) after the hot water treatment of the present invention means a value measured by the method described in the examples. ΔMR is a difference between the moisture absorption rate at a temperature of 30 ° C and a humidity of 90% RH after a slight exercise, and the moisture absorption rate at an external temperature of 20 ° C and a humidity of 65% RH. That is, ΔMR is an indicator of hygroscopicity, and the higher the ΔMR, the better the wearing comfort. The moisture absorption rate difference (?MR) of the present invention means a value after hot water treatment, and it is very important to exhibit hygroscopicity even after hot water treatment such as dyeing. When the ΔMR of the core-sheath type composite fiber after hot water treatment is 2.0% or more, the stuffing feeling in the clothes is lowered, and the wearing comfort is obtained. The ΔMR of the core-sheath type composite fiber after hot water treatment is preferably 3.0% or more, more preferably 3.5% or more, and most preferably 4.0% or more. On the other hand, when the ΔMR of the core-sheath type composite fiber after hot water treatment is 10% or less, the workability and the usability are good, and the durability at the time of use is excellent.
本发明的芯鞘型复合纤维，热水处理后的复合纤维色调变化值△b优选为3.0以下。本发明所述的热水处理前后复合纤维色调的变化值△b是实施例记载的方法所测定的值。热水处理前后复合纤维色调的变化值△b在3.0以下的话，热水处理后纤维的黄变少，可得到良好品质的纤维。热水处理前后复合纤维色调的变化值△b优选为2.0以下，更优选为1.5以下，进一步优选为1.0以下。In the core-sheath type composite fiber of the present invention, the color fiber change value Δb of the composite fiber after the hot water treatment is preferably 3.0 or less. The change value Δb of the color tone of the composite fiber before and after the hot water treatment according to the present invention is a value measured by the method described in the examples. When the change value Δb of the color tone of the composite fiber before and after the hot water treatment is 3.0 or less, the yellowing of the fiber after the hot water treatment is small, and a fiber of good quality can be obtained. The change value Δb of the color tone of the composite fiber before and after the hot water treatment is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.0 or less.
本发明的芯鞘型复合纤维，当纤维横截面上至少有一部分芯成分露出在表面，纤维横截面的外周长R与露出在表面部分的芯成分的长度总和rS的比rS/R满足0.05～0.40时，对纤维断面形状没有特定的限制，根据用途及特性要求可以进行相应的选择。同时，对露出在表面部分的芯成分的个数也没有特定的限制，例如，图1(a)～(c)所示的1处，图1(d)、(e)所示的2处，图1(f)、(g)所示的3处，图1(h)～(j)所示的4处有露出在表面的部分的断面形状，但并不限于上述列举。从抑制延伸及假捻工程的融着、染色等热水处理时芯成分吸湿性聚合物的溶出、以及使用时磨耗耐久性的角度考虑，露出在表面的芯成分部分越少越好，因此，优选图1(a)～(c)所示的露出在表面的芯成分的部分为1处的断面形状。更具体得，优选图1(a)、(b)所示的偏芯芯鞘型、图1(c)所示的鞘成分为C型的芯鞘型断面形状。同时，图1(j)所示各个露出在表面的芯成分部分的长度不一致的情况也可以。再者，图1(k)～(m)所示的断面的外形为扁平形、茧形、三叶形都可以。In the core-sheath type composite fiber of the present invention, when at least a part of the core component of the fiber cross section is exposed on the surface, the ratio r S /R of the outer circumferential length R of the fiber cross section and the total length r S of the core component exposed at the surface portion is satisfied. When the viscosity is 0.05 to 0.40, there is no particular limitation on the shape of the fiber cross-section, and the corresponding selection can be made according to the use and characteristics. Meanwhile, there is no particular limitation on the number of core components exposed on the surface portion, for example, one position shown in Figs. 1(a) to (c) and two places shown in Figs. 1(d) and (e). In the three places shown in FIGS. 1(f) and (g), the four portions shown in FIGS. 1(h) to (j) have a cross-sectional shape of a portion exposed on the surface, but are not limited to the above. From the viewpoint of suppressing the elution of the core component hygroscopic polymer during hot water treatment such as fusion and dyeing, and the abrasion durability at the time of use, the core component portion exposed on the surface is preferably as small as possible. It is preferable that the portion of the core component exposed on the surface shown in FIGS. 1(a) to 1(c) has a cross-sectional shape of one. More specifically, it is preferable that the eccentric core sheath type shown in Figs. 1(a) and 1(b) and the sheath component shown in Fig. 1(c) have a C-shaped core-sheath cross-sectional shape. At the same time, the lengths of the core component portions exposed on the surface shown in Fig. 1(j) may not coincide. Further, the outer shape of the cross section shown in Figs. 1(k) to (m) may be a flat shape, a meander shape, or a trilobal shape.
本发明的芯鞘型复合纤维，对纤维的形态没有特定的限定，单丝、复丝、短纤等各种形态都可以。In the core-sheath type composite fiber of the present invention, the form of the fiber is not particularly limited, and various forms such as a monofilament, a multifilament, and a staple fiber may be used.
本发明的芯鞘型复合纤维，可以进行与一般的纤维同样的假捻及捻线加工，织造及编织也可以用与一般纤维同样的方法。The core-sheath type composite fiber of the present invention can be subjected to the same false twisting and twisting processing as a general fiber, and the weaving and knitting can be carried out in the same manner as in the case of a general fiber.
本发明的芯鞘型复合纤维和/或由假捻丝形成的纤维构造体的形态，没有进行特别的限制，根据公知的方法，机织物、编织物、毛圈布帛、不织布、纺纱、填充棉等都可以。同时，本发明的芯鞘型复合纤维和/或由假捻丝形成的纤维构造体，可以是任何编织物组织，平织、斜纹织、朱子织或这些的变化织，经编、纬编、圆编、蕾丝编或这些的变化编等都可以被采用。The form of the core-sheath type composite fiber of the present invention and/or the fiber structure formed of the false twisted wire is not particularly limited, and according to a known method, a woven fabric, a knitted fabric, a terry cloth, a non-woven fabric, a spinning, and a filling are used. Cotton can be used. Meanwhile, the core-sheath type composite fiber of the present invention and/or the fiber structure formed of the false twisted silk may be any woven fabric, plain weave, twill weave, woven fabric, or a woven weave, warp knitting, weft knitting, Circular knitting, lace knitting, or variations of these can be used.
本发明的芯鞘型复合纤维，可以与其他纤维组合，也可以与其他纤维形成混纺纱以后，通过交织或交编形成纤维构造体，The core-sheath type composite fiber of the present invention may be combined with other fibers, or may be formed into a blended yarn with other fibers, and then formed into a fiber structure by interlacing or interlacing.
本发明的芯鞘型复合纤维的制造方法如下所示。The method for producing the core-sheath type composite fiber of the present invention is as follows.
本发明的芯鞘型复合纤维的制造方法，可以使用公知的熔融纺丝法、延伸方法、假捻加工方法。In the method for producing the core-sheath type composite fiber of the present invention, a known melt spinning method, an extension method, and a false twist processing method can be used.
本发明在熔融纺丝前，优选将芯成分、鞘成分进行干燥至含水率300ppm以下。含水率在300ppm以下的话，可以抑制熔融纺丝时因加水分解产生的分子量下降以及由水分引起的发泡，能够进行稳定纺丝。含水率更优选100ppm以下，最优选50ppm以下。In the present invention, it is preferred to dry the core component and the sheath component to a water content of 300 ppm or less before melt spinning. When the water content is 300 ppm or less, it is possible to suppress a decrease in molecular weight due to hydrolysis by desorption during melt spinning and foaming by moisture, and it is possible to perform stable spinning. The water content is more preferably 100 ppm or less, and most preferably 50 ppm or less.
本发明，将事前干燥过的切片向螺杆型或热板型熔融纺丝机进行供给，芯成分与鞘成分分别进行熔融、通过计量泵进行计量。然后，导入到在纺丝箱体中被加热的纺丝组件内，在纺丝组件内将熔融聚合物进行滤过后，通过芯鞘型复合纺丝喷丝板将芯成分与鞘成分进行合流形成芯鞘构造，从纺丝喷丝板吐出形成纤维丝条。从纺丝喷丝板吐出的纤维丝条，经过冷却装置进行冷却固化，通过第一罗拉进行引取，通过第2罗拉在络纱机上进行卷取，得到卷取丝。而且，为了提高纺丝操业性、生产性、纤维的机械特性，有必要在纺丝喷丝板下部设置2～20cm长的加热筒或保温筒。同时，可以通过给油装置给纤维丝条进行给油，也可以通过交络装置对纤维丝条进行交络。 In the present invention, the previously dried chips are supplied to a screw type or hot plate type melt spinning machine, and the core component and the sheath component are separately melted and metered by a metering pump. Then, it is introduced into a spinning assembly heated in a spinning box, and after the molten polymer is filtered in the spinning assembly, the core component and the sheath component are combined by a core-sheath type composite spinning spinneret. The core sheath structure is spun from a spinneret to form a fiber strand. The fiber yarn spun from the spinning spinneret is cooled and solidified by a cooling device, taken up by the first roller, and wound up on the winder by the second roller to obtain a wound wire. Further, in order to improve the spinning workability, productivity, and mechanical properties of the fiber, it is necessary to provide a heating cylinder or a heat insulating cylinder having a length of 2 to 20 cm in the lower portion of the spinning spinneret. At the same time, the fiber strands can be supplied with oil by means of an oil supply device, or the fiber strands can be entangled by means of an interlacing device.
熔融纺丝的纺丝温度，根据芯成分、鞘成分的熔点及耐热性等可以进行相应的选择，优选为240～320℃。纺丝温度在240℃以上的话，由于从纺丝喷丝板吐出的纤维丝条的伸长粘度低，吐出安定，尤其是纺丝张力不会过高，能够抑制断丝。纺丝温度更优选在250℃以上，最优选在260℃以上。另一方面，纺丝温度在320℃以下的话，可以抑制纺丝时的热分解、纤维机械性能的降低及着色。纺丝温度更优选在310℃以下，最优选在300℃以下。The spinning temperature of the melt spinning can be appropriately selected depending on the core component, the melting point of the sheath component, and the heat resistance, and is preferably 240 to 320 °C. When the spinning temperature is 240 ° C or higher, the elongation of the fiber strands discharged from the spinneret is low, and the discharge is stable, and in particular, the spinning tension is not excessively high, and the yarn breakage can be suppressed. The spinning temperature is more preferably 250 ° C or higher, and most preferably 260 ° C or higher. On the other hand, when the spinning temperature is 320 ° C or lower, thermal decomposition at the time of spinning, reduction in fiber mechanical properties, and coloring can be suppressed. The spinning temperature is more preferably 310 ° C or lower, and most preferably 300 ° C or lower.
熔融纺丝时的纺丝速度，根据芯成分和鞘成分的组成、纺丝温度等可以进行适当的选择。先进行熔融纺丝及卷取后，再另外进行延伸或假捻两段工程法的场合的纺丝速度优选为500～6000m/分。纺丝速度在500m/分以上的话，丝条的运行安定，能够抑制断丝。两段工程法的场合的纺丝速度更优选1000m/分以上，最优选1500m/分以上。另一方面，纺丝速度在6000m/分以下的话，通过抑制纺丝张力没有断丝，能进行安定纺丝。两工程法的场合的纺丝速度更优选4500m/分以下，最优选4000m/分以下。同时，暂且不进行卷取，纺丝与延伸同时进行的一段工程法的场合的纺丝速度，低速罗拉优选500～5000m/分，高速罗拉优选2500～6000m/分。低速罗拉及高速罗拉在上述范围内的话，丝条走行安定的同时能够抑制断丝，可以进行安定纺丝。一段工程法的场合的纺丝速度，更优选低速罗拉1000～4500m/分、高速罗拉3500～5500m/分，最优选低速罗拉1500～4000m/分、高速罗拉4000～5000m/分。The spinning speed at the time of melt spinning can be appropriately selected depending on the composition of the core component and the sheath component, the spinning temperature, and the like. The spinning speed in the case of melt-spinning and coiling, and then performing the extension or false twist two-stage engineering method is preferably 500 to 6000 m/min. When the spinning speed is 500 m/min or more, the running of the yarn is stable, and the yarn breakage can be suppressed. The spinning speed in the case of the two-stage engineering method is more preferably 1000 m/min or more, and most preferably 1500 m/min or more. On the other hand, when the spinning speed is 6,000 m/min or less, stable spinning can be performed by suppressing the spinning tension without breaking the yarn. The spinning speed in the case of the two engineering methods is more preferably 4,500 m/min or less, and most preferably 4,000 m/min or less. At the same time, the spinning speed in the case of the one-stage engineering method in which the winding and the stretching are performed at the same time is preferably 500 to 5000 m/min for the low speed roller and 2500 to 6000 m/min for the high speed roller. When the low-speed roller and the high-speed roller are within the above range, the yarn can be stabilized while being broken, and the spinning can be performed stably. The spinning speed in the case of one-stage engineering method is more preferably a low-speed roller of 1000 to 4,500 m/min, a high-speed roller of 3,500 to 5,500 m/min, and most preferably a low-speed roller of 1,500 to 4,000 m/min and a high-speed roller of 4000 to 5,000 m/min.
一段工程法或两段工程法进行延伸的场合，一段延伸法或两段以上的多段延伸法都可以。延伸时的加热方法，对走行丝条可以进行直接或间接加热的装置，并未进行特定的限制。加热方法具体地可以列举的有，加热罗拉、热针、热板、温水、热水等的液体浴、热空、蒸汽等的气体浴、激光等，但并不限于上述列举。这些加热方法可以单独使用，也可以进行复合使用。加热方法从加热温度的控制、对走行丝条的均匀加热、避免装置复杂性等角度考虑，优先采用与加热罗拉的接触、热针的接触、与热板的接触、液体浴的浸渍。Where an engineering method or a two-stage engineering method is extended, a one-stage extension method or a multi-stage extension method of two or more stages may be used. The heating method at the time of extension and the means for directly or indirectly heating the running yarn are not specifically limited. Specific examples of the heating method include a liquid bath such as a heating roller, a hot needle, a hot plate, warm water, and hot water, a gas bath such as hot air or steam, a laser, or the like, but the invention is not limited thereto. These heating methods can be used singly or in combination. The heating method preferably takes contact with the heating roller, the contact of the hot needle, the contact with the hot plate, and the immersion of the liquid bath from the viewpoints of the control of the heating temperature, the uniform heating of the running yarn, and the avoidance of the complexity of the apparatus.
进行延伸的场合的延伸温度，根据芯成分、鞘成分的聚合物的外推熔融起始温度以及延伸后纤维的强度、伸度等可以进行适当的选择，优选为50～150℃。延伸温度在50℃以上的话，对供给延伸的丝条能进行充分的预热，延伸时的热变形均一，能抑制纤度斑的发生。延伸温度更优选60℃以上，最优选70℃以上。另一方面，延伸温度在150℃以下的话，能够抑制因与加热罗拉的接触引起的纤维间的融着以及热分解，工程通过性及品质良好。同时，由于延伸罗拉上的纤维润滑性好，能抑制断丝，进行稳定延伸。延伸温度更优选145℃以下，最优选140℃以下。同时，必要时也可以进行60～150℃的热定型。The elongation temperature in the case of stretching may be appropriately selected depending on the core component, the extrapolated melting initiation temperature of the polymer of the sheath component, and the strength and elongation of the fiber after stretching, and is preferably 50 to 150 °C. When the stretching temperature is 50° C. or higher, the yarn to be stretched can be sufficiently preheated, and the thermal deformation during stretching is uniform, and generation of fine spots can be suppressed. The stretching temperature is more preferably 60 ° C or higher, and most preferably 70 ° C or higher. On the other hand, when the stretching temperature is 150° C. or less, it is possible to suppress the fusion between the fibers and the thermal decomposition due to the contact with the heating roller, and the engineering passability and quality are good. At the same time, since the fiber on the extension roller has good lubricity, it can suppress the broken yarn and perform stable extension. The stretching temperature is more preferably 145 ° C or lower, and most preferably 140 ° C or lower. At the same time, heat setting at 60 to 150 ° C can be performed if necessary.
延伸时的延伸倍率，根据延伸前纤维的伸度、延伸后纤维的强度和伸度等可以进行相应的选择，优选1.02～7.0倍。延伸倍率在1.02倍以上的话，通过延伸纤维的强度以及伸度等机械特性提高。延伸倍率更优选1.2倍以上，最优选1.5倍以上。另一方面，延伸倍率在7.0倍以下的话，能抑制延伸时的断丝，进行安定的延伸。延伸倍率更优选6.0倍以下，最优选5.0倍以下。The stretching ratio at the time of stretching can be appropriately selected depending on the elongation of the fiber before stretching, the strength and elongation of the fiber after stretching, and the like, and is preferably 1.02 to 7.0 times. When the stretching ratio is 1.02 times or more, the mechanical properties such as strength and elongation of the expanded fiber are improved. The stretching ratio is more preferably 1.2 times or more, and most preferably 1.5 times or more. On the other hand, when the stretching ratio is 7.0 or less, it is possible to suppress breakage during stretching and to perform stable extension. The stretching ratio is more preferably 6.0 times or less, and most preferably 5.0 times or less.
延伸时的延伸速度，根据延伸方法是一段工程法还是二段工程法中的任何一种可以进行相应的选择。一段工程法的场合，上述纺丝速度的高速罗拉的速度与延伸速度相当。二段工程法进行延伸的场合的延伸速度优选为30～1000m/分。延伸速度在30m/分以上的话，走行丝条安定，能够抑制断丝。二段工程法延伸的场合的延伸速度更优选50m/分以上，最优选为100m/分以上。另一方面，延伸速度在1000m/分以下的话，能够抑制延伸时的断丝，进行安定延伸。二段工程法进行延伸的场合的延伸速度更优选为900m/分以下，最优选为800m/分以下。The extension speed at the time of extension can be selected according to whether the extension method is one of the engineering method or the second-stage engineering method. In the case of a section of engineering, the speed of the high speed roller of the above spinning speed is equivalent to the speed of extension. The extension speed in the case where the two-stage engineering method is extended is preferably 30 to 1000 m/min. When the extension speed is 30 m/min or more, the running yarn is stable and the yarn breakage can be suppressed. The elongation speed in the case where the two-stage engineering method is extended is more preferably 50 m/min or more, and most preferably 100 m/min or more. On the other hand, when the stretching speed is 1000 m/min or less, it is possible to suppress breakage during stretching and to perform stable extension. The elongation speed in the case where the two-stage engineering method is extended is more preferably 900 m/min or less, and most preferably 800 m/min or less.
进行假捻加工的场合，除选择只采用1段加热器即所谓的高弹加工以外，还可以选择采用1段加热器和2段加热器即所谓的低弹加工。加热器的加热方法可以采用接触式或非接触式。假捻加工机具体的可以列举的有，摩擦磁盘式、皮带轮式、别针式等，但并不限于上述列举。In the case of false twisting, in addition to the so-called high-elastic processing using only one-stage heater, a one-stage heater and a two-stage heater, so-called low-elastic processing, can be selected. The heating method of the heater can be contactless or non-contact. Specific examples of the false twisting machine include a friction disk type, a pulley type, a pin type, and the like, but are not limited to the above examples.
假捻加工进行的场合的加热器的温度，根据芯成分、鞘成分聚合物的外推熔融起始温度可以进行相应的选择，优选为120～210℃。加热器温度在120℃以上的话，对供给假捻加工的丝条能进行充分地预热，伴随着延伸的热变形均一，能抑制纤度斑的发生。加热器的温度更优选为140℃ 以上，最优选为160℃以上。另一方面，加热器的温度在210℃以下的话，由于能够抑制因与加热器的接触引起的纤维间的融着以及热分解，断丝以及对加热器的污染减少，工程通过性及品质良好。加热器的温度更优选200℃以下，最优选190℃以下。The temperature of the heater in the case where the false twist processing is performed can be appropriately selected depending on the core component and the extrapolated melting onset temperature of the sheath component polymer, and is preferably 120 to 210 °C. When the heater temperature is 120 ° C or more, the yarn for the false twist processing can be sufficiently preheated, and the thermal deformation accompanying the extension is uniform, and the occurrence of the fineness can be suppressed. The temperature of the heater is more preferably 140 ° C The above is most preferably 160 ° C or higher. On the other hand, when the temperature of the heater is 210 ° C or less, it is possible to suppress the fusion between the fibers and the thermal decomposition caused by the contact with the heater, and the wire breakage and the contamination of the heater are reduced, and the engineering passability and quality are good. . The temperature of the heater is more preferably 200 ° C or lower, and most preferably 190 ° C or lower.
进行假捻加工的场合的延伸倍率，根据假捻加工前的纤维的伸度、假捻加工后纤维的强度及伸度等可以进行适当的选择，优选为1.01～2.5倍。延伸倍率为1.01倍以上的话，通过延伸纤维的强度及伸度等机械特性提高。延伸倍率更优选1.2倍以上，最优选1.5倍以上。另一方面，延伸倍率在2.5倍以下的话，能够抑制假捻加工时的断丝，可以进行安定的假捻加工。延伸倍率更优选2.2倍以下，最优选2.0倍以下。The stretching ratio in the case of the false twisting processing can be appropriately selected depending on the elongation of the fiber before the false twist processing, the strength and the elongation of the fiber after the false twist processing, and is preferably 1.01 to 2.5 times. When the stretching ratio is 1.01 or more, the mechanical properties such as strength and elongation of the extended fiber are improved. The stretching ratio is more preferably 1.2 times or more, and most preferably 1.5 times or more. On the other hand, when the stretching ratio is 2.5 or less, the yarn breakage during the false twist processing can be suppressed, and the stable false twist processing can be performed. The stretching ratio is more preferably 2.2 times or less, and most preferably 2.0 times or less.
进行假捻加工的场合的加工速度，可以进行适当的选择，优选为200～1000m/分。加工速度在200m/分以上的话，丝条走行安定，能抑制断丝。加工速度更优选300m/分以上，最优选400m/分以上。另一方面，加工速度在1000m/分以下的话，能够抑制假捻加工时的断丝，可以进行安定的假捻加工。加工速度更优选900m/分以下，最优选800m/分以下。The processing speed in the case of performing the false twist processing can be appropriately selected, and is preferably 200 to 1000 m/min. When the processing speed is 200 m/min or more, the yarn is stable and can suppress broken yarn. The processing speed is more preferably 300 m/min or more, and most preferably 400 m/min or more. On the other hand, when the processing speed is 1000 m/min or less, the yarn breakage during the false twist processing can be suppressed, and the stable false twist processing can be performed. The processing speed is more preferably 900 m/min or less, and most preferably 800 m/min or less.
本发明中，必要时，可以对纤维或者纤维构造体任一状态时进行染色。本发明中，染料优先采用分散染料。In the present invention, if necessary, it is possible to dye the fiber or the fiber structure in any state. In the present invention, the dye is preferably a disperse dye.
本发明的染色方法，没有进行特别的限定，根据公知的方法，可以采用液流染、滚筒式染、轴染以及卷染等。The dyeing method of the present invention is not particularly limited, and according to a known method, liquid flow dyeing, drum dyeing, shaft dyeing, and dyeing can be employed.
本发明中，对燃料的浓度和染色温度不在特别限定，可以采用公知的方法。同时，必要时，可以在染色加工前进行精炼，也可以在染色加工后进行还原洗净。In the present invention, the concentration of the fuel and the dyeing temperature are not particularly limited, and a known method can be employed. At the same time, if necessary, it can be refined before the dyeing process, or after the dyeing process.
本发明的芯鞘型复合纺丝纤维及由其形成的假捻丝、纤维构造体的吸湿性优异。因此，可以用于要求舒适性及品质的用途。例如，一般衣料用途、运动衣料用途、寝具用途、室内装饰用途、资材用途等，但并不限于上述列举。The core-sheath type composite spun fiber of the present invention and the pseudofilament yarn and the fiber structure formed therefrom are excellent in hygroscopicity. Therefore, it can be used for applications requiring comfort and quality. For example, general clothing use, sports clothing use, bedding use, interior decoration use, and use of materials, etc., are not limited to the above list.
下面，通过实施例对本发明作详细地说明。同时，实施例中的各特性值通过以以下的方法测试。Hereinafter, the present invention will be described in detail by way of examples. Meanwhile, each characteristic value in the examples was tested by the following method.
A.芯成分、鞘成分的吸湿率差(△MR)A. Difference in moisture absorption rate of core component and sheath component (ΔMR)
将芯成分或鞘成分的聚合物作为样品，先在60℃下热风干燥30分钟后，在温度20℃、湿度65％RH的ESPEC社制恒温恒湿机LHU-123内静置24小时，测定聚合物的重量(W1)；接着在温度30℃、湿度90％RH的恒温恒湿机内静置24小时，测定聚合物的重量为(W2)。然后，在105℃下热风干燥2小时，测定绝干后的聚合物重量为(W3)。根据下记公式用聚合物的重量W1、W3计算出从绝干状态到20℃、湿度65％RH氛围下静置24小时后的吸湿率MR1(％)，根据下记公式用聚合物的重量W2、W3计算出绝干状态到30℃、湿度90％RH氛围下静置24小时后的吸湿率MR2(％)，然后根据下记公式算出吸湿率差(△MR)。并且，1个样品测定5回，取平均值作为吸湿率差(△MR)。The polymer of the core component or the sheath component was sampled by hot air drying at 60 ° C for 30 minutes, and then allowed to stand in a constant temperature and humidity machine LHU-123 manufactured by ESPEC at a temperature of 20 ° C and a humidity of 65% RH for 24 hours. The weight of the polymer (W1) was followed by standing in a constant temperature and humidity machine at a temperature of 30 ° C and a humidity of 90% RH for 24 hours, and the weight of the polymer was determined to be (W2). Then, it was dried by hot air at 105 ° C for 2 hours, and the weight of the polymer after absolute drying was measured as (W3). According to the following formula, the moisture absorption rate MR1 (%) after standing for 24 hours from the dry state to 20 ° C and a humidity of 65% RH was calculated from the weights W1 and W3 of the polymer, and the weight of the polymer was used according to the following formula. W2 and W3 calculated the moisture absorption rate MR2 (%) after leaving the dry state to 30 ° C and a humidity of 90% RH for 24 hours, and then calculated the moisture absorption rate difference (ΔMR) according to the following formula. Further, one sample was measured five times, and the average value was taken as the moisture absorption rate difference (ΔMR).
MR1(％)＝{(W1-W3)/W3}×100，MR1(%)={(W1-W3)/W3}×100,
MR2(％)＝{(W2-W3)/W3}×100，MR2(%)={(W2-W3)/W3}×100,
吸湿率差(△MR)(％)＝MR2-MR1。Hygroscopic rate difference (ΔMR) (%) = MR2-MR1.
B.外推熔融起始温度B. Extrapolating the melting initiation temperature
取芯成分、鞘成分的聚合物以及通过实施例得到的纤维作为试样，采用TA Instruments社制的Q2000型差示扫描量热仪(DSC)，测定外推熔融起始温度。首先，在氮气氛围下将5mg的试样以50℃/分的升温速度从0℃升温至280℃，在280℃的状态下保持5分钟消除热历史。然后，从280℃骤冷至0℃，再次以3℃/分的速度从0℃升温至280℃，温度变调幅度为±1℃，温度变调周期60秒后进行升温，进行TMDSC的测定。根据JISK7121：1987(塑料的转变温度的测定方法)9.1的标准，根据第2回升温过程中观测到的融解峰算出外推熔融起始温度。1个样品测定3回，其平均值作为外推熔融起始温度。并且，观测到多个融解峰的场合，根据最低温侧的融解峰算出外推熔融起始温度。 The core component, the sheath component polymer, and the fiber obtained in the example were used as a sample, and the extrapolation melting onset temperature was measured using a Q2000 type differential scanning calorimeter (DSC) manufactured by TA Instruments. First, a sample of 5 mg was heated from 0 ° C to 280 ° C at a temperature increase rate of 50 ° C / min in a nitrogen atmosphere, and the heat history was maintained at 280 ° C for 5 minutes. Then, it was quenched from 280 ° C to 0 ° C, and further heated from 0 ° C to 280 ° C at a rate of 3 ° C / min. The temperature change range was ±1 ° C, and the temperature was changed for 60 seconds, and then the temperature was raised to measure TMDSC. The extrapolated melting onset temperature was calculated from the melting peak observed during the second temperature rise in accordance with the standard of JISK7121:1987 (method of measuring the transition temperature of plastic). One sample was measured three times, and the average value was used as the extrapolation melting onset temperature. Further, when a plurality of melting peaks are observed, the extrapolated melting onset temperature is calculated from the melting peak on the lowest temperature side.
