EP0496313A1 - Non-woven reinforced with a meltbinder - Google Patents
Non-woven reinforced with a meltbinder Download PDFInfo
- Publication number
- EP0496313A1 EP0496313A1 EP92100815A EP92100815A EP0496313A1 EP 0496313 A1 EP0496313 A1 EP 0496313A1 EP 92100815 A EP92100815 A EP 92100815A EP 92100815 A EP92100815 A EP 92100815A EP 0496313 A1 EP0496313 A1 EP 0496313A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibers
- aramid
- structural units
- aromatic
- binding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 52
- 238000002844 melting Methods 0.000 claims abstract description 22
- 230000008018 melting Effects 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 14
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 104
- 239000004760 aramid Substances 0.000 claims description 58
- 239000004745 nonwoven fabric Substances 0.000 claims description 36
- 241000531908 Aramides Species 0.000 claims description 25
- 229920006231 aramid fiber Polymers 0.000 claims description 24
- 150000004985 diamines Chemical class 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 19
- -1 aromatic dicarboxylic acids Chemical class 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 150000004984 aromatic diamines Chemical class 0.000 claims description 14
- 229920002614 Polyether block amide Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000004952 Polyamide Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 238000007596 consolidation process Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims description 3
- 239000012779 reinforcing material Substances 0.000 claims description 3
- 238000004260 weight control Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000000155 melt Substances 0.000 abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 230000006735 deficit Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- RYYUUQPLFHRZOY-UHFFFAOYSA-N 4-[2-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC=C1OC1=CC=C(N)C=C1 RYYUUQPLFHRZOY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JGGQWILNAAODRS-UHFFFAOYSA-N n-methyl-4-[4-(methylamino)phenyl]aniline Chemical compound C1=CC(NC)=CC=C1C1=CC=C(NC)C=C1 JGGQWILNAAODRS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- UYKMUCOPNRSDQV-UHFFFAOYSA-N (2-chloronaphthalene-1-carbonyl) 2-chloronaphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OC(=O)C3=C4C=CC=CC4=CC=C3Cl)=C(Cl)C=CC2=C1 UYKMUCOPNRSDQV-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- GIHNOTXJWBTPSU-UHFFFAOYSA-N 2,3,3-trimethyl-2-phenylindene-1,1-dicarboxylic acid Chemical compound CC1(C)C2=CC=CC=C2C(C(O)=O)(C(O)=O)C1(C)C1=CC=CC=C1 GIHNOTXJWBTPSU-UHFFFAOYSA-N 0.000 description 1
- ZFUZWDOHDRDMEM-UHFFFAOYSA-N 2-[4-[2-[4-(2-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=C(OC2=CC=C(C=C2)C(C)(C)C2=CC=C(C=C2)OC2=C(C=CC=C2)N)C=CC=C1.NC=1C=C(OC2=CC=C(C=C2)C(C)(C)C2=CC=C(C=C2)OC2=CC(=CC=C2)N)C=CC1.NC1=CC=C(OC2=CC=C(C=C2)C(C)(C)C2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1.NC1=CC=C(OC2=CC=C(C=C2)S(=O)(=O)C2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1 ZFUZWDOHDRDMEM-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- RAAGZOYMEQDCTD-UHFFFAOYSA-N 2-fluorobenzoyl chloride Chemical compound FC1=CC=CC=C1C(Cl)=O RAAGZOYMEQDCTD-UHFFFAOYSA-N 0.000 description 1
- BMGKQFRMINVVPP-UHFFFAOYSA-N 2-phenoxybenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1OC1=CC=CC=C1 BMGKQFRMINVVPP-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- IRGLJXDQKZROHB-UHFFFAOYSA-N 3-methyl-1,1-dioxo-1-benzothiophen-2-amine Chemical compound NC=1S(C2=C(C=1C)C=CC=C2)(=O)=O IRGLJXDQKZROHB-UHFFFAOYSA-N 0.000 description 1
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 1
- JLAQSGPVQBKFPA-UHFFFAOYSA-N 4-(2-cyclohexa-2,4-dien-1-ylidenepropyl)aniline Chemical compound C1C=CC=CC1=C(C)CC1=CC=C(N)C=C1 JLAQSGPVQBKFPA-UHFFFAOYSA-N 0.000 description 1
- LFEWXDOYPCWFHR-UHFFFAOYSA-N 4-(4-carboxybenzoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C=C1 LFEWXDOYPCWFHR-UHFFFAOYSA-N 0.000 description 1
- CQPBLBQMIFRGLU-UHFFFAOYSA-N 4-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC1=C2 CQPBLBQMIFRGLU-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- HDRMTMPFYALIQG-UHFFFAOYSA-N 4-amino-3-(4-aminophenoxy)-n-phenylbenzamide Chemical compound C1=CC(N)=CC=C1OC1=CC(C(=O)NC=2C=CC=CC=2)=CC=C1N HDRMTMPFYALIQG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VZBODTFKKZLBCL-UHFFFAOYSA-N C1(=CC=CC=C1)C=1C(=C(S(C=1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C(=O)O)C(=O)O Chemical compound C1(=CC=CC=C1)C=1C(=C(S(C=1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C(=O)O)C(=O)O VZBODTFKKZLBCL-UHFFFAOYSA-N 0.000 description 1
- HUKHTHOZQTUTKC-UHFFFAOYSA-N C1(=CC=CC=C1)[ClH]C(=O)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)[ClH]C(=O)C1=CC=CC=C1 HUKHTHOZQTUTKC-UHFFFAOYSA-N 0.000 description 1
- OXBUBXCVNPPENN-UHFFFAOYSA-N C1=C(C=CC2=CC(=CC=C12)C(=O)O)C(=O)O.S1C(=C(C=C1)C(=O)O)C(=O)O Chemical compound C1=C(C=CC2=CC(=CC=C12)C(=O)O)C(=O)O.S1C(=C(C=C1)C(=O)O)C(=O)O OXBUBXCVNPPENN-UHFFFAOYSA-N 0.000 description 1
- RSDXVNXYTSXBKT-UHFFFAOYSA-N CC=1C=C(C=CC1N)C1=CC(=C(N)C=C1)C.NC1=C(OC2=NC(=CC=C2)OC2=C(C=CC=C2)N)C=CC=C1.NC1=C(OC2=C(C=CC=C2)OC2=C(C=CC=C2)N)C=CC=C1.NC=1C(=NC=CC1)N.ClC1=C(C=CC(C1)(N)Cl)N.C1(=CC=C(C=C1)N)N.C1(=CC(=CC=C1)N)N Chemical compound CC=1C=C(C=CC1N)C1=CC(=C(N)C=C1)C.NC1=C(OC2=NC(=CC=C2)OC2=C(C=CC=C2)N)C=CC=C1.NC1=C(OC2=C(C=CC=C2)OC2=C(C=CC=C2)N)C=CC=C1.NC=1C(=NC=CC1)N.ClC1=C(C=CC(C1)(N)Cl)N.C1(=CC=C(C=C1)N)N.C1(=CC(=CC=C1)N)N RSDXVNXYTSXBKT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920003368 Kevlar® 29 Polymers 0.000 description 1
- 229920003369 Kevlar® 49 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- BIEKBSBBVXEVMS-UHFFFAOYSA-N NC=1C=C(OC2=CC=C(C=C2)S(=O)(=O)C2=CC=C(C=C2)OC2=CC(=CC=C2)N)C=CC1.NC=1C=C(OC2=CC=C(C=C2)SC2=CC=C(C=C2)OC2=CC(=CC=C2)N)C=CC1.NC1=CC=C(OC2=CC=C(C=C2)SC2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1.FC(C=1C=C(OC2=CC=C(C=C2)C(C)(C)C2=CC=C(C=C2)OC2=CC(=C(C=C2)N)C(F)(F)F)C=CC1N)(F)F Chemical compound NC=1C=C(OC2=CC=C(C=C2)S(=O)(=O)C2=CC=C(C=C2)OC2=CC(=CC=C2)N)C=CC1.NC=1C=C(OC2=CC=C(C=C2)SC2=CC=C(C=C2)OC2=CC(=CC=C2)N)C=CC1.NC1=CC=C(OC2=CC=C(C=C2)SC2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1.FC(C=1C=C(OC2=CC=C(C=C2)C(C)(C)C2=CC=C(C=C2)OC2=CC(=C(C=C2)N)C(F)(F)F)C=CC1N)(F)F BIEKBSBBVXEVMS-UHFFFAOYSA-N 0.000 description 1
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000005010 aminoquinolines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000004746 geotextile Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/542—Adhesive fibres
- D04H1/549—Polyamides
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/4334—Polyamides
- D04H1/4342—Aromatic polyamides
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43835—Mixed fibres, e.g. at least two chemically different fibres or fibre blends
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/74—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being orientated, e.g. in parallel (anisotropic fleeces)
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/249949—Two or more chemically different fibers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31728—Next to second layer of polyamide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/69—Autogenously bonded nonwoven fabric
- Y10T442/692—Containing at least two chemically different strand or fiber materials
Definitions
- the present invention relates to a new melt-bond-strengthened nonwoven based on aramid fibers, a process for its production and the use of this nonwoven as a filter material, as an insulating material or as a reinforcing material.
- Nonwovens are generally known and represent a separate category of textile fabrics.
- nonwovens are formed directly from individual fibers or filaments.
- the cohesion of such nonwovens can be produced by the fibers' inherent adhesion and / or by mechanical and / or chemical consolidation.
- DE-A-26 00 209 discloses a heat-resistant sheet material which is produced by eating or heating a woven or knitted fabric or a sheet material from a mixture of aromatic polyamide fibers. Of these fibers, one type acts as a binding agent and the other type acts as a supporting fiber. The heat-melt treatment deforms the binding fiber and forms a porous sheet material that has good paint impregnation properties. The necessary strength is only achieved through impregnation.
- a filter material which consists of glass fibers which are strengthened by means of aromatic polyamide fibers.
- the polymer fibers are deformed by heat and cause a kind of "sintering process" to strengthen the glass fleece.
- the strength of these nonwovens also leaves something to be desired.
- the object of the present invention is to provide a novel nonwoven fabric made from aromatic polyamides with improved strength.
- aramid is to be understood as meaning a polyamide which has essentially azomatic residues in the polymer chain, for example more than 80 mol% of which is composed of aromatic monomer units.
- Fusible and non-fusible aramid fibers can be used as the supporting fiber. Furthermore, the strength and the modulus of the supporting aramid fibers can be selected within wide limits.
- aramid fibers of high strength and high modulus are essentially aramids built up from p-aromatic radicals, such as poly- (p-phenylene-terephthalamide). Examples of this are the products KEVLAR® 29 and KEVLAR® 49 from Du Pont. These aramids are insoluble in organic solvents.
- medium strength and medium modulus aramid fibers are aramids which contain a substantial proportion of aromatic m compounds, such as poly (m-phenylene terephthalamide), poly (m-phenylene isophthalamide) or poly (p-phenylene) isophthalamide).
- aromatic m compounds such as poly (m-phenylene terephthalamide), poly (m-phenylene isophthalamide) or poly (p-phenylene) isophthalamide).
- examples of such aramids are the products NOMEX® from Du Pont. These aramids are insoluble in common solvents.
- supporting fibers made from aramids which are soluble in organic solvents, in particular from those aramides which are soluble in polar aprotic solvents, such as dimethylformamide or dimethyl sulfoxide.
- aromatic polyamides based on terephthalic acid and 3- (p-aminophenoxy) -4-aminobenzanilide as described in DE-A-21 44 126; or aromatic polyamides based on terephthalic acid, p-phenylenediamine and 3,4'-diaminodiphenyl ether, as described in DE-C-25 56 883 and DE-A-30 07 063, or aromatic polyamides based on terephthalic acid and selected Shares of selected diamines, as described in DE-A-35 10 655, -36 05 394 and in EP-A-199 090.
- Aramid fibers made of copolyamides which are soluble in organic polyamide solvents and contain at least 95 mol%, based on the polyamide, of recurring structural units of the formulas Ia, Ib, Ic and Id are particularly preferably used -OC-Ar1-CO- (Ia), and up to 5 mol% m bonds containing structural units derived from aromatic dicarboxylic acids and / or from aromatic diamines (Ie) and / or (If), the sum of the molar proportions of the structural units (Ia) + (Ie) and the molar proportions of the structural units (Ib) + (Ic) + (Id) + (If) are essentially the same size, and the proportions of the diamine components (Ib), (Ic) and (Id) in relation to the total amount of this diamine component are within the following limits: or containing at least 95 mol%, based on the polyamide, of recurring structural units of the formulas Ia, Ig, Ib and I
- Aramides containing these structural units of the formulas (Ia) to (Ig) are known from EP-A-364 891, -364 892 and -364 893 and the content of these publications is also the content of the present description.
- thermoplastically processable aramid fibers can be used as binding fibers, as long as these fibers can be melted practically completely and the supporting aramid fibers stick together. This is usually done with the formation of so-called "tie sails". It is preferred to use thermoplastically processable aramid fibers which are soluble in organic solvents.
- Binder fibers based on thermoplastically processable aromatic polyetheramides are particularly preferably used.
- aromatic copolyetheramides which are known from DE-A-38 18 208 or from DE-A-38 18 209; aromatic polyamides known from EP-A-366,316, EP-A-384,980, EP-A-384,981 and EP-A-384,984 can also be used.
- Binding fibers based on these aramids can be processed thermoplastically and are particularly good Melting behavior and lead to nonwovens with excellent strength.
- Ar3 can be a mononuclear or condensed dinuclear aromatic divalent radical or a radical of the formula -Ar7-Q-Ar7-, in which Ar7 has the meaning defined above and Q is a direct CC bond or an -O-, -CO-, -S-, -SO- or -SO2 bridge means.
- Ar3 can be heterocyclic-aromatic or preferably carbocyclic-aromatic radicals. Heterocyclic aromatic radicals preferably have one or two oxygen and / or sulfur and / or nitrogen atoms in the nucleus.
- Ar5 and Ar6 are generally carbocyclic-aromatic arylene radicals whose free valences are in the para or meta position or in a comparable parallel or angled position to one another, preferably mononuclear aromatic radicals.
- Ar7 generally has one of the meanings defined for Ar5 or Ar6.
- residues -Ar3-, -Ar4-, -Ar5- and -Ar6- are p-phenylene, m-phenylene, biphenyl-4,4'-diyl or naphthalene-1,4-diyl.
- substituents which are optionally on the radicals -Ar1- to -Ar6- are branched or in particular straight-chain C1-C1 alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl or n- Hexyl, as well as the corresponding perfluoro derivatives with up to six carbon atoms or the corresponding alkoxy derivatives. Methyl is preferred.
- halogen substituents are bromine or especially chlorine.
- aromatic polyetheramides of the formula II which are preferably used in accordance with the invention are produced by a targeted molecular weight control by non-stoichiometric addition of the monomer units, the sum of the mole fractions x, y and z being one, but the sum of x and z not being equal to y and x being the Can assume zero value.
- z is greater than x.
- the ends of the polymer chain are completely closed by adding reagents which react in the polymer to form groups which do not react further.
- the end groups are independent of one another and can be the same or different and are preferably selected from a group of the formulas III, IV, V and / or VI.
- the terminal nitrogen in formula (II) is an imide nitrogen.
- E represents a hydrogen or a halogen atom, in particular a chlorine, bromine or fluorine atom, or an organic radical, for example an aryl (oxy) group.
- the aromatic polyether amide of the formula II can be prepared by reacting one or more dicarboxylic acid derivatives with one or more diamines by the solution, precipitation or melt condensation process, one of the components being used in a stoichiometric deficit and a chain lock agent being added after the polycondensation has ended.
- thermoplastic aromatic polyamides of the formula II which are preferably used according to the invention are further distinguished by the fact that they have an average molecular weight in the range from 5000 to 50,000 and a low melt viscosity which does not exceed 10,000 Pas.
- Examples of compounds of the formula (VII) are: Terephthalic acid Terephthalic acid dichloride Diphenyl terephthalate Isophthalic acid Diphenyl isophthalate Isophthaloyl chloride Phenoxy terephthalic acid Phenoxytherephthalic acid dichloride Phenoxyterephthalic acid diphenyl ester Di (n-hexyloxy) terephthalic acid Bis (n-hexyloxy) terephthalic acid dichloride Bis- (n-hexyloxy) terephthalic acid diphenyl ester 2,5-furanedicarboxylic acid 2,5-furandicarboxylic acid chloride 2,5-furan diphenyl ester Thiophene dicarboxylic acid Naphthalene-2,6-dicarboxylic acid Diphenyl ether 4,4'-dicarboxylic acid Benzophenone 4,4'-dicarboxylic acid Isopropylidene-4,4'-di
- Aromatic diamines of the formula (IX) are: 2,2-bis- [4- (3-trifluoromethyl-4-aminophenoxy) phenyl] propane Bis- [4- (4-aminophenoxy) phenyl] sulfide Bis- [4- (3-aminophenoxy) phenyl] sulfide Bis- [4- (3-aminophenoxy) phenyl] sulfone Bis- [4- (4-aminophenoxy) phenyl] sulfone 2,2-bis- [4- (4-aminophenoxy) phenyl] propane 2,2-bis [4- (3-aminophenoxy) phenyl] propane 2,2-bis- [4- [4- (2-aminophenoxy) phenyl] propane 1,1,1,3,3,3-hexafluoro-2,2-bis- [4- (4-aminophenoxy) phenyl] propane,
- the polyetheramides used according to the invention are preferably prepared via solution condensation
- the solution condensation of the aromatic dicarboxylic acid dichloride with the aromatic diamines takes place in aprotic, polar solvents of the amide type, e.g. in N, N-dimethyl-acetamide, preferably in N-methyl-2-pyrrolidone.
- these solvents can be added in a known manner to increase the solvency or to stabilize the polyether amide solutions, halide salts of the first and / or second group of the periodic system.
- Preferred additives are calcium chloride and / or lithium chloride.
- the condensation is carried out without the addition of salt, since the aromatic polyetheramides described above are notable for high solubility in the amide-type solvents mentioned above.
- a monofunctional aromatic acid chloride or acid anhydride is added, for example, at the end of the polymerization reaction as a chain lock Benzoyl chloride, fluorobenzoyl chloride, diphenylcarboxylic acid chloride, phenoxybenzoyl chloride or else phthalic anhydride, naphthalic anhydride, chloronaphthalic anhydride.
- Such chain locking agents can optionally be substituted, preferably with fluorine or chlorine atoms.
- Benzoyl chloride or phthalic anhydride is preferably used, particularly preferably benzoyl chloride.
- a monofunctional, preferably aromatic amine for example fluoraniline, chloroaniline, 4-aminodiphenylamine, aminobiphenylamine, aminodiphenyl ether, aminobenzophenone or aminoquinoline, is used as chain closing agent after the end of the polycondensation.
- diacid chloride is polycondensed in a deficit with diamine and then the remaining reactive amino groups are deactivated with a monofunctional acid chloride or diacid anhydride.
- the diacid chloride is used in a deficit and polycondensed with a diamine.
- the remaining reactive amino end groups are then deactivated with a monofunctional, preferably aromatic, optionally substituted acid chloride or acid anhydride.
- the chain locking agent ie the monofunctional amine or acid chloride or acid anhydride, is preferably used in a stoichiometric or superstoichiometric amount, based on the diacid or diamine component.
- the molar ratio is particularly preferably in the range from 0.90 to 0.99 and 1.01 to 1.10, particularly preferably in the range from 0.93 to 0.98 and 1.02 to 1.07, in particular in the range from 0.95 to 0.97 and 1.03 to 1.05.
- the polycondensation temperatures are usually between -20 and +120 ° C, preferably between +10 and +100 ° C. Particularly good results are achieved at reaction temperatures between +10 and + 80 ° C.
- the polycondensation reactions are preferably carried out such that 2 to 40, preferably 5 to 30,% by weight of polycondensate are present in the solution after the reaction has ended.
- the solution can be diluted with N-methyl-2-pyrrolidone or other solvents, e.g. DMF, DMAC or butyl cellosolve, if necessary, or concentrated under reduced pressure (thin film evaporator).
- the hydrogen chloride formed, loosely bound to the amide solvent is removed by adding acid-binding auxiliaries.
- acid-binding auxiliaries lithium hydroxide, calcium hydroxide, but in particular calcium oxide, propylene oxide, ethylene oxide or ammonia are suitable.
- pure water is used as the "acid-binding" agent, which dilutes the hydrochloric acid and at the same time serves to precipitate the polymer.
- the copolyamide solutions according to the invention described above are filtered, degassed and further processed in a manner known per se to give aramid fibers or threads.
- additives can also be added to the solutions.
- suitable amounts of additives can also be added to the solutions.
- a precipitant can be added to the solution and the coagulated product can be filtered off.
- Typical precipitants are, for example, water, methanol, acetone, which may also contain pH-controlling additives such as May contain ammonia or acetic acid.
- the isolation is preferably carried out by comminuting the polymer solution with an excess of water in a cutting mill.
- the finely crushed coagulated polymer particles facilitate the subsequent washing steps (removal of the secondary products formed from the hydrochloric acid) and drying of the polymer (avoiding inclusions) after filtration. Subsequent shredding is also unnecessary, since a free-flowing product is created directly.
- the aromatic polyamides of the formula II which are preferably used according to the invention have surprisingly good mechanical properties and high glass transition temperatures.
- the Staudinger index [ ⁇ ] o is in the range from 0.4 to 1.5 dl / g, preferably in the range from 0.5 to 1.3 dl / g, particularly preferably in the range from 0.6 to 1.1 dl / g G.
- the glass transition temperatures are generally above 180 ° C., preferably above 200 ° C., the processing temperatures in the range from 320 to 380 ° C., preferably in the range from 330 to 370 ° C., particularly preferably in the range from 340 to 360 ° C.
- polyamides can be processed using extrusion processes since the melt viscosity does not exceed 10,000 Pas.
- the extrusion can be carried out on conventional single or twin screw extruders.
- the nonwovens according to the invention can be produced in any of the ways known per se. Staple fibers or short fibers or also continuous filaments from the two types of aramid can be used. The formation of the fleece can take place via dry or wet processing.
- At least one type of fiber is an aramide that is not soluble in organic solvents, processing with staple or short fibers is preferred.
- carded nonwovens In such a case, it is preferred to produce carded nonwovens.
- the two types of fibers are preferably mixed before carding.
- nonwovens according to the invention can, however, also be produced by other conventional nonwoven formation techniques, for example by wet nonwoven technology (in particular for producing paper-like nonwovens) or aerodynamic or hydrodynamic nonwoven formation (in particular for producing bulky nonwovens).
- the invention relates in particular to papers based on the nonwovens according to the invention, which are characterized by a content of approximately 70 to 98% by weight, in particular 80 to 90% by weight, of load-bearing aramid fibers in the form of staple fibers which are fibrillated and a content from about 2 to 30% by weight, in particular 10 to 20% by weight, of binding fibers made of thermoplastic aramides, which are solidified by melting the carrier fibers onto the binding fibers or by practically completely melting the binding fibers.
- the stack lengths of the supporting aramid fibers are generally 2 to 6 mm.
- the fibers can be made by cutting or tearing. These fibers are preferably fibrillated by mechanical processing, for example by treating an aqueous suspension of the aramid staple fibers in a dissolver.
- the aramid binding fibers are preferably used in the form of staple fibers.
- the staple length of the binding fibers preferably corresponds approximately to the staple length of the carrier fibers.
- the binder fibers can be used as such, i.e. prior fibrillation is not absolutely necessary.
- the two types of fibers which in turn can be in the form of mixtures, are mixed together. This is generally done in an aqueous medium.
- the suspension produced in this way is applied to a sieve pad, the aqueous medium being separated off and the fibers which have been felted together remaining on the pad.
- the fabric obtained in this way is stabilized and / or solidified by heat treatment. If necessary, the heat treatment is carried out under pressure.
- Typical temperatures for the consolidation step depend on the fiber types selected in the individual case and can be determined by a person skilled in the art using simple test series.
- the papers produced in this way - depending on the consolidation conditions used - either have practically no binding fibers, i.e. the binding fibers have melted so completely through the consolidation step that their fiber shape has been lost, or some of the melting fibers have been preserved, and only the carrier fibers have melted onto the binding fibers.
- the papers according to the invention can be used in particular for the production of laminates, for example as top layers in the reinforcement of "honeycomb laminates", as described in WO-A-84/04727 or in the reinforcement of network materials, as in EP-A- 158,234.
- the nonwovens produced in a first step can optionally be pre-consolidated before final consolidation. This can be done for example by needles.
- the final consolidation to the nonwovens according to the invention is carried out by heating the initially obtained nonwoven to a temperature at which the binding fibers melt and / or deform thermoplastic, whereby they usually form so-called "binding sails" at the crossing points of the supporting aramid fibers while losing their fiber structure.
- the heating can be carried out by treatment with a hot carrier medium, for example with air, or by treatment with hot rollers or calenders, which may have a surface structure, and impart an embossed structure to the nonwoven fabric.
- the duration of the heat treatment depends, for example, on the desired end properties, on the dimensions of the Fleece and the nature of the types of fibers forming the fleece.
- the melting point of the binding fibers is usually at least 10 ° C. below the melting or decomposition point of the supporting fibers, in particular more than 30 ° C. below the melting or decomposition point of the supporting fibers.
- the melting point of the binding fibers below the melting or decomposition point of the supporting fibers so that they do not experience any significant changes in properties during the heat treatment.
- the character of the nonwovens according to the invention is also influenced by the proportion of melt binders. Depending on the area of application, a voluminous nonwoven with only a few bonding points is preferred or an almost flat connection, e.g. for laminates.
- Typical values for the proportion of melt binder are in the range of 20-80% by weight of binder fiber, based on the amounts of binder fiber and load-bearing fiber.
- the basis weights of the nonwovens according to the invention and the individual titer and stack lengths of both types of fibers can be varied within wide limits and adapted to the requirements of the further processing processes and the area of use.
- Typical values for the grammages are 30 to 500 g / m2.
- Typical values for the individual titer of the fibers are in the range from 0.5 to 5 dtex.
- the filaments or staple fibers making up the nonwovens according to the invention can have a practically round cross section or can also have other shapes, such as dumbbell, kidney-shaped, triangular or tri or multilobal cross sections. Hollow fibers can be used. Furthermore, the two types of fibers can be combined in the form of bicomponent or multicomponent fibers, the binding component filling at least part of the fiber surface.
- the supporting aramid fibers are spun from solvents in a known manner, and the thermoplastic aramids can be spun from the solution or from the melt.
- the nonwovens according to the invention consist practically exclusively of aromatic polyamides and thus have all the advantages of these polymers, such as chemical and thermal stability, extremely good flame resistance and good compatibility with one another. They also have all the advantages of melt-bonded nonwovens, i.e. good tear and tear behavior.
- the nonwovens according to the invention can be finished in a conventional manner, for example by adding antistatic agents, dyes or biocidal additives.
- the nonwovens according to the invention can be used in particular in areas where high stability (chemical, thermal and mechanical) is required.
- examples include the use as filter materials, as insulating materials (thermal and electrical) and as reinforcing materials for different substrates (e.g. plastics or as geotextiles).
- the suspension obtained is dewatered by filtration and the filter cake obtained is applied to a hot plate at about 300 ° C. and dried at this temperature; the drying process is supported by treating the side of the filter cake facing away from the heating plate with an iron of approximately 300 ° C.
- the papers produced in this way can then be further consolidated by treatment in a heating press.
- Table 1 shows the production conditions of different aramid papers and their strengths. The strength values were determined by recording force-expansion diagrams on 1.5 cm wide test strips of the papers. The measurements were carried out with an Instron tester. The clamping length was 50 mm. The strength values are based on the basis weight of the paper.
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Abstract
Description
Die vorliegende Erfindung betrifft einen neuen schmelzbinderverfestigten Vliesstoff auf Basis von Aramidfasern, ein Verfahren zu dessen Herstellung, sowie die Verwendung dieses Vliesstoffes als Filtermaterial, als Isoliermaterial oder als Verstärkungsmaterial.The present invention relates to a new melt-bond-strengthened nonwoven based on aramid fibers, a process for its production and the use of this nonwoven as a filter material, as an insulating material or as a reinforcing material.
Vliesstoffe sind allgemein bekannt und stellen eine eigene Kategorie textiler Flächengebilde dar. Im Gegensatz zu herkömmlichen textilen Flächengebilden, wie Geweben, Gewirken oder Gestricken, werden Vliesstoffe unmittelbar aus Einzelfasern oder Filamenten gebildet. Der Zusammenhalt solcher Vliese kann dabei durch die den Fasern eigene Haftung und/oder durch eine Verfestigung auf mechanischem und/oder auf chemischem Wege hergestellt werden.Nonwovens are generally known and represent a separate category of textile fabrics. In contrast to conventional textile fabrics, such as woven, knitted or knitted fabrics, nonwovens are formed directly from individual fibers or filaments. The cohesion of such nonwovens can be produced by the fibers' inherent adhesion and / or by mechanical and / or chemical consolidation.
Aus der DE-A-26 00 209 ist ein hitzebeständiges Bahnenmaterial bekannt, das durch Fressen oder Erhitzen eines Gewebes oder Gewirkes oder eines Bahnenmaterials aus einem Gemisch aus aromatischen Polyamidfasern hergestellt wird. Von diesen Fasern wirkt die eine Sorte als Bindemittel und die andere Sorte wirkt als tragende Faser. Durch die Wärmeschmelzbehandlung wird die Bindefaser deformiert und es bildet sich ein poröses Bahnenmaterial, das eine gute Lackimprägnierbarkeit besitzt. Die notwendige Festigkeit wird nur durch die Imprägnierung erreicht.DE-A-26 00 209 discloses a heat-resistant sheet material which is produced by eating or heating a woven or knitted fabric or a sheet material from a mixture of aromatic polyamide fibers. Of these fibers, one type acts as a binding agent and the other type acts as a supporting fiber. The heat-melt treatment deforms the binding fiber and forms a porous sheet material that has good paint impregnation properties. The necessary strength is only achieved through impregnation.
Aus der US-A-3,920,428 ist ein Filtermaterial bekannt, das aus Glasfasern besteht, die mittels aromatischen Polyamidfasern verfestigt sind. Auch hier werden die Polymerfasern durch Hitze deformiert und bewirken durch eine Art "Sinterprozeß" eine Verfestigung des Glasvlieses. Die Festigkeit dieser Vliese läßt ebenfalls noch zu wünschen übrig.From US-A-3,920,428 a filter material is known which consists of glass fibers which are strengthened by means of aromatic polyamide fibers. Here, too, the polymer fibers are deformed by heat and cause a kind of "sintering process" to strengthen the glass fleece. The strength of these nonwovens also leaves something to be desired.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung eines neuartigen Vliesstoffes aus aromatischen Polyamiden mit verbesserter Festigkeit.The object of the present invention is to provide a novel nonwoven fabric made from aromatic polyamides with improved strength.
Gelöst wird diese Aufgabe durch den Vliesstoff gemäß Anspruch 1.This object is achieved by the nonwoven fabric according to claim 1.
Infolge des praktisch vollständigen Aufschmelzens der Bindefasern und des Zusammenlaufens der diese Fasern bildenden Materials in den Kreuzungspunkten der tragenden Aramidfasern, meist unter Ausbildung von sogenannten "Bindersegeln" wird eine erhebliche Zunahme der Festigkeit der Vliesstoffe festgestellt.As a result of the practically complete melting of the binding fibers and the convergence of the material forming these fibers at the crossing points of the supporting aramid fibers, usually with the formation of so-called "binder sails", a considerable increase in the strength of the nonwovens is found.
Unter dem Begriff "Aramid" ist im Rahmen der vorliegenden Beschreibung ein Polyamid zu verstehen, das im wesentlichen azomatische Reste in der Polymerkette aufweist, beispielsweise zu mehr als 80 Mol-% aus aromatischen Monomereinheiten aufgebaut ist.In the context of the present description, the term “aramid” is to be understood as meaning a polyamide which has essentially azomatic residues in the polymer chain, for example more than 80 mol% of which is composed of aromatic monomer units.
Zur Herstellung des erfindungsgemäßen Vliesstoffes sind praktisch alle Kombinationen von Aramidfasern zu verwenden, solange die Bindefaser aus thermoplastischem Aramid besteht und die tragende Faser einen gegenüber dem Schmelzpunkt der Bindefaser erhöhten Schmelz- oder Zersetzungspunkt aufweist, so das die Bindefaser praktisch vollständig aufgeschmolzen werden kann, ohne das die tragende Faser dabei wesentlich verändert wird.Practically all combinations of aramid fibers are to be used to produce the nonwoven fabric according to the invention, as long as the binding fiber consists of thermoplastic aramid and the supporting fiber has a melting or decomposition point which is higher than the melting point of the binding fiber, so that the binding fiber can be melted practically completely without this the supporting fiber is significantly changed.
Als tragende Faser lassen sich schmelzbare und nicht schmelzbare Aramidfasern einsetzen. Ferner können die Festigkeit und der Modul der tragenden Aramidfasern innerhalb weiter Grenzen gewählt werden.Fusible and non-fusible aramid fibers can be used as the supporting fiber. Furthermore, the strength and the modulus of the supporting aramid fibers can be selected within wide limits.
Beispiele für Aramidfasern hoher Festigkeit und hohen Moduls sind im wesentlichen aus p-aromatischen Resten aufgebaute Aramide, wie Poly-(p-phenylen-terephthalamid). Beispiele dafür sind die Produkte KEVLAR® 29 und KEVLAR® 49 der Fa. Du Pont. Diese Aramide sind in organischen Lösungsmitteln unlöslich.Examples of aramid fibers of high strength and high modulus are essentially aramids built up from p-aromatic radicals, such as poly- (p-phenylene-terephthalamide). Examples of this are the products KEVLAR® 29 and KEVLAR® 49 from Du Pont. These aramids are insoluble in organic solvents.
Beispiele für Aramidfasern mittlerer Festigkeit und mittleren Moduls sind Aramide, die einen wesentlichen Anteil an aromatischen m-Verbindungen enthalten, wie Poly-(m-phenylen-terephthalamid), Poly-(m-phenylen-isophthalamid) oder Poly-(p-phenylen-isophthalamid). Beispiele für solche Aramide die Produkte NOMEX® der Fa. Du Pont. Diese Aramide sind in gängigen Lösungsmitteln unlöslich.Examples of medium strength and medium modulus aramid fibers are aramids which contain a substantial proportion of aromatic m compounds, such as poly (m-phenylene terephthalamide), poly (m-phenylene isophthalamide) or poly (p-phenylene) isophthalamide). Examples of such aramids are the products NOMEX® from Du Pont. These aramids are insoluble in common solvents.
Bevorzugt setzt man tragende Fasern aus in organischen Lösungsmitteln löslichen Aramiden ein, insbesondere aus solchen Aramiden, die in polaren aprotischen Lösungsmitteln, wie Dimethylformamid oder Dimethylsulfoxid, löslich sind.It is preferred to use supporting fibers made from aramids which are soluble in organic solvents, in particular from those aramides which are soluble in polar aprotic solvents, such as dimethylformamide or dimethyl sulfoxide.
Dazu zählen beispielsweise lösliche aromatische Polyamide auf Basis von Terephthalsäure und 3-(p-Aminophenoxy)-4-aminobenzanilid, wie in der DE-A-21 44 126 beschrieben; oder aromatischen Polyamide auf Basis von Terephthalsäure, p-Phenylendiamin und 3,4'-Diaminodiphenylether, wie in der DE-C-25 56 883 und in der DE-A-30 07 063 beschrieben, oder aromatische Polyamide auf Basis von Terephthalsäure und ausgewählten Anteilen ausgewählter Diamine, wie in der DE-A-35 10 655, -36 05 394 und in der EP-A-199 090 beschrieben.These include, for example, soluble aromatic polyamides based on terephthalic acid and 3- (p-aminophenoxy) -4-aminobenzanilide, as described in DE-A-21 44 126; or aromatic polyamides based on terephthalic acid, p-phenylenediamine and 3,4'-diaminodiphenyl ether, as described in DE-C-25 56 883 and DE-A-30 07 063, or aromatic polyamides based on terephthalic acid and selected Shares of selected diamines, as described in DE-A-35 10 655, -36 05 394 and in EP-A-199 090.
Besonders bevorzugt verwendet man tragende Aramidfasern aus in organischen Polyamid-Lösungsmitteln löslichen Copolyamide enthaltend mindestens 95 Mol-%, bezogen auf das Polyamid, an wiederkehrenden Struktureinheiten der Formeln Ia, Ib, Ic und Id
-OC-Ar¹-CO- (Ia),
und bis zu 5 Mol-% m-Bindungen enthaltende, von aromatischen Dicarbonsäuren und/oder von aromatischen Diaminen abgeleitete Struktureinheiten (Ie) und/oder (If), wobei die Summe der Molanteile der Struktureinheiten (Ia)+(Ie) und der Molanteile der Struktureinheiten (Ib)+(Ic)+(Id)+(If) im wesentlichen gleich groß sind, und die Anteile der Diaminkomponenten (Ib), (Ic) und (Id) im Verhältnis zur Gesamtmenge dieser Diaminkomponente innerhalb folgender Grenzen liegen:
oder enthaltend mindestens 95 Mol-%, bezogen auf das Polyamid, an wiederkehrenden Struktureinheiten der Formeln Ia, Ig, Ib und Id
-OC-Ar¹-CO- (Ia),
-HN-Ar²-NH- (Ig),
und bis zu 5 Mol% m-Bindungen enthaltende, von aromatischen Dicarbonsäuren und/oder von aromatischen Diaminen abgeleitete Struktureinheiten (Ie) und/oder (If), wobei die Summen der Molanteile der Struktureinheiten (Ia)+(Ie) und der Molanteile der Struktureinheiten (Ig)+(Ib)+(Id)+(If) im wesentlichen gleichgroß sind, und die Anteile der Diaminkomponenten (Ig), (Ib) und (Id) im Verhältnis zur Gesamtmenge dieser Diaminkomponenten innerhalb folgender Grenzen liegen:
oder enthaltend mindestens 95 Mol-%, bezogen auf das Polyamid, an wiederkehrenden Struktureinheiten der Formeln Ia, Ig, Ib und Ic
-OC-Ar¹-CO- (Ia),
-HN-Ar²-NH- (Ig),
und bis zu 5 Mol-% m-Bindungen enthaltende, von aromatischen Dicarbonsäuren und/oder von aromatischen Diaminen abgeleitete Struktureinheiten (Ie) und/oder (If), wobei die Summe der Molanteile der Struktureinheiten (Ia)+(Ie) und der Molanteile der Struktureinheiten (Ig)+(Ib)+(Ic)+(If) im wesentlichen gleich groß sind, und die Anteile der Diaminkomponenten (Ig), (Ib) und (Ic) im Verhältnis zur Gesamtmenge dieser Diaminkomponenten innerhalb folgender Grenzen liegen:
dabei bedeuten in diesen Formeln (Ia) bis (Ig)
-Ar¹- und -Ar²- zweiwertige aromatische Reste, deren Valenzbindungen in para- oder vergleichbarer koaxialer oder paralleler Stellung stehen und die durch einen oder zwei inerte Reste, wie Alkyl, Alkoxy oder Halogen substituiert sein können, und
-R¹ und -R² sind voneinander verschiedene niedere Alkylreste oder niedere Alkoxyreste oder Halogenatome. Beispiele für -Ar¹- und -Ar²- sind Naphthalin-1,4-diyl und bevorzugt p-Phenylen.Aramid fibers made of copolyamides which are soluble in organic polyamide solvents and contain at least 95 mol%, based on the polyamide, of recurring structural units of the formulas Ia, Ib, Ic and Id are particularly preferably used
-OC-Ar¹-CO- (Ia),
and up to 5 mol% m bonds containing structural units derived from aromatic dicarboxylic acids and / or from aromatic diamines (Ie) and / or (If), the sum of the molar proportions of the structural units (Ia) + (Ie) and the molar proportions of the structural units (Ib) + (Ic) + (Id) + (If) are essentially the same size, and the proportions of the diamine components (Ib), (Ic) and (Id) in relation to the total amount of this diamine component are within the following limits:
or containing at least 95 mol%, based on the polyamide, of recurring structural units of the formulas Ia, Ig, Ib and Id
-OC-Ar¹-CO- (Ia),
-HN-Ar²-NH- (Ig),
and up to 5 mol% containing m bonds, of aromatic dicarboxylic acids and / or of aromatic diamines derived structural units (Ie) and / or (If), the sums of the molar proportions of the structural units (Ia) + (Ie) and the molar proportions of the structural units (Ig) + (Ib) + (Id) + (If) being essentially the same size , and the proportions of the diamine components (Ig), (Ib) and (Id) in relation to the total amount of these diamine components are within the following limits:
or containing at least 95 mol%, based on the polyamide, of recurring structural units of the formulas Ia, Ig, Ib and Ic
-OC-Ar¹-CO- (Ia),
-HN-Ar²-NH- (Ig),
and up to 5 mol% m bonds containing structural units derived from aromatic dicarboxylic acids and / or from aromatic diamines (Ie) and / or (If), the sum of the molar proportions of the structural units (Ia) + (Ie) and the molar proportions of the structural units (Ig) + (Ib) + (Ic) + (If) are essentially the same size, and the proportions of the diamine components (Ig), (Ib) and (Ic) in relation to the total amount of these diamine components are within the following limits:
mean in these formulas (Ia) to (Ig)
-Ar¹- and -Ar²- divalent aromatic radicals whose valence bonds are in a para- or comparable coaxial or parallel position and which can be substituted by one or two inert radicals, such as alkyl, alkoxy or halogen, and
-R¹ and -R² are different lower alkyl radicals or lower alkoxy radicals or halogen atoms. Examples of -Ar¹- and -Ar²- are naphthalene-1,4-diyl and preferably p-phenylene.
Aramide enthaltend diese Struktureinheiten der Formeln (Ia) bis (Ig) sind aus den EP-A-364 891, -364 892 und -364 893 bekannt und der Inhalt dieser Publikationen ist ebenfalls Inhalt der vorliegenden Beschreibung.Aramides containing these structural units of the formulas (Ia) to (Ig) are known from EP-A-364 891, -364 892 and -364 893 and the content of these publications is also the content of the present description.
Als Bindefasern können alle an sich bekannten thermoplastisch verarbeitbaren Aramidfasern eingesetzt werden, solange sich diese Fasern praktisch vollständig aufschmelzen lassen und die tragenden Aramidfasern verkleben. Dies erfolgt meist unter Ausbildung von sogenannten "Bindesegeln". Bevorzugt verwendet man thermoplastisch verarbeitbare Aramidfasern, die in organischen Lösungsmitteln löslich sind.All known thermoplastically processable aramid fibers can be used as binding fibers, as long as these fibers can be melted practically completely and the supporting aramid fibers stick together. This is usually done with the formation of so-called "tie sails". It is preferred to use thermoplastically processable aramid fibers which are soluble in organic solvents.
Besonders bevorzugt setzt man Bindefasern auf Basis von thermoplastisch verarbeitbaren aromatischen Polyetheramiden ein.Binder fibers based on thermoplastically processable aromatic polyetheramides are particularly preferably used.
Dazu zählen beispielsweise die aromatischen Copolyetheramide, die aus der DE-A-38 18 208 oder aus der DE-A-38 18 209 bekannt sind; ferner lassen sich auch aromatische Polyamide, die aus der EP-A-366,316, EP-A-384,980, EP-A-384,981 und EP-A-384,984 bekannt sind, verwenden.These include, for example, the aromatic copolyetheramides which are known from DE-A-38 18 208 or from DE-A-38 18 209; aromatic polyamides known from EP-A-366,316, EP-A-384,980, EP-A-384,981 and EP-A-384,984 can also be used.
Besonders bevorzugt setzt man Bindefasern aus thermoplastisch verarbeitbaren aromatischen Copolyetheramiden der Formel II ein
worin
Ar³ einen zweiwertigen substituierten oder unsubstituierten aromatischen Rest bedeutet, dessen freie Valenzen sich in para- oder meta-Stellung oder in vergleichbarer paralleler oder gewinkelter Stellung zueinander befinden,
Ar⁴ eine der für Ar³ angegebenen Bedeutungen haben kann oder eine Gruppe -Ar⁷-Z-Ar⁷- darstellt,
wobei Z eine -C(CH₃)₂- oder -O-Ar⁷-O- Brücke ist und
Ar⁷ für einen zweiwertigen aromatischen Rest steht,
Ar⁵ und Ar⁶ gleich oder verschieden voneinander sind und für einen substituierten oder unsubstituierten para- oder meta-Arylenrest stehen,
Y eine -C(CH₃)₂-, SO₂-, -S- oder -C(CF₃)₂-Brücke darstellt,
wobei
- a) das Polyetheramid ein mittleres Molekulargewicht (Zahlenmittel) im Bereich von 5000 bis 50000 aufweist,
- b) die Molekulargewichtskontrolle gezielt durch nicht-stöchiometrische Zugabe der Monomereinheiten erfolgt, wobei die Summe der Molenbrüche x, y und z eins ist, die Summe von x und z nicht gleich y ist und x den Wert null annehmen kann, und
- c) die Enden der Polymerkette praktisch vollständig mit monofunktionellen, im Polymer nicht weiterreagierenden Resten R³ verschlossen sind, die unabhängig voneinander gleich oder verschieden sein können.
wherein
Ar³ is a divalent substituted or unsubstituted aromatic radical whose free valences are in the para or meta position or in a comparable parallel or angled position to one another,
Ar⁴ can have one of the meanings given for Ar³ or represents a group -Ar⁷-Z-Ar⁷-,
where Z is a -C (CH₃) ₂- or -O-Ar⁷-O bridge and
Ar⁷ represents a divalent aromatic radical,
Ar⁵ and Ar⁶ are the same or different from one another and represent a substituted or unsubstituted para- or meta-arylene radical,
Y represents a -C (CH₃) ₂-, SO₂-, -S- or -C (CF₃) ₂ bridge,
in which
- a) the polyether amide has an average molecular weight (number average) in the range from 5000 to 50,000,
- b) the molecular weight control is carried out specifically by non-stoichiometric addition of the monomer units, the sum of the mole fractions x, y and z being one, the sum of x and z not being y and x being able to assume the value zero, and
- c) the ends of the polymer chain are almost completely closed with monofunctional radicals R³ which do not react further in the polymer and which, independently of one another, can be the same or different.
Bindefasern auf Basis dieser Aramide sind thermoplastisch verarbeitbar, zeichnen sich durch ein besonders gutes Schmelzverhalten aus und führen zu Vliesstoffen mit einer ausgezeichneten Festigkeit.Binding fibers based on these aramids can be processed thermoplastically and are particularly good Melting behavior and lead to nonwovens with excellent strength.
Bei Ar³ kann es sich um einen einkernigen oder kondensierten zweikernigen aromatischen zweiwertigen Rest handeln oder um einen Rest der Formel -Ar⁷-Q-Ar⁷-, worin Ar⁷ die oben definierte Bedeutung besitzt und Q eine direkte C-C-Bindung ist oder eine -O-, -CO-, -S-, -SO- oder -SO₂-Brücke bedeutet.
Bei Ar³ kann es sich um heterocyclisch-aromatische oder bevorzugt um carbocyclisch-aromatische Reste handeln. Heterocyclisch-aromatische Reste weisen vorzugsweise ein oder zwei Sauerstoff- und/oder Schwefel- und/oder Stickstoffatome in Kern auf.
Bei Ar⁵ und Ar⁶ handelt es sich im allgemeinen um carbocyclisch-aromatische Arylenreste, deren freie Valenzen sich in para- oder meta-Stellung oder in vergleichbarer paralleler oder gewinkelter Stellung zueinander befinden, vorzugsweise handelt es sich um einkernige aromatische Reste.
Ar⁷ hat im allgemeinen eine der für Ar⁵ bzw. Ar⁶ definierten Bedeutungen .Ar³ can be a mononuclear or condensed dinuclear aromatic divalent radical or a radical of the formula -Ar⁷-Q-Ar⁷-, in which Ar⁷ has the meaning defined above and Q is a direct CC bond or an -O-, -CO-, -S-, -SO- or -SO₂ bridge means.
Ar³ can be heterocyclic-aromatic or preferably carbocyclic-aromatic radicals. Heterocyclic aromatic radicals preferably have one or two oxygen and / or sulfur and / or nitrogen atoms in the nucleus.
Ar⁵ and Ar⁶ are generally carbocyclic-aromatic arylene radicals whose free valences are in the para or meta position or in a comparable parallel or angled position to one another, preferably mononuclear aromatic radicals.
Ar⁷ generally has one of the meanings defined for Ar⁵ or Ar⁶.
Beispiele für Reste -Ar³-, -Ar⁴-, -Ar⁵- und -Ar⁶- sind p-Phenylen, m-Phenylen, Biphenyl-4,4'-diyl oder Naphthalin-1,4-diyl.Examples of residues -Ar³-, -Ar⁴-, -Ar⁵- and -Ar⁶- are p-phenylene, m-phenylene, biphenyl-4,4'-diyl or naphthalene-1,4-diyl.
Beispiele für Substituenten, die sich gegebenenfalls an den Resten -Ar¹- bis -Ar⁶- befinden, sind verzweigte oder insbesondere geradkettige C₁-C₆ Alkylreste, wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, n-Pentyl oder n-Hexyl, sowie die entsprechenden Perfluorderivate mit bis zu sechs C-Atomen oder die entsprechenden Alkoxyderivate. Bevorzugt wird Methyl.Examples of substituents which are optionally on the radicals -Ar¹- to -Ar⁶- are branched or in particular straight-chain C₁-C₁ alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl or n- Hexyl, as well as the corresponding perfluoro derivatives with up to six carbon atoms or the corresponding alkoxy derivatives. Methyl is preferred.
Beispiele für Halogensubstituenten sind Brom oder insbesondere Chlor.Examples of halogen substituents are bromine or especially chlorine.
Die erfindungsgemäß bevorzugt verwendeten aromatischen Polyetheramide der Formel II werden durch eine gezielte Molekulargewichtskontrolle durch nicht stöchiometrische Zugabe der Monomereinheiten hergestellt, wobei die Summe der Molenbrüche x, y und z eins ist, die Summe von x und z aber nicht gleich y sein darf und x den Wert Null annehmen kann. In einer bevorzugten Ausführung ist z größer als x.The aromatic polyetheramides of the formula II which are preferably used in accordance with the invention are produced by a targeted molecular weight control by non-stoichiometric addition of the monomer units, the sum of the mole fractions x, y and z being one, but the sum of x and z not being equal to y and x being the Can assume zero value. In a preferred embodiment, z is greater than x.
Nach Abschluß der Polykondensationsreaktion werden die Enden der Polymerkette durch Zugabe von Reagenzien, die im Polymer zu nicht weiterreagierenden Gruppen reagieren, vollständig verschlossen. Die Endgruppen sind dabei unabhängig voneinander, und können gleich oder verschieden sein und werden bevorzugt aus einer Gruppe der Formeln III, IV, V und/oder VI ausgewählt.
Für den Fall der Endgruppen V und/oder VI, ist der terminale Stickstoff in Formel (II) ein Imidstickstoff.In the case of the end groups V and / or VI, the terminal nitrogen in formula (II) is an imide nitrogen.
E stellt in den oben angegebenen Formeln ein Wasserstoff- oder ein Halogenatom, insbesondere ein Chlor-, Brom- oder Fluoratom, oder einen organischen Rest, beispielsweise eine Aryl(oxy)gruppe dar.In the formulas given above, E represents a hydrogen or a halogen atom, in particular a chlorine, bromine or fluorine atom, or an organic radical, for example an aryl (oxy) group.
Das aromatische Polyetheramid der Formel II kann durch Umsetzung von ein oder mehreren Dicarbonsäurederivaten mit einem oder mehreren Diaminen nach dem Lösungs-, Fällungs- oder Schmelzkondensationsverfahren hergestellt werden, wobei eine der Komponenten im stöchiometrischen Unterschuß eingesetzt wird und nach Beendigung der Polykondensation ein Kettenverschlußmittel zugegeben wird.The aromatic polyether amide of the formula II can be prepared by reacting one or more dicarboxylic acid derivatives with one or more diamines by the solution, precipitation or melt condensation process, one of the components being used in a stoichiometric deficit and a chain lock agent being added after the polycondensation has ended.
Es wurde gefunden, daß sich thermoplastische aromatische Polyetheramide die sehr gute mechanischen Eigenschaften besitzen über konventionelle Techniken herstellen lassen, wenn
- a) das Molekulargewicht durch Verwendung nicht stöchiometrischer Mengen der Monomeren gezielt kontrolliert wird,
- b) die Enden der Polymerkette durch monofunktionelle, im Polymer nicht weiter reagierende Verbindungen vollständig verschlossen werden, und vorzugsweise
- c) der Gehalt an anorganischen Verunreinigungen im Polymer nach der Aufarbeitung und Isolierung 500 ppm nicht übersteigt.
- a) the molecular weight is specifically controlled by using non-stoichiometric amounts of the monomers,
- b) the ends of the polymer chain are completely closed by monofunctional compounds which do not react further in the polymer, and preferably
- c) the content of inorganic impurities in the polymer after processing and isolation does not exceed 500 ppm.
Die erfindungsgemäß bevorzugt eingesetzten thermoplastischen aromatischen Polyamide der Formel II zeichnen sich ferner dadurch aus, daß diese ein mittleres Molekulargewicht im Bereich von 5000 bis 50000 und eine niedrige Schmelzviskosität, die 10 000 Pas nicht überschreitet, aufweisen.The thermoplastic aromatic polyamides of the formula II which are preferably used according to the invention are further distinguished by the fact that they have an average molecular weight in the range from 5000 to 50,000 and a low melt viscosity which does not exceed 10,000 Pas.
Zur Herstellung dieser bevorzugten Polyetheramide eignen sich folgende Verbindungen:
Dicarbonsäurederivate der Formel (VII)
W - CO - Ar³ - CO - W (VII)
wobei Ar³ die oben angegebene Bedeutung hat, und W ein Fluor-, Chlor-, Brom- oder Jodatom, bevorzugt ein Chloratom, oder eine -OH oder OR⁴ Gruppe, wobei R⁴ ein verzweigter oder unverzweigter aliphatischer oder aromatischer Rest ist, darstellen kann.The following compounds are suitable for the preparation of these preferred polyetheramides:
Dicarboxylic acid derivatives of the formula (VII)
W - CO - Ar³ - CO - W (VII)
wherein Ar³ has the meaning given above, and W can represent a fluorine, chlorine, bromine or iodine atom, preferably a chlorine atom, or an -OH or OR⁴ group, where R⁴ is a branched or unbranched aliphatic or aromatic radical.
Beispiele für Verbindungen der Formel (VII) sind:
Terephthalsäure
Terephthalsäuredichlorid
Terephthalsäurediphenylester
Isophthalsäure
Isophthalsäurediphenylester
Isophthalsäurechlorid
Phenoxyterephthalsäure
Phenoxytherephthalsäuredichlorid
Phenoxyterephthalsäurediphenylester
Di(n-Hexyloxy)terephthalsäure
Bis-(n-Hexyloxy)terepthalsäuredichlorid
Bis-(n-Hexyloxy)terephthalsäurediphenylester
2,5-Furandicarbonsäure
2,5-Furandicarbonsäurechlorid
2,5-Furandiphenylester
Thiophendicarbonsäure
Naphthalin-2,6-dicarbonsäure
Diphenylether-4,4'-dicarbonsäure
Benzophenon-4,4'-dicarbonsäure
Isopropyliden-4,4'-dibenzoesäure
Diphenylsulfon-4,4'-dicarbonsäure
Tetraphenylthiophen-dicarbonsäure
Diphenylsulfoxid-4,4'-dicarbonsäure
Diphenylthioether-4,4'-dicarbonsäure
Trimethylphenylindandicarbonsäure
Als aromatische Diamine der Formel (VIII)
H₂N - Ar⁴ - NH₂ (VIII)
in der Ar⁴- die oben angegebene Bedeutung hat, eigenen sich vorzugsweise folgende Verbindungen:
m-Phenylendiamin
p-Phenylendiamin
2,4-Dichlor-p-phenylendiamin
Diaminopyridin
Bis(aminophenoxy)benzol
2,6-Bis(aminophenoxy)pyridin
3,3'-Dimethylbenzidin
4,4'- und 3,4'-Diaminodiphenylether
Isopropyliden-4,4'-dianilin
p,p'- und m,m'-Bis(4-aminophenylisopropyliden)benzol
4,4'- und 3,3'-Diaminobenzophenon
4,4'- und 3,3'-Diaminodiphenylsulfon
Bis(2-amino-3-methylbenzo)thiophen-S,S-dioxid
Als aromatische Diamine kommen ferner solche der Formel (IX) in Betracht
H₂N - Ar⁵ - O - Ar⁶ - Y - Ar⁶ - O - Ar⁵ - NH₂ (IX)
wobei Ar⁵, Ar⁶ und Y die oben angegebene Bedeutung haben.Examples of compounds of the formula (VII) are:
Terephthalic acid
Terephthalic acid dichloride
Diphenyl terephthalate
Isophthalic acid
Diphenyl isophthalate
Isophthaloyl chloride
Phenoxy terephthalic acid
Phenoxytherephthalic acid dichloride
Phenoxyterephthalic acid diphenyl ester
Di (n-hexyloxy) terephthalic acid
Bis (n-hexyloxy) terephthalic acid dichloride
Bis- (n-hexyloxy) terephthalic acid diphenyl ester
2,5-furanedicarboxylic acid
2,5-furandicarboxylic acid chloride
2,5-furan diphenyl ester
Thiophene dicarboxylic acid
Naphthalene-2,6-dicarboxylic acid
Diphenyl ether 4,4'-dicarboxylic acid
Benzophenone 4,4'-dicarboxylic acid
Isopropylidene-4,4'-dibenzoic acid
Diphenylsulfone-4,4'-dicarboxylic acid
Tetraphenylthiophene dicarboxylic acid
Diphenyl sulfoxide-4,4'-dicarboxylic acid
Diphenylthioether-4,4'-dicarboxylic acid
Trimethylphenylindane dicarboxylic acid
As aromatic diamines of the formula (VIII)
H₂N - Ar⁴ - NH₂ (VIII)
in which Ar⁴- has the meaning given above, the following compounds are preferably suitable:
m-phenylenediamine
p-phenylenediamine
2,4-dichloro-p-phenylenediamine
Diaminopyridine
Bis (aminophenoxy) benzene
2,6-bis (aminophenoxy) pyridine
3,3'-dimethylbenzidine
4,4'- and 3,4'-diaminodiphenyl ether
Isopropylidene-4,4'-dianiline
p, p'- and m, m'-bis (4-aminophenylisopropylidene) benzene
4,4'- and 3,3'-diaminobenzophenone
4,4'- and 3,3'-diaminodiphenyl sulfone
Bis (2-amino-3-methylbenzo) thiophene-S, S-dioxide
Aromatic diamines which may also be used are those of the formula (IX)
H₂N - Ar⁵ - O - Ar⁶ - Y - Ar⁶ - O - Ar⁵ - NH₂ (IX)
where Ar⁵, Ar⁶ and Y have the meaning given above.
Als aromatische Diamine der Formel (IX) kommen in Betracht:
2,2-Bis-[4-(3-trifluormethyl-4-aminophenoxy)phenyl]propan
Bis-[4-(4-aminophenoxy)phenyl]sulfid
Bis-[4-(3-aminophenoxy)phenyl]sulfid
Bis-[4-(3-aminophenoxy)phenyl]sulfon
Bis-[4-(4-aminophenoxy)phenyl]sulfon
2,2-Bis-[4-(4-aminophenoxy)phenyl]propan
2,2-Bis-[4-(3-aminophenoxy)phenyl]propan
2,2-Bis-[4-(2-aminophenoxy)phenyl]propan
1,1,1,3,3,3-Hexafluor-2,2-bis-[4-(4-aminophenoxy)phenyl]
propan,
Der Herstellung der erfindungsgemäß eingesetzten Polyetheramide erfolgt bevorzugt über Lösungskondensationsprozesse.Aromatic diamines of the formula (IX) are:
2,2-bis- [4- (3-trifluoromethyl-4-aminophenoxy) phenyl] propane
Bis- [4- (4-aminophenoxy) phenyl] sulfide
Bis- [4- (3-aminophenoxy) phenyl] sulfide
Bis- [4- (3-aminophenoxy) phenyl] sulfone
Bis- [4- (4-aminophenoxy) phenyl] sulfone
2,2-bis- [4- (4-aminophenoxy) phenyl] propane
2,2-bis [4- (3-aminophenoxy) phenyl] propane
2,2-bis- [4- (2-aminophenoxy) phenyl] propane
1,1,1,3,3,3-hexafluoro-2,2-bis- [4- (4-aminophenoxy) phenyl]
propane,
The polyetheramides used according to the invention are preferably prepared via solution condensation processes.
Die Lösungskondensation des aromatischen Dicarbonsäuredichlorids mit den aromatischen Diaminen erfolgt in aprotischen, polaren Lösungsmitteln vom Amidtyp, wie z.B. in N,N-Dimethyl-acetamid, vorzugsweise in N-Methyl-2-pyrrolidon. Gegebenenfalls können diesen Lösungsmitteln in bekannter Weise zur Erhöhung der Lösefähigkeit, bzw. zur Stabilisierung der Polyetheramidlösungen, Halogenidsalze der ersten und/oder zweiten Gruppe des periodischen Systems zugesetzt werden. Bevorzugte Zusätze sind Calciumchlorid und/oder Lithiumchlorid. In einer bevorzugten Ausführungsform wird die Kondensation ohne Salzzusatz durchgeführt, da sich die oben beschriebenen aromatischen Polyetheramide durch eine hohe Löslichkeit in den obengenannten Lösungsmitteln des Amidtyps auszeichnen.The solution condensation of the aromatic dicarboxylic acid dichloride with the aromatic diamines takes place in aprotic, polar solvents of the amide type, e.g. in N, N-dimethyl-acetamide, preferably in N-methyl-2-pyrrolidone. Optionally, these solvents can be added in a known manner to increase the solvency or to stabilize the polyether amide solutions, halide salts of the first and / or second group of the periodic system. Preferred additives are calcium chloride and / or lithium chloride. In a preferred embodiment, the condensation is carried out without the addition of salt, since the aromatic polyetheramides described above are notable for high solubility in the amide-type solvents mentioned above.
Die erfindungsgemäß bevorzugt eingesetzten Polyamide der Formel II erlauben eine thermoplastische Verarbeitung nach Standardmethoden. Sie lassen sich herstellen, wenn mindestens eine der Ausgangskomponenten im stöchiometrischen Unterschuß eingesetzt wird. Auf diese Weise ist es möglich eine Begrenzung des Molekulargewichtes entsprechend der bekannten Carothers Gleichung zu erreichen:
wobei
q = Molverhältnis der Disäurekomponenten zu AminkomponentenThe polyamides of the formula II preferably used according to the invention allow thermoplastic processing by standard methods. They can be produced if at least one of the starting components is used in the stoichiometric deficit. In this way it is possible to limit the molecular weight according to the well-known Carothers equation:
in which
q = molar ratio of the diacid components to amine components
Beim Arbeiten mit einem Unterschuß an Säuredichlorid wird am Ende der Polymerisationsreaktion als Kettenverschlußmittel ein monofunktionelles aromatisches Säurechlorid oder Säureanhydrid zugegeben, beispielsweise Benzoylchlorid, Fluorbenzoylchlorid Diphenylcarbonsäurechlorid, Phenoxybenzoylchlorid oder aber Phthalsäureanhydrid, Naphthalsäureanhydrid, Chlornaphthalsäuranhydrid.When working with a deficit of acid dichloride, a monofunctional aromatic acid chloride or acid anhydride is added, for example, at the end of the polymerization reaction as a chain lock Benzoyl chloride, fluorobenzoyl chloride, diphenylcarboxylic acid chloride, phenoxybenzoyl chloride or else phthalic anhydride, naphthalic anhydride, chloronaphthalic anhydride.
Derartige Kettenverschlußmittel können gegebenenfalls substituiert sein, vorzugsweise mit Fluor- oder Chloratomen. Bevorzugt wird Benzoylchlorid oder Phthalsäureanhydrid, besonders bevorzugt Benzoylchlorid, eingesetzt.Such chain locking agents can optionally be substituted, preferably with fluorine or chlorine atoms. Benzoyl chloride or phthalic anhydride is preferably used, particularly preferably benzoyl chloride.
Wird mit einem Unterschuß an Diaminkomponente gearbeitet, so wird nach Ende der Polykondensation als Kettenverschlußmittel ein monofunktionelles, vorzugsweise aromatisches Amin eingesetzt, beispielsweise Fluoranilin, Chloranilin, 4-Aminodiphenylamin, Aminobiphenylamin, Aminodiphenylether, Aminobenzophenon oder Aminochinolin.If a deficit of diamine component is used, a monofunctional, preferably aromatic amine, for example fluoraniline, chloroaniline, 4-aminodiphenylamine, aminobiphenylamine, aminodiphenyl ether, aminobenzophenone or aminoquinoline, is used as chain closing agent after the end of the polycondensation.
In einer besonders bevorzugten Ausführungsform des Polykondensationsverfahrens wird Disäurechlorid im Unterschuß mit Diamin polykondensiert und anschließend werden die verbliebenen reaktiven Aminogruppen mit einem monofunktionellen Säurechlorid oder Disäureanhydrid desaktiviert.In a particularly preferred embodiment of the polycondensation process, diacid chloride is polycondensed in a deficit with diamine and then the remaining reactive amino groups are deactivated with a monofunctional acid chloride or diacid anhydride.
In einer weiteren bevorzugten Ausführungsform wird das Disäurechlorid im Unterschuß eingesetzt und mit einem Diamin polykondensiert. Anschließend werden mit einem monofunktionellen, vorzugsweise aromatischen, gegebenenfalls substituierten Säurechlorid oder Säureanhydrid, die verbliebenen reaktiven Aminoendgruppen desaktiviert.In a further preferred embodiment, the diacid chloride is used in a deficit and polycondensed with a diamine. The remaining reactive amino end groups are then deactivated with a monofunctional, preferably aromatic, optionally substituted acid chloride or acid anhydride.
Das Kettenverschlußmittel, d.h. das monofunktionelle Amin bzw. Säurechlorid oder Säureanhydrid, wird dabei bevorzugt in einer stöchiometrischen oder überstöchiometrischen Menge, bezogen auf die Disäure- bzw. Diaminkomponente, eingesetzt.The chain locking agent, ie the monofunctional amine or acid chloride or acid anhydride, is preferably used in a stoichiometric or superstoichiometric amount, based on the diacid or diamine component.
Zur Herstellung der erfindungsgemäß bevorzugt eingesetzten aromatischen Polyamide kann das Mol-Verhältnis q (Säurekomponenten zu Diaminkomponenten) im Bereich von 0,90 bis 1,10 variiert werden, wobei exakte Stöchiometrie (q = 1) der bifunktionellen Komponenten ausgeschlossen ist. Besonders bevorzugt liegt das Mol-Verhältnis im Bereich von 0,90 bis 0,99 und 1,01 bis 1,10, besonders bevorzugt im Bereich von 0,93 bis 0,98 und 1,02 bis 1,07, insbesondere im Bereich von 0,95 bis 0,97 und 1,03 bis 1,05.To produce the aromatic polyamides preferably used according to the invention, the molar ratio q (acid components to diamine components) can be varied in the range from 0.90 to 1.10, exact stoichiometry (q = 1) of the bifunctional components being excluded. The molar ratio is particularly preferably in the range from 0.90 to 0.99 and 1.01 to 1.10, particularly preferably in the range from 0.93 to 0.98 and 1.02 to 1.07, in particular in the range from 0.95 to 0.97 and 1.03 to 1.05.
Die Polykondensationstemperaturen liegen üblicherweise zwischen -20 und +120 °C, bevorzugt zwischen +10 und +100 °C. Besonders gute Ergebnisse werden bei Reaktionstemperaturen zwischen +10 und + 80 °C erzielt. Die Polykondensationsreaktionen werden vorzugsweise so ausgeführt, daß nach Abschluß der Reaktion 2 bis 40, vorzugsweise 5 bis 30 Gew.-% an Polykondensat in der Lösung vorliegen. Für spezielle Anwendungen kann die Lösung bei Bedarf mit N-Methyl-2-pyrrolidon oder anderen Lösungsmitteln, beispielsweise DMF, DMAC oder Butylcellosolve, verdünnt werden oder unter vermindertem Druck konzentriert werden (Dünnschichtverdampfer).The polycondensation temperatures are usually between -20 and +120 ° C, preferably between +10 and +100 ° C. Particularly good results are achieved at reaction temperatures between +10 and + 80 ° C. The polycondensation reactions are preferably carried out such that 2 to 40, preferably 5 to 30,% by weight of polycondensate are present in the solution after the reaction has ended. For special applications, the solution can be diluted with N-methyl-2-pyrrolidone or other solvents, e.g. DMF, DMAC or butyl cellosolve, if necessary, or concentrated under reduced pressure (thin film evaporator).
Nach Beendigung der Polykondensation wird der entstandene, locker an das Amidlösungsmittel gebundene Chlorwasserstoff durch Zugabe säurebindender Hilfsstoffe entfernt. Geeignet sind dafür beispielsweise Lithiumhydroxyd, Calciumhydroxyd, insbesondere aber Calciumoxid, Propylenoxid, Ethylenoxid oder Ammoniak. In einer besonderen Ausführungsform wird als "säurebindendes" Mittel reines Wasser verwendet, welches die Salzsäure verdünnt und gleichzeitig zur Ausfällung des Polymeren dient. Zur Herstellung von geformten Gebilden gemäß der vorliegenden Erfindung werden die oben beschriebenen erfindungsgemäßen Copolyamidlösungen filtriert, entgast und in an sich bekannter Weise zu Aramidfasern- oder -fäden weiterverarbeitet.After the polycondensation has ended, the hydrogen chloride formed, loosely bound to the amide solvent, is removed by adding acid-binding auxiliaries. For example, lithium hydroxide, calcium hydroxide, but in particular calcium oxide, propylene oxide, ethylene oxide or ammonia are suitable. In a particular embodiment, pure water is used as the "acid-binding" agent, which dilutes the hydrochloric acid and at the same time serves to precipitate the polymer. For the production of shaped structures according to the present invention, the copolyamide solutions according to the invention described above are filtered, degassed and further processed in a manner known per se to give aramid fibers or threads.
Gegebenenfalls können den Lösungen noch geeignete Mengen an Additiven zugesetzt werden. Beispiele sind Lichtstabilisatoren, Antioxidationsmittel, Flammschutzmittel, Antistatika, Farbstoffe, Farbpigmente oder Füllstoffe.If necessary, suitable amounts of additives can also be added to the solutions. Examples are light stabilizers, antioxidants, flame retardants, antistatic agents, dyes, color pigments or fillers.
Zur Isolierung des Polyetheramids kann die Lösung mit einem Fällungsmittel versetzt und das koagulierte Produkt abfiltriert werden. Typische Fällungsmittel sind beispielsweise Wasser, Methanol, Aceton, die gegebenenfalls auch pH-kontrollierende Zusätze wie z.B. Ammoniak oder Essigsäure enthalten können.To isolate the polyether amide, a precipitant can be added to the solution and the coagulated product can be filtered off. Typical precipitants are, for example, water, methanol, acetone, which may also contain pH-controlling additives such as May contain ammonia or acetic acid.
Bevorzugt erfolgt die Isolierung durch Zerkleinern der Polymerlösung mit einem Überschuß an Wasser in einer Schneidmühle. Die fein zerkleinerten koagulierten Polymerteilchen erleichtern die nachfolgenden Waschschritte (Entfernen der aus der Salzsäure gebildeten Folgeprodukte) und die Trocknung des Polymeren (Vermeiden von Einschlüssen) nach Abfiltration. Auch eine nachträgliche Zerkleinerung erübrigt sich, da direkt ein rieselfähiges Produkt entsteht.The isolation is preferably carried out by comminuting the polymer solution with an excess of water in a cutting mill. The finely crushed coagulated polymer particles facilitate the subsequent washing steps (removal of the secondary products formed from the hydrochloric acid) and drying of the polymer (avoiding inclusions) after filtration. Subsequent shredding is also unnecessary, since a free-flowing product is created directly.
Außer der beschriebenen Lösungskondensation, die als leicht zugängliches Verfahren gilt, können wie bereits erwähnt, auch andere übliche Verfahren zur Herstellung von Polyamiden, wie beispielsweise Schmelz-, oder Feststoffkondensation, angewendet werden. Auch diese Verfahren beinhalten neben der Kondensation unter Regelung der Molmasse, Reinigungs- oder Waschschritte sowie den Zusatz geeigneter Additive. Die Additive können darüber hinaus auch dem isolierten Polymer bei der thermoplastischen Verarbeitung zugesetzt werden.In addition to the solution condensation described, which is considered to be an easily accessible process, as already mentioned, other customary processes for the production of polyamides, such as melt or solid condensation, can also be used. In addition to condensation with regulation of the molar mass, these processes also include cleaning or washing steps and the addition of suitable additives. The additives can also be added to the isolated polymer during thermoplastic processing.
Die erfindungsgemäß bevorzugt eingesetzten aromatischen Polyamide der Formel II besitzen überraschend gute mechanische Eigenschaften und hohe Glastemperaturen. Der Staudingerindex [η]o liegt im Bereich von 0,4 bis 1,5 dl/g, bevorzugt im Bereich von 0,5 bis 1,3 dl/g, besonders bevorzugt im Bereich von 0,6 bis 1,1 dl/g. Die Glastemperaturen liegen im allgemeinen über 180 °C, bevorzugt über 200 °C, die Verarbeitungstemperaturen im Bereich von 320 bis 380 °C, bevorzugt im Bereich von 330 bis 370 °C, besonders bevorzugt im Bereich von 340 bis 360 °C.The aromatic polyamides of the formula II which are preferably used according to the invention have surprisingly good mechanical properties and high glass transition temperatures. The Staudinger index [η] o is in the range from 0.4 to 1.5 dl / g, preferably in the range from 0.5 to 1.3 dl / g, particularly preferably in the range from 0.6 to 1.1 dl / g G. The glass transition temperatures are generally above 180 ° C., preferably above 200 ° C., the processing temperatures in the range from 320 to 380 ° C., preferably in the range from 330 to 370 ° C., particularly preferably in the range from 340 to 360 ° C.
Die Verarbeitung dieser Polyamide kann über Extrusionsprozesse erfolgen, da die Schmelzviskositäten 10.000 Pas nicht überschreiten. Die Extrusion kann auf üblichen Ein- oder Zweischneckenextrudern erfolgen.These polyamides can be processed using extrusion processes since the melt viscosity does not exceed 10,000 Pas. The extrusion can be carried out on conventional single or twin screw extruders.
Die Herstellung der erfindungsgemäßen Vliesstoffe kann auf jede der an sich bekannten Weisen erfolgen. Zu Einsatz können Stapelfasern oder Kurzfasern oder auch Endlosfilamente aus den beiden Aramidsorten gelangen. Die Vliesbildung kann über trockene oder nasse Verarbeitung erfolgen.The nonwovens according to the invention can be produced in any of the ways known per se. Staple fibers or short fibers or also continuous filaments from the two types of aramid can be used. The formation of the fleece can take place via dry or wet processing.
Handelt es sich bei mindestens einer Fasersorte um ein nicht in organischen Lösungsmitteln lösliches Aramid, so wird man vorzugsweise die Verarbeitung über Stapel- oder Kurzfasern wählen.If at least one type of fiber is an aramide that is not soluble in organic solvents, processing with staple or short fibers is preferred.
Bevorzugt stellt man in einem solchen Falle Kardenvliese her. Dabei erfolgt die Mischung der beiden Fasersorten bevorzugt vor der Kardierung.In such a case, it is preferred to produce carded nonwovens. The two types of fibers are preferably mixed before carding.
Ebenso lassen sich die erfindungsgemäßen Vliesstoffe aber auch nach anderen an sich üblichen Vliesbildungstechniken herstellen, beispielsweise durch Naßvliestechnik (insbesondere zur Herstellung papierähnlicher Vliesstoffe) oder die aerodynamische oder die hydrodynamische Vliesbildung (insbesondere zur Herstellung fülliger Vliesstoffe).Likewise, the nonwovens according to the invention can, however, also be produced by other conventional nonwoven formation techniques, for example by wet nonwoven technology (in particular for producing paper-like nonwovens) or aerodynamic or hydrodynamic nonwoven formation (in particular for producing bulky nonwovens).
Die Erfindung betrifft insbesondere Papiere auf Basis der erfindungsgemäßen Vliesstoffe, die gekennzeichnet sind durch einen Gehalt von etwa 70 bis 98 Gew.-%, insbesondere 80 bis 90 Gew.-% von tragenden Aramidfasern in Form von Stapelfasern, die fibrilliert sind, und einen Gehalt von etwa 2 bis 30 Gew.-%, insbesondere 10 bis 20 Gew.-% von Bindefasern aus thermoplastischen Aramiden, die durch ein Anschmelzen der Trägerfasern an die Bindefasern oder durch ein praktisch vollständiges Aufschmelzen der Bindefasern verfestigt sind.The invention relates in particular to papers based on the nonwovens according to the invention, which are characterized by a content of approximately 70 to 98% by weight, in particular 80 to 90% by weight, of load-bearing aramid fibers in the form of staple fibers which are fibrillated and a content from about 2 to 30% by weight, in particular 10 to 20% by weight, of binding fibers made of thermoplastic aramides, which are solidified by melting the carrier fibers onto the binding fibers or by practically completely melting the binding fibers.
Die Stapellängen der tragenden Aramidfasern betragen im allgemeinen 2 bis 6 mm.The stack lengths of the supporting aramid fibers are generally 2 to 6 mm.
Die Fasern können durch Schneiden oder durch Reißen hergestellt werden. Vorzugsweise wird eine Fibrillierung dieser Fasern durch mechanisches Bearbeiten durchgeführt, beispielsweise durch Behandeln einer wäßrigen Suspension der Aramidstapelfasern in einem Dissolver. Die Aramidbindefasern werden bevorzugt in Form von Stapelfasern eingesetzt. Die Stapellänge der Bindefasern entspricht vorzugsweise etwa der Stapellänge der Trägerfasern. Die Bindefasern können als solche eingesetzt werden, d.h. ein vorhergehendes Fibrillieren ist nicht unbedingt erforderlich.The fibers can be made by cutting or tearing. These fibers are preferably fibrillated by mechanical processing, for example by treating an aqueous suspension of the aramid staple fibers in a dissolver. The aramid binding fibers are preferably used in the form of staple fibers. The staple length of the binding fibers preferably corresponds approximately to the staple length of the carrier fibers. The binder fibers can be used as such, i.e. prior fibrillation is not absolutely necessary.
Zur Herstellung des Papiers werden die beiden Fasertypen, die ihrerseits in Form von Gemischen vorliegen können, miteinander vermischt. Dies erfolgt im allgemeinen in wäßrigem Medium. Die derart hergestellte Suspension wird auf eine Siebunterlage aufgebracht, wobei das wäßrige Medium abgetrennt wird und die miteinander verfilzten Fasern auf der Unterlage zurückbleiben. Das auf diese Weise erhaltene Flächengebilde wird durch Hitzebehandlung stabilisiert und/oder endverfestigt. Gegebenenfalls wird die Hitzebehandlung unter Druck durchgeführt.To produce the paper, the two types of fibers, which in turn can be in the form of mixtures, are mixed together. This is generally done in an aqueous medium. The suspension produced in this way is applied to a sieve pad, the aqueous medium being separated off and the fibers which have been felted together remaining on the pad. The fabric obtained in this way is stabilized and / or solidified by heat treatment. If necessary, the heat treatment is carried out under pressure.
Typische Temperaturen für den Verfestigungsschritt sind von den im Einzelfall ausgewählten Fasertypen abhängig und können vom Fachmann anhand von einfachen Versuchsreihen ermittelt werden. Die auf diese Weise hergestellten Papiere weisen - je nach angewendeten Verfestigungsbedingungen - entweder praktisch keine Bindefasern mehr auf, d.h. die Bindefasern sind durch den Verfestigungsschritt so vollständig aufgeschmolzen, daß ihre Faserform verloren gegangen ist, oder die Schmelzfasern sind zum Teil erhalten geblieben, und es ist lediglich ein Anschmelzen der Trägerfasern an die Bindefasern erfolgt.Typical temperatures for the consolidation step depend on the fiber types selected in the individual case and can be determined by a person skilled in the art using simple test series. The papers produced in this way - depending on the consolidation conditions used - either have practically no binding fibers, i.e. the binding fibers have melted so completely through the consolidation step that their fiber shape has been lost, or some of the melting fibers have been preserved, and only the carrier fibers have melted onto the binding fibers.
Die erfindungsgemäßen Papiere können insbesondere zur Herstellung von Schichtstoffen verwendet werden, beispielsweise als Deckschichten bei der Verstärkung von "Honeycomb-Schichtstoffen", wie in der WO-A-84/04727 beschrieben oder bei der Verstärkung von Netzwerkstoffen, wie in der EP-A-158,234 beschrieben.The papers according to the invention can be used in particular for the production of laminates, for example as top layers in the reinforcement of "honeycomb laminates", as described in WO-A-84/04727 or in the reinforcement of network materials, as in EP-A- 158,234.
Die in einem ersten Schritt hergestellten Vliese können gegebenenfalls vor der Endverfestigung noch vorverfestigt werden. Dies kann beispielsweise durch Nadeln erfolgen.The nonwovens produced in a first step can optionally be pre-consolidated before final consolidation. This can be done for example by needles.
Die Endverfestigung zu den erfindungsgemäßen Vliesstoffen erfolgt durch Erhitzen des anfänglich erhaltenen Vlieses auf eine Temperatur, bei der die Bindefasern schmelzen und/oder sich thermoplastisch verformen, wobei sie unter Verlust ihrer Faserstruktur meist sogenannte "Bindesegel" an den Kreuzungspunkten der tragenden Aramidfasern ausbilden. Das Erhitzen kann durch Behandlung mit einem heißen Trägermedium, beispielsweise mit Luft erfolgen, oder durch Behandlung mit heißen Walzen oder Kalandern, die gegebenenfalls eine Oberflächenstruktur aufweisen, und dem Vliesstoff eine Prägestruktur verleihen.The final consolidation to the nonwovens according to the invention is carried out by heating the initially obtained nonwoven to a temperature at which the binding fibers melt and / or deform thermoplastic, whereby they usually form so-called "binding sails" at the crossing points of the supporting aramid fibers while losing their fiber structure. The heating can be carried out by treatment with a hot carrier medium, for example with air, or by treatment with hot rollers or calenders, which may have a surface structure, and impart an embossed structure to the nonwoven fabric.
Die Dauer der Wärmebehandlung richtet sich z.B. nach den gewünschten Endeigenschaften, nach den Dimensionen des Vlieses und der Natur der das Vlies bildenden Fasersorten. Der Schmelzpunkt der Bindefasern liegt üblicherweise mindestens 10 °C unter dem Schmelz- oder Zersetzungspunkt der tragenden Fasern, insbesondere mehr als 30 °C unter dem Schmelz- oder Zersetzungspunkt der tragenden Fasern.The duration of the heat treatment depends, for example, on the desired end properties, on the dimensions of the Fleece and the nature of the types of fibers forming the fleece. The melting point of the binding fibers is usually at least 10 ° C. below the melting or decomposition point of the supporting fibers, in particular more than 30 ° C. below the melting or decomposition point of the supporting fibers.
Bevorzugt wählt man den Schmelzpunkt der Bindefasern soweit unter dem Schmelz- oder Zersetzungspunkt der tragenden Fasern, so daß diese noch keine wesentlichen Eigenschaftsänderungen während der Wärmebehandlung erfahren.It is preferred to choose the melting point of the binding fibers below the melting or decomposition point of the supporting fibers so that they do not experience any significant changes in properties during the heat treatment.
Der Charakter der erfindungsgemäßen Vliesstoffe wird auch durch den Anteil an Schmelzbindern beeinflußt. Je nach Einsatzgebiet wird ein fülliger Vliesstoff mit nur wenigen Verklebungspunkten bevorzugt oder eine fast flächige Verbindung, z.B. für Schichtstoffe. Typische Werte für den Anteil an Schmelzbinder liegen im Bereich von 20-80 Gew.-% Bindefaser, bezogen auf die Mengen aus Bindefaser und tragender Faser.The character of the nonwovens according to the invention is also influenced by the proportion of melt binders. Depending on the area of application, a voluminous nonwoven with only a few bonding points is preferred or an almost flat connection, e.g. for laminates. Typical values for the proportion of melt binder are in the range of 20-80% by weight of binder fiber, based on the amounts of binder fiber and load-bearing fiber.
Die Flächengewichte der erfindungsgemäßen Vliesstoffe und die Einzeltiter und Stapellängen beider Fasersorten können in weiten Grenzen variiert werden und den Anforderungen der Weiterverarbeitungsprozesse und des Einsatzgebietes angepaßt werden. Typische Werte für die Flächengewichte betragen 30 bis 500 g/m². Typische Werte für die Einzeltiter der Fasern liegen im Bereich von 0,5 bis 5 dtex.The basis weights of the nonwovens according to the invention and the individual titer and stack lengths of both types of fibers can be varied within wide limits and adapted to the requirements of the further processing processes and the area of use. Typical values for the grammages are 30 to 500 g / m². Typical values for the individual titer of the fibers are in the range from 0.5 to 5 dtex.
Die die erfindungsgemäßen Vliesstoffe aufbauenden Filamente oder Stapelfasern können einem praktisch runden Querschnitt besitzen oder auch andere Formen aufweisen, wie hantel-, nierenförmige-, dreieckige- bzw. tri- oder multilobale Querschnitte. Es sind Hohlfasern einsetzbar. Ferner lassen sich die beiden Fasertypen in Form von Bi- oder Mehrkomponentenfasern kombinieren, wobei die Bindekomponente mindestens einen Teil der Faseroberfläche ausfüllt.The filaments or staple fibers making up the nonwovens according to the invention can have a practically round cross section or can also have other shapes, such as dumbbell, kidney-shaped, triangular or tri or multilobal cross sections. Hollow fibers can be used. Furthermore, the two types of fibers can be combined in the form of bicomponent or multicomponent fibers, the binding component filling at least part of the fiber surface.
Während bei den tragenden Verstärkungsfasern im allgemeinen auf hohe Werte für Festigkeit und Modul geachtet wird, können als schmelzende Matrixfasern auch weitgehend unorientierte Fasern verwendet werden.While high values for strength and modulus are generally taken into account in the load-bearing reinforcing fibers, largely unoriented fibers can also be used as the melting matrix fibers.
Zur Vliesherstellung werden die tragenden Aramid-Fasern in bekannter Weise aus Lösungmitteln ersponnen, und die thermoplastischen Aramide können aus der Lösung oder aus der Schmelze ersponnen werden.For the production of nonwovens, the supporting aramid fibers are spun from solvents in a known manner, and the thermoplastic aramids can be spun from the solution or from the melt.
Die erfindungsgemäßen Vliesstoffe bestehen praktisch ausschließlich aus aromatischen Polyamiden und weisen somit alle Vorteile dieser Polymeren auf, wie chemische und thermische Stabilität, eine extrem gute Flammfestigkeit und eine gute Verträglichkeit miteinander. Sie weisen weiterhin alle Vorteile schmelzgebundener Vliesstoffe auf, also etwa ein gutes Reiß- und Weiterreißverhalten.The nonwovens according to the invention consist practically exclusively of aromatic polyamides and thus have all the advantages of these polymers, such as chemical and thermal stability, extremely good flame resistance and good compatibility with one another. They also have all the advantages of melt-bonded nonwovens, i.e. good tear and tear behavior.
Die erfindungsgemäßen Vliesstoffe können in an sich üblicher Weise ausgerüstet sein, beispielsweise durch Zusatz von Antistatika, Farbstoffen oder bioziden Zusätzen.The nonwovens according to the invention can be finished in a conventional manner, for example by adding antistatic agents, dyes or biocidal additives.
Die erfindungsgemäßen Vliesstoffe lassen sich insbesondere auf Gebieten einsetzen, wo hohe Stabilitäten (chemisch, thermisch und mechanisch) gefragt sind. Beispiele dafür sind der Einsatz als Filtermaterialien, als Isoliermaterialien (thermisch und elektrisch) sowie als Verstärkungsmaterialien für unterschiedliche Substrate (z.B. Kunststoffe oder als Geotextilien).The nonwovens according to the invention can be used in particular in areas where high stability (chemical, thermal and mechanical) is required. Examples include the use as filter materials, as insulating materials (thermal and electrical) and as reinforcing materials for different substrates (e.g. plastics or as geotextiles).
Die nachfolgenden Beispiele beschreiben die Erfindung ohne diese zu begrenzen. Mengenangaben beziehen sich auf das Gewicht, sofern nichts anderes angegeben ist.The following examples describe the invention without limiting it. Quantities refer to the weight, unless otherwise stated.
Allgemeine Arbeitsvorschrift betreffend Herstellung von Aramidpapieren aus Faserpulp
Stapelfasern des Einzelfasertiters von 1,8 dtex aus Aramiden auf der Basis von Terephthalsäure, p-Phenylendiamin, Dimethylbenzidin und Bis-(4-aminophenoxy)-benzol der Schnittlänge 6 mm werden zu etwa 1 % in Wasser suspendiert und etwa 1,5 bis 2 Stunden im Dissolver bei etwa 1200 Umdrehungen/min behandelt, so daß die Stapelfasern fibrillieren. Überschüssiges Wasser wird abgesaugt und der erhaltene Faserpulp wird in feuchtem Zustand in Wasser aufgeschlämmt und mit unterschiedlichen Anteilen (vergl. Tabelle 1) Stapelfasern einer Schnittlänge von 6 mm aus schmelzbarem Aramid vermischt. Bei dem schmelzbaren Aramid handelt es sich um ein Copolymeres auf der Basis von Terephthalsäure, Isophthalsäure und 2,2'-Bis-(4-aminophenoxyphenyl)-propan, dessen Endgruppen mit Benzoylchlorid verschlossen sind.General working instructions regarding the production of aramid paper from fiber pulp
Staple fibers with a single fiber titer of 1.8 dtex from aramids based on terephthalic acid, p-phenylenediamine, dimethylbenzidine and bis- (4-aminophenoxy) benzene with a cutting length of 6 mm are suspended in water to about 1% and about 1.5 to 2 Treated for hours in a dissolver at about 1200 revolutions / min so that the staple fibers fibrillate. Excess water is suctioned off and the fiber pulp obtained is slurried in water in the moist state and mixed with different proportions (see Table 1) of staple fibers with a cutting length of 6 mm made of fusible aramid. The fusible aramide is a copolymer based on terephthalic acid, isophthalic acid and 2,2'-bis (4-aminophenoxyphenyl) propane, the end groups of which are sealed with benzoyl chloride.
Die erhaltene Suspension wird durch Abfiltrieren entwässert und der erhaltene Filterkuchen wird auf eine Heizplatte von etwa 300°C aufgebracht und bei dieser Temperatur getrocknet; dabei wird der Trocknungsvorgang durch Behandlung der der Heizplatte abgewandten Seite des Filterkuchens mit einem Bügeleisen von etwa 300°C unterstützt.The suspension obtained is dewatered by filtration and the filter cake obtained is applied to a hot plate at about 300 ° C. and dried at this temperature; the drying process is supported by treating the side of the filter cake facing away from the heating plate with an iron of approximately 300 ° C.
Die auf diese Weise hergestellten Papiere können anschließend noch durch Behandlung in einer Heizpresse weiter verfestigt werden. In der folgenden Tabelle 1 werden die Herstellungsbedingungen unterschiedlicher Aramidpapiere und deren Festigkeiten dargestellt. Die Festigkeitswerte wurden durch die Aufnahmen von Kraft-Dehnungsdiagrammen an 1,5 cm breiten Probestreifen der Papiere festgestellt. Die Messungen wurden mit einem Instron-Tester durchgeführt. Die Einspannlänge betrug dabei 50 mm. Die Festigkeitswerte sind auf das Flächengewicht des Papiers bezogen.
Man arbeitet nach der allgemeinen Vorschrift wie unter Beispielen 1 bis 10 beschrieben. Abweichend dazu werden Stapelfasern aus Aramiden auf der Basis von Terephthalsäure, p-Phenylendiamin, Dimethylbenzidin und Bis-(4-aminophenoxy)-benzol der Schnittlänge 2 mm verwendet. Die Schnittlänge der Aramid-Bindefasern beträgt wie bei den obigen Beispielen jeweils 6 mm.The general procedure is as described in Examples 1 to 10. In contrast to this, staple fibers made from aramids based on terephthalic acid, p-phenylenediamine, dimethylbenzidine and bis- (4-aminophenoxy) benzene with a cutting length of 2 mm are used. The cutting length of the aramid binder fibers is 6 mm, as in the examples above.
Einzelheiten zur Herstellung und zu den Eigenschaften der Papiere sind in der folgenden Tabelle 2 dargestellt.
Claims (13)
-OC-Ar¹-CO- (Ia),
und die Anteile der Diaminkomponenten (Ib), (Ic) und (Id) im Verhältnis zur Gesamtmenge dieser Diaminkomponente innerhalb folgender Grenzen liegen: worin
-Ar¹- und -Ar²- zweiwertige aromatische Reste bedeuten, deren Valenzbindungen in para- oder vergleichbarer koaxialer oder paralleler-Stellung stehen und die durch einen oder zwei inerte Reste, wie Alkyl, Alkoxy oder Halogen substituiert sein können, und worin
-R¹ und -R² unabhängig voneinander niedere Alkylreste oder niedere Alkoxyreste oder Halogenatome bedeuten.Nonwoven fabric according to claim 2, characterized in that aramides (copolyamides) which contain at least 95 mol%, based on the polyamide, of recurring structural units of the formulas Ia, Ib, Ic and Id are used as supporting fibers in organic solvents.
-OC-Ar¹-CO- (Ia),
and the proportions of the diamine components (Ib), (Ic) and (Id) in relation to the total amount of this diamine component are within the following limits: wherein
-Ar¹- and -Ar²- are divalent aromatic radicals, the valence bonds of which are in a para- or comparable coaxial or parallel position and which can be substituted by one or two inert radicals, such as alkyl, alkoxy or halogen, and in which
-R¹ and -R² independently of one another denote lower alkyl radicals or lower alkoxy radicals or halogen atoms.
-OC-Ar¹-CO- (Ia),
-HN-Ar²-NH- (Ig),
-OC-Ar¹-CO- (Ia),
-HN-Ar²-NH- (Ig),
-OC-Ar¹-CO- (Ia),
-HN-Ar²-NH- (Ig),
und die Anteile der Diaminkomponenten (Ig), (Ib) und (Ic) im Verhältnis zur Gesamtmenge dieser Diaminkomponenten innerhalb folgender Grenzen liegen:
-OC-Ar¹-CO- (Ia),
-HN-Ar²-NH- (Ig),
and the proportions of the diamine components (Ig), (Ib) and (Ic) in relation to the total amount of these diamine components are within the following limits:
Ar³ einen zweiwertigen substituierten oder unsubstituierten aromatischen Rest bedeutet, dessen freie Valenzen sich in para- oder meta-Stellung oder in vergleichbarer paralleler oder gewinkelter Stellung zueinander befinden,
Ar⁴ eine der für Ar³ angegebenen Bedeutungen haben kann oder eine Gruppe -Ar⁷-Z-Ar⁷- darstellt,
wobei Z eine -C(CH₃)₂- oder -O-Ar⁷-O- Brücke ist und Ar⁷ für einen zweiwertigen aromatischen Rest steht,
Ar⁵ und Ar⁶ gleich oder verschieden voneinander sind und für einen substituierten oder unsubstituierten para- oder meta-Arylenrest stehen,
Y eine -C(CH₃)₂-, -SO₂-, -S- oder -C(CF₃)₂-Brücke darstellt, wobei
Ar³ is a divalent substituted or unsubstituted aromatic radical whose free valences are in the para or meta position or in a comparable parallel or angled position to one another,
Ar⁴ can have one of the meanings given for Ar³ or represents a group -Ar⁷-Z-Ar⁷-,
where Z is a -C (CH₃) ₂- or -O-Ar⁷-O- bridge and Ar⁷ is a divalent aromatic radical,
Ar⁵ and Ar⁶ are the same or different from one another and represent a substituted or unsubstituted para- or meta-arylene radical,
Y represents a -C (CH₃) ₂-, -SO₂-, -S- or -C (CF₃) ₂ bridge, wherein
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4101674 | 1991-01-22 | ||
| DE4101674 | 1991-01-22 |
Publications (2)
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| EP0496313A1 true EP0496313A1 (en) | 1992-07-29 |
| EP0496313B1 EP0496313B1 (en) | 1996-07-17 |
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| EP92100815A Expired - Lifetime EP0496313B1 (en) | 1991-01-22 | 1992-01-18 | Non-woven reinforced with a meltbinder |
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| EP (1) | EP0496313B1 (en) |
| JP (1) | JPH04352860A (en) |
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| US5662728A (en) * | 1992-12-31 | 1997-09-02 | Hoechst Celanese Corporation | Particulate filter structure |
| US5667900A (en) * | 1993-01-04 | 1997-09-16 | E. I. Du Pont De Nemours And Company | Aramid paper with high surface smoothness |
| JP3300529B2 (en) * | 1994-03-31 | 2002-07-08 | 日鉄鉱業株式会社 | Antistatic filtering material and method for producing the same |
| US5827430A (en) * | 1995-10-24 | 1998-10-27 | Perry Equipment Corporation | Coreless and spirally wound non-woven filter element |
| US6383623B1 (en) | 1999-08-06 | 2002-05-07 | Tex Tech Industries Inc. | High performance insulations |
| US20050039836A1 (en) * | 1999-09-03 | 2005-02-24 | Dugan Jeffrey S. | Multi-component fibers, fiber-containing materials made from multi-component fibers and methods of making the fiber-containing materials |
| US6241899B1 (en) * | 2000-02-28 | 2001-06-05 | Maritza L. Ramos | Disposable filter bags for pool cleaners |
| US6363620B1 (en) * | 2000-07-21 | 2002-04-02 | Callaway Golf Company | Apparatus and method for measuring the loft angle and the lie angle of a golf club |
| US6712939B2 (en) | 2001-02-26 | 2004-03-30 | Cuno Incorporated | Process for manufacturing wet-felted and thermally bonded porous structures and porous structures formed by the process |
| WO2003015894A1 (en) | 2001-08-09 | 2003-02-27 | Dainippon Ink And Chemicals, Inc. | Heat-resistant filter |
| US20030082974A1 (en) * | 2001-08-30 | 2003-05-01 | Samuels Michael R. | Solid sheet material especially useful for circuit boards |
| MXPA04002396A (en) * | 2001-09-12 | 2005-04-11 | Basofil Fibers Llc | Nonwoven highloft flame barrier. |
| US7276166B2 (en) * | 2002-11-01 | 2007-10-02 | Kx Industries, Lp | Fiber-fiber composites |
| WO2005047597A2 (en) * | 2003-11-07 | 2005-05-26 | Koslow Technlogies Corporation | Fiber-fiber composites |
| JP2005307360A (en) * | 2004-04-16 | 2005-11-04 | Du Pont Teijin Advanced Paper Kk | Aramid tissue material and electrical and electronic part using the same |
| US7815993B2 (en) * | 2006-12-15 | 2010-10-19 | E.I. Du Pont De Nemours And Company | Honeycomb from paper having flame retardant thermoplastic binder |
| US7771810B2 (en) * | 2006-12-15 | 2010-08-10 | E.I. Du Pont De Nemours And Company | Honeycomb from paper having a high melt point thermoplastic fiber |
| US7819936B2 (en) * | 2007-08-22 | 2010-10-26 | E.I. Du Pont De Nemours And Company | Filter felts and bag filters comprising blends of fibers derived from diamino diphenyl sulfone and heat resistant fibers |
| US20090107922A1 (en) * | 2007-10-26 | 2009-04-30 | General Electric Company | Membrane, water treatment system, and associated method |
| US8118975B2 (en) * | 2007-12-21 | 2012-02-21 | E. I. Du Pont De Nemours And Company | Papers containing fibrids derived from diamino diphenyl sulfone |
| US7803247B2 (en) * | 2007-12-21 | 2010-09-28 | E.I. Du Pont De Nemours And Company | Papers containing floc derived from diamino diphenyl sulfone |
| US8114251B2 (en) * | 2007-12-21 | 2012-02-14 | E.I. Du Pont De Nemours And Company | Papers containing fibrids derived from diamino diphenyl sulfone |
| ES2523728T3 (en) | 2010-06-15 | 2014-12-01 | Ahlstrom Corporation | Scrubbed fibrous support containing apergaminable synthetic fibers and method of manufacture |
| US9437348B2 (en) * | 2010-12-17 | 2016-09-06 | 3M Innovative Properties Company | Electrical insulation material |
| EP2661522B1 (en) | 2011-01-04 | 2016-10-19 | Teijin Aramid B.V. | Paper comprising microfilaments |
| CN104562434B (en) * | 2015-01-04 | 2017-02-22 | 上海特安纶纤维有限公司 | Polysulfonamide permanent flame-retardant heat-insulation warm-keeping fabric sheet and preparation method thereof |
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- 1992-01-18 DE DE59206760T patent/DE59206760D1/en not_active Expired - Fee Related
- 1992-01-18 ES ES92100815T patent/ES2091954T3/en not_active Expired - Lifetime
- 1992-01-18 AT AT92100815T patent/ATE140493T1/en not_active IP Right Cessation
- 1992-01-21 IE IE920180A patent/IE74904B1/en not_active IP Right Cessation
- 1992-01-21 US US07/823,376 patent/US5393601A/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
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| IE920180A1 (en) | 1992-07-29 |
| DE59206760D1 (en) | 1996-08-22 |
| ES2091954T3 (en) | 1996-11-16 |
| IE74904B1 (en) | 1997-08-13 |
| ATE140493T1 (en) | 1996-08-15 |
| EP0496313B1 (en) | 1996-07-17 |
| JPH04352860A (en) | 1992-12-07 |
| US5393601A (en) | 1995-02-28 |
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