KR20160134639A - Fiber having phase separation structure and manufacturing method for such fiber - Google Patents

Abstract

Despite having a phase separation structure, it has a small fineness of fineness, suppresses occurrence of uneven dyeing and fluff, suppresses durability of fiber properties for long-term storage or tumble drying, excellent hygroscopicity and excellent antistatic property under low- It is an object of the present invention to provide a fiber in which elution of a hydrophilic compound is inhibited during dyeing or use. The fiber having the phase separation structure is made of a copolymer of a hydrophobic polymer and a hydrophilic polymer, and has a continuous phase and a dispersed phase by a phase separation structure. The maximum diameter of the dispersed phase in the fiber cross section is 1 to 40 nm, and the% (hi) is 0.1 to 1.5%.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a fiber having a phase separation structure,

The present invention relates to fibers having a phase-separated structure. More particularly, the present invention relates to a dye-sensitized solar cell which is excellent in durability, hygroscopicity of fiber properties to long-term storage and drying of tumble, low hygroscopicity, The present invention relates to a fiber which is excellent in antistatic property and can be preferably used for medical use in which elution of a hydrophilic compound is suppressed at the time of dyeing or use.

Since polyester fibers are inexpensive and have excellent mechanical properties, they are widely used. However, because of insufficient hygroscopicity, it has drawbacks such as generation of feeling of sweat during high-humidity in summer and generation of static electricity in low-humidity in winter. The frictional electromotive force of polyethylene terephthalate as a general purpose polyester is about 7000 to 9000 V in a standard state at a temperature of 20 占 폚 and a humidity of 40% RH. The smaller the value of the frictional voltage is, the more difficult it is to generate the static electricity, and the better the wearing comfort is. In the case of polyethylene terephthalate, it can be said that the fiber is very poor in antistatic property.

To improve the above drawbacks, various proposals have been made so far on a method of imparting antistaticity to polyester fibers. As a general method for imparting antistatic properties, copolymerization of a hydrophilic compound with a polyester or addition of a hydrophilic compound can be mentioned. By these methods, although it is possible to improve the antistatic property, it is in the present state that sufficient antistatic property can not be obtained under a low temperature and low humidity environment such as a room where the humidity is very low due to outdoor use in the winter or heating.

For example, Patent Document 1 proposes an antistatic polyester fiber to which a polyoxyalkylene glycol and an organic metal salt are added as a hydrophilic compound to a polyester. In this proposal, polyoxyalkylene glycol is dispersed in polyester fibers to impart antistatic properties.

Patent Document 2 proposes a core-sheath composite fiber in which polyethylene glycol-copolymerized polyester is core and polypropylene terephthalate is superimposed. In this proposal, polyesters copolymerized with polyethylene glycol arranged on the padding impart antistatic properties to the polyester fibers.

Japanese Patent Application Laid-Open No. 7-173725 Japanese Patent Application Laid-Open No. 11-93022

However, in the method described in the above Patent Document 1, the frictional electrification voltage is as low as 600 V at a temperature of 20 ° C and a humidity of 40% RH, so that the electrification property is good. However, under a low temperature and low humidity environment such as a temperature of 10 ° C and a humidity of 10% There is a problem that antistatic properties are not expressed. Further, since the polyester and the hydrophilic compound are not copolymerized, there is a problem that the hydrophilic compound elutes at the time of dyeing or use, resulting in low antistatic durability.

Also in the method described in Patent Document 2, the frictional electrification voltage is as low as 400 V at a temperature of 20 ° C and a humidity of 40% RH in the same manner as in the method described in Patent Document 1, There is a problem that sufficient antistatic property is not exhibited under a low temperature and low humidity environment.

Further, in any case, when polyethylene glycol which is incompatible with polyester is used as a hydrophilic compound, there is a problem that the unevenness of the fineness is large, uneven dyeing and lint are generated. Further, since the oxidative decomposition of polyethylene glycol is not inhibited, oxidative decomposition proceeds by long-term storage or tumble drying, and the problem of deterioration of fiber properties such as antistatic property and mechanical property under hygroscopicity and low temperature and low humidity environment there was.

Disclosure of the Invention The object of the present invention is to solve the above problems of the prior art, and it is an object of the present invention to provide a dye-sensitized solar cell which is excellent in antistatic property under hygroscopicity and low temperature and low humidity environment And a fiber which can be preferably employed for medical use in which elution of a hydrophilic compound is inhibited in dyeing or in use.

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a hydrophilic polymer which comprises a copolymer of a hydrophobic polymer and a hydrophilic polymer, has a continuous phase and a dispersed phase by a phase separation structure, has a maximum diameter of 1 to 40 nm, (hi) of 0.1 to 1.5%.

The fiber of the present invention preferably has a copolymer of a hydrophobic polymer and a hydrophilic polymer exposed on at least a part of the surface of the fiber, preferably the hydrophobic polymer is polyester and the hydrophilic polymer is polyethylene glycol .

Further, the fiber of the present invention was heated under a mixed gas atmosphere of nitrogen: oxygen = 80 vol%: 20 vol% at a mixed gas flow rate of 200 ml / min, at a heating rate of 30 캜 / min from 160 캜 to 160 캜, (DTG), it is preferable that the time taken to reach 160 DEG C is 0 minute, and the time up to the half-value of elevated temperature is 120 minutes or more. It is also preferable that the antioxidant is at least one selected from the group consisting of a phenol compound, a sulfur compound and a hindered amine compound, and the content of the antioxidant is 0.01 to 2.0 wt% Can be employed.

The fiber of the present invention preferably has a frictional electromotive force of 3000 V or less measured at a temperature of 10 DEG C and a humidity of 10% RH in accordance with JIS L1094.

Further, a method of producing a fiber characterized in that a spinning speed is 10000 to 40000 s ^-1 when a copolymer of the hydrophobic polymer and the hydrophilic polymer is passed through the spinneret is preferably employed.

(Effects of the Invention)

According to the present invention, it is possible to provide a dye-sensitized solar cell which is excellent in durability of fiber properties for long-term storage or tumble drying, hygroscopicity, low temperature and low humidity environment It is possible to provide a fiber having excellent antistatic property and inhibiting elution of a hydrophilic compound at the time of dyeing or use. This fiber can be preferably used particularly in medical applications.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph showing a fiber cross section of a fiber having a phase separation structure according to the present invention. Fig.
2 is a photograph for illustrating a fiber longitudinal section of a fiber having a phase-separated structure according to the present invention.

The fiber of the present invention is composed of a copolymer of a hydrophobic polymer and a hydrophilic polymer and has a continuous phase and a dispersed phase by a phase separation structure and has a maximum diameter of 1 to 40 nm and a variation degree of fineness U% hi) is 0.1 to 1.5%. The fibers of the present invention have a phase separation structure, but as shown in Fig. 1, since a fine and uniform dispersed phase is formed in the fiber cross section, the unevenness in fineness is small and the occurrence of uneven dyeing and fluff is suppressed. In addition, since the hydrophobic polymer and the hydrophilic polymer are copolymerized with each other, hygroscopicity and antistatic property can be imparted to the fibers, and durability against hygroscopicity and antistatic property is obtained because the elution of the hydrophilic compound is inhibited during dyeing or use. Further, as shown in Fig. 2, since a fine, uniformly striped dispersed phase is formed in a direction parallel to the fiber axis on the fiber longitudinal cross section, even under a low temperature and low humidity environment, the fiber having low frictional electrification voltage Can be obtained.

The hydrophobic polymer in the present invention can be preferably employed without particular limitation as long as copolymerization with the hydrophilic polymer is possible. Specific examples of the hydrophobic polymer include aromatic polyesters such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and polyhexamethylene terephthalate, polylactic acid, polyglycolic acid, polyethylene adipate, polypropylene adipate, poly Aliphatic polyesters such as butylene adipate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate and polycaprolactone. . Among them, polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate are preferable because they are excellent in mechanical properties and durability, and are easy to handle at the time of production and use.

The hydrophilic polymer in the present invention can be preferably employed without particular limitation, as long as it can be copolymerized with the hydrophobic polymer. It is possible to impart antistaticity to the fiber by copolymerizing the hydrophilic polymer with the hydrophilic polymer. Specific examples of the hydrophilic polymer include homopolymers such as polyethylene glycol and polypropylene glycol, copolymers such as polyethylene glycol-polypropylene glycol copolymer and polyethylene glycol-polybutylene glycol copolymer, and the like. Do not. Among them, polyethylene glycol and polypropylene glycol are preferable because they are good in handleability at the time of production and use.

The fiber of the present invention is composed of a copolymer of a hydrophobic polymer and a hydrophilic polymer. Unlike melt blending such as polymer blending, since the hydrophobic polymer and the hydrophilic polymer form a covalent bond by copolymerization, the elution of the hydrophilic polymer from the fibers is inhibited, and during the manufacturing process or when the product is used A fiber having a small change in fiber properties and having excellent durability can be obtained.

The fibers of the present invention have a phase-separated structure. This phase separation structure is specifically expressed in the course of copolymerization of the hydrophobic polymer and the hydrophilic polymer as the polymerization reaction progresses. In other words, unlike the phase separation structure which is developed by melt mixing of the non-use polymer compound, in the present invention, a fine and homogeneous dispersed phase is formed because of the phase separation structure that is developed along with the progress of the polymerization reaction. Since the dispersed phase is fine and uniform, the resulting fibers have a phase separation structure, and the unevenness of the fineness is small and the occurrence of uneven dyeing and fluff is suppressed. In addition, since it has a phase separation structure, it is possible to obtain a fiber having excellent antistatic property under a low-temperature and low-humidity environment.

Specific examples of the phase separation expressed along with the progress of the polymerization reaction are shown. In the case of a copolymer of polyethylene terephthalate as a hydrophobic polymer and polyethylene glycol as a hydrophilic polymer, since the polarity of bis (β-hydroxyethyl) terephthalate, which is a precursor of polyethylene terephthalate, and polyethylene glycol are close to each other at the beginning of the polycondensation reaction, And the reaction system is transparent. Upon the progress of the polycondensation reaction, a polyethylene terephthalate-polyethylene glycol copolymer is produced. When about one hour has elapsed from the initiation of polymerization, phase separation occurs and the reaction system becomes cloudy. This phase-separated structure is a copolymer having a low polarity in the polyethylene terephthalate-polyethylene glycol copolymer, that is, a copolymer having a high proportion of polyethylene terephthalate in the molecular chain and a copolymer having a high polarity, that is, a polyethylene glycol A high proportion of the copolymer is produced, and the copolymer is expressed by the difference in polarity.

The fiber of the present invention has a continuous phase and a dispersed phase by 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. When the proportion of the hydrophobic polymer is higher than that of the hydrophilic polymer, the " hydrophobic polymer-hydrophilic polymer copolymer ", which has a high proportion of the hydrophobic polymer occupying in the molecular chain, becomes a continuous phase and the ratio of the hydrophilic polymer in the molecular chain is high. Polymeric copolymer " becomes a dispersed phase. On the other hand, when the proportion of the hydrophilic polymer is larger than that of the hydrophobic polymer, the " hydrophobic polymer-hydrophilic polymer copolymer ", which has a high proportion of the hydrophilic polymer occupying in the molecular chain, becomes a continuous phase, and the " hydrophobic polymer - hydrophilic polymer copolymer " becomes a dispersed phase. In either case, since both of the continuous phase and the dispersed phase are composed of " hydrophobic polymer-hydrophilic polymer copolymer ", and the composition ratio thereof is different, it is a phase-separated structure having a very high affinity between the continuous phase and the dispersed phase. For this reason, it has been found that the stability in the melt state of the disperse phase is very high, and that the disperse phase forms a phase separation structure difficult to coarsen in the melt state. Therefore, it has become clear that unevenness in fineness when fibers are formed by melt spinning is improved, and elution of hydrophilic compounds during dyeing or use can be suppressed.

In the present invention, when a polyester is used as the hydrophobic polymer, an ester-forming dicarboxylic acid other than terephthalic acid may be used as the dicarboxylic acid component of the polyester. Specific examples of the ester-forming dicarboxylic acid include adipic acid, isophthalic acid, sebacic acid, phthalic acid, 4,4'-diphenyldicarboxylic acid, 5-sodium sulfoisophthalic acid, Dicarboxylic acids such as phthalic acid and 5- (tetraalkyl) phosphonium sulfoisophthalic acid, and ester-forming derivatives thereof, and the like, but the present invention is not limited thereto.

In the present invention, when a polyester is used as the hydrophobic polymer, 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 .

In the present invention, when polyethylene terephthalate is used as the hydrophobic polymer and polyethylene glycol is used as the hydrophilic polymer, the number average molecular weight of the polyethylene glycol is preferably 7000 to 20,000. When the number average molecular weight of the polyethylene glycol is 7000 or more, the phase-separated structure is expressed by copolymerization with polyethylene terephthalate. The number average molecular weight of the polyethylene glycol is more preferably 7500 or more, and still more preferably 8000 or more. On the other hand, if the number average molecular weight of the polyethylene glycol is 20,000 or less, the polycondensation reaction between polyethylene terephthalate and polyethylene glycol is high, so that unreacted polyethylene glycol can be reduced. Further, copolymerization with polyethylene terephthalate results in formation of a stable phase separation structure in which the dispersed phase is fine and uniform, the coarsening at the time of melt retention is suppressed, and after the completion of the polycondensation reaction, This is preferable because discharge from detention is stabilized and operability is improved. In addition, it is preferable that homogeneous fibers having a small degree of unevenness in fineness and suppressing the occurrence of uneven dyeing and fluff can be obtained. The number average molecular weight of the polyethylene glycol is more preferably 17000 or less, and still more preferably 15000 or less.

In the present invention, when polyethylene terephthalate is used as the hydrophobic polymer and polyethylene glycol is used as the hydrophilic polymer, 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, it is preferable because a fiber excellent in hygroscopicity and antistatic property can be obtained. The copolymerization ratio of polyethylene glycol is more preferably 11% by weight or more, and still more preferably 12% by weight or more. On the other hand, when 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 when the polymerization reaction is completed after the completion of the polycondensation reaction, This is preferable because the discharge is stabilized and operability is improved. It is also preferable that homogeneous fibers having a small degree of unevenness in fineness and having uneven dyeing and suppressing the occurrence of fluffs can be obtained, and the fibers and the mechanical properties of the fiber structure composed thereof are improved. The copolymerization ratio of polyethylene glycol is more preferably 19% by weight or less, and still more preferably 18% by weight or less.

In the present invention, the inventors of the present invention have studied the phase separation structure composed of a hydrophobic polymer (polyethylene terephthalate) -hydrophilic polymer (polyethylene glycol) copolymer. As a result, as described above, the phase separation structure Therefore, when the shear is applied in the molten state, the phase separation structure is slightly oxidized and finally disappears. However, the present inventors have discovered a specific phenomenon that the phase separation structure is again expressed when the application of the shear is stopped and a predetermined time elapses. Although the fibers will be described in detail in the production method of the fibers described later, by using this specific phenomenon, it has been succeeded in obtaining fibers having a small degree of unevenness in dyeing, uneven dyeing, and suppressed the occurrence of fluffs despite having a phase separation structure.

The copolymer of the hydrophobic polymer and the hydrophilic polymer in the present invention may be modified in various ways by adding a secondary additive. As specific examples of the secondary additives, there may be mentioned additives such as a compatibilizer, a plasticizer, an ultraviolet absorber, an infrared absorber, a fluorescent brightener, a release agent, an antibacterial agent, a nucleating agent, a heat stabilizer, an antioxidant, an antistatic agent, Gelling agents, latexes, fillers, inks, coloring agents, dyes, pigments, perfumes, and the like. These secondary additives may be used singly or in combination.

The maximum diameter of the dispersed phase in the fiber cross section of the fibers 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. If the maximum diameter of the dispersed phase in the fiber cross section is 1 nm or more, fibers having excellent hygroscopicity and antistatic properties can be obtained. 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. On the other hand, if the maximum diameter of the dispersed phase in the fiber cross section is 40 nm or less, the fiber and the fiber structure made of the fiber have good mechanical properties and excellent durability. In addition, since it is a fine and uniformly dispersed phase, discharge from the spinneret during spinning is stabilized, workability is improved, fineness of fineness is small, and occurrence of uneven dyeing and fluff is suppressed. The maximum diameter of the dispersed phase in the fiber cross section is more preferably 37 nm or less, more preferably 35 nm or less, particularly preferably 30 nm or less.

The maximum diameter of the dispersed phase in the fiber longitudinal cross section of the fiber of the present invention is preferably 1 to 40 nm. The details of the method for measuring the maximum diameter of the dispersed phase on the fiber cross section will be described later. The maximum diameter of the dispersed phase in the fiber longitudinal cross section is the maximum value of the diameter of the dispersed phase in the direction perpendicular to the fiber axis. When the maximum diameter of the dispersed phase in the fiber longitudinal cross section is 1 nm or more, it is preferable because fibers having excellent hygroscopicity and antistatic property can be obtained. The maximum diameter of the dispersed phase in the fiber longitudinal cross section is more preferably 3 nm or more, more preferably 5 nm or more, and particularly preferably 10 nm or more. On the other hand, if the maximum diameter of the dispersed phase in the fiber longitudinal cross section is 40 nm or less, it is preferable because the fibers and the fiber structure made of the fibers have good mechanical properties and excellent durability. Further, since it is a fine and uniformly dispersed phase, discharge from the spinneret during spinning is stabilized, workability is improved, fineness of fineness is small, occurrence of uneven dyeing and generation of fluff is suppressed. The maximum diameter of the dispersed phase in the fiber cross section is more preferably 37 nm or less, more preferably 35 nm, and particularly preferably 30 nm or less.

The total fineness of the fibers of the present invention is not particularly limited and may be appropriately selected depending on the application and required properties, but is preferably 10 to 500 dtex. When the total fineness of the fibers is 10 dtex or more, the yarn breakage is small, the processability is good, the occurrence of fluff is small during use, and the durability is excellent. The total fineness of the fibers is more preferably 30 dtex or more, and still more preferably 50 dtex or more. On the other hand, if the total fineness of the fibers is 500 dtex or less, it is preferable that the fiber and the fibrous structure are not impaired in flexibility. The total fineness of the fibers is more preferably 400 dtex or less, and still more preferably 300 dtex or less.

The strength of the fiber of the present invention is not particularly limited and can be appropriately selected depending on the application and required characteristics, but is preferably 2.0 to 5.0 cN / dtex from the viewpoint of mechanical properties. When the strength of the fiber is 2.0 cN / dtex or more, it is preferable that the yarn breaks less in the spinning, drawing, weaving, and forming processes, and is excellent in durability at the time of use in addition to good processability. The strength of the fiber is more preferably 2.5 cN / dtex or more, and still more preferably 3.0 cN / dtex or more. On the other hand, if the strength of the fiber is 5.0 cN / dtex or less, it is preferable that the fiber and the fibrous structure are not impaired in flexibility.

The elongation of the fiber of the present invention is not particularly limited and can be appropriately selected depending on the application and required characteristics, but is preferably 10 to 60% from the viewpoint of processability. When the elongation of the fiber is 10% or more, the abrasion resistance of the fiber and the fibrous structure is improved, the processability is good, the occurrence of fluff is small during use and the durability is good. The elongation of the fiber is more preferably 15% or more, and still more preferably 20% or more. On the other hand, if the elongation of the fibers is 60% or less, the dimensional stability of the fibers and the fiber structure is improved, which is preferable. 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 may be appropriately selected depending on the application and required properties. It is preferable that the initial tensile resistance measured according to 8.10 of JIS L1013: 1999 is 10 to 100 cN / dtex Do. If the initial tensile resistance of the fiber is 10 cN / dtex or more, it is preferable because the processability and processability are good and the mechanical properties are excellent. The initial tensile resistance of the fiber is more preferably 15 cN / dtex or more, and more preferably 20 cN / dtex or more. On the other hand, if the initial tensile resistance of the fiber is 100 cN / dtex or less, it is preferable since the flexibility of the fiber and the fiber structure is not impaired. 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 depending on the application and required characteristics, but it is preferably 3 to 100 탆. When the fiber diameter of the fiber is 3 m or more, it is preferable that the fiber is excellent in the processability in the preparation and in the high-order processing, and the fiber having excellent mechanical properties is obtained. The fiber diameter of the fiber is more preferably 5 탆 or more, and more preferably 7 탆 or more. On the other hand, if the fiber diameter of the fiber is 100 탆 or less, the flexibility of the fiber and the fiber structure is not deteriorated. The fiber diameter of the fiber is more preferably 70 탆 or less, and more preferably 50 탆 or less.

The boiling water shrinkage ratio of the fibers of the present invention is preferably 3 to 15%. If the boiling water shrinkage ratio of the fibers is 3% or more, the fabric can be shrunk by heat shrinking to increase the weaving density, and the weaving tension in the weaving process can be suppressed to an appropriate range to produce a high density fabric. Further, it is not necessary to weave under a high tension force when producing a high-density fabric, and occurrence of fluff or shrinkage in the weaving process can be suppressed, so that a fabric with few defects can be produced with good processability. The boiling water shrinkage ratio of the fibers is more preferably 4% or more, and still more preferably 5% or more. On the other hand, if the water boiling water shrinkage ratio of the fibers is 15% or less, the degree of orientation of the molecular chains during the treatment in boiling water is not extremely lowered, and the strength drop after the boiling water treatment is small. It is also preferable that the fabric can be shrunk sufficiently by heat shrinking the fabric, and a flexible fabric can be obtained. The boiling water shrinkage ratio of the fibers is more preferably 12% or less, and further 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 fluctuation value U% is an index of thickness irregularity in the fiber length direction, and the smaller the fineness fluctuation value U% (hi), the smaller the thickness irregularity in the longitudinal direction of the fiber. The fineness fluctuation value U% (hi) is preferably as small as possible from the viewpoint of process transparency and durability, but the lower limit is 0.1% as a manufacturable range. On the other hand, if the fiber fineness fluctuation value U% (hi) is 1.5% or less, uniformity in the fiber length direction is excellent, and fluctuation of the working tension in the regular diameter process, weaving, and forming process can be suppressed. In addition, it is preferable that the lint and the yarn are not easily broken, and defects such as uneven dyeing and staining are less likely to occur when dyed, so that a high-quality fiber structure is obtained. The fineness variation value U% (hi) of the fiber is more preferably 1.2% or less, more preferably 1.0% or less, and particularly preferably 0.9% or less.

The single yarn diameter CV% of the fibers of the present invention is preferably 0.1 to 15%. From the viewpoint of process passability and durability, the smaller the diameter is, the better, but the lower the productionable range is, 0.1%. On the other hand, when the monofilament diameter CV% of the fibers is 15% or less, occurrence of fluff at the time of manufacture and use can be suppressed, and defects such as uneven dyeing and staining are less likely to occur when dyed, . The single yarn diameter CV% of the fibers is more preferably 12% or less, further preferably 10% or less, particularly preferably 7% or less.

The single yarn fineness CV% of the fibers 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 transparency and durability, but the lower limit is 0.1% as a manufacturable range. On the other hand, when the single yarn fineness of the fibers is not more than 15%, occurrence of fluff at the time of manufacture and use can be suppressed, and defects such as uneven dyeing and staining are less likely to occur when dyed, . The single yarn fineness CV of the fibers is more preferably 12% or less, more preferably 10% or less, and particularly preferably 7% or less.

The single yarn strength CV% of the fibers 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 durability, but the lower limit is 0.1% as a manufacturable range. On the other hand, when the single yarn strength CV% of the fibers is 20% or less, generation of napping during production and use can be suppressed, and defects such as uneven dyeing and staining are less likely to occur when dyed, . The single yarn strength CV% of the fibers 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 fibers of the present invention is preferably 0.1 to 40%. The single yarn length CV% is preferably as small as possible from the viewpoint of process passability and durability, but the lower limit is 0.1% as a manufacturable range. On the other hand, when the single yarn endurance CV% of the fibers is 40% or less, occurrence of fluff at the time of manufacture and use can be suppressed, and defects such as uneven dyeing and staining are less likely to occur when dyed, . The single yarn CV% of the fibers is more preferably 37% or less, more preferably 35% or less, and particularly preferably 30% or less.

The fibers of the present invention were obtained by heating the fibers at 160 DEG C after raising the temperature from room temperature to 160 DEG C at a mixed gas flow rate of 200 mL / min and a heating rate of 30 DEG C / min in a mixed gas atmosphere of nitrogen: oxygen = 80 vol% In the cleavage weight analysis (DTG), it is preferable that the time to reach 160 DEG C is 0 minute, and the time to the elevated half value point is 120 minutes or more. Details of the method of measuring the rising half-value point will be described later, but this evaluation method is adopted as the acceleration test assuming durability against long-term storage or tumble drying. The inventors of the present invention found that a fiber having a phase-separated structure composed of a hydrophobic polymer (polyethylene terephthalate) -hydrophilic polymer (polyethylene glycol) copolymer exhibits a rise peak (Polyethylene glycol) is degraded, and the hygroscopicity is lost as the polyethylene glycol is decomposed to decrease the moisture absorption rate difference DELTA MR. Further, the antistatic property under low temperature and low humidity environments is lost and the frictional electrification voltage is increased . The time up to the half-lifted point is preferable from the viewpoints of hygroscopicity for long-term storage or tumble drying, antistatic properties under low-temperature and low-humidity environments, and durability of fiber properties such as mechanical properties. More preferably, the time to the elevated half-value point is 180 minutes or more, more preferably 240 minutes or more, and particularly preferably 360 minutes or more.

The moisture absorption rate difference (? MR) of the fibers of the present invention is preferably 1 to 10%. The details of the measurement method of ΔMR 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 of clothes after light exercise and the moisture absorption rate at a temperature of 20 ° C. and a humidity of 65% The difference in the rate is ΔMR. That is,? MR is an index of hygroscopicity, and the higher the value of? MR, the better the wearing comfort. If the DELTA MR of the fiber is 1% or more, the sweatiness in the clothes is preferable because the feel is less and the wearing comfort is expressed. The ΔMR of the fiber is more preferably 1.5% or more, and further preferably 2% or more. On the other hand, if the DELTA MR of the fiber is 10% or less, it is preferable because the processability and handling property are good and durability at the time of use is excellent. The ΔMR of the fiber is more preferably 9% or less, and further preferably 8% or less.

Since the hydrophobic polymer and the hydrophilic polymer are copolymerized with each other in the fiber of the present invention, dissolution of the hydrophilic polymer by hot water or the like is suppressed unlike the case where the hydrophobic polymer and the hydrophilic polymer are melt-mixed. Therefore, the durability of the hygroscopic property is high and can be suitably employed as the fibrous structure.

The fiber of the present invention preferably has a frictional electrification voltage of 3000 V or less at a temperature of 10 캜 and a humidity of 10% RH. The details of the method of measuring the friction voltage will be described later, but the friction voltage is an indicator of the static electricity. The lower the value of the friction voltage, the more the static electricity is suppressed. The frictional voltage is preferably as small as possible from the viewpoint of wearing comfort. In addition, it is preferable that the frictional electrification voltage is lower than the temperature and humidity conditions such as a temperature of 20 占 폚 and a humidity of 40% RH as well as an environment of low temperature and humidity such as a temperature of 10 占 폚 and a humidity of 10% RH It is preferable to exhibit excellent antistatic property because the friction voltage is low. When the friction voltage of the fiber at a temperature of 10 ° C and a humidity of 10% RH is 3000 V or less, static electricity is less likely to be generated even in a low temperature and low humidity environment such as a room where the humidity is very low due to outdoor use in winter, It is preferable because it is excellent in comfort. The friction voltage of the fiber at 10 ° C and 10% RH is more preferably 2500 V or less, and more preferably 2000 V or less.

The fiber of the present invention can be a composite fiber comprising a copolymer of a hydrophobic polymer and a hydrophilic polymer and a (co) polymer other than the copolymer. At this time, it is preferable that the copolymer of the hydrophobic polymer and the hydrophilic polymer is exposed to at least a part of the surface of the fiber. For example, when a copolymer of a hydrophobic polymer and a hydrophilic polymer is used as a core component of a core-sheath composite fiber and a copolymer of a hydrophobic polymer and a hydrophilic polymer completely coated with a supercritical component, It is preferable that the copolymer of the hydrophobic polymer and the hydrophilic polymer be exposed to at least a part of the surface of the fiber because the fiber having excellent hygroscopicity and antistatic property can be obtained. Also, even when a copolymer of a hydrophobic polymer and a hydrophilic polymer is used as a core component of a core-sheath composite fiber, at least a part of the core component may be exposed on the surface of the fiber and a copolymer of the hydrophobic polymer and the hydrophilic polymer may be dispersed , At least a part of the conductive component may be exposed on the surface of the fiber.

The fiber of the present invention preferably contains an antioxidant. The addition of the antioxidant is preferable because it not only inhibits the oxidative decomposition of the hydrophilic polymer due to long-term storage or tumble drying but also improves the durability of the fiber properties such as hygroscopicity, antistatic property under low-temperature and low-humidity conditions, and mechanical properties . The present inventors have also found that a fiber having a phase separation structure composed of a hydrophobic polymer (polyethylene terephthalate) -hydrophilic polymer (polyethylene glycol) copolymer according to the present invention has a uniform structure of polyethylene terephthalate-polyethylene glycol copolymer The present inventors have discovered a method capable of containing a sufficient amount of an antioxidant in a fiber as described later and have a phase separation structure and inhibited the oxidation and decomposition, It is possible to stably obtain fibers having excellent durability of fiber properties such as antistatic properties and mechanical properties under an environment.

The antioxidant in the present invention is preferably selected from phenol compounds, sulfur compounds, and hindered amine compounds. These antioxidants may be used alone or in combination of two or more.

The phenolic compound in the present invention is a radical chain reaction inhibitor having a phenolic structure, and specific examples thereof include 2,6-t-butyl-p-cresol, butylhydroxyanisole, 2,6-t- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl- (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl- Ethyl} 2,4,8,10-tetraoxaspiro {5,5} undecane, 1-dimethyl-2 - {? - (3-t- butyl-4-hydroxy-5-methylphenyl) propionyloxy} Methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5- (4-hydroxy-3'-t-butylphenyl) butyric acid} glycol ester, tocopherol, pentaerythritol-tetrakis (3- Di-t-butyl-4-hydroxyphenol) propionate), 2,4,6-tris (3 ', 5'- Mesitylene, 1,3,5-tris [[4- (1,1-dimethylethyl) -3-hydroxy-2,6-dimethylphenyl] methyl] -1,3,5-triazine- , 4,6 (1H, 3H, 5H) -tione, and the like, but are not limited thereto. These phenol compounds may be used alone or in combination of two or more. Among them, pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate (Irganox1010, manufactured by BASF), 2,4,6- T-butyl [4 - (1,1-dimethylethyl) - < / RTI > Methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione (THANOX1790 manufactured by Tokyo Chemical Industry Co., Ltd.) Can be preferably employed since the decomposition inhibiting effect is high.

The sulfur-based antioxidant of the present invention is a sulfur-based antioxidant that itself oxidizes by reducing peroxides without generating radicals. Specific examples thereof include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3 '-Thiodipropionate, distearyl 3,3'-thiodipropionate, and the like, but are not limited thereto. These sulfur-based antioxidants may be used alone or in combination of two or more.

The hindered amine-based compound in the present invention is a hindered amine antioxidant that has the effect of trapping radicals generated by ultraviolet rays or heat, and having an effect of regenerating a phenol-based antioxidant that functions as an antioxidant and is inactivated Tetraethyl-4-piperidyl-1,6-hexamethylenediamine and N (N, N'-bis - (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{6- (1,1,3,3-tetramethylbutyl) amino- -Triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene {(2,2,6,6-tetramethyl- N, N '' - tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine Diazin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10- diamine and dimethyl succinate and 4-hydroxy-2,2,6,6- 1-piperidine ethanol, poly [(6-morpholino-s-triazine-2,4 -Diyl) [2,2,6,6-tetramethyl-4-piperidyl] imino] -hexamethylene [(2,2,6,6-tetramethyl-4- piperidyl) imino] , 2,2,6,6-tetramethyl-4-piperidyl] imino] -hexamethylene [(2,2,6,6-tetramethyl- , 6,6-tetramethyl-4-piperidylimino]], 1,6-hexanediamine-N, N'-bis (1,2,2,6,6-pentamethyl- Dill) and a methylated polymer of morpholine-2,4,6-trichloro-1,3,5-triazine, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza- (2,3-epoxy-propyl) dispyro- [5,1,11,2] -heneic acid-21-one, and the like. These hindered amine compounds may be used alone, or two or more of them may be used in combination. Among them, a high molecular weight type hindered amine compound having a molecular weight of 1,000 or more is preferable from the viewpoint of inhibiting elution from the inside of the fiber by washing or cleaning using an organic solvent. Particularly, 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 (CHIMASSORB2020 made by BASF) can be favorably employed since it has a high effect of inhibiting oxidation decomposition.

The content of the antioxidant in the fiber of the present invention is preferably 0.01 to 2.0 wt% of the fiber weight. By incorporating a sufficient amount of an antioxidant in the fiber to exhibit an antioxidant effect, it is possible to inhibit oxidative decomposition of the hydrophilic compound due to long-term storage or tumble drying, and it is possible to suppress the oxidation and decomposition of the hydrophilic compound, The durability of the fiber properties of the fibers is improved. When the content of the antioxidant is 0.01% by weight or more, it is preferable because the oxidative decomposition inhibiting effect can be imparted to the fibers. The content of the antioxidant is more preferably 0.05% by weight or more, more preferably 0.1% by weight or more, particularly preferably 0.15% by weight or more. On the other hand, if the content of the antioxidant is 2.0% by weight or less, the color tone of the fiber will not deteriorate and the mechanical properties will not be impaired. The content of the antioxidant is more preferably 1.7% by weight or less, more preferably 1.5% by weight or less, particularly preferably 1.0% by weight or less.

The fiber of the present invention is not particularly limited as far as the cross-sectional shape of the fiber is, and may be a circular circular cross section or a non-circular cross section. Specific examples of the non-circular cross section include, but are not limited to, multi-leaf, polygonal, flat, elliptical, C-shaped, H-shaped, S-shaped, T-shaped, W-shaped, X-shaped and Y-shaped.

The fiber of the present invention is not particularly limited as to the shape of the fiber, and may be any of monofilament, multifilament, and staple.

Like the ordinary fibers, the fibers of the present invention can be processed into twisted yarns or twisted yarns, so that weaving and knitting can be handled in the same manner as ordinary fibers.

The form of the fiber structure made of the fiber of the present invention is not particularly limited, and it can be made into a fabric, a knitted fabric, a pile fabric, a nonwoven fabric, a spun yarn, a filling cotton and the like according to a known method. The fibrous structure composed of the fibers of the present invention may be any of a woven structure or a plain structure and may be a plain weave, a twill weave, a weave weave or a weave, a warp, a weave, Can be adopted.

The fibers of the present invention may be used in combination with other fibers by way of teaching, knitting or the like in the case of a fiber structure, or may be formed into a fiber structure after being mixed with other fibers.

Next, a method for producing a copolymer of a hydrophobic polymer and a hydrophilic polymer used in the present invention will be described. As a specific example, a method of producing a phase-separated structure comprising a polyester-polyethylene glycol copolymer using polyester as a hydrophobic polymer and polyethylene glycol as a hydrophilic polymer will be described below.

In the present invention, at the time of producing the polyester-polyethylene glycol copolymer, first, the polyester component is subjected to an esterification reaction or an ester exchange reaction alone to obtain a polyester oligomer. Next, the polyester oligomer is added to a reaction tank to which polyethylene glycol is added in advance. When polyethylene glycol is a solid at this time, it is preferable to melt by heating at 70 DEG C or higher, and further, after addition of the polyester oligomer to polyethylene glycol, stir sufficiently. Thus, in addition to the improvement in the polycondensation reactivity of polyethylene glycol, the diffusion of polyethylene glycol into the polyester oligomer proceeds rapidly, and when the phase separation structure is developed along with the progress of the polycondensation reaction, the polyethylene glycol is fine and uniform, A stabilized dispersed phase in which coarsening is suppressed can be formed. In order to reduce the unreacted polyethylene glycol, it is necessary that the polyester oligomer and the polyethylene glycol are mixed and stirred in a commercial state for at least 1 hour or more. In the phase-separated structure of the obtained polyester-polyethylene glycol copolymer, if the dispersed phase is fine and uniform and the coarsening at the time of melt retention is suppressed, the unevenness of the fineness when fibers are formed by melt spinning is small, Is suppressed. If polyethylene glycol is added to the molten polyester oligomer, polyethylene glycol having a low specific gravity relative to the polyester is localized in the upper layer of the reaction tank, and a considerable time is required for the polyethylene glycol to diffuse into the polyester oligomer did. As a result, the reaction rate between the polyethylene glycol and the polyester decreases, and the unreacted polyethylene glycol finally remains. In such a case, the dispersed phase is easily coarsened at the time of melt retention, and not only becomes a cause of unevenness in fineness when fiber is formed by melt spinning, but also the polyethylene glycol component of the hydrophilic polymer is easy to elute at the time of dyeing or use, So that it may cause deterioration of durability of the electric property.

In the present invention, any of the esterification reaction, transesterification reaction and polycondensation reaction may be a general catalyst for producing polyester. Although the esterification reaction proceeds without a catalyst, a titanium compound or the like may be added as a catalyst. Specific examples of the ester exchange reaction catalyst include compounds such as magnesium, manganese, calcium, cobalt, zinc, lithium and titanium, but are not limited thereto. Specific examples of the polycondensation reaction catalyst include, but are not limited to, compounds such as antimony, titanium, and germanium.

In the present invention, a phosphorus compound may be added as a heat stabilizer to improve heat resistance and color tone of the fiber. Specific examples of the phosphorus compound include a phosphoric acid compound, a phosphorous acid compound, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, an aposphonic acid compound, an aposphinic acid compound, and a phosphine compound. These phosphorus compounds may be used singly or in combination.

In the present invention, a phosphorus compound may be added as a heat stabilizer at any stage of producing the polyester-polyethylene glycol copolymer. The phosphorus compound may be added at any stage before or after the esterification reaction or before or after the ester exchange reaction. Further, in order to further improve the heat resistance and color tone, a phosphorus compound may be further added during the period from the start of the polycondensation reaction to the end of the polycondensation reaction after the addition of the polycondensation catalyst. When this heat stabilizer is not added, the molecular weight of the polyethylene glycol of the hydrophilic polymer is lowered, the stability of the melt stability of the dispersed phase is lowered, and the fiber unfavorability is deteriorated when the fiber is made into fiber by melt spinning.

In the present invention, it is possible to add an antioxidant at an arbitrary stage, and it is also possible to add an antioxidant at any stage, and before and after the esterification reaction, before and after the transesterification reaction and after the polycondensation catalyst is added, It may be added at any stage. When the polycondensation reaction is added between the initiation and the end of the polycondensation reaction, the polycondensation reaction tank may be either decompression or normal pressure. As described above, the fiber having the phase-separated structure of the polyester-polyethylene glycol copolymer in the present invention has a higher oxidation-decomposability than the fiber composed of the polyester-polyethylene glycol copolymer having a uniform structure having no phase separation structure Therefore, it is preferable to contain a sufficient amount of the antioxidant in the fibers, and it is preferable that the antioxidant is inactivated by the thermal decomposition during the esterification reaction, the transesterification reaction, the polycondensation reaction, and the antioxidant is prevented from scattering under reduced pressure during the polycondensation reaction , It is preferable that an antioxidant is added immediately before the end of the polycondensation reaction and the inside of the polycondensation reaction tank is stirred at atmospheric pressure.

In the present invention, in order to increase the molecular weight of the hydrophobic polymer (polyester) -hydrophilic polymer (polyethylene glycol) copolymer, the solid phase polymerization may be carried out using the copolymer obtained by the above method. The apparatus and method for solid phase polymerization are not particularly limited, but heat treatment is carried out under an inert gas atmosphere or under reduced pressure. Specific examples of the inert gas include, but are not limited to, nitrogen, helium, and carbon dioxide gas. When the pressure is reduced, the pressure in the apparatus is preferably 133 Pa or less, and the time required for the solid-state polymerization reaction can be shortened by lowering the pressure. The solid phase polymerization treatment temperature is preferably 150 to 240 ° C. When the solid phase polymerization treatment temperature is 150 캜 or higher, the polymerization reaction proceeds and the molecular weight can be increased, which is preferable. The solid-state polymerization treatment temperature is more preferably 170 DEG C or higher, and still more preferably 190 DEG C or higher. On the other hand, if the solid-state polymerization treatment temperature is 240 캜 or lower, it is preferable because the thermal decomposition can be suppressed and the molecular weight can be reduced and the coloring can be suppressed. The solid phase polymerization treatment temperature is more preferably 235 DEG C or lower, and further preferably 230 DEG C or lower.

(Polyethylene) -hydrophilic polymer (polyethylene glycol) copolymer of the above-mentioned hydrophobic polymer (polyester). (Hereinafter referred to as BHT) in an esterification reaction tank or an ester exchange reaction tank by an esterification reaction of terephthalic acid and ethylene glycol or an ester exchange reaction of dimethyl terephthalate and ethylene glycol Is synthesized. When BHT is transferred from the reaction tank through a transfer pipe to a polycondensation reactor heated to 250 to 270 캜, polyethylene glycol which has been melted by heating in a polycondensation reactor is introduced in advance, and BHT is transferred thereinto. Thereafter, the mixture is stirred for about 1 hour to sufficiently diffuse the polyethylene glycol in the BHT. Subsequently, a polycondensation catalyst is added and the pressure is reduced to 500 Pa or lower, 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 is a polymer having a low polarity copolymer, that is, a molecular chain of polyethylene terephthalate, along with progress of a polycondensation reaction of BHT which is a precursor of polyethylene terephthalate and polyethylene glycol A copolymer having a high ratio of polyethylene terephthalate and a copolymer having a high polarity, that is, a copolymer having a high ratio of polyethylene glycol occupying in the molecular chain, is produced. The size of the dispersed phase in the phase separation structure can be controlled by the number average molecular weight or copolymerization ratio of the polyethylene glycol, the temperature or stirring speed of the polycondensation reaction, or the degree of polymerization (molecular weight) of the polyethylene terephthalate-polyethylene glycol copolymer Do.

As a method of producing the fiber of the present invention, a known melt spinning method can be used. However, since the copolymer of the hydrophobic polymer and the hydrophilic polymer of the present invention forms a phase-separated structure and the range of selectable conditions is narrow, the hydrophobic polymer and the hydrophilic polymer It is necessary to appropriately set the conditions of the preparation according to the characteristics of the copolymer. However, according to the specific example of the production method described later, it is possible to stably obtain fibers having a small degree of unevenness in fineness and having uneven dyeing and suppressed the occurrence of fluff even though they have a phase separation structure.

Generally, in the case of an emergency polymer blend or a polymer alloy system, the polymer is expanded from the spinneret to cause the expansion of the radiation due to the barrel effect and the fibrillation behavior is likely to become unstable. In the extreme case, . Also, the obtained fibers have a large unevenness in fineness, and become low in quality due to uneven dyeing or fluff. As a method for reducing the expansion of radiation due to the Barrus effect, improvement of discharge stability due to lowering of the discharge linear velocity and shear rate as described in JP-A-2009-79318, and Japanese Patent Application Laid- , Improvement of compatibility by the addition of a compatibilizing agent, and the like are well known. Since the phase-separated structure is formed also for the copolymer of the hydrophobic polymer and the hydrophilic polymer of the present invention, the discharge linear velocity and the shear rate are lowered for the purpose of suppressing the expansion of the radiation due to the barrel effect. However, The fibers obtained by this method had a large unevenness in fineness, and showed many uneven dyeing and lint. However, the inventors of the present invention found that discharge can be stabilized by increasing the discharge linear velocity and shear rate, as opposed to a general method of reducing the expansion of radiation due to the Barrus effect, and even though it has a phase separation structure And it is made possible to stably obtain fibers in which unevenness in fineness is small and occurrence of uneven dyeing or fluff is suppressed. This is because, when the phase separation structure comprising the hydrophobic polymer (polyethylene terephthalate) -hydrophilic polymer (polyethylene glycol) copolymer is sheared in the molten state as described above, the phase separation structure is differentially oxidized and finally disappears, And the phase separation structure is again expressed after a certain period of time elapses.

In the present invention, the shear rate when the copolymer of the hydrophobic polymer and the hydrophilic polymer passes through the spinneret is preferably set to 10000 to 40000 s ^-1 . The shear rate at the time of 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. When the shearing speed when passing through the spinneret is 10000 s < ^{-1 &} gt ;, it is preferable because the discharge from the spinneret is stabilized, the unevenness of the fineness is small, and the occurrence of uneven dyeing and fluff is suppressed. Shear rate as it passes through the spinneret is more preferably at least 12000s ^-1, and more preferably at least 15000s ^-1. On the other hand, when the shearing speed when passing through the spinneret is 40000 s ^-1 or less, the radiation stress is not excessively increased and the discharge from the spinneret is stabilized, thereby suppressing the occurrence of shark skins and melt printers, The fibers are small, and the fibers are prevented from being unevenly dyed and the occurrence of fluff is obtained. Shear rate as it passes through the spinneret is more preferably not more than 38000s ^-1 and, 35000s ^-1 and more preferably less than or equal to.

In the production of the fiber of the present invention, 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. When the discharging linear velocity is 10 m / min or more, discharge from the spinneret is stabilized, which results in a fiber having small unevenness in fineness and suppressing occurrence of uneven dyeing and fluff. The discharge linear velocity is more preferably 15 m / min or more, and more preferably 20 m / min or more. On the other hand, when the discharging linear velocity is 100 m / min or less, the radiation stress is not excessively increased, and the discharging from the spinneret is stabilized, so that generation of shark skins and melt printers is suppressed and the uniformity of the fineness is small, Is suppressed from being generated. The discharge linear velocity is more preferably 90 m / min or less, and further preferably 80 m / min or less.

In the production of the fiber of the present invention, it is preferable that the radiation draft is 10 to 300. The radiation draft can be calculated by dividing the spinning speed by the ejection linewidth. A radiation draft of 10 or more is preferable because productivity is improved. The radiation draft is more preferably 20 or more, and still more preferably 30 or more. On the other hand, when the radiation draft is 300 or less, the radiation stress is not excessively increased, which is preferable because the yarn becomes uneven and the yarn unevenness and the occurrence of fluffs are suppressed. The radiation draft is more preferably 250 or less, and still more preferably 200 or less.

As the spinneret used in the present invention, a known spinneret can be used, and the number of discharge holes can be appropriately selected in accordance with the desired number of filaments. The diameter of the discharge hole can be appropriately selected according to the shear rate, the discharge linear velocity, and the radiation draft, but is preferably 0.05 to 0.50 mm. When the diameter of the ejection hole is 0.05 mm or more, the pressure in the spinning pack is not excessively increased, the ejection from the spinneret is stabilized, the unevenness in fineness is small, and the fibers are prevented from being unevenly stained and the occurrence of fluff is obtained. The discharge hole diameter is more preferably 0.10 mm or more, and more preferably 0.15 mm or more. On the other hand, if the diameter of the discharge hole is 0.50 mm or less, it is preferable that the back pressure of the spinneret is not insufficient and the discharge unevenness among the discharge holes of the spinneret is suppressed. It is also preferable that the radiation 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 further preferably 0.30 mm or less.

In the present invention, it is preferable to dry the copolymer of the hydrophobic polymer and the hydrophilic polymer to make the water content to be 300 ppm or less before the melt spinning. If the water content is 300 ppm or less, it is preferable because the molecular weight due to hydrolysis during melt spinning and foaming due to moisture are suppressed and stable spinning can be performed. The water content is more preferably 200 ppm or less, and further preferably 100 ppm or less.

In the present invention, an antioxidant may be added during melt spinning. As described above, the fibers having the phase separation structure made of the hydrophobic polymer (polyester) -hydrophilic polymer (polyethylene glycol) copolymer in the present invention are made of a polyester-polyethylene glycol copolymer having a uniform structure and having no phase separation structure It is preferable to contain a sufficient amount of the antioxidant in the fibers because of the high oxidative decomposability as compared with the fibers. Further, as compared with the case where the antioxidant is added during the production of the polyester-polyethylene glycol copolymer, It is preferable to prevent scattering of the antioxidant under the action of heat and to prevent inactivation of the antioxidant by thermal decomposition. As a method of adding an antioxidant when performing melt spinning, there is a method in which a polyester-polyethylene glycol copolymer and an antioxidant are preliminarily dry-blended and then charged into a melt-spinning machine, a method in which a polyester- Into a melt-spinning machine, but the present invention is not limited thereto.

In the present invention, a pre-dried polyester-polyethylene glycol copolymer chip is supplied to a melting radiator such as extruder type or pressure-melt type, melted, and metered by a metering pump. Thereafter, the molten polymer is introduced into the warmed spinning pack in the spinning block, and the molten polymer is filtered in the spinning pack, and then discharged from the spinneret to obtain fiber spinning. The fiber yarn discharged from the spinneret is cooled and solidified by a cooling device, pulled by a first godet roller, and taken up by a winder through a second godet roller to be wound. In addition, a heating cylinder or a heat-insulating cylinder having a length of 2 to 20 cm may be provided at the lower portion of the spinneret, if necessary, in order to improve the performance of production, productivity and mechanical properties of the fiber. Further, it is also possible to refuel the fiber yarn using the oil supply device, or to intertwine the fiber yarn using an entangling device.

The spinning temperature in the melt spinning can be appropriately selected depending on the melting point and heat resistance of the copolymer of the hydrophobic polymer and the hydrophilic polymer, and is preferably 240 to 320 ° C. If the spinning temperature is 240 占 폚 or higher, the extensional viscosity of the fiber yarn discharged from the spinneret is sufficiently lowered, so that the discharge is stabilized and the spinning tension is not excessively increased so that the yarn breakage can be suppressed. The spinning temperature is more preferably 250 DEG C or higher, and still more preferably 260 DEG C or higher. On the other hand, when the spinning temperature is 320 ° C or lower, it is preferable because thermal decomposition at the time of spinning can be suppressed and the mechanical properties of the fiber can be reduced or coloring can be suppressed. The spinning temperature is more preferably 310 ° C or less, and further preferably 300 ° C or less.

The spinning rate in the melt spinning can be appropriately selected depending on the composition of the copolymer of the hydrophobic polymer and the hydrophilic polymer, the spinning temperature, the radiation draft, and the like. It is preferable that the spinning speed in the case of the two process methods of performing the melt spinning once and wound up and separately drawing is 500 to 5000 m / min. When the spinning speed is 500 m / min or more, it is preferable because the running yarn is stabilized and the yarn breakage can be suppressed. In the case of the two-step process, the spinning speed is more preferably 1000 m / min or more, and more preferably 1500 m / min or more. On the other hand, if the spinning speed of the two process method is 5000 m / min or less, it is preferable because the fiber yarn can be sufficiently cooled and stable spinning can be performed. In the case of the two-step process, the spinning speed is more preferably 4500 m / min or less, and further preferably 4000 m / min or less. It is preferable that the spinning speed in the case of one process of simultaneously spinning and drawing is 500 to 5000 m / min for the low speed roller and 3000 to 6000 m / min for the high speed roller. When the low speed roller and the high speed roller are within the above range, it is preferable that the running yarn is stable and the breakage of the yarn can be suppressed and stable radiation can be performed. In the case of the one process method, it is more preferable to set the spinning speed of the low speed roller at 1000 to 4500 m / min and the speed of the high speed roller at 3500 to 5500 m / Is more preferable.

In the case of conducting the stretching by the one-step process or the two-step process, any one of a single-step stretching method and a two-step or multi-step stretching method may be employed. The heating method in stretching is not particularly limited as long as it is an apparatus capable of heating the running yarn directly or indirectly. Specific examples of the heating method include, but are not limited to, a heating roller, a thermal pin, a hot plate, a liquid bath such as hot water or hot water, a gas bath such as a hot air (heated air), steam or the like. These heating methods may be used alone or in combination. As the heating method, it is preferable to control the heating temperature, uniform heating to the running yarn, contact with the heating roller from the viewpoint that the apparatus is not complicated, contact with thermal pins, contact with the heating plate, have.

The stretching magnification in the case of stretching can be appropriately selected according to the strength and elongation of the fiber after stretching, but is preferably 1.02 to 7.0 times. When the draw ratio is 1.02 or more, it is preferable because the mechanical properties such as the strength and elongation of the fiber can be improved by stretching. The draw ratio is more preferably 1.2 times or more, more preferably 1.5 times or more. On the other hand, if the stretching ratio is 7.0 times or less, breakage of the yarn at the time of stretching is suppressed and stable stretching can be performed, which is preferable. 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, and is preferably 60 to 150 ° C. If the stretching temperature is 60 占 폚 or higher, the yarns supplied to the stretching are sufficiently preheated, and thermal deformation at the time of stretching becomes uniform so that occurrence of unevenness in the fineness can be suppressed. The stretching temperature is more preferably 65 ° C or higher, and further preferably 70 ° C or higher. On the other hand, if the stretching temperature is 150 캜 or lower, the thermal decomposition of the fibers can be suppressed. Further, since the slip property of the fiber with respect to the stretching roller is improved, it is preferable that the breaking of the yarn is suppressed and stable stretching can be performed. The stretching temperature is more preferably 145 ° C or lower, and further preferably 140 ° C or lower. If necessary, the thermal setting may be performed at 60 to 150 ° C.

The stretching speed in the case of stretching can be appropriately selected depending on whether the stretching method is one process or two process. In the case of the one process method, the speed of the high-speed roller at the above-mentioned spinning speed corresponds to the drawing speed. The stretching speed in the case of performing the stretching by the two-step process is preferably 30 to 1000 m / min. If the stretching speed is 30 m / min or more, it is preferable because the running yarn is stabilized and the yarn breakage can be suppressed. In the case of drawing by the two-step process, the drawing speed is more preferably 50 m / min or more, and further preferably 100 m / min or more. On the other hand, if the stretching speed is 1000 m / min or less, breakage of the yarn at the time of stretching is suppressed and stable stretching can be performed. More preferably, the drawing speed is 800 m / min or less, and more preferably 500 m / min or less when the drawing is performed by the two process method.

In the present invention, dyeing may be performed in any state of the fiber or the fiber structure as required. In the present invention, a disperse dye can be preferably employed as a 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 preferably employed according to a known method.

In the present invention, no particular limitation is imposed on the dye concentration or dyeing temperature, and a known method can be preferably employed. If necessary, refining may be performed before the dyeing process, or reduction washing may be performed after the dyeing process.

The fiber of the present invention and the fibrous structure composed of the fiber of the present invention are excellent in antistatic properties in hygroscopicity and low-temperature and low-humidity environments, and inhibited elution of the hydrophilic compound in dyeing or in use. Therefore, it can be suitably used in applications where dignity and comfort are required. Examples include, but are not limited to, general medical use, sports medical use, acupuncture use, interior use, material use, and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. The characteristic values in the examples were obtained by the following methods.

A. island

Under the environment of a temperature of 20 DEG C and a humidity of 65% RH, 100 m of the fiber obtained in the Example was wound off with the use of an INTEC electric inspecting machine. The weight of the obtained failure was measured, and the fineness (dtex) was calculated using the following equation. The measurement was performed five times for one sample, and the average value was determined as the fineness.

Fineness (dtex) = weight of fiber 100 m (g) x 100

B. Strength, elongation

The strength and elongation were calculated in accordance with JIS L1013: 1999 (test method for chemical fiber filament yarn) 8.5 using the fibers obtained by the examples as samples. Under the conditions of a temperature of 20 占 폚 and a humidity of 65% RH, a tensile test was carried out under the conditions of an initial sample length of 20 cm and a tensile speed of 20 cm / min using Autograph AG-50NISMS type manufactured by Shimadzu Corporation. (CN / dtex) is calculated by dividing the stress (cN) at the point showing the maximum load by the fineness (dtex), and the elongation (L1) of the point showing the maximum load and the initial sample length (%). The measurement was performed ten times for one sample, and the average value was determined as the strength and elongation.

Elongation (%) = {(L1-L0) / L0} x100

C. Toughness

The toughness of the fiber was calculated by the following formula using the strength (cN / dtex) and elongation (%) calculated in B above.

Toughness = Strength x (elongation) ^1/2

D. Initial tensile resistance

The initial tensile resistance was calculated according to JIS L1013: 1999 (chemical fiber filament yarn test method) 8.10 using fibers as samples in accordance with the examples. A tensile force test is carried out in the same manner as in the above B, and a load-elongation curve is drawn to obtain a maximum point of a change in load with respect to a change in elongation near the origin of the curve, and the equation described in JIS L1013: 1999 (test method of chemical fiber filament yarn) To calculate the initial tensile resistance (cN / dtex). In addition, the measurement was performed five times for one sample, and the average value was taken as initial tensile resistance.

E. Boiling water shrinkage

Under the environment of a temperature of 20 占 폚 and a humidity of 65% RH, a failure (winding 10 times) made of the fiber obtained in the Example was carried out using a 1 m / week aligner and allowed to stand for 24 hours. Thereafter, a load of 0.09 cN / dtex was applied to the failure under the above environment to measure the sample length (L0). Then, the failure was treated with boiling water at 98 ° C for 15 minutes without any load, air dried for 24 hours, and a load of 0.09 cN / dtex was applied to the sample to measure the sample length (L1). Boiling water shrinkage percentage (%) was calculated by the following equation using sample lengths (L0, L1) before and after treatment in boiling water. The measurement was carried out three times with respect to one sample, and the average value was defined as boiling water shrinkage percentage.

Boiling water shrinkage percentage (%) = {(L0-L1) / L0)} 100

F. Maximum diameter of dispersed phase in fiber cross section

After the fibers obtained by the examples were embedded in an epoxy resin, the fibers were cut in a direction perpendicular to the fiber axis together with the epoxy resin using LKB-Ultramicrotome LKB-2088 to obtain an ultra slim piece having a thickness of about 100 nm. The obtained thin section was dyed in the vapor phase of ruthenium tetroxide at room temperature for about 4 hours, and then the dyed surface was cut into an ultra-microtome to prepare an ultrathin slice dyed with ruthenium tetroxide. For the dyed ultra slim piece, a cross section perpendicular to the fiber axis, that is, a fiber cross section was observed under the condition of an accelerating voltage of 100 kV by using a transmission type electron microscope (TEM) H-7100FA manufactured by Hitachi and a microphotograph of the fiber cross section was taken did. Observations were made at magnifications of 2000, 8000, 20000, and 40000 times, and at the time of taking a microscopic photograph, the highest magnification was selected so that at least 300 dispersed images can be observed. For the photographed photographs, the diameter of 300 dispersed phases randomly extracted by using an image analysis software (WinROOP manufactured by Mitani Shoji) was measured, and the maximum value thereof was defined as the maximum diameter (nm) of the dispersed phase in the fiber cross section. Since the dispersed phase existing in the fiber cross section is not necessarily a true circle, when the true circle is not true, the area is measured and the diameter when converted into a true circle is adopted as the diameter of the dispersed phase.

G. Maximum diameter of dispersed phase in fiber cross section

After the fibers obtained by the examples were embedded in an epoxy resin, the fibers were cut in a direction parallel to the fiber axis together with the epoxy resin using LKB-Ultra Microtome LKB-2088 to obtain an ultra slim piece having a thickness of about 100 nm. The obtained thin section was dyed in the vapor phase of ruthenium tetroxide at room temperature for about 4 hours, and then the dyed surface was cut into an ultra-microtome to prepare an ultrathin slice dyed with ruthenium tetroxide. For the dyed ultrathin slice, a cross section parallel to the fiber axis, that is, a fiber cross section was observed under the condition of an acceleration voltage of 100 kV using a transmission electron microscope (TEM) H-7100FA type manufactured by Hitachi, and a microphotograph of the fiber cross- did. Observation was performed at magnifications of 2000, 8000, 20000, and 40000 times, and when the micrograph was taken, the highest magnification was selected to observe the dispersed phase of at least 300 stripes. For the photographed photographs, the diameter of 300 dispersed phases randomly extracted by using an image analysis software (WinROOF manufactured by Mitani Shoji) was measured, and the maximum value thereof was defined as the maximum diameter (nm) of the dispersed phase in the fiber longitudinal section. The diameter of the dispersed phase on the fiber longitudinal cross section was measured in the direction perpendicular to the fiber axis.

H. Finite variation value U% (hi)

The fiber fineness value U% (hi) was measured with a Wester tester 4-CX manufactured by Zellweger Uster using a fiber obtained in the example as a sample at a measuring speed of 200 m / min, a measuring time of 2.5 min, U% (half inert) was measured under the condition of twist number 12000 / m (S twist). The measurement was carried out five times with respect to one sample, and the average value was determined as the variation degree of the fineness U% (hi).

I. Single yarn diameter CV%

After the fibers obtained in the Examples were deposited with a platinum-palladium alloy, the cross section perpendicular to the fiber axis, that is, the fiber cross section was observed using a Hitachi S-Type 4000 electron microscope (SEM) I photographed a microscope. Observations were made at magnifications of 100 times, 300 times, 500 times, 1000 times, 3000 times, 5000 times, and 10000 times, respectively. When taking a microscope photograph, the highest magnification which can observe all single fibers in the sample was selected. For the photographed pictures, the monocular diameter was measured using image analysis software (WinROOF manufactured by Mitani Shoji). When the number of single yarns in a sample is 50 or more, the number of single yarns of 50 single yarns extracted at random is measured. When the number of single yarns in a sample is less than 50, a total of 50 single yarns having a single yarn diameter of 50 Respectively. Since the fiber cross section is not necessarily a true circle, when the circle is not a circle, the area is measured and converted to a circle, and the diameter is adopted as the diameter. After calculating the average value (X) of the monoclinic diameters and the standard deviation (?) Of monoclinic diameters, the monoclinic diameters CV% were calculated by the following formula.

Single yarn diameter CV% = (? / X) 占 100

≪ SEP > CV &

The monofilament fineness was measured by dividing the fiber obtained in Example by a single yarn and then measuring the length of the sample to be measured 25 mm and the fineness (denier conversion value) of the sample to be measured by using an Auto-Vibro Fineness Scanner DC-11 g, and a vibration of 1880 Hz was applied thereto. In the case where the number of single yarns in the sample is 20 or more, the single yarn fineness of twenty single yarns extracted randomly is measured. When the number of single yarns in the sample is less than 20, a total of twenty single yarn single yarn sizes Respectively. After calculating the average value (X) of the single yarn fineness and the standard deviation (?) Of the single yarn fineness, the single yarn fineness CV% was calculated by the following formula.

Single yarn count CV% = (sigma / X) x 100

K. Single yarn strength CV%, single yarn CV%

The monofilament strength and monofilament elongation were calculated in accordance with JIS L1013: 1999 (test method for chemical fiber filament yarn) 8.5 after the monofilament was decomposed into monofilaments using the fibers obtained by the examples. Tensile test was conducted under the conditions of an initial sample length of 5 cm and a tensile rate of 20 cm / min using an Autograph AG-50NISMS model manufactured by Shimadzu Corporation under an environment of a temperature of 20 캜 and a humidity of 65% RH. (%) Was calculated by the following equation using the elongation (L1) of the point showing the maximum load and the initial sample length (L0), and the stress (cN) at the point showing the maximum load was regarded as the single yarn strength. In the case where the number of single yarns in the sample is 50 or more, the single yarn tenacity and single yarn elongation of 50 single yarns randomly extracted are measured. When the number of single yarns in the sample is less than 50, a total of 50 single yarns Single yarn strength and single yarn elongation were measured. After calculating the average value (X) and standard deviation (?) For each of the single yarn strength and the single yarn elongation, the single yarn strength CV% and the single yarn elongation CV% were calculated by the following formula.

Elongation (%) = {(L1-L0) / L0} x100

Single yarn strength CV% = (? / X) 占 100

Single yarn elongation CV% = (sigma / X) x 100

L. Content of Unreacted PEG (Polyethylene Glycol)

500 mg of the fiber obtained in the examples was weighed into a screw tube and 2 ml of hexafluoroisopropanol was added and allowed to stand for 24 hours under an environment of a temperature of 20 캜 and a humidity of 65% RH to dissolve. 2 mL of chloroform was added to the screw tube, and the mixture was transferred to a 100 mL volumetric flask. Then, 6 mL of chloroform was added to the residue in the screw tube and transferred to the above-mentioned volumetric flask, and acetonitrile was added to the volumetric flask. The components precipitated by adding acetonitrile were removed by filtration, and the filtrate was concentrated to dryness using this separator, and the filtrate was dissolved in 5 mL of acetonitrile. Transferring 1 ml of the solution after crystallization to a 10 ml volumetric flask, diluting with 10 ml of acetonitrile, filtering with a 0.45 탆 PTFE filter, and using this as a sample for HPLC measurement. Using this sample, HPLC measurement was carried out with an HPLC apparatus (LC-20A manufactured by Shimadzu Corporation) under the following conditions. PEG contained in the sample for HPLC measurement was quantified by a calibration curve of a previously prepared standard substance (PEG) The unreacted PEG content (wt%) contained in the fibers obtained by the examples was calculated. Further, the measurement was carried out five times with respect to one sample, and the average value was regarded as the unreacted PEG content.

Column: Inertsil ODS-3 (inner diameter 3 mm, length 150 mm, particle diameter 5 μm) manufactured by JEI Science Co.,

Detector: ELSD, Shimadzu Corporation

Migration layer: water (solvent A), acetonitrile (solvent B)

Time program: 0 → 15 minutes (Solvent A: Solvent B = 0: 100) 15 → 25 minutes (Solvent A: Solvent B = 0: 100)

Flow rate: 0.8 mL / min

Injection amount: 10 μl

Column temperature: 45 ° C

Standard substance: PEG

M. Antioxidant Content

To 500 mg of the fiber obtained in the Example was added 25 mL of a 1 mol / L sodium methoxide-methanol solution and 25 mL of methyl acetate, refluxed for 1 hour and then neutralized by adding 2 mL of acetic acid. The neutralized mixture was concentrated to dryness using a rotary evaporator, and 50 mL of water was added. The mixture was extracted with chloroform (20 mL) and separated into chloroform layer and aqueous layer. The chloroform layer was concentrated to dryness using a rotary evaporator, and 2.5 mL of chloroform was added thereto to prepare a sample for chromatographic measurement. The GC measurement or the HPLC measurement was carried out using this sample, and the antioxidant contained in the sample for chromatographic measurement was quantified by the calibration curve of the standard substance (the antioxidant used in the examples), and the amount of the antioxidant contained in the fibers The antioxidant content (wt%) was calculated. The measurement was carried out five times with respect to one sample, and the average value was used as the antioxidant content.

N. Time to the rising half-point

10 mg of a sample was placed in an aluminum container using the fiber obtained in the examples and subjected to a mixed gas flow rate of 200 mL / min under a mixed gas atmosphere of nitrogen: oxygen = 80% by volume: 20% by volume with a Seiko instrument TG-DTA, After raising the temperature from room temperature to 160 ° C at 30 ° C / min, holding at 160 ° C for 360 minutes. Thereafter, the microgravity weight analysis (DTG) was performed using analysis software (Seiko Instruments, Muse), and the time (min) to the rising half-value point of the DTG peak was calculated did. When the rising half point of the DTG peak appears before reaching 160 캜, the time up to the half lifting point is set to a negative value. If the DTG peak is not observed during 160 min at 160 캜, The time was over 360 minutes. Further, the measurement was performed five times for one sample, and the average value was set to a time up to the half height point of increase.

O. Friction Voltage

About 2 g of a cylindrical weave was produced using an eicosane-knitted circular knitting machine NCR-BL (diameter of 3 inches diameter (8.9 cm), 27 gauge) using the fiber obtained in the examples as a sample, and then 1 g / L sodium nitrate The solution was refined in an aqueous solution containing surfactant monomolecular BK-80 manufactured by Kakakaku Corporation at 80 ° C for 20 minutes, and then dried in a hot air dryer at 60 ° C for 60 minutes.

The frictional voltage (V) was calculated according to JIS L1094: 1997 (Test method for chargeability of textiles and knitted fabrics) 5.2 under a temperature of 10 ° C and a humidity of 10% RH, using a cylindrical weave after refining as a sample. Further, the measurement was performed five times for one sample, and the average value was determined as a friction voltage.

P. Absorption rate difference (ΔMR)

The moisture absorptivity (%) was calculated in accordance with JIS L1096: 2010 (Test method for fabric and knitted fabrics) 8.10, using a cylindrical weave after refining made in the same manner as in O above. First, the cylindrical weave was vacuum-dried at 110 DEG C for 24 hours, and the weight (W0) of the cylindrical weave at the time of full-scale was measured. Then, the weight of the cylindrical braid (W1) was measured, and the temperature was measured at a temperature of 30 DEG C and a humidity of 90% RH in a LHU- The cylinder weave was allowed to stand for 24 hours in the humidified thermo-hygrostat and the weight (W2) of the cylinder weave was measured. The moisture absorption rate MR1 (%) at the time of standing for 24 hours under an atmosphere of a temperature of 20 DEG C and a humidity of 65% RH from the absolutely dry state by the weights W0 and W1 of the cylindrical weaves is calculated and the weights W0 and W2 The moisture absorption rate [MR2 (%)] at the time of standing for 24 hours in an atmosphere of a temperature of 30 deg. C and a humidity of 90% RH from the absolutely exposed state by the following formula was calculated. The measurement was carried out five times with respect to one sample, and the average value was defined as a moisture absorption rate difference (? MR).

Moisture absorption rate difference (? MR) (%) = MR2-MR1

Q. Weight reduction rate after hydrothermal treatment

About 2 g of a circular knitted fabric was produced using a fiber-knitted fabric NCR-BL (3-inch half diameter (8.9 cm), 27 gauge) manufactured by Kyocera Corporation with a sample as a sample, Cylindrical weights were immersed in ethanol at a temperature of 25 ° C and a treatment time of 1 minute. The immersion in ethanol was repeated three times in total to remove the emulsion adhering to the cylindrical weave. After drying for 60 minutes in a hot air drier at 60 ° C, the weight (W0) of the cylindrical weave was measured. New ethanol was used for each immersion. Then, hydrothermal treatment was performed under the conditions of a bath ratio of 1: 100, a treatment temperature of 100 占 폚, and a treatment time of 60 minutes. After the hydrothermal treatment, the cylindrical braid was dried for 60 minutes in a hot-air dryer at 60 占 폚, and the weight (W1) of the cylindrical braid was measured. The weight reduction ratio (%) after hydrothermal treatment was calculated by the following formula using the weights (W0, W1) of the cylindrical weave. The measurement was carried out three times for one sample, and the average value was determined as a weight reduction rate.

Weight reduction rate (%) = {(W0-W1) / W0)} 100

R. Evenness

The cylindrical weave after the refining as prepared above was subjected to dry heat setting at 160 DEG C for 2 minutes and 4 wt% of Kayalon Polyster Black EX-SF200 manufactured by Nippon Kayaku Co., Ltd. as a dispersion dye was added to the cylindrical weave after dry heat setting to adjust the pH to 5.0 In a dyeing solution adjusted to a ratio of 1: 100, a dyeing temperature of 130 캜, and a dyeing time of 60 minutes. In Examples 38 to 47, 4% by weight of Cathilon Blue FB-DP manufactured by Hodogaya Chemical Co., Ltd. as a cationic dye was added and the pH was adjusted to 4.0. The dye ratio was adjusted to 1: 100, Time of 60 minutes. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. [ , &Quot; no staining unevenness was confirmed ", " almost uniformly stained and slight staining unevenness was confirmed ", " not uniformly stained and clearly staining unevenness was confirmed & , And ∘ and ◎ were passed.

S. elegance

By agreement of five inspector who has experience of grade judgment of more than five years about cylinder weave after dyeing in R mentioned above, "there is no lint and there is no lint, and dignity is excellent" ◎, "there is almost no lint and dignity is excellent" ?, &Quot; and " A " were judged to be " Good ", " Good ", and " Good "

Example 1

After about 100 kg of bis (? -Hydroxyethyl) terephthalate was fed into the esterification reaction tank and maintained at a temperature of 250 占 폚, 89.2 kg of high purity terephthalic acid (manufactured by Mitsui Chemicals) and 39.8 kg of ethylene glycol (manufactured by Nippon Shokubai) Was continuously supplied over 2.5 hours. After completion of the feeding, 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 (PEG6000S manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 8300 melted by heating at 70 占 폚 were successively added to the polycondensation tank, Through the transfer pipe connecting the reaction tank and the polycondensation tank, 110.6 kg of the obtained esterification reaction product was transferred to the polycondensation tank heated to 250 deg. After the completion of the transition, the mixture was stirred at 250 ° C for 1 hour. Thereafter, 180 g of pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (Irganox1010, manufactured by BASF) was added as an antioxidant , 120 g of silicon (TSF433, manufactured by Momentive Performance Materials, Ltd.) as a defoaming agent, and 30 g of trimethyl phosphate (Wako Pure Chemical Industries, Ltd.) as a heat stabilizer were added and stirred for 10 minutes. Then, 30 g of antimony trioxide, And the mixture was stirred for 5 minutes. Subsequently, the temperature in the polycondensation tank was raised from 250 DEG C to 285 DEG C over 60 minutes, the pressure in the polycondensation tank was reduced from atmospheric pressure to 25Pa, and the polymerization reaction was carried out for 3 hours. The polymerization reaction product was discharged into a strand form in cold water, cooled, and immediately cut to obtain a polymerization reaction product in the form of pellets. The copolymerization ratio of polyethylene glycol in the obtained polymerization reaction product was 14% by weight, and it was confirmed by ¹ H-NMR.

The obtained pellets were vacuum-dried at 150 DEG C for 12 hours (water content after drying was 95 ppm), and then supplied to an extruder type spinning machine to be melted and spinning was carried out at a spinning temperature of 290 DEG C and a discharge rate of 57 g / Mm, number of discharge holes: 36, round hole) to obtain a discharge yarn. The discharged yarn was cooled by a cooling wind having a wind speed of 20 DEG C and an air speed of 20 m / min. The yarn was fed by an oil supply device to be converged and pulled by a first godet roller rotating at 3000 m / min. Rolled into a winder through a second godet roller which was rotated to obtain an unstretched yarn of 190 dtex-36f. The obtained undrawn yarn was drawn under conditions of a first hot roller temperature of 90 DEG C, a second hot roller temperature of 130 DEG C, and a draw ratio of 1.9 to obtain drawn yarn of 100 dtex-36f.

Table 1 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. The obtained fibers had good fiber properties such as strength and toughness. The fibers had a phase-separated structure. 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 cross-section was 31 nm, and was very finely dispersed. In addition, while having a phase separation structure, U% (hi) was 1.0%, and it was a very homogeneous fiber. As for the warp characteristics, the antistatic property and hygroscopicity were excellent. In addition, the weight loss rate after the hydrothermal treatment was also low, so that the elution of the hydrophilic compound was inhibited, and the level of uniformity and durability were acceptable.

Examples 2 to 4

A drawn liner was produced in the same manner as in Example 1 except that the copolymerization ratio of the hydrophilic polymer, the discharge amount, the spinneret (discharge hole diameter, discharge hole length, number of discharge holes) were changed as shown in Table 1.

Table 1 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. As the copolymerization ratio of the hydrophilic polymer is lowered, the fiber properties such as strength and toughness are improved, and the maximum diameter of the dispersed phase in the fiber cross section and the fiber cross section becomes smaller, and the U% (hi) becomes better. On the other hand, regarding the antistatic property and hygroscopicity, the copolymerization ratio of the hydrophilic polymer was improved.

Examples 5 to 7

A drawn liner was produced in the same manner as in Example 4 except that the diameter of the discharge hole of the spinneret was changed as shown in Table 1.

Table 1 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. As the diameter of the discharge hole is reduced to increase the shear rate at the time of passing through the spinneret, the fiber properties such as strength and toughness are improved, and the maximum diameter of the dispersed phase in the fiber cross section and the fiber cross section becomes smaller and U% (hi) It 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 properties and the fabric-forming properties of the obtained fibers. Even when the copolymerization ratio of the hydrophilic polymer was changed, the U% (hi) was low and homogeneous fibers were obtained.

Examples 10 and 11

A spinning lug 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. Polyethylene glycol (PEG10000 manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 11,000 was used as the hydrophilic polymer, and polyethylene glycol (PEG20000 manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 20,000 was used in Example 11.

Table 2 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Even when the number average molecular weight of the hydrophilic polymer was changed, the fiber properties such as strength, toughness and the like were good, and fibers with a low U% (hi) were obtained.

Examples 12 and 13

The spinning speed was changed as shown in Table 2, and a drawn yarn was produced in the same manner as in Example 1 except that the draw ratio was set to 5.7 times in Example 12 and 2.85 times in Example 13.

Table 2 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Even when the spinning speed was changed, the fiber properties such as strength and toughness were good, and fibers with a low U% (hi) were obtained.

Example 14

To the obtained polymerization reaction product, a citrate chelate titanium complex corresponding 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 were maintained at a temperature of 240 ° C and a pressure of 1.2 × 10 ⁵ Pa The esterification reaction was carried out until the temperature of the effluent became less than 90 캜 to obtain an esterification reaction product. Subsequently, 16.7 kg of 1,3-propanediol, 16.8 kg of polyethylene glycol (PEG6000S manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 8300 melted by heating at 70 占 폚 were successively introduced into the polycondensation tank, Through the transfer pipe connecting the polycondensation tank, 110.6 kg of the obtained esterification reaction product was transferred to the polycondensation tank heated to 240 deg. After the completion of the transition, the mixture was stirred at 240 ° C for 1 hour. Thereafter, 180 g of pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (Irganox1010, manufactured by BASF) was added as an antioxidant , 120 g of silicon (TSF433, manufactured by Momentive Products Materials Co., Ltd.) as a defoaming agent, and 30 g of trimethyl phosphate (Wako Pure Chemical Industries) as a heat stabilizer were added and stirred for 10 minutes. 11 g of magnesium acetate tetrahydrate And stirred for 5 minutes. Subsequently, the temperature in the polycondensation tank was raised from 240 DEG C to 280 DEG C over 60 minutes, the pressure in the polycondensation tank was reduced from atmospheric pressure to 40 Pa, and the polymerization reaction was carried out for 3 hours. The polymerization reaction product was discharged into a strand form in cold water, cooled, and immediately cut to obtain a polymerization reaction product in the form of pellets. The copolymerization ratio of polyethylene glycol in the obtained polymerization reaction product was 14% by weight, and it was confirmed by ¹ H-NMR.

The obtained pellets were vacuum-dried at 150 DEG C for 12 hours, and then supplied to an extruder-type spinner and melted to obtain a spinneret (discharge hole diameter: 0.23 mm, discharge hole length: 0.60 mm, discharge hole number: 36 , A round hole) to obtain a discharge yarn. The discharged yarn was cooled by a cooling wind having a wind speed of 20 DEG C and an air speed of 20 m / min. The yarn was fed by a refueling device to be converged and pulled by a first godet roller rotating at 3000 m / min. Rolled into a winder through a second godet roller which was rotated to obtain an unstretched yarn of 190 dtex-36f. The obtained undrawn filament was drawn under conditions of a first hot roller temperature of 55 캜, a second hot roller temperature of 130 캜, and a draw ratio of 1.9 to obtain drawn yarn of 100 dtex-36 f.

Table 2 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Even when the hydrophobic polymer was changed to polypropylene terephthalate, the fiber properties such as strength and toughness were good, and the fibers having a low U% (hi) were obtained.

Example 15

To the resulting polymerization reaction product, a citrate chelate titanium complex corresponding 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 were maintained at a temperature of 220 ° C and a pressure of 1.2 x 10 ⁵ Pa The esterification reaction was carried out in the esterification reaction tank until the temperature of the effluent was less than 90 캜 to obtain an esterification reaction product. Subsequently, 19.7 kg of 1,4-butanediol, 16.8 kg of polyethylene glycol (PEG6000S manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 8300 melted by heating at 70 占 폚 were successively introduced into the polycondensation tank, 110.6 kg of the obtained esterification reaction product was transferred to a polycondensation tank heated to 220 占 폚 through a transfer pipe connecting the combination. After the completion of the transition, the mixture was stirred at 220 ° C for 1 hour. Thereafter, 180 g of pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (Irganox1010, manufactured by BASF) was added as an antioxidant , 120 g of silicon (TSF433, manufactured by Momentive Products Materials Co., Ltd.) as a defoaming agent, and 30 g of trimethyl phosphate (Wako Pure Chemical Industries) as a heat stabilizer were added and stirred for 10 minutes. 11 g of magnesium acetate tetrahydrate And stirred for 5 minutes. Subsequently, the temperature in the polycondensation tank was raised from 220 DEG C to 250 DEG C over 60 minutes, the pressure in the polycondensation tank was reduced from atmospheric pressure to 60 Pa, and the polymerization reaction was carried out for 3 hours. The polymerization reaction product was discharged into a strand form in cold water, cooled, and immediately cut to obtain a polymerization reaction product in the form of pellets. The copolymerization ratio of polyethylene glycol in the obtained polymerization reaction product was 14% by weight, and it was confirmed by ¹ H-NMR.

The obtained pellets were vacuum-dried at 150 占 폚 for 12 hours, and then supplied to an extruder-type radiator to be melted and spinnerized at a spinning temperature of 260 占 폚 and a discharge rate of 57 g / min. , A round hole) to obtain a discharge yarn. The discharged yarn was cooled by a cooling wind having a wind speed of 20 DEG C and an air speed of 20 m / min. The yarn was fed by an oil supply device to be converged and pulled by a first godet roller rotating at 3000 m / min. And wound on a winder through a rotating second godet roller to obtain an undrawn yarn of 190 dtex-36f. The obtained undrawn filament was drawn under conditions of a first hot roller temperature of 65 캜, a second hot roller temperature of 130 캜, and a draw ratio of 1.9 to obtain drawn yarn of 100 dtex-36f.

Table 2 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Even when the hydrophobic polymer was changed to polybutylene terephthalate, the fiber properties such as strength and toughness were good, and fibers with a low U% (hi) were obtained.

Comparative Example 1

Spinning and drawing were carried out in the same manner as in Example 1 using polyethylene terephthalate (intrinsic viscosity IV = 0.66).

Table 3 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Strength, toughness and the like, and a fiber having a low U% (hi) and a homogeneous property was obtained. However, since it is a fiber composed only of a hydrophobic polymer, it does not have a phase separation structure. The foaming property was excellent in uniformity and durability, but the frictional electrification voltage was 9800 V, the antistatic property was very low, the ΔMR was 0.1%, and the hygroscopicity was also very low.

Comparative Examples 2 to 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. Polyethylene glycol (PEG4000 manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 3,400 in Comparative Example 2, polyethylene glycol (PEG6000 manufactured by Aldrich) having a number average molecular weight of 6,000 in Comparative Example 3, and number average molecular weight of 100,000 in Comparative Example 4 were used as the hydrophilic polymer Of polyethylene glycol (R-150 manufactured by Meisei Chemical Industries, Ltd.) was used.

Table 3 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. In Comparative Example 2, the fiber characteristics such as strength and toughness were good, and the fibers with low U% (hi) and homogeneity were obtained. However, since the number average molecular weight of the polyethylene glycol was less than 7000, it did not have a phase separation structure. Although the foaming property was excellent in uniformity and durability, the frictional electrification voltage was 7600 V, and the antistatic property was poor. In Comparative Example 3, as in Comparative Example 2, the fiber characteristics such as strength and toughness were good, the U% (hi) was low and the fibers were homogeneous. However, since the number average molecular weight of polyethylene glycol was less than 7000, I did not have it. In addition, although the foaming property was excellent in uniformity and durability, the frictional electrification voltage was 6900 V and the antistatic property was poor. In Comparative Example 4, since the number average molecular weight of the polyethylene glycol was high, the maximum diameter of the dispersed phase in the fiber cross section and the fiber cross section was large and a coarse phase separation structure was formed. For this reason, in addition to low fiber properties such as strength and toughness, the fibers are highly heterogeneous with high U% (hi) and can not withstand use. And the uniformity and dignity of the fabric were very poor.

Comparative Example 5

A softener 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 properties and the fabric-forming properties of the obtained fibers. Since the copolymerization ratio of the hydrophilic polymer is high, the discharge from the spinneret is unstable. As a result, in addition to the extremely low fiber properties such as strength and toughness, the fiber has a high U% (hi) and is highly heterogeneous. It was not possible. And the uniformity and dignity of the fabric were very poor.

Comparative Examples 6 and 7

Except that the copolymerization ratio of the hydrophilic polymer, the discharge amount, the spinneret (discharge hole diameter, discharge hole length, discharge hole number) were changed as shown in Table 3, and the stretching magnification was changed to 3.3 times in Comparative Examples 6 and 7, I made a kite company.

Table 3 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. In Comparative Example 6, since the shearing speed at the time of spinning and spinning was low, the discharge from the spinneret was very unstable. As a result, in addition to the extremely low fiber properties such as strength and toughness, U% (hi) It is a homogeneous fiber and can not withstand use. And the uniformity and dignity of the fabric were very poor. In Comparative Example 7, since the shearing speed at the time of spinning was high, the radiation stress became high and the discharge from the spinneret became unstable. As a result, the U% (hi) was slightly high and the fiber had poor homogeneity. The uniformity and uniformity of the fabric properties did not reach acceptable levels.

Comparative Example 8

After the BHT was carried out in Example 4, polyethylene glycol was put into a polycondensation tank in powder form without heating and melting from above, and polymerization was started immediately without stirring at 250 ° C for 1 hour after the introduction of polyethylene glycol A drawn yarn was produced in the same manner as in Example 4 except for that.

Table 3 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Since polymerization was started in a state in which polyethylene glycol was added in powder form and polyethylene glycol was not added and stirring was not performed and dispersion of the polyethylene glycol in the esterification reaction product was insufficient, As a result, even when the fiber was formed by melt spinning, the maximum diameter of the dispersed phase in the fiber cross section and the fiber cross section was large, and a coarse phase separation structure was formed. Therefore, the fiber characteristics such as strength and toughness are low, the U% (hi) is high, and the fibers have poor homogeneity. The uniformity and uniformity of the fabric properties did not reach acceptable levels.

Comparative Example 9

After about 100 kg of bis (? -Hydroxyethyl) terephthalate was fed into the esterification reaction tank and maintained at a temperature of 250 占 폚, 89.2 kg of high purity terephthalic acid (manufactured by Mitsui Chemicals) and 39.8 kg of ethylene glycol (manufactured by Nippon Shokubai) Was continuously supplied over 2.5 hours. After completion of the feeding, the esterification reaction was carried out for 2 hours to obtain an esterification reaction product. 110.6 kg of the obtained esterification reaction product was transferred to a polycondensation tank heated to 250 DEG C through a transfer pipe connecting the esterification reaction tank and the polycondensation tank, and stirred at 250 DEG C for 1 hour. Silicon (Momentive Performance, 30 g of trimethyl phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) as a heat stabilizer was added and stirred for 10 minutes. Then, 30 g of antimony trioxide and 22 g of manganese acetate were added as a polymerization catalyst and stirred for 5 minutes. Subsequently, the temperature in the polycondensation tank was raised from 250 DEG C to 285 DEG C over 60 minutes, the pressure in the polycondensation tank was reduced from atmospheric pressure to 25Pa, and polymerization was carried out for 2 hours and 30 minutes. Thereafter, the inside of the polycondensation tank was purged with nitrogen and returned to the atmospheric pressure. 14.4 kg of polyethylene glycol (PEG6000S manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 8300 in the powder state and 1 kg of pentaerythritol tetra 180 g of kiss (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (manufactured by BASF, Irganox1010) was added to the polycondensation tank, and the pressure in the polycondensation tank was reduced And polymerization was carried out for 30 minutes. The polymerization reaction product was discharged into a strand form in cold water, cooled, and immediately cut to obtain a polymerization reaction product in the form of pellets. Using the obtained pellets, a drawn lint was produced in the same manner as in Example 4.

Table 3 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Since the polymerization reaction time after addition of polyethylene glycol in powder form and the addition of polyethylene glycol is short, a coarse phase separation structure is formed in the polymerization reaction product. As a result, even when fiberization is carried out by melt spinning, The maximum diameter of the dispersed phase was large and a coarse phase separation structure was formed. For this reason, it was a fiber having a high U% (hi) and lacking homogeneity. In addition, since the polymerization reaction time after addition of polyethylene glycol was short, the unreacted PEG content and the weight loss rate after hydrothermal treatment were all high and did not reach acceptable levels in terms of uniformity and dignity.

Comparative Example 10

, 12 kg of polyethylene glycol (PEG6000S manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 8300, 88 kg of polyethylene terephthalate (IV = 0.66), 12 kg of pentaerythritol-tetrakis (3- (3,5- 4-hydroxyphenol) propionate) (Irganox1010, manufactured by BASF) was melt-kneaded at 285 DEG C using a biaxial extruder and cut to about 5 mm to prepare pellets. As in Example 4, .

Table 3 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. When the polyethylene terephthalate and the polyethylene glycol were melt kneaded, the maximum diameter of the dispersed phase in the fiber cross section and the fiber cross section was large, the U% (hi) was high, and the fiber was poor in homogeneity. Further, the unreacted PEG content and the weight loss rate after hydrothermal treatment were all high, and the level of uniformity and quality did not reach the acceptable level.

Comparative Example 11

A drawn lint yarn was produced in the same manner as in Comparative Example 2 except that the addition amount of the antioxidant (added before the start of the polycondensation reaction) in Comparative Example 2 was changed to 600 g.

Table 3 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Strength, toughness and the like were good, U% (hi) was low, and homogeneous fibers were obtained. However, since the number average molecular weight of the polyethylene glycol was less than 7000, it did not have a phase separation structure. Although the foaming property was excellent in uniformity and durability, the frictional electrification voltage was 7200 V and the antistatic property was poor.

Example 16

After about 100 kg of bis (? -Hydroxyethyl) terephthalate was charged into the esterification reaction tank and maintained at a temperature of 250 占 폚, 89.2 kg of high purity terephthalic acid (manufactured by Mitsui Chemicals) and 39.8 kg of ethylene glycol The slurry was continuously supplied over 2.5 hours. After completion of the feeding, 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 (PEG6000S manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 8300 melted by heating at 70 DEG C were sequentially added to the polycondensation tank, Through the transfer pipe connecting the reaction tank and the polycondensation tank, 110.6 kg of the obtained esterification reaction product was transferred to the polycondensation tank heated to 250 ° C. After the completion of the transition, the mixture was stirred at 250 ° C for 1 hour. Thereafter, 180 g of pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (Irganox1010, manufactured by BASF) was added as an antioxidant , 120 g of silicon (TSF433, manufactured by Momentive Performance Materials, Ltd.) as a defoaming agent, and 30 g of trimethyl phosphate (Wako Pure Chemical Industries, Ltd.) as a heat stabilizer were added and stirred for 10 minutes. Then, 30 g of antimony trioxide, And the mixture was stirred for 5 minutes. Subsequently, the temperature in the polycondensation tank was raised from 250 DEG C to 285 DEG C over 60 minutes, the pressure in the polycondensation tank was reduced from atmospheric pressure to 25Pa, and the polymerization reaction was carried out for 3 hours. Thereafter, a pentaerythritol-tetrakis (3- (3,5-di-tert-butylphenol) was added as an antioxidant (added after the initiation of the polycondensation reaction) to a container having a thickness of 0.2 mm and an inner volume of 500 cm 3 produced by injection molding of a polyethylene terephthalate sheet (Butyl-4-hydroxyphenol) propionate) (Irganox1010, manufactured by BASF) was added thereto, and the mixture was added from the upper part of the reaction vessel. The inside of the polycondensation tank was purged with nitrogen and returned to normal pressure. After stirring for 10 minutes, , Cooled and immediately cut to obtain a polymerization reaction product in the form of pellets. Using the obtained pellets, a drawn lint was produced in the same manner as in Example 4.

Table 4 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Strength, toughness and the like were good, U% (hi) was low, and the fibers were homogeneous. Further, by adding an antioxidant after the initiation of the polycondensation reaction, scattering of the antioxidant under vacuum in the polycondensation reaction and inactivation of the antioxidant by thermal decomposition are suppressed, the content of the antioxidant in the fiber is high, The time was more than 360 minutes, and the oxidative decomposition was suppressed. In addition, the weight loss rate after the electrolytic treatment, the hygroscopicity treatment and the hydrothermal treatment was good, and the level was also acceptable with respect to uniformity and dignity.

Examples 17 to 19

The antioxidant added after the initiation of the polycondensation reaction in Example 16 was changed to 2,4,6-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) mesitylene (ADEKA (1,1-dimethylethyl) -3-hydroxy-2,6-dimethylphenyl] methyl] - 384 g of 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione (THANOX 1790, manufactured by TOKYO KASEI KOGYO CO., LTD.) And dibutylamine-1,3,5-tri Azine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6- Piperidyl) butylamine (CHIMASSORB2020, manufactured by BASF) was changed to 384 g.

Table 4 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Even when an antioxidant was used, the fiber properties such as strength and toughness were good, U% (hi) was low, and the fibers were homogeneous. Further, with any antioxidant, the content of the antioxidant in the fibers was high when the antioxidant was added after the initiation of the polycondensation reaction, and the time until the half-value point of increase was 360 minutes or longer, and the oxidative decomposition was suppressed. In addition, the weight loss rate after the electrolytic treatment, the hygroscopicity treatment and the hydrothermal treatment was good, and the level was also acceptable with respect to uniformity and dignity.

Examples 20 to 22

As the antioxidant to be added after the start of the polycondensation reaction without adding an antioxidant before the start of the polycondensation reaction in Example 16, pentaerythritol tetrakis (3- (3,5-di-t- 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, respectively.

Table 4 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Even when the addition amount of the antioxidant added after the initiation of the polycondensation reaction was changed, the fiber properties such as strength and toughness were good, U% (hi) was low, and the fibers were homogeneous. The content of the antioxidant in the fibers was high in any addition amount, and the time until the half-value point of increase was 360 minutes or longer, and the oxidative decomposition was also suppressed. In addition, the weight loss rate after the electrolytic treatment, the hygroscopicity treatment and the hydrothermal treatment was good, and the level was also acceptable with respect to uniformity and dignity.

Example 23

In the extruder-type emitter, the pellets obtained in Example 4 were extruded from a main feeder using pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate , Irganox 1010) was supplied from the sub feeder at a weight ratio of 100: 0.4.

Table 4 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Strength, toughness and the like were good, U% (hi) was low, and the fibers were homogeneous. Further, by adding an antioxidant during melt spinning, the content of the antioxidant in the fibers was high, and the time to the half-value point of increase was 360 minutes or longer, and the oxidative decomposition was suppressed. In addition, the weight loss rate after the electrolytic treatment, the hygroscopicity treatment and the hydrothermal treatment was good, and the level was also acceptable with respect to uniformity and dignity.

Example 24

In the extruder-type emitter, the pellet produced without adding the antioxidant before the polycondensation reaction in Example 4 was pelletized from the main feeder by pentaerythritol-tetrakis (3- (3,5-di-t- -Hydroxyphenol) propionate (manufactured by BASF, Irganox 1010) was supplied from the sub feeder at a weight ratio of 100: 0.4.

Table 4 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Strength, toughness and the like were good, U% (hi) was low, and the fibers were homogeneous. Further, by adding an antioxidant during melt spinning, the content of the antioxidant in the fibers was high and the time to the half-value point of increase was 360 minutes or longer, and the oxidative decomposition was suppressed. In addition, the weight loss rate after the electrolytic treatment, the hygroscopicity treatment and the hydrothermal treatment was good, and the level was also acceptable with respect to uniformity and dignity.

Example 25

To the obtained polymerization reaction product, a citrate chelate titanium complex corresponding 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 were maintained at a temperature of 240 ° C and a pressure of 1.2 × 10 ⁵ Pa The esterification reaction was carried out until the temperature of the effluent became less than 90 캜 to obtain an esterification reaction product. Subsequently, 16.7 kg of 1,3-propanediol, 16.8 kg of polyethylene glycol (PEG6000S manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 8300 melted by heating at 70 占 폚 were successively introduced into the polycondensation tank, Through the transfer pipe connecting the polycondensation tank, 110.6 kg of the obtained esterification reaction product was transferred to the polycondensation tank heated to 240 deg. After the completion of the transition, the mixture was stirred at 240 ° C for 1 hour. Thereafter, 180 g of pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (Irganox1010, manufactured by BASF) was added as an antioxidant , 120 g of silicon (Momentive Performance Materials, TSF433) as a defoaming agent and 30 g of trimethyl phosphate (Wako Pure Chemical Industries, Ltd.) as a heat stabilizer were added and stirred for 10 minutes. Then, 11 g of magnesium acetate tetrahydrate as a polymerization catalyst was added The mixture was stirred for 5 minutes. Subsequently, the temperature in the polycondensation tank was raised from 240 DEG C to 280 DEG C over 60 minutes, the pressure in the polycondensation tank was reduced from atmospheric pressure to 40 Pa, and the polymerization reaction was carried out for 3 hours. Thereafter, a pentaerythritol-tetrakis (3- (3,5-di-tert-butyloxycarbonyl) -1,3-dioxolane was added as an antioxidant (added after the initiation of the polycondensation reaction) to a container having a thickness of 0.2 mm and an inner volume of 500 cm 3 produced by injection molding a polypropylene terephthalate sheet. 4-hydroxyphenol) propionate (manufactured by BASF, Irganox 1010) was added thereto, and the mixture was added from the upper part of the reaction vessel. The inside of the polycondensation tank was purged with nitrogen and returned to normal pressure. After stirring for 10 minutes, The mixture was discharged in a strand form in cold water, cooled, and immediately cut to obtain a polymerization reaction product in the form of pellets. Using the obtained pellets, a drawn lint was produced in the same manner as in Example 14.

Table 4 shows the evaluation results of the fiber properties and the fabric-forming properties 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 the fibers were homogeneous. Further, the time up to the half-height elevation point was 360 minutes or longer, and the oxidative decomposition was also suppressed. In addition, the weight loss rate after the electrolytic treatment, the hygroscopicity treatment and the hydrothermal treatment was good, and the level was also acceptable with respect to uniformity and dignity.

Example 26

To the resulting polymerization reaction product, a citrate chelate titanium complex corresponding 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 were maintained at a temperature of 220 ° C and a pressure of 1.2 x 10 ⁵ Pa The esterification reaction was carried out in the esterification reaction tank until the temperature of the effluent was less than 90 캜 to obtain an esterification reaction product. Subsequently, 19.7 kg of 1,4-butanediol, 16.8 kg of polyethylene glycol (PEG6000S manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 8300 melted by heating at 70 占 폚 were successively introduced into the polycondensation tank, 110.6 kg of the obtained esterification reaction product was transferred to a polycondensation tank heated to 220 占 폚 through a transfer pipe connecting the combination. After the completion of the transition, the mixture was stirred at 220 ° C for 1 hour. Thereafter, 180 g of pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (Irganox1010, manufactured by BASF) was added as an antioxidant , 120 g of silicon (Momentive Performance Materials, TSF433) as a defoaming agent and 30 g of trimethyl phosphate (Wako Pure Chemical Industries, Ltd.) as a heat stabilizer were added and stirred for 10 minutes. Then, 11 g of magnesium acetate tetrahydrate as a polymerization catalyst was added The mixture was stirred for 5 minutes. Subsequently, the temperature in the polycondensation tank was raised from 220 DEG C to 250 DEG C over 60 minutes, the pressure in the polycondensation tank was reduced from atmospheric pressure to 60 Pa, and the polymerization reaction was carried out for 3 hours. Thereafter, a pentaerythritol-tetrakis (3- (3,5-di (tert-butyldimethylsilyl) terephthalate was added as an antioxidant (added after the initiation of the polycondensation reaction) to a container having a thickness of 0.2 mm and an inner volume of 500 cm 3 produced by injection molding a polybutylene terephthalate sheet. (4-hydroxyphenol) propionate) (Irganox1010, manufactured by BASF) was added thereto, and the mixture was added from the upper part of the reaction vessel. The inside of the polycondensation tank was purged with nitrogen and returned to normal pressure. After stirring for 10 minutes, Was discharged into a strand shape in cold water, cooled, and immediately cut to obtain a pellet-shaped polymerization reaction product. Using the obtained pellets, a drawn lint was produced in the same manner as in Example 15.

Table 4 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Even when the hydrophobic polymer was changed to polybutylene terephthalate, the fiber properties such as strength and toughness were good, U% (hi) was low, and the fibers were homogeneous. Further, the time up to the half-height elevation point was 360 minutes or longer, and the oxidative decomposition was also suppressed. In addition, the weight loss rate after the electrolytic treatment, the hygroscopicity treatment and the hydrothermal treatment was good, and the level was also acceptable with respect to uniformity and dignity.

Examples 27 to 36

In the extruder-type emitter, the pellets produced in Example 1, Example 28, and Example 3 were used in Examples 27, 35, and 36; the pellets prepared in Example 3 were used in Example 28; In Example 32, the pellets produced in Example 8, in Example 33, and in Example 34, the pellets produced in Example 10 and the pellets produced in Example 11 in Example 11 were fed 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, Is the same as Example 3, Example 29 is similar to Example 5, Example 30 is similar to Example 6, Example 31 is similar to Example 7, Example 32 is similar to Example 8, and Example 33 Are the same as those in Example 10, Example 34 is the same as Example 11 , Example 35 was similar to Example 12, and Example 36 was similar to Example 13 to produce a drawn yarn.

Table 5 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. Even when the number average molecular weight and copolymerization ratio of the hydrophilic polymer, the shear rate at the time of spinning and spinning, and the spinning speed were changed, the fiber characteristics such as strength and toughness were good, U% (hi) was low and homogeneous fibers . Further, by adding an antioxidant during melt spinning, the content of the antioxidant in the fiber was high, and the time until the half-value point of increase was more than 360 minutes, and the oxidative decomposition was suppressed. In addition, the weight loss rate after the electrolytic treatment, the hygroscopicity treatment and the hydrothermal treatment was good, and the level was also acceptable with respect to uniformity and dignity.

Example 37

A drawn lint yarn was produced in the same manner as in Example 4 except that the addition 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 properties and the fabric-forming properties of the obtained fibers. Strength, toughness and the like were good, U% (hi) was low, and the fibers were homogeneous. As for the warp characteristics, the antistatic property and hygroscopicity were excellent. In addition, the weight loss rate after the hydrothermal treatment was low, the elution of the hydrophilic compound was inhibited, and the level of uniformity and durability were acceptable.

Example 38

A slurry composed of 8.7 kg of dimethyl terephthalate, 370 g of 5-sodium sodium sulfoisophthalate (SSIA) (manufactured by Sanyo Chemical Industries, Ltd.) and 5.6 kg of ethylene glycol (manufactured by Nippon Shokubai Co.) was introduced into the transesterification reaction tank, 21.5 g of lithium acetate dihydrate as a catalyst and 2 g of cobalt acetate tetrahydrate were added and ester exchange reaction was carried out at 240 캜 for 2 hours to obtain an ester exchange reaction product. Subsequently, 1.2 kg of polyethylene glycol (PEG6000S manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 8300 melted by heating at 70 占 폚 was charged into the polycondensation tank, and then, through a transit pipe connecting the transesterification tank and the polycondensation tank, The transesterification reaction product was transferred to a polycondensation tank heated to 240 ° C. After the completion of the transition, the mixture was stirred at 240 ° C for 1 hour. Thereafter, 15 g of pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (Irganox1010, manufactured by BASF) was added as an antioxidant 7 g of silicon as a defoaming agent (TSF433, manufactured by Momentive Products Ltd.) and 4.3 g of trimethyl phosphate (Wako Pure Chemical Industries, Ltd.) as a heat stabilizer were added and stirred for 10 minutes. 3 g of antimony trioxide And stirred for 5 minutes. Subsequently, the temperature in the polycondensation tank was raised from 240 DEG C to 285 DEG C over 60 minutes, the pressure in the polycondensation tank was reduced from atmospheric pressure to 25Pa, and the polymerization reaction was carried out for 3 hours. Thereafter, a pentaerythritol-tetrakis (3- (3,5-di-tert-butylphenol) was added as an antioxidant (added after the initiation of the polycondensation reaction) to a container having a thickness of 0.2 mm and an inner volume of 500 cm 3 produced by injection molding of a polyethylene terephthalate sheet (Butyl-4-hydroxyphenol) propionate) (Irganox1010, manufactured by BASF) was added thereto, and the mixture was added from the upper part of the reaction vessel. The inside of the polycondensation tank was purged with nitrogen and returned to normal pressure. After stirring for 10 minutes, , Cooled and immediately cut to obtain a polymerization reaction product in the form of pellets. Using the obtained pellets, a drawn lint was produced in the same manner as in Example 4. The SSIA copolymerization ratio 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 properties and the fabric-forming properties of the obtained fibers. Strength, toughness and the like were good, U% (hi) was low, and the fibers were homogeneous. In addition, the time to the elevated half-value point was more than 360 minutes, and the oxidative decomposition was suppressed, and the antistatic property, hygroscopicity, and weight reduction rate after hydrothermal treatment were also good. In addition, since 5-sodium sulfoisophthalic acid is copolymerized, it exhibits a cationic salt-like property, and it has a satisfactory level of uniformity and dignity.

Examples 39, 40

And the copolymerization ratio of 5-sodium sulfoisophthalic acid was changed as shown in Table 6, a drawn yarn was produced in the same manner as in Example 38.

Table 6 shows the evaluation results of the fiber properties and the fabric-forming properties 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, U% (hi) was low, and the fibers were homogeneous. In addition, the time to the elevated half-value point was 360 minutes or longer, and the oxidative decomposition was suppressed, and the antistatic property, hygroscopicity, and weight reduction rate after hydrothermal treatment were also good. In addition, the level of uniformity and dignity were acceptable.

Examples 41 and 42

A drawn lint 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 properties and the fabric-forming properties of the obtained fibers. Even when the copolymerization ratio of the hydrophilic polymer was changed, the fiber properties such as strength and toughness were good, U% (hi) was low, and the fibers were homogeneous. In addition, the time to the elevated half-value point was 360 minutes or longer, and the oxidative decomposition was suppressed, and the antistatic property, hygroscopicity, and weight reduction rate after hydrothermal treatment were also good. In addition, the level of uniformity and dignity were acceptable.

Examples 43 to 47

In Examples 38 to 42, when the melt spinning was carried out without adding the antioxidant after the initiation of the polycondensation reaction, the pellets obtained in each of the Examples were extruded in the extruder type radiator from the main feeder and pentaerythritol tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (manufactured by BASF, Irganox1010) was supplied from the sub feeder at a weight ratio of 100: 0.4, .

Table 6 shows the evaluation results of the fiber properties and the fabric-forming properties of the obtained fibers. In any case, the fiber properties such as strength and toughness were good, U% (hi) was low, and the fibers were homogeneous. In addition, the time to the elevated half-value point was more than 360 minutes, and the oxidative decomposition was suppressed, and the antistatic property, hygroscopicity, and weight reduction rate after hydrothermal treatment were also good. In addition, the level of uniformity and dignity were acceptable.

≪ Industrial Availability >

Although the fibers of the present invention have a phase-separated structure, they have a low degree of unevenness in fineness, are uneven in dyeing and are suppressed from occurrence of fluff, and have excellent durability of fiber properties for long-term storage or tumble drying, hygroscopicity, The antistatic property is excellent and the elution of the hydrophilic compound is suppressed at the time of dyeing or use. Therefore, it can be suitably used as a fibrous structure such as a medical woven fabric or a nonwoven fabric.

Claims (10)

Wherein the fiber has a continuous phase and a dispersed phase by a phase separation structure and has a maximum diameter of 1 to 40 nm in a dispersed phase in the fiber cross section and a fineness variation value U% 1.5%. ≪ / RTI > The method according to claim 1,
Wherein the copolymer of the hydrophobic polymer and the hydrophilic polymer is exposed on at least a part of the surface of the fiber. 3. The method according to claim 1 or 2,
Wherein the hydrophobic polymer is a polyester. 4. The method according to any one of claims 1 to 3,
Wherein the hydrophilic polymer is polyethylene glycol. 5. The method according to any one of claims 1 to 4,
Characterized in that the friction voltage measured at a temperature of 10 DEG C and a humidity of 10% RH is 3000 V or less based on JIS L1094. 6. The method according to any one of claims 1 to 5,
The fibers were heated in a mixed gas atmosphere of nitrogen: oxygen = 80 vol%: 20 vol% at a mixed gas flow rate of 200 ml / min at a heating rate of 30 캜 / min from room temperature to 160 캜, (DTG), the time to reach 160 DEG C is 0 minute, and the time to the half-life point is 120 minutes or more. 7. The method according to any one of claims 1 to 6,
A fiber characterized by containing an antioxidant. 8. The method of claim 7,
Wherein the antioxidant is at least one selected from the group consisting of a phenol compound, a sulfur compound, and a hindered amine compound. 9. The method according to claim 7 or 8,
Wherein the content of the antioxidant is 0.01 to 2.0% by weight of the fiber. 10. A method for producing a fiber according to any one of claims 1 to 9,
Wherein the copolymer of the hydrophobic polymer and the hydrophilic polymer is radiated so that a shear rate when passing through the spinneret is 10000 to 40000 s < ^{-1 &} gt ;.

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