EASILY DYEABLE POLYETHYLENE TEREPHTALATE FIBRE AND PROCESS FOR PREPARING THE SAME

Abstract: Fine polyethylene terephthalate fiber having a monofila­ ment denier of not more than about 4 deniers is spun at a high spinning speed of not less than 7,000 m/min, the polyethylene terephthalate filaments extruded from a spinneret having a plu­ rality of spinning holes being passed through a heating zone provided beneath the spinneret and then being bundled by a bundling guide positioned beneath the point of completion of filament fining, which point exists within or below the heating zone. The obtained fiber has a highly improved dyeability.

Description: Background of the invention Field of the invention The invention relates to a polyethylene terephthalate fibre of improved dyeability and to a process for the preparation thereof. More particularly, the invention relates to an easily dyeable polyethylene terephthalate fibre which can be dyed at 100°C, i.e., under normal pressure, without the use of a carrier after being false twisted and to a process for preparing the fibre by high-speed spinning at a spinning speed of not less than 7,000 m/min, and taking up a bundle of the filaments without using godet rolls. Description of the prior art Polyethylene terephthalate fibres are widely used in the garment industry. They are, however, poor in dyeability, and, thus, it is necessary to dye them by using a high-pressure dyeing machine at a high temperature of about 130°C and under a high pressure or by using a carrier of an organic solvent. High-temperature and high-pressure dyeing have disadvantages in that much energy is necessary and in that the fibres cannot be substantially used in combination with other fibres, such as wool, acrylic fibres, or polyurethane fibres, which fibres are degraded during high-temperature and high-pressure dyeing. On the other hand, carrier dyeing has disadvantages in that, due to the use of an organic solvent as the carrier, the process is complicated, the odour of the used solvent remains on the product, and treatment of the waste liquor is difficult. Therefore, it is very advantageous if a polyethylene terephthalate fibre which can be dyed at a temperature lower than 130°C can be obtained. Particularly, if it is possible to dye a polyethylene terephthalate fibre at a temperature not higher than 100°C, i.e., under normal pressure, the following advantages can be attained: energy can be saved, the use of a carrier is unnecessary, and excellent new textiles, such as mixed knitted or woven fabrics, can be obtained since the polyethylene terephthalate fibres can be used in combination with other fibres such as wool, acrylic fibres, or polyurethane fibres which are degraded by dyeing at 130°C. Therefore, the utility of the polyethylene terephthalate fibres can be increased. Such an easily dyeable polyethylene terephthalate fibre has another advantage in that the use of an expensive high-pressure dyeing machine, the control of which is complicated, is unnecessary, i.e., an inexpensive and simple dyeing machine such as a jigger can be used. A method in which a third component, such as a compound having a metal sulfonate group, is copolymerized with polyethylene terephthalate is known as a method for improving the dyeability of a polyethylene terephthalate fibre. However, in this method, the thermal and mechanical properties, such as the melting point and strength, inherent to polyethylene terephthalate may be deteriorated. In addition, it is still impossible to dye the resultant fibre in combination with wool, an acrylic fibre, or a polyurethane fibre without the use of a carrier. Further, such a copolymerized polyethylene terephthalate may often have a poor light fastness when dyed. GB-A-2 002 680 describes a single step draw spinning process for the manufacture of polyester yarns in which two fluid environments of different temperatures are used for the treatment of the material of the filaments. Thereafter this material is wound up at a speed in excess of 5500 metres/min. The yarn obtained has a generally high boiling water shrinkage. GB-A-2 078 605 describes a polyester fibre suitable for a raw yarn for a woven or knitted fabric. The process for producing this fibre is based on a spin-draw-take-up process in which a stretch treatment is carried out at a stretch ratio of not more than 20% after the solidification of the fibre but before the taking up. The boiling water shrinkage of the obtained fibre is very high, and this prior art is completely silent concerning the dyeability of the resulting fibre. Japanese Examined Patent Publication (Kokoku) No. 35-3104 discloses that highly oriented filaments having practical, satisfactory properties can be obtained by high-speed spinning, in which melt-spun polyethylene terephthalate filaments are taken up at a speed of not less than 4,000 m/min even if the filaments are not