EP0665311B1 - Aminated cellulosic synthetic fibers - Google Patents

Aminated cellulosic synthetic fibers Download PDF

Info

Publication number
EP0665311B1
EP0665311B1 EP95100299A EP95100299A EP0665311B1 EP 0665311 B1 EP0665311 B1 EP 0665311B1 EP 95100299 A EP95100299 A EP 95100299A EP 95100299 A EP95100299 A EP 95100299A EP 0665311 B1 EP0665311 B1 EP 0665311B1
Authority
EP
European Patent Office
Prior art keywords
cellulose
group
substituted
synthetic fibers
fibers
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
Application number
EP95100299A
Other languages
German (de)
French (fr)
Other versions
EP0665311A1 (en
Inventor
Andreas Dr. Schrell
Werner Hubert Dr. Russ
Bernd Dr. Huber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dystar Textilfarben GmbH and Co Deutschland KG
Original Assignee
Dystar Textilfarben GmbH and Co Deutschland KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE19944402711 external-priority patent/DE4402711A1/en
Priority claimed from DE19944422758 external-priority patent/DE4422758A1/en
Application filed by Dystar Textilfarben GmbH and Co Deutschland KG filed Critical Dystar Textilfarben GmbH and Co Deutschland KG
Publication of EP0665311A1 publication Critical patent/EP0665311A1/en
Application granted granted Critical
Publication of EP0665311B1 publication Critical patent/EP0665311B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • D01F2/04—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts from cuprammonium solutions
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/22—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose by the dry spinning process
    • 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre
    • D06P5/225—Aminalization of cellulose; introducing aminogroups into cellulose
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/921—Cellulose ester or ether

