CN106164349B

CN106164349B - Fiber and its manufacturing method with phase separation structure

Info

Publication number: CN106164349B
Application number: CN201580015835.7A
Authority: CN
Inventors: 鹿野秀和; 中川顺; 中川顺一; 荒西义高; 田中阳郎; 田中阳一郎
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2014-03-25
Filing date: 2015-03-19
Publication date: 2019-04-23
Anticipated expiration: 2035-03-19
Also published as: CN106164349A; TW201600662A; KR102250972B1; JPWO2015146790A1; JP6582980B2; TWI638919B; WO2015146790A1; KR20160134639A

Abstract

The issue of the present invention is to provide a kind of fibers, although the fiber has phase separation structure, but fiber number unevenness is small, dyeing is uneven, fluffing generation is suppressed, and relative to the excellent antistatic property under long-term keeping, the durability of the fiber properties of roller drying, hygroscopicity, low temperature and low humidity degree environment, in dyeing, in use, the dissolution of hydrophilic compounds is suppressed.The fiber with phase separation structure is characterized in that, copolymer comprising hydrophobic polymer and hydrophilic macromolecule, with continuous phase and dispersed phase based on phase separation structure, the maximum gauge of dispersed phase in fiber cross section is 1~40nm, and fiber number change value U% (hi) is 0.1~1.5%.

Description

Fiber and its manufacturing method with phase separation structure

Technical field

The present invention relates to a kind of fibers with phase separation structure.More specifically, it is related to a kind of fiber, though the fiber It is right that there is phase separation structure, but fiber number unevenness is small, and dyeing is uneven, fluffing generation is suppressed, and relative to long-term keeping, rolling Antistatic property under the durabilities of the fiber properties of cylinder dry (tumbler drying), hygroscopicity, low temperature and low humidity degree environment is excellent It is different, dyeing when, in use, hydrophilic compounds dissolution be suppressed, dress material purposes can be suitable for.

Background technique

Polyester fiber is cheap, and mechanical property is excellent, because due to extensive with using on the way.However, due to lacking moisture absorption Property, thus have the shortcomings that it is following it is such have it is to be solved: bored wet sense is generated in the high humidity of summer, when low humidity in winter produces Raw electrostatic, etc..The voltage that is charged by friction of polyethylene terephthalate as usually used polyester in temperature is 20 DEG C, humidity be 40%RH standard state under be 7000~9000V or so.For being charged by friction voltage, value is smaller, more It is not easy static electrification, snugness of fit is more excellent.In the case where polyethylene terephthalate, it may be said that be to lack very much to resist The fiber of static behaviour.

In order to improve above-mentioned disadvantage, about the method for assigning antistatic property to polyester fiber, have been presented for so far Kinds of schemes.As the usual method for assigning antistatic property, copolymerising hydrophilic compound in the polyester can be enumerated or poly- The methods of hydrophilic compounds are added in ester.Status is, although antistatic property can be improved by these methods, in winter It is outdoor, due to using heating equipment and leading to the low-down interior of humidity etc. under low temperature and low humidities degree environment, be unable to get adequately Antistatic property.

For example, proposed in patent document 1 in the polyester add as hydrophilic compounds polyether polyols and Antistatic polyester fiber obtained from organic metal salt.In the motion, by dispersing polyoxy alkylidene two in polyester fiber Alcohol, to assign antistatic property.

Propose in patent document 2 has the polyester of polyethylene glycol to be as core, with polypropylene terephthalate to be copolymerized The core sheath composite fibre of sheath.In the motion, there is the polyester of polyethylene glycol by the copolymerization configured in core, thus to polyester fiber Assign antistatic property.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 7-173725 bulletin

Patent document 2: Japanese Unexamined Patent Publication 11-93022 bulletin

Summary of the invention

Problems to be solved by the invention

However, in the method that above patent document 1 is recorded, although under conditions of temperature is 20 DEG C, humidity is 40%RH, It is low to be charged by friction voltage, is 600V, antistatic property is good, but exists temperature is 10 DEG C, humidity is the low temperature and low humidities such as 10%RH It spends under environment, does not show project as sufficient antistatic property.In addition, since polyester and hydrophilic compounds are not total to It is poly-, thus there are following such projects: in dyeing or in use, hydrophilic compounds dissolve out, the durability of antistatic property It is low.

It is also same as method described in Patent Document 1 in method described in Patent Document 2, although temperature be 20 DEG C, it is wet Degree is low under conditions of 40%RH, to be charged by friction voltage, is 400V, and antistatic property is good, but existing in temperature is 10 DEG C, humidity Not show project as sufficient antistatic property under the low temperature and low humidities degree environment such as 10%RH.

In addition, in any case, having and using incompatible polyethylene glycol as hydrophilic compounds in the polyester In the case of fiber number it is uneven big, occur that dyeing is uneven, such project of fluffing.Moreover, because the oxygenolysis of polyethylene glycol not by Inhibit, thus there are following such projects: by taking care of for a long time or roller drying, oxygenolysis carry out, hygroscopicity, low temperature are low The fiber properties such as antistatic property, mechanical property under humidity environment reduce.

Problem of the present invention is that solving above-mentioned problem of the prior art point, a kind of fiber is provided, although the fiber has There is phase separation structure, but fiber number unevenness is small, dyeing is uneven, fluffing generation is suppressed, and hygroscopicity, low temperature and low humidity degree environment Under excellent antistatic property, dyeing when, in use, hydrophilic compounds dissolution be suppressed, dress material purposes can be suitable for.

Means for solving the problems

Above-mentioned project of the invention can be solved by following fibers, and the fiber has phase separation structure, comprising hydrophobic Property macromolecule and hydrophilic macromolecule copolymer, and there is continuous phase and dispersed phase based on phase separation structure, fiber is transversal The maximum gauge of dispersed phase in face is 1~40nm, and fiber number change value U% (hi) is 0.1~1.5%.

In addition, preferably the copolymer of hydrophobic polymer and hydrophilic macromolecule is in fibre for fiber of the invention At least part in dimension table face is exposed, it is preferred to use: hydrophobic polymer is polyester, and hydrophilic macromolecule is polyethylene glycol.

In addition, for fiber of the invention, it is preferred that in nitrogen: oxygen=80vol%:20vol% mixed gas Under atmosphere, mixed gas flow be 200mL/ minute, with 30 DEG C/min of heating rate from room temperature to after 160 DEG C, guarantor It is held under conditions of 160 DEG C, when carrying out thermoconductive TGA (DTG) for the fiber, is up to 160 DEG C of time as 0 In the case where minute, until the time for rising half value point is 120 minutes or more.Additionally, it is preferred that using: contain antioxidant, antioxygen Agent be selected from phenolic compound, sulphur class compound, be obstructed at least one of amine compound, the content of antioxidant is fibre Tie up 0.01~2.0 weight % of weight.

In addition, for fiber of the invention, it is preferred that JIS L1094 is based on, temperature is 10 DEG C, humidity is The voltage that is charged by friction measured under conditions of 10%RH is 3000V or less.

Further, it may be preferred that using the manufacturing method of following fibers, the method is characterized in that, with hydrophobic polymer with The shear velocity when copolymer of hydrophilic macromolecule passes through spinning head becomes 10000~40000s^-1Mode carry out spinning.

The effect of invention

Through the invention, it is possible to provide a kind of fiber, although the fiber has phase separation structure, fiber number unevenness is small, dye Color is uneven, fluffing generation is suppressed, moreover, relative to long-term keeping, the durability of the fiber properties of roller drying, moisture absorption Property, the excellent antistatic property under low temperature and low humidity degree environment, in dyeing, in use, the dissolution of hydrophilic compounds is suppressed.On It states fiber and is especially suitable for dress material purposes.

Detailed description of the invention

[Fig. 1] Fig. 1 by the example fiber with phase separation structure of the invention fiber cross section replace attached drawing use Photo.

[Fig. 2] Fig. 2 by the example fiber with phase separation structure of the invention fiber longitudinal section replace attached drawing use Photo.

Specific embodiment

Fiber of the invention includes the copolymer of hydrophobic polymer and hydrophilic macromolecule, and is had based on mutually separation knot The continuous phase and dispersed phase of structure, the maximum gauge of the dispersed phase in fiber cross section are 1~40nm, fiber number change value U% (hi) It is 0.1~1.5%.For fiber of the invention, although there is phase separation structure, as shown in Figure 1, in fiber cross section In form fine and uniform dispersed phase, thus, fiber number unevenness is small, and dyeing is uneven, fluffing generation is suppressed.In addition, logical It crosses and is copolymerized hydrophobic polymer and hydrophilic macromolecule, so that not only hygroscopicity, antistatic property, Er Qie can be assigned to fiber When dyeing, in use, the dissolution of hydrophilic compounds is suppressed, accordingly, with respect to hygroscopicity, antistatic property, with durability.This Outside, as shown in Fig. 2, in fiber longitudinal section, point of fine and uniform striated is formed with along the direction parallel with fiber axis Therefore dephasing even if available under low temperature and low humidity degree environment, is charged by friction that voltage is also low, the fiber of excellent antistatic property.

For the hydrophobic polymer in the present invention, as long as can be copolymerized with hydrophilic macromolecule, so that it may without spy Not Xian Zhi ground suitably use.As the concrete example of hydrophobic polymer, polyethylene terephthalate can be enumerated, is poly- to benzene The aromatic polyesters such as naphthalate, polybutylene terephthalate (PBT), poly terephthalic acid 1,6-HD ester, poly- cream Acid, polyglycolic acid, polyethylene glycol adipate, polypropylene glycol adipate, poly adipate succinic acid ester, poly- succinic acid second two Alcohol ester, poly- amber acid propylene glycol ester, polybutylene succinate, polyethylene glycol sebacate, poly- decanedioic acid propylene glycol ester, the poly- last of the ten Heavenly stems Aliphatic polyesters 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, when manufacture and when using Treatability it is good, thus preferably.

For the hydrophilic macromolecule in the present invention, as long as can be copolymerized with hydrophobic polymer, so that it may without spy Not Xian Zhi ground suitably use.By the way that antistatic property can be assigned to fiber to hydrophobic polymer copolymerising hydrophilic macromolecule.Make For the concrete example of hydrophilic macromolecule, the homopolymers such as polyethylene glycol, polypropylene glycol, the copolymerization of polyethylene glycol propylene glycol can be enumerated Copolymers such as object, polyethylene glycol butanediol copolymer etc., but it is not limited to these.Wherein, polyethylene glycol, polypropylene glycol are being made Treatability when making and when using is good, thus preferably.

Fiber of the invention includes the copolymer of hydrophobic polymer and hydrophilic macromolecule.As being blended with polymer Melting mixing is different, and hydrophobic polymer forms covalent bond, therefore, hydrophilic macromolecule by copolymerization with hydrophilic macromolecule Be suppressed from the dissolution in fiber, can be obtained between process during fabrication, using product when, the variation of fiber properties is small, durable The excellent fiber of property.

Fiber of the invention has phase separation structure.The phase separation structure is in polymerization reaction progress, hydrophobic polymer It is specifically presented during being copolymerized with hydrophilic macromolecule.That is, with incompatible high-molecular compound is passed through Melting mixing and the phase separation structure that presents is different, in the present invention, due to being the mutually separation presented as polymerization reaction carries out Structure, thus form fine and uniform dispersed phase.Since dispersed phase is fine and uniform, thus while obtained fiber has phase Separated structure, but fiber number unevenness is small, and dyeing is uneven, fluffing generation is suppressed.In addition, due to phase separation structure, thus, The fiber of the excellent antistatic property under low temperature and low humidity degree environment can be obtained.

The mutually separation presented about the progress with polymerization reaction, shows concrete example.As hydrophobic polymer In the case where polyethylene terephthalate, the copolymer as the polyethylene glycol of hydrophilic macromolecule, at the beginning of polycondensation reaction Phase, due to bis- (beta-hydroxy ethyl) esters of the terephthalic acid (TPA) of the precursor as polyethylene terephthalate and polyethylene glycol Polarity is close, thus is in compatible state, and reaction system is transparent.With the progress of polycondensation reaction, poly terephthalic acid second is generated Diol ester-ethylene glycol copolymer begins to pass through about 1 hour from polymerization, becomes phase-separated state, reaction system gonorrhoea.Poly- In ethylene glycol terephthalate-ethylene glycol copolymer, low polar copolymer, i.e. polyethylene terephthalate are generated Shared ratio high copolymer and highly polar copolymer, i.e. polyethylene glycol ratio shared in strand in strand The high copolymer of example, the phase separation structure be the polar difference by above-mentioned low polar copolymer and highly polar copolymer and It presents.

Fiber of the invention has continuous phase and dispersed phase based on phase separation structure.Constitute continuous phase and dispersed phase at Divide and changes with the ratio that hydrophobic polymer and hydrophilic macromolecule are copolymerized.In the ratio of hydrophobic polymer When more than hydrophilic macromolecule, the high " hydrophobic polymer-hydrophily height of hydrophobic polymer ratio shared in strand Molecule copolymer " becomes continuous phase, hydrophilic macromolecule ratio shared in strand it is high " hydrophobic polymer-is hydrophilic Property high-molecular copolymer " become dispersed phase.On the other hand, when the ratio of hydrophilic macromolecule is more than hydrophobic polymer, parent Aqueous high molecular ratio shared in strand high " hydrophobic polymer-hydrophilic macromolecule copolymer " becomes continuous Phase, hydrophobic polymer ratio shared in strand high " hydrophobic polymer-hydrophilic macromolecule copolymer " become Dispersed phase.In any case, continuous phase, two side of dispersed phase are by " hydrophobic polymer-hydrophilic macromolecule copolymer " shape At therefore it, is the very high phase separation structure of compatibility of continuous phase and dispersed phase that only its ratio of components is different.Consequently found that It is very high to form stability of the dispersed phase when melting delay, dispersed phase is not easy the coarsening phase separation knot during melting delay Structure.Thus, it can be known that it is uneven to improve fiber number when carrying out fibrosis by melt spinning, also, in dyeing, in use, It can inhibit the dissolution of hydrophilic compounds.

It,, can also as the dicarboxylic acid component of polyester in the case where using polyester as hydrophobic polymer in the present invention Use the dicarboxylic acids of the ester formative in addition to terephthalic acid (TPA).The concrete example of dicarboxylic acids as ester formative can enumerate oneself Diacid, M-phthalic acid, decanedioic acid, phthalic acid, 4,4 '-biphenyl dicarboxylic acids, 5-sodium sulfo isophthalate, isophthalic two Formic acid -5- Sulfonic Lithium, M-phthalic acid -5- sulfonic acid (tetraalkyl)Equal dicarboxylic acids and their ester formative derivative etc., but It is not limited to these.

In the present invention, in the case where using polyester as hydrophobic polymer, as the diol component of polyester, it can also make With the glycol of the ester formative in addition to ethylene glycol.The concrete example of glycol as ester formative can enumerate propylene glycol, fourth two Alcohol, hexylene glycol, cyclohexanediol, diethylene glycol, 1,6- hexylene glycol, neopentyl glycol and their ester formative derivative etc., but not It is limited to these.

In the present invention, use polyethylene terephthalate as hydrophobic polymer, use polyethylene glycol as In the case where hydrophilic macromolecule, the number-average molecular weight of polyethylene glycol is preferably 7000~20000.The equal molecule of the number of polyethylene glycol When amount is 7000 or more, phase separation structure is presented and the copolymerization with polyethylene terephthalate, thus, pass through progress Fibrosis and the fiber that excellent antistatic property can be obtained, thus preferably.The number-average molecular weight of polyethylene glycol be more preferably 7500 with On, further preferably 8000 or more.On the other hand, when the number-average molecular weight of polyethylene glycol is 20000 or less, poly- terephthaldehyde The polycondensation reaction of sour glycol ester and polyethylene glycol is high, can reduce unreacted polyethylene glycol, thus preferably.In addition, passing through With the copolymerization of polyethylene terephthalate, coarsening when dispersed phase is fine and uniform, melting is detained can be formed and pressed down The stable phase separation structure of system is steady from the discharge of polycondensation slot, the discharge in spinning from spinning head after polycondensation reaction Fixed, operability becomes well, thus preferably.In addition, can be obtained, fiber number unevenness is small, dyeing is uneven, the generation of fluffing is repressed The fiber of homogeneous, thus preferably.The number-average molecular weight of polyethylene glycol be more preferably 17000 hereinafter, further preferably 15000 with Under.

In the present invention, use polyethylene terephthalate as hydrophobic polymer, use polyethylene glycol as In the case where hydrophilic macromolecule, the copolymerization rate of polyethylene glycol is preferably 10~20 weight %.The copolymerization rate of polyethylene glycol is 10 When weight % or more, the fiber of hygroscopicity and excellent antistatic property can be obtained, thus preferably.The copolymerization rate of polyethylene glycol is more excellent It is selected as 11 weight % or more, further preferably 12 weight % or more.On the other hand, the copolymerization rate of polyethylene glycol is 20 weight % When following, by the copolymerization with polyethylene terephthalate, fine and uniform phase separation structure can be formed, it is anti-in polycondensation To stablize from the discharge of polycondensation slot, in spinning from the discharge of spinning head after answering, operability becomes well, thus preferably.Separately Outside, it can be obtained that fiber number unevenness is small, dyeing is uneven, the fiber of the repressed homogeneous of generation of fluffing, fiber and formed by it The mechanical property of fiber construct becomes well, thus preferably.The copolymerization rate of polyethylene glycol be more preferably 19 weight % hereinafter, into One step is preferably 18 weight % or less.

In the present invention, inventors are to by hydrophobic polymer (polyethylene terephthalate)-hydrophilic macromolecule The phase separation structure that (polyethylene glycol) copolymer is formed has made intensive studies, as a result, it has been found that following such special phenomenons: Since the very high phase separation structure of the compatibility for being as described above continuous phase and dispersed phase thus assigns in the molten state When shearing, phase separation structure differential dispersion disappears soon, but stopping assigns when shearing and passing through certain time, and phase is presented again Separated structure.It is described in detail in the manufacturing method of aftermentioned fiber, by efficiently using above-mentioned special phenomenon, thus Although successfully obtaining with phase separation structure but fiber number unevenness being small, dyeing is uneven, the repressed fiber of generation of fluffing.

The copolymer of hydrophobic polymer and hydrophilic macromolecule in the present invention can be the secondary additive of addition and into The copolymers of various modifications is gone.As the concrete example of secondary additive, can enumerate expanding material, plasticizer, ultraviolet absorbing agent, Infrared absorbent, release agent, antibacterial agent, nucleating agent, heat stabilizer, antioxidant, antistatic agent, is prevented fluorescent whitening agent Toner, regulator, delustering agent, defoaming agent, 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, and can also be used together by more than one.

The maximum gauge of dispersed phase in the fiber cross section of fiber of the invention is 1~40nm.In fiber cross section The detailed measuring method of the maximum gauge of dispersed phase illustrates below.The maximum gauge of dispersed phase in fiber cross section is When 1nm or more, the fiber of hygroscopicity and excellent antistatic property can be obtained.The maximum gauge of dispersed phase in fiber cross section is more excellent It is selected as 3nm or more, further preferably 5nm or more, particularly preferably 10nm or more.On the other hand, point in fiber cross section When the maximum gauge of dephasing is 40nm or less, fiber and good, the durability by the mechanical property of its fiber construct formed It is excellent.In addition, stablizing due to being fine and uniform dispersed phase, thus in spinning from the discharge of spinning head, operability becomes Well, and fiber number unevenness is small, can inhibit the generation that dyeing is uneven, fluffs.The maximum gauge of dispersed phase in fiber cross section More preferably 37nm hereinafter, further preferably 35nm hereinafter, particularly preferably 30nm or less.

The maximum gauge of dispersed phase in the fiber longitudinal section of fiber of the invention is preferably 1~40nm.Fiber longitudinal section In the detailed measuring method of maximum gauge of dispersed phase illustrate below.It should be noted that in so-called fiber longitudinal section Dispersed phase maximum gauge, refer to for the direction vertical with fiber axis dispersed phase diameter maximum value.Fiber is vertical to be cut When the maximum gauge of dispersed phase in face is 1nm or more, the fiber of hygroscopicity and excellent antistatic property can be obtained, thus preferably. The maximum gauge of dispersed phase in fiber longitudinal section is more preferably 3nm or more, further preferably 5nm or more, particularly preferably 10nm or more.On the other hand, it when the maximum gauge of the dispersed phase in fiber longitudinal section is 40nm or less, fiber and is formed by it Fiber construct mechanical property it is good, excellent in te pins of durability, thus preferably.In addition, due to being fine and uniform dispersed phase, Thus in spinning from the discharge of spinning head stablize, operability becomes well, also, fiber number unevenness is small, can inhibit dyeing unevenness, The generation of fluffing, thus preferably.The maximum gauge of dispersed phase in fiber longitudinal section is more preferably 37nm hereinafter, further preferably For 35nm, particularly preferably 30nm or less.

The total fiber number of fiber of the invention is not particularly limited, can depending on the application, require characteristic and suitably select, preferably 10~500dtex.When the total fiber number of fiber is 10dtex or more, not only fracture of wire is few, and process passability is good, moreover, 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 30dtex or more, further preferably For 50dtex or more.On the other hand, when the total fiber number of fiber is 500dtex or less, when forming fiber and fiber construct, Flexibility will not be damaged, thus preferably.The total fiber number of fiber be more preferably 400dtex hereinafter, further preferably 300dtex with Under.

The intensity of fiber of the invention is not particularly limited, can depending on the application, require characteristic and suitably select, from mechanical special From the viewpoint of property, preferably 2.0~5.0cN/dtex.When the intensity of fiber is 2.0cN/dtex or more, not only in spinning, drawing It is few the process interruptions silk such as process to be stretched, weaves, make up process, process passability is good, and excellent in te pins of durability when using, thus It is preferred that.The intensity of fiber is more preferably 2.5cN/dtex or more, further preferably 3.0cN/dtex or more.On the other hand, fine When the intensity of dimension is 5.0cN/dtex or less, when forming fiber and fiber construct, flexibility will not be damaged, thus it is excellent Choosing.

The elongation of fiber of the invention is not particularly limited, can depending on the application, require characteristic and suitably select, from process From the viewpoint of passability, preferably 10~60%.When the elongation of fiber is 10% or more, not only fiber and fibre structure The abrasion performance of body becomes well, and process passability is good, and the generation fluffed when use is few, durability become well, because And it is preferred that.The elongation of fiber is more preferably 15% or more, further preferably 20% or more.On the other hand, the elongation of fiber When rate is 60% or less, the dimensional stability of fiber and fiber construct becomes well, thus preferably.The elongation of fiber is more Preferably 55% hereinafter, further preferably 50% or less.

The initial tensile resistance degree of fiber of the invention is not particularly limited, can depending on the application, require characteristic and suitably select It selects, the initial tensile resistance degree measured according to the 8.10 of JIS L1013:1999 is preferably 10~100cN/dtex.At the beginning of fiber When beginning stretch-resistant degree is 10cN/dtex or more, process passability, treatability are good, and mechanical property is excellent, thus preferably.It is fine The initial tensile resistance degree of dimension is more preferably 15cN/dtex or more, further preferably 20cN/dtex or more.On the other hand, fine When the initial tensile resistance degree of dimension is 100cN/dtex or less, the flexibility of fiber and fiber construct will not be damaged, thus It is preferred that.The initial tensile resistance degree of fiber is more preferably 90cN/dtex hereinafter, further preferably 80cN/dtex or less.

The fiber footpath of fiber of the invention is not particularly limited, can depending on the application, require characteristic and suitably select, preferably 3~100 μm.When the fiber footpath of fiber is 3 μm or more, it is good to can be obtained spinning operability, the process passability in advanced processing, The excellent fiber of mechanical property, thus preferably.The fiber footpath of fiber is more preferably 5 μm or more, further preferably 7 μm or more. On the other hand, when the fiber footpath of fiber is 100 μm or less, the flexibility of fiber and fiber construct will not be damaged, thus it is excellent Choosing.The fiber footpath of fiber is more preferably 70 μm hereinafter, further preferably 50 μm or less.

The boiling water shrinkage of fiber of the invention is preferably 3~15%.It, can when the boiling water shrinkage of fiber is 3% or more It, can by the weaving tension inhibition in weaving process in the range of appropriateness by making fabric be heat-shrinked to improve weaving density Highdensity fabric is manufactured, thus preferably.In addition, do not need to be weaved under high tension when manufacturing high-density fabric, it can Inhibit fluffing in weaving process, suede must generation, can the process passability few fabric of manufacturing defect well, thus preferably. The boiling water shrinkage of fiber is more preferably 4% or more, further preferably 5% or more.On the other hand, the boiling water shrinkage of fiber When being 15% or less, when being handled with boiling water, the degree of orientation of strand will not be reduced extremely, the intensity drop after boiling water treating It is low small, thus preferably.In addition, shrinking fiber sufficiently using the processing for being heat-shrinked fabric, soft fabric can be obtained, because And it is preferred that.The boiling water shrinkage of fiber is more preferably 12% hereinafter, further preferably 10% or less.

The fiber number change value U% (hi) of fiber of the invention is 0.1~1.5%.Fiber number change value U% is fibre length side To thickness unevenness index, fiber number change value U% (hi) is smaller, indicates that the thickness unevenness of the length direction of fiber is smaller.From From the viewpoint of process passability, quality, fiber number change value U% (hi) is the smaller the better, but as the range that can be manufactured, and 0.1% It is lower limit.On the other hand, when the fiber number change value U% (hi) of fiber is 1.5% or less, the uniformity in fibre length direction is excellent It is different, can inhibit in warping process, weave, make up process etc. in machine tensions variation, thus preferably.In addition, being not susceptible to Hair, fracture of wire are not likely to produce dyeing unevenness, dye the disadvantages of striped, the fiber construct of high-quality can be obtained in dyeing, because And it is preferred that.The fiber number change value U% (hi) of fiber is more preferably 1.2% hereinafter, further preferably 1.0% hereinafter, especially excellent It is selected as 0.9% or less.

The filament diameter CV% of fiber of the invention is preferably 0.1~15%.It is examined from process passability, the viewpoint of quality Consider, filament diameter CV% is the smaller the better, but is lower limit as the range that can be manufactured, 0.1%.On the other hand, the monofilament of fiber is straight When diameter CV% is 15% or less, it not only can inhibit during fabrication and when use fluff, but also be not likely to produce when dyeing Dyeing is uneven, dyes the disadvantages of striped, and the fiber construct of high-quality can be obtained, thus preferably.The filament diameter CV% of fiber More preferably 12% hereinafter, further preferably 10% hereinafter, particularly preferably 7% or less.

The filament number CV% of fiber of the invention is preferably 0.1~15%.It is examined from process passability, the viewpoint of quality Consider, filament number CV% is the smaller the better, but is lower limit as the range that can be manufactured, 0.1%.On the other hand, the monofilament of fiber is fine When to spend CV% be 15% or less, it not only can inhibit during fabrication and when use fluff, but also be not likely to produce when dyeing Dyeing is uneven, dyes the disadvantages of striped, and the fiber construct of high-quality can be obtained, thus preferably.The filament number CV% of fiber More preferably 12% hereinafter, further preferably 10% hereinafter, particularly preferably 7% or less.

The filament strength CV% of fiber of the invention is preferably 0.1~20%.It is examined from process passability, the viewpoint of quality Consider, filament strength CV% is the smaller the better, but is lower limit as the range that can be manufactured, 0.1%.On the other hand, the monofilament of fiber is strong When to spend CV% be 20% or less, it not only can inhibit during fabrication and when use fluff, but also be not likely to produce when dyeing Dyeing is uneven, dyes the disadvantages of striped, and the fiber construct of high-quality can be obtained, thus preferably.The filament strength CV% of fiber More preferably 15% hereinafter, further preferably 12% hereinafter, particularly preferably 10% or less.

The monofilament elongation CV% of fiber of the invention is preferably 0.1~40%.It is examined from process passability, the viewpoint of quality Consider, monofilament elongation CV% is the smaller the better, but is lower limit as the range that can be manufactured, 0.1%.On the other hand, the monofilament of fiber When elongation CV% is 40% or less, it not only can inhibit during fabrication and when use fluff, but also be not easy when dyeing The disadvantages of generating uneven dyeing, dyeing striped, can be obtained the fiber construct of high-quality, thus preferably.The monofilament of fiber extends Rate CV% is more preferably 37% hereinafter, further preferably 35% hereinafter, particularly preferably 30% or less.

For fiber of the invention, it is preferred that in nitrogen: oxygen=80vol%:20vol% mixed-gas atmosphere Under, mixed gas flow be 200mL/ minutes, with 30 DEG C/min of heating rate from room temperature to after 160 DEG C, be held in It is supreme in the case where being up to 160 DEG C of time as 0 minute when carrying out thermoconductive TGA (DTG) under conditions of 160 DEG C The time for rising half value point is 120 minutes or more.The detailed measuring method for rising half value point illustrates below, using this evaluation side Method is as the accelerated test for assuming the durability relative to long-term keeping, roller drying.Present inventors confirm, right Having by hydrophobic polymer (polyethylene terephthalate)-hydrophilic macromolecule (polyethylene glycol) altogether in the present invention The fiber for the phase separation structure that polymers is formed, the rising peak in thermoconductive TGA (DTG) at 160 DEG C is by hydrophily high score The decomposition of sub (polyethylene glycol) and generate, along with the decomposition of the polyethylene glycol, hygroscopicity is lost, and hydroscopicity poor (△ MR) drops Low, in turn, the antistatic property under low temperature and low humidity degree environment is lost, and is charged by friction voltage raising.From relative to long-term keeping, roller The viewpoint of the durabilities of fiber properties such as antistatic property, mechanical property dry, under hygroscopicity, low temperature and low humidity degree environment is examined Consider, the time for reaching rising half value point, the longer the better.The time for reaching rising half value point is more preferably 180 minutes or more, into one Step preferably 240 minutes or more, particularly preferably 360 minutes or more.

The hydroscopicity of fiber of the invention poor (△ MR) is preferably 1~10%.The detailed measuring method of △ MR is below Illustrate, under conditions of △ MR has assumed that temperature and humidity i.e. temperature is 30 DEG C, humidity is 90%RH in the clothes after light exercise The difference of hydroscopicity under conditions of hydroscopicity and temperature as ambient atmos temperature and humidity are 20 DEG C, humidity is 65%RH.That is, △ MR is hygroscopic index, and the value of △ MR is higher, and snugness of fit is higher.When the △ MR of fiber is 1% or more, in clothes Bored wet sense is few, shows snugness of fit, thus preferably.The △ MR of fiber is more preferably 1.5% or more, further preferably 2% More than.On the other hand, when the △ MR of fiber is 10% or less, process passability, treatability are good, and durability when use is excellent It is different, thus preferably.The △ MR of fiber is more preferably 9% hereinafter, further preferably 8% or less.

For fiber of the invention, since hydrophobic polymer and hydrophilic macromolecule are copolymerized, thus with thin The case where aqueous high molecular is from hydrophilic macromolecule melting mixing is different, and dissolution of the hydrophilic macromolecule into hot water etc. is pressed down System.Therefore, hygroscopic durability is high, can be suitble to be employed as fiber construct.

For fiber of the invention, electricity is charged by friction under conditions of preferable temperature is 10 DEG C, humidity is 10%RH Pressure is 3000V or less.The detailed measuring method for being charged by friction voltage illustrates that being charged by friction voltage is antistatic property below Index, the value for being charged by friction voltage is lower, can more inhibit 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, the not only friction in the case where temperature is 20 DEG C, humidity is 40%RH isothermal humidity environment Electrified voltage is low, and in the case where temperature is 10 DEG C, humidity is the low temperature and low humidities degree environment such as 10%RH, and it is also low to be charged by friction voltage, Excellent antistatic property is presented.The voltage that is charged by friction of fiber under conditions of temperature is 10 DEG C, humidity is 10%RH is When 3000V or less, even if outdoor in winter, due to using heating equipment leading to the low temperature and low humidities such as the low-down interior of humidity It spends under environment, the generation of electrostatic is also few, and snugness of fit is excellent, thus preferably.The condition that temperature is 10 DEG C, humidity is 10%RH Under the voltage that is charged by friction of fiber be more preferably 2500V hereinafter, further preferably 2000V or less.

Fiber of the invention is formed as copolymer by hydrophobic polymer and hydrophilic macromolecule and in addition The composite fibre that other (co) polymers are formed.At this point, it is preferred that the copolymer of hydrophobic polymer and hydrophilic macromolecule is in fibre At least part in dimension table face is exposed.For example, with compound as core sheath using the copolymer of hydrophobic polymer and hydrophilic macromolecule The core component of fiber, by the completely coating fiber of sheath ingredient, with the copolymer of hydrophobic polymer and hydrophilic macromolecule be sea The island component of island composite fibre is compared by the completely coating fiber of sea component, and hydrophobic polymer and hydrophilic macromolecule are total to The fiber of hygroscopicity, excellent antistatic property can be obtained when at least part of fiber surface is exposed in polymers, thus preferably.It needs Even if being noted that using the copolymer of hydrophobic polymer and hydrophilic macromolecule as the core component of core sheath composite fibre In the case of, as long as at least part of core component is exposed in fiber surface, even if with hydrophobic polymer and hydrophily In the case that high molecular copolymer is the island component of island-in-sea type composite fiber, as long as at least part of island component is in fiber surface Exposing.

Fiber of the invention preferably comprises antioxidant.By containing antioxidant, thus not only inhibit because it is long-term certainly, The oxygenolysis of hydrophilic macromolecule caused by roller drying, and improve the hygroscopicity, under low temperature and low humidity degree environment resist it is quiet The durability of the fiber properties such as electrical property, mechanical property, thus preferably.In addition, having in the present invention is (poly- by hydrophobic polymer Ethylene glycol terephthalate) fiber of phase separation structure that-hydrophilic macromolecule (polyethylene glycol) copolymer is formed, and do not have There is polyethylene terephthalate-ethylene glycol copolymer fiber containing homogeneous texture of phase separation structure to compare, oxygen It is high to change decomposability, for the above subject, as described later, present inventors, which have found, can make in fiber containing enough The method of antioxidant, by the method, so as to inhibit oxygenolysis, can stablize while with phase separation structure Ground obtains the fiber of the excellent in te pins of durability of fiber properties such as antistatic property, the mechanical property under hygroscopicity, low temperature and low humidity degree environment.

Antioxidant in the present invention is preferably selected from that phenolic compound, sulphur class compound, be obstructed amine compound.These are anti- Oxidant can be used only a kind, can also be used in combination of two or more.

Phenolic compound in the present invention is that the radical chain reaction inhibitor with phenol structure can be lifted as concrete example 2,6- Butylated Hydroxytoluene, butylated hydroxyanisole (BHA), 2,6- tert-butyl -4- ethyl -phenol, β-(3,5- di-t-butyl -4- hydroxyl out Base phenyl) propionic acid stearyl, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol), 2,2 '-di-2-ethylhexylphosphine oxides (4- ethyl- 6- tert-butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol)s, bis- { 1,1- dimethyl -2- { β-(uncles 3- of 3,9- Butyl -4- hydroxy-5-methyl base phenyl) propiono oxygroup } ethyl } 2,4,8,10- tetra- oxaspiro { 5,5 } hendecane, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane, (3,5- di-t-butyl -4- hydroxyl benzyl of 1,3,5- trimethyl -2,4,6- three Base) benzene, bis- { 3,3 '-bis--(4 '-hydroxyls -3 '-tert-butyl-phenyl) butyric acid } diol esters, tocopherol, pentaerythrite-four (3- (3, 5- di-t-butyl -4- hydroxyl phenol) propionic ester), 2,4,6- tri- (3 ', 5 '-di-t-butyls -4 '-hydroxybenzyl) mesitylene, 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 be used only a kind, can also be used in combination of 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-butyls -4 '-hydroxybenzyl) mesitylene (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 inhibiting the effect of oxygenolysis good, thus preferably use.

Sulphur class compound in the present invention is the sulphur class antioxygen for restoring peroxide with not generating free radicals, itself being oxidized Agent can enumerate 3,3 '-thiodipropionic acid dilauryl esters, 3,3 '-thiodipropionic acid myristyl esters, 3,3 '-as concrete example Thiodipropionic acid distearyl base ester etc., but it is not limited to these.These sulphur class antioxidants can be used only a kind, can also and with 2 kinds with On.

The amine compound that is obstructed in the present invention is the free radical generated under the action of ultraviolet light, heat with capture, makes The amine antioxidant of being obstructed of the regenerated effect of phenol antioxidant for functioning but having inactivated as antioxidant, as tool Body example can enumerate bis- (2,2,6,6- tetramethyl -4- piperidyl -1, the 6- hexa-methylenes two of dibutylamine -1,3,5-triazines-N, N ' - Condensation polymer, poly- [{ 6- (1,1,3,3- tetramethyl butyl) amino-of amine and N- (2,2,6,6- tetramethyl -4- piperidyl) butylamine 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 bis--(butyl-(N- methyl -2,2,6,6- tetramethyl piperidine - 4- yl) amino)-triazine -2- base) -4,7- diaza decane -1,10- diamines 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- piperidyls) and morpholine -2,4,6- Methylated polymer object, -20 (the 2,3- epoxy of 2,2,4,4- tetramethyl -7- oxa- -3,20- diaza of three chloro- 1,3,5- triazines Base-propyl) two spiral shells-[5,1,11,2]-heneicosane -21- ketone polymer etc., but it is not limited to these.These amine systems of being obstructed Can be used only by closing object by a kind, can also be used in combination of two or more.Wherein, from inhibit due to washing, using organic solvent carry out cleaning and From the viewpoint of the caused dissolution from fibrous inside, the high molecular weight type of preferably 1000 or more molecular weight is obstructed amine system chemical combination Object.Especially, bis- (2,2,6,6- tetramethyl -4- piperidyl -1, the 6- hexa-methylenes two of dibutylamine -1,3,5-triazines-N, N ' - The condensation polymer (BASF CHIMASSORB2020) of amine and N- (2,2,6,6- tetramethyl -4- piperidyl) butylamine is due to inhibiting oxygen It is good to change the effect decomposed, thus preferably uses.

The content of antioxidant in fiber of the invention is preferably 0.01~2.0 weight % of fibre weight.In order to send out Antioxidant effect is waved, by being comprised in enough antioxidants in fiber, to can inhibit because of long-term keeping, roller drying Caused by hydrophilic compounds oxygenolysis, improve the hygroscopicity, the antistatic property under low temperature and low humidity degree environment, mechanical property The durability of equal fiber properties, thus preferably.When the content of antioxidant is 0.01 weight % or more, it can assign and inhibit to fiber The effect of oxygenolysis, thus preferably.The content of antioxidant is more preferably 0.05 weight % or more, and further preferably 0.1 Weight % or more, particularly preferably 0.15 weight % or more.On the other hand, when the content of antioxidant is 2.0 weight % or less, The tone of fiber will not deteriorate, and will not damage mechanical property, thus preferably.The content of antioxidant is more preferably 1.7 weights % is measured hereinafter, further preferably 1.5 weight % are hereinafter, particularly preferably 1.0 weight % or less.

For fiber of the invention, the cross sectional shape about fiber is not particularly limited, and can be the circle of round type Tee section is also possible to 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 fiber of the invention, the form about fiber is not particularly limited, and can be monofilament (monofilament), any forms such as multifilament (multifilament), staple fiber (staple).

It is same as general fiber for fiber of the invention, the processing such as false twisting, twisted filament can be carried out, for weaving, It makes up, processing can also be carried out similarly with general fiber.

The form of fiber construct comprising fiber of the invention is not particularly limited, and can be made according to known methods Fabric compiles object, pile fabric, non-woven fabrics or spun yarn, filling cotton etc..In addition, the fiber construct comprising fiber of the invention Can be it is any knit tissue or marshalling knit, can suitably use plain cloth, twills, satin fabric or their variation Knit, warp knit, weft knitting, it is round knitting, lace eyelet stitch or they variation compile etc..

Fiber of the invention can be compiled etc. and other fiber combinations when fiber construct is made by interweaving, handing over, can also be Fiber construct is made after forming the mixed filament with other fibers.

Next, to the manufacturing method of the copolymer of hydrophobic polymer used in the present invention and hydrophilic macromolecule into Row explanation.As concrete example, hereinafter shows and use polyester as hydrophobic polymer, use polyethylene glycol as hydrophily height The manufacturing method for the phase separation structure of molecule formed by polyester-ethylene glycol copolymer.

In the present invention, when manufacturing polyester-ethylene glycol copolymer, firstly, implementing esterification to independent polyester component Or ester exchange reaction, obtain polyester oligomer.It is added with polyethylene glycol in advance next, above-mentioned polyester oligomer is added to In reactive tank.It should be noted that at this point, polyethylene glycol be solid in the case where, it is preferred that be previously heated to 70 DEG C with Above make its melting, and then after adding polyester oligomer into polyethylene glycol, is sufficiently stirred.By so operating, no The polycondensation reaction of polyethylene glycol is only improved, and diffusion of the polyethylene glycol in polyester oligomer is quickly carried out, with The progress of polycondensation reaction and when phase separation structure is presented, the coarsening that can be formed when fine and uniform, melting is detained is repressed Stable dispersed phase.It should be noted that needing to reduce unreacted polyethylene glycol by polyester oligomer and polyethylene glycol It is mixed under compatible state at least 1 hour or more.The obtained phase separation structure formed by polyester-ethylene glycol copolymer In, if coarsening when dispersed phase is fine and uniform, melting is detained is suppressed, fibrosis is being carried out by melt spinning When, fiber number unevenness is small, can inhibit the generation that dyeing is uneven, fluffs.If contrary to the above, polyethylene glycol is added to melting Polyester oligomer in, then specific gravity is locally present lower than the polyethylene glycol of polyester in the upper layer in reactive tank, and polyethylene glycol is to poly- Diffusion in ester oligomer needs for quite a long time.Therefore, the reactivity of polyethylene glycol and polyester reduces, and causes unreacted Polyethylene glycol final residue.In this case, dispersed phase is easy to happen coarsening when melting and being detained, and not only spins by melting Silk and reason when carrying out fibrosis as fiber number unevenness, and in dyeing, when use hydrophilic macromolecule polyethylene glycol The reason of ingredient will be easy to dissolve out, and become the durability reduction of hygroscopicity, antistatic property, it is therefore desirable to pay attention to.

In the present invention, in any reaction in esterification, ester exchange reaction, polycondensation reaction, manufacture polyester can be used When common catalyst.For esterification, it can be carried out under no catalyst, but the conducts such as titanium compound can also be added Catalyst.The concrete example of catalyst as ester exchange reaction can enumerate the compounds such as magnesium, manganese, calcium, cobalt, zinc, lithium, titanium, but not It is limited to these.The concrete example of catalyst as polycondensation reaction, can enumerate the compound of antimony, titanium, germanium etc., but be not limited to these.

In the present invention, in order to improve heat resistance, the tone of fiber, 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 Close object, phosphonous compound, phosphinous compound, phosphine compound etc..These phosphorus compounds can be used alone, can also and with more Kind.

In the present invention, the phosphatization as heat stabilizer can be added in manufacture polyester-ethylene glycol copolymer any stage Close object, can before and after esterification, before and after ester exchange reaction any stage addition.In addition, in order to further increase heat resistance, Tone can will depressurize after adding polycondensation catalyst in reactive tank, additional during since polycondensation reaction until end Add phosphorus compound.In the case where not adding the heat stabilizer, the molecular weight of the polyethylene glycol of hydrophilic macromolecule is reduced, dispersion Stability is detained in the melting of phase to be reduced, and when carrying out fibrosis by melt spinning, becomes the main original for deteriorating fiber number unevenness Cause.

In the present invention, antioxidant can be added in the arbitrary stage, it can be before and after esterification；Before and after ester exchange reaction； It will be depressurized in reactive tank after addition polycondensation catalyst, in any stage addition since polycondensation reaction until end.From When polycondensation reaction is added during starting until end, decompression, any state in normal pressure can be in polycondensation reaction slot.Such as Upper described, the fiber with the phase separation structure formed by polyester-ethylene glycol copolymer in the present invention divides with without phase Polyester-ethylene glycol copolymer fiber containing homogeneous texture from structure is compared, and oxygenolysis is high, it is therefore preferable that making Contain enough antioxidants in fiber, from preventing from causing because of the thermal decomposition in esterification, ester exchange reaction, polycondensation reaction Antioxidant inactivation, from the viewpoint of antioxidant disperses under reduced pressure in polycondensation reaction, be preferably in polycondensation reaction Antioxidant will be added before terminating, and make to become normal pressure in polycondensation reaction slot and be stirred.

In the present invention, in order to improve hydrophobic polymer (polyester)-hydrophilic macromolecule (polyethylene glycol) copolymer point Son amount, the copolymer that benefit can be used to obtain with the aforedescribed process carry out solid phase.Device and method about solid phase does not have There is special limitation, is heated under non-active gas atmosphere or under decompression.As the concrete example of non-active gas, can lift Nitrogen, helium, carbon dioxide etc. out, but it is not limited to these.When being depressurized, preferably make the pressure 133Pa in device hereinafter, this Outside, by reduction pressure, the time required for solid-phase polymerization can be shortened, thus preferably.The treatment temperature of solid phase is excellent It is selected as 150~240 DEG C.When the treatment temperature of solid phase is 150 DEG C or more, polymerization reaction may make to carry out, improve molecular weight, Thus preferably.The treatment temperature of solid phase is more preferably 170 DEG C or more, further preferably 190 DEG C or more.On the other hand, When the treatment temperature of solid phase is 240 DEG C or less, thermal decomposition can inhibit, inhibit molecular weight to reduce, coloring, thus preferably.Gu The treatment temperature of phase-polymerization is more preferably 235 DEG C hereinafter, further preferably 230 DEG C or less.

Above-mentioned hydrophobic polymer (polyester)-hydrophilic macromolecule (polyethylene glycol) copolymer manufacturing method is shown Other concrete examples.It is handed over using the esterification or dimethyl terephthalate (DMT) of terephthalic acid (TPA) and ethylene glycol and the ester of ethylene glycol Change reaction, in esterification slot or ester exchange reaction slot, synthesize bis- (beta-hydroxy ethyl) esters of terephthalic acid (TPA) oligomer (with Under, otherwise referred to as BHT).It is piped by transfer, by BHT from the reactive tank to the polycondensation reaction for being heated to 250~270 DEG C When slot shifts, the polyethylene glycol for having heated melting is put into polycondensation reaction slot in advance, shifts BHT thereto.Then, by into It stirs within row about 1 hour, spreads polyethylene glycol sufficiently in BHT.Next, addition polycondensation catalyst, be decompressed to 500Pa with Under, it carries out reacting for 3~5 hours in 260~300 DEG C, polyethylene terephthalate-polyethylene glycol copolymerization can be obtained as a result, Object.

It is raw with the progress of the polycondensation reaction of the BHT and polyethylene glycol of the precursor as polyethylene terephthalate At low polar copolymer, i.e. polyethylene terephthalate in strand the shared high copolymer of ratio and high pole Property copolymer, the i.e. polyethylene glycol high copolymer of ratio shared in strand, it is above-mentioned (poly- to benzene by hydrophobic polymer Naphthalate)-hydrophilic macromolecule (polyethylene glycol) copolymer formed phase separation structure be by above-mentioned low polar The polar difference of copolymer and highly polar copolymer and present.In addition, the size of the dispersed phase in phase separation structure can Pass through the number-average molecular weight of polyethylene glycol, the copolymerization rate, the temperature of polycondensation reaction, mixing speed or polyethylene terephthalate Ester-ethylene glycol copolymer degree of polymerization (molecular weight) is controlled.

As the manufacturing method of fiber of the invention, well known melt spinning method can be used, due to hydrophobicity of the invention The copolymer of macromolecule and hydrophilic macromolecule forms phase separation structure, as the selectable narrow range of spinning condition, therefore, needs Spinning condition is suitably set according to the characteristic of hydrophobic polymer and the copolymer of hydrophilic macromolecule.However, according to aftermentioned Manufacturing method concrete example, although having phase separation structure, but still can stably obtain that fiber number unevenness is small, dyeing is uneven, rises The repressed fiber of generation of hair.

In general, incompatible polymer blend, polymer alloy system in, just from spinning head discharge polymer Afterwards, due to Barus effect, spinning threadling is expanded, and refinement behavior is easy to become unstable, in extreme circumstances, sometimes can not Carry out fibrosis.In addition, obtained fiber is also because uneven big, the generation dyeing unevenness of fiber number, fluffing due to cause to become low-quality.It closes The method of the expansion of spinning threadling caused by reducing because of Barus effect, it is known to following methods: such as Japanese Unexamined Patent Publication 2009- Recorded in No. 79318 bulletins, by reducing discharge linear velocity, shear velocity improves discharge stability；Such as Japanese Unexamined Patent Publication It is recorded in 2011-202289 bulletin, compatibility is improved by adding expanding material；Etc..About hydrophobicity of the invention The copolymer of macromolecule and hydrophilic macromolecule, also due to phase separation structure is formed, therefore, although in order to inhibit to imitate because of John Burroughs The expansion of spinning threadling caused by answering, and discharge linear velocity, shear velocity are reduced, but unstable from the discharge of spinning head, it obtains Fiber fiber number it is uneven big, it is seen that a large amount of dyeing is uneven, fluffing.But, present inventors have found, with reduce because The conventional method of the expansion of spinning threadling can make on the contrary, by improving discharge linear velocity, shear velocity caused by Barus effect From the discharge of spinning head stabilize, although have phase separation structure, can stably obtain fiber number unevenness it is small, dyeing not , the repressed fiber of generation to fluff.This is considered because as described above, by hydrophobic polymer (poly terephthalic acid second Diol ester) phase separation structure that is formed of-hydrophilic macromolecule (polyethylene glycol) copolymer has following such characteristics: it is melting In the case where assigning shearing under state, phase separation structure differential dispersion disappears soon, but stops assigning and shear and by a timing Between when, phase separation structure is presented again.

Shearing speed in the present invention, when the copolymer of hydrophobic polymer and hydrophilic macromolecule preferably being made to pass through spinning head Degree is 10000~40000s^-1.Shear velocity when passing through spinning head depends on the discharge-amount of every single hole of spinning head, discharge hole The melt viscosity of the copolymer of diameter, hydrophobic polymer and hydrophilic macromolecule.Shear velocity when passing through spinning head is 10000s^-1When above, stablize from the discharge of spinning head, can be obtained that fiber number unevenness is small, dyeing is uneven, the generation of fluffing is repressed Fiber, thus preferably.Shear velocity when passing through spinning head is more preferably 12000s^-1More than, further preferably 15000s^-1 More than.On the other hand, shear velocity when passing through spinning head is 40000s^-1When following, spinning stress is not too high, from spinning head Discharge stablize, therefore, the generation that sharkskin (sharkskin), melt fracture (melt fracture) etc. can be obtained is suppressed, is fine The uneven repressed fiber of generation that is small, dyeing uneven fluffing of degree, thus preferably.Shear velocity when passing through spinning head is more excellent It is selected as 38000s^-1Hereinafter, further preferably 35000s^-1Below.

In the manufacture of fiber of the invention, discharge linear velocity is preferably 10~100m/ minutes.Discharge linear velocity depends on spray The discharge-amount of every single hole of silk head, discharge aperture, hydrophobic polymer and hydrophilic macromolecule copolymer melt viscosity.It spits Out linear velocity be 10m/ minute or more when, from the discharge of spinning head stablize, can be obtained fiber number unevenness it is small, dyeing unevenness, fluff Repressed fiber occurs, thus preferably.Discharge linear velocity is more preferably 15m/ minutes or more, further preferably 20m/ minutes More than.On the other hand, when discharge linear velocity is 100m/ minutes or less, spinning stress is not too high, steady from the discharge of spinning head Fixed, therefore, the generation that can be obtained sharkskin, melt fracture etc. is suppressed, fiber number unevenness is small, dyeing is uneven, the generation of fluffing is suppressed Fiber, thus preferably.Discharge linear velocity is more preferably 90m/ minutes hereinafter, further preferably 80m/ minutes or less.

In the manufacture of fiber of the invention, spin-draw ratio is preferably 10~300.Spin-draw ratio can be by fast with spinning Degree is calculated divided by discharge linear velocity.When spin-draw ratio is 10 or more, productivity becomes well, thus preferably.Spin-drawing Than being more preferably 20 or more, further preferably 30 or more.On the other hand, when spin-draw ratio is 300 or less, spinning stress is not Can be excessively high, spinnability becomes that the repressed fiber of generation that fiber number unevenness is small, dyeing is uneven, fluffs well can be obtained, thus excellent Choosing.Spin-draw ratio is more preferably 250 hereinafter, further preferably 200 or less.

Spinning head used in the present invention can be used well known spinning head, discharge hole count can as expected silk number it is appropriate Selection.Discharge aperture can suitably be selected according to shear velocity, discharge linear velocity, spin-draw ratio, preferably 0.05~0.50mm. When discharge aperture is 0.05mm or more, the pressure in filament spinning component is not too high, stablizes from the discharge of spinning head, fiber number can be obtained The uneven repressed fiber of generation that is small, dyeing uneven fluffing, thus preferably.Discharge aperture is more preferably 0.10mm or more, into One step is preferably 0.15mm or more.On the other hand, when discharge aperture is 0.50mm or less, the backside pressure of spinning head will not Foot, the discharge that can inhibit between the discharge hole of spinning head is uneven, thus preferably.Furthermore it is possible to which spinning speed is not made to reduce and improve Spin-draw ratio, productivity become well, thus preferably.Discharge aperture is more preferably 0.40mm hereinafter, further preferably 0.30mm or less.

In the present invention, preferably before carrying out melt spinning, make being total to for hydrophobic polymer and hydrophilic macromolecule in advance Polymers is dry, makes moisture content 300ppm or less.When moisture content is 300ppm or less, in melt spinning, cause because of hydrolysis Molecular weight reduce, be suppressed because foaming caused by moisture, can steadily carry out spinning, thus preferably.Moisture content is more preferable For 200ppm hereinafter, further preferably 100ppm or less.

In the present invention, antioxidant can be added when carrying out melt spinning.As described above, having by hydrophobic in the present invention Property macromolecule (polyester)-hydrophilic macromolecule (polyethylene glycol) copolymer fiber of phase separation structure for being formed, and do not have phase Polyester-ethylene glycol copolymer fiber containing homogeneous texture of separated structure is compared, and oxygenolysis is high, it is therefore preferable that Make in fiber containing enough antioxidants, it is and total in manufacture polyester-polyethylene glycol in addition, by being added in melt spinning The case where adding when polymers is compared, and can inhibit dispersing, because of antioxidant caused by thermally decomposing for the antioxidant under vacuum Inactivation, thus preferably.As the method for adding antioxidant when carrying out melt spinning, following methods can be enumerated: in advance by polyester- Ethylene glycol copolymer and antioxidant are dry-mixed, then put into the method in melt spinning machine；From respective feeder to molten Melt the method that polyester-ethylene glycol copolymer and antioxidant are put into spinning machine；Etc., but it is not limited to these.

In the present invention, the polyester-ethylene glycol copolymer clast dried in advance is supplied to extruder type, is added The melt spinning machine for pressing fusion etc., makes its melting, is measured with metering pump.Then, it is directed into spinning block (spin Block the heated filament spinning component in), is filtered molten polymer in filament spinning component, then spues from spinning head, Form fiber strand silk.It for the fiber strand silk to spue from spinning head, is cooled to solidify using cooling device, with the 1st godet Drawing, via the 2nd godet, is wound using up- coiler (winder), forms undrawn yarn.It should be noted that in order to mention As needed the heating of 2~20cm long can be arranged in spinning head lower part in high spinning operability, productivity, the mechanical property of fiber Cylinder, heat-preservation cylinder.In addition, it is possible to use feeding means is to fiber strand silk oil supply, it is possible to use interlacing device is assigned to fiber strand silk Interlacing.

Spinning temperature in melt spinning can be according to the fusing point of hydrophobic polymer and the copolymer of hydrophilic macromolecule, resistance to Hot equal appropriate selection, preferably 240~320 DEG C.When spinning temperature is 240 DEG C or more, from the fiber strand silk of spinning head discharge Elongation viscosity sufficiently reduce, thus spue and stablize, in addition, spinning tension will not become excessively high, can inhibit fracture of wire, thus excellent Choosing.Spinning temperature is more preferably 250 DEG C or more, further preferably 260 DEG C or more.On the other hand, spinning temperature be 320 DEG C with When lower, thermal decomposition when spinning can inhibit, can inhibit reduction, the coloring of the mechanical property of fiber, thus preferably.Spinning temperature is more Preferably 310 DEG C hereinafter, further preferably 300 DEG C or less.

Spinning speed in melt spinning can be according to the composition of hydrophobic polymer and the copolymer of hydrophilic macromolecule, spinning The appropriate selection such as silk temperature, spin-draw ratio.Two works for formerly carrying out melt spinning and being wound and then separately being stretched Spinning speed in the case where sequence method is preferably 500~5000m/ minutes.When spinning speed is 500m/ minutes or more, traveling silk Item is stablized, and can inhibit fracture of wire, thus preferably.Spinning speed in the case where two process methods is more preferably 1000m/ minutes or more, Further preferably 1500m/ minutes or more.On the other hand, it when the spinning speed of two process methods is 5000m/ minutes or less, can incite somebody to action Fiber strand silk is fully cooled, and can carry out stable spinning, thus preferably.Spinning speed in the case where two process methods is more preferably 4500m/ minutes hereinafter, further preferably 4000m/ minutes or less.In addition, carrying out spinning simultaneously for not being wound first For the spinning speed in the case where a process method of stretching, preferably makes low speed roller 500~5000m/ minutes, make high speed roller It is 3000~6000m/ minutes.When low speed roller and high speed roller are in above-mentioned range, not only traveling strand is stablized, but also can inhibit Fracture of wire can carry out stable spinning, thus preferably.For the spinning speed in the case where a process method, more preferably make low Fast roller be 1000~4500m/ minutes, make high speed roller 3500~5500m/ minutes, further preferably make low speed roller 1500~ 4000m/ minutes, make high speed roller 4000~5000m/ minutes.

In the case where being stretched using a process method or two process methods, using a stage pulling method or two-stage with On multistage pulling method in any method carry out.As the heating means in stretching, 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 baths, the laser such as the liquid baths such as plate, warm water, hot water, hot-air (heating air), steam etc., but it is not limited to these.These add Hot method can be used alone, and can also be used together by more than one.As heating means, carried out from control heating temperature, to traveling strand uniform From the viewpoint of heating, device are uncomplicated, preferably using contact with heating roller, with it is fast-selling contact and contact heater plate, in liquid The method impregnated in body bath.

Stretching ratio in the case where being stretched can suitably be selected according to intensity, elongation of the fiber after stretching etc., Preferably 1.02~7.0 times.When stretching ratio is 1.02 times or more, intensity, elongation of fiber etc. can be improved by stretching Mechanical property, thus preferably.Stretching ratio is more preferably 1.2 times or more, further preferably 1.5 times or more.On the other hand, it draws When to stretch multiplying power be 7.0 times or less, it can inhibit fracture of wire when stretching, can carry out stable stretching, thus it is preferred.Stretching ratio is more excellent 6.0 times are selected as hereinafter, further preferably 5.0 times or less.

Draft temperature in the case where being stretched can suitably be selected according to intensity, elongation of the fiber after stretching etc., Preferably 60~150 DEG C.When draft temperature is 60 DEG C or more, the preheating of the strand for stretching is sufficiently carried out, when stretching Thermal deformation becomes the generation that uniformly can inhibit fiber number unevenness, thus preferably.Draft temperature is more preferably 65 DEG C or more, further Preferably 70 DEG C or more.On the other hand, when draft temperature is 150 DEG C or less, it can inhibit the thermal decomposition of fiber, thus preferably.Separately Outside, fiber becomes well relative to the sliding property of draw roll, thus can inhibit fracture of wire, can carry out stable stretching, thus preferably. Draft temperature is more preferably 145 DEG C hereinafter, further preferably 140 DEG C or less.In addition, as needed, 60~150 DEG C can be carried out Heat fixation.

Which in a process method or two process methods tensile speed in the case where being stretched can be according to drawing process Kind etc. and suitably selected.In the case where one process method, the speed of the high speed roller of above-mentioned spinning speed is equivalent to tensile speed. Tensile speed in the case where being stretched using two process methods is preferably 30~1000m/ minutes.Tensile speed is 30m/ minutes When above, traveling strand is stablized, and can inhibit fracture of wire, thus preferably.Stretching speed in the case where being stretched using two process methods Degree more preferably 50m/ minutes or more, further preferably 100m/ minutes or more.On the other hand, tensile speed is 1000m/ points When below clock, fracture of wire when stretching can inhibit, can carry out stable stretching, thus preferably.It is stretched using two process methods In the case of tensile speed be more preferably 800m/ minutes hereinafter, further preferably 500m/ minutes or less.

In the present invention, as needed, it can be dyed 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 suitably can use cheese dyeing according to known methods Machine, liquid-flow dyeing machine, drum dyeing machine, package dyeing machine, dye jigger, high pressure jig etc..

It in the present invention, is not particularly limited about dye strength, dyeing temperature, can suitably use well known method.Separately Outside, as needed, it can be carried out before dyeing process concise, reduction washing can also be carried out after dyeing process.

Fiber of the invention and dyeing containing its fiber construct is uneven, generation of fluffing is suppressed is hygroscopicity, low Excellent antistatic property under warm low-humidity environment, dyeing when, use when hydrophilic compounds dissolution be suppressed.Therefore, may be used Require quality, comfort with suitably using on the way.For example, general dress material purposes, movement 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 described in more detail by embodiment.It should be noted that each characteristic value in embodiment is benefit The value acquired with the following method.

A. fiber number

In the environment of temperature is 20 DEG C, humidity is 65%RH, INTEC system electronic gauging machine (Japanese original text: electronic is used Dipping machine), strand takes the fiber 100m as obtained from embodiment.The weight for measuring obtained hank knotting calculates fiber number using following formula (dtex).It should be noted that 5 measurements are carried out for 1 sample, using its average value as fiber number.

Fiber number (dtex)=100m fiber weight (g) × 100

B. intensity, elongation

For intensity and elongation, the fiber as obtained from embodiment is as sample, according to JIS L1013: 1999 (chemical fiber filament yarn test methods) 8.5 are calculated.In the environment of temperature is 20 DEG C, humidity is 65%RH, make With Shimadzu Seisakusho Ltd.'s autoclave AG-50NISMS type, in the item that initial samples length is 20cm, tensile speed is 20cm/ minutes Tension test is carried out under part.With the stress (cN) for the point for showing peak load divided by fiber number (dtex), intensity (cN/ is calculated Dtex), elongation is calculated using following formula using the elongation (L1) and initial samples length (L0) of the point of display peak load (%).It should be noted that 10 measurements are carried out for 1 sample, using its average value as intensity and elongation.

Elongation (%)={ (L1-L0)/L0 } × 100

C. toughness

Using the intensity (cN/dtex) and elongation (%) calculated in above-mentioned B, the toughness of fiber is calculated using following formula.

Toughness=intensity × (elongation)^1/2

D. initial tensile resistance degree

For initial tensile resistance degree, using the fiber obtained using embodiment as sample, according to JIS L1013: 1999 (chemical fiber filament yarn test methods) 8.10 are calculated.It is carried out similarly tension test with above-mentioned B, draws load- Extension curve finds out the maximum point of the load variations relative to variable elongation, uses JIS near the origin of the curve The formula recorded in L1013:1999 (chemical fiber filament yarn test method) 8.10 calculates initial tensile resistance degree (cN/ dtex).It should be noted that 5 measurements are carried out for 1 sample, using its average value as initial tensile resistance degree.

E. boiling water shrinkage

In the environment of temperature is 20 DEG C, humidity is 65%RH, using 1m/ weeks gauging machine, make by passing through embodiment Obtained fibroplastic hank knotting (volume number 10 encloses), stands 24 hours.Then, in the present context, apply 0.09cN/ to hank knotting The load of dtex measures specimen length L0.Next, handled in 98 DEG C of boiling water zero loadly hank knotting 15 minutes, it is then empty Gas is 24 hours dry, applies the load of 0.09cN/dtex to hank knotting, measures specimen length L1.Using in boiling water before and after the processing Specimen length L0, L1, utilize following formula calculate boiling water shrinkage (%).It should be noted that carrying out 3 surveys for 1 sample It is fixed, using its average value as boiling water shrinkage.

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

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

With epoxy resin embedding fiber as obtained from embodiment, then using LKB ultramicrotome LKB-2088, The ultra-thin section of thickness about 100nm is obtained along the direction cutting fibre vertical with fiber axis together with epoxy resin.By what is obtained Ultra-thin section keeps in the gas phase of ruthenium tetroxide, at normal temperature about 4 hours and is dyed, and is then cut off with ultramicrotome Face through dyeing, the ultra-thin section that production is dyed with ruthenium tetroxide.For the ultra-thin section through dyeing, Hitachi's system is used Transmission electron microscope (TEM) H-7100FA type cuts vertical with fiber axis under conditions of acceleration voltage is 100kV Face, i.e. fiber cross section are observed, and the microscope photo of fiber cross section is shot.With 2000 times, 8000 times, 20000 times, 40000 times of each multiplying power is observed, and when shooting microscope photo, selection can observe the highest of 300 or more dispersed phases Multiplying power.300 points randomly selected are measured using image analysis software (three paddy business WinROOF) for the photo of shooting The diameter of dephasing, using its maximum value as the maximum gauge (nm) of the dispersed phase in fiber cross section.Due in fiber cross section Existing dispersed phase is not necessarily positive round, therefore, in the case where not being positive round, measure area, using when being scaled positive round Diameter of the diameter as dispersed phase.

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

With epoxy resin embedding fiber as obtained from embodiment, then using LKB ultramicrotome LKB-2088, The ultra-thin section of thickness about 100nm is obtained along the direction cutting fibre parallel with fiber axis together with epoxy resin.By what is obtained Ultra-thin section keeps in the gas phase of ruthenium tetroxide, at normal temperature about 4 hours and is dyed, and is then cut off with ultramicrotome Face through dyeing, the ultra-thin section that production is dyed with ruthenium tetroxide.For the ultra-thin section through dyeing, Hitachi's system is used Transmission electron microscope (TEM) H-7100FA type cuts parallel with fiber axis under conditions of acceleration voltage is 100kV Face, i.e. fiber longitudinal section are observed, and the microscope photo of fiber longitudinal section is shot.With 2000 times, 8000 times, 20000 times, 40000 times of each multiplying power is observed, and when shooting microscope photo, selects the dispersion it is observed that 300 or more striateds The highest multiplying power of phase.Random choosing is measured using image analysis software (three paddy business WinROOF) for the photo of shooting The diameter of 300 dispersed phases taken, using its maximum value as the maximum gauge (nm) of the dispersed phase in fiber longitudinal section.It needs Illustrate, for the diameter of the dispersed phase in fiber longitudinal section, is measured for the direction vertical with fiber axis.

H. fiber number change value U% (hi)

For fiber number change value U% (hi), the fiber as obtained from embodiment uses Star ェ Le as sample ベガーウースターウースターテスター 4-CX, finding speed be 200m/ minutes, minute 2.5 Minute, measurement fibre length are 500m, twisting count is measurement U% (half inert) under conditions of 12000/m (S twirl).It needs It is bright, 5 measurements are carried out for 1 sample, using its average value as fiber number change value U% (hi).

I. filament diameter CV%

With platinum-palladium alloy will the fiber as obtained from embodiment vapor deposition after, use Hitachi's scanning electron microscope (SEM) S-4000 type observes section, the i.e. fiber cross section vertical with fiber axis, shoots the microscope photo of fiber cross section. It is observed with 100 times, 300 times, 500 times, 1000 times, 3000 times, 5000 times, 10000 times of each multiplying power, shooting microscope shines When piece, the highest multiplying power it is observed that whole monofilament in sample is selected.For the photo of shooting, image analysis software is used (three paddy business WinROOF) measures filament diameter.In the case that number of monofilaments in the sample is 50 or more, measurement is random The filament diameter for 50 monofilament chosen, in the case that number of monofilaments in the sample is less than 50, using making under the same conditions The multiple samples made measure the filament diameter of total 50 monofilament.Since fiber cross section is not necessarily positive round, not In the case where being positive round, area is measured, using diameter when being scaled positive round as filament diameter.Calculate being averaged for filament diameter It is worth the standard deviation (σ) of (X), filament diameter, then calculates filament diameter CV% using following formula.

Filament diameter CV%=(σ/X) × 100

J. filament number CV%

For filament number, the fiber as obtained from embodiment is broken down into monofilament, so as sample Afterwards, using サーチ society automatic vibration formula fineness tester DC-11, make to measure specimen length 25mm, assign measurement sample Fiber number (danier scaled value) × 0.4g load, apply frequency be 1880Hz vibration, be measured.List in the sample In the case that silk number is 20 or more, the filament number of 20 monofilament randomly selected is measured, number of monofilaments in the sample is insufficient In the case where 20, using the multiple samples manufactured under the same conditions, the filament number of total 20 monofilament is measured.It calculates single Then the standard deviation (σ) of the average value (X) of silk size, filament number calculates filament number CV% using following formula.

Filament number CV%=(σ/X) × 100

K. filament strength CV%, monofilament elongation CV%

For filament strength and monofilament elongation, the fiber as obtained from embodiment is as sample, by its point Then solution Cheng Dansi is calculated according to JIS L1013:1999 (chemical fiber filament yarn test method) 8.5.It is in temperature 20 DEG C, humidity be 65%RH in the environment of, using Shimadzu Seisakusho Ltd.'s オートグラ Off AG-50NISMS type, in initial samples Length is 5cm, tensile speed carries out tension test under conditions of being 20cm/ minutes.It will show the stress of the point of peak load (cN) it is used as filament strength, is calculated using the elongation (L1) and initial samples length (L0) of the point of display peak load using following formula Monofilament elongation (%) out.In the case that number of monofilaments in the sample is 50 or more, 50 monofilament randomly selected are measured Filament strength and monofilament elongation use what is manufactured under the same conditions in the case that number of monofilaments in the sample is less than 50 Multiple samples measure the filament strength and monofilament elongation of total 50 monofilament.About filament strength, monofilament elongation, respectively Average value (X), standard deviation (σ) are calculated, then, using following formula, calculates filament strength CV%, monofilament elongation CV%.

Elongation (%)={ (L1-L0)/L0 } × 100

Filament strength CV%=(σ/X) × 100

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

L. the content of unreacted PEG (polyethylene glycol)

500mg fiber as obtained from embodiment is weighed into screw thread test tube (screw tube), addition 2mL hexafluoro is different Propyl alcohol stands 24 hours, makes it dissolve in the environment of temperature is 20 DEG C, humidity is 65%RH.It is added into screw thread test tube Mixed liquor is moved to 100mL volumetric flask by 2mL chloroform, and then the residue into screw thread test tube adds 6mL chloroform, is moved to above-mentioned In volumetric flask, and then acetonitrile is added into volumetric flask, be settled to 100mL.Using filtering by by addition acetonitrile be precipitated at Point remove, concentrated the filtrate to using evaporator it is dry, with 5mL acetonitrile constant volume.Solution after 1mL constant volume is moved into 10mL capacity Bottle, is settled to 10mL with acetonitrile, is then filtered with 0.45 μm of PTFE filter, measures obtained filtrate as HPLC Use sample.Using the sample, under the following conditions, using HPLC device (Shimadzu Seisakusho Ltd. LC-20A), HPLC survey is carried out It is fixed, using the standard curve of ready-made standard substance (PEG), the PEG contained in HPLC measurement sample is quantified, Calculate the unreacted PEG content (wt%) contained in the fiber as obtained from embodiment.It should be noted that for 1 examination Sample carries out 5 measurements, using its average value as unreacted PEG content.

(internal diameter 3mm, length 150mm, partial size are 5 μ to column: ジーエ Le サイエ Application ス Inertsil ODS-3 m)

Detector: Shimadzu Seisakusho Ltd. ELSD

Mobile phase: water (solvent A), acetonitrile (solvent B)

Time-program(me): 0 → 15 minute (solvent A: solvent B=60:40 → 0:100), 15 → 25 minutes (solvent As: solvent B =0:100)

Flow velocity: 0.8mL/ minutes

Injection rate: 10 μ L

Column temperature: 45 DEG C

Standard substance: PEG

M. oxidation preventive content

Added in the fiber as obtained from embodiment to 500mg the 1mol/L of 25mL sodium methoxide-methanol solution and 25mL methyl acetate, flow back within 1 hour, then adds 2mL acetic acid and is neutralized.Using rotary evaporator, make after neutralizing Mixed liquor is concentrated to dryness, and is added 50mL water, is then extracted with 20mL chloroform, be separated into chloroform layer and water layer.Use rotation Chloroform layer is concentrated to dryness by evaporator, adds 2.5mL chloroform, chromatography determination sample is made.Using the sample, GC is carried out Measurement or HPLC measurement use chromatography determination using the standard curve of standard substance (antioxidant used in embodiment) The antioxidant contained in sample is quantified, and the oxidation preventive content contained in the fiber as obtained from embodiment is calculated (wt%).It should be noted that 5 measurements are carried out for 1 sample, using its average value as oxidation preventive content.

N. reach the time for rising half value point

10mg sample is put into aluminium vessel by the fiber as obtained from embodiment as sample, utilizes セイ U ーイ Application ス Star Le メ Application ト TG-DTA, in nitrogen: under oxygen=80vol%:20vol% mixed-gas atmosphere, making mixed gas Flow is 200mL/ minutes, with 30 DEG C/min of heating rate from room temperature to 160 DEG C, is then kept for 360 points in 160 DEG C Clock.Then, thermoconductive TGA (DTG) is carried out using analysis software (セイコーイ Application ス Star Le メ Application ト system, Muse), it will The time for reaching 160 DEG C, calculate the peak DTG reached the time (min) for rising half value point as 0 minute.Before reaching 160 DEG C In the case where the rising half value point for the peak DTG occur, the time for being up to rising half value point is denoted as negative value, is that 160 DEG C keep 360 In the case where not observing the peak DTG during minute, the time for being up to rising half value point is denoted as 360 minutes or more.It needs to illustrate , 5 measurements are carried out for 1 sample, using its average value as the time for reaching rising half value point.

O. it is charged by friction voltage

The fiber as obtained from embodiment uses English light industry circular knitter NCR-BL (barrel dliameter 3 as sample Inch half (8.9cm), 27gauge), production about 2g is tubular knitted, is then containing 1g/L sodium carbonate, solar corona chemistry control surface It is 20 minutes concise in 80 DEG C in the aqueous solution of activating agent サンモー Le BK-80, then done in 60 DEG C of hot air drying machine Dry 60 minutes.

For being charged by friction voltage (V), will be concise after it is tubular knitted be used as sample, temperature be 10 DEG C, it is wet Degree is to be calculated under 10%RH atmosphere according to JIS L1094:1997 (fabric and the charging property test method for compiling object) 5.2.It needs It is noted that carry out 5 measurements for 1 sample, using its average value as being charged by friction voltage.

P. hydroscopicity is poor (△ MR)

By made in the same manner as above-mentioned O it is concise after it is tubular knitted as sample, (knitted according to JIS L1096:2010 Object and compile object blank test method) 8.10 moisture rate, calculate hydroscopicity (%).Firstly, in 110 DEG C to it is tubular knitted into It is dried in vacuo within row 24 hours, the tubular knitted weight (W0) when measurement parches.Next, it is adjusted at 20 DEG C of temperature, In the エスペッ Network constant temperature and humidity machine LHU-123 of humidity 65%RH, make tubular knitted standing 24 hours, measures tubular needle The weight (W1) of fabric, then it is adjusted at 30 DEG C of temperature, humidity 90%RH constant temperature and humidity machine in make it is tubular knitted quiet It sets 24 hours, measures tubular knitted weight (W2).It is calculated from the state of parching by tubular knitted weight W0, W1 in temperature 20 DEG C, the hydroscopicity MR1 (%) for standing 24 hours under humidity 65%RH atmosphere, by tubular knitted weight W0, W2 calculate from The hydroscopicity MR2 (%) when state is stood 24 hours under 30 DEG C of temperature, humidity 90%RH atmosphere is parched, is calculated and is inhaled using following formula Wet rate is poor (△ MR).It should be noted that 5 measurements are carried out for 1 sample, using its average value as the poor (△ of hydroscopicity MR)。

Poor (△ MR) (the %)=MR2-MR1 of hydroscopicity

Q. the weight reduction rates after hot water treatment

The fiber as obtained from embodiment uses English light industry circular knitter NCR-BL (barrel dliameter 3 as sample Inch half (8.9cm), 27gauge), production about 2g is tubular knitted, then bath raio is 1:50, treatment temperature is 25 DEG C, place The reason time is to be impregnated into ethyl alcohol under conditions of 1 minute by tubular knitted.Total 3 dippings in ethanol are repeated, The finish being attached on tubular knitted is removed, drying in 60 minutes is carried out in 60 DEG C of hot air drying machine, then measures cylinder The weight (W0) of shape knitted fabric.It should be noted that using new ethyl alcohol in each dipping.Next, being 1 in bath raio: 100, hot water treatment is carried out under conditions for the treatment of temperature is 100 DEG C, the processing time is 60 minutes.In 60 DEG C of hot air drying machine The interior tubular knitted carry out drying in 60 minutes to after hot water treatment, then measures tubular knitted weight (W1).Use cylinder Weight W0, W1 of shape knitted fabric, the weight reduction rates (%) using following formula, after calculating hot water treatment.It should be noted that being directed to 1 sample carries out 3 measurements, using its average value as weight reduction rates.

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

R. equalization

For made in the same manner as above-mentioned O it is concise after it is tubular knitted, in 160 DEG C of progress xeothermic fixation in 2 minutes, needle To tubular knitted after xeothermic fixation, Japanese chemical drug Kayalon Polyester of the 4 weight % of addition as disperse dyes Black EX-SF200, in the dyeing liquor that pH is adjusted to 5.0, bath raio is 1:100, dyeing temperature is 130 DEG C, dyeing Time is to be dyed under conditions of 60 minutes.It should be noted that 4 weight % of addition are as sun in embodiment 38~47 The hodogaya chemical industry Cathilon Blue FB-DP of ionic dye, in the dyeing liquor that pH is adjusted to 4.0, Bath raio is 1:100, dyeing temperature is 130 DEG C, dyeing time is dyed under conditions of being 60 minutes.For the tubular after dyeing Knitted fabric carries out following judgements by 5 inspectoral panel discussions with 5 years or more quality judging experiences: will " very It is colored evenly, does not find that dyeing is uneven completely " it is determined as ◎, " it will substantially evenly be colored, and almost not find dyeing not " it is determined as zero, " almost not by level dyeing, indistinctly confirm dyeing uneven " is determined as △, will " not by level dyeing, It is uneven clearly to confirm dyeing " be determined as ×, using zero, ◎ as qualification.

S. quality

For tubular knitted after dyeing in above-mentioned R, pass through 5 inspections with 5 years or more quality judging experiences The panel discussion of member, carries out following judgements: " will be completely absent fluffing, quality is very excellent " and be determined as ◎, " will there's almost no Hair, excellent quality " is determined as zero, " will have fluffing, poor quality " and be determined as △, will " there are a large amount of fluffings, quality is excessively poor " Be determined as ×, using zero, ◎ as qualification.

Embodiment 1

Bis- (beta-hydroxy ethyl) the ester about 100kg of terephthalic acid (TPA) are put into esterification slot, are kept in 250 DEG C of temperature Afterwards, through 2.5 hours successively supplying high purity terephthalic acid (TPA) (Mitsui Chemicals system) 89.2kg and ethylene glycol (Japanese catalyst system) 39.8kg slurry.After supply, carries out esterification 2 hours, obtain esterification reaction product.Next, successively to contracting The poly- second two of ethylene glycol (Japanese catalyst system) 13.6kg, the number-average molecular weight 8300 for being heated to 70 DEG C and having melted are put into poly- slot Then alcohol (Sanyo chemical conversion industry PEG6000S) 16.8kg is piped by the transfer of connection esterification slot and polycondensation slot, will Obtained esterification reaction product 110.6kg is transferred in the polycondensation slot for being heated to 250 DEG C.After the completion of transfer, stirred in 250 DEG C It mixes 1 hour.Then, pentaerythrite-four (3- (3,5- bis- uncles of the addition as antioxidant (being added before polycondensation reaction starts) Butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, silicon (the モメ Application ティ Block as defoaming agent パ Off ォーマ Application スマテリア Le ズ system, TSF433) 120g, trimethyl phosphate (the He Guangchun medicine as heat stabilizer System) 30g and stir 10 minutes, then, addition as the antimony trioxide 30g of polymerization catalyst, manganese acetate 22g and stirring 5 minutes. Next, the temperature in polycondensation slot is warming up to 285 DEG C from 250 DEG C through 60 minutes, while by the pressure in polycondensation slot from atmosphere Pressure is decompressed to 25Pa, then, carries out polymerization reaction 3 hours.Polymerization reaction product is spued with harness shape into cold water and is made It is cooled down, and is cut obtain granular polymerization reaction product immediately.It utilizes¹The polymerization that H-NMR confirmed is anti- The copolymerization rate for answering the polyethylene glycol in product is 14 weight %.

After carrying out 12 hours being dried in vacuo to obtained particle in 150 DEG C (the moisture content 95ppm after dry), it is supplied to To extruder type spinning machine and make its melting, under conditions of spinning temperature is 290 DEG C, discharge-amount is 57g/ minutes, from spinneret Spue obtains spinning strand head (discharge aperture is 0.23mm, and a length of 0.60mm in discharge hole, discharge hole count is 36, circular hole).With This is spun strand cooling by 20m/ minutes 20 DEG C of wind-warm syndrome, wind speed cooling winds, is assigned finish with feeding means and is made its boundling, uses It is used with the 1st godet drawing of rotation in 3000m/ minutes via the 2nd godet rotated with speed identical with the 1st godet Up- coiler winding, obtains the undrawn yarn of 190dtex-36f.The 1st heat roller temperature is 90 DEG C, the 2nd heat roller temperature is 130 DEG C, Stretching ratio stretches obtained undrawn yarn under conditions of being 1.9 times, obtains the drawn yarn of 100dtex-36f.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 1.It is the intensity of obtained fiber, tough The fiber properties such as property are good.Fiber has phase separation structure, and the maximum gauge of the dispersed phase in fiber cross section is 30nm, fiber The maximum gauge of dispersed phase in longitudinal section is 31nm, and pole is imperceptibly dispersed.In addition, though there is phase separation structure, but U% (hi) is 1.0%, is very uniform fiber.About cloth and silk characteristic, antistatic property, hygroscopicity are very excellent.In addition, hot Weight reduction rates after water process are also low, and the dissolution of hydrophilic compounds is suppressed, also, equalization, quality are also qualified water It is flat.

Embodiment 2~4

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

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 1.With hydrophilic macromolecule The copolymerization rate is lower, and the fiber properties such as intensity, toughness improve, and the maximum of fiber cross section and the dispersed phase in fiber longitudinal section is straight Diameter reduces, and U% (hi) becomes good.On the other hand, getting higher with the copolymerization rate of hydrophilic macromolecule, antistatic property, moisture absorption Property becomes good.

Embodiment 5~7

In addition to this discharge aperture for changing spinning head as shown in table 1 makes drawn yarn similarly to Example 4.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 1.With the becoming smaller of discharge aperture, Shear velocity when passing through spinning head is got higher, and the fiber properties such as intensity, toughness improve, in fiber cross section and fiber longitudinal section The maximum gauge of dispersed phase reduces, and U% (hi) becomes good.

Embodiment 8,9

The copolymerization rate of hydrophilic macromolecule is changed as shown in table 2, and in addition to this, production stretches similarly to Example 7 Silk.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 2.Even if changing hydrophily In the case where high molecular the copolymerization rate, U% (hi) is also low, has obtained the fiber of homogeneous.

Embodiment 10,11

Number-average molecular weight, the spinning head (discharge aperture) of hydrophilic macromolecule are changed as shown in table 2, in addition to this, with Embodiment 4 similarly makes drawn yarn.It should be noted that being divided equally in embodiment 10 using number as hydrophilic macromolecule The polyethylene glycol (Sanyo chemical conversion industry PEG10000) of son amount 11000, uses number-average molecular weight 20000 in embodiment 11 Polyethylene glycol (Sanyo chemical conversion industry PEG20000).

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

Embodiment 12,13

Spinning speed is changed as shown in table 2, in embodiment 12, makes 5.7 times of stretching ratio, in embodiment 13, Make 2.85 times of stretching ratio, in addition to this, makes drawn yarn similarly to Example 1.

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

Embodiment 14

The citric acid Ti chelator of 10ppm will be equivalent in terms of titanium atom relative to obtained polymerization reaction product to be scaled Complex compound, high purity terephthalic acid (Mitsui Chemicals system) 82.5kg and 1,3-PD 49.1kg are remaining temperature 240 DEG C, pressure 1.2 × 10⁵In the esterification slot of Pa, esterification is carried out, until the temperature of distillate is lower than 90 DEG C, obtains ester Change reaction product.Next, the number for successively putting into 1,3-PD 16.7kg into polycondensation slot, being heated to 70 DEG C and having melted Polyethylene glycol (Sanyo chemical conversion industry PEG6000S) 16.8kg of average molecular weight 8300, then, by connecting esterification slot It is piped with the transfer of polycondensation slot, obtained esterification reaction product 110.6kg is transferred to and has been heated to 240 DEG C of polycondensation slot In.After the completion of transfer, stirred 1 hour in 240 DEG C.Then, addition is as antioxidant (adding before polycondensation reaction starts) Pentaerythrite-four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, as disappearing Silicon (モメ Application ティ Block パフォーマ Application スマテリア Le ズ system, TSF433) 120g of infusion, as heat stabilizer Trimethyl phosphate (He Guangchun medicine system) 30g and stir 10 minutes, then, addition as polymerization catalyst magnesium acetate four hydration Object 11g is simultaneously stirred 5 minutes.Next, the temperature in polycondensation slot is warming up to 280 DEG C from 240 DEG C through 60 minutes, while by polycondensation Pressure in slot is decompressed to 40Pa from atmospheric pressure, then, carries out polymerization reaction 3 hours.By polymerization reaction product with harness shape It spues and is allowed to cool into cold water, cut obtain granular polymerization reaction product immediately.It utilizes¹H-NMR is true The copolymerization rate for the polyethylene glycol in polymerization reaction product accepted is 14 weight %.

After 150 DEG C carry out vacuum drying in 12 hours to obtained particle, supplies it to extruder type spinning machine and make Its melt, under conditions of spinning temperature is 265 DEG C, discharge-amount is 57g/ minute, from spinning head (discharge aperture be 0.23mm, The a length of 0.60mm in discharge hole, discharge hole count are 36, circular hole) spuing obtains spinning strand.With 20 DEG C of wind-warm syndrome, wind speed 20m/ minutes Cooling wind by this, to spin strand cooling, assign finish with feeding means and make its boundling, to rotate within 3000m/ minute the 1st Godet drawing, via the 2nd godet rotated with speed identical with the 1st godet, is wound with up- coiler, is obtained The undrawn yarn of 190dtex-36f.The 1st heat roller temperature is 55 DEG C, the 2nd heat roller temperature is 130 DEG C, stretching ratio is 1.9 times Under conditions of obtained undrawn yarn is stretched, obtain the drawn yarn of 100dtex-36f.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 2.Even if by hydrophobicity high score In the case that son is changed to polypropylene terephthalate, the fiber properties such as intensity, toughness are also good, and U% (hi) is also low, obtain The fiber of homogeneous is arrived.

Embodiment 15

The citric acid Ti chelator of 10ppm will be equivalent in terms of titanium atom relative to obtained polymerization reaction product to be scaled Complex compound, high purity terephthalic acid (Mitsui Chemicals system) 82.5kg and 1,4-butanediol 89.5kg are remaining temperature 220 DEG C, pressure 1.2 × 10⁵In the esterification slot of Pa, esterification is carried out, until the temperature of distillate is lower than 90 DEG C, obtains ester Change reaction product.Next, the number for successively putting into 1,4-butanediol 19.7kg into polycondensation slot, being heated to 70 DEG C and having melted Polyethylene glycol (Sanyo chemical conversion industry PEG6000S) 16.8kg of average molecular weight 8300, then, by connecting esterification slot It is piped with the transfer of polycondensation slot, obtained esterification reaction product 110.6kg is transferred to and has been heated to 220 DEG C of polycondensation slot In.After the completion of transfer, stirred 1 hour in 220 DEG C.Then, addition is as antioxidant (adding before polycondensation reaction starts) Pentaerythrite-four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, as disappearing Silicon (モメ Application ティ Block パフォーマ Application スマテリア Le ズ system, TSF433) 120g of infusion, as heat stabilizer Trimethyl phosphate (He Guangchun medicine system) 30g and stir 10 minutes, then, addition as polymerization catalyst magnesium acetate four hydration Object 11g is simultaneously stirred 5 minutes.Next, the temperature in polycondensation slot is warming up to 250 DEG C from 220 DEG C through 60 minutes, while by polycondensation Pressure in slot is decompressed to 60Pa from atmospheric pressure, then, carries out polymerization reaction 3 hours.By polymerization reaction product with harness shape It spues and is allowed to cool into cold water, cut obtain granular polymerization reaction product immediately.It utilizes¹H-NMR is true The copolymerization rate for the polyethylene glycol in polymerization reaction product accepted is 14 weight %.

After 150 DEG C carry out vacuum drying in 12 hours to obtained particle, supplies it to extruder type spinning machine and make It is melted, and from spinning head, (discharge aperture is 0.23mm, is spat under conditions of spinning temperature is 260 DEG C, discharge-amount is 57g/ minutes Portal a length of 0.60mm, and discharge hole count is 36, circular hole) spuing obtains spinning strand.With 20 DEG C of wind-warm syndrome, wind speed 20m/ minutes This is spun strand cooling by cooling wind, is assigned finish with feeding means and is made its boundling, and the 1st to rotation in 3000m/ minutes is led Roll dies drawing, via the 2nd godet rotated with speed identical with the 1st godet, is wound with up- coiler, obtains 190dtex- The undrawn yarn of 36f.Under conditions of the 1st heat roller temperature is 65 DEG C, the 2nd heat roller temperature is 130 DEG C, stretching ratio is 1.9 times Obtained undrawn yarn is stretched, the drawn yarn of 100dtex-36f is obtained.

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

Comparative example 1

Using polyethylene terephthalate (intrinsic viscosity IV=0.66), implements spinning similarly to Example 1, draws It stretches.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 3.The fiber properties such as intensity, toughness Well, U% (hi) is low, has obtained the fiber of homogeneous.However, due to being the fiber only formed by hydrophobic polymer, because without With phase separation structure.About cloth and silk characteristic, although equalization, quality are very excellent, being charged by friction voltage is 9800V, is resisted Static behaviour is very low, and △ MR is 0.1%, and hygroscopicity is also very low.

Comparative example 2~4

The number-average molecular weight of hydrophilic macromolecule is changed as shown in table 3, in addition to this, is made similarly to Example 4 Drawn yarn.It should be noted that in comparative example 2, using the polyethylene glycol of number-average molecular weight 3400 as hydrophilic macromolecule (Sanyo chemical conversion industry PEG4000) uses polyethylene glycol (the ア Le De リッチ system of number-average molecular weight 6000 in comparative example 3 PEG6000), (bright at chemical industry system R-150) using the polyethylene glycol of number-average molecular weight 100000 in comparative example 4.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 3.It is intensity, tough in comparative example 2 The fiber properties such as property are good, and U% (hi) is low, has obtained the fiber of homogeneous.However, the number-average molecular weight due to polyethylene glycol is lower than 7000, thus, do not have phase separation structure.Electricity is charged by friction although equalization, quality are very excellent about cloth and silk characteristic Pressure is 7600V, and antistatic property is poor.Also same as comparative example 2 in comparative example 3, although the fiber properties such as intensity, toughness are good, U% (hi) is low, has obtained the fiber of homogeneous, but since the number-average molecular weight of polyethylene glycol is lower than 7000, thus, without phase point From structure.In addition, although equalization, quality are very excellent, being charged by friction voltage is 6900V, antistatic about cloth and silk characteristic Property is poor.In comparative example 4, since the number-average molecular weight of polyethylene glycol is high, thus, point in fiber cross section and fiber longitudinal section The maximum gauge of dephasing is big, forms coarse phase separation structure.Therefore, the fiber properties such as intensity, toughness are low, and U% (hi) the very inhomogeneous fiber of Gao Erwei, intolerant in use.About cloth and silk characteristic, equalization, quality are excessively poor.

Comparative example 5

The copolymerization rate of hydrophilic macromolecule is changed as shown in table 3, and in addition to this, production stretches similarly to Example 8 Silk.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 3.Due to hydrophilic macromolecule The copolymerization rate is high, thus becomes unstable from the discharge of spinning head, as a result, the fiber properties such as intensity, toughness are very low, and U% (hi) the very inhomogeneous fiber of Gao Erwei, intolerant 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 be long, Discharge hole count), 3.3 times of stretching ratio are made in comparative example 6,7, in addition to this, production stretches similarly to Example 12 Silk.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 3.In comparative example 6, due to logical Shear velocity when crossing spinning head is low, thus, become highly unstable from the discharge of spinning head, as a result, the fibers such as intensity, toughness Characteristic is very low, and the very inhomogeneous fiber of U% (hi) Gao Erwei, intolerant in use.About cloth and silk characteristic, equalization, Quality is excessively poor.In comparative example 7, since shear velocity when passing through spinning head is high, thus, spinning stress is got higher, from spinneret The discharge of head becomes unstable, as a result, U% (hi) is slightly higher, is a lack of the fiber of homogenieity.About cloth and silk characteristic, equalization, product Matter is not up to qualified horizontal.

Comparative example 8

In embodiment 4, after shifting BHT, from not heating melting is put into polycondensation slot thereon but pulverulence it is poly- Ethylene glycol after putting into polyethylene glycol, does not carry out stirring for 1 hour in 250 DEG C, but immediately begins to polymerize in turn, except this it Outside, drawn yarn is made similarly to Example 4.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 3.Due to being added with pulverulence Polyethylene glycol, and be not stirred after putting into polyethylene glycol, in dispersion of the polyethylene glycol in esterification reaction product Start to polymerize in the state of insufficient, therefore, in polymerization reaction product, forms coarse phase separation structure, as a result, i.e. Make in the case where carrying out fibrosis using melt spinning, the maximum gauge of fiber cross section and the dispersed phase in fiber longitudinal section Also big, form coarse phase separation structure.Therefore, the fiber properties such as intensity, toughness are low, and U% (hi) is high and is a lack of homogeneous The fiber of property.About cloth and silk characteristic, equalization, quality are not up to qualified horizontal.

Comparative example 9

Bis- (beta-hydroxy ethyl) the ester about 100kg of terephthalic acid (TPA) are put into esterification slot, are kept in 250 DEG C of temperature Afterwards, through 2.5 hours successively supplying high purity terephthalic acid (TPA) (Mitsui Chemicals system) 89.2kg and ethylene glycol (Japanese catalyst system) 39.8kg slurry.After supply, carries out esterification 2 hours, obtain esterification reaction product.By connecting esterification The transfer of slot and polycondensation slot is piped, and obtained esterification reaction product 110.6kg is transferred to and has been heated to 250 DEG C of polycondensation slot In, it then, is stirred 1 hour in 250 DEG C, adds silicon (the モメ Application ティ Block パフォーマ Application スマテ as defoaming agent リア Le ズ system, TSF433) 120g, as heat stabilizer trimethyl phosphate (He Guangchun medicine system) 30g and stir 10 minutes, so Afterwards, addition as the antimony trioxide 30g of polymerization catalyst, manganese acetate 22g and is stirred 5 minutes.Next, through 60 minutes by polycondensation Temperature in slot is warming up to 285 DEG C from 250 DEG C, while the pressure in polycondensation slot is decompressed to 25Pa from atmospheric pressure, then, carries out Polymerization reaction 30 minutes 2 hours.Then, to nitrogen purging is carried out in polycondensation slot, restore to normal pressure, add powder into polycondensation slot Polyethylene glycol (Sanyo chemical conversion industry PEG6000S) 14.4kg of the number-average molecular weight 8300 of state, as antioxidant ( Polycondensation reaction is added after starting) pentaerythrite-four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Pressure in polycondensation slot is decompressed to 25Pa from atmospheric pressure by Irganox1010) 180g, then, is carried out polymerization reaction 30 minutes. Polymerization reaction product is spued with harness shape into cold water and is allowed to cool, is cut obtain granular polymerization immediately Reaction product.Using obtained particle, drawn yarn is made similarly to Example 4.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 3.Due to being added with pulverulence Polyethylene glycol, and the polymerization reaction time added after polyethylene glycol is short, thus, it is formd in polymerization reaction product coarse Phase separation structure, as a result, even if in the case where carrying out fibrosis using melt spinning, fiber cross section and fiber longitudinal section In dispersed phase maximum gauge it is also big, form coarse phase separation structure.Therefore, U% (hi) is high, is a lack of homogenieity Fiber.In addition, since the polymerization reaction time after addition polyethylene glycol is short, thus, after unreacted PEG content, hot water treatment Weight reduction rates are high, and equalization, quality are also not up to qualified horizontal.

Comparative example 10

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

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

Comparative example 11

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

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 3.The fiber properties such as intensity, toughness Well, U% (hi) is low, has obtained the fiber of homogeneous.However, the number-average molecular weight due to polyethylene glycol is lower than 7000, no With phase separation structure.About cloth and silk characteristic, although equalization, quality are very excellent, being charged by friction voltage is 7200V, is resisted Static behaviour is poor.

Embodiment 16

Bis- (beta-hydroxy ethyl) the ester about 100kg of terephthalic acid (TPA) are put into esterification slot, are kept in 250 DEG C of temperature Afterwards, through 2.5 hours successively supplying high purity terephthalic acid (TPA) (Mitsui Chemicals system) 89.2kg and ethylene glycol (Japanese catalyst system) 39.8kg slurry.After supply, carries out esterification 2 hours, obtain esterification reaction product.Next, successively to contracting The poly- second two of ethylene glycol (Japanese catalyst system) 13.6kg, the number-average molecular weight 8300 for being heated to 70 DEG C and having melted are put into poly- slot Then alcohol (Sanyo chemical conversion industry PEG6000S) 14.4kg is piped by the transfer of connection esterification slot and polycondensation slot, will Obtained esterification reaction product 110.6kg is transferred in the polycondensation slot for being heated to 250 DEG C.After the completion of transfer, stirred in 250 DEG C It mixes 1 hour.Then, pentaerythrite-four (3- (3,5- bis- uncles of the addition as antioxidant (being added before polycondensation reaction starts) Butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, silicon (the モメ Application ティ Block as defoaming agent パ Off ォーマ Application スマテリア Le ズ system, TSF433) 120g, trimethyl phosphate (the He Guangchun medicine as heat stabilizer System) 30g and stir 10 minutes, then, addition as the antimony trioxide 30g of polymerization catalyst, manganese acetate 22g and stirring 5 minutes. Next, the temperature in polycondensation slot is warming up to 285 DEG C from 250 DEG C through 60 minutes, while by the pressure in polycondensation slot from atmosphere Pressure is decompressed to 25Pa, then, carries out polymerization reaction 3 hours.Then, it is injection moulded by polyethylene terephthalate sheet material And manufactured thickness 0.2mm, internal volume 500cm³Container in, be loaded as antioxidant (adding after polycondensation reaction starts) Pentaerythrite-four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 480g, from anti- It answers tank top to add, to nitrogen purging is carried out in polycondensation slot, restores to normal pressure, stir after ten minutes, by polymerization reaction product It is spued and is allowed to cool into cold water with harness shape, cut obtain granular polymerization reaction product immediately.It uses Obtained particle, makes drawn yarn similarly to Example 4.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 4.The fiber properties such as intensity, toughness Well, U% (hi) is low, is the fiber of homogeneous.In addition, by adding antioxidant after polycondensation reaction starts, so that polycondensation is anti- The dispersing of antioxidant under the vacuum answered is suppressed because of the inactivation of antioxidant caused by thermal decomposition, anti-in fiber Oxygenate content is high, reaches time showing 360 minutes or more for rising half value point, and oxygenolysis is suppressed.In addition, antistatic Property, the weight reduction rates after hygroscopicity, hot water treatment it is also good, equalization, quality are also qualified horizontal.

Embodiment 17~19

It is changed in embodiment 17 for the antioxidant added after polycondensation reaction starts in embodiment 16 It is 2,4,6- tri- (3 ', 5 '-di-t-butyls -4 '-hydroxybenzyl) mesitylene (ADEKA system, アデカスタ Block AO-330) 420g changes it to 1,3,5- tri- [[4- (1,1- dimethyl ethyl) -3- hydroxyl -2,6- dimethyl benzenes in embodiment 18 Base] methyl] -1,3,5-triazines -2,4,6 (1H, 3H, 5H)-triketones (Tokyo chemical conversion industry system, THANOX1790) 384g, in reality It applies in example 19, changes it to bis- (2,2,6, the 6- tetramethyl -4- piperidyls -1,6- six of dibutylamine -1,3,5-triazines-N, N ' - The condensation polymer (BASF CHIMASSORB2020) of methylene diamine and N- (2,2,6,6- tetramethyl -4- piperidyl) butylamine In addition to this 384g makes drawn yarn similarly to Example 4.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 4.Using any antioxidant In the case where, the fiber properties such as intensity, toughness are good, and U% (hi) is low, are the fiber of homogeneous.In addition, for any anti-oxidant For agent, antioxidant is added after polycondensation reaction starts, the oxidation preventive content in fiber is high as a result, reaches rising half Time showing 360 minutes or more of value point, oxygenolysis is suppressed.In addition, the weight after antistatic property, hygroscopicity, hot water treatment It is also good to measure slip, equalization, quality are also qualified horizontal.

Embodiment 20~22

In embodiment 16, antioxidant is not added before polycondensation reaction starts, for what is added after polycondensation reaction starts As antioxidant pentaerythrite-four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010), it is changed to 480g in embodiment 20, is changed to 1200g in embodiment 21, changed in embodiment 22 Drawn yarn is in addition to this made similarly to Example 4 for 2400g.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 4.Even if anti-in polycondensation changing In the case where the additive amount of the antioxidant added after should starting, the fiber properties such as intensity, toughness are also good, and U% (hi) is also low, It is the fiber of homogeneous.In addition, the oxidation preventive content in fiber is high in the case where arbitrary additive amount, reach rising half Time showing 360 minutes or more of value point, oxygenolysis is also suppressed.In addition, after antistatic property, hygroscopicity, hot water treatment Weight reduction rates are also good, and equalization, quality are also qualified horizontal.

Embodiment 23

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

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 4.The fiber properties such as intensity, toughness Well, U% (hi) is low, is the fiber of homogeneous.In addition, by adding antioxidant in melt spinning, thus anti-in fiber Oxygenate content is high, reaches time showing 360 minutes or more for rising half value point, and oxygenolysis is suppressed.In addition, antistatic Property, the weight reduction rates after hygroscopicity, hot water treatment it is also good, equalization, quality are also qualified horizontal.

Embodiment 24

In extruder type spinning machine, since main feed device supply in example 4 polycondensation reaction before do not add antioxygen Agent and the particle made supply pentaerythrite-four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) from secondary feeder (BASF system, Irganox1010) makes its weight ratio 100:0.4 in addition to this make drawn yarn similarly to Example 4.

Embodiment 25

The citric acid Ti chelator of 10ppm will be equivalent in terms of titanium atom relative to obtained polymerization reaction product to be scaled Complex compound, high purity terephthalic acid (Mitsui Chemicals system) 82.5kg and 1,3-PD 49.1kg are remaining temperature 240 DEG C, pressure 1.2 × 10⁵In the esterification slot of Pa, esterification is carried out, until the temperature of distillate is lower than 90 DEG C, obtains ester Change reaction product.Next, the number for successively putting into 1,3-PD 16.7kg into polycondensation slot, being heated to 70 DEG C and having melted Polyethylene glycol (Sanyo chemical conversion industry PEG6000S) 16.8kg of average molecular weight 8300, then, by connecting esterification slot It is piped with the transfer of polycondensation slot, obtained esterification reaction product 110.6kg is transferred to and has been heated to 240 DEG C of polycondensation slot In.After the completion of transfer, stirred 1 hour in 240 DEG C.Then, addition is as antioxidant (adding before polycondensation reaction starts) Pentaerythrite-four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, as disappearing Silicon (モメ Application ティ Block パフォーマ Application スマテリア Le ズ system, TSF433) 120g of infusion, as heat stabilizer Trimethyl phosphate (He Guangchun medicine system) 30g and stir 10 minutes, then, addition as polymerization catalyst magnesium acetate four hydration Object 11g is simultaneously stirred 5 minutes.Next, the temperature in polycondensation slot is warming up to 280 DEG C from 240 DEG C through 60 minutes, while by polycondensation Pressure in slot is decompressed to 40Pa from atmospheric pressure, then, carries out polymerization reaction 3 hours.Then, by poly terephthalic acid the third two Alcohol ester sheet material is injection moulded and manufactured thickness 0.2mm, internal volume 500cm³Container in, be loaded as antioxidant and (contracting It is poly- reaction start after add) pentaerythrite-four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 480g is added from reactor tank top, to nitrogen purging is carried out in polycondensation slot, is restored to normal pressure, is stirred 10 points Polymerization reaction product is spued with harness shape into cold water and is allowed to cool, cut obtain graininess immediately by Zhong Hou Polymerization reaction product.Using obtained particle, drawn yarn is made similarly to Example 14.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 4.Even if by hydrophobicity high score In the case that son is changed to polypropylene terephthalate, the fiber properties such as intensity, toughness are also good, and U% (hi) is also low, are The fiber of homogeneous.In addition, reaching time showing 360 minutes or more for rising half value point, oxygenolysis is also suppressed.In addition, anti- Weight reduction rates after static behaviour, hygroscopicity, hot water treatment are also good, and equalization, quality are also qualified horizontal.

Embodiment 26

The citric acid Ti chelator of 10ppm will be equivalent in terms of titanium atom relative to obtained polymerization reaction product to be scaled Complex compound, high purity terephthalic acid (Mitsui Chemicals system) 82.5kg and 1,4-butanediol 89.5kg are remaining temperature 220 DEG C, pressure 1.2 × 10⁵In the esterification slot of Pa, esterification is carried out, until the temperature of distillate is lower than 90 DEG C, obtains ester Change reaction product.Next, the number for successively putting into 1,4-butanediol 19.7kg into polycondensation slot, being heated to 70 DEG C and having melted Polyethylene glycol (Sanyo chemical conversion industry PEG6000S) 16.8kg of average molecular weight 8300, then, by connecting esterification slot It is piped with the transfer of polycondensation slot, obtained esterification reaction product 110.6kg is transferred to and has been heated to 220 DEG C of polycondensation slot In.After the completion of transfer, stirred 1 hour in 220 DEG C.Then, addition is as antioxidant (adding before polycondensation reaction starts) Pentaerythrite-four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 180g, as disappearing Silicon (モメ Application ティ Block パフォーマ Application スマテリア Le ズ system, TSF433) 120g of infusion, as heat stabilizer Trimethyl phosphate (He Guangchun medicine system) 30g and stir 10 minutes, then, addition as polymerization catalyst magnesium acetate four hydration Object 11g is simultaneously stirred 5 minutes.Next, the temperature in polycondensation slot is warming up to 250 DEG C from 220 DEG C through 60 minutes, while by polycondensation Pressure in slot is decompressed to 60Pa from atmospheric pressure, then, carries out polymerization reaction 3 hours.Then, by poly terephthalic acid fourth two Alcohol ester sheet material is injection moulded and manufactured thickness 0.2mm, internal volume 500cm³Container in, be loaded as antioxidant and (contracting It is poly- reaction start after add) pentaerythrite-four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 480g is added from reactor tank top, to nitrogen purging is carried out in polycondensation slot, is restored to normal pressure, is stirred 10 points Polymerization reaction product is spued with harness shape into cold water and is allowed to cool, cut obtain graininess immediately by Zhong Hou Polymerization reaction product.Using obtained particle, drawn yarn is made similarly to Example 15.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 4.Even if by hydrophobicity high score In the case that son is changed to polybutylene terephthalate (PBT), the fiber properties such as intensity, toughness are also good, and U% (hi) is also low, are The fiber of homogeneous.In addition, reaching time showing 360 minutes or more for rising half value point, oxygenolysis is also suppressed.In addition, anti- Weight reduction rates after static behaviour, hygroscopicity, hot water treatment are also good, and equalization, quality are also qualified horizontal.

Embodiment 27~36

In extruder type spinning machine, in embodiment 27,35,36, made in embodiment 1 is supplied from main feed device Grain, in embodiment 28, the particle made from main feed device supply embodiment 3 in embodiment 29~31, is supplied from main feed device The particle made in embodiment 4, in embodiment 32, the particle made from main feed device supply embodiment 8, in embodiment 33, The particle that makes from main feed device supply embodiment 10 in embodiment 34, makes from main feed device supply embodiment 11 Particle, from secondary feeder supply pentaerythrite-four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010), make its weight ratio 100:0.4, embodiment 27 operates similarly with example 1, embodiment 28 and embodiment 3 operate in the same way, and embodiment 29 operates similarly to Example 5, and embodiment 30 operates similarly to Example 6, embodiment 31 It 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 It operates in the same way, makes drawn yarn.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 5.Even if high in change hydrophily The number-average molecular weight and the copolymerization rate of molecule, shear velocity when passing through spinning head, in the case where spinning speed, intensity, toughness etc. Fiber properties are also good, and U% (hi) is also low, are the fibers of homogeneous.In addition, by adding antioxidant in melt spinning, from And the content of the antioxidant in fiber is high, reaches time showing 360 minutes or more for rising half value point, oxygenolysis is pressed down System.In addition, the weight reduction rates after antistatic property, hygroscopicity, hot water treatment are also good, equalization, quality are also qualified horizontal.

Embodiment 37

In embodiment 4, the additive amount of antioxidant (adding before polycondensation reaction starts) is changed to 600g, except this it Outside, drawn yarn is made similarly to Example 4.

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

Embodiment 38

Into ester exchange reaction slot, investment is by dimethyl terephthalate (DMT) 8.7kg, 5-sodium sulfo isophthalate dimethyl ester (SSIA) slurry that (Sanyo's chemical conversion industry system) 370g, ethylene glycol (Japanese catalyst system) 5.6kg are formed, addition are anti-as transesterification Lithium acetate dihydrate 21.5g, the cobalt acetate tetrahydrate 2g for answering catalyst, in 240 DEG C progress ester exchange reaction 2 hours, obtain To ester exchange reaction product.Next, investment is heated to 70 DEG C and the number-average molecular weight 8300 that has melted into polycondensation slot Polyethylene glycol (Sanyo chemical conversion industry PEG6000S) 1.2kg, then, by the transfer for connecting ester exchange reaction slot and polycondensation slot Piping, obtained ester exchange reaction product is transferred in the polycondensation slot for being heated to 240 DEG C.After the completion of transfer, in 240 DEG C Stirring 1 hour.Then, pentaerythrite-four (3- (3,5- bis- of the addition as antioxidant (being added before polycondensation reaction starts) Tertiary butyl-4-hydroxy phenol) propionic ester) (BASF system, Irganox1010) 15g, silicon (the モメ Application ティ Block as defoaming agent パ Off ォーマ Application スマテリア Le ズ system, TSF433) 7g, the trimethyl phosphate (He Guangchun medicine system) as heat stabilizer 4.3g is simultaneously stirred 10 minutes, then, is added the antimony trioxide 3g as polymerization catalyst and is stirred 5 minutes.Next, through 60 points Temperature in polycondensation slot is warming up to 285 DEG C from 240 DEG C by clock, while the pressure in polycondensation slot is decompressed to 25Pa from atmospheric pressure, Then, it carries out polymerization reaction 3 hours.Then, it is injection moulded and manufactured thickness by polyethylene terephthalate sheet material 0.2mm, internal volume 500cm³Container in, be loaded as the pentaerythrite-of antioxidant (adding after polycondensation reaction starts) Four (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010) 40g, add from reactor tank top Add, to nitrogen purging is carried out in polycondensation slot, restore to normal pressure, stirring after ten minutes, by polymerization reaction product with harness shape to It spues and is allowed to cool in cold water, cut obtain granular polymerization reaction product immediately.Using obtained particle, Drawn yarn is made similarly to Example 4.It should be noted that SSIA the copolymerization rate shown in table 6 is to contain in polymerization reactant Element sulphur weight ratio.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 6.The fiber properties such as intensity, toughness Well, U% (hi) is low, is the fiber of homogeneous.In addition, reaching time showing 360 minutes or more for rising half value point, oxygenolysis It is suppressed, the weight reduction rates after antistatic property, hygroscopicity, hot water treatment are also good.In addition, since copolymerization has isophthalic diformazan Acid -5- sodium sulfonate, thus show cation dyeable, equalization, quality are also qualified horizontal.

Embodiment 39,40

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

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 6.Even if in change isophthalic diformazan In the case where the copolymerization rate of acid -5- sodium sulfonate, the fiber properties such as intensity, toughness are also good, and U% (hi) is also low, are the fibres of homogeneous Dimension.In addition, reaching time showing 360 minutes or more for rising half value point, oxygenolysis is suppressed, antistatic property, hygroscopicity, heat Weight reduction rates after water process are also good.In addition, equalization, quality are also qualified horizontal.

Embodiment 41,42

The copolymerization rate of hydrophilic macromolecule is changed as shown in table 6, in addition to this, is made and is stretched in the same manner as embodiment 38 Silk.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 6.Even if high in change hydrophily In the case where the copolymerization rate of molecule, the fiber properties such as intensity, toughness are also good, and U% (hi) is also low, are the fibers of homogeneous.In addition, Reach time showing 360 minutes or more for rising half value point, oxygenolysis is suppressed, after antistatic property, hygroscopicity, hot water treatment Weight reduction rates it is also good.In addition, equalization, quality are also qualified horizontal.

Embodiment 43~47

In embodiment 38~42, antioxidant is not added after polycondensation reaction starts, when carrying out melt spinning, is being squeezed Out in type spinning machine, particle obtained in each embodiment is supplied from main feed device, supplies pentaerythrite-four from secondary feeder (3- (3,5- di-t-butyl -4- hydroxyl phenol) propionic ester) (BASF system, Irganox1010), makes its weight ratio 100:0.4, In addition to this, drawn yarn is made in the same manner as each embodiment.

By the fiber properties of obtained fiber and cloth and silk characteristic evaluation result is shown in table 6.In all cases, intensity, The fiber properties such as toughness are good, and U% (hi) is low, are the fibers of homogeneous.In addition, reaching the time showing for rising half value point 360 minutes or more, oxygenolysis was suppressed, and the weight reduction rates after antistatic property, hygroscopicity, hot water treatment are also good.In addition, Equalization, quality are also qualified horizontal.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

Industrial availability

For fiber of the invention, although having phase separation structure, fiber number unevenness is small, and dyeing is uneven, fluffing Occur to be suppressed, and relative to long-term keeping, durability, hygroscopicity, the low temperature and low humidity degree ring of the fiber properties of roller drying Excellent antistatic property under border, in dyeing, in use, the dissolution of hydrophilic compounds is suppressed.Therefore, clothing can be suitable as The fiber construct of knitted woven item, the non-woven fabrics of material etc..

Claims

1. a kind of fiber, the fiber has phase separation structure, which is characterized in that the fiber includes hydrophobic polymer and parent The copolymer of aqueous high molecular, and there is continuous phase and dispersed phase based on phase separation structure, the dispersed phase in fiber cross section Maximum gauge be 1~40nm, fiber number change value U% (hi) be 0.1~1.5%,

The hydrophobic polymer is polyester, and the hydrophilic macromolecule is polyethylene glycol, the equal molecule of the number of the polyethylene glycol Amount is 7000~20000.

2. fiber according to claim 1, which is characterized in that the copolymerization of the hydrophobic polymer and hydrophilic macromolecule Object exposes at least part of fiber surface.

3. fiber according to claim 1 or 2, which is characterized in that JIS L1094 is based on, temperature is 10 DEG C, humidity is The voltage that is charged by friction measured under conditions of 10%RH is 3000V or less.

4. fiber according to claim 1 or 2, which is characterized in that in nitrogen: oxygen=80vol%:20vol% gaseous mixture Under body atmosphere, mixed gas flow be 200mL/ minutes, with 30 DEG C/min of heating rate from room temperature to after 160 DEG C, It is held under conditions of 160 DEG C, when carrying out thermoconductive TGA (DTG) for the fiber, is up to 160 DEG C of time conduct In the case where 0 minute, until the time for rising half value point is 120 minutes or more.

5. fiber according to claim 1 or 2, which is characterized in that contain antioxidant.

6. fiber according to claim 5, which is characterized in that the antioxidant is selected from phenolic compound, sulphur class Close at least one of object, hindered amine compound.

7. fiber according to claim 5, which is characterized in that the content of the antioxidant be fibre weight 0.01~ 2.0 weight %.

8. fiber according to claim 6, which is characterized in that the content of the antioxidant be fibre weight 0.01~ 2.0 weight %.

9. the manufacturing method of fiber according to any one of claims 1 to 8, which is characterized in that with the hydrophobic polymer Shear velocity when passing through spinning head with the copolymer of hydrophilic macromolecule becomes 10000~40000s^-1Mode carry out spinning.

10. a kind of fiber construct, which is characterized in that it uses following fibers at least part: including hydrophobicity high score The copolymer of son and hydrophilic macromolecule, and there is continuous phase and dispersed phase based on phase separation structure, and fiber cross section In dispersed phase maximum gauge be 1~40nm, fiber number change value U% (hi) be 0.1~1.5%,

The hydrophobic polymer is polyester, and the hydrophilic macromolecule is polyethylene glycol, the equal molecule of the number of the polyethylene glycol Amount is 7000~20000,

The fiber construct is based on JIS L1094, the friction band measured under conditions of temperature is 10 DEG C, humidity is 10%RH Piezoelectric voltage is 3000V or less.

11. a kind of fiber construct, which is characterized in that it uses following fibers at least part: including hydrophobicity high score The copolymer of son and hydrophilic macromolecule, and there is continuous phase and dispersed phase based on phase separation structure, and fiber cross section In dispersed phase maximum gauge be 1~40nm, fiber number change value U% (hi) be 0.1~1.5%,

Weight reduction rates after the hot water treatment of the fiber construct are 0.6~6.3%.

12. a kind of fiber construct, which is characterized in that it uses following fibers at least part: including hydrophobicity high score The copolymer of son and hydrophilic macromolecule, and there is continuous phase and dispersed phase based on phase separation structure, and fiber cross section In dispersed phase maximum gauge be 1~40nm, fiber number change value U% (hi) be 0.1~1.5%,

In nitrogen: being 200mL/ minutes, with 30 in mixed gas flow under oxygen=80vol%:20vol% mixed-gas atmosphere DEG C/min heating rate from room temperature to after 160 DEG C, under conditions of being held in 160 DEG C, for the fiber construct into When row thermoconductive TGA (DTG), in the case where being up to 160 DEG C of time as 0 minute, until the time for rising half value point is 120 minutes or more.

13. fiber construct described in any one of 0~12 according to claim 1, which is characterized in that described high comprising hydrophobicity The copolymer of molecule and hydrophilic macromolecule and there is continuous phase based on phase separation structure and dispersed phase and fiber is transversal The maximum gauge of dispersed phase in face is that the fiber of 1~40nm contains antioxidant.

14. fiber construct according to claim 13, which is characterized in that antioxidant is selected from phenolic compound, sulphur Based compound, be obstructed at least one of amine compound.

15. fiber construct according to claim 13, which is characterized in that the content of antioxidant is fibre weight 0.01~2.0 weight %.