CN110484992B - Melt anisotropic aromatic polyester fiber and method for producing same - Google Patents
Melt anisotropic aromatic polyester fiber and method for producing same Download PDFInfo
- Publication number
- CN110484992B CN110484992B CN201910762745.4A CN201910762745A CN110484992B CN 110484992 B CN110484992 B CN 110484992B CN 201910762745 A CN201910762745 A CN 201910762745A CN 110484992 B CN110484992 B CN 110484992B
- Authority
- CN
- China
- Prior art keywords
- aromatic polyester
- melt
- less
- filament
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention provides a high-quality melt anisotropic aromatic polyester fiber having a fine filament fineness, which is free from fibrillation, filament breakage, and the like in the back winding and heat treatment steps, and which is excellent in the subsequent step passability. The melt anisotropic aromatic polyester fiber is characterized in that: the composite yarn is a composite yarn having a filament fineness of 4.0dtex or less and formed of an aromatic polyester exhibiting anisotropy when melted, and has a fluff number of less than 3 in a filament length of 100 ten thousand m. The aromatic polyester fiber preferably has a total fineness of 10dtex or more and 500dtex or less, and a number of monofilaments in a range of 3 to 1000.
Description
The application date is2015, 3 and 31 daysApplication number is201580011621.2(PCT/JP2015/ 060292)The invention is named asMelt anisotropic aromatic polyester fiber and method for producing sameIs a divisional application of the patent application of (2).
Technical Field
The present invention relates to a fine fiber (composite yarn having a filament fineness of 4.0dtex or less) formed of a melt anisotropic aromatic polyester.
Background
The melt anisotropic aromatic polyester is a polymer formed of rigid molecular chains, and in melt spinning, the molecular chains can be highly oriented in the fiber axis direction. It is also known that the melt anisotropic aromatic polyester is polymerized in a solid state, and the spun fiber is subjected to a heat treatment at a high temperature to cause solid-phase polymerization, whereby the fiber obtained by melt spinning can have the highest strength and elastic modulus. Because of these characteristics, melt anisotropic aromatic polyester fibers have been used for silk screen printing gauze, scrim, wire reinforcements for various electric products, protective bags, plastic reinforcements, and tension elements for optical fibers. In recent years, a substrate for a printed circuit board has been expected to have excellent high-frequency characteristics such as a low dielectric constant and a low dielectric loss tangent and dimensional stability. In addition, recently, along with miniaturization and thinning of a mobile phone, a personal computer, and a tablet pc, a demand for a melt anisotropic aromatic polyester fiber having a relatively small total fineness and a relatively small single-filament fineness has been expected.
However, highly oriented melt anisotropic aromatic polyester fibers are less likely to stretch after spinning due to low elongation at break. Therefore, in order to attenuate the filament fineness, the target filament fineness must be obtained at the stage of spinning. As a method for producing a melt anisotropic aromatic polyester fiber having a small single filament fineness, for example, patent document 1 proposes the following method: a sea-island type composite fiber comprising a water-dispersible polyester as a sea component and a melt anisotropic aromatic polyester as an island component is wound into a yarn package, and the sea component is dissolved in water in the form of a yarn package, whereby a melt anisotropic aromatic polyester fiber having a single filament fineness of 0.05 to 1.0dtex and a strength of 20cN/dtex or more after heat treatment is obtained.
(1) A shear rate of 1000sec at the melting point +20℃ for melting anisotropic aromatic polyester was used -1 Polymers having a melt viscosity of less than 500 Poise; (2) The shear rate when passing through the nozzle was set to 10 3 ～10 9 sec -1 The method comprises the steps of carrying out a first treatment on the surface of the (3) The discharge linear velocity of the nozzle is set to be 5-40 m/min; (4) The winding speed is set to be 150 m/min to 8000 m/min; (5) Setting the ratio of winding speed to ejection linear speed to be more than 20; (6) the temperature of the spinneret is set to be more than the melting point of +15 ℃; and (7) setting the temperature of the fiber at 30cm from the nozzle surface after ejection to be Tm-150 ℃ or lower.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2010-216052
Patent document 2: japanese patent laid-open No. 6-166909
Disclosure of Invention
Problems to be solved by the invention
However, in the method of patent document 1, after the sea-island type composite fiber is rewound into a cheese, a dissolution treatment in water is necessary, and thus the subsequent reelability becomes difficult. In addition, since the heat treatment causes inter-filament adhesion, filament quality is deteriorated due to filament breakage and fibrillation of the subsequent solution Shu Zhong.
In contrast, in the method of patent document 2, although the fine denier per filament fiber can be stably spun by a usual spinneret, there is an advantage of low cost, fibrillation, filament breakage and filament breakage due to a decrease in strength per 1 filament are liable to occur when unwinding the fiber in rewinding or the like, and the quality of the obtained fiber is poor.
The invention aims at: provided is a high-quality melt anisotropic aromatic polyester fiber which is thin and does not undergo fibrillation, filament breakage, and the like.
Means for solving the problems
The present inventors have studied carefully and as a result found the present invention. That is, the object of the present invention is achieved by providing a melt anisotropic aromatic polyester fiber characterized in that: the composite yarn is a composite yarn having a filament fineness of 4.0dtex or less and formed of an aromatic polyester exhibiting anisotropy when melted, and has a fluff number of less than 3 in a filament length of 100 ten thousand m. The aromatic polyester fiber preferably has a total fineness of 10dtex or more and 500dtex or less, and a number of monofilaments in a range of 3 to 1000. The present invention also provides a process for producing the above-mentioned melt anisotropic aromatic polyester fiber, comprising melt-spinning an aromatic polyester exhibiting anisotropy when melted to obtain a composite yarn having a filament fineness of 4.0dtex or less, wherein the process comprises using a melt point +30 ℃ and a shear rate of 1000sec -1 The melt viscosity of the aromatic polyester is 10Poise to 50Poise, and the spinning winding tension is 5cN to 60 cN.
Effects of the invention
The melt anisotropic aromatic polyester fiber of the present invention has a filament fineness of 4.0dtex or less, but is a high-quality fiber excellent in the post-process passability without filament breakage and fibrillation.
Drawings
FIG. 1 is a schematic explanatory view showing an example of a melt spinning apparatus used in the present invention.
Detailed Description
The present invention will be described in detail below.
The aromatic polyester in the present invention is an aromatic polyester which exhibits anisotropy when melted. The aromatic polyester exhibiting anisotropy in melting refers to an aromatic polyester having a property that allows light to pass through a temperature range in which the polyester sample powder can flow when the temperature is raised by placing the polyester sample powder on a heating sample stage between 2 polarizing plates orthogonal to each other at 90 °. Such an aromatic polyester is an aromatic polyester formed from an aromatic dicarboxylic acid, an aromatic diol and/or an aromatic hydroxycarboxylic acid and derivatives thereof as shown in Japanese patent publication No. 56-18016 and Japanese patent publication No. 55-20008, and in some cases, a copolymer of the above-mentioned compound with an alicyclic dicarboxylic acid, an alicyclic diol, an aliphatic diol and derivatives thereof is also included. Among them, examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 4' -dicarboxybiphenyl, 2, 6-dicarboxybiphenyl, 1, 2-bis (4-carboxyphenoxy) ethane, and the like, and compounds obtained by substituting hydrogen of the aromatic ring with an alkyl group, an aryl group, an alkoxy group, or a halogen group. As the aromatic diol, there is used, examples thereof include hydroquinone, resorcinol, 4' -dihydroxybiphenyl, 4' -dihydroxybenzophenone, 4' -dihydroxydiphenylmethane, and 4,4' -dihydroxydiphenylethane, 2-bis (4-hydroxyphenyl) propane, 4' -dihydroxydiphenylether 4,4' -dihydroxydiphenyl sulfone, 4' -dihydroxydiphenyl sulfide, 2, 6-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, and the like, and compounds obtained by substituting hydrogen in the aromatic ring of these compounds with an alkyl group, an aryl group, an alkoxy group, or a halogen group. Examples of the aromatic hydroxycarboxylic acid include p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxynaphthalene-6-carboxylic acid, 1-hydroxynaphthalene-5-carboxylic acid, and compounds obtained by substituting hydrogen of an aromatic ring of these with an alkyl group, an aryl group, an alkoxy group, or a halogen group. Examples of the alicyclic dicarboxylic acid include trans-1, 4-dicarboxycyclohexane, cis-1, 4-dicarboxycyclohexane and the like, and compounds obtained by substituting hydrogen in the aromatic ring with an alkyl group, an aryl group, an alkoxy group or a halogen group. Examples of the alicyclic and aliphatic diols include trans-1, 4-dihydroxycyclohexane, cis-1, 4-dihydroxycyclohexane, ethylene glycol, 14-butanediol, and xylylene glycol.
Among these combinations, examples of the aromatic polyesters preferred in the present invention include (1) copolyesters containing 40 to 70 mol% of p-hydroxybenzoic acid residues and/or 2-hydroxynaphthalene-6-carboxylic acid residues, 15 to 30 mol% of the above-mentioned aromatic dicarboxylic acid residues and 15 to 30 mol% of aromatic diol residues; (2) Copolyesters formed from terephthalic acid and/or isophthalic acid and chlorohydroquinone, phenyl hydroquinone and/or hydroquinone; and (3) a copolyester containing 20 to 80 mol% of p-hydroxybenzoic acid residue and 20 to 80 mol% of 2-hydroxynaphthalene-6-carboxylic acid residue.
When the aromatic polyester used in the present invention is obtained by using these raw materials, the polycondensation reaction may be carried out as it is or by esterification of an aliphatic or aromatic monocarboxylic acid or a derivative thereof, an aliphatic alcohol or a phenol or a derivative thereof, or the like. The polycondensation reaction may be a known bulk polymerization, solution polymerization, suspension polymerization, or the like, and the obtained polymer may be used as a sample for spinning as it is, or may be a sample for spinning after heat treatment in a powder form in an inert gas or under reduced pressure. Alternatively, the pellets may be first pelletized and then used by an extruder.
Other polymers or additives (pigments, carbon, heat stabilizers, ultraviolet absorbers, lubricants, optical brighteners, etc.) may be contained in the components within a range that does not substantially deteriorate the physical properties of the melt anisotropic aromatic polyester fibers.
In the aromatic polyester of the present invention, there is a molecular weight range suitable for spinning. The "flow start temperature" was used as a physical property value corresponding to the molecular weight suitable for the melt spinning conditions. As for the "flow initiation temperature", a flow tester CFT-500 manufactured by Shimadzu corporation was used, and a nozzle having a diameter of 1mm and a length of 10mm was used at a pressure of 100kg/cm 2 In the state of (2), the aromatic polyester sample was heated at 4℃per minute, and the sample was allowed to flow through the nozzle to give an apparent viscosity of 4,800 Pa.s, and the temperature at this time was defined as "flow start temperature".
The "flow initiation temperature" of the melt anisotropic aromatic polyester of the present invention is suitably 290 to 330 ℃.
The melt anisotropic aromatic polyester fiber of the present invention has a single filament fineness of 4.0dtex or less, preferably 2.5dtex or less, and more preferably 1.0dtex or less. The total fineness is preferably 10dtex or more and 500dtex or less, more preferably 15dtex or more and 450dtex or less, and still more preferably 20dtex or more and 400dtex or less. The number of filaments is preferably in the range of 3 to 1000, more preferably 10 to 800, and even more preferably 20 to 600.
As for the melt anisotropic aromatic polyester suitable for melt spinning of the present invention, the shear rate is 1000sec at the melting point +30℃ -1 The melt viscosity is 10Poise or more and 50Poise or less. Within this range, an aromatic polyester fiber having a single filament fineness of 4.0dtex or less can be stably produced. That is, when the melt viscosity is less than 10Poise, the polymer extruded from the spinneret tends to be water-drop-shaped, and the stability of spinning tends to be insufficient. If the melt viscosity exceeds 50Poise, the filament drag decreases, and the filament breakage accompanying the fineness decrease tends to occur, resulting in insufficient spinning stability. Further, regarding the melt viscosity, a capillary rheometer (CAPILOGRAPH) (model 1B manufactured by Toyo Seisakusho Co., ltd.) was used, and an aromatic polyester sample was heated at a melting point of +30℃by a nozzle having a diameter of 0.5mm and a length of 5mm, and 1000sec was applied when the sample passed through the nozzle -1 The viscosity at this time is defined as the melt viscosity.
The aromatic polyester fiber of the present invention is produced by using a melt spinning apparatus such as that shown in fig. 1. In fig. 1, 1 is a spinneret, 2 is a spin pack, 3 is a spinneret, 4 is a heater, and 5 is a heat-insulating cylinder.
In melt spinning, a known method can be used for melt extrusion of aromatic polyesters. For melt spinning, aromatic polyesters are usually pelletized using an extruder type extruder. The extruded resin is sent to the spinneret 1 through a pipe, is measured by a known measuring device (not shown) such as a gear pump, passes through a filter in the spin pack 2, and then enters the spinneret 3. The temperature from the polymer piping to the spinneret 3 is preferably not lower than the melting point of the aromatic polyester and not higher than the thermal decomposition temperature.
By providing the heater 4 and the heat-insulating cylinder 5 directly below the spinneret 3, the diameter of the discharged fibers can be stabilized, and the variation in the surface temperature of the spinneret and the atmosphere temperature below the spinneret due to the external gas can be suppressed, so that the refining by the air flow can be made uniform, and there is a tendency that the filaments are easily spun stably without breakage, fluff generation, and the like.
In addition, the shearing speed in the spinneret hole was set to 10 4 ～10 5 sec -1 Is suitable. The shear rate γ referred to in the present invention was determined by the following equation.
γ＝4Q/πr 3
(wherein r is the radius (cm) of the spinneret hole and Q is the polymer ejection amount (cm) per single hole 3 /sec))
When the amount is within the above range, the orientation of the fibers becomes sufficient, and the fibers having a fine fineness tend to be easily obtained and the target physical properties tend to be easily obtained.
In the case of aromatic polyester fibers, since it is difficult to stretch the fibers in a post-process after spinning and winding, it is preferable to jet out the resin through fine holes as much as possible in order to obtain a composite yarn having a fineness of 4.0dtex or less. Therefore, the diameter (diameter) of the spinneret is preferably 0.2mm or less, more preferably 0.18mm or less.
As described above, after the predetermined oiling agent is applied to the spun aromatic polyester fiber by the oiling device 6, the spun aromatic polyester fiber is drawn by the first godet 7 and the second godet 8 and wound around the spool 9 (spinning spool). The winding speed is preferably 400 m/min to 2000 m/min, more preferably 600 m/min to 1800 m/min. The yarn winding tension measured between the second godet 8 and the spinning reel 9 is preferably 5cN or more and 60cN or less, more preferably 10cN or more and 50cN or less, and still more preferably 20cN or more and 40cN or less. When the tension is less than 5cN, the fiber is loosened and the fiber is wound around the godet 8, resulting in a defective shape of the spool 9. In the subsequent rewinding step, the winding drum having a defective shape is liable to be broken by yarn breakage or the like, and the filaments are liable to be broken, thereby deteriorating productivity and quality. In general, if the filament fineness is more than 4.0dtex, the shape of the spinning reel is not deformed and stable winding is possible even if the filament fineness is about 70 to 100cN, but if the filament fineness is less than 4.0dtex, the filament breakage during spinning and filament breakage and fibrillation in the subsequent rewinding step are caused and productivity and quality are deteriorated if the filament fineness is more than 60 cN. In the present invention, the spinning winding tension means a value obtained by measuring the tension applied when winding the yarn on the spool 9.
In producing the aromatic polyester fiber of the present invention, it is important to set the spinning winding tension to 5cN or more and 60cN or less. The prior aromatic polyester fiber mainly uses industrial materials such as ropes and cables, has thick total fineness and single yarn fineness of more than 4.0dtex, and the strength of each single yarn is generally more than 20cN. When the filament fineness is 4.0dtex or less, the strength of each filament becomes low, and even a little damage is liable to cause fibrillation, filament breakage and filament breakage. In addition, since the elongation of the aromatic polyester fiber is extremely low compared with that of a general polyester fiber, the aromatic polyester fiber cannot absorb the tensile force applied to the fiber, and also becomes a cause of fibrillation and yarn breakage. When the fineness of the filaments is 4.0dtex or less, the bulk density of the spinning reel increases. At this time, the overlapped filaments are likely to sink into each other, and when the fibers of the spinning reel are unwound, the filaments interfere with each other, and fibrillation, filament breakage, and the like are caused. Accordingly, in the present invention, the winding tension is set to 5cN or more and 60cN or less at the time of spinning, the load applied to the filaments at the time of spinning winding is reduced as much as possible, the bulk density of the spinning reel is reduced as much as possible, the sinking of the filaments is reduced, and fibrillation, filament breakage and filament breakage are prevented, thereby making the melt anisotropic aromatic polyester fiber high quality.
The melt anisotropic aromatic polyester fiber obtained by the above-described production method is a high-quality fiber which is free from filament breakage and fibrillation even when it is a fine fiber having a filament fineness of 4.0dtex or less, and which is excellent in the subsequent step-through property even when it is subjected to the later-described back-winding and heat treatment.
The strength of the fiber obtained by melt-spinning the melt-anisotropic aromatic polyester is preferably 3.0cN/dtex or more, more preferably 5.0cN/dtex or more. The elongation is preferably 0.5% or more, more preferably 1.0% or more. The elastic modulus is preferably 300cN/dtex or more, more preferably 400cN/dtex or more.
The melt anisotropic aromatic polyester fiber obtained by spinning may be used as it is, or may be further strengthened and highly elastic by heat treatment. In this case, the fiber of the spinning reel is preferably temporarily rewound into a package with another heat treatment reel before the heat treatment. In this case, as described above, by setting the spin winding tension in the spinning step to 5cN or more and 60cN or less, the unwinding Shu Xingbian of the fiber in the rewinding can be made good, and a high-quality yarn free from filament breakage and yarn breakage can be obtained. In rewinding the roll for heat treatment, the bulk density of the bag is preferably 0.01g/cc or more and 1.0g/cc or less, more preferably 0.8g/cc or less, in order to uniformly perform solid-phase polymerization. The bulk density is a value calculated from the occupied volume Vf (cc) of the fiber and the mass Wf (g) of the fiber, which are obtained from the outer dimensions of the bag and the outer dimensions of the heat treatment roll serving as the core material, and using Wf/Vf. The occupied volume Vf is a value calculated by measuring the outer dimensions of the package and assuming that the rewinding spool is rotationally symmetrical, and Wf is a value calculated from the fineness and the winding length or a value measured by using the difference in mass between before and after winding. In order to reduce the bulk density, the rewinding speed is preferably 500 m/min or less, more preferably 400 m/min or less.
It is preferable to heat-treat the molten anisotropic aromatic polyester fiber at a temperature equal to or lower than the melting point of the fiber. Thus, solid-phase polymerization of the aromatic polyester fiber can be performed, and the strength and elastic modulus can be improved. Further, since the fibers tend to be easily fused together during the heat treatment, it is preferable to stepwise raise the temperature from the normal temperature to a temperature equal to or lower than the melting point in order to prevent the fusion between the fibers.
In order to stably perform solid-phase polymerization in the heat treatment, the heat treatment is preferably performed under an inert gas atmosphere. However, in terms of cost, in the case of using dry air, it is preferable to dehumidify it in advance to a dew point of-40 ℃. That is, if moisture is present during solid-phase polymerization, hydrolysis may be induced, and the strength may not be sufficiently improved.
The heat-treated fiber may be supplied as a product as it is, but in order to improve the product conveying efficiency, it is preferable to rewind the fiber again on a paper tube or the like. In the rewinding after the heat treatment, the upper limit of the rewinding speed is not particularly limited, but is preferably 500 m/min or less, more preferably 400 m/min or less, from the viewpoint of reducing damage to the fibers.
As described above, the heat treatment can further efficiently and stably produce a high-strength, high-elastic-modulus, high-quality melt anisotropic aromatic polyester fiber. The strength of the fiber obtained by the heat treatment is preferably 10.0cN/dtex or more, more preferably 12.0cN/dtex or more, and still more preferably 20.0cN/dtex or more. The elongation is preferably 1.0% or more, more preferably 2.0% or more. The elastic modulus is preferably 400cN/dtex or more, more preferably 500cN/dtex or more.
The melt anisotropic aromatic polyester fiber of the present invention is a high-quality fiber having a fluff number of less than 3 in 100 ten thousand m filament length and having no problem in post-steps such as weaving. More preferably, the fluff number is less than 2, still more preferably less than 1. Such a fiber can be obtained by the above-described production method.
Examples
The present invention will be specifically described below with reference to examples. Examples and comparative examples aromatic polyester fibers were spun using the melt spinning apparatus of fig. 1. The present invention is not limited to the examples described below. The evaluation in the examples was performed in the following manner.
1) Tensile test (Strength, elongation, elastic modulus)
The breaking strength elongation and the elastic modulus (initial tensile strength) were obtained by the standard time test of JISL 1013 (2010) using a tensile tester AGS-500NX manufactured by Shimadzu corporation, the sample length being 200mm and the tensile speed being 200 mm/min, and the average value of 10 points was represented.
2) Tension of spinning winding
The running tension between the second godet 8 and the capstan 9 of FIG. 1 was measured 3 times during the spinning winding using an electronic tensiometer CM-100R manufactured by Jin Jinggong machine Co., ltd, and the running tension was expressed as an average value.
3) Evaluation of spinning operability
The spinning operability when spinning is performed for 2 hours or more is evaluated as follows.
The yarn was not broken, and the yarn was stably spun.
Delta filament breakage occurred within 5 times in the 2 hour spin.
The yarn breaks for several times, and cannot be wound.
4) Evaluation of the reverse winding of the spinning dope
The operability when rewinding the 50000m spun fiber onto an iron reel was evaluated as follows.
The backwinding can be stably performed without occurrence of monofilament breakage or wire breakage.
Filament breakage and wire breakage occurred at delta.
The x was broken multiple times and could not be rewound to the end.
5) Evaluation of heat-treated yarn rewind
The following was conducted to evaluate the operability when the 50000m heat-treated fiber was rewound on a product paper tube.
The backwinding can be stably performed without occurrence of monofilament breakage or wire breakage.
Monofilament breakage occurs at delta.
The x was broken multiple times and could not be rewound to the end.
6) Evaluation of fluff number
The filament length of 100 ten thousand m was measured on the heat-treated fiber using a fluff finder F9-AN manufactured by CHUN electric Co., ltd., and the measurement results were evaluated as follows.
The number of the fluff is less than 1
The number of the delta fluff is more than 1 and less than 3
The number of the x fluff is more than 3
7) Running test of guide rail
The fibers were brought into contact with a 4mm diameter ceramic rod rail at a contact angle of 60℃and under a tension of 120g/cm at 300m/min 2 Under the conditions of 1 ten thousand m of heat-treated wires were run, and the process-passing properties were evaluated from the amount of deposited material on the rail as follows.
The amount of the piled-up particles is less than 1mg
The delta stacking amount is more than 1mg and less than 3mg
The x stacking amount is 3mg or more
Example 1
As the aromatic polyester exhibiting melt anisotropy, an aromatic polyester obtained by polymerizing 40 moles of p-acetoxybenzoic acid, 15 moles of terephthalic acid, 5 moles of isophthalic acid and 20.2 moles of 4,4' -diacetoxybiphenyl was used. The aromatic polyester has a melting point of 340 ℃, and a shear rate of 1000sec at a melting point of +30℃ -1 The melt viscosity at this time was 30Poise. The aromatic polyester in 140 ℃ in a vacuum dryer drying 24 hours, after the water ratio is 5ppm, using a single screw extruder melt extrusion, using a gear pump metering, resin to the spinning package. The spinning temperature from the extruder outlet to the spin pack at this time was 360 ℃. The resin was discharged at a discharge rate of 11.6 cc/min using a spinneret having 48 holes with a pore diameter of 0.09 mm. Spray in the directionThe obtained resin was fed with an oil solution, and then fed into a first godet and then into a second godet, and 48 filaments were wound on a spool at 867 m/min at the same time, to obtain an aromatic polyester fiber. The winding tension (spinning winding tension) at this time was 20cN. In winding for about 120 minutes, no filament breakage occurred, and spinning operability was good. The total fineness of the obtained fiber was 144.3dtex, the strength was 7.1cN/dtex, the elongation was 2.1% and the elastic modulus was 480cN/dtex. Then, the spinning dope was rewound from the spinning dope roll to the heat treatment dope roll at 300 m/min. In the rewinding of 50000m, no filament breakage or filament breakage occurred, and winding was performed well and operability was also good. After the fiber was treated at 310℃for 10 hours in nitrogen, it was rewound from the heat-treated reel to the paper tube at 300 m/min. In the rewinding of 50000m, no filament breakage or filament breakage occurred, and winding was performed well and operability was also good. The fibers thus obtained were each of 144.3dtex, 3.0dtex per filament, 26.0cN/dtex in strength, 2.4% in elongation and 1000cN/dtex in elastic modulus. The number of fluff of the heat-treated fiber wound around the paper tube was 0 in 100 ten thousand m measurement, and the fiber was of good quality. In addition, the amount of deposits on the rail in the rail operation test was small, and the process passing performance was good. The spinning conditions and the results are shown together in table 1.
Examples 2 to 16
An aromatic polyester fiber was obtained by spinning the same as in example 1, except that the total fineness, the single filament fineness and the spinning winding tension were changed as shown in table 1, using the aromatic polyester used in example 1. Then, the obtained aromatic polyester fiber was rewound from the spinning reel onto a heat treatment reel, treated in nitrogen, and rewound from the heat treatment reel onto a paper tube in the same manner as in example 1, to obtain a heat-treated aromatic polyester fiber. As shown in Table 1, the rewinding of the aromatic polyester fibers was satisfactory without filament breakage or filament breakage before and after the heat treatment. The number of fluff of the heat-treated fiber was 0 even in the 100-ten thousand-meter measurement, and the fiber had good quality. The amount of deposits on the rail in the rail operation test was small, and the process passing performance was good.
Example 17, 18
The use of a shear rate of 1000sec at a melting point +30℃ -1 An aromatic polyester fiber was obtained by spinning in the same manner as in example 1, except that the spinning temperature was changed to obtain aromatic polyesters having melt viscosities of 20Poise and 40 Poise. Then, the obtained aromatic polyester fiber was rewound from the spinning reel onto a heat treatment reel, treated in nitrogen, and rewound from the heat treatment reel onto a paper tube in the same manner as in example 1, to obtain a heat-treated aromatic polyester fiber. As shown in Table 1, the rewinding of the aromatic polyester fibers was satisfactory without filament breakage or filament breakage before and after the heat treatment. The number of fluff of the heat-treated fiber was 0 even in the 100-ten thousand-meter measurement, and the fiber had good quality. The amount of deposits on the rail in the rail operation test was small, and the process passing performance was good.
Comparative example 1
A resin was discharged and spun with the addition of an oiling agent in the same manner as in example 1, except that the spinning winding tension was changed to 4 cN. However, immediately after winding up on the spool 9, the yarn is released from the godet 8, and yarn breakage occurs.
Comparative example 2
An aromatic polyester fiber after heat treatment was obtained in the same manner as in example 1, except that the spin-winding tension was changed to 70 cN. The filament breakage and filament breakage occurred in the rewinding of the aromatic polyester fiber before and after the heat treatment, and the fluff number of the fiber after the heat treatment was 98 in 100 ten thousand m measurement, and the quality was poor. In the rail operation test, a large amount of deposits on the rail are generated, and the process passing performance is poor.
Reference example 1
Spinning was performed in the same manner as in comparative example 1, except that the single filament fineness was changed to 5.0 dtex. However, immediately after winding up on the spool 9, the yarn is released from the godet 8, and yarn breakage occurs.
Reference example 2
An aromatic polyester fiber after heat treatment was obtained in the same manner as in comparative example 2, except that the single filament fineness was changed to 5.0 dtex. The aromatic polyester fiber is preferably rewound without filament breakage or filament breakage before and after heat treatment. The number of fluff of the heat-treated fiber was 0 even in the 100-ten thousand-meter measurement, and the fiber had good quality. The amount of deposits on the rail in the rail operation test was small, and the process passing performance was good.
Comparative example 3, 4
Except that the melting point +30 ℃ and the shear rate 1000sec were used -1 The same spinning as in example 1 was carried out except that the aromatic polyesters having melt viscosities of 5Poise and 70Poise were used, but neither comparative examples 3 and 4 could be wound.
TABLE 1
As described above, the heat-treated melt anisotropic aromatic polyester fibers of examples 1 to 18 were excellent in yarn quality, and were free from yarn breakage during the warping step and weft knitting during the processing into a fabric, and were excellent in process-passing performance. The fibers obtained in comparative example 2 had a warping step and yarn breakage during weft knitting, and were poor in step-through property.
Industrial applicability
The melt anisotropic aromatic polyester fiber of the present invention obtained by the above-described production method is fine, but has the characteristics of high strength and high elastic modulus, and is free from filament breakage and fibrillation, and has a fluff number of less than 3 in 100 ten thousand m, thereby greatly improving the post-process trafficability.
Therefore, the present invention can be widely used in the fields of general industrial materials, electric materials (particularly, as tension elements), civil engineering and construction materials, protective clothing, sports applications, automobile parts, rubber reinforcing materials, acoustic materials, general clothing, and the like. Examples of useful applications include ropes, nets, fishing nets, base cloths for printed circuit boards, airbags, airships, base cloths for domes, etc., rider clothes, fishing lines, various lines (sailboats, paragliders, balloons, kite lines), blind ropes, supporting lines for screen windows, various lines in automobiles and airplanes, force transmission lines for electric products and robots, etc., and examples of particularly useful applications include base cloths for printed circuit boards, especially base cloths for products that have strong demands for fineness refinement, improvement of weaving properties, improvement of fabric quality, and need to suppress generation of fluff in a process, and are most suitable for use.
Symbol description
1. Spinning head
2. Spinning bag
3. Spinneret nozzle
4. Heater
5. Thermal insulation cylinder
6. Oil feeding device
7. First godet roll
8. Second godet
9. And (3) a winding drum.
Claims (5)
1. A melt anisotropic aromatic polyester fiber characterized in that:
the heat-treated fiber is formed from a composite yarn obtained by melt spinning at a melt point +30 ℃ and a shear rate of 1000sec, wherein the spin winding tension is set to 5cN to 60cN -1 A melt viscosity of 10Poise or more and 50Poise or less, and a filament fineness of 4.0dtex or less of an aromatic polyester exhibiting anisotropy when melted,
the strength of the fiber is more than 20.0cN/dtex,
the fluff number in the filament length of 100 ten thousand m is less than 3.
2. The melt anisotropic aromatic polyester fiber of claim 1, wherein:
the total fineness is 10dtex to 500dtex, and the number of filaments is 3 to 1000.
3. The melt anisotropic aromatic polyester fiber according to claim 1 or 2, wherein:
the 50000m can be rewound on the product paper tube without filament breakage.
4. The melt anisotropic aromatic polyester fiber according to claim 1 or 2, wherein:
the fibers were brought into contact with a 4mm diameter ceramic rod rail at a contact angle of 60℃and under a tension of 120g/cm at 300m/min 2 When 1 ten thousand m of the yarn is run, the deposit amount of the deposit on the rail is less than 1mg.
5. A melt anisotropic aromatic polyester composite yarn characterized in that:
it is obtained by a shear rate of 1000sec at a temperature of +30℃from the melting point -1 The melt viscosity is 10Poise or more and 50Poise or less, and the melt anisotropic aromatic polyester composite yarn is formed by melt-spinning an aromatic polyester having a filament fineness of 4.0dtex or less, and the melt winding tension is set to 5cN or more and 60cN or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910762745.4A CN110484992B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014197585 | 2014-09-26 | ||
| JP2014-197585 | 2014-09-26 | ||
| CN201580011621.2A CN106062260B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropy aromatic polyester fiber and its manufacturing method |
| CN201910762745.4A CN110484992B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
| PCT/JP2015/060292 WO2016047179A1 (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580011621.2A Division CN106062260B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropy aromatic polyester fiber and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110484992A CN110484992A (en) | 2019-11-22 |
| CN110484992B true CN110484992B (en) | 2023-05-30 |
Family
ID=55580721
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580011621.2A Active CN106062260B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropy aromatic polyester fiber and its manufacturing method |
| CN201910762745.4A Active CN110484992B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580011621.2A Active CN106062260B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropy aromatic polyester fiber and its manufacturing method |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6608376B2 (en) |
| KR (1) | KR101969558B1 (en) |
| CN (2) | CN106062260B (en) |
| TW (1) | TWI650453B (en) |
| WO (1) | WO2016047179A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108505137B (en) * | 2018-03-27 | 2020-08-11 | 东华大学 | Thermotropic liquid crystal polyarylester fiber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6245726A (en) * | 1985-08-23 | 1987-02-27 | Sumitomo Chem Co Ltd | Production of aromatic polyester fiber |
| JP2006299474A (en) * | 2005-04-22 | 2006-11-02 | Kuraray Co Ltd | Ultrafine melt-anisotropic aromatic polyester fiber |
| JP2010084301A (en) * | 2008-10-02 | 2010-04-15 | Toray Ind Inc | Liquid-crystal polyester fiber |
| JP2012158851A (en) * | 2011-02-01 | 2012-08-23 | Kb Seiren Ltd | Method for manufacturing aromatic polyester fiber |
| JP2013133576A (en) * | 2011-12-27 | 2013-07-08 | Toray Ind Inc | Liquid crystal polyester multifilament |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06166909A (en) | 1992-09-30 | 1994-06-14 | Kuraray Co Ltd | Production of melt anisotropic aromatic polyester ultrafine fiber |
| JP3913527B2 (en) * | 2001-10-30 | 2007-05-09 | ポリプラスチックス株式会社 | Totally aromatic polyesteramide and polyesteramide resin composition |
| JP2005035714A (en) * | 2003-07-18 | 2005-02-10 | Toray Ind Inc | Yarn winder and yarn winding method |
| JP4983689B2 (en) * | 2008-03-28 | 2012-07-25 | 東レ株式会社 | Method for producing liquid crystal polyester fiber |
| EP2407583B1 (en) * | 2009-03-11 | 2013-10-09 | Toray Industries, Inc. | Liquid crystal polyester fibers and method for producing the same |
| JP2010216052A (en) | 2009-03-19 | 2010-09-30 | Kuraray Co Ltd | Sea-island type conjugate fiber and ultrafine melt-anisotropic aromatic polyester fiber obtained from the sea-island type conjugate fiber |
| JP5327109B2 (en) * | 2009-03-23 | 2013-10-30 | 東レ株式会社 | Liquid crystalline polyester fiber and winding package |
| MY166937A (en) * | 2011-04-01 | 2018-07-25 | Polyplastics Co | Wholly Aromatic Polyester and Polyester Resin Composition |
| JP6121867B2 (en) * | 2013-10-18 | 2017-04-26 | Ｋｂセーレン株式会社 | Method for producing aromatic polyester fiber |
| JP6121866B2 (en) * | 2013-10-18 | 2017-04-26 | Ｋｂセーレン株式会社 | Method for producing aromatic polyester fiber |
-
2015
- 2015-03-31 CN CN201580011621.2A patent/CN106062260B/en active Active
- 2015-03-31 KR KR1020167024121A patent/KR101969558B1/en active IP Right Grant
- 2015-03-31 CN CN201910762745.4A patent/CN110484992B/en active Active
- 2015-03-31 JP JP2016549971A patent/JP6608376B2/en active Active
- 2015-03-31 WO PCT/JP2015/060292 patent/WO2016047179A1/en active Application Filing
- 2015-04-01 TW TW104110608A patent/TWI650453B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6245726A (en) * | 1985-08-23 | 1987-02-27 | Sumitomo Chem Co Ltd | Production of aromatic polyester fiber |
| JP2006299474A (en) * | 2005-04-22 | 2006-11-02 | Kuraray Co Ltd | Ultrafine melt-anisotropic aromatic polyester fiber |
| JP2010084301A (en) * | 2008-10-02 | 2010-04-15 | Toray Ind Inc | Liquid-crystal polyester fiber |
| JP2012158851A (en) * | 2011-02-01 | 2012-08-23 | Kb Seiren Ltd | Method for manufacturing aromatic polyester fiber |
| JP2013133576A (en) * | 2011-12-27 | 2013-07-08 | Toray Ind Inc | Liquid crystal polyester multifilament |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2016047179A1 (en) | 2017-07-06 |
| TWI650453B (en) | 2019-02-11 |
| KR20170034784A (en) | 2017-03-29 |
| CN110484992A (en) | 2019-11-22 |
| CN106062260A (en) | 2016-10-26 |
| WO2016047179A1 (en) | 2016-03-31 |
| CN106062260B (en) | 2019-09-17 |
| TW201612370A (en) | 2016-04-01 |
| JP6608376B2 (en) | 2019-11-20 |
| KR101969558B1 (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI602963B (en) | Liquid crystal polyester fiber and method for preparing the same | |
| EP2799600B1 (en) | Liquid-crystalline polyester multifilament | |
| JP5791284B2 (en) | Method for producing aromatic polyester fiber | |
| JP5286827B2 (en) | Liquid crystal polyester fiber | |
| JP6855683B2 (en) | Liquid crystal polyester multifilament | |
| JP5428271B2 (en) | Method for producing liquid crystal polyester fiber | |
| JP2013133576A (en) | Liquid crystal polyester multifilament | |
| CN110484992B (en) | Melt anisotropic aromatic polyester fiber and method for producing same | |
| JP2013133575A (en) | Liquid crystal polyester multifilament for filament separation | |
| JP6121867B2 (en) | Method for producing aromatic polyester fiber | |
| JP5187224B2 (en) | Method for producing molten liquid crystalline polyester fiber | |
| JP6121866B2 (en) | Method for producing aromatic polyester fiber | |
| JP6834270B2 (en) | Liquid crystal polyester multifilament | |
| JP6834269B2 (en) | Liquid crystal polyester multifilament | |
| JP5327116B2 (en) | Liquid crystal polyester fiber and method for producing the same | |
| CN108914228A (en) | Geotextile high mould flatness polyester industrial yarn and its production method | |
| JP2016191179A (en) | Liquid crystal polyester multifilament | |
| JP7472787B2 (en) | Liquid crystal polyester multifilament and advanced processed products made therefrom | |
| JP6953776B2 (en) | Liquid crystal polyester multifilament | |
| JP2016089308A (en) | Manufacturing method of liquid crystal polyester fiber | |
| JP2015030920A (en) | Liquid crystalline polyester fiber and method for producing the same | |
| CN117999384A (en) | Liquid crystal polyester fiber and method for producing same | |
| JP2009052161A (en) | Conjugated fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |