EP1489206B1 - Fibre de polyester et textile préparé au moyen de cette fibre - Google Patents

Fibre de polyester et textile préparé au moyen de cette fibre Download PDF

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Publication number
EP1489206B1
EP1489206B1 EP04022765A EP04022765A EP1489206B1 EP 1489206 B1 EP1489206 B1 EP 1489206B1 EP 04022765 A EP04022765 A EP 04022765A EP 04022765 A EP04022765 A EP 04022765A EP 1489206 B1 EP1489206 B1 EP 1489206B1
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Prior art keywords
fiber
ratio
weight
poly
polymer
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EP1489206A3 (fr
EP1489206A2 (fr
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Jinichiro Kato
Katsuhiro Fujimoto
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters

Definitions

  • the present invention relates to a poly(trimethylene terephthalate)-base fiber and, more specifically, to a poly(trimethylene terephthalate)-base fiber dyeable into a dark shade by either one or both of a cationic dye and a disperse dye under atmospheric pressure, and also relates to a fabric using the fiber.
  • the poly(trimethylene terephthalate) fiber is an epoch-making fiber having all at the same time a soft touch attributable to the low modulus, the excellent elastic recovery analogous to a nylon fiber, and properties analogous to a poly(ethylene terephthalate) fiber, such as a wash-and-wear property, dimensional stability and good color fastness.
  • properties analogous to a poly(ethylene terephthalate) fiber such as a wash-and-wear property, dimensional stability and good color fastness.
  • the poly(trimethylene terephthalate) fiber has a problem in the dyeability. That is, known poly(trimethylene terephthalate) fibers have a problem in their dyeing because the dye is limited to a disperse dye and dyeing into dark shade can be attained only at a high temperature of from 110 to 120°C.
  • the dye which can dye the fiber is limited to a disperse dye and this means that the resulting dyed product is low in the brilliance and slightly inferior in the color fastness against dry cleaning solvent, abrasion in wet state, dye sublimation and the like.
  • the temperature for attaining the dyeing into dark shade is from 110 to 120°C and this means that composite fiber fabric with other fibers which thermally decompose at the above-described high temperatures cannot be dyed.
  • the poly(trimethylene terephthalate) fiber with other fiber such as polyurethane elastic fiber, wool, silk or acetate fiber, a blend fabric having softness and touch unattainable by conventional techniques can be obtained.
  • these other fibers have a problem in that when the temperature exceeds 110°C at the dyeing stage, the fiber greatly decreases in the tenacity or loses transparency and turns white, and thereby the commercial value is seriously impaired.
  • a technique for rendering a poly(trimethylene terephthalate) fiber dyeable with a dye other than a disperse dye, for example, a cationic dye is not known at all.
  • a method of copolymerizing a polyester by adding thereto a sulfonic acid metal salt group or an isophthalic acid having a quaternary phosphonium sulfonate group before the completion of the polycondensation reaction is known, though its application to a poly(trimethylene terephthalate) fiber is not specifically described.
  • the fiber obtained as such is not dyeable with a cationic dye under atmospheric pressure and has high modulus, therefore, only a fabric having rigid and stiff touch can be obtained.
  • a dicarboxylic acid such as adipic acid and isophthalic acid or an alkyl ester thereof as a copolymerizing component together with an isophthalic acid having a sulfonic acid metal salt group
  • the fiber obtained as such also has high modulus and only a fabric having stiff touch can be obtained.
  • a fiber having good dyeability with a disperse dye and having low modulus and excellent elastic recovery for example, a poly(trimethylene terephthalate) fiber disclosed in Japanese Patent Publication (Kokai) No. 52-5320 is known. Furthermore, a method of dyeing a poly(trimethylene terephthalate) fiber using a disperse dye under atmospheric pressure is disclosed in Japanese Unexamined International Publication (Kohyo) No. 9-509225. However, these fibers cannot be dyed at all with a cationic dye under atmospheric pressure.
  • the present inventors have particularly studied thereon and, as a result, have found that in these techniques disclosed in the above-described known arts, the dyeing with a disperse dye under atmospheric pressure can be performed only with a very low dye concentration.
  • the dye concentration used in Examples of Japanese Unexamined International Publication (Kohyo) No. 9-509225 is at most 0.5% owf (the unit "% owf" as used herein is a dye concentration in the dye solution shown by the wt% of dyed fabric).
  • the dye concentration In the field of clothing, a fabric dyed into dark shade is demanded similarly to fabrics dyed into light or medium shade. In such dyeing into dark shade, the dye concentration must be 4% owf or more and in some cases, 10% owf or more.
  • sufficiently high dye exhaustion cannot be attained under atmospheric pressure and therefore, the fiber cannot be dyed into a dark shade.
  • GB-A-1507358 discloses a copolyester obtained by melt-condensing terephthalic acid with a diol component consisting of (i) 1,3-propanediol or 1,4-butane diol, and (ii) an aliphatic diol having 5 to 10 carbon atoms or cycloaliphatic diol with 8 to 12 carbon atoms.
  • the copolyester exhibits an intrinsic viscosity of ⁇ 0.6 dl/g.
  • One object of the present invention is to provide a poly(trimethylene terephthalate)-based fiber dyeable into a dark shade under atmospheric pressure using either one or both of a cationic dye and a disperse dye.
  • Another object of the present invention is to provide a poly(trimethylene terephthalate)-based fiber capable of giving a composite fiber product in blend or in union with polyurethane elastic fiber, wool, silk, acetate fiber or the like, which can be dyed without impairing the physical properties of the fiber combined having relatively low heat resistance.
  • Still another object of the present invention is to provide a union woven fabric, blend yarn fabric or union knitted fabric composed of a poly(trimethylene terephthalate)-based fiber capable of fast dyeing under atmospheric pressure in combination with other fiber material.
  • One specific object of the present invention includes providing a fabric made of a blend of a polyurethane elastic fiber and a poly(trimethylene terephthalate)-based fiber, which can be fast dyed by a simple method using an atmospheric dyeing facility in common use.
  • the present inventors have found that the above-described objects can be attained by a polyester fiber prepared using, as the polymer, poly(trimethylene terephthalate) with which a specific third component is copolymerized at a specific copolymerizing ratio, such that the fiber has a peak temperature of loss tangent, a modulus and an elastic recovery each falling within an extremely limited range.
  • the present invention has been accomplished based on this finding.
  • the present invention is directed to a polyester resin satisfying the following conditions (1) - (3):
  • the present inventions pertains to a polyester fiber characterized in that the polyester fiber satisfies the following conditions (1), (2) and (3):
  • the present invention also relates to a first process for producing said polyester fiber said process comprising the following steps (1) to (4):
  • An alternative process comprises the following steps (1) to (4):
  • the present invention provides a fiber comprising a polyester obtained by copolymerizing a third component with poly(trimethylene terephthalate), and also provides a fabric using the polyester fiber, wherein the third component is at least one selected from the group consisting of (1) an aliphatic or alicyclic glycol having from 4 to 12 carbon atoms in a copolymerizing ratio of from 1.5 to 12 wt%, (2) an aliphatic or alicyclic dicarboxylic acid having from 2 to 14 carbon atoms or isophthalic.acid in a copolymerizing ratio of from 3 to 9 wt%, and (3) a poly(alkylene glycol) in a copolymerizing ratio of from 3 to 10 wt%, the fiber has a peak temperature of loss tangent of from 85 to 102°C, and the modulus Q (g/d) and the elastic recovery R (%) of the fiber satisfy the following formula (1): 0.18 ⁇ Q / R ⁇ 0.45
  • the polymer constituting the polyester fiber of the present invention is a polyester obtained by copolymerizing a specific amount of third component with poly(trimethylene terephthalate).
  • the "poly(trimethylene terephthalate)" as used herein means a polyester consisting of a terephthalic acid as the acid component and a trimethylene glycol (also called 1,3-propanediol) as the diol component.
  • the aliphatic glycol and the alicyclic glycol is selected from 1,4-butane diol, neopentyl glycol, 1,6-hexamethylene glycol, 1,4-cyclohexane dimethanol, 1,3-cyclohexane dimethanol and 1,2-cyclohexane dimethanol.
  • 1,4-butane diol 1,6-hexamethylene glycol, neopentyl glycol and cyclohexane dimethanol are preferred because the polymer can have excellent properties with respect to whiteness, thermal decomposability and color fastness to light. In view of high polymerization rate and good color fastness to dry cleaning solvent, 1,4-butane diol is more preferred.
  • the copolymerizing ratio of the glycol to the poly(trimethylene terephthalate) must be from 1.5 to 12 wt% based on the weight of polymer. If the copolymerizing ratio is less than 1.5 wt%, the fiber cannot be dyed with a cationic dye under atmospheric pressure.
  • the copolymerizing ratio of glycol is greatly correlated with the modulus, modulus recovery, melting point, glass transition point and dyeability. If the copolymerizing ratio exceeds 12 wt%, the melting point or glass transition point largely decreases and the touch turns hard at the stage of after-working represented by heatsetting or in the ordinary use represented by ironing, or the fabric after dyeing is disadvantageously reduced in the color fastness to dry cleaning solvent.
  • the copolymerizing ratio of glycol is preferably from 2 to 10 wt%, more preferably from 3 to 7 wt%.
  • aliphatic or alicyclic dicarboxylic acid having from 2 to 14 carbon atoms for use in the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptanoic diacid, octanoic diacid, sebacic acid, dodecanoic diacid, 2-methylglutaric acid, 2-methyladipic acid, fumaric acid, maleic acid, itaconic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexnedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid.
  • poly(trimethylene terephthalate) dyeing into dark shade using a disperse dye under atmospheric pressure can be attained.
  • aliphatic or alicyclic dicarboxylic acids and isophthalic acid sebacic acid, dodecanoic diacid, 1,4-cyclohexanedicarboxylic acid and isophthalic acid are preferred because of high polymerization rate at the copolymerization and excellent color fastness to light, and in view of excellent whiteness of polymer, isophthalic acid is more preferred.
  • the copolymerizing ratio of the aliphatic or alicyclic dicarboxylic acid or the isophthalic acid to the poly(trimethylene terephthalate) must be from 3 to 9 wt% based on the weight of polymer. If the copolymerizing ratio is less than 3 wt%, the fiber cannot be dyed into dark shade under atmospheric pressure, whereas if the copolymerizing ratio exceeds 9 wt%, the melting point or glass transition point excessively decreases and the touch turns hard at the stage of converting processing represented by heatsetting or in the ordinary use represented by ironing, or the fabric after dyeing is disadvantageously reduced in the color fastness to dry cleaning solvent.
  • the copolymerizing ratio of the aliphatic or alicyclic dicarboxylic acid or the isophthalic acid is preferably from 3 to 8 wt%, more preferably from 3 to 7 wt%.
  • a poly(alkylene glycol) may also be used as the copolymerizing component.
  • a glycol or an acid is copolymerized as the third component
  • the melting point inevitably decreases and, as a result, the spinnability deteriorates or the fiber obtained may have bad handleability and undergo melt-adhesion to a heat source or considerable shrinkage due to the heat at the converting processing.
  • a poly(alkylene glycol) is used as the third component, the melting point scarcely decreases and the above-described problems do not occur. This is considered to be because the poly(alkylene glycol) component has a large molecular weight and therefore, is localized in the polymer.
  • the poly(alkylene glycol) used may be any of poly(ethylene glycol), poly(trimethylene glycol), poly(tetramethylene glycol) and a copolymer thereof, however, in view of heat stability, poly(ethylene glycol) is most preferred.
  • the poly(alkylene glycol) preferably has an average molecular weight of from 300 to 20,000. If the average molecular weight is less than 300, the poly(alkylene glycol) contained has a fairly low molecular weight and is removed by vacuum distillation at the polymerization under high vacuum and the amount of poly(alkylene glycol) contained in the polymer obtained cannot be constant. As a result, the feed yarns are not uniformalized in the elongation tenacity, dyeability, thermal property and the like, and the products are dispersed in property.
  • the average molecular weight of poly(alkylene glycol) is preferably from 400 to 10,000, more preferably from 500 to 5,000.
  • the copolymerizing ratio of poly(alkylene glycol) to the poly(trimethylene terephthalate) must be from 3 to 10 wt% based on the weight of polymer. If the ratio of poly(alkylene glycol) is less than 3 wt%, dyeing into a heavy shade with a disperse dye under atmospheric pressure cannot be attained, whereas if the ratio of poly(alkylene glycol) exceeds 10 wt%, the polymer is reduced in the heat resistance and seriously deteriorates in the polymerizability and spinnability, moreover, the glass transition excessively decreases and the touch turns hard at the stage of converting processing represented by heat setting or in the ordinary use represented by ironing, or the fabric after dyeing is disadvantageously reduced to a severe extent in the color fastness against dry cleaning solvent or light.
  • the copolymerizing ratio of poly(alkylene glycol) is preferably from 4 to 8 wt%.
  • a fourth component may also be blended by the copolymerization within the range of not inhibiting the objects of the present invention. Even if a fourth component is used, the above-described copolymerizing ratio must be kept so as not to inhibit the objects of the present invention.
  • the ester-forming sulfonate compound and at least one component selected from the group consisting of (1) an aliphatic or alicyclic glycol having from 4 to 12 carbon atoms, (2) an aliphatic or alicyclic dicarboxylic acid having from 2 to 14 carbon atoms or isophthalic acid, and (3) a poly(alkylene glycol) are copolymerized, a polyester fiber dyeable with both a cationic dye and a disperse dye under atmospheric pressure can be obtained.
  • the copolymerizing ratio is preferably such that the ester-forming sulfonate compound is from 1.2 to 2.5 mol% and at least one component selected from (1) to (3) above is from 3 to 7 wt%.
  • various additives such as a delustering agent, a thermal stabilizer, an antifoaming agent, a color toning agent, a flame retardant, an antioxidant, an ultra-violet absorbing agent, a crystallization nuclear agent and a fluorescent whitening agent may be copolymerized or mixed in the polyester fiber of the present invention.
  • the molecular weight of the polyester for use in the present invention can be specified by the intrinsic viscosity.
  • the intrinsic viscosity [ ⁇ ] is from 0.4 to 1.2. With such an intrinsic viscosity, a polyester fiber having high tenacity and excellent spinnability can be obtained. If the intrinsic viscosity is less than 0.3, the polymer becomes unstable in the spinnability due to excessively low polymerization degree and the fiber obtained is not satisfied in the tenacity, whereas if the intrinsic viscosity exceeds 2.0, the melt viscosity is excessively high and, as a result, weighing in the gear pump cannot be smoothly performed and the spinnability decreases due to ejection failure or the like.
  • the polymer constituting the polyester fiber of the present invention can be fundamentally polymerized by a known method. More specifically, a third component may be added in a conventional production process of poly(trimethylene terephthalate), at any stage during the ester interchange reaction and subsequent polycondensation reaction between a terephthalic acid or a terephthalic acid lower ester such as dimethyl terephthalate and a trimethylene glycol.
  • the aliphatic or alicyclic dicarboxylic acid or the isophthalic acid is preferably added before the ester interchange reaction because the reaction with a trimethylene glycol must be accelerated, and a poly(alkylene glycol) is preferably added after the completion of ester interchange so as to prevent the polymer from losing the whiteness or bumping at the pressure reduction.
  • a metal acetate, a titanium alkoxide or the like is preferably used as the catalyst in an amount of from 0.01 to 0.1 wt% because the reaction rate, the whiteness of polymer and the heat stability all can be satisfied.
  • the reaction temperature is approximately from 200 to 240°C.
  • an antimony oxide, a titanium alkoxide and the like may be used as the catalyst and in particular, when a titanium alkoxide is used, it can serve also as an ester interchange catalyst.
  • the catalytic amount is, in view of the reaction rate and the whiteness of polymer, from 0.01 to 0.1 wt% based on the total carboxylic acid amount.
  • the reaction temperature is from 240 to 280°C and the vacuum degree is from 0.13 to 133.3 Pa (0.001 to 1 torr).
  • the above-described additives may be added at any stage during the polymerization process, however, in order to minimize the reaction inhibition, they are preferably added at any stage after the completion of ester interchange reaction.
  • the polymer constituting the polyester fiber of the present invention may be increased in the molecular weight by subjecting the polymer obtained by the above-described method to solid state polymerization in an inert gas such as nitrogen or argon or under reduced pressure.
  • an inert gas such as nitrogen or argon or under reduced pressure.
  • the solid state polymerization may be performed by a known method used, for example, for poly(ethylene terephthalate) as it is, however, the intrinsic viscosity of prepolymer before the solid state polymerization is preferably from 0.4 to 0.8 so as to increase the whiteness, the solid state polymerization temperature is preferably from 170 to 230°C, and the polymerization period, which may vary depending on the desired viscosity, is usually on the order of from 3 to 36 hours.
  • the polymer constituting the polyester fiber of the present invention may also be produced by blending two kinds of polymers so as to have an objective copolymerized composition.
  • poly(trimethylene terephthalate) having copolymerized therewith 5 wt% of 1,4-butanediol may be produced by blending 95 wt% of poly(trimethylene terephthalate) and 5 wt% of polybutylene terephthalate.
  • the "blending" as used herein may be performed by blending the components in a polymerization vessel to allow the ester interchange reaction to satisfactorily proceed and then discharging them or more simply by reacting the components in the chip-blend state in an extruder. Even when such a method is employed, a homogeneous polymer can be obtained because the ester interchange rate is sufficiently high.
  • the above-described preferred catalytic amount and reaction temperature are preferably combined with the use of a thermal stabilizer or a coloring inhibitor.
  • the thermal stabilizer is preferably a pentavalent or trivalent phosphorus compound.
  • the thermal stabilizer is preferably added in an amount of from 0.01 to 0.07 wt% based on the polymer.
  • the coloring inhibitor include cobalt acetate and cobalt formate.
  • the coloring inhibitor is preferably added in an amount of from 0.01 to 0.07 wt% based on the polymer.
  • solid state polymerization of the prepolymer is a very effective method for increasing the whiteness.
  • the polymer obtained as such can maintain excellent whiteness even when the polymer is formed into a fiber.
  • the whiteness is, in terms of b value which is described later, from -2 to 10, preferably from -1 to 6.
  • the additive examples include a basic metal salt such as lithium acetate, lithium carbonate, lithium formate, sodium acetate, sodium carbonate, sodium formate, sodium hydroxide, calcium hydroxide and potassium hydroxide.
  • the amount of the additive added is from 20 to 400 mol%, preferably from 70 to 200 mol%, based on the ester-forming sulfonate compound.
  • the polyester fiber of the present invention may have either a continuous filament or a staple form.
  • the fiber may comprise either a multifilament or a monofilament.
  • the total denier is not particularly limited but it is preferably from 5 to 1,000 d and in the case of use for clothing, more preferably from 5 to 200 d.
  • the single yarn denier is also not particularly limited but preferably from 0.0001 to 10 d.
  • the cross-sectional form is also not particularly limited and may be round, triangular, flat, star or w-shaped or the like, and furthermore, may be either solid or hollow.
  • the peak temperature of loss tangent (hereinafter simply referred to as "Tmax") determined by the measurement of dynamic viscoelasticity from 85 to 102°C when the third component is at least one selected from the group consisting of (1) an aliphatic or alicyclic glycol having from 4 to 12 carbon atoms in a copolymerizing ratio of from 1.5 to 12 wt%, (2) an aliphatic or alicyclic dicarboxylic acid having from 2 to 14 carbon atoms or isophthalic acid in a copolymerizing ratio of from 3 to 9 wt%, and (3) a poly(alkylene glycol) in a copolymerizing ratio of from 3 to 10 wt%.
  • Tmax peak temperature of loss tangent
  • Tmax corresponds to the molecular density in the amorphous area, therefore, the smaller this value is, the smaller the molecular density in the amorphous area is and the larger the gap portion for entry of the dye is, whereby entering of the dye is facilitated and in turn the dye exhaustion increases.
  • the Tmax is a structure factor of the fiber, accordingly, even among polymers having the same copolymerized composition, the value varies depending on the spinning conditions such as spinning temperature, spinning rate, draw ratio, heat treatment temperature, caustic reduction treatment and dyeing conditions, or converting processing conditions.
  • the Tmax value greatly varies depending on the heat setting temperature, therefore, it is important to control Tmax to fall within the above-described range by changing the heat setting temperature.
  • the way of establishing the heatsetting temperature is roughly described below. In the case of the polyester fiber specified in the present invention, when the heat setting temperature is from room temperature to about 150°C, Tmax gradually increases, however, when the heat setting temperature reaches about 160°C or more, Tmax subsequently greatly reduces.
  • the changing ratio varies by respective copolymerizing ratios, therefore, studies must be made while examining the relationship between the heat setting temperature and Tmax.
  • the heat setting temperature exceeds 115°C, the effect of improving dyeability is small and atmospheric dyeability cannot be attained.
  • the heat setting temperature is excessively low, the amorphous part becomes too coarse and the dye may easily enter therein but at the same time, disadvantageously come out therefrom with ease.
  • the color fastness particularly the color fastness to dry cleaning solvent, color fastness rubbing in wet state or, color fastness to laundering decreases.
  • the Tmax range is preferably from 85 to 102°, more preferably from 90 to 98°C when at least one selected from the group consisting of (1) an aliphatic or alicyclic glycol having from 4 to 12 carbon atoms in a copolymerizing ratio of from 1.5 to 12 wt%, (2) an aliphatic or alicyclic dicarboxylic acid having from 2 to 14 carbon atoms or isophthalic acid in a copolymerizing ratio of from 3 to 9 wt%, and (3) a poly(alkylene glycol) in a copolymerizing ratio of from 3 to 10 wt% is used as the third component.
  • the modulus Q (g/d) and the elastic recovery R (%) after 20% elongation and subsequent standing for 1 minute must satisfy the following formula (1).
  • the fabric obtained from the polyester fiber of the present invention can have a soft touch comparable or superior to nylon unlike the fabric obtained from a conventional polyester fiber. 0.18 ⁇ Q / R ⁇ 0.45
  • the modulus is usually from 25 to 40 g/d and the elastic recovery is from 70 to 99%.
  • Tmax of the fiber must be from 85 to 115°C and the modulus Q (g/d) and elastic recovery R (%) of the fiber must satisfy formula (1), from the same reasons as the grounds for Tmax and formula (1) described above in detail.
  • the polyester fiber of the present invention can be obtained by the following method.
  • the polyester fiber of the present invention can be obtained by melting a polymer dried to a water content of at least 100 ppm, preferably 50 ppm or less, using an extruder or the like and extruding the molten polymer from the spinneret, followed by taking up and subsequently drawing.
  • taking up and subsequently drawing means a so-called conventional spinning process where the yarn obtained by spinning is taken up by a bobbin or the like and then drawn using a different separate apparatus, or a so-called spin-draw process where the spinning and the drawing are directly connected, more specifically, the polymer extruded from the spinneret is completely cooled and solidified and then contacted a several turns or more around a first roll rotating at a constant rate so as to completely cut the transmission of tension before and after the roll, and then the yarn is drawn between the first roll and a second roll disposed next to the first roll.
  • the spinning temperature at the melt spinning of polymer is suitably from 240 to 280°C. If the spinning temperature is less than 240°C, a stable molten state may hardly be obtained due to the excessively low temperature and the fiber obtained is largely mottled and also fails in having a satisfactorily high tenacity or elongation. If the spinning temperature exceeds 320°C, the thermal decomposition aggressively takes place and the yarn obtained is colored and also fails in having a satisfactorily high tenacity or elongation.
  • the yarn taking-up rate is not particularly limited but the yarn is usually taken up at 2,000 m/min or less. If the taking-up rate exceeds 3,500 m/min, the crystallization proceeds before the taking up and the draw ratio at the drawing step cannot be increased, therefore, the molecules cannot be oriented, as a result, a sufficiently high yarn tenacity or elastic recovery may not be obtained or winding up takes place to prevent disengaging of a bobbin or the like from the take-up machine.
  • the draw ratio at the drawing is suitably from 2 to 4 times, preferably from 2.2 to 3.7 times, more preferably from 2.5 to 3.5 times.
  • the draw ratio is less than 2 times, the polymer cannot be satisfactorily oriented by the drawing and the yarn obtained has a low elastic recovery, failing in satisfying formula (1), whereas if it exceeds 4 times, yarn breaking takes place very often and the drawing cannot be stably performed.
  • the temperature in the drawing zone at the drawing is suitably from 35 to 70°C, more preferably from 40 to 65°C. If the drawing zone temperature is less than 30°C, yarn breaking occurs very often at the drawing and fibers cannot be continuously obtained, whereas if it exceeds 80°C, the slipping property of fiber to the heating zone such as drawing roll is deteriorated and single yarns are very often broken to give a yarn full of broken filaments, or the polymers slip through from each other and cannot be sufficiently oriented and therefore, the elastic recovery decreases.
  • the yarn after the drawing must be heat treated.
  • the heat treatment temperature is suitably from 110 to 180°C. If the heat treatment temperature is less than 90°C, crystallization of the fiber does hot proceed satisfactorily and the elastic recovery deteriorates, whereas if the temperature exceeds 200°C, the fiber is broken in the heat treatment zone and cannot be drawn.
  • a molten multifilament extruded from the spinneret is passed through a heat reserving zone in a length of from 2 to 80 cm, which is disposed right below the spinneret and kept at an atmospheric temperature of from 30 to 200°C, to prevent the abrupt cooling.
  • the molten multifilament is abruptly cooled and the resulting solid multifilament is contacted around a first roll heated at from 40 to 70°C and rotating at a rate of 300 to 3,000 m/min, then without taking it up, is contacted around a second roll heated at from 120 to 160°C to draw the multifilament to from 1.5 to 3 times between the first roll and the second roll rotating at a higher rate than the first roll, and then taken up using a take-up machine at a rate lower than the second roll.
  • an interlacing treatment may be performed.
  • an undrawn yarn once taken up at a spinning rate of from 300 to 3,000 m/min may be taken up through the above-described first and second rolls.
  • the molten multifilament extruded from the spinneret is, without abruptly cooling it, immediately passed through a heat reserving region in a length of from 5 to 30 cm, which is disposed right below the spinneret and kept at an atmospheric temperature of from 5 to 150°C, to suppress abrupt cooling, and then the molten multifilament is abruptly cooled into a solidified multifilament and then subjected to the subsequent drawing step.
  • the polymer By the passing through a heat reserving region, the polymer can be prevented from producing of fine crystal or amorphous areas having an extreme orientation ascribable to the abrupt cooling and can form an amorphous structure easy to draw at the drawing step and, as a result, the fiber obtained can have physical properties required in the present invention.
  • the poly(trimethylene terephthalate) has by far a higher crystallization rate compared with a polyester such as poly(ethylene terephthalate), therefore, the above-described gradual cooling is very effective in preventing production fine crystal or amorphous areas having an extreme orientation. If the atmospheric temperature is less than 30°C, abrupt cooling results and the draw ratio is difficult to increase, whereas if it exceeds 200°C, yarn breaking is liable to occur.
  • the temperature in the heat reserving region is preferably from 40 to 200°C, more preferably from 50 to 150°C.
  • the length of heat reserving region is preferably from 5 to 30 cm.
  • the yarn spinning rate is, in terms of the contacting rate around a first roll, from 300 to 3,000 m/min. If the spinning rate is less than 300 m/min, excellent spinning stability may be attained but the productivity greatly decreases, whereas if it exceeds 3,000 m/min, orientation of the amorphous area or partial crystallization proceeds before the taking up and at the drawing step, the draw ratio cannot be increased and, as a result, the molecules cannot be oriented and a sufficiently high yarn tenacity cannot be obtained.
  • the spinning rate is preferably from 1,500 to 2,700 m/min.
  • the rate of the take-up machine must be lower than the rate of the second roll so as to relax the orientation in the amorphous area of fiber.
  • the relax ratio (take-up rate/second roll rate) is approximately from 0.95 to 0.99, preferably from 0.95 to 0.98.
  • the rate of the second roll is determined by the draw ratio but it is usually from 600 to 6,000 m/min.
  • the draw ratio between the first roll and the second roll is suitably from 1.3 to 3 times, preferably from 2 to 2.7 times. If the draw ratio is 1.3 times or less, the polymer cannot be satisfactorily oriented by the drawing and the fiber obtained is low in the tenacity or elastic recovery, whereas if it exceeds 3 times, broken filaments are severely generated in the yarn and the drawing cannot be stably performed.
  • the first roll temperature is from 40 to 70°C. With a temperature in this range, a system capable of easy drawing can be created.
  • the temperature of the second roll on which heat setting is performed is from 120 to 160°C.
  • the fiber obtained has poor thermal stability, is prone to thermal deformation or aging change and deteriorates in the coloring property, whereas if it exceeds 160°C, broken filaments are generated or yarn breaking occurs and the spinning cannot be stably performed.
  • the second roll temperature is preferably from 120 to 150°C.
  • U% is a parameter for showing the evenness in the cross section of a fiber.
  • U% is 2.5% or less and, in some cases, 1.5% or less.
  • the polyester fiber thus obtained is used by itself or as a part of fabric to provide a fabric having excellent properties in the softness, stretchability and coloration.
  • the other fiber is not particularly limited.
  • a fiber such as a stretch fiber represented by polyurethane elastic fiber, a cellulose fiber, wool, silk or an acetate fiber
  • a characteristic feature incapable of being obtained by a blend fabric using a nylon fiber or a poly(ethylene terephthalate) fiber may be brought out.
  • the composite fabric can be dyed using a cationic dye and/or a disperse dye under atmospheric pressure and at the same time, can have a unique touch favored with softness and stretchability which cannot be attained by conventional techniques.
  • the polyester fiber of the present invention can be dyed into dark shade with a cationic dye or a disperse dye or with both dyes and by virtue of this feature, a polyurethane elastic fiber can be dyed without causing any staining and in turn can have softness and touch different from composite fabrics of a nylon fabric with a stretch fiber represented by a polyurethane elastic fiber.
  • a particularly preferred example of the fabric is a composite fabric of the poly(trimethylene terephthalate) fiber with a stretch fiber represented by a polyurethane elastic fiber.
  • the fabric of the present invention is not particularly limited on the shape and the weaving and knitting method and can be produced by a known method.
  • Examples thereof include plain weave woven fabrics using the polyester fiber of the present invention for warp yarn and weft yarn, woven fabrics such as reversible woven fabric, and knitted fabrics such as tricot and raschel fabric.
  • doubling, composite twisting or interlacing may also be applied.
  • the stretch fiber for use in the present invention is not particularly limited but examples thereof include a dry spun or melt spun polyurethane elastic fiber and a polyester-based elastic fiber represented by poly(butylene terephthalate) fiber and poly(tetramethylene glycol) copolymerized poly(butylene terephthalate) fiber.
  • the content of the polyester fiber of the present invention is not particularly limited but it is preferably from 60 to 98%.
  • the fabric of the present invention can be dyed, for example, after the weave-knitting, by a conventional process through scouring, pre-setting, dyeing and final setting. If desired, a caustic reduction treatment may also be applied after the scouring but before the dyeing.
  • the scouring may be performed at a temperature of from 40 to 98°C.
  • the fabric is preferably scoured while relaxing it so as to improve the elasticity.
  • the heatsetting temperature is from 120 to 190°C, preferably from 140 to 180°C
  • the heatsetting time is from 10 seconds to 5 minutes, preferably from 20 seconds to 3 minutes.
  • the dyeing may be performed without using a carrier at a temperature of from 70 to 150°C, preferably from 90 to 120°C, more preferably from 90 to 100°C.
  • a carrier for attaining uniform dyeing, it is preferred to use acetic acid or sodium hydroxide to control the pH according to the dye and at the same time to use a dispersing agent comprising a surfactant.
  • an alkali metal or alkaline earth metal salt such as sodium sulfate, sodium nitrate, potassium sulfate and calcium sulfate, is particularly preferably added to the dye bath so as to improve the brilliance of a dyed product.
  • the fabric may be subjected to soaping or reduction cleaning by a known method.
  • a known method may be used.
  • the treatment may be performed in an alkali aqueous solution such as sodium carbonate and sodium hydroxide using a reducing agent such as sodium hydrosulfite.
  • the polyester fiber of the present invention is characterized in that despite a cationic dye dyeable fabric, the amount and rate of caustic reduction can be industrially controlled.
  • the polyester fiber of the present invention after the caustic reduction can be more intensified in the softness and additionally, due to the presence of microscopic pores on the order of a few ⁇ m on the fiber surface, also can have characteristic features such as dry feeling and brilliant color.
  • the atmospheric disperse dye-dyeable polyester fiber of the present invention also exhibits similar caustic reduction properties.
  • the poly(trimethylene terephthalate)-base fiber of the present invention can be used according to the above-described use forms for clothing such as outer clothing, inner wears, lining and sportswear, and additionally for materials such as carpet feed yarn, padding cloth and flocky cloth.
  • the intrinsic viscosity [ ⁇ ] was measured at 35°C with o-chlorophenol using an Ostwald's viscometer.
  • a loss tangent (tan ⁇ ) and a dynamic viscoelasticity at each temperature were measured in a dry air at a measurement frequency of 110 Hz and a temperature-rising rate of 5°C/min using LEOVIBRON manufactured by Orienteck K.K. From the values obtained, a loss tangent-temperature curve was configured and Tmax (°C) as a peak temperature of the loss tangent was determined on the curve.
  • the modulus was measured according to JIS-L-1013.
  • the melting point was measured at a temperature-rising rate of 20°C/min in a nitrogen stream flowing at 100 ml/min using DSC manufactured by Seiko Electric Corporation. A peak value at the peak of melting was used as the melting point.
  • a fiber was fixed to a tensile tester with a chuck-to-chuck distance of 20 cm, elongated at a pulling rate of 20 cm/min to an elongation of 20%, then allowed to stand for 1 minute, and thereafter shrunk at the same rate. In this way, a stress-strain curve was configured.
  • the elongation when the stress became 0 during the shrinking was defined as a residual elongation (X).
  • the degree of yellow tinting of the fiber obtained was measured using a "b" value.
  • the b value was measured using a color computer manufactured by Suga Shikenki K.K. The larger the b value is, the higher the degree of yellow tinting.
  • a single end fed knitted fabric (circular knitting, plain stitch fabric, gauge: 28) of polyester fiber was used as a sample.
  • the sample was scoured at 70°C for 20 minutes in hot water containing 2 g/l of Scourol 400 (a nonionic surfactant, produced by Kao Corporation) (bath ratio: 1:50), dried by a tumbler dryer, heat set at 180°C for 30 seconds using a pin tenter and then tested.
  • the dye used was KAYACRYL BLUE GSL-ED (a cationic dye, produced by Nippon Kayaku K.K.) and the dyeing was performed using 40% owf of the dye at a bath ratio of 1:50 and 95°C for 30 minutes.
  • As additives 0.25 ⁇ g/l of acetic acid and 3 g/l of sodium sulfate were added to control the pH.
  • a single end fed knitted fabric (circular knitting, plain stitch, gauge: 28) of polyester fiber was used as a sample.
  • the sample was scoured at 70°C for 20 minutes in hot water containing 2 g/l of Scourol 400 (bath ratio: 1:50), dried by a tumbler dryer, heat set at 180°C for 30 seconds using a pin tenter and then tested.
  • the dye used was Kayaron Polyester Blue 3RSF (a disperse dye, produced by Nippon Kayaku Co., Ltd.) and the dyeing was performed using 6% owf of the dye at a bath ratio of 1:50 and 95°C for 60 minutes.
  • a dispersing agent 0.5 g/l of Niccasunsolt 7000 (an anionic surfactant, produced by Nikka Chemicals Co., Ltd.) was used, and the pH was adjusted to 5 by adding 0.25 ml/l of acetic acid and 1 g/l of sodium acetate.
  • the dye exhaustion was obtained by determining an absorbency A of the dye stock solution and an absorbency a of the initial dye bath solution after the dyeing using a spectrophotometer and substituting the absorbency values to the following formula.
  • the absorbency used was a value at 580 nm which is the maximum absorption wavelength of the dye.
  • Dye Exhaustion ( A - a ) / A ⁇ 100 ( % )
  • the color depth for showing the degree of dark shade attained by the dyeing was evaluated using K/S.
  • the K/S value was determined by measuring a spectral reflectance R of the dyed sample cloth and substituting R to the Kubelka-Munk formula shown below.
  • the R value used is a value at the maximum absorption wavelength of the dye.
  • the color fastness to dry cleaning was evaluated according to JIS-L-0860, the color fastness to light was according to JIS-L-0842, the color fastness to laundering was according to JIS-J-0844, and the color fastness to rubbing in dry or wet state was according to JIS-L-0849.
  • liquid staining was tested for evaluating the color fastness to dry cleaning.
  • the U% was measured using Uster Tester 3. manufactured by Zerveger Uster K.K.
  • TMG trimethylene glycol
  • DIMT dimethyl terephthalate
  • SIPP tetrabutylphosphonium 5-sulfoisophthalate
  • the polymer chip obtained was dried and then spun at a spinning temperature of 265°C and a spinning rate of 1,200 m/min using a spinneret having 36 orifices (diameter: 0.23 mm) each having a round cross section to prepare undrawn yarns.
  • the undrawn yarns obtained were draw-twisted using a hot roll at 50°C and a hot plate at 140°C at a draw ratio of 3.0 times and a drawing rate of 600 m/min to obtain drawn yarns of 50 d/36 f.
  • the fiber had physical properties such that the melting point was 231°C, the density was 1.32 g/cm 3 , the tenacity was 3.4 g/d, the elongation was 37%, Tmax was 110°C, U% was 1.2%, the modulus was 22 g/d, and the elastic recovery was 87%.
  • the Q/R value of drawn yarn was 0.25 and satisfied formula (1).
  • the b value of fiber was 6.1.
  • the polyester fiber obtained in this Example had a cationic dye exhaustion as large as 72% at 95°C for 30 minutes, and a very brilliant dyed product could be obtained.
  • a poly(trimethylene terephthalate) homopolymer was obtained in the same manner as in Example 1 except that SIPP was not used.
  • the polymer obtained had an intrinsic viscosity of 0.63.
  • This polymer chip was spun and drawn in the same manner as in Reference Example 1 to obtain a fiber.
  • the fiber obtained had a melting point of 236°C, Tmax of 111°C, a tenacity of 3.6 g/d, an elongation of 35%, a modulus of 23 g/d and a modulus recovery of 88%.
  • the Q/R value of this fiber was 0.26 and satisfied formula (1).
  • polyester fiber obtained in this Comparative Example had a cationic dye exhaustion of 6% at 95°C for 30 minutes, thus, could not be dyed into dark shade.
  • the polymer chip obtained was dried and then spun at a spinning temperature of 265°C and a spinning rate of 1,200 m/min using a spinneret having 36 orifices (diameter: 0.23 mm) each having a round cross section to prepare undrawn yarns.
  • the undrawn yarns obtained were draw-twisted using a hot roll at 60°C and a hot plate at 140°C at a draw ratio of 2.9 times and a drawing rate of 600 m/min to obtain drawn yarns of 50 d/36 f.
  • the fiber had physical properties such that the melting point was 224°C, Tmax was 98°C, the tenacity was 3.6 g/d, the elongation was 40%, U% was 1.2%, the modulus was 23 g/d, the elastic recovery was 83% and the b value was 4.5.
  • the Q/R value of this fiber was 0.28 and satisfied formula (1).
  • the polyester fiber obtained in this Example had a disperse dye exhaustion as high as 78% at 95°C for 60 minutes.
  • a fiber was prepared according to Reference Example 1.
  • the polyester fiber obtained was subjected to 2) Evaluation of Dyeability of Polyester Fiber with Disperse Dye of (7) Evaluation Test of Dyeability.
  • the polyester fiber obtained in this Example had Tmax in excess of 102°C.
  • This fiber had a disperse dye exhaustion of 36% at 95°C for 60 minutes, thus, could not be dyed into dark shade.
  • the dyeing was performed at a dyeing concentration of 0.5% owf, the dye exhaustion was improved to 81%. From this result, it is seen that the poly(trimethylene terephthalate) fiber exhibits dyeability under atmospheric pressure at a low dye concentration, however, when the dye concentration is increased, the fiber does not exhibit dyeability under atmospheric pressure.
  • C6-2G cyclohexane dimethanol
  • Example 1 Polymerization and spinning were performed in the same manner as in Example 1 except that ethylene glycol (hereinafter simply referred to as "2G") was used in place of 4G and the ratio of TMG to 2G was changed.
  • 2G ethylene glycol
  • the results obtained are shown in Table 1.
  • the polymer obtained was colored yellow and the fiber obtained was also colored yellow as having a b value of 18.3 and could not be used for uses required to have whiteness, such as inner wear.
  • a warp knitted fabric was prepared using the polyester fiber of Example 1 and Loica of 210 denier (polyurethane-based stretch fiber, produced by Asahi Chemical Industry Co., Ltd.).
  • the knitting gauge was 28 G
  • the loop length was 1,080 mm/480 course for polyester fiber and 112 mm/480 course for stretch fiber
  • the driving density was 90 course 25.4 mm (inch).
  • the ratio of polyester fiber mixed was set to 75.5%.
  • the grey fabric obtained was subjected to relax scouring at 90°C for 2 minutes and then to dry heatsetting at 160°C for 1 minute. Subsequently, the fabric was dyed at 95°C for 60 minutes at a pH of 6 adjusted by acetic acid and at a liquor to goods ratio of 1:30 using 8% owf of Dianics Black BG-FS (disperse dye, produced by Dystar Japan) in the presence of 0.5 g/l of Niccasansolt 1200 as a dyeing aid.
  • Dianics Black BG-FS diserse dye, produced by Dystar Japan
  • the dyed product obtained had an L value for indicating the black brightness of 11.7, revealing satisfactory dyeing. Furthermore, the dyed product had color fastness to laundry of class 5, color fastness to rubbing in wet state of class 5 and color fastness to light of class 4 and exhibited soft, highly stretching and excellent touch with tensiness and resiliency.
  • a warp knitted fabric was prepared using nylon 6 fiber spun by a conventional process and Loica in the same manner as in Example 22 and dyed using 7% owf of Kayaron Black BGL (acid dye, produced by Nippon Kayaku Co., Ltd.) at 95°C for 60 minutes.
  • the dyed product obtained had an L value of 12.3 and this fabric had color fastness to light of class 2 to 3.
  • a plain weave woven fabric (warp density: 140 yarns/25.4 mm, weft: 80 yarns/25.4 mm) was prepared using a polyester fiber of 75 d/36 f obtained in the same manner as in Example 16 for warp yarns and cuprammonium rayon of 75 d/44 f for weft yarns.
  • This plain weave woven fabric was scoured by a conventional process and then mercerized. The mercerization was performed by immersing the fabric in a 75% aqueous sodium hydroxide solution at an ordinary temperature. Thereafter, the fabric was neutralized, washed with water, preset at 180°C for 30 seconds, and then subjected to one bath one step dyeing with a disperse dye and a reactive dye without using a carrier.
  • the disperse dye used was Kayaron Polyester Blue BRSF (disperse dye, produced by Nippon Kayaku Co., Ltd.) and the reactive dye used was Drimarene Blue X-SGN (produced by Sandoz A.G.).
  • the dyeing solution was prepared by adding the dyes to an aqueous solution having added thereto 50 g/l of sodium sulfate and 15 g/l of sodium carbonate and adjusted to a pH of 11, using 1 g/l of Disper TL (produced by Meisei Chemical Works Ltd.) as a dispersing agent. The dyeing was performed at a dye concentration of 2% owf, a liquor to goods ratio of 1:50 and 95°C for 1 hour.
  • the fabric was soaped using 1 g/l of Gran Up P (nonionic surfactant, produced by Sanyo Chemical Industries Ltd.) at a liquor to goods ratio of 1:50 and 80°C for 10 minutes.
  • the dyed fabric was finished by a conventional process.
  • the dyed product obtained was uniformly dyed and had soft touch and dry feeling, which could not be attained by conventional woven fabrics.
  • the dyed product had K/S of 22.7, color fastness to dry cleaning solvent of class 3, color fastness to rubbing in wet state of class 4, and color fastness to light of class 4.
  • a plain weave woven fabric was manufactured using a polyester fiber of 75 d/36 f obtained in the same manner as in Example 1 for both the weft and warp yarns, and then dyed.
  • the fabric obtained had no dry feeling but was extremely soft and exhibited stretchability of about 7% in the weft direction.
  • the polyester fiber of Example 1 was twisted at 300 T/m and starched by a roller. Using this fiber for warp yarns and using diacetate (100 d/150 f) for weft yarns, a plain weave woven fabric (warp: 120 yarns/25.4 mm, weft: 80 yarns/25.4 mm) was prepared.
  • the fabric was then subjected to one bath one step dyeing at 95°C using Kayaron Polyester Blue 3RSF (produced by Nippon Kayaku Co., Ltd.) as a disperse dye for polyester fiber, and Kayaron Fast Blue RD200 (produced by Nippon Kayaku Co., Ltd.) as a disperse dye for diacetate, each at a dye concentration of 5% owf under weakly acidic conditions in the presence of a dispersing agent.
  • the fabric was soaped at 70°C for 20 minutes in a weak alkali bath containing 1 g/l of soda ash and 0.5 g/l of nonionic detergent.
  • the dyed product obtained was an excellent dyed product having K/S of 22.2. Furthermore, the dyed product had color fastness to dry cleaning solvent of class 3 to 4, color fastness to light of class 4, soft touch and excellent brilliance.
  • the polymer chip obtained was dried and then spun at a spinning temperature of 265°C and a spinning rate of 1,200 m/min using a spinneret having 36 orifices (diameter: 0.23 mm) each having a round cross section to prepare undrawn yarns.
  • the undrawn yarns obtained were draw-twisted using a hot roll at 60°C and a hot plate at 140°C at a draw ratio of 2.9 times and a drawing rate of 600 m/min to obtain drawn yarns of 50 d/36 f.
  • the fiber had physical properties such that the melting point was 219°C, Tmax was 100°C, the tenacity was 3.5 g/d, the elongation was 43%, U% was 1.0%, the modulus was 24 g/d, the elastic recovery was 82% and the b value was 7.6.
  • the Q/R value of this fiber was 0.29 and satisfied formula (1).
  • the polyester fiber obtained in this Example had a disperse dye exhaustion as high as 81% at 95°C for 60 minutes. After the dyeing, a single end fed knitted fabric was produced and examined on the color fastness to dry cleaning solvent. Then, the dyed product did not fade and the solution staining was class 3.
  • the dyed product also had good dyed color fastness such that the color fastness to light was class 4 to 5, the color fastness to rubbing in dry or wet state was class 5 and the color fastness to laundry was class 5.
  • Example 25 The experiment of Example 25 was repeated by varying the copolymerizing ratio of dimethyl isophthalate.
  • the test and evaluation results of fibers obtained are shown together in Table 2.
  • Comparative Example 8 the fiber was inferior in the dyeability due to the excessively low copolymerizing ratio and in Comparative Example 9, the color fastness to dry cleaning solvent was reduced due to the excessively high copolymerizing ratio.
  • Example 14 The experiment of Example 14 was repeated except that trimethyl phosphite were not used. The physical properties of fiber were not changed but the fiber had a b value of 12.3, thus, slightly turned yellow.
  • a warp knitted fabric was prepared using the polyester fiber of Example 10 and Loica of 210 denier (polyurethane-based stretch fiber, produced by Asahi Chemical Industry Co., Ltd.).
  • the knitting gauge was 28 GAG
  • the loop length was 1,080 mm/480 course for polyester fiber and 112 mm/480 course for stretch fiber
  • the driving density was 90 course 25.4 mm (inch).
  • the ratio of polyester fiber mixed was set to 75.5%.
  • the grey fabric obtained was subjected to relax scouring at 90°C for 2 minutes and then to dry heatsetting at 160°C for 1 minute. Subsequently, the fabric was dyed at 95°C for 60 minutes at a pH of 6 adjusted by acetic acid and at a liquor to goods ratio of 1:30 using 8% owf of Dianics Black BG-FS (disperse dye, produced by Dystar Japan) in the presence of 0.5 g/l of Niccasunsolt 1200 (produced by Nikka Chemical Co., Ltd.) as a dyeing aid.
  • Dianics Black BG-FS diserse dye, produced by Dystar Japan
  • the dyed product obtained had an L value for indicating the black brightness of 11.3, revealing satisfactory dyeing. Furthermore, the dyed product had color fastness to laundry of class 5, color fastness to rubbing in wet state of class'4 and color fastness to light of class 4 and exhibited soft, highly stretching and excellent touch with tensiness and resiliency.
  • the polymer chip obtained was dried and then spun at a spinning temperature of 265°C and a spinning rate of 1,200 m/min using a spinneret having 36 holes (diameter: 0.23 mm) each having a round cross section to prepare undrawn yarns.
  • the undrawn yarns obtained were draw-twisted using a hot roll at 50°C and a hot plate at 140°C at a draw ratio of 2.9 times and a drawing rate of 600 m/min to obtain drawn yarns of 50 d/36 f.
  • the fiber had physical properties such that the melting point was 232°C, Tmax was 92°C, the tenacity was 3.1 g/d, the elongation was 43%, U% was 1.1%, the modulus was 20 g/d, the elastic recovery was 89% and the b value was 8.2.
  • the Q/R value of this fiber was 0.22 and satisfied formula (1).
  • the polyester fiber obtained in this Example had a disperse dye exhaustion as high as 92% at 95°C for 60 minutes.
  • Example 18 Polymerization and spinning were performed in the same manner as in Example 18 by varying the kind of poly(alkylene glycol). The test and evaluation results obtained are shown together in Table 3. In any Example, the fiber satisfied formula (1) and exhibited excellent dyeability, high color fastness and good physical properties.
  • Example 18 The experiment of Example 18 was repeated by varying the copolymerizing ratio of poly(ethylene glycol). The results obtained are shown in Table 3. In Comparative Example 10, the dyeability was deficient due to the excessively low copolymerizing ratio and in Comparative Example 11, the color fastness to dry cleaning solvent was deteriorated due to the excessively high copolymerizing ratio. The whiteness of fiber was also reduced.
  • a warp knitted fabric was prepared using the polyester fiber of Example 18 and Loica of 210 denier (polyurethane-base stretch fiber, produced by Asahi Chemical Industry Co., Ltd.). The knitting conditions were set such that the gauge was 28 G, the loop length was 1,080 mm/480 course for polyester fiber and 112 mm/480 course for stretch fiber, and the driving density was 90 course/25.4 mm. The ratio of polyester fiber mixed was set to 75.5%.
  • the grey fabric obtained was subjected to relax scouring at 90°C for 2 minutes and then to dry heatsetting at 160°C for 1 minute. Subsequently, the fabric was dyed at 95°C for 60 minutes at a pH of 6 adjusted by acetic acid and at a liquor to goods ratio of 1:30 using 8% owf of Dianics Black BG-FS (produced by Dystar Japan) in the presence of 0.5 g/l of Niccasansolt 1200 as a dyeing aid.
  • the dyed product obtained had an L value for indicating the black brightness of 11.0, revealing satisfactory dyeing.
  • the fiber had color fastness to laundry of class 5, color fastness to abrasion in wet state of class 4 and color fastness to light of class 4 and the dyed fabric exhibited soft, highly stretching and excellent touch with tensiness and resiliency.
  • Poly(trimethylene terephthalate) having an intrinsic viscosity of 0.9 and poly(butylene terephthalate) having an intrinsic viscosity of 1.0 were mixed at a ratio of 94.8:5.2 and the mixture was extruded as it was.
  • a poly(trimethylene terephthalate) fiber was obtained by copolymerizing 5.2 wt% of 1,4-butane diol in the same manner as in Example 17.
  • the fiber obtained was almost equal to the fiber of Example 17 and had a tenacity of 3.6 g/d, an elongation of 43%, U% of 0.7%, a modulus of 23 g/d, an elastic recovery of 81%, a b value of 4.4, a Q/R value of 0.28, Tmax of 97°C and a disperse dye exhaustion at 95°C for 60 minutes of 84%.
  • the poly(trimethylene terephthalate)-based fiber of the present invention can be substantially dyed into desired shade with either one or both of a cationic dye and a disperse dye under atmospheric pressure.
  • the poly(trimethylene terephthalate)-based fiber of the present invention is a fiber material having wash-and-wear property, dimensional stability, good color fastness, dry touch feeling and suitability for caustic reduction treatment analogous to general-purpose polyester fiber, and also having softness analogous to nylon fiber.
  • the poly(trimethylene terephthalate)-based fiber of the present invention is a fiber material suitable for the production of a fast dyed product from a composite fabric with a stretch fabric represented by polyurethane elastic fiber, a fiber material having low heat resistance such as wool, silk and acetate fiber, or a cellulose fiber dyeable under atmospheric pressure.
  • a fast dyed fabric can be produced by a simple dyeing method using a general-purpose atmospheric dyeing facility without impairing the properties of fiber and this is an industrially noteworthy effect of the present invention.

Claims (6)

  1. Résine de polyester satisfaisant les conditions (1) à (3) suivantes :
    (1) la résine de polyester comprend un copolyester obtenu en copolymérisant de l'acide téréphtalique ou du téréphtalate de diméthyle, du triméthylène glycol et au moins un composé choisi dans le groupe consistant en les composés (a), (b) et (c) suivants :
    (a) le 1,4-butane diol en un rapport de copolymérisation de 1,5 à 12 % sur la base du poids du copolyester ;
    (b) un acide dicarboxylique aliphatique ou alicyclique ayant de 2 à 14 atomes de carbone ou de l'acide isophtalique en un rapport de copolymérisation de 3 à 9 % sur la base du poids du polymère ; et
    (c) un poly(alcoylène glycol) ayant une masse moléculaire de 300 à 20.000 en un rapport de copolymérisation de 3 à 10 % sur la base du poids du polymère ;
    (2) la résine a une viscosité intrinsèque de 0,4 à 1,2 mesurée à 35°C avec de l'ortho-chlorophénol en utilisant un viscosimètre d'Ostwald ; et
    (3) la résine a un degré de jaunissement tel que représenté par une valeur b de -2 à 10.
  2. Résine de polyester suivant la revendication 1, dans laquelle le glycol défini sous (a) est présent en un rapport de copolymérisation de 3 à 10 % sur la base du poids du polymère.
  3. Fibre de polyester, caractérisée en ce que la fibre de polyester satisfait les conditions (1), (2) et (3) suivantes :
    (1) la fibre de polyester est composée d'une résine de polyester comprenant un copolyester obtenu en copolymérisant de l'acide téréphtalique ou du téréphtalate de diméthyle, du triméthylène glycol et au moins un composé choisi dans le groupe consistant en les composés (a), (b) et (c) suivants :
    (a) le 1,4-butane diol en un rapport de copolymérisation de 1,5 à 12 % sur la base du poids du copolyester ;
    (b) un acide dicarboxylique aliphatique ou alicyclique ayant de 2 à 14 atomes de carbone ou de l'acide isophtalique en un rapport de copolymérisation de 3 à 9 % sur la base du poids du polymère ; et
    (c) un poly(alcoylène glycol) ayant une masse moléculaire de 300 à 20.000 en un rapport de copolymérisation de 3 à 10 % sur la base du poids du polymère ;
    (2) la fibre a une température de crête de la tangente de perte de 85 à 102°C ;
    (3) la relation entre le module Q (g/d) et la récupération R élastique (%) de la fibre satisfait la formule (1) suivante : 0 , 18 □ Q / R □ 0 , 45
    Figure imgb0012
  4. Fibre de polyester suivant la revendication 3, caractérisée en ce que la fibre de polyester a une valeur b représentant un degré d'un paramètre de jaunissement de -2 à 10.
  5. Procédé de production de la fibre de polyester telle que définie à la revendication 3 ou 4, caractérisé en ce que le procédé comprend les stades (1) à (4) suivants :
    (1) on extrude la résine de polyester à une température de filage de 240 à 280°C ; la résine de polyester comprenant un copolyester obtenu en copolymérisant de l'acide téréphtalique ou du téréphtalate de diméthyle, du triméthylène glycol et au moins un composé choisi dans le groupe consistant en les composés (a), (b) et (c) suivants :
    (a) le 1,4-butane diol en un rapport de copolymérisation de 1,5 à 12 % sur la base du poids du copolyester ;
    (b) un acide dicarboxylique aliphatique ou alicyclique ayant de 2 à 14 atomes de carbone ou de l'acide isophtalique en un rapport de copolymérisation de 3 à 9 % sur la base du poids du polymère ; et
    (c) un poly(alcoylène glycol) ayant une masse moléculaire de 300 à 20.000 en un rapport de copolymérisation de 3 à 10 % sur la base du poids du polymère ;
    (2) on bobine le fil solidifié sous la forme d'un fil non étiré à une vitesse de bobinage inférieure ou égale à 2.000 m à la minute sur un bobinoir ;
    (3) on étire le fil non étiré séparément à un rapport d'étirage de 2 à 4 à une température de 35 à 70°C ; et
    (4) on traite le fil étiré thermiquement à une température allant de 110 à 180°C avant de le renvider sur un bobinoir.
  6. Procédé de production de la fibre de polyester telle que définie à la revendication 3 ou 4, caractérisé en ce que le procédé comprend les stades (1) à (4) suivants :
    (a) on extrude une résine de polyester par la filière à une température de filage de 240 à 280°C ; la résine de polyester comprenant un copolyester obtenu en copolymérisant de l'acide téréphtalique ou du téréphtalate de diméthyle, du triméthylène glycol et au moins un composé choisi dans le groupe consistant en les composés (a), (b) et (c) suivants :
    (a) le 1,4-butane diol en un rapport de copolymérisation de 1,5 à 12 % sur la base du poids du copolyester ;
    (b) un acide dicarboxylique aliphatique ou alicyclique ayant de 2 à 14 atomes de carbone ou de l'acide isophtalique en un rapport de copolymérisation de 3 à 9 % sur la base du poids du polymère ; et
    (c) un poly(alcoylène glycol) ayant une masse moléculaire de 300 à 20.000 en un rapport de copolymérisation de 3 à 10 % sur la base du poids du polymère ;
    (2) on fait passer les filaments fondus extrudés dans une zone de réserve de chaleur ayant une longueur de 5 à 30 cm, qui est disposée juste en dessous de la buse de filage, la température de la zone étant maintenue à une température de 50 à 150°C, puis on refroidit les filaments extrudés immédiatement de manière à les solidifier après qu'ils ont passé la zone de refroidissement retardée ;
    (3) on met les filaments solidifiés en contact autour d'un premier rouleau chauffé entre 40 et 70°C et tournant à une vitesse de rotation de 1.500 à 3.000 m/minute, puis on met les filaments en contact autour d'un deuxième rouleau chauffé entre 120 et 160°C sans les enrouler tout en étirant les filaments à un rapport d'étirage de 1,5 à 3 fois entre le premier et le deuxième rouleau, la vitesse de rotation du deuxième rouleau étant plus grande que la vitesse de rotation du premier rouleau ; et
    (4) on renvide ensuite les filaments étirés en utilisant un bobinoir que l'on fait tourner à une vitesse plus petite que celle du deuxième rouleau.
EP04022765A 1997-08-18 1998-08-18 Fibre de polyester et textile préparé au moyen de cette fibre Expired - Lifetime EP1489206B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP23549297 1997-08-18
JP23549297 1997-08-18
JP24530197 1997-09-10
JP24530197 1997-09-10
EP98937854A EP1006220A4 (fr) 1997-08-18 1998-08-18 Fibre de polyester et textile prepare au moyen de cette fibre

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP98937854A Division EP1006220A4 (fr) 1997-08-18 1998-08-18 Fibre de polyester et textile prepare au moyen de cette fibre

Publications (3)

Publication Number Publication Date
EP1489206A2 EP1489206A2 (fr) 2004-12-22
EP1489206A3 EP1489206A3 (fr) 2005-01-05
EP1489206B1 true EP1489206B1 (fr) 2007-02-21

Family

ID=26532160

Family Applications (2)

Application Number Title Priority Date Filing Date
EP04022765A Expired - Lifetime EP1489206B1 (fr) 1997-08-18 1998-08-18 Fibre de polyester et textile préparé au moyen de cette fibre
EP98937854A Withdrawn EP1006220A4 (fr) 1997-08-18 1998-08-18 Fibre de polyester et textile prepare au moyen de cette fibre

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP98937854A Withdrawn EP1006220A4 (fr) 1997-08-18 1998-08-18 Fibre de polyester et textile prepare au moyen de cette fibre

Country Status (7)

Country Link
EP (2) EP1489206B1 (fr)
JP (1) JP3226931B2 (fr)
KR (2) KR100359149B1 (fr)
AT (1) ATE354601T1 (fr)
DE (1) DE69837169T2 (fr)
ES (1) ES2278255T3 (fr)
WO (1) WO1999009238A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6331264B1 (en) 1999-03-31 2001-12-18 E. I. Du Pont De Nemours And Company Low emission polymer compositions
US6576340B1 (en) 1999-11-12 2003-06-10 E. I. Du Pont De Nemours And Company Acid dyeable polyester compositions
TW572927B (en) * 1999-12-15 2004-01-21 Asahi Chemical Corp Trimethyleneterephthalate copolymer
US6312805B1 (en) 2000-02-11 2001-11-06 E.I. Du Pont De Nemours And Company Cationic dyeability modifier for use with polyester and polyamide
KR100635839B1 (ko) * 2000-07-14 2006-10-18 데이진 가부시키가이샤 폴리에스테르 섬유
US6316586B1 (en) 2000-08-15 2001-11-13 E. I. Du Pont De Nemours And Company Copolyether composition and processes therefor and therewith
US6331606B1 (en) 2000-12-01 2001-12-18 E. I. Du Pont De Nemours And Comapny Polyester composition and process therefor
US6479619B1 (en) 2001-03-15 2002-11-12 E. I. Du Pont De Nemours And Company Sulfoisophthalic acid solution process therewith
US6706852B2 (en) 2002-07-02 2004-03-16 E. I. Du Pont De Nemours And Company Partially ester-exchanged SIPM and process therewith
WO2009079499A1 (fr) * 2007-12-18 2009-06-25 Shell Oil Company Fibre polymère contenant un ignifuge, son processus de production, et matériau contenant de telles fibres
JP5758807B2 (ja) * 2009-10-20 2015-08-05 帝人フロンティア株式会社 ポリエステル繊維およびその製造方法および布帛および繊維製品
CN102838780B (zh) 2011-06-23 2014-09-24 杜邦公司 改性纳米颗粒、其制备方法及其用于提高纤维基材之阳离子染色性的用途
KR101125253B1 (ko) * 2011-10-28 2012-03-21 주식회사 지클로 음이온 고분자 염과 셀룰로오스로 조성되는 스킨-코어 섬유 및 이의 제조방법

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3671379A (en) * 1971-03-09 1972-06-20 Du Pont Composite polyester textile fibers
US3900527A (en) * 1973-04-16 1975-08-19 Monsanto Co Production of basic dyeable polyester from terephthalic acid
DE2431072C3 (de) * 1974-06-28 1980-04-30 Bayer Ag, 5090 Leverkusen Thermoplastische Copolyester und Verfahren zu ihrer Herstellung
JP3215714B2 (ja) * 1992-04-21 2001-10-09 株式会社クラレ 易染性ポリエステル繊維
JP3266222B2 (ja) * 1993-09-02 2002-03-18 東洋紡績株式会社 ポリエステル被覆弾性糸
JPH08269820A (ja) * 1995-04-04 1996-10-15 Asahi Chem Ind Co Ltd 易染性の改質ポリエステル繊維およびその製造方法

Also Published As

Publication number Publication date
EP1006220A1 (fr) 2000-06-07
WO1999009238A1 (fr) 1999-02-25
KR100359149B1 (ko) 2002-11-01
ES2278255T3 (es) 2007-08-01
ATE354601T1 (de) 2007-03-15
DE69837169T2 (de) 2008-01-03
KR20020048993A (ko) 2002-06-24
EP1489206A3 (fr) 2005-01-05
EP1489206A2 (fr) 2004-12-22
JP3226931B2 (ja) 2001-11-12
EP1006220A4 (fr) 2001-10-31
KR100359347B1 (ko) 2002-10-31
KR20010022988A (ko) 2001-03-26
DE69837169D1 (de) 2007-04-05

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