Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
• • 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
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
• • 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
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/70—Material containing nitrile groups
  • D06P3/702—Material containing nitrile groups dyeing of material in the gel state
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/70—Material containing nitrile groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/70—Material containing nitrile groups
  • D06P3/708—Material containing nitrile groups using reactive dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/70—Material containing nitrile groups
  • D06P3/74—Material containing nitrile groups using acid dyes

Definitions

• the present invention relates to a new process for dyeing polyacrylonitrile fibers in the gel state during fiber formation.
• the invention further relates to the use of anionic dyes for this dyeing process.
• polyacrylonitrile can be colored with cationic dyes.
• pure polyacrylonitrile is difficult to dye. It is therefore customary to add ionogenic and nonionic comonomers during the polymerization.
• the ionogenic comonomers have sulfo or sulfonate groups and thus enable the chemical
• binding of ionic dyes whose coloring ion is a cation (basic dyes).
• the nonionic comonomers serve as internal plasticizers and can increase the absorption rate of the dyes during dyeing. It is also known that such acrylic fibers can be dyed with cationic dyes after the exhaust process or during the spinning process, when the fibers are in the gel state. Such methods are e.g. described in GB-A 991 957, GB 992 195 and GB 1 056 731.
• Polyacrylonitrile fibers can be dyed with anionic dyes.
• the present invention thus relates to a process for dyeing non-cationically modified polyacrylonitrile fibers during the spinning process when the fibers are in the gel state, characterized in that at least one anionic dye from the group of acid dyes, direct dyes or reactive dyes is used as the dye.
• polyacrylonitrile fibers are understood to mean those fibers which consist of at least 85% by weight of polymerized acrylonitrile.
• the polyacrylonitrile fibers to be dyed according to the invention are preferably ternary copolymers containing 89-95% by weight of acrylonitrile, 4-10% by weight of a nonionic comonomer and 0.5-1% by weight of an ionogenic comonomer with at least one sulfo or sulfonate group.
• nonionogenic comonomers dicyanoethylene, itaconic acid, polyethylene oxide, vinylidine chloride, methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride.
• ionogenic comonomers are: AMPS (2-acrylamido-2-methylpropanesulfonate, allylsulfonate, methallylsulfonate, styrene sulfonic acid, vinyl sulfonic acid.
• the polyacrylonitrile fibers to be dyed according to the invention are also to be understood as meaning modacrylic fibers.
• Modacrylic fibers preferably contain less than 85% by weight, in particular 50 to 80% by weight, of polymerized acrylonitrile, 49 to 12% by weight of polymerized vinyl chloride or vinylidene chloride, 1 to 3% by weight of an ionogenic comonomer, preferably styrene sulfonic acid and Methallylsulfonate, and 0 to 5 wt .-% of a non-ionic comonomer, preferably alkyl acrylamide, the sum of all components being added to 100 wt .-%.
• the method according to the invention is used in the context of wet spinning.
• the fiber-forming acrylonitrile polymer which was previously dissolved in a solvent, is spun into an aqueous precipitation bath, whereby polyacrylonitrile fibers are formed.
• Suitable solvents for the fiber-forming acrylonitrile polymer are dimethylformamide, dimethylacetamide, acetone, nitrophenol, oxypyrrolidone and dimethyloxamide, and aqueous solutions of zinc chloride, sodium and ammonium thiocyanide and nitric acid.
• the process according to the invention is a so-called "inline dyeing process" of wet-spun polyacrylonitrile fibers in the gel state, which is known in principle.
• the dye bath can be positioned at different points in the spinning line during the dyeing process.
• the dye bath is usually positioned either during the pre-stretching process, after the
• gel state refers to acrylonitrile fibers immediately after leaving the spinneret until just before fiber formation is complete. Usually a fiber in the gel state has a water content of 2 to
• the finished fiber After leaving the gel state, the finished fiber has no or only a very low water content of approximately 0 to 1.5% by weight and at most contains residues of solvents in the ppm range.
• the fiber is still very amorphous and is dyed very quickly.
• the solvent content in the fiber is still very high, which leads to rapid contamination of the dye bath.
• the fiber is also very sensitive at this stage.
• the speed of the thread is approximately 2 to 14 m / min., Preferably 8 to 14 m / min.
• the pre-stretching and washing process has already removed almost all solvent residues, which is particularly advantageous if aqueous sodium or ammonium thiocyanide is used as the solvent.
• the speed of the thread is approximately 4 to 42 m / min, preferably 18 to 28 m / min and is therefore still slow enough to allow the dye bath to be exhausted in approximately 0.4 to 8, preferably 0.5 to 5 seconds.
• the dyeing rate is highest in this case.
• the speed of the thread in this phase of the spinning process is very high, namely generally 60 to 140 m / min, preferably 100 to 140 m / min, which complicates sufficient exhaustion of the dye bath.
• the affinity of the fiber is very low, which requires a higher dye bath concentration if you want to dye deeper shades.
• dye baths customary in the prior art are suitable as gel dye baths, starting from very simple dye baths up to complicated dye baths with high liquor circulation, spray plates, air passages and steam passages.
• the contact time of the thread with the dyebath is on average 0.3 to 10 sec.
• the temperature of the dyebath is generally 20 to 95 ° C, preferably 30 to 60 ° C.
• Acid dyes which are assigned to the following classes of dyes are suitable for the process according to the invention: mono- or polyazo dyes, anthraquinone dyes, triphenylmethane dyes, triphendioxazine dyes, phthalocyanine dyes,
• Metal complex dyes xanthene and thiazine dyes, which preferably have one or two sulfo and / or carboxyl groups. Dyes of this type are listed in the Color Index, where they are subdivided into metal complex dyes, leveling dyes, semi-whale dyes and whale dyes according to their application properties.
• sulfo groups are free and those which have one or two sulfo groups and or carboxyl groups.
• Direct dyes suitable for the process according to the invention are those from the classes of mono- or polyazo dyes, anthraquinone, triphendioxazine, metal complex and xanthene dyes, which preferably have one or two sulfo and / or carboxyl groups.
• Preferred direct dyes are:
• the following types of dyes which have at least one reactive group are suitable as reactive dyes: mono- or polyazo dyes, metal complex dyes, triphendioxazine dyes and phthalocyanine dyes.
• the dye cushions mentioned preferably have one or two reactive groups from the series monochlorotriazine, dichlorotriazine, sulfatoethyl sulfone, triacryl formal,
• Formaldehyde derivatives trichloropyrimidine, (alkoxy) monochlorotriazine, monochlorodifluoropyrimidine, dichlorophthalazine, methyltaurinoethylsulfone, sulfatoethylsulfonacrylamide, ⁇ -bromoacrylamide, dichloropyridazone, acrylamide, sulfonic acid N (ß-chloroethyl) amid, dichlo yrimidoxylchloromethylchloride, , Alkyl or
• Reactive Yellow 3 18, 22, 86, 154, 30, 60, 11, 55, 111, 66, 37: 1, 123, 39, 113, 5, 59, 37, 125, 143, 148, 132
• Reactive Orange 4 72, 49, 87, 52, 79, 48, 89
• Reactive Red 3 58, 2, 11, 109B, 47, 92, 56, 151, 124, 97, 21: 1, 166, 83, 155, 30, 91,
• Reactive Blue 2 13, 32, 109, 19B, 62, 88, 10, 74, 113, 93, 155, 150, 69, 6, 84, 19, 114, 182, 172
• the dyes can be added to the dyebath in the usual form, e.g. in the form of an aqueous solution, which may contain other auxiliaries such as may contain quaternary araliphatic ammonium compounds.
• the dyeings obtained are notable for great depth of color and very good fastness properties, in particular light and wet fastness properties.
• a spinning solution was prepared from 25% by weight of polyacrylonitrile and 75% by weight.
• DMF Dimethylformamide
• This solution was spun into a spinning bath of aqueous DMF (DMF content 10 to 20% by weight) at a temperature of 60 ° C.
• the cable was washed 4 times and pre-stretched 3 times.
• the cable thus obtained had a composition of 560 kilotex with a water content of 20% by weight and a DMF content of 5% by weight.
• the cable was then passed through at a speed of 15 m / min
• a spinning solution was prepared from 13% by weight of polyacrylonitrile, 40% by weight of sodium rhodanide (NaSCN) and 37% by weight of water. This solution was spun in a spinning bath of aqueous sodium rhodanide solution (NaSCN content 5 to 20% by weight) at a temperature of 2 ° C. The cable was washed 4 times and pre-stretched 2 times. The cable thus obtained had a composition of 3300 Kilotex with a water content of
• the cable was then passed through a dye bath at a speed of 25 m / min. The immersion time was 4 seconds at a temperature of 60 ° C.
• the dye bath contained 0.3% by weight of Acid Yellow 242, 0.2% by weight of Acid Red 425 and 3.2% by weight of Acid Black 099 based on the finished cable.
• the mixture was then washed twice, fully stretched and then at 120 ° C. for 6 min. dried. A well-colored deep gray filament with good wet and light fastness was obtained.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Dispersion Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Toxicology (AREA)
• Coloring (AREA)
• Artificial Filaments (AREA)
• Paper (AREA)

Applications Claiming Priority (3)

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• 2000
  • 2000-06-02 DE DE10027338A patent/DE10027338A1/de not_active Withdrawn
• 2001
  • 2001-05-30 WO PCT/EP2001/006132 patent/WO2001092634A1/de active Application Filing
  • 2001-05-30 US US10/296,409 patent/US20030167575A1/en not_active Abandoned
  • 2001-05-30 MX MXPA02011863A patent/MXPA02011863A/es not_active Application Discontinuation
  • 2001-05-30 EP EP01945211A patent/EP1425463A1/de not_active Withdrawn
  • 2001-05-30 CN CN01810486A patent/CN1432086A/zh active Pending
  • 2001-05-30 JP JP2002500023A patent/JP2003535231A/ja not_active Withdrawn
  • 2001-05-30 BR BR0111394-1A patent/BR0111394A/pt not_active IP Right Cessation
  • 2001-05-31 TW TW090113142A patent/TWI284692B/zh not_active IP Right Cessation

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