subjected to drawing. U.S. Patent Nos. 4,156,071, 4,134,882, and 4,195,051 and Seni Gakkaishi, 37 , No. 4, pages T135 to T142 (1981) disclose that polyethylene terephthalate fibres obtained by high-speed spinning at not less than 4,000 m/min have a higher dyeability than do polyethylene terephthalate fibres obtained by a conventional process in which polyethylene terephthalate is melt spun at a low speed and the resultant filaments are then subjected to drawing. The polyethylene terephthalate fibre disclosed in U.S. Patent No. 4,156,071 has a high dyeability since it is spun at a speed of about 4,000 m/min. However, the fibre has a serious practical disadvantage in that the fibre is elongated by a relatively low load at the weaving or knitting step due to the low first yield stress, and, thus, a fabric obtained from the fibre may often have uneven dyeing or a poor quality. Also, the fibre has an initial modulus of about 442 cN/tex (50 g/d), which is approximately equal to that of a cellulose acetate fibre and, thus, does not maintain excellent hands inherent to a conventional polyethylene terephthalate fibre. The polyethylene terephthalate fibre disclosed in U.S. Patent No. 4,134,882 has a long period of not less than 30 nm, a low distribution of birefringence across the transverse cross section of a filament, and a high dyeability. This fibre may be prepared by a process disclosed in U.S. Patent No. 4,195,051, in which process a spinneret having nozzles of a length diameter ratio larger than usual is used and spun filaments are taken up at a speed of not less than 5,200 yards/min (i.e., 4,700 m/min). In these two U.S. Patents, examples are given in which spinning is carried out at a speed of from 4,950 m/min to 7,200 m/min. However, in the disclosed process, the higher the spinning speed, the greater the air drag, with the result that yarn breakage may often occur. In order to avoid this problem, it is necessary to increase the fineness of the filaments to be spun (i.e., decrease the surface area per unit weight) as the spinning speed is increased. It has conventionally been impossible to obtain a polyethylene terephthalate filament fibre having a fineness of not more than 4.5 dtex (4 deniers), i.e., a surface area per unit weight of not less than 1,400 cm²/g, which is suitable for making garments at a spinning speed of not less than 7,000 m/min. In addition, the polyethylene terephthalate fibre obtained by this process cannot have a dyeability enabling it to be dyed under normal pressure even after the fibre is false twisted. By the process disclosed in Seni Gakkaishi, 37 , No. 4, pages T135 to T142 (1981), in which process polyethylene terephthalate is spun at a high speed while cooling the as-spun filaments with cooling air of -2°C immediately after extrusion from the spinneret, a polyethylene terephthalate filament fibre of a fineness of not less than 6.4 dtex (5.8 deniers) (i.e., a surface area per unit weight of not more than 1190 cm²/g) can be obtained at a spinning speed of from 7,000 m/min to 9,000 m/min. This publication further discloses that the polyethylene terephthalate fibre obtained at a spinning speed of not less than 7,000 m/min has a high dyeability which is further improved as the spinning speed increases. However, the fibre cannot have a dyeability enabling it to be dyed under normal pressure even after false twisting is carried out. As was mentioned above, in known high-speed spinning processes, it is impossible to spin a polyethylene terephthalate filament fibre having a fineness of not more than about 4.5 dtex (4 deniers) at a speed of not less than 7,000 m/min, and, thus, a polyethylene terephthalate fibre which can be dyed under normal pressure after false twisting cannot be obtained. Japanese Unexamined Patent Publication (Kokai) No. 51-7216 discloses a process for preparing a polyester fibre at a spinning speed of from 2,000 m/min to 5,000 m/min, in which process the as-spun filaments are bundled at a point not more than 25 cm beneath the hardening point (i.e., the point of completion of fining) of the filaments. However, even if the process as such is applied in high-speed spinning of not less than 7,000 m/min, spinning is impossible due to the frequent occurrence of yarn breakage. This publication is completely silent concerning means for making possible spinning at a speed of not less than 7,000 m/min. Summary of the invention It is an object of the present invention to provide a polyethylene terephthalate fibre from which a false-twisted fibre which can be dyed under normal pressure can be obtained. It is another object of the present invention to provide a process for preparing a polyethylene terephthalate fibre having a fineness of not more than about 4.5 dtex, i.e., a surface area per unit weight of not less than 1,400 cm²/g, at a spinning speed of not less than 7,000 m/min. It is a further object of the present invention to provide a process for preparing a polyethylene terephthalate fibre in which a spun fibre is taken up into a package of a high package form quality under a low winding tension without using godet rolls. The inventors have made extensive studies in an attempt to attain the above-mentioned objects and have found that if extruded polyethylene terephthalate filaments are passed through a heating zone provided beneath a spinneret, the heating zone having a certain temperature, and then are bundled by a bundling guide positioned beneath the point of completion of fining of the filaments, which point exists within or below the heating zone, the stability of spinning at a high speed is extremely improved. Thus, it is possible to effect the spinning of a fine polyethylene terephthalate fibre having a monofilament fineness of not more than about 4.5 dtex (i.e., a surface area per unit weight of not less than 1,400 cm²/g) at a spinning speed of not less than 7,000 m/min, and taking up a bundle of the filaments without using godet rolls, and the obtained fibre has a highly improved dyeability. Thus, the present invention provides an easily dyeable polyethylene terephthalate fibre, characterized by an intrinsic viscosity of the polymer of from 0.50 to 1.0, an initial modulus of from 534 cN/tex to 1157 cN/tex, a surface area per unit weight of from 1,400 cm²/g to 4,000 cm²/g, and a peak temperature (T max ) at which the dynamic loss tangent (tan δ) measured at a frequency of 110 Hz becomes maximum and a maximum tan δ value (tan δ) max satisfying the following relationship (1) or (2): (1) 105°C<T max ≦115°C and 0.135<(tan δ) max ≦0.190 (2) 110°C<T max ≦115°C and 0. 110≦(tan δ) max ≦0.135 The easily dyeable polyethylene terephthalate fibre is prepared, according to the present invention, by a process characterized by melt-spinning polyethylene terephthalate through a spinneret having a plurality of spinning holes at a spinning speed of not less than 7,000 m/min, and taking up a bundle of the filaments without using godet rolls, in which a group of extruded filaments is passed through a heating zone defined over a length of not less than 5 cm from the bottom surface of the spinneret, is maintained at a temperature of from 150°C to 300°C, and then is bundled into a filament bundle by means of a bundling guide positioned so as to satisfy the following conditions (a) and (b): (a) said position should be not less than 5 cm beneath the point of completion of fining of the group of filaments (b) the tension imposed on the filament bundle 5 cm beneath said position of the bundling guide should be not more than 0.36 cN/dtex. Brief description of the drawings Figure 1 is a graph illustrating the relationships of T max values and (tan δ) max values. Figure 2 is a schematic view illustrating an embodiment of an apparatus to be employed in the process according to the present invention, which apparatus has no godet rolls. Figure 3 is a graph schematically illustrating the dynamic loss tangent (tan δ)-temperature (T) curve. Figure 4 is a schematic view illustrating the point of completion of fining of a filament being processed by the process according to the present invention. Figure 5A is a schematic plan view illustrating an oiling nozzle guide arrangement usable for the present invention. Figure 5B is a schematic front view of the oiling nozzle part of the guide arrangement shown in Fig. 5A. Figure 6A is a schematic side view of a bundling guide usable for the present invention. Figure 6B is a schematic plan view of the bundling guide shown in Fig. 6A. Description of the preferred embodiments The process for preparing a polyethylene terephthalate fibre according to the present invention will now be described in detail with reference to Fig. 2. Molten polyethylene terephthalate is extruded from a spinneret 2, having a plurality of spinning holes and provided in a heated spinhead 1, into a group of filaments 4. The filament group 4 is passed through a heating zone defined in a heating cylinder 3 while being gradually fined, is cooled by cooling air 6, and then is bundled and oiled by an oiling nozzle guide 5. Fining of the individual filaments of the filament group 4 is suddenly completed above the oiling nozzle guide 5, which fining is explained hereinafter. Thus, the oiling nozzle guide or bundling guide is positioned not less than 5 cm beneath the point of completion of fining of the filaments, and, in addition, the filament bundle receives a tension of not more than 0.36 cN/dtex 5 cm beneath the oiling nozzle guide or bundling guide. The filament bundle is then taken up by a take-up unit 7. The polyethylene terephthalate usable for the present invention may be prepared by known polymerization processes and may optionally contain a thermal stabilizer, a flaking agent, an anti-static agent, or the like. The polyethylene terephthalate has an intrinsic viscosity of from 0.50 to 1.0. If the intrinsic viscosity is less than 0.50, the resultant polyethylene terephthalate fibre may have a low strength so that the fibre cannot be utilized for garments. If the intrinsic viscosity is more than 1.0, melt spinning at a high speed may be impossible. Preferably, the polyethylene terephthalate has an intrinsic viscosity of from 0.55 to 0.70. The polyethylene terephthalate fibre according to the present invention has an initial modulus of from 534 cN/tex to 1157 cN/tex, preferably from 623 cN/tex to 1068 cN/tex. If the initial modulus is less than 534 cN/tex, the polyethylene terephthalate fibre may lose excellent hands inherent to a conventional polyethylene terephthalate fibre and have a poor resiliency after the false twisting thereof. On the other hand, a polyethylene terephthalate fibre having an initial modulus of 1157 cN/tex cannot be obtained without subjecting the fibre to drawing even if the spinning speed and the intrinsic viscosity of the polymer are selected within any range. The polyethylene terephthalate fibre has a surface area per unit weight of from 1,400 cm²/g to 4,000 cm²/g, preferably from 1,600 cm²/g to 3,000 cm²/g, more preferably from 1,900 cm²/g to 3,000 cm²/g. In the case of a filament having a circular cross section, the surface area per unit weight may be calculated from a fineness D (dtex) and a density ρ (g/cm³) according to the following equation: Surface area per unit weight (cm²/g) =2 900,000π ρD In the case of a filament having a noncircular cross section, the surface area per unit weight may be calculated from the peripheral length l (cm) of the cross section of the filament determined from a micrograph of the cross section, a density ρ (g/cm³), and a fineness D (dtex) according to the following equation: Surface area per unit weight (cm²/g)=900,000 I/D If the surface area per unit weight is less than 1,400 cm²/g, the fibre has a poor dyeability and cannot be dyed under normal pressure after the false twisting thereof. On the other hand, a polyethylene terephthalate fibre having a surface area per unit weight of more than 4,000 cm²/g cannot be obtained by high-speed spinning of more than 7,000 m/min. Further, the polyethylene terephthalate fibre according to the present invention has a peak temperature (T max ) at which the dynamic loss tangent (tan δ) measured at a frequency of 110 Hz becomes maximum and a maximum tan δ value (tan δ) max satisfying one of the following relationships: (1) 105°C<T max ≦115°C and 0. 135<(tan δ) max ≦0. 190 (2) 110°C<T max ≦115°C and 0.110≦(tan δ) max ≦0.135 The above-mentioned ranges (1) and (2) are represented by oblique lines in Fig. 1, in which the area (1) corresponds to the range (1) above and the area (2) corresponds to the range (2) above. In this connection, it should be noted that the polyethylene terephthalate fibre described and claimed in our European Patent Application No. 0056963 (filed on January 16, 1982 and published on 04.08.82), has a peak temperature (T max ) and a maximum tan δ value (tan δ) max falling within the following range: 85°C≦T max ≦110°C and 0.115≦(tan δ) max ≦0.135 This range is indicated by (3) in Fig. 1. Therefore, the fibre of the present invention is clearly different from the fibre in the above-mentioned European patent application. A polyethylene terephthalate fibre having a T max greater than 115°C or greater than 110°C but not greater than 115°C and a (tan δ) max less than 0.110 has a poor dyeability so that a false-twisted fiber obtained therefrom cannot be dyed at 100°C and be practically acceptable even if the fiber has a surface area per unit weight within any range. A polyethylene terephthalate having a T max not greater than 110°C and a (tan δ) max not greater than 0.135 has a good dyeability but is difficult to stably produce unless the intrinsic viscosity of the polyethylene terephthalate is less than 0.50 since yarn breakage often occurs during spinning. On the other hand, if the intrinsic viscosity of the polyethylene terephthalate is less than 0.5, yarn breakage often occurs during false twisting. A polyethylene terephthalate fibre having a T max not greater than 105°C and a (tan δ) max greater than 0.135 has a good dyeability but a low first yield stress before and after false twisting so that the fibre may easily be elongated by a relatively low load, and, thus, the disappearance of crimp and uneven dyeing may often result. Further, a polyethylene terephthalate fibre having a T max greater than 105°C but not greater than 115°C and a (tan δ) max greater than 0.190 has a poor dyeability and, thus, cannot be dyed under normal pressure even after false twisting or has too low an initial modulus, i.e., less than 534 cN/tex. Preferably, the polyethylene terephthalate fibre has a T max within a range of 105°C<T max ≦113°C and a (tan δ) max within a range of 0.135<(tan δ) max ≦0.180. In the present invention, the easily dyeable polyethylene terephthalate fibre is prepared by melt spinning the polymer through a spinneret, having a plurality of holes, at a spinning speed of not less than 7,000 m/min and taking up a bundle of the filaments without using godet rolls. Conventional known spinnerets may be employed. The spinning speed is the running speed of the filament bundle after the completion of filament fining, which speed is identical to the take-up speed in a case where no godet rolls are used. In the process according to the present invention, the polyethylene terephthalate filaments extruded from the spinneret are passed through a heating zone defined over a length of not less than 5 cm from the bottom surface of the spinneret and are maintained at a temperature of from 150°C to 300°C. Such a heating zone may be formed by providing below the spinneret a cylindrical heater having an inner diameter corresponding to the number of extruded filaments and the arrangement of the spinneret holes or by feeding a heating fluid over a length of not less than 5 cm from the bottom surface of the spinneret. If the heating zone is less than 5 cm, stable spinning cannot be carried out at a high speed. The upper limit of the length of the heating zone is not critical, but a length of not more than 100 cm is preferred from the viewpoints of economy and ease in operation of the apparatus. The optimum length of the heating zone may depend on the intrinsic viscosity of the polymer, the extrusion temperature, or the fineness of the extruded filaments but is in general from 20 cm to 50 cm. The atmosphere in the heating zone may be composed of air, nitrogen, or steam, but air is preferred from the viewpoint of economy. If the temperature of the heating zone is lower than 150°C, a satisfactory heating effect cannot be obtained so that spinning at a speed of not less than 7,000 m/min is impossible. If the temperature is higher than 300°C, stable spinning is impossible due to the occurrence of inter-filament fusion or frequent yarn breakage. The temperature of the heating zone herein refers to the temperature of the atmosphere near the filaments in the heating zone. The group of filaments is bundled by means of a bundling guide positioned at least 5 cm beneath the point of completion of filament fining after the fining of individual filaments is completed within or below the heating zone. In high-speed spinning in which molten polyethylene terephthalate is extruded from a spinneret and the thus-formed filaments are taken up at a speed of not less than about 5,000 m/min, there is known, for example, from G. Perez and C. Lecluse, "International Man-Made Fibers Conference", Dornbirn, Austria, 1979 the existance of a point at which the extruded filaments suddenly become fine during spinning so that they have a fineness finally desired. In the present invention, this point is confirmed, and this point herein is referred to as the point of completion of filament fining. Figure 4 illustrates the shape of a filament near the point of completion of filament fining of filaments obtained at a spinning speed of 5,400 m/min, described in the above-mentioned publication. In the process of the present invention, the air drag imposed on the filaments can be greatly reduced by the bundling of the group of filaments through the bundling guide so that the occurrence of filament breakage is extremely reduced, and, thus, very stable spinning becomes possible. If the bundling guide is positioned less than 5 cm beneath the point of completion of filament fining, the filaments may be brought into contact with each other above the point of completion of filament fining so that filament breakage often occurs, and, thus, spinning becomes very unstable. The air drag increases in proportion to the distance between the point of completion of filament fining and the bundling guide. Thus, the tension imposed on the group of filaments 5 cm beneath the bundling guide may vary depending on the position of the bundling guide. In this connection, in the process of the present invention, it is necessary that the tension imposed on the filament bundle 5 cm beneath the bundling guide be not more than 0.36 cN/dtex, preferably not more than 0.27 cN/dtex. If the tension is more than 0.36 cN/dtex, filament breakage often occurs, and a package of a good package form quality can not be obtained, even if a take-up unit is located in the vicinity of the bundling guide, unless godet rolls are used. The use of a bundling guide as mentioned above may cause filament breakage due to the friction between the guide surface and the filaments, depending upon the material of the guide. Therefore, it is preferable that the group of filaments be bundled while being oiled, using an oiling nozzle guide as the bundling guide. By oiling the filaments with an oiling nozzle guide while bundling, the friction between the group of filaments and the oiling nozzle guide can be reduced, and, in addition, the filaments can be cooled concurrently with the bundling thereof so that inter-filament fusion or adhesion can be avoided. Of course, this oiling can be the oiling necessary for the finishing of a multifilament yarn. An example of the oiling nozzle guide usable for the present invention is illustrated in Figs. 5A and 5B. The oiling nozzle guide 8 has a cut 13 of a V or U shape at the end thereof and a nozzle 9 at the bottom of the cut 13. The nozzle 9 is connected to a metering gear pump 11 for feeding an oiling agent via an oil path 10 and a hose 12. The guide 8 can act to guide and bundle the filaments and to apply the oiling agent metered and fed to the guide 8 by the gear pump 11 to the filaments. In the process according to the present invention, the filament bundle may optionally be subjected to entangling treatment by turbulent air between the bundling guide and the take-up unit. The oiling nozzle guide, take-up unit, and other devices necessary for melt spinning may be known devices. Also, the oiling agent usable for the present invention may be an emulsion-type or neat-type oiling agent and may have a known composition. The surface area per unit weight of the polyethylene terephthalate fibre according to the present invention may be controlled by suitably adjusting the fineness of the filaments by changing the extrusion rate of polyethylene terephthalate or by changing the spinning speed or by suitably defining the cross section of the filaments by changing the shape of the holes of the spinneret. According to the process of the present invention, polyethylene terephthalate can be stably spun into a fibre of not more than about 4.5 dtex at a high speed of 7,000 m/min, and a package of a good package form quality can be obtained without using godet rolls. The obtained fibre can be practically used as such without subjecting it to drawing and has an excellent dyeability so that a false-twisted fibre obtained therefrom can be dyed under normal pressure. The polyethylene terephthalate fibre according to the present invention may be subjected to false twisting by using any conventional false-twisting machines or draw-false-twisting machines. The false-twisting machines may be spindle-type or friction-type false-twisting machines. In the examples described hereinbelow, the dyeability of a polyethylene terephthalate fibre was evaluated after the fibre was subjected to false twisting under optimum conditions. The following are methods for measuring parameters for specifying the structural properties referred to in the present invention. Dyeability The dyeability is evaluated by the degree of equilibrium dye absorption. A sample is dyed with a disperse dye, Resolin Blue FBL (registered trademark of Bayer A.G.), at a dye concentration of 3% o.w.f., at a liquor-to-goods ratio of 50:1, and at a temperature of 100°C. Further, a dispersing agent, Disper TL (tradename of Marybishi Yuka Co.), is added to the dye bath in an amount of 1 g/l, which dye bath is adjusted to a pH of 6 by adding acetic acid. The employed sample is a fabric knitted on a knitting machine with one feeder using an untextured yarn or a false-twisted yarn which has been scoured in water containing 2 g/l of Scourol FC (tradename of Kao-Atlas Co.) at 60°C for 20 minutes, dried, and conditioned at 65% R.H. and 20°C. After dyeing for one hour at the dyeing temperature, the amount of dye remaining in the dye bath is determined by measuring the absorbance, and the degree of dye absorption (%) is calculated by subtracting the amount of the remaining dye from the initial amount of the employed dye, dividing the difference by the initial amount of dye, and multiplying the result by 100. The term "a fibre can be dyed under normal pressure" as used herein means that a fiber can be dyed to a degree of equilibrium dye absorption, as defined above, of 85% or more. Dynamic loss tangent (tan δ) The dynamic loss tangent (tan δ) is determined by using an apparatus for measuring dynamic viscoelasticity, Rheo-Vibron DDV-IIc, manufactured by Toyo Baldwin Co., at a sample amount of 0.1 mg and at a frequency of 110 Hz in dry air at a temperature increasing at a rate of 10°C/min. Thus, a tan δ-temperature curve as schematically illustrated in Fig. 3 is obtained. From the curve, the peak temperature (T max ) at which tan δ becomes maximum and the maximum tan δ value (tan δ) max are determined. Initial modulus The initial modulus is determined by measuring the tensile stress (cN/tex) at 1% elongation with a tensile tester under the conditions of a yarn length of 10 cm, a stress rate of 5 cm/min, and a chart speed of 250 cm/min at a temperature of 25°C and a relative humidity of 60%. Tensile strength and elongation The tensile strength and elongation are measured with a tensile tester under the conditions of a yarn length of 25 cm and a stress rate of 30 cm/min. Shrinkage in boiling water Shrinkage in boiling water is determined by the following formula: Shrinkage in boilng water (%)= L₀-L L ×100 In the formula L₀ is the length of a sample under a load of 0.09 g/dtex, and L is the length of the sample under a load of 0.09 g/dtex after the sample is dipped in boiling water for 30 minutes without the load. Intrinsic viscosity The intrinsic viscosity is determined by measuring η sp /c at 35°C, varying the concentration of the polymer and using o-chlorophenol as the solvent, and extrapolating the η sp /c to a concentration of 0. The present invention is further described below with reference to the following non-limitative examples. Example 1 A polyethylene terephthalate containing 0.5% by weight of titanium oxide and having an intrinsic viscosity of 0.61 was melt spun at various spinning speeds by using the spinning machine illustrated in Fig. 2. The spinning machine had a spinneret of 24 holes having a diameter of 0.23 mm, a heating cylinder of a length of 30 cm, and a high-speed take-up unit positioned 3 m beneath the spinneret surface. A polyethylene terephthalate multifilament of 55.6 dtex/24 filaments was obtained. The individual filaments had a surface area per unit weight of 2,035 cm²/g. The temperature of the spinneret head was 300°C, and the temperature in the heating cylinder (the temperature in the heating zone) was 250°C. The oiling nozzle guide illustrated in Figs. 5A and 5B was positioned 25 cm beneath the point of completion of fining of the filaments. The peak temperature (T max ), maximum tan δ value (tan δ) max , initial modulus, tensile strength at breakage, elongation at breakage, and shrinkage in boiling water of the resultant multifilament were evaluated. The results are shown in Tables 1 and 2. The multifilament was then false twisted under the conditions shown in Table 3, and the dyeability of the multifilament before and after false twisting was evaluated. The results are shown in Table 2. From the results, it was confirmed that if a polyethylene terephtalate multifilament has a surface area per unit weight of 2,035 cm²/g, a T max ranging from 105°C to 115°C, and a (tan δ) max of less than 0.190, the false-twisted yarn can be dyed under normal pressure, i.e., at 100°C. Example 2 A polyethylene terephthalate containing 0.5% by weight of titanium oxide and having an intrinsic viscosity of 0.61 was melt spun, at various spinning speeds, by using the spinning machine illustrated in Fig. 2. The spinning machine had a spinneret of 12 holes of a diameter of 0.35 mm, a heating cylinder of a length of 20 cm, and a high-speed take-up unit positioned 3 m beneath the spinneret surface. A polyethylene terephthalate multifilament of 55.6 dtex/12 filaments was obtained. The individual filaments had a surface area per unit weight of 1,400 cm²/g. The temperature of the spinneret head was 295°C, and the temperature of the heating cylinder (the temperature in the heating zone) was 235°C. The oiling nozzle guide illustrated in Figs. 5A and 5B was positioned 20 cm beneath the point of completion of fining of the filaments. The T max , (tan δ) max , initial modulus, tensile strength at breakage, elongation at breakage and shrinkage in boiling water of the resultant multifilament were evaluated. The results are shown in Tables 4 and 5. The multifilament was then false twisted under the conditions shown in Table 3, and the dyeability of the false-twisted multifilament was evaluated. The results are shown in Table 5. From the results, it was confirmed that if a polyethylene terephthalate multifilament has a surface area per unit weight of 1,400 cm²/g, a T max ranging from 111°C to 115°C, and a (tan δ) max of not more than 0.135, the false-twisted yarn can be dyed under normal pressure at 100°C. Example 3 A polyethylene terephthalate containing 0.5% by weight of titanium oxide and having an intrinsic viscosity of 0.61 was melt spun, at various spinning speeds, by using the spinning machine illustrated in Fig. 2. The spinning machine had a spinneret of 36 holes of a diameter of 0.23 mm, a heating cylinder of a length of 30 cm, and a high-speed take-up unit positioned 3 m beneath the spinneret surface. A polyethylene terephthalate multifilament of 83.4 dtex/36 filaments was obtained. The individual filaments had a surface area per unit weight of 2,035 cm²/g. The temperature of the spinneret head was 295°C, and the temperature of the heating cylinder (the temperature in the heating zone) was 250°C. An oiling nozzle guide illustrated in Figs. 5A and 5B was positioned 25 cm beneath the point of completion of fining of the filaments. The T max , (tan δ) max , initial modulus, tensile strength at breakage, elongation at breakage, and shrinkage in boiling water of the resultant multifilament were evaluated. The results are shown in Tables 7 and 8. The multifilament was then false twisted under the conditions shown in Table 6, and the dyeability of the false-twisted multifilament was evaluated. The results are shown in Table 8. Example 4 A polyethylene terephthalate having an intrinsic viscosity of 0.61 and a melting point of 255°C was melt spun, at a spinning speed of 8,000 m/min, into a multifilament of 83.4 dtex/36 filaments by using the melt-spinning machine illustrated in Fig. 2, the length and temperature of the heating cylinder and the position of the oiling nozzle guide or the bundling guide being varied as shown in Table 9. In Run Nos. 14 to 25, the bundling guide illustrated in Figs. 6A and 6B was used, and in Run Nos. 26 to 28, the oiling nozzle guide illustrated in Figs. 5A and 5B was used. The employed spinneret had 36 holes of a diameter of 0.23 mm and a temperature of 290°C. The take-up unit was positioned 2 m beneath the oiling nozzle guide or the bundling guide. The point of completion of fining of the filaments as shown in Table 9 was confirmed by measuring with a Diameter-Monitor 460A/2 (tradename of Zimmer A.G.) the diameter of the filaments being spun. The evaluated spinning stability and package form quality are shown in Table 9. In the table, Run Nos. 15, 16, 17, 19, 20, 21, 22, 23, 24, 26, 27, and 28 fall within the range of the present invention, in which the spinning stability and package form quality are both excellent or good. Example 5 A polyethylene terephthalate having an intrinsic viscosity of 0.61 and a melting point of 255°C was melt spun, at a spinning speed of from 5,000 to 8,000 m/min, into a multifilament of 83.4 dtex/36 filaments by using the melt-spinning machine illustrated in Fig. 2. In all the runs, the bundling guide illustrated in Figs. 6A and 6B was used. The other conditions were identical to those in Example 4. The results are shown in Table 10. In Run Nos. 29 and 30, which fall within the range of the present invention, the spinning stability and package form quality were both excellent. The false-twisted yarns obtained from the resultant multifilaments of Run Nos. 29 and 30 could be dyed under normal pressure.

Claims: Easily dyeable polyethylene terephthalate fibre, characterized by an intrinsic viscosity of the polymer of from 0.50 to 1.0, an initial modulus of from 534 cN/tex to 1157 cN/tex, a surface area per unit weight of from 1,400 cm²/g to 4,000 cm²/g, and a peak temperature (T max ) at which the dynamic loss tangent (tan δ) measured at a frequency of 110 Hz becomes maximum and a maximum tan δ value (tan δ) max satisfying the following relationship (1 ) or (2): (1) 105°C<T max ≦115°C and 0.135<(tan δ) max ≦0.190 (2) 110°C<T max ≦115°C and 0.110≦(tan δ) max ≦0.135 Fibre as claimed in claim 1, wherein the intrinsic viscosity of the polymer ranges from 0.55 to 0.70. Fibre as claimed in claim 1, wherein the initial modulus ranges from 623 cN/tex to 1068 cN/tex. Fibre as claimed in claim 1, wherein the surface area per unit weight ranges from 1,600 cm²/g to 3,000 cm²/g. Fibre as claimed in claim 4, wherein the surface area per unit weight ranges from 1,900 cm²/g to 3,000 cm²/g. Fibre as claimed in claim 1, wherein the T max and the (tan δ) max are in the range of 105°C<T max ≦113°C and 0.135<(tan δ) max ≦0.180, respectively. A process for preparing a fibre as claimed in claim 1, characterized by melt-spinning polyethylene terephthalate through a spinneret having a plurality of spinning holes at a spinning speed of not less than 7,000 m/min and taking up a bundle of the filaments without using godet rolls, in which a group of extruded filaments is passed through a heating zone defined over a length of not less than 5 cm from the bottom surface of the spinneret, is maintained at a temperature of from 150°C to 300°C, and then is bundled into a filament bundle by means of a bundling guide positioned so as to satisfy the following conditions (a) and (b): (a) said position should be not less than 5 cm beneath the point of completion of fining of the group of filaments (b) the tension imposed on the filament bundle 5 cm beneath said position of the bundling guide should be not more than 0.36 cN/dtex. A process as claimed in claim 7, wherein the length of the heating zone ranges from 20 cm to 50 cm. A process as claimed in claim 7, wherein the temperature of the heating zone ranges from 190°C to 300°C. A process as claimed in claim 7, wherein an oiling nozzle guide is used as the bundling guide, and the group of filaments is bundled while being oiled into a filament bundle. A process as claimed in claim 7, wherein the bundling guide is positioned so that the tension imposed on the filament bundle 5 cm beneath the bundling guide is not more than 0.27 cN/dtex.

Inventors: MAKINO, HIROYUKI, MATSUO, TERUHIKO
Applicants: ASAHI KASEI KOGYO KABUSHIKI KAISHA
Application year: 1983
Main classification: D01F6
IPC codes: D01D5, D01F6