WO2006095661A1

WO2006095661A1 - Means for producing extremely fine filament of wholly aromatic polyester

Info

Publication number: WO2006095661A1
Application number: PCT/JP2006/304182
Authority: WO
Inventors: Akihiro Suzuki
Original assignee: University Of Yamanashi
Priority date: 2005-03-11
Filing date: 2006-02-27
Publication date: 2006-09-14
Also published as: JPWO2006095661A1; JP5082100B2

Abstract

A means for producing an extremely fine filament of a wholly aromatic polyester and a non-woven fabric comprising the filament, characterized in that a tensile force of 30 MPa per single yarn is imparted to a wholly aromatic polyester filament and the filament is heated by a infrared ray flux, to thereby form an extremely fine filament which has been drawn at a draw ratio of seven or more, exhibits high molecular orientation and has a size of 20 μm or less, and in that a non-woven fabric comprising extremely fine filaments of a wholly aromatic polyester is produced through piling up the above drawn filaments on a conveyer. The above means allows the production of a drawn filament of a wholly aromatic polyester and a non-woven fabric comprising the filament without the need for an apparatus being special, highly precise or of high level, with the use of a simple and easy means.

Description

MECHANISM MANUFACTURING METHOD FOR FULL AROMATIC POLYESTER extra fine filament raft

The present invention relates to a stretched wholly aromatic polyester filament, a method for producing the same, and a production apparatus therefor, in particular, it is stretched at a magnification of 7 times or more obtained by a simple stretching means, and further at a high magnification of 15 times or more. The invention relates to the production of ultrafine wholly aromatic polyester flame candy having a capacity of 20 / im or less. Background art

Fully aromatic polyester fibers are used in various fields as industrial materials due to their excellent properties such as high strength, high elastic modulus and high heat resistance. It has been difficult to reduce the fiber diameter because fully aromatic polyester fibers have poor spinnability and stretchability. Therefore, the conventional wholly aromatic polyester filaments have a large fiber diameter, so when used for industrial materials such as ropes, they lack flexibility and have problems in use characteristics. In the past, reducing the diameter of the wholly aromatic polyester fiber has been carried out by examining the spinning conditions of the wholly aromatic polyester fiber (for example, Japanese Patent Laid-Open No. Sho 62-1-7 7 2 1 1). JP-A-1-2 7 2 8 1 2).

-On the other hand, the present invention relates to a technique for stretching filament flames by infrared heating, Various techniques have been conventionally used (for example, JP 2003-1661 "I 5 publication, International Publication No. 00-No. 73556 Pamphlet, Akiyasu Suzuki, and others 1 Journal of Applied Polymer Science, vol. 83, p. 1 7 1 1— 1 7 1 6, 2002, Akiyasu Suzuki, etc. 1 Proceedings of the Society of Polymer Science, Japan Society of Polymer Science, 2001 May 7 ', 50-4, p 787 , Akiyasu Suzuki, 1 other Journal of Applied Polymer Science, ol. 88, p. 3279-3283, 2003, Akiyasu Suzuki, 1 other Journal of

Applied Polymer Science, v o l. 90, p. 1 955—1 958, 2003). However, these were not sufficient to realize that fully aromatic polyester filaments were stretched in a high magnification and highly molecularly oriented form.

In addition, conventional nonwoven fabrics made of wholly aromatic polyester fibers are made by cutting fully aromatic polyester fibers into several centimeters, laminating them into card webs, punching them for a couple of dollars, and making them into nonwoven fabrics. Needless to say, there are many processes such as needle punching, and it is cost-effective.Because it consists of short fibers, the strength of the nonwoven fabric depends on the entanglement of the fibers, and all aromatic polyester fibers originally have The high strength is not used effectively. Disclosure of the invention

Problems to be solved by the invention

The present invention is a further development of the above-described conventional technology. The purpose of the present invention is to provide a wholly aromatic polymer that is easily stretched by a simple means without adopting a special spinning method. It is to be able to obtain a reester filament. Another object is to make it possible to produce a wholly aromatic polyester filament with high quality, a small filament diameter, and stable production. Yet another object is to make it possible to produce a long-fiber nonwoven fabric made of wholly aromatic polyester filaments. Means for solving the problem

The present invention relates to a stretched wholly aromatic polyester filament. The fully aromatic polyester filament means a filament mainly composed of a fully aromatic polyester polymer. Filaments are fibers that have a substantially continuous length, and are distinguished from short fibers of short length (a few millimeters to a few centimeters). The filament in the present invention includes a single filament composed of a single filament and a multifilament cage composed of a plurality of filament filaments. In the tension applied to a single filament, it is expressed as “per single yarn”, but in a single filament, it means “j per single filament, and in multifilament it constitutes“ individual ” "Per filament".

A typical example of polyester used as a fiber is polyethylene terephthalate, which is flexible because it has an ethylene group in the molecule. The wholly aromatic polyester polymer in the present invention is a synthetic polymer in which all such methylene group and ethylene group are replaced with aromatic groups in the molecule, and is also called polyarylate. These wholly aromatic polyesters have a high melting point and a high elasticity and high elasticity by molecular orientation. It is characterized by becoming a mentament. Many wholly aromatic polyesters also form thermomorphic liquid crystals. The wholly aromatic polyester polymer has a trade name Vectran synthesized by transesterification from P-hydroxybenzoic acid (HBA) and 6-hydroxy-12-naphthoic acid (HNA). There is also a trade name Conol synthesized by copolymerization of P-hydroxybenzoic acid (HBA) with diacetoxybiphenyl, terephthalic acid and isophthalic acid. In addition to these examples, filamentous flames composed of wholly aromatic polyesters shown in the above definition are included in the wholly aromatic polyester filaments of the present invention.

The wholly aromatic polyester filament in the present invention includes a case where the skeleton (core portion) of the filament is made of the wholly aromatic polyester polymer and the surface (sheath portion) is made of other polymer. With such a configuration, the spinnability of the wholly aromatic polyester can be improved. Polyethylene-1,6-naphthalate (PEN) and poly-1,4-cyclohexanedimethylene terephthalate (PCT), which are heat-resistant polyesters, are particularly effective as the polymer for the sheath portion. Polyethers such as polyphenylene ether and modified products thereof can also be used.

The present invention provides a means for drawing the original filament. The original wholly aromatic polyester filament in the present invention may be one that has already been produced as a wholly aromatic polyester filament yarn and wound up on a bobbin or the like. It became a fully aromatic polyester filament by cooling and solidification. The material may be used as a wholly aromatic polyester filament that is subsequently used in the spinning process and becomes a raw material for the stretching means of the present invention. Therefore, the case where the solvent is included in the spinning process is included, as in the case where some solvent in the spinning process is included.

The original wholly aromatic polyester filament in the present invention is used even if it has been molecularly oriented through a spinning process or a drawing process. The fully aromatic polyester melt shows a thermopick liquid crystal, and is molecularly oriented only by spinning, and can be drawn at a higher magnification even from such highly oriented molecular filaments. is there. The filament is preferably a filament whose molecular orientation is limited by devising spinning conditions in the spinning process. In the present invention, the strength of the original filament is preferably an unstretched filament of 1 OGPa or less per single yarn, more preferably 5 GPa or less, and most preferably 1 GPa or less. I like it. As clarified in the present invention of the present inventor, general-purpose thermoplastic resin filaments such as Nai Nya Polyethylene terephthalate can be stretched at ultra-high magnification with infrared rays even with a highly molecular oriented original filament. A molecularly oriented filament is obtained. It has been clarified that stretchability increases in fully aromatic polyester filaments due to the limited degree of molecular orientation.

The original wholly aromatic polyester filament of the present invention is heated to an appropriate stretching temperature by an infrared light beam irradiated by an infrared heating means (including a laser). Infrared rays heat the original filament, but it is preferable that the range to be heated to a suitable temperature for drawing is within 4 mm (8 mm in length) in the axial direction of the filaments at the center of the filament. More preferably, heating is performed at 3 mm or less, most preferably 2 mm or less. The present invention makes it possible to stretch with a high degree of molecular orientation by rapidly stretching in a narrow region, and even with high magnification stretching, it is possible to reduce stretching breakage. When the filament irradiated with this infrared light bundle is a multifilament, the above “center of filament” means the center of the filament bundle of multifilament.

In this case, the infrared light beam is preferably irradiated from a plurality of locations. This is because, in a wholly aromatic polyester filament cocoon, heating from only one side of the filament cocoon has a high melting temperature and a short heating time. Such irradiation from a plurality of places may be performed by a plurality of light sources of infrared light beams, but by reflecting a light beam from a single light source with a mirror, a plurality of times, It can also be achieved by irradiating along the passage. Mirrors can be used not only for fixed types but also for rotating types such as polygon mirrors.

As another means for irradiation from a plurality of locations, there is a means for irradiating a light source from a plurality of light sources to the original filament from a plurality of locations. A high-power light source can be obtained by using a plurality of laser oscillation devices that are stable and inexpensive with a relatively small laser light source. In the wholly aromatic polyester filament of the present invention, a method using a plurality of light sources is effective because it requires a high cocoon density.

Infrared light has a wavelength of 0.78 mm to 1 mm. It is centered on the absorption of 3.5 m of the C-C bond of the polymer compound, from 0.78 jt m to 2 O m. Degree The near infrared range is particularly preferred. These infrared rays are focused by a mirror or lens in a linear or dotted manner, and the heating area of the total aromatic polyester filament is reduced to within 4 mm in the vertical direction of the filament by heating called a spot heater or line heater. A heater can be used. In particular, the line heater is suitable for simultaneously heating a plurality of wholly aromatic polyester filaments.

For the infrared heating of the present invention, heating by a laser is particularly preferable. Among these, a carbon dioxide laser with a wavelength of 10.6 im and a Y AG (yttrium, aluminum, galnet) laser with a wavelength of 1.06 m are particularly preferable. An argon laser can also be used. Lasers can reduce the radiation range to a small size and are concentrated on a specific wavelength, so there is little wasted energy. The carbon dioxide laser of the present invention has a power density of 1 OWZcm ² or more, preferably 1 OOWZcm ² or more, and most preferably 150 WZcm ² or more. This is because high-power stretching of the present invention can be achieved by concentrating energy of high power density in a narrow stretching region. The laser density in the present invention is characterized in that it requires a watt density several steps higher than that of the conventional general-purpose fiber polymer shown in the inventor's prior invention. In the present invention, a force characterized by using light beams from a plurality of directions <<, and the watt density in that case is the sum of the watt densities from the respective irradiation directions.

The present invention is characterized in that the tension at which the wholly aromatic polyester filament is drawn is controlled to be very small. The drawing tension in the present invention is preferably 30 MPa or less, more preferably 1 OMPa or less, most preferably per single yarn. Is stretched by making it 5 MPa or less. If it exceeds 30 MPa, it is easy for breakage to occur, and in order to stretch at a high magnification, it is desirable to be within such a tension range. Stretching of a wholly aromatic polyester filament usually requires a stretching tension of several hundred MPa, but the present invention is characterized by a stretching tension that is 1 to 2 orders of magnitude smaller. With such a low stretching tension, the draw ratio is 7 times or more, and depending on the conditions, 20 times or more, and even 30 times or more, an extremely large magnification can be realized. The draw temperature is extremely high, around the melting point. Since it is a very narrow stretch region while maintaining the temperature, it seems that it can be deformed by avoiding the cutting of the wholly aromatic polyester filament.

As described above, the present invention is characterized by being stretched with a very small tension. The stretching tension in the stretching of the present invention is characterized in that the stretching is also performed by a tension given by its own weight. This is in principle different from general stretching, in which stretching is performed by the tension given by the speed difference between the rollers or by the tension due to scraping. In the present invention, the optimum tension can be selected by changing the free fall distance of the self-weight of the wholly aromatic polyester filament applied to the heating part (determined by the free-falling distance from the heating part). . A force that makes it difficult to find an optimum tension with a small stretching tension. The present invention is characterized in that the stretching tension can be easily controlled by a simple means of a falling distance by its own weight. In particular, at the start of the stretching of the present invention, that is, at the start of stretching, the drop distance and the laser power density are changed in various ways to find the optimum stretching tension, and from that state and the stretching ratio to the inter-roller stretching. It can be guided. In the present invention, the stretched ratio of the obtained stretched wholly aromatic polyester filament is

The film is stretched at an ultrahigh magnification of 7 times or more, preferably 20 times or more, more preferably 30 times or more, and most preferably 50 times or more. In the present invention, a fully aromatic polyester filament with originally poor stretchability can be realized at a high magnification of 30 times or more, and further 50 times or more with such a simple device, and the filament diameter is small due to the high magnification. Filament was obtained. In addition, it is generally difficult to spin with fully aromatic polyester fiber. A relatively thick filament that is stable during the spinning process is obtained, and a fiber with a small filament diameter is obtained by stretching at a high magnification by the stretching of the present invention. Contributes to the stable production of the entire production system.

In the present invention, by enabling high-strength drawing in this way, it is possible to produce ultrafine wholly aromatic polyester filaments with a filament diameter of 20 im or less, 10 m or less, and 5 m or less under favorable conditions. There is a feature in doing. Even if all aromatic polyester fibers have high mechanical properties such as strength and elastic modulus, if the filament diameter is large, the ropes are not flexible enough, and the protective clothing is not comfortable to wear. In addition, even in non-woven fabrics such as filters, the small filament diameter improves various performances and increases the force baring power. Therefore, the quality of these products could be improved by reducing the filament diameter in the present invention.

In the continuous method of the present invention, the original all aromatic polyester filaments fed from the filament feeding means are stretched. The delivery means is a fully aromatic polymer at a constant delivery speed by combining two-ply rollers and several stages of drive rollers. Various types can be used as long as they can deliver ester filaments. In addition, the drawn filament is wound up as necessary, and the winding speed is a means for winding up the wholly aromatic polyester filament at a constant feeding speed such as a combination of a nip roller and several stages of driving rollers. Power used. The apparatus for producing a wholly aromatic polyester filament cocoon of the present invention constituted by these delivery means or take-up means is capable of delivering filaments so as to obtain a predetermined draw ratio by measuring the diameter of the drawn filaments. It would be desirable to have control means configured to control the speed or the take-up speed, or both the take-up speed and the delivery speed of the filament.

In the present invention, it is preferable to provide a guide for regulating the position of the original filament immediately before the infrared light beam hits the original filament. Heating of the original flame candy with infrared luminous flux is characterized by the fact that it is heated in a very narrow range, and it is necessary to regulate the position of the wholly aromatic polyester flame candy in order to enable heating in that narrow range. There is. It is possible to have such a function depending on the shape of the outlet of the blow pipe described below, but the blow pipe is easy to vent the gas that sends the wholly aromatic polyester filament, and easy to pass the wholly aromatic polyester filament. It is preferred that the position of the wholly aromatic polyester filament raft is regulated by a simple guide after that. In the conventional normal stretching, since the stretching tension is large, no guide is required. However, in the present invention, since the elongation / stretching force is small, the stretching ratio is large, and the heating range is narrow, a slight fluctuation or fluctuation of the stretching point greatly affects the stability of stretching. Therefore, guide just before the drawing point Providing tools greatly contributes to the stability of stretching. As the guide in the present invention, a combination of a thin tube, a groove, a comb, a thin bar, or the like can be used.

The guide tool preferably has a position control mechanism configured so that the position of the filament can be finely adjusted by the guide tool. It is necessary to control the position of the guide tool in the X and Y directions in order to accurately fit the filament travel position in the narrow area of the laser beam.

The original wholly aromatic polyester filament sent out by the delivery means of the filament raft can be sent by the gas flowing in the running direction of the original wholly aromatic polyester filament through the air duct. desirable. This is because in the present invention, since the stretching tension is small, there is a case where the stretching tension cannot be kept constant due to the resistance of the guide filament while the original filament is running. The gas flowing through the blower tube is usually room temperature gas, but heated air is used to preheat the original wholly aromatic polyester filament. In addition, in order to prevent the original wholly aromatic polyester filament from being oxidized, an inert gas such as nitrogen gas is used. Note that the air pipe does not necessarily have a cylindrical shape, and may have a groove shape. It is only necessary that the original wholly aromatic polyester filament flows along with the gas. The cross section of the tube is preferably a circle, but may be rectangular or other shapes. The gas flowing in the pipe may be supplied from one of the branched pipes, or may be supplied by a hole or the like from the outer pipe to the inner pipe in a double pipe. The air entangled nozzle of filament raft used for interlace spinning of synthetic fibers is also used as the blower tube of the present invention. Moreover, like the nonwoven fabric manufacture in the present invention, free fall In the case of stretching by the above method, it is also possible to give a stretching tension to the filament by the momentum of the air by the blower tube of the present invention.

The stretching of the wholly aromatic polyester filament in the present invention is characterized in that a plurality of original wholly aromatic polyester filaments can be combined and stretched in the same infrared light flux. Normally, when a plurality of original filaments are stretched together in an infrared luminous flux, sticking occurs between the drawn filaments. In addition, due to such sticking, stretchability is often hindered, and high-strength stretching is often impossible. In the wholly aromatic polyester filament of the present invention, since the heat resistance of the original filament is high and the heat resistance is further improved by drawing, a plurality of original filaments are drawn together. However, it was confirmed by a force experiment that the high-strength drawing can be performed stably without causing a sticking force. With multiple pieces, it was possible to stretch 2 or more, and in some cases, 5 or more. As a result, the efficiency of the infrared stretching method could be remarkably improved.

In the subsequent process, the stretched wholly aromatic polyester filament of the present invention is wound around a bobbin, cheese, or the like to obtain a product in the form of a bobbin or cheese roll. In these windings, it is desirable that the stretched wholly aromatic polyester filament is wound while being traversed. This is because a uniform winding form can be secured by traversing. With ultra-fine wholly aromatic polyester filaments, thread breakage and fluff generation force << most problematic force In the present invention, it is possible to wind with a small winding tension because of its high molecular orientation and low stretching tension. It becomes possible. Therefore, the present invention is also characterized in that thread breakage and fluff can be reduced. Note that multiple original When the lament is stretched at the same time and wound at the same time, it can be wound while being twisted by a twisting machine. However, since the filament traveling speed is fast in the present invention, the interlace entanglement method makes it It is preferable to entangle and wind.

After the stretching process of the present invention, a heating device having a heating zone can be provided to heat-treat the stretched all aromatic polyester filament. Heating can be performed by a method of passing through a heated gas, a radiant heating such as infrared heating, a method of passing through a heating roller, or a combination thereof. The heat treatment brings various effects such as reducing the thermal shrinkage of the stretched wholly aromatic polyester filament, increasing the crystallinity, reducing the time-dependent change of the wholly aromatic polyester filament, and improving the Young's modulus. . In the case of the nonwoven fabric of the present invention, the heat treatment may be performed on a conveyor.

The stretched wholly aromatic polyester filament of the present invention can be scraped off after further stretching. As the means for stretching in the subsequent stage, the infrared stretching means performed in the previous stage can be used, but when the ultrafine fully aromatic polyester filament has already been obtained by sufficiently stretching at the previous stage. For example, stretching between rollers such as a normal godeck roller or pin stretching can be used.

The present invention is characterized in that stable stretching is controlled by controlling the watt density of the infrared light flux, such as a constant stretching tension and stretching ratio. Also, by measuring the stretched filament diameter and feeding it back, the winding speed or delivery speed, or both the take-up speed and delivery speed can be controlled so that a product with a constant filament diameter can be obtained. It is characterized by controlling. In the present invention, the draw ratio is large. Because, although the filament diameter is drawn is likely to change, by constantly controlling it, the stable production could fl ¹ Ukoto.

By integrating the stretched wholly aromatic polyester filaments in the present invention on a traveling conveyor, a nonwoven fabric made of stretched wholly aromatic polyester filaments can be produced, and in particular, the strength and elastic modulus are large. It has the feature that fully aromatic polyester filaments can be made into non-woven fabrics without breaking them. In the production of non-woven fabrics from wholly aromatic polyester filaments, it is preferable to increase the stretching tension of the filaments with the force of the air from the blower pipe in addition to the tension at which the flamen is dropped by its own weight. Since the filaments accumulated on the conveyor have a small filament diameter, they are simply formed into a sheet by pressing or the like due to the entanglement of the filaments. If necessary, it can be used with increased integration by means of entanglement such as needle punch or water jet, bonding with an adhesive or an adhesive fiber, thermal bonding with hot embossing, or the like.

The orientation degree f of the filament in the present invention is represented by the following X-ray half width method.

f (%) = [(9 O-H / 2) Z 9 0] 1 0 0

Here, H represents the half value of the intensity distribution along the Debye ring on the face having the main peak of the crystal of the wholly aromatic polyester fiber.

Further, the draw ratio in the present invention; I is represented by the following formula from the diameter do of the original filament and the diameter d of the filament yarn after drawing. In this case, the filament density is constant. To calculate. The filament diameter is measured with a scanning electron microscope (SEM) at an average value of 10 points based on a photograph taken at a magnification of 3500 times or 100 times.

λ = (d oZ d) ²

In the present invention, the method for measuring the tensile strength and elastic modulus of the filament is to determine the measured value per single yarn by J 〖S and 1 0 1 3. The invention's effect

According to the present invention, it is possible to easily obtain ultrafine drawn filaments by simple means without using special spinning means for fully aromatic polyester filaments. These stretched wholly aromatic polyester filaments provide stable production and high quality, increase the flexibility of industrial products such as ropes on the product side, and comfort in clothing such as protective clothing. In heat resistant filters, filter performance can be improved by reducing the filament diameter.

Furthermore, according to the present invention, it is possible to easily produce a long-fiber nonwoven fabric made of a very fine wholly aromatic polyester filament. The wholly aromatic polyester fiber non-woven fabric on the market consists of wholly aromatic polyester short fibers, and it is necessary to make the wholly aromatic polyester fibers difficult to cut into short fibers. The process was complicated. Moreover, the strength of the resulting nonwoven fabric depended on the strength of the entanglement of short fibers, and the high strength of wholly aromatic polyester fibers was not utilized. The nonwoven fabric comprising the wholly aromatic polyester filament of the present invention is a long fiber, It can be produced directly into a non-woven fabric during the stretching process. As a result, non-woven fabric for filters is directly produced. Moreover, since it is a nonwoven fabric which consists only of long fibers, it also has the characteristic that it is a nonwoven fabric which does not have the fiber dough when cutting into short fibers. Brief Description of Drawings

FIG. 1 shows a process conceptual diagram of a continuous process for producing a stretched wholly aromatic polyester filament of the present invention.

FIG. 2 shows an example of the arrangement of mirrors for irradiating the original filament lamp of the present invention with infrared rays from a plurality of locations. FIG. A is a plan view and FIG. B is a side view.

FIG. 3 is another example of irradiating the original filament of the present invention with an infrared light beam from a plurality of locations, and shows a plan view in the case of having a plurality of light sources.

FIG. 4 shows a conceptual diagram of the process when a plurality of fully aromatic polyester filaments of the present invention are redrawn.

FIG. 5 is a conceptual diagram of an air duct used in the present invention.

FIG. 6 shows a conceptual diagram of a process for producing a nonwoven fabric composed of stretched wholly aromatic polyester filaments of the present invention.

FIG. 7 is a chart showing changes in the filament diameter and physical properties of a wholly aromatic polyester filament frame stretched according to the present invention. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an example of an embodiment of the present invention will be described with reference to the drawings. FIG. 1 shows an example of the continuous process of the present invention. The original wholly aromatic polyester filament 1 is fed from the state of being repelled by the reel 11 and is fed from the feeding nip rollers 13a and 13b through the comb 12 at a constant speed. The delivered original filament 1 is controlled in position by a guide 15 and lowered at a constant speed. The guide tool 15 accurately determines the laser irradiation position and the travel position of the filament. In the figure, an injection needle with an inner diameter of 0.5 mm was used. In addition, thin pipes can be used, and snail wires shown in Fig. 6 can also be used. The laser beam 6 is irradiated on the heating filament M having a certain width from the laser oscillation device 5 to the traveling original filament 1 immediately below the guide 15. The laser beam 6 is preferably irradiated from a plurality of locations shown in FIGS. The original filament is drawn by the dead weight of the original filament and the drawn filament heated by the laser beam 6, or the drawing tension provided by the take-off nip roller 19, and the drawn all aromatic polyester filament 16 It is desirable to descend and pass through the heat treatment zone 17 provided for the descending process. The stretched wholly aromatic polyester filament 16 passes through a pulley 18, passes through take-up nip rollers 19 a and 19 b, and is wound around a take-up reel 20. In this case, the path of the fully aromatic polyester filament 16 stretched to the pulley 18 is extended as a free fall track p of the fully aromatic polyester filament, and the straight line to the pulley 18 There is a case where it is stretched as a simple trajectory q and a case where it is stretched as an intermediate trajectory. At the intermediate position between trajectory q and trajectory P and trajectory q, the force at which the bow I tension is applied to the stretching tension In that case, the stretching tension is 3 0 It is desirable to be MP a or less. The stretching tension can also be measured by providing a pulley 18 with a tension measuring mechanism. As another method, it can be estimated from the relationship between the same delivery speed, laser irradiation conditions, stretch ratio, etc. by batch method load cell measurement. Before winding with the take-up reel 2 0, between the heated draw rolls 2 1 a, 2 1 b and the draw rolls 2 2 a, 2 2 b, depending on the ratio of the speed of the draw rolls 2 1 and 2 2 Further, it can be stretched. In this case, the heat-treated zone 17 of the stretched wholly aromatic polyester filament can also be provided after the stretching roller 22. In addition, when multiple original filaments are stretched simultaneously, it is desirable to air entangle the filaments using the interlace method or the like immediately before the bow I reel. In addition, a filament diameter measuring device is installed at a position just before entering the pulley 18 or the take-up roller 19 and the measured filament diameter is fed back to control the take-up speed or the delivery speed, so that it is always constant. A product with a uniform filament diameter can be obtained at a draw ratio of.

FIG. 2 shows an example of means for irradiating the original filament from a plurality of locations with the infrared light beam employed in the present invention. Figure A is a plan view and Figure B is a side view. The infrared beam 3 1 a irradiated from the infrared irradiator passes through the area P (in the dotted line in the figure) through which the original filament 1 passes, reaches the mirror 3 2, and becomes the infrared beam 3 1 b reflected by the mirror 3 2. Reflected by the mirror 3 3 to become an infrared luminous flux 3 1 c. The infrared luminous flux 3 1 c irradiates the original filament through the region P after 120 degrees from the irradiation position of the first original filament. The infrared light beam 3 1 c that has passed through the region P is reflected by the mirror 3 4 to become the infrared light beam 3 I d, and reflected by the mirror 35 to become the infrared light beam 3 1 e. Infrared luminous flux 3 1 e through region P, Irradiate the original filament 1 after 120 degrees, which is the opposite of the infrared luminous flux 3 1 c just before the irradiation position of the first original filament. As described above, the original filament 1 can uniformly heat the original filament 1 from a symmetrical position by 120 degrees by the three infrared light beams 3 1 a, 3 1 c, and 3 1 e.

FIG. 3 is a plan view showing an example of using a plurality of light sources as another example of means for irradiating the original filament from a plurality of locations with the infrared light beam employed in the present invention. The infrared luminous flux 4 1 a radiated from the infrared radiation device is radiated to the original wholly aromatic polyester filament 1. In addition, an infrared luminous flux 4 1 b radiated from another infrared radiation device is also radiated to the original wholly aromatic polyester filament 1. Further, an infrared luminous flux 41c emitted from another infrared radiation device is also emitted to the original wholly aromatic polyester filament 1. In this way, radiation from a plurality of light sources can be made into a high-power light source by using a plurality of laser oscillators which are relatively small-scale light sources and which are stable and inexpensive. Although the figure shows a case where there are three light sources, two or more than four can be used. In particular, when there are a plurality of raw filaments, stretching with such a plurality of light sources is particularly effective.

FIG. 4 shows an example in which a plurality of wholly aromatic polyester filaments that have already been stretched according to the present invention are fed simultaneously and stretched simultaneously. Pobin 5 1 a, 5 1 b, 5 1 c, 5 1 d, 5 1 e wound fully aromatic polyester filament 5 2 a, 5 2 b, 5 2 c, 5 2 d, 5 2 “e” is sent through the air pipe 5 3 and the pipe 5 4, collected in the air manifold 5 5, and becomes an aggregate of filaments 5 6. It should be noted that the wholly aromatic polyester filament 5 2 in the blower pipe 5 3 and pipe 5 4 is complicated in the figure. Not shown. The unstretched raw filament has low strength and Young's modulus, and the stretched filament 52 has a small fineness and cannot withstand the tension. Therefore, the bobbin 51 rotates at a constant speed and the delivery tension is reduced. It is preferable to have power. The sent filament aggregate 56 is adjusted by the pitch variable mechanism 57 so that the traveling position is the center of the laser beam 58. The variable pitch mechanism 57 is provided with a guide 59, and the position of the filament is finely adjusted by the rack 60 and the gear 61. Although the example in which the pitch variable mechanism 57 is adjusted in only one direction is shown in the figure, a set of racks and gears can be provided in the perpendicular direction and adjusted in the XY axis direction. The filament assembly 56 whose position is adjusted by the pitch variable mechanism 57 is heated and stretched by the laser beam 58, the take-up speed is adjusted to be constant by the take-off mechanism 62, and is driven by the motor M. The take-up bobbin 6 is wound around 3. In this figure, the laser beam 58 is shown by a single line, but it is desirable that the laser beam is a plurality of light beams shown in FIGS. In addition, the figure shows an example in which the bobbin 63 is wound directly. However, it is preferable that the bobbin 63 is wound by twisting or entangled between filaments by interlace or the like. In addition, FIG. 4 shows an example of re-stretching by infrared rays. However, re-stretching can be performed by other stretching means such as normal roller stretching and zone stretching. Note that the air introduced into the blower pipe 5 3 and the pipe 5 4 is guided to the passage of the original filament 1, the filament is sent by the flow of air, and the tension given by the wind speed of the air is as follows. Takes into account the stretching tension. Although Fig. 4 was described as an example of redrawing of drawn filaments, the same mechanism was used as a means of drawing a plurality of unstretched original filaments. Can also be used.

FIG. 5 shows an example of an air duct used in the present invention. Fig. A shows that the air introduced from the arrow a joins the main pipe 7 1 through the branch pipe 7 2 and the main pipe 71 passing through one force. Figure B shows a double pipe 7 3 with a hollow inside, and the air introduced from the arrow b is led to the passage of the flame 卜 through a number of holes 7 4 provided on the inner wall of the double pipe . Figure C shows an example of a nozzle used as an air entanglement nozzle 7 5 used for interlace spinning. Air is blown from both sides c 1 and c 2. In this way, the air is actively sent in the traveling direction of the flamen pass in the present invention, because in the present invention, the stretching tension is small, so that the traveling of the filament is hindered by the resistance of the guide tool or the like. In addition, when the tension cannot be positively applied by the winding tension as in the case of manufacturing a nonwoven fabric, the stretching tension can be applied by the air force. The nozzle shown in Fig. C can also be used for winding the interlace after stretching according to the present invention. In addition, the blast pipe shown in Fig. 5 is a tube-shaped one with a part of the force released to form a groove.

FIG. 6 shows an example of the production of the nonwoven fabric of the present invention. Many original fully aromatic polyester filaments 1 force Bobbins 8 1 are wound on the base 8 2 and attached to the base 8 2 (only 3 are shown in the figure to avoid complications). These raw fully aromatic polyester filaments 卜 1 a, 1 b, 1 c are passed through the sniper wires 8 3 a, 8 3 b, 8 3 c, which are guide tools, and the delivery nip rolls 8 4 a, 8 4 b It is sent out by rotation. The original wholly aromatic polyester filament 1 that has been sent out It is reheated by the line-shaped infrared light beam emitted from the external radiation device 85. The range of the heated part N due to infrared rays in the running process of the original wholly aromatic polyester filament 1 is shown by diagonal lines. The light flux that has passed through the original wholly aromatic polyester filament 1 without being absorbed is reflected by the concave mirror 86 shown by the dotted line and returned to the heating part N to be condensed. A concave mirror is also provided on the infrared radiation device 65 side (however, a window is opened at the advancing portion of the light beam from the infrared radiation device), but this is omitted in the figure. The original wholly aromatic polyester filament 1 is heated by the radiant heat of infrared rays in the heating section N, and is stretched by the weight of the wholly aromatic polyester filament itself below that part, and the fully aromatic polyester filament is stretched. Filaments 8 7 a, 8 7 b and 8 7 c are collected on the moving conveyor 8 8 to form the web 8 9. From the back of the core 88, air is sucked in the direction of the arrow d by negative pressure suction, which contributes to the stability of the web 89. The negative pressure d 'is pulled by the tension exerted on the stretched wholly aromatic polyester filament 87, contributing to thinning of the wholly aromatic polyester filament and an increase in the degree of orientation. Is considered part of the tension. Although omitted in the figure, many pobbins 8 1 of the original fully aromatic polyester fabric 1 are installed in multiple stages in the direction of the conveyor 8 8, and the nip rollers 84 and infrared radiation devices 85 are multi-staged. It is designed to increase the productivity of Web 89. In addition, when providing the delivery nip rolls 84 and the like in multiple stages in the traveling direction as described above, the infrared radiation device 85 and the concave mirror 86 can also serve several stages. Note that if the tension of the filament is not enough, the negative pressure from the bottom of the conveyor is insufficient, and if the stretching and orientation are small, the original filament 1 force << It is also used in consideration of the tension that is guided by the pipe and given by the wind speed at which the air from the blow pipe is sent out. Example 1

A multi-filament (60 filaments) prepared by spinning a polymer synthesized by transesterification from p-hydroxybenzoic acid (HB A) and 6-hydroxy-12-naphthoic acid (HNA) as the original fully aromatic polyester filament. ) It was used. This filament was already molecularly oriented during the spinning process, and had a filament diameter of 25.0 μm, Young's modulus of 1 5. I GPa, and tensile strength of 1. 19 GP a. Using this original multifilament, the laser of 1W laser output of 1W was applied to the drawing device shown in Fig. 1 and drawn using a mirror shown in Fig. 2 with a beam diameter of 4 mm. The infrared irradiation device was extended using the mirror shown in Fig. 2. The original filament was sent at a feed rate of 0.5m Zmin, and the experiment was carried out by changing the winding speed with a tension of 30MPa or less while changing the laser power density in various ways. At 3 OM Pa or higher, drawing breaks frequently occurred, and it was preferable to draw at 1 OM Pa or lower. A filament having a fiber diameter of 4.6 βηΛ (drawing ratio: 29.5) was obtained at a winding speed of 9.42 mZ. The stretched tensile strength was 1.88 GPa and the Young's modulus was 31.6 GPa. A filament having a fiber diameter of 2.3 / im (drawing ratio: 11.8.4) was obtained at a take-up speed of 28.3 mZ. The stretched tensile strength was 2.1 2 GPa and the Young's modulus was 39.2 GPa. A filament having a fiber diameter of 2.4 mm (drawing ratio 10 08. 3) was obtained at a cutting speed of 37.7 minutes. This total The stretched tensile strength was 1.89 GPa and the Young's modulus was 36.9 GPa. In this way, although it is a group of filaments that are already molecularly oriented, a draw ratio of several tens to 100 times or more can be obtained, and the conventional method can obtain a wholly aromatic polyester filament of 20 β m or less. However, in the present invention, an ultrafine filament of 5 mm or less could be easily obtained. In addition, the strength and elastic modulus of the filaments obtained thereby double. Example 2

A filament made of wholly aromatic polyester synthesized from P-hydroxybenzoic acid (HBA) and 6, hydroxy-2-naphthoic acid (HNA) is used as the core, and a polymer consisting of polyethylene 1,6-naphthalate (P EN) is used. The following stretching experiment was conducted using the core-sheath filament as the sheath as the original wholly aromatic polyester filament. This filamentous filament had a filament diameter of 103.2 m, Young's modulus of 10 · 43 3, tensile strength of 0.72 GPa, and elongation of 12.8%. Using this original filament, 10.6 mm laser radiation with a laser output of 10 W was applied to the drawing device in Fig. 1 and drawn with a beam diameter of 4 mm using the mirror in Fig. 2. . Figure 7 shows the experimental results. The draw ratio is 7 times or more, 20 times or more, and 50 times or more under good conditions. In addition, even though it is an original filament whose molecular orientation is advanced even in an unstretched state, both strength and elastic modulus are increased by more than 2 times, 3 times to 4 times and 6 times in elastic modulus due to stretching. Example 3

In Example 2, drawn filaments (filament diameter 14.1 m) obtained at a delivery speed of 0 · 5 mZm in and a cutting speed of 18.8 m were used as raw materials at 200 ° C. 1. Heat treatment with a load of 7 MPa (heat treatment 1), filament heat treatment 25. Heat treatment with a load of 2MPa (heat treatment 2), flamen! 3 per 1 load of 5MPa The effect of heat treatment was tested by applying heat treatment (heat treatment 3). By heat treatment 1, filament diameter 1 3. I jUm, breaking strength 2.81 GPa, Young's modulus 67. 2GPa, by heat treatment 2 ': Filament diameter 1 2.7〃m, breaking strength 3. OGPa, Young's modulus 70 3 GPa, heat treatment 3 gave a filament diameter of 12.5 m, breaking strength 3. 12 GPa, Young's modulus 75 .. 4 GPa. In addition, the differential scanning calorimetry (DSC) measurement of the filament before heat treatment showed a melting point of 260.2 ° C. By performing heat treatments 1, 2, and 36.3, 263.7 ° C, 26 3.9 ° C, 264.7 ° C, and the melting point is also improved. Industrial applicability

The stretched wholly aromatic ultrafine filament according to the present invention is used as an industrial material and has a thin fiber diameter. Therefore, when it is used in ropes and fabrics, it becomes a flexible and easy-to-use product.

Claims

1. A raw filament made of wholly aromatic polyester filament is heated with an infrared light beam, and the heated original filament is fed with a tensile force of 3 O M Pa or less per yarn.

Mainly s stretched by stretched wholly aromatic polyester filament

of

A method for producing firewood.

2. A method for producing a stretched wholly aromatic polyester filament cocoon, wherein the original filament enclosure in claim 1 comprises a plurality of filaments.

3. The stretched wholly aromatic polyester foam in which the infrared luminous flux in claim 1 is heated from at least two directions within a range of 4 mm vertically in the axial direction of the frame at the center of the original filament. Method for manufacturing lament.

4. The method for producing a stretched wholly aromatic polyester filament, wherein the stretch ratio of the wholly aromatic polyester filament in claim 1 is 7 times or more.

5. The method for producing a stretched wholly aromatic polyester filament, wherein the stretched wholly aromatic polyester filament yarn in claim 1 is heat-treated by a heating zone provided after stretching.

6. The method for producing a stretched wholly aromatic polyester filament yarn, wherein the stretched wholly aromatic polyester filament according to claim 1 is further stretched.

7. A stretched wholly aromatic polyester filament, wherein the stretched wholly aromatic polyester filament according to claim 1 is accumulated on a traveling conveyor. A method for producing a nonwoven fabric comprising

8. A means for sending out the original filament made of wholly aromatic polyester filament, and an infrared luminous flux emitting device configured to heat the delivered raw filament by being irradiated with infrared luminous flux from a plurality of locations; ,

A means controlled to be stretched by 7 times or more by applying a tension of 3 OM Pa or less per single yarn to the heated original filament;

An apparatus for producing a stretched wholly aromatic polyester filament.

9. The infrared luminous flux radiated by the infrared luminous flux emitting device in claim 8 is configured to be heated within a range of 4 mm vertically in the axial direction of the filament at the center of the original filament. A device for producing stretched wholly aromatic polyester filaments.

1 0. An apparatus for producing a stretched wholly aromatic polyester filament foam, wherein the external light beam radiation device according to claim 8 is a laser oscillation device.

1 1. The stretched wholly aromatic polyester filament manufacturing apparatus, wherein the infrared light beam emitting device according to claim 8 has a mirror for reflecting the same light beam and irradiating the original filament from a plurality of locations.

1 2. The stretched wholly aromatic polyester filament manufacturing apparatus, wherein the infrared light beam emitting apparatus according to claim 8 has a plurality of light sources that irradiate the original filament sheet from a plurality of locations.

1 3. The heating device further comprising a heating zone in the stretching means in claim 8. An apparatus for producing a stretched wholly aromatic polyester filament, wherein the stretched wholly aromatic polyester filament is configured to be heat-treated.

4. The stretched wholly aromatic polyester filament production apparatus according to claim 8, further comprising a stretching means in the stretched wholly aromatic polyester filament production apparatus.

5. In claim 8, a guide for regulating the position of the original filament jar is provided before the original filament jar is heated with an infrared light beam.

Furthermore, the manufacturing apparatus of the stretched wholly aromatic polyester flame candy which has a position control apparatus which can finely adjust the guide position of this guide tool.

6. An apparatus for producing stretched wholly aromatic polyester filaments, wherein the control in claim 8 is configured to control the delivery speed by measuring the diameter of the stretched filament.

7. The apparatus for producing a drawn wholly aromatic polyester filament according to claim 8 has means for taking out the drawn filament, and the control measures the diameter of the drawn filament, An apparatus for producing stretched wholly aromatic polyester filament yarns that is configured to control both the winding speed of filament foam or both the winding speed and the delivery speed of the filament.

8. A conveyor running in the apparatus for producing the stretched wholly aromatic polyester filament raft according to claim 8 is provided, and the stretched fiber is placed on the conveyor. A non-woven fabric manufacturing apparatus comprising stretched wholly aromatic polyester filaments, configured to accumulate ramen straw.

1 9. The stretched wholly aromatic polyester filament of claim 1 comprises a polymer synthesized by transesterification from P-hydroxybenzoic acid (HBA) and 6-hydroxy-2-naphthoic acid (HNA), A stretched wholly aromatic polyester filament yarn having a draw ratio of 30 times or more, an X-ray orientation degree of 91% or more, and a filament diameter of 1 O / im or less.

20. The above-mentioned stretched wholly aromatic polyester filament in the range 1 of I bluish is a wholly aromatic poly synthesized from p-hydroxybenzoic acid (HBA) and 6-hydroxy-2-naphthoic acid (HNA): It is made of a core-sheathed filament with a filament made of steal as a core and a polymer made of polyethylene 1,6-naphthalate (PEN) as a sheath. The filament diameter is 30 times or more. A stretched wholly aromatic polyester filament having a μm or less, a breaking strength of 2 GPa or more, and a Young's modulus of 50 GPa or more.