WO2022181558A1 - 耐熱性高タフネス繊維、その製造方法、および耐熱性高タフネスフィルム - Google Patents
耐熱性高タフネス繊維、その製造方法、および耐熱性高タフネスフィルム Download PDFInfo
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- WO2022181558A1 WO2022181558A1 PCT/JP2022/007028 JP2022007028W WO2022181558A1 WO 2022181558 A1 WO2022181558 A1 WO 2022181558A1 JP 2022007028 W JP2022007028 W JP 2022007028W WO 2022181558 A1 WO2022181558 A1 WO 2022181558A1
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- WO
- WIPO (PCT)
- Prior art keywords
- heat
- phenylenediamine
- fiber
- less
- monomer units
- Prior art date
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 202
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 153
- 239000004760 aramid Substances 0.000 claims abstract description 112
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 110
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 99
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 86
- -1 isophthaloyl Chemical group 0.000 claims abstract description 74
- 238000002844 melting Methods 0.000 claims abstract description 33
- 230000008018 melting Effects 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims description 178
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 84
- 238000009987 spinning Methods 0.000 claims description 46
- 238000005345 coagulation Methods 0.000 claims description 43
- 230000015271 coagulation Effects 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000009835 boiling Methods 0.000 claims description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 19
- 239000010419 fine particle Substances 0.000 claims description 15
- 150000001408 amides Chemical class 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004581 coalescence Methods 0.000 claims 1
- 239000003779 heat-resistant material Substances 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 88
- 239000000243 solution Substances 0.000 description 77
- 239000010408 film Substances 0.000 description 56
- 208000012886 Vertigo Diseases 0.000 description 41
- 239000000843 powder Substances 0.000 description 30
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 28
- 239000001110 calcium chloride Substances 0.000 description 28
- 229910001628 calcium chloride Inorganic materials 0.000 description 28
- 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 26
- 230000000052 comparative effect Effects 0.000 description 25
- 150000001412 amines Chemical class 0.000 description 24
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 24
- 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 19
- 238000012695 Interfacial polymerization Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000007654 immersion Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 229920006231 aramid fiber Polymers 0.000 description 8
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 8
- 239000012210 heat-resistant fiber Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910017053 inorganic salt Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229920000561 Twaron Polymers 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000004762 twaron Substances 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000010409 thin film Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000004984 aromatic diamines Chemical class 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
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 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
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 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
- PIVFDRVXTFJSIW-UHFFFAOYSA-N benzene-1,4-dicarbonyl bromide Chemical compound BrC(=O)C1=CC=C(C(Br)=O)C=C1 PIVFDRVXTFJSIW-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 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
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000013305 flexible fiber Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 229920001778 nylon Polymers 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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
- D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
- D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/063—Load-responsive characteristics high strength
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/16—Physical properties antistatic; conductive
Definitions
- the present invention relates to a heat-resistant high-toughness fiber, a method for producing the same, and a heat-resistant high-toughness film. More specifically, the present invention relates to a heat-resistant and high-toughness fiber having an excellent balance of overall physical properties including strength, elongation, heat resistance, and optional knot strength and/or conductivity, a method for producing the same, and a heat-resistant fiber. It relates to a high toughness film.
- High-strength, high-modulus fibers can provide a high-strength structure, but if the elongation is low, they will break without being able to absorb large deformations.
- the strength and elongation of these fibers are in a trade-off relationship, and it has been difficult to develop high-toughness fibers that satisfy both strength and elongation.
- Patent Document 1 Japanese Patent Application Laid-Open No. 59-100710
- Patent Document 2 Japanese Patent Application Laid-Open No. 2000-144527
- Patent Document 3 reports a method of obtaining a polyester fiber having a strength of 8 to 9 g/de and an elongation of 10 to 15% by adjusting the positions of oiling and bundling.
- Patent Document 3 Japanese Patent Application Laid-Open No.
- Patent Document 3 reports a polyester fiber having a strength of 8 to 10 cN/dtex and an elongation of 20 to 25% or more by controlling the temperature history on the spinning line. However, they are all general-purpose fibers and have relatively low heat resistance.
- fibers made of wholly aromatic polyamide are particularly useful as high-strength, heat-resistant, and flame-retardant fibers.
- para-type wholly aromatic polyamide fibers composed of paraphenylene terephthalamide have high strength and high elastic modulus, so they are widely used as industrial materials such as reinforcing materials for various matrices and ropes.
- meta-type wholly aromatic polyamide fiber composed of metaphenylene isophthalamide is a flexible fiber in addition to heat resistance. Used for industrial purposes.
- the mechanical properties of these aramid fibers are para-type breaking strength of 15 to 20 cN/dtex, breaking elongation of 1 to 5% (“Kevlar” (registered trademark) manufactured by DuPont, “Twaron” (registered trademark) manufactured by Teijin Limited. Trademark)), etc., and the meta type has a breaking strength of 3 to 6 cN / dtex and a breaking elongation of 30 to 60% (“Nomex” (registered trademark) manufactured by DuPont Co., Ltd., “Conex” manufactured by Teijin Ltd. (registered trademark)), and applications have been developed in consideration of the physical properties of these fibers.
- a high-strength, high-elasticity film can provide a high-strength structure, but if the elongation is low, it will break without being able to relax against large deformation.
- the strength and elongation of these films are in a trade-off relationship, and it has been difficult to develop a high toughness film that satisfies both strength and elongation.
- Patent Document 10 Japanese Patent Application Laid-Open No. 2003-176354
- Patent Document 11 Japanese Patent Application Laid-Open No. 3-138129
- Patent Document 11 reports a high-strength film with more excellent heat resistance. and is not sufficient for use in high temperature ranges.
- the object of the present invention is to provide a heat-resistant, high-toughness fiber and a heat-resistant, high-toughness film that have a good balance between strength and elongation while having high heat resistance.
- a further object of the present invention is to provide a heat-resistant and high-toughness fiber excellent in knot strength and/or conductivity, and a film having a good balance between strength and elongation while having high heat resistance. .
- the inventors of the present invention have found that by making a polymer obtained by copolymerizing a plurality of specific monomers in a specific ratio into fibers or films, it is possible to achieve high heat resistance while maintaining high heat resistance. Also found that a heat-resistant and highly tough fiber or film having well-balanced strength and elongation can be obtained, and completed the present invention. The present inventors have also found that knot strength and/or electrical conductivity are further enhanced in such heat-resistant and high-toughness fibers, and have completed the present invention.
- a heat-resistant high-toughness fiber having a breaking strength of 3.5 to 15 cN/dtex, a breaking elongation of 5 to 30%, and a melting point of 290° C. or higher; 2.
- high toughness fiber 3.
- the molar ratio of the meta-phenylenediamine and/or the isophthaloyl monomer units to the para-phenylenediamine and/or the terephthaloyl monomer units is in the range of 10 or more and less than 70:90 or less and more than 30.
- the heat-resistant high-toughness fiber according to 4 above which further has a knot strength of 4.4 to 5.6 cN/dtex; 6. 4 or above, wherein the molar ratio of the meta-phenylenediamine and/or the isophthaloyl monomer unit to the para-phenylenediamine and/or the terephthaloyl monomer unit is in the range of 40 or more and less than 70:60 or less and more than 30 5.
- the breaking strength is 8.0 cN/dtex or more and less than 15.0 cN/dtex, the breaking elongation is more than 5.0% and 20.0% or less, and the dry heat dimensional change rate at 300 ° C. is 5.
- the heat resistant high toughness fiber according to any one of the above 1 to 3, 8. 7, wherein the molar ratio of the meta-phenylenediamine and/or the isophthaloyl monomer units to the para-phenylenediamine and/or the terephthaloyl monomer units is in the range of 10 or more and less than 40:90 or less and more than 60.
- the heat-resistant high-toughness fiber according to 9 above containing 6 to 40% by mass of the conductive fine particles; 11. 11.
- a method for producing a heat-resistant and high-toughness fiber comprising the following steps (1) to (6): (1) A copolymerized aramid polymer comprising at least three monomer units selected from the group consisting of metaphenylenediamine, paraphenylenediamine, isophthaloyl and terephthaloyl, wherein the metaphenylenediamine and/or the isophthaloyl
- the molar ratio of the monomer unit and the paraphenylenediamine and/or the terephthaloyl monomer unit is in the range of 10 or more and less than 70:90 or less and more than 30, and the weight average molecular weight is 400,000 to 1,000,000.
- the spinning dope is obtained by dissolving the copolymer aramid polymer in an amide solvent in an amount of 5 to 30% by mass, and the coagulation bath contains the amide solvent in an amount of 1 to 20% by mass.
- a heat-resistant high-toughness film comprising coalescing is provided.
- the heat-resistant and high-toughness fiber obtained by the present invention has heat resistance that can withstand a use environment of 250 ° C. or higher, and at the same time, has a breaking strength of 3.5 to 15 cN / dtex and a breaking elongation of 5 to 30. %, it can be suitably used in protective clothing applications that supplement strength and flexibility in addition to heat resistance, rubber reinforcement applications that require elongation, and the like.
- the heat-resistant and high-toughness film obtained in the present invention has a breaking strength of 80 to 150 MPa, a breaking elongation of 5 to 30%, a glass transition temperature of 250 ° C. or higher, and a heat resistance at 300 ° C. It has an excellent balance of physical properties with a shrinkage rate of 5% or less, so it can be suitably used in applications where strength and elongation are required in a high temperature range.
- the heat-resistant high-toughness fiber of the present invention is characterized by having a breaking strength of 3.5 to 15 cN/dtex, a breaking elongation of 5 to 30%, and a melting point of 290° C. or higher.
- Polymers constituting such heat-resistant and high-toughness fibers are generally wholly aromatic polyamides (hereinafter sometimes referred to as aramids), in particular meta-type and / or para-type aromatic diamine components, meta-type and / or It contains a copolymer composed of a para-type aromatic dicarboxylic acid component.
- the wholly aromatic polyamide composed of a copolymerized aramid polymer is randomly copolymerized, and preferably at least selected from the group consisting of metaphenylenediamine, paraphenylenediamine, isophthaloyl and terephthaloyl. It contains three types of monomeric units. Examples of combinations of these monomer units are shown in Table 1 below.
- the heat-resistant and high-toughness fibers generally preferably contain the three types of monomer units shown in Examples 1 to 4, and depending on the application, those containing the four types of monomer units shown in Example 5, Those containing the three types of monomeric units shown in 4 may be more preferred.
- the heat-resistant and high-toughness film generally contains three types of monomer units shown in Examples 1 to 4 and two types of monomer units shown in Examples 6 and 7.
- the molar ratio of meta-phenylenediamine and/or isophthaloyl monomer units and para-phenylenediamine and/or terephthaloyl monomer units is 10 or more and less than 70:90 or less 30 preferably in the range of
- a first aspect of the heat-resistant and high-toughness fiber according to the present invention may have a breaking strength of 7 to 15 cN/dtex, a breaking elongation of 10 to 30%, and a melting point of 290°C or higher.
- the mol% of meta-phenylenediamine and/or isophthaloyl monomer units is 40 or more and less than 70
- the mol% of paraphenylenediamine and/or terephthaloyl monomer units is 60 or less and more than 30.
- the mol% of meta-phenylenediamine and/or isophthaloyl monomer units is 50 or more and less than 70, and the mol% of paraphenylenediamine and/or terephthaloyl monomer units is 50 or less and more than 30.
- the mol% of meta-phenylenediamine and/or isophthaloyl monomer units is 50 or more and less than 67, and the mol% of paraphenylenediamine and/or terephthaloyl monomer units is 50 or less and more than 33. preferable.
- the mol % of meta-phenylenediamine and/or isophthaloyl monomer units is 70 or more, the intended strength may not be achieved.
- the mol % of the metaphenylenediamine and/or isophthaloyl monomer units is less than 40, the resulting polymer may not be dissolved in the amide-based solvent described later and may not be spun.
- the breaking strength of the heat-resistant high-toughness fiber which is the first aspect, is 7 to 15 cN/dtex, and the lower limit is preferably 8.0 cN/dtex or more. If the breaking strength is less than 3.5 cN/dtex, the high toughness that is the object of the present invention may be insufficient.
- the breaking elongation of the heat-resistant high-toughness fiber of the first aspect is generally 10% to 30%, preferably 15% to 25%, more preferably 20% to 25% or more. If the elongation at break is less than 10%, the elongation is not sufficient, and high toughness may not be exhibited sufficiently. On the other hand, when the elongation at break exceeds 30%, sufficient strength may not be obtained.
- the melting point of the heat-resistant high-toughness fiber which is the first aspect, must be 290°C or higher, preferably 300°C or higher. If the melting point is lower than 290°C, the performance as a heat-resistant fiber cannot be exhibited.
- the dry heat dimensional change rate at 250° C. is preferably less than 2%, more preferably 1.5% or less, and further preferably 1.0% or less. Preferably, 0.5% or less is particularly preferable. If the dry heat dimensional change rate is 2% or more, the performance as a heat-resistant fiber may not be sufficiently exhibited.
- the breaking strength is 7.0 to 15.0 cN/dtex and the knot strength is 4.4 to 5.6 cN/dtex (42.3% to 50% ), a breaking elongation of 10 to 30%, and a melting point of 290° C. or higher.
- Examples of reports on high knot strength fibers include the following.
- para-oriented aramid fibers are pre-dried at a low temperature and subjected to steam treatment to achieve a strength of 21.4 g/de and a knot strength of 7.5 to 8.4 g/de. (36-39%) high toughness para-aramid fibers.
- the heat-resistant high-toughness fiber which is the second aspect of the present invention, has heat resistance that can withstand a use environment of 250 ° C. or higher, and at the same time, has an excellent balance of the combination of breaking strength, knot strength and breaking elongation. Therefore, it can be suitably used in safety ropes, fall prevention materials, and the like.
- the heat-resistant high-toughness fiber of the second embodiment has a metaphenylenediamine and/or isophthaloyl monomer unit mol% of the total of 50 or more and less than 68 mol%, and a paraphenylenediamine and/or terephthaloyl monomer unit mol% of It is preferable that the total is 50 or less and more than 32, the mol% of metaphenylenediamine and/or isophthaloyl monomer units is 55 or more and less than 63, and the mol% of paraphenylenediamine and/or terephthaloyl monomer units is the total is more preferably 45 or less and more than 37, the mol% of metaphenylenediamine and/or isophthaloyl monomer units is 55 or more and less than 60, and the mol% of paraphenylenediamine and/or terephthaloyl monomer units is the total is particularly preferably 45 or less and more than 40.
- the desired knot strength may not be obtained. If the mol % of metaphenylenediamine and/or isophthaloyl monomer units is less than 50, the resulting polymer may not be dissolved in the amide-based solvent described later and may not be spun.
- the knot strength of the heat-resistant high-toughness fiber of the second aspect is 4.4 to 5.6 cN/dtex (42.3% to 50%), preferably 4.9 to 5.6 cN/dtex (45 % to 50%). If the knot strength is less than 4.4 cN/dtex, the intended strength may not be obtained. On the other hand, if the knot strength exceeds 5.6 cN/dtex, the intended breaking elongation may not be obtained.
- the percentage (%) in parentheses for knot strength described herein indicates the ratio of knot strength to breaking strength, and the higher the knot strength ratio, the more flexible and flexible the fiber. Good balance of strength.
- the breaking strength of the heat-resistant high-toughness fiber of the second aspect is 7.0 to 15.0 cN/dtex, and the lower limit is more preferably 8.0 cN/dtex or more. If the breaking strength is less than 7.0 cN/dtex, the desired strength may not be obtained.
- the breaking elongation of the heat-resistant high-toughness fiber of the second aspect is generally 10% to 30%, preferably 15% to 25%, more preferably 20% to 25%. If the elongation at break is less than 10%, it may not be sufficient to achieve the well-balanced physical properties that are the object of the present invention. If the elongation at break exceeds 30%, sufficient strength may not be obtained.
- the melting point of the heat-resistant high-toughness fiber which is the second aspect, is generally 290°C or higher, preferably 300°C or higher. If the melting point is lower than 290°C, the performance as a heat-resistant fiber may not be exhibited.
- the dry heat dimensional change rate at 250° C. is generally preferably less than 2%, more preferably 1.5% or less, further preferably 1.0% or less, 0.5% or less is particularly preferable. If the dry heat dimensional change rate is 2% or more, the performance as a heat-resistant fiber may not be sufficiently exhibited.
- the weight-average molecular weight of the heat-resistant high-toughness fiber which is the second embodiment, is preferably 400,000 to 1,000,000 according to the analysis method described later. If the weight-average molecular weight of the heat-resistant high-toughness fiber is less than 400,000, the breaking strength may be significantly reduced. In addition, when the molecular weight of the heat-resistant and high-toughness fiber exceeds 1,000,000, the wholly aromatic polyamide solution is too viscous to spin out from the spinneret, making it difficult to handle, and special equipment may be required.
- the heat-resistant high-toughness fiber which is the second aspect, can obtain not only strength but also well-balanced physical properties such as excellent knot strength, and has heat resistance and flame retardancy. It can be effectively used for fall prevention materials for falling prevention measures for receiving structures such as earth and sand, snow, etc., and fiber products such as safety ropes and safety nets for ensuring the safety of workers working at heights.
- the heat-resistant high-toughness fiber, which is the second aspect included in the applications such as the fall prevention material, safety rope, and safety net is preferably 30 to 100% by mass, more preferably 50 to 100% by mass. Preferably, 80 to 100% by mass is more preferable, and 100% is most preferable. If the content of the copolymer aramid fiber is less than 50%, the characteristics of the heat-resistant and high-toughness fiber of the present invention may not be exhibited sufficiently.
- the breaking strength is 8.0 cN/dtex or more and less than 15.0 cN/dtex, and the breaking elongation is more than 5.0% and 20.0% or less. and a dry heat dimensional change rate at 300° C. of less than 5%.
- the mol% of meta-phenylenediamine and/or isophthaloyl monomer units is 10 or more and less than 40, and the mol% of paraphenylenediamine and/or terephthaloyl monomer units is 90 or less and more than 60.
- the mol% of meta-phenylenediamine and/or isophthaloyl monomer units is 20 or more and less than 40, and the mol% of paraphenylenediamine and/or terephthaloyl monomer units is 80 or less and more than 60. preferable.
- both meta-phenylenediamine and isophthaloyl monomer units it is the sum of these (meta-phenylenediamine and isophthaloyl monomer units).
- both paraphenylenediamine and terephthaloyl monomer units it is the sum of these (paraphenylenediamine and terephthaloyl monomer units).
- the mol % of meta-phenylenediamine and/or isophthaloyl monomer units is 40 or more, the desired strength and thermal stability may not be achieved. Further, when the mol % of metaphenylenediamine and/or isophthaloyl monomer units is less than 10, the obtained polymer may not be dissolved in the amide-based solvent described later, and may not be spun.
- the breaking strength of the heat-resistant high-toughness fiber of the third aspect is generally 8.0 cN/dtex or more and less than 15.0 cN/dtex, and the lower limit is more preferably 9.0 cN/dtex or more. If the breaking strength is less than 8.0 cN/dtex, the high toughness that is the object of the present invention may be insufficient.
- the elongation at break is generally greater than 5.0% and 20% or less, preferably 7.0% to 15.0%, more preferably 10.0% to 15.0%. If the elongation at break is less than 5.0%, the elongation is not sufficient and the high toughness may not be sufficiently exhibited. On the other hand, when the elongation at break exceeds 20.0%, sufficient strength may not be obtained.
- the dry heat dimensional change at 300° C. of the heat-resistant high-toughness fiber of the third aspect is generally less than 5%, preferably 4% or less. If the dry heat dimensional change rate is 5% or more, the performance as a heat-resistant fiber may not be sufficiently exhibited.
- the fiber contains conductive fine particles, has an electrical resistivity of 10 3 ⁇ cm or less, a breaking strength of 3.5 to 10 cN/dtex, and an elongation at break of of 10 to 30% and a melting point of 290° C. or higher.
- fibers having conductivity can be suitably used in the case of imparting static elimination performance in addition to the effect of imparting conductivity depending on the method of use. Because of these properties, conductive fibers are mainly used as general-purpose fibers and applied to clothing and industrial applications, and are still one of the most important functional fibers today.
- conductive fibers have been disclosed, for example, the fiber surface is plated with a metal to impart conductivity, and the raw material polymer is filled with conductive particles and spun to provide conductivity.
- heat resistance is one of the performances required in material development.
- fibers made of wholly aromatic polyamide sometimes referred to as aramid fibers
- Conductive fibers that have been widely used so far are nylon and acrylic fibers, which may not be suitable for applications that require heat resistance.
- electrical conductivity can be imparted to heat-resistant fibers such as wholly aromatic polyamides, the range of applications can be expected to expand.
- Patent Document 7 JP-A-2-216264 (Patent Document 7) and JP-A-2006-2213 (Patent Document 8), the surface of aramid fiber is coated with copper sulfide or silver to achieve conductivity.
- Patent Document 9 discloses a method of obtaining a conductive para-aramid fiber by adding carbon nanotubes and conductive fine particles other than carbon nanotubes to a spinning solution and spinning. .
- the method of coating the fiber surface to impart conductivity requires surface treatment, which poses a problem in terms of productivity, and in terms of quality, there is a problem in durability due to wear and the like.
- the conductive fine particles are held inside the fiber, so the durability of the conductivity is relatively high, but it leads to the deterioration of the mechanical properties of the fiber.
- the conductive heat-resistant high-toughness fiber of the fourth aspect has heat resistance that can withstand a use environment of 250 ° C.
- the electrical resistivity is 10 3 Since it exhibits a high conductivity of ⁇ cm or less, it can be suitably used, for example, in protective clothing applications that require strength, flexibility, and high electrostatic properties.
- the heat-resistant high-toughness fiber which is the fourth aspect of the present invention, contains 50 or more and less than 70 mol% of meta-phenylenediamine and/or isophthaloyl monomer units, and para-phenylenediamine and/or terephthaloyl monomer units. It is preferable that the mol % of the total is 50 or less and more than 30, the mol % of the meta-phenylenediamine and/or isophthaloyl monomer units is 50 or more and less than 67, and the mol of the para-phenylenediamine and/or terephthaloyl monomer units. % is more preferably 50 or less and more than 33 of the total.
- the mol % of meta-phenylenediamine and/or isophthaloyl monomer units is 70 or more, the desired strength may not be achieved. On the other hand, if the mol % of meta-phenylenediamine and/or isophthaloyl monomer units is less than 50, the resulting polymer may not be dissolved in the amide-based solvent described later and may not be spun.
- the electrical resistivity of the heat-resistant high-toughness fiber of the fourth aspect is generally 10 3 ⁇ cm or less, more preferably 700 ⁇ cm or less, still more preferably 500 ⁇ cm or less, and most preferably 200 ⁇ cm or less.
- the electrical resistivity is preferably as low as possible because sufficient electrostaticity can be obtained, but as described later, it is preferable to adjust it as appropriate in view of the balance with the target strength, elongation, spinnability, and the like.
- the breaking strength of the heat-resistant high-toughness fiber of the fourth aspect is generally 3.5 to 10 cN/dtex, preferably 4.0 to 10.0 cN/dtex, more preferably 4.0 to 7.0 cN/dtex. 0 cN/dtex. If the breaking strength is less than 3.5 cN/dtex, the strength is insufficient for applications such as protective clothing aimed at by the present invention.
- the breaking elongation of the electrically conductive, heat-resistant, high-toughness fiber of the present invention is 10% to 30%, more preferably 10% to 20%. If the elongation at break is less than 10%, the elongation is not sufficient and the flexibility may not be exhibited sufficiently.
- the melting point of the conductive heat-resistant high-toughness fiber of the present invention is generally 290° C. or higher, preferably 300° C. or higher. If the melting point is lower than 290°C, the performance as a heat-resistant fiber may not be sufficiently exhibited.
- the heat-resistant and high-toughness film according to the present invention generally has a breaking strength of 80 to 150 MPa, a breaking elongation of 5 to 30%, a glass transition temperature of 250 ° C. or higher, and a heat resistance at 300 ° C. Shrinkage rate is 5% or less.
- the breaking strength is generally 80-150 MPa, preferably 100-150 MPa. If the breaking strength is less than 80 MPa, the strength for use as a heat-resistant film is insufficient.
- the breaking elongation of the heat-resistant and high-toughness film of the present invention is 5% to 30%, more preferably 5% to 20%. If the elongation at break is less than 5%, the elongation is not sufficient and the flexibility may not be exhibited sufficiently.
- the glass transition temperature is generally 250° C. or higher, preferably 280° C. or higher. If the glass transition temperature is lower than 250°C, the performance as a heat-resistant film may not be sufficiently exhibited.
- the dry heat dimensional change rate at 300° C. is generally 5% or less, preferably 4% or less. When the dry heat dimensional change rate exceeds 5%, the performance as a heat-resistant film may not be sufficiently exhibited.
- the heat-resistant and high-toughness film according to the present invention generally comprises three monomer units selected from the group consisting of meta-phenylenediamine, para-phenylenediamine, isophthaloyl and terephthaloyl, or two monomer units of meta-phenylenediamine and terephthaloyl, or comprising a copolymerized aramid polymer containing two types of monomer units, paraphenylenediamine and isophthaloyl.
- those containing three types of monomer units shown in Examples 1 to 4 and those containing two types of monomer units shown in Examples 6 and 7 are preferred, as shown in Examples 6 and 7.
- Those containing two types of monomeric units may be more preferred.
- the mol% of meta-phenylenediamine and/or isophthaloyl monomer units is 10 or more and less than 60, and the mol% of paraphenylenediamine and/or terephthaloyl monomer units is 90 or less and more than 40. More preferably, the mol% of meta-phenylenediamine and/or isophthaloyl monomer units is 20 or more and less than 60, and the mol% of paraphenylenediamine and/or terephthaloyl monomer units is 80 or less and more than 40. . If the mol % of meta-phenylenediamine and/or isophthaloyl monomer units is 60 or more, the desired strength may not be achieved. On the other hand, when the mol % of metaphenylenediamine and/or isophthaloyl monomer units is less than 10, the resulting polymer may not be dissolved in the amide-based solvent described later, and film formation may not be possible.
- Aromatic diamine components used as raw materials for wholly aromatic polyamides include meta-phenylenediamine, para-phenylenediamine, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, etc., and halogen, carbon Derivatives having substituents such as alkyl groups with numbers 1 to 3 can be exemplified.
- Examples of raw materials for the aromatic dicarboxylic acid component that constitutes the wholly aromatic polyamide of the present invention include aromatic dicarboxylic acid halides.
- Examples of 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. can be done.
- para-type aromatic dicarboxylic acid halides include terephthalic acid halides such as terephthalic acid chloride and terephthalic acid bromide, and derivatives having substituents such as halogens and alkoxy groups having 1 to 3 carbon atoms on the aromatic ring thereof. can be exemplified.
- Polymerization methods for the wholly aromatic polyamides of the present invention include organic solvent systems (e.g., tetrahydrofuran) that are not good solvents for the resulting polyamides, including metaphenylenediamine and isophthalic chloride, and inorganic acid acceptors and soluble neutral salts.
- organic solvent systems e.g., tetrahydrofuran
- a method of neutralizing with calcium hydroxide, calcium oxide, etc. solution polymerization, JP-A-8-074121, JP-A-10-88421), etc., but not limited thereto. do not have.
- the weight-average molecular weight of the wholly aromatic polyamide copolymer (also referred to as a copolymerized aramid polymer) used in the present invention is 400,000 according to the analysis method described later, from the viewpoint of being able to form a fiber having a breaking strength that can withstand practical use. ⁇ 1 million is preferred. If the weight-average molecular weight is less than 400,000, not only is the strength at break remarkably reduced, but also stable spinning may not be possible. Further, when the molecular weight exceeds 1,000,000, when preparing and spinning the wholly aromatic polyamide solution to be described later, the viscosity is too high and handling is difficult, sometimes requiring dedicated equipment.
- a mixture of a low-molecular-weight polymer and a high-molecular-weight polymer can be used as the polymer within the molecular weight range defined in the present invention, and the total molecular weight may be within the molecular weight range defined by adjusting the mixing ratio. For example, when a polymer having a weight average molecular weight of 200,000 and a polymer having a weight average molecular weight of 800,000 are mixed, and the weight average molecular weight of the mixed polymer is 600,000, such a mixture is There is no problem in using .
- the wholly aromatic polyamide fiber of the present invention uses the wholly aromatic polyamide obtained by the above-described production method, and undergoes the following steps of spinning solution preparation, spinning and coagulation, washing, boiling water drawing, and dry heat treatment. , manufactured through a hot drawing process.
- spinning solution preparation step In the spinning solution preparation step, the wholly aromatic polyamide of the present invention is dissolved in a solvent to prepare a spinning solution (also called dope or spinning dope).
- a spinning solution also called dope or spinning dope.
- an amide-based solvent is usually used, and examples thereof include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and dimethylacetamide (DMAc). Among these, it is preferable to use NMP or DMAc from the viewpoint of solubility and handling safety.
- Concentrated sulfuric acid can also be used as a solvent in the present invention. When concentrated sulfuric acid is used, the concentration is preferably 95% or higher, more preferably 98% or higher. When concentrated sulfuric acid is used, air-gap spinning using water can also be performed in the coagulation step, which will be described later.
- the solution concentration an appropriate concentration may be appropriately selected from the viewpoint of the solidification rate and polymer solubility in the subsequent spinning and solidification process, and is usually in the range of 5 to 30% by mass. is necessary.
- the solution concentration is preferably in the range of 10 to 30% by mass, more preferably 15 to 25% by mass in order to achieve stable spinning. is more preferable.
- the solution concentration is preferably in the range of 5 to 25% by mass, and in order to achieve stable spinning, it is preferably in the range of 7 to 20% by mass. more preferred.
- the heat-resistant high-toughness fiber which is the fourth aspect of the present invention
- Such addition amount is more preferably 10 to 35% by mass, more preferably 20 to 30% by mass. If the concentration of the conductive fine particles is less than 6% by mass, the desired conductivity cannot be exhibited, and if it exceeds 40% by mass, the desired strength may not be obtained.
- the conductive fine particles are metal fine particles, metal oxides, carbon black (also referred to as conductive carbon black), and the like, which themselves exhibit conductive performance, unless they inhibit fiber formation.
- conductive carbon black is preferred in the present invention from the standpoint of manufacturing technology.
- the conductive carbon black preferably has a surface specific resistance of 10 to 10 8 ⁇ , more preferably 10 2 to 10 6 ⁇ , and more preferably 10 3 to 10 ⁇ when measured at a temperature of 20°C and a humidity of 65%. 10 5 ⁇ is more preferred. If the surface resistivity of the conductive carbon black is within the above range, it is preferable for obtaining a conductive heat-resistant high-toughness fiber having electrical resistivity, which is the object of the present invention.
- the surface specific resistance ( ⁇ ) of conductive carbon black is obtained by adding 25% of conductive carbon black to the polymer solution obtained in Example 10 below, and applying it on a glass cloth with a 3 ml applicator. After that, it is washed with water and dried, and heat-treated in an electric furnace at 330° C. for 2 minutes to obtain a test piece, and the surface specific resistance is measured with Hiresta UP (manufactured by Mitsubishi Chemical Co., Ltd.).
- the particle size of the conductive carbon black is not particularly problematic as long as it is sufficiently small relative to the cross section of the fiber, but the particle size is preferably in the range of 5 to 500 nm, more preferably in the range of 10 to 50 nm. is more preferred. If the particle size is larger than 500 nm, the fiber strength is lowered, and if the particle size is less than 5 nm, the dispersibility deteriorates due to self-aggregation.
- an inorganic salt may be introduced into the dope, preferably 0 to 20% by mass of the inorganic salt relative to the dope, and 0 to 10% by mass of the inorganic salt to obtain stable spinnability. is more preferred.
- chloride salts such as calcium chloride, magnesium chloride and lithium chloride are preferably used.
- the dope obtained above is spun into a coagulating liquid and coagulated.
- the spinning device is not particularly limited, and a conventionally known wet spinning device can be used.
- the number of spinning holes in the spinneret, the diameter of the spinning holes, the state of arrangement, etc. of the spinneret are not particularly limited as long as they can be stably wet-spun.
- a multi-hole spinneret for 0.2 mm staple fibers or the like can be used.
- the temperature of the dope during spinning from the spinneret is preferably 20 to 90°C, more preferably 70 to 90°C.
- the coagulation bath used to obtain the fiber of the present invention is an aqueous solution containing 1 to 20% by mass, preferably 3 to 15% by mass, of an amide solvent. The temperature of this aqueous solution is preferably in the range of 50-90°C. Further, when concentrated sulfuric acid is used as a solvent in the spinning solution preparation step, water can be used as the coagulation bath.
- the coagulation bath may contain an inorganic salt such as calcium chloride or magnesium chloride in an amount of preferably 30% by mass or more, more preferably 35 to 45% by mass.
- an inorganic salt such as calcium chloride or magnesium chloride in an amount of preferably 30% by mass or more, more preferably 35 to 45% by mass.
- the obtained coagulated yarn is thoroughly washed in an aqueous washing bath and sent to a boiling water drawing step.
- the draw ratio in the boiling water drawing bath should be in the range of 1.1 to 5.0 times, more preferably in the range of 1.1 to 3.0 times.
- the strength of the finally obtained fiber can be ensured by performing the drawing within the range of the draw ratio and increasing the molecular chain orientation.
- a dry heat treatment step is preferably performed on the fibers that have undergone the washing and drawing steps.
- the fibers that have been washed in the above washing step are subjected to a dry heat treatment at 100 to 250°C.
- Dry heat treatment is preferably carried out in the range of 100 to 200°C.
- the temperature of the dry heat treatment mentioned above refers to the set temperature of fiber heating means such as a hot plate and a heating roller.
- the fiber subjected to the dry heat treatment is subjected to a hot drawing process.
- the hot-stretching step stretching is performed while heat-treating in the range of 290 to 380°C.
- the treatment temperature is preferably in the range of 290-350°C. If the temperature is less than 290°C, high-ratio drawing cannot be performed, and if it exceeds 380°C, discoloration or breakage of the fiber may occur.
- the draw ratio should be in the range of 2.0 to 10.0 times, preferably 3.0 to 10.0 times.
- the temperature of the hot drawing treatment refers to the set temperature of fiber heating means such as a hot plate and a heating roller.
- the above-described washing process, boiling water drawing process, and hot drawing process are generally common to both the amide system and the sulfuric acid system.
- the total draw ratio of the boiling water draw ratio and the hot draw ratio in the present invention is generally preferably 5 to 7 times or more. If the total draw ratio is less than 5 times, the target strength and/or conductivity may not be achieved. A person skilled in the art can appropriately adjust the boiling water draw ratio and the hot draw ratio in consideration of the condition of the process.
- the heat-resistant and high-toughness film of the present invention is prepared by adding the undiluted polymer solution containing the copolymerized wholly aromatic polyamide obtained by the above-described production method into a solvent such as alcohol or water, reprecipitating and separating the mixture, It can be dissolved again in a solvent and used for forming a film. Further, it is preferable to use the undiluted polymer solution as it is or after adjusting the concentration appropriately after polymerization for film formation. The concentration at this time can be adjusted by concentration or dilution with a solvent. As such a solvent, the same ones as those exemplified as the polymerization solvent can be used. Moreover, it is preferable that the film is produced by a solution film-forming method.
- the solution film-forming method includes a dry-wet method, a dry method, a wet method, and the like, and the dry-wet method and the dry method are preferable in that a film having good surface properties can be obtained.
- the undiluted solution is extruded directly from the spinneret into the film-forming bath, or once extruded onto a support such as a drum and introduced into the wet bath together with the support. is preferred.
- This bath generally consists of an aqueous medium, and may contain an organic solvent, an inorganic salt, and the like in addition to water. Salts and organic solvents contained in the film can be extracted by passing it through a wet bath.
- the time for passing through these wet baths depends on the thickness of the film, it is preferably 10 seconds to 30 minutes.
- the polymer exiting the wet bath may be stretched longitudinally, then dried, stretched transversely and heat treated. In that case, these treatments are generally at 100 to 500° C. and preferably for a total time of 1 second to 30 minutes.
- the undiluted solution is extruded from a die onto a support such as a drum or an endless belt to form a thin film, and then the solvent is scattered from the thin film layer and dried until the thin film has self-retaining properties. Drying conditions are preferably room temperature to 300° C. and within 60 minutes.
- the film is peeled off from the support and introduced into the wet process, where desalting, solvent removal, etc. are performed in the same manner as in the above wet process.
- further stretching, drying and heat treatment may be performed.
- the film is dried on a drum, endless belt, or the like, and the self-retaining film is peeled off from the support.
- drying, stretching, and heat treatment may be performed to remove the residual solvent. These treatments are preferably carried out at 100 to 500° C. for 1 second to 30 minutes in total.
- D is the value obtained by directly converting the total fineness value (dtex) into mass
- S D / (1000000 xd). The number of repeated measurements at this time was 5, and the average value was taken as the electrical resistivity.
- melting point of fiber The melting point of the fiber was determined by thermomechanical analysis according to JIS-K-7197. The melting point was defined as the apex temperature of the peak detected on the high temperature side or the temperature at which peak detection became impossible due to dissolution of the fiber.
- Example 1 Copolymerized aramid polymer containing 67 mol% of meta-phenylenediamine and isophthaloyl monomer units and 33 mol% of para-phenylenediamine and terephthaloyl monomer units by interfacial polymerization according to JP-B-47-10863. A powder was synthesized. At this time, both isophthaloyl chloride and terephthaloyl chloride were used as acid chloride monomers so that the mass ratio was 2:1. Both meta-phenylenediamine and para-phenylenediamine were used as amine monomers so that the mass ratio was 2:1. The weight average molecular weight was 800,000.
- the polymer powder and calcium chloride were dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a clear polymer solution.
- NMP N-methyl-2-pyrrolidone
- the polymer solution was adjusted so that the mass concentration of the copolymerized aramid polymer was 16% and the mass concentration of calcium chloride was 3%.
- This polymer solution was heated to 85°C and spun as a spinning dope through a spinneret with a hole diameter of 0.1 mm and 100 circular ejection holes into a coagulation bath at 85°C.
- the composition of this coagulation bath is 44% by mass of calcium chloride, 3% by mass of NMP, and 53% by mass of the remaining water. After that, it was temporarily pulled out into the air.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 2.4 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the resulting fiber had a fineness of 1.3 dtex, a breaking strength of 10.4 cN/dtex, a breaking elongation of 23%, a melting point of 307°C, and a dry heat dimensional change at 250°C of 1.00%.
- Example 2 By interfacial polymerization according to Example 1, a copolymerized aramid polymer powder containing 60 mol% of meta-phenylenediamine and isophthaloyl monomer units and 40 mol% of para-phenylenediamine and terephthaloyl monomer units was synthesized. . At this time, both isophthaloyl chloride and terephthaloyl chloride were used as acid chloride monomers so that the mass ratio was 3:2. As amine monomers, both meta-phenylenediamine and para-phenylenediamine were used so that the mass ratio was 3:2. The weight average molecular weight was 640,000.
- the polymer powder and calcium chloride were dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a clear polymer solution.
- NMP N-methyl-2-pyrrolidone
- the polymer solution was adjusted so that the mass concentration of the copolymerized aramid polymer was 16% and the mass concentration of calcium chloride was 3%.
- This polymer solution was heated to 85°C and spun as a spinning dope through a spinneret with a hole diameter of 0.1 mm and 100 circular ejection holes into a coagulation bath at 85°C.
- the composition of this coagulation bath is 44% by mass of calcium chloride, 3% by mass of NMP, and 53% by mass of the remaining water. After that, it was temporarily pulled out into the air.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 2.5 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the resulting fiber had a fineness of 1.8 dtex, a breaking strength of 9.2 cN/dtex, a breaking elongation of 22%, a melting point of 319°C, and a dry heat dimensional change at 250°C of 0.70%.
- Example 3 By interfacial polymerization according to Example 1, a copolymerized aramid polymer powder containing 56 mol% of meta-phenylenediamine and isophthaloyl monomer units and 44 mol% of para-phenylenediamine and terephthaloyl monomer units of the total was synthesized. . At this time, both isophthaloyl chloride and terephthaloyl chloride were used as acid chloride monomers so that the mass ratio was 5:4. Both meta-phenylenediamine and para-phenylenediamine were used as amine monomers, and the mass ratio was adjusted to 5:4. The weight average molecular weight was 450,000.
- the polymer powder and calcium chloride were dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a clear polymer solution.
- NMP N-methyl-2-pyrrolidone
- the polymer solution was adjusted so that the mass concentration of the copolymerized aramid polymer was 20% and the mass concentration of calcium chloride was 2%.
- This polymer solution was heated to 85°C and spun as a spinning dope through a spinneret with a hole diameter of 0.1 mm and 100 circular ejection holes into a coagulation bath at 85°C.
- the composition of this coagulation bath is 44% by mass of calcium chloride, 3% by mass of NMP, and 53% by mass of the remaining water. After that, it was temporarily pulled out into the air.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 2.4 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the resulting fiber had a fineness of 1.54 dtex, a breaking strength of 11.1 cN/dtex, a breaking elongation of 24%, a melting point of 313°C, and a dry heat dimensional change at 250°C of 0.30%.
- the polymer powder and calcium chloride were dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a clear polymer solution.
- NMP N-methyl-2-pyrrolidone
- the polymer solution was adjusted so that the mass concentration of the copolymerized aramid polymer was 21% and the mass concentration of calcium chloride was 3%.
- This polymer solution was spun under the conditions of Example 1 to obtain a wholly aromatic polyamide fiber.
- the boiling water draw ratio was 2.4 times and the hot plate draw ratio was 3.0 times.
- the resulting fiber had a fineness of 1.7 dtex, a breaking strength of 4.6 cN/dtex, a breaking elongation of 33%, a melting point of 333°C, and a dry heat dimensional change at 250°C of 0.87%.
- Example 4 Copolymerized aramid polymer containing 67 mol% of meta-phenylenediamine and isophthaloyl monomer units and 33 mol% of para-phenylenediamine and terephthaloyl monomer units by interfacial polymerization according to JP-B-47-10863. A powder was synthesized. At this time, both isophthaloyl chloride and terephthaloyl chloride were used as acid chloride monomers so that the mass ratio was 2:1. Both meta-phenylenediamine and para-phenylenediamine were used as amine monomers so that the mass ratio was 2:1. The weight average molecular weight was 800,000.
- the polymer powder and calcium chloride were dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a clear polymer solution.
- NMP N-methyl-2-pyrrolidone
- the polymer solution was adjusted so that the mass concentration of the copolymerized aramid polymer was 16% and the mass concentration of calcium chloride was 3%.
- This polymer solution was heated to 85°C and spun as a spinning dope through a spinneret with a hole diameter of 0.1 mm and 100 circular ejection holes into a coagulation bath at 85°C.
- the composition of this coagulation bath is 44% by mass of calcium chloride, 3% by mass of NMP, and 53% by mass of the remaining water. After that, it was temporarily pulled out into the air.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 2.4 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the resulting fiber has a weight average molecular weight of 800,000, a fineness of 1.3 dtex, a breaking strength of 10.4 cN/dtex, a knot strength of 4.4 cN/dtex, a breaking elongation of 23%, a melting point of 307°C, and a dry heat dimension at 250°C.
- the rate of change was 1.00%.
- Example 5 Copolymerized aramid polymer powder containing 56 mol% of meta-phenylenediamine and isophthaloyl monomer units and 44 mol% of para-phenylenediamine and terephthaloyl monomer units by interfacial polymerization according to JP-B-47-10863. was synthesized. At this time, both isophthaloyl chloride and terephthaloyl chloride were used as acid chloride monomers so that the mass ratio was 5:4. Both meta-phenylenediamine and para-phenylenediamine were used as amine monomers, and the mass ratio was adjusted to 5:4. The weight average molecular weight was 450,000.
- the polymer powder and calcium chloride were dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a clear polymer solution.
- NMP N-methyl-2-pyrrolidone
- the polymer solution was adjusted so that the mass concentration of the copolymerized aramid polymer was 20% and the mass concentration of calcium chloride was 2%.
- This polymer solution was heated to 85°C and spun as a spinning dope through a spinneret with a hole diameter of 0.1 mm and 100 circular ejection holes into a coagulation bath at 85°C.
- the composition of this coagulation bath is 44% by mass of calcium chloride, 3% by mass of NMP, and 53% by mass of the remaining water. After that, it was temporarily pulled out into the air.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 2.4 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the resulting fiber has a weight average molecular weight of 450,000, a fineness of 1.54 dtex, a breaking strength of 11.1 cN/dtex, a knot strength of 4.9 cN/dtex (45%), a breaking elongation of 24%, and a melting point of 313°C and 250°C.
- the dry heat dimensional change rate at was 0.30%.
- Example 6 Copolymerized aramid polymer powder containing 50 mol % of meta-phenylenediamine and isophthaloyl monomer units and 50 mol % of para-phenylenediamine and terephthaloyl monomer units by interfacial polymerization according to JP-B-47-10863. was synthesized. At this time, both isophthaloyl chloride and terephthaloyl chloride were used as acid chloride monomers so that the mass ratio was 1:1. Both meta-phenylenediamine and para-phenylenediamine were used as amine monomers so that the mass ratio was 1:1. The weight average molecular weight was 640,000.
- the polymer powder and calcium chloride were dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a clear polymer solution.
- NMP N-methyl-2-pyrrolidone
- the polymer solution was adjusted so that the mass concentration of the copolymerized aramid polymer was 16% and the mass concentration of calcium chloride was 3%.
- This polymer solution was heated to 85°C and spun as a spinning dope through a spinneret with a hole diameter of 0.1 mm and 100 circular ejection holes into a coagulation bath at 85°C.
- the composition of this coagulation bath is 44% by mass of calcium chloride, 3% by mass of NMP, and 53% by mass of the remaining water. After that, it was temporarily pulled out into the air.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 2.5 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the resulting fiber has a weight average molecular weight of 640,000, a fineness of 1.8 dtex, a breaking strength of 11.8 cN/dtex, a knot strength of 5.6 cN/dtex (48%), a breaking elongation of 22%, and a melting point of 301°C and 250°C.
- the dry heat dimensional change rate at was 0.70%.
- Example 7 After dissolving the amine monomer in NMP, the solution was cooled to 0° C., and the acid chloride monomer was added while stirring with a mechanical stirrer. At this time, adjustments were made so that the meta-phenylenediamine unit was 29 mol% of the total, the para-phenylenediamine and terephthaloyl monomer units were 71 mol%, and the mass concentration of the polymer after polymerization was 10.7% with respect to the entire solution. . In addition, terephthalic acid chloride was used as the acid chloride monomer, and both meta-phenylenediamine and para-phenylenediamine were used as the amine monomers in a weight ratio of 4:3.
- This polymer solution was heated to 85°C and spun as a spinning dope through a spinneret with a hole diameter of 0.1 mm and 100 circular ejection holes into a coagulation bath at 85°C.
- the composition of this coagulation bath is 43% by mass of calcium chloride, 10% by mass of NMP, and 47% by mass of the remaining water. After cooling, it was once pulled out in the air to obtain a coagulated filament.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 2.0 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the resulting fiber had a fineness of 1.3 dtex, a breaking strength of 10.5 cN/dtex, a breaking elongation of 15.0%, and a dry heat dimensional change rate at 300°C of 2.0%.
- Example 8 By solution polymerization according to Example 7, a polymer solution containing a copolymerized aramid polymer containing 33 mol % of meta-phenylenediamine units and 67 mol % of para-phenylenediamine and terephthaloyl monomer units was synthesized. At this time, terephthaloyl chloride was used as the acid chloride monomer. Both meta-phenylenediamine and para-phenylenediamine were used as amine monomers so that the mass ratio was 2:1. The weight average molecular weight was 620,000. This polymer solution was heated to 85° C. and spun into a coagulation bath at 85° C.
- This coagulation bath is 45% by mass of calcium chloride, 12% by mass of NMP, and 43% by mass of the remaining water. After cooling, it was once pulled out in the air to obtain a coagulated filament.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 2.0 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the obtained fiber had a fineness of 1.5 dtex, a breaking strength of 10.6 cN/dtex, a breaking elongation of 13.0%, and a dry heat dimensional change rate at 300° C. of 2.1%.
- Example 9 By solution polymerization according to Example 7, a polymer solution containing a copolymerized aramid polymer containing 25 mol % of meta-phenylenediamine units and 75 mol % of para-phenylenediamine and terephthaloyl monomer units was synthesized. At this time, terephthaloyl chloride was used as the acid chloride monomer. Both meta-phenylenediamine and para-phenylenediamine were used as amine monomers so that the mass ratio was 1:1. The weight average molecular weight was 580,000. This polymer solution was heated to 85° C. and spun into a coagulation bath at 85° C.
- the composition of this coagulation bath is 40% by mass of calcium chloride, 10% by mass of NMP, and 50% by mass of the remaining water. After that, it was temporarily pulled out into the air.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 2.3 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the resulting fiber had a fineness of 1.5 dtex, a breaking strength of 12.0 cN/dtex, a breaking elongation of 13.0%, and a dry heat dimensional change rate at 300° C. of 1.9%.
- the composition of this coagulation bath is 40% by mass of calcium chloride, 10% by mass of NMP, and 50% by mass of the remaining water. After that, it was temporarily pulled out into the air.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 2.3 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the resulting fiber had a fineness of 2.0 dtex, a breaking strength of 6.3 cN/dtex, a breaking elongation of 12.0%, and a dry heat dimensional change rate at 300°C of 15%.
- Example 10 Copolymerized aramid polymer containing 67 mol% of meta-phenylenediamine and isophthaloyl monomer units and 33 mol% of para-phenylenediamine and terephthaloyl monomer units by interfacial polymerization according to JP-B-47-10863. A powder was synthesized. At this time, both isophthaloyl chloride and terephthaloyl chloride were used as acid chloride monomers so that the mass ratio was 2:1. Both meta-phenylenediamine and para-phenylenediamine were used as amine monomers so that the mass ratio was 2:1. The weight average molecular weight was 660,000.
- This polymer powder and conductive carbon black particles were dissolved and dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a polymer solution.
- NMP N-methyl-2-pyrrolidone
- the mass concentration of the copolymerized aramid polymer was adjusted to 16% relative to the polymer solution, and the conductive carbon black was adjusted to 30% by mass relative to the aramid polymer.
- This polymer solution was heated to 85°C and spun as a spinning dope through a spinneret with a hole diameter of 0.1 mm and 100 circular ejection holes into a coagulation bath at 85°C.
- the composition of this coagulation bath is 43% by mass of calcium chloride, 4% by mass of NMP, and 53% by mass of the remaining water. After that, it was temporarily pulled out into the air.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 1.4 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the obtained fiber had a fineness of 2.0 dtex, a breaking strength of 4.9 cN/dtex, a breaking elongation of 14%, a melting point of 301° C., and an electric resistivity of 61.1 ⁇ cm.
- Example 11 Copolymerized aramid polymer powder containing 60 mol % of meta-phenylenediamine and isophthaloyl monomer units and 40 mol % of para-phenylenediamine and terephthaloyl monomer units by interfacial polymerization according to JP-B-47-10863. was synthesized. At this time, both isophthaloyl chloride and terephthaloyl chloride were used as acid chloride monomers so that the mass ratio was 3:2. As amine monomers, both meta-phenylenediamine and para-phenylenediamine were used so that the mass ratio was 3:2. The weight average molecular weight was 650,000.
- This polymer powder and conductive carbon black particles were dissolved and dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a polymer solution.
- NMP N-methyl-2-pyrrolidone
- the mass concentration of the copolymerized aramid polymer was adjusted to 18% relative to the polymer solution, and the conductive carbon black was adjusted to 25% relative to the aramid polymer.
- This polymer solution was heated to 85°C and spun as a spinning dope through a spinneret with a hole diameter of 0.1 mm and 100 circular ejection holes into a coagulation bath at 88°C.
- the composition of this coagulation bath is 44% by mass of calcium chloride, 2% by mass of NMP, and 54% by mass of the remaining water. After that, it was temporarily pulled out into the air.
- the coagulated threads were washed with water in the first and second water washing baths, and the total immersion time at this time was 200 seconds.
- the first and second aqueous washing bath temperatures used were 20° C. and 30° C., respectively.
- the washed yarn was stretched 2.5 times in boiling water at 90°C, then immersed in hot water at 90°C for 40 seconds and washed.
- the resulting fiber had a fineness of 1.7 dtex, a breaking strength of 5.2 cN/dtex, a breaking elongation of 16%, a melting point of 306° C. and an electrical resistivity of 171 ⁇ cm.
- This polymer powder and conductive carbon black particles were dissolved and dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a polymer solution.
- NMP N-methyl-2-pyrrolidone
- the mass concentration of the copolymerized aramid polymer was adjusted to 18% relative to the polymer solution, and the conductive carbon black was adjusted to 25% relative to the aramid polymer.
- This polymer solution was spun under the conditions of Example 10 to obtain a wholly aromatic polyamide fiber.
- the drawing ratio of boiling water was limited to 3.0 times, and the drawing ratio of the hot plate was limited to 1.3 times.
- the resulting fiber had a fineness of 1.9 dtex, a breaking strength of 4.9 cN/dtex, a breaking elongation of 17% and a melting point of 340°C. Since the total stretch ratio was not sufficiently obtained as described above, the electrical resistivity showed a high value of 7.98 ⁇ 10 6 ⁇ cm.
- This polymer powder and conductive carbon black particles were dissolved and dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a polymer solution.
- NMP N-methyl-2-pyrrolidone
- the mass concentration of the copolymerized aramid polymer was adjusted to 21% relative to the polymer solution, and the conductive carbon black was adjusted to 5% relative to the aramid polymer.
- This polymer solution was spun under the conditions of Example 10 to obtain a wholly aromatic polyamide fiber.
- the boiling water draw ratio was 2.5 times, and the hot plate draw ratio was 3.2 times.
- the resulting fiber had a fineness of 1.7 dtex, a breaking strength of 6.4 cN/dtex, a breaking elongation of 21%, a melting point of 304° C. and an electric resistivity of 2.69 ⁇ 10 6 ⁇ cm.
- This polymer powder and conductive carbon black particles (surface resistivity is 10 4 ⁇ ) were dissolved and dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a polymer solution.
- NMP N-methyl-2-pyrrolidone
- the mass concentration of the copolymerized aramid polymer was adjusted to 16% with respect to the polymer solution, and the conductive carbon black was adjusted to 45% with respect to the aramid polymer.
- Example 10 This polymer solution was spun under the conditions of Example 10 to obtain a wholly aromatic polyamide fiber. At this time, the boiling water draw ratio was limited to 1.1 times, and the hot plate draw ratio was limited to 2.5 times. The resulting fiber had a fineness of 7.0 dtex, a breaking strength of 1.9 cN/dtex, a breaking elongation of 13%, a melting point of 313° C. and an electrical resistivity of 8.5 ⁇ cm. Table 5 shows the physical properties of the fibers obtained in Examples 10-11 and Comparative Examples 12-15.
- Example 12 A copolymerized aramid polymer powder containing 56 mol % of metaphenylene isophthalamide units and 44 mol % of paraphenylene terephthalamide units was synthesized by interfacial polymerization according to JP-B-47-10863. At this time, both isophthaloyl chloride and terephthaloyl chloride were used as acid chloride monomers so that the mass ratio was 5:4. Both meta-phenylenediamine and para-phenylenediamine were used as amine monomers, and the mass ratio was adjusted to 5:4. The weight average molecular weight was 470,000. This polymer powder was dissolved in 99.8% sulfuric acid to obtain a clear polymer solution. At this time, the mass concentration of the copolymerized aramid polymer was adjusted to 18% with respect to the polymer solution.
- This polymer solution is heated to 60° C. to prepare a spinning stock solution, which is passed through a spinneret heated to 70° C. and having a hole diameter of 0.08 mm and 100 circular discharge holes, and is immersed in water at 5° C. through an air gap length of 8 mm. It was discharged and spun.
- the yarn was passed through an immersion length (effective coagulation bath length) of 5 cm at a yarn speed of 30 m/min, and then pulled out into the air.
- the coagulated threads were washed in the first to third water washing baths, and the total immersion time was 30 seconds.
- the temperatures of the first to third aqueous washing baths were 20°C, 30°C and 60°C, respectively.
- the washed yarn was stretched 1.2 times in boiling water at 90°C.
- the resulting fiber had a fineness of 1.2 dtex, a breaking strength of 10.1 cN/dtex, a breaking elongation of 19%, a melting point of 310°C, and a dry heat dimensional change at 250°C of 0.5%.
- Example 13 By solution polymerization according to Example 7, a polymer solution containing a copolymerized aramid polymer containing 50 mol % of metaphenylenediamine units and 50 mol % of terephthaloyl monomer units was synthesized. At this time, terephthaloyl chloride was used as the acid chloride monomer. Metaphenylenediamine was used as the amine monomer. The weight average molecular weight was 560,000. This polymer solution was placed on a glass plate and thinned by a doctor blade method. It was then dried at 100° C. for 5 minutes and introduced into a water bath to remove the solvent. Then, it was dried at 100° C.
- the obtained film had a film thickness of 15 ⁇ m, a breaking strength of 130 MPa, a breaking elongation of 17.0%, a glass transition temperature of 320° C., and a dry heat dimensional change at 300° C. of 0.5%.
- Example 14 By solution polymerization according to Example 7, a polymer solution containing a copolymerized aramid polymer containing 25 mol % of meta-phenylenediamine units and 75 mol % of para-phenylenediamine and terephthaloyl monomer units was synthesized. At this time, terephthaloyl chloride was used as the acid chloride monomer. Both meta-phenylenediamine and para-phenylenediamine were used as amine monomers so that the mass ratio was 1:1. The weight average molecular weight was 580,000. This polymer solution was formed into a film by the same method as in Example 13 to obtain a copolymer aramid film.
- the resulting film had a film thickness of 15 ⁇ m, a breaking strength of 120 MPa, a breaking elongation of 6.0%, a glass transition temperature of 280° C., and a dry heat dimensional change at 300° C. of 3.0%.
- Comparative Example 16 The polymer solution synthesized in Comparative Example 8 was formed into a film in the same manner as in Example 13 to obtain a copolymer aramid film.
- the resulting film had a film thickness of 15 ⁇ m, a breaking strength of 50 MPa, a breaking elongation of 13%, a glass transition temperature of 260° C., and a dry heat dimensional change at 300° C. of 5.8%.
- the heat-resistant and high-toughness fiber according to the present invention has an excellent balance of strength, elongation, and heat-resistant physical properties. It can be suitably used for applications that compensate for mechanical properties. In addition, it can be applied to a new heat-resistant and high-toughness material that has appropriate strength and flexibility in reinforcing material applications, such as a material in the field of rubber reinforcement that requires a lot of deformation and strength. Furthermore, it can be applied to a new heat-resistant and high-toughness material that has appropriate strength and flexibility for use as a fall prevention material, such as a material for safety ropes that are deformed frequently and require strength.
- the fiber of the present invention can maintain high conductivity and electrostatic properties even in high temperature environments. It is also useful as a reinforcing fiber for resin structural materials exposed to the environment. Furthermore, the heat-resistant and high-toughness film according to the present invention has an excellent balance of physical properties such as strength, elongation, glass transition temperature, and heat shrinkage, so it is particularly useful in applications that require strength and elongation in a high temperature range. is.
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Abstract
Description
したがって、アラミド繊維相当の耐熱性を有しながらも、強度と伸度のバランスがとれた合成繊維を得ることは有用であるが、従来技術では得られていなかった。
1.破断強度が3.5~15cN/dtexであり、破断伸度が5~30%であり、かつ、融点が290℃以上であることを特徴とする耐熱性高タフネス繊維、
2.前記耐熱性高タフネス繊維が、メタフェニレンジアミン、パラフェニレンジアミン、イソフタロイルおよびテレフタロイルからなる群から選ばれる少なくとも3種のモノマー単位を含む共重合アラミド重合体を含んでなる、上記1に記載の耐熱性高タフネス繊維、
3.前記メタフェニレンジアミンおよび/または前記イソフタロイルモノマー単位と、前記パラフェニレンジアミンおよび/または前記テレフタロイルモノマー単位とのモル比率が10以上70未満:90以下30超の範囲にある、上記2に記載の耐熱性高タフネス繊維、
4.前記破断強度が7~15cN/dtexであり、前記破断伸度が10~30%であり、かつ、250℃における乾熱寸法変化率が2%未満である、上記1~3のいずれか一項に記載の耐熱性高タフネス繊維、
5.さらに結節強度が4.4~5.6cN/dtexである、上記4に記載の耐熱性高タフネス繊維、
6.前記メタフェニレンジアミンおよび/または前記イソフタロイルモノマー単位と、前記パラフェニレンジアミンおよび/または前記テレフタロイルモノマー単位とのモル比率が40以上70未満:60以下30超の範囲にある、上記4または5に記載の耐熱性高タフネス繊維、
7.前記破断強度が8.0cN/dtex以上15.0cN/dtex未満であり、前記破断伸度が5.0%より大きく20.0%以下であり、かつ、300℃における乾熱寸法変化率が5%未満である、上記1~3のいずれか一項に記載の耐熱性高タフネス繊維、
8.前記メタフェニレンジアミンおよび/または前記イソフタロイルモノマー単位と、前記パラフェニレンジアミンおよび/または前記テレフタロイルモノマー単位とのモル比率が10以上40未満:90以下60超の範囲にある、上記7に記載の耐熱性高タフネス繊維、
9.繊維中に導電性微粒子を含み、電気抵抗率が103Ωcm以下であり、かつ、前記破断強度が3.5~10cN/dtexである、上記1~3のいずれか一項に記載の耐熱性高タフネス繊維、
10.前記導電性微粒子を6~40質量%含む、上記9に記載の耐熱性高タフネス繊維、
11.前記導電性微粒子が導電性カーボンブラックである、上記9または10に記載の耐熱性高タフネス繊維、
12.前記メタフェニレンジアミンおよび/または前記イソフタロイルモノマー単位と、前記パラフェニレンジアミンおよび/または前記テレフタロイルモノマー単位とのモル比率が50以上70未満:50以下30超の範囲にある、上記9~11のいずれか一項に記載の耐熱性高タフネス繊維、
13.耐熱性高タフネス繊維の製造方法であって、下記の工程(1)~(6):
(1)メタフェニレンジアミン、パラフェニレンジアミン、イソフタロイルおよびテレフタロイルからなる群から選ばれる少なくとも3種のモノマー単位を含んでなる共重合アラミド重合体であって、該メタフェニレンジアミンおよび/または該イソフタロイルモノマー単位と、該パラフェニレンジアミンおよび/または該テレフタロイルモノマー単位とのモル比率が10以上70未満:90以下30超の範囲にあり、かつ、重量平均分子量が40万~100万である共重合アラミド重合体を用意し、
(2)該共重合アラミド重合体を溶媒に溶解させて紡糸用ドープを調製し、
(3)該紡糸用ドープを紡糸口金に通し、凝固浴中に紡出して凝固糸を得、
(4)該凝固糸を水性洗浄浴で水洗し、引き続き沸水延伸浴中で1.1~5.0倍の範囲で延伸して繊維を得、
(5)該繊維に100~250℃の範囲で乾熱処理を施し、そして
(6)該乾熱処理後の繊維に、290~380℃の範囲で熱処理を加えながら、延伸倍率2.0~10.0倍の範囲で熱延伸を施す
ことを特徴とする耐熱性高タフネス繊維の製造方法、
14.前記紡糸用ドープが、前記共重合アラミド重合体をアミド系溶媒に5~30質量%の範囲で溶解させたものであり、かつ、前記凝固浴が前記アミド系溶媒を1~20質量%含有する、上記13に記載の製造方法、
15.前記紡糸用ドープが、前記共重合アラミド重合体を濃度95%以上の濃硫酸に5~30質量%の範囲で溶解させたものであり、かつ、前記凝固浴が水を含む、上記13に記載の製造方法、そして
16.破断強度が80~150MPaであり、破断伸度が5~30%であり、ガラス転移温度が250℃以上であり、かつ、300℃における熱収縮率が5%以下であり、さらにメタフェニレンジアミン、パラフェニレンジアミン、イソフタロイルおよびテレフタロイルからなる群から選ばれる3種のモノマー単位、またはメタフェニレンジアミンとテレフタロイルの2種のモノマー単位、またはパラフェニレンジアミンとイソフタロイルの2種のモノマー単位を含む共重合アラミド重合体を含んでなる、耐熱性高タフネスフィルム、
が提供される。
本発明の耐熱性高タフネス繊維は、破断強度が3.5~15cN/dtexであり、破断伸度が5~30%であり、かつ、融点が290℃以上であることを特徴とする。かかる耐熱性高タフネス繊維を構成するポリマーは、一般に全芳香族ポリアミド(以下、アラミドと称する場合がある)であり、特にメタ型および/またはパラ型の芳香族ジアミン成分と、メタ型および/またはパラ型の芳香族ジカルボン酸成分とを構成成分とする共重合体を含むものである。
また、本発明の耐熱性高タフネスフィルムにおいては、メタフェニレンジアミン、パラフェニレンジアミン、イソフタロイルおよびテレフタロイルからなる群から選ばれる3種のモノマー単位、またはメタフェニレンジアミンとテレフタロイルの2種のモノマー単位、またはパラフェニレンジアミンとイソフタロイルの2種のモノマー単位を含む。これらモノマー単位の組合せ例1~4、6、7を下記表1に示す。
上記組合せ例のうち、耐熱性高タフネスフィルムは、一般に例1~4に示す3種のモノマー単位や、例6、7に示す2種類のモノマー単位を含む。
紡糸液調製工程においては、本発明の全芳香族ポリアミドを溶媒に溶解して、紡糸液(ドープ、紡糸用ドープとも呼ぶ)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、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)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、本発明では濃硫酸を溶媒に用いることもできる。濃硫酸を用いる場合、95%以上の濃度が好ましく、さらに好ましくは、98%以上である。濃硫酸を用いる場合、後述する凝固工程において水を用いたエアギャップ紡糸を行うこともできる。
紡糸・凝固工程においては、上記で得られたドープを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、紡糸孔径、配列状態等は特に制限する必要はなく、例えば、紡糸孔数が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ることができる。
本発明の繊維を得るために用いる凝固浴としては、アミド系溶媒を1~20質量%を含む水溶液であり、好ましくは3~15質量%含む水溶液である。この水溶液の温度は50~90℃の範囲が好ましい。また、上記紡糸液調製工程において濃硫酸を溶媒に使用した場合、凝固浴として水を用いることができ、その場合の凝固浴温度は0~20℃の範囲が好ましい。
上記のように、ドープを紡糸口金から凝固液中に紡出して凝固浴を通過させて凝固糸を得る。
得られた凝固糸は、水性洗浄浴にて十分水洗され、沸水延伸工程に送られる。沸水延伸浴中の延伸倍率は1.1~5.0倍の範囲が必要であり、1.1~3.0倍の範囲がより好ましい。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強度を確保することができる。
上記の洗浄・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、上記の洗浄工程により洗浄が実施された繊維を、100~250℃の範囲で乾熱処理をする。好ましくは100~200℃の範囲で乾熱処理をする。また、乾熱処理は定長下で行うのが好ましい。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。
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、290~380℃の範囲で熱処理を加えながら延伸を実施する。処理温度は、好ましく290~350℃の範囲である。290℃に満たない場合、高倍率延伸ができないため不適であり、380℃を超えると繊維の変色や断糸が起きる可能性がある。熱延伸工程において、延伸倍率は、2.0~10.0倍の範囲が必要であり、好ましくは3.0~10.0倍の範囲である。なお、熱延伸処理の温度は、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。
なお、上述した洗浄工程、沸水延伸工程から熱延伸工程は、一般にアミド系、硫酸系ともに共通である。
本発明の耐熱性高タフネスフィルムは、前述した製造方法によって得られた共重合全芳香族ポリアミドを含むポリマー原液を、アルコール、水などの溶媒の中に投入し、再沈、分離された後、再び溶媒に溶解させてフィルムの成形に用いることができる。さらには、好ましくはポリマー原液をそのまま、もしくは重合後に適宜濃度を調整して製膜に用いることが好ましい。この時の濃度の調整は濃縮、もしくは溶媒での希釈により行うことができる。かかる溶媒としては、重合溶媒として例示したものと同様なものを使用できる。
また、成膜は、溶液製膜法により製造されることが好ましい。溶液製膜法としては、乾湿式法、乾式法または湿式法などが挙げられるが、乾湿式法または乾式法が、表面性のよいフィルムが得られる点で好ましい。
湿式法で製膜する場合には、該原液を口金から直接製膜用浴中に押出するか、または一旦ドラムなどの支持体上に押出し、支持体ごと湿式浴中に導入する方法を用いるのが好ましい。この浴は一般に水系媒体からなるものであり、水の他に有機溶媒や無機塩などを含有していてもよい。湿式浴を通すことでフィルム中に含有された塩類や有機溶媒などの抽出を行うことができる。これら湿式浴全体を通過する時間はフィルムの厚みにもよるが、10秒~30分であることが好ましい。
延伸フィルムの場合は、湿式浴を出たポリマーを、長手方向に延伸され、次いで乾燥、横延伸、熱処理に付しても良い。その場合、これらの処理は一般に100~500℃で、合計でl秒~30分であることが好ましい。
乾湿式法で製膜する場合は該原液を口金からドラム、エンドレスベルトなどの支持体上に押出して薄膜とし、次いでかかる薄膜層から溶媒を飛散させ薄膜が自己保持性を持つまで乾燥する。乾燥条件は室温~300℃、60分以内が好ましい。乾式工程を終えたフィルムは支持体から剥離されて湿式工程に導入し、上記の湿式法と同様に脱塩、脱溶媒などを行う。延伸フィルムの場合は、さらに延伸、乾燥、熱処理を行ってもよい。
乾式法のプロセスを採用した場合には、ドラム、エンドレスベルトなどの上で乾燥し、自己保持性を持ったフィルムを、これら支持体から剥離する。延伸フィルムの場合は、さらに残存溶媒を除去するための乾燥、延伸、熱処理を行ってもよい。これらの処理は100~500℃で、合計で1秒~30分で行うのが好ましい。
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。
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。
引張試験機(インストロン社製、型式:5565)を用いて、JIS-L-1015に準じ、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
引張試験機(インストロン社製、型式:5565)を用いて、JIS-L-1013:2010化学繊維フィラメント糸試験方法8.6.1(標準時試験)に準じて測定した。
東亜電波工業社製のSM-8210極超絶縁計を使用し、相対湿度65RH%雰囲気中において測定した。繊維の試料長を10cm(L(cm))とし、この試料長間に0.5KVの電圧をかけ、そのときの電気抵抗率R(Ω)を測定し、導電糸の断面積をS(cm2)としてρ(Ωcm)=R×(S/L)より求めた。本発明の実施例および比較例においては、Sは繊維の密度d=1.39g/cm3とみなし、Dは総繊度値(dtex)をそのまま質量に読み替えた値として、S=D/(1000000×d)より求めた。また、この時の繰り返し測定数は5とし、その平均値を電気抵抗率とした。
JIS-L-1013に準じ、B法に準拠した測定を実施し、250℃または300℃における寸法変化率を求めた。
繊維の融点はJIS-K-7197に準じ、熱機械分析により求めた。得られたサンプルのピークのうち、高温側に検出されたピークの頂点温度または、繊維の溶解によりピーク検出が不可能となった温度を融点とした。
フィルムの引張試験時の最大応力は、エー・アンド・デイテンシロンを用いて、JIS K 7127に準拠して測定を行い、応力および伸度が最大となる値を記録した。試験片は、幅10mm、長さ50mmの試料とし、引張速度は20mm/minとした。
フィルムの軟化点、および熱収縮率は、日立ハイテクサイエンス製の熱機械分析装置TMAを用いて、JIS K 7196およびJIS K 7197に準拠して測定を行った。
特公昭47-10863号公報に準じた界面重合により、メタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の67モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が33モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が2:1となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が2:1となるようにした。重量平均分子量は80万であった。この重合体粉末および塩化カルシウムを、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、共重合アラミド重合体の質量濃度が16%、塩化カルシウムが3%になるよう調整した。
実施例1に準じた界面重合により、メタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の60モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が40モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が3:2となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が3:2となるようにした。重量平均分子量は64万であった。この重合体粉末および塩化カルシウムを、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共重合アラミド重合体の質量濃度が16%、塩化カルシウムが3%になるよう調整した。
実施例1に準じた界面重合により、メタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の56モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が44モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が5:4となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が5:4となるようにした。重量平均分子量は45万であった。この重合体粉末および塩化カルシウムを、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共重合アラミド重合体の質量濃度が20%、塩化カルシウムが2%になるよう調整した。
実施例1に準じた界面重合により、メタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の75モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が25モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が3:1となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が3:1となるようにした。重量平均分子量は61万であった。この重合体粉末および塩化カルシウムを、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共重合アラミド重合体の質量濃度が21%、塩化カルシウムが3%になるよう調整した。
特公昭47-10863号公報に準じた界面重合によりメタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の33モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が67モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が1:2となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が1:2となるようにした。本ポリマーはNMPをはじめとする溶媒への良好な溶解性を示さないことから、紡糸することができなかった。
メタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の100モル%である全芳香族ポリアミド繊維(帝人(株)製「コーネックス」)の物性測定をしたところ、繊度2.2dtex、破断強度4.9cN/dtex、破断伸度40%、融点測定不可(400℃以上)、250℃における乾熱寸法変化率は0.20%であった。
パラフェニレンジアミンおよびテレフタロイルモノマー単位が100モル%からなる全芳香族ポリアミド繊維(帝人(株)製「トワロン」(登録商標))の物性測定をしたところ、繊度2.0dtex、破断強度21cN/dtex、破断伸度3%、融点測定不可(400℃以上)、250℃における乾熱寸法変化率は0%であった。
実施例1~3及び比較例1~4で得られた繊維の物性を表2に示す。
特公昭47-10863号公報に準じた界面重合により、メタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の67モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が33モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が2:1となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が2:1となるようにした。重量平均分子量は80万であった。この重合体粉末および塩化カルシウムを、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、共重合アラミド重合体の質量濃度が16%、塩化カルシウムが3%になるよう調整した。
特公昭47-10863号公報に準じた界面重合によりメタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の56モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が44モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が5:4となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が5:4となるようにした。重量平均分子量は45万であった。この重合体粉末および塩化カルシウムを、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共重合アラミド重合体の質量濃度が20%、塩化カルシウムが2%になるよう調整した。
特公昭47-10863号公報に準じた界面重合によりメタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の50モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が50モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が1:1となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が1:1となるようにした。重量平均分子量は64万であった。この重合体粉末および塩化カルシウムを、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共重合アラミド重合体の質量濃度が16%、塩化カルシウムが3%になるよう調整した。
パラフェニレンジアミンおよびテレフタロイルモノマー単位が全体の100モル%である全芳香族コポリアミド繊維(帝人(株)製「テクノーラ」)の物性測定をしたところ、繊度1.67dtex、破断強度26.96cN/dtex、結節強度4.6cN/dtex(16.9%)、破断伸度6.1%、融点500℃以上、280℃における乾熱寸法変化率は0.30%であった。
特公昭47-10863号公報に準じた界面重合によりメタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の33モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が67モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が1:2となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が1:2となるようにした。本ポリマーはNMPをはじめとする溶媒への良好な溶解性を示さないことから、紡糸することができなかった。
パラフェニレンジアミンおよびテレフタロイルモノマー単位が全体の100モル%からなる全芳香族ポリアミド繊維(帝人(株)製「トワロン」)のポリマー溶液とメタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の100モル%である全芳香族ポリアミド繊維(帝人(株)製「コーネックス」)のポリマー溶液を5:95質量比で混合した。このポリマー溶液を実施例4の条件で紡糸し、全芳香族ポリアミド繊維を得た。得られた繊維の物性測定をしたところ、繊度1.8dtex、破断強度22.4cN/dtex、結節強度3.7cN/dtex(16.5%)破断伸度4.6%、融点測定不可(400℃以上)、250℃における乾熱寸法変化率は0%であった。
実施例4~6及び比較例5~7で得られた繊維の物性を表3に示す。
NMPに対しアミンモノマーを溶解した後、この溶液を0℃まで冷却し、メカニカルスターラーで攪拌しながら酸クロライドモノマーを投入した。この際、メタフェニレンジアミン単位が全体の29モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が71モル%、溶液全体に対して重合後のポリマーの質量濃度が10.7%になるよう調整した。また、酸クロライドモノマーはテレフタル酸クロライドを使用し、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が4:3となるようにした。重合の進行による粘度および溶液温度の上昇が停滞したことを確認後、上記酸クロリドモノマーと等量の水酸化カルシウムを投入し、透明になるまで攪拌することで、共重合アラミド重合体を含むポリマー溶液を作成した。重量平均分子量は69万であった。
実施例7に準じた溶液重合により、メタフェニレンジアミン単位が全体の33モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が67モル%である共重合アラミド重合体を含むポリマー溶液を合成した。この際、酸クロライドモノマーはテレフタル酸クロライドを使用した。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が2:1となるようにした。重量平均分子量は62万であった。このポリマー溶液を85℃に加温し紡糸原液として、孔径0.1mm、孔数100の吐出孔が円形の紡糸口金から85℃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45質量%、NMPが12質量%、残りの水が43質量%であり、浸漬長(有効凝固浴長)100cm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て凝固糸条を得た。
実施例7に準じた溶液重合により、メタフェニレンジアミン単位が全体の25モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が75モル%である共重合アラミド重合体を含むポリマー溶液を合成した。この際、酸クロライドモノマーはテレフタル酸クロライドを使用した。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が1:1となるようにした。重量平均分子量は58万であった。このポリマー溶液を85℃に加温し紡糸原液として、孔径0.1mm、孔数100の吐出孔が円形の紡糸口金から85℃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40質量%、NMPが10質量%、残りの水が50質量%であり、浸漬長(有効凝固浴長)100cm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。
実施例7に準じた溶液重合により、メタフェニレンジアミン単位が全体の66モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が34モル%である共重合アラミド重合体を含むポリマー溶液を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドを使用し、質量比が1:2となるようにした。また、アミンモノマーはメタフェニレンジアミンを使用した。重量平均分子量は58万であった。このポリマー溶液を85℃に加温し紡糸原液として、孔径0.1mm、孔数100の吐出孔が円形の紡糸口金から85℃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40質量%、NMPが10質量%、残りの水が50質量%であり、浸漬長(有効凝固浴長)100cm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。
実施例7に準じた溶液重合により、メタフェニレンジアミン単位が全体の9モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が91モル%である共重合アラミド重合体を含むポリマー溶液を合成した。この際、酸クロライドモノマーはテレフタル酸クロライドを使用した。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が6:14となるようにした。重合の進行とともにポリマーの溶解性が低下し、NMPをはじめとする溶媒への溶解性を示さなくなったことから、紡糸することができなかった。
メタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の100モル%である全芳香族ポリアミド繊維(帝人(株)製「コーネックス(登録商標)」)の物性測定をしたところ、繊度2.2dtex、破断強度4.8cN/dtex、破断伸度39.0%、300℃における乾熱寸法変化率は5.0%であった。
パラフェニレンジアミンおよびテレフタロイルモノマー単位が100モル%からなる全芳香族ポリアミド繊維(帝人(株)製「トワロン(登録商標)」)の物性測定をしたところ、繊度2.0dtex、破断強度22cN/dtex、破断伸度2.5%、300℃における乾熱寸法変化率は0%であった。本繊維は破断伸度が5.0%未満であることから高タフネス性を発揮には不十分である。
実施例7~9及び比較例8~11で得られた繊維の物性を表4に示す。
特公昭47-10863号公報に準じた界面重合により、メタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の67モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が33モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が2:1となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が2:1となるようにした。重量平均分子量は66万であった。この重合体粉末および導電性カーボンブラック粒子(表面固有抵抗が104Ω)を、N-メチル-2-ピロリドン(NMP)に溶解、分散させ、ポリマー溶液を得た。この際、ポリマー溶液に対して共重合アラミド重合体の質量濃度が16%、アラミド重合体に対して導電性カーボンブラックが30質量%になるよう調整した。
特公昭47-10863号公報に準じた界面重合によりメタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の60モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が40モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が3:2となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が3:2となるようにした。重量平均分子量は65万であった。この重合体粉末および導電性カーボンブラック粒子(表面固有抵抗が104Ω)を、N-メチル-2-ピロリドン(NMP)に溶解、分散させ、ポリマー溶液を得た。この際、ポリマー溶液に対して共重合アラミド重合体の質量濃度が18%、アラミド重合体に対して導電性カーボンブラックが25%になるよう調整した。
特公昭47-10863号公報に準じた界面重合によりメタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の75モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が25モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が3:1となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が3:1となるようにした。重量平均分子量は70万であった。この重合体粉末および導電性カーボンブラック粒子(表面固有抵抗が104Ω)を、N-メチル-2-ピロリドン(NMP)に溶解・分散させ、ポリマー溶液を得た。この際、ポリマー溶液に対して共重合アラミド重合体の質量濃度が18%、アラミド重合体に対して導電性カーボンブラックが25%になるよう調整した。
特公昭47-10863号公報に準じた界面重合によりメタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の33モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が64モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が1:2となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が1:2となるようにした。本ポリマーはNMPをはじめとする溶媒への良好な溶解性を示さないことから、紡糸することができなかった。
メタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の67モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が33モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が2:1となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が2:1となるようにした。重量平均分子量は59万であった。この重合体粉末および導電性カーボンブラック粒子(表面固有抵抗が104Ω)を、N-メチル-2-ピロリドン(NMP)に溶解・分散させ、ポリマー溶液を得た。この際、ポリマー溶液に対して共重合アラミド重合体の質量濃度が21%、アラミド重合体に対して導電性カーボンブラックが5%になるよう調整した。
メタフェニレンジアミンおよびイソフタロイルモノマー単位が全体の67モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が33モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が2:1となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が2:1となるようにした。重量平均分子量は66万であった。この重合体粉末および導電性カーボンブラック粒子(表面固有抵抗が104Ω)を、N-メチル-2-ピロリドン(NMP)に溶解・分散させ、ポリマー溶液を得た。この際、ポリマー溶液に対して共重合アラミド重合体の質量濃度が16%、アラミド重合体に対して導電性カーボンブラックが45%になるよう調整した。
実施例10~11及び比較例12~15で得られた繊維の物性を表5に示す。
特公昭47-10863号公報に準じた界面重合によりメタフェニレンイソフタルアミド単位が全体の56モル%、パラフェニレンテレフタルアミド単位が44モル%である共重合アラミド重合体粉末を合成した。この際、酸クロライドモノマーはイソフタル酸クロライドおよびテレフタル酸クロライドの双方を使用し、質量比が5:4となるようにした。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が5:4となるようにした。重量平均分子量は47万であった。この重合体粉末を、99.8%の硫酸に溶解させ、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共重合アラミド重合体の質量濃度が18%になるよう調整した。
実施例7に準じた溶液重合により、メタフェニレンジアミン単位が全体の50モル%、テレフタロイルモノマー単位が50モル%である共重合アラミド重合体を含むポリマー溶液を合成した。この際、酸クロライドモノマーはテレフタル酸クロライドを使用した。また、アミンモノマーはメタフェニレンジアミンを使用した。重量平均分子量は56万であった。このポリマー溶液をガラス板の上にのせ、ドクターブレード法により、薄膜化させた。次いで、100℃で5分間乾燥させ、水浴中に導入し溶媒を除去した。その後、100℃で30分乾燥させ、全芳香族ポリアミドフィルムを得た。得られたフィルムは、膜厚15μm、破断強度130MPa、破断伸度17.0%、ガラス転移温度320℃、300℃における乾熱寸法変化率は0.5%であった。
実施例7に準じた溶液重合により、メタフェニレンジアミン単位が全体の25モル%、パラフェニレンジアミンおよびテレフタロイルモノマー単位が75モル%である共重合アラミド重合体を含むポリマー溶液を合成した。この際、酸クロライドモノマーはテレフタル酸クロライドを使用した。また、アミンモノマーはメタフェニレンジアミンおよびパラフェニレンジアミンの双方を使用し質量比が1:1となるようにした。重量平均分子量は58万であった。 このポリマー溶液を実施例13と同様の方法により製膜し、共重合アラミドフィルムを得た。得られたフィルムは、膜厚15μm、破断強度120MPa、破断伸度6.0%、ガラス転移温度280℃、300℃における乾熱寸法変化率は3.0%であった。
比較例8により合成したポリマー溶液を実施例13と同様の方法により製膜し、共重合アラミドフィルムを得た。得られたフィルムは、膜厚15μm、破断強度50MPa、破断伸度13%、ガラス転移温度260℃、300℃における乾熱寸法変化率は5.8%であった。
Claims (16)
- 破断強度が3.5~15cN/dtexであり、破断伸度が5~30%であり、かつ、融点が290℃以上であることを特徴とする耐熱性高タフネス繊維。
- 前記耐熱性高タフネス繊維が、メタフェニレンジアミン、パラフェニレンジアミン、イソフタロイルおよびテレフタロイルからなる群から選ばれる少なくとも3種のモノマー単位を含んでなる共重合アラミド重合体である、請求項1に記載の耐熱性高タフネス繊維。
- 前記メタフェニレンジアミンおよび/または前記イソフタロイルモノマー単位と、前記パラフェニレンジアミンおよび/または前記テレフタロイルモノマー単位とのモル比率が10以上70未満:90以下30超の範囲にある、請求項2に記載の耐熱性高タフネス繊維。
- 前記破断強度が7~15cN/dtexであり、前記破断伸度が10~30%であり、かつ、250℃における乾熱寸法変化率が2%未満である、請求項1~3のいずれか一項に記載の耐熱性高タフネス繊維。
- さらに結節強度が4.4~5.6cN/dtexである、請求項4に記載の耐熱性高タフネス繊維。
- 前記メタフェニレンジアミンおよび/または前記イソフタロイルモノマー単位と、前記パラフェニレンジアミンおよび/または前記テレフタロイルモノマー単位とのモル比率が40以上70未満:60以下30超の範囲にある、請求項4または5に記載の耐熱性高タフネス繊維。
- 前記破断強度が8.0cN/dtex以上15.0cN/dtex未満であり、前記破断伸度が5.0%より大きく20.0%以下であり、かつ、300℃における乾熱寸法変化率が5%未満である、請求項1~3のいずれか一項に記載の耐熱性高タフネス繊維。
- 前記メタフェニレンジアミンおよび/または前記イソフタロイルモノマー単位と、前記パラフェニレンジアミンおよび/または前記テレフタロイルモノマー単位とのモル比率が10以上40未満:90以下60超の範囲にある、請求項7に記載の耐熱性高タフネス繊維。
- 繊維中に導電性微粒子を含み、電気抵抗率が103Ωcm以下であり、かつ、前記破断強度が3.5~10cN/dtexである、請求項1~3のいずれか一項に記載の耐熱性高タフネス繊維。
- 前記導電性微粒子を6~40質量%含む、請求項9に記載の耐熱性高タフネス繊維。
- 前記導電性微粒子が導電性カーボンブラックである、請求項9または10に記載の耐熱性高タフネス繊維。
- 前記メタフェニレンジアミンおよび/または前記イソフタロイルモノマー単位と、前記パラフェニレンジアミンおよび/または前記テレフタロイルモノマー単位とのモル比率が50以上70未満:50以下30超の範囲にある、請求項9~11のいずれか一項に記載の耐熱性高タフネス繊維。
- 耐熱性高タフネス繊維の製造方法であって、下記の工程(1)~(6):
(1)メタフェニレンジアミン、パラフェニレンジアミン、イソフタロイルおよびテレフタロイルからなる群から選ばれる少なくとも3種のモノマー単位を含んでなる共重合アラミド重合体であって、該メタフェニレンジアミンおよび/または該イソフタロイルモノマー単位と、該パラフェニレンジアミンおよび/または該テレフタロイルモノマー単位とのモル比率が10以上70未満:90以下30超の範囲にあり、かつ、重量平均分子量が40万~100万である共重合アラミド重合体を用意し、
(2)該共重合アラミド重合体を溶媒に溶解させて紡糸用ドープを調製し、
(3)該紡糸用ドープを紡糸口金に通し、凝固浴中に紡出して凝固糸を得、
(4)該凝固糸を水性洗浄浴で水洗し、引き続き沸水延伸浴中で1.1~5.0倍の範囲で延伸して繊維を得、
(5)該繊維に100~250℃の範囲で乾熱処理を施し、そして
(6)該乾熱処理後の繊維に、290~380℃の範囲で熱処理を加えながら、延伸倍率2.0~10.0倍の範囲で熱延伸を施す
ことを特徴とする耐熱性高タフネス繊維の製造方法。 - 前記紡糸用ドープが、前記共重合アラミド重合体をアミド系溶媒に5~30質量%の範囲で溶解させたものであり、かつ、前記凝固浴が前記アミド系溶媒を1~20質量%含有する、請求項13に記載の製造方法。
- 前記紡糸用ドープが、前記共重合アラミド重合体を濃度95%以上の濃硫酸に5~30質量%の範囲で溶解させたものであり、かつ、前記凝固浴が水を含む、請求項13に記載の製造方法。
- 破断強度が80~150MPaであり、破断伸度が5~30%であり、ガラス転移温度が250℃以上であり、かつ、300℃における熱収縮率が5%以下であり、さらに
メタフェニレンジアミン、パラフェニレンジアミン、イソフタロイルおよびテレフタロイルからなる群から選ばれる3種のモノマー単位、またはメタフェニレンジアミンとテレフタロイルの2種のモノマー単位、またはパラフェニレンジアミンとイソフタロイルの2種のモノマー単位を含む共重合アラミド重合体を含んでなる、耐熱性高タフネスフィルム。
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