Definitions

  • the invention relates to aminated cellulosic synthetic fibers, processes for their Manufacture and its use.
  • cellulose regenerated fibers are the same (in the following also referred to as viscose fibers) essentially the cotton fibers.
  • viscose fibers essentially the cotton fibers.
  • At the current state of the art are for dyeing cellulosic natural or Regenerate fiber alkalis, as well as electrolytes necessary to to achieve satisfactory fixation results with reactive dyes.
  • cellulose regenerated fibers will be important that previously without additional process steps in high dye affinity, i.e. salt and alkali free dyeable, modifications were transferred. Fibers modified in this way are similar to their chemical behavior animal fibers such as wool or silk, and can under neutral conditions with anionic dyes, without further Salt or alkali additives are colored.
  • DE-A-1494547 describes a process for producing and Dyeing threads and staple fibers from regenerated cellulose, at which the viscose is spun with an N-vinyl lactam polymer adds.
  • EP-A-0 546 476 describes a method for Production of a modified fiber material and for dyeing it Fiber material with anionic textile dyes, which one Fiber material modified in such a way that it is in aqueous solution with an aliphatic compound containing amino and ester groups impregnated and subjected to heat treatment.
  • the so modified Fiber material can be mixed with water-soluble, anionic dyes, in particular fiber-reactive dyes, from low-electrolyte or completely electrolyte-free and / or low-alkali or completely alkali-free Dyeing liquor can be dyed.
  • water-soluble, anionic dyes in particular fiber-reactive dyes, from low-electrolyte or completely electrolyte-free and / or low-alkali or completely alkali-free Dyeing liquor can be dyed.
  • This object is surprisingly achieved by adding one amine-substituted cellulose derivative to form a viscose mass or alkali cellulose, or by adding to a cellulose solution.
  • N N-diallyl-N-methyl-N-dodecylammonium halide
  • N N-diallyl-N-methyl-N-octylammonium halide
  • N N-diallyl-N-methyl-N-decylammonium halide
  • N N-diallyl-N, N-dimethylammonium halide
  • N N-diallyl-N, N-dimethylammonium chloride.
  • ester group is a sulfato or phosphato group or a C 1 -C 4 alkanoyl group, phenylsulfonyloxy or one on the benzene nucleus by substituents from the group carboxy, C 1 -C 4 alkyl, C 1 - C 4 alkoxy and nitro substituted phenylsulfonyloxy group.
  • Cellulose derivatives are also suitable for those compounds which act as a reactive residue the amino component has an ⁇ -chloro- ⁇ -hydroxy or epoxy substitution exhibit.
  • such parts of the molecule are generally reactive understand that with hydroxyl groups, for example of cellulose, or amino and thiol groups, for example wool and silk, can react and are able to form a covalent chemical bond.
  • a cellulose component for the production of the amine-substituted Cellulose derivatives have become carboxymethyl cellulose, hydroxyethyl cellulose, Hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, Sulfoethyl cellulose, carboxymethyl sulfoethyl cellulose, Hydroxypropylsulfoethyl cellulose, hydroxyethylsulfoethyl cellulose, Methylsulfoethyl cellulose and ethyl sulfoethyl cellulose have been found to be suitable.
  • the process for making the aminated cellulosic synthetic fibers is carried out either by alkaline cellulose digestion (Alkali cellulose), reacted with carbon disulfide, the xanthate in Sodium hydroxide solution dissolves and the viscose spinning solution thus obtained amine-substituted cellulose derivatives or by adding the amine-substituted cellulose derivatives are added directly to the alkali cellulose and then xanthogenized. By subsequent spinning in an acidic spinning bath the modified viscose fibers according to the invention are obtained.
  • the nitrogenous compounds used for the present process are in an aqueous medium or expediently with the aid of emulsifiers incorporated into the viscose spinning mass and show a good with the viscose Compatibility.
  • the amine-substituted cellulose derivative is added in an amount of 1 to 20%, preferably 1 to 12 wt .-%, based on the Cellulose content of the dope before precipitation and shaping.
  • the expert current process for producing cellulosic fibers from solution such as the cupro process, the lyocell process and the Process on low substituted cellulose ethers, so produced Cellulose dissolved in a suitable organic solvent with which amine-substituted cellulose derivative added and directly from the solution to fibers spun.
  • the best thing to do is to meter in immediately before spinning, where the interference and homogeneous distribution by known mixing systems can be done with the help of static or dynamic mixing systems.
  • the Dosing can also be done in any preliminary stage with the Spinning mass production take place.
  • the aminated celluloses used as additives have degrees of polymerization between 300 and 1000 anhydroglucose units and viscosities from 300 to 1500 mPas.
  • the degree of polymerization should not be less than 300 because otherwise there is a risk that the prefabricated aminated cellulose after the spinning is washed out of the fiber.
  • the prefabricated ones used to manufacture the modified viscose Cellulose derivatives can, due to their solubility in water or in aqueous alkali solution, stir well into the spinning mass.
  • the filterability of the viscose shows no deterioration in comparison with additive free samples, so that no clogging of the in the course of the spinning process Spinneret can be observed.
  • the deformation of the viscose is done according to usual and known methods, such as. B. with spinnerets, one subsequent precipitating bath and, if appropriate, further post-treatment baths.
  • the present invention also relates to a method for the production a colored or printed textile material made from regenerated cellulose fibers, characterized in that a viscose or alkali cellulose amine-substituted cellulose derivative and after the viscose spinning process Fibers spinning, or by making said cellulose derivative from a cellulose solution adds and spins fibers from the solution, the fibers into a fabric or Knitted fabrics processed and this with one or more reactive dyes in Absence of additional electrolyte salt or alkali colors or prints.
  • the textile modified fiber material used in the invention Dyeing process can be used in all processing states, so as Yarn, flake, sliver and piece goods (fabric) are available.
  • the modified textile fiber materials are dyed according to the invention analogous to known dyeing methods and printing processes for dyeing and printing of fiber materials with water-soluble textile dyes and under Application of the temperature ranges known for this and usual amounts of dye, but with the exception that for the dye baths, Block process, printing pastes and ink jet formulations an addition of alkaline compounds, as they are usually used to fix fiber-reactive dyes are used, is not necessary and also on usual Additions to electrolyte salts can be dispensed with. It is therefore one pH between 4.5 and 8.5 and, when using commercially available Reactive dyes, in the presence of an electrolyte salt content of 0.01 to 0.5% by weight, based on the coloring solution, colored or printed. Without that Amination of the cellulose fibers according to the invention would be this electrolyte content too small for a successful dyeing process by a factor of 20 to 1000.
  • Dyeing processes which can be used according to the invention are, for example, the various exhaust processes, such as dyeing on the jigger and on the reel runner or dyeing from a long and short liquor, dyeing in jet dyeing machines, dyeing by padding-cold dwelling or padding -Hot steam fixing process.
  • the dyeing methods which can be used according to the invention also include the printing techniques, including ink-jet printing and transfer printing.
  • the dyes that are used to dye the modified cellulose are generally anionic in nature.
  • the fiber-reactive ones are particularly suitable Textile dyes containing hydroxyl groups, for example cellulose, or Amino and thiol groups, for example wool and silk, from synthetic polymers, such as polyamides, or also modified polymers, just the aminated celluloses, can react and a covalent bond able to enter.
  • a fiber-reactive component on textile dyes especially the sulfatoethylsulfonyl, vinylsulfonyl, chlorotriazinyl, Fluorotriazinyl, as well as combinations of these "anchor systems" called. Unless otherwise stated, these are in the examples below parts listed parts by weight.
  • a hydroxyethyl cellulose modified with N- (2-sulfatoethyl) piperazine (viscosity 925 mPas, DP approx.) Is placed in an industrial spinning viscose with a cellulose content of 8.9%, an alkali content of 5% and a viscosity of 38 falling ball seconds at 30 ° C. 700) stirred in.
  • the procedure is as follows: 16.2 parts of the modified hydroxyethyl cellulose are pasted with 49 parts of water and mixed with 436 parts of spin viscose. This premix is stirred into 2522 parts of spin viscose.
  • the spinning mass is spun into fibers using a customary viscose spinning process in a sulfuric acid, sodium and zinc sulfate-containing bath, stretched in acidic baths, cut, washed, prepared and dried. 10 parts of these dry viscose fibers are then mixed with 100 parts of water in a dyeing apparatus. The mixture is heated to 60 ° C. and a total of 0.1 part of a 50% electrolyte-containing (predominantly sodium-containing) dye powder of the formula known from published patent application 19 43 904 is metered in. over a period of 30 minutes. After a run-on time of 5 minutes, the remaining liquor is drained off and the material is washed out and dried using standard methods. A deep red color with very good fastness properties is obtained.
  • a spun viscose as described in Example 1 is a cellulose modified in accordance with the information in Example 1 of US Pat. No. 4,464,523 with a nitrogen content of 2.9%, a viscosity of 825 mPas (2% solution in water) and a DP -Value of approx. 700 mixed in.
  • the procedure is as described in Example 1 of the present application.
  • the spinning mass is spun into fibers using a customary viscose spinning process in a sulfuric acid, sodium and zinc sulfate-containing bath, stretched in acidic baths, cut, washed, prepared and dried. After weaving, a textile viscose fabric is obtained which can be further processed directly in a dyeing process using the block method.
  • an aqueous dye solution containing 20 parts of the dye of the formula known from EP-A-0 158 233, Example 1, and contains 3 parts of a commercially available nonionic wetting agent dissolved, applied to the fabric at 25 ° C. by means of a padder with a liquor absorption of 80%, based on the weight of the fabric.
  • the fabric padded with the dye solution is wound onto a dock, wrapped in a plastic sheet, left to stand at 40 to 50 ° C. for 4 hours and then with cold and hot water, which may or may not contain a commercial surfactant, and then again with cold water, if necessary rinsed and dried.
  • a strong, uniformly colored yellow coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.
  • Example 1 A spinning viscose as described in Example 1 is used accordingly the details of Example 28 of published patent application DE 41 25 752 A1 modified potato starch stirred in. The procedure is the same Information in Example 1 of the present application.
  • a fiber which can be dyed using a conventional pull-out method.
  • 20 parts of the pretreated viscose fiber are treated in a dyeing machine with 200 parts of an aqueous liquor which, based on the weight of the dry goods, contains 1.5% of the reactive dye of the formula known from EP-A-0 061 151, example 4, in a commercially available form and composition.
  • the fiber is dyed with this liquor at 80 ° C. for 30 minutes.
  • the dyeing thus produced is further processed by rinsing and soaping in the customary manner. The result is a lively orange color with the good fastness properties customary for reactive dyes.
  • Example 1 A spinning viscose as described in Example 1 is used accordingly modified the details of Example 2 of DE-A-1 593 657 Hydroxyethylcellulose stirred in. The procedure is the same Information in Example 1 of the present application.
  • a fiber made of modified viscose is obtained, which can be dyed in a pull-out process without salt and alkali additives.
  • 30 parts of viscose yarn are wound on a cross-wound bobbin and the yarn is treated in a yarn dyeing machine, the 450 parts (based on the weight of the goods) of a liquor, the 0.6 parts, based on the initial weight of the goods, of an electrolyte-containing dye (predominantly containing sodium chloride) general Formula, known from DE-A-28 40 380, example 1, contains and heats to 80 ° C., the liquor being pumped alternately from the inside to the outside and from the outside to the inside. After 60 minutes at this temperature, the liquor is drained off, rinsed and washed according to the usual conditions, the dyeing obtained. An irrespective yellow colored fiber with generally good fastness properties for reactive dyes is obtained.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Coloring (AREA)

Abstract

Aminated cellulosic synthetic fibres are obtd. by adding an amine-substd. cellulose deriv. (II) to a viscose material or alkali cellulose (III) and processing by the viscose spinning method, or by adding (II) to a cellulose soln. and spinning to give fibres. (II) consists of polymers of unsatd. amines with cellulose or cellulose components (2), or reaction prods. of (2) with amines of formula (1a) or (1b): Y = ester gp.; A + N + one or two 1-4C alkylene gps. = bivalent heterocyclic gp.; A = O or a gp. of formula R-N, R-CH or Z-R1R2N+; R = H, amino, 1-6C alkyl (opt. substd. with 1 or 2 amino, sulpho, OH, sulphato, phosphato or COOH gps.) or 3-8C alkyl with 1 or 2 in-chain O and/or NH gps. (opt. substd. with one gp. as above, except phosphato); R1, R2 = H, Me or Et; Z = anion; B = -NH2, R1R3N- or Z- R1R2R4N+-; R3 = Me or Et; R4 = H, Me or Et; alkylene = 2-6C alkylene (opt. substd. with 1 or 2 OH) or 3-8C alkylene with 1 or 2 in-chain O and/or NH; alk = 2-6C alkylene, or 3-8C alkylene with 1 or 2 in-chain O and/or NH, pref. 2-6C alkylene; m = 1 or 2; n = 1-4; the amino, OH and ester gps. can be on prim., sec. or tert. C atoms of the alkylene gp. Also claimed is a process for the prodn. of dyed or printed cellulosic synthetic fibre materials, by producing the aminated fibres as above, converting into woven or knitted fabric, and dyeing or printing this with reactive dye(s), pref. at pH 4.5-8.5, in the absence of electrolyte salts or alkali.

Description

Die Erfindung betrifft aminierte cellulosische Synthesefasern, Verfahren zu ihrer Herstellung und ihre Verwendung.The invention relates to aminated cellulosic synthetic fibers, processes for their Manufacture and its use.

In ihrem Färbeverhalten gleichen Cellulose-Regeneratfasern (im folgenden auch als Viskosefasern bezeichnet) im wesentlichen den Baumwollfasern. Beim derzeitigen Stand der Technik sind zum Färben cellulosischer Natur- oder Regeneratfaser alkalispendende Mittel, sowie Elektrolyte notwendig, um befriedigende Fixierergebnisse mit Reaktivfarbstoffen zu erzielen. Für ökologisch verbesserte Färbeverfahren stellen gerade diese notwendigen Zusätze nicht zu akzeptierende Umweltbelastungen dar. Für die Zukunft von zunehmender Bedeutung werden daher Cellulose-Regeneratfasern sein, die zuvor ohne zusätzliche Prozeßschritte in hoch farbstoffaffine, d.h. salz- und alkalifrei färbbare, Modifikationen überführt wurden. So veränderte Fasern ähneln in ihrem chemischen Verhalten tierischen Fasern, wie Wolle oder Seide, und können unter neutralen Bedingungen mit anionischen Farbstoffen, ohne weitere Salz- oder Alkalizusätze, gefärbt werden.In their dyeing behavior, cellulose regenerated fibers are the same (in the following also referred to as viscose fibers) essentially the cotton fibers. At the current state of the art are for dyeing cellulosic natural or Regenerate fiber alkalis, as well as electrolytes necessary to to achieve satisfactory fixation results with reactive dyes. For ecological improved dyeing processes do not deliver these necessary additives accepting environmental pollution. For the future of increasing Therefore, cellulose regenerated fibers will be important that previously without additional process steps in high dye affinity, i.e. salt and alkali free dyeable, modifications were transferred. Fibers modified in this way are similar to their chemical behavior animal fibers such as wool or silk, and can under neutral conditions with anionic dyes, without further Salt or alkali additives are colored.

Modifizierungen von Viskose sind in der Literatur bereits beschrieben. Die Deutsche Offenlegungsschrift 1 948 487 beschreibt ein Verfahren zur Herstellung von Viskosefasern mit neuartigen Färbeeigenschaften. Die Herstellung gestaltet sich aber äußerst aufwendig und unwirtschaftlich. Darüberhinaus kommen Polyaminamide zum Einsatz, die den nativen Charakter der Faser bedeutend stören. Dies kommt beispielsweise durch Verwendung von Dispersionsfarbstoffen beim späteren Färben zum Ausdruck. Auch die Deutsche Auslegeschrift 1 469 062 beschäftigt sich mit "aminalisierten Fasern". Bei den Zusätzen handelt es sich um Aminoethyl- und Diethylaminocellulosen in hohen Konzentrationen, das Einfärben geschieht ausschließlich mit Säurefarbstoffen.Modifications of viscose have already been described in the literature. The German Offenlegungsschrift 1 948 487 describes a method for Manufacture of viscose fibers with new coloring properties. The Manufacturing is extremely complex and uneconomical. In addition, polyaminamides are used, which have the native character significantly disrupt the fiber. This is done, for example, by using Disperse dyes for later dyeing. The German too Auslegeschrift 1 469 062 deals with "aminalized fibers". Both Additives are high in aminoethyl and diethylaminocelluloses Concentrations, the coloring is done exclusively with acid dyes.

Die DE-A-1494547 beschreibt ein Verfahren zur Herstellung und zum Färben von Fäden und Stapelfasern aus regenerierter Cellulose, bei welchem man der Viskose vor dem Verspinnen ein N-Vinyllactam-Polymer zusetzt. Die EP-A-0 546 476 beschreibt dagegen ein Verfahren zur Herstellung eines modifizierten Fasermaterials und zum Färben dieses Fasermaterials mit anionischen Textilfarbstoffen, bei welchem man das Fasermaterial in der Weise modifiziert, daß man es in wäßriger Lösung mit einer amino- und estergruppenhaltigen aliphatischen Verbindung imprägniert und einer Hitzebehandlung unterwirft. Das so modifizierte Fasermaterial kann mit wasserlöslichen, anionischen Farbstoffen, insbesondere faserreaktiven Farbstoffen, aus elektrolytarmer oder gänzlich elektrolytfreier und/oder alkaliarmer oder gänzlich alkalifreier Färbeflotte gefärbt werden. DE-A-1494547 describes a process for producing and Dyeing threads and staple fibers from regenerated cellulose, at which the viscose is spun with an N-vinyl lactam polymer adds. In contrast, EP-A-0 546 476 describes a method for Production of a modified fiber material and for dyeing it Fiber material with anionic textile dyes, which one Fiber material modified in such a way that it is in aqueous solution with an aliphatic compound containing amino and ester groups impregnated and subjected to heat treatment. The so modified Fiber material can be mixed with water-soluble, anionic dyes, in particular fiber-reactive dyes, from low-electrolyte or completely electrolyte-free and / or low-alkali or completely alkali-free Dyeing liquor can be dyed.

Es bestand daher ein großer Bedarf nach einem Verfahren, das eine cellulosische Synthesefaser liefert, die bezüglich Färben mit Reaktivfarbstoffen bedeutend affiner als herkömmliche Cellulosefasern ist und sich auch sonst bei den gewünschten Eigenschaften, wie z.B. dem Warengriff, von diesen unterscheidet.There has therefore been a great need for a method that uses cellulosic Synthetic fiber supplies that are significant in terms of dyeing with reactive dyes is more affine than conventional cellulose fibers and is also common with the desired properties, such as the goods handle, of these differs.

Diese Aufgabe wird überraschenderweise gelöst durch Beimischen eines aminsubstituierten Cellulosederivats zu einer Viskosemasse oder Alkalicellulose, oder durch Beimischen zu einer Celluloselösung.This object is surprisingly achieved by adding one amine-substituted cellulose derivative to form a viscose mass or alkali cellulose, or by adding to a cellulose solution.

Gegenstand der vorliegenden Erfindung sind aminierte cellulosische Synthesefasern, hergestellt indem man einer Viskosemasse oder Alkalicellulose ein aminsubstituiertes Cellulosederivat zusetzt und nach dem Viskosespinnverfahren Fasern spinnt, oder indem man einer Celluloselösung besagtes Cellulosederivat zusetzt und aus der Lösung Fasern spinnt, dadurch gekennzeichnet, daß die aminsubstituierten Cellulosederivate Polymerisate aus olefinisch ungesättigten Aminen mit Cellulose oder mit Cellulosekomponenten sind;
oder daß die aminsubstituierten Cellulosederivate Umsetzungsprodukte von Cellulose oder Cellulosekomponenten mit Aminen der allgemeinen Formel (1a) oder (1b)

Figure 00020001
Figure 00020002
sind, in welchen bedeuten:

Y
ist eine Estergruppe;
A und N
bilden zusammen mit 1 oder 2 Alkylengruppen von 1 bis 4 C-Atomen den bivalenten Rest eines heterocyclischen Ringes, worin
A
ein Sauerstoffatom oder eine Gruppe der allgemeinen Formel (a), (b) oder (c)
Figure 00040001
ist, in welchen
R
ein Wasserstoffatom oder eine Aminogruppe ist oder eine Alkylgruppe von 1 bis 6 C-Atomen bedeutet, die durch 1 oder 2 Substituenten aus der Gruppe Amino, Sulfo, Hydroxy, Sulfato, Phosphato und Carboxy substituiert sein kann, oder eine Alkylgruppe von 3 bis 8 C-Atomen ist, die durch 1 oder 2 Gruppen der Formeln -O- und -NH- oder eine Kombination davon unterbrochen ist und durch eine Amino-, Sulfo-, Hydroxy-, Sulfato- oder Carboxygruppe substituiert sein kann,
R1
Wasserstoff, Methyl oder Ethyl ist,
R2
Wasserstoff, Methyl oder Ethyl ist und
Z(-)
ein Anion bedeutet;
B
ist die Aminogruppe der Formel H2N- oder eine Amino- oder Ammoniumgruppe der allgemeinen Formel (d) oder (e)
Figure 00040002
in welchen
R1, R2 und Z(-)
eine der obengenannten Bedeutungen besitzen,
R3
Methyl oder Ethyl ist und
R4
Wasserstoff, Methyl oder Ethyl bedeutet;
p
ist die Zahl 1 oder 2;
alkylen
ist ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen, der durch 1 oder 2 Hydroxygruppen substituiert sein kann, oder ist ein geradkettiger oder verzweigter Alkylenrest von 3 bis 8 C-Atomen, der durch 1 oder 2 Gruppen der Formeln -O- und -NH- oder eine Kombination davon unterbrochen ist;
alk
ist ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen, oder ist ein geradkettiger oder verzweigter Alkylenrest von 3 bis 8 C-Atomen, der durch 1 oder 2 Gruppen der Formeln -O- und -NH- oder eine Kombination davon unterbrochen ist und ist bevorzugt ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen;
m
ist die Zahl 1 oder 2;
n
ist eine Zahl von 1 bis 4;
die Amino-, Hydroxy- und Estergruppen können sowohl an einem primären, sekundären oder tertiären C-Atom des Alkylenrestes gebunden sein.The present invention relates to aminated cellulosic synthetic fibers, produced by adding an amine-substituted cellulose derivative to a viscose composition or alkali cellulose and spinning fibers by the viscose spinning process, or by adding said cellulose derivative to a cellulose solution and spinning fibers from the solution, characterized in that the amine-substituted polymer are from olefinically unsaturated amines with cellulose or with cellulose components;
or that the amine-substituted cellulose derivatives are reaction products of cellulose or cellulose components with amines of the general formula (1a) or (1b)
Figure 00020001
Figure 00020002
are in which mean:
Y
is an ester group;
A and N
together with 1 or 2 alkylene groups of 1 to 4 carbon atoms form the divalent radical of a heterocyclic ring, in which
A
an oxygen atom or a group of the general formula (a), (b) or (c)
Figure 00040001
is in which
R
is a hydrogen atom or an amino group or denotes an alkyl group of 1 to 6 C atoms which can be substituted by 1 or 2 substituents from the group amino, sulfo, hydroxy, sulfato, phosphato and carboxy, or an alkyl group of 3 to 8 C. -Atoms which is interrupted by 1 or 2 groups of the formulas -O- and -NH- or a combination thereof and which can be substituted by an amino, sulfo, hydroxyl, sulfato or carboxy group,
R 1
Is hydrogen, methyl or ethyl,
R 2
Is hydrogen, methyl or ethyl and
Z (-)
means an anion;
B
is the amino group of the formula H 2 N or an amino or ammonium group of the general formula (d) or (e)
Figure 00040002
in which
R 1 , R 2 and Z (-)
have one of the meanings mentioned above,
R 3
Is methyl or ethyl and
R 4
Represents hydrogen, methyl or ethyl;
p
is the number 1 or 2;
alkylene
is a straight-chain or branched alkylene radical of 2 to 6 C atoms, which can be substituted by 1 or 2 hydroxyl groups, or is a straight-chain or branched alkylene radical of 3 to 8 C atoms, which is substituted by 1 or 2 groups of the formulas -O- and -NH- or a combination thereof is interrupted;
alk
is a straight-chain or branched alkylene radical of 2 to 6 C atoms, or is a straight-chain or branched alkylene radical of 3 to 8 C atoms which is interrupted by 1 or 2 groups of the formulas -O- and -NH- or a combination thereof and is preferably a straight-chain or branched alkylene radical of 2 to 6 carbon atoms;
m
is the number 1 or 2;
n
is a number from 1 to 4;
the amino, hydroxyl and ester groups can be bound to a primary, secondary or tertiary carbon atom of the alkylene radical.

Die besagten Polymerisate können durch Polymerisation von

  • A) Monomeren oder Monomerenmischungen aus der Gruppe der
  • a) N-Vinylimidazole, welche am heterocyclischen Ring durch bis zu drei C1-C12-Alkylreste substituiert sein und in N-quaternisierter Form oder in Salzform vorliegen können,
  • b) fünf- bis achtgliedrigen N-Vinyllactame, welche am Ring durch bis zu drei C1-C12-Alkylreste substituiert sein können,
  • c) Acrylsäure- oder Methacrylsäure-dialkylaminoalkylester mit insgesamt bis zu 30 C-Atomen im Dialkylaminoalkyl-Rest, welche in N-quaternisierter Form oder in Salzform vorliegen können,
  • d) N-(Dialkylaminoalkyl)-acrylsäureamide- oder -methacrylsäureamide mit insgesamt bis zu 30 C-Atomen in Dialkylaminoalkyl-Rest, welche in N-quaternisierter Form oder in Salzform vorliegen können, und
  • e) Diallyl-C1-C12-alkylamine oder deren Salze oder Diallyl-di(C1-C12-alkyl)-ammonium-Verbindungen,
    • wobei als weitere Comonomere zu (A) noch
  • f) monoethylenisch ungesättigte C3-C10-Carbonsäuren und deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze,
  • g) monoethylenisch ungesättigte C3-C10-Carbonsäureester sowie
  • h) mindestens zwei ethylenisch ungesättigte, nicht konjugierte Doppelbindungen im Molekül enthaltende Verbindungen vorhanden sein können, in Gegenwart von
    •
  • B) Monosacchariden, Oligosacchariden, Polysacchariden, thermisch oder mechanisch behandelten, oxidativ, hydrolytisch oder enzymatisch abgebauten Polysacchariden, oxidierten hydrolytisch oder enzymatisch abgebauten Polysacchariden, chemisch modifizierten Mono-, Oligo- und Polysacchariden oder Mischungen der genannten Verbindungen (B) im Gewichtsverhältnis (A):(B) von (95 bis 20):(5 bis 80) hergestellt werden.
    • The said polymers can be obtained by polymerizing
  • A) monomers or monomer mixtures from the group of
  • a) N-vinylimidazoles which are substituted on the heterocyclic ring by up to three C 1 -C 12 -alkyl radicals and can be present in N-quaternized form or in salt form,
  • b) five- to eight-membered N-vinyllactams, which can be substituted on the ring by up to three C 1 -C 12 -alkyl radicals,
  • c) acrylic acid or methacrylic acid dialkylaminoalkyl esters with a total of up to 30 carbon atoms in the dialkylaminoalkyl radical, which may be present in N-quaternized form or in salt form,
  • d) N- (dialkylaminoalkyl) acrylic acid amides or methacrylic acid amides having a total of up to 30 carbon atoms in the dialkylaminoalkyl radical, which may be present in N-quaternized form or in salt form, and
  • e) diallyl-C 1 -C 12 -alkylamines or their salts or diallyl-di (C 1 -C 12 -alkyl) -ammonium compounds,
    • where as further comonomers to (A)
  • f) monoethylenically unsaturated C 3 -C 10 carboxylic acids and their alkali metal, alkaline earth metal or ammonium salts,
  • g) monoethylenically unsaturated C 3 -C 10 carboxylic acid esters and
  • h) at least two ethylenically unsaturated, non-conjugated double bonds may be present in the molecule containing compounds, in the presence of
  • B) monosaccharides, oligosaccharides, polysaccharides, thermally or mechanically treated, oxidatively, hydrolytically or enzymatically degraded polysaccharides, oxidized hydrolytically or enzymatically degraded polysaccharides, chemically modified mono-, oligo- and polysaccharides or mixtures of the compounds (B) mentioned in the weight ratio (A) : (B) from (95 to 20) :( 5 to 80).

    • Es hat sich in vielen Fällen bewährt, Polymerisate, bei denen als Monomere (A) entweder die Verbindungen (a), (c), (d) und (e) jeweils alleine oder Mischungen aus 5 bis 95 Gew.-% einer Verbindung (b) und 95 bis 5 Gew.-% einer oder mehrere der Monomere (a), (c), (d), (e), (f), (g) und (h) eingesetzt werden, wobei (h) maximal in einer Menge bis zu 5 Gew.-%, bezogen auf die Gesamtmenge aller Monomeren (A), verwendet wird, einzusetzen.It has proven itself in many cases, polymers in which the monomers (A) either compounds (a), (c), (d) and (e) each alone or mixtures from 5 to 95% by weight of a compound (b) and 95 to 5% by weight of one or several of the monomers (a), (c), (d), (e), (f), (g) and (h) are used, where (h) at most in an amount up to 5 wt .-%, based on the Total amount of all monomers (A) is used.

    Gute Ergebnisse werden auch erhalten, wenn als aminsubstituierte Cellulosederivate Polymerisate aus N,N-Diallyl-N,N-di(C1-C12)-alkylammoniumhalogeniden und Cellulose oder Cellulosekomponenten verwendet werden. Hierbei hat es sich als günstig erwiesen, N,N-Diallyl-N-methyl-N-dodecylammoniumhalogenid, N,N-Diallyl-N-methyl-N-octylammoniumhalogenid, N,N-Diallyl-N-Methyl-N-decylammoniumhalogenid, N,N-Diallyl-N,N-dimethylammoniumhalogenid, insbesondere N,N-Diallyl-N,N-dimethylammoniumchlorid zu verwenden. Good results are also obtained if polymers of N, N-diallyl-N, N-di (C 1 -C 12 ) alkylammonium halides and cellulose or cellulose components are used as amine-substituted cellulose derivatives. It has proven to be advantageous here: N, N-diallyl-N-methyl-N-dodecylammonium halide, N, N-diallyl-N-methyl-N-octylammonium halide, N, N-diallyl-N-methyl-N-decylammonium halide, N, N-diallyl-N, N-dimethylammonium halide, in particular N, N-diallyl-N, N-dimethylammonium chloride.

    Besonders geeignet sind aminogruppenhaltige Verbindungen, bei denen die Estergruppe eine Sulfato- oder Phosphatogruppe ist oder eine C1-C4-Alkanoylgruppe, Phenylsulfonyloxy- oder eine am Benzolkern durch Substituenten aus der Gruppe Carboxy, C1-C4-Alkyl, C1-C4-Alkoxy und Nitro substituierte Phenylsulfonyloxygruppe ist.Particularly suitable are compounds containing amino groups, in which the ester group is a sulfato or phosphato group or a C 1 -C 4 alkanoyl group, phenylsulfonyloxy or one on the benzene nucleus by substituents from the group carboxy, C 1 -C 4 alkyl, C 1 - C 4 alkoxy and nitro substituted phenylsulfonyloxy group.

