KR101225585B1 - Process for preparing aromatic polyamide filament - Google Patents
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- KR101225585B1 KR101225585B1 KR1020100137839A KR20100137839A KR101225585B1 KR 101225585 B1 KR101225585 B1 KR 101225585B1 KR 1020100137839 A KR1020100137839 A KR 1020100137839A KR 20100137839 A KR20100137839 A KR 20100137839A KR 101225585 B1 KR101225585 B1 KR 101225585B1
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- aromatic polyamide
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- polyamide filament
- spinning
- coagulation bath
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- 239000004760 aramid Substances 0.000 title claims abstract description 17
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 230000015271 coagulation Effects 0.000 claims abstract description 45
- 238000005345 coagulation Methods 0.000 claims abstract description 45
- 238000009987 spinning Methods 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims abstract description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 11
- 238000012643 polycondensation polymerization Methods 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 230000001112 coagulating effect Effects 0.000 description 14
- 239000010410 layer Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000004952 Polyamide Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000578 dry spinning Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- -1 aromatic dicarboxylic acid halide Chemical class 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- IQNTUYCIRRCRDY-UHFFFAOYSA-N 2,5-dichlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC(Cl)=C(C(Cl)=O)C=C1Cl IQNTUYCIRRCRDY-UHFFFAOYSA-N 0.000 description 1
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 description 1
- MSWAXXJAPIGEGZ-UHFFFAOYSA-N 2-chlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(Cl)=C1 MSWAXXJAPIGEGZ-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- NTNUPCREDHXJEL-UHFFFAOYSA-N 2-methylbenzene-1,4-dicarbonyl chloride Chemical compound CC1=CC(C(Cl)=O)=CC=C1C(Cl)=O NTNUPCREDHXJEL-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- XYQUZYVBQYBQDB-UHFFFAOYSA-N naphthalene-1,5-dicarbonyl chloride Chemical compound C1=CC=C2C(C(=O)Cl)=CC=CC2=C1C(Cl)=O XYQUZYVBQYBQDB-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- 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
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
본 발명은 방향족 폴리아미드 필라멘트 제조방법에 있어서, p-페닐렌디아민과 테레프탈로일클로라이드를 축중합으로 제조된 중합물을 황산에서 용해시켜 방사도프를 제조하는 단계, 및 상기 방사도프를 방사구금을 통해 방사한 후, 공기층 및 응고조을 연속적으로 통과시키는 단계를 포함하고, 상기 응고조는 출구방향으로 아래로 경사진 것을 특징으로 하는 방향족 폴리아미드 필라멘트의 제조방법을 제공한다.The present invention provides a method for producing an aromatic polyamide filament, comprising dissolving a polymer prepared by polycondensation of p-phenylenediamine and terephthaloyl chloride in sulfuric acid to prepare a spinning dope, and the spinning dope through a spinneret. After spinning, continuously passing the air layer and the coagulation bath, wherein the coagulation bath provides a method for producing an aromatic polyamide filament, which is inclined downward in the outlet direction.
Description
본 발명은 방향족 폴리아미드 필라멘트의 제조방법으로, 구체적으로 본 응고조를 출구방향으로 아래로 경사지게 설계함으로써, 응고액의 수면이 안정되고 균일한 응고가 이루어져 내피로성이 개선된 방향족 폴리아미드 섬유의 제조방법에 관한 것이다.The present invention is a method for producing an aromatic polyamide filament, specifically, by designing the coagulation bath to be inclined downward in the exit direction, the surface of the coagulating solution is stable and uniform coagulation is produced to produce an aromatic polyamide fiber with improved fatigue resistance It is about a method.
전방향족 폴리아미드 필라멘트는 미국특허 제 3,869,492 호 및 미국특허 제 3,869,430 호 등에 게재되어 있는 바와 같이, 방향족 디아민과 방향족 디에시드클로라이드를 N-메틸-2-피롤리돈을 포함하는 중합용매 중에서 중합시켜 전방향족 폴리아미드 중합체를 제조하는 공정과, 상기 중합체를 농황산 용매에 용해시켜 방사원액을 제조하는 공정과, 상기 방사원액을 방사 구금으로부터 방사하여 방사된 방사물을 비응고성 유체층을 통해 응고액 욕조내로 통과시켜 필라멘트를 형성하는 공정과, 상기 필라멘트를 수세, 건조 및 열처리하는 공정들을 거쳐 제조된다.The wholly aromatic polyamide filaments are prepared by polymerizing aromatic diamine and aromatic dieside chloride in a polymerization solvent containing N-methyl-2-pyrrolidone, as disclosed in US Pat. Nos. 3,869,492 and 3,869,430. Preparing an aromatic polyamide polymer; dissolving the polymer in a concentrated sulfuric acid solvent to produce a spinning stock solution; spinning the spinning stock solution from a spinneret and spinning the spinning material into a coagulant bath through a non-coagulating fluid layer. It is manufactured through a process of forming a filament by passing through, and a process of washing, drying and heat treating the filament.
응고액에 관련된 종래의 기술은 한국공개특허 제2008-22832호에서 응고액의 온도를 -5℃ 이하로 유지하여 방사된 방사물을 급속냉각시킴으로써 스킨층이 두껍게 형성되도록 하는 방법을 제시하고 있다. 또한, 일본공개특허 제11-189916호는 통과필라멘트 질량에 대한 응고액량 비를 조절함으로써 고강도, 고탄성 아라미드 섬유를 제조하는 방법을 제시하고 있다. 응고액 질량/속도에 관한 특허’인 미국등록특허 제4,965,033와 일본공개특허 제11-189916호는 응고액질량과 필라멘트질량의 비, 방사튜브 내에서의 필라멘트의 속도와 응고액 속도의 비, 오리피스의 직경 등을 제한하고 있다. 미국등록특허 제5,330,698에서는 응고액 온도를 40~80℃로 유지하여 높은 신도를 얻을 수 있는 방법을 제시하고 있다. 한국등록특허 제177,856호에서는 분출관의 분출구 각도(θ2)가 90°를 초과하면 응고욕의 수면이 흔들리고 섬유간의 마찰 저항이 상승하고 응고욕의 유입면에 소용돌이가 발생하게 되며 40°미만시 응고점이 분출관 내부에서 이루어지기 힘들기 때문에, 분출관의 분출구 각도(θ2)를 40° ~ 90°로 제한하는 방법을 제시하고 있다.The prior art related to the coagulation solution is disclosed in Korean Patent Laid-Open No. 2008-22832 to maintain the temperature of the coagulation solution below -5 ° C to rapidly cool the radiated spinning material so that the skin layer is formed thick. In addition, Japanese Patent Laid-Open No. 11-189916 discloses a method for producing a high strength, high elastic aramid fiber by adjusting the ratio of the amount of coagulated liquid to the mass of the filament passed. U.S. Patent No. 4,965,033 and Japanese Patent Application Laid-Open No. 11-189916, Patents on Coagulation Fluid Mass / Speed, disclose the ratio of coagulation liquid mass and filament mass, the ratio of filament speed and coagulation liquid velocity in the spinning tube, orifice. The diameter and the like. U.S. Patent No. 5,330,698 proposes a method for obtaining high elongation by maintaining the coagulating solution temperature at 40 ~ 80 ℃. In Korean Patent No. 177,856, when the spout angle (θ2) of the spout pipe exceeds 90 °, the water surface of the coagulation bath is shaken, the frictional resistance between the fibers increases, the vortex occurs on the inflow surface of the coagulation bath, and the solidification point is less than 40 °. Since it is hard to make this inside a blower pipe, the method of restricting the blower outlet angle (theta) 2 of a blower pipe to 40 degrees-90 degrees is proposed.
종래에는 응고조는 상단 및 하단의 직경이 거의 동일하여 응고조 내의 응고액 양이 지나치게 많아 경제성이 떨어지고, 균일한 응고와 배향이 이뤄지기 전에 응고조 내의 응고액 수면이 흔들리게 되면서 균일한 응고를 방해하여 원사의 내피로성이 떨어진다는 문제점이 발생한다. Conventionally, the coagulation bath is almost the same diameter of the top and bottom, so the amount of coagulating fluid in the coagulation bath is too large, and the economic efficiency is low, and the surface of the coagulating fluid in the coagulation bath is shaken before uniform coagulation and orientation is achieved, thus preventing uniform coagulation. There is a problem that the fatigue resistance of the yarn is poor.
본 발명은 응고조를 출구방향으로 아래로 경사지게 설계함으로써, 응고조 내의 일정한 공기층간의 거리를 유지하기 위한 응고액의 양이 감소하여 응고액의 수면이 안정되고 균일한 응고가 이루어져 내피로성이 개선된 방향족 폴리아미드 필라멘트의 제조방법을 제공하는 것을 목적으로 한다.The present invention is designed by inclining the coagulation tank downward in the outlet direction, the amount of coagulation liquid is reduced to maintain the distance between the air layers in the coagulation tank is stabilized, the surface of the coagulation liquid is stable and uniform coagulation is made to improve fatigue resistance It is an object to provide a method for producing an aromatic polyamide filament.
상기한 과제를 해결하기 위하여, 본 발명의 적절한 실시 형태에 따르면, 방향족 폴리아미드 필라멘트 제조방법에 있어서, p-페닐렌디아민과 테레프탈로일클로라이드를 축중합으로 제조된 중합물을 황산에서 용해시켜 방사도프를 제조하는 단계, 및 상기 방사도프를 방사구금을 통해 방사한 후, 공기층 및 응고조을 연속적으로 통과시키는 단계를 포함하고, 상기 응고조는 출구방향으로 아래로 경사진 것을 특징으로 하는 방향족 폴리아미드 필라멘트의 제조방법을 제공한다.In order to solve the above problems, according to a preferred embodiment of the present invention, in the method for producing an aromatic polyamide filament, p-phenylenediamine and terephthaloyl chloride are prepared by dissolving a polymer produced by condensation polymerization in sulfuric acid. And a step of continuously passing the air layer and the coagulation bath after spinning the spinning dope through the spinneret, wherein the coagulation bath is inclined downward in the outlet direction. It provides a manufacturing method.
본 발명의 다른 적절한 실시 형태에 따르면, 상기 응고조의 내벽면 경사각은 10 내지 80도인 것이 바람직하다.According to another suitable embodiment of the present invention, the inclination angle of the inner wall surface of the coagulation bath is preferably 10 to 80 degrees.
본 발명의 또 다른 적절한 실시 형태에 따르면, 상기 방법에 의해 제조된 방향족 폴리아미드 필라멘트를 제공한다.According to another suitable embodiment of the present invention, there is provided an aromatic polyamide filament produced by the above method.
본 발명은 응고조를 출구방향으로 아래로 경사지게 설계함으로써, 응고조 내의 응고액이 경사면을 따라 방사도프에 의해 아래로 내려가면서 일정한 공기층간의 거리를 유지하기 위한 응고액의 양이 감소하여 응고액의 수면이 안정되고 균일한 응고가 이루어져 내피로성이 개선된다. 또한 응고액의 양도 현저하게 줄일 수 있어, 생산 원가를 절감효과도 기대된다.The present invention is designed by inclining the coagulation tank downward in the outlet direction, the amount of coagulation liquid to maintain a constant distance between the air layers while the coagulating liquid in the coagulation tank is lowered down by the radiation dope along the inclined surface to reduce the coagulation liquid Sleep is stable and uniform coagulation improves fatigue resistance. In addition, the amount of coagulant can also be significantly reduced, reducing production costs.
도 1은 종래의 폴리아미드 건습식 방사장치의 개략도이다.
도 2는 본 발명의 폴리아미드 건습식 방사장치의 개략도이다.1 is a schematic view of a conventional polyamide wet and dry spinning apparatus.
2 is a schematic view of the polyamide wet-and-dry spinning apparatus of the present invention.
이하, 본 발명에 따른 실시예의 구성 및 작용을 상세히 설명한다.Hereinafter, the configuration and operation of the embodiment according to the present invention will be described in detail.
본 발명에 따르면, 폴리아미드 중합체의 용해도를 높이기 위하여 N-메틸-2-피롤리돈(NMP)에 염화칼슘을 첨가하여 중합용매를 만들고, 상기 중합용매에 방향족 디아민과 방향족 디카르복실산 할라이드를 1:1의 몰비로 투입하여 중합시켜서 고유점도 등의 물성이 향상된 파라 폴리아미드 중합체를 제조할 수 있다. According to the present invention, in order to increase the solubility of the polyamide polymer, calcium chloride is added to N-methyl-2-pyrrolidone (NMP) to make a polymerization solvent, and aromatic diamine and aromatic dicarboxylic acid halide is added to the polymerization solvent. A para polyamide polymer having improved physical properties such as intrinsic viscosity can be prepared by adding a polymer in a molar ratio of 1: 1.
본 발명에서 사용할 수 있는 방향족 디아민은 파라페닐렌 디아민, 4,4'-디아미노비페닐, 2-메틸-파라페닐렌디아민, 2-클로로-파라페닐렌디아민, 2,6-나프탈렌디아민, 1,5-나프탈렌디아민, 4,4'-디아미노벤즈아닐리드 등을 사용할 수 있다. Aromatic diamines that can be used in the present invention are paraphenylene diamine, 4,4'-diaminobiphenyl, 2-methyl-paraphenylenediamine, 2-chloro-paraphenylenediamine, 2,6-naphthalenediamine, 1 , 5-naphthalenediamine, 4,4'-diaminobenzanilide, and the like can be used.
본 발명에서 사용할 수 있는 방향족 디카르복실산 할라이드는 테레프탈로일 클로라이드(TPC), 4,4'-벤조일 클로라이드, 2-클로로테레프탈로일 클로라이드, 2,5-디클로로테레프탈로일 클로라이드, 2-메틸테레프탈로일 클로라이드, 2,6-나프탈렌카르복실산 클로라이드, 1,5-나프탈렌디카르복실산 클로라이드 등을 들 수 있다.Aromatic dicarboxylic acid halides that can be used in the present invention include terephthaloyl chloride (TPC), 4,4'-benzoyl chloride, 2-chloroterephthaloyl chloride, 2,5-dichloroterephthaloyl chloride, 2-methyl Terephthaloyl chloride, 2,6-naphthalenecarboxylic acid chloride, 1,5-naphthalenedicarboxylic acid chloride, etc. are mentioned.
본 발명은 상기한 NMP와 염화칼슘의 혼합용매에 파라-페닐렌디아민을 첨가한 후, 테레프탈로일 클로라이드(TPC)를 투입하여 중합시켜서 파라-폴리아미드 중합용액을 얻는다. 본 발명에서 폴리아미드의 고유점도는 5.5 내지 7.0이 바람직하다. 이때 5.5 미만이면 섬유의 강도가 떨어지고 7.0을 초과하면 용해성이 저하된다.In the present invention, para-phenylenediamine is added to the mixed solvent of NMP and calcium chloride, and then terephthaloyl chloride (TPC) is added to polymerize to obtain a para-polyamide polymerization solution. Intrinsic viscosity of the polyamide in the present invention is preferably 5.5 to 7.0. If it is less than 5.5, the strength of the fiber decreases. If it exceeds 7.0, the solubility decreases.
방사는 습식, 건식, 건습식 등이 사용 가능하지만 특히 건습식 방사법에서 균일한 구조의 방향족 폴리아미드 섬유 제조가 가능하므로 내피로성이 우수한 섬유 제조가 가능하다. Spinning may be wet, dry, or wet, but in particular, the wet and dry spinning method enables the production of an aromatic polyamide fiber having a uniform structure, thereby making it possible to manufacture fibers having excellent fatigue resistance.
본 발명에 따른 건습식 방사공정을 구체적으로 설명하면, 기어펌프로부터 방향족 폴리아미드 용액을 정량적으로 공급하면, 방사노즐을 통해 토출된 방사원액이 수직방향으로 공기층을 통과하여 응고액의 계면에 도달한다. 사용한 방사노즐의 형태는 통상 원형이다. 용도 면에서 타이어코드 및 산업용임을 감안하고, 용액의 균일한 냉각을 위한 노즐 간격을 고려하여, 노즐 개수는 200 내지 1,500가 바람직하다.The dry wet spinning process according to the present invention will be described in detail. When the aromatic polyamide solution is quantitatively supplied from the gear pump, the spinning stock solution discharged through the spinning nozzle passes through the air layer in the vertical direction and reaches the interface of the coagulating solution . The shape of the spinning nozzle used is usually circular. Considering the tire cord and the industrial in terms of use, in consideration of the nozzle interval for uniform cooling of the solution, the number of nozzles is preferably 200 to 1,500.
방사노즐을 통과한 섬유상의 방사원액이 응고조 내의 응고액 속에서 응고될 때, 유체의 직경이 크게 되면 표면과 내부 사이에 응고속도의 차이가 커지므로 치밀하고 균일한 조직의 섬유를 얻기가 힘들어진다. 그러므로 방향족 폴리아미드 용액을 방사할 때 동일한 토출량이라도 적절한 공기층을 유지함으로써 방사된 섬유가 보다 가는 직경을 지니며 응고액 속으로 입수할 수 있다. 너무 짧은 공기층 거리는 빠른 표면층 응고와 탈용매 과정에서 발생하는 미세공극 발생분율이 증가하여 연신비 증가에 방해가 되므로 방사속도를 높이기 힘든 반면, 너무 긴 공기층 거리는 필라멘트의 점착과 분위기 온도, 습도의 영향을 상대적으로 많이 받아 공정안정성을 유지하기 힘들다. 상기 공기층은 바람직하게는 3 내지 20mm이다. When the fibrous spinning stock solution passing through the spinning nozzle is solidified in the coagulating solution in the coagulation bath, if the diameter of the fluid is large, the difference in the coagulation rate between the surface and the inside becomes large, making it difficult to obtain a dense and uniform fiber. Lose. Therefore, even when the aromatic polyamide solution is spun, even the same discharge amount can be obtained into the coagulating solution with a thinner diameter by maintaining an appropriate air layer. Too short air gap distances increase the rate of micropores generated during rapid surface layer solidification and desolvation, which hinders the increase in elongation ratio, while too long air gap distances are associated with filament adhesion, atmospheric temperature, and humidity. It is difficult to maintain process stability by receiving a lot. The air layer is preferably 3 to 20 mm.
본 발명은 상기 응고조는 출구방향으로 아래로 경사진 것이 바람직하다. 응고조내의 응고액이 경사면을 따라 방사도프에 의해 아래로 내려가면서 일정한 공기층간의 거리를 유지하기 위한 응고액의 양이 감소하여 응고액의 수면이 안정되고 응고조 내의 응고액의 흐름도 원활해진다. In the present invention, the coagulation bath is preferably inclined downward in the outlet direction. As the coagulating liquid in the coagulation bath is lowered along the inclined plane by the radiation dope, the amount of coagulating solution for maintaining the distance between the air layers is reduced, so that the surface of the coagulating solution is stabilized and the flow of the coagulating solution in the coagulation bath is smoothed.
본 발명에서 응고조의 내벽면의 경사각은 10 내지 80도가 바람직하며 더욱 바람직하게는 15 내지 45도이다. 경사각이 10도 미만이면 응고액 수면의 안정성이 떨어지고, 80도를 초과하면 방사도프에서 용매 추출이 어려워진다. In the present invention, the inclination angle of the inner wall surface of the coagulation bath is preferably 10 to 80 degrees, more preferably 15 to 45 degrees. If the inclination angle is less than 10 degrees, the stability of the surface of the coagulated liquid is poor, and if it exceeds 80 degrees, it is difficult to extract the solvent from the spinning dope.
실시예 및 비교예의 물성 평가는 아래와 같이 측정 또는 평가하였다. The physical property evaluation of an Example and a comparative example was measured or evaluated as follows.
1) 멀티필라멘트의 모듈러스와 강신도 측정방법 1) How to measure modulus and strength of multifilament
원사를 표준상태인 조건, 즉 25℃ 온도와 상대습도 55RH%인 상태인 항온 항습실에서 24시간 방치 후 ASTM 2255 방법으로 시료를 인장 시험기를 통해 측정한다.After leaving the yarn in a standard condition, that is, a constant temperature and humidity chamber at a temperature of 25 ° C. and a relative humidity of 55 RH% for 24 hours, the sample is measured by a tensile tester using the ASTM 2255 method.
2) 내피로도2) Even with fatigue
내피로성은 원사끼리 loop 를 만든 후 상하 반복운동을 하여 끊어질 때까지의 횟수를 측정하여 평가하였다.Fatigue resistance was evaluated by measuring the number of times until the yarn was broken by looping up and down.
<비교예1, 실시예1 내지 4><Comparative Example 1, Examples 1 to 4>
중합 공정을 거쳐 고유점도가 6.3인 폴리(파라페닐렌테레프탈아미드) 중합 레진을 제조한 후, 상기 중합 레진을 99.9%의 농황산에 용해시켜 중합체 함량이 19.3중량%인 광학적 비등방성 방사 도프를 제조하였다. 제조된 방사 도프를 홀 직경 64 미크론인 1000홀의 방사 구금을 통해 방사한 후 공기층을 통과한 후 황산농도가 8%인 5℃의 응고액을 통과시켜 실을 권취하였다. 응고액내의 황산을 제거하기 위한 수세, 중화 공정을 실시하였다. 수세공정과 중화공정시의 얀 장력은 0.5g/d로 하고, 표면온도가 155℃인 한 쌍의 롤로 구성된 건조장치에서 얀 장력 1g/d로 건조하고 유제를 부여한 다음 와인더에 권취하였다. 표 1에 응고조 내면벽 경사각, 필라멘트의 물성 및 내피로도를 나타내었다.After preparing a poly (paraphenylene terephthalamide) polymerized resin having an intrinsic viscosity of 6.3 through a polymerization process, the polymerized resin was dissolved in 99.9% concentrated sulfuric acid to prepare an optically anisotropic spinning dope having a polymer content of 19.3% by weight. . The spinning dope was spun through a 1000-hole spinneret having a hole diameter of 64 microns, and then passed through an air layer, and then wound through a coagulating solution having a concentration of 8% sulfuric acid at 5 ° C. A water washing and neutralization step was carried out to remove sulfuric acid from the coagulation solution. Yarn tension during washing and neutralization was 0.5 g / d, and the yarn tension was 1 g / d in a drying device composed of a pair of rolls having a surface temperature of 155 ° C., and an emulsion was applied to the winder. Table 1 shows the inclination angle of the solidification tank inner wall, the properties of the filament and the fatigue resistance.
Cycle 횟수Fatigue resistance
Cycle count
이상 실시예를 들어 본 발명을 설명하였으나, 본 발명은 이에 제한되는 것은 아니다. 상기 실시예는 본 발명의 취지 및 범위를 벗어나는 않고 수정되거나 변경될 수 있으며, 당업자는 이러한 수정과 변경도 본 발명에 속하는 것임을 알 수 있을 것이다.Although the present invention has been described with reference to the above embodiments, the present invention is not limited thereto. The above embodiments may be modified or changed without departing from the spirit and scope of the present invention, and those skilled in the art will recognize that such modifications and changes also belong to the present invention.
a : 응고조의 내벽면 경사각a: inclination angle of the inner wall surface of the solidification tank
Claims (3)
p-페닐렌디아민과 테레프탈로일클로라이드를 축중합으로 제조된 고유점도(I.V) 5.5 내지 7.0의 중합물을 황산에서 용해시켜 방사도프를 제조하는 단계, 및
상기 방사도프를 방사구금을 통해 방사한 후, 공기층 및 응고조를 연속적으로 통과시키는 단계를 포함하고,
상기 응고조는 출구방향으로 아래로 경사지고, 응고조의 내벽면 경사각은 10 내지 80도이며,
상기 방향족 폴리아미드 필라멘트는 하기의 조건을 만족하는 것을 특징으로 하는 방향족 폴리아미드 필라멘트의 제조방법.
1) 강력 : 34 내지 37kg
2) 모듈러스 : 612g/d 이상
3) 내피로성 싸이클 횟수 : 110회 이상
In the method for producing an aromatic polyamide filament,
preparing a spinning dope by dissolving a polymer of intrinsic viscosity (IV) 5.5 to 7.0 prepared by condensation polymerization of p-phenylenediamine and terephthaloyl chloride in sulfuric acid, and
After the spinning dope through the spinneret, and continuously passing through the air layer and the coagulation bath,
The coagulation tank is inclined downward in the exit direction, the inclination angle of the inner wall surface of the coagulation tank is 10 to 80 degrees,
The aromatic polyamide filament is a method for producing an aromatic polyamide filament, characterized in that the following conditions.
1) Strong: 34 to 37kg
2) Modulus: More than 612g / d
3) Fatigue Resistance Cycle: More than 110 times
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| WO2017173887A1 (en) * | 2016-04-08 | 2017-10-12 | 山东万圣博科技股份有限公司 | Device for accelerating coagulation bath process used in high-speed spinning of para-aramid fibers |
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| JPS59228012A (en) | 1983-06-10 | 1984-12-21 | Asahi Chem Ind Co Ltd | Wet spinning process |
| JP2004270067A (en) * | 2003-03-07 | 2004-09-30 | Teijin Ltd | Dry-wet spinning apparatus |
| JP2006336152A (en) | 2005-06-02 | 2006-12-14 | Teijin Techno Products Ltd | Dry-wet spinning apparatus |
| KR20080062598A (en) * | 2006-12-29 | 2008-07-03 | 주식회사 효성 | Method for producing polymer fibers and poly (ｐ-phenylene terephthalamide) fibers prepared using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS59228012A (en) | 1983-06-10 | 1984-12-21 | Asahi Chem Ind Co Ltd | Wet spinning process |
| JP2004270067A (en) * | 2003-03-07 | 2004-09-30 | Teijin Ltd | Dry-wet spinning apparatus |
| JP2006336152A (en) | 2005-06-02 | 2006-12-14 | Teijin Techno Products Ltd | Dry-wet spinning apparatus |
| KR20080062598A (en) * | 2006-12-29 | 2008-07-03 | 주식회사 효성 | Method for producing polymer fibers and poly (ｐ-phenylene terephthalamide) fibers prepared using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017173887A1 (en) * | 2016-04-08 | 2017-10-12 | 山东万圣博科技股份有限公司 | Device for accelerating coagulation bath process used in high-speed spinning of para-aramid fibers |
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