JP4202361B2 - Clothing - Google Patents

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JP4202361B2
JP4202361B2 JP2005507293A JP2005507293A JP4202361B2 JP 4202361 B2 JP4202361 B2 JP 4202361B2 JP 2005507293 A JP2005507293 A JP 2005507293A JP 2005507293 A JP2005507293 A JP 2005507293A JP 4202361 B2 JP4202361 B2 JP 4202361B2
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elastic fiber
weight
ester
crystal melting
clothing
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JPWO2004113599A1 (en
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正夫 内田
茂 森岡
文惣 永阪
斉治 溝端
昭二 牧野
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帝人ファイバー株式会社
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Priority to PCT/JP2004/008940 priority patent/WO2004113599A1/en
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/86Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber

Description

  The present invention relates to a polyetherester elastic fiber that has good moisture absorption / release properties, reversibly expands / contracts by water absorption / release water, and can provide a fabric that exhibits unprecedented comfort especially in sports and inner applications.

BACKGROUND ART Conventionally, polyurethane elastic fibers are mainly used as elastic fibers for clothing and industrial materials, but have the disadvantages of poor heat resistance, chemical resistance, and weather resistance (light). In addition, since a dry spinning process is necessary for production, solvent recovery is required, and there is a problem of low productivity and high energy consumption. Furthermore, polyurethane elastic fibers are difficult to recycle and have many problems for the coming of a recycling society in the future, such as generation of harmful gases when burned.

  Against this backdrop, polyether ester elastic fibers, which can be melt-spun and have a highly crystalline polyester such as polyalkylene terephthalate as a hard segment and polyalkylene glycol as a soft segment, have high productivity. It has been put to practical use by taking advantage of its excellent heat resistance and heat setability. Further, since it is recyclable and no harmful gas is generated, future development is expected as an elastic fiber suitable for a recycling society (for example, Japanese Patent Publication No. 47-14054, Japanese Patent Publication No. 48-10346). No., JP-A-57-77317, etc.).

  As such a polyether ester elastic fiber, a polyether ester elastic fiber using polybutylene terephthalate as a hard segment and polyoxybutylene glycol as a soft segment is used as an elastic performance comparable to that of a polyurethane elastic fiber. . However, both of these hard segments and soft segments are generally hydrophobic, and almost no polyether ester elastic fiber having hydrophilic properties such as hygroscopicity and water absorption is practically used.

  On the other hand, in the pamphlet of International Publication No. 00/47802, an elastic fiber imparted with moisture absorption performance is proposed, but a specific example of a polyurethane elastic body containing a water-absorbing resin having a water absorption rate of 500 to 4,000% by weight is provided. It is only described.

  Moreover, there is a limit to improving the comfort of a fiber or even a garment simply by making the fiber itself hygroscopic as previously proposed, and there is a need for an elastic fiber having a new function. It has been.

  The present invention has been made against the background of the above-described prior art, and its purpose is to have a good hygroscopic property and to reversibly expand and contract reversibly by absorbing and releasing water, thereby obtaining a fabric having excellent comfort and being recyclable. An object of the present invention is to provide polyetherester elastic fibers, and fabrics and clothing using the same.

  As a result of repeated studies in view of the background technology, the present inventors have found that the object of the present invention can be achieved by the following polyether ester elastic fiber.

1. It is an elastic fiber made of a polyether ester elastomer having polybutylene terephthalate as a hard segment and polyoxyethylene glycol as a soft segment, and has a moisture absorption rate of 5% or more at 35 ° C. and 95% RH and a water absorption elongation rate of 10% or more. A garment comprising at least a part of a certain polyether ester elastic fiber.

2. 2. The garment according to 1, wherein an organic sulfonic acid metal salt represented by the following general formula (1) is copolymerized with the polyether ester elastomer, and the elastic fiber has an intrinsic viscosity of 0.9 or more.
(Wherein R1 is an aromatic hydrocarbon group or aliphatic hydrocarbon group, X1 is an ester-forming functional group, X2 is the same or different ester-forming functional group or hydrogen atom as X1, or M1 is an alkali metal or alkaline earth) Metal, j represents 1 or 2)

3. The clothing according to 2, wherein the elastic fiber has a boiling water shrinkage of 10% or more.

4). The clothing according to 2, wherein the organic sulfonic acid metal salt is a compound represented by the following general formula (2).
(In the formula, R2 represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and M2 represents an alkali metal or alkaline earth gold salt.)

5. The clothing according to 2, wherein the copolymerization amount of the organic sulfonic acid metal salt is in the range of 0.1 to 20 mol% based on the acid component constituting the polyether ester elastomer.

6). The elastic fiber has two crystal melting peaks in a DSC curve obtained by a differential scanning calorimeter, and the ratio Hm1 / Hm2 between the crystal melting peak height Hm1 on the low temperature side and the crystal melting peak height Hm2 on the high temperature side is 0. 1. The garment according to 1, which is in the range of 6 to 1.2 and has a breaking elongation of 400% or more.

7. The polyether ester elastic fiber for clothing according to 6, wherein the crystal melting peak temperature Tm1 on the low temperature side and the crystal melting peak temperature Tm2 on the high temperature side of the two crystal melting peaks satisfy the following formula.
200 ° C ≦ Tm1 <Tm2 ≦ 225 ° C

8). Clothing in any one of 1, 2, 6 whose ratio of a hard segment: soft segment is the range of 30: 70-70: 30 on the basis of a weight.

9. On the surface of the elastic fiber, an oil agent of 0.5 to 5.0% by weight based on the fiber weight is attached, and in the oil agent, at least one selected from the group consisting of mineral oil, silicone, and aliphatic ester The seed smoothing agent accounts for 70 to 100% by weight of the oil, and the ether-based or ester-based nonionic surfactant accounts for 0 to 30% by weight of the oil. Clothing .

10. The clothing of 9 whose viscosity in 30 degreeC of an oil agent is 5 * 10 < -6 > -4 * 10 < -5 > m < 2 > / s.

11. 2. The garment according to 1, wherein the garment is underwear or sportswear or lining or stockings or socks.

  The elastic fiber of the present invention is an elastic fiber made of a polyether ester elastomer having polybutylene terephthalate as a hard segment and polyoxyethylene glycol as a soft segment.

  The polybutylene terephthalate which is a hard segment preferably contains at least 70 mol% of butylene terephthalate units. The content of butylene terephthalate is more preferably 80 mol% or more, and still more preferably 90 mol% or more.

  The polybutylene terephthalate may be copolymerized with other components as long as the achievement of the object of the present invention is not substantially impaired. As the other copolymerization component, for the dicarboxylic acid component, for example, naphthalenedicarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenyloxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, adipic acid, sebacic acid, Examples thereof include aromatic, aliphatic and alicyclic dicarboxylic acid components such as 1,4-cyclohexanedicarboxylic acid. Furthermore, trifunctional or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid may be used as a copolymerization component. Examples of the diol component include aliphatic, alicyclic, and aromatic diol components such as trimethylene glycol, ethylene glycol, cyclohexane-1,4-dimethanol, and neopentyl glycol. Furthermore, a trifunctional or higher functional polyol such as glycerin, trimethylolpropane, or pentaerythritol may be used as a copolymerization component.

  On the other hand, polyoxyethylene glycol which is a soft segment preferably contains at least 70 mol% of oxyethylene glycol units. The content of oxyethylene glycol is more preferably 80 mol% or more, and still more preferably 90 mol% or more. For example, propylene glycol, tetramethylene glycol, glycerin and the like may be copolymerized with the polyoxyethylene glycol within a range in which the achievement of the object of the present invention is not substantially impaired.

  The number average molecular weight of the polyoxyethylene glycol is preferably 400 to 8000, and particularly preferably 1000 to 6000.

  In the present invention, the hard segment: soft segment weight ratio is preferably in the range of 70:30 to 30:70, more preferably in the range of 60:40 to 40:60. When the weight ratio of the hard segment exceeds 70%, the elongation of the elastic fiber becomes low, and it becomes difficult to use for high stretch applications, and the hygroscopicity tends to be lowered. Further, if the weight ratio of the hard segment is less than 30%, the ratio of the polybutylene terephthalate crystal part tends to be low, so the strength tends to decrease, and it becomes difficult to copolymerize all of the added polyoxyethylene glycol. Higher processing processes such as scouring and dyeing, and washing fastness when used as products tend to be inferior.

  In the present invention, it is important that the elastic fiber has a moisture absorption rate of 5% or more at 35 ° C. and 95% RH and a water absorption elongation rate of 10% or more. As a result, the woven or knitted fabric made of such elastic fibers stretches when the sweat is absorbed, opens the eyes of the woven or knitted fabric to release the moisture inside the garment, and shrinks when dried. Thus, the fabric of the knitted and knitted fabric is clogged and has a so-called self-adjusting function that does not let the temperature inside the garment escape.

  When the moisture absorption rate is less than 5%, there is a sticky feeling and stuffiness, and when the water absorption elongation rate is less than 10%, the reversible stretch / shrinkage characteristics due to water absorption / release are insufficient, and the knitted or knitted fabric eyes are sufficiently opened or closed. Therefore, a fabric excellent in comfort cannot be obtained. On the other hand, in the elastic fiber of the present invention composed of the above-described polyether ester, if the moisture absorption rate or the water absorption elongation rate becomes too large, the elastic performance, heat resistance, weather resistance (light) resistance, chemical resistance, etc. deteriorate. Tend to. For this reason, the moisture absorption is preferably in the range of 5 to 45%, more preferably in the range of 10 to 40%. Further, the water absorption elongation is preferably in the range of 10 to 100%, more preferably in the range of 10 to 80%, and still more preferably in the range of 15 to 60%.

  In the present invention, 0.5 to 5.0% by weight of an oil agent is attached to the surface of the elastic fiber based on the weight of the fiber, and the oil agent includes a group consisting of mineral oil, silicone, and aliphatic ester. It is preferable that at least one smoothing agent selected from 70% to 100% by weight of the oil agent.

  The above smoothing agents such as mineral oil, silicone, and aliphatic ester rarely swell elastic fibers, and there is no increase in friction and deterioration of mechanical properties due to this, and the process stability in the yarn making process and post-processing process is low. It becomes good. The content of these smoothing agents (the total content in the case where a plurality of types are used) is 70 to 100% by weight, so that the running stability at the time of yarn production is improved, abnormal yarn elongation and scum Occurrence can be suppressed.

As said mineral oil, that whose viscosity in 30 degreeC is 5 * 10 < -6 > -4 * 10 < -5 > m < 2 > / s is preferable, and mineral oil of this viscosity range volatilizes this mineral oil during storage. Therefore, the oil composition ratio on the elastic fiber is hardly changed, and high smoothness can be maintained. In addition, the silicone is preferably polydimethylsiloxane, and its viscosity at 30 ° C. is preferably 5 × 10 −6 to 4 × 10 −5 m 2 / s for the same reason as in the case of mineral oil. . Furthermore, the aliphatic ester is a compound such as a fatty acid monoalkyl ester, an aliphatic dicarboxylic acid dialkyl ester, a mono- or multi-fatty acid ester of an aliphatic polyhydric alcohol, and preferably has a molecular weight in the range of 250 to 550. By setting the molecular weight within this range, high smoothness can be maintained. Examples of preferably used aliphatic esters include fatty acid monoalkyl esters such as octyl octanoate, octyl stearate, isotridecyl laurate, isotridecyl oleate, lauryl oleate, and the like, and aliphatic dicarboxylic acid dialkyl esters. Examples thereof include diisooctyl adipate, and examples of mono- or multi-fatty acid esters of aliphatic polyhydric alcohols include trimethylolpropane trioctanate. Of these, fatty acid monoalkyl esters are preferred.

On the other hand, the ether-based or ester-based nonionic surfactant preferably has a viscosity at 30 ° C. of 8 × 10 −6 to 5 × 10 −5 m 2 / s. Preferred examples of the ether-based nonionic surfactant include polyalkylene glycol alkyl ether and polyalkylene glycol aryl ether, and examples of the ester-based nonionic surfactant include alkylene oxide adducts of polyhydric alcohol partial esters. Of these, polyalkylene glycol alkyl ether is preferred. In this case, when the carbon number of the alkyl group is in the range of 8 to 20, the elastic fiber is less likely to swell and high smoothness can be achieved at the same time. The number of carbon atoms of the alkylene group of the polyalkylene glycol chain is preferably 2 to 3, more preferably 2, and the chain number (number of moles of ethylene oxide added to the alcohol) is suitably in the range of 3 to 20. By setting it as the range of this chain number, compatibility with the smoothing agent which consists of said mineral oil, silicone, or aliphatic ester does not fall.

When the above-described mineral oil, silicone, etc. have a viscosity at 30 ° C. of 5 × 10 −6 to 2 × 10 −5 m 2 / s, the above ether-based or ester-based nonionic surfactant is not necessarily used. Although it may not be contained in the oil agent, in the case where the viscosity exceeds 2 × 10 −5 m 2 / s, it is easy to handle that the nonionic surfactant is contained in an amount of 30% by weight or less. Is preferable.

  Although the oil agent used by this invention is comprised from said component, you may add a small amount of another compounding agent within the range which does not impair the objective of this invention as needed. For example, a small amount of smoothing aids such as other nonionic surfactants, anionic or cationic ionic surfactants, antioxidants, stability improvers such as ultraviolet absorbers may be added.

In addition, the above-mentioned oil agent used in the present invention preferably has a viscosity at 30 ° C. of 5 × 10 −6 to 4 × 10 −5 m 2 / s. By setting it as the range of this viscosity, an oil agent component cannot volatilize easily during preservation | save of an elastic fiber, and high smoothness can be maintained. In addition, when the viscosity at 30 ° C. of the oil is as high as 2 × 10 −5 to 4 × 10 −5 m 2 / s, when it is applied as a neat oil during spinning, for example, it is heated to 2 × 10 It is preferable to set it to −5 m 2 / s or less. However, it is preferable to keep the temperature of the oil agent at 60 ° C. at most at Anno because it affects the fiber properties obtained when the oil agent is heated to a very high temperature.

  Next, the amount of the oil agent attached to the elastic fiber is preferably 0.5 to 5.0% by weight, more preferably 1.0 to 4.0% by weight, based on the weight of the fiber. Sometimes troubles such as yarn breakage and scum are less likely to occur, and process stability is improved.

  The high moisture absorption rate and water absorption elongation rate described above are obtained by copolymerizing the above-mentioned polyether ester elastomer with an organic sulfonic acid metal salt represented by the following general formula (1) and setting the intrinsic viscosity of the elastic fiber to 0.9 or more. This can be achieved more easily.

  In the formula, R1 is an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aromatic hydrocarbon group having 6 to 15 carbon atoms or an aliphatic hydrocarbon group having 10 or less carbon atoms. Particularly preferred R 1 is an aromatic hydrocarbon group having 6 to 12 carbon atoms, particularly a benzene ring. M1 is an alkali metal or alkaline earth metal, and j is 1 or 2. Among them, those in which M1 is an alkali metal (for example, lithium, sodium or potassium) and j is 1 are preferable. X1 represents an ester-forming functional group, and X2 represents the same or different ester-forming functional group as X1, or represents a hydrogen atom, but is preferably an ester-forming functional group. The ester-forming functional group may be any group that reacts with and bonds to the main chain or terminal of the polyether ester, and specifically includes the following groups.

(In the above formula, R ′ represents a lower alkyl group or a phenyl group, a and d represent an integer of 1 to 10, and b represents an integer of 2 to 6.)

  Preferable specific examples of the organic sulfonic acid metal salt represented by the general formula (1) include sodium 3,5-dicarbomethoxybenzenesulfonate, potassium 3,5-dicarbomethoxybenzenesulfonate, 3,5-dicarboxylate. Lithium carbomethoxybenzenesulfonate, sodium 3,5-dicarboxybenzenesulfonate, potassium 3,5-dicarboxybenzenesulfonate, lithium 3,5-dicarboxybenzenesulfonate, 3,5-di (β-hydroxyethoxy) Carbonyl) sodium benzenesulfonate, potassium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, lithium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, 2,6-dicarbomethoxynaphthalene 4-sulphonic acid sodium rim, 2,6 -Potassium dicarbomethoxynaphthalene-4-sulfonate, lithium 2,6-dicarbomethoxynaphthalene-4-sulfonate, sodium 2,6-dicarboxynaphthalene-4-sulfonate, 2,6-dicarbomethoxysphthalene -1-sodium sulfonate, 2,6-dicarbomethoxynaphthalene-3-sodium sulfonate, 2,6-dicarbomethoxynaphthalene-4,8-sodium disulfonate, 2,6-dicarboxynaphthalene-4,8 Examples thereof include sodium disulfonate, sodium 2,5-bis (hydroethoxy) benzenesulfonate, α-sodium sulfosuccinic acid, and the like. The said organic sulfonic acid metal salt may be used individually by 1 type, or may be used together 2 or more types.

  In the present invention, copolymerization of an organic sulfonic acid metal salt represented by the following general formula (2) can easily increase the intrinsic viscosity of the polyetherester elastomer to 0.9 or more. It is preferable in that the moisture absorption rate and water absorption elongation rate of the elastic fiber can be remarkably increased. According to our research, it has been found that by copolymerizing such organic sulfonic acid metal salts, it is possible to achieve a very high level of 20% or more of water absorption elongation and easily obtain a fabric with superior comfort. .

In the formula, R2 is an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is the same as the definition of R1 in the general formula (1) described above, M2 is an alkali metal or an alkaline earth metal, It is the same as the definition of M1 in Formula (1). Preferable specific examples of such organic sulfonic acid metal salts include sodium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, potassium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, 3,5 -Li (β-hydroxyethoxycarbonyl) benzenesulfonic acid lithium and the like are exemplified.

  If the copolymerization amount of the organic sulfonic acid metal salt is too large, the melting point of the elastic fiber is lowered, and the heat resistance, weather resistance (light), chemical resistance, etc. tend to be lowered. It is preferable to set it as the range of 0.1-20 mol% on the basis of the total acid component to comprise. On the other hand, even if the amount of copolymerization is too small, the moisture absorption rate and the water absorption elongation rate tend to decrease, and it is more preferably in the range of 0.5 to 15 mol%.

  The polyether ester elastomer used in the present invention is obtained by subjecting a raw material containing, for example, dimethyl terephthalate, tetramethylene glycol, and polyoxyethylene glycol to a transesterification reaction in the presence of a transesterification catalyst to produce bis (ω-hydroxybutyl) terephthalate. And / or forming an oligomer, and then performing melt polycondensation under high temperature and reduced pressure in the presence of a polycondensation catalyst and a stabilizer.

  As the transesterification catalyst, an alkali metal salt such as sodium, an alkaline earth metal salt such as magnesium or calcium, or a metal compound such as titanium, zinc or manganese is preferably used.

  As the polycondensation catalyst, it is preferable to use a germanium compound, an antimony compound, a titanium compound, a cobalt compound, or a tin compound. The amount of the catalyst used is not particularly limited as long as it is a necessary amount for proceeding the transesterification reaction and polycondensation reaction, and a plurality of catalysts can be used in combination.

  Further, the addition of a hindered phenol compound or a hindered amine compound, which will be described later, to the polyether ester not only suppresses a decrease in the intrinsic viscosity of the polymer during melt spinning, but also provides the obtained elasticity. It also has an effect of suppressing heat deterioration, oxidation deterioration, light deterioration, etc. of the fiber, and is more preferable.

  Especially, since it has the effect which accelerates | stimulates the polycondensation reaction of the polyetherester elastomer of this invention to use the hindered phenol type compound which has a double bond in the molecule | numerator shown by following General formula (3). It is more preferable in that an elastic fiber having a high intrinsic viscosity is easily obtained, and a polyether ester elastic fiber having high hygroscopicity and water absorption elongation can be easily produced.

  In the formula (3), the substituents R3 and R4 each independently represent a monovalent organic group having 1 to 6 carbon atoms, and when either or both of the substituents R3 and R4 are present, A plurality of substituents may be the same or different, m and n are each independently an integer of 0 to 4, and R5 represents a hydrogen atom or an organic group having 1 to 5 carbon atoms. .

  Specific examples of the hindered phenol compound having a double bond in the molecule include the following compounds (4) to (7). Among them, the one represented by the following formula (4) is particularly preferable because it is easy to obtain the above-described elastic fiber having high hygroscopicity and water absorption elongation.

  The transesterification catalyst can be supplied at the initial stage of the transesterification reaction in addition to the preparation of the raw material. The stabilizer can be supplied before the beginning of the polycondensation reaction, but it is preferably added at the end of the transesterification reaction. Furthermore, the polycondensation catalyst can be supplied by the early stage of the polycondensation reaction step.

  In addition to the above-mentioned method, the method of making the intrinsic viscosity of the elastic fiber 0.9 or more is a method of solid-phase polymerization of a polyether ester elastomer, a chain extender in the synthesis stage of a polyester ether elastomer or a melt spinning stage. A method of using can also be adopted. Preferable specific examples of the chain extender used at this time include oxazoline compounds such as 2,2'-bis (2-oxazoline), N, N'-terephthaloylbiscaprolactam and the like.

  As described above, it is preferable that the elastic fiber has an intrinsic viscosity of 0.9 or more in addition to the above-described polyether ester elastomer. When the intrinsic viscosity is 0.9 or more, a very high moisture absorption rate and water absorption elongation rate can be realized, and a fabric excellent in comfort can be easily obtained. On the other hand, when the intrinsic viscosity is too large, not only the yarn-making property is lowered but also the production cost is increased. For this reason, the intrinsic viscosity is more preferably in the range of 0.9 to 1.2.

  In the elastic fiber, the elongation at break is set to 400% or more, the hygroscopicity can be set to 5% or more, and the water absorption elongation can be set to 10% or more. This is preferable in that thread breakage due to blurring can be reduced. As said breaking elongation, the range of 400-900% is more preferable, More preferably, it is the range of 400-800%.

  Moreover, it is more preferable that the elastic fiber has a boiling water shrinkage of 10% or more in order to make the hygroscopicity 5% or more and the water absorption elongation 10% or more.

  The elastic fiber of the present invention is, for example, a pelletized polyether ester melted and extruded from a spinneret, and kept at least 10 cm, preferably at least 15 cm from directly under the die, within 5 m from immediately below the die, preferably Is applied at a position within 4 m, and is taken up at a take-up speed of 300 to 1200 m / min, preferably 400 to 980 m / min, and the take-up draft rate is further set to 1.3 to 1.6 of the take-up speed, preferably It can manufacture by winding up by 1.4-1.5. However, if the take-up draft is less than 1.3, the tension applied to the fibers is insufficient between the godet rollers and between the godet rollers and the take-up machine, and the fibers come into contact with the godet rollers and break the yarn. As mentioned above, keep the bottom of the base warm, keep the spinning speed as low as possible, keep the distance to the oil application device not long, so that the orientation does not advance, and the elastic fiber after taking up is as much fiber as possible In order to prevent the fibers from being stretched, it is preferable to reduce the winding draft as much as possible within the range in which the fibers can be wound in order to achieve a moisture absorption rate of 5% or more and a water absorption elongation rate of 10% or more. From this point of view, it is not preferable to stretch or further heat-treat the elastic fiber after winding it or continuously after pulling it.

  On the other hand, even an elastic fiber made of a polyether ester that is not substantially copolymerized with an organic sulfonic acid metal salt has an elasticity of 35% at 95% RH of 5% or more and a water absorption elongation of 10% or more. It can be a fiber.

  That is, the elastic fiber has two crystal melting peaks in the DSC curve obtained by the differential scanning calorimeter, and the ratio Hm1 / Hm2 between the crystal melting peak height Hm1 on the low temperature side and the crystal melting peak height Hm2 on the high temperature side. In the range of 0.6 to 1.2 and the elongation at break of 400% or more can easily achieve the high moisture absorption rate and water absorption elongation rate as described above.

  As described above, it is preferable that the ratio of the hard segment: soft segment of the polyether ester is 30:70 to 70:30 based on the weight. However, the ratio of the hard segment is set to 70% by weight or less. This is preferable when the ratio of Hm1 / Hm2 is 1.2 or less.

  As described above, the reason why Hm1 / Hm2 is in the range of 0.6 to 1.2 shows a high moisture absorption rate and water absorption elongation rate as follows. The two crystal melting peaks are thought to be due to the presence of two types of crystals that are significantly different in size. The low temperature peak is the melting temperature peak of the small crystal and the high temperature peak is the large size of the crystal. Presumed to be the melting temperature peak. This is almost confirmed by scanning the cross-section of the fiber with an atomic force microscope for hard and soft, and considering the hard part as a crystalline hard segment and the soft part as a soft segment. In addition, it is considered that the polyether ester exhibits hygroscopicity when the polyoxyethylene glycol constituting the soft segment sorbs and hydrates water molecules. From the above, when Hm1 / Hm2 is 1.2 or less, the number of small-sized crystals is small and the number of crystal crosslinking points that constrain the hard segment is small. This is thought to be because the moisture absorption rate and the water absorption elongation are remarkably improved. On the other hand, when Hm1 / Hm2 is 0.6 or more, the number of crystal crosslinking points does not decrease too much, the elongation elasticity of the fiber is maintained high, and the fiber physical properties are at a practical level. A more preferable range of Hm1 / Hm2 is 0.8 to 1.2.

  Moreover, it is preferable that temperature Tm1 and Tm2 of two crystal melting peaks are 200 degreeC or more, and sufficient heat resistance can be maintained. On the other hand, the crystal melting peak temperatures Tm1 and Tm2 are preferably 225 ° C. or lower, and the elasticity of the fiber can be increased. This is probably because Tm1 and Tm2 are in such a relationship that the crystal size does not become too large and the number of crystal crosslinking points does not decrease too much.

  Furthermore, as described above, the breaking elongation of the elastic fiber is preferably 400% or more, more preferably in the range of 500 to 1000%, and still more preferably in the range of 600 to 900%. When the breaking elongation is 400% or more, higher moisture absorption and water absorption elongation can be achieved. Further, since the breaking elongation is sufficiently large during knitting / weaving, the elastic fiber is less likely to be broken even by slight fluctuations in process conditions.

  The elastic fiber having the above two crystal melting peak temperatures is obtained by, for example, extruding the pelletized polyether ester by melting it from the spinneret and keeping it warm for at least 10 cm, preferably at least 15 cm from directly below the base. The oil agent is applied at a position within 5 m, preferably within 4 m from directly under the base, and the take-up speed is 300 to 1200 m / min, preferably 400 to 980 m / min. It can manufacture by winding by 0-1.2, Preferably it is 1.0-1.1. In other words, as described above, the temperature below the base is kept warm, the spinning speed is kept as low as possible, the distance to the oil application device is not increased so that the orientation does not progress, and the elastic fiber after being pulled is as much as possible. Taking up the winding draft as small as possible so that the fibers are not stretched does not increase the size of the small crystals, and the above two crystal dissolution peak heights are in the range of 0.6 to 1.2. Is preferable. From this point of view, it is not preferable to stretch or further heat-treat the polyether ester elastic fiber after winding it or continuously after pulling it.

  Hereinafter, the present invention will be described specifically by way of examples. In addition, each physical property in an Example was measured with the following method.

(1) Moisture absorption rate The sample was conditioned for 24 hours in a constant temperature and humidity chamber adjusted to predetermined conditions, and the moisture absorption rate was determined from the weight of the absolutely dry sample and the weight of the humidity control sample by the following equation.
Moisture absorption rate (%) = (weight of humidity control sample−weight of absolute dry sample) × 100 / weight of absolute dry sample

(2) Water absorption elongation rate / Hygroscopic elongation rate Fibers are collected, treated with boiling water for 30 minutes under no tension, air-dried and conditioned at 20 ° C. and 65% RH, and then under no tension in a non-contact 160 ° C. environment The yarn subjected to dry heat treatment for 2 minutes at 20 ° C. in an environment of 65% RH for 24 hours and subjected to a load of 0.88 × 10 −3 cN / dtex was measured. After that, the yarn was dipped in softened water adjusted to 20 ° C. for 1 minute, then pulled up from the water, and the moisture remaining on the fiber surface was air-dried at 20 ° C. and 65% RH. After sandwiching, placing on a horizontal table and placing a weight of 1.5 g / cm 2 and leaving for 2 seconds to wipe off excess moisture on the fiber surface, 10 seconds later, 0.88 × 10 −3 cN / dtex The length measured by applying the load is the "thread length at the time of water absorption" and The elongation rate was calculated. All measurements were performed in an environment of 20 ° C. and 65% RH.
Water absorption elongation = (yarn length at water absorption−yarn length at drying) ÷ yarn length at drying × 100%
In the same manner as described above, the “yarn length during drying” was measured, and then the yarn thus measured was conditioned for 24 hours in a constant temperature and humidity chamber adjusted to 35 ° C. and 95% RH, and then the constant temperature and humidity chamber. Then, the length measured by applying a load of 0.88 × 10 −3 cN / dtex was defined as “the length of the yarn at the time of moisture absorption”, and the moisture absorption elongation rate was calculated by the following formula.
Hygroscopic elongation = (yarn length when absorbing moisture−yarn length when drying) ÷ yarn length when drying × 100%

(3) Breaking strength / breaking elongation It measured by performing a tensile test using a Tensilon RTM-100 tensile tester manufactured by Toyo Baldwin in a constant temperature and humidity chamber adjusted to 20 ° C. × 65% RH.

(4) Sticky feeling, stuffiness The elastic fiber is knitted at 132 g / m 2 using a cylinder knitting machine, and this is put on the elbows and knees of 5 people who choose it arbitrarily. Evaluated. The results are shown as sticky feeling, stuffiness feeling less (small) and larger (large), respectively.

(5) Crystal melting peak temperatures Tm1, Tm2
Using a differential scanning calorimeter (TA Instrument 2920 type DSC), the measurement was performed by scanning at a rate of temperature increase of 20 ° C./min under a nitrogen stream. Of the two crystal melting peaks, the peak temperature on the low temperature side was Tm1, and the peak temperature on the high temperature side was Tm2.

(6) Ratio of crystal melting peak height Hm1 / Hm2
Among the above two crystal melting peaks, the height from the baseline to the crystal melting peak top on the low temperature side (peak temperature Tm1 side) and the high temperature side (peak temperature Tm2 side) is measured as Hm1 and Hm2, respectively. The ratio Hm1 / Hm2 was determined.

[Example 1]
100 parts by weight of dimethyl terephthalate, 23 parts by weight of 40% ethylene glycol solution of sodium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate (5.0 mol% based on the total acid components), polyoxyethylene glycol (Number average molecular weight 4000) 113.4 parts by weight, 1,4-butanediol 73.5 parts by weight (1.4 mol times the total acid component), and 0.4 parts by weight of tetrabutyl titanate as a catalyst were charged into the reaction vessel. The transesterification was carried out at an internal temperature of 200 ° C. When about 80% of the theoretical amount of methanol was distilled, 0.4 part by weight of the hindered phenol compound (4) was added, and then a polycondensation reaction was started by raising the temperature and reducing the pressure. The polycondensation reaction was carried out to 30 mmHg over about 30 minutes, and further over 3 minutes to 3 mmHg. Thereafter, the reaction was carried out for 200 minutes at an internal temperature of 250 ° C. under a vacuum of 1 mmHg. At that time, the following hindered phenol compound (8) 1 part by weight and 2 parts by weight of the following hindered amine compound (9) were added, followed by further reaction at 250 ° C. for 20 minutes under a vacuum of 1 mmHg or less for 20 minutes. The intrinsic viscosity of the produced polyether ester elastomer was 1.10, and the weight ratio of polybutylene terephthalate (hard segment) / polyoxyethylene glycol (soft segment) was 50/50.

The obtained polyetherester elastomer was melted at 230 ° C. and extruded from the spinneret at a discharge rate of 3.05 g / min. At this time, 9 cm was kept from directly under the base. An oil agent composed of 100% polydimethylsiloxane having a viscosity of 1 × 10 −5 m 2 / s at 30 ° C. at a position 3 m below the die is applied to the molten polymer by 3.0% by weight based on the fiber weight. The film was taken up at 510 m / min and further taken up at 750 m (winding draft 1.47) to obtain a polyether ester elastic fiber having 44 dtex / filament. The results are shown in Table 1.

Next, the elastic fiber was knitted to 132 g / m 2 using a cylindrical knitting machine. After leaving this knit in an environment of 20 ° C. and 65% RH for 24 hours, and further immersing it in 20 ° C. softened water for 1 minute, removing it from the water, and removing the water adhering to the knit surface with filter paper Then, the opening of each knit was observed. As a result, it was confirmed that the knit opening was increased after being immersed in softened water.

[Example 2]
An elastic fiber having an intrinsic viscosity of 1.16 was obtained in the same manner as in Example 1 except that polyoxyethylene glycol (number average molecular weight 2000) was used instead of polyoxyethylene glycol (number average molecular weight 4000). The results are shown in Table 1.

[Example 3]
The intrinsic viscosity was 1 except that the copolymerization ratio of polyoxyethylene glycol (number average molecular weight 4000) was changed so that the weight ratio of hard segment / soft segment was 60/40% by weight. .12 polyetherester elastic filaments were obtained. The results are shown in Table 1.

[Example 4]
The copolymerization amount of 5-Na sulfoisophthalic acid dihydroxyethyl ester (same as sodium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate) was adjusted to 2. A polyetherester elastic filament having an intrinsic viscosity of 1.18 was obtained in the same manner as in Example 1 except that the amount was 0 mol%. The results are shown in Table 1.

[Comparative Example 1]
Similar to Example 1 except that dimethyl 5-Na sulfoisophthalate was used instead of 5-hydroxysulfoisophthalic acid dihydroxyethyl ester (same as sodium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate) A polyether ester elastomer having an intrinsic viscosity of 1.10 was obtained by performing a synthesis reaction. Using this polyetherester elastomer, melt spinning was performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 5 and Comparative Example 2]
Elastic fibers were obtained in the same manner as in Example 1 except that the spinning speed and the winding speed were changed as shown in Table 1. The results are shown in Table 1.

[Comparative Example 3]
The elastic fiber obtained by the same method as in Example 1 was stretched at a stretch ratio of 2.0 times between two non-heated rollers to obtain a wound elastic fiber. The results are shown in Table 1.

[Example 6]
Men's underwear and sports using the elastic fiber obtained in Example 1 as a circular knitting (smooth) with a warp density of 52 / 2.54 cm and a weft density of 60 / 2.54 cm, which was used for the armpit and chest. Created wear (both upper body). These underwear and sportswear were each worn by 5 people and exercised for 2 hours, but both of them were less sticky and non-sticky than those not using the above elastic fibers, and were excellent in comfort. It was.

[Example 7]
Polyether ester comprising 49.8 parts by weight of polybutylene terephthalate as a hard segment and 50.2 parts by weight of polyoxyethylene glycol having a molecular weight of 4000 as a soft segment is melted at 230 ° C. and discharged from a spinneret at a discharge rate of 3.05 g / Melt extruded in minutes. At this time, 9 cm was kept from directly under the base. An oil agent composed of 100% polydimethylsiloxane having a viscosity of 1 × 10 −5 m 2 / s at 30 ° C. at a position 3 m below the die is applied to the molten polymer by 3.0% by weight based on the fiber weight. The sample was taken up at 705 m / min and further taken up at 750 m / min (winding draft 1.06) to obtain an elastic fiber of 40 denier / filament. The results are shown in Table 2.

The elastic fiber was made into a knit of 132 g / m 2 , which was left in an environment of 20 ° C. and 65 RH% for 24 hours, and further left in a constant temperature and humidity chamber of 35 ° C. and 95 RH% for 24 hours. Each opening was observed, and it was confirmed that the voids were large at 35 ° C. and 95 RH%.

Furthermore, after the 132 g / m 2 knit prepared separately was left in an environment of 20 ° C. and 65 RH% for 24 hours, it was immersed in softened water adjusted to 20 ° C. for 1 minute and pulled out of the water, After the moisture remaining in the filter was sandwiched between filter papers, the openings of the knit were observed, but it was confirmed that the voids became large after being immersed in the softened water.

[Examples 8 to 11, Comparative Example 4]
Elastic fibers were obtained in the same manner as in Example 7 except that the ratio of polyoxyethylene glycol, spinning speed, and winding speed were changed as shown in Table 2. The results are shown in Table 2.

  Further, as in Example 7, the knit openings of the knit before and after moisture absorption and before and after water absorption were observed, respectively, but it was confirmed that Examples 8 to 11 had larger gaps as in Example 7, In Comparative Example 4, the voids hardly changed.

[Example 12]
Men's underwear and sportswear were created and evaluated using the elastic fiber obtained in Example 7 in the same manner as in Example 6, but both were sticky compared to those not using the elastic fiber. There was little feeling of stuffiness and excellent comfort.

  Since the elastic fiber of the present invention is made of a polyether ester, it is excellent in recyclability. In addition, the elastic fiber of the present invention has a good moisture absorption and release property, and reversibly expands and contracts by absorbing and releasing water. Therefore, the elastic fiber expresses a self-adjusting function that changes the opening of the fabric by absorbing and releasing water, and has excellent comfort. Can be obtained. For this reason, the above-mentioned elastic fiber is used as clothing, and it exhibits excellent performance in applications such as sports clothing, innerwear, lining, stockings, and socks.

Claims (11)

  1. It is an elastic fiber made of a polyether ester elastomer having polybutylene terephthalate as a hard segment and polyoxyethylene glycol as a soft segment, and has a moisture absorption rate of 5% or more at 35 ° C. and 95% RH and a water absorption elongation rate of 10% or more. A garment comprising at least a part of a certain polyether ester elastic fiber.
  2. The garment according to claim 1, wherein an organic sulfonic acid metal salt represented by the following general formula (1) is copolymerized with the polyether ester elastomer, and the elastic fiber has an intrinsic viscosity of 0.9 or more.
    (Wherein R1 is an aromatic hydrocarbon group or aliphatic hydrocarbon group, X1 is an ester-forming functional group, X2 is the same or different ester-forming functional group or hydrogen atom as X1, or M1 is an alkali metal or alkaline earth) Metal, j represents 1 or 2)
  3. The clothing according to claim 2, wherein the elastic fiber has a boiling water shrinkage of 10% or more.
  4. The clothing according to claim 2, wherein the organic sulfonic acid metal salt is a compound represented by the following general formula (2).
    (In the formula, R2 represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and M2 represents an alkali metal or alkaline earth gold salt.)
  5. The clothing according to claim 2, wherein the amount of copolymerization of the organic sulfonic acid metal salt is in the range of 0.1 to 20 mol% based on the acid component constituting the polyetherester elastomer.
  6. The elastic fiber has two crystal melting peaks in a DSC curve obtained by a differential scanning calorimeter, and the ratio Hm1 / Hm2 between the crystal melting peak height Hm1 on the low temperature side and the crystal melting peak height Hm2 on the high temperature side is 0. in the range of .6~1.2, clothing according to claim 1, wherein a breaking elongation of 400% or more.
  7. The clothing according to claim 6, wherein the crystal melting peak temperature Tm1 on the low temperature side and the crystal melting peak temperature Tm2 on the high temperature side of the two crystal melting peaks satisfy the following formula.
    200 ° C ≦ Tm1 <Tm2 ≦ 225 ° C
  8. The ratio of a hard segment: soft segment is the range of 30: 70-70: 30 on the basis of a weight, The clothing in any one of Claims 1, 2, 6.
  9. On the surface of the elastic fiber, 0.5 to 5.0% by weight of an oil agent is attached based on the fiber weight, and in the oil agent, at least one selected from the group consisting of mineral oil, silicone and aliphatic ester 7. The smoothing agent according to claim 1, wherein 70 to 100% by weight of the oil agent is occupied, and an ether-based or ester-based nonionic surfactant accounts for 0 to 30% by weight of the oil agent. Clothing .
  10. Viscosity at 30 ° C. of oil agent, garment of claim 9 wherein the 5 × 10 -6 ~4 × 10 -5 m 2 / s.
  11. The garment according to claim 1, wherein the garment is underwear or sportswear or lining or stockings or socks.
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