JP2023110161A - Meta-type whole aromatic polyamide fiber and production method of the same - Google Patents
Meta-type whole aromatic polyamide fiber and production method of the same Download PDFInfo
- Publication number
- JP2023110161A JP2023110161A JP2022011417A JP2022011417A JP2023110161A JP 2023110161 A JP2023110161 A JP 2023110161A JP 2022011417 A JP2022011417 A JP 2022011417A JP 2022011417 A JP2022011417 A JP 2022011417A JP 2023110161 A JP2023110161 A JP 2023110161A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- tensile strength
- meta
- alkali resistance
- aromatic polyamide
- 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.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 107
- 239000004760 aramid Substances 0.000 title claims abstract description 42
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000003513 alkali Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000007654 immersion Methods 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000691 measurement method Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 12
- 238000009987 spinning Methods 0.000 description 23
- 238000005406 washing Methods 0.000 description 23
- 229920000742 Cotton Polymers 0.000 description 22
- 239000002904 solvent Substances 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 20
- 230000001681 protective effect Effects 0.000 description 18
- 239000000126 substance Substances 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 238000002845 discoloration Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 230000015271 coagulation Effects 0.000 description 11
- 238000005345 coagulation Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- -1 polymetaphenylene isophthalamide Polymers 0.000 description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 10
- 150000001408 amides Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 230000001678 irradiating effect Effects 0.000 description 8
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000005259 measurement 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
- 239000002253 acid Substances 0.000 description 4
- 150000004984 aromatic diamines Chemical class 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
- 238000004132 cross linking Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- IRBICNVNOXDYKS-UHFFFAOYSA-N 1-chlorocyclohexa-3,5-diene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(Cl)(C(Cl)=O)C1 IRBICNVNOXDYKS-UHFFFAOYSA-N 0.000 description 1
- OCZKRTWSBSEECY-UHFFFAOYSA-N 1-methoxycyclohexa-3,5-diene-1,3-dicarbonyl chloride Chemical compound COC1(C(Cl)=O)CC(C(Cl)=O)=CC=C1 OCZKRTWSBSEECY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- NGULVTOQNLILMZ-UHFFFAOYSA-N 2-bromobenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(Br)=C1 NGULVTOQNLILMZ-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
- LKGQTURGJNTDLR-UHFFFAOYSA-N 2-chlorobenzene-1,3-diamine Chemical compound NC1=CC=CC(N)=C1Cl LKGQTURGJNTDLR-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- QDBOAKPEXMMQFO-UHFFFAOYSA-N 4-(4-carbonochloridoylphenyl)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=C(C(Cl)=O)C=C1 QDBOAKPEXMMQFO-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- LHSXSRQUGCHBPG-UHFFFAOYSA-N 4-(aminomethoxy)aniline Chemical compound NCOC1=CC=C(N)C=C1 LHSXSRQUGCHBPG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-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
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 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
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical group NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VIUHYPPHBQZSPF-UHFFFAOYSA-N naphthalene-1,4-dicarbonyl chloride Chemical compound C1=CC=C2C(C(=O)Cl)=CC=C(C(Cl)=O)C2=C1 VIUHYPPHBQZSPF-UHFFFAOYSA-N 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
- NZZGQZMNFCTNAM-UHFFFAOYSA-N naphthalene-2,6-dicarbonyl chloride Chemical compound C1=C(C(Cl)=O)C=CC2=CC(C(=O)Cl)=CC=C21 NZZGQZMNFCTNAM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 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
- 239000012466 permeate Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
Abstract
Description
本発明は、優れた引張強度を有しつつ、耐光性と、耐アルカリ性が可及的に改善されたメタ型全芳香族ポリアミド繊維に関する。 The present invention relates to a meta-type wholly aromatic polyamide fiber having excellent tensile strength and improved light resistance and alkali resistance as much as possible.
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及び難燃性に優れていることは周知であり、また、これらの全芳香族ポリアミドはアミド系極性溶媒に可溶であり、全芳香族ポリアミドを該溶媒に溶解した重合体溶液から乾式紡糸、湿式紡糸、半乾半湿式紡糸等の方法により繊維となし得ることもよく知られている。 Conventionally, it is well known that wholly aromatic polyamides produced from aromatic diamines and aromatic dicarboxylic acid dihalides are excellent in heat resistance and flame retardancy. It is also well known that a polymer solution in which a wholly aromatic polyamide is dissolved in the solvent can be made into fibers by methods such as dry spinning, wet spinning, and semi-dry and semi-wet spinning.
これら全芳香族ポリアミドのうち、ポリメタフェニレンイソフタルアミドで代表されるメタ型全芳香族ポリアミド（「メタアラミド」と称されることもある）の繊維は、耐熱・難燃性繊維として特に有用なものであり、これらの特性を発揮する分野、例えば、フィルター、電子部品等の産業用途や、耐熱性、防炎性、耐炎性が重視される防護衣等の防災安全衣料用途等に用いられている。 Among these wholly aromatic polyamides, fibers of meta-type wholly aromatic polyamide (sometimes referred to as "meta-aramid") represented by polymetaphenylene isophthalamide are particularly useful as heat-resistant and flame-retardant fibers. It is used in fields where these characteristics are exhibited, for example, industrial applications such as filters and electronic parts, and disaster prevention safety clothing applications such as protective clothing where heat resistance, flame resistance, and flame resistance are emphasized. .
そして、特に消火活動時に着用する消防服などの防護衣料においては耐薬品性の向上が求められている。つまり、酸アルカリ消火器や強化液消火器は、強アルカリ性の薬剤が用いられており、使用時に直接接触することは少ないが、消火作業時に飛沫などに暴露され防護服の劣化が進行することが考えられることから、防護衣料において難燃性・耐熱性だけでなく耐薬品性として耐アルカリ性も重要な物性となる。 In particular, protective clothing such as firefighting clothing worn during firefighting activities is required to have improved chemical resistance. In other words, acid-alkaline fire extinguishers and reinforced liquid fire extinguishers use strong alkaline agents, and direct contact is rare during use. Therefore, not only flame retardancy and heat resistance but also alkali resistance as chemical resistance are important physical properties in protective clothing.
しかし、従来メタ型全芳香族ポリアミドにおける耐薬品性の改善としては、耐酸性に着目した検討がなされており、その手段としては、酸化性雰囲気下で高温、長時間処理による架橋（特許文献１参照）、ハロゲン化物、イオウ等による高温気相処理による架橋（特許文献２、３、４参照）、リン酸等の鉱酸の水溶液に浸漬した後、熱処理して架橋する方法（特許文献５参照）などがある。 However, in order to improve the chemical resistance of conventional meta-type wholly aromatic polyamides, studies have been made focusing on acid resistance. ), cross-linking by high-temperature vapor phase treatment with halides, sulfur, etc. (see Patent Documents 2, 3, and 4), and a method of cross-linking by immersing in an aqueous solution of mineral acid such as phosphoric acid and then heat-treating (see Patent Document 5). )and so on.
これらの手段は、主に分子鎖を架橋することで耐薬品性を改善しており、耐酸性以外に耐アルカリ性も改善されているものと考えられるが、これらの方法では耐薬品性は向上するものの、繊維の初期強度が低下するため実用に耐えないという問題があった。そこで、特定のフェノール樹脂を混合する方法が提案されている（特許文献６参照）。この方法は、芳香族ポリアミドと混合されたフェノール樹脂との間で一部架橋反応が進行するために耐薬品性が向上していると推定されているが、他に難燃剤を固定化するなどの目的で反応性の高いものが用いられることが多く、安定した性能を得ることが困難であった。 These means improve chemical resistance mainly by cross-linking the molecular chains, and are thought to improve not only acid resistance but also alkali resistance, but these methods improve chemical resistance. However, there is a problem that the initial strength of the fiber is lowered, so that it cannot be put to practical use. Therefore, a method of mixing a specific phenol resin has been proposed (see Patent Document 6). This method is presumed to have improved chemical resistance due to the partial cross-linking reaction between the aromatic polyamide and the mixed phenolic resin. For this purpose, highly reactive materials are often used, and it has been difficult to obtain stable performance.
一方、耐アルカリ性については、高温の亜硫酸ガス等の硫黄化合物蒸気下で繊維を処理し、芳香族ポリアミド中に硫黄を導入させることで耐アルカリ性を向上させる方法（特許文献７参照）が提案されている。しかしながら、この方法であっても依然として耐アルカリ性が不十分であり、さらなる改善が所望されていた。 On the other hand, with regard to alkali resistance, a method of improving alkali resistance by treating fibers under sulfur compound vapor such as high-temperature sulfurous acid gas and introducing sulfur into aromatic polyamide has been proposed (see Patent Document 7). there is However, even with this method, the alkali resistance is still insufficient, and further improvement has been desired.
本発明は上記の背景に鑑みなされたものであり、その目的は、優れた引張強度を有し、かつ、耐光性と、耐アルカリ性に優れたメタ型全芳香族ポリアミド繊維を提供することにある。 The present invention has been made in view of the above background, and its object is to provide a meta-type wholly aromatic polyamide fiber that has excellent tensile strength, light resistance, and alkali resistance. .
発明者は、上記の課題を解決するため鋭意検討を重ねた結果、メタ型全芳香族ポリアミド繊維を製造するに際し、特定の条件下で繊維に紫外線を含む光を照射することにより、従来のメタ型全芳香族ポリアミド繊維対比引張強度を低下させることなく、耐光性と、耐アルカリ性に優れた繊維を提供できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the inventors have found that when producing meta-type wholly aromatic polyamide fibers, by irradiating the fibers with light containing ultraviolet rays under specific conditions, the conventional meta The inventors have found that it is possible to provide a fiber excellent in light resistance and alkali resistance without lowering the tensile strength relative to the type of wholly aromatic polyamide fiber, and have completed the present invention.
即ち、本発明によれば、
１．引張強度が３．５～７．０ｃＮ／ｄｔｅｘであり、以下に示す測定方法で示される耐アルカリ性が９５％以上であり、且つ、ＪＩＳ Ｌ ０８４３（光源：キセノン）における耐光性が４級以上であることを特徴とするメタ型全芳香族ポリアミド繊維、
（耐アルカリ性の測定方法）
繊維を７５℃の水酸化ナトリウム１０質量％水溶液中に浸漬、６時間静置したのち、流水で十分に水洗、乾燥する。浸漬処理前の引張強度（Ｆ０とする）と、浸漬処理後の引張強度（Ｆ１とする）を測定し、以下の式により耐アルカリ性を求める。
耐アルカリ性＝（Ｆ１／Ｆ０）×１００（％）、
及び、
２．メタ型全芳香族ポリアミド繊維を製造するに際し、繊維の残存水分量が繊維質量全体に対して０．１質量％以下となるように乾燥したのち、繊維表面温度が、１００～３５０℃に加熱された状態で、不活性ガス雰囲気で波長２５０～４００ｎｍの紫外線を含む光を紫外線の照射強度が１００～１５０ｍＷ／ｃｍ２で、２０秒以上照射する工程を含むことを特徴とするメタ型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. It has a tensile strength of 3.5 to 7.0 cN/dtex, an alkali resistance of 95% or more as measured by the following measurement method, and a light resistance of grade 4 or higher according to JIS L 0843 (light source: xenon). A meta-type wholly aromatic polyamide fiber characterized by
(Method for measuring alkali resistance)
The fiber is immersed in a 10% by mass aqueous solution of sodium hydroxide at 75° C., allowed to stand for 6 hours, washed thoroughly with running water, and dried. The tensile strength before immersion treatment (referred to as F0 ) and the tensile strength after immersion treatment (referred to as F1 ) are measured, and the alkali resistance is determined by the following formula.
Alkali resistance = (F 1 /F 0 ) x 100 (%),
as well as,
2. When producing the meta-type wholly aromatic polyamide fiber, after drying so that the residual moisture content of the fiber is 0.1% by mass or less with respect to the total fiber mass, the fiber surface temperature is heated to 100 to 350 ° C. 250 to 400 nm wavelength light containing ultraviolet rays in an inert gas atmosphere with an ultraviolet irradiation intensity of 100 to 150 mW/cm 2 for 20 seconds or more. a method for producing a polyamide fiber,
is provided.
本発明によれば、優れた引張強度を有し、かつ、耐光性と、耐アルカリ性に優れたメタ型全芳香族ポリアミド繊維を得ることができる。 According to the present invention, a meta-type wholly aromatic polyamide fiber having excellent tensile strength, light resistance and alkali resistance can be obtained.
以下、本発明について詳細を説明する。
本発明におけるメタ型全芳香族ポリアミドは、メタ型芳香族ジアミンとメタ型芳香族ジカルボン酸ハライドとを原料として、例えば溶液重合や界面重合させることにより製造されるポリアミドであるが、本発明の目的を阻害しない範囲内で、例えばパラ型等の他の共重合成分を共重合したものであってもよい。
The present invention will be described in detail below.
The meta-type wholly aromatic polyamide in the present invention is a polyamide produced by, for example, solution polymerization or interfacial polymerization using a meta-type aromatic diamine and a meta-type aromatic dicarboxylic acid halide as raw materials. may be obtained by copolymerizing other copolymerization components, such as para-type, within a range that does not impede.
上記メタ型芳香族ジアミンとしては、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及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－ジアミノクロルベンゼン、２，６－ジアミノクロルベンゼン等を使用することができる。なかでも、メタフェニレンジアミン又はメタフェニレンジアミンを７０モル％以上含有する上記の混合ジアミンが好ましい。 Examples of the meta-type aromatic diamines include metaphenylenediamine, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, etc., and substituents such as halogens and alkyl groups having 1 to 3 carbon atoms on the aromatic rings thereof. such as 2,4-toluylenediamine, 2,6-toluylenediamine, 2,4-diaminochlorobenzene, 2,6-diaminochlorobenzene and the like. Among them, meta-phenylenediamine or the mixed diamine containing 70 mol % or more of meta-phenylenediamine is preferable.
また、上記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、及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－クロルイソフタル酸クロライド、３－メトキシイソフタル酸クロライドを使用することができる。なかでも、イソフタル酸クロライド又はイソフタル酸クロライドを７０モル％以上含有する上記の混合カルボン酸ハライドが好ましい。 In addition, the above meta-type aromatic dicarboxylic acid halides 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 on the aromatic rings thereof, For example, 3-chloroisophthalic acid chloride and 3-methoxyisophthalic acid chloride can be used. Among them, isophthalic acid chloride or the mixed carboxylic acid halide containing 70 mol % or more of isophthalic acid chloride is preferable.
上記のジアミンとジカルボン酸ハライド以外で使用し得る共重合成分としては、芳香族ジアミンとして、パラフェニレンジアミン、２，５－ジアミノクロルベンゼン、２，５－ジアミノブロムベンゼン、アミノアニシジン等のベンゼン誘導体、１，５－ナフチレンジアミン、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルケトン、４，４’－ジアミノジフェニルアミン、４，４’－ジアミノジフェニルメタン等が挙げられ、一方、芳香族ジカルボン酸ハライドとして、テレフタル酸クロライド、１，４－ナフタレンジカルボン酸クロライド、２，６－ナフタレンジカルボン酸クロライド、４，４’－ビフェニルジカルボン酸クロライド、４，４’－ジフェニルエーテルジカルボン酸クロライド等が挙げられる。 Copolymerization components that can be used in addition to the above diamines and dicarboxylic acid halides include aromatic diamines such as paraphenylenediamine, 2,5-diaminochlorobenzene, 2,5-diaminobromobenzene, and benzene derivatives such as aminoanisidine. , 1,5-naphthylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ketone, 4,4′-diaminodiphenylamine, 4,4′-diaminodiphenylmethane, etc., while aromatic Dicarboxylic acid halides include terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4'-biphenyldicarboxylic acid chloride, 4,4'-diphenyletherdicarboxylic acid chloride, and the like. .
これらの共重合成分の共重合比は、あまりに多くなりすぎるとメタ型全芳香族ポリアミドの特性が低下しやすいので、ポリアミドの全酸成分を基準として２０モル％以下が好ましい。特に、好適なメタ型全芳香族ポリアミドは、全繰返し単位の８０モル％以上がメタフェニレンイソフタルアミド単位からなるポリアミドであり、なかでもポリメタフェニレンイソフタルアミドが好ましい。
かようなメタ型全芳香族ポリアミドの重合度は、３０℃において９７質量％濃硫酸を溶媒として測定した固有粘度（ＩＶ）が１．３～３．０の範囲が適当である。
If the copolymerization ratio of these copolymerization components is too high, the properties of the meta-type wholly aromatic polyamide tend to deteriorate, so the copolymerization ratio is preferably 20 mol % or less based on the total acid components of the polyamide. Particularly preferred meta-type wholly aromatic polyamides are polyamides in which 80 mol % or more of all repeating units are metaphenylene isophthalamide units, and polymetaphenylene isophthalamide is particularly preferred.
The degree of polymerization of such a meta-type wholly aromatic polyamide is appropriately such that the intrinsic viscosity (IV) measured at 30° C. using 97 mass % concentrated sulfuric acid as a solvent is in the range of 1.3 to 3.0.
次にここで得られたメタ型全芳香族ポリアミドを溶解する溶媒に溶解して紡糸ドープを調整するが、重合後メタ型全芳香族ポリアミドを単離せずそのまま紡糸ドープとすることも可能である。ここで用いる溶媒としてアミド系溶媒を一般的に用いることができ、主なアミド系溶媒としては、Ｎ－メチル－２－ピロリドン（以下、ＮＭＰと称する場合がある）、ジメチルホルムアミド（以下、ＤＭＦと称する場合がある）、ジメチルアセトアミド（以下、ＤＭＡｃと称する場合がある）等を例示することができる。これらのなかでは溶解性と取り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。 Next, a spinning dope is prepared by dissolving the meta-type wholly aromatic polyamide obtained here in a solvent that dissolves it, but it is also possible to use the spinning dope as it is without isolating the meta-type wholly aromatic polyamide after polymerization. . As the solvent used here, an amide solvent can generally be used, and the main amide solvents include N-methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP), dimethylformamide (hereinafter referred to as DMF). , dimethylacetamide (hereinafter sometimes referred to as DMAc), and the like. Among these, it is preferable to use NMP or DMAc from the viewpoint of solubility and handling safety.
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、例えば、ポリマーがポリメタフェニレンイソフタルアミドで溶媒がＮＭＰの場合には、通常は１０～３０質量％の範囲とすることが好ましい。 As the concentration of the solution, an appropriate concentration may be appropriately selected from the viewpoint of the solidification rate in the next spinning and solidifying process and the solubility of the polymer. For example, the polymer is polymetaphenylene isophthalamide and the solvent is NMP. In the case of , it is usually preferable to make the range from 10 to 30% by mass.
本発明においては、市場が要求する明るい色の繊維を得るために、この紡糸ドープに、有機顔料をポリマー成分あたり０．１～２．０質量％となるよう添加して着色することができるが、所望の濃度の着色とするためには顔料の種類によって添加量を調整する必要がある。ここで使用される有機顔料としては、アゾ系、フタロシアニン系、ペリノン系、ペリレン系、アンスラキノン系等の顔料が挙げられるが、これらに限定されるものではない。 In the present invention, an organic pigment can be added to the spinning dope in an amount of 0.1 to 2.0% by mass based on the polymer component for coloring in order to obtain brightly colored fibers required by the market. , it is necessary to adjust the amount added according to the type of pigment in order to obtain a desired color density. The organic pigments used here include azo, phthalocyanine, perinone, perylene, and anthraquinone pigments, but are not limited to these.
次に、上記のとおり顔料分散体溶液と連続的に混合されて作成された紡糸ドープを凝固液中へ紡出し凝固させる。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。また、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、孔形状等は特に制限する必要はなく、例えば、孔数が５００～３００００個、紡糸孔径が０．０５～０．２ｍｍのスフ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紡糸ドープの温度は、１０～９０℃の範囲が適当である。
Next, the spinning dope prepared by continuously mixing with the pigment dispersion solution as described above is spun into the coagulation liquid and coagulated. The spinning device is not particularly limited, and a conventionally known wet spinning device can be used. In addition, the number of spinning holes, the arrangement state, the shape of the holes, etc. of the spinneret do not have to be particularly limited as long as they can be stably wet-spun. A multi-hole spinneret or the like for staple fibers of up to 0.2 mm may be used.
The temperature of the spinning dope during spinning from the spinneret is suitably in the range of 10 to 90°C.
本発明の繊維を得るために用いる凝固浴の例としては、無機塩を含まないアミド系溶媒の濃度４５～６０質量％の水溶液を、浴液の温度１０～３５℃の範囲で用いる。アミド系溶媒の濃度が４５質量％未満ではスキンが厚い構造となってしまい、洗浄工程における洗浄効率が低下し、最終繊維に溶媒が残存することとなる。また、アミド系溶媒の濃度が６０質量％を超える場合には、繊維内部に至るまで均一な凝固を行うことができず、このため、繊維成形加工時に単糸が切断するなどの不具合が多く発生する。なお、凝固浴中への繊維の浸漬時間は、０．１～３０秒の範囲が適当である。 As an example of the coagulation bath used to obtain the fiber of the present invention, an aqueous solution of an amide-based solvent containing no inorganic salt and having a concentration of 45 to 60% by weight is used at a temperature of 10 to 35°C. If the concentration of the amide-based solvent is less than 45% by mass, the skin will have a thick structure, the washing efficiency in the washing process will decrease, and the solvent will remain in the final fiber. In addition, when the concentration of the amide-based solvent exceeds 60% by mass, uniform coagulation cannot be performed to the inside of the fiber, and for this reason, many problems such as breakage of single yarns occur during fiber molding processing. do. It should be noted that the immersion time of the fiber in the coagulation bath is suitably in the range of 0.1 to 30 seconds.
次に凝固浴にて凝固して得られた繊維が可塑状態にあるうちに、可塑延伸浴中にて繊維を延伸処理する。可塑延伸浴液としては特に限定されるものではなく、従来公知の浴液を採用することができる。 Next, while the fibers coagulated in the coagulation bath are in a plastic state, the fibers are drawn in a plastic drawing bath. The plastic stretching bath liquid is not particularly limited, and conventionally known bath liquids can be employed.
本発明の繊維を得るためには、可塑延伸浴中の延伸倍率を、３．５～５．０倍の範囲とすることが好ましく、さらに好ましくは３．７～４．５倍の範囲とする。本発明の繊維の製造においては、可塑延伸浴中にて特定倍率の範囲で可塑延伸することにより、凝固糸中からの脱溶剤を促進することができる。 In order to obtain the fiber of the present invention, the draw ratio in the plastic drawing bath is preferably in the range of 3.5 to 5.0 times, more preferably in the range of 3.7 to 4.5 times. . In the production of the fiber of the present invention, the removal of the solvent from the coagulated yarn can be promoted by plastically drawing the fiber in a plastic drawing bath at a specific ratio.
可塑延伸浴中での延伸倍率が３．５倍未満である場合には、凝固糸中からの脱溶剤が不十分となる場合がある。また、引張強度が不十分となり、紡績工程等の加工工程における取り扱いが困難となる場合がある。一方で、延伸倍率が５．０倍を超える場合には、単糸切れが発生するため、工程安定性が悪くなることがある。
可塑延伸浴の温度は、１０～９０℃の範囲が好ましい。好ましくは温度２０～９０℃の範囲にあると、工程安定性がよい。
If the draw ratio in the plastic drawing bath is less than 3.5 times, the removal of the solvent from the coagulated yarn may be insufficient. In addition, the tensile strength becomes insufficient, and handling in processing steps such as spinning may become difficult. On the other hand, if the draw ratio exceeds 5.0 times, single yarn breakage may occur, resulting in poor process stability.
The temperature of the plastic drawing bath is preferably in the range of 10 to 90°C. Preferably, when the temperature is in the range of 20 to 90°C, process stability is good.
次に、繊維中に残留している溶剤を洗浄する。この工程においては、可塑延伸浴にて延伸された繊維を、十分に洗浄する。洗浄は、得られる繊維の品質面に影響を及ぼすことから、多段で行うことが好ましい。特に、洗浄工程における洗浄浴の温度および洗浄浴液中のアミド系溶媒の濃度は、繊維からのアミド系溶媒の抽出状態および洗浄浴からの水の繊維中への浸入状態に影響を与える。このため、これらを最適な状態とする目的においても、洗浄工程を多段とし、温度条件およびアミド系溶媒の濃度条件を制御することが好ましい。 Next, the solvent remaining in the fibers is washed away. In this step, the fibers drawn in the plastic drawing bath are thoroughly washed. Washing is preferably carried out in multiple stages because it affects the quality of the resulting fiber. In particular, the temperature of the washing bath and the concentration of the amide-based solvent in the washing bath liquid in the washing process affect the state of extraction of the amide-based solvent from the fibers and the state of penetration of water from the washing bath into the fibers. Therefore, for the purpose of optimizing these conditions, it is preferable to perform the washing process in multiple stages and to control the temperature conditions and the concentration conditions of the amide solvent.
洗浄の温度条件およびアミド系溶媒の濃度条件については、最終的に得られる繊維の品質を満足できるものであれば、特に限定されるものではない。ただし、最初の洗浄浴を６０℃以上の高温とすると、水の繊維中への浸入が一気に起こるため、繊維中に巨大なボイドが生成し、品質の劣化を招く。このため、最初の洗浄浴は、３０℃以下の低温とすることが好ましい。 The temperature conditions for washing and the concentration conditions for the amide-based solvent are not particularly limited as long as the quality of the finally obtained fiber can be satisfied. However, if the first washing bath is heated to a temperature of 60° C. or higher, water will permeate into the fibers at once, resulting in the formation of huge voids in the fibers and deterioration of quality. For this reason, it is preferable that the initial cleaning bath be at a low temperature of 30° C. or less.
繊維中に溶媒が残っている場合、該繊維の耐アルカリ性や耐光性を低下させる上に、該繊維を用いた製品の加工、および当該繊維を用いて形成された製品の使用における難燃性や環境安全性においても好ましくない。このため、本発明に用いられる繊維に含まれる溶媒量は、０．２質量％以下であり、より好ましくは０．１５質量％以下であり、０．１質量％以下であることが特に好ましい。 When the solvent remains in the fiber, the alkali resistance and light resistance of the fiber are reduced, and the flame retardancy and flame retardancy in the processing of the product using the fiber and the use of the product formed using the fiber are reduced. It is also unfavorable in terms of environmental safety. Therefore, the amount of solvent contained in the fibers used in the present invention is 0.2% by mass or less, more preferably 0.15% by mass or less, and particularly preferably 0.1% by mass or less.
次に、乾熱処理工程においては、洗浄工程を経た繊維を、乾燥・熱処理する。乾熱処理の方法としては特に限定されるものではないが、例えば、熱ローラー、熱板等を用いる方法を挙げることができる。 Next, in the dry heat treatment step, the fibers that have undergone the washing step are dried and heat treated. The method of dry heat treatment is not particularly limited, but examples thereof include a method using a heat roller, a heat plate, or the like.
本発明においては、この乾熱処理工程中で、残存水分量が繊維質量全体に対して０．１質量％以下となるように乾燥したのち、不活性ガス雰囲気で波長２５０～４００ｎｍの紫外線を含む光を照射することが肝要である。照射する光の波長が２５０ｎｍ未満の場合は特に未照射のものと変わらず、耐アルカリ性の向上がみられなくなり、一方、照射する光の波長が４００ｎｍを越える場合においても同様に耐アルカリ性の向上がみられなくなる。照射する光の波長は２６０～３９０ｎｍがより好ましく、２７０～３８０ｎｍが特に好ましい。 In the present invention, in this dry heat treatment step, after drying so that the residual moisture content is 0.1% by mass or less with respect to the entire fiber mass, light containing ultraviolet rays with a wavelength of 250 to 400 nm is used in an inert gas atmosphere. It is essential to irradiate When the wavelength of the irradiated light is less than 250 nm, there is no improvement in the alkali resistance, which is the same as that of the unirradiated one. become invisible. The wavelength of light to be irradiated is more preferably 260 to 390 nm, particularly preferably 270 to 380 nm.
このときの紫外線照射強度は、１００～１５０ｍＷ／ｃｍ２であることが必要であり、好ましくは１２０～１４５ｍＷ／ｃｍ２であり、１３０～１４０ｍＷ／ｃｍ２が特に好ましい。
また、紫外線の照射時間は、２０秒以上であることが必要であり、２０～４５秒行うことが好ましく、より好ましくは、２０秒～４０秒であり、２０秒～３５秒が特に好ましい。
At this time, the ultraviolet irradiation intensity must be 100 to 150 mW/cm 2 , preferably 120 to 145 mW/cm 2 , particularly preferably 130 to 140 mW/cm 2 .
The irradiation time of the ultraviolet rays must be 20 seconds or longer, preferably 20 to 45 seconds, more preferably 20 to 40 seconds, particularly preferably 20 to 35 seconds.
照射強度は、一般的に強いほど効果が得られるが、１５０ｍＷ／ｃｍ２での照射において耐アルカリ性の向上は十分に発現されておりそれ以上の強い照射を行っても大きな効果が期待されないため効率的でない。
照射時間は一般的に長いほど効果が得られるが、４５秒以上の照射では効果の向上が小さくなるため効率的でない。さらに長時間の照射では、処理装置が大きくなってしまうため、不適切である。
In general , the higher the irradiation intensity, the more effective it is. untargetable.
In general, the longer the irradiation time, the more effective the effect can be obtained. Furthermore, irradiation for a long time is inappropriate because the processing apparatus becomes large.
紫外線照射時の繊維表面温度は、１００℃～３５０℃であることが必要であり、１００～３３０℃がより好ましく、１６０～３００℃が特に好ましい。
この際、繊維表面温度が１００℃よりも低いと空気中の水分を吸着してしまう可能性が高く好ましくない。一方繊維表面温度が３５０℃よりも高いと変色等の変化がみられるようになりやすく好ましくない。
The fiber surface temperature during ultraviolet irradiation must be 100 to 350.degree. C., more preferably 100 to 330.degree. C., and particularly preferably 160 to 300.degree.
At this time, if the fiber surface temperature is lower than 100° C., it is highly likely that moisture in the air will be adsorbed, which is not preferable. On the other hand, if the fiber surface temperature is higher than 350° C., changes such as discoloration are likely to occur, which is not preferable.
なお、この紫外線照射は、残存水分量が繊維質量全体に対して０．１質量％以下となったあと、どの時点（工程）で実施してもよく、また、紫外線照射後にさらに熱処理を継続してもよい。
このように乾熱処理および紫外線照射を経ることにより、最終的に、本発明のメタ型全芳香族ポリアミド繊維を得ることができる。
This ultraviolet irradiation may be performed at any point (step) after the residual moisture content reaches 0.1% by mass or less with respect to the entire fiber mass, and the heat treatment may be continued after the ultraviolet irradiation. may
Through such dry heat treatment and ultraviolet irradiation, the meta-type wholly aromatic polyamide fiber of the present invention can be finally obtained.
乾熱処理および紫外線照射が施されたメタ型全芳香族ポリアミド繊維には、必要に応じて、さらに捲縮加工を施してもよい。さらに、捲縮加工後は、適当な繊維長に切断し、次工程に提供してもよい。また、場合によっては、マルチフィラメントヤーンとして巻き取ってもよい。 The meta-type wholly aromatic polyamide fiber that has been subjected to dry heat treatment and ultraviolet irradiation may be further crimped, if necessary. Furthermore, after the crimping process, the fibers may be cut into appropriate fiber lengths and supplied to the next step. In some cases, it may be wound as a multifilament yarn.
かくして得られた本発明のメタ型全芳香族ポリアミド繊維は、引張強度が３．５～７．０ｃＮ／ｄｔｅｘであり、後述の測定方法で示される耐アルカリ性が９５％以上であり、且つ、ＪＩＳ Ｌ ０８４３（光源：キセノン）における耐光性が４級以上であることが必要である。 The thus-obtained meta-type wholly aromatic polyamide fiber of the present invention has a tensile strength of 3.5 to 7.0 cN/dtex, an alkali resistance of 95% or more as measured by the measurement method described below, and meets JIS The light resistance in L 0843 (light source: xenon) must be grade 4 or higher.
ここで、該メタ型全芳香族ポリアミド繊維の引張強度が３．５ｃＮ／ｄｔｅｘ未満の場合は、防護衣料用途として十分な強度ではなくなり、一方、該メタ型全芳香族ポリアミド繊維の引張強度が７．０ｃＮ／ｄｔｅｘを越える場合は、繊維が固くなり防護衣料にした時の着用感が悪くなる。 Here, when the tensile strength of the meta-type wholly aromatic polyamide fiber is less than 3.5 cN/dtex, the strength is not sufficient for use in protective clothing, while the tensile strength of the meta-type wholly aromatic polyamide fiber is 7 If it exceeds 0 cN/dtex, the fiber becomes hard and the feeling of wearing when used as protective clothing becomes poor.
また、本発明のメタ型全芳香族ポリアミド繊維の耐アルカリ性が９５％未満の場合、防護衣料用途として十分な強度を維持できなくなり、防護衣料の寿命が短くなる。
さらに、本発明のメタ型全芳香族ポリアミド繊維のＪＩＳ Ｌ ０８４３（光源：キセノン）における耐光性が４級未満未満の場合、日光による変色が目立ち、屋外使用の多い防護衣料には不適切である。
In addition, if the alkali resistance of the meta-type wholly aromatic polyamide fiber of the present invention is less than 95%, it will not be able to maintain sufficient strength for use in protective clothing, and the life of the protective clothing will be shortened.
Furthermore, when the light resistance of the meta-type wholly aromatic polyamide fiber of the present invention in JIS L 0843 (light source: xenon) is less than grade 4, discoloration due to sunlight is noticeable, making it unsuitable for protective clothing that is often used outdoors. .
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。
なお、実施例中の「部」および「％」は特に断らない限りすべて質量基準に基づく値であり、量比は特に断らない限り質量比を示す。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。
The present invention will be described in detail below with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to the following Examples and Comparative Examples.
All "parts" and "%" in the examples are values based on mass unless otherwise specified, and quantitative ratios indicate mass ratios unless otherwise specified. Each physical property value in Examples and Comparative Examples was measured by the following methods.
＜固有粘度（Ｉ．Ｖ．）＞
ポリマーを９７％濃硫酸に溶解し、オストワルド粘度計を用い３０℃で測定した。
<Intrinsic viscosity (I.V.)>
The polymer was dissolved in 97% concentrated sulfuric acid and measured at 30°C using an Ostwald viscometer.
＜繊度＞
ＪＩＳ Ｌ１０１５に基づき、正量繊度のＡ法に準拠した測定を実施し、見掛繊度にて表記した。
<Fineness>
Based on JIS L1015, measurement was carried out in conformity with the A method of regular fineness, and the apparent fineness was expressed.
＜引張強度、引張伸度＞
ＪＩＳ Ｌ１０１５に基づき、インストロン社製 型番５５６５を用いて、以下の条件で測定した引張破断強度、引張破断伸度の値を繊維の引張強度、引張伸度とした。
（測定条件）
つかみ間隔 ：２０ｍｍ
初荷重 ：０．０４４ｃＮ（１／２０ｇ）／ｄｔｅｘ
引張速度 ：２０ｍｍ／分
<Tensile strength, tensile elongation>
Based on JIS L1015, the values of tensile strength at break and tensile elongation at break measured under the following conditions using model number 5565 manufactured by Instron were used as the tensile strength and tensile elongation of the fiber.
(Measurement condition)
Grip interval: 20mm
Initial load: 0.044cN (1/20g)/dtex
Tensile speed: 20mm/min
＜明度Ｌ値＞
得られた原綿をカード機で十分に開繊し、１．３グラム取り出して直径３０ｍｍの測定用の円形セルに詰め、分光色彩計 ＳＤ７０００（日本電色工業製）を用いて測定した。
<Brightness L value>
The obtained raw cotton was sufficiently opened by a carding machine, 1.3 g was taken out, packed in a circular cell for measurement with a diameter of 30 mm, and measured using a spectral colorimeter SD7000 (manufactured by Nippon Denshoku Industries).
＜耐アルカリ性＞
（耐アルカリ性の測定方法）
繊維を７５℃の水酸化ナトリウム１０質量％水溶液中に浸漬、６時間静置したのち、流水で十分に水洗、乾燥する。浸漬処理前の引張強度（Ｆ０とする）と、浸漬処理後の引張強度（Ｆ１とする）を測定し、以下の式により耐アルカリ性を求める。
耐アルカリ性＝（Ｆ１／Ｆ０）×１００（％）
<Alkali resistance>
(Method for measuring alkali resistance)
The fiber is immersed in a 10% by mass aqueous solution of sodium hydroxide at 75° C., allowed to stand for 6 hours, washed thoroughly with running water, and dried. The tensile strength before immersion treatment (referred to as F0 ) and the tensile strength after immersion treatment (referred to as F1 ) are measured, and the alkali resistance is determined by the following formula.
Alkali resistance = (F 1 /F 0 ) x 100 (%)
＜耐光性＞
ＪＩＳ Ｌ ０８４３（光源：キセノン）に準じて測定を行い、ブルースケールを用いて級判定を行った。
<Light resistance>
The measurement was performed according to JIS L 0843 (light source: xenon), and the grade was determined using a blue scale.
［実施例１］
乾燥窒素雰囲気下の反応容器に、水分率が１００ｐｐｍ以下のＮ，Ｎ－ジメチルアセトアミド（ＤＭＡｃ）７２１．５質量部を秤量し、このＤＭＡｃ中にメタフェニレンジアミン９７．２質量部（５０．１８モル％）を溶解させ、０℃に冷却した。この冷却したＤＭＡｃ溶液に、さらにイソフタル酸クロライド（以下ＩＰＣと略す）１８１．３質量部（４９．８２モル％）を徐々に攪拌しながら添加し、重合反応を行った。
[Example 1]
721.5 parts by mass of N,N-dimethylacetamide (DMAc) having a moisture content of 100 ppm or less was weighed into a reaction vessel under a dry nitrogen atmosphere, and 97.2 parts by mass (50.18 mol) of metaphenylenediamine was added to this DMAc. %) was dissolved and cooled to 0°C. To this cooled DMAc solution, 181.3 parts by mass (49.82 mol %) of isophthaloyl chloride (hereinafter abbreviated as IPC) was gradually added with stirring to carry out a polymerization reaction.
次に、平均粒径が１０μｍ以下の水酸化カルシウム粉末を６６．６質量部秤量し、重合反応が完了したポリマー溶液に対してゆっくり加え、中和反応を実施した。水酸化カルシウムの投入が完了した後、さらに４０分間攪拌して、透明なポリマードープを得た。
得られたポリマードープからポリメタフェニレンイソフタルアミドを単離してＩＶを測定したところ、１．６５であった。また、ポリマードープ中のポリマー濃度は、１７質量％であった。
Next, 66.6 parts by mass of calcium hydroxide powder having an average particle size of 10 μm or less was weighed and slowly added to the polymer solution in which the polymerization reaction had been completed to carry out a neutralization reaction. After the addition of calcium hydroxide was completed, the mixture was further stirred for 40 minutes to obtain a transparent polymer dope.
Polymetaphenylene isophthalamide was isolated from the resulting polymer dope and IV was measured to be 1.65. Moreover, the polymer concentration in the polymer dope was 17% by mass.
上記で得られた透明なポリマードープをそのまま紡糸ドープとして孔径０．０７ｍｍ、孔数５００の紡糸口金から、浴温度３０℃の凝固浴中に吐出して紡糸した。凝固液の組成は、水／ＤＭＡｃ＝４５／５５（質量％）であり、凝固浴中に糸速７ｍ／分で吐出させ、紡糸した。 The transparent polymer dope obtained above was discharged as it was into a coagulation bath at a bath temperature of 30° C. through a spinneret with a hole diameter of 0.07 mm and 500 holes for spinning. The composition of the coagulation liquid was water/DMAc=45/55 (mass %), and the liquid was discharged into the coagulation bath at a yarn speed of 7 m/min for spinning.
引き続き、温度４０℃の水／ＤＭＡｃ＝４５／５５の組成の可塑延伸浴中にて、３．７倍の延伸倍率で延伸を行った。
延伸後、２０℃の水／ＤＭＡｃ＝７０／３０の浴（浸漬長１．８ｍ）、続いて２０℃の水浴（浸漬長３．６ｍ）で洗浄し、さらに６０℃の温水浴（浸漬長５．４ｍ）に通して十分に洗浄を行った。
Subsequently, the film was stretched at a draw ratio of 3.7 times in a plastic drawing bath having a composition of water/DMAc=45/55 at a temperature of 40°C.
After stretching, it was washed in a water/DMAc = 70/30 bath at 20°C (immersion length 1.8 m), followed by washing in a water bath at 20°C (immersion length 3.6 m), and further in a hot water bath at 60°C (immersion length 5 .4 m) for thorough washing.
洗浄後、表面温度１８０℃の熱ローラーを用いて乾燥を行い、残存水分量が繊維質量全体に対して０．１質量％以下とした後、トウ温度を１００℃に保ったまま不活性ガスとして窒素（Ｎ２）が充填されたゾーンにて波長２５０～４００ｎｍの紫外線を含む光を照射できるＵＶ－Ｂランプを用いて紫外線の照射を３０秒間行った。この時のＵＶ照射強度は、１００ｍＷ／ｃｍ２であった。
次いで、表面温度３００℃の熱ローラーを用いて乾熱処理を施し、メタ型全芳香族ポリアミド繊維をトウの状態で紙管に巻き取った。
After washing, it is dried using a hot roller with a surface temperature of 180 ° C. After the residual moisture content is 0.1% by mass or less with respect to the total fiber mass, the tow temperature is kept at 100 ° C. and an inert gas is used. Ultraviolet irradiation was performed for 30 seconds using a UV-B lamp capable of irradiating light containing ultraviolet rays with a wavelength of 250 to 400 nm in a zone filled with nitrogen (N 2 ). The UV irradiation intensity at this time was 100 mW/cm 2 .
Then, dry heat treatment was performed using a heat roller with a surface temperature of 300° C., and the meta-type wholly aromatic polyamide fiber was wound around a paper tube in the form of a tow.
さらに得られたトウ状態の繊維を束ねてクリンパーを通し、捲縮を付与した後、カッターでカットして５１ｍｍの短繊維とすることにより、原綿を得た。得られた原綿の繊度は、２．２ｄｔｅｘ，引張強度３．９ｃＮ／ｄｔｅｘ、破断伸度１９％と防護衣料に用いるのに問題のない物性であった。得られた原綿をよく開繊し、繊維方向を揃えて測定用のセルへ入れ、分光色彩計ＳＤ７０００（日本電色工業製）を用いて明度の測定を行った結果、明度Ｌは８８であった。さらに、ＪＩＳ Ｌ ０８４３（光源：キセノン）に準じて耐光性を測定し級判定を行った結果、４級と判断される変色しか確認されなかった。 The obtained towed fibers were bundled, passed through a crimper, crimped, and then cut with a cutter into 51 mm short fibers to obtain raw cotton. The obtained raw cotton had a fineness of 2.2 dtex, a tensile strength of 3.9 cN/dtex, and a breaking elongation of 19%, which were satisfactory physical properties for use in protective clothing. The raw cotton thus obtained was thoroughly opened, and the fibers were aligned in the direction of the fibers, placed in a measurement cell, and the lightness was measured using a spectral colorimeter SD7000 (manufactured by Nippon Denshoku Industries Co., Ltd.). As a result, the lightness L was 88. rice field. Furthermore, as a result of measuring the light resistance according to JIS L 0843 (light source: xenon) and performing class judgment, only discoloration judged to be class 4 was confirmed.
また、耐アルカリ性の評価として得られた繊維を７５℃の水酸化ナトリウム１０質量％水溶液中に浸漬、６時間静置したのち、流水で十分に水洗、乾燥した後の引張強度は、３．７ｃＮ／ｄｔｅｘとなり、耐アルカリ性は、９５％と良好であった。よって、優れた引張強度を有し、かつ、耐光性と、耐アルカリ性に優れたメタ型全芳香族ポリアミド繊維を得ることができた。 In addition, the fiber obtained as an evaluation of alkali resistance was immersed in a 10% by mass aqueous solution of sodium hydroxide at 75 ° C., allowed to stand for 6 hours, washed thoroughly with running water, and dried. The tensile strength was 3.7 cN. /dtex, and the alkali resistance was as good as 95%. Therefore, a meta-type wholly aromatic polyamide fiber having excellent tensile strength, light resistance, and alkali resistance could be obtained.
［比較例１］
紫外線照射時に不活性ガスを用いず空気中で行った以外は、全て実施例１と同じ方法で実施し、５１ｍｍにカットされた原綿を得た。得られた原綿の繊度は、２．２ｄｔｅｘ，引張強度３．４ｃＮ／ｄｔｅｘ、破断伸度２４％と防護衣料に用いるには引張強度が不足していた。明度Ｌは、８６であった。耐光性は、３－４級と変色が実施例１より大きいものとなった。薬品処理後の引張強度は、２．９ｃＮ／ｄｔｅｘ、耐アルカリ性は、８５％であり高い耐アルカリ性を得ることはできなかった。
[Comparative Example 1]
A raw cotton cut to 51 mm was obtained in the same manner as in Example 1, except that the UV irradiation was performed in the air without using an inert gas. The obtained raw cotton had a fineness of 2.2 dtex, a tensile strength of 3.4 cN/dtex, and a breaking elongation of 24%, which were insufficient for use in protective clothing. The lightness L was 86. The light fastness was grade 3-4 and discoloration was greater than that of Example 1. The tensile strength after the chemical treatment was 2.9 cN/dtex, and the alkali resistance was 85%, and high alkali resistance could not be obtained.
［比較例２］
紫外線照射を行わなかった以外は、全て実施例１と同じ方法で実施し、５１ｍｍにカットされた原綿を得た。得られた原綿の繊度は、２．２ｄｔｅｘ，引張強度３．９ｃＮ／ｄｔｅｘ、破断伸度２６％と防護衣料に用いるのに問題のない物性であった。明度Ｌは、９１であった。耐光性３級と大きく変色が確認された。薬品処理後の引張強度は、３．４ｃＮ／ｄｔｅｘ、耐アルカリ性は、８７％であり高い耐アルカリ性を得ることはできなかった。
[Comparative Example 2]
A raw cotton cut to 51 mm was obtained in the same manner as in Example 1, except that the ultraviolet irradiation was not performed. The obtained raw cotton had a fineness of 2.2 dtex, a tensile strength of 3.9 cN/dtex, and a breaking elongation of 26%, which were satisfactory physical properties for use in protective clothing. The lightness L was 91. Light fastness grade 3 and large discoloration were confirmed. The tensile strength after the chemical treatment was 3.4 cN/dtex, and the alkali resistance was 87%, and high alkali resistance could not be obtained.
［実施例２］
実施例１と同じ方法でポリマー溶液を作成した。ＩＶは、１．６５であり、ポリマードープ中のポリマー濃度は、１７質量％であった。
得られたポリマー溶液に、Ｐｉｇｍｅｎｔ Ｂｌｕｅ１５の粉末をポリマー成分の質量に対し２．０質量％となるよう添加した後、該ポリマー溶液を十分に撹拌し顔料を均一に分散させた。これを減圧脱泡して紡糸ドープとした。
上記紡糸ドープを用い紡糸・延伸・洗浄は、実施例１と同様に実施した。
[Example 2]
A polymer solution was prepared in the same manner as in Example 1. The IV was 1.65 and the polymer concentration in the polymer dope was 17% by weight.
Pigment Blue 15 powder was added to the obtained polymer solution so as to be 2.0% by mass with respect to the mass of the polymer component, and then the polymer solution was sufficiently stirred to uniformly disperse the pigment. This was defoamed under reduced pressure to obtain a spinning dope.
Spinning, drawing and washing were carried out in the same manner as in Example 1 using the above spinning dope.
洗浄後、表面温度１８０℃の熱ローラーを用いて乾燥を行い、残存水分量が繊維質量全体に対して０．１質量％以下とした後、トウ温度を１００℃に保ったまま不活性ガスとして窒素（Ｎ２）が充填されたゾーンにて波長２５０～４００ｎｍの紫外線を含む光を照射できるＵＶ－Ｂランプを実施例１より距離を近づけて紫外線の照射を２５秒間行った。この時のＵＶ照射強度は、１２０ｍＷ／ｃｍ２であった。
次いで、表面温度３００℃の熱ローラーを用いて乾熱処理を施し、メタ型全芳香族ポリアミド繊維をトウの状態で紙管に巻き取った。
After washing, it is dried using a hot roller with a surface temperature of 180 ° C. After the residual moisture content is 0.1% by mass or less with respect to the total fiber mass, the tow temperature is kept at 100 ° C. and an inert gas is used. In the zone filled with nitrogen (N 2 ), a UV-B lamp capable of irradiating light containing ultraviolet rays with a wavelength of 250 to 400 nm was brought closer than in Example 1, and ultraviolet irradiation was performed for 25 seconds. The UV irradiation intensity at this time was 120 mW/cm 2 .
Then, dry heat treatment was performed using a heat roller with a surface temperature of 300° C., and the meta-type wholly aromatic polyamide fiber was wound around a paper tube in the form of a tow.
さらに得られたトウ状態の繊維を束ねてクリンパーを通し、捲縮を付与した後、カッターでカットして５１ｍｍの短繊維とすることにより、原綿を得た。得られた原綿の繊度は、１．７ｄｔｅｘ，引張強度３．３ｃＮ／ｄｔｅｘ、破断伸度３２％と防護衣料に用いるのに問題のない物性であった。明度Ｌは４０であった。耐光性は、４級と変色が少ないものであり、薬品処理後の引張強度は、３．１ｃＮ／ｄｔｅｘ、耐アルカリ性は、９４％と良好なものであった。よって、優れた引張強度を有し、かつ、耐光性と、耐アルカリ性に優れたメタ型全芳香族ポリアミド繊維を得ることができた。 The obtained towed fibers were bundled, passed through a crimper, crimped, and then cut with a cutter into 51 mm short fibers to obtain raw cotton. The raw cotton thus obtained had a fineness of 1.7 dtex, a tensile strength of 3.3 cN/dtex, and a breaking elongation of 32%, which were satisfactory physical properties for use in protective clothing. The lightness L was 40. The light fastness was grade 4, indicating little discoloration, the tensile strength after chemical treatment was 3.1 cN/dtex, and the alkali resistance was good at 94%. Therefore, a meta-type wholly aromatic polyamide fiber having excellent tensile strength, light resistance, and alkali resistance could be obtained.
［比較例３］
実施例２と同じ方法で紡糸ドープを作成し、紡糸・延伸・洗浄まで実施した。
洗浄後、表面温度１８０℃の熱ローラーを用いて乾燥を行い、残存水分量が繊維質量全体に対して０．１質量％以下とした後、トウ温度を４５℃まで冷やしたのちに４５℃に保ったまま不活性ガスとして窒素（Ｎ２）が充填されたゾーンにて波長２５０～４００ｎｍの紫外線を含む光を照射できるＵＶ－Ｂランプを用いて紫外線の照射を２５秒間行った。この時のＵＶ照射強度は、１２０ｍＷ／ｃｍ２であった。
次いで、表面温度３００℃の熱ローラーを用いて乾熱処理を施し、メタ型全芳香族ポリアミド繊維をトウの状態で紙管に巻き取った。
[Comparative Example 3]
A spinning dope was prepared in the same manner as in Example 2, and spinning, drawing and washing were carried out.
After washing, the fiber is dried using a hot roller with a surface temperature of 180°C to make the remaining moisture content 0.1% by mass or less based on the total fiber mass, and then the tow temperature is cooled to 45°C and then to 45°C. In the zone filled with nitrogen (N 2 ) as an inert gas while maintaining the state, ultraviolet irradiation was performed for 25 seconds using a UV-B lamp capable of irradiating light including ultraviolet rays having a wavelength of 250 to 400 nm. The UV irradiation intensity at this time was 120 mW/cm 2 .
Then, dry heat treatment was performed using a heat roller with a surface temperature of 300° C., and the meta-type wholly aromatic polyamide fiber was wound around a paper tube in the form of a tow.
さらに得られたトウ状態の繊維を束ねてクリンパーを通し、捲縮を付与した後、カッターでカットして５１ｍｍの短繊維とすることにより、原綿を得た。得られた原綿の繊度は、１．７ｄｔｅｘ、引張強度３．５ｃＮ／ｄｔｅｘ、破断伸度２８％と防護衣料に用いるのに問題のない物性であった。
明度Ｌは、４０、耐光性は、３－４級の変色が確認された。薬品処理後の引張強度は、２．９ｃＮ／ｄｔｅｘ、耐アルカリ性は、８３％であり高い耐アルカリ性を得ることはできなかった。
The obtained towed fibers were bundled, passed through a crimper, crimped, and then cut with a cutter into 51 mm short fibers to obtain raw cotton. The raw cotton thus obtained had a fineness of 1.7 dtex, a tensile strength of 3.5 cN/dtex, and a breaking elongation of 28%, which were satisfactory physical properties for use in protective clothing.
The lightness L was 40, and the light resistance was confirmed to be grade 3-4 discoloration. The tensile strength after the chemical treatment was 2.9 cN/dtex, and the alkali resistance was 83%, so high alkali resistance could not be obtained.
［比較例４］
実施例２と同じ方法で紡糸ドープを作成し、紡糸・延伸・洗浄まで実施した。
洗浄後、表面温度１８０℃の熱ローラーを用いて乾燥を行い、残存水分量が繊維質量全体に対して０．１質量％以下とした後、トウ温度を１００℃に保ったまま不活性ガスとして窒素（Ｎ２）が充填されたゾーンにて波長２５０～４００ｎｍの紫外線を含む光を照射できるＵＶ－Ｂランプを実施例２より距離を開けて紫外線の照射を９０秒間行った。この時のＵＶ照射強度は、８０ｍＷ／ｃｍ２であった。
次いで、表面温度３００℃の熱ローラーを用いて乾熱処理を施し、メタ型全芳香族ポリアミド繊維をトウの状態で紙管に巻き取った。
[Comparative Example 4]
A spinning dope was prepared in the same manner as in Example 2, and spinning, drawing and washing were carried out.
After washing, it is dried using a hot roller with a surface temperature of 180 ° C. After the residual moisture content is 0.1% by mass or less with respect to the total fiber mass, the tow temperature is kept at 100 ° C. and an inert gas is used. In a zone filled with nitrogen (N 2 ), a UV-B lamp capable of irradiating light containing ultraviolet rays with a wavelength of 250 to 400 nm was used at a greater distance than in Example 2, and irradiation with ultraviolet rays was performed for 90 seconds. The UV irradiation intensity at this time was 80 mW/cm 2 .
Then, dry heat treatment was performed using a heat roller with a surface temperature of 300° C., and the meta-type wholly aromatic polyamide fiber was wound around a paper tube in the form of a tow.
さらに得られたトウ状態の繊維を束ねてクリンパーを通し、捲縮を付与した後、カッターでカットして５１ｍｍの短繊維とすることにより、原綿を得た。得られた原綿の繊度は、１．７ｄｔｅｘ、引張強度３．５ｃＮ／ｄｔｅｘ、破断伸度３３％と防護衣料に用いるのに問題のない物性であった。
明度Ｌは４０、耐光性は４級と変色の少ないものであったが、薬品処理後の引張強度は３．１ｃＮ／ｄｔｅｘ、耐アルカリ性は８９％であり高い耐アルカリ性を得ることはできなかった。
The obtained towed fibers were bundled, passed through a crimper, crimped, and then cut with a cutter into 51 mm short fibers to obtain raw cotton. The obtained raw cotton had a fineness of 1.7 dtex, a tensile strength of 3.5 cN/dtex, and a breaking elongation of 33%, which were satisfactory physical properties for use in protective clothing.
The lightness L was 40, and the light resistance was grade 4, indicating little discoloration. However, the tensile strength after chemical treatment was 3.1 cN/dtex, and the alkali resistance was 89%, so high alkali resistance could not be obtained. .
［実施例３］
実施例１と同じ方法で得られた透明なポリマー溶液よりポリメタフェニレンイソフタルアミドを単離したのち、アミド系溶媒であるＮ－メチル－２－ピロリドン（ＮＭＰ）にポリマー濃度２４％となるよう溶解し、紡糸ドープとした。
得られたポリマー溶液を紡糸液として、孔径０．０７ｍｍ、孔数３００の口金より、凝固浴温度８５℃の浴中に吐出して紡糸した。凝固液の組成は、水／塩化カルシウム／ＮＭＰ（質量比）＝５５／４１／４であり、凝固浴中に糸速７ｍ／分で吐出し紡糸した。
次いで得られた凝固糸を、３０℃の水浴（浸漬長８．０ｍ）、９８℃の温水浴（浸漬長５．２ｍ）中で１．４５倍に延伸し、さらに９８℃の温水浴（浸漬長０．４ｍ）中で洗浄を行った。
[Example 3]
After isolating polymetaphenylene isophthalamide from the transparent polymer solution obtained in the same manner as in Example 1, it was dissolved in N-methyl-2-pyrrolidone (NMP), an amide solvent, so that the polymer concentration was 24%. and made into a spinning dope.
The obtained polymer solution was used as a spinning solution, and spun by being discharged into a coagulation bath temperature of 85° C. through a spinneret with a hole diameter of 0.07 mm and 300 holes. The composition of the coagulation liquid was water/calcium chloride/NMP (mass ratio)=55/41/4, and the liquid was spun into the coagulation bath at a yarn speed of 7 m/min.
Next, the obtained coagulated yarn is stretched 1.45 times in a 30°C water bath (immersion length 8.0 m) and a 98°C warm water bath (immersion length 5.2 m), and further stretched in a 98°C warm water bath (immersion length 5.2 m). 0.4 m long).
洗浄後、表面温度１８０℃の熱ローラーを用いて乾燥を行い、残存水分量が繊維質量全体に対して０．１質量％以下とした後、表面温度３５０℃の熱ローラーを用いて乾熱処理を施しながら、トウ温度を３４５℃に保ったまま不活性ガスとして窒素（Ｎ２）が充填されたゾーンにて波長２５０～４００ｎｍの紫外線を含む光を照射できるＵＶ－Ｂランプを実施例２より近い距離から紫外線の照射を２０秒間行ったのち、トウの状態で紙管に巻き取った。この時のＵＶ照射強度は、１５０ｍＷ／ｃｍ２であった。 After washing, it is dried using a heat roller with a surface temperature of 180°C, and after the residual moisture content is 0.1% by mass or less with respect to the total fiber mass, dry heat treatment is performed using a heat roller with a surface temperature of 350°C. While maintaining the tow temperature at 345 ° C., a UV-B lamp that can irradiate light including ultraviolet rays with a wavelength of 250 to 400 nm in a zone filled with nitrogen (N 2 ) as an inert gas is closer than that of Example 2. After irradiating ultraviolet rays from a distance for 20 seconds, the tow was wound around a paper tube. The UV irradiation intensity at this time was 150 mW/cm 2 .
さらに得られたトウ状態の繊維を束ねてクリンパーを通し、捲縮を付与した後、カッターでカットして５１ｍｍの短繊維とすることにより、原綿を得た。得られた原綿の繊度は、２．２ｄｔｅｘ，引張強度５．２ｃＮ／ｄｔｅｘ、破断伸度３６％と防護衣料に用いるのに問題のない物性であった。明度Ｌは、８６であった。耐光性は、４－５級と変色が僅かであった。また薬品処理後の引張強度は、５．１ｃＮ／ｄｔｅｘ、耐アルカリ性は、９８％と非常に良好なものであった。よって、優れた引張強度を有し、かつ、耐光性と、耐アルカリ性に優れたメタ型全芳香族ポリアミド繊維を得ることができた。 The obtained towed fibers were bundled, passed through a crimper, crimped, and then cut with a cutter into 51 mm short fibers to obtain raw cotton. The obtained raw cotton had a fineness of 2.2 dtex, a tensile strength of 5.2 cN/dtex, and a breaking elongation of 36%, which were satisfactory physical properties for use in protective clothing. The lightness L was 86. The light resistance was grade 4-5, indicating slight discoloration. The tensile strength after chemical treatment was 5.1 cN/dtex, and the alkali resistance was 98%, both of which were very good. Therefore, a meta-type wholly aromatic polyamide fiber having excellent tensile strength, light resistance, and alkali resistance could be obtained.
［比較例５］
紫外線照射時に不活性ガスを用いず空気中で行った以外は、全て実施例３と同じ方法で実施し、５１ｍｍにカットされた原綿を得た。得られた原綿の繊度は、２．２ｄｔｅｘ，引張強度４．９ｃＮ／ｄｔｅｘ、破断伸度３３％と防護衣料に用いるのに問題のない物性であった。明度Ｌは、８５であった。耐光性は、３－４級の変色が確認された。薬品処理後の引張強度は、４．５ｃＮ／ｄｔｅｘ、耐アルカリ性は、９２％であり高い耐アルカリ性を得ることはできなかった。
[Comparative Example 5]
A raw cotton cut to 51 mm was obtained in the same manner as in Example 3, except that the UV irradiation was performed in the air without using an inert gas. The raw cotton thus obtained had a fineness of 2.2 dtex, a tensile strength of 4.9 cN/dtex, and a breaking elongation of 33%, which were satisfactory physical properties for use in protective clothing. The lightness L was 85. As for the light fastness, discoloration of grade 3-4 was confirmed. The tensile strength after the chemical treatment was 4.5 cN/dtex, and the alkali resistance was 92%, and high alkali resistance could not be obtained.
［比較例６］
実施例３と同じ方法で紡糸ドープを作成し、紡糸・延伸・洗浄まで実施した。
洗浄後、表面温度１８０℃の熱ローラーを用いて乾燥を行い、残存水分量が繊維質量全体に対して０．１質量％以下とした後、表面温度３７０℃の熱ローラーを用いて乾熱処理を施しながら、トウ温度を３６５℃に保ったまま不活性ガスとして窒素（Ｎ２）が充填されたゾーンにて波長２５０～４００ｎｍの紫外線を含む光を照射できるＵＶ－Ｂランプを実施例２より近い距離から紫外線の照射を２０秒間行ったのち、トウの状態で紙管に巻き取った。この時のＵＶ照射強度は、１５０ｍＷ／ｃｍ２であった。
[Comparative Example 6]
A spinning dope was prepared in the same manner as in Example 3, and spinning, drawing and washing were carried out.
After washing, it is dried using a hot roller with a surface temperature of 180°C, and after the residual moisture content is 0.1% by mass or less with respect to the total fiber mass, dry heat treatment is performed using a hot roller with a surface temperature of 370°C. While maintaining the tow temperature at 365 ° C., a UV-B lamp capable of irradiating light including ultraviolet rays with a wavelength of 250 to 400 nm in a zone filled with nitrogen (N 2 ) as an inert gas is closer to that of Example 2. After irradiating ultraviolet rays from a distance for 20 seconds, the tow was wound around a paper tube. The UV irradiation intensity at this time was 150 mW/cm 2 .
さらに得られたトウ状態の繊維を束ねてクリンパーを通し、捲縮を付与した後、カッターでカットして５１ｍｍの短繊維とすることにより、原綿を得た。得られた原綿の繊度は、２．１ｄｔｅｘ，引張強度４．３ｃＮ／ｄｔｅｘ、破断伸度２７％と防護衣料に用いるのに問題のない物性であった。明度Ｌは７８であった。耐光性は３－４級の変色が確認された。薬品処理後の引張強度は３．８ｃＮ／ｄｔｅｘ、耐アルカリ性は８８％であり高い耐アルカリ性を得ることはできなかった。 The obtained towed fibers were bundled, passed through a crimper, crimped, and then cut with a cutter into 51 mm short fibers to obtain raw cotton. The obtained raw cotton had a fineness of 2.1 dtex, a tensile strength of 4.3 cN/dtex, and a breaking elongation of 27%, which were satisfactory physical properties for use in protective clothing. The lightness L was 78. As for the light fastness, discoloration of grade 3-4 was confirmed. The tensile strength after the chemical treatment was 3.8 cN/dtex, and the alkali resistance was 88%, so high alkali resistance could not be obtained.
［比較例７］
紫外線照射を行わなかった以外は、全て実施例３と同じ方法で実施し、５１ｍｍにカットされた原綿を得た。得られた原綿の繊度は、２．２ｄｔｅｘ，引張強度５．３ｃＮ／ｄｔｅｘ、破断伸度４０％と防護衣料に用いるのに問題のない物性であった。明度Ｌは、８８であり、耐光性３級の変色が確認された。薬品処理後の引張強度は、３．４ｃＮ／ｄｔｅｘ、耐アルカリ性は、９０％であり高い耐アルカリ性を得ることはできなかった。
実施例１～３、比較例１～７により得られたメタ型全芳香族ポリアミド繊維の物性をまとめて表１に示す。
[Comparative Example 7]
A raw cotton cut to 51 mm was obtained in the same manner as in Example 3, except that the ultraviolet irradiation was not performed. The obtained raw cotton had a fineness of 2.2 dtex, a tensile strength of 5.3 cN/dtex, and a breaking elongation of 40%, which were satisfactory physical properties for use in protective clothing. The lightness L was 88, and discoloration of the third grade of light fastness was confirmed. The tensile strength after the chemical treatment was 3.4 cN/dtex, and the alkali resistance was 90%, so high alkali resistance could not be obtained.
Table 1 summarizes the physical properties of the meta-type wholly aromatic polyamide fibers obtained in Examples 1-3 and Comparative Examples 1-7.
本発明によれば、優れた引張強度を有し、かつ、耐光性と、耐アルカリ性に優れたメタ型全芳香族ポリアミド繊維が提供されるので、その工業的価値は極めて大きい。 INDUSTRIAL APPLICABILITY According to the present invention, a meta-type wholly aromatic polyamide fiber having excellent tensile strength, light resistance, and alkali resistance is provided, and its industrial value is extremely high.
Claims (2)
（耐アルカリ性の測定方法）
繊維を７５℃の水酸化ナトリウム１０質量％水溶液中に浸漬、６時間静置したのち、流水で十分に水洗、乾燥する。浸漬処理前の引張強度（Ｆ０とする）と、浸漬処理後の引張強度（Ｆ１とする）を測定し、以下の式により耐アルカリ性を求める。
耐アルカリ性＝（Ｆ１／Ｆ０）×１００（％） It has a tensile strength of 3.5 to 7.0 cN/dtex, an alkali resistance of 95% or more as measured by the following measurement method, and a light resistance of grade 4 or higher according to JIS L 0843 (light source: xenon). A meta-type wholly aromatic polyamide fiber characterized by comprising:
(Method for measuring alkali resistance)
The fiber is immersed in a 10% by mass aqueous solution of sodium hydroxide at 75° C., allowed to stand for 6 hours, washed thoroughly with running water, and dried. The tensile strength before immersion treatment (referred to as F0 ) and the tensile strength after immersion treatment (referred to as F1 ) are measured, and the alkali resistance is determined by the following formula.
Alkali resistance = (F 1 /F 0 ) x 100 (%)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022011417A JP2023110161A (en) | 2022-01-28 | 2022-01-28 | Meta-type whole aromatic polyamide fiber and production method of the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022011417A JP2023110161A (en) | 2022-01-28 | 2022-01-28 | Meta-type whole aromatic polyamide fiber and production method of the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2023110161A true JP2023110161A (en) | 2023-08-09 |
Family
ID=87546302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022011417A Pending JP2023110161A (en) | 2022-01-28 | 2022-01-28 | Meta-type whole aromatic polyamide fiber and production method of the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2023110161A (en) |
-
2022
- 2022-01-28 JP JP2022011417A patent/JP2023110161A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4647680B2 (en) | Easy-dyeing meta-type wholly aromatic polyamide fiber | |
| JP5710593B2 (en) | Meta-type wholly aromatic polyamide fiber | |
| JP5852127B2 (en) | Original meta-type wholly aromatic polyamide fiber | |
| JP7248507B2 (en) | Spin-dyed meta-type wholly aromatic polyamide fiber and method for producing the same | |
| JP7028682B2 (en) | Original meta-type all-aromatic polyamide fiber and its manufacturing method, and flame-retardant spun yarn and flame-retardant cut-off spun yarn made of the fiber. | |
| JP6873768B2 (en) | I Ching meta-type total aromatic polyamide fiber with excellent flame retardancy and its manufacturing method | |
| JP2023110161A (en) | Meta-type whole aromatic polyamide fiber and production method of the same | |
| JP2011202326A (en) | Fiber structure including easy-to-dye meta-wholly aromatic polyamide staple fiber | |
| JP6960275B2 (en) | Light-colored original meta-type total aromatic polyamide fiber | |
| JP2018154943A (en) | Meta-type wholly aromatic polyamide fiber having excellent flame retardancy and method for producing the same | |
| JP2013133569A (en) | Spun yarn of spun-dyed meta-type wholly aromatic polyamide fiber | |
| JP7267821B2 (en) | Method for producing recycled meta-type wholly aromatic polyamide fiber | |
| JP2020117831A (en) | Easily-dyeable meta-type wholly aromatic polyamide fiber, and method for producing the same | |
| JP2001172819A (en) | Method for producing meta-form aromatic polyamide fiber | |
| JP2021179029A (en) | Wholly aromatic polyamide fiber, and method for producing the same | |
| JP2015042790A (en) | Stretch-broken spun yarn comprising spun-dyed meta-type wholly aromatic polyamide | |
| WO2022185683A1 (en) | Spun-dyed meta-type wholly aromatic polyamide fiber and method for production thereof | |
| JP2012052250A (en) | Stretch-broken spun yarn including meta-type wholly aromatic polyamide fiber | |
| JP2001114889A (en) | Method for producing meta aromatic polyamide solution | |
| JP2005042262A (en) | Method for producing easily dyeable meta-type wholly aromatic polyamide fiber | |
| JP2023144211A (en) | Spun-dyed meta-type wholly aromatic polyamide fiber and method for producing the same | |
| JP6523026B2 (en) | Black meta-type wholly aromatic polyamide fiber | |
| JP2021107588A (en) | Spun-dyed meta-type wholly aromatic polyamide fiber having excellent light resistance and manufacturing method thereof | |
| JP5718654B2 (en) | Meta-type wholly aromatic polyamide fiber | |
| JP2019157289A (en) | Fire retardant yarn |