JP2021179029A - Wholly aromatic polyamide fiber, and method for producing the same - Google Patents
Wholly aromatic polyamide fiber, and method for producing the same Download PDFInfo
- Publication number
- JP2021179029A JP2021179029A JP2020083712A JP2020083712A JP2021179029A JP 2021179029 A JP2021179029 A JP 2021179029A JP 2020083712 A JP2020083712 A JP 2020083712A JP 2020083712 A JP2020083712 A JP 2020083712A JP 2021179029 A JP2021179029 A JP 2021179029A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyamide
- total aromatic
- cross
- linking agent
- 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.)
- Granted
Links
- 239000004760 aramid Substances 0.000 title claims abstract description 95
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 94
- 239000000835 fiber Substances 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000009987 spinning Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 15
- 150000001408 amides Chemical class 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 238000001542 size-exclusion chromatography Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 36
- 238000000034 method Methods 0.000 abstract description 24
- 230000015271 coagulation Effects 0.000 abstract description 10
- 238000005345 coagulation Methods 0.000 abstract description 10
- 239000004971 Cross linker Substances 0.000 abstract 1
- 208000012886 Vertigo Diseases 0.000 description 29
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 11
- 229910017053 inorganic salt Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 150000001718 carbodiimides Chemical class 0.000 description 7
- 238000002144 chemical decomposition reaction Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002166 wet spinning Methods 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229920006231 aramid fiber Polymers 0.000 description 4
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- -1 polyphenylene isophthalamide Polymers 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002250 progressing effect Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LKGQTURGJNTDLR-UHFFFAOYSA-N 2-chlorobenzene-1,3-diamine Chemical compound NC1=CC=CC(N)=C1Cl LKGQTURGJNTDLR-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- 229920006292 Polyphenylene isophthalamide Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- YAZXITQPRUBWGP-UHFFFAOYSA-N benzene-1,3-dicarbonyl bromide Chemical compound BrC(=O)C1=CC=CC(C(Br)=O)=C1 YAZXITQPRUBWGP-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
Abstract
Description
本発明は、耐熱性、難燃性、機械物性などの優れた性質を持った全芳香族ポリアミド繊維において、使用環境により化学分解が進行してなる分子量が低下した全芳香族ポリアミドに、架橋剤を用いて合成することにより、実用的に十分に高い繊維、およびその製造する方法に関するものである。 The present invention is a cross-linking agent for a total aromatic polyamide fiber having excellent properties such as heat resistance, flame retardancy, and mechanical properties, and having a reduced molecular weight due to chemical decomposition progressing depending on the usage environment. It relates to a fiber that is practically sufficiently high by synthesizing using the above, and a method for producing the same.
従来、芳香族ジアミンと芳香族ジカルボン酸ジハライドとから製造される全芳香族ポリアミドが耐熱性および難燃性に優れていることは周知であり、かかる全芳香族ポリアミドのうち、ポリフェニレンイソフタルアミドで代表される全芳香族ポリアミド（以下アラミドと称する場合がある。）の繊維は、耐熱・難燃性繊維として特に有用なものである。これらの特性を発揮して、例えば防護衣等の防災安全衣料用途や耐熱フィルター、電子部品、高強度ケーブル等の産業用途に用いられている。しかし、このような高度な耐熱・難燃特性が求められる使用環境は、高温や湿熱、腐食性の薬品、紫外線等に曝される場合がほとんどである。したがって、長期の使用後は化学分解が進行しポリマーの分子量が著しく低下することから、機械物性が低下するため廃棄することとなる。全芳香族ポリアミドおよびその布帛や紡績糸を廃棄する際は、化学的安定性および難燃性の観点から焼却処分等を行うことができないため、埋め立てによる処分をせざるを得ないのが現状である。 It is well known that all aromatic polyamides produced from aromatic diamines and aromatic dicarboxylic acid dihalides have excellent heat resistance and flame retardancy, and among such all aromatic polyamides, polyphenylene isophthalamide is a representative. The fiber of the total aromatic polyamide (hereinafter sometimes referred to as aramid) is particularly useful as a heat-resistant and flame-retardant fiber. By demonstrating these characteristics, it is used, for example, in disaster prevention and safety clothing applications such as protective clothing, and in industrial applications such as heat resistant filters, electronic components, and high-strength cables. However, in most cases, the usage environment where such high heat resistance and flame retardant properties are required is exposed to high temperature, moist heat, corrosive chemicals, ultraviolet rays, and the like. Therefore, after long-term use, chemical decomposition proceeds and the molecular weight of the polymer is remarkably lowered, so that the mechanical properties are lowered and the polymer is discarded. When disposing of all aromatic polyamides and their fabrics and spun yarns, incineration cannot be performed from the viewpoint of chemical stability and flame retardancy, so the current situation is that they must be disposed of by landfill. be.
資源の廃棄処分とする課題の解決に当たり、リサイクル技術が検討されている。
全芳香族ポリアミド繊維のリサイクル技術としては、特開２０１４−７０１３３号公報や特開２００７−３２１０６９号公報には、アラミド繊維を製造・加工する工程において発生するアラミド繊維屑を無機塩含有溶媒と混合し、せん断等をかけることでアラミド溶解物（ドープ）を製造する方法を報告している。また、特開平７−２８６０６１号公報や特開２００７−３２１３１０号公報には、上記のようにして作成したアラミドドープを水中でせん断を与えながら攪拌することでフィブリッド化させ、構造材へ使用可能なアラミドパルプとする方法が報告されている。このようなアラミドドープは湿式紡糸手法により再紡糸し、再びアラミド繊維とすることもできる。しかし、人為的および環境的要因により標準状態よりも分子量が大きく低下したポリマー（繊維）を用いる場合は、紡糸性が悪くなるためリサイクルドープを使用して再度繊維を得ることが難しくなるだけでなく、実用に十分な強度を得ることができないなどの課題があった。
Recycling technology is being studied to solve the problem of disposing of resources.
As a technique for recycling all aromatic polyamide fibers, Japanese Patent Application Laid-Open No. 2014-70133 and Japanese Patent Application Laid-Open No. 2007-321609 describe aramid fiber waste generated in the process of manufacturing and processing aramid fiber mixed with an inorganic salt-containing solvent. However, a method for producing an aramid lysate (dope) by applying shear or the like is reported. Further, in JP-A-7-286061 and JP-A-2007-321310, the aramid dope prepared as described above can be made into a fibrid by stirring in water while applying shear, and can be used as a structural material. A method of making aramid pulp has been reported. Such an aramid dope can be respun by a wet spinning method to obtain aramid fibers again. However, when a polymer (fiber) whose molecular weight is significantly lower than the standard state due to human and environmental factors is used, not only is it difficult to obtain the fiber again by using the recycle dope because the spinnability is deteriorated. There are problems such as the inability to obtain sufficient strength for practical use.
したがって、近年地球環境に対する配慮から、使用環境により化学分解が進行した繊維であってもリサイクルを可能にできる技術革新が求められており、低分子量全芳香族ポリアミドから繊維を製造する方法が開発できれば工業的および環境的に非常に有用なものとなる。 Therefore, in recent years, due to consideration for the global environment, technological innovation that enables recycling of fibers that have undergone chemical decomposition depending on the usage environment is required, and if a method for producing fibers from low molecular weight total aromatic polyamides can be developed. It will be very useful industrially and environmentally.
本発明の目的は、かかる背景における問題点を解消し、耐熱性、難燃性、機械物性など
の優れた性質を持った全芳香族ポリアミド繊維において、使用環境により化学分解が進行してなる分子量が低下した全芳香族ポリアミドに、架橋剤を用いて合成することにより、実用的に十分に高い繊維、およびその製造する方法を提供することにある。
An object of the present invention is to solve the problems in the background, and to obtain a molecular weight of a total aromatic polyamide fiber having excellent properties such as heat resistance, flame retardancy, and mechanical properties, in which chemical decomposition proceeds depending on the usage environment. It is an object of the present invention to provide a practically sufficiently high fiber and a method for producing the fiber by synthesizing the total aromatic polyamide having a reduced value by using a cross-linking agent.
本発明者は、上記の課題を解決するために鋭意検討をおこなった結果、分子量の低い全芳香族ポリアミドに、架橋剤を添加したドープを用いて紡糸することで、強度の低い低分子量ポリアミドの分子間架橋を形成し、実用に十分な強度を持った全芳香族ポリアミド繊維が得られることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventor spins a low molecular weight total aromatic polyamide with a dope to which a cross-linking agent is added to obtain a low molecular weight low molecular weight polyamide. We have found that a total aromatic polyamide fiber having sufficient strength for practical use can be obtained by forming an intermolecular crosslink, and have completed the present invention.
すなわち本発明によれば、
１．重量平均分子量が２０万以上〜４５万未満である全芳香族ポリアミドと架橋剤から構成される成分を含有する全芳香族ポリアミド繊維であって、破断強度が３．０〜６．０ｃＮ／ｄｔｅｘであることを特徴とする全芳香族ポリアミド繊維、
２．前記の架橋剤が、カルボジイミドである前記１に記載の全芳香族ポリアミド繊維、
３．前記の架橋剤の構造が分子内にカルボジイミド基を２個以上もつカルボジイミド架橋剤である前記１、または２に記載の全芳香族ポリアミド繊維、そして、
４．サイズ排除クロマトグラフィーにより測定した重量平均分子量が２０万以上〜４５万未満である全芳香族ポリアミドと架橋剤を溶媒に溶解させて全芳香族ポリアミド紡糸用ドープを調製し、該紡糸用ドープを、凝固液に紡出した後、延伸および熱セット処理し、得られた繊維の破断強度が３．０〜６．０ｃＮ／ｄｔｅｘであることを特徴とする全芳香族ポリアミド繊維の製造方法。
５．前記の架橋剤がカルボジイミドである前記４記載の全芳香族ポリアミド繊維の製造方法、
６．前記の架橋剤の構造が分子内にカルボジイミド基を２個以上もつカルボジイミド架橋剤である前記４、または５に記載の全芳香族ポリアミド繊維の製造方法、
７．前記の全芳香族ポリアミド紡糸用ドープ内に、全芳香族ポリアミドに対して、前記の架橋剤を０．１〜１０質量％を含む、前記４〜６のいずれか１項に記載の全芳香族ポリアミド繊維の製造方法、
８．前記の全芳香族ポリアミドが、ポリメタフェニレンイソフタルアミド、およびその共重合体を含む、前記４〜７のいずれか１項に記載の全芳香族ポリアミド繊維の製造方法、９．前記の全芳香族ポリアミド紡糸用ドープが、１５〜３０質量％の全芳香族ポリアミドを含むアミド系溶媒溶液であり、該アミド系溶媒がＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルスルフォキシドからなる群から選ばれた少なくとも１種の溶媒である前記４〜８のいずれか１項に記載の全芳香族ポリアミド繊維の製造方法、
が提供される。
That is, according to the present invention.
1. 1. A total aromatic polyamide fiber containing a component composed of a total aromatic polyamide having a weight average molecular weight of 200,000 or more and less than 450,000 and a cross-linking agent, and having a breaking strength of 3.0 to 6.0 cN / dtex. All aromatic polyamide fibers, characterized by being
2. 2. The total aromatic polyamide fiber according to 1 above, wherein the cross-linking agent is carbodiimide.
3. 3. The all-aromatic polyamide fiber according to 1 or 2 above, wherein the structure of the cross-linking agent is a carbodiimide cross-linking agent having two or more carbodiimide groups in the molecule, and
4. A dope for total aromatic polyamide spinning was prepared by dissolving a total aromatic polyamide having a weight average molecular weight of 200,000 or more and less than 450,000 measured by size exclusion chromatography and a cross-linking agent in a solvent, and the dope for spinning was prepared. A method for producing a total aromatic polyamide fiber, which is spun into a coagulating liquid, then drawn and heat-set, and the resulting fiber has a breaking strength of 3.0 to 6.0 cN / dtex.
5. 4. The method for producing an all-aromatic polyamide fiber according to 4, wherein the cross-linking agent is carbodiimide.
6. The method for producing an all-aromatic polyamide fiber according to 4 or 5, wherein the cross-linking agent is a carbodiimide cross-linking agent having two or more carbodiimide groups in the molecule.
7. Item 2. The total aromatic according to any one of 4 to 6, wherein the total aromatic polyamide spinning dope contains 0.1 to 10% by mass of the above-mentioned cross-linking agent with respect to the total aromatic polyamide. Polyamide fiber manufacturing method,
8. 9. The method for producing a total aromatic polyamide fiber according to any one of 4 to 7 above, wherein the total aromatic polyamide contains polymethaphenylene isophthalamide and a copolymer thereof. The dope for total aromatic polyamide spinning is an amide-based solvent solution containing 15 to 30% by mass of total aromatic polyamide, and the amide-based solvent is N, N-dimethylformamide, N, N-dimethylacetamide, N. The method for producing a total aromatic polyamide fiber according to any one of 4 to 8 above, which is at least one solvent selected from the group consisting of -methyl-2-pyrrolidone and dimethylformamide.
Is provided.
本発明によれば、重量平均分子量が２０万以上〜４５万未満の分子量が極めて低い全芳香族ポリアミドを、通常の湿式紡糸で生産することは不可能であるが、架橋剤を用いることにより、繊維を製造することが可能になり、得られる繊維の破断強度が良好な全芳香族ポリアミド繊維が提供される。また、本発明で使用する全芳香族ポリアミドは、使用環境により化学分解が進んでいる状態であってもリサイクル原料として紡糸できる点で環境配慮へ大きく貢献でき、本発明の工業的価値は極めて大きい。 According to the present invention, it is impossible to produce a total aromatic polyamide having an extremely low molecular weight of 200,000 or more and less than 450,000 by weight average molecular weight by ordinary wet spinning, but by using a cross-linking agent, it is possible. It becomes possible to produce a fiber, and a total aromatic polyamide fiber having a good breaking strength of the obtained fiber is provided. Further, the all-aromatic polyamide used in the present invention can greatly contribute to environmental consideration in that it can be spun as a recycled raw material even in a state where chemical decomposition is progressing depending on the usage environment, and the industrial value of the present invention is extremely large. ..
また、本発明の製造方法は、架橋剤を導入した紡糸ドープの状態では架橋反応が起こらず、紡糸の過程（紡糸とは吐出から延伸、巻き取りまで含む）で架橋反応が進行するため、紡糸性に影響がなく工程通過性に優れ、品質の安定した繊維を得ることができる。さらには、架橋反応のための追加の処理工程が必要ないため、合理的な生産が可能である。 Further, in the production method of the present invention, the cross-linking reaction does not occur in the state of spinning dope in which a cross-linking agent is introduced, and the cross-linking reaction proceeds in the process of spinning (spinning includes from discharge to drawing and winding). It is possible to obtain fibers with stable quality without affecting the properties and having excellent process passability. Furthermore, rational production is possible because no additional treatment step is required for the crosslinking reaction.
以下、本発明について詳細を説明する。
本発明の全芳香族ポリアミド繊維を構成する全芳香族ポリアミド（以下アラミドと称する場合がある。）は、芳香族ジアミン成分と芳香族ジカルボン酸成分とから構成されるものであり、本発明の目的を損なわない範囲内で、他の共重合成分が共重合されていてもよい。
Hereinafter, the present invention will be described in detail.
The total aromatic polyamide (hereinafter sometimes referred to as aramid) constituting the total aromatic polyamide fiber of the present invention is composed of an aromatic diamine component and an aromatic dicarboxylic acid component, and is an object of the present invention. Other copolymerization components may be copolymerized as long as the above is not impaired.
本発明において特に好ましく使用されるのは、力学特性、耐熱性、難燃性に優れ、環境要因により低分子量化が起きやすい用途に使用されている観点から、メタフェニレンイソフタルアミド単位を主成分とするメタ型全芳香族ポリアミドである。メタフェニレンイソフタルアミド単位から構成されるメタ型全芳香族ポリアミドとしては、メタフェニレンイソフタルアミド単位が、全繰り返し単位の９０モル％以上であることが好ましく、さらに好ましくは９５モル％以上、特に好ましくは１００モルである。 Particularly preferably used in the present invention is a metaphenylene isophthalamide unit as a main component from the viewpoint that it has excellent mechanical properties, heat resistance and flame retardancy, and is used for applications in which low molecular weight is likely to occur due to environmental factors. It is a meta-type total aromatic polyamide. The meta-type total aromatic polyamide composed of metaphenylene isophthalamide units preferably contains 90 mol% or more of all repeating units, more preferably 95 mol% or more, and particularly preferably 95 mol% or more. It is 100 mol.
そして、本発明の全芳香族ポリアミドの原料となるメタ型芳香族ジアミン成分としては、メタフェニレンジアミン、３，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルスルホン等、および、これらの芳香環にハロゲン、炭素数１〜３のアルキル基等の置換基を有する誘導体、例えば、２，４−トルイレンジアミン、２，６−トルイレンジアミン、２，４−ジアミノクロロベンゼン、２，６−ジアミノクロロベンゼン等を例示することができる。なかでも、メタフェニレンジアミンのみ、または、メタフェニレンジアミンを８５モル％以上、好ましくは９０モル％以上、特に好ましくは９５モル％以上含有する混合ジアミンであることが好ましい。 The meta-aromatic diamine component used as a raw material for the total aromatic polyamide of the present invention includes metaphenylenediamine, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, and the like, and aromatic rings thereof. Derivatives having a substituent such as a halogen or an alkyl group having 1 to 3 carbon atoms, for example, 2,4-toluylene diamine, 2,6-toluylene diamine, 2,4-diaminochlorobenzene, 2,6-diaminochlorobenzene. Etc. can be exemplified. Among them, a mixed diamine containing only meta-phenylenediamine or a mixed diamine containing 85 mol% or more, preferably 90 mol% or more, particularly preferably 95 mol% or more of meta-phenylenediamine is preferable.
全芳香族ポリアミドを構成するメタ型芳香族ジカルボン酸成分の原料としては、例えば、メタ型芳香族ジカルボン酸ハライドを挙げることができる。メタ型芳香族ジカルボン酸ハライドとしては、イソフタル酸クロライド、イソフタル酸ブロマイド等のイソフタル酸ハライド、および、これらの芳香環にハロゲン、炭素数１〜３のアルコキシ基等の置換基を有する誘導体、例えば３−クロロイソフタル酸クロライド等を例示することができる。なかでも、イソフタル酸クロライドそのもの、または、イソフタル酸クロライドを８５モル％以上、好ましくは９０モル％以上、特に好ましくは９５モル％以上含有する混合カルボン酸ハライドであることが好ましい。 Examples of the raw material of the meta-aromatic dicarboxylic acid component constituting the total aromatic polyamide include meta-aromatic dicarboxylic acid halide. Examples of the meta-aromatic dicarboxylic acid halide include isophthalic acid halides such as isophthalic acid chloride and isophthalic acid bromide, and derivatives having substituents such as halogens and alkoxy groups having 1 to 3 carbon atoms in these aromatic rings, for example, 3. − Chloroisophthalic acid chloride and the like can be exemplified. Among them, isophthalic acid chloride itself or a mixed carboxylic acid halide containing isophthalic acid chloride in an amount of 85 mol% or more, preferably 90 mol% or more, particularly preferably 95 mol% or more is preferable.
上記メタアラミドの合成方法としてはメタフェニレンジアミンとイソフタル酸クロライドとを含む生成ポリアミドの良溶媒ではない有機溶媒系（例えばテトラヒドロフラン）と無機の酸受容剤ならびに可溶性中性塩を含む水溶液系とを接触させることによって、ポリメタフェニレンイソフタルアミド重合体の粉末を単離する方法（特公昭４７−１０８６３号公報）、またはアミド系溶媒で上記ジアミンと酸クロライドを溶液重合し次いで水酸化カルシウム、酸化カルシウム等で中和する方法（特開平８−０７４１２１号公報、特開平１０−８８４２１号公報）などに記載の方法が挙げられるが、これに限定されるものではない。なお、本発明にはメタアラミドポリマーとしてメタアラミド繊維から構成される布帛や紡績糸など繊維構造物を使用することもできる。 As a method for synthesizing the metaaramid, an organic solvent system (for example, tetrahydrofuran) containing metaphenylenediamine and isophthalic acid chloride, which is not a good solvent, and an aqueous solution system containing an inorganic acid acceptor and a soluble neutral salt are brought into contact with each other. By doing so, a method for isolating a powder of a polymethaphenylene isophthalamide polymer (Japanese Patent Publication No. 47-10863), or solution polymerization of the above diamine and acid chloride with an amide-based solvent, and then using calcium hydroxide, calcium oxide, etc. Examples thereof include, but are not limited to, the method described in the method for neutralizing (Japanese Patent Laid-Open No. 8-074121, Japanese Patent Application Laid-Open No. 10-88421) and the like. In the present invention, a fiber structure such as a cloth or a spun yarn composed of a meta-aramid fiber can also be used as the meta-aramid polymer.
本発明に用いられる全芳香族ポリアミドの重量平均分子量は、本発明の手法において、使用環境により化学分解が進行してなる分子量が低下した全芳香族ポリアミドを原料とした際に、架橋させて実用に耐え得る破断強度を持つ繊維を形成し得る観点から、本発明で生産する、架橋させる前のポリアミド原料の分子量（重量平均分子量）は、後述する分析方法に従い２０万以上〜４５万未満である。好ましくは２０万〜４０万、より好ましくは３０万〜４０万である。なお、重量平均分子量が２０万に満たない場合、延伸不良により十分な強度が発現しない、或いは紡調が安定せず生産が行えないという問題が発生する。
また、分子量が４５万を超える場合は、通常の湿式紡糸設備にて実用に耐え得る破断強度を持つ繊維を得ることができるため、本発明を適用する意義はない。
The weight average molecular weight of the total aromatic polyamide used in the present invention is practically crosslinked in the method of the present invention when the total aromatic polyamide whose molecular weight is reduced due to the progress of chemical decomposition depending on the usage environment is used as a raw material. From the viewpoint of forming a fiber having a breaking strength that can withstand the above-mentioned, the molecular weight (weight average molecular weight) of the polyamide raw material produced in the present invention before cross-linking is 200,000 or more and less than 450,000 according to the analysis method described later. .. It is preferably 200,000 to 400,000, more preferably 300,000 to 400,000. If the weight average molecular weight is less than 200,000, there arises a problem that sufficient strength is not developed due to poor drawing, or the spinning is not stable and production cannot be performed.
Further, when the molecular weight exceeds 450,000, it is not meaningful to apply the present invention because it is possible to obtain a fiber having a breaking strength that can withstand practical use in a normal wet spinning facility.
カルボジイミド架橋剤は分子間架橋構造を効率的に形成させる必要がある観点から、１分子内にカルボジイミド基を２つ以上有する構造であることが好ましい。また、紡糸ドープの段階では架橋構造は形成せずに、紡糸中に架橋構造を形成させる観点からカルボジイミド基が好ましい。 The carbodiimide cross-linking agent preferably has a structure having two or more carbodiimide groups in one molecule from the viewpoint that it is necessary to efficiently form an intermolecular cross-linking structure. Further, a carbodiimide group is preferable from the viewpoint of forming a crosslinked structure during spinning without forming a crosslinked structure at the stage of spinning dope.
カルボジイミド基はポリマー末端と反応した際、イソシアネート基を遊離し得ることから作業環境保全の観点で、下記式（ｉ）に示すような多環状カルボジイミドを使用することが特に好ましい。なお、下記化学構造は１例であり、本発明の目的を損なわない範囲内であれば特に限定されるものではない。 Since the carbodiimide group can liberate the isocyanate group when it reacts with the polymer terminal, it is particularly preferable to use a polycyclic carbodiimide as shown in the following formula (i) from the viewpoint of protecting the working environment. The following chemical structure is an example, and is not particularly limited as long as it does not impair the object of the present invention.
（式（ｉ）中、ＸおよびＡｒ１〜Ａｒ４は、脂肪族基、脂環族基、芳香族基またはこれらの組み合わせである結合基であり、ヘテロ原子、置換基を含んでいてもよい。） In formula (i), X and Ar 1 to Ar 4 are an aliphatic group, an alicyclic group, an aromatic group or a bonding group which is a combination thereof, and may contain a heteroatom and a substituent. .)
本発明の全芳香族ポリアミド繊維は、上記の製造方法によって得られたメタアラミド重合体を用いて、例えば、以下に説明する紡糸液調製工程、紡糸・凝固工程、洗浄工程、沸水延伸工程、乾熱処理工程、熱延伸工程を経て製造される。 The total aromatic polyamide fiber of the present invention uses the metaaramid polymer obtained by the above production method, for example, a spinning liquid preparation step, a spinning / coagulation step, a washing step, a boiling water drawing step, and a dry heat treatment described below. Manufactured through a process and a heat stretching process.
紡糸液調製工程においては、メタアラミド重合体を溶媒に溶解して、紡糸液（ドープ）を調製する。紡糸液の調製にあたっては、通常アミド系溶媒を用い、該溶媒としては、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡｃ）、ジメチルスルフォキシド（ＤＭＳＯ）等を例示することができる。これらの中では溶解性と取扱い安全性の観点から、ＮＭＰ、またはＤＭＡｃを用いることが好ましい。また、アミド系溶媒は、少なくとも１種、または２種以上の混合溶媒を用いてもよい。 In the spinning solution preparation step, the metaaramid polymer is dissolved in a solvent to prepare a spinning solution (dope). An amide-based solvent is usually used in the preparation of the spinning solution, and the solvent includes N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) and the like. Can be exemplified. Among these, it is preferable to use NMP or DMAc from the viewpoint of solubility and handling safety. Further, as the amide solvent, at least one kind or a mixed solvent of two or more kinds may be used.
本発明において繊維構造物を原料として利用する場合、繊維を溶解するために紡糸液（ドープ）中に無機塩を導入する必要があり、全芳香族ポリアミド繊維に対して１〜５０質量％の無機塩を含有するアミド系溶媒を使用することが肝要である。 When the fiber structure is used as a raw material in the present invention, it is necessary to introduce an inorganic salt into the spinning solution (dope) in order to dissolve the fiber, and 1 to 50% by mass of the inorganic salt with respect to the total aromatic polyamide fiber. It is important to use an amide solvent containing a salt.
５０質量％を超える無機塩を含むと繊維の溶解速度は上がるが、紡糸溶液の濃度調整が難しくなる。なお、無機塩としては塩化カルシウム、塩化マグネシウム、塩化リチウムなどの塩化物塩を使用することが好ましい。 If an inorganic salt exceeding 50% by mass is contained, the dissolution rate of the fiber increases, but it becomes difficult to adjust the concentration of the spinning solution. As the inorganic salt, it is preferable to use chloride salts such as calcium chloride, magnesium chloride and lithium chloride.
溶液濃度としては、次工程である紡糸・凝固工程での凝固速度および重合体の溶解性の観点から、適当な濃度を適宜選択すればよく、通常は１０〜３０質量％の範囲とすることが好ましい。安定な紡糸を達成するためには１５〜２５質量％の範囲とすることがさらに好ましい。 As the solution concentration, an appropriate concentration may be appropriately selected from the viewpoint of the coagulation rate in the spinning / coagulation step, which is the next step, and the solubility of the polymer, and is usually in the range of 10 to 30% by mass. preferable. In order to achieve stable spinning, the range is more preferably in the range of 15 to 25% by mass.
架橋剤はメタアラミド重合体に対して０．１質量％以上２０質量％未満導入することが好ましく、良好な紡糸性を得るためには０．１〜１０質量％がさらに好ましい。より強固な架橋構造を形成し、十分な破断強度を発揮するためには１〜１０質量％導入することがより好ましい。カルボジイミド架橋剤が０．１質量％未満であった場合、十分な破断強度を発揮することができず、２０質量％以上であった場合、含有量が多すぎて紡糸性が著しく低下するため繊維を得ることができない。 The cross-linking agent is preferably introduced in an amount of 0.1% by mass or more and less than 20% by mass with respect to the metaaramid polymer, and more preferably 0.1 to 10% by mass in order to obtain good spinnability. In order to form a stronger crosslinked structure and exhibit sufficient breaking strength, it is more preferable to introduce 1 to 10% by mass. If the carbodiimide cross-linking agent is less than 0.1% by mass, sufficient breaking strength cannot be exhibited, and if it is 20% by mass or more, the content is too large and the spinnability is significantly deteriorated. Cannot be obtained.
本発明ではドープ中に無機塩を導入することもできるが、良好な繊維を得るためにはドープに対して０〜２０質量％の無機塩を含むことが好ましく、安定した紡糸性を得るためには０〜１０質量％の無機塩がさらに好ましい。 In the present invention, an inorganic salt can be introduced into the dope, but in order to obtain good fibers, it is preferable to contain 0 to 20% by mass of the inorganic salt with respect to the dope, and in order to obtain stable spinnability. Is more preferably 0 to 10% by mass of an inorganic salt.
ここで、２０質量％を超えた無機塩を含むと凝固速度が速くなりすぎてしまい、繊維中に多数のボイドを形成することから目的の物性を持った繊維を得ることができない。なお、無機塩としては塩化カルシウム、塩化マグネシウム、塩化リチウムなどの塩化物塩を使用することが好ましい。 Here, if an inorganic salt exceeding 20% by mass is contained, the coagulation rate becomes too high, and a large number of voids are formed in the fiber, so that the fiber having the desired physical characteristics cannot be obtained. As the inorganic salt, it is preferable to use chloride salts such as calcium chloride, magnesium chloride and lithium chloride.
かくして得られた全芳香族ポリアミド紡糸液は、紡糸・凝固工程において凝固液中に紡出して凝固させる。紡糸装置としては特に限定されるものではなく、従来公知の湿式紡糸装置を使用することができる。安定して湿式紡糸できるものであれば、紡糸口金の紡糸孔数、配列状態は特に制限する必要はなく、例えば、孔数が１０〜３００００個、紡糸孔径が０．０３〜０．２ｍｍのステープルファイバー用の多ホール紡糸口金等を用いてもよい。また、紡糸口金から紡出する際のドープの温度は、２０〜９０℃の範囲が適当であるが、特に７０〜９０℃が好ましい。 The total aromatic polyamide spinning liquid thus obtained is spun into the coagulating liquid in the spinning / coagulation step and coagulated. The spinning device is not particularly limited, and a conventionally known wet spinning device can be used. The number of spinning holes and the arrangement state of the spinneret are not particularly limited as long as they can be stably wet-spun. For example, staples having 10 to 30,000 holes and a spinning hole diameter of 0.03 to 0.2 mm. A multi-hole spinneret for fibers or the like may be used. The temperature of the dope when spinning from the spinneret is preferably in the range of 20 to 90 ° C, but is particularly preferably 70 to 90 ° C.
本発明の全芳香族ポリアミド繊維を得るために用いる凝固浴としては、塩化カルシウム、塩化リチウム、塩化マグネシウム等の無機塩を３０質量％以上、好ましくは３５〜４５質量％含み、アミド系溶剤を１〜２０質量％、好ましくは３〜１５質量％含む水溶液を５０〜９５℃の範囲で用いる。また、実質的に無機塩を含まないアミド系溶媒の水溶液を用いる方法も知られており、このような凝固液を使用することもできる。 The coagulation bath used to obtain the total aromatic polyamide fiber of the present invention contains 30% by mass or more, preferably 35 to 45% by mass of inorganic salts such as calcium chloride, lithium chloride and magnesium chloride, and contains 1 amide solvent. An aqueous solution containing ~ 20% by mass, preferably 3 to 15% by mass is used in the range of 50 to 95 ° C. Further, a method using an aqueous solution of an amide-based solvent that does not substantially contain an inorganic salt is also known, and such a coagulating liquid can also be used.
かくして得られた凝固糸は水性洗浄浴にて十分水洗され、湿式延伸工程に送られる。通常、湿式延伸は沸水延伸浴中で行われ、その際の延伸倍率は１．５〜５．０倍が適当であり、さらに好ましくは２．０〜３．５倍の範囲である。本発明においては、湿式延伸を当該倍率の範囲で行い、分子鎖配向を上げることにより、最終的に得られる繊維の破断強度を確保することができる。 The coagulated yarn thus obtained is sufficiently washed with water in an aqueous washing bath and sent to a wet drawing step. Usually, wet stretching is performed in a boiling water stretching bath, and the stretching ratio at that time is preferably 1.5 to 5.0 times, more preferably 2.0 to 3.5 times. In the present invention, the breaking strength of the finally obtained fiber can be ensured by performing wet stretching within the range of the magnification and increasing the molecular chain orientation.
上記洗浄・湿式延伸工程を経た繊維に対して、好ましくは、乾熱処理工程を実施する。乾熱処理工程においては、上記洗浄・湿式延伸工程により洗浄と延伸が実施された繊維を、好ましくは１００〜２５０℃、さらに好ましくは１００〜２００℃の範囲で、乾熱処理をする。ここで、乾熱処理は、特に限定されないが、定長下で行うのが好ましい。前記の温度範囲をはずれると、乾燥が不十分となるか、結晶化の進行により、後述する延伸工程に影響をあたえるため好ましくない。
なお、上記の乾熱処理の温度は、熱板、加熱ローラーなどの繊維加熱手段の設定温度をいう。
A dry heat treatment step is preferably performed on the fibers that have undergone the washing / wet stretching step. In the dry heat treatment step, the fibers washed and stretched by the above washing / wet stretching step are subjected to dry heat treatment in a range of preferably 100 to 250 ° C, more preferably 100 to 200 ° C. Here, the dry heat treatment is not particularly limited, but is preferably performed under a fixed length. If it deviates from the above temperature range, drying becomes insufficient or crystallization progresses, which affects the stretching step described later, which is not preferable.
The temperature of the above-mentioned dry heat treatment refers to the set temperature of the fiber heating means such as a hot plate and a heating roller.
本発明においては、上記乾熱処理工程を経た繊維に対して、熱延伸工程を施す。熱延伸工程においては、２９０〜３７０℃で熱処理を加えながら、延伸を実施する。好ましくは３１０〜３４０℃である。延伸倍率は１．２〜５．０倍が適当であり、さらに好ましくは１．５〜３．５倍の範囲である。前記の温度、延伸倍率の範囲をはずれると、目的とする強度を得ることができなくなるか、著しく繊維の破断が増加し、工程性に影響を与えるた
め好ましくない。
In the present invention, the fiber that has undergone the dry heat treatment step is subjected to a heat drawing step. In the heat stretching step, stretching is carried out while applying heat treatment at 290 to 370 ° C. It is preferably 310 to 340 ° C. The draw ratio is preferably 1.2 to 5.0 times, more preferably 1.5 to 3.5 times. If the temperature and the draw ratio are out of the range, the desired strength cannot be obtained, or the fiber breakage increases remarkably, which is not preferable because it affects the processability.
以上の方法により得られる本発明の架橋を有する全芳香族ポリアミド繊維の破断強度は３．０〜６．０ｃＮ／ｄｔｅｘである。破断強度が３．０ｃＮ／ｄｔｅｘ未満である場合、繊維の機械物性が劣ることから工程通過性に支障が出るだけでなく、製品の耐久性が低下するため実用に適さない繊維となる。本発明の架橋を有する全芳香族ポリアミドからなる繊維の破断強度は、６．０ｃＮ／ｄｔｅｘ以上の繊維を得る場合、本発明の低分子量ポリマーの架橋を有するポリマーでは、延伸倍率をさらに高める必要があり、著しく毛羽が多いまたは繊維の破断が生じるため、安定的に繊維を得ることができない。 The breaking strength of the total aromatic polyamide fiber having the crosslink of the present invention obtained by the above method is 3.0 to 6.0 cN / dtex. When the breaking strength is less than 3.0 cN / dtex, the mechanical properties of the fiber are inferior, which not only hinders the process passability but also reduces the durability of the product, which makes the fiber unsuitable for practical use. When a fiber made of a totally aromatic polyamide having a crosslink of the present invention has a breaking strength of 6.0 cN / dtex or more, it is necessary to further increase the draw ratio in the polymer having a crosslink of the low molecular weight polymer of the present invention. There is a lot of fluff or the fiber is broken, so that the fiber cannot be obtained stably.
さらに、単繊維繊度は０．５〜１５．０ｄｔｅｘである。該単繊維繊度が０．５ｄｔｅｘ未満、または１５ｄｔｅｘを超えると、工程通過性が劣り、安定な紡糸を達成することが出来ない。 Further, the single fiber fineness is 0.5 to 15.0 dtex. If the single fiber fineness is less than 0.5 dtex or more than 15 dtex, the process passability is poor and stable spinning cannot be achieved.
以下、実施例および比較例により、本発明を詳細に説明するが、本発明の範囲は、以下の実施例及び比較例に制限されるものではない。尚、実施例および比較例における各物性値は、下記の方法で測定した。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to the following Examples and Comparative Examples. The physical property values in Examples and Comparative Examples were measured by the following methods.
［重量平均分子量Ｍｗ］
ＪＩＳ−Ｋ−７２５２に準じ、サイズ排除クロマトグラフィー用カラムを装着した高速液体クロマトグラフィー装置にて分析をおこない、展開溶媒にはジメチルホルムアミド（塩化リチウムを０．０１モル％含有）を用いて測定した。なお、標準分子量サンプルとしてはシグマアルドリッチ製ポリスチレンセット（ピークトップ分子量Ｍｐ＝４００〜２００００００）を用いた。
[Weight average molecular weight Mw]
Analysis was performed by a high performance liquid chromatography device equipped with a size exclusion chromatography column according to JIS-K-7252, and measurement was performed using dimethylformamide (containing 0.01 mol% lithium chloride) as the developing solvent. .. As the standard molecular weight sample, a polystyrene set manufactured by Sigma-Aldrich (peak top molecular weight Mp = 400 to 2000000) was used.
［単糸繊度］
ＪＩＳ Ｌ １０１５に準じ、正量繊度のＡ法に準拠した測定を実施し、見掛け繊度にて表記した。
[Single thread fineness]
Measurements were carried out in accordance with JIS L 1015 and in accordance with the method A of positive fineness, and are expressed in terms of apparent fineness.
［破断強度］
引張試験機（インストロン社製、型式：５５６５）を用いて、ＪＩＳ Ｌ １０１５に基づき、以下の条件で測定した。
（測定条件）
つかみ間隔 ：２０ｍｍ
初荷重 ：０．０４４ｃＮ（１／２０ｇ／ｄｔｅｘ）
引張速度 ：２０ｍｍ／分
[Breaking strength]
Measurement was performed under the following conditions based on JIS L 1015 using a tensile tester (manufactured by Instron, model: 5565).
(Measurement condition)
Grab interval: 20 mm
Initial load: 0.044cN (1 / 20g / dtex)
Tensile speed: 20 mm / min
［カルボジイミド架橋剤］
カルボジイミド架橋剤は下記式（ｉｉ）に示すものを使用した。
[Carbodiimide cross-linking agent]
As the carbodiimide cross-linking agent, the one represented by the following formula (ii) was used.
［実施例１］
メタ型全芳香族ポリアミド（重量平均分子量３５万）および該重合物に対して質量比で１０％のカルボジイミド架橋剤粉末を溶解させ、Ｎ−メチル−２−ピロリドン（ＮＭＰ）に溶解させた後、透明なポリマー溶液を得た。この際、ポリマー溶液に対してメタ型全芳香族ポリアミドの質量濃度が２０％になるよう調整した。
[Example 1]
A meta-type total aromatic polyamide (weight average molecular weight 350,000) and a carbodiimide cross-linking agent powder having a mass ratio of 10% with respect to the polymer were dissolved, dissolved in N-methyl-2-pyrrolidone (NMP), and then dissolved. A clear polymer solution was obtained. At this time, the mass concentration of the meta-type total aromatic polyamide was adjusted to 20% with respect to the polymer solution.
このポリマー溶液を８９℃に加温し紡糸原液として、孔径０．１２ｍｍ、孔数１００の吐出孔が円形の紡糸口金から７０℃の凝固浴中に吐出して紡糸した。この凝固浴の組成は、塩化カルシウムが４３質量％、ＮＭＰが３質量％、残りの水が５４質量％であり、浸漬長（有効凝固浴長）１２０ｃｍにて糸速５．０ｍ／分で通過させた後、いったん空気中に引き出した。 This polymer solution was heated to 89 ° C. and used as a spinnery stock solution, which was spun by discharging it into a coagulation bath at 70 ° C. from a spinning spout having a hole diameter of 0.12 mm and a hole number of 100 and a circular discharge hole. The composition of this coagulation bath is 43% by mass of calcium chloride, 3% by mass of NMP, 54% by mass of the remaining water, and passes through at a thread speed of 5.0 m / min at an immersion length (effective coagulation bath length) of 120 cm. After letting it, it was once pulled out into the air.
この凝固糸条を第１〜第２水洗浄浴にて水洗し、この際の総浸漬時間は２３０秒とした。なお、第１〜第２水性洗浄浴温度はそれぞれ２０、３０℃の水を用いた。次に、この洗浄糸条を９０℃の沸水中にて２．５倍に延伸し、引続き９５℃の温水中に５０秒浸漬し、洗浄した。 The coagulated yarn was washed with water in the first and second water washing baths, and the total immersion time at this time was set to 230 seconds. Water at 20 and 30 ° C. was used as the first and second aqueous washing bath temperatures, respectively. Next, the washing yarn was stretched 2.5 times in boiling water at 90 ° C., and subsequently immersed in warm water at 95 ° C. for 50 seconds for washing.
次に表面温度１７０℃のローラーに巻回して乾熱処理した後、表面温度３２０℃の熱板にて１．７５倍に延伸し、メタ型全芳香族ポリアミド繊維を得た。得られた繊維は単繊維繊度２．０ｄｔｅｘ、破断強度３．３ｃＮ／ｄｔｅｘであった。 Next, it was wound around a roller having a surface temperature of 170 ° C. and subjected to a dry heat treatment, and then stretched 1.75 times on a hot plate having a surface temperature of 320 ° C. to obtain a meta-type total aromatic polyamide fiber. The obtained fibers had a single fiber fineness of 2.0 dtex and a breaking strength of 3.3 cN / dtex.
［実施例２］
メタ型全芳香族ポリアミド重合物（重量平均分子量３５万）および該重合物に対して質量比で５％のカルボジイミド架橋剤を溶解させ、Ｎ−メチル−２−ピロリドン（ＮＭＰ）に溶解させた後、透明なポリマー溶液を得た。この際、ポリマー溶液に対してメタ型全芳香族ポリアミド重合物の質量濃度が２０％になるよう調整した。
[Example 2]
After dissolving a meta-type total aromatic polyamide polymer (weight average molecular weight 350,000) and a carbodiimide cross-linking agent having a mass ratio of 5% to the polymer, and dissolving it in N-methyl-2-pyrrolidone (NMP). , A clear polymer solution was obtained. At this time, the mass concentration of the meta-type total aromatic polyamide polymer was adjusted to 20% with respect to the polymer solution.
このポリマー溶液を実施例１に記載の方法と同様の方法により架橋メタ型全芳香族ポリアミド繊維を得た。得られた繊維は単繊維繊度２．１ｄｔｅｘ、破断強度３．１ｃＮ／ｄｔｅｘであった。 A crosslinked meta-type total aromatic polyamide fiber was obtained from this polymer solution by the same method as that described in Example 1. The obtained fibers had a single fiber fineness of 2.1 dtex and a breaking strength of 3.1 cN / dtex.
［実施例３］
メタ型全芳香族ポリアミド重合物（重量平均分子量４０万）および該重合物に対して質量比で１％のカルボジイミド架橋剤を溶解させ、Ｎ−メチル−２−ピロリドン（ＮＭＰ）に溶解させた後、透明なポリマー溶液を得た。この際、ポリマー溶液に対してメタ型全芳香族ポリアミド重合物の質量濃度が２０％になるよう調整した。
[Example 3]
After dissolving a meta-type total aromatic polyamide polymer (weight average molecular weight 400,000) and a carbodiimide cross-linking agent having a mass ratio of 1% to the polymer, and dissolving it in N-methyl-2-pyrrolidone (NMP). , A clear polymer solution was obtained. At this time, the mass concentration of the meta-type total aromatic polyamide polymer was adjusted to 20% with respect to the polymer solution.
このポリマー溶液を実施例１に記載の方法と同様の方法により架橋メタ型全芳香族ポリアミド繊維を得た。得られた繊維は単繊維繊度２．６ｄｔｅｘ、破断強度４．３ｃＮ／ｄｔｅｘであった。 A crosslinked meta-type total aromatic polyamide fiber was obtained from this polymer solution by the same method as that described in Example 1. The obtained fibers had a single fiber fineness of 2.6 dtex and a breaking strength of 4.3 cN / dtex.
［比較例１］
メタ型全芳香族ポリアミド（重量平均分子量３５万）を、Ｎ−メチル−２−ピロリドン（ＮＭＰ）に溶解させ、透明なポリマー溶液を得た。この際、ポリマー溶液に対してメタ型全芳香族ポリアミドの質量濃度が２０％になるよう調整した。
[Comparative Example 1]
Meta-type total aromatic polyamide (weight average molecular weight 350,000) was dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a transparent polymer solution. At this time, the mass concentration of the meta-type total aromatic polyamide was adjusted to 20% with respect to the polymer solution.
このポリマー溶液を実施例１に記載の方法と同様の方法により紡糸、水洗、延伸、乾熱処理しようとしたが、延伸工程において多量の断糸が発生し、安定してメタ型全芳香族ポリアミド繊維を得ることはできなかった。得られた繊維は単繊維繊度２．４ｄｔｅｘ、破
断強度０．６ｃＮ／ｄｔｅｘであった。
An attempt was made to spin, wash, draw, and dry heat treat this polymer solution by the same method as that described in Example 1, but a large amount of yarn breakage occurred in the drawing step, and the meta-type total aromatic polyamide fiber was stably generated. Could not get. The obtained fibers had a single fiber fineness of 2.4 dtex and a breaking strength of 0.6 cN / dtex.
［比較例２］
メタ型全芳香族ポリアミド（重量平均分子量４０万）を、Ｎ−メチル−２−ピロリドン（ＮＭＰ）に溶解させ、透明なポリマー溶液を得た。この際、ポリマー溶液に対してメタ型全芳香族ポリアミドの質量濃度が２０％になるよう調整した。
[Comparative Example 2]
Meta-type total aromatic polyamide (weight average molecular weight 400,000) was dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a transparent polymer solution. At this time, the mass concentration of the meta-type total aromatic polyamide was adjusted to 20% with respect to the polymer solution.
このポリマー溶液を実施例１に記載の方法と同様の方法により紡糸、水洗、延伸、乾熱処理しようとしたが、延伸工程において断糸が発生し、安定してメタ型全芳香族ポリアミド繊維を得ることはできなかった。得られた繊維は単繊維繊度２．９ｄｔｅｘ、破断強度２．３ｃＮ／ｄｔｅｘであった。 An attempt was made to spin, wash, draw, and dry heat treat this polymer solution by the same method as that described in Example 1, but yarn breakage occurred in the drawing step, and a meta-type total aromatic polyamide fiber was stably obtained. I couldn't. The obtained fibers had a single fiber fineness of 2.9 dtex and a breaking strength of 2.3 cN / dtex.
本発明によれば、通常の湿式紡糸では不可能である重量平均分子量が２０万以上〜４５万未満の全芳香族ポリアミドを原料ポリマーとして用いて、架橋剤を適用することにより、繊維の破断強度が３．０〜６．０ｃＮ／ｄｔｅｘと良好な全芳香族ポリアミド繊維が提供される。また、本発明で使用する全芳香族ポリアミドは使用環境により化学分解が進んでいる状態であってもリサイクル原料として紡糸できる点で環境負荷低減へ大きく貢献でき、本発明の工業的価値は極めて大きい。 According to the present invention, by applying a cross-linking agent using a total aromatic polyamide having a weight average molecular weight of 200,000 or more and less than 450,000 as a raw material polymer, which is impossible by ordinary wet spinning, the breaking strength of the fiber A good total aromatic polyamide fiber with a value of 3.0 to 6.0 cN / dtex is provided. Further, the all-aromatic polyamide used in the present invention can greatly contribute to the reduction of the environmental load in that it can be spun as a recycled raw material even in a state where chemical decomposition is progressing depending on the usage environment, and the industrial value of the present invention is extremely large. ..
さらに本発明の製造方法は、架橋剤を導入した紡糸ドープ作成時には架橋反応が起こらず、紡糸の過程で架橋反応が進行するため、紡糸性に影響がなく該繊維を得ることができ、架橋反応を起こすための追加の処理工程が必要ないことから、効率的な製造を行うことができる。 Further, in the production method of the present invention, the cross-linking reaction does not occur at the time of producing the spinning dope into which the cross-linking agent is introduced, and the cross-linking reaction proceeds in the process of spinning. Since no additional processing step is required to cause the above, efficient manufacturing can be performed.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020083712A JP7465716B2 (en) | 2020-05-12 | 2020-05-12 | Wholly aromatic polyamide fiber and method for producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020083712A JP7465716B2 (en) | 2020-05-12 | 2020-05-12 | Wholly aromatic polyamide fiber and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021179029A true JP2021179029A (en) | 2021-11-18 |
| JP7465716B2 JP7465716B2 (en) | 2024-04-11 |
Family
ID=78511036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020083712A Active JP7465716B2 (en) | 2020-05-12 | 2020-05-12 | Wholly aromatic polyamide fiber and method for producing same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7465716B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117363007A (en) * | 2023-12-08 | 2024-01-09 | 烟台泰和新材高分子新材料研究院有限公司 | Modified aramid stock solution and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008156800A (en) | 2006-12-26 | 2008-07-10 | Teijin Techno Products Ltd | Flame-resistant meta-type wholly aromatic polyamide fibers |
| JP5778378B2 (en) | 2008-02-28 | 2015-09-16 | 帝人株式会社 | Nonaqueous electrolyte battery separator and nonaqueous electrolyte secondary battery |
| JP2012119225A (en) | 2010-12-02 | 2012-06-21 | Teijin Ltd | Separator for nonaqueous electrolyte battery, and nonaqueous electrolyte battery |
| JP2013177716A (en) | 2012-01-30 | 2013-09-09 | Teijin Ltd | Wholly aromatic polyamide regenerated fiber and method for producing the same |
| JP2014025183A (en) | 2012-07-30 | 2014-02-06 | Teijin Ltd | Process for producing recycled wholly aromatic polyamide fiber |
-
2020
- 2020-05-12 JP JP2020083712A patent/JP7465716B2/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117363007A (en) * | 2023-12-08 | 2024-01-09 | 烟台泰和新材高分子新材料研究院有限公司 | Modified aramid stock solution and preparation method and application thereof |
| CN117363007B (en) * | 2023-12-08 | 2024-02-23 | 烟台泰和新材高分子新材料研究院有限公司 | Modified aramid stock solution and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7465716B2 (en) | 2024-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2010229582A (en) | Method for producing para-type wholly aromatic copolyamide fiber | |
| WO2010035834A1 (en) | Easily dyeable meta-form wholly aromatic polyamide fiber | |
| JP5265868B2 (en) | Ultrafine meta-type wholly aromatic polyamide fiber and its manufacturing method | |
| JP2010163506A (en) | Process for producing aromatic copolyamide | |
| JP7465716B2 (en) | Wholly aromatic polyamide fiber and method for producing same | |
| JP2010180493A (en) | Method for producing aromatic copolyamide fiber | |
| JP3937050B2 (en) | Method for producing meta-type wholly aromatic polyamide fiber and fiber obtained thereby | |
| JP3995532B2 (en) | Method for producing dense meta-type wholly aromatic polyamide fiber | |
| JP7267821B2 (en) | Method for producing recycled meta-type wholly aromatic polyamide fiber | |
| JP6873768B2 (en) | I Ching meta-type total aromatic polyamide fiber with excellent flame retardancy and its manufacturing method | |
| JP2018154954A (en) | Spun-dyed meta-type wholly aromatic polyamide fiber and method for producing the same, and flame-retardant spun yarn and flame-retardant stretch-broken spun yarn comprising the fiber | |
| JP2011047088A (en) | Para-oriented wholly aromatic copolyamide fiber and method for producing the same | |
| JP2018154943A (en) | Meta-type wholly aromatic polyamide fiber having excellent flame retardancy and method for producing the same | |
| JP2011213815A (en) | Method for producing aromatic copolyamide and fiber comprising aromatic copolyamide obtained by the method | |
| JP2021179028A (en) | Chemical-resistant meta-type wholly aromatic polyamide fiber and method for producing the same | |
| JP7315378B2 (en) | Meta-type wholly aromatic polyamide fiber and method for producing the same | |
| JP2001172819A (en) | Method for producing meta-form aromatic polyamide fiber | |
| JP4664794B2 (en) | Method for producing meta-type aromatic polyamide fiber | |
| JP2019157290A (en) | Fire retardant stretch-broken yarn | |
| JP3929342B2 (en) | Method for producing dense meta-type wholly aromatic polyamide fiber | |
| JP7372118B2 (en) | Easily dyeable meta-type wholly aromatic polyamide fiber and method for producing the same | |
| JP2003342832A (en) | Method for producing meta-type wholly aromatic polyamide fiber having excellent shrinkage stability | |
| JP2007154355A (en) | Meta-aromatic polyamide fiber and method for producing the same | |
| JP2005054315A (en) | Method for producing dense meta-type wholly aromatic polyamide fiber | |
| JP2024027796A (en) | Highly heat resistant/highly tough fiber and method of producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230207 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20231025 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20231031 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20231225 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20240312 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240401 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7465716 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |