WO2016047179A1 - Melt anisotropic aromatic polyester fiber and method for producing same - Google Patents
Melt anisotropic aromatic polyester fiber and method for producing same Download PDFInfo
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- WO2016047179A1 WO2016047179A1 PCT/JP2015/060292 JP2015060292W WO2016047179A1 WO 2016047179 A1 WO2016047179 A1 WO 2016047179A1 JP 2015060292 W JP2015060292 W JP 2015060292W WO 2016047179 A1 WO2016047179 A1 WO 2016047179A1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
Definitions
- the present invention relates to a fine fiber fiber (multifilament having a single yarn fineness of 4.0 dtex or less) made of a melt anisotropic aromatic polyester.
- melt anisotropic aromatic polyester is a polymer composed of rigid molecular chains, and in melt spinning, the molecular chains can be highly oriented in the fiber axis direction.
- melt anisotropic aromatic polyester undergoes a polymerization reaction in a solid state, the highest strength among the fibers obtained by melt spinning is obtained by heat-treating the fiber after spinning at a high temperature and solid-phase polymerization. It is known to have an elastic modulus. Because of these characteristics, melt-anisotropic aromatic polyester fibers have traditionally been used in silk woven fabrics for screen printing, sail cloths, cord reinforcements for various electrical products, protective gloves, plastic reinforcements, and optical fiber tension members. Has been.
- melt-anisotropic aromatic polyester fibers have a low elongation at break and are therefore almost impossible to stretch after spinning. For this reason, in order to reduce the single yarn fineness, it is necessary to achieve the target single yarn fineness at the spinning stage.
- a method for producing a melt anisotropic aromatic polyester fiber having a fine single yarn fineness for example, in Patent Document 1, a sea-island type composite fiber using a water dispersible polyester as a sea component and a melt anisotropic aromatic polyester as an island component is used.
- a melt-anisotropic aromatic with a single yarn fineness of 0.05 to 1.0 dtex and a strength after heat treatment of 20 cN / dtex or more by wrapping around cheese and dissolving sea components in water in the form of cheese A method for obtaining a polyester fiber has been proposed.
- Patent Document 2 in a melt spinning method in which an aromatic polyester capable of forming an anisotropic molten phase is discharged from a nozzle having a diameter of 0.1 mm or less and spun and wound, the following condition (1)
- a method for producing a melt-anisotropic aromatic polyester ultrafine fiber characterized by using (7) to (7) has been proposed.
- the method of Patent Document 2 has the advantage that fibers having a fine single yarn fineness can be stably spun with a normal spinneret and has the advantage of low cost, but the fiber is unwound during rewinding or the like. , Fibrillation, single yarn breakage, and yarn breakage easily occur due to a decrease in strength per single yarn, and the quality of the resulting fiber is poor.
- An object of the present invention is to provide a high-quality melt-anisotropic aromatic polyester fiber that is fine but has no fibrillation or single yarn breakage.
- an object of the present invention is a multifilament having a single yarn fineness of 4.0 dtex or less made of an aromatic polyester that exhibits anisotropy when melted, and the number of fluffs at a yarn length of 1 million meters is less than 3. It is achieved by the melt anisotropic aromatic polyester fiber.
- This aromatic polyester fiber preferably has a total fineness of 10 dtex or more and 500 dtex or less and a filament number of 3 to 1000.
- the present invention also relates to a method for producing an aromatic polyester fiber obtained by melt spinning an aromatic polyester exhibiting anisotropy at the time of melting to obtain a multifilament having a single yarn fineness of 4.0 dtex or less. Melting point + 30 ° C., shear rate 1000 sec ⁇ This is also a method for producing the above-mentioned melt-anisotropic aromatic polyester fiber using an aromatic polyester having a melt viscosity of 1 to 50 poise and a spinning winding tension of 5 cN to 60 cN.
- the melt-anisotropic aromatic polyester fiber of the present invention is a high-grade one that has excellent single-fiber fineness of 4.0 dtex or less and excellent post-process passability without single yarn breakage and fibrillation.
- the aromatic polyester in the present invention is an aromatic polyester that exhibits anisotropy when melted.
- the aromatic polyester that exhibits anisotropy when melted is a temperature at which the polyester sample powder can flow when heated by placing the polyester sample powder on a heated sample stage between two polarizing plates orthogonal to each other by 90 °. In the region, it means having the property of transmitting light.
- aromatic polyesters include aromatic dicarboxylic acids, aromatic diols and / or aromatic hydroxycarboxylic acids, and derivatives thereof described in Japanese Patent Publication No. 56-18016 and Japanese Patent Publication No. 55-20008.
- a copolymer of these with an alicyclic dicarboxylic acid, an alicyclic diol, an aliphatic diol or a derivative thereof is also included.
- the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 4,4′-dicarboxydiphenyl, 2,6-dicarboxynaphthalene, 1,2-bis (4-carboxyphenoxy) ethane, and the like. And those obtained by substituting hydrogen of a group ring with an alkyl, aryl, alkoxy or halogen group.
- Aromatic diols include hydroquinone, resorcin, 4,4 ′ ′-dihydroxydiphenyl, 4 ′, 4′-dihydroxybenzophenone, 4,4′- dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylethane, 2,2-bis (4 -Hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, etc.
- aromatic hydroxycarboxylic acid examples include p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxynaphthalene-6-carboxylic acid, 1-hydroxynaphthalene-5-carboxylic acid, etc., and hydrogen of these aromatic rings. Examples thereof include those substituted with an alkyl, aryl, alkoxy or halogen group.
- Alicyclic dicarboxylic acids include trans-1,4-dicarboxycyclohexane, cis-1,4-dicarboxycyclohexane, etc., and hydrogens of these aromatic rings substituted with alkyl, aryl, alkoxy, or halogen groups Is mentioned.
- Examples of the alicyclic and aliphatic diols include trans-1,4-dihydroxycyclohexane, cis-1,4-dihydroxycyclohexane, ethylene glycol, 14-butanediol, and xylylenediol.
- preferred aromatic polyesters in the present invention include, for example, (1) p-hydroxybenzoic acid residue and / or 2-hydroxynaphthalene-6-carboxylic acid residue of 40 to 70 mol% and the above Copolyester composed of 15-30 mol% aromatic dicarboxylic acid residue and 15-30 mol% aromatic diol residue, (2) Consists of terephthalic acid and / or isophthalic acid and chlorohydroquinone, phenylhydroquinone and / or hydroquinone And (3) a copolyester composed of 20 to 80 mol% of p-hydroxybenzoic acid residues and 20 to 80 mol% of 2-hydroxynaphthalene-6-carboxylic acid residues.
- esterification as it is or with an aliphatic or aromatic monocarboxylic acid or a derivative thereof, an aliphatic alcohol or a phenol or a derivative thereof, or the like.
- polycondensation reaction known block polymerization, solution polymerization, suspension polymerization and the like can be adopted, and the obtained polymer may be used as it is as a spinning sample, or in a powdery inert gas, Or it is good also as a sample for spinning by heat-processing under pressure reduction. Alternatively, it may be granulated once by an extruder.
- the aromatic polyester in the present invention has a molecular weight range suitable for spinning.
- “Flow start temperature” is used as a physical property value corresponding to the molecular weight suitable for the melt spinning conditions.
- “Flow start temperature” is a flow tester CFT-500 manufactured by Shimadzu Corporation, and the temperature of an aromatic polyester sample is increased at 4 ° C./min with a nozzle having a diameter of 1 mm and a length of 10 mm at a pressure of 100 kg / cm 2. And the temperature at which the sample flows through the nozzle and gives an apparent viscosity of 4,800 Pascal seconds.
- the “flow start temperature” of the melt-anisotropic aromatic polyester in the present invention is preferably 290 to 330 ° C.
- the single yarn fineness of the melt-anisotropic aromatic polyester fiber in the present invention is 4.0 dtex or less, preferably 2.5 dtex or less, more preferably 1.0 dtex or less.
- the range of the total fineness is preferably 10 dtex or more and 500 dtex or less, more preferably 15 dtex or more and 450 dtex or less, and further preferably 20 dtex or more and 400 dtex or less.
- the range of the number of filaments is preferably 3 to 1000, more preferably 10 to 800, and still more preferably 20 to 600.
- the melt-anisotropic aromatic polyester suitable for melt spinning of the present invention has a melting viscosity of 10 poise or more and 50 poise or less at a melting point of + 30 ° C. and a shear rate of 1000 sec ⁇ 1 . Within this range, it is suitable for stably producing aromatic polyester fibers having a single yarn fineness of 4.0 dtex or less. That is, when the melt viscosity is less than 10 poise, the polymer extruded from the die tends to be wrinkled and tends to lack spinning stability. When the melt viscosity exceeds 50 poise, the spinnability is lowered, so that there is a possibility that single yarn breakage may occur as the fineness is reduced, and the spinning stability tends to be lacking.
- melt viscosity was measured by using a capillograph (Model 1B, manufactured by Toyo Seiki Seisakusho Co., Ltd.) with a nozzle having a diameter of 0.5 mm and a length of 5 mm. It is defined as the viscosity at a shear rate of -1 .
- the aromatic polyester fiber of the present invention is produced, for example, by using a melt spinning apparatus as shown in FIG.
- 1 is a spinning head
- 2 is a spinning pack
- 3 is a spinneret
- 4 is a heater
- 5 is a heat retaining cylinder.
- melt spinning a known method may be used for melt extrusion of the aromatic polyester.
- the aromatic polyester is usually pelletized so as to be suitable for melt spinning, and an extruder type extruder is used.
- the extruded resin passes through a pipe, is sent to the spinning head 1, is metered by a known metering device (not shown) such as a gear pump, passes through a filter in the spinning pack 2, and then enters the spinneret 3.
- the temperature from the polymer pipe to the spinneret 3 is preferably not less than the melting point of the aromatic polyester and not more than the thermal decomposition temperature.
- the diameter of the discharged fiber is stabilized, and changes in the spinneret surface temperature and the atmospheric temperature under the spinneret can be suppressed by the outside air, There is a tendency that thinning by the draft becomes uniform, and there is no yarn breakage or fluff generation, and stable spinning tends to occur.
- the shear rate in the spinneret hole is 10 4 to 10 5 sec ⁇ 1 .
- the hole diameter (diameter) of the spinneret is preferably 0.2 mm or less, and more preferably 0.18 mm or less.
- the aromatic polyester fiber spun as described above is applied with a predetermined oil agent by the oil agent applying device 6, and then taken up by the first godet roll 7 and the second godet roll 8, and is taken up by a take-up bobbin 9 (spinning take-up bobbin). ).
- the winding speed is preferably 400 m / min or more and 2000 m / min or less, more preferably 600 m / min or more and 1800 m / min or less.
- the spinning winding tension measured between the second godet roll 8 and the spinning winding bobbin 9 is preferably 5 cN or more and 60 cN or less, more preferably 10 cN or more and 50 cN or less, and further preferably 20 cN or more and 40 cN or less.
- the fiber When the tension is less than 5 cN, the fiber is loosened, whereby the yarn is wound around the godet roll 8 or the winding bobbin 9 has a defective shape.
- the bobbin having a defective shape is liable to be broken or broken due to traversing or the like in the subsequent rewinding process, and the productivity and quality are lowered.
- the fiber Normally, if the fiber exceeds a single yarn fineness of 4.0 dtex, it can be stably wound even if the spinning winding tension is about 70 to 100 cN without causing the shape of the spinning winding bobbin to collapse.
- the spinning winding tension is a value measured for the tension applied when winding with the winding bobbin 9.
- the spinning winding tension is 5 cN or more and 60 cN or less.
- Conventional aromatic polyester fibers are mainly used for industrial materials such as ropes and cables. The total fineness is thick, the single yarn fineness exceeds 4.0 dtex, and the strength per single yarn is generally 20 cN or more. It was. When the single yarn fineness is 4.0 dtex or less, the strength per single yarn is reduced, and fibrillation, single yarn breakage and breakage easily occur even with slight damage.
- the aromatic polyester fiber has an extremely low elongation as compared with a general polyester fiber, the tension applied to the fiber cannot be absorbed, which causes fibrillation and yarn breakage.
- the winding tension is set to 5 cN or more and 60 cN or less at the time of spinning, the burden on the yarn at the time of spinning winding is reduced as much as possible, and the bulk density of the spinning winding bobbin is reduced as much as possible.
- melt anisotropic aromatic polyester fiber obtained by the above production method is a fine fiber having a single yarn fineness of 4.0 dtex or less, there is no single yarn breakage or fibrillation in the rewinding or heat treatment described later, It is of high quality with excellent subsequent process passability.
- the strength of the fiber obtained by melt spinning the melt anisotropic aromatic polyester is preferably 3.0 cN / dtex or more, and more preferably 5.0 cN / dtex or more. Further, the elongation is preferably 0.5% or more, and more preferably 1.0% or more. Furthermore, the elastic modulus is preferably 300 cN / dtex or more, and more preferably 400 cN / dtex or more.
- the melt-anisotropic aromatic polyester fiber obtained by spinning can be used as it is, it can be further increased in strength and elasticity by heat treatment.
- the fiber of the spin-winding bobbin is once wound around another bobbin for heat treatment before heat treatment to form a package.
- the bulk density of the package be 0.01 g / cc or more and 1.0 g / cc or less, and 0.8 g / cc or less so that solid phase polymerization can proceed uniformly when the heat treatment bobbin is rolled back. More preferably.
- the bulk density is calculated by Wf / Vf from the occupied volume Vf (cc) of the fiber and the mass Wf (g) of the fiber obtained from the outer dimension of the package and the outer dimension of the heat treatment bobbin as the core material. Value.
- the occupied volume Vf is a value obtained by actually measuring the outer dimensions of the package and assuming that the wound bobbin is rotationally symmetric, and Wf is calculated from the fineness and the winding length. It is a value measured by a value or a mass difference before and after winding.
- the rewinding speed is preferably 500 m / min or less, and more preferably 400 m / min or less.
- the heat treatment is preferably performed at a temperature not higher than the melting point of the melt anisotropic aromatic polyester fiber.
- the solid phase polymerization of the aromatic polyester fiber proceeds and the strength and elastic modulus can be improved. It should be noted that, since there is a tendency that the fibers are easily fused during the heat treatment, it is preferable to raise the temperature stepwise from room temperature to a temperature below the melting point in order to prevent fusion between the fibers.
- the heat treatment is preferably performed in an inert gas atmosphere.
- dry air is used from the viewpoint of cost, it is desirable to dehumidify in advance to a dew point of -40 ° C or lower. That is, if water is present during solid phase polymerization, hydrolysis may be induced and the strength may not be sufficiently increased.
- the fiber after heat treatment can be used as a product as a package, it is preferably rewound around a paper tube or the like in order to increase the product carrying efficiency.
- 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 fiber.
- the strength of the fiber obtained by heat treatment as described above is preferably 10.0 cN / dtex or more, more preferably 12.0 cN / dtex or more, and further preferably 20.0 cN / dtex or more.
- the elongation is preferably 1.0% or more, and more preferably 2.0% or more.
- the elastic modulus is preferably 400 cN / dtex or more, and more preferably 500 cN / dtex or more.
- the melt-anisotropic aromatic polyester fiber of the present invention has a number of fluffs of less than 3 at a yarn length of 1 million m, and is of high quality without any trouble in subsequent processes such as weaving. More preferably, the number of fluff is less than 2, and still more preferably less than 1. Such a fiber can be obtained by the production method described above.
- Spinning operability evaluation Spinning operability when spinning for 2 hours or more was evaluated as follows. ⁇ Stable spinning with no yarn breakage. ⁇ : No more than 5 yarn breaks occurred during spinning for 2 hours. X Thread breakage occurred frequently and could not be wound.
- Example 1 As an aromatic polyester exhibiting melt anisotropy, an aromatic polyester polymerized with 40 mol of p-acetoxybenzoic acid, 15 mol of terephthalic acid, 5 mol of isophthalic acid and 20.2 mol of 4,4′-diacetoxydiphenyl was used. . This aromatic polyester had a melting point of 340 ° C., a melting point of + 30 ° C., and a melt viscosity at a shear rate of 1000 sec ⁇ 1 of 30 poise. The aromatic polyester was dried in a vacuum dryer at 140 ° C.
- the obtained fiber had a total fineness of 144.3 dtex, a single yarn fineness of 3.0 dtex, a strength of 26.0 cN / dtex, an elongation of 2.4%, and an elastic modulus of 1000 cN / dtex.
- the number of fluffs of the heat-treated fiber wound around the paper tube was 0 during the measurement of 1 million meters, which was a good quality. Also, in the guide running test, the amount of deposits on the guide was small and the process passability was good. The spinning conditions and results are shown in Table 1.
- Examples 2 to 16 An aromatic polyester fiber was obtained by spinning in the same manner as in Example 1 except that the aromatic polyester used in Example 1 was used and the total fineness, single yarn fineness, and spinning winding tension were changed as shown in Table 1. Next, in the same manner as in Example 1, the obtained aromatic polyester fiber was wound from a spinning winding bobbin onto a heat-treated bobbin, treated in nitrogen, and wound from the heat-treated bobbin to a paper tube to obtain a heat-treated aromatic polyester fiber. It was. As shown in Table 1, the rewinding of the aromatic polyester fiber was good with no single yarn breakage or yarn breakage before and after the heat treatment. The number of fluffs of the fiber after the heat treatment was 0 during 1 million meter measurement, which was a good quality. Also in the guide running test, the amount of deposits on the guide was small, and the process passability was good.
- Example 17 and 18 An aromatic polyester fiber was obtained by spinning in the same manner as in Example 1 except that an aromatic polyester having a melting point of + 30 ° C. and a melt viscosity of 20 poise and 40 poise at a shear rate of 1000 sec ⁇ 1 was used and the spinning temperature was changed. Next, in the same manner as in Example 1, the obtained aromatic polyester fiber was wound from a spinning winding bobbin onto a heat-treated bobbin, treated in nitrogen, and wound from the heat-treated bobbin to a paper tube to obtain a heat-treated aromatic polyester fiber. It was. As shown in Table 1, the rewinding of the aromatic polyester fiber was good with no single yarn breakage or yarn breakage before and after the heat treatment. The number of fluffs of the fiber after the heat treatment was 0 during 1 million meter measurement, which was a good quality. Also in the guide running test, the amount of deposits on the guide was small, and the process passability was good.
- melt-anisotropic aromatic polyester fibers after heat treatment of Examples 1 to 18 have good yarn quality, and when processed into a woven fabric, there is no warping process or yarn breakage during weft driving, and process passability. was excellent. What was obtained from Comparative Example 2 had a warping process and yarn breakage by weft driving, and the process passing ability was poor.
- the melt-anisotropic aromatic polyester fiber of the present invention obtained by the production method as described above has the characteristics of high strength and high elastic modulus despite being a fine material, has no single yarn breakage or fibrillation, and has a million The number of fluff is less than 3 at m, and the post-process passability is greatly improved.
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Abstract
Description
また、特許文献2では、異方性溶融相を形成し得る芳香族ポリエステルを、直径0.1mm以下の細孔のノズルより吐出して紡糸し巻き取る溶融紡糸方法において、以下の条件(1)~(7)を用いることを特徴とする、溶融異方性芳香族ポリエステル極細繊維の製造方法が提案されている。
(1)溶融異方性芳香族ポリエステルの融点+20℃の剪断速度1000sec-1における溶融粘度が500Poise未満であるポリマーを用いること(2)ノズル通過時の剪断速度を103~109sec-1とすること(3)ノズルにおける吐出線速度を5m/分以上40m/分以下とすること(4)巻取速度を150m/分以上8000m/分以下とすること(5)吐出線速度に対する巻取速度比を20以上とすること(6)紡糸口金温度を融点+15℃以上とすること(7)吐出後ノズル面から30cm離れた時点での繊維の温度をTm-150℃以下とすること However, highly oriented melt-anisotropic aromatic polyester fibers have a low elongation at break and are therefore almost impossible to stretch after spinning. For this reason, in order to reduce the single yarn fineness, it is necessary to achieve the target single yarn fineness at the spinning stage. As a method for producing a melt anisotropic aromatic polyester fiber having a fine single yarn fineness, for example, in Patent Document 1, a sea-island type composite fiber using a water dispersible polyester as a sea component and a melt anisotropic aromatic polyester as an island component is used. A melt-anisotropic aromatic with a single yarn fineness of 0.05 to 1.0 dtex and a strength after heat treatment of 20 cN / dtex or more by wrapping around cheese and dissolving sea components in water in the form of cheese A method for obtaining a polyester fiber has been proposed.
In Patent Document 2, in a melt spinning method in which an aromatic polyester capable of forming an anisotropic molten phase is discharged from a nozzle having a diameter of 0.1 mm or less and spun and wound, the following condition (1) A method for producing a melt-anisotropic aromatic polyester ultrafine fiber characterized by using (7) to (7) has been proposed.
(1) melting anisotropic aromatic that the melt viscosity at a shear rate of 1,000 sec -1 of melting point + 20 ° C. of the polyester used polymer is less than 500Poise (2) 3 the shear rate during passage through the nozzles 10 ~ 10 9 sec -1 (3) The discharge linear velocity at the nozzle is 5 m / min or more and 40 m / min or less (4) The winding speed is 150 m / min or more and 8000 m / min or less (5) Winding with respect to the discharge linear velocity The speed ratio should be 20 or more. (6) The spinneret temperature should be melting point + 15 ° C or higher. (7) The fiber temperature at 30 cm away from the nozzle surface after discharge should be Tm-150 ° C or lower.
γ=4Q/πr3
(但し、rは紡糸口金孔の半径(cm)、Qは単孔当たりのポリマー吐出量(cm3/sec))
上記範囲であると、繊維の配向が十分となり、細繊度の繊維が得られやすく、目的の物性が得られやすい傾向にある。 Further, it is preferable that the shear rate in the spinneret hole is 10 4 to 10 5 sec −1 . The shear rate γ referred to in the present invention is determined by the following equation.
γ = 4Q / πr 3
(Where r is the radius of the spinneret hole (cm), Q is the amount of polymer discharged per single hole (cm 3 / sec))
Within the above range, the orientation of the fibers becomes sufficient, fibers with a fineness are easily obtained, and the desired physical properties tend to be obtained.
JISL 1013(2010)の標準時試験に準じ、島津製作所製の引張り試験機AGS-500NXを用い、試料長200mm、引張り速度200mm/分にて破断強伸度及び弾性率(初期引張抵抗度)を求め、10点の平均値で表した。 1) Tensile test (strength, elongation, elastic modulus)
In accordance with the standard time test of JISL 1013 (2010), using a tensile tester AGS-500NX manufactured by Shimadzu Corporation, obtain the breaking elongation and elastic modulus (initial tensile resistance) at a sample length of 200 mm and a pulling speed of 200 mm / min. Expressed as an average of 10 points.
金井工機社製の電子式張力計CM-100Rを用い、紡糸巻取り中、図1の第二ゴデットロール8と巻取りボビン9間の走行張力を3回測定し、その平均値で表した。 2) Spinning winding tension Using the electronic tension meter CM-100R manufactured by Kanai Koki Co., Ltd., the traveling tension between the second godet roll 8 and the winding bobbin 9 in FIG. Expressed as an average value.
2時間以上紡糸した際の紡糸操業性を下記のように評価した。
○ 糸切れがなく安定的に紡糸ができた。
△ 2時間の紡糸中に5回以内の糸切れが発生した。
× 糸切れが多発して巻き取りができなかった。 3) Spinning operability evaluation Spinning operability when spinning for 2 hours or more was evaluated as follows.
○ Stable spinning with no yarn breakage.
Δ: No more than 5 yarn breaks occurred during spinning for 2 hours.
X Thread breakage occurred frequently and could not be wound.
紡糸後の繊維を鉄ボビンに50000m巻き返した時の操業性を下記のように評価した。
○ 単糸切れや糸切れがなく安定的に巻き返しができた。
△ 単糸切れや糸切れが発生した。
× 糸切れが多発して最後まで巻き返しができなかった。 4) Evaluation of Spinning Spinning Rewinding The operability when the spun fiber was wound on an iron bobbin by 50000 m was evaluated as follows.
○ There was no single thread breakage or thread breakage, and the rewinding was stable.
△ Single thread breakage or thread breakage occurred.
× The yarn breakage occurred frequently and could not be rewound to the end.
熱処理後の繊維を製品紙管に50000m巻き返したときの操業性を下記のように評価した。
○ 単糸切れや糸切れがなく安定的に巻き返しができた。
△ 単糸切れが発生した。
× 糸切れが多発して最後まで巻き返しができなかった。 5) Evaluation of rewinding of heat treated yarn The operability when the fiber after the heat treatment was rewound about 50000 m in the product paper tube was evaluated as follows.
○ There was no single thread breakage or thread breakage, and the rewinding was stable.
△ Single thread breakage occurred.
× The yarn breakage occurred frequently and could not be rewound to the end.
熱処理後の繊維を春日電気(株)製、毛羽発見器F9-AN型を用いて、100万mの糸長を測定し、測定結果を下記のように評価した。
○ 毛羽数1個未満
△ 毛羽数1個以上3個未満
× 毛羽数3個以上 6) Evaluation of the number of fluff The heat-treated fiber was measured for a yarn length of 1 million m using a fluff detector F9-AN manufactured by Kasuga Denki Co., Ltd., and the measurement results were evaluated as follows.
○ Less than 1 fluff △ 1 to less than 3 fluff × 3 or more fluff
直径4mmのセラミック棒ガイドに接触角60°で繊維を接触させながら1万mの熱処理糸を300m/min、張力120g/cm2の条件で走行させ、ガイドへの付着物の堆積量から工程通過性を下記のように評価した。
○ 堆積量が1mg未満
△ 堆積量が1mg以上3mg未満
× 堆積量が3mg以上 7) Guide running test A 10,000 m heat treated yarn was run under conditions of 300 m / min and tension of 120 g / cm 2 while contacting a fiber with a 4 mm diameter ceramic rod guide at a contact angle of 60 °, The process passability was evaluated as follows from the deposited amount.
○ Accumulation amount is less than 1mg
△ Deposit amount is 1mg or more and less than 3mg × Deposit amount is 3mg or more
溶融異方性を示す芳香族ポリエステルとして、p-アセトキシ安息香酸40モル、テレフタル酸15モル、イソフタル酸5モル及び4,4’-ジアセトキシジフェニル20.2モルで重合した芳香族ポリエステルを用いた。この芳香族ポリエステルの融点は340℃であり、融点+30℃、剪断速度1000sec-1における溶融粘度は30Poiseであった。この芳香族ポリエステルを140℃の真空乾燥機中で24時間乾燥し、水分率5ppmとした後、単軸押出機にて溶融押出し、ギアポンプで計量して、紡糸パックに樹脂を供給した。このときの押出機出口から紡糸パックまでの紡糸温度は360℃とした。孔径0.09mmの孔を48個有する紡糸口金より吐出量11.6cc/分で樹脂を吐出した。吐出した樹脂に油剤を付与し、第一ゴデットロール、次いで第二ゴデットロールに導き、48フィラメント共に867m/分にて巻取りボビンに巻き取り、芳香族ポリエステル繊維を得た。このときの巻取り張力(紡糸巻取り張力)は20cNであった。約120分間の巻き取り中、糸切れは発生せず、紡糸操業性は良好であった。なお、得られた繊維の総繊度は144.3dtex、強度は7.1cN/dtex、伸度は2.1%、弾性率は480cN/dtexであった。次いで、紡糸巻取りボビンから熱処理ボビンへ300m/分で巻き返しを行った。50000mの巻き返し中、単糸切れや糸切れは発生せず、巻き取りは良好に実施でき、操業性も良好であった。この繊維を、310℃で10時間、窒素中で処理した後、熱処理ボビンから紙管へ300m/分で巻き返しを行った。50000mの巻き返し中、単糸切れや糸切れは発生せず、巻き取りは良好に実施でき、操業性も良好であった。なお、得られた繊維は総繊度144.3dtex 、単糸繊度3.0dtex、強度26.0cN/dtex、伸度2.4%、弾性率1000cN/dtexの繊維が得られた。紙管に巻き取った熱処理後繊維の毛羽数は、100万m測定中0個であり、良好な品位であった。また、ガイド走行テストにおいてもガイドへの堆積物の量が少なく、工程通過性は良好であった。上記紡糸条件及び結果を表1に合わせて示す。 [Example 1]
As an aromatic polyester exhibiting melt anisotropy, an aromatic polyester polymerized with 40 mol of p-acetoxybenzoic acid, 15 mol of terephthalic acid, 5 mol of isophthalic acid and 20.2 mol of 4,4′-diacetoxydiphenyl was used. . This aromatic polyester had a melting point of 340 ° C., a melting point of + 30 ° C., and a melt viscosity at a shear rate of 1000 sec −1 of 30 poise. The aromatic polyester was dried in a vacuum dryer at 140 ° C. for 24 hours to obtain a moisture content of 5 ppm, melt-extruded with a single screw extruder, measured with a gear pump, and supplied to the spinning pack. The spinning temperature from the extruder outlet to the spinning pack at this time was 360 ° C. Resin was discharged at a discharge rate of 11.6 cc / min from a spinneret having 48 holes with a hole diameter of 0.09 mm. An oil agent was applied to the discharged resin, led to the first godet roll and then the second godet roll, and both 48 filaments were wound on a winding bobbin at 867 m / min to obtain an aromatic polyester fiber. The winding tension (spinning winding tension) at this time was 20 cN. During winding for about 120 minutes, yarn breakage did not occur and spinning operability was good. The total fineness of the obtained fiber was 144.3 dtex, the strength was 7.1 cN / dtex, the elongation was 2.1%, and the elastic modulus was 480 cN / dtex. Subsequently, the spinning winding bobbin was rewound at 300 m / min from the heat treatment bobbin. No single yarn breakage or yarn breakage occurred during the rewinding of 50000 m, the winding could be performed well, and the operability was also good. This fiber was treated in nitrogen at 310 ° C. for 10 hours, and then wound from a heat-treated bobbin to a paper tube at 300 m / min. No single yarn breakage or yarn breakage occurred during the rewinding of 50000 m, the winding could be performed well, and the operability was also good. The obtained fiber had a total fineness of 144.3 dtex, a single yarn fineness of 3.0 dtex, a strength of 26.0 cN / dtex, an elongation of 2.4%, and an elastic modulus of 1000 cN / dtex. The number of fluffs of the heat-treated fiber wound around the paper tube was 0 during the measurement of 1 million meters, which was a good quality. Also, in the guide running test, the amount of deposits on the guide was small and the process passability was good. The spinning conditions and results are shown in Table 1.
実施例1で用いた芳香族ポリエステルを用い、総繊度、単糸繊度、紡糸巻取り張力を表1の通り変えた以外は実施例1と同様に紡糸して芳香族ポリエステル繊維を得た。次いで、実施例1と同様に、得られた芳香族ポリエステル繊維を紡糸巻取りボビンから熱処理ボビンに巻き返し、窒素中で処理し、熱処理ボビンから紙管へ巻き返して熱処理後の芳香族ポリエステル繊維を得た。表1に示す通り、芳香族ポリエステル繊維の巻き返しは、熱処理前と後で共に単糸切れや断糸の発生はなく、良好であった。熱処理後の繊維の毛羽数も、100万m測定中0個であり、良好な品位であった。ガイド走行テストにおいてもガイドへの堆積物の量が少なく、工程通過性は良好であった。 [Examples 2 to 16]
An aromatic polyester fiber was obtained by spinning in the same manner as in Example 1 except that the aromatic polyester used in Example 1 was used and the total fineness, single yarn fineness, and spinning winding tension were changed as shown in Table 1. Next, in the same manner as in Example 1, the obtained aromatic polyester fiber was wound from a spinning winding bobbin onto a heat-treated bobbin, treated in nitrogen, and wound from the heat-treated bobbin to a paper tube to obtain a heat-treated aromatic polyester fiber. It was. As shown in Table 1, the rewinding of the aromatic polyester fiber was good with no single yarn breakage or yarn breakage before and after the heat treatment. The number of fluffs of the fiber after the heat treatment was 0 during 1 million meter measurement, which was a good quality. Also in the guide running test, the amount of deposits on the guide was small, and the process passability was good.
融点+30℃、剪断速度1000sec-1における溶融粘度が20Poise及び40Poiseである芳香族ポリエステルを用い、紡糸温度を変更した以外は、実施例1と同様に紡糸して芳香族ポリエステル繊維を得た。次いで、実施例1と同様に、得られた芳香族ポリエステル繊維を紡糸巻取りボビンから熱処理ボビンに巻き返し、窒素中で処理し、熱処理ボビンから紙管へ巻き返して熱処理後の芳香族ポリエステル繊維を得た。表1に示す通り、芳香族ポリエステル繊維の巻き返しは、熱処理前と後で共に単糸切れや断糸の発生はなく、良好であった。熱処理後の繊維の毛羽数も、100万m測定中0個であり、良好な品位であった。ガイド走行テストにおいてもガイドへの堆積物の量が少なく、工程通過性は良好であった。 [Examples 17 and 18]
An aromatic polyester fiber was obtained by spinning in the same manner as in Example 1 except that an aromatic polyester having a melting point of + 30 ° C. and a melt viscosity of 20 poise and 40 poise at a shear rate of 1000 sec −1 was used and the spinning temperature was changed. Next, in the same manner as in Example 1, the obtained aromatic polyester fiber was wound from a spinning winding bobbin onto a heat-treated bobbin, treated in nitrogen, and wound from the heat-treated bobbin to a paper tube to obtain a heat-treated aromatic polyester fiber. It was. As shown in Table 1, the rewinding of the aromatic polyester fiber was good with no single yarn breakage or yarn breakage before and after the heat treatment. The number of fluffs of the fiber after the heat treatment was 0 during 1 million meter measurement, which was a good quality. Also in the guide running test, the amount of deposits on the guide was small, and the process passability was good.
紡糸巻取り張力を4cNに変えた以外は実施例1と同様に樹脂を吐出し、油剤を付与し、紡糸した。ところが、巻取りボビン9に巻きつけた途端、ゴデットロール8に糸が取られ、すぐ糸切れとなった。 [Comparative Example 1]
Except that the spinning winding tension was changed to 4 cN, the resin was discharged in the same manner as in Example 1, the oil agent was applied, and spinning was performed. However, as soon as it was wound around the take-up bobbin 9, the yarn was taken up by the godet roll 8, and the yarn was broken immediately.
紡糸巻取り張力を70cNに変えた以外は、実施例1と同様に熱処理後の芳香族ポリエステル繊維を得た。芳香族ポリエステル繊維の巻き返しは、熱処理前と後で共に単糸切れや断糸の発生があり、熱処理後の繊維の毛羽数は、100万m測定中、98個であり、品位の悪いものであった。ガイド走行テストではガイドへの堆積物が大量に発生し、工程通過性は悪いものであった。 [Comparative Example 2]
An aromatic polyester fiber after heat treatment was obtained in the same manner as in Example 1 except that the spinning winding tension was changed to 70 cN. In the rewinding of the aromatic polyester fiber, single yarn breakage or breakage occurs both before and after the heat treatment, and the number of fluffs of the fiber after the heat treatment is 98 during the measurement of 1 million meters, which is of poor quality. there were. In the guide running test, a large amount of deposits were generated on the guide, and the process passability was poor.
単糸繊度を5.0dtexに変えた以外は比較例1と同様に紡糸した。ところが、巻取りボビン9に巻きつけた途端、ゴデットロール8に糸が取られ、すぐ糸切れとなった。 [Reference Example 1]
Spinning was performed in the same manner as in Comparative Example 1 except that the single yarn fineness was changed to 5.0 dtex. However, as soon as it was wound around the take-up bobbin 9, the yarn was taken up by the godet roll 8, and the yarn was broken immediately.
単糸繊度を5.0dtexに変えた以外は比較例2と同様に熱処理後の芳香族ポリエステル繊維を得た。芳香族ポリエステル繊維の巻き返しは、熱処理前と後で共に単糸切れや断糸の発生はなく良好であった。また、熱処理後の繊維の毛羽数も、100万m測定中、0個であり、良好な品位であった。ガイド走行テストにおいてもガイドへの堆積物の量が少なく、工程通過性は良好であった。 [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 yarn fineness was changed to 5.0 dtex. The rewinding of the aromatic polyester fiber was good with no occurrence of single yarn breakage or yarn breakage before and after the heat treatment. Further, the number of fluffs of the fiber after the heat treatment was 0 during the measurement of 1 million meters, which was a good quality. Also in the guide running test, the amount of deposits on the guide was small, and the process passability was good.
融点+30℃、剪断速度1000sec-1における溶融粘度が5Poise及び70Poiseである芳香族ポリエステルを用いた以外は、実施例1と同様にして紡糸したが、比較例3、4共に巻取りできなかった。
[Comparative Examples 3 and 4]
Spinning was carried out in the same manner as in Example 1 except that an aromatic polyester having a melt viscosity of 5 poise and 70 poise at a melting point of + 30 ° C. and a shear rate of 1000 sec −1 was used.
2 紡糸パック
3 紡糸口金
4 ヒーター
5 保温筒
6 油剤付与装置
7 第一ゴデットロール
8 第二ゴデットロール
9 巻取りボビン 1 Spinning head
2 Spin Pack 3 Spinneret 4 Heater 5 Insulating Cylinder 6
Claims (3)
- 溶融時に異方性を示す芳香族ポリエステルからなる単糸繊度4.0dtex以下のマルチフィラメントであって、糸長100万mにおける毛羽数が3未満であることを特徴とする溶融異方性芳香族ポリエステル繊維。 A melt-anisotropic aromatic characterized in that it is a multifilament having a single yarn fineness of 4.0 dtex or less made of an aromatic polyester exhibiting anisotropy at the time of melting, and the number of fluffs at a yarn length of 1 million m is less than 3 Polyester fiber.
- 総繊度が10dtex以上、500dtex以下、フィラメント数が3~1000の範囲である請求項1記載の溶融異方性芳香族ポリエステル繊維。 The melt-anisotropic aromatic polyester fiber according to claim 1, wherein the total fineness is 10 dtex or more and 500 dtex or less, and the number of filaments is 3 to 1000.
- 溶融時に異方性を示す芳香族ポリエステルを溶融紡糸し、単糸繊度4.0dtex以下のマルチフィラメントを得る芳香族ポリエステル繊維の製造方法において、融点+30℃、剪断速度1000sec-1における溶融粘度が、10Poise以上、50Poise以下である芳香族ポリエステルを用い、紡糸巻取り張力が5cN以上、60cN以下であることを特徴とする請求項1または2記載の芳香族ポリエステル繊維の製造方法。 In the method for producing an aromatic polyester fiber obtained by melt spinning an aromatic polyester exhibiting anisotropy when melted to obtain a multifilament having a single yarn fineness of 4.0 dtex or less, the melt viscosity at a melting point of + 30 ° C. and a shear rate of 1000 sec −1 is: The method for producing an aromatic polyester fiber according to claim 1 or 2, wherein an aromatic polyester having a viscosity of 10 poise or more and 50 poise or less is used, and a spinning winding tension is 5 cN or more and 60 cN or less.
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