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WO2015146790A1 - Fibre à structure de séparation de phase et procédé de fabrication d'une telle fibre - Google Patents

Fibre à structure de séparation de phase et procédé de fabrication d'une telle fibre Download PDF

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Publication number
WO2015146790A1
WO2015146790A1 PCT/JP2015/058297 JP2015058297W WO2015146790A1 WO 2015146790 A1 WO2015146790 A1 WO 2015146790A1 JP 2015058297 W JP2015058297 W JP 2015058297W WO 2015146790 A1 WO2015146790 A1 WO 2015146790A1
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Prior art keywords
fiber
polyethylene glycol
antioxidant
copolymer
hydrophilic polymer
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PCT/JP2015/058297
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English (en)
Japanese (ja)
Inventor
秀和 鹿野
中川　順一
荒西　義高
田中　陽一郎
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Toray Industries Inc
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Toray Industries Inc
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Priority to CN201580015835.7A priority Critical patent/CN106164349B/zh
Priority to JP2015515321A priority patent/JP6582980B2/ja
Priority to KR1020167018263A priority patent/KR102250972B1/ko
Publication of WO2015146790A1 publication Critical patent/WO2015146790A1/fr
Anticipated expiration legal-status Critical
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • 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
    • D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

Definitions

  • the present invention relates to a fiber having a phase separation structure. More specifically, despite having a phase separation structure, the fineness spots are small, the occurrence of dyed spots and fluff is suppressed, and further, the durability of the fiber characteristics against long-term storage and tumbler drying, moisture absorption
  • the present invention relates to a fiber that can be suitably used for apparel and has excellent antistatic properties in a low-temperature and low-humidity environment and suppresses elution of a hydrophilic compound during dyeing or use.
  • Polyester fibers are used in a wide range of applications because they are inexpensive and have excellent mechanical properties. However, since it has poor hygroscopicity, it has drawbacks to be solved such as generation of stuffiness at high humidity in summer and generation of static electricity at low humidity in winter.
  • the frictional voltage of polyethylene terephthalate which is a general-purpose polyester, is about 7000 to 9000 V in a standard state at a temperature of 20 ° C. and a humidity of 40% RH. The smaller the value of the frictional voltage, the less likely to be charged with static electricity, and the better the wearing comfort. In the case of polyethylene terephthalate, it can be said that the fiber has extremely poor antistatic properties.
  • Patent Document 1 proposes an antistatic polyester fiber in which polyoxyalkylene glycol and an organic metal salt are added as a hydrophilic compound to polyester.
  • antistatic properties are imparted by dispersing polyoxyalkylene glycol in polyester fibers.
  • Patent Document 2 proposes a core-sheath composite fiber having a polyester copolymerized with polyethylene glycol as a core and polypropylene terephthalate as a sheath.
  • the antistatic property is imparted to the polyester fiber by the polyester copolymerized with polyethylene glycol disposed in the core.
  • the object of the present invention is to solve the above-mentioned problems of the prior art, and despite having a phase separation structure, the fineness spots are small, the occurrence of dyed spots and fluff is suppressed, and further, moisture absorption It is an object of the present invention to provide a fiber that can be suitably used for apparel applications, and has excellent antistatic properties in an environment and low temperature and low humidity environment, and the elution of a hydrophilic compound is suppressed during dyeing and use.
  • the above-mentioned problem of the present invention is that it comprises a copolymer of a hydrophobic polymer and a hydrophilic polymer, has a continuous phase and a dispersed phase by a phase separation structure, and the maximum diameter of the dispersed phase in the fiber cross section is 1 to
  • the copolymer of the hydrophobic polymer and the hydrophilic polymer is preferably exposed on at least a part of the fiber surface, and the hydrophobic polymer is a polyester, It can be suitably employed that the conductive polymer is polyethylene glycol.
  • TMG differential thermogravimetric analysis
  • the time to reach 160 ° C. is 0 minute, and the time to the rising half-point is preferably 120 minutes or more.
  • it contains an antioxidant, and the antioxidant is at least one selected from a phenolic compound, a sulfur compound, and a hindered amine compound, and the content of the antioxidant is 0.01-2. 0% by weight can be suitably employed.
  • the fiber of the present invention preferably has a frictional voltage of 3000 V or less measured at a temperature of 10 ° C. and a humidity of 10% RH based on JIS L1094.
  • the fineness spots are small, the occurrence of dyed spots and fluff is suppressed, and further, the durability of the fiber properties against long-term storage and tumbler drying Further, it is possible to provide a fiber that is excellent in hygroscopicity and antistatic property in a low-temperature and low-humidity environment, and in which elution of the hydrophilic compound is suppressed during dyeing and use. This fiber can be suitably used particularly for clothing applications.
  • FIG. 1 is a drawing-substituting photograph illustrating a fiber cross section of a fiber having a phase separation structure of the present invention.
  • FIG. 2 is a drawing-substituting photograph illustrating a fiber longitudinal section of a fiber having a phase separation structure of the present invention.
  • the fiber of the present invention comprises a copolymer of a hydrophobic polymer and a hydrophilic polymer, has a continuous phase and a dispersed phase with a phase separation structure, and the maximum diameter of the dispersed phase in the fiber cross section is 1 to 40 nm. Yes, the fineness fluctuation value U% (hi) is 0.1 to 1.5%.
  • the fiber of the present invention has a phase separation structure, it forms a fine and uniform dispersed phase in the cross section of the fiber as shown in FIG. 1, so that fineness spots are small, and dyed spots and fluff are generated. Is suppressed.
  • the hydrophobic polymer in the present invention is not particularly limited as long as it can be copolymerized with a hydrophilic polymer, and can be suitably used.
  • Specific examples of the hydrophobic polymer include aromatic polyesters such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polylactic acid, polyglycolic acid, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyethylene succinate, Examples thereof include aliphatic polyesters such as polypropylene succinate, polybutylene succinate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, and polycaprolactone, but are not limited thereto.
  • polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate are preferable because they are excellent in mechanical properties and durability, and are easy to handle during production and use.
  • the hydrophilic polymer in the present invention is not particularly limited as long as it can be copolymerized with a hydrophobic polymer, and can be suitably used. By copolymerizing a hydrophilic polymer with a hydrophobic polymer, it becomes possible to impart antistatic properties to the fiber.
  • Specific examples of the hydrophilic polymer include homopolymers such as polyethylene glycol and polypropylene glycol, and copolymers such as polyethylene glycol-polypropylene glycol copolymer and polyethylene glycol-polybutylene glycol copolymer. It is not limited to. Of these, polyethylene glycol and polypropylene glycol are preferable because they are easy to handle during production and use.
  • the fiber of the present invention is made of a copolymer of a hydrophobic polymer and a hydrophilic polymer. Unlike melt blending like polymer blends, hydrophobic polymer and hydrophilic polymer form a covalent bond by copolymerization, so the elution of the hydrophilic polymer from the fiber is suppressed, making it It is possible to obtain a fiber excellent in durability with little change in fiber characteristics between processes at the time or during use of a product.
  • the fiber of the present invention has a phase separation structure.
  • This phase separation structure is specifically expressed in the process in which the polymerization reaction proceeds and the hydrophobic polymer and the hydrophilic polymer are copolymerized. That is, unlike the phase separation structure expressed by melt mixing of incompatible polymer compounds, in the present invention, a fine and uniform dispersed phase is formed because the phase separation structure is developed as the polymerization reaction proceeds. Since the dispersed phase is fine and uniform, the resulting fibers have a phase separation structure, but the fineness spots are small, and the occurrence of dyed spots and fluff is suppressed. Moreover, since it has a phase separation structure, it is possible to obtain a fiber having excellent antistatic properties in a low temperature and low humidity environment.
  • phase separation that develops as the polymerization reaction progresses.
  • the polarity of bis ( ⁇ -hydroxyethyl) terephthalate which is a precursor of polyethylene terephthalate
  • the reaction system is transparent.
  • a polyethylene terephthalate-polyethylene glycol copolymer is formed. After about 1 hour from the start of polymerization, a phase separation state occurs, and the reaction system becomes cloudy.
  • This phase-separated structure includes a polyethylene terephthalate-polyethylene glycol copolymer having a low polarity copolymer, that is, a copolymer having a high proportion of polyethylene terephthalate in the molecular chain, and a high polarity copolymer, that is, a molecular chain.
  • a copolymer having a high proportion of polyethylene glycol in the interior is produced, and is expressed by the difference in polarity.
  • the fiber of the present invention has a continuous phase and a dispersed phase due to a phase separation structure.
  • the components constituting the continuous phase and the dispersed phase vary depending on the copolymerization ratio of the hydrophobic polymer and the hydrophilic polymer.
  • the “hydrophobic polymer-hydrophilic polymer copolymer” having a higher proportion of the hydrophobic polymer in the molecular chain becomes the continuous phase.
  • a “hydrophobic polymer-hydrophilic polymer copolymer” having a high proportion of the hydrophilic polymer in the molecular chain becomes the dispersed phase.
  • the “hydrophobic polymer-hydrophilic polymer copolymer” having a higher proportion of the hydrophilic polymer in the molecular chain is a continuous phase.
  • a “hydrophobic polymer-hydrophilic polymer copolymer” having a high proportion of the hydrophobic polymer in the molecular chain becomes the dispersed phase.
  • both the continuous phase and the dispersed phase are composed of a “hydrophobic polymer-hydrophilic polymer copolymer”, and the composition ratio is different. Phase separation structure with extremely high properties.
  • ester-forming dicarboxylic acid other than terephthalic acid may be used as the dicarboxylic acid component of the polyester.
  • ester-forming dicarboxylic acids include adipic acid, isophthalic acid, sebacic acid, phthalic acid, 4,4′-diphenyldicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 5- (tetra Examples include, but are not limited to, dicarboxylic acids such as (alkyl) phosphonium sulfoisophthalic acid and ester-forming derivatives thereof.
  • an ester-forming diol other than ethylene glycol may be used as the diol component of the polyester.
  • Specific examples of the ester-forming diol include, but are not limited to, propanediol, butanediol, hexanediol, cyclohexanediol, diethylene glycol, hexamethylene glycol, neopentyl glycol, and ester-forming derivatives thereof.
  • the number average molecular weight of polyethylene glycol is preferably 7000 to 20000. If the number average molecular weight of polyethylene glycol is 7000 or more, a phase separation structure is expressed by copolymerization with polyethylene terephthalate, and therefore, fibers having excellent antistatic properties can be obtained by fiberizing.
  • the number average molecular weight of polyethylene glycol is more preferably 7500 or more, and further preferably 8000 or more.
  • the number average molecular weight of polyethylene glycol is more preferably 17000 or less, and further preferably 15000 or less.
  • the copolymerization ratio of polyethylene glycol is preferably 10 to 20% by weight. If the copolymerization ratio of polyethylene glycol is 10% by weight or more, fibers excellent in hygroscopicity and antistatic properties can be obtained, which is preferable.
  • the copolymerization rate of polyethylene glycol is more preferably 11% by weight or more, and further preferably 12% by weight or more.
  • the copolymerization ratio of polyethylene glycol is 20% by weight or less, a fine and uniform phase separation structure is formed by copolymerization with polyethylene terephthalate, and after discharging from the polycondensation tank after spinning reaction or spinning, It is preferable because discharge from the spinneret is stable and operability is improved. In addition, it is preferable because homogeneous fibers with small fineness spots and suppressed generation of dyed spots and fluff can be obtained, and the mechanical properties of the fibers and the fiber structure composed thereof are favorable.
  • the copolymerization ratio of polyethylene glycol is more preferably 19% by weight or less, and further preferably 18% by weight or less.
  • phase separation structure composed of a hydrophobic polymer (polyethylene terephthalate) -hydrophilic polymer (polyethylene glycol) copolymer
  • the inventors have determined that the affinity between the continuous phase and the dispersed phase is as described above. Since the phase separation structure is extremely high, when the shear is applied in the molten state, the phase separation structure is finely dispersed and eventually disappears, but when the application of the shear is stopped and a certain time elapses, the phase separation structure appears again. I found a peculiar phenomenon. Although described in detail in the fiber manufacturing method described later, by utilizing this unique phenomenon, fineness spots are small and the occurrence of dyed spots and fluff is suppressed despite having a phase separation structure. Succeeded in obtaining a good fiber.
  • the copolymer of the hydrophobic polymer and the hydrophilic polymer in the present invention may be one that has been subjected to various modifications by adding secondary additives.
  • secondary additives include compatibilizers, plasticizers, UV absorbers, infrared absorbers, fluorescent brighteners, mold release agents, antibacterial agents, nucleating agents, thermal stabilizers, antioxidants, and charging Examples include, but are not limited to, inhibitors, anti-coloring agents, regulators, matting agents, antifoaming agents, preservatives, gelling agents, latexes, fillers, inks, coloring agents, dyes, pigments, and fragrances. These secondary additives may be used alone or in combination.
  • the maximum diameter of the dispersed phase in the fiber cross section of the fiber of the present invention is 1 to 40 nm. Details of the method for measuring the maximum diameter of the dispersed phase in the fiber cross section will be described later.
  • the maximum diameter of the dispersed phase in the fiber cross section is more preferably 3 nm or more, further preferably 5 nm or more, and particularly preferably 10 nm or more.
  • the maximum diameter of the dispersed phase in the fiber cross section is 40 nm or less, the mechanical properties of the fiber and the fiber structure formed thereof are good and the durability is excellent.
  • the maximum diameter of the dispersed phase in the fiber cross section is more preferably 37 nm or less, still more preferably 35 nm or less, and particularly preferably 30 nm or less.
  • the maximum diameter of the dispersed phase in the fiber longitudinal section of the fiber of the present invention is preferably 1 to 40 nm. Details of the method for measuring the maximum diameter of the dispersed phase in the fiber longitudinal section will be described later.
  • the maximum diameter of the dispersed phase in the fiber longitudinal section is the maximum value of the diameter of the dispersed phase with respect to the direction perpendicular to the fiber axis. If the maximum diameter of the dispersed phase in the longitudinal section of the fiber is 1 nm or more, it is preferable because a fiber excellent in hygroscopicity and antistatic property can be obtained.
  • the maximum diameter of the dispersed phase in the longitudinal section of the fiber is more preferably 3 nm or more, further preferably 5 nm or more, and particularly preferably 10 nm or more.
  • the maximum diameter of the dispersed phase in the fiber longitudinal section is 40 nm or less, it is preferable because the mechanical properties of the fiber and the fiber structure composed thereof are good and the durability is excellent.
  • the maximum diameter of the dispersed phase in the fiber longitudinal section is more preferably 37 nm or less, still more preferably 35 nm, and particularly preferably 30 nm or less.
  • the total fineness of the fiber of the present invention is not particularly limited and can be appropriately selected according to the application and required characteristics, but is preferably 10 to 500 dtex. If the total fineness of the fiber is 10 dtex or more, it is preferable because the yarn breakage is small and the process passability is good, the generation of fluff is small during use, and the durability is excellent.
  • the total fineness of the fiber is more preferably 30 dtex or more, and further preferably 50 dtex or more. On the other hand, if the total fineness of the fibers is 500 dtex or less, the flexibility is not impaired when the fibers and fiber structures are formed.
  • the total fineness of the fiber is more preferably 400 dtex or less, and further preferably 300 dtex or less.
  • the strength of the fiber of the present invention is not particularly limited and can be appropriately selected according to the application and required characteristics, but is preferably 2.0 to 5.0 cN / dtex from the viewpoint of mechanical characteristics. If the strength of the fiber is 2.0 cN / dtex or more, there are few yarn breaks in the spinning, drawing process, weaving, knitting process, etc., in addition to good process passability, and excellent durability during use. preferable.
  • the strength of the fiber is more preferably 2.5 cN / dtex or more, and further preferably 3.0 cN / dtex or more. On the other hand, if the strength of the fiber is 5.0 cN / dtex or less, the flexibility is not impaired when the fiber and the fiber structure are formed.
  • the elongation of the fiber of the present invention is not particularly limited and can be appropriately selected according to the application and required characteristics, but is preferably 10 to 60% from the viewpoint of process passability. If the elongation of the fiber is 10% or more, the abrasion resistance of the fiber and the fiber structure is good, and the process passability is good. In addition, the occurrence of fluff is small during use, and the durability is good. Therefore, it is preferable.
  • the elongation of the fiber is more preferably 15% or more, and further preferably 20% or more. On the other hand, if the elongation of the fiber is 60% or less, it is preferable because the dimensional stability of the fiber and the fiber structure becomes good.
  • the elongation of the fiber is more preferably 55% or less, and further preferably 50% or less.
  • the initial tensile resistance of the fiber of the present invention is not particularly limited and can be appropriately selected according to the application and required characteristics.
  • the initial tensile resistance measured according to JIS L1013: 1999 8.10 is 10 It is preferably ⁇ 100 cN / dtex. If the initial tensile resistance of the fiber is 10 cN / dtex or more, the process passability and handleability are good, and the mechanical properties are excellent, which is preferable.
  • the initial tensile resistance of the fiber is more preferably 15 cN / dtex or more, and further preferably 20 cN / dtex or more.
  • the initial tensile resistance of the fiber is 100 cN / dtex or less, the flexibility of the fiber and the fiber structure is not impaired, which is preferable.
  • the initial tensile resistance of the fiber is more preferably 90 cN / dtex or less, and further preferably 80 cN / dtex or less.
  • the fiber diameter of the fiber of the present invention is not particularly limited and can be appropriately selected according to the application and required characteristics, but is preferably 3 to 100 ⁇ m. If the fiber diameter is 3 ⁇ m or more, it is preferable because the yarn-manufacturing operability and process passability in high-order processing are good, and fibers having excellent mechanical properties can be obtained.
  • the fiber diameter of the fiber is more preferably 5 ⁇ m or more, and further preferably 7 ⁇ m or more. On the other hand, a fiber diameter of 100 ⁇ m or less is preferable because the flexibility of the fiber and the fiber structure is not impaired.
  • the fiber diameter of the fiber is more preferably 70 ⁇ m or less, and further preferably 50 ⁇ m or less.
  • the boiling water shrinkage of the fiber of the present invention is preferably 3 to 15%. If the boiling water shrinkage of the fiber is 3% or more, it is preferable because the weaving density can be increased by heat shrinking the fabric, and the weaving tension in the weaving process can be suppressed to an appropriate range to produce a high-density fabric. . Furthermore, it is not necessary to weave under high tension when producing a high-density fabric, it is possible to suppress the occurrence of fluff and sink marks in the weaving process, and it is preferable because a fabric with few defects can be produced with good processability. .
  • the boiling water shrinkage of the fiber is more preferably 4% or more, and further preferably 5% or more.
  • the boiling water shrinkage of the fiber is 15% or less, the orientation degree of the molecular chain is not extremely reduced during the treatment with boiling water, and the strength reduction after the boiling water treatment is small, which is preferable. Further, it is preferable because the fiber can be sufficiently contracted by a process of thermally contracting the fabric, and a flexible fabric can be obtained.
  • the boiling water shrinkage of the fiber is more preferably 12% or less, and still more preferably 10% or less.
  • the fineness variation value U% (hi) of the fiber of the present invention is 0.1 to 1.5%.
  • the fineness variation value U% is an index of thickness variation in the fiber longitudinal direction, and the smaller the fineness variation value U% (hi), the smaller the thickness variation in the longitudinal direction of the fiber.
  • the fineness fluctuation value U% (hi) is preferably as small as possible from the viewpoint of process passability and quality, but the lower limit is 0.1% as a manufacturable range.
  • the fiber fineness variation value U% (hi) is 1.5% or less, the uniformity in the longitudinal direction of the fiber is excellent, and fluctuations in processing tension are suppressed in the warping process, weaving, knitting process, etc. This is preferable because it can be performed.
  • the fineness variation value U% (hi) of the fiber is more preferably 1.2% or less, still more preferably 1.0% or less, and particularly preferably 0.9% or less.
  • the single yarn diameter CV% of the fiber of the present invention is preferably 0.1 to 15%.
  • the single yarn diameter CV% is preferably as small as possible from the viewpoint of process passability and quality, but the lower limit is 0.1% as a manufacturable range.
  • the single yarn diameter CV% of the fiber is 15% or less, generation of fluff can be suppressed during production and use, and defects such as dyed spots and dyed streaks are less likely to occur when dyed, This is preferable because a high-quality fiber structure can be obtained.
  • the single yarn diameter CV% of the fiber is more preferably 12% or less, still more preferably 10% or less, and particularly preferably 7% or less.
  • the single yarn fineness CV% of the fiber of the present invention is preferably 0.1 to 15%.
  • the single yarn fineness CV% is preferably as small as possible from the viewpoint of process passability and quality, but 0.1% is the lower limit as a manufacturable range.
  • the single yarn fineness CV% of the fiber is 15% or less, the generation of fluff can be suppressed during production and use, and defects such as dyed spots and dyed streaks are less likely to occur when dyed, This is preferable because a high-quality fiber structure can be obtained.
  • the single yarn fineness CV% of the fiber is more preferably 12% or less, still more preferably 10% or less, and particularly preferably 7% or less.
  • the single yarn strength CV% of the fiber of the present invention is preferably 0.1 to 20%.
  • the single yarn strength CV% is preferably as small as possible from the viewpoint of process passability and quality, but the lower limit is 0.1% as a manufacturable range.
