EP1489206A2 - Polyesterfaser und daraus hergestellte Flächengebilde - Google Patents
Polyesterfaser und daraus hergestellte Flächengebilde Download PDFInfo
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- EP1489206A2 EP1489206A2 EP04022765A EP04022765A EP1489206A2 EP 1489206 A2 EP1489206 A2 EP 1489206A2 EP 04022765 A EP04022765 A EP 04022765A EP 04022765 A EP04022765 A EP 04022765A EP 1489206 A2 EP1489206 A2 EP 1489206A2
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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 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 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.
- 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.
- the caustic reduction rate of the polyester fiber of the present invention is on the same level as that of an ordinary poly(ethylene terephthalate) fiber which is not cationic dye dyeable, and the caustic reduction treatment thereof can be performed by a known method.
- the thus-treated polyester fiber of the present invention can be characterized in that the touch is more soft and, due to the presence of microscopic pores of about a few ⁇ m on the fiber surface, a dry feeling is also present and dyeing in more brilliant color can be attained.
- ester-forming sulfonate compounds include 5-sodium sulfoisophthalate, 5-potassium sulfoisophthalate, 4-sodium sulfo-2,6-naphthalenedicaboxylate, 2-sodium sulfo-4-hydroxybenzoate, tetramethylphosphonium 3,5-dicarboxybenzene sulfonate, tetrabutylphosphonium 3,5-dicarboxybenzene sulfonate, tributylmethylphosphonium 3,5-dicarboxybenzene sulfonate, tetrabutylphosphonium 2,6-dicarboxynaphthalene-4-sulfonate, tetramethylphosphonium 2,6-dicarboxynaphthalene-4-sulfonate, ammonium 3,5-dicarboxybenzene sulfonate, and ester derivatives thereof, such as methyl, dimethyl and ester.
- aliphatic glycol and the alicyclic glycol each having from 4 to 12 carbon atoms include 1,2-butane diol, 1,3-butane diol, 1,4-butane diol, neopentyl glycol, 1,5-pentamethylene glycol, 1,6-hexamethylene glycol, heptamethylene glycol, octamethylene glycol, decamethylene glycol, dodecamethylene glycol, 1,4-cyclohexane diol, 1,3-cyclohexane diol, 1,2-cyclohexane diol, 1,4-cyclohexane dimethanol, 1,3-cyclohexane dimethanol and 1,2-cyclohexane dimethanol.
- 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.
- 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 average molecular weight of poly(alkylene glycol) is preferably from 400 to 10,000, more preferably from 500 to 5,000.
- 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 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 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 must be from 85 to 115°C when the third component is an ester-forming sulfonate compound, and 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 97 to 112°C when an ester-forming sulfonate compound is used as the third component, and 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
- 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 320°C, preferably from 240 to 300°C, more preferably 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 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 30 to 80°C, preferably 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 90 to 200°C, preferably from 100 to 190°, more preferably 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 extruded from the spinneret is, without abruptly cooling it, immediately passed through a heat reserving region 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 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 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 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.
- 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 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.
- a polymer was prepared in the same manner as in Example 1 except that the copolymerizing ratio of SIPP was 0.3 mol%.
- the test and evaluation results of fiber obtained are shown together in Table 1.
- the copolymerizing ratio of ester-forming sulfonate compound was less than 0.5 mol% and the fiber had a cationic dye exhaustion of 30% at 95°C for 30 minutes, thus, could not be dyed into dark shade.
- a fiber was prepared through polymerization and spinning in the same manner as in Example 1 except that the copolymerizing ratio of SIPP was 6 mol%.
- the test and evaluation results thereof are shown together in Table 1.
- yarn breaking was generated frequently, revealing bad spinnability.
- the fiber was dyed at 95%, the yarn was shrunk and turned hard, as a result, a fabric having good touch could not be obtained.
- the fabric obtained was reduced in the color fastness to dry cleaning solvent as compared with the fabric of Example 1.
- Example 1 the draw ratio was changed to 3.3 times.
- the fiber obtained was excessively oriented and had Tmax in excess of 115°C.
- the cationic dye exhaustion was 45%. Furthermore, in the fiber obtained, many broken filaments were generated.
- Example 2 Polymerization and spinning were performed in the same manner as in Example 1 except that the hot roll temperature was 25°C. At the drawing, yarn breaking was generated frequently and a fiber could not be continuously obtained. Also, polymerization and spinning were performed in the same manner as in Example 1 except that the hot roll temperature was 80°C. The yarn melted to adhere the hot roll at the drawing and single filament breaking was generated frequently. Furthermore, the fiber obtained was full of broken filaments and U% was bad and as high as 3.2.
- Polymerization and spinning were performed in the same manner as in Example 1 except that the hot plate temperature was 70°C.
- a fiber could be obtained without problems such as yarn breaking and generation of broken filaments.
- the fiber obtained had an elastic recovery as low as 55% and the Q/R value was 0.49 and could not satisfy formula (1).
- Polymerization and spinning were performed in the same manner as in Example 1 except that the hot plate temperature was 200°C. The fiber was broken on the hot plate and could not be drawn.
- Spinning was performed using a poly(ethylene terephthalate) fiber obtained by copolymerizing 2.5 mol% of 5-sodium sulfoisophthalate.
- the fiber obtained exhibited a tenacity of 4.2 g/d, an elongation of 30%, a modulus of 100 g/d, an elastic recovery of 31%, a Q/R value of 3.2 and Tmax of 131°C.
- the cation dye exhaustion at 95°C for 30 minutes was 36%.
- a poly(ethylene terephthalate) fiber obtained by copolymerizing 3 mol% of 5-sodium sulfo isophthalate was knitted in the same manner as in Example 12 to prepare a single stitch knitted fabric.
- This single stitch knitted fabric was subjected to a caustic reduction treatment in the same manner as in Example 12, then the knitted fabric was completely decomposed, dissolved and lost.
- the poly(ethylene terephthalate) fiber obtained by copolymerizing 3 mol% of 5-sodium sulfoisophthalate could not be substantially subjected to a caustic reduction treatment due to its excessively high reduction rate.
- the dyed product did not fade.
- the solution staining was class 4 to 5 with both the cationic dye and the disperse dye. Also, good results were obtained about the color fastness to light (class 4 to 5), the color fastness to rubbing in dry or wet state (class 5) and the color fastness to laundry (class 5).
- Example 2 The fiber obtained in Example 2 was cut to obtain staples each having a fiber length of 39 mm.
- a filament of 20 d/2 f obtained in the same manner as in Example 2 a composite yarn having a filament mixed ratio of 11 wt% was obtained, where the staples were arrayed in the sheath.
- This composite yarn was woven into a woven fabric consisting of warp yarns (weaving density: 146 yarns/25.4 mm) and weft yarns (weaving density: 77 yarns/25.4 mm).
- the woven fabric obtained was dyed at 95°C according to the method described in Example 9.
- the dyed fabric had K/S of 25.3, revealing dyeing into dark shade. Furthermore, the fabric obtained had excellent properties with respect to tensiness, resiliency, and repulsion.
- Example 2 The polymer obtained in Example 2 was subjected to solid state polymerization at 200°C for 24 hours in nitrogen to obtain a polymer having an intrinsic viscosity of 1.0. This polymer was spun in the same manner as in Example 1.
- the fiber obtained had physical properties such that the tenacity was 4.0 g/d, the elongation was 32%, U% was 1.0%, the modulus was 23 g/d, the elastic recovery was 91%, the Q/R value was 0.25, Tmax was 110°C and the b value was 4.3.
- 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 polyester fiber obtained in this Example had a disperse dye exhaustion as high as 78% at 95°C for 60 minutes.
- Example 1 Using the polymer of Comparative Example 1, a fiber was prepared according to 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. However, when 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
- a warp knitted fabric was prepared using the polyester fiber of Example 16 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/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 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 16 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 16 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 3.
- Comparative Example 19 the fiber was inferior in the dyeability due to the excessively low copolymerizing ratio and in Comparative Example 20, the color fastness to dry cleaning solvent was reduced due to the excessively high copolymerizing ratio.
- Example 29 The experiment of Example 29 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 25 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/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 33 The experiment of Example 33 was repeated by varying the copolymerizing ratio of poly(ethylene glycol). The results obtained are shown in Table 4.
- Comparative Example 21 the dyeability was deficient due to the excessively low copolymerizing ratio and in Comparative Example 22, 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 33 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.
- 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 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 (dispersing agent, produced by Meisei Chemical Works Ltd.). The dyeing was performed at a dye concentration of 2% owf, a liquor to goods ratio of 1:50 and 100°C for 1 hour. After the dyeing, the fabric was soaped using 1 g/l of Gran Up P (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.
- a plain weave woven fabric was manufactured using the polyester fiber of 75 d/36 f obtained 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.
- a plain weave woven fabric (warp: 140 yarns/3.54, weft: 80 yarns/25.4) was prepared using the polyester fiber of 75 d/36 f obtained in Example 1 for warp yarns and weft yarns.
- This plain weave woven fabric was scoured by a conventional process, treated for caustic reduction of 20% using a 10% aqueous sodium hydroxide solution, then preset and dyed in the same manner as in Example 42, and finally heatset at 180°C for 30 seconds.
- ester-forming sulfonate compound is 5-sodium sulfoisophthalate and/or tetramethylphosphonium 3,5-dicarboxybenzene sulfonate (wherein the alkyl group is an alkyl group having from 1 to 10 carbon atoms) and the copolymerizing ratio thereof is from 1.2 to 2.5 mol%.
- a polyester fiber which is a poly(trimethylene terephthalate) fiber obtained by copolymerizing an ester-forming sulfonate compound in a copolymerizing ratio of from 1.2 to 2.5 mol% with from 3 to 7 wt% of at least one selected from the group consisting of (1) an aliphatic or alicyclic glycol having from 4 to 12 carbon, (2) an aliphatic or alicyclic dicarboxylic acid having from 2 to 14 carbon atoms or isophthalic acid, and (3) a poly(alkylene glycol), wherein the fiber has a peak temperature of loss tangent of from 85 to 115°C and the relationship between modulus Q (g/d) and elastic recovery R (%) of the fiber satisfies the following formula (1): 0.18 ⁇ Q/R ⁇ 0.45
- polyester fiber as above which has b value of from -2 to 10.
- a blend fabric comprising the polyester fiber as above in combination with a stretch fiber.
- a fabric partly or entirely comprising the polyester fiber as above , which is dyed with a cationic dye and/or a disperse dye.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
- Materials For Medical Uses (AREA)
- Nonwoven Fabrics (AREA)
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 (de) | 1997-08-18 | 1998-08-18 | Polyesterfaser und daraus hergestellte textile flächengebilde |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP98937854A Division EP1006220A4 (de) | 1997-08-18 | 1998-08-18 | Polyesterfaser und daraus hergestellte textile flächengebilde |
Publications (3)
Publication Number | Publication Date |
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EP1489206A2 true EP1489206A2 (de) | 2004-12-22 |
EP1489206A3 EP1489206A3 (de) | 2005-01-05 |
EP1489206B1 EP1489206B1 (de) | 2007-02-21 |
Family
ID=26532160
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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EP04022765A Expired - Lifetime EP1489206B1 (de) | 1997-08-18 | 1998-08-18 | Polyesterfaser und daraus hergestellte Flächengebilde |
EP98937854A Withdrawn EP1006220A4 (de) | 1997-08-18 | 1998-08-18 | Polyesterfaser und daraus hergestellte textile flächengebilde |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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EP98937854A Withdrawn EP1006220A4 (de) | 1997-08-18 | 1998-08-18 | Polyesterfaser und daraus hergestellte textile flächengebilde |
Country Status (7)
Country | Link |
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EP (2) | EP1489206B1 (de) |
JP (1) | JP3226931B2 (de) |
KR (2) | KR100359149B1 (de) |
AT (1) | ATE354601T1 (de) |
DE (1) | DE69837169T2 (de) |
ES (1) | ES2278255T3 (de) |
WO (1) | WO1999009238A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009079499A1 (en) * | 2007-12-18 | 2009-06-25 | Shell Oil Company | Polymer fiber containing flame retardant, process for producing the same, and material containing such fibers |
US20120207955A1 (en) * | 2009-10-20 | 2012-08-16 | Teijin Fibers Limited | Polyester fiber, method for producing the same, cloth, textile product, and polyester formed article |
Families Citing this family (11)
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 |
CN1193120C (zh) * | 2000-07-14 | 2005-03-16 | 帝人株式会社 | 聚酯纤维 |
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 |
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 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1507358A (en) * | 1974-06-28 | 1978-04-12 | Bayer Ag | Process for producing thermoplastic copolyesters |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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 |
-
1998
- 1998-08-18 DE DE69837169T patent/DE69837169T2/de not_active Expired - Lifetime
- 1998-08-18 KR KR1020027005495A patent/KR100359149B1/ko not_active IP Right Cessation
- 1998-08-18 WO PCT/JP1998/003660 patent/WO1999009238A1/ja not_active Application Discontinuation
- 1998-08-18 JP JP51302799A patent/JP3226931B2/ja not_active Expired - Lifetime
- 1998-08-18 EP EP04022765A patent/EP1489206B1/de not_active Expired - Lifetime
- 1998-08-18 ES ES04022765T patent/ES2278255T3/es not_active Expired - Lifetime
- 1998-08-18 AT AT04022765T patent/ATE354601T1/de not_active IP Right Cessation
- 1998-08-18 EP EP98937854A patent/EP1006220A4/de not_active Withdrawn
- 1998-08-18 KR KR1020007001596A patent/KR100359347B1/ko not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1507358A (en) * | 1974-06-28 | 1978-04-12 | Bayer Ag | Process for producing thermoplastic copolyesters |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009079499A1 (en) * | 2007-12-18 | 2009-06-25 | Shell Oil Company | Polymer fiber containing flame retardant, process for producing the same, and material containing such fibers |
US20120207955A1 (en) * | 2009-10-20 | 2012-08-16 | Teijin Fibers Limited | Polyester fiber, method for producing the same, cloth, textile product, and polyester formed article |
US9334608B2 (en) * | 2009-10-20 | 2016-05-10 | Teijin Frontier Co., Ltd. | Polyester fiber, method for producing the same, cloth, textile product, and polyester formed article |
Also Published As
Publication number | Publication date |
---|---|
ES2278255T3 (es) | 2007-08-01 |
ATE354601T1 (de) | 2007-03-15 |
EP1489206A3 (de) | 2005-01-05 |
EP1006220A1 (de) | 2000-06-07 |
DE69837169D1 (de) | 2007-04-05 |
DE69837169T2 (de) | 2008-01-03 |
KR100359347B1 (ko) | 2002-10-31 |
EP1489206B1 (de) | 2007-02-21 |
EP1006220A4 (de) | 2001-10-31 |
KR100359149B1 (ko) | 2002-11-01 |
JP3226931B2 (ja) | 2001-11-12 |
KR20020048993A (ko) | 2002-06-24 |
KR20010022988A (ko) | 2001-03-26 |
WO1999009238A1 (fr) | 1999-02-25 |
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