KR930011311B1 - Process for preparation of nylon-46 fiber - Google Patents
Process for preparation of nylon-46 fiber Download PDFInfo
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- KR930011311B1 KR930011311B1 KR1019910022199A KR910022199A KR930011311B1 KR 930011311 B1 KR930011311 B1 KR 930011311B1 KR 1019910022199 A KR1019910022199 A KR 1019910022199A KR 910022199 A KR910022199 A KR 910022199A KR 930011311 B1 KR930011311 B1 KR 930011311B1
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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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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Abstract
Description
본 발명은 내열성이 우수한 나이론-46 섬유의 제조방법에 관한 것으로 보다 구체적으로 설명하면 고열에서의 내열성을 증대시켜주기 위하여 고상중합해서 얻어진 높은 점도의 나이론-46 폴리머를 용융방사, 연신하여 우수한 물성을 가지며 고온에서도 안정한 나이론-46 섬유의 제조방법에 관한 것이다.The present invention relates to a method for producing nylon-46 fibers having excellent heat resistance. More specifically, the present invention relates to a nylon-46 polymer of high viscosity obtained by solid-phase polymerization in order to increase heat resistance at high heat. And a method for producing nylon-46 fibers which are stable even at high temperatures.
나이론-46 섬유는 다른 섬유에 비하여 나이론-46 폴리머 자체의 특성으로 인한 고강도, 고탄성의 물성을 나타내므로 각종 산업용 섬유소재로서 각광을 받고 있으나, 제조공정상 다른 폴리아미드계 섬유보다 결정화속도가 상당히 빠르고, 결정화도가 높아 상당한 제약이 뒤따를 뿐 아니라 특별한 제조공정이 요구되는 문제점이 있었다.Nylon-46 fiber has a high strength and high elasticity due to the properties of nylon-46 polymer itself compared to other fibers, so it has been spotlighted as various industrial fiber materials, but the crystallization rate is considerably faster than other polyamide fibers in the manufacturing process, The high degree of crystallinity is accompanied by significant constraints, there was a problem that requires a special manufacturing process.
예전부터 폴리아미드 수지를 이용하여 열안정성 및 고강력을 나타내는 섬유 및 그 제조방법이 많이 알려져 있으나, 이들은 주로 나이론-6, 나이론-66 폴리머를 이용한 것이고, 그 중 일본특개소 56-149429는 나이론-46 폴리머를 이용한 것이나 플라스틱으로서의 가능성만이 제안되어 있다.In the past, a fiber and a method of producing the fiber having a high thermal stability and a high strength using a polyamide resin are known, but these are mainly made of nylon-6, nylon-66 polymer, among which Japanese Patent Application No. 56-149429 is a nylon- Only the possibility of using 46 polymers and plastics is proposed.
그 이유는 일반적으로 나이론-46 폴리머의 융점이 285℃로 매우 높고, 공정온도조건의 폭이 매우 좁기 때문에 용융시 열 열화(thermal degradation)가 심하게 일어나서 성형하기가 곤란하였으며, 이와 같은 현상이 특히 섬유화하는 경우에 더욱 현저하게 발생되기 때문이었다.The reason is generally that the melting point of the nylon-46 polymer is very high at 285 ° C., and the process temperature conditions are very narrow, so that thermal degradation occurs during melting, making it difficult to form. This is because it occurs more remarkably when.
또한 용융방사가 나이론-46 폴리머는 결정화속도가 나이론-6과 비교할때는 수십배, 나이론-66과 비교할때는 약 5배 이상으로 대단히 빠르기 때문에 특별한 공정을 거치지 않고서는 물성이 우수한 나이론-46 섬유를 제조할 수 없었다.In addition, the melt-spun nylon-46 polymer has a very fast crystallization rate of several tens of times compared to nylon-6 and about five times higher than that of nylon-66. Thus, nylon-46 fibers having excellent physical properties can be produced without a special process. Could not.
아울러 고강도 및 내열성이 우수한 섬유를 제조하는 방사공정에 있어서도 융점이 높은 폴리머나 RV(상대점도)가 큰 폴리머를 사용하기 때문에 용융폴리머를 방사구금으로 압출할때 대단히 높은 전단력을 받게되며, 더욱이 나이론-46 폴리머는 결정화속도가 매우 빠르기 때문에 방사공정에서 발생되어서는 아니되는 결정의 핵인 구정이 미연신사에 생성되있었다.In addition, in the spinning process for producing high strength and heat resistant fibers, polymers with high melting points or polymers with high RV (relative viscosity) are used, and thus, very high shear force is exerted when the molten polymer is extruded into spinnerets. Because of the very fast crystallization rate, polymers were formed in unstretched yarns, the nuclei of crystals, which should not occur in the spinning process.
따라서 방사구금으로 토출될때 다이 스웰(die swell)현상에 의해 곡사가 발생되었고, 이 곡사가 완화되지도 않은체 그대로 서서히 냉각되면서 권취 되었기 때문에 연신공정에서 고배율로의 연신이 곤란하였으며, 연신사의 강도가 낮고, 강도의 변동율이 크게 나타날 뿐 아니라 내피로성이 떨어지는 등의 문제점이 있었다.Therefore, when discharged into the spinneret, the curved star was generated due to die swell phenomenon, and the curved star was gradually cooled without being relaxed and thus wound up as it was, and thus it was difficult to draw at high magnification in the stretching process. It was low, and there was a problem such as not only a large variation in strength but also a low fatigue resistance.
본 발명자들은 이와 같은 종래의 제반문제점을 예의 검토한 결과 고상중합해서 얻은 높은 점도의 나이론-46 폴리머를 용융방사, 연신하여 나이론-46 섬유를 제조함에 있어서, 방사온도 및 체류시간을 제어하고, 방사구금직하부에 가열통을 설치하여 방사시 열 열화를 최소화하고, 방사시 곡사를 방지하며, 미연신사내에 구정이 발생되는 것을 억제하여 미연신사의 균제도 및 연신성을 향상시켜줌으로서 연신공정에서 통상의 고배향 연신을 적용가능케하여 우수한 물성과 조업성을 갖는 본 발명 나이론-46 섬유의 제조방법을 완성하기에 이르렀다.The present inventors have diligently studied such conventional problems, and as a result of melt spinning and stretching the high viscosity nylon-46 polymer obtained by solid state polymerization, controlling the spinning temperature and the residence time, By installing a heating tube under the prison, it minimizes thermal deterioration during spinning, prevents howitzer during spinning, and suppresses the occurrence of Chinese New Year in unstretched yarn, thereby improving the uniformity and stretchability of unstretched yarns. The application of the highly oriented stretching has led to the completion of the method for producing the nylon-46 fiber of the present invention having excellent physical properties and operability.
이하 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명에서 사용하는 나이론-46 폴리머는 반복단위의 90몰% 이상이의 단위로 이루어진 것이고, RV는 3.5∼4.0, 융점은 285℃이상의 것이다.Nylon-46 polymer used in the present invention is 90 mol% or more of the repeating unit It consists of a unit, RV is 3.5-4.0, melting | fusing point is 285 degreeC or more.
본 발명은 이와 같은 나이론-46 폴리머를 용융방사함에 있어서, 열 열화를 방지하기 위하여 폴리머의 용융방사온도를 융점보다 약 10∼50℃정도 높게하되 용융체류시간, 다시 말해서 용융익스트루더내의 용융부에서부터 방사구금공으로 토출될때까지의 시간을 3.5∼8.0분의 범위내로 제어하고, 방사구금으로 토출되는 폴리머의 스트레스를 감소시키고 용융구역을 증대시킴으로서 냉각에 의한 결정화의 지연효과와 곡사현상을 방지하기 의하여 방사구금의 직하부에 설치되며 구금직하의 분위기 온도를 용융방사온도와 같게 하거나 이보다 50℃ 정도 높게 조절할 수 있도록 한 길이가 50∼300mm 정도인 가열통을 통과시키면서 통상의 방법으로 퀀칭고화 및 고배향 연신처리하여 나이론-46 섬유를 제조하였다.In the present invention, in melt spinning the nylon-46 polymer, in order to prevent thermal degradation, the melt spinning temperature of the polymer is about 10 to 50 ° C. higher than the melting point, but the melt residence time, that is, the melt portion in the melt extruder. To control the time from discharge to spinneret hole within 3.5 ~ 8.0 minutes, reduce the stress of polymer discharged to spinneret and increase melting zone to prevent delayed crystallization and curvature by cooling. It is installed directly below the spinneret and quenched and solidified in the usual way while passing through a heating tube of 50 ~ 300mm in length so that the atmosphere temperature under the prison can be controlled to be equal to or higher than the melt spinning temperature by 50 ℃. Stretching produced nylon-46 fibers.
본 발명에서 용융온도에 따른 체류시간별 RV 관계는 아래의 그림 1과 같았다.In the present invention, the RV relationship according to the residence time according to the melting temperature is shown in Figure 1 below.