  • the single yarn strength CV% of the fiber is 20% or less, the generation of fluff can be suppressed during production and use, and defects such as dyed spots and dyed streaks are less likely to occur when dyed, This is preferable because a high-quality fiber structure can be obtained.
  • the single yarn strength CV% of the fiber is more preferably 15% or less, still more preferably 12% or less, and particularly preferably 10% or less.
  • the single yarn elongation CV% of the fiber of the present invention is preferably 0.1 to 40%.
  • the single yarn elongation CV% is preferably as small as possible from the viewpoint of process passability and quality, but the lower limit is 0.1% as a manufacturable range.
  • the single yarn elongation CV% of the fiber is 40% or less, generation of fluff can be suppressed during production and use, and defects such as dyed spots and dyed streaks are less likely to occur when dyed. Since a high-quality fiber structure can be obtained, it is preferable.
  • the single yarn elongation CV% of the fiber is more preferably 37% or less, still more preferably 35% or less, and particularly preferably 30% or less.
  • TCG differential thermogravimetric analysis
  • it is preferable that the time to reach 160 ° C. is 0 minute, and the time to the rising half-value point is 120 minutes or more. Although the details of the method for measuring the rising half-value point will be described later, this evaluation method was adopted as an accelerated test assuming durability against long-term storage and tumbler drying.
  • the present inventors conducted differential thermogravimetric analysis (DTG) at 160 ° C.
  • the time to the rising half-value point is more preferably 180 minutes or more, further preferably 240 minutes or more, and particularly preferably 360 minutes or more.
  • the difference in moisture absorption ( ⁇ MR) of the fiber of the present invention is preferably 1 to 10%.
  • the details of the measurement method of MR will be described later, but the moisture absorption rate at a temperature of 30 ° C. and a humidity of 90% RH assuming the temperature and humidity in the clothes after light exercise, and the outside air temperature humidity at a temperature of 20 ° C. and a humidity of 65% RH
  • the difference in moisture absorption is ⁇ MR. That is, ⁇ MR is a hygroscopic index, and the higher the value of ⁇ MR, the better the wearing comfort. If the ⁇ MR of the fibers is 1% or more, it is preferable because the feeling of stuffiness in the clothes is small and wearing comfort is expressed.
  • the ⁇ MR of the fiber is more preferably 1.5% or more, and further preferably 2% or more. On the other hand, if the ⁇ MR of the fiber is 10% or less, the process passability and handleability are good, and the durability during use is excellent, which is preferable.
  • the ⁇ MR of the fiber is more preferably 9% or less, and further preferably 8% or less.
  • the fiber of the present invention is a copolymer of a hydrophobic polymer and a hydrophilic polymer
  • the hydrophilic polymer to hot water or the like is different from the case where the hydrophobic polymer and the hydrophilic polymer are melt-mixed. Elution is suppressed. Therefore, hygroscopic durability is high and can be suitably employed as a fiber structure.
  • the fiber of the present invention preferably has a frictional voltage of 3000 V or less at a temperature of 10 ° C. and a humidity of 10% RH.
  • the frictional voltage is an antistatic index, and the lower the value of the frictional voltage, the more the generation of static electricity is suppressed.
  • the frictional voltage is preferably as small as possible from the viewpoint of wearing comfort. Furthermore, it is not only in a temperature and humidity environment such as a temperature of 20 ° C. and a humidity of 40% RH, but also at a low temperature such as a temperature of 10 ° C. and a humidity of 10% RH. It is preferable that the frictional voltage is low in a humidity environment and exhibits excellent antistatic properties.
  • the friction band voltage of the fiber at a temperature of 10 ° C and a humidity of 10% RH is 3000 V or less, there is little generation of static electricity even in low-temperature and low-humidity environments such as outdoors in winter and indoors where the humidity has become very low due to the use of heating. It is preferable because it is excellent in wearing comfort.
  • the friction band voltage of the fiber at a temperature of 10 ° C. and a humidity of 10% RH is more preferably 2500 V or less, and further preferably 2000 V or less.
  • the fiber of the present invention can be a composite fiber made of a copolymer of a hydrophobic polymer and a hydrophilic polymer and other (co) polymers other than this.
  • the copolymer of the hydrophobic polymer and the hydrophilic polymer is preferably exposed on at least a part of the fiber surface.
  • the fiber of the present invention preferably contains an antioxidant.
  • an antioxidant not only suppresses the oxidative degradation of hydrophilic polymers due to long-term storage and tumbler drying, but also the properties of fibers such as hygroscopicity, antistatic properties in low temperature and low humidity environments, and mechanical properties. Since durability improves, it is preferable.
  • the present inventors have found that the fibers having a phase separation structure composed of a hydrophobic polymer (polyethylene terephthalate) -hydrophilic polymer (polyethylene glycol) copolymer in the present invention have a uniform structure without a phase separation structure.
  • the antioxidant in the present invention is preferably selected from phenol compounds, sulfur compounds, and hindered amine compounds. These antioxidants may use only 1 type and may use 2 or more types together.
  • the phenolic compound in the present invention is a radical chain reaction inhibitor having a phenol structure, and specific examples thereof include 2,6-t-butyl-p-cresol, butylhydroxyanisole, 2,6-t-butyl-4. -Ethylphenol, stearyl- ⁇ - (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis ⁇ 1,1-dimethyl-2- ⁇ - (3- t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ ethyl ⁇ 2,4,8,10-tetraoxaspiro ⁇ 5,5 ⁇ undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylpheny
  • phenol compounds may be used alone or in combination of two or more.
  • pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (manufactured by BASF, Irganox 1010), 2,4,6-tris (3 ′, 5′-di) -T-Butyl-4'-hydroxybenzyl) mesitylene (manufactured by ADEKA, ADK STAB AO-330), 1,3,5-tris [[4- (1,1-dimethylethyl) -3-hydroxy-2,6- [Dimethylphenyl] methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by Tokyo Chemical Industry Co., Ltd., THANOX 1790) has a high oxidative degradation inhibitory effect and can be suitably used. .
  • the sulfur-based compound in the present invention is a sulfur-based antioxidant that reduces peroxide without generating radicals and oxidizes itself.
  • Specific examples include dilauryl 3,3′-thiodipropionate, dimyristyl. Examples include, but are not limited to, 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, and the like.
  • These sulfur type antioxidants may use only 1 type, and may use 2 or more types together.
  • the hindered amine compound in the present invention is a hindered amine antioxidant that has an effect of trapping radicals generated by ultraviolet rays or heat and regenerating a phenolic antioxidant deactivated by functioning as an antioxidant.
  • These hindered amine compounds may be used alone or in combination of two or more. Especially, it is preferable that it is a high molecular weight type
  • dibutylamine-1,3,5-triazine-N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2, 6,6-Tetramethyl-4-piperidyl) butylamine polycondensate (CHIMASSORB2020 manufactured by BASF) has a high oxidative degradation inhibitory effect and can be suitably used.
  • the content of the antioxidant in the fiber of the present invention is preferably 0.01 to 2.0% by weight of the fiber weight.
  • a sufficient amount of antioxidant in the fiber to exhibit the antioxidant effect it is possible to suppress oxidative degradation of hydrophilic compounds due to long-term storage and tumbler drying, hygroscopic, low temperature and low humidity environment It is preferable because durability of fiber properties such as antistatic properties and mechanical properties below is improved.
  • the content of the antioxidant is 0.01% by weight or more, the effect of suppressing oxidative degradation can be imparted to the fiber, which is preferable.
  • the content of the antioxidant is more preferably 0.05% by weight or more, further preferably 0.1% by weight or more, and particularly preferably 0.15% by weight or more.
  • the content of the antioxidant is 2.0% by weight or less, the color tone of the fiber is not deteriorated, and the mechanical properties are not impaired.
  • the content of the antioxidant is more preferably 1.7% by weight or less, further preferably 1.5% by weight or less, and particularly preferably 1.0% by weight or less.
  • the fiber of the present invention is not particularly limited with respect to the cross-sectional shape of the fiber, and may be a perfect circular cross section or a non-circular cross section.
  • Specific examples of non-circular cross sections include, but are not limited to, multi-leaf, polygon, flat, oval, C-shaped, H-shaped, S-shaped, T-shaped, W-shaped, X-shaped, Y-shaped, etc. Not.
  • the fiber of the present invention is not particularly limited with respect to the form of the fiber, and may be any form such as monofilament, multifilament, and staple.
  • the fibers of the present invention can be processed into false twists and twisted yarns as in general fibers, and weaving and knitting can be handled in the same manner as general fibers.
  • the form of the fiber structure composed of the fiber of the present invention is not particularly limited, and can be a woven fabric, a knitted fabric, a pile fabric, a nonwoven fabric, a spun yarn, a stuffed cotton, or the like according to a known method.
  • the fiber structure composed of the fibers of the present invention may be any woven or knitted structure, such as plain weave, twill weave, satin weave, or these changed weaves, warp knitting, weft knitting, circular knitting, lace knitting or These change knitting can be suitably employed.
  • the fiber of the present invention may be combined with other fibers by knit or knitting when making a fiber structure, or may be made into a fiber structure after blended yarn with other fibers.
  • a method for producing a copolymer of a hydrophobic polymer and a hydrophilic polymer used in the present invention will be described.
  • a method for producing a phase separation structure composed of a polyester-polyethylene glycol copolymer using polyester as a hydrophobic polymer and polyethylene glycol as a hydrophilic polymer is shown below.
  • the polyester component alone is subjected to esterification or transesterification to obtain a polyester oligomer.
  • the polyester oligomer is added to a reaction vessel to which polyethylene glycol has been added in advance.
  • the polyethylene glycol is solid, it is preferably heated and melted at 70 ° C. or higher, and after adding the polyester oligomer to the polyethylene glycol, it is preferable to sufficiently stir.
  • phase-separated structure comprising a polyester-polyethylene glycol copolymer
  • the dispersed phase is fine and uniform, and coarsening during melt residence is suppressed, fineness unevenness is small when fiberized by melt spinning. , The occurrence of dyed spots and fluff is suppressed.
  • polyethylene glycol is added into the molten polyester oligomer, the polyethylene glycol having a low specific gravity relative to the polyester is localized in the upper layer in the reaction vessel, and the polyethylene glycol diffuses into the polyester oligomer. It took quite a while. For this reason, the reaction rate of polyethylene glycol and polyester falls, and unreacted polyethylene glycol finally remains.
  • the dispersed phase tends to coarsen during melt residence and not only causes fineness spots when fiberized by melt spinning, but also the polyethylene glycol component of the hydrophilic polymer is eluted during dyeing and use. Care is required because it becomes easy and the durability of hygroscopicity and antistatic property decreases.
  • a general catalyst for producing polyester can be used in any of esterification reaction, transesterification reaction and polycondensation reaction.
  • the esterification reaction proceeds even without a catalyst, but a titanium compound or the like may be added as a catalyst.
  • Specific examples of the transesterification catalyst include, but are not limited to, compounds such as magnesium, manganese, calcium, cobalt, zinc, lithium, and titanium.
  • Specific examples of the polycondensation reaction catalyst include, but are not limited to, compounds such as antimony, titanium, and germanium.
  • a phosphorus compound may be added as a heat stabilizer in order to improve the heat resistance and color tone of the fiber.
  • the phosphorus compound include phosphoric acid compounds, phosphorous acid compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. These phosphorus compounds may be used alone or in combination.
  • the phosphorus compound can be added as a heat stabilizer at any stage for producing the polyester-polyethylene glycol copolymer, and may be added at any stage before or after the esterification reaction or before or after the transesterification reaction. .
  • this heat stabilizer is not added, the molecular weight of the polyethylene glycol, which is a hydrophilic polymer, is lowered, the melt retention stability of the dispersed phase is lowered, and this becomes a factor of worsening fineness spots when fiberized by melt spinning.
  • an antioxidant can be added at any stage. Before and after the esterification reaction, before and after the transesterification reaction, and after adding the polycondensation catalyst, the pressure in the reaction tank is reduced and the polycondensation reaction is started. It may be added at any stage until completion. When the polycondensation reaction is added between the start and the end of the polycondensation reaction, the inside of the polycondensation reaction tank may be under reduced pressure or normal pressure.
  • the fiber having a phase separation structure made of a polyester-polyethylene glycol copolymer in the present invention is more oxidatively decomposable than a fiber made of a polyester-polyethylene glycol copolymer having a uniform structure without a phase separation structure.
  • an antioxidant in the fiber.
  • the deactivation of the antioxidant due to thermal decomposition during the esterification reaction, transesterification reaction, or polycondensation reaction from the viewpoint of preventing the antioxidant from scattering under reduced pressure, it is preferable to add an antioxidant just before the end of the polycondensation reaction and to stir the polycondensation reaction tank at normal pressure.
  • solid phase polymerization may be performed using the copolymer obtained by the above method. Good.
  • the heat treatment is performed under an inert gas atmosphere or under reduced pressure.
  • the inert gas include, but are not limited to, nitrogen, helium, carbon dioxide gas, and the like.
  • the pressure in the apparatus is preferably set to 133 Pa or less, and further, the time required for the solid phase polymerization reaction can be shortened by lowering the pressure.
  • the treatment temperature for solid phase polymerization is preferably 150 to 240 ° C.
  • a treatment temperature of solid-phase polymerization of 150 ° C. or higher is preferable because the polymerization reaction proceeds and the molecular weight can be increased.
  • the treatment temperature of the solid phase polymerization is more preferably 170 ° C. or higher, and further preferably 190 ° C. or higher.
  • the processing temperature of solid phase polymerization is 240 ° C. or lower, it is preferable because thermal decomposition can be suppressed and molecular weight reduction and coloring can be suppressed.
  • the treatment temperature of the solid phase polymerization is more preferably 235 ° C. or less, and further preferably 230 ° C. or less.
  • polyethylene glycol that has been heated and melted in advance is introduced into the polycondensation reaction vessel, and BHT is transferred thereto. Thereafter, the polyethylene glycol is sufficiently diffused into the BHT by stirring for about 1 hour. Subsequently, a polycondensation catalyst is added, the pressure is reduced to 500 Pa or less, and the reaction is carried out at 260 to 300 ° C. for 3 to 5 hours to obtain a polyethylene terephthalate-polyethylene glycol copolymer.
  • the phase separation structure composed of the hydrophobic polymer (polyethylene terephthalate) -hydrophilic polymer (polyethylene glycol) copolymer has a low polarity as the polycondensation reaction between polyethylene terephthalate precursor BHT and polyethylene glycol proceeds.
  • Copolymer that is, a copolymer having a high proportion of polyethylene terephthalate in the molecular chain
  • a highly polar copolymer that is, a copolymer having a high proportion of polyethylene glycol in the molecular chain. It is expressed by the difference in polarity.
  • the size of the dispersed phase in the phase separation structure is controlled by the number average molecular weight and copolymerization rate of polyethylene glycol, the temperature and stirring speed of the polycondensation reaction, or the degree of polymerization (molecular weight) of the polyethylene terephthalate-polyethylene glycol copolymer. Is possible.
  • the copolymer of the hydrophobic polymer and the hydrophilic polymer of the present invention forms a phase separation structure, and the yarn is produced. Since the range that can be selected as the conditions is narrow, it is necessary to appropriately set the spinning conditions according to the characteristics of the copolymer of the hydrophobic polymer and the hydrophilic polymer. However, according to a specific example of the production method described later, it is possible to stably obtain fibers in which fineness spots are small and generation of dyed spots and fluff is suppressed despite having a phase separation structure.
  • the copolymer of the hydrophobic polymer and the hydrophilic polymer of the present invention also forms a phase separation structure, the discharge linear velocity and shear rate are reduced for the purpose of suppressing the swell of the spinning wire due to the ballast effect.
  • the discharge from the spinneret was unstable, and the resulting fibers had large fineness spots, and many dyed spots and fluff were observed.
  • the present inventors have found that the discharge from the spinneret can be stabilized by increasing the discharge line speed and the shearing speed, contrary to the general method of reducing the swell of the spinning line due to the ballast effect.
  • phase separation structure composed of a hydrophobic polymer (polyethylene terephthalate) -hydrophilic polymer (polyethylene glycol) copolymer becomes finely dispersed when shearing is applied in the molten state as described above. This is considered to be due to the fact that the phase separation structure appears again after a certain period of time has elapsed after the application of shearing has stopped, although it disappears.
  • the shear rate when the copolymer of the hydrophobic polymer and the hydrophilic polymer passes through the spinneret is preferably 10,000 to 40,000 s ⁇ 1 .
  • the shear rate when passing through the spinneret is determined by the discharge amount per single hole of the spinneret, the discharge hole diameter, and the melt viscosity of the copolymer of the hydrophobic polymer and the hydrophilic polymer.
  • a shear rate of 10,000 s -1 or more when passing through the spinneret is preferable because fibers from the spinneret can be stably discharged, the fineness unevenness is small, and the occurrence of dyed spots and fluff is suppressed.
  • a shear rate of passing through the spinneret is 12000S -1 or more, more preferably 15000S -1 or more.
  • the shear rate when passing through the spinneret is 40000 s -1 or less, the spinning stress will not be too high, and the discharge from the spinneret will be stable, so the occurrence of sharkskin, melt fracture, etc. is suppressed, This is preferable because fibers with small fineness spots and suppressed generation of dyed spots and fluff are obtained.
  • a shear rate of passing through the spinneret is 38000S -1 or less, and more preferably 35000S -1 or less.
  • the discharge linear velocity is preferably 10 to 100 m / min.
  • the discharge linear velocity is determined by the discharge amount per single hole of the spinneret, the discharge hole diameter, and the melt viscosity of the copolymer of the hydrophobic polymer and the hydrophilic polymer.
  • a discharge linear velocity of 10 m / min or more is preferable because a fiber from which the discharge from the spinneret is stable, the fineness spots are small, and the occurrence of dyed spots and fluff is suppressed can be obtained.
  • the discharge linear velocity is more preferably 15 m / min or more, and further preferably 20 m / min or more.
  • the discharge linear velocity is 100 m / min or less, the spinning stress does not become too high, and the discharge from the spinneret is stable, so the occurrence of sharkskin and melt fracture is suppressed, the fineness spots are small, and dyeing is performed. This is preferable because a fiber in which generation of spots and fluff is suppressed can be obtained.
  • the discharge linear velocity is more preferably 90 m / min or less, and further preferably 80 m / min or less.
  • the spinning draft is preferably 10 to 300.
  • the spinning draft can be calculated by dividing the spinning speed by the discharge linear speed.
  • a spinning draft of 10 or more is preferable because productivity is improved.
  • the spinning draft is more preferably 20 or more, and further preferably 30 or more.
  • the spinning draft is 300 or less, the spinning stress is not excessively high, the spinning property is good, the fineness unevenness is small, and the fibers in which the occurrence of dyed spots and fluff is suppressed are preferable.
  • the spinning draft is more preferably 250 or less, and even more preferably 200 or less.
  • the spinneret used in the present invention a known one can be used, and the number of discharge holes can be appropriately selected according to the desired number of filaments.
  • the discharge hole diameter can be appropriately selected according to the shear rate, the discharge linear velocity, and the spinning draft, but is preferably 0.05 to 0.50 mm. If the discharge hole diameter is 0.05 mm or more, the pressure in the spin pack does not become too high, the discharge from the spinneret is stable, the fineness unevenness is small, and the fibers in which the occurrence of dyed spots and fluff is suppressed can be obtained. Therefore, it is preferable.
  • the discharge hole diameter is more preferably 0.10 mm or more, and further preferably 0.15 mm or more.
  • the discharge hole diameter is 0.50 mm or less, it is preferable because the back surface pressure of the spinneret is not insufficient, and the discharge spots between the discharge holes of the spinneret are suppressed. Further, it is preferable because the spinning draft can be increased without lowering the spinning speed and the productivity is improved.
  • the discharge hole diameter is more preferably 0.40 mm or less, and still more preferably 0.30 mm or less.
  • the copolymer of the hydrophobic polymer and the hydrophilic polymer it is preferable to dry the copolymer of the hydrophobic polymer and the hydrophilic polymer so that the water content is 300 ppm or less before performing melt spinning.
  • a water content of 300 ppm or less is preferable because molecular weight reduction due to hydrolysis and foaming due to moisture are suppressed during melt spinning, and spinning can be performed stably.
  • the water content is more preferably 200 ppm or less, and still more preferably 100 ppm or less.
  • an antioxidant may be added during melt spinning.
  • the fiber having a phase separation structure made of the hydrophobic polymer (polyester) -hydrophilic polymer (polyethylene glycol) copolymer in the present invention is a polyester-polyethylene glycol having a uniform structure having no phase separation structure. Compared with the fiber made of a copolymer, it has high oxidative decomposability, so it is preferable to contain a sufficient amount of an antioxidant in the fiber. Furthermore, by adding it during melt spinning, the polyester-polyethylene glycol copolymer can be added.
  • a method of adding an antioxidant when performing melt spinning a method in which a polyester-polyethylene glycol copolymer and an antioxidant are dry blended in advance and then put into a melt spinning machine, a polyester-polyethylene glycol copolymer and an antioxidant are added. Examples include, but are not limited to, a method of feeding the agent from a separate feeder into a melt spinning machine.
  • a polyester-polyethylene glycol copolymer chip which has been dried in advance is supplied to a melt spinning machine such as an extruder type or a pressure melter type and melted, and then measured with a measuring pump. Then, after introducing into the spinning pack heated in the spinning block and filtering the molten polymer in the spinning pack, it is discharged from the spinneret to form fiber yarns.
  • the fiber yarn discharged from the spinneret is cooled and solidified by a cooling device, taken up by a first godet roller, wound up by a winder through a second godet roller, and taken up as a wound yarn.
  • a heating cylinder or a thermal insulation cylinder having a length of 2 to 20 cm may be provided below the spinneret as necessary. Moreover, you may supply oil to a fiber yarn using an oil supply apparatus, and you may give an entanglement to a fiber yarn using an entanglement apparatus.
  • the spinning temperature in melt spinning can be appropriately selected according to the melting point and heat resistance of the copolymer of the hydrophobic polymer and the hydrophilic polymer, but is preferably 240 to 320 ° C. If the spinning temperature is 240 ° C. or higher, the elongation viscosity of the fiber yarn discharged from the spinneret is sufficiently lowered, so that the discharge is stable, and further, the spinning tension is not excessively high and the yarn breakage is suppressed. This is preferable.
  • the spinning temperature is more preferably 250 ° C. or higher, and further preferably 260 ° C. or higher. On the other hand, a spinning temperature of 320 ° C.
  • the spinning temperature is more preferably 310 ° C. or lower, and further preferably 300 ° C. or lower.
  • the spinning speed in melt spinning can be appropriately selected according to the composition of the copolymer of the hydrophobic polymer and the hydrophilic polymer, the spinning temperature, the spinning draft, and the like.
  • the spinning speed is preferably 500 to 5000 m / min in the case of the two-step method in which the melt spinning is once performed and wound and then separately drawn.
  • a spinning speed of 500 m / min or more is preferable because the running yarn is stable and yarn breakage can be suppressed.
  • the spinning speed in the two-step method is more preferably 1000 m / min or more, and further preferably 1500 m / min or more.
  • the spinning speed of the two-step method is 5000 m / min or less, the fiber yarn can be sufficiently cooled, and stable spinning can be performed, which is preferable.
  • the spinning speed in the two-step method is more preferably 4500 m / min or less, and further preferably 4000 m / min or less.
  • the spinning speed in the one-step method in which spinning and stretching are performed simultaneously without winding is preferably 500 to 5000 m / min for the low speed roller and 3000 to 6000 m / min for the high speed roller. It is preferable that the low-speed roller and the high-speed roller are within the above ranges because the running yarn is stabilized, yarn breakage can be suppressed, and stable spinning can be performed.
  • the spinning speed in the one-step method is more preferably 1000 to 4500 m / min for the low speed roller, 3500 to 5500 m / min for the high speed roller, 1500 to 4000 m / min for the low speed roller, and 4000 to 5000 m / min for the high speed roller. More preferably.
  • the heating method in stretching is not particularly limited as long as it is a device that can directly or indirectly heat the traveling yarn.
  • Specific examples of the heating method include, but are not limited to, a heating roller, a hot pin, a hot plate, a liquid bath such as hot water and hot water, a hot air (heated air), a gas bath such as steam, and a laser. These heating methods may be used alone or in combination. Heating methods include control of the heating temperature, uniform heating of the running yarn, and contact with the heating roller, contact with the hot pin, contact with the hot plate, and immersion in a liquid bath from the viewpoint of not complicating the device. It can be suitably employed.
  • the draw ratio in the case of drawing can be appropriately selected according to the strength and elongation of the fiber after drawing, but is preferably 1.02 to 7.0 times.
  • a draw ratio of 1.02 or more is preferable because mechanical properties such as fiber strength and elongation can be improved by drawing.
  • the draw ratio is more preferably 1.2 times or more, and further preferably 1.5 times or more.
  • the draw ratio is 7.0 times or less, yarn breakage during drawing is suppressed, and stable drawing can be performed.
  • the draw ratio is more preferably 6.0 times or less, and still more preferably 5.0 times or less.
  • the stretching temperature in the case of stretching can be appropriately selected according to the strength and elongation of the fiber after stretching, but is preferably 60 to 150 ° C.
  • a drawing temperature of 60 ° C. or higher is preferable because the yarn supplied to the drawing is sufficiently preheated, the thermal deformation during drawing becomes uniform, and the occurrence of fineness spots can be suppressed.
  • the stretching temperature is more preferably 65 ° C. or higher, and further preferably 70 ° C. or higher.
  • a stretching temperature of 150 ° C. or lower is preferable because thermal decomposition of the fiber can be suppressed.
  • the stretching temperature is more preferably 145 ° C. or less, and further preferably 140 ° C. or less. Further, heat setting at 60 to 150 ° C. may be performed as necessary.
  • the stretching speed in the case of stretching can be appropriately selected depending on whether the stretching method is a one-step method or a two-step method.
  • the speed of the high-speed roller corresponding to the spinning speed corresponds to the stretching speed.
  • the stretching speed is preferably 30 to 1000 m / min. A stretching speed of 30 m / min or more is preferable because the running yarn is stable and yarn breakage can be suppressed.
  • the stretching speed is more preferably 50 m / min or more, and further preferably 100 m / min or more.
  • a stretching speed of 1000 m / min or less is preferable because yarn breakage during stretching can be suppressed and stable stretching can be performed.
  • the stretching speed when stretching by the two-step method is more preferably 800 m / min or less, and further preferably 500 m / min or less.
  • a disperse dye can be suitably employed as the dye.
  • the dyeing method in the present invention is not particularly limited, and a cheese dyeing machine, a liquid dyeing machine, a drum dyeing machine, a beam dyeing machine, a jigger, a high-pressure jigger and the like can be suitably employed according to a known method.
  • the dye concentration and dyeing temperature there is no particular limitation on the dye concentration and dyeing temperature, and a known method can be suitably employed. If necessary, scouring may be performed before the dyeing process, or reduction cleaning may be performed after the dyeing process.
  • the fiber of the present invention and the fiber structure comprising the same have suppressed dyeing spots and fluff generation, are excellent in hygroscopicity and antistatic properties in a low-temperature and low-humidity environment, and dissolves hydrophilic compounds during dyeing and use Is suppressed. Therefore, it can be suitably used in applications where quality and comfort are required. Examples include, but are not limited to, general clothing uses, sports clothing uses, bedding uses, interior uses, and material uses.
  • Fineness (dtex) weight of fiber 100 m (g) ⁇ 100
  • the initial tensile resistance was calculated according to JIS L1013: 1999 (chemical fiber filament yarn test method) 8.10. A tensile test was performed in the same manner as in B above to draw a load-elongation curve, and the maximum point of load change with respect to elongation change was obtained near the origin of this curve, and JIS L1013: 1999 (chemical fiber filament yarn test method) 8.10. The initial tensile resistance (cN / dtex) was calculated using the formula described. The measurement was performed 5 times per sample, and the average value was defined as the initial tensile resistance.
  • a skein (10 turns) made of the fiber obtained by the example was prepared using a 1 m / circular measuring machine and allowed to stand for 24 hours. I put it. Thereafter, in this environment, a sample length L0 was measured by applying a load of 0.09 cN / dtex to the skein. Next, the skein was treated in boiling water at 98 ° C. with no load for 15 minutes and then air-dried for 24 hours. A load of 0.09 cN / dtex was applied to the skein to measure the sample length L1.
  • TEM transmission electron microscope
  • H-7100FA manufactured by Hitachi
  • the cross section parallel to the fiber axis was observed with respect to the stained ultrathin section.
  • a micrograph of the surface was taken. Observation was performed at respective magnifications of 2000 times, 8000 times, 20000 times, and 40000 times, and when taking a micrograph, the highest magnification at which 300 or more streaky dispersed phases could be observed was selected.
  • the image analysis software WinROOF manufactured by Mitani Shoji Co., Ltd.
  • the diameter of 300 randomly dispersed phases was measured and the maximum value was taken as the maximum diameter (nm) of the dispersed phase in the fiber longitudinal section.
  • the diameter of the dispersed phase in the fiber longitudinal section was measured with respect to the direction perpendicular to the fiber axis.
  • Fineness fluctuation value U% (hi) The fineness variation value U% (hi) is obtained by using the fiber obtained in the example as a sample and using a Worcester tester 4-CX manufactured by Zerbegger Worcester, measuring speed 200 m / min, measuring time 2.5 minutes, measured fiber length U% (half inert) was measured under conditions of 500 m and a twist number of 12000 / m (S twist). The measurement was performed five times for each sample, and the average value was defined as the fineness variation value U% (hi).
  • the single yarn diameter of 50 single yarns randomly selected is measured.
  • the number of single yarns in the sample is less than 50, a plurality of yarns manufactured under the same conditions are measured.
  • the single yarn diameter of a total of 50 single yarns was measured using the above samples. Since the fiber cross section is not necessarily a perfect circle, the area was measured when it was not a perfect circle, and the diameter when converted to a perfect circle was adopted as the single yarn diameter.
  • the single yarn diameter CV% was calculated by the following formula.
  • Single yarn diameter CV% ( ⁇ / X) ⁇ 100
  • the single yarn elongation (%) was calculated by the following equation using the stress (cN) at the point indicating the maximum load as the single yarn strength and using the elongation (L1) at the point indicating the maximum load and the initial sample length (L0).
  • the number of single yarns in the sample is 50 or more, the single yarn strength and the single yarn elongation of 50 randomly extracted yarns are measured.
  • the number of single yarns in the sample is less than 50, the same applies.
  • the single yarn strength and single yarn elongation of a total of 50 single yarns were measured.
  • the time to the rising half-value point is set to a negative value. If no DTG peak is observed while holding at 160 ° C for 360 minutes, The time to half point was set to 360 minutes or more. The measurement was performed five times for each sample, and the average value was defined as the time to the rising half-value point.
  • Friction band voltage After using the fiber obtained by the example as a sample, about 2 g of cylindrical knitting was produced using a circular knitting machine NCR-BL (bottle diameter 3 inch and half (8.9 cm), 27 gauge) manufactured by Eiko Sangyo. After scouring at 80 ° C. for 20 minutes in an aqueous solution containing 1 g / L of sodium carbonate and a surfactant Sunmol BK-80 manufactured by Nikka Chemical, it was dried for 60 minutes in a hot air dryer at 60 ° C.
  • NCR-BL bottle diameter 3 inch and half (8.9 cm), 27 gauge
  • the frictional voltage (V) is calculated in accordance with JIS L1094: 1997 (chargeability test method for woven fabrics and knitted fabrics) 5.2 under the atmosphere of a temperature of 10 ° C. and a humidity of 10% RH using a scoured tubular knitting as a sample. did. In addition, the measurement was performed 5 times per sample, and the average value was defined as the frictional voltage.
  • the moisture absorption rate (%) was calculated according to the moisture content of JIS L1096: 2010 (woven fabric and knitted fabric test method) 8.10 using a scoured tubular knitting produced in the same manner as O above as a sample.
  • the tube knitting was vacuum-dried at 110 ° C. for 24 hours, and the weight (W0) of the tube knitting when completely dried was measured.
  • the tube knitting was left in the constant temperature and humidity chamber LHU-123 manufactured by ESPEC adjusted to a temperature of 20 ° C. and a humidity of 65% RH for 24 hours, and after measuring the weight (W1) of the tube knitting, the temperature was 30 ° C.
  • the cylinder knitting was left for 24 hours in a thermo-hygrostat adjusted to a humidity of 90% RH, and the weight (W2) of the cylinder knitting was measured.
  • the dyeing was performed under the condition of a dyeing time of 60 minutes.
  • a dyeing time 60 minutes.
  • “It is dyed very uniformly and no dyed spots are observed” ⁇ Stained and almost no dyed spots are found '' ⁇ , ⁇ Almost not evenly dyed and slightly dyed spots are seen '' ⁇ , ⁇ Uniformly dyed and spotted spots are not clearly seen '' Was determined to be “x”, and ⁇ and ⁇ were determined to be acceptable.
  • Example 1 About 100 kg of bis ( ⁇ -hydroxyethyl) terephthalate was charged into the esterification reactor and maintained at a temperature of 250 ° C., then 89.2 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 39.8 kg of ethylene glycol (manufactured by Nippon Shokubai) Were sequentially fed over 2.5 hours. After completion of the supply, the esterification reaction was carried out for 2 hours to obtain an esterification reaction product. Subsequently, 13.6 kg of ethylene glycol (manufactured by Nippon Shokubai), 16.8 kg of polyethylene glycol having a number average molecular weight of 8300 melted by heating to 70 ° C.
  • the temperature in the polycondensation tank was raised from 250 ° C. to 285 ° C. over 60 minutes, and the pressure in the polycondensation tank was reduced from atmospheric pressure to 25 Pa, and then the polymerization reaction was performed for 3 hours.
  • the polymerization reaction product was discharged into cold water in a strand form, cooled, and immediately cut to obtain a pelletized polymerization reaction product. It was confirmed by 1 H-NMR that the copolymerization ratio of polyethylene glycol in the obtained polymerization reaction product was 14% by weight.
  • the obtained pellets were vacuum-dried at 150 ° C. for 12 hours (water content after drying: 95 ppm), then supplied to an extruder-type spinning machine to melt, and a spinneret (discharge) at a spinning temperature of 290 ° C. and a discharge rate of 57 g / min.
  • a spun yarn was obtained by discharging from a hole diameter of 0.23 mm, a discharge hole length of 0.60 mm, a discharge hole number of 36, and a round hole. The spun yarn is cooled by cooling air with an air temperature of 20 ° C.
  • An undrawn yarn of 190 dtex-36f was obtained by winding with a winder via a second godet roller rotating at the same speed as the dead roller.
  • the obtained undrawn yarn was drawn under conditions of a first hot roller temperature of 90 ° C., a second hot roller temperature of 130 ° C. and a draw ratio of 1.9 times to obtain a drawn yarn of 100 dtex-36f.
  • Table 1 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • the obtained fiber had good fiber properties such as strength and toughness.
  • the fibers had a phase separation structure, and the maximum diameter of the dispersed phase in the fiber cross section was 30 nm, and the maximum diameter of the dispersed phase in the fiber longitudinal section was 31 nm, and they were very finely dispersed. Further, while having a phase separation structure, U% (hi) was 1.0%, which was a very homogeneous fiber. Regarding the fabric properties, the antistatic property and the hygroscopic property were extremely excellent. Moreover, the weight reduction rate after the hot water treatment was low, elution of the hydrophilic compound was suppressed, and the leveling and quality were acceptable levels.
  • Examples 2-4 A drawn yarn was produced in the same manner as in Example 1 except that the copolymerization ratio, discharge amount, and spinneret (discharge hole diameter, discharge hole length, discharge hole number) of the hydrophilic polymer were changed as shown in Table 1.
  • Table 1 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • the fiber properties such as strength and toughness improve, the maximum diameter of the dispersed phase in the fiber cross section and fiber cross section decreases, and U% (hi) improves. It was.
  • the antistatic property and hygroscopicity were improved as the copolymerization rate of the hydrophilic polymer increased.
  • Examples 5-7 A drawn yarn was produced in the same manner as in Example 4 except that the discharge hole diameter of the spinneret was changed as shown in Table 1.
  • Table 1 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. As the discharge hole diameter decreases and the shear rate when passing through the spinneret increases, the fiber properties such as strength and toughness improve, and the maximum diameter of the dispersed phase in the fiber cross section and fiber longitudinal section decreases, and U% (hi ) Was good.
  • Examples 8 and 9 A drawn yarn was produced in the same manner as in Example 7 except that the copolymerization ratio of the hydrophilic polymer was changed as shown in Table 2.
  • Table 2 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the copolymerization rate of the hydrophilic polymer was changed, U% (hi) was low, and a homogeneous fiber was obtained.
  • Examples 10 and 11 A drawn yarn was produced in the same manner as in Example 4 except that the number average molecular weight of the hydrophilic polymer and the spinneret (discharge hole diameter) were changed as shown in Table 2.
  • the hydrophilic polymer polyethylene glycol having a number average molecular weight of 11000 (PEG 10000 manufactured by Sanyo Chemical Industries) was used in Example 10, and polyethylene glycol having a number average molecular weight of 20000 (PEG 20000 manufactured by Sanyo Chemical Industries) was used in Example 11.
  • Table 2 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the number average molecular weight of the hydrophilic polymer was changed, the fiber characteristics such as strength and toughness were good, U% (hi) was low, and uniform fibers were obtained.
  • Examples 12 and 13 A drawn yarn was produced in the same manner as in Example 1 except that the spinning speed was changed as shown in Table 2 and the draw ratio was changed to 5.7 times in Example 12 and 2.85 times in Example 13.
  • Table 2 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the spinning speed was changed, fiber properties such as strength and toughness were good, U% (hi) was low, and uniform fibers were obtained.
  • Example 14 Citrate chelate titanium complex equivalent to 10 ppm in terms of titanium atom, 82.5 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals), and 49.1 kg of 1,3-propanediol are obtained at a temperature of 240 ° C.
  • the esterification reaction tank maintained at a pressure of 1.2 ⁇ 10 5 Pa, the esterification reaction was performed until the temperature of the distillate fell below 90 ° C. to obtain an esterification reaction product.
  • the temperature in the polycondensation tank was raised from 240 ° C. to 280 ° C. over 60 minutes, and the pressure in the polycondensation tank was reduced from atmospheric pressure to 40 Pa, and then the polymerization reaction was performed for 3 hours.
  • the polymerization reaction product was discharged into cold water in a strand form, cooled, and immediately cut to obtain a pelletized polymerization reaction product. It was confirmed by 1 H-NMR that the copolymerization ratio of polyethylene glycol in the obtained polymerization reaction product was 14% by weight.
  • the obtained pellets were vacuum-dried at 150 ° C. for 12 hours, then supplied to an extruder-type spinning machine and melted, and a spinneret (discharge hole diameter 0.23 mm, discharge hole length at a spinning temperature of 265 ° C. and a discharge rate of 57 g / min. 0.60 mm, 36 discharge holes, round holes) to obtain a spun yarn.
  • the spun yarn is cooled by cooling air with an air temperature of 20 ° C. and an air speed of 20 m / min, applied with an oil agent by a lubricating device, converged, and taken up by a first godet roller rotating at 3000 m / min.
  • An undrawn yarn of 190 dtex-36f was obtained by winding with a winder via a second godet roller rotating at the same speed as the dead roller.
  • the obtained undrawn yarn was drawn under conditions of a first hot roller temperature of 55 ° C., a second hot roller temperature of 130 ° C. and a draw ratio of 1.9 times to obtain a drawn yarn of 100 dtex-36f.
  • Table 2 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the hydrophobic polymer was changed to polypropylene terephthalate, the fiber properties such as strength and toughness were good, U% (hi) was low, and uniform fibers were obtained.
  • Example 15 Citrate chelate titanium complex equivalent to 10 ppm in terms of titanium atom, 82.5 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 89.5 kg of 1,4-butanediol, and a temperature of 220 ° C.
  • the esterification reaction tank maintained at a pressure of 1.2 ⁇ 10 5 Pa, the esterification reaction was performed until the temperature of the distillate fell below 90 ° C. to obtain an esterification reaction product.
  • the temperature in the polycondensation tank was raised from 220 ° C. to 250 ° C. over 60 minutes, and the pressure in the polycondensation tank was reduced from atmospheric pressure to 60 Pa, and then the polymerization reaction was performed for 3 hours.
  • the polymerization reaction product was discharged into cold water in a strand form, cooled, and immediately cut to obtain a pelletized polymerization reaction product. It was confirmed by 1 H-NMR that the copolymerization ratio of polyethylene glycol in the obtained polymerization reaction product was 14% by weight.
  • the obtained pellets were vacuum-dried at 150 ° C. for 12 hours, then supplied to an extruder-type spinning machine, melted, and spinneret (discharge hole diameter 0.23 mm, discharge hole length at a spinning temperature of 260 ° C. and a discharge rate of 57 g / min. 0.60 mm, 36 discharge holes, round holes) to obtain a spun yarn.
  • the spun yarn is cooled by cooling air with an air temperature of 20 ° C. and an air speed of 20 m / min, applied with an oil agent by a lubricating device, converged, and taken up by a first godet roller rotating at 3000 m / min.
  • An undrawn yarn of 190 dtex-36f was obtained by winding with a winder via a second godet roller rotating at the same speed as the dead roller.
  • the obtained undrawn yarn was drawn under conditions of a first hot roller temperature of 65 ° C., a second hot roller temperature of 130 ° C. and a draw ratio of 1.9 times to obtain a drawn yarn of 100 dtex-36f.
  • Table 2 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the hydrophobic polymer was changed to polybutylene terephthalate, fiber properties such as strength and toughness were good, U% (hi) was low, and homogeneous fibers were obtained.
  • Table 3 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Fiber characteristics such as strength and toughness were good, U% (hi) was low, and homogeneous fibers were obtained. However, since it is a fiber composed only of a hydrophobic polymer, it did not have a phase separation structure. Regarding the fabric characteristics, although the leveling property and quality were extremely excellent, the frictional voltage was 9800 V, the antistatic property was extremely low, ⁇ MR was 0.1%, and the hygroscopicity was extremely low.
  • Comparative Examples 2-4 A drawn yarn was produced in the same manner as in Example 4 except that the number average molecular weight of the hydrophilic polymer was changed as shown in Table 3.
  • the hydrophilic polymer polyethylene glycol having a number average molecular weight of 3400 (PEG 4000 manufactured by Sanyo Chemical Industries) was used in Comparative Example 2, polyethylene glycol having a number average molecular weight of 6000 (PEG 6000 manufactured by Aldrich) in Comparative Example 3, and number average in Comparative Example 4.
  • Polyethylene glycol having a molecular weight of 100,000 R-150 manufactured by Meisei Chemical Industry
  • Table 3 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • fiber properties such as strength and toughness were good, U% (hi) was low, and homogeneous fibers were obtained.
  • the number average molecular weight of polyethylene glycol was less than 7000, it did not have a phase separation structure.
  • the fabric characteristics although the leveling property and the quality were extremely excellent, the frictional voltage was 7600 V, which was inferior in the antistatic property.
  • Comparative Example 3 as in Comparative Example 2, fiber properties such as strength and toughness were good, U% (hi) was low, and homogeneous fibers were obtained, but the number average molecular weight of polyethylene glycol was 7000. Therefore, it did not have a phase separation structure.
  • the fabric characteristics were excellent in leveling and quality, but the frictional voltage was 6900 V, which was inferior in antistatic performance.
  • Comparative Example 4 since the number average molecular weight of polyethylene glycol was high, the maximum diameter of the dispersed phase in the fiber cross section and fiber longitudinal section was large, and a coarse phase separation structure was formed. Therefore, in addition to low fiber properties such as strength and toughness, U% (hi) is high and the fiber is extremely heterogeneous and cannot be used. As for the fabric properties, the leveling and quality were extremely inferior.
  • Comparative Example 5 A drawn yarn was produced in the same manner as in Example 8 except that the copolymerization ratio of the hydrophilic polymer was changed as shown in Table 3.
  • Table 3 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Due to the high copolymerization rate of the hydrophilic polymer, the discharge from the spinneret becomes unstable. As a result, the fiber properties such as strength and toughness are extremely low, and U% (hi) is high and extremely heterogeneous. The fiber was unbearable for use. As for the fabric properties, the leveling and quality were extremely inferior.
  • Comparative Examples 6 and 7 The copolymerization rate, discharge amount, and spinneret (discharge hole diameter, discharge hole length, discharge hole number) of the hydrophilic polymer were changed as shown in Table 3, and the draw ratio was 3.3 times for both Comparative Examples 6 and 7. Except for the above, a drawn yarn was produced in the same manner as in Example 12.
  • Table 3 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • Comparative Example 6 since the shear rate at the time of passing through the spinneret is low, the discharge from the spinneret becomes extremely unstable. As a result, the fiber characteristics such as strength and toughness are extremely low, and U% (hi) is High and very heterogeneous fibers, which could not be used. As for the fabric properties, the leveling and quality were extremely inferior.
  • Comparative Example 7 since the shear rate when passing through the spinneret is high, the spinning stress becomes high and the discharge from the spinneret becomes unstable. As a result, U% (hi) is slightly high and the fiber lacks homogeneity. there were. As for the fabric properties, the leveling quality and quality did not reach acceptable levels.
  • Example 4 After the transfer of BHT, polyethylene glycol was charged from above into a polycondensation tank in a powder state without being heated and melted. Furthermore, immediately after the addition of polyethylene glycol, stirring was not performed at 250 ° C. for 1 hour. A stretched yarn was prepared in the same manner as in Example 4 except that the polymerization was started.
  • Table 3 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • Polyethylene glycol was added in a powder state, and further, no stirring was performed after the addition of polyethylene glycol, and polymerization was started with insufficient dispersion of polyethylene glycol in the esterification reaction product.
  • the maximum diameter of the dispersed phase in the fiber cross section and fiber longitudinal section was large, and a coarse phase separation structure was formed. Therefore, the fiber characteristics such as strength and toughness are low, U% (hi) is high, and the fiber lacks homogeneity.
  • the leveling quality and quality did not reach acceptable levels.
  • Comparative Example 9 About 100 kg of bis ( ⁇ -hydroxyethyl) terephthalate was charged into the esterification reactor and maintained at a temperature of 250 ° C., then 89.2 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 39.8 kg of ethylene glycol (manufactured by Nippon Shokubai) Were sequentially fed over 2.5 hours. After completion of the supply, the esterification reaction was carried out for 2 hours to obtain an esterification reaction product. After transferring 110.6 kg of the obtained esterification reaction product to a polycondensation tank heated to 250 ° C.
  • the mixture was stirred at 250 ° C. for 1 hour, 120 g of silicon (manufactured by Momentive Performance Materials, TSF433) as an antifoaming agent, 30 g of trimethyl phosphate (manufactured by Wako Pure Chemical Industries) as a thermal stabilizer and stirring for 10 minutes, 30 g of antimony trioxide as a polymerization catalyst, Manganese acetate 22g was added and stirred for 5 minutes. Subsequently, the temperature in the polycondensation tank was increased from 250 ° C. to 285 ° C.
  • the pressure was reduced from 25 to 25 Pa, and then the polymerization reaction was performed for 30 minutes.
  • the polymerization reaction product was discharged into cold water in a strand form, cooled, and immediately cut to obtain a pelletized polymerization reaction product. Using the obtained pellets, a drawn yarn was produced in the same manner as in Example 4.
  • Table 3 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • Table 3 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • polyethylene terephthalate and polyethylene glycol were melt-kneaded, the maximum diameter of the dispersed phase in the fiber cross-section and fiber cross-section was large, U% (hi) was high, and the fiber lacked homogeneity.
  • both the unreacted PEG content and the weight loss after hot water treatment were high, and the leveling quality and quality did not reach acceptable levels.
  • Comparative Example 11 In Comparative Example 2, a drawn yarn was produced in the same manner as in Comparative Example 2, except that the amount of the antioxidant (added before the start of the polycondensation reaction) was changed to 600 g.
  • Table 3 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Fiber characteristics such as strength and toughness were good, U% (hi) was low, and homogeneous fibers were obtained. However, since the number average molecular weight of polyethylene glycol was less than 7000, it did not have a phase separation structure. As for the fabric characteristics, although the leveling property and the quality were extremely excellent, the frictional voltage was 7200 V, which was inferior in antistatic performance.
  • Example 16 About 100 kg of bis ( ⁇ -hydroxyethyl) terephthalate was charged into the esterification reactor and maintained at a temperature of 250 ° C., then 89.2 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 39.8 kg of ethylene glycol (manufactured by Nippon Shokubai) Were sequentially fed over 2.5 hours. After completion of the supply, the esterification reaction was carried out for 2 hours to obtain an esterification reaction product. Subsequently, 13.6 kg of ethylene glycol (manufactured by Nippon Shokubai), 14.4 kg of polyethylene glycol having a number average molecular weight of 8300 melted by heating to 70 ° C.
  • the temperature in the polycondensation tank was raised from 250 ° C. to 285 ° C. over 60 minutes, and the pressure in the polycondensation tank was reduced from atmospheric pressure to 25 Pa, and then the polymerization reaction was performed for 3 hours. Thereafter, pentaerythritol-tetrakis (3- (3,5-) was added as an antioxidant (added after the start of the polycondensation reaction) to a container having a thickness of 0.2 mm and an internal volume of 500 cm 3 prepared by injection molding a polyethylene terephthalate sheet.
  • Table 4 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • the fiber characteristics such as strength and toughness were good, U% (hi) was low, and the fiber was homogeneous.
  • an antioxidant after the start of the polycondensation reaction, scattering of the antioxidant under vacuum during the polycondensation reaction and deactivation of the antioxidant due to thermal decomposition are suppressed, and The antioxidant content was high, the time to the rising half-value point was 360 minutes or more, and oxidative decomposition was suppressed.
  • the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were good, and the leveling property and quality were acceptable.
  • Example 17-19 the antioxidant added after the start of the polycondensation reaction was used.
  • Example 17 2,4,6-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) mesitylene (manufactured by ADEKA) was used.
  • Table 4 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • the fiber characteristics such as strength and toughness were good, U% (hi) was low, and the fiber was homogeneous.
  • the content of the antioxidant in the fiber is high, the time to the rising half-point is over 360 minutes, It was suppressed.
  • the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were good, and the leveling property and quality were acceptable.
  • Example 16 an antioxidant was not added before the start of the polycondensation reaction, but pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxy) was added as an antioxidant added after the start of the polycondensation reaction.
  • a drawn yarn was produced in the same manner as in Example 4 except that phenol) propionate) (manufactured by BASF, Irganox 1010) was changed to 480 g in Example 20, 1200 g in Example 21, and 2400 g in Example 22.
  • Table 4 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the addition amount of the antioxidant added after the start of the polycondensation reaction was changed, the fiber characteristics such as strength and toughness were good, and the U% (hi) was low and the fiber was homogeneous. Furthermore, in any addition amount, the antioxidant content in the fiber was high, the time to the rising half-point was 360 minutes or more, and oxidative degradation was also suppressed. In addition, the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were good, and the leveling property and quality were acceptable.
  • Example 23 In the extruder type spinning machine, the pellets obtained in Example 4 were transferred from the main feeder to pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (manufactured by BASF, Irganox 1010). ) was supplied from the sub-feeder at a weight ratio of 100: 0.4, and a drawn yarn was produced in the same manner as in Example 4.
  • Table 4 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • the fiber characteristics such as strength and toughness were good, U% (hi) was low, and the fiber was homogeneous.
  • an antioxidant at the time of melt spinning, the content of the antioxidant in the fiber was high, the time to the rising half-point was 360 minutes or more, and oxidative degradation was suppressed.
  • the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were good, and the leveling property and quality were acceptable.
  • Example 24 In the extruder type spinning machine, the pellets produced without adding the antioxidant before the start of the polycondensation reaction in Example 4 were transferred from the main feeder to pentaerythritol-tetrakis (3- (3,5-di-t-butyl). -4-Hydroxyphenol) propionate) (manufactured by BASF, Irganox 1010) was prepared in the same manner as in Example 4 except that the weight ratio of 100: 0.4 was supplied from the sub-feeder.
  • Table 4 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • the fiber characteristics such as strength and toughness were good, U% (hi) was low, and the fiber was homogeneous.
  • an antioxidant at the time of melt spinning, the content of the antioxidant in the fiber was high, the time to the rising half-point was 360 minutes or more, and oxidative degradation was suppressed.
  • the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were good, and the leveling property and quality were acceptable.
  • Example 25 Citrate chelate titanium complex equivalent to 10 ppm in terms of titanium atom, 82.5 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals), and 49.1 kg of 1,3-propanediol are obtained at a temperature of 240 ° C.
  • the esterification reaction tank maintained at a pressure of 1.2 ⁇ 10 5 Pa, the esterification reaction was performed until the temperature of the distillate fell below 90 ° C. to obtain an esterification reaction product.
  • the temperature in the polycondensation tank was raised from 240 ° C. to 280 ° C. over 60 minutes, and the pressure in the polycondensation tank was reduced from atmospheric pressure to 40 Pa, and then the polymerization reaction was performed for 3 hours. Thereafter, pentaerythritol-tetrakis (3- (3,5-) was added as an antioxidant (added after the start of the polycondensation reaction) to a container having a thickness of 0.2 mm and an internal volume of 500 cm 3 prepared by injection molding a polypropylene terephthalate sheet.
  • Table 4 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the hydrophobic polymer was changed to polypropylene terephthalate, the fiber characteristics such as strength and toughness were good, and U% (hi) was low, and the fiber was homogeneous. Furthermore, the time to the rising half-value point was 360 minutes or more, and oxidative decomposition was also suppressed. In addition, the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were good, and the leveling property and quality were acceptable.
  • Example 26 Citrate chelate titanium complex equivalent to 10 ppm in terms of titanium atom, 82.5 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 89.5 kg of 1,4-butanediol, and a temperature of 220 ° C.
  • the esterification reaction tank maintained at a pressure of 1.2 ⁇ 10 5 Pa, the esterification reaction was performed until the temperature of the distillate fell below 90 ° C. to obtain an esterification reaction product.
  • the temperature in the polycondensation tank was raised from 220 ° C. to 250 ° C. over 60 minutes, and the pressure in the polycondensation tank was reduced from atmospheric pressure to 60 Pa, and then the polymerization reaction was performed for 3 hours. Thereafter, pentaerythritol-tetrakis (3- (3,5) was added as an antioxidant (added after the start of the polycondensation reaction) to a container having a thickness of 0.2 mm and an internal volume of 500 cm 3 prepared by injection molding a polybutylene terephthalate sheet.
  • Table 4 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the hydrophobic polymer was changed to polybutylene terephthalate, the fiber characteristics such as strength and toughness were good, U% (hi) was low, and the fiber was homogeneous. Furthermore, the time to the rising half-value point was 360 minutes or more, and oxidative decomposition was also suppressed. In addition, the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were good, and the leveling property and quality were acceptable.
  • Example 27-36 In the extruder type spinning machine, the pellets produced in Example 1 in Examples 27, 35, and 36, the pellets produced in Example 3 in Example 28, the pellets produced in Example 4 in Examples 29-31, In Example 32, the pellets produced in Example 8, the pellets produced in Example 10 in Example 33, and the pellets produced in Example 11 in Example 34 were transferred from the main feeder to pentaerythritol-tetrakis (3- (3,5 -Di-t-butyl-4-hydroxyphenol) propionate) (Irganox 1010, manufactured by BASF) was supplied from a sub-feeder at a weight ratio of 100: 0.4. Example 27 was prepared in the same manner as in Example 1.
  • Example 29 is the same as Example 5
  • Example 30 is the same as Example 6
  • Example 31 is the same as Example 7.
  • Example 32 is the same as Example 8
  • Example 33 is the same as Example 10
  • Example 34 is the same as Example 11
  • Example 35 is the same as Example 12
  • Example 36 Produced a drawn yarn in the same manner as in Example 13.
  • Table 5 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the number average molecular weight and copolymerization rate of the hydrophilic polymer, the shear rate when passing through the spinneret, and the spinning rate are changed, the fiber properties such as strength and toughness are good, and U% (hi) is low and homogeneous. Fiber. Furthermore, by adding an antioxidant at the time of melt spinning, the content of the antioxidant in the fiber was high, the time to the rising half-point was 360 minutes or more, and oxidative degradation was suppressed. In addition, the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were good, and the leveling property and quality were acceptable.
  • Example 37 a drawn yarn was produced in the same manner as in Example 4 except that the amount of the antioxidant (added before the start of the polycondensation reaction) was changed to 600 g.
  • Table 5 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • the fiber characteristics such as strength and toughness were good, U% (hi) was low, and the fiber was homogeneous.
  • the fabric properties the antistatic property and the hygroscopic property were extremely excellent.
  • the weight reduction rate after the hot water treatment was low, elution of the hydrophilic compound was suppressed, and the leveling and quality were acceptable levels.
  • Example 38 A slurry composed of 8.7 kg of dimethyl terephthalate, dimethyl 5-sodium sulfoisophthalate (SSIA) (manufactured by Sanyo Chemical Industries), and 5.6 kg of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) was charged into the transesterification reaction tank. As a result, 21.5 g of lithium acetate dihydrate and 2 g of cobalt acetate tetrahydrate were added, and the transesterification was carried out at 240 ° C. for 2 hours to obtain a transesterification product.
  • SSIA dimethyl 5-sodium sulfoisophthalate
  • ethylene glycol manufactured by Nippon Shokubai Co., Ltd.
  • the temperature in the polycondensation tank was raised from 240 ° C. to 285 ° C. over 60 minutes, and the pressure in the polycondensation tank was reduced from atmospheric pressure to 25 Pa, and then the polymerization reaction was performed for 3 hours. Thereafter, pentaerythritol-tetrakis (3- (3,5-) was added as an antioxidant (added after the start of the polycondensation reaction) to a container having a thickness of 0.2 mm and an internal volume of 500 cm 3 prepared by injection molding a polyethylene terephthalate sheet.
  • Di-t-butyl-4-hydroxyphenol) propionate (BASF, Irganox 1010) 40 g was added from the top of the reaction vessel, the inside of the polycondensation tank was purged with nitrogen, returned to normal pressure, stirred for 10 minutes, and polymerized The reaction product was discharged into cold water in a strand form, cooled, and immediately cut to obtain a pelletized polymerization reaction product. Using the obtained pellets, a drawn yarn was produced in the same manner as in Example 4.
  • the SSIA copolymerization rate shown in Table 6 is the ratio of the weight of the sulfur element contained in the polymerization reaction product.
  • Table 6 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • the fiber characteristics such as strength and toughness were good, U% (hi) was low, and the fiber was homogeneous. Furthermore, the time to the rising half-point was 360 minutes or more, the oxidative decomposition was suppressed, and the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were also good. Further, since 5-sodium sulfoisophthalic acid was copolymerized, it exhibited cationic dyeability, and the leveling quality and quality were acceptable.
  • Examples 39 and 40 A drawn yarn was produced in the same manner as in Example 38 except that the copolymerization rate of 5-sodium sulfoisophthalic acid was changed as shown in Table 6.
  • Table 6 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the copolymerization ratio of 5-sodium sulfoisophthalic acid was changed, the fiber characteristics such as strength and toughness were good, and the U% (hi) was low and the fiber was homogeneous. Furthermore, the time to the rising half-point was 360 minutes or more, the oxidative decomposition was suppressed, and the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were also good. Moreover, leveling quality and quality were acceptable levels.
  • Examples 41 and 42 A drawn yarn was produced in the same manner as in Example 38 except that the copolymerization ratio of the hydrophilic polymer was changed as shown in Table 6.
  • Table 6 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the copolymerization ratio of the hydrophilic polymer was changed, the fiber characteristics such as strength and toughness were good, U% (hi) was low, and the fiber was homogeneous. Furthermore, the time to the rising half-point was 360 minutes or more, the oxidative decomposition was suppressed, and the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were also good. Moreover, leveling quality and quality were acceptable levels.
  • Table 6 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
  • fiber properties such as strength and toughness were good, U% (hi) was low, and the fiber was homogeneous. Furthermore, the time to the rising half-point was 360 minutes or more, the oxidative decomposition was suppressed, and the antistatic property, hygroscopicity, and the weight reduction rate after the hot water treatment were also good. Moreover, leveling quality and quality were acceptable levels.
  • the fiber of the present invention has a phase separation structure, the fineness spots are small, the occurrence of dyed spots and fluff is suppressed, and the durability of the fiber characteristics against long-term storage and tumbler drying It is excellent in hygroscopicity and antistatic properties in a low-temperature and low-humidity environment, and the elution of hydrophilic compounds is suppressed during dyeing and use. Therefore, it can be suitably used as a fiber structure such as a woven or knitted fabric or a non-woven fabric for clothing.

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Abstract

Le problème décrit par la présente invention est de fournir une fibre pour laquelle, en dépit d'une structure de séparation de phase, une irrégularité de finesse est petite, l'irrégularité de coloration et le lainage sont supprimés, la durabilité de caractéristiques de fibre par rapport au stockage à long terme et au séchage par culbutage sont excellents, les caractéristiques anti-électriques dans des environnements à basse température et basse humidité sont excellentes, et l'élution d'un composé hydrophile lors de la teinture ou lors de l'usage de la fibre est supprimée. La présente invention se rapporte à une fibre ayant une structure de séparation de phase. La fibre est caractérisée en ce : qu'elle comprend un copolymère d'un polymère hydrophobe et d'un polymère hydrophile; qu'elle possède une phase continue et une phase dispersée selon une structure de séparation de phase; que le diamètre maximal de phase dispersée dans une section transversale fibre est compris entre 1 et 40 nm; et que la valeur de fluctuation de finesse U % (hi) est comprise entre 0,1 à 1,5 %.
PCT/JP2015/058297 2014-03-25 2015-03-19 Fibre à structure de séparation de phase et procédé de fabrication d'une telle fibre Ceased WO2015146790A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201580015835.7A CN106164349B (zh) 2014-03-25 2015-03-19 具有相分离结构的纤维及其制造方法
JP2015515321A JP6582980B2 (ja) 2014-03-25 2015-03-19 相分離構造を有する繊維およびその製造方法
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WO2020095910A1 (fr) * 2018-11-06 2020-05-14 東レ株式会社 Tissu non tissé filé-lié, fibre filée-liée et tissu non tissé stratifié
EP3744888A4 (fr) * 2018-01-25 2021-05-05 Toray Industries, Inc. Tissu non-tissé filé-lié
JP2022167302A (ja) * 2021-04-23 2022-11-04 東レ株式会社 スパンボンド不織布の製造方法

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CN113122952B (zh) * 2021-03-30 2022-07-15 新疆蓝山屯河科技股份有限公司 一种pbat纤维及制备方法
CN114540982B (zh) * 2022-02-18 2023-01-06 华南理工大学 一种皮芯型复合纤维束及其制备方法和应用
CN120026401B (zh) * 2025-04-22 2025-07-22 东华大学 一种具有梯度结构的吸湿速干聚丙烯纤维及其制备方法

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WO2020095910A1 (fr) * 2018-11-06 2020-05-14 東レ株式会社 Tissu non tissé filé-lié, fibre filée-liée et tissu non tissé stratifié
JP2022167302A (ja) * 2021-04-23 2022-11-04 東レ株式会社 スパンボンド不織布の製造方法
JP7619145B2 (ja) 2021-04-23 2025-01-22 東レ株式会社 スパンボンド不織布の製造方法

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