EP0790334B1 - Leicht färbbare Metabindungen enthaltende aromatische Polyamidfasern - Google Patents

Leicht färbbare Metabindungen enthaltende aromatische Polyamidfasern Download PDF

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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
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Prior art keywords
linkage
phosphate
meta
aromatic polyamide
fibers according
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EP0790334A1 (de
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Akihiro Ohba
Koki Sasaki
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Teijin Ltd
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Teijin Ltd
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Priority to JP6215736A priority Critical patent/JP2971338B2/ja
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Priority to DE69610484T priority patent/DE69610484T2/de
Priority to ES96102132T priority patent/ES2150031T3/es
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    • 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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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Polyamides (AREA)

Claims (17)

  1. Aromatische Polyamidfasern welche Metabindungen enthalten, und welche leicht mit kationischen Farben färbbar sind, wobei die Fasern aus einer Zusammensetzung bestehen, welche ein Metabindungen enthaltendes, aromatisches Polyamid, welches ein Alkyl-Benzolsulfonsäureoniumsalz beinhaltet, umfasst, wobei letzteres ausgewählt ist, aus der Gruppe aus Tetrabutylphosphonium-hexylbenzolsulfonat, Tributylbenzylphosphonium-hexylbenzolsulfonat, Tetraphenylphosphonium-dodecylbenzolsulfonat, Tributylphenylphosphonium-dodecylbenzolsulfonat, Tetrabutylphosphonium-dodecylbenzolsulfonat und Tributylbenzylammonium-dodecylbenzolsulfonat.
  2. Fasern nach Anspruch 1, worin mindestens 85 Molprozent der Struktureinheiten des Metabindungen enthaltenden, aromatischen Polyamids Poly-m-Phenylen-isophthalamid sind, welches aus 2 Struktureinheiten der folgenden chemischen Formeln besteht:
    Figure 00230001
  3. Fasern nach Anspruch 1, worin der Oniumalkylbenzolsulfonat-Gehalt zwischen 2,8 und 7,0 Molprozent bezüglich der Struktureinheiten des Metabindungen enthaltenden, aromatischen Polyamids beträgt.
  4. Fasern nach Anspruch 1, worin das Alkylbenzolsulfonat Dodecylbenzolsulfonat ist.
  5. Fasern nach Anspruch 1, worin das Oniumsalz Tetrabutylphosphononiumsalz ist.
  6. Fasern nach Anspruch 1, worin das Oniumsalz ein Tributylbenzylammoniumsalz ist.
  7. Fasern nach einem der Ansprüche 1 bis 6, worin die Metabindungen enthaltende, aromatische Polyamidzusammensetzung ferner ein halogenhaltiges Alkylphosphat oder halogenhaltiges Phenylphosphat enthält.
  8. Fasern nach Anspruch 7, worin das halogenhaltige Alkylphosphat tris(β-Chloropropyl)-phosphat ist.
  9. Fasern nach Anspruch 7, worin das halogenhaltige Phenylphosphat tris(Dichlorophenyl)-phosphat ist.
  10. Fasern nach Anspruch 7, worin der Gehalt an halogenhaltigem Alkylphosphat oder halogenhaltigem Phenylphosphat 0,5 bis 5,0 Gew. % beträgt, bezogen auf das Metabindungen enthaltende, aromatische Polyamid.
  11. Fasern nach einem der Ansprüche 1 bis 6, worin die Metabindungen enthaltende, aromatische Polyamidzusammensetzung ferner ein halogenhaltiges Alkylphosphat oder halogenhaltiges Phenylphosphat und einen Ultraviolett-Absorber enthält.
  12. Fasern nach Anspruch 11, worin das halogenhaltige Alkylphosphat tris(β-Chloropropyl)-phosphat ist.
  13. Fasern nach Anspruch 11, worin das halogenhaltige Phenylphosphat tris(Dichlorophenyl)-phosphat ist.
  14. Fasern nach Anspruch 11, worin der Gehalt an halogenhaltigem Alkylphosphat oder halogenhaltigem Phenylphosphat 0,5 bis 5,0 Gew.-% beträgt, bezogen auf das Metabindungen enthaltende, aromatische Polyamid.
  15. Fasern nach Anspruch 11, worin der UV-Absorbergehalt 2,0 bis 6 Gew.-% beträgt, bezogen auf das Metabindungen enthaltende, aromatische Polyamid.
  16. Fasern nach Anspruch 11, worin der Ultraviolett-Absorber ein Benzotriazol-basierender Ultraviolett-Absorber ist.
  17. Fasern nach Anspruch 16, worin der Ultraviolett-Absorber 2-[2-Hydroxy-3,5-bis (α,α'-dimethylbenzyl)-phenyl]-2H-benzotriazol ist.
EP96102132A 1994-09-09 1996-02-14 Leicht färbbare Metabindungen enthaltende aromatische Polyamidfasern Expired - Lifetime EP0790334B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP6215736A JP2971338B2 (ja) 1994-09-09 1994-09-09 易染性メタ型芳香族ポリアミド繊維
EP96102132A EP0790334B1 (de) 1994-09-09 1996-02-14 Leicht färbbare Metabindungen enthaltende aromatische Polyamidfasern
DE69610484T DE69610484T2 (de) 1994-09-09 1996-02-14 Leicht färbbare Metabindungen enthaltende aromatische Polyamidfasern
ES96102132T ES2150031T3 (es) 1994-09-09 1996-02-14 Fibras de poliamidas aromaticas que contienen enlaces en meta, facilmente teñibles.

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JP6215736A JP2971338B2 (ja) 1994-09-09 1994-09-09 易染性メタ型芳香族ポリアミド繊維
EP96102132A EP0790334B1 (de) 1994-09-09 1996-02-14 Leicht färbbare Metabindungen enthaltende aromatische Polyamidfasern

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EP0790334A1 EP0790334A1 (de) 1997-08-20
EP0790334B1 true EP0790334B1 (de) 2000-09-27

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JP2971338B2 (ja) * 1994-09-09 1999-11-02 帝人株式会社 易染性メタ型芳香族ポリアミド繊維
JP2001098470A (ja) * 1999-09-30 2001-04-10 Teijin Ltd 全芳香族ポリアミド繊維の染色方法
JP4624542B2 (ja) * 2000-11-13 2011-02-02 帝人テクノプロダクツ株式会社 全芳香族ポリアミド繊維の染色方法
JP4647680B2 (ja) 2008-09-29 2011-03-09 帝人テクノプロダクツ株式会社 易染色性メタ型全芳香族ポリアミド繊維
JP4804590B1 (ja) 2010-04-14 2011-11-02 帝人テクノプロダクツ株式会社 メタ型全芳香族ポリアミド繊維
JP2013204210A (ja) * 2012-03-29 2013-10-07 Teijin Ltd 染色されたアラミド繊維およびアラミド繊維の染色方法
KR102305241B1 (ko) 2014-04-09 2021-09-24 티코나 엘엘씨 대전방지 중합체 조성물
US9822254B2 (en) 2014-04-09 2017-11-21 Ticona Llc Camera module
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
CN113072808A (zh) * 2021-03-16 2021-07-06 株洲时代新材料科技股份有限公司 间位芳纶树脂液、间位芳纶纤维、芳纶制品及其制备方法
CN119877130A (zh) * 2025-02-20 2025-04-25 四川大学 磺化聚芳噁二唑作为纤维染色助剂的应用、纺丝原液、改性纤维以及改性纤维的染色方法

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CA959608A (en) * 1970-08-14 1974-12-24 Kazuo Kitamura Process for dyeing fibers or fabrics of aromatic polyamide
JPS53122817A (en) * 1977-03-30 1978-10-26 Teijin Ltd Wholly aromatic polyamide fibers having improved flame resistance
EP0006564B1 (de) * 1978-06-26 1981-12-30 Ciba-Geigy Ag 2-(2-Hydroxy-3.5-disubstituiertes-phenyl)-2H-benzotriazol und damit stabilisierte Mischungen
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 (ja) * 1988-02-26 1989-09-05 Teijin Ltd 耐炎性繊維
JP2971338B2 (ja) * 1994-09-09 1999-11-02 帝人株式会社 易染性メタ型芳香族ポリアミド繊維

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DE69610484T2 (de) 2001-05-10
ES2150031T3 (es) 2000-11-16
JPH0881827A (ja) 1996-03-26
DE69610484D1 (de) 2000-11-02
EP0790334A1 (de) 1997-08-20
JP2971338B2 (ja) 1999-11-02

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