그림 1의 그래프로 알 수 있는 바와 같이 본 발명에서 폴리머의 용융체류시간이 3.5분 미만일 경우에는 폴리머가 충분하게 용융되지 않을 뿐 아니라 RV가 높아서 방사시 전단력이 커지게 되어 곡사현상이 발생되고, 용융체류시간이 8.0분을 초과할 경우에는 RV가 너무 떨어져서 고강도의 물성을 얻을 수 없었고, 사출기내에서 폴리머가 분해 또는 열화되어 폴리머의 물성이 저하될 뿐 아니라 용융폴리머가 고점도, 고전단력을 갖게 되어 안정된 공정관리가 어렵게 되고 방사성이 떨어지게 된다.As can be seen from the graph of Figure 1, in the present invention, if the melt residence time of the polymer is less than 3.5 minutes, not only the polymer is not sufficiently melted, but also the RV is high and the shear force increases during spinning, causing curvature and melting. If the residence time exceeds 8.0 minutes, the RV is too low to obtain high-strength properties, and the polymer decomposes or deteriorates in the injection molding machine, thereby degrading the physical properties of the polymer and making the molten polymer highly viscous and high shear. Process control becomes difficult and radioactive.
이와 같이 본 발명의 제조방법으로 제조된 나이론-46 섬유는 나이론-46 폴리머를 용융방사온도를 융점보다 높은 온도로 유지하면서 용융체류시간을 제어하고, 방사구금직하의 분위기 온도를 방사온도와 같거나 이보다 높게 조절하면서 제조한 것이기 때문에 방사시 열 열화가 최소화되고, 곡사가 방지되며, 미연신사내에 구정이 발생되는 것이 억제되어 미연신사의 균제도 및 연신성을 향상시킬 수 있음으로 해서 연신공정에서 통상의 고배향 연신 처리를 적용시킬 수 있는 우수한 물성의 조업성을 갖게 된다.As described above, the nylon-46 fiber prepared by the manufacturing method of the present invention controls the melt residence time while maintaining the melt-spinning temperature of the nylon-46 polymer at a temperature higher than the melting point, and the atmospheric temperature directly below the spinneret is equal to the spinning temperature. Since it is manufactured with higher control than this, thermal deterioration during spinning is minimized, and howling is prevented, and it is possible to prevent spheroidism from occurring in the undrawn yarn, so that the uniformity and stretchability of the undrawn yarn can be improved. It has excellent operability in the physical properties to which the highly oriented stretching treatment can be applied.
[실시예 1∼4 및 비교실시예 1∼10][Examples 1 to 4 and Comparative Examples 1 to 10]
나이론-46 폴리머를 익스투루더형 용융방사기와 40개의 노즐 구멍을 갖는 방사구금으로 용융방사하고, 방사구금직하에 설치되는 가열통을 통과시키면서 퀀칭고화시키고, 다단연신하여 나이론-46 섬유를 제조하였다.The nylon-46 polymer was melt spun with an extruder type melt spinning machine and a spinneret having 40 nozzle holes, quenched and passed through a heating tube installed directly under the spinneret, and multi-stretched to prepare a nylon-46 fiber. .
실시예 및 비교실시예의 조건과 제조된 섬유의 물성은 표 1과 같다.The conditions of the examples and comparative examples and the physical properties of the fibers produced are shown in Table 1.
[표 1]TABLE 1
단) RV : 상대점도RV: Relative Viscosity
MP : 폴리머융점MP: polymer melting point
T : 방사온도T: radiation temperature
내열강력유지율은 방사전, 후의 폴리머 RV 변화에 대한 백분율임.Heat-resistant strength retention is a percentage of polymer RV change before and after spinning.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019910022199A KR930011311B1 (en) | 1991-12-05 | 1991-12-05 | Process for preparation of nylon-46 fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019910022199A KR930011311B1 (en) | 1991-12-05 | 1991-12-05 | Process for preparation of nylon-46 fiber |
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| Publication Number | Publication Date |
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| KR930013233A KR930013233A (en) | 1993-07-21 |
| KR930011311B1 true KR930011311B1 (en) | 1993-11-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1019910022199A KR930011311B1 (en) | 1991-12-05 | 1991-12-05 | Process for preparation of nylon-46 fiber |
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| KR100829484B1 (en) * | 2002-03-22 | 2008-05-16 | 주식회사 코오롱 | A polyamide 4.6 multi filament, and a process of preparing for the same |
| KR101999017B1 (en) | 2017-12-24 | 2019-07-10 | 주식회사 포스코 | High manganese galvanized steel sheet and method for manufacturing the same |
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