CN106164349A - There is fiber and the manufacture method thereof of phase separation structure - Google Patents

Abstract

The problem of the present invention is to provide a kind of fiber, although described fiber has phase separation structure, but fiber number inequality is little, dyeing is uneven, the generation of fluffing is suppressed, and relative to the excellent antistatic property under long-term keeping, the durability of fiber properties of cylinder dry, hygroscopicity, low temperature and low humidity degree environment, when dyeing, the time of use, the dissolution of hydrophilic compounds is suppressed.This fiber with phase separation structure is characterised by, comprise the copolymer of hydrophobic polymer and hydrophilic macromolecule, there is continuous phase based on phase separation structure and dispersion phase, the maximum gauge of the dispersion phase in fiber cross section is 1～40nm, and fiber number variation value U% (hi) is 0.1～1.5%.

Description

There is fiber and the manufacture method thereof of phase separation structure

Technical field

The present invention relates to a kind of fiber with phase separation structure.More specifically, relate to a kind of fiber, though described fiber So having phase separation structure, but fiber number inequality is little, dyeing is uneven, the generation of fluffing is suppressed, and relative to long-term keeping, rolling The antistatic behaviour that cylinder is dried under the durability of fiber properties of (tumbler drying), hygroscopicity, low temperature and low humidity degree environment is excellent Different, when dyeing, the time of use, the dissolution of hydrophilic compounds is suppressed, can be suitable for dress material purposes.

Background technology

Polyester fiber is cheap, and mechanical property is excellent, because using in purposes widely.But, owing to lacking moisture absorption Property, thus exist and following such have shortcoming to be solved: produce vexed wet sense when the high humidity in summer, produce during low humidity in the winter time Raw electrostatic, etc..The voltage that is charged by friction as the polyethylene terephthalate of normally used polyester is 20 in temperature DEG C, humidity be 40%RH standard state under be 7000～about 9000V.For being charged by friction voltage, its value is the least, more Being difficult to static electrification, snugness of fit is the most excellent.In the case of polyethylene terephthalate, it may be said that be to lack very much to resist Electrostatic fiber.

In order to improve above-mentioned shortcoming, about the method giving antistatic behaviour to polyester fiber, have been presented for up to now Kinds of schemes.As for giving the usual method of antistatic behaviour, copolymerising hydrophilic compound or poly-in the polyester can be enumerated Ester adds the methods such as hydrophilic compounds.Present situation is, although by these methods, can improve antistatic behaviour, but in the winter time Outdoor, owing to using heating equipment to cause under the low temperature and low humidity degree environment such as the low-down indoor of humidity, it is impossible to obtain sufficiently Antistatic behaviour.

Such as, patent documentation 1 proposes add in the polyester the polyether polyols as hydrophilic compounds and Organic metal salt and the antistatic polyester fiber that obtains.In this motion, by disperseing polyoxy alkylidene two in polyester fiber Alcohol, thus give antistatic behaviour.

Patent documentation 2 proposes and has the polyester of Polyethylene Glycol as core with copolymerization, with PTT be The core sheath composite fibre of sheath.In this motion, there is the polyester of Polyethylene Glycol by the copolymerization of configuration in core, thus to polyester fiber Give antistatic behaviour.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 7-173725 publication

Patent documentation 2: Japanese Unexamined Patent Publication 11-93022 publication

Summary of the invention

Invent problem to be solved

But, in the method that above-mentioned patent documentation 1 is recorded, although temperature be 20 DEG C, under conditions of humidity is 40%RH, Being charged by friction voltage low, for 600V, antistatic behaviour is good, but exist temperature be 10 DEG C, humidity be the low temperature and low humidities such as 10%RH Under degree environment, do not show the such problem of sufficient antistatic behaviour.Further, since polyester and hydrophilic compounds are not carried out altogether Poly-, thus there is following such problem: when dyeing or when using, hydrophilic compounds dissolution, the durability of antistatic behaviour Low.

In the method that patent documentation 2 is recorded, as the method also recorded with patent documentation 1, although temperature be 20 DEG C, wet Degree is under conditions of 40%RH, and it is low to be charged by friction voltage, and for 400V, antistatic behaviour is good, but existing in temperature is 10 DEG C, humidity For under the low temperature and low humidity degree environment such as 10%RH, do not show the such problem of sufficient antistatic behaviour.

It addition, in either case, all have and use incompatible Polyethylene Glycol as hydrophilic compounds in the polyester In the case of fiber number uneven big, occur that dyeing is uneven, such problem of fluffing.Be additionally, since the oxidation Decomposition of Polyethylene Glycol not by Suppression, thus there is following such problem: by long-term keeping or cylinder dry, oxidation Decomposition is carried out, and hygroscopicity, low temperature are low The fiber properties such as antistatic behaviour under humidity environment, mechanical property reduce.

The problem of the present invention is to solve above-mentioned problem of the prior art point, it is provided that a kind of fiber, although described fiber tool Having phase separation structure, but fiber number inequality is little, dyeing is uneven, the generation of fluffing is suppressed, and hygroscopicity, low temperature and low humidity degree environment Under excellent antistatic property, dyeing time, use time, the dissolution of hydrophilic compounds be suppressed, dress material purposes can be suitable for.

For solving the means of problem

The problem of the above-mentioned present invention can be solved by following fiber, and described fiber has phase separation structure, comprises hydrophobic Property macromolecule and hydrophilic macromolecule copolymer, and there is continuous phase based on phase separation structure and dispersion phase, fiber is transversal The maximum gauge of the dispersion phase in face is 1～40nm, and fiber number variation value U% (hi) is 0.1～1.5%.

It addition, for the fiber of the present invention, preferably hydrophobic polymer and the copolymer of hydrophilic macromolecule are at fibre Exposing at least partially of dimension table face, it is preferred to use: hydrophobic polymer is polyester, and hydrophilic macromolecule is Polyethylene Glycol.

Additionally, for the fiber of the present invention, it is preferred that at nitrogen: the mixed gas of oxygen=80vol%:20vol% Under atmosphere, mixed gas flow be 200mL/ minute, with the programming rates of 30 DEG C/min after room temperature to 160 DEG C, protect Under conditions of being held in 160 DEG C, when carrying out thermoconductive TGA (DTG) for described fiber, it is up to the time of 160 DEG C as 0 In the case of minute, the time to rising half value point is more than 120 minutes.Additionally, it is preferred that use: containing antioxidant, antioxygen Agent is at least one in phenolic compound, sulfur compounds, hindered amine based compound, and the content of antioxidant is fine 0.01～2.0 weight % of dimension weight.

Additionally, for the fiber of the present invention, it is preferred that based on JIS L1094, temperature be 10 DEG C, humidity be The voltage that is charged by friction recorded under conditions of 10%RH is below 3000V.

Further, it may be preferred that use the manufacture method of following fiber, the method is characterized in that, with hydrophobic polymer with The copolymer of hydrophilic macromolecule becomes 10000～40000s by shear rate during spinning head^-1Mode carry out spinning.

The effect of invention

Passing through the present invention, it is possible to provide a kind of fiber, although described fiber has phase separation structure, but fiber number inequality is little, dye Color is uneven, the generation of fluffing is suppressed, and, relative to long-term keeping, the durability of fiber properties of cylinder dry, moisture absorption Property, excellent antistatic property under low temperature and low humidity degree environment, when dyeing, the time of use, the dissolution of hydrophilic compounds is suppressed.On State fiber and be especially suitable for dress material purposes.

Accompanying drawing explanation

[Fig. 1] Fig. 1 is that the replacement accompanying drawing of the fiber cross section of the fiber with phase separation structure of the example present invention uses Photo.

[Fig. 2] Fig. 2 is that the replacement accompanying drawing of the fiber longitudinal section of the fiber with phase separation structure of the example present invention uses Photo.

Detailed description of the invention

The fiber package of the present invention is containing the copolymer of hydrophobic polymer with hydrophilic macromolecule, and has based on separated knot The continuous phase of structure and dispersion phase, the maximum gauge of the dispersion phase in fiber cross section is 1～40nm, fiber number variation value U% (hi) It is 0.1～1.5%.For the fiber of the present invention, although there is phase separation structure, but as it is shown in figure 1, at fiber cross section In define fine and uniform dispersion phase, thus, fiber number inequality is little, and dyeing is uneven, the generation of fluffing is suppressed.It addition, it is logical Cross hydrophobic polymer and hydrophilic macromolecule copolymerization, thus not only can give hygroscopicity, antistatic behaviour, Er Qie to fiber During dyeing, use time, the dissolution of hydrophilic compounds be suppressed, accordingly, with respect to hygroscopicity, antistatic behaviour, there is durability.This Outward, as in figure 2 it is shown, in fiber longitudinal section, be formed with dividing of fine and uniform striated along the direction parallel with fiber axis Dephasing, therefore, even if available under low temperature and low humidity degree environment, it is the lowest to be charged by friction voltage, the fiber of excellent antistatic property.

For the hydrophobic polymer in the present invention, as long as can be with hydrophilic macromolecule copolymerization, it is possible to there is no spy Xian Zhi not use suitably on ground.As the concrete example of hydrophobic polymer, polyethylene terephthalate can be enumerated, gather benzene The aromatic polyesters such as naphthalate, polybutylene terephthalate (PBT), poly terephthalic acid 1,6-HD ester, poly-breast Acid, polyglycolic acid, 10PE27, polypropylene glycol adipate, poly adipate succinic acid ester, poly-succinic acid second two Alcohol ester, poly-succinic acid propylene glycol ester, polybutylene succinate, polyethylene glycol sebacate, poly-decanedioic acid propylene glycol ester, the poly-last of the ten Heavenly stems The aliphatic polyester such as succinate adipate, polycaprolactone etc., but it is not limited to these.Wherein, polyethylene terephthalate, poly- Propylene glycol ester terephthalate, the mechanical property of polybutylene terephthalate (PBT), excellent in te pins of durability, during manufacture and when using Treatability good, thus preferably.

For the hydrophilic macromolecule in the present invention, as long as can be with hydrophobic polymer copolymerization, it is possible to there is no spy Xian Zhi not use suitably on ground.By to hydrophobic polymer copolymerising hydrophilic macromolecule, antistatic behaviour can be given to fiber.Make For the concrete example of hydrophilic macromolecule, the homopolymer such as Polyethylene Glycol, polypropylene glycol, polyethylene glycol propylene glycol copolymerization can be enumerated The copolymers etc. such as thing, polyethylene glycol butanediol copolymer, but it is not limited to these.Wherein, Polyethylene Glycol, polypropylene glycol are in system Treatability when making and when using is good, thus preferably.

The fiber package of the present invention is containing the copolymer of hydrophobic polymer with hydrophilic macromolecule.It is blended such with polymer Melting mixing is different, and hydrophobic polymer and hydrophilic macromolecule form covalent bond, therefore, hydrophilic macromolecule by copolymerization Dissolution from fiber is suppressed, and when can get inter process during fabrication, use goods, the change of fiber properties is little, durable Property excellent fiber.

The fiber of the present invention has phase separation structure.This phase separation structure be carry out in polyreaction, hydrophobic polymer Specifically present during carrying out copolymerization with hydrophilic macromolecule.That is, with by incompatible macromolecular compound Melting mixing and the phase separation structure that presents is different, in the present invention, carry out and being separated of presenting owing to being as polyreaction Structure, thus form fine and uniform dispersion phase.Owing to dispersion phase is fine and uniform, thus while the fiber obtained has phase Isolating construction, but fiber number inequality is little, and dyeing is uneven, the generation of fluffing is suppressed.Further, since have phase separation structure, thus, The fiber of the excellent antistatic property under available low temperature and low humidity degree environment.

Present about the carrying out along with polyreaction is separated, it is shown that concrete example.As hydrophobic polymer Polyethylene terephthalate, as the copolymer of the Polyethylene Glycol of hydrophilic macromolecule in the case of, at the beginning of polycondensation reaction Phase, due to double (beta-hydroxy ethyl) ester of the p-phthalic acid of the precursor as polyethylene terephthalate and Polyethylene Glycol Polarity is close, is therefore at compatible state, and reaction system is transparent.Along with the carrying out of polycondensation reaction, generate poly terephthalic acid second Diol ester-ethylene glycol copolymer, begins to pass through about 1 hour from polymerization, becomes phase-separated state, reaction system nebulousurine.Poly- In ethylene glycol terephthalate-ethylene glycol copolymer, generate the copolymer of low polarity, i.e. polyethylene terephthalate Copolymer that ratio shared in strand is high and the ratio shared in strand of highly polar copolymer, i.e. Polyethylene Glycol The copolymer that example is high, this phase separation structure be the copolymer by above-mentioned low polarity with the difference of the polarity of highly polar copolymer and Present.

The fiber of the present invention has continuous phase based on phase separation structure and dispersion phase.Composition continuous phase becomes with dispersion phase Divide and carry out the ratio of copolymerization along with hydrophobic polymer with hydrophilic macromolecule and change.Ratio at hydrophobic polymer Time more than hydrophilic macromolecule, " hydrophobic polymer-hydrophilic height that hydrophobic polymer ratio shared by strand is high Molecule copolymer " become continuous phase, " the hydrophobic polymer-hydrophilic that hydrophilic macromolecule ratio shared by strand is high Property high-molecular copolymer " become dispersion phase.On the other hand, when the ratio of hydrophilic macromolecule is more than hydrophobic polymer, parent " hydrophobic polymer-hydrophilic macromolecule copolymer " that aqueous high molecular ratio shared by strand is high becomes continuous Phase, " hydrophobic polymer-hydrophilic macromolecule copolymer " that hydrophobic polymer ratio shared by strand is high becomes Dispersion phase.In any case, continuous phase, dispersion phase two side are by " hydrophobic polymer-hydrophilic macromolecule copolymer " shape Becoming, simply its ratio of components is different, therefore, is the phase separation structure that continuous phase is the highest with the affinity of dispersion phase.Consequently found that, Forming the dispersion phase stability when melted delay the highest, dispersion phase is difficult to the separated knot of coarsening during melted delay Structure.Thus, it can be known that it is uneven to improve fiber number when being carried out fibrosis by melt spinning, and, when dyeing, the time of use, The dissolution of hydrophilic compounds can be suppressed.

In the present invention, in the case of using polyester as hydrophobic polymer, as the dicarboxylic acid component of polyester, it is possible to The dicarboxylic acids of use ester formative in addition to p-phthalic acid.As the concrete example of the dicarboxylic acids of ester formative, can be enumerated oneself Diacid, M-phthalic acid, decanedioic acid, phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 5-sodium sulfo isophthalate, isophthalic two Formic acid-5-Sulfonic Lithium, M-phthalic acid-5-sulfonic acid (tetraalkyl)Deng dicarboxylic acids and their ester formative derivant etc., but It is not limited to these.

In the present invention, in the case of using polyester as hydrophobic polymer, as the diol component of polyester, it is possible to make Glycol by the ester formative in addition to ethylene glycol.As the concrete example of the glycol of ester formative, propylene glycol, fourth two can be enumerated Alcohol, hexanediol, cyclohexanediol, diethylene glycol, 1,6-hexanediol, neopentyl glycol and their ester formative derivant etc., but not It is limited to these.

In the present invention, using polyethylene terephthalate as hydrophobic polymer, using Polyethylene Glycol conduct In the case of hydrophilic macromolecule, the number-average molecular weight of Polyethylene Glycol is preferably 7000～20000.The equal molecule of number of Polyethylene Glycol When amount is more than 7000, presented phase separation structure by the copolymerization with polyethylene terephthalate, thus, by carrying out Fibrosis and the fiber of available excellent antistatic property, thus preferably.The number-average molecular weight of Polyethylene Glycol be more preferably 7500 with On, more preferably more than 8000.On the other hand, when the number-average molecular weight of Polyethylene Glycol is less than 20000, poly-terephthaldehyde The polycondensation reaction of acid glycol ester and Polyethylene Glycol is high, can reduce unreacted Polyethylene Glycol, thus preferably.It addition, pass through With the copolymerization of polyethylene terephthalate, coarsening when dispersion phase is fine and uniform, melted to be detained can be formed and pressed down System stable phase separation structure, after polycondensation reaction terminates from the discharge of polycondensation groove, when spinning steady from the discharge of spinning head Fixed, operability becomes good, thus preferably.Additionally, available fiber number inequality is little, dyeing is uneven, fluffing generation is repressed The fiber of homogenizing, thus preferably.The number-average molecular weight of Polyethylene Glycol is more preferably less than 17000, more preferably 15000 with Under.

In the present invention, using polyethylene terephthalate as hydrophobic polymer, using Polyethylene Glycol conduct In the case of hydrophilic macromolecule, the copolymerization rate of Polyethylene Glycol is preferably 10～20 weight %.The copolymerization rate of Polyethylene Glycol is 10 Time more than weight %, available hygroscopicity and the fiber of excellent antistatic property, thus preferably.The copolymerization rate of Polyethylene Glycol is more excellent Elect more than 11 weight % as, more preferably more than 12 weight %.On the other hand, the copolymerization rate of Polyethylene Glycol is 20 weight % Time following, by the copolymerization with polyethylene terephthalate, fine and uniform phase separation structure can be formed, anti-in polycondensation From the discharge of polycondensation groove after should terminating, stablizing from the discharge of spinning head when spinning, operability becomes good, thus preferably.Separately Outward, available fiber number inequality is little, dyeing is uneven, the fiber that repressed homogenizing occurs of fluffing, fiber and being formed by it The mechanical property of fiber construct becomes good, thus preferably.The copolymerization rate of Polyethylene Glycol is more preferably below 19 weight %, enters One step is preferably below 18 weight %.

In the present invention, people are to by hydrophobic polymer (polyethylene terephthalate)-hydrophilic macromolecule in invention The phase separation structure that (Polyethylene Glycol) copolymer is formed conducts in-depth research, found that following such special phenomenon: The phase separation structure the highest with the affinity of dispersion phase owing to being described above as continuous phase, thus, give in the molten state During shearing, phase separation structure differential dispersion, disappear soon, but stop giving shearing and through certain time, again present phase Isolating construction.The manufacture method of fiber described later is described in detail, by effectively utilizing above-mentioned special phenomenon, thus Although successfully obtaining and there is phase separation structure but fiber number inequality is little, dyeing is uneven, the repressed fiber of generation of fluffing.

Hydrophobic polymer in the present invention and the copolymer of hydrophilic macromolecule can be to add secondary additive and enter Go the copolymer of various modification.As the concrete example of secondary additive, can enumerate bulking agent, plasticizer, UV absorbent, Infrared absorbent, fluorescent whitening agent, releasing agent, antibacterial, nucleator, heat stabilizer, antioxidant, antistatic agent, prevent Toner, regulator, delustering agent, defoamer, preservative, gelating agent, latex, filler, ink, colouring matter, dyestuff, pigment, perfume (or spice) Material etc., but it is not limited to these.These secondary additives can be used alone, it is possible to and with multiple.

The maximum gauge of the dispersion phase in the fiber cross section of the fiber of the present invention is 1～40nm.In fiber cross section The detailed assay method of the maximum gauge of dispersion phase illustrates below.The maximum gauge of the dispersion phase in fiber cross section is During more than 1nm, available hygroscopicity and the fiber of excellent antistatic property.The maximum gauge of the dispersion phase in fiber cross section is more excellent Elect more than 3nm as, more preferably more than 5nm, particularly preferably more than 10nm.On the other hand, dividing in fiber cross section When the maximum gauge of dephasing is below 40nm, fiber and the mechanical property of fiber construct formed by it are good, durability Excellent.Further, since be fine and uniform dispersion phase, thus stable from the discharge of spinning head when spinning, and operability becomes Well, and fiber number inequality is little, can suppress the generation that dyeing is uneven, fluff.The maximum gauge of the dispersion phase in fiber cross section More preferably below 37nm, more preferably below 35nm, particularly preferably below 30nm.

The maximum gauge of the dispersion phase in the fiber longitudinal section of the fiber of the present invention is preferably 1～40nm.Fiber longitudinal section In the detailed assay method of maximum gauge of dispersion phase illustrate below.It should be noted that in so-called fiber longitudinal section The maximum gauge of dispersion phase, refer to the maximum of the diameter of dispersion phase for the direction vertical with fiber axis.Fiber is vertical to be cut When the maximum gauge of the dispersion phase in face is more than 1nm, available hygroscopicity and the fiber of excellent antistatic property, thus preferably. The maximum gauge of the dispersion phase in fiber longitudinal section is more preferably more than 3nm, more preferably more than 5nm, particularly preferably More than 10nm.On the other hand, when the maximum gauge of the dispersion phase in fiber longitudinal section is below 40nm, fiber and being formed by it The mechanical property of fiber construct good, excellent in te pins of durability, thus preferably.Further, since be fine and uniform dispersion phase, Thus stable from the discharge of spinning head when spinning, operability becomes good, and, fiber number inequality is little, can suppress dyeing uneven, The generation of fluffing, thus preferably.The maximum gauge of the dispersion phase in fiber longitudinal section is more preferably below 37nm, further preferably For 35nm, particularly preferably below 30nm.

The total fiber number of the fiber of the present invention is not particularly limited, can according to purposes, require that characteristic suitably selects, be preferably 10～500dtex.When the total fiber number of fiber is more than 10dtex, not only fracture of wire is few, and operation is good by property, and, using The generation of Shi Qimao is few, excellent in te pins of durability, thus preferably.The total fiber number of fiber is more preferably more than 30dtex, further preferably For more than 50dtex.On the other hand, when the total fiber number of fiber is below 500dtex, when forming fiber and fiber construct, Without compromising on flexibility, thus preferably.The total fiber number of fiber is more preferably below 400dtex, more preferably 300dtex with Under.

The intensity of the fiber of the present invention is not particularly limited, can according to purposes, require that characteristic suitably selects, special from machinery From the viewpoint of property, preferably 2.0～5.0cN/dtex.When the intensity of fiber is more than 2.0cN/dtex, not only in spinning, draw Stretch operation, weave, to make up the process interruption silks such as operation few, operation is good by property, and excellent in te pins of durability when using, thus Preferably.The intensity of fiber is more preferably more than 2.5cN/dtex, more preferably more than 3.0cN/dtex.On the other hand, fine When the intensity of dimension is below 5.0cN/dtex, when forming fiber and fiber construct, without compromising on flexibility, thus excellent Choosing.

The percentage elongation of the fiber of the present invention is not particularly limited, can according to purposes, require that characteristic suitably selects, from operation From the viewpoint of property, preferably 10～60%.When the percentage elongation of fiber is more than 10%, not only fiber and fibre structure The abrasion performance of body becomes good, and operation is good by property, and when using, the generation of fluffing is few, and durability becomes good, because of And it is preferred.The percentage elongation of fiber is more preferably more than 15%, and more preferably more than 20%.On the other hand, the elongation of fiber When rate is less than 60%, the dimensional stability of fiber and fiber construct becomes good, thus preferably.The percentage elongation of fiber is more It is preferably less than 55%, more preferably less than 50%.

The incipient extension opposing degree of the fiber of the present invention is not particularly limited, can according to purposes, require that characteristic is suitably selected Select, be preferably 10～100cN/dtex according to the 8.10 of the JIS L1013:1999 incipient extension opposing degree recorded.At the beginning of fiber When beginning stretch-resistant degree is more than 10cN/dtex, operation is good by property, treatability, and mechanical property is excellent, thus preferably.Fine The incipient extension opposing degree of dimension is more preferably more than 15cN/dtex, more preferably more than 20cN/dtex.On the other hand, fine When the incipient extension opposing degree of dimension is below 100cN/dtex, without compromising on fiber and the flexibility of fiber construct, thus Preferably.The incipient extension opposing degree of fiber is more preferably below 90cN/dtex, more preferably below 80cN/dtex.

The fiber footpath of the fiber of the present invention is not particularly limited, can according to purposes, require that characteristic suitably selects, be preferably 3～100 μm.When the fiber footpath of fiber is more than 3 μm, the operation in available spinning operability, senior processing is good by property, The fiber that mechanical property is excellent, thus preferably.The fiber footpath of fiber is more preferably more than 5 μm, more preferably more than 7 μm. On the other hand, when the fiber footpath of fiber is below 100 μm, without compromising on fiber and the flexibility of fiber construct, thus excellent Choosing.The fiber footpath of fiber is more preferably below 70 μm, more preferably below 50 μm.

The boiling water shrinkage of the fiber of the present invention is preferably 3～15%.When the boiling water shrinkage of fiber is more than 3%, can Improve weaving density by making fabric thermal contraction, the weaving tension in weaving process is suppressed in the scope of appropriateness, can Manufacture highdensity fabric, thus preferably.Additionally, when manufacturing high-density fabric, it is not necessary to weave under high tension, can Fluffing in suppression weaving process, floss must generation, can operation by property manufacturing defect is few well fabric, thus preferably. The boiling water shrinkage of fiber is more preferably more than 4%, and more preferably more than 5%.On the other hand, the boiling water shrinkage of fiber When being less than 15%, when processing with boiling water, the degree of orientation of strand will not extremely reduce, the intensity fall after boiling water treating Low little, thus preferably.The processing of fabric thermal contraction is made to make fiber fully shrink it addition, available, available soft fabric, because of And it is preferred.The boiling water shrinkage of fiber is more preferably less than 12%, and more preferably less than 10%.

Fiber number variation value U% (hi) of the fiber of the present invention is 0.1～1.5%.Fiber number variation value U% is fibre length side To the uneven index of thickness, fiber number variation value U% (hi) is the least, represents that the thickness inequality of the length direction of fiber is the least.From From the viewpoint of operation passes through property, quality, fiber number variation value U% (hi) is the smaller the better, but as the scope that can manufacture, 0.1% It it is lower limit.On the other hand, when fiber number variation value U% (hi) of fiber is less than 1.5%, the uniformity in fibre length direction is excellent Different, can suppress at warping process, weave, make up the variation of machine tensions in operation etc., thus preferably.Additionally, be not susceptible to Hair, fracture of wire, when dyeing, be not likely to produce the shortcomings such as uneven, the dyeing striped of dyeing, the fiber construct of available high-quality, because of And it is preferred.Fiber number variation value U% (hi) of fiber more preferably less than 1.2%, more preferably less than 1.0%, the most excellent Elect less than 0.9% as.

The filament diameter CV% of the fiber of the present invention is preferably 0.1～15%.Examined by the viewpoint of property, quality from operation Considering, filament diameter CV% is the smaller the better, but as the scope that can manufacture, 0.1% is lower limit.On the other hand, the monofilament of fiber is straight When footpath CV% is less than 15%, fluff when not only can suppress during fabrication and use, and be not likely to produce when dyeing The shortcomings such as dyeing is uneven, dyeing striped, the fiber construct of available high-quality, thus preferably.The filament diameter CV% of fiber More preferably less than 12%, more preferably less than 10%, particularly preferably less than 7%.

Filament number CV% of the fiber of the present invention is preferably 0.1～15%.Examined by the viewpoint of property, quality from operation Considering, filament number CV% is the smaller the better, but as the scope that can manufacture, 0.1% is lower limit.On the other hand, the monofilament of fiber is fine When degree CV% is less than 15%, fluff when not only can suppress during fabrication and use, and be not likely to produce when dyeing The shortcomings such as dyeing is uneven, dyeing striped, the fiber construct of available high-quality, thus preferably.Filament number CV% of fiber More preferably less than 12%, more preferably less than 10%, particularly preferably less than 7%.

The filament strength CV% of the fiber of the present invention is preferably 0.1～20%.Examined by the viewpoint of property, quality from operation Considering, filament strength CV% is the smaller the better, but as the scope that can manufacture, 0.1% is lower limit.On the other hand, the monofilament of fiber is strong When degree CV% is less than 20%, fluff when not only can suppress during fabrication and use, and be not likely to produce when dyeing The shortcomings such as dyeing is uneven, dyeing striped, the fiber construct of available high-quality, thus preferably.The filament strength CV% of fiber More preferably less than 15%, more preferably less than 12%, particularly preferably less than 10%.

The monofilament percentage elongation CV% of the fiber of the present invention is preferably 0.1～40%.Examined by the viewpoint of property, quality from operation Considering, percentage elongation CV% is the smaller the better for monofilament, but as the scope that can manufacture, 0.1% is lower limit.On the other hand, the monofilament of fiber When percentage elongation CV% is less than 40%, fluff when not only can suppress during fabrication and use, and be difficult to when dyeing Produce dyeing inequality, dye the shortcomings such as striped, the fiber construct of available high-quality, thus preferably.The monofilament elongation of fiber Rate CV% is more preferably less than 37%, and more preferably less than 35%, particularly preferably less than 30%.

For the fiber of the present invention, it is preferred that at nitrogen: the mixed-gas atmosphere of oxygen=80vol%:20vol% Under, mixed gas flow be 200mL/ minute, with the programming rates of 30 DEG C/min after room temperature to 160 DEG C, be held in When carrying out thermoconductive TGA (DTG) under conditions of 160 DEG C, it is up to time of 160 DEG C as in the case of 0 minute, supreme The time rising half value point is more than 120 minutes.The detailed assay method rising half value point illustrates below, uses this evaluation side Method is as assuming relative to long-term keeping, the accelerated test of the durability of cylinder dry.Present inventors confirm, right Having by hydrophobic polymer (polyethylene terephthalate)-hydrophilic macromolecule (Polyethylene Glycol) altogether in the present invention The fiber of the phase separation structure that polymers is formed, the rising peak in thermoconductive TGA (DTG) when 160 DEG C is by hydrophilic high score The son decomposition of (Polyethylene Glycol) and produce, along with the decomposition of this Polyethylene Glycol, hygroscopicity is lost, and moisture absorption rate variance (△ MR) drops Low, and then, the antistatic behaviour under low temperature and low humidity degree environment is lost, and is charged by friction voltage and improves.From relative to long-term keeping, cylinder The viewpoint of the durability of the fiber properties such as antistatic behaviour under that be dried, hygroscopicity, low temperature and low humidity degree environment, mechanical property is examined Considering, the time reaching rising half value point, the longer the better.The time reaching to rise half value point is more preferably more than 180 minutes, enters one Step preferably more than 240 minutes, particularly preferably more than 360 minutes.

The moisture absorption rate variance (△ MR) of the fiber of the present invention is preferably 1～10%.The detailed assay method of △ MR is below Illustrate, △ MR assumed that in the clothes after light exercise humiture i.e. temperature be 30 DEG C, under conditions of humidity is 90%RH The difference that hydroscopicity and the temperature as ambient atmos humiture are 20 DEG C, humidity is the hydroscopicity under conditions of 65%RH.That is, △ MR is hygroscopic index, and the value of △ MR is the highest, and snugness of fit is the highest.When the △ MR of fiber is more than 1%, in clothes Vexed wet sense is few, performance snugness of fit, thus preferably.The △ MR of fiber is more preferably more than 1.5%, and more preferably 2% Above.On the other hand, when the △ MR of fiber is less than 10%, operation is good by property, treatability, and durability during use is excellent Different, thus preferably.The △ MR of fiber is more preferably less than 9%, and more preferably less than 8%.

For the fiber of the present invention, owing to hydrophobic polymer is copolymerized with hydrophilic macromolecule, thus with dredging Aqueous high molecular is different from the situation of hydrophilic macromolecule melting mixing, and hydrophilic macromolecule dissolution in hot water etc. is pressed down System.Therefore, hygroscopic durability is high, can be suitable for using as fiber construct.

For the fiber of the present invention, preferable temperature is 10 DEG C, humidity is to be charged by friction electricity under conditions of 10%RH Pressure is below 3000V.The detailed assay method being charged by friction voltage illustrates below, and being charged by friction voltage is antistatic behaviour Index, the value being charged by friction voltage is the lowest, more can suppress the generation of electrostatic.From the viewpoint of snugness of fit, it is charged by friction Voltage is the smaller the better, it is further preferred that, not only temperature be 20 DEG C, humidity be the friction under 40%RH isothermal humidity environment Electrified voltage is low, and temperature be 10 DEG C, humidity be under the low temperature and low humidity degree environment such as 10%RH, it is the lowest to be charged by friction voltage, Present the antistatic behaviour of excellence.Temperature be 10 DEG C, humidity be that the voltage that is charged by friction of fiber under conditions of 10%RH is During below 3000V, though outdoor in the winter time, due to use heating equipment and cause the low temperature and low humidities such as the low-down indoor of humidity Under degree environment, the generation of electrostatic is also few, and snugness of fit is excellent, thus preferably.Temperature is 10 DEG C, humidity is the condition of 10%RH Under the voltage that is charged by friction of fiber be more preferably below 2500V, more preferably below 2000V.

The fiber of the present invention is formed as copolymer by hydrophobic polymer and hydrophilic macromolecule and in addition The composite fibre that other (co) polymer are formed.Now, the copolymer of preferably hydrophobic polymer and hydrophilic macromolecule is at fibre Exposing at least partially of dimension table face.Such as, it is combined for core sheath with the copolymer with hydrophobic polymer with hydrophilic macromolecule The core composition of fiber, the fiber being coated to completely by sheath composition, with the copolymer of hydrophobic polymer and hydrophilic macromolecule as sea The island component of island composite fibre, the fiber being coated to completely by sea component are compared, and hydrophobic polymer is total to hydrophilic macromolecule Polymers at fiber surface when exposing at least partially, available hygroscopicity, the fiber of excellent antistatic property, thus preferably.Need Even if being noted that at the core composition being core sheath composite fibre with the copolymer of hydrophobic polymer Yu hydrophilic macromolecule In the case of, as long as at least some of of core composition exposes at fiber surface, even if with hydrophobic polymer and hydrophilic In the case of high molecular copolymer is the island component of island-in-sea type composite fiber, as long as island component is at least some of at fiber surface Expose.

The fiber of the present invention preferably comprises antioxidant.By containing antioxidant, thus not only suppression because of the most certainly, Cylinder dry and the oxidation Decomposition of hydrophilic macromolecule that causes, and improve under hygroscopicity, low temperature and low humidity degree environment anti-quiet Electrically, the durability of the fiber properties such as mechanical property, thus preferably.It addition, having by hydrophobic polymer in the present invention is (poly- Ethylene glycol terephthalate) fiber of phase separation structure that formed of-hydrophilic macromolecule (Polyethylene Glycol) copolymer, and do not have The fiber having the polyethylene terephthalate-ethylene glycol copolymer containing homogeneous texture of phase separation structure is compared, oxygen Changing decomposability high, for above-mentioned problem, as described later, present inventors are found that and can make in fiber containing enough The method of antioxidant, by described method, thus can be while there is phase separation structure, inhibited oxidation decomposes, and can stablize Ground obtains the fiber of the excellent in te pins of durability of the fiber properties such as the antistatic behaviour under hygroscopicity, low temperature and low humidity degree environment, mechanical property.

Antioxidant in the present invention is preferably selected from phenolic compound, sulfur compounds, hindered amine based compound.These resist Oxidant can only use a kind, it is possible to and use two or more.

Phenolic compound in the present invention is the radical chain reaction inhibitor with phenol structure, as concrete example, can lift Go out 2,6-Butylated Hydroxytoluene, butylated hydroxyanisole (BHA), the 2,6-tert-butyl group-4-ethyl-phenol, β-(3,5-di-t-butyl-4-hydroxyl Base phenyl) propanoic acid stearyl, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-ethyl- 6-tert-butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), double { 1,1-dimethyl-2-{ β-(uncle 3-of 3,9- Butyl-4-hydroxy-5-methyl base phenyl) propiono epoxide } ethyl } 2,4,8,10-tetra-oxaspiro { 5,5} hendecane, 1,1,3-tri- (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-hydroxyl benzyl Base) benzene, double { 3,3 '-bis--(4 '-hydroxyl-3 '-tert-butyl-phenyl) butanoic acid } diol ester, tocopherol, tetramethylolmethane-four (3-(3, 5-di-t-butyl-4-hydroxyl phenol) propionic ester), 2,4,6-tri-(3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl) sym-trimethylbenzene., 1, 3,5-tri-[[4-(1,1-dimethyl ethyl)-3-hydroxyl-2,6-3,5-dimethylphenyl] methyl]-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone etc., but it is not limited to these.These phenolic compounds can only use a kind, it is possible to and use two or more.Wherein, season Penta tetrol-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010), 2,4,6-tri-(3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl) sym-trimethylbenzene. (ADEKA system, ア デ カ ス タ Block AO-330), 1,3,5-tri-[[4-(1, 1-dimethyl ethyl)-3-hydroxyl-2,6-3,5-dimethylphenyl] methyl]-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone (east Capital chemical conversion industry system, THANOX1790) due to inhibited oxidation decompose effective, thus preferably use.

Sulfur compounds in the present invention is not to be produced to be reduced peroxide, self oxidized sulfur class antioxygen by base Agent, as concrete example, can enumerate 3,3 '-thiodipropionic acid dilauryl ester, 3, and 3 '-thiodipropionic acid myristyl ester, 3,3 '- Thiodipropionic acid distearyl ester etc., but it is not limited to these.These sulfur class antioxidants can only use a kind, it is possible to and with 2 kinds with On.

Hindered amine based compound in the present invention be have catch ultraviolet, heat effect under produce free radical, make As antioxidant function but the hindered amine system antioxidant of effect of the phenol antioxidant regeneration inactivated, as tool Style, can enumerate dibutylamine-1,3,5-triazines-N, N '-bis-(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa-methylene two The condensation polymer of amine and N-(2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly-[6-(1,1,3,3-tetramethyl butyl) amino- 1,3,5-triazine-2,4-diyl } and (2,2,6,6-tetramethyl-4-piperidyl) imino group] hexa-methylene { (2,2,6,6-tetramethyl Base-4-piperidyl) imino group], N, N ', N ", N " '-four-(4,6-is double-(butyl-(N-methyl-2,2,6,6-tetramethyl piperidine- 4-yl) amino)-triazine-2-base)-4,7-diaza decane-1,10-diamidogen and dimethyl succinate and 4-hydroxyl-2,2,6,6- The polymer of tetramethyl-1-piperidine ethanol, poly-[(6-morpholinyl (morpholino) guanamine, 4-diyl) [2,2,6,6-tetra- Methyl-4-piperidyl] imino group]-hexa-methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino group]), poly-[(6-morpholinyl Guanamine, 4-diyl) [2,2,6,6-tetramethyl-4-piperidyl] imino group]-hexa-methylene [(2,2,6,6-tetramethyl-4- Piperidyl) imino group]], 1,6-hexane diamine-N, N '-bis-(1,2,2,6,6-pentamethyl-4-piperidyl) and morpholine-2,4,6- The methylated polymer thing of three chloro-1,3,5-triazines, 2,2,4,4-tetramethyl-7-oxa--3,20-diaza-20 (2,3-epoxy Base-propyl group) polymer etc. of two spiral shells-[5,1,11,2]-heneicosane-21-ketone, but it is not limited to these.These hindered amine systems Compound can only use a kind, it is possible to and use two or more.Wherein, from suppression due to washing, use the cleaning that carries out of organic solvent and From the viewpoint of the dissolution from fibrous inside caused, the preferably high molecular type hindered amine system chemical combination of molecular weight more than 1000 Thing.Especially, dibutylamine-1,3,5-triazines-N, N '-bis-(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa-methylene two The condensation polymer (BASF CHIMASSORB2020) of amine and N-(2,2,6,6-tetramethyl-4-piperidyl) butylamine is due to suppression oxygen Change the effective of decomposition, thus preferably use.

The content of the antioxidant in the fiber of the present invention is preferably 0.01～2.0 weight % of fibre weight.In order to send out Wave antioxidant effect, by making enough antioxidants be comprised in fiber, thus can suppress because of long-term keeping, cylinder dry And the oxidation Decomposition of the hydrophilic compounds caused, improve the antistatic behaviour under hygroscopicity, low temperature and low humidity degree environment, mechanical property Deng the durability of fiber properties, thus preferably.When the content of antioxidant is more than 0.01 weight %, suppression can be given to fiber The effect of oxidation Decomposition, thus preferably.The content of antioxidant is more preferably more than 0.05 weight %, and more preferably 0.1 More than weight %, more than particularly preferably 0.15 weight %.On the other hand, when the content of antioxidant is below 2.0 weight %, The tone of fiber will not deteriorate, also without compromising on mechanical property, thus preferably.The content of antioxidant is more preferably 1.7 weights Amount below %, more preferably below 1.5 weight %, below particularly preferably 1.0 weight %.

For the fiber of the present invention, the cross sectional shape about fiber is not particularly limited, and can be the circle of round type Tee section, it is also possible to be noncircular cross section.As the concrete example of noncircular cross section, can enumerate multi-leaf-shaped, polygon, pancake, Ellipse, C font, H font, S font, T-shaped, W font, X font, Y-shaped etc., but it is not limited to these.

For the fiber of the present invention, the form about fiber is not particularly limited, and can be monofilament (monofilament), the arbitrarily form such as multifilament (multifilament), chopped fiber (staple).

For the fiber of the present invention, as general fiber, the processing such as false twisting, twisted filament can be carried out, for weaving, Make up, it is possible to process in the same manner as general fiber.

The form of the fiber construct of the fiber comprising the present invention is not particularly limited, and can make according to known methods Fabric, volume thing, pile fabric, non-woven fabrics or spun yarn, filling cotton etc..It addition, comprise the fiber construct of the fiber of the present invention Can be any knit tissue or marshalling knit, plain cloth, twills, satin fabric or their change can be used suitably Knit, warp knit, weft knitting, round knitting, petinet ocular tissue or their change volume etc..

The fiber of the present invention can be when making fiber construct by intertexture, friendship volume etc. and other fiber combinations, it is possible to Fiber construct is made after forming the mixed filament with other fibers.

It follows that the manufacture method of the hydrophobic polymer used in the present invention with the copolymer of hydrophilic macromolecule is entered Row explanation.As concrete example, hereinafter it is shown with polyester high as hydrophilic as hydrophobic polymer, use Polyethylene Glycol The manufacture method of the phase separation structure formed by polyester-ethylene glycol copolymer of molecule.

In the present invention, when manufacturing polyester-ethylene glycol copolymer, first, independent polyester component is implemented esterification Or ester exchange reaction, obtain polyester oligomer.Polyethylene Glycol it is added with in advance it follows that added to by above-mentioned polyester oligomer In reactive tank.It should be noted that now, in the case of Polyethylene Glycol is solid, it is preferred that be previously heated to 70 DEG C with Above make it melt, and then after adding polyester oligomer in Polyethylene Glycol, be sufficiently stirred for.By so operation, no Only improve the polycondensation reaction of Polyethylene Glycol, and Polyethylene Glycol diffusion in polyester oligomer is quickly carried out, along with The carrying out of polycondensation reaction and when presenting phase separation structure, coarsening when can form fine and uniform, melted delay is repressed Stable dispersion phase.It should be noted that in order to reduce unreacted Polyethylene Glycol, need polyester oligomer and Polyethylene Glycol Mix and blend more than at least 1 hour under compatible state.The phase separation structure formed by polyester-ethylene glycol copolymer obtained In, it is suppressed if dispersion phase is fine and uniform, melt coarsening when being detained, is then being carried out fibrosis by melt spinning Time, fiber number inequality is little, can suppress the generation that dyeing is uneven, fluff.If contrary to the above, Polyethylene Glycol is added to melted Polyester oligomer in, then proportion locally lies in the upper strata in reactive tank less than the Polyethylene Glycol of polyester, and Polyethylene Glycol is to poly- Diffusion in ester oligomer needs considerable time.Therefore, Polyethylene Glycol reduces with the response rate of polyester, causes unreacted Polyethylene Glycol final residue.In this case, dispersion phase is susceptible to coarsening when melted delay, is not only being spun by melted Silk and carry out becoming during fibrosis the reason that fiber number is uneven, and when dyeing, the Polyethylene Glycol of the time of use hydrophilic macromolecule Composition will easily dissolution, become hygroscopicity, antistatic behaviour durability reduce reason, it is therefore desirable to note.

In the present invention, in the arbitrarily reaction in esterification, ester exchange reaction, polycondensation reaction, manufacture polyester can be used Time common catalyst.For esterification, can carry out under without catalyst, but also can add the conducts such as titanium compound Catalyst.As the concrete example of the catalyst of ester exchange reaction, the compounds such as magnesium, manganese, calcium, cobalt, zinc, lithium, titanium can be enumerated, but not It is limited to these.As the concrete example of the catalyst of polycondensation reaction, the compound of antimony, titanium, germanium etc. can be enumerated, but be not limited to these.

In the present invention, in order to improve the thermostability of fiber, tone, phosphorus compound can be added as heat stabilizer.As phosphorus The concrete example of compound, can enumerate phosphate cpd, phosphorons acid compound, phosphinic acid compounds, phosphinic compounds, phosphine oxide Compound, phosphonous compound, phosphinous compound, phosphine compound etc..These phosphorus compounds can be used alone, it is possible to and with many Kind.

In the present invention, the phosphatization as heat stabilizer can be added in any stage manufacturing polyester-ethylene glycol copolymer Compound, can any stage before and after esterification, before and after ester exchange reaction add.It addition, in order to improve further thermostability, Tone, can reduce pressure adding after polycondensation catalyst in by reactive tank, in the period started to terminating from polycondensation reaction, add Add phosphorus compound.In the case of this heat stabilizer, the molecular weight of the Polyethylene Glycol of hydrophilic macromolecule reduces, dispersion The melted delay stability of phase reduces, and when carrying out fibrosis by melt spinning, becomes make fiber number inequality deteriorate the most former Cause.

In the present invention, antioxidant can be added in the arbitrary stage, can be before and after esterification；Before and after ester exchange reaction； To reduce pressure in reactive tank after adding polycondensation catalyst, add in any stage started to terminating from polycondensation reaction.From During the period interpolation that polycondensation reaction starts to terminating, can be any state in decompression, normal pressure in polycondensation reaction groove.As Upper described, the fiber with the phase separation structure formed by polyester-ethylene glycol copolymer in the present invention, divides mutually with not having Fiber from the polyester-ethylene glycol copolymer containing homogeneous texture of structure is compared, and oxidation Decomposition is high, it is therefore preferable that make Containing enough antioxidant in fiber, cause because of the thermal decomposition esterification, ester exchange reaction, polycondensation reaction from preventing Antioxidant inactivation, from the viewpoint of in polycondensation reaction, under reduced pressure antioxidant disperses, in polycondensation reaction be preferably Antioxidant will be added before end, and become normal pressure in making polycondensation reaction groove and be stirred.

In the present invention, in order to improve dividing of hydrophobic polymer (polyester)-hydrophilic macromolecule (Polyethylene Glycol) copolymer Son amount, the copolymer that profit can be used to obtain with the aforedescribed process carries out solid phase.Device and method about solid phase does not has There is restriction especially, under non-active gas atmosphere or under decompression, carry out heat treated.As the concrete example of non-active gas, can lift Go out nitrogen, helium, carbon dioxide etc., but be not limited to these.When reducing pressure, preferably making the pressure in device is below 133Pa, this Outward, by reducing pressure, the time required for solid-phase polymerization can be shortened, thus preferably.The treatment temperature of solid phase is excellent Elect 150～240 DEG C as.When the treatment temperature of solid phase is more than 150 DEG C, polyreaction can be made to carry out, improve molecular weight, Thus preferably.The treatment temperature of solid phase is more preferably more than 170 DEG C, more preferably more than 190 DEG C.On the other hand, When the treatment temperature of solid phase is less than 240 DEG C, can suppress thermal decomposition, Inhibitory molecules amount reduces, coloring, thus preferably.Gu The treatment temperature of phase-polymerization is more preferably less than 235 DEG C, more preferably less than 230 DEG C.

The manufacture method of above-mentioned hydrophobic polymer (polyester)-hydrophilic macromolecule (Polyethylene Glycol) copolymer is shown Other concrete examples.P-phthalic acid is utilized to hand over the esterification of ethylene glycol or the ester of dimethyl terephthalate (DMT) and ethylene glycol Change reaction, in esterification groove or ester exchange reaction groove, the oligomer of double (beta-hydroxy ethyl) ester of synthesis p-phthalic acid (with Under, otherwise referred to as BHT).By transfer pipe arrangement, by BHT from this reactive tank to the polycondensation reaction being heated to 250～270 DEG C During groove transfer, in polycondensation reaction groove, put into the Polyethylene Glycol adding thermal melting in advance, shift BHT wherein.Then, by entering Row stirring in about 1 hour, makes Polyethylene Glycol fully spread in BHT.It follows that interpolation polycondensation catalyst, be decompressed to 500Pa with Under, carry out reaction in 3～5 hours, thus, available polyethylene terephthalate-Polyethylene Glycol copolymerization in 260～300 DEG C Thing.

Along with BHT and the carrying out of the polycondensation reaction of Polyethylene Glycol of the precursor as polyethylene terephthalate, give birth to Become copolymer and high pole that the copolymer of low polarity, the i.e. polyethylene terephthalate ratio shared by strand is high Property copolymer, copolymer that ratio that i.e. Polyethylene Glycol is shared in strand is high, above-mentioned (poly-to benzene by hydrophobic polymer Naphthalate)-hydrophilic macromolecule (Polyethylene Glycol) copolymer formed phase separation structure by above-mentioned low polarity The difference of the polarity of copolymer and highly polar copolymer and present.It addition, the size of the dispersion phase in phase separation structure can By the number-average molecular weight of Polyethylene Glycol, copolymerization rate, the temperature of polycondensation reaction, mixing speed or polyethylene terephthalate The degree of polymerization (molecular weight) of ester-ethylene glycol copolymer is controlled.

As the manufacture method of the fiber of the present invention, known melt spinning method can be used, due to the hydrophobicity of the present invention Macromolecule forms phase separation structure with the copolymer of hydrophilic macromolecule, as the selectable narrow range of spinning condition, therefore, needs Spinning condition is suitably set according to the characteristic of hydrophobic polymer Yu the copolymer of hydrophilic macromolecule.But, according to aftermentioned The concrete example of manufacture method, although there is phase separation structure, but still can stably obtain that fiber number inequality is little, dyeing is uneven, rise The repressed fiber of generation of hair.

Generally, incompatible polymer blend, polymer alloy system in, just from spinning head discharge polymer After, due to Barus effect, spinning threadling expands, and refinement behavior easily becomes unstable, in extreme circumstances, sometimes cannot Carry out fibrosis.It addition, the fiber obtained is also because fiber number is uneven greatly, occur dyeing inequality, fluffing to cause becoming low-quality.Close Method in the expansion reducing the spinning threadling caused because of Barus effect, it is known to following method: such as Japanese Unexamined Patent Publication 2009- Described in No. 79318 publications, improve discharge stability by reduction discharge linear velocity, shear rate；Such as Japanese Unexamined Patent Publication Described in 2011-202289 publication, improve the compatibility by adding bulking agent；Etc..Hydrophobicity about the present invention Macromolecule and the copolymer of hydrophilic macromolecule, also due to form phase separation structure, therefore, although in order to suppress because John Burroughs is imitated The expansion of the spinning threadling answered and cause, and reduce discharge linear velocity, shear rate, but unstable from the discharge of spinning head, obtain The fiber number of fiber uneven big, it is seen that substantial amounts of dyeing is uneven, fluffing.But, present inventors find, with reduce because of Barus effect and the conventional method of the expansion of spinning threadling that causes is contrary, by improving discharge linear velocity, shear rate, can make Must be from the discharge stabilisation of spinning head, although having phase separation structure, but still can stably obtain fiber number inequality little, dyeing not All, the repressed fiber of generation of fluffing.This is considered because, as it has been described above, by hydrophobic polymer (poly terephthalic acid second Diol ester) phase separation structure that formed of-hydrophilic macromolecule (Polyethylene Glycol) copolymer has following such characteristic: melted Give in the case of shearing under state, phase separation structure differential dispersion, disappear soon, but stop giving shearing and through a timing Between time, again present phase separation structure.

In the present invention, preferably make the hydrophobic polymer copolymer with hydrophilic macromolecule by shearing speed during spinning head Degree is 10000～40000s^-1.The discharge-amount of every single hole of spinning head, discharge hole is depended on by shear rate during spinning head The melt viscosity of the copolymer of footpath, hydrophobic polymer and hydrophilic macromolecule.By shear rate during spinning head it is 10000s^-1Time above, stable from the discharge of spinning head, available fiber number inequality is little, and dyeing generation uneven, fluffing is repressed Fiber, thus preferably.It is more preferably 12000s by shear rate during spinning head^-1Above, more preferably 15000s^-1 Above.On the other hand, it is 40000s by shear rate during spinning head^-1Time following, spinning stress will not be too high, from spinning head Discharge stable, therefore, the generation of available sharkskin (sharkskin), melt fracture (melt fracture) etc. is suppressed, fine Degree uneven little, dyeing inequality, the repressed fiber of generation of fluffing, thus preferably.More excellent by shear rate during spinning head Elect 38000s as^-1Hereinafter, more preferably 35000s^-1Below.

In the manufacture of the fiber of the present invention, discharge linear velocity is preferably 10～100m/ minute.Discharge linear velocity depends on spray The melt viscosity of the copolymer of the silk discharge-amount of every single hole of head, discharge aperture, hydrophobic polymer and hydrophilic macromolecule.Tell Going out linear velocity when being more than 10m/ minute, stable from the discharge of spinning head, available fiber number inequality is little, dyeing is uneven, fluffing There is repressed fiber, thus preferably.Discharge linear velocity is more preferably more than 15m/ minute, more preferably 20m/ minute Above.On the other hand, when discharge linear velocity is less than 100m/ minute, spinning stress will not be too high, steady from the discharge of spinning head Fixed, therefore, occurring of available sharkskin, melt fracture etc. is suppressed, fiber number inequality is little, dyeing uneven, the generation of fluffing is suppressed Fiber, thus preferably.Discharge linear velocity is more preferably less than 90m/ minute, more preferably less than 80m/ minute.

In the manufacture of the fiber of the present invention, spin-draw ratio is preferably 10～300.Spin-draw ratio can be by fast with spinning Degree calculates divided by discharge linear velocity.When spin-draw ratio is more than 10, productivity ratio becomes good, thus preferably.Spin-drawing Ratio more preferably more than 20, more preferably more than 30.On the other hand, when spin-draw ratio is less than 300, spinning stress is not Can be too high, spinnability becomes good, and available fiber number inequality is little, dyeing is uneven, the repressed fiber of generation of fluffing, thus excellent Choosing.Spin-draw ratio is more preferably less than 250, and more preferably less than 200.

The spinning head used in the present invention can use known spinning head, and discharge hole count can be suitable according to desired silk number Select.Discharge aperture suitably can select according to shear rate, discharge linear velocity, spin-draw ratio, preferably 0.05～0.50mm. When discharge aperture is more than 0.05mm, the pressure in filament spinning component will not be too high, stable from the discharge of spinning head, available fiber number Uneven little, dyeing inequality, the repressed fiber of generation of fluffing, thus preferably.Discharge aperture is more preferably more than 0.10mm, enters One step is preferably more than 0.15mm.On the other hand, when discharge aperture is below 0.50mm, the backside pressure of spinning head will not Foot, can suppress the discharge between the discharge hole of spinning head uneven, thus preferably.Furthermore it is possible to do not make spinning speed reduce and improve Spin-draw ratio, productivity ratio becomes good, thus preferably.Discharge aperture is more preferably below 0.40mm, more preferably Below 0.30mm.

In the present invention, preferably before carrying out melt spinning, make being total to of hydrophobic polymer and hydrophilic macromolecule in advance Polymers is dried, and making moisture content is below 300ppm.When moisture content is below 300ppm, when melt spinning, cause because of hydrolysis Molecular weight reduce, the foaming that causes because of moisture is suppressed, and can stably carry out spinning, thus preferably.Moisture content is more preferably For below 200ppm, more preferably below 100ppm.

In the present invention, antioxidant can be added when carrying out melt spinning.As it has been described above, having by hydrophobic in the present invention Property macromolecule (polyester)-hydrophilic macromolecule (Polyethylene Glycol) the copolymer fiber of phase separation structure that formed, and not there is phase The fiber of the polyester-ethylene glycol copolymer containing homogeneous texture of isolating construction is compared, and oxidation Decomposition is high, it is therefore preferable that Make containing enough antioxidants in fiber, additionally, by adding when melt spinning, common with at manufacture polyester-Polyethylene Glycol Situation about adding during polymers is compared, and can suppress the antioxidant dispersing, causing because of thermal decomposition of the antioxidant under vacuum Inactivation, thus preferably.As the method adding antioxidant when carrying out melt spinning, following methods can be enumerated: in advance by polyester- Ethylene glycol copolymer and antioxidant are dry mixed, and then put into the method in melt spinning machine；From respective feeder to molten Melt polyester-ethylene glycol copolymer and the method for antioxidant of putting in spinning-drawing machine；Etc., but it is not limited to these.

In the present invention, the chip of the polyester-ethylene glycol copolymer being dried in advance is supplied to extruder type, adds The melt spinning machine of pressure fusion etc. so that it is melted, measures with dosing pump.Then, spinning block (spin it is directed into Block) the heated filament spinning component in, filters molten polymer in filament spinning component, then spues from spinning head, Form fiber strand silk.For the fiber strand silk spued from spinning head, chiller is utilized to be cooled to solidification, with the 1st godet Tractive, via the 2nd godet, utilizes up-coiler (winder) to be wound, and forms undrawn yarn.It should be noted that in order to carry High spinning operability, productivity ratio, the mechanical property of fiber, as required, can arrange the heating of 2～20cm length in spinning head bottom Cylinder, heat-preservation cylinder.It addition, be used as feeding means to fiber strand silk oil supply, it is possible to use interlacing device gives to fiber strand silk Interlacing.

Spinning temperature in melt spinning can be according to hydrophobic polymer and the fusing point of the copolymer of hydrophilic macromolecule, resistance to Hot grade suitably selects, preferably 240～320 DEG C.When spinning temperature is more than 240 DEG C, the fiber strand silk spued from spinning head Elongation viscosity fully reduce, thus it is stable to spue, additionally, spinning tension will not become too high, can suppress fracture of wire, thus excellent Choosing.Spinning temperature is more preferably more than 250 DEG C, more preferably more than 260 DEG C.On the other hand, spinning temperature be 320 DEG C with Time lower, thermal decomposition during spinning can be suppressed, can suppress the reduction of the mechanical property of fiber, coloring, thus preferably.Spinning temperature is more It is preferably less than 310 DEG C, more preferably less than 300 DEG C.

Spinning speed in melt spinning can according to the composition of hydrophobic polymer and the copolymer of hydrophilic macromolecule, spin Silk temperature, spin-draw ratio etc. suitably select.Formerly carry out melt spinning and be wound, carry out two works that stretch the most separately Spinning speed in the case of sequence method is preferably 500～5000m/ minute.When spinning speed is more than 500m/ minute, traveling silk Bar is stable, can suppress fracture of wire, thus preferably.Spinning speed in the case of two operation methods is more preferably more than 1000m/ minute, More preferably more than 1500m/ minute.On the other hand, when the spinning speed of two operation methods is less than 5000m/ minute, can be by Fiber strand silk is sufficiently cool, can carry out stable spinning, thus preferably.Spinning speed in the case of two operation methods is more preferably Less than 4500m/ minute, more preferably less than 4000m/ minute.It addition, carry out spinning for being the most first wound simultaneously For the spinning speed in the case of an operation method of stretching, preferably making low speed roller is 500～5000m/ minute, makes high speed roller It is 3000～6000m/ minute.When low speed roller and high speed roller are in above-mentioned scope, not only traveling strand is stable, and can suppress Fracture of wire, can carry out stable spinning, thus preferably.For the spinning speed in the case of an operation method, more preferably make low Speed roller is 1000～4500m/ minute, and making high speed roller is 3500～5500m/ minute, further preferably make low speed roller be 1500～ 4000m/ minute, making high speed roller was 4000～5000m/ minute.

In the case of utilizing an operation method or two operation methods to stretch, an available stage pulling method or two-stage with On multistage pulling method in any method carry out.As stretching in heating means, as long as can directly or indirectly by The device of traveling strand heating, is just not particularly limited.As the concrete example of heating means, heating roller, fast sale, heating can be enumerated Gas bath, the laser etc. such as the liquid bath such as plate, warm water, hot water, hot-air (adding hot-air), steam, but it is not limited to these.These add By the use of thermal means can be used alone, it is possible to and with multiple.As heating means, from controlling heating-up temperature, traveling strand being carried out uniformly From the viewpoint of heating, device are uncomplicated, preferably use contact with heating roller contact with fast-selling and contact heater plate, at liquid The method of dipping in body bath.

Stretching ratio in the case of stretching suitably can select according to the intensity of fiber after stretching, percentage elongation etc., It is preferably 1.02～7.0 times.When stretching ratio is more than 1.02 times, the intensity of fiber, percentage elongation etc. can be improved by stretching Mechanical property, thus preferably.Stretching ratio is more preferably more than 1.2 times, more preferably more than 1.5 times.On the other hand, draw Stretch multiplying power when being less than 7.0 times, fracture of wire during stretching can be suppressed, can carry out stable stretching, thus preferably.Stretching ratio is more excellent Elect less than 6.0 times as, more preferably less than 5.0 times.

Draft temperature in the case of stretching suitably can select according to the intensity of fiber after stretching, percentage elongation etc., It is preferably 60～150 DEG C.When draft temperature is more than 60 DEG C, the preheating to the strand for stretching is fully carried out, during stretching Thermal deformation becomes uniform, can suppress the generation that fiber number is uneven, thus preferably.Draft temperature is more preferably more than 65 DEG C, further It is preferably more than 70 DEG C.On the other hand, when draft temperature is less than 150 DEG C, the thermal decomposition of fiber can be suppressed, thus preferably.Separately Outward, fiber becomes good relative to the sliding of draw roll, thus can suppress fracture of wire, can carry out stable stretching, thus preferably. Draft temperature is more preferably less than 145 DEG C, more preferably less than 140 DEG C.It addition, as required, 60～150 DEG C can be carried out Heat fixation.

Which in an operation method or two operation methods draw speed in the case of stretching can be according to drawing process Plant and wait and suitably select.In the case of one operation method, the speed of the high speed roller of above-mentioned spinning speed is equivalent to draw speed. Draw speed in the case of utilizing two operation methods to stretch is preferably 30～1000m/ minute.Draw speed is 30m/ minute Time above, traveling strand is stable, can suppress fracture of wire, thus preferably.Stretching speed in the case of utilizing two operation methods to stretch Degree more preferably more than 50m/ minute, more preferably more than 100m/ minute.On the other hand, draw speed is that 1000m/ divides Time below clock, fracture of wire during stretching can be suppressed, can carry out stable stretching, thus preferably.Two operation methods are utilized to carry out stretching In the case of draw speed be more preferably less than 800m/ minute, more preferably less than 500m/ minute.

In the present invention, as required, can dye under the free position in fiber or fiber construct.The present invention In, as dyestuff, preferably use disperse dyes.

Colouring method in the present invention is not particularly limited, and can suitably use cheese dyeing according to known methods Machine, liquid-flow dyeing machine, drum dyeing machine, package dyeing machine, dye jigger, high pressure jig etc..

In the present invention, it is not particularly limited about dye strength, dyeing temperature, can suitably use known method.Separately Outward, as required, can carry out before Colour Difference concise, it is possible to carry out after Colour Difference reduction washing.

The fiber of the present invention and the generation uneven, fluffing of the dyeing containing its fiber construct are suppressed, hygroscopicity, low Excellent antistatic property under temperature low-humidity environment, time when dyeing, use, the dissolution of hydrophilic compounds is suppressed.Therefore, may be used The purposes requiring quality, comfortableness uses suitably.Such as, general dress material purposes, motion dress material purposes, bedding can be enumerated Purposes, upholstery purposes, material purposes etc., but it is not limited to these.

Embodiment

Hereinafter, the present invention is illustrated in greater detail by embodiment.It should be noted that each characteristic value in embodiment is profit The value tried to achieve by following method.

A. fiber number

Temperature be 20 DEG C, in the environment of humidity is 65%RH, use the electronic gauging machine of INTEC system (Japanese original text: Chi), strand takes the fiber 100m obtained by embodiment.Measure the weight of the hank knotting obtained, use following formula to calculate fiber number (dtex).Measure it should be noted that carry out 5 times for 1 sample, be averaged value as fiber number.

Weight (g) × 100 of fiber number (dtex)=100m fiber

B. intensity, percentage elongation

For intensity and percentage elongation, using the fiber that obtained by embodiment as sample, according to JIS L1013: 1999 (chemical fiber filament yarn test methods) 8.5 calculate.It is 20 DEG C in temperature, in the environment of humidity is 65%RH, makes By Shimadzu Seisakusho Ltd.'s autoclave AG-50NISMS type, it is the bar of 20cm/ minute at a length of 20cm of initial samples, draw speed Tension test is carried out under part.With the stress (cN) of the point of display peak load divided by fiber number (dtex), calculate intensity (cN/ Dtex), use elongation (L1) and the initial samples length (L0) of the point of display peak load, utilize following formula, calculate percentage elongation (%).Measure it should be noted that carry out 10 times for 1 sample, be averaged value as intensity and percentage elongation.

Percentage elongation (%)={ (L1-L0)/L0} × 100

C. toughness

Use the intensity (cN/dtex) and percentage elongation (%) calculated in above-mentioned B, utilize following formula to calculate the toughness of fiber.

Toughness=intensity × (percentage elongation)^1/2

D. incipient extension opposing degree

For incipient extension opposing degree, using utilize embodiment to obtain fiber as sample, according to JIS L1013: 1999 (chemical fiber filament yarn test methods) 8.10 calculate.Carry out tension test in the same manner as above-mentioned B, draw load- Extension curve, near the initial point of this curve, obtains the maximum point of the load variations relative to variable elongation, uses JIS Formula described in L1013:1999 (chemical fiber filament yarn test method) 8.10, calculates incipient extension opposing degree (cN/ dtex).Measure it should be noted that carry out 5 times for 1 sample, be averaged value as incipient extension opposing degree.

E. boiling water shrinkage

It is 20 DEG C in temperature, in the environment of humidity is 65%RH, uses the gauging machine in 1m/ week, make by passing through embodiment The fibroplastic hank knotting (rolling up several 10 circles) obtained, stands 24 hours.Then, in the present context, 0.09cN/ is applied to hank knotting The load of dtex, measures specimen length L0.It follows that process hank knotting in the boiling water of 98 DEG C 15 minutes zero loadly, then empty Dry 24 hours of air dry, applies the load of 0.09cN/dtex to hank knotting, measures specimen length L1.Use before and after processing in boiling water Specimen length L0, L1, utilize following formula to calculate boiling water shrinkage (%).Survey it should be noted that carry out 3 times for 1 sample Fixed, it is averaged value as boiling water shrinkage.

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

F. the maximum gauge of the dispersion phase in fiber cross section

The fiber obtained by embodiment with epoxy resin embedding, then uses LKB ultramicrotome LKB-2088, Together with epoxy resin, along the direction cutting fibre vertical with fiber axis, obtain the ultrathin section of thickness about 100nm.By obtain Ultrathin section in the gas phase of ruthenium tetroxide, keep about 4 hours at normal temperatures dyeing, then cut off with ultramicrotome Dyed face, the ultrathin section that making ruthenium tetroxide is dyeed.For dyed ultrathin section, use Hitachi's system Transmission electron microscope (TEM) H-7100FA type, under conditions of accelerating potential is 100kV, cuts vertical with fiber axis Face, i.e. fiber cross section are observed, the microphotograph of shooting fiber cross section.With 2000 times, 8000 times, 20000 times, Each multiplying power of 40000 times is observed, and during shooting microphotograph, selection can observe the highest of the dispersion phase of more than 300 Multiplying power.For the photo of shooting, use image analysis software (three paddy business WinROOF), measure 300 points randomly selected The diameter of dephasing, using its maximum as the maximum gauge (nm) of the dispersion phase in fiber cross section.Due in fiber cross section The dispersion phase existed is not necessarily positive round, therefore, in the case of being not positive round, measures area, uses when being scaled positive round Diameter is as the diameter of dispersion phase.

G. the maximum gauge of the dispersion phase in fiber longitudinal section

The fiber obtained by embodiment with epoxy resin embedding, then uses LKB ultramicrotome LKB-2088, Together with epoxy resin, along the direction cutting fibre parallel with fiber axis, obtain the ultrathin section of thickness about 100nm.By obtain Ultrathin section in the gas phase of ruthenium tetroxide, keep about 4 hours at normal temperatures dyeing, then cut off with ultramicrotome Dyed face, the ultrathin section that making ruthenium tetroxide is dyeed.For dyed ultrathin section, use Hitachi's system Transmission electron microscope (TEM) H-7100FA type, under conditions of accelerating potential is 100kV, cuts parallel with fiber axis Face, i.e. fiber longitudinal section are observed, the microphotograph of shooting fiber longitudinal section.With 2000 times, 8000 times, 20000 times, Each multiplying power of 40000 times is observed, and during shooting microphotograph, selects it is observed that the dispersion of the striated of more than 300 The highest multiplying power of phase.For the photo of shooting, use image analysis software (three paddy business WinROOF), measure random choosing The diameter of the dispersion phase of 300 taken, using its maximum as the maximum gauge (nm) of the dispersion phase in fiber longitudinal section.Need Illustrate, for the diameter of the dispersion phase in fiber longitudinal section, measure for the direction vertical with fiber axis.

H. fiber number variation value U% (hi)

For fiber number variation value U% (hi), using the fiber that obtained by embodiment as sample, use Star ェ Le ベ ガ ウ ス タ ウ ス タ テ ス タ 4-CX, finding speed be 200m/ minute, minute be 2.5 Minute, mensuration fibre length is 500m, under conditions of twisting count is 12000/m (S sth. made by twisting), measures U% (half inert).Need Bright, carry out 5 times for 1 sample and measure, be averaged value as fiber number variation value U% (hi).

I. filament diameter CV%

After the fiber that will be obtained by embodiment with platinum-palladium alloy is deposited with, use Hitachi's scanning electron microscope (SEM) S-4000 type, observes the cross section vertical with fiber axis, i.e. fiber cross section, the microphotograph of shooting fiber cross section. With 100 times, 300 times, 500 times, 1000 times, 3000 times, 5000 times, each multiplying power of 10000 times observe, shooting microscope shine During sheet, select it is observed that the highest multiplying power of whole monofilament in sample.For the photo of shooting, use image analysis software (three paddy business WinROOF), measures filament diameter.In the case of monofilament number in the sample is more than 50, measure random The filament diameter of 50 monofilament chosen, in the case of monofilament number in the sample is less than 50, uses and makes under the same conditions The multiple samples made, measure the filament diameter adding up to 50 monofilament.Owing to fiber cross section is not necessarily positive round, therefore, not In the case of being positive round, measure area, use diameter when being scaled positive round as filament diameter.Calculate the average of filament diameter Value (X), the standard deviation (σ) of filament diameter, then utilize following formula to calculate filament diameter CV%.

Filament diameter CV%=(σ/X) × 100

J. filament number CV%

For filament number, using the fiber that obtained by embodiment as sample, it is broken down into monofilament, so After, use サ チ society automatic vibration formula fineness tester DC-11, making mensuration specimen length is 25mm, gives and measures sample The load of fiber number (danier scaled value) × 0.4g, applying frequency is the vibration of 1880Hz, is measured.List in the sample In the case of silk number is more than 20, measuring the filament number of 20 monofilament randomly selected, monofilament number in the sample is not enough In the case of 20, use the multiple samples manufactured under the same conditions, measure the filament number adding up to 20 monofilament.Calculate list The meansigma methods (X) of silk size, the standard deviation (σ) of filament number, then utilize following formula to calculate filament number CV%.

Filament number CV%=(σ/X) × 100

K. filament strength CV%, monofilament percentage elongation CV%

For filament strength and monofilament percentage elongation, using the fiber that obtained by embodiment as sample, by its point Solution becomes monofilament, then, calculates according to JIS L1013:1999 (chemical fiber filament yarn test method) 8.5.In temperature it is 20 DEG C, in the environment of humidity is 65%RH, use Shimadzu Seisakusho Ltd.'s オ ト グ ラ Off AG-50NISMS type, at initial samples A length of 5cm, draw speed are to carry out tension test under conditions of 20cm/ minute.Stress by the point of display peak load (cN) as filament strength, use elongation (L1) and the initial samples length (L0) of the point of display peak load, utilize following formula, calculate Go out monofilament percentage elongation (%).In the case of monofilament number in the sample is more than 50,50 monofilament that mensuration randomly selects Filament strength and monofilament percentage elongation, in the case of monofilament number in the sample is less than 50, use manufactures under the same conditions Multiple samples, measure filament strength and the monofilament percentage elongation adding up to 50 monofilament.About filament strength, monofilament percentage elongation, respectively Calculate meansigma methods (X), standard deviation (σ), then, utilize following formula, calculate filament strength CV%, monofilament percentage elongation CV%.

Percentage elongation (%)={ (L1-L0)/L0} × 100

Filament strength CV%=(σ/X) × 100

Monofilament percentage elongation CV%=(σ/X) × 100

L. the content of unreacted PEG (Polyethylene Glycol)

Weighing the fiber that obtains by embodiment of 500mg in screw thread test tube (screw tube), interpolation 2mL hexafluoro is different Propanol, is 20 DEG C in temperature, in the environment of humidity is 65%RH, stands 24 hours so that it is dissolve.Add in screw thread test tube 2mL chloroform, moves to 100mL volumetric flask by mixed liquor, and then the residue in screw thread test tube adds 6mL chloroform, moves to above-mentioned In volumetric flask, and then in volumetric flask, add acetonitrile, be settled to 100mL.Utilize and filter the one-tenth that will separate out by adding acetonitrile Divide and remove, use vaporizer to concentrate the filtrate to do, with 5mL acetonitrile constant volume.Solution after 1mL constant volume is moved to 10mL capacity Bottle, is settled to 10mL with acetonitrile, then filters with the PTFE filter of 0.45 μm, the filtrate obtained is measured as HPLC Use sample.Use this sample, under the following conditions, utilize HPLC device (Shimadzu Seisakusho Ltd. LC-20A), carry out HPLC survey Fixed, utilize the standard curve of ready-made standard substance (PEG), the PEG contained is carried out quantitatively in HPLC measurement sample, Calculate the unreacted PEG content (wt%) contained in the fiber obtained by embodiment.It should be noted that for 1 examination Sample carries out 5 times and measures, and is averaged value as unreacted PEG content.

Post: (internal diameter is 3mm to ジ エ Le サ イ エ Application ス Inertsil ODS-3, a length of 150mm, and particle diameter is 5 μ m)

Detector: Shimadzu Seisakusho Ltd. ELSD

Flowing phase: water (solvent orange 2 A), acetonitrile (solvent B)

Temporal sequence: 0 → 15 minute (solvent orange 2 A: solvent B=60:40 → 0:100), 15 → 25 minutes (solvent orange 2 As: solvent B =0:100)

Flow velocity: 0.8mL/ minute

Injection rate: 10 μ L

Column temperature: 45 DEG C

Standard substance: PEG

M. oxidation preventive content

Add in the fiber that 500mg is obtained by embodiment the 1mol/L of 25mL Feldalat NM-methanol solution and 25mL methyl acetate, carries out backflow in 1 hour, then adds 2mL acetic acid and is neutralized.Use rotary evaporator, after making neutralization Mixed liquor is concentrated to dryness, and adds 50mL water, then extracts with 20mL chloroform, be separated into chloroform layer and water layer.Use and rotate Vaporizer, is concentrated to dryness chloroform layer, adds 2.5mL chloroform, makes chromatography determination sample.Use this sample, carry out GC Measure or HPLC measures, utilize the standard curve of standard substance (antioxidant used in embodiment), chromatography determination is used The antioxidant contained in sample carries out quantitatively, calculating the oxidation preventive content contained in the fiber obtained by embodiment (wt%).Measure it should be noted that carry out 5 times for 1 sample, be averaged value as oxidation preventive content.

N. reach to rise the time of half value point

Using the fiber that obtained by embodiment as sample, 10mg sample is put in aluminium vessel, utilizes セ イ U イ Application ス Star Le メ Application ト TG-DTA, at nitrogen: under the mixed-gas atmosphere of oxygen=80vol%:20vol%, make mixed gas Flow is 200mL/ minute, with the programming rates of 30 DEG C/min from room temperature to 160 DEG C, then keeps 360 points in 160 DEG C Clock.Then, use analysis software (セ イ U イ Application ス Star Le メ Application ト system, Muse) to carry out thermoconductive TGA (DTG), will Reach the time of 160 DEG C as 0 minute, calculate the time (min) reaching to rise half value point at DTG peak.Before reaching 160 DEG C In the case of there is the rising half value point at DTG peak, the time being up to rise half value point is designated as negative value, is that 160 DEG C keep 360 In the case of not observing DTG peak during minute, the time being up to rise half value point is designated as more than 360 minutes.Need explanation , carry out 5 times for 1 sample and measure, be averaged value as the time reaching to rise half value point.

O. voltage it is charged by friction

Using the fiber that obtained by embodiment as sample, use English light industry circular knitter NCR-BL (barrel dliameter 3 Inch half (8.9cm), 27gauge), make about 2g tubular knitted, then containing 1g/L sodium carbonate, solar corona chemistry control surface In the aqueous solution of activating agent サ Application モ Le BK-80, concise 20 minutes in 80 DEG C, then dry in the hot air drying machine of 60 DEG C Dry 60 minutes.

For being charged by friction voltage (V), tubular knitted as sample using after concise, temperature be 10 DEG C, wet Degree, under 10%RH atmosphere, calculates according to JIS L1094:1997 (fabric and the charging property test method of volume thing) 5.2.Need It is noted that carrying out 5 times for 1 sample measures, and is averaged value as being charged by friction voltage.

P. moisture absorption rate variance (△ MR)

Using make in the same manner as above-mentioned O concise after tubular knitted as sample, (knit according to JIS L1096:2010 Thing and compile thing blank test method) 8.10 moisture rate, calculate hydroscopicity (%).First, in 110 DEG C to tubular knitted enter Row vacuum drying in 24 hours, measures the tubular knitted weight (W0) when parching.It follows that adjusted one-tenth temperature 20 DEG C, In the エ ス ペ ッ Network constant temperature and humidity machine LHU-123 of humidity 65%RH, make tubular knitted standing 24 hours, measure tubular pin The weight (W1) of fabric, then adjusted one-tenth temperature 30 DEG C, humidity 90%RH constant temperature and humidity machine in make tubular knitted quiet Put 24 hours, measure tubular knitted weight (W2).Calculated from the state of parching in temperature by tubular knitted weight W0, W1 20 DEG C, the hydroscopicity MR1 (%) standing 24 hours under humidity 65%RH atmosphere, by tubular knitted weight W0, W2 calculate from The state that parches stands 24 little hydroscopicity MR2 (%) constantly under temperature 30 DEG C, humidity 90%RH atmosphere, utilizes following formula to calculate suction Wet rate variance (△ MR).Measure it should be noted that carry out 5 times for 1 sample, be averaged value as moisture absorption rate variance (△ MR)。

Moisture absorption rate variance (△ MR) (%)=MR2-MR1

Q. the weight reduction rates after hot water treatment

Using the fiber that obtained by embodiment as sample, use English light industry circular knitter NCR-BL (barrel dliameter 3 Inch half (8.9cm), 27gauge), make about 2g tubular knitted, then bath raio be 1:50, treatment temperature be 25 DEG C, place The reason time is to be impregnated into tubular knitted in ethanol under conditions of 1 minute.Total 3 dippings in ethanol are repeated, Remove the oil preparation being attached on tubular knitted, carry out 60 minutes being dried in the hot air drying machine of 60 DEG C, then measure cylinder The weight (W0) of shape knitted fabric.It should be noted that use new ethanol when dipping every time.It follows that be 1 in bath raio: 100, treatment temperature be 100 DEG C, the process time be to carry out hot water treatment under conditions of 60 minutes.At the hot air drying machine of 60 DEG C In carry out 60 minutes being dried to tubular knitted after hot water treatment, then measure tubular knitted weight (W1).Use cylinder Weight W0 of shape knitted fabric, W1, utilize following formula, calculates the weight reduction rates after hot water treatment (%).It should be noted that for 1 sample carries out 3 times and measures, and is averaged value as weight reduction rates.

Weight reduction rates (%)=(W0-W1)/W0) } × 100

R. equalization

For make in the same manner as above-mentioned O concise after tubular knitted, in 160 DEG C carry out 2 minutes xeothermic fixing, pin To xeothermic fixing after tubular knitted, add the 4 weight % Japanese chemical medicine Kayalon Polyester as disperse dyes Black EX-SF200, in pH regulator is become the dyeing liquor of 5.0, bath raio be 1:100, dyeing temperature be 130 DEG C, dyeing Time is to dye under conditions of 60 minutes.It should be noted that in embodiment 38～47, add 4 weight % as sun The hodogaya chemical industry Cathilon Blue FB-DP of ionic dye, in pH regulator is become the dyeing liquor of 4.0, Bath raio is 1:100, dyeing temperature is 130 DEG C, dyeing time is to dye under conditions of 60 minutes.For the tubular after dyeing Knitted fabric, by the inspectoral panel discussion of 5 quality judging experiences with more than 5 years, carries out following judgement: will be " the most equal It is colored evenly, does not finds dyeing inequality completely " it is judged to ◎, " will substantially evenly be colored, and almost not find to dye not All " it is judged to zero, " the most not by level dyeing, indistinctly confirm dyeing inequality " is judged to △, will " not by level dyeing, Clearly confirm dyeing inequality " be judged to ×, using zero, ◎ is as qualified.

S. quality

For in above-mentioned R dyeing after tubular knitted, by the inspection of 5 quality judging experiences with more than 5 years The panel discussion of member, carries out following judgement: " will be completely absent fluffing, quality is the most excellent " and be judged to ◎, will " there's almost no Hair, excellent quality " it is judged to zero, " fluffing, poor quality will be there is " and be judged to △, " a large amount of fluffing will be there is, quality is excessively poor " Be judged to ×, using zero, ◎ is as qualified.

Embodiment 1

Put into double (beta-hydroxy ethyl) the ester about 100kg of p-phthalic acid to esterification groove, keep in the temperature of 250 DEG C After, supplying high purity p-phthalic acid (Mitsui Chemicals system) 89.2kg and ethylene glycol (Japan's catalyst system) successively through 2.5 hours 39.8kg slurry.After supply terminates, carry out esterification 2 hours, obtain esterification reaction product.It follows that successively to contracting Poly-groove puts into ethylene glycol (Japan catalyst system) 13.6kg, is heated to 70 DEG C and the poly-second two of number-average molecular weight 8300 that melted Alcohol (Sanyo chemical conversion industry PEG6000S processed) 16.8kg, then, by connecting esterification groove and the transfer pipe arrangement of polycondensation groove, will The esterification reaction product 110.6kg obtained is transferred to be heated in the polycondensation groove of 250 DEG C.After having shifted, stir in 250 DEG C Mix 1 hour.Then, tetramethylolmethane-four (3-(3,5-bis-uncles as antioxidant (adding before polycondensation reaction starts) are added Butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, silicon (モ メ Application テ ィ Block as defoamer パ Off ォ マ Application ス マ テ リ ア Le ズ system, TSF433) 120g, trimethyl phosphate (medicine pure with light as heat stabilizer System) 30g stir 10 minutes, then, adds antimony trioxide 30g, manganese acetate 22g as polymerization catalyst and stirs 5 minutes. It follows that the temperature in polycondensation groove is warming up to 285 DEG C from 250 DEG C through 60 minutes, simultaneously by the pressure in polycondensation groove from air Pressure is decompressed to 25Pa, then, carries out polyreaction 3 hours.Polyreaction product is made so that wire harness shape spues in cold water Its cooling, carries out cutting and obtaining granular polyreaction product immediately.Utilize¹The polymerization that H-NMR confirms to obtain is anti- The copolymerization rate answering the Polyethylene Glycol in product is 14 weight %.

After 150 DEG C of granules to obtaining carry out vacuum drying in 12 hours (dried moisture content 95ppm), it is supplied to To extruder type spinning-drawing machine and make it melt, spinning temperature be 290 DEG C, under conditions of discharge-amount is 57g/ minute, from spray webbing Head (discharge aperture is 0.23mm, a length of 0.60mm in discharge hole, and discharge hole count is 36, circular hole) spues and obtains spinning strand.With This is spun strand cooling by pathogenic wind-warm 20 DEG C, the cooling wind of wind speed 20m/ minute, gives oil preparation with feeding means and makes its boundling, uses With the 1st godet tractive of rotation in 3000m/ minute, via the 2nd godet rotated with the speed identical with the 1st godet, use Winder winding around, obtain the undrawn yarn of 190dtex-36f.The 1st heat roller temperature be 90 DEG C, the 2nd heat roller temperature be 130 DEG C, The undrawn yarn obtained is stretched under conditions of being 1.9 times by stretching ratio, obtains the drawn yarn of 100dtex-36f.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 1.The intensity of the fiber obtained, tough The fiber properties such as property are good.Fiber has phase separation structure, and the maximum gauge of the dispersion phase in fiber cross section is 30nm, fiber The maximum gauge of the dispersion phase in longitudinal section is 31nm, and pole disperses imperceptibly.Although it addition, have phase separation structure, but U% (hi) is 1.0%, is very uniform fiber.About cloth and silk characteristic, antistatic behaviour, hygroscopicity are the most excellent.It addition, it is hot Weight reduction rates after water processes is the lowest, and the dissolution of hydrophilic compounds is suppressed, and, equalization, quality are also qualified water Flat.

Embodiment 2～4

Change as shown in table 1 the copolymerization rate of hydrophilic macromolecule, discharge-amount, spinning head (discharge aperture, discharge hole length, Discharge hole count), in addition, make drawn yarn similarly to Example 1.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 1.Along with hydrophilic macromolecule The step-down of copolymerization rate, the fiber properties such as intensity, toughness improves, and the maximum of the dispersion phase in fiber cross section and fiber longitudinal section is straight Footpath reduces, and U% (hi) becomes good.On the other hand, along with the uprising of copolymerization rate of hydrophilic macromolecule, antistatic behaviour, moisture absorption Property becomes good.

Embodiment 5～7

Change the discharge aperture of spinning head as shown in table 1, in addition, make drawn yarn similarly to Example 4.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 1.Along with the diminishing of discharge aperture, Being uprised by shear rate during spinning head, the fiber properties such as intensity, toughness improves, in fiber cross section and fiber longitudinal section The maximum gauge of dispersion phase reduces, and U% (hi) becomes good.

Embodiment 8,9

Change the copolymerization rate of hydrophilic macromolecule as shown in table 2, in addition, make stretching similarly to Example 7 Silk.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 2.Even if changing hydrophilic In the case of high molecular copolymerization rate, U% (hi) is the lowest, has obtained the fiber of homogenizing.

Embodiment 10,11

Change the number-average molecular weight of hydrophilic macromolecule, spinning head (discharge aperture) as shown in table 2, in addition, with Embodiment 4 similarly makes drawn yarn.It should be noted that as hydrophilic macromolecule, use number to divide equally in embodiment 10 The Polyethylene Glycol (Sanyo chemical conversion industry PEG10000 processed) of son amount 11000, uses number-average molecular weight 20000 in embodiment 11 Polyethylene Glycol (Sanyo chemical conversion industry PEG20000 processed).

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 2.Even if changing hydrophilic In the case of high molecular number-average molecular weight, the fiber properties such as intensity, toughness is also good, and U% (hi) is the lowest, has obtained homogenizing Fiber.

Embodiment 12,13

Changing spinning speed as shown in table 2, in embodiment 12, making stretching ratio is 5.7 times, in embodiment 13, Making stretching ratio is 2.85 times, in addition, makes drawn yarn similarly to Example 1.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 2.Even if changing spinning speed In the case of degree, the fiber properties such as intensity, toughness is also good, and U% (hi) is the lowest, has obtained the fiber of homogenizing.

Embodiment 14

By relative to the polyreaction product obtained to be scaled in terms of titanium atom the citric acid Ti chelator being equivalent to 10ppm Complex, high purity terephthalic acid's (Mitsui Chemicals system) 82.5kg and 1,3-PD 49.1kg, remaining temperature 240 DEG C, pressure 1.2 × 10⁵In the esterification groove of Pa, carry out esterification, until the temperature of distillation is less than 90 DEG C, obtain ester Change reaction product.It follows that put into 1,3-PD 16.7kg successively in polycondensation groove, be heated to 70 DEG C and the number that melted Polyethylene Glycol (the Sanyo chemical conversion industry PEG6000S processed) 16.8kg of average molecular weight 8300, then, by connecting esterification groove With the transfer pipe arrangement of polycondensation groove, the esterification reaction product 110.6kg obtained is transferred to be heated to the polycondensation groove of 240 DEG C In.After having shifted, stir 1 hour in 240 DEG C.Then, add as antioxidant (adding before polycondensation reaction starts) Tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, conduct disappear Silicon (モ メ Application テ ィ Block パ Off ォ マ Application ス マ テ リ ア Le ズ system, the TSF433) 120g of infusion, as heat stabilizer Trimethyl phosphate (medicine system pure with light) 30g and stir 10 minutes, then, add the magnesium acetate four as polymerization catalyst and be hydrated Thing 11g also stirs 5 minutes.It follows that the temperature in polycondensation groove is warming up to 280 DEG C from 240 DEG C through 60 minutes, simultaneously by polycondensation Pressure in groove is decompressed to 40Pa from atmospheric pressure, then, carries out polyreaction 3 hours.By polyreaction product with wire harness shape Spue in cold water and be allowed to cool, carry out immediately cutting and obtaining granular polyreaction product.Utilize¹H-NMR is true The copolymerization rate of the Polyethylene Glycol in the polyreaction product obtained of accepting is 14 weight %.

After 150 DEG C of granules to obtaining carry out vacuum drying in 12 hours, it is supplied to extruder type spinning-drawing machine and makes It melts, spinning temperature be 265 DEG C, under conditions of discharge-amount is 57g/ minute, from spinning head (discharge aperture is 0.23mm, The a length of 0.60mm in discharge hole, discharge hole count is 36, circular hole) spue and obtain spinning strand.With pathogenic wind-warm 20 DEG C, wind speed 20m/ minute Cooling wind by this spin strand cooling, with feeding means give oil preparation and make its boundling, in order to 3000m/ minute rotate the 1st Godet tractive, via the 2nd godet rotated with the speed identical with the 1st godet, with winder winding around, obtain The undrawn yarn of 190dtex-36f.The 1st heat roller temperature be 55 DEG C, the 2nd heat roller temperature be 130 DEG C, stretching ratio be 1.9 times Under conditions of the undrawn yarn obtained is stretched, obtain the drawn yarn of 100dtex-36f.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 2.Even if by hydrophobicity high score In the case of son is changed to PTT, the fiber properties such as intensity, toughness is also good, and U% (hi) is the lowest, Arrive the fiber of homogenizing.

Embodiment 15

By relative to the polyreaction product obtained to be scaled in terms of titanium atom the citric acid Ti chelator being equivalent to 10ppm Complex, high purity terephthalic acid's (Mitsui Chemicals system) 82.5kg and BDO 89.5kg, remaining temperature 220 DEG C, pressure 1.2 × 10⁵In the esterification groove of Pa, carry out esterification, until the temperature of distillation is less than 90 DEG C, obtain ester Change reaction product.It follows that put into BDO 19.7kg successively in polycondensation groove, be heated to 70 DEG C and the number that melted Polyethylene Glycol (the Sanyo chemical conversion industry PEG6000S processed) 16.8kg of average molecular weight 8300, then, by connecting esterification groove With the transfer pipe arrangement of polycondensation groove, the esterification reaction product 110.6kg obtained is transferred to be heated to the polycondensation groove of 220 DEG C In.After having shifted, stir 1 hour in 220 DEG C.Then, add as antioxidant (adding before polycondensation reaction starts) Tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, conduct disappear Silicon (モ メ Application テ ィ Block パ Off ォ マ Application ス マ テ リ ア Le ズ system, the TSF433) 120g of infusion, as heat stabilizer Trimethyl phosphate (medicine system pure with light) 30g and stir 10 minutes, then, add the magnesium acetate four as polymerization catalyst and be hydrated Thing 11g also stirs 5 minutes.It follows that the temperature in polycondensation groove is warming up to 250 DEG C from 220 DEG C through 60 minutes, simultaneously by polycondensation Pressure in groove is decompressed to 60Pa from atmospheric pressure, then, carries out polyreaction 3 hours.By polyreaction product with wire harness shape Spue in cold water and be allowed to cool, carry out immediately cutting and obtaining granular polyreaction product.Utilize¹H-NMR is true The copolymerization rate of the Polyethylene Glycol in the polyreaction product obtained of accepting is 14 weight %.

After 150 DEG C of granules to obtaining carry out vacuum drying in 12 hours, it is supplied to extruder type spinning-drawing machine and makes It melts, spinning temperature be 260 DEG C, discharge-amount be that from spinning head, (discharge aperture is 0.23mm, tells under conditions of 57g/ minute Portal a length of 0.60mm, and discharge hole count is 36, circular hole) spue and obtain spinning strand.With pathogenic wind-warm 20 DEG C, wind speed 20m/ minute This is spun strand cooling by cooling wind, gives oil preparation with feeding means and makes its boundling, leads in order to the 1st of rotation in 3000m/ minute the Roll dies tractive, via the 2nd godet rotated with the speed identical with the 1st godet, with winder winding around, obtain 190dtex- The undrawn yarn of 36f.The 1st heat roller temperature be 65 DEG C, the 2nd heat roller temperature be 130 DEG C, under conditions of stretching ratio is 1.9 times The undrawn yarn obtained is stretched, obtains the drawn yarn of 100dtex-36f.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 2.Even if by hydrophobic polymer In the case of being changed to polybutylene terephthalate (PBT), the fiber properties such as intensity, toughness is also good, and U% (hi) is the lowest, obtains The fiber of homogenizing.

Comparative example 1

Use polyethylene terephthalate (intrinsic viscosity IV=0.66), implement spinning similarly to Example 1, draw Stretch.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 3.The fiber properties such as intensity, toughness Well, U% (hi) is low, has obtained the fiber of homogenizing.But, owing to being the fiber only formed by hydrophobic polymer, thus not There is phase separation structure.About cloth and silk characteristic, although equalization, quality are the most excellent, but being charged by friction voltage is 9800V, anti- Static behaviour is the lowest, and △ MR is 0.1%, and hygroscopicity is the lowest.

Comparative example 2～4

Change the number-average molecular weight of hydrophilic macromolecule as shown in table 3, in addition, make similarly to Example 4 Drawn yarn.It should be noted that as hydrophilic macromolecule, in comparative example 2, use the Polyethylene Glycol of number-average molecular weight 3400 (Sanyo chemical conversion industry PEG4000 processed), in comparative example 3, uses Polyethylene Glycol (the ア Le De リ ッ チ system of number-average molecular weight 6000 PEG6000), in comparative example 4, use the Polyethylene Glycol (bright one-tenth chemical industry R-150) of number-average molecular weight 100000.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 3.In comparative example 2, intensity, tough Property etc. fiber properties good, U% (hi) is low, has obtained the fiber of homogenizing.But, owing to the number-average molecular weight of Polyethylene Glycol is less than 7000, thus, not there is phase separation structure.About cloth and silk characteristic, although equalization, quality are the most excellent, but are charged by friction electricity Pressure is 7600V, and antistatic behaviour is poor.In comparative example 3 also as comparative example 2, although the fiber properties such as intensity, toughness is good, U% (hi) is low, has obtained the fiber of homogenizing, but owing to the number-average molecular weight of Polyethylene Glycol is less than 7000, thus, do not have and divide mutually From structure.It addition, about cloth and silk characteristic, although equalization, quality are the most excellent, but being charged by friction voltage is 6900V, antistatic Property is poor.In comparative example 4, owing to the number-average molecular weight of Polyethylene Glycol is high, thus, dividing in fiber cross section and fiber longitudinal section The maximum gauge of dephasing is big, defines thick phase separation structure.Therefore, the fiber properties such as intensity, toughness is low, and U% (hi) the most inhomogeneous fiber of Gao Erwei, is weak in use.About cloth and silk characteristic, equalization, quality are excessively poor.

Comparative example 5

Change the copolymerization rate of hydrophilic macromolecule as shown in table 3, in addition, make stretching similarly to Example 8 Silk.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 3.Due to hydrophilic macromolecule Copolymerization rate is high, thus becomes unstable as a result, the fiber properties such as intensity, toughness is the lowest from the discharge of spinning head, and U% (hi) the most inhomogeneous fiber of Gao Erwei, is weak in use.About cloth and silk characteristic, equalization, quality are excessively poor.

Comparative example 6,7

Change as shown in table 3 the copolymerization rate of hydrophilic macromolecule, discharge-amount, spinning head (discharge aperture, discharge hole length, Discharge hole count), all making stretching ratio in comparative example 6,7 is 3.3 times, in addition, makes stretching similarly to Example 12 Silk.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 3.In comparative example 6, due to logical Shear rate when crossing spinning head is low, thus, become highly unstable as a result, the fiber such as intensity, toughness from the discharge of spinning head Characteristic is the lowest, and the most inhomogeneous fiber of U% (hi) Gao Erwei, is weak in use.About cloth and silk characteristic, equalization, Quality is excessively poor.In comparative example 7, due to high by shear rate during spinning head, thus, spinning stress uprises, from spray webbing The discharge of head becomes unstable as a result, U% (hi) is slightly higher, is a lack of homogeneous fiber.About cloth and silk characteristic, equalization, product Matter is not up to qualified level.

Comparative example 8

In embodiment 4, after transfer BHT, put in polycondensation groove from it and do not add heat fusing but pulverulence poly- Ethylene glycol, and then, put into after Polyethylene Glycol, do not carry out stirring in 1 hour in 250 DEG C, but immediately begin to polymerization, except this it Outward, drawn yarn is made similarly to Example 4.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 3.Owing to adding with pulverulence Polyethylene Glycol, and be not stirred, in Polyethylene Glycol dispersion in esterification reaction product after putting into Polyethylene Glycol Start polymerization under insufficient state, therefore, in polyreaction product, define thick phase separation structure as a result, be Make utilize melt spinning carry out Fibrotic in the case of, the maximum gauge of the dispersion phase in fiber cross section and fiber longitudinal section Also big, define thick phase separation structure.Therefore, the fiber properties such as intensity, toughness is low, and U% (hi) is high and is a lack of homogenizing The fiber of property.About cloth and silk characteristic, equalization, quality are not up to qualified level.

Comparative example 9

In esterification groove, put into double (beta-hydroxy ethyl) the ester about 100kg of p-phthalic acid, keep in the temperature of 250 DEG C After, supplying high purity p-phthalic acid (Mitsui Chemicals system) 89.2kg and ethylene glycol (Japan's catalyst system) successively through 2.5 hours 39.8kg slurry.After supply terminates, carry out esterification 2 hours, obtain esterification reaction product.By connecting esterification The transfer pipe arrangement of groove and polycondensation groove, is transferred to be heated to the polycondensation groove of 250 DEG C by the esterification reaction product 110.6kg obtained In, then, stir 1 hour in 250 DEG C, add silicon (the モ メ Application テ ィ Block パ Off ォ マ Application ス マ テ as defoamer リ ア Le ズ system, TSF433) 120g, as trimethyl phosphate (medicine system pure with the light) 30g of heat stabilizer and stir 10 minutes, so After, add antimony trioxide 30g, manganese acetate 22g as polymerization catalyst and stir 5 minutes.It follows that through 60 minutes by polycondensation Temperature in groove is warming up to 285 DEG C from 250 DEG C, from atmospheric pressure, the pressure in polycondensation groove is decompressed to 25Pa simultaneously, then, carries out Polyreaction 2 hours 30 minutes.Then, to carrying out nitrogen purging in polycondensation groove, recover to normal pressure, in polycondensation groove, add powder The Polyethylene Glycol of the number-average molecular weight 8300 of state (Sanyo chemical conversion industry PEG6000S processed) 14.4kg, as antioxidant ( Polycondensation reaction is added after starting) tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, is decompressed to 25Pa by the pressure in polycondensation groove from atmospheric pressure, then, carries out polyreaction 30 minutes. Polyreaction product is allowed to cool so that wire harness shape spues in cold water, carries out immediately cutting and obtaining granular polymerization Reaction product.Use the granule obtained, make drawn yarn similarly to Example 4.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 3.Owing to adding with pulverulence Polyethylene Glycol, and it is short to add the polymerization reaction time after Polyethylene Glycol, thus, define thick in polyreaction product Even if phase separation structure as a result, utilize melt spinning carry out Fibrotic in the case of, fiber cross section and fiber longitudinal section In the maximum gauge of dispersion phase also big, define thick phase separation structure.Therefore, U% (hi) is high, is a lack of homogeneous Fiber.Further, since the polymerization reaction time after interpolation Polyethylene Glycol is short, thus, after unreacted PEG content, hot water treatment Weight reduction rates is the highest, and equalization, quality are also not up to qualified level.

Comparative example 10

Use double screw extruder, in 285 DEG C, polyethylene terephthalate (IV=0.66) 88kg, number are divided equally Polyethylene Glycol (the Sanyo chemical conversion industry PEG6000S processed) 12kg of son amount 8300, tetramethylolmethane-four (3-as antioxidant (3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 150g melting mixing, cut into 5mm left Right and make granule, make drawn yarn similarly to Example 4.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 3.By poly terephthalic acid second In the case of diol ester and Polyethylene Glycol melting mixing, the maximum gauge of the dispersion phase in fiber cross section and fiber longitudinal section Greatly, U% (hi) is high, is a lack of homogeneous fiber.It addition, the weight reduction rates after unreacted PEG content, hot water treatment is equal Height, equalization, quality are also not up to qualified level.

Comparative example 11

In comparative example 2, the addition of antioxidant (before polycondensation reaction starts add) is changed to 600g, except this it Outward, drawn yarn is made in the same manner as comparative example 2.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 3.The fiber properties such as intensity, toughness Well, U% (hi) is low, has obtained the fiber of homogenizing.But, owing to the number-average molecular weight of Polyethylene Glycol is less than 7000, therefore, no There is phase separation structure.About cloth and silk characteristic, although equalization, quality are the most excellent, but being charged by friction voltage is 7200V, anti- Static behaviour is poor.

Embodiment 16

In esterification groove, put into double (beta-hydroxy ethyl) the ester about 100kg of p-phthalic acid, keep in the temperature of 250 DEG C After, supplying high purity p-phthalic acid (Mitsui Chemicals system) 89.2kg and ethylene glycol (Japan's catalyst system) successively through 2.5 hours 39.8kg slurry.After supply terminates, carry out esterification 2 hours, obtain esterification reaction product.It follows that successively to contracting Poly-groove puts into ethylene glycol (Japan catalyst system) 13.6kg, is heated to 70 DEG C and the poly-second two of number-average molecular weight 8300 that melted Alcohol (Sanyo chemical conversion industry PEG6000S processed) 14.4kg, then, by connecting esterification groove and the transfer pipe arrangement of polycondensation groove, will The esterification reaction product 110.6kg obtained is transferred to be heated in the polycondensation groove of 250 DEG C.After having shifted, stir in 250 DEG C Mix 1 hour.Then, tetramethylolmethane-four (3-(3,5-bis-uncles as antioxidant (adding before polycondensation reaction starts) are added Butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, silicon (モ メ Application テ ィ Block as defoamer パ Off ォ マ Application ス マ テ リ ア Le ズ system, TSF433) 120g, trimethyl phosphate (medicine pure with light as heat stabilizer System) 30g stir 10 minutes, then, adds antimony trioxide 30g, manganese acetate 22g as polymerization catalyst and stirs 5 minutes. It follows that the temperature in polycondensation groove is warming up to 285 DEG C from 250 DEG C through 60 minutes, simultaneously by the pressure in polycondensation groove from air Pressure is decompressed to 25Pa, then, carries out polyreaction 3 hours.Then, by polyethylene terephthalate sheet material injection moulding And the thickness 0.2mm made, internal volume 500cm³Container in, be loaded as antioxidant (after polycondensation reaction starts add) Tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 480g, from instead Answer tank top to add, to carrying out nitrogen purging in polycondensation groove, recover to normal pressure, after stirring 10 minutes, by polyreaction product It is allowed to cool so that wire harness shape spues in cold water, carries out immediately cutting and obtaining granular polyreaction product.Use The granule obtained, makes drawn yarn similarly to Example 4.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 4.The fiber properties such as intensity, toughness Well, U% (hi) is low, is the fiber of homogenizing.Additionally, by adding antioxidant after polycondensation reaction starts, thus polycondensation is anti- The inactivation of the antioxidant dispersing, causing because of thermal decomposition of the antioxidant under vacuum in Ying is suppressed, resisting in fiber Oxygenate content is high, reaches to rise the time showing more than 360 minutes of half value point, and oxidation Decomposition is suppressed.It addition, antistatic Property, weight reduction rates after hygroscopicity, hot water treatment also good, equalization, quality are also qualified level.

Embodiment 17～19

For the antioxidant added after polycondensation reaction starts in embodiment 16, in embodiment 17, changed Be 2,4,6-tri-(3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl) sym-trimethylbenzene. (ADEKA system, ア デ カ ス タ Block AO-330) 420g, in embodiment 18, changes it to 1,3,5-tri-[[4-(1,1-dimethyl ethyl)-3-hydroxyl-2,6-dimethyl benzenes Base] methyl]-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones (Tokyo chemical conversion industry system, THANOX1790) 384g, in reality Execute in example 19, change it to dibutylamine-1,3,5-triazines-N, N '-bis-(2,2,6,6-tetramethyl-4-piperidyl-1,6-six Methylene diamine and the condensation polymer (BASF CHIMASSORB2020) of N-(2,2,6,6-tetramethyl-4-piperidyl) butylamine 384g, in addition, makes drawn yarn similarly to Example 4.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 4.Using any antioxidant In the case of, the fiber properties such as intensity, toughness is all good, and U% (hi) is low, for the fiber of homogenizing.Additionally, for any antioxidation For agent, all adding antioxidant after polycondensation reaction starts, thus, the oxidation preventive content in fiber is high, reaches to rise half The time showing of value point more than 360 minutes, oxidation Decomposition is suppressed.It addition, the weight after antistatic behaviour, hygroscopicity, hot water treatment Amount slip is also good, and equalization, quality are also qualified levels.

Embodiment 20～22

In embodiment 16, without antioxidant before polycondensation reaction starts, for add after polycondensation reaction starts As antioxidant tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010), in embodiment 20, it is changed to 480g, in embodiment 21, is changed to 1200g, change in embodiment 22 For 2400g, in addition, make drawn yarn similarly to Example 4.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 4.Even if it is anti-in polycondensation in change In the case of the addition of the antioxidant that should add after starting, the fiber properties such as intensity, toughness is also good, and U% (hi) is the lowest, It it is the fiber of homogenizing.Additionally, in the case of arbitrary addition, the oxidation preventive content in fiber is the highest, reach to rise half The time showing of value point more than 360 minutes, oxidation Decomposition is also suppressed.It addition, after antistatic behaviour, hygroscopicity, hot water treatment Weight reduction rates is also good, and equalization, quality are also qualified levels.

Embodiment 23

In extruder type spinning-drawing machine, the granule obtained from main feed device supply embodiment 4, from secondary feeder supply season Penta tetrol-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) so that it is weight ratio is 100:0.4, in addition, makes drawn yarn similarly to Example 4.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 4.The fiber properties such as intensity, toughness Well, U% (hi) is low, is the fiber of homogenizing.Additionally, by adding antioxidant when melt spinning, thus resisting in fiber Oxygenate content is high, reaches to rise the time showing more than 360 minutes of half value point, and oxidation Decomposition is suppressed.It addition, antistatic Property, weight reduction rates after hygroscopicity, hot water treatment also good, equalization, quality are also qualified levels.

Embodiment 24

In extruder type spinning-drawing machine, from main feed device supply in example 4 before polycondensation reaction starts without antioxygen Agent and the granule that makes, from secondary feeder supply tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) so that it is weight ratio is 100:0.4, in addition, makes drawn yarn similarly to Example 4.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 4.The fiber properties such as intensity, toughness Well, U% (hi) is low, is the fiber of homogenizing.Additionally, by adding antioxidant when melt spinning, thus resisting in fiber Oxygenate content is high, reaches to rise the time showing more than 360 minutes of half value point, and oxidation Decomposition is suppressed.It addition, antistatic Property, weight reduction rates after hygroscopicity, hot water treatment also good, equalization, quality are also qualified levels.

Embodiment 25

By relative to the polyreaction product obtained to be scaled in terms of titanium atom the citric acid Ti chelator being equivalent to 10ppm Complex, high purity terephthalic acid's (Mitsui Chemicals system) 82.5kg and 1,3-PD 49.1kg, remaining temperature 240 DEG C, pressure 1.2 × 10⁵In the esterification groove of Pa, carry out esterification, until the temperature of distillation is less than 90 DEG C, obtain ester Change reaction product.It follows that put into 1,3-PD 16.7kg successively in polycondensation groove, be heated to 70 DEG C and the number that melted Polyethylene Glycol (the Sanyo chemical conversion industry PEG6000S processed) 16.8kg of average molecular weight 8300, then, by connecting esterification groove With the transfer pipe arrangement of polycondensation groove, the esterification reaction product 110.6kg obtained is transferred to be heated to the polycondensation groove of 240 DEG C In.After having shifted, stir 1 hour in 240 DEG C.Then, add as antioxidant (adding before polycondensation reaction starts) Tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, conduct disappear Silicon (モ メ Application テ ィ Block パ Off ォ マ Application ス マ テ リ ア Le ズ system, the TSF433) 120g of infusion, as heat stabilizer Trimethyl phosphate (medicine system pure with light) 30g and stir 10 minutes, then, add the magnesium acetate four as polymerization catalyst and be hydrated Thing 11g also stirs 5 minutes.It follows that the temperature in polycondensation groove is warming up to 280 DEG C from 240 DEG C through 60 minutes, simultaneously by polycondensation Pressure in groove is decompressed to 40Pa from atmospheric pressure, then, carries out polyreaction 3 hours.Then, by poly terephthalic acid the third two Alcohol ester sheet material injection moulding and the thickness 0.2mm, the internal volume 500cm that make³Container in, be loaded as antioxidant (contracting Poly-reaction is added after starting) tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 480g, adds from retort top, to carrying out nitrogen purging in polycondensation groove, recovers to normal pressure, stirs 10 points Zhong Hou, is allowed to cool polyreaction product so that wire harness shape spues in cold water, carries out immediately cutting and obtaining graininess Polyreaction product.Use the granule obtained, make drawn yarn similarly to Example 14.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 4.Even if by hydrophobicity high score In the case of son is changed to PTT, the fiber properties such as intensity, toughness is also good, and U% (hi) is the lowest, is The fiber of homogenizing.Additionally, reach to rise the time showing more than 360 minutes of half value point, oxidation Decomposition is also suppressed.It addition, it is anti- Weight reduction rates after static behaviour, hygroscopicity, hot water treatment is also good, and equalization, quality are also qualified levels.

Embodiment 26

By relative to the polyreaction product obtained to be scaled in terms of titanium atom the citric acid Ti chelator being equivalent to 10ppm Complex, high purity terephthalic acid's (Mitsui Chemicals system) 82.5kg and BDO 89.5kg, remaining temperature 220 DEG C, pressure 1.2 × 10⁵In the esterification groove of Pa, carry out esterification, until the temperature of distillation is less than 90 DEG C, obtain ester Change reaction product.It follows that put into BDO 19.7kg successively in polycondensation groove, be heated to 70 DEG C and the number that melted Polyethylene Glycol (the Sanyo chemical conversion industry PEG6000S processed) 16.8kg of average molecular weight 8300, then, by connecting esterification groove With the transfer pipe arrangement of polycondensation groove, the esterification reaction product 110.6kg obtained is transferred to be heated to the polycondensation groove of 220 DEG C In.After having shifted, stir 1 hour in 220 DEG C.Then, add as antioxidant (adding before polycondensation reaction starts) Tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, conduct disappear Silicon (モ メ Application テ ィ Block パ Off ォ マ Application ス マ テ リ ア Le ズ system, the TSF433) 120g of infusion, as heat stabilizer Trimethyl phosphate (medicine system pure with light) 30g and stir 10 minutes, then, add the magnesium acetate four as polymerization catalyst and be hydrated Thing 11g also stirs 5 minutes.It follows that the temperature in polycondensation groove is warming up to 250 DEG C from 220 DEG C through 60 minutes, simultaneously by polycondensation Pressure in groove is decompressed to 60Pa from atmospheric pressure, then, carries out polyreaction 3 hours.Then, by poly terephthalic acid fourth two Alcohol ester sheet material injection moulding and the thickness 0.2mm, the internal volume 500cm that make³Container in, be loaded as antioxidant (contracting Poly-reaction is added after starting) tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 480g, adds from retort top, to carrying out nitrogen purging in polycondensation groove, recovers to normal pressure, stirs 10 points Zhong Hou, is allowed to cool polyreaction product so that wire harness shape spues in cold water, carries out immediately cutting and obtaining graininess Polyreaction product.Use the granule obtained, make drawn yarn similarly to Example 15.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 4.Even if by hydrophobicity high score In the case of son is changed to polybutylene terephthalate (PBT), the fiber properties such as intensity, toughness is also good, and U% (hi) is the lowest, is The fiber of homogenizing.Additionally, reach to rise the time showing more than 360 minutes of half value point, oxidation Decomposition is also suppressed.It addition, it is anti- Weight reduction rates after static behaviour, hygroscopicity, hot water treatment is also good, and equalization, quality are also qualified levels.

Embodiment 27～36

In extruder type spinning-drawing machine, in embodiment 27,35,36, from main feed device supply embodiment 1 make Grain, in embodiment 28, the granule made from main feed device supply embodiment 3, in embodiment 29～31, supply from main feed device The granule made in embodiment 4, in embodiment 32, the granule made from main feed device supply embodiment 8, in embodiment 33, The granule made from main feed device supply embodiment 10, in embodiment 34, makes from main feed device supply embodiment 11 Granule, from secondary feeder supply tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) so that it is weight ratio is 100:0.4, embodiment 27 operates similarly to Example 1, embodiment 28 and embodiment 3 similarly operate, and embodiment 29 operates similarly to Example 5, and embodiment 30 operates similarly to Example 6, embodiment 31 Operating similarly to Example 7, embodiment 32 operates similarly to Example 8, and embodiment 33 operates similarly to Example 10, Embodiment 34 operates similarly to Example 11, and embodiment 35 operates similarly to Example 12, embodiment 36 and embodiment 13 Similarly operate, make drawn yarn.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 5.Even if it is high at change hydrophilic The number-average molecular weight of molecule and copolymerization rate, by shear rate during spinning head, spinning speed in the case of, intensity, toughness etc. Fiber properties is also good, and U% (hi) is the lowest, is the fiber of homogenizing.Additionally, by adding antioxidant when melt spinning, from And the content of the antioxidant in fiber is high, reaching to rise the time showing more than 360 minutes of half value point, oxidation Decomposition is pressed down System.It addition, the weight reduction rates after antistatic behaviour, hygroscopicity, hot water treatment is also good, equalization, quality are also qualified levels.

Embodiment 37

In embodiment 4, the addition of antioxidant (before polycondensation reaction starts add) is changed to 600g, except this it Outward, drawn yarn is made similarly to Example 4.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 5.The fiber properties such as intensity, toughness Well, U% (hi) is low, is the fiber of homogenizing.About cloth and silk characteristic, antistatic behaviour, hygroscopicity are the most excellent.It addition, at hot water Weight reduction rates after reason is the lowest, and the dissolution of hydrophilic compounds is suppressed, and, equalization, quality are also qualified levels.

Embodiment 38

Put in ester exchange reaction groove by dimethyl terephthalate (DMT) 8.7kg, 5-sodium sulfo isophthalate dimethyl ester (SSIA) (Sanyo's chemical conversion industry system) 370g, ethylene glycol (the Japan's catalyst system) slurry that 5.6kg is formed, add anti-as ester exchange Answer Quilonorm (SKB) dihydrate 21.5g, the cobalt acetate tetrahydrate 2g of catalyst, carry out ester exchange reaction 2 hours in 240 DEG C, To ester exchange reaction product.It is heated to 70 DEG C and the number-average molecular weight 8300 that melted it follows that put in polycondensation groove Polyethylene Glycol (Sanyo chemical conversion industry PEG6000S processed) 1.2kg, then, by connecting the transfer of ester exchange reaction groove and polycondensation groove Pipe arrangement, is transferred to be heated in the polycondensation groove of 240 DEG C by the ester exchange reaction product obtained.After having shifted, in 240 DEG C Stir 1 hour.Then, tetramethylolmethane-four (3-(3,5-bis-as antioxidant (adding before polycondensation reaction starts) is added Tertiary butyl-4-hydroxy phenol) propionic ester) (BASF system, Irganox1010) 15g, silicon (モ メ Application テ ィ Block as defoamer パ Off ォ マ Application ス マ テ リ ア Le ズ system, TSF433) 7g, trimethyl phosphate (medicine system pure with light) as heat stabilizer 4.3g also stirs 10 minutes, then, adds the antimony trioxide 3g as polymerization catalyst and stirs 5 minutes.It follows that through 60 points Temperature in polycondensation groove is warming up to 285 DEG C from 240 DEG C by clock, from atmospheric pressure, the pressure in polycondensation groove is decompressed to 25Pa simultaneously, Then, polyreaction is carried out 3 hours.Then, at the thickness that polyethylene terephthalate sheet material injection moulding is made 0.2mm, internal volume 500cm³Container in, be loaded as the tetramethylolmethane of antioxidant (after polycondensation reaction starts add)- Four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 40g, adds from retort top Add, to carrying out nitrogen purging in polycondensation groove, recover to normal pressure, after stirring 10 minutes, by polyreaction product with wire harness shape to Cold water spues and is allowed to cool, carry out immediately cutting and obtaining granular polyreaction product.Use the granule obtained, Make drawn yarn similarly to Example 4.It should be noted that the SSIA copolymerization rate shown in table 6 is to contain in polymerization reactant The ratio of weight of element sulphur.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 6.The fiber properties such as intensity, toughness Well, U% (hi) is low, is the fiber of homogenizing.Additionally, reach to rise the time showing more than 360 minutes of half value point, oxidation Decomposition Being suppressed, the weight reduction rates after antistatic behaviour, hygroscopicity, hot water treatment is the best.Further, since copolymerization has isophthalic diformazan Acid-5-sodium sulfonate, thus display cation dyeable, equalization, quality are also qualified levels.

Embodiment 39,40

Change the copolymerization rate of 5-sodium sulfo isophthalate as shown in table 6, in addition, in the same manner as embodiment 38 Make drawn yarn.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 6.Even if at change isophthalic diformazan In the case of the copolymerization rate of acid-5-sodium sulfonate, the fiber properties such as intensity, toughness is also good, and U% (hi) is the lowest, is the fibre of homogenizing Dimension.Additionally, reach to rise the time showing more than 360 minutes of half value point, oxidation Decomposition is suppressed, antistatic behaviour, hygroscopicity, heat Weight reduction rates after water processes is the best.It addition, equalization, quality are also qualified levels.

Embodiment 41,42

Change the copolymerization rate of hydrophilic macromolecule as shown in table 6, in addition, make stretching in the same manner as embodiment 38 Silk.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 6.Even if it is high at change hydrophilic In the case of the copolymerization rate of molecule, the fiber properties such as intensity, toughness is also good, and U% (hi) is the lowest, is the fiber of homogenizing.Additionally, Reaching to rise the time showing more than 360 minutes of half value point, oxidation Decomposition is suppressed, after antistatic behaviour, hygroscopicity, hot water treatment Weight reduction rates the best.It addition, equalization, quality are also qualified levels.

Embodiment 43～47

In embodiment 38～42, without antioxidant after polycondensation reaction starts, when carrying out melt spinning, squeezing Go out in type spinning-drawing machine, supply, from main feed device, the granule obtained each embodiment, from secondary feeder supply tetramethylolmethane-four (3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester) (BASF system, Irganox1010) so that it is weight ratio is 100:0.4, In addition, drawn yarn is made in the same manner as each embodiment.

The fiber properties of the fiber obtained and the evaluation result of cloth and silk characteristic are shown in table 6.In all cases, intensity, The fiber properties such as toughness are all good, and U% (hi) is the lowest, is the fiber of homogenizing.Additionally, reach to rise the time showing of half value point More than 360 minutes, oxidation Decomposition was suppressed, and the weight reduction rates after antistatic behaviour, hygroscopicity, hot water treatment is the best.It addition, Equalization, quality are also qualified levels.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

Industrial applicability

For the fiber of the present invention, although have phase separation structure, but fiber number inequality is little, dyeing is uneven, fluffing Occur to be suppressed, and relative to long-term keeping, the durability of fiber properties of cylinder dry, hygroscopicity, low temperature and low humidity degree ring Excellent antistatic property under border, when dyeing, the time of use, the dissolution of hydrophilic compounds is suppressed.Therefore, clothing can be suitable as The fiber construct of the knitted woven item of material, non-woven fabrics etc..

Claims (10)

1. a fiber, described fiber has phase separation structure, it is characterised in that described fiber package is containing hydrophobic polymer and parent The copolymer of aqueous high molecular, and there is continuous phase based on phase separation structure and dispersion phase, the dispersion phase in fiber cross section Maximum gauge be 1～40nm, fiber number variation value U% (hi) is 0.1～1.5%.

Fiber the most according to claim 1, it is characterised in that described hydrophobic polymer and the copolymerization of hydrophilic macromolecule Thing exposing at least partially at fiber surface.

Fiber the most according to claim 1 and 2, it is characterised in that described hydrophobic polymer is polyester.

4. according to the fiber according to any one of claims 1 to 3, it is characterised in that described hydrophilic macromolecule is poly-second two Alcohol.

5. according to the fiber according to any one of Claims 1 to 4, it is characterised in that based on JIS L1094, be 10 in temperature DEG C, humidity be the voltage that is charged by friction recorded under conditions of 10%RH be below 3000V.

6. according to the fiber according to any one of Claims 1 to 5, it is characterised in that at nitrogen: oxygen=80vol%:20vol% Mixed-gas atmosphere under, mixed gas flow be 200mL/ minute, with the programming rates of 30 DEG C/min from room temperature to After 160 DEG C, be held in 160 DEG C under conditions of, when carrying out thermoconductive TGA (DTG) for described fiber, be up to 160 DEG C Time as in the case of 0 minute, is more than 120 minutes to rising time of half value point.

7. according to the fiber according to any one of claim 1～6, it is characterised in that containing antioxidant.

Fiber the most according to claim 7, it is characterised in that described antioxidant is selected from phenolic compound, sulfur class At least one in compound, hindered amine compound.

9. according to the fiber described in claim 7 or 8, it is characterised in that the content of described antioxidant is fibre weight 0.01～2.0 weight %.

10. the manufacture method of the fiber according to any one of claim 1～9, it is characterised in that with described hydrophobic polymer 10000～40000s are become by shear rate during spinning head with the copolymer of hydrophilic macromolecule^-1Mode carry out spinning.