C.芯/鞘复合比例C. Core/sheath composite ratio
通过作为芯鞘型复合纤维原料的芯成分的重量与鞘成分的重量，算出芯/鞘复合比(重量比)。The core/sheath composite ratio (weight ratio) was calculated from the weight of the core component as the core-sheath type composite fiber raw material and the weight of the sheath component.
D.断丝D. broken wire
根据各实施例所记载的假捻条件，对10小时加工期间断丝的次数进行计数，作为断丝回数。According to the false twist conditions described in the respective examples, the number of broken wires during the 10-hour processing was counted as the number of broken wires.
E.堆积物E. Deposits
根据各实施例所记载的假捻条件，对10小时加工后延伸假捻机的加热器、冷却板、摩擦磁盘、导丝器进行观察，[堆积物基本没有]计为◎，[堆积物有少许]计为○，[堆积物多]计为△，[堆积物非常多]计为×，○与◎为合格。According to the false twist conditions described in the respective examples, the heater, the cooling plate, the friction disk, and the yarn guide of the extended false twisting machine after 10 hours of processing were observed, and [the deposit was substantially absent] was counted as ◎, [the deposit was A little is counted as ○, [more deposits] is counted as Δ, [very much deposit] is counted as ×, and ○ and ◎ are qualified.
F.纤度F. fineness
在温度20℃、湿度65％RH的环境下，用INTEC制的电动检尺机，取实施例所得的纤维100m。测定所得到的重量，用下记公式计算出纤度(dtex)。并且，1个样品测定5回，取平均值作为纤度。The fiber obtained in the examples was taken in an environment of a temperature of 20 ° C and a humidity of 65% RH using an electric scale machine manufactured by INTEC. The obtained weight was measured, and the fineness (dtex) was calculated by the following formula. Further, one sample was measured five times, and an average value was taken as the fineness.
纤度(dtex)＝纤维100m的重量(g)×100。Denier (dtex) = weight (g) of the fiber 100 m × 100.
G.强度、伸度G. Strength, elongation
强度及伸度是指，通过实施例得到的纤维作为试料，通过JIS L1013：2010(化学纤维长丝试验方法)8.5.1基准算出。在温度20℃、湿度65％RH的环境下，用Orientec社制的テンシロンUTM-III-100型仪器，初期试料场20cm、引张速度20cm/分的条件下进行引张试验。最大荷重时所示点的应力(cN)除以纤度(dtex)计算出强度(cN/dtex)，用最大荷重所示点的伸长(L1)与初期试料长(L0)通过下记公式算得伸度(％)。并且，一个样品测试10回，其平均值作为强度与伸度。The strength and the elongation are calculated by the fiber obtained in the examples as a sample, and are calculated in accordance with JIS L1013:2010 (Chemical Fiber Filament Test Method) 8.5.1. The tensile test was carried out under the conditions of a temperature of 20 ° C and a humidity of 65% RH using a テンシロンUTM-III-100 instrument manufactured by Orientec, under the condition of an initial sample field of 20 cm and an extension speed of 20 cm/min. The stress (cN) at the point indicated by the maximum load is divided by the fineness (dtex) to calculate the strength (cN/dtex), and the elongation (L1) at the point indicated by the maximum load and the initial sample length (L0) are passed through the following formula. Calculated the degree of stretch (%). Also, one sample was tested 10 times, and the average value was taken as the strength and the elongation.
伸度(％)＝{(L1-L0)/L0}×100。The elongation (%) = {(L1 - L0) / L0} × 100.
H.纤维横截面外周长R、露出在表面部分的芯成分长度的最大值rM、露出在表面部分的芯成分的长度总和rS、rM/R、rS/RH. fiber outer peripheral length R, maximum value of core component length exposed at the surface portion r M , total length of core components exposed at the surface portion r S , r M /R, r S /R
将实施例所得的纤维用环氧树脂进行包埋，用Reichert社制的FC·4E型Cryo sectioning system进行冻结，在具备砖石小刀的Reichert-Nissei ultracut N(凹凸显微镜)下用进行切割。然后，切削表面即纤维横截面在白金-钯金合金下镀气，采用日立制造的S-4000型电子显微镜(SEM)在1000倍下进行观察，拍摄纤维横截面的显微镜照片。从得到的照片中随机取出30张，用图像处理软件(三谷商事制WINROOF)测定所有的纤维横截面外周长、以及所有的露出在表面部分的芯成分的长度后，取30个算出平均值，分别为纤维横截面外周长R、露出在表面部分的芯成分的最大长度rM、露出在表面部分的芯成分的长度总和rS。The fiber obtained in the example was embedded in an epoxy resin, frozen by a FC·4E Cryo sectioning system manufactured by Reichert Co., Ltd., and cut under a Reichert-Nissei ultracut N (concave-convex microscope) equipped with a masonry knife. Then, the cutting surface, that is, the fiber cross section, was plated under a platinum-palladium-gold alloy, and observed at 1000 times using an S-4000 electron microscope (SEM) manufactured by Hitachi, and a micrograph of the fiber cross section was taken. 30 sheets were randomly taken out from the obtained photographs, and the outer circumference of all the cross-sections of the fibers and the length of all the core components exposed on the surface portions were measured by image processing software (WINROOF), and 30 average values were calculated. They are the outer peripheral length R of the fiber cross-section, the maximum length r M of the core component exposed at the surface portion, and the total length r S of the core component exposed at the surface portion.
并且，各纤维横截面上，露出在表面的芯成分部分是1处的场合，这个部分的长度即为露出在表面部分的芯成分长度的最大值rM以及露出在表面部分的芯成分的长度总和rS。另一方面，各纤维的横截面上，算出露出在表面的芯成分部分有2处以上的场合，各纤维横截面上露出在表面部分的芯成分长度的最大值以及露出在表面部分的芯成分的长度总和后，取30根算平均值，作为露出在表面部分的芯成分长度的最大值rM，及露出在表面部分的芯成分的长度总和rS。Further, in the cross section of each fiber, when the core component portion exposed on the surface is one, the length of this portion is the maximum value r M of the length of the core component exposed at the surface portion and the length of the core component exposed at the surface portion. The sum r S . On the other hand, when two or more core component portions are exposed on the cross section of each fiber, the maximum value of the core component length exposed on the surface portion of each fiber cross section and the core component exposed on the surface portion are obtained. After the sum of the lengths, 30 average values are taken as the maximum value r M of the length of the core component exposed on the surface portion, and the sum of the lengths of the core components exposed at the surface portion r S .
rM/R、rS/R，是通过下记公式用上述算出的纤维横截面的外周长R、露出在表面部分的芯成分长度的最大值rM、露出在表面部分的芯成分的长度总和rS算出。r M /R and r S /R are the outer peripheral length R of the fiber cross section calculated by the above formula, the maximum value r M of the core component length exposed on the surface portion, and the length of the core component exposed on the surface portion. The sum r S is calculated.
纤维横截面外周长R与露出在表面部分的芯成分长度的最大值rM的比rM/R＝rM/R，The ratio r m /R = r M /R of the outer peripheral length R of the fiber cross section to the maximum value r M of the length of the core component exposed at the surface portion,
横截面外周长R与露出在表面部分的芯成分的长度总和rS的比rS/R＝rS/R。The ratio r S /R = r S /R of the total length R S of the cross-sectional outer perimeter R to the core component exposed at the surface portion.
I.精炼后、热水处理后的吸湿率差(△MR)I. Difference in moisture absorption rate after refining and hot water treatment (△MR)
取实施例得到的纤维作为试样，用英光产业制圆编机NCR-BL(釜径3英寸半(8.9cm)、27针)制作2g的筒编物后，在炭酸钠1g/L、含有日华化学制界面活性剂BK-80水溶液中，80℃条件下精炼20分钟后，在60℃条件下热风干燥机内干燥60分钟，得到精炼后的筒编物。同时，将精炼后的筒编物在浴比1：100、处理温度130℃、处理时间60分钟的条件下进行热水处理后，在 60℃的条件下热风干燥机内干燥60分钟后，得到热水处理后的筒编物。The fiber obtained in the example was used as a sample, and 2 g of a cylinder was produced by a NCR-BL (3 inch and a half (8.9 cm), 27 needles) of the Incheon Industrial Co., Ltd., and then contained in sodium carbonate 1 g/L. After refining for 20 minutes at 80 ° C in an aqueous solution of BK-80 surfactant, it was dried in a hot air dryer at 60 ° C for 60 minutes to obtain a cylinder after refining. At the same time, after the refining cylinder is subjected to hot water treatment at a bath ratio of 1:100, a treatment temperature of 130 ° C, and a treatment time of 60 minutes, After drying in a hot air dryer at 60 ° C for 60 minutes, a tubular composition after hot water treatment was obtained.
吸湿率(％)是用精炼后以及热水处理后的筒编物，以JIS L1096：2010(织物及编织物的胚布试验方法)8.10的水分率为基准算出。首先，在60℃下热风干燥30分钟后，在温度20℃、湿度65％RH的ESPEC社制恒温恒湿机LHU-123内静置24小时，测定筒编物的重量(W1)；接着在温度30℃、湿度90％RH的恒温恒湿机内静置24小时，测定筒编物的重量为(W2)。然后，在105℃下热风干燥2小时，测定绝干后的筒编物重量为(W3)。根据下记公式用聚合物的重量W1、W3计算出从绝干状态到20℃、湿度65％RH氛围下静置24小时后的吸湿率MR1(％)，根据下记公式用筒编物的重量W2、W3计算出绝干状态到30℃、湿度90％RH氛围下静置24小时后的吸湿率MR2(％)，然后根据下记公式算出吸湿率差(△MR)。并且，1个样品测定5回，取平均值作为吸湿率差(△MR)。The moisture absorption rate (%) is calculated from the water content of JIS L1096:2010 (the fabric test method of the woven fabric and the woven fabric) 8.10 based on the cylinder knitted fabric after the refining and the hot water treatment. First, it was dried by hot air at 60 ° C for 30 minutes, and then allowed to stand in a constant temperature and humidity machine LHU-123 manufactured by ESPEC at a temperature of 20 ° C and a humidity of 65% RH for 24 hours, and the weight of the package (W1) was measured; The temperature was 30 ° C and the humidity was 90% RH in a constant temperature and humidity machine for 24 hours, and the weight of the cylinder was measured as (W2). Then, it was dried by hot air at 105 ° C for 2 hours, and the weight of the package after drying was measured as (W3). According to the following formula, the moisture absorption rate MR1 (%) after standing for 24 hours from the dry state to 20 ° C and humidity 65% RH atmosphere was calculated from the weights W1 and W3 of the polymer, and the tube was knitted according to the following formula. The weights W2 and W3 were calculated from the absolute dry state to a moisture absorption rate MR2 (%) after standing for 24 hours in an atmosphere of 30 ° C and a humidity of 90% RH, and then the moisture absorption rate difference (ΔMR) was calculated according to the following formula. Further, one sample was measured five times, and the average value was taken as the moisture absorption rate difference (ΔMR).
MR1(％)＝{(W1-W3)/W3}×100，MR1(%)={(W1-W3)/W3}×100,
MR2(％)＝{(W2-W3)/W3}×100，MR2(%)={(W2-W3)/W3}×100,
吸湿率差(△MR)(％)＝MR2-MR1。Hygroscopic rate difference (ΔMR) (%) = MR2-MR1.
J.融着J. Melting
上述I得到的热水处理后的筒编物用白金-钯金合金进行镀气，日立社制走查型电子显微镜(SEM)S-4000型在1000倍的条件下观察，随机拍摄5个视野的显微镜照片。得到的5枚照片中，融着的部位的合计作为融着。The hot-water treated tubular package obtained by the above I was gas-plated with a platinum-palladium-gold alloy, and was observed under a 1000-fold condition by a Hitachi electronic microscope (SEM) S-4000 model, and 5 fields of view were randomly taken. Microscope photo. Among the five photographs obtained, the total of the melted parts was melted.
K.鞘破裂K. sheath rupture
上述I得到的热水处理后的筒编物用白金-钯金合金进行镀气，日立社制走查型电子显微镜(SEM)S-4000型在1000倍的条件下观察，随机拍摄5个视野的显微镜照片。得到的5枚照片中，鞘破裂的部位的合计作为鞘破裂处。The hot-water treated tubular package obtained by the above I was gas-plated with a platinum-palladium-gold alloy, and was observed under a 1000-fold condition by a Hitachi electronic microscope (SEM) S-4000 model, and 5 fields of view were randomly taken. Microscope photo. Among the five photographs obtained, the total number of sites where the sheath was broken was used as a sheath rupture.
L.均染性L. Level dyeing
与上述I同样的方法制得精炼后的筒编物，在160℃条件下热定型2分钟，对干热定型后的筒编物，在添加有1.3wt％日本化药制的分散染料Kayalon Polyester Blue UT-YA、调整PH值为5.0的染色液中，浴比1：100、染色温度130℃，染色时间60分钟的条件下进行染色。同时，鞘成分是阳离子可染聚酯的场合，在添加有1.0wt％日本化药制备的阳离子染料Kayacrtyl Blue 2RL-ED、调整PH值为4.0的染色液中，浴比为1：100、染色温度130℃、染色时间为60分钟的条件下进行染色。The refining cylinder was prepared in the same manner as in the above I, and heat-set at 160 ° C for 2 minutes. After the dry heat setting, the dispersion was added with 1.3 wt% of the disperse dye Kayalon Polyester made by Nippon Kayaku. Blue UT-YA was adjusted in a dyeing solution having a pH of 5.0 at a bath ratio of 1:100, a dyeing temperature of 130 ° C, and a dyeing time of 60 minutes. Meanwhile, when the sheath component is a cationic dyeable polyester, the bath ratio is 1:100, dyeing in a dyeing solution adjusted to a pH of 4.0 with a cationic dye Kayacrtyl Blue 2RL-ED prepared by adding 1.0 wt% of a Japanese chemical. The dyeing was carried out under the conditions of a temperature of 130 ° C and a dyeing time of 60 minutes.
染色后的筒编物，经过5位有5年以上品质判定经验的检测员的合议，[染色非常均一，完全没有染斑]时判为◎，[染色基本均一，基本上没有染斑]判定为○，[不能说完全均一染色，稍微有些淡淡的染斑]判定为△，[没有均一染色，有明显的染斑]判定为×，○与◎的场合判定为合格。The dyed tube-shaped fabric was judged by the inspectors of five people who had more than 5 years of quality judgment experience. When the dyeing was very uniform, there was no staining at all, it was judged as ◎, [staining was basically uniform, basically no staining] ○, [Cannot say that the uniform dyeing, slightly faint staining] was judged as Δ, [no uniform dyeing, and there was significant staining], and it was judged as ×, and ○ and ◎ were judged as pass.
M.品质M. Quality
上述L制得的染色后的筒编物，经过5位有5年以上品质判定经验的检测员的合议，[完全没有毛羽、品质极其优异]时判为◎，[基本没有毛羽，品质优异]判定为○，[有毛羽、品质低下]判定为△，[有很多毛羽、品质极其低下]判定为×，○与◎的场合判定为合格。The dyed cylinders obtained by the above-mentioned L are judged by the inspectors who have 5 years of experience in quality judgment, and [when there is no hairiness and excellent quality], it is judged as ◎, [there is basically no hairiness, and the quality is excellent] When it was judged as ○, [with hairiness and low quality] was judged as Δ, [there were many hairiness and the quality was extremely low], and it was judged as ×, and ○ and ◎ were judged as pass.
N.热水处理前后复合纤维的色调变化值△bN. Hue change value of composite fiber before and after hot water treatment △b
将与前述I项同样的方法制得的筒编物在浴比1：100、处理温度130℃、处理时间20分钟的条件下进行热水处理后，在60℃的热风干燥机内干燥60分钟，形成热水处理后的筒编物。将热水处理前与热水处理后的筒编物分别用色差计(USTC-datacolor)进行测定，热水处理前的筒编物b值为b1，热水处理后的筒编物b值为b2，根据如下式子算出热水处理前后的△b值，△b＝b2-b1。测试5回取平均值。The tubular product prepared in the same manner as in the above item I was subjected to hot water treatment at a bath ratio of 1:100, a treatment temperature of 130 ° C, and a treatment time of 20 minutes, and then dried in a hot air dryer at 60 ° C for 60 minutes. Forming a tubular braid after hot water treatment. The cylinders before and after the hot water treatment were respectively measured by a color difference meter (USTC-datacolor), the b value of the cylinder before the hot water treatment was b1, and the value of the drum after the hot water treatment was b value. B2, the Δb value before and after the hot water treatment is calculated according to the following formula, Δb=b2-b1. Test 5 back to the average.
实施例1Example 1
以共聚合了30wt％数均分子量8300g/mol的聚乙二醇(三洋化成工业制PEG6000S)的聚对苯二甲酸乙二醇酯作为芯成分，以聚对苯二甲酸乙二醇酯(IV＝0.66)作为鞘成分，分别在150℃条 件下真空干燥12小时后，按芯成分20wt％、鞘成分80wt％的配比向螺杆型复合纺丝机内供给分别进行熔融，在纺丝温度285℃、吐出量为36g/分下从芯鞘型复合用纺丝喷丝板(孔数：36、断面形状：图1(a))吐出，纺出丝条。纺出的丝条在风温20℃、风速20m/分的冷风下进行冷却，通过给油装置进行给油收束，2500m/分回转的第1段罗拉进行拉伸，通过与第一段罗拉同样的回转速度的第2段罗拉卷取，得到144dtex-36f的未延伸丝。然后，采用延伸假捻机(加捻部：摩擦磁盘式、加热器部：接触式)，将得到的未延伸丝在加热器温度170℃、倍率1.7倍的条件下进行延伸假捻，得到84dtex-36f的假捻丝。Polyethylene terephthalate (30 wt% of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd. PEG 6000S) having a number average molecular weight of 8300 g/mol was copolymerized as a core component, and polyethylene terephthalate (IV) was used. =0.66) as a sheath component, respectively at 150 ° C After vacuum drying for 12 hours, the mixture was supplied to a screw-type composite spinning machine at a ratio of 20% by weight of the core component and 80% by weight of the sheath component, and melted at a spinning temperature of 285 ° C and a discharge amount of 36 g / min. The sheath-type composite spinneret (number of holes: 36, sectional shape: Fig. 1 (a)) was discharged, and the yarn was spun. The spun yarn is cooled under cold air with a wind temperature of 20 ° C and a wind speed of 20 m / min. The oil feed device is subjected to oil-contracting, and the first section of the roller is rotated at 2,500 m/min, and the first section of the roller is passed. The second stage roller of the same turning speed is taken up to obtain an unstretched yarn of 144 dtex-36f. Then, using an extension false twisting machine (twisting section: friction disk type, heater part: contact type), the obtained unstretched yarn was subjected to extension false twisting at a heater temperature of 170 ° C and a magnification of 1.7 times to obtain 84 dtex. -36f fake silk.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表1所示。假捻时的断丝回数为0回，假捻后加热器及导轨上的堆积物几乎未发现，工程通过性极其良好。同时，热水处理后吸湿性基本没有降低，热水处理后吸湿性也良好。并且，纤维间的融着未发现，鞘虽然有少许的破裂，但是均染性、品质都达到合格水平。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 1. The number of broken wires at the time of false twist is 0, and the deposits on the heater and the guide rail are hardly found after the false twist, and the engineering passability is extremely good. At the same time, the hygroscopicity after the hot water treatment is not substantially lowered, and the hygroscopicity after the hot water treatment is also good. Moreover, the fusion between the fibers was not found, and although the sheath was slightly broken, the level of dyeing and quality reached an acceptable level.
实施例2～5Examples 2 to 5
芯/鞘复合比例按表1所示变更以外，其余与实施例1同样的方法制得假捻丝。The false twist yarn was obtained in the same manner as in Example 1 except that the core/sheath composite ratio was changed as shown in Table 1.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表1所示。芯成分与鞘成分的复合比例变更的场合，工程通过性及布帛特性均良好。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 1. When the composite ratio of the core component and the sheath component is changed, the engineering passability and the fabric properties are good.
实施例6～10Examples 6 to 10
断面形状按表1所示进行变更以外，其余与实施例1同样的方法制得假捻丝。A false twist yarn was obtained in the same manner as in Example 1 except that the cross-sectional shape was changed as shown in Table 1.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表1所示。断面形状变更的场合，工程通过性、布帛特性均良好。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 1. When the cross-sectional shape is changed, the engineering passability and the fabric characteristics are good.
实施例11、12Examples 11, 12
实施例11的喷丝板孔数为72、实施例12吐出量为28g/分、喷丝板的孔数变为72以外，其余与实施例1同样的方法制得假捻丝。In the same manner as in Example 1, the false twist yarn was obtained in the same manner as in Example 1 except that the number of the orifices of the spinneret of Example 11 was 72, the discharge amount of Example 12 was 28 g/min, and the number of the orifices of the spinneret was changed to 72.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表1所示。纤度与单丝纤度变小的情况下，工程通过性与布帛特性也均良好。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 1. When the fineness and the fineness of the single yarn become small, the engineering passability and the fabric characteristics are also good.
实施例13～19、比较例1～5Examples 13 to 19 and Comparative Examples 1 to 5
芯成分的共聚合成分聚乙二醇的数均分子量、共聚合率以及芯/鞘复合比例如表2所示，比较例3除了延伸假捻机的加热器温度变为150℃以外，其余与实施例1同样的方法制得假捻丝。The number average molecular weight, the copolymerization ratio, and the core/sheath recombination ratio of the polyethylene glycol copolymerization component of the core component are shown in Table 2, respectively. In Comparative Example 3, except that the heater temperature of the extension false twister was 150 ° C, In the same manner as in Example 1, a false twist yarn was obtained.
得到纤维的纤维特性、布帛特性以及工程通过性的评价结果如表2所示。实施例13～19，聚乙二醇的数均分子量、共聚合率以及芯/鞘复合比例变更的场合，工程通过性、布帛的特性均良好。比较例1精炼后的吸湿性降低，其结果是热水处理后的吸湿性也极其差。比较例2虽然精炼后的吸湿性比较高，热水处理后吸湿性大幅度下降，热水处理后吸湿性低，并且工程通过性不良，均染性及品质都未达到合格水平。比较例3芯成分的外推熔融起始温度低，同时，未检测出比较例4芯成分的外推熔融起始温度，因为不具有结晶性，断丝及堆积物极其多，工程通过性极其不良。同时，发现有多处融着与鞘破裂，均染性及品质都未达到合格水平。并且，观察融着与鞘破裂的显微镜照片，发现芯成分吸湿性聚合物有溶出，热水处理后芯成分吸湿性聚合物溶出导致热水处理后吸湿性大幅下降，热水处理后吸湿性极其低。比较例5与比较例2同样，精炼后吸湿性虽然高，热水处理后吸湿性大幅度降低，热水处理后吸湿性低，并且工程通过性不良、均染性及品质都未达到合格水平。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 2. In Examples 13 to 19, when the number average molecular weight, the copolymerization ratio, and the core/sheath recombination ratio of the polyethylene glycol were changed, the properties of the workability and the fabric were good. In Comparative Example 1, the hygroscopicity after refining was lowered, and as a result, the hygroscopicity after hot water treatment was extremely poor. In Comparative Example 2, although the hygroscopicity after refining was relatively high, the hygroscopicity after the hot water treatment was greatly lowered, the hygroscopicity after the hot water treatment was low, and the engineering passability was poor, and the leveling property and the quality did not reach the acceptable level. In the comparative example 3, the extrapolation melting onset temperature of the core component was low, and the extrapolation melting onset temperature of the core component of Comparative Example 4 was not detected, because there was no crystallinity, the filaments and deposits were extremely large, and the engineering passability was extremely high. bad. At the same time, it was found that there were many fusions and sheath ruptures, and the level of dyeing and quality did not reach the qualified level. Further, by observing the micrograph of the fusion and the sheath rupture, it was found that the core component hygroscopic polymer was eluted, and the core component hygroscopic polymer was eluted after the hot water treatment, and the hygroscopicity was greatly lowered after the hot water treatment, and the hygroscopicity after the hot water treatment was extremely high. low. In Comparative Example 5, similarly to Comparative Example 2, the hygroscopicity after refining was high, the hygroscopicity after hot water treatment was greatly lowered, the hygroscopicity after hot water treatment was low, and the poor engineering passability, leveling property, and quality did not reach the acceptable level. .
实施例20～28、比较例6～8Examples 20 to 28 and Comparative Examples 6 to 8
聚乙二醇的数均分子量、共聚合率如表3所示共聚合所得的聚对苯二甲酸丁二醇酯作为芯成分、聚对苯二甲酸丁二醇酯(IV＝0.66)作为鞘成分，纺丝温度为255℃，芯/鞘复合比例如表3所示，实施例22、比较例7、8除了延伸假捻机的加热器温度变更为150℃以外，其余按实施例7同样的方法制得假捻丝。The number average molecular weight and the copolymerization ratio of the polyethylene glycol are as shown in Table 3, and the polybutylene terephthalate obtained by copolymerization as a core component and polybutylene terephthalate (IV = 0.66) is used as a sheath. The composition, the spinning temperature was 255 ° C, and the core/sheath composite ratio was as shown in Table 3. In Example 22 and Comparative Examples 7 and 8, the temperature of the heater of the extension false twisting machine was changed to 150 ° C, and the same procedure as in Example 7 was carried out. The method produces a false twist.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表3所示。实施例20～28 中，聚乙二醇数均分子量、共聚合率以及芯/鞘复合比例变更的场合，工程通过性及布帛特性均良好。比较例6精炼后的吸湿性低，其结果是热水处理后的吸湿性也极其差。比较例7虽然精炼后的吸湿性高，热水处理后的吸湿性大幅度降低，热水处理后的吸湿性低，并且工程通过性不良，均染性及品质都未达到合格的水平。由于比较例8芯成分的外推熔融起始温度低，断丝及堆积物非常多，工程通过性也极其不良。并且，精炼后的吸湿性低，其结果是热水处理后的吸湿性极其差。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 3. Examples 20-28 In the case where the number average molecular weight, the copolymerization ratio, and the core/sheath recombination ratio of the polyethylene glycol were changed, the engineering passability and the fabric properties were good. In Comparative Example 6, the hygroscopicity after refining was low, and as a result, the hygroscopicity after hot water treatment was extremely poor. In Comparative Example 7, although the hygroscopicity after refining was high, the hygroscopicity after hot water treatment was largely lowered, the hygroscopicity after hot water treatment was low, and the engineering passability was poor, and the leveling property and quality were not at a satisfactory level. Since the extrapolation melting initiation temperature of the core component of Comparative Example 8 was low, there were many broken wires and deposits, and the engineering passability was extremely poor. Further, the hygroscopicity after refining is low, and as a result, the hygroscopicity after hot water treatment is extremely poor.
实施例29～31Examples 29 to 31
实施例29、30中芯成分为数均分子量3400g/mol的聚乙二醇(三洋化成工业制PEG4000S)共聚合得到的尼龙6，实施例31除了ARKEMA制“PEBAX MH1657”变更以外，其余按实施例1同样的方法制得假捻丝。In the examples 29 and 30, the core component was nylon 6 obtained by copolymerization of polyethylene glycol having a number average molecular weight of 3,400 g/mol (PEG4000S manufactured by Sanyo Chemical Industries Co., Ltd.), and Example 31 was changed except for the "PEBAX MH1657" manufactured by ARKEMA. 1 The same method was used to make false silk.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表4所示。芯成分变为聚醚酰胺的场合，工程通过性及布帛特性均良好。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 4. When the core component is changed to a polyether amide, both workability and fabric properties are good.
实施例32Example 32
芯成分为东丽制“PAS-40N”，除了延伸假捻机的加热器温度变更为150℃以外，其余按实施例1同样的方法制得假捻丝。The core component was "PAS-40N" manufactured by Toray Industries, and the false twist yarn was obtained in the same manner as in Example 1 except that the temperature of the heater of the extension false twisting machine was changed to 150 °C.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表4所示。芯成分变为聚醚酯酰胺的场合，工程通过性及布帛特性均良好。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 4. When the core component is changed to a polyether ester amide, both workability and fabric properties are good.
实施例33Example 33
除了鞘成分为共聚合了1.5mol％的间苯二甲酸-5-磺酸钠以及1.0wt％的数均分子量1000g/mol聚乙二醇(三洋化成工业制PEG1000)的聚对苯二甲酸乙二醇酯(IV＝0.66)以外，其余按实施例1同样的方法制得假捻丝。In addition to the sheath component, 1.5 mol% of sodium isophthalate-5-sulfonate and 1.0 wt% of polyethylene terephthalate having a number average molecular weight of 1000 g/mol polyethylene glycol (Sanyo Chemical Co., Ltd. PEG 1000) were copolymerized. A false twist yarn was obtained in the same manner as in Example 1 except for the glycol ester (IV = 0.66).
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表4所示。鞘成分使用阳离子可染聚酯的场合，工程通过性及布帛特性均良好。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 4. When the sheath component is a cationic dyeable polyester, the engineering passability and the fabric properties are good.
比较例9Comparative Example 9
除了断面形状变更为如图2所示以外，其余按实施例1同样的方法制得假捻丝。A false twist yarn was obtained in the same manner as in Example 1 except that the cross-sectional shape was changed as shown in Fig. 2 .
得到的纤维的纤维特性、布帛特性及工程通过性的评价结果如表4所示。没有断丝，几乎未发现堆积物，工程通过性良好。但是，虽然没有融着，由于芯成分吸湿性聚合物完全被鞘成分包裹，热水处理时随着吸湿性聚合物的体积膨胀，发现多处鞘部分破裂。其结果是，均染性及品质都未达到合格水平。Table 4 shows the results of fiber properties, fabric properties, and engineering passability of the obtained fibers. There is no broken wire, almost no deposits are found, and the engineering passability is good. However, although there was no fusion, since the core component hygroscopic polymer was completely covered by the sheath component, and the volume of the hygroscopic polymer was expanded during hot water treatment, it was found that a plurality of sheath portions were broken. As a result, the level of dyeing and quality did not reach the acceptable level.
比较例10、11Comparative Examples 10, 11
参考特开平6-200473号公报所记载的实施例2、4，比较例10中芯成分为共聚合了17wt％平均分子量3000g/mol的聚乙二醇的聚对苯二甲酸乙二醇酯，鞘成分为聚对苯二甲酸乙二醇酯(IV＝0.66)；比较例11中芯成分为共聚合了17wt％平均分子量3000g/mol的聚乙二醇的聚对苯二甲酸乙二醇酯，鞘成分为尼龙6，除了芯/鞘复合比例如表4所示变更以外，按实施例7同样的方法制得假捻丝。With reference to Examples 2 and 4 described in JP-A-6-200473, the core component of the comparative example 10 is polyethylene terephthalate copolymerized with polyethylene glycol having an average molecular weight of 3000 g/mol of 17 wt%. The sheath component was polyethylene terephthalate (IV=0.66); the core component of Comparative Example 11 was polyethylene terephthalate copolymerized with 17 wt% polyethylene glycol having an average molecular weight of 3000 g/mol. The sheath component was nylon 6, and a false twist yarn was obtained in the same manner as in Example 7 except that the core/sheath composite ratio was changed as shown in Table 4.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表4所示。比较例10、11断丝及堆积物多，工程通过性不良。同时，发现融着及鞘破裂，均染性及品质都没达到合格水平。并且，观测融着与鞘破裂的显微镜照片，发现芯成分吸湿性聚合物有溶出，热水处理后芯成分吸湿性聚合物溶出导致热水处理后吸湿性大幅度下降，热水处理后吸湿性低。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 4. In Comparative Examples 10 and 11, there were many broken wires and deposits, and the engineering passability was poor. At the same time, it was found that the fusion and sheath rupture did not reach the acceptable level of dyeing and quality. Further, by observing the micrograph of the fusion and the sheath rupture, it was found that the core component hygroscopic polymer was eluted, and the core component hygroscopic polymer was eluted after the hot water treatment, resulting in a drastic decrease in hygroscopicity after hot water treatment, and hygroscopicity after hot water treatment. low.
比较例12Comparative Example 12
参考特开平9-13257号公报所记载的实施例1，芯成分为共聚合了3.5mol％间苯二甲酸-5-磺酸钠盐的聚对苯二甲酸乙二醇酯(IV＝0.66)，鞘成分为共聚合了8wt％平均分子量20000g/mol聚乙二醇的尼龙6，除了芯/鞘复合比例如表4所示变更以外，按实施例1同样的方法制得假捻丝。In the first embodiment described in JP-A-9-13257, the core component is polyethylene terephthalate (IV = 0.66) copolymerized with 3.5 mol% of sodium isophthalate-5-sulfonate. The sheath component was nylon 6 in which 8 wt% of an average molecular weight of 20,000 g/mol of polyethylene glycol was copolymerized, and a pseudofilament yarn was obtained in the same manner as in Example 1 except that the core/sheath recombination ratio was changed as shown in Table 4.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表4所示。由于鞘成分是吸 湿性聚合物，露出在表面的吸湿性聚合物部分多，断丝及堆积物很多，工程通过性不良。同时，发现融着及鞘破裂，均染性及品质都没达到合格水平。并且，热水处理后吸湿性低。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 4. Because the sheath component is sucking The wet polymer has a large amount of hygroscopic polymer exposed on the surface, a large number of broken wires and deposits, and poor engineering passability. At the same time, it was found that the fusion and sheath rupture did not reach the acceptable level of dyeing and quality. Moreover, the hygroscopicity after the hot water treatment is low.
比较例13Comparative Example 13
参考特开2007-131980号公报所记载的实施例1，芯成分为共聚合了30wt％平均分子量5000g/mol聚乙二醇的聚对苯二甲酸乙二醇酯，鞘成分为共聚合了1.5mol％间苯二甲酸-5-磺酸钠盐和1.0wt％重均分子量1000g/mol聚乙二醇的聚对苯二甲酸乙二醇酯(IV＝0.66)，除了芯/鞘复合比例如表4所示变更以外，按实施例7同样的方法制得假捻丝。In the example 1 described in JP-A-2007-131980, the core component was polyethylene terephthalate copolymerized with 30 wt% of an average molecular weight of 5000 g/mol of polyethylene glycol, and the sheath component was copolymerized by 1.5. Mol% isophthalic acid-5-sulfonic acid sodium salt and 1.0 wt% polyethylene terephthalate (IV = 0.66) having a weight average molecular weight of 1000 g/mol polyethylene glycol, except for the core/sheath composite ratio Fake silk yarns were obtained in the same manner as in Example 7 except for the changes shown in Table 4.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表4所示。断丝及堆积物较多，工程通过性不良。同时，发现融着及鞘破裂，均染性及品质都没达到合格水平。并且，观测融着与鞘破裂的显微镜照片，发现芯成分的吸湿性聚合物有溶出，热水处理后芯成分吸湿性聚合物溶出导致热水处理后吸湿性大幅度下降，热水处理后吸湿性低。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 4. Broken wire and many deposits, poor engineering passability. At the same time, it was found that the fusion and sheath rupture did not reach the acceptable level of dyeing and quality. Further, microscopic photographs of the fusion and the rupture of the sheath were observed, and it was found that the hygroscopic compound of the core component was eluted, and the hygroscopicity of the core component after the hot water treatment was dissolved, so that the hygroscopicity after the hot water treatment was greatly lowered, and the moisture absorption after the hot water treatment was absorbed. Low sex.
比较例14Comparative Example 14
除了芯成分为聚对苯二甲酸乙二醇酯(IV＝0.66)，鞘成分为共聚合了1.5mol％间苯二甲酸-5-磺酸钠盐、1.0wt％数均分子量1000g/mol的聚乙二醇(三洋化成工业制PEG1000)的聚对苯二甲酸乙二醇酯(IV＝0.66)作了变更以外，其余按实施例1同样的方法制得假捻丝。In addition to the core component of polyethylene terephthalate (IV = 0.66), the sheath component is copolymerized with 1.5 mol% sodium isophthalate-5-sulfonate, 1.0 wt% number average molecular weight 1000 g/mol. A pseudo-twisted yarn was obtained in the same manner as in Example 1 except that polyethylene terephthalate (IV = 0.66) of polyethylene glycol (PEG-1 manufactured by Sanyo Chemical Industries, Ltd.) was changed.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表4所示。没有断丝，基本上没有发现堆积物，工程通过性良好。同时，也没有融着和鞘破裂，染色性和品质均良好，由于芯成分和鞘成分都不是吸湿性聚合物，吸湿性极其差。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 4. There is no broken wire, basically no deposits are found, and the engineering passability is good. At the same time, there is no fusion and sheath rupture, and the dyeability and quality are good. Since the core component and the sheath component are not hygroscopic polymers, the hygroscopicity is extremely poor.
比较例15、16Comparative Examples 15, 16
除了纤维横截面的rM/R、rS/R如表4所示的纺丝喷丝板作了变更以外，其余按实施例7同样的方法制得假捻丝。A false twist yarn was obtained in the same manner as in Example 7 except that the fiber cross-section r M /R and r S /R were changed as shown in Table 4.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表4所示。比较例15没有断丝，也没有发现堆积物，工程通过性良好。虽然热水处理后的吸湿性良好，rM/R、rS/R也小，但是由于芯成分吸湿性聚合物露出在表面部分少，随着芯成分的体积膨胀发现多处鞘部分发生了破裂，均染性与品质都未达到合格水平。比较例16中rM/R、rS/R都大，由于芯成分吸湿性聚合物露出在表面的部分多，导致断丝及堆积物都比较多。同时，虽然热水处理后的吸湿性良好，但是融着的部位非常多，均染性与品质都未达到合格水平。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 4. In Comparative Example 15, there was no broken yarn, and no deposit was found, and the engineering passability was good. Although the hygroscopicity after hot water treatment is good, r M /R and r S /R are small, but since the core component hygroscopic polymer is exposed to a small amount on the surface portion, a plurality of sheath portions are found to occur as the core component expands. The rupture, levelness and quality did not reach the qualified level. In Comparative Example 16, r M /R and r S /R were both large, and since the core component hygroscopic polymer was exposed to a large portion on the surface, the number of broken wires and deposits was relatively large. At the same time, although the hygroscopicity after hot water treatment is good, there are many melting parts, and the level of dyeing and quality are not up to the qualified level.
比较例17Comparative Example 17
除了芯鞘复合比例如表4所示进行变更以外，其余按实施例1同样的方法制得假捻丝。A false twist yarn was obtained in the same manner as in Example 1 except that the core-sheath composite ratio was changed as shown in Table 4, for example.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表4所示。没有断丝，基本没发现堆积物，工程通过性良好。同时，由于芯成分吸湿性聚合物的复合比例低，热水处理后的吸湿性低。并且，rM/R、rS/R小，由于吸湿性聚合物露出在表面部分少，随着芯成分的体积膨胀发现有鞘部分破裂，均染性及品质都未达到合格水平。The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 4. There is no broken wire, basically no deposits are found, and the engineering passability is good. At the same time, since the composite ratio of the core component hygroscopic polymer is low, the hygroscopicity after hot water treatment is low. Further, since r M /R and r S /R are small, since the hygroscopic polymer is exposed to a small amount on the surface portion, the sheath portion is broken as the volume of the core component is expanded, and the leveling property and quality are not at an acceptable level.
比较例18Comparative Example 18
除了使用单成分用纺丝喷丝板(孔数：36、圆孔)以外，其余按实施例1同样的方法制得假捻丝。A false twist yarn was obtained in the same manner as in Example 1 except that a single-component spinneret (pore number: 36, round hole) was used.
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表4所示。由于只是吸湿性聚合物形成的纤维，断丝及堆积物非常的多，工程通过性不好。热水处理后的吸湿性虽然很高，但发现多处融着，均染性及品质都未达到合格水平。 The evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 4. Because it is only a fiber formed by a hygroscopic polymer, there are many broken wires and deposits, and the engineering passability is not good. Although the hygroscopicity after hot water treatment was high, it was found that many places were fused, and the level of dyeing and quality did not reach the acceptable level.
Figure PCTCN2016111763-appb-000005
Figure PCTCN2016111763-appb-000005
Figure PCTCN2016111763-appb-000006
Figure PCTCN2016111763-appb-000006
Figure PCTCN2016111763-appb-000007
Figure PCTCN2016111763-appb-000007
Figure PCTCN2016111763-appb-000008
Figure PCTCN2016111763-appb-000008

Claims (14)

  1. 一种芯鞘型复合纤维，其特征在于：所述芯鞘型复合纤维的芯成分和鞘成分均为结晶性聚合物，且芯成分为吸湿性聚合物；所述芯鞘型复合纤维的横截面上至少有一部分芯成分露出在表面，且横截面外周长R与露出在表面部分的芯成分的长度总和rS的比rS/R为0.05～0.40；所述芯鞘型复合纤维的外推熔融起始温度在150℃以上，且热水处理后的吸湿率差△MR为2.0～10.0％。A core-sheath type composite fiber characterized in that the core component and the sheath component of the core-sheath type composite fiber are both crystalline polymers, and the core component is a hygroscopic polymer; and the core-sheath type composite fiber is transverse have a cross section at least a portion of the core component exposed on the surface, and the sum of the cross-sectional length r S R and the outer perimeter of the surface of the exposed portion of the core component ratio r S / R is from 0.05 to 0.40; the core-sheath type composite fibers of the outer The melt initiation temperature is 150 ° C or higher, and the moisture absorption rate difference ΔMR after hot water treatment is 2.0 to 10.0%.
  2. 根据权利要求1所述的芯鞘型复合纤维，其特征在于：所述芯鞘型复合纤维的横截面外周长R与露出在表面部分的芯成分长度的最大值rM的比rM/R为0.01～0.20。The core-sheath type composite fiber according to claim 1, wherein a ratio of an outer peripheral length R of the cross-section of the core-sheath type composite fiber to a maximum value r M of the length of the core component exposed at the surface portion is r M /R It is 0.01 to 0.20.
  3. 根据权利要求1或2所述的芯鞘型复合纤维，其特征在于：所述芯成分与鞘成分的重量比为10/90～70/30。The core-sheath type composite fiber according to claim 1 or 2, wherein the weight ratio of the core component to the sheath component is from 10/90 to 70/30.
  4. 根据权利要求1～3任一项所述的芯鞘型复合纤维，其特征在于：热水处理前后复合纤维的色调变化值△b为3.0以下。The core-sheath type composite fiber according to any one of claims 1 to 3, wherein the color fiber change value Δb of the composite fiber before and after the hot water treatment is 3.0 or less.
  5. 根据权利要求1～4任一项所述的芯鞘型复合纤维，其特征在于：所述芯鞘型复合纤维中含有如式1所示结构的半受阻酚类抗氧化剂；The core-sheath type composite fiber according to any one of claims 1 to 4, wherein the core-sheath type composite fiber contains a semi-hindered phenol antioxidant having a structure represented by Formula 1;
    Figure PCTCN2016111763-appb-100001
    Figure PCTCN2016111763-appb-100001
    其中，R1为碳氢、氧、氮元素中任何一种结合形成的半受阻酚类抗氧化剂，R2为氢、碳氢、氧、氮元素中任何一种结合形成的半受阻酚类抗氧化剂。Wherein R1 is a semi-hindered phenolic antioxidant formed by combining any one of hydrocarbon, oxygen and nitrogen, and R2 is a semi-hindered phenolic antioxidant formed by combining any one of hydrogen, hydrocarbon, oxygen and nitrogen.
  6. 根据权利要求1～5任一项所述的芯鞘型复合纤维，其特征在于：所述芯成分的吸湿性聚合物是以聚醚为共聚合成分的聚醚酯、聚醚酰胺、聚醚酰胺酯中的至少一种。The core-sheath type composite fiber according to any one of claims 1 to 5, wherein the hygroscopic polymer of the core component is a polyether ester, a polyether amide or a polyether having a polyether as a copolymer component. At least one of amide esters.
  7. 根据权利要求6所述的芯鞘型复合纤维，其特征在于：所述聚醚酯以芳香族二元羧酸与脂肪族二元醇为主要构成成分，聚醚为共聚合成分。The core-sheath type composite fiber according to claim 6, wherein the polyether ester has an aromatic dicarboxylic acid and an aliphatic diol as main constituent components, and the polyether is a copolymer component.
  8. 根据权利要求7所述的芯鞘型复合纤维，其特征在于：所述脂肪族二元醇为乙二醇，所述聚醚的数均分子量为4000～30000g/mol。The core-sheath type composite fiber according to claim 7, wherein the aliphatic diol is ethylene glycol, and the polyether has a number average molecular weight of 4,000 to 30,000 g/mol.
  9. 根据权利要求8所述的芯鞘型复合纤维，其特征在于：聚醚的共聚合率为10～35wt％。The core-sheath type composite fiber according to claim 8, wherein the polyether has a copolymerization ratio of 10 to 35 wt%.
  10. 根据权利要求7所述的芯鞘型复合纤维，其特征在于：所述脂肪族二元醇为1，4-丁二醇，所述聚醚的数均分子量为2000～30000g/mol。The core-sheath type composite fiber according to claim 7, wherein the aliphatic diol is 1,4-butanediol, and the polyether has a number average molecular weight of from 2,000 to 30,000 g/mol.
  11. 根据权利要求10所述的芯鞘型复合纤维，其特征在于：聚醚的共聚合率为10～60wt％。The core-sheath type composite fiber according to claim 10, wherein the polyether has a copolymerization ratio of 10 to 60% by weight.
  12. 根据权利要求1～11任一项所述的芯鞘型复合纤维，其特征在于：所述鞘成分为阳离子可染聚酯。The core-sheath type composite fiber according to any one of claims 1 to 11, wherein the sheath component is a cationic dyeable polyester.
  13. 由2根以上的权利要求1～12任一项所述芯鞘型复合纤维合捻形成的假捻丝。A false twist yarn formed of two or more core-sheath type composite fibers according to any one of claims 1 to 12.
  14. 一种至少一部分使用权利要求1～12任一项所述芯鞘型复合纤维和/或权利要求13所述假捻丝的纤维构造体。 A fiber structure using at least a part of the core-sheath type composite fiber according to any one of claims 1 to 12 and/or the false twist yarn according to claim 13.
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