    Als Amine haben sich besonders die Verbindungen N-(β-Sulfatoethyl)-piperazin, N-(2-Sulfatoethyl)-piperazinsulfat, N-[β-(β'-Sulfatoethoxy)-ethyl]-piperazin, N-(γ-Sulfato-β-hydroxy-propyl)-piperidin, N-(γ-Sulfato-β-hydroxy-propyl)-pyrrolidin, N-β-Sulfatoethyl-piperidin, 2-Sulfato-3-hydroxy-1-amino-propan, 3-Sulfato-2-hydroxy-1-amino-propan, 1 -Sulfato-3-hydroxy-2-amino-propan, 3-Hydroxy-1-sulfato-2-amino-propan, 2,3-Disulfato-1-amino-propan, 1 ,3-Disulfato-2-aminopropan oder ein Derivat dieser Verbindungen mit einer der vorstehend genannten Estergruppe statt der Sulfatogruppe im Sinne der vorliegenden Erfindung bewährt.The compounds N- (β-sulfatoethyl) piperazine, N- (2-sulfatoethyl) piperazine sulfate, N- [β- (β'-sulfatoethoxy) ethyl] piperazine, N- (γ-sulfato-β-hydroxypropyl) piperidine, N- (γ-sulfato-β-hydroxypropyl) pyrrolidine, N-β-sulfatoethyl-piperidine, 2-sulfato-3-hydroxy-1-aminopropane, 3-sulfato-2-hydroxy-1-aminopropane, 1-sulfato-3-hydroxy-2-aminopropane, 3-hydroxy-1-sulfato-2-aminopropane, 2,3-disulfato-1-aminopropane, 1,3-disulfato-2-aminopropane or a derivative of these compounds with any of the above mentioned ester group instead of the sulfato group in the sense of the present Invention proven.

    Darüberhinaus sind für die Modifizierung und Herstellung der aminsubstituierten Cellulosederivate auch solche Verbindungen geeignet, die als reaktiven Rest an der Aminokomponente eine α-Chlor-β-hydroxy- oder Epoxy-Substitution aufweisen. Weiterhin sind unter reaktiv im allgemeinen solche Molekülteile zu verstehen, die mit Hydroxylgruppen, beispielsweise von Cellulose, oder Amino- und Thiolgruppen, beispielsweise von Wolle und Seide reagieren können und eine kovalente chemische Bindung einzugehen vermögen.In addition, the amine substituted for the modification and manufacture Cellulose derivatives are also suitable for those compounds which act as a reactive residue the amino component has an α-chloro-β-hydroxy or epoxy substitution exhibit. Furthermore, such parts of the molecule are generally reactive understand that with hydroxyl groups, for example of cellulose, or amino and thiol groups, for example wool and silk, can react and are able to form a covalent chemical bond.

    Als Cellulosekomponente für die Herstellung der aminsubstituierten Cellulosederivate haben sich Carboxymethylcellulose, Hydroxyethylcellulose, Hydroxypropylcellulose, Carboxymethylhydroxyethylcellulose, Sulfoethylcellulose, Carboxymethylsulfoethylcellulose, Hydroxypropylsulfoethylcellulose, Hydroxyethylsulfoethylcellulose, Methylsulfoethylcellulose und Ethylsulfoethylcellulose als geeignet erwiesen. As a cellulose component for the production of the amine-substituted Cellulose derivatives have become carboxymethyl cellulose, hydroxyethyl cellulose, Hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, Sulfoethyl cellulose, carboxymethyl sulfoethyl cellulose, Hydroxypropylsulfoethyl cellulose, hydroxyethylsulfoethyl cellulose, Methylsulfoethyl cellulose and ethyl sulfoethyl cellulose have been found to be suitable.

    Das Verfahren zur Herstellung der aminierten cellulosischen Synthesefasern wird durchgeführt, indem man entweder Cellulose alkalisch aufschließt (Alkalicellulose), mit Schwefelkohlenstoff umsetzt, das Xanthogenat in Natronlauge löst und der so erhaltenen Viskosespinnlösung die aminsubstituierten Cellulosederivate zusetzt oder indem man die aminsubstituierten Cellulosederivate direkt zur Alkalicellulose zugibt und dann xanthogeniert. Durch anschließendes Verspinnen in einem sauren Spinnbad werden die erfindungsgemäßen modifizierten Viskosefasern erhalten.The process for making the aminated cellulosic synthetic fibers is carried out either by alkaline cellulose digestion (Alkali cellulose), reacted with carbon disulfide, the xanthate in Sodium hydroxide solution dissolves and the viscose spinning solution thus obtained amine-substituted cellulose derivatives or by adding the amine-substituted cellulose derivatives are added directly to the alkali cellulose and then xanthogenized. By subsequent spinning in an acidic spinning bath the modified viscose fibers according to the invention are obtained.

    Die für das vorliegende Verfahren benutzten stickstoffhaltigen Verbindungen werden in wäßrigem Medium oder zweckmäßig auch mit Hilfe von Emulgatoren in die Viskosespinnmasse eingearbeitet und zeigen mit der Viskose eine gute Verträglichkeit. Der Zusatz des aminsubstituierten Cellulosederivats erfolgt in einer Menge von 1 bis 20 %, vorzugsweise 1 bis 12 Gew.-%, bezogen auf den Cellulosegehalt der Spinnmasse vor der Fällung und Verformung.The nitrogenous compounds used for the present process are in an aqueous medium or expediently with the aid of emulsifiers incorporated into the viscose spinning mass and show a good with the viscose Compatibility. The amine-substituted cellulose derivative is added in an amount of 1 to 20%, preferably 1 to 12 wt .-%, based on the Cellulose content of the dope before precipitation and shaping.

    Werden die erfindungsgemäßen Fasern nach anderen üblichen, dem Fachmann geläufigen Verfahren zur Herstellung cellulosischer Fasern aus Lösung heraus, wie beispielsweise dem Cuproverfahren, dem Lyocellverfahren und dem Verfahren über niedrig substituierte Celluloseether, hergestellt, so wird die Cellulose in einem geeigneten organischen Lösemittel gelöst, mit dem aminsubstituierten Cellulosederivat versetzt und direkt aus der Lösung zu Fasern versponnen. Am günstigsten ist ein Zudosieren unmittelbar vor der Verspinnung, wobei die Einmischung und homogene Verteilung durch bekannte Mischsysteme mit Hilfe von statischen oder dynamischen Mischsystemen erfolgen kann. Das Zudosieren kann aber auch in einer beliebigen Vorstufe bei der Spinnmasseherstellung erfolgen.Are the fibers of the invention according to other usual, the expert current process for producing cellulosic fibers from solution, such as the cupro process, the lyocell process and the Process on low substituted cellulose ethers, so produced Cellulose dissolved in a suitable organic solvent with which amine-substituted cellulose derivative added and directly from the solution to fibers spun. The best thing to do is to meter in immediately before spinning, where the interference and homogeneous distribution by known mixing systems can be done with the help of static or dynamic mixing systems. The Dosing can also be done in any preliminary stage with the Spinning mass production take place.

    Die als Zusätze dienenden aminierten Cellulosen haben Polymerisationsgrade zwischen 300 und 1000 Anhydroglucoseeinheiten und Viskositäten von 300 bis 1500 mPas. Der Polymerisationsgrad sollte nicht kleiner als 300 sein, da ansonsten die Gefahr besteht, daß die vorgefertigte aminierte Cellulose nach dem Verspinnen aus der Faser ausgewaschen wird.The aminated celluloses used as additives have degrees of polymerization between 300 and 1000 anhydroglucose units and viscosities from 300 to 1500 mPas. The degree of polymerization should not be less than 300 because otherwise there is a risk that the prefabricated aminated cellulose after the spinning is washed out of the fiber.

    Die zur Herstellung der modifizierten Viskose genutzten vorgefertigten Cellulosederivate lassen sich, aufgrund der Löslichkeit in Wasser oder in wäßriger Alkalilösung, in guter Verteilung direkt in die Spinnmasse einrühren. Die Filtrierbarkeit der Viskose zeigt keine Verschlechterung im Vergleich mit zusatzfreien Proben, so daß im Zuge des Spinnvorganges kein Verstopfen der Spinndüse zu beobachten ist. Die Verformung der Viskose wird nach üblichen und bekannten Methoden durchgeführt, wie z. B. mit Spinndüsen, einem nachfolgenden Fällbad, sowie gegebenenfalls weiteren Nachbehandlungsbädern.The prefabricated ones used to manufacture the modified viscose Cellulose derivatives can, due to their solubility in water or in aqueous alkali solution, stir well into the spinning mass. The filterability of the viscose shows no deterioration in comparison with additive free samples, so that no clogging of the in the course of the spinning process Spinneret can be observed. The deformation of the viscose is done according to usual and known methods, such as. B. with spinnerets, one subsequent precipitating bath and, if appropriate, further post-treatment baths.

    Gegenstand der vorliegenden Erfindung ist auch ein Verfahren zur Herstellung eines gefärbten oder bedruckten Textilmaterials aus Celluloseregeneratfasern, dadurch gekennzeichnet, daß man einer Viskosemasse oder Alkalicellulose ein aminsubstituiertes Cellulosederivat zusetzt und nach dem Viskosespinnverfahren Fasern spinnt, oder indem man einer Celluloselösung besagtes Cellulosederivat zusetzt und aus der Lösung Fasern spinnt, die Fasern zu einem Gewebe oder Gewirke verarbeitet und dieses mit einem oder mehreren Reaktivfarbstoffen in Abwesenheit von zusätzlichem Elektolytsalz oder Alkali färbt oder bedruckt.The present invention also relates to a method for the production a colored or printed textile material made from regenerated cellulose fibers, characterized in that a viscose or alkali cellulose amine-substituted cellulose derivative and after the viscose spinning process Fibers spinning, or by making said cellulose derivative from a cellulose solution adds and spins fibers from the solution, the fibers into a fabric or Knitted fabrics processed and this with one or more reactive dyes in Absence of additional electrolyte salt or alkali colors or prints.

    Das textile modifizierte Fasermaterial, das in das erfindungsgemäße Färbeverfahren eingesetzt wird, kann in allen Verarbeitungszuständen, so als Garn, Flocke, Kammzug und Stückware (Gewebe) vorliegen.The textile modified fiber material used in the invention Dyeing process can be used in all processing states, so as Yarn, flake, sliver and piece goods (fabric) are available.

    Das erfindungsgemäße Färben der modifizierten textilen Fasermaterialien erfolgt analog bekannten Färbeweisen und Druckverfahren zum Färben und Bedrucken von Fasermaterialien mit wasserlöslichen textilen Farbstoffen und unter Anwendung der hierfür bekanntermaßen eingesetzten Temperaturbereiche und üblichen Farbstoffmengen, jedoch mit der Ausnahme, daß für die Färbebäder, Klotzverfahren, Druckpasten und Ink-Jet-Formulierungen ein Zusatz von alkalisch wirkenden Verbindungen, wie sie üblicherweise zur Fixierung von faserreaktiven Farbstoffen benutzt werden, nicht nötig ist und auch auf übliche Zusätze an Elektrolytsalzen verzichtet werden kann. Es wird daher bei einem pH-Wert zwischen 4,5 und 8,5 und, bei Verwendung handelsüblicher Reaktivfarbstoffe, in Gegenwart eines Elektrolytsalzgehaltes von 0,01 bis 0,5 Gew.-%, bezogen auf die Färbelösung, gefärbt oder gedruckt. Ohne die erfindungsgemäße Aminierung der Cellulosefasern wäre dieser Elektrolytgehalt für ein erfolgreiches Färbeverfahren um den Faktor 20 bis 1000 zu gering.The modified textile fiber materials are dyed according to the invention analogous to known dyeing methods and printing processes for dyeing and printing of fiber materials with water-soluble textile dyes and under Application of the temperature ranges known for this and usual amounts of dye, but with the exception that for the dye baths, Block process, printing pastes and ink jet formulations an addition of alkaline compounds, as they are usually used to fix fiber-reactive dyes are used, is not necessary and also on usual Additions to electrolyte salts can be dispensed with. It is therefore one pH between 4.5 and 8.5 and, when using commercially available Reactive dyes, in the presence of an electrolyte salt content of 0.01 to 0.5% by weight, based on the coloring solution, colored or printed. Without that Amination of the cellulose fibers according to the invention would be this electrolyte content too small for a successful dyeing process by a factor of 20 to 1000.

    Färbeverfahren, die erfindungsgemäß eingesetzt werden können, sind beispielsweise die verschiedenen Ausziehverfahren, wie das Färben auf dem Jigger und auf der Haspelkufe oder das Färben aus langer und kurzer Flotte, das Färben in Jet-Färbemaschinen, das Färben nach Klotz-Kaltverweilverfahren oder nach einem Klotz-Heißdampf-Fixierverfahren.
    Zu den erfindungsgemäß nutzbaren Färbeverfahren zählen auch die Drucktechniken, einschließlich des Ink-Jet-Printings und des Transferdruckes.    Dyeing processes which can be used according to the invention are, for example, the various exhaust processes, such as dyeing on the jigger and on the reel runner or dyeing from a long and short liquor, dyeing in jet dyeing machines, dyeing by padding-cold dwelling or padding -Hot steam fixing process.
    The dyeing methods which can be used according to the invention also include the printing techniques, including ink-jet printing and transfer printing.

    Die Farbstoffe, die zum Färben der modifizierten Cellulose genutzt werden, sind im allgemeinen anionischer Natur. Besonders geeignet sind die faserreaktiven Textilfarbstoffe, die mit Hydroxylgruppen, beispielsweise von Cellulose, oder Amino- und Thiolgruppen, beispielsweise von Wolle und Seide, von synthetischen Polymeren, wie Polyamiden, oder auch modifizierten Polymeren, eben den aminierten Cellulosen, reagieren können und eine kovalente Bindung einzugehen vermögen. Als faserreaktive Komponente an den Textilfarbstoffen seien besonders der Sulfatoethylsulfonyl-, Vinylsulfonyl-, Chlortriazinyl-, Fluortriazinyl-, sowie Kombinationen dieser "Ankersysteme" genannt. Wenn nicht anders angegeben, sind die in den nachfolgenden Beispielen angeführten Teile Gewichtsteile. The dyes that are used to dye the modified cellulose are generally anionic in nature. The fiber-reactive ones are particularly suitable Textile dyes containing hydroxyl groups, for example cellulose, or Amino and thiol groups, for example wool and silk, from synthetic polymers, such as polyamides, or also modified polymers, just the aminated celluloses, can react and a covalent bond able to enter. As a fiber-reactive component on textile dyes especially the sulfatoethylsulfonyl, vinylsulfonyl, chlorotriazinyl, Fluorotriazinyl, as well as combinations of these "anchor systems" called. Unless otherwise stated, these are in the examples below parts listed parts by weight.

    Beispiel 1example 1

    In eine betriebsübliche Spinnviskose mit einem Cellulosegehalt von 8,9 %, einem Alkaligehalt von 5 % und einer Viskosität von 38 Kugelfallsekunden bei 30°C wird eine mit N-(2-Sulfatoethyl)-piperazin modifizierte Hydroxyethylcellulose (Viskosität 925 mPas, DP ca. 700) eingerührt. Dabei wird wie folgt verfahren: 16,2 Teile der modifizierten Hydroxyethylcellulose werden mit 49 Teilen Wasser angeteigt und mit 436 Teilen Spinnviskose vermischt. Diese Vormischung wird in 2522 Teile Spinnviskose eingerührt. Nach dem Entgasen wird die Spinnmasse nach betriebsüblichen Viskosespinnverfahren in ein schwefelsaures, Natrium- und Zinksulfat-haltiges Bad zu Fasern versponnen, in sauren Bädern verstreckt, geschnitten, gewaschen, präpariert und getrocknet. 10 Teile dieser trockenen Viskosefasern werden dann in einer Färbeapparatur mit 100 Teilen Wasser versetzt. Man heizt auf 60°C auf und dosiert insgesamt 0,1 Teile eines 50 %igen elektrolythaltigen (vorwiegend natriumhaltigen) Farbstoffpulvers der Formel, bekannt aus der Offenlegungsschrift 19 43 904,

    Figure 00110001
    über eine Zeit von 30 Minuten zu. Nach einer Nachlaufzeit von 5 Minuten wird die Restflotte abgelassen und das Material nach gängigen Methoden ausgewaschen und getrocknet. Man erhält eine farbstarke tiefrote Färbung mit sehr guten Gebrauchsechtheiten. A hydroxyethyl cellulose modified with N- (2-sulfatoethyl) piperazine (viscosity 925 mPas, DP approx.) Is placed in an industrial spinning viscose with a cellulose content of 8.9%, an alkali content of 5% and a viscosity of 38 falling ball seconds at 30 ° C. 700) stirred in. The procedure is as follows: 16.2 parts of the modified hydroxyethyl cellulose are pasted with 49 parts of water and mixed with 436 parts of spin viscose. This premix is stirred into 2522 parts of spin viscose. After degassing, the spinning mass is spun into fibers using a customary viscose spinning process in a sulfuric acid, sodium and zinc sulfate-containing bath, stretched in acidic baths, cut, washed, prepared and dried. 10 parts of these dry viscose fibers are then mixed with 100 parts of water in a dyeing apparatus. The mixture is heated to 60 ° C. and a total of 0.1 part of a 50% electrolyte-containing (predominantly sodium-containing) dye powder of the formula known from published patent application 19 43 904 is metered in.
    Figure 00110001
    over a period of 30 minutes. After a run-on time of 5 minutes, the remaining liquor is drained off and the material is washed out and dried using standard methods. A deep red color with very good fastness properties is obtained.

    Beispiel 2Example 2

    10 Teile der entsprechend Beispiel 1 modifizierten Viskosefasern werden in eine Färbeapparatur überführt und in einem Flottenverhältnis von 1:10 mit einer wäßrigen Flotte behandelt, die - bezogen auf das Warengewicht der trockenen Ware - 0,1 Teile eines Reaktivfarbstoffes der Formel, bekannt aus der Deutschen Offenlegungsschrift 24 12 964,

    Figure 00120001
    gelöst enthält, behandelt. Man färbt die Fasermischung 30 Minuten bei 80°C. Die Weiterbehandlung der so erzeugten Färbung erfolgt durch Spülen und Seifen in der üblichen Weise. Man erhält eine tiefblaue Färbung mit den nach dem Stand der Technik üblichen sehr guten Gebrauchsechtheiten.10 parts of the viscose fibers modified in accordance with Example 1 are transferred to a dyeing apparatus and treated in a liquor ratio of 1:10 with an aqueous liquor which, based on the fabric weight of the dry fabric, 0.1 parts of a reactive dye of the formula known from the German Laid-open specification 24 12 964,
    Figure 00120001
    contains dissolved, treated. The fiber mixture is dyed at 80 ° C. for 30 minutes. The dyeing thus produced is further treated by rinsing and soaping in the customary manner. A deep blue color is obtained with the very good fastness properties customary according to the prior art.

    Beispiel 3Example 3

    In eine wie unter Beispiel 1 beschriebene Spinnviskose wird eine entsprechend den Angaben des Beispiels 1 der US-Patentanmeldung 4 464 523 modifizierte Cellulose mit einem Stickstoffgehalt von 2,9 %, einer Viskosität von 825 mPas (2 %ige Lösung in Wasser) und einem DP-Wert von ca. 700 untergemischt. Dabei verfährt man entsprechend den Angaben des Beispiels 1 der vorliegenden Anmeