EP0790334B1 - Easily dyeable meta-linkage-containing aromatic polyamide fibres - Google Patents
Easily dyeable meta-linkage-containing aromatic polyamide fibres Download PDFInfo
- Publication number
- EP0790334B1 EP0790334B1 EP96102132A EP96102132A EP0790334B1 EP 0790334 B1 EP0790334 B1 EP 0790334B1 EP 96102132 A EP96102132 A EP 96102132A EP 96102132 A EP96102132 A EP 96102132A EP 0790334 B1 EP0790334 B1 EP 0790334B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- linkage
- phosphate
- meta
- aromatic polyamide
- fibers according
- 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.)
- Expired - Lifetime
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- 239000004760 aramid Substances 0.000 title claims description 49
- 229920003235 aromatic polyamide Polymers 0.000 title claims description 49
- 239000000835 fiber Substances 0.000 claims description 75
- 150000003839 salts Chemical class 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 23
- 150000002367 halogens Chemical class 0.000 claims description 23
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 claims description 21
- -1 alkyl phosphate Chemical compound 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 16
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 16
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 16
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 16
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical group CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- VBVCYAZECWLFHP-UHFFFAOYSA-N dodecyl benzenesulfonate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 VBVCYAZECWLFHP-UHFFFAOYSA-N 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- 239000012964 benzotriazole Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 5
- BYCIIWVBRLCFRL-UHFFFAOYSA-N tris(2,3-dichlorophenyl) phosphate Chemical group ClC1=CC=CC(OP(=O)(OC=2C(=C(Cl)C=CC=2)Cl)OC=2C(=C(Cl)C=CC=2)Cl)=C1Cl BYCIIWVBRLCFRL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- XWTOMWARSPYOAY-UHFFFAOYSA-N dodecyl benzenesulfonate;tetraphenylphosphanium Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XWTOMWARSPYOAY-UHFFFAOYSA-N 0.000 claims description 3
- KTUVYMAZYSSBKC-UHFFFAOYSA-N hexyl benzenesulfonate Chemical compound CCCCCCOS(=O)(=O)C1=CC=CC=C1 KTUVYMAZYSSBKC-UHFFFAOYSA-N 0.000 claims description 3
- ASTWQNQEEBYIKI-UHFFFAOYSA-N hexyl benzenesulfonate tetrabutylphosphanium Chemical compound C(CCCCC)OS(=O)(=O)C1=CC=CC=C1.C(CCC)[P+](CCCC)(CCCC)CCCC ASTWQNQEEBYIKI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical group CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 58
- 238000009987 spinning Methods 0.000 description 48
- 238000004043 dyeing Methods 0.000 description 35
- 239000000243 solution Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 18
- 238000009849 vacuum degassing Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 238000011088 calibration curve Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- XEVAGRPVCOHVIE-UHFFFAOYSA-N dodecyl benzenesulfonate phosphane Chemical compound P.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 XEVAGRPVCOHVIE-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WJKFAAUFDYIGBN-UHFFFAOYSA-N (3,3-dichloro-3-phenylpropyl) dihydrogen phosphate Chemical compound OP(O)(=O)OCCC(Cl)(Cl)C1=CC=CC=C1 WJKFAAUFDYIGBN-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- LZDHIQDKAYUDND-UHFFFAOYSA-N biphenylene-1,2-diamine Chemical compound C1=CC=C2C3=C(N)C(N)=CC=C3C2=C1 LZDHIQDKAYUDND-UHFFFAOYSA-N 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- WJRMGBWBIGOIOF-UHFFFAOYSA-N dodecyl benzenesulfonate;propan-2-amine Chemical compound CC(C)N.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 WJRMGBWBIGOIOF-UHFFFAOYSA-N 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- MIGQZJQRFLUXSV-UHFFFAOYSA-N phosphoric acid;tris(2-chloropropyl) phosphate Chemical compound OP(O)(O)=O.CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl MIGQZJQRFLUXSV-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- JZZBTMVTLBHJHL-UHFFFAOYSA-N tris(2,3-dichloropropyl) phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Cl)CCl)OCC(Cl)CCl JZZBTMVTLBHJHL-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
Definitions
- the present invention relates to meta-linkage-containing aromatic polyamide fibers which are dyeable with cationic dyes.
- Meta-linkage-containing aromatic polyamide fibers have molecular skeletons consisting almost totally of aromatic rings, and thus have excellent heat resistance, flame retardance and flame proofness.
- such fibers are suitable for use as industrial materials for which heat resistance is required, and for use in clothing and interior decoration for which flame retardance and flame proofness are considered important; they are rapidly attaining wider use especially in the fields of clothing, bedding materials and interior decoration which take advantage of their flame retardance and flame proofness.
- These fields usually employ dyed fibers, but while meta-linkage-containing aromatic polyamide fibers have excellent physical characteristics, their rigid polymer chains make them very difficult to dye by conventional methods.
- 3,695,992 proposes polyporous aromatic polyamide fibers with an improved dyeing property, having a pore size, void volume and density within specific ranges; nevertheless, the dyeing property of these fibers has not been sufficient, and associated drawbacks have included difficulty in setting the dyeing conditions because of the required pigments and organic dyeing aids during the dyeing, as well as difficulty in disposal of the waste liquors after use.
- aromatic polyamides are usually prepared by reacting a dicarboxylic halide with a diamine, the sodium sulfonate groups when present react with the acid halide, making it impossible to obtain a polymer with satisfactory physical properties.
- EP-A-O 212 948 discloses a process for dyeing aromatic fibers a deep shade. To this end a large amount of surfactants is incorporated into the fibers.
- One of the recommended surfactants is isopropylammonium dodecylbenzenesulfonate.
- the present invention provides meta-linkage-containing aromatic polyamide fibers easily dyeable with cationic dyes, the fibers consisting of a composition which comprises a meta-linkage-containing aromatic polyamide incorporating at least one alkylbenzenesulfonic acid onium salt selected from the group consisting of tetrabutylphosphonium hexylbenzenesulfonate, tributylbenzylphosphonium hexylbenzenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate, tributylphenylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate and tributylbenzylammonium dodecylbenzenesulfonate.
- the meta-linkage-containing aromatic polyamide to be used according to the present invention consists of aromatic rings constituting the main skeleton, which have amide linkages at the meta-positions.
- Particularly preferred among such meta-linkage-containing aromatic polyamides is a poly-m-phenylene isophthalamide consisting of repeating units represented by the following chemical formula.
- the meta-linkage-containing aromatic polyamide may also be a copolymer comprising less than 15 mole percent of a third component.
- At least 85 mole percent of the repeating units of the meta-linkage containing aromatic polyamide are a poly-m-phenylene isophthalamide consisting of the repeating units of the above chemical formula.
- Monomers constituting the third component may be aromatic diamine components such as, for example, para-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, paraxylylenediamine, biphenylenediamine, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,5-naphthalenediamine; and as acid components, aromatic dicarboxylic acids such as, for example, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, particularly preferred of which is terephthalic acid.
- aromatic diamines and aromatic dicarboxylic acids may have a portion of the hydrogen atoms on their aromatic rings substituted with halogen atoms or alkyl
- This type of meta-linkage-containing aromatic polyamide may be produced by a publicly known interfacial polymerization or low-temperature solution polymerization method.
- the degree of polymerization of the polymer in terms of the intrinsic viscosity (IV) of a 0.5 g/100 ml solution in N-methyl-2-pyrrolidone at 30°C, is preferably 1.3 to 1.9 dl/g.
- the alkylbenzenesulfonic acid onium salt combined with the meta-linkage-containing aromatic polyamide is a compound selected from tetrabutylphosphonium hexylbenzenesulfonate, tributylbenzylphosphonium hexylbenzenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate, tributylphenylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate and tributylbenzylammonium dodecylbenzenesulfonate.
- tetrabutylphosphonium dodecylbenzenesulfonate and tributylbenzylammonium dodecylbenzenesulfonate are particularly preferred, because of their ready availability, excellent thermal stability and high solubility in dimethylacetoamide and N-methyl-2-pyrrolidone, which are good solvents for the meta-linkage-containing aromatic polyamide.
- the amount of the alkylbenzenesulfonic acid onium salt to be combined with the meta-linkage-containing aromatic polyamide is preferably between 2.8 and 7.0 mole percent, and more preferably between 3.5 and 7.0 mole percent with respect to the repeating units of the meta-linkage-containing aromatic polyamide. At less than 2.8 mole percent, an adequate improving effect on the dyeing property may not be achieved, while at greater than 7.0 mole percent the single filaments may be more prone to breakage during the fiber production process.
- composition constituting the meta-linkage-containing aromatic polyamide fibers of the present invention which contains the meta-linkage-containing aromatic polyamide incorporating the onium alkylbenzenesulfonate, preferably further contains a halogen-containing alkyl phosphate or a halogen-containing phenyl phosphate (hereunder referred to collectively as "halogen-containing alkyl (phenyl) phosphate").
- halogen-containing alkyl (phenyl) phosphate hereunder referred to collectively as "halogen-containing alkyl (phenyl) phosphate”
- halogen-containing alkyl (phenyl) phosphates there may be mentioned compounds such as tris( ⁇ -chloropropyl) phosphate, tris(2,3-dichloropropyl) phosphate, tris(chloroethyl) phosphate, phenyldichloropropyl phosphate and tris(dichlorophenyl) phosphate.
- these compounds have been found to have virtually no effect of improving dyeing properties when they alone are combined with meta-linkage-containing aromatic polyamides, they exhibit a specific dyeing property-improving effect when used in tandem with an alkylbenzenesulfonic acid onium salt.
- the content of the halogen-containing alkyl (phenyl) phosphate in the polymer is preferably 0.5 to 5.0 wt%, and more preferably 1.8 to 5.0 wt% with respect to the meta-linkage-containing aromatic polyamide. At less than 0.5 wt% the specific dyeing property-improving effect may not be obtained, and at greater than 5 wt% dye spots may appear during the dyeing process, while the dyeing property-improving effect may not be so greatly enhanced.
- meta-linkage-containing aromatic polyamide composition constituting the meta-linkage-containing containing aromatic polyamide fibers of the present invention preferably further contains an ultraviolet absorber.
- Meta-linkage-containing aromatic polyamide fibers made of such a composition not only have a more excellent dyeing property, but also impart excellent light fastness to the dyed product.
- the ultraviolet absorber is preferably a benzotriazole-based ultraviolet absorbing compound. This is because meta-linkage-containing aromatic polyamides have an ultraviolet absorbance range of from 340 to 360 nm, and most benzotriazole-based compounds have maximum absorbance wavelengths within this range.
- meta-linkage-containing aromatic polyamides undergo considerable yellowing upon exposure to light rays, as a result of their molecular structure characteristics. Consequently, even if the dyeing property is improved to provide finely dyed fibers, their value as marketable dyed fibers is reduced by half when the color shade is altered due to yellowing after dyeing. Thus, by combining excellent light fastness with the excellent dyeing property, their value is greatly increased as meta-linkage-containing aromatic polyamide fibers with an improved dyeing property.
- benzotriazole-based ultraviolet absorbing compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis( ⁇ , ⁇ '-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl-5-chlorobenzoazole and 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole.
- 2-[2-hydroxy-3,5-bis( ⁇ , ⁇ '-dimethylbenzyl)phenyl]-2H-benzotriazole is particularly preferred because of its heat resistance and high solubility in dimethylacetoamide and N-methyl-2-pyrrolidone, which are good solvents for the meta-linkage-containing aromatic polyamide.
- the amount of the ultraviolet absorber to be added is preferably 2.0 to 6.0 wt%, and particularly 3.0 to 5.0 wt% with respect to the meta-linkage-containing aromatic polyamide. If the amount is less than 2.0 wt% the anti-yellowing effect may not be exhibited, and even if it is added at greater than 6.0 wt% no further improvement in the anti-yellowing effect may result, while the workability of the fibers during the production process may be reduced.
- the mixture of the meta-linkage-containing aromatic polyamide with the alkylbenzenesulfonic acid onium salt, halogen-containing alkyl (phenyl) phosphate and ultraviolet absorber may be accomplished by a method wherein the meta-linkage-containing aromatic polyamide is added to a solvent and mixed therewith to make a solution to which solutions of the alkylbenzenesulfonic acid onium salt, halogen-containing alkyl (phenyl) phosphate and ultraviolet absorber each in appropriate solvents are then added and mixed therewith, or an alternative method in which the meta-linkage-containing aromatic polyamide, alkylbenzenesulfonic acid onium salt, halogen-containing alkyl (phenyl) phosphate and ultraviolet absorber are combined into a mixture which is then dissolved in a solvent.
- the dope obtained in this manner may then be formed into fibers by a publicly known method.
- An example of a typical fiber-forming method involves addition of the alkylbenzenesulfonic acid onium salt, halogen-containing alkyl (phenyl) phosphate and benzotriazole-based ultraviolet absorber to an N-methyl-2-pyrrolidone solution containing a poly-m-phenylene isophthalamide polymer, to prepare a dope.
- the dope is extruded from a nozzle into an aqueous inorganic solution whose main component is calcium chloride, stretched after coagulation and washing with water, and then further stretched on a hot plate at 300-325°C and crystallized, and finally subjected to oiling to complete the fibers.
- staple fibers they are crimped, cut and then spun to obtain easily dyeable spun fibers.
- the easily dyeable meta-linkage-containing aromatic polyamide fibers of the present invention obtained in the manner described above have an excellent dyeing property and light fastness without any loss in the excellent heat resistance, flame retardance and flame proofness of the original meta-linkage-containing aromatic polyamide fibers, and thus may be effectively applied for clothing, bedding and interior decorations which require coloring.
- the addition of the halogen-containing alkyl (phenyl) phosphate provides further improvement in the flame retardance while drastically improving the dyeing property and lowering the dyeing cost compared to addition of the alkylbenzenesulfonic acid onium salt alone, and addition of the ultraviolet absorber, particularly a benzotriazole-based ultraviolet absorbing compound, drastically improves the light fastness, allowing the fibers to be applied in the fields of clothing, bedding and interior decorations in the same manner as existing common fibers.
- Crimped fibers were collectively cut to a length of 50 mm and dyed at 30°C for 90 minutes using a dyeing solution comprising 8% o.w.f. Estrol Navy Blue N-RL (product of Sumitomo Chemical Co., Ltd.), 0.3 g/l acetic acid and 25 g/l sodium nitrate to a fiber/dyeing solution ratio (liquor ratio) of 1:40, after which a solution comprising 1 g/l hydrosulfite, 1 g/l Amiladin D (product of Dai-ichi Kogyo Seiyaku Co., Ltd.) and 1 g/l sodium hydroxide was used at a liquor ratio of 1:40 for reductive washing at 80°C for 30 minutes, followed by water washing and drying.
- a dyeing solution comprising 8% o.w.f. Estrol Navy Blue N-RL (product of Sumitomo Chemical Co., Ltd.)
- a fiber/dyeing solution ratio (li
- a 1.3g portion of the fibers was stuffed into a cell having a diameter of 31 mm and a depth of 13 mm, and a CM-2002 Minolta spectrophotometric colorimeter was used for colorimetry with a 10° field of view, a D76 light source and regular reflection elimination, using the value L* as an index of the dyeing property.
- the polymer was dissolved in N-methyl-2-pyrrolidone (NMP) to a concentration of 0.5 g/100 ml, and an Ostwald's viscometer was used for measurement at 30°C.
- NMP N-methyl-2-pyrrolidone
- the fineness of the fibers was measured according to JIS-L-1015.
- the tensile strength of the fibers was measured according to JIS-L-1074, with a 20 mm long test sample, an initial load of 1/20 g/1.1 dtex(de) and an elongation rate of 20 mm/min.
- 0.1 cc of an aqueous (NH 4 ) 2 SO 4 solution of known concentration is dropped onto test filtration paper, and a calibration curve is prepared based on fluorescent X-ray quantitative analysis after vacuum drying.
- About 50 mg of the fibers and about 20 mg of calcium chloride are dissolved in 5.0 cc of NMP by heating at 110°C for 1 hour, and after dropping a standard amount (0.1 cc) on the test filtration paper, it is vacuum dried.
- the sample is then quantitatively analyzed by fluorescent X-ray analysis, the sulfur concentration of the fibers is calculated based on the previously prepared calibration curve, and this is converted into the content on the assumption that all of the sulfur is derived from the alkylbenzenesulfonic acid onium salt.
- a calibration curve is prepared by fluorescent X-ray analysis of a standard phosphorus sample of known concentration, the phosphorus concentration of the fibers is calculated, and this is converted into a content on the assumption that all of the phosphorus is derived from the alkyl (phenyl) phosphate.
- a test tube 120 mm x 10 mm ⁇ , pyrex
- 4 ml of concentrated hydrochloric acid is added and the tube is sealed.
- the sealed tube is heated at 130°C for about 6 hours for hydrolysis.
- the sealed tube is cooled to room temperature and opened.
- the total contents of the test tube are then transferred to a 50 ml separatory funnel, 5 ml of chloroform is added, and the mixture is adequately shaken and allowed to stand, after which the chloroform phase is removed.
- This extraction procedure with chloroform is repeated 3 times, all of the chloroform phases are combined and concentrated to 2-3 ml, and the solution is then analyzed by liquid chromatography (LC).
- LC liquid chromatography
- sample crimped and cut to lengths of 38-76 mm
- the dispersed sample is affixed to a mount to a width of 18-22 mm and a thickness of 2-3 mm, as shown in Fig. 1.
- the mount is then set onto a metallic flask.
- the metallic flask is set into a fade tester (Model CF-20N, product of Shimazu Laboratories), and irradiated for a prescribed time with an arc current of 15-17 A and an internal temperature of 42-45°C.
- a 30g portion of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved in 110g of NMP and further mixed with 3.6g of phosphonium dodecylbenzenesulfonate, and the solution was subjected to vacuum degassing to make a spinning dope.
- the dope was heated to 85°C and then used for wet spinning into a spinning bath from a spinning nozzle with 200 holes, each with a diameter of 0.07 mm.
- the composition of the spinning bath was 40 wt% calcium chloride, 5 wt% NMP and 55 wt% water, and the temperature of the spinning bath was 85°C.
- the filaments were given a course of about 100 cm through the spinning bath, and were drawn at a rate of 6.2 m/min.
- the filaments were then washed with water, stretched to a draw ratio of 2.4 in 95°C hot water, and dried using a roll at 200°C, after which they were stretched to a draw ratio of 1.75 on a 320°C hot plate to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- the total draw ratio was 4.2.
- a 30g portion of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved in 110g of NMP and further mixed with a solution of 3.6g of tributylbenzylammonium dodecylbenzenesulfonate in 2g NMP, and the solution was subjected to vacuum degassing to make a spinning dope.
- This dope was used for spinning and stretching in the same manner as in Example 1, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- This dope was used for stretching in the same manner as in Example 1, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- the dope was heated to 85°C and then used for wet spinning into a spinning bath from a spinning nozzle with 200 holes each with a diameter of 0.07 mm.
- the composition of the spinning bath was 40 wt% calcium chloride, 5 wt% NMP and 55 wt% water, and the temperature of the spinning bath was 85°C.
- the filaments were given a course of about 100 cm through the spinning bath, and were drawn at a rate of 6.2 m/min.
- the filaments were then washed with water, stretched to a draw ratio of 2.4 in 95°C hot water, and dried using a roll at 200°C, after which they were stretched to a draw ratio of 1.75 on a 320°C hot plate to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- the total draw ratio was 4.2.
- a 2.25g portion of tetrabutylphosphonium dodecylbenzenesulfonate and 2.4g of tris( ⁇ -chloropropyl) phosphate were dissolved in 110g of NMP, and then 30g of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved therein and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 6, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- a 3.6g portion of tris( ⁇ -chloropropyl) phosphate was dissolved in 110g of NMP, and then 30g of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved therein and the solution was subjected to vacuum degassing to make a spinning dope.
- This dope was used for spinning and stretching in the same manner as in Example 6, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- a 2.25g portion of tetrabutylphosphonium dodecylbenzenesulfonate and 0.45g of tris( ⁇ -chloropropyl) phosphate were dissolved in 110g of NMP, and then 30g of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved therein and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 6, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- Onium salt alkylbenzenesulfonic acid onium salt
- Onium salt content mole percent with respect to polymer
- Phosphate halogen-containing alkyl (phenyl) phosphate
- Phosphate content weight percent based on polymer
- the composition of the spinning bath was 40 wt% calcium chloride, 5 wt% NMP and 55 wt% water, and the temperature of the spinning bath was 85°C.
- the filaments were given a course of about 100 cm through the spinning bath, and were drawn at a rate of 6.2 m/min.
- the filaments were then washed with water, stretched to a draw ratio of 2.4 in 95°C hot water, and dried using a roll at 200°C, after which they were stretched to a draw ratio of 1.75 on a 320°C hot plate to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- the stretched filaments were crimped with a crimper, and cut to a length of 51 mm with a cutter.
- the filaments were dyed with Estrol Navy Blue N-2RL (product of Sumitomo Chemical Co., Ltd.) by the method described above, and the dyed filaments were measured for light fastness with a fade tester (Model CF20N, Shimazu Laboratories) by the method described above.
- This dope was used for spinning and stretching in the same manner as in Example 12, to obtain stretched filaments with 440 dtex (400 de)/200 filaments. The obtained stretched filaments were crimped, cut, dyed and measured for light fastness by the same method as in Example 12.
- This dope was used for spinning and stretching in the same manner as in Example 12, to obtain stretched filaments with 440 dtex (400 de)/200 filaments. The obtained stretched filaments were crimped, cut, dyed and measured for light fastness by the same method as in Example 12.
- This dope was used for spinning and stretching in the same manner as in Example 12, to obtain stretched filaments with 440 dtex (400 de)/200 filaments. The obtained stretched filaments were crimped, cut, dyed and measured for light fastness by the same method as in Example 12.
- the obtained stretched filaments were crimped, cut, dyed and measured for light fastness by the same method as in Example 12.
- Onium salt tributylbenzylammonium dodecylbenzenesulfonate
- Onium salt content mole percent with respect to polymer
- Phosphate tris( ⁇ -chloropropyl) phosphate
- Phosphate content weight percent with respect to polymer
- Ultraviolet absorber 2-[2-hydroxy-3,5-bis( ⁇ , ⁇ '-dimethylbenzyl)phenyl]-2H- benzotriazole
- Ultraviolet absorber content weight percent based on polymer
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Description
- The present invention relates to meta-linkage-containing aromatic polyamide fibers which are dyeable with cationic dyes.
- Meta-linkage-containing aromatic polyamide fibers have molecular skeletons consisting almost totally of aromatic rings, and thus have excellent heat resistance, flame retardance and flame proofness. As a result, such fibers are suitable for use as industrial materials for which heat resistance is required, and for use in clothing and interior decoration for which flame retardance and flame proofness are considered important; they are rapidly attaining wider use especially in the fields of clothing, bedding materials and interior decoration which take advantage of their flame retardance and flame proofness. These fields usually employ dyed fibers, but while meta-linkage-containing aromatic polyamide fibers have excellent physical characteristics, their rigid polymer chains make them very difficult to dye by conventional methods.
- A number of methods have been proposed in order to use meta-linkage-containing aromatic polyamide fibers in these fields. For example, in Japanese Unexamined Patent Publication No. 50-59522 there have been proposed pigmented fibers obtained by incorporating meta-linkage-containing aromatic polyamide fibers with a specific pigment; because the fibers are incorporated with the pigment during the production process, however, there is a drawback of considerable efficiency loss when colors are changed, which means that the method cannot be adapted well to small-lot production and more time is required to respond to client's orders. As a means of improving the dyeing property, Japanese Unexamined Patent Publication No. 55-21406 (U.S. Patent No. 4,278,779) has proposed a method of adding a polymer copolymerized with xylylenediamine; however, since a third component is copolymerized with the polymer chain, polymerization equipment and polymer stocking equipment must be specialized for the particular polymer used, which presents a problem of increased cost. In addition, Japanese Examined Patent Publication No. 52-43930 (U.S. Patent No. 3,695,992) proposes polyporous aromatic polyamide fibers with an improved dyeing property, having a pore size, void volume and density within specific ranges; nevertheless, the dyeing property of these fibers has not been sufficient, and associated drawbacks have included difficulty in setting the dyeing conditions because of the required pigments and organic dyeing aids during the dyeing, as well as difficulty in disposal of the waste liquors after use.
- There has also been proposed in, for example, Japanese Examined Patent Publication No. 44-11168 (U.S. Patent No. 3,506,990), a meta-linkage-containing aromatic polyamide prepared by copolymerization with a compound having sulfonate groups introduced therein. This polymer, however, has certain disadvantages in that purification of the starting material is very difficult, and it is impossible to obtain a stable polymer with the necessary degree of polymerization and whiteness. Furthermore, production of aromatic polyamides prepared by copolymerization with components having sodium sulfonate groups is disclosed in Japanese Unexamined Patent Publication Nos. 48-96827 and 51-26320, and in U.S. Patent Nos. 3,039,990, 3,142,662 and 3,409,596. However, although aromatic polyamides are usually prepared by reacting a dicarboxylic halide with a diamine, the sodium sulfonate groups when present react with the acid halide, making it impossible to obtain a polymer with satisfactory physical properties.
- EP-A-O 212 948 discloses a process for dyeing aromatic fibers a deep shade. To this end a large amount of surfactants is incorporated into the fibers. One of the recommended surfactants is isopropylammonium dodecylbenzenesulfonate.
- In light of the aforementioned problems of the prior art, it is an object of the present invention to provide, by inexpensive and simple means, meta-linkage-containing aromatic polyamide fibers with excellent dyeing properties which may be used in the fields of bedding, clothing and interior decorating.
- In order to achieve the above-mentioned object, the present invention provides meta-linkage-containing aromatic polyamide fibers easily dyeable with cationic dyes, the fibers consisting of a composition which comprises a meta-linkage-containing aromatic polyamide incorporating at least one alkylbenzenesulfonic acid onium salt selected from the group consisting of tetrabutylphosphonium hexylbenzenesulfonate, tributylbenzylphosphonium hexylbenzenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate, tributylphenylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate and tributylbenzylammonium dodecylbenzenesulfonate.
- The meta-linkage-containing aromatic polyamide to be used according to the present invention consists of aromatic rings constituting the main skeleton, which have amide linkages at the meta-positions. Particularly preferred among such meta-linkage-containing aromatic polyamides is a poly-m-phenylene isophthalamide consisting of repeating units represented by the following chemical formula.
- The meta-linkage-containing aromatic polyamide may also be a copolymer comprising less than 15 mole percent of a third component.
- In preferred fibers at least 85 mole percent of the repeating units of the meta-linkage containing aromatic polyamide are a poly-m-phenylene isophthalamide consisting of the repeating units of the above chemical formula.
- Monomers constituting the third component may be aromatic diamine components such as, for example, para-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, paraxylylenediamine, biphenylenediamine, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,5-naphthalenediamine; and as acid components, aromatic dicarboxylic acids such as, for example, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, particularly preferred of which is terephthalic acid. These aromatic diamines and aromatic dicarboxylic acids may have a portion of the hydrogen atoms on their aromatic rings substituted with halogen atoms or alkyl groups such as methyl.
- This type of meta-linkage-containing aromatic polyamide may be produced by a publicly known interfacial polymerization or low-temperature solution polymerization method. The degree of polymerization of the polymer, in terms of the intrinsic viscosity (IV) of a 0.5 g/100 ml solution in N-methyl-2-pyrrolidone at 30°C, is preferably 1.3 to 1.9 dl/g.
- The alkylbenzenesulfonic acid onium salt combined with the meta-linkage-containing aromatic polyamide is a compound selected from tetrabutylphosphonium hexylbenzenesulfonate, tributylbenzylphosphonium hexylbenzenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate, tributylphenylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate and tributylbenzylammonium dodecylbenzenesulfonate. Among these, tetrabutylphosphonium dodecylbenzenesulfonate and tributylbenzylammonium dodecylbenzenesulfonate are particularly preferred, because of their ready availability, excellent thermal stability and high solubility in dimethylacetoamide and N-methyl-2-pyrrolidone, which are good solvents for the meta-linkage-containing aromatic polyamide.
- In order to obtain an adequate effect on the dyeing property, the amount of the alkylbenzenesulfonic acid onium salt to be combined with the meta-linkage-containing aromatic polyamide is preferably between 2.8 and 7.0 mole percent, and more preferably between 3.5 and 7.0 mole percent with respect to the repeating units of the meta-linkage-containing aromatic polyamide. At less than 2.8 mole percent, an adequate improving effect on the dyeing property may not be achieved, while at greater than 7.0 mole percent the single filaments may be more prone to breakage during the fiber production process.
- The composition constituting the meta-linkage-containing aromatic polyamide fibers of the present invention, which contains the meta-linkage-containing aromatic polyamide incorporating the onium alkylbenzenesulfonate, preferably further contains a halogen-containing alkyl phosphate or a halogen-containing phenyl phosphate (hereunder referred to collectively as "halogen-containing alkyl (phenyl) phosphate"). The meta-linkage-containing aromatic polyamide fibers made of such a composition have more excellent dyeing properties.
- As halogen-containing alkyl (phenyl) phosphates there may be mentioned compounds such as tris(β-chloropropyl) phosphate, tris(2,3-dichloropropyl) phosphate, tris(chloroethyl) phosphate, phenyldichloropropyl phosphate and tris(dichlorophenyl) phosphate. Although these compounds have been found to have virtually no effect of improving dyeing properties when they alone are combined with meta-linkage-containing aromatic polyamides, they exhibit a specific dyeing property-improving effect when used in tandem with an alkylbenzenesulfonic acid onium salt.
- The content of the halogen-containing alkyl (phenyl) phosphate in the polymer is preferably 0.5 to 5.0 wt%, and more preferably 1.8 to 5.0 wt% with respect to the meta-linkage-containing aromatic polyamide. At less than 0.5 wt% the specific dyeing property-improving effect may not be obtained, and at greater than 5 wt% dye spots may appear during the dyeing process, while the dyeing property-improving effect may not be so greatly enhanced.
- The above-mentioned meta-linkage-containing aromatic polyamide composition constituting the meta-linkage-containing containing aromatic polyamide fibers of the present invention preferably further contains an ultraviolet absorber. Meta-linkage-containing aromatic polyamide fibers made of such a composition not only have a more excellent dyeing property, but also impart excellent light fastness to the dyed product.
- The ultraviolet absorber is preferably a benzotriazole-based ultraviolet absorbing compound. This is because meta-linkage-containing aromatic polyamides have an ultraviolet absorbance range of from 340 to 360 nm, and most benzotriazole-based compounds have maximum absorbance wavelengths within this range.
- As is well-known, meta-linkage-containing aromatic polyamides undergo considerable yellowing upon exposure to light rays, as a result of their molecular structure characteristics. Consequently, even if the dyeing property is improved to provide finely dyed fibers, their value as marketable dyed fibers is reduced by half when the color shade is altered due to yellowing after dyeing. Thus, by combining excellent light fastness with the excellent dyeing property, their value is greatly increased as meta-linkage-containing aromatic polyamide fibers with an improved dyeing property.
- Preferred examples of benzotriazole-based ultraviolet absorbing compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α'-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl-5-chlorobenzoazole and 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole. Among these, 2-[2-hydroxy-3,5-bis(α,α'-dimethylbenzyl)phenyl]-2H-benzotriazole is particularly preferred because of its heat resistance and high solubility in dimethylacetoamide and N-methyl-2-pyrrolidone, which are good solvents for the meta-linkage-containing aromatic polyamide.
- The amount of the ultraviolet absorber to be added is preferably 2.0 to 6.0 wt%, and particularly 3.0 to 5.0 wt% with respect to the meta-linkage-containing aromatic polyamide. If the amount is less than 2.0 wt% the anti-yellowing effect may not be exhibited, and even if it is added at greater than 6.0 wt% no further improvement in the anti-yellowing effect may result, while the workability of the fibers during the production process may be reduced.
- The mixture of the meta-linkage-containing aromatic polyamide with the alkylbenzenesulfonic acid onium salt, halogen-containing alkyl (phenyl) phosphate and ultraviolet absorber may be accomplished by a method wherein the meta-linkage-containing aromatic polyamide is added to a solvent and mixed therewith to make a solution to which solutions of the alkylbenzenesulfonic acid onium salt, halogen-containing alkyl (phenyl) phosphate and ultraviolet absorber each in appropriate solvents are then added and mixed therewith, or an alternative method in which the meta-linkage-containing aromatic polyamide, alkylbenzenesulfonic acid onium salt, halogen-containing alkyl (phenyl) phosphate and ultraviolet absorber are combined into a mixture which is then dissolved in a solvent. The dope obtained in this manner may then be formed into fibers by a publicly known method.
- An example of a typical fiber-forming method involves addition of the alkylbenzenesulfonic acid onium salt, halogen-containing alkyl (phenyl) phosphate and benzotriazole-based ultraviolet absorber to an N-methyl-2-pyrrolidone solution containing a poly-m-phenylene isophthalamide polymer, to prepare a dope. The dope is extruded from a nozzle into an aqueous inorganic solution whose main component is calcium chloride, stretched after coagulation and washing with water, and then further stretched on a hot plate at 300-325°C and crystallized, and finally subjected to oiling to complete the fibers. For staple fibers, they are crimped, cut and then spun to obtain easily dyeable spun fibers.
- The easily dyeable meta-linkage-containing aromatic polyamide fibers of the present invention obtained in the manner described above have an excellent dyeing property and light fastness without any loss in the excellent heat resistance, flame retardance and flame proofness of the original meta-linkage-containing aromatic polyamide fibers, and thus may be effectively applied for clothing, bedding and interior decorations which require coloring. In particular, the addition of the halogen-containing alkyl (phenyl) phosphate provides further improvement in the flame retardance while drastically improving the dyeing property and lowering the dyeing cost compared to addition of the alkylbenzenesulfonic acid onium salt alone, and addition of the ultraviolet absorber, particularly a benzotriazole-based ultraviolet absorbing compound, drastically improves the light fastness, allowing the fibers to be applied in the fields of clothing, bedding and interior decorations in the same manner as existing common fibers.
- The present invention is explained below by way of the examples. The measured values in the examples and comparative examples were obtained by the following methods.
- Crimped fibers were collectively cut to a length of 50 mm and dyed at 30°C for 90 minutes using a dyeing solution comprising 8% o.w.f. Estrol Navy Blue N-RL (product of Sumitomo Chemical Co., Ltd.), 0.3 g/l acetic acid and 25 g/l sodium nitrate to a fiber/dyeing solution ratio (liquor ratio) of 1:40, after which a solution comprising 1 g/l hydrosulfite, 1 g/l Amiladin D (product of Dai-ichi Kogyo Seiyaku Co., Ltd.) and 1 g/l sodium hydroxide was used at a liquor ratio of 1:40 for reductive washing at 80°C for 30 minutes, followed by water washing and drying. A 1.3g portion of the fibers was stuffed into a cell having a diameter of 31 mm and a depth of 13 mm, and a CM-2002 Minolta spectrophotometric colorimeter was used for colorimetry with a 10° field of view, a D76 light source and regular reflection elimination, using the value L* as an index of the dyeing property.
- The polymer was dissolved in N-methyl-2-pyrrolidone (NMP) to a concentration of 0.5 g/100 ml, and an Ostwald's viscometer was used for measurement at 30°C.
- The fineness of the fibers was measured according to JIS-L-1015.
- The tensile strength of the fibers was measured according to JIS-L-1074, with a 20 mm long test sample, an initial load of 1/20 g/1.1 dtex(de) and an elongation rate of 20 mm/min.
- As a standard sulfur sample, 0.1 cc of an aqueous (NH4)2SO4 solution of known concentration is dropped onto test filtration paper, and a calibration curve is prepared based on fluorescent X-ray quantitative analysis after vacuum drying. About 50 mg of the fibers and about 20 mg of calcium chloride are dissolved in 5.0 cc of NMP by heating at 110°C for 1 hour, and after dropping a standard amount (0.1 cc) on the test filtration paper, it is vacuum dried. The sample is then quantitatively analyzed by fluorescent X-ray analysis, the sulfur concentration of the fibers is calculated based on the previously prepared calibration curve, and this is converted into the content on the assumption that all of the sulfur is derived from the alkylbenzenesulfonic acid onium salt.
- In the same manner as above, a calibration curve is prepared by fluorescent X-ray analysis of a standard phosphorus sample of known concentration, the phosphorus concentration of the fibers is calculated, and this is converted into a content on the assumption that all of the phosphorus is derived from the alkyl (phenyl) phosphate.
- About 20 mg of a sample dried at 105°C for 60 minutes is measured into a test tube (120 mm x 10 mmΦ, pyrex), 4 ml of concentrated hydrochloric acid is added and the tube is sealed. The sealed tube is heated at 130°C for about 6 hours for hydrolysis. After completion of hydrolysis, the sealed tube is cooled to room temperature and opened. The total contents of the test tube are then transferred to a 50 ml separatory funnel, 5 ml of chloroform is added, and the mixture is adequately shaken and allowed to stand, after which the chloroform phase is removed. This extraction procedure with chloroform is repeated 3 times, all of the chloroform phases are combined and concentrated to 2-3 ml, and the solution is then analyzed by liquid chromatography (LC). Separately, a test sample is prepared for a calibration curve, which is obtained by the same procedure as described above. The calibration curve is used to quantify the benzotriazole-based compound in the sample.
- About 2g of sample (crimped and cut to lengths of 38-76 mm) is taken and dispersed with a hand card. The dispersed sample is affixed to a mount to a width of 18-22 mm and a thickness of 2-3 mm, as shown in Fig. 1. The mount is then set onto a metallic flask. The metallic flask is set into a fade tester (Model CF-20N, product of Shimazu Laboratories), and irradiated for a prescribed time with an arc current of 15-17 A and an internal temperature of 42-45°C. The difference in the degree of discoloration of the "irradiated" and "non-irradiated" sections of the irradiated sample is judged visually against the difference in discoloration of a simultaneously irradiated blue scale (JIS L0841, product of Japan Standards Association).
- A 30g portion of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved in 110g of NMP and further mixed with 3.6g of phosphonium dodecylbenzenesulfonate, and the solution was subjected to vacuum degassing to make a spinning dope.
- The dope was heated to 85°C and then used for wet spinning into a spinning bath from a spinning nozzle with 200 holes, each with a diameter of 0.07 mm. The composition of the spinning bath was 40 wt% calcium chloride, 5 wt% NMP and 55 wt% water, and the temperature of the spinning bath was 85°C. The filaments were given a course of about 100 cm through the spinning bath, and were drawn at a rate of 6.2 m/min. The filaments were then washed with water, stretched to a draw ratio of 2.4 in 95°C hot water, and dried using a roll at 200°C, after which they were stretched to a draw ratio of 1.75 on a 320°C hot plate to obtain stretched filaments with 440 dtex (400 de)/200 filaments. The total draw ratio was 4.2.
- A 30g portion of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved in 110g of NMP and further mixed with a solution of 3.6g of tributylbenzylammonium dodecylbenzenesulfonate in 2g NMP, and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 1, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- A 5.7g portion of tetrabutylphosphonium dodecylbenzenesulfonate was dissolved in 110g of NMP, and then 30g of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved therein and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 1, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- A 2.7g portion of tetrabutylphosphonium dodecylbenzenesulfonate was dissolved in 110g of NMP, and then 30g of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved therein and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 1, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- A 6.0g portion of tetrabutylphosphonium dodecylbenzenesulfonate was dissolved in 110g of NMP, and then 30g of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved therein and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for stretching in the same manner as in Example 1, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- The measurement results of the physical properties of the fibers obtained in Examples 1 to 5 are given in Table 1 below. All of the fibers in these examples were found to have satisfactory dyeing properties, high strength, and satisfactory spinning properties.
Onium salt content of fibers Strength (g/de) Ductility (%) Dyeing property L* value Example 1 4.4 5.0 44 22.0 Example 2 4.0 4.9 45 22.5 Example 3 7.0 4.6 42 19.5 Example 4 3.3 5.0 43 25.0 Example 5 7.4 4.0 39 19.0 Onium salt: alkylbenzenesulfonic acid onium salt Content: mole percent with respect to polymer - A 30g portion of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved in 110g of NMP, and then 3.6g of phosphonium dodecylbenzenesulfonate and 1.5g of tris(β-chloropropyl) phosphate were mixed therewith and the solution was subjected to vacuum degassing to make a spinning dope.
- The dope was heated to 85°C and then used for wet spinning into a spinning bath from a spinning nozzle with 200 holes each with a diameter of 0.07 mm. The composition of the spinning bath was 40 wt% calcium chloride, 5 wt% NMP and 55 wt% water, and the temperature of the spinning bath was 85°C. The filaments were given a course of about 100 cm through the spinning bath, and were drawn at a rate of 6.2 m/min. The filaments were then washed with water, stretched to a draw ratio of 2.4 in 95°C hot water, and dried using a roll at 200°C, after which they were stretched to a draw ratio of 1.75 on a 320°C hot plate to obtain stretched filaments with 440 dtex (400 de)/200 filaments. The total draw ratio was 4.2.
- A 30g portion of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved in 110g of NMP, and then a solution of 3.6g of tributylbenzylammonium dodecylbenzenesulfonate and 1.5g of tris(β-chloropropyl) phosphate in 2g of NMP was mixed therewith and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 6, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- A 3.6g portion of tetrabutylphosphonium dodecylbenzenesulfonate and 1.5g of tris(dichlorophenyl) phosphate were dissolved in 110g of NMP, and then 30g of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved therein and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 6, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- A 2.25g portion of tetrabutylphosphonium dodecylbenzenesulfonate and 2.4g of tris(β-chloropropyl) phosphate were dissolved in 110g of NMP, and then 30g of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved therein and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 6, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- A 3.6g portion of tris(β-chloropropyl) phosphate was dissolved in 110g of NMP, and then 30g of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved therein and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 6, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- A 2.25g portion of tetrabutylphosphonium dodecylbenzenesulfonate and 0.45g of tris(β-chloropropyl) phosphate were dissolved in 110g of NMP, and then 30g of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved therein and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 6, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- A 3.6g portion of tetrabutylphosphonium dodecylbenzenesulfonate and 0.9g of tris(β-chloropropyl) phosphate were dissolved in 110g of NMP, and then 30g of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved therein and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 6, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- The measurement results of the physical properties of the fibers obtained in Examples 6 to 11 and Comparative Example 1 are given in Table 2 below. All of the fibers in the examples were found to have satisfactory dyeing properties, high strength, and satisfactory spinning properties. However, the fibers of Comparative Example 1 had a very poor dyeing property, and thus it was found that the tris(β-chloropropyl) phosphate by itself had no effect of improving the dyeing property.
Onium salt content of fibers Phosphate content of fibers Strength (g/de) (g/1.1 dtex) Ductility (%) Dyeing property L* value Ex. 6 4.4 3.0 4.9 44 19.0 Ex. 7 4.0 3.0 4.9 44 19.5 Ex. 8 4.4 3.0 5.0 44 19.0 Ex. 9 2.8 4.8 4.8 39 21.5 Comp. Ex. 1 0 7.2 4.0 36 34.0 Ex. 10 2.8 0.9 5.0 45 26.5 Ex. 11 2.8 6.0 4.4 31 21.5 Onium salt: alkylbenzenesulfonic acid onium salt Onium salt content: mole percent with respect to polymer Phosphate: halogen-containing alkyl (phenyl) phosphate Phosphate content: weight percent based on polymer - A 30g portion of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved in 110g of NMP, and then 3.6g of tributylbenzylammonium dodecylbenzenesulfonate, 1.5g of tris(β-chloropropyl) phosphate and 0.6g of 2-[2-hydroxy-3,5-bis(α,α'-dimethylbenzyl)phenyl]-2H-benzotriazole were mixed therewith and the solution was subjected to vacuum degassing to make a spinning dope. The dope was heated to 85°C and then used for wet spinning into a spinning bath from a spinning nozzle with 200 holes each with a diameter of 0.07 mm. The composition of the spinning bath was 40 wt% calcium chloride, 5 wt% NMP and 55 wt% water, and the temperature of the spinning bath was 85°C. The filaments were given a course of about 100 cm through the spinning bath, and were drawn at a rate of 6.2 m/min. The filaments were then washed with water, stretched to a draw ratio of 2.4 in 95°C hot water, and dried using a roll at 200°C, after which they were stretched to a draw ratio of 1.75 on a 320°C hot plate to obtain stretched filaments with 440 dtex (400 de)/200 filaments. The stretched filaments were crimped with a crimper, and cut to a length of 51 mm with a cutter. The filaments were dyed with Estrol Navy Blue N-2RL (product of Sumitomo Chemical Co., Ltd.) by the method described above, and the dyed filaments were measured for light fastness with a fade tester (Model CF20N, Shimazu Laboratories) by the method described above.
- A 30g portion of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved in 110g of NMP, and then 3.6g of tributylbenzylammonium dodecylbenzenesulfonate, 1.5g of tris(β-chloropropyl) phosphate and 1.2g of 2-[2-hydroxy-3,5-bis(α,α'-dimethylbenzyl)phenyl]-2H-benzotriazole were mixed therewith and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 12, to obtain stretched filaments with 440 dtex (400 de)/200 filaments. The obtained stretched filaments were crimped, cut, dyed and measured for light fastness by the same method as in Example 12.
- A 30g portion of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved in 110g of NMP, and then 3.6g of tributylbenzylammonium dodecylbenzenesulfonate, 1.5g of tris(β-chloropropyl) phosphate and 1.8g of 2-[2-hydroxy-3/5-bis(α,α'-dimethylbenzyl)phenyl]-2H-benzotriazole were mixed therewith and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 12, to obtain stretched filaments with 440 dtex (400 de)/200 filaments. The obtained stretched filaments were crimped, cut, dyed and measured for light fastness by the same method as in Example 12.
- A 30g portion of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved in NMP, and then 3.9g of tributylbenzylammonium dodecylbenzenesulfonate and 1.5g of tris(β-chloropropyl) phosphate were mixed therewith and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 12, to obtain stretched filaments with 440 dtex (400 de)/200 filaments. The obtained stretched filaments were crimped, cut, dyed and measured for light fastness by the same method as in Example 12.
- A 30g portion of poly-m-phenylene isophthalamide with an IV of 1.35 dl/g was dissolved in 110g of NMP, and then 3.6g of tributylbenzylammonium dodecylbenzenesulfonate, 1.5g of tris(β-chloropropyl) phosphate and 2.4g of 2-[2-hydroxy-3,5-bis(α,α'-dimethylbenzyl)phenyl]-2H-benzotriazole were mixed therewith and the solution was subjected to vacuum degassing to make a spinning dope. This dope was used for spinning and stretching in the same manner as in Example 8, to obtain stretched filaments with 440 dtex (400 de)/200 filaments.
- There was considerable breakage of single filaments during the spinning and stretching process, and a great deal of fuming on the 320°C hot plate.
- The obtained stretched filaments were crimped, cut, dyed and measured for light fastness by the same method as in Example 12.
- The measurement results for Examples 12 to 16 are given in Table 3. All of the fibers in the examples had satisfactory filament quality, dyeing properties and light fastness, except that the fibers of Example 15 did not have an improved light fastness.
Onium salt content of fibers Phosphate content of fibers Ultraviolet absorber content of fibers Strength (g/1.1 dtex) (g/de) Ductility (%) Light fastness (degree) Ex. 12 4.7 5.0 2.0 5.0 44 3 Ex. 13 4.7 5.0 4.0 4.9 43 4 Ex. 14 4.7 5.0 6.0 4.9 42 4-5 Ex. 15 5.1 5.0 0.0 5.1 46 1-2 Ex. 16 4.7 5.0 8.0 4.4 38 4-5 Onium salt: tributylbenzylammonium
dodecylbenzenesulfonateOnium salt content: mole percent with respect to polymer Phosphate: tris(β-chloropropyl) phosphate Phosphate content: weight percent with respect to polymer Ultraviolet absorber: 2-[2-hydroxy-3,5-bis(α,α'-dimethylbenzyl)phenyl]-2H- benzotriazole Ultraviolet absorber content: weight percent based on polymer
Claims (17)
- Meta-linkage-containing aromatic polyamide fibers easily dyeable with cationic dyes, the fibers consisting of a composition which comprises a meta-linkage-containing aromatic polyamide incorporating an alkylbenzenesulfonic acid onium salt selected from the group consisting of tetrabutylphosphonium hexylbenzenesulfonate, tributylbenzylphosphonium hexylbenzenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate, tributylphenylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate and tributylbenzylammonium dodecylbenzenesulfonate.
- Fibers according to claim 1, wherein the onium alkylbenzenesulfonate content is between 2.8 and 7.0 mole percent with respect to the repeating units of the meta-linkage-containing aromatic polyamide.
- Fibers according to claim 1, wherein the alkylbenzenesulfonate is dodecylbenzenesulfonate.
- Fibers according to claim 1, wherein the onium salt is a tetrabutylphosphonium salt.
- Fibers according to claim 1, wherein the onium salt is a tributylbenzylammonium salt.
- Fibers according to any of claims 1 to 6, wherein the meta-linkage-containing aromatic polyamide composition further contains a halogen-containing alkyl phosphate or halogen-containing phenyl phosphate.
- Fibers according to claim 7, wherein the halogen-containing alkyl phosphate is tris(β-chloropropyl) phosphate.
- Fibers according to claim 7, wherein the halogen-containing phenyl phosphate is tris(dichlorophenyl) phosphate.
- Fibers according to claim 7, wherein the halogen-containing alkyl phosphate or halogen-containing phenyl phosphate content is 0.5 to 5.0 wt% with respect to the meta-linkage-containing aromatic polyamide.
- Fibers according to any of claims 1 to 6, wherein the meta-linkage-containing aromatic polyamide composition further contains a halogen-containing alkyl phosphate or halogen-containing phenyl phosphate and an ultraviolet absorber.
- Fibers according to claim 11, wherein the halogen-containing alkyl phosphate is tris(β-chloropropyl) phosphate.
- Fibers according to claim 11, wherein the halogen-containing phenyl phosphate is tris(dichlorophenyl) phosphate.
- Fibers according to claim 11, wherein the halogen-containing alkyl phosphate or halogen-containing phenyl phosphate content is 0.5 to 5.0 wt% with respect to the meta-linkage-containing aromatic polyamide.
- Fibers according to claim 11, wherein the ultraviolet absorber content is 2.0 to 6.0 wt% with respect to the meta-linkage-containing aromatic polyamide.
- Fibers according to claim 11, wherein the ultraviolet absorber is a benzotriazole-based ultraviolet absorber.
- Fibers according to claim 16, wherein the ultraviolet absorber is 2-[2-hydroxy-3,5-bis(α,α'-dimethylbenzyl)phenyl]-2H-benzotriazole.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6215736A JP2971338B2 (en) | 1994-09-09 | 1994-09-09 | Easily dyeable meta-type aromatic polyamide fiber |
EP96102132A EP0790334B1 (en) | 1994-09-09 | 1996-02-14 | Easily dyeable meta-linkage-containing aromatic polyamide fibres |
DE69610484T DE69610484T2 (en) | 1994-09-09 | 1996-02-14 | Easily dyeable aromatic polyamide fibers containing meta bonds |
ES96102132T ES2150031T3 (en) | 1994-09-09 | 1996-02-14 | AROMATIC POLYAMID FIBERS CONTAINING LINKS IN META, EASILY DYEABLE. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6215736A JP2971338B2 (en) | 1994-09-09 | 1994-09-09 | Easily dyeable meta-type aromatic polyamide fiber |
EP96102132A EP0790334B1 (en) | 1994-09-09 | 1996-02-14 | Easily dyeable meta-linkage-containing aromatic polyamide fibres |
Publications (2)
Publication Number | Publication Date |
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EP0790334A1 EP0790334A1 (en) | 1997-08-20 |
EP0790334B1 true EP0790334B1 (en) | 2000-09-27 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP96102132A Expired - Lifetime EP0790334B1 (en) | 1994-09-09 | 1996-02-14 | Easily dyeable meta-linkage-containing aromatic polyamide fibres |
Country Status (4)
Country | Link |
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EP (1) | EP0790334B1 (en) |
JP (1) | JP2971338B2 (en) |
DE (1) | DE69610484T2 (en) |
ES (1) | ES2150031T3 (en) |
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JP2971338B2 (en) * | 1994-09-09 | 1999-11-02 | 帝人株式会社 | Easily dyeable meta-type aromatic polyamide fiber |
JP2001098470A (en) * | 1999-09-30 | 2001-04-10 | Teijin Ltd | Method for dyeing wholly aromatic polyamide fiber |
JP4624542B2 (en) * | 2000-11-13 | 2011-02-02 | 帝人テクノプロダクツ株式会社 | Dyeing method for wholly aromatic polyamide fiber |
JP4647680B2 (en) | 2008-09-29 | 2011-03-09 | 帝人テクノプロダクツ株式会社 | Easy-dyeing meta-type wholly aromatic polyamide fiber |
JP4804590B1 (en) | 2010-04-14 | 2011-11-02 | 帝人テクノプロダクツ株式会社 | Meta-type wholly aromatic polyamide fiber |
JP2013204210A (en) * | 2012-03-29 | 2013-10-07 | Teijin Ltd | Dyed aramid fiber and method for dyeing aramid fiber |
CN106164153A (en) * | 2014-04-09 | 2016-11-23 | 提克纳有限责任公司 | Antistatic polymer composite |
US9822254B2 (en) | 2014-04-09 | 2017-11-21 | Ticona Llc | Camera module |
KR102627886B1 (en) | 2017-12-05 | 2024-01-19 | 티코나 엘엘씨 | Aromatic polymer compositions for use in camera modules |
CN113072808A (en) * | 2021-03-16 | 2021-07-06 | 株洲时代新材料科技股份有限公司 | Meta-aramid resin liquid, meta-aramid fiber, aramid product and preparation method thereof |
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FR2102278B1 (en) * | 1970-08-14 | 1975-04-18 | Teijin Ltd | |
JPS53122817A (en) * | 1977-03-30 | 1978-10-26 | Teijin Ltd | Wholly aromatic polyamide fibers having improved flame resistance |
EP0006564B1 (en) * | 1978-06-26 | 1981-12-30 | Ciba-Geigy Ag | 2-(3.5-disubstituted-2-hydroxyphenyl)-2h-benzotriazoles and stabilized compositions containing them |
US4668234A (en) * | 1985-08-15 | 1987-05-26 | E. I. Du Pont De Nemours And Company | Aromatic polyamide fibers and process for stabilizing such fibers with surfactants |
CA1282213C (en) * | 1985-12-16 | 1991-04-02 | E. I. Du Pont De Nemours And Company | Aromatic polyamide fibers and processes for making such fibers |
JPH01221537A (en) * | 1988-02-26 | 1989-09-05 | Teijin Ltd | Flame-resistant fiber |
JP2971338B2 (en) * | 1994-09-09 | 1999-11-02 | 帝人株式会社 | Easily dyeable meta-type aromatic polyamide fiber |
-
1994
- 1994-09-09 JP JP6215736A patent/JP2971338B2/en not_active Expired - Fee Related
-
1996
- 1996-02-14 ES ES96102132T patent/ES2150031T3/en not_active Expired - Lifetime
- 1996-02-14 DE DE69610484T patent/DE69610484T2/en not_active Expired - Lifetime
- 1996-02-14 EP EP96102132A patent/EP0790334B1/en not_active Expired - Lifetime
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ES2150031T3 (en) | 2000-11-16 |
DE69610484T2 (en) | 2001-05-10 |
DE69610484D1 (en) | 2000-11-02 |
JP2971338B2 (en) | 1999-11-02 |
EP0790334A1 (en) | 1997-08-20 |
JPH0881827A (en) | 1996-03-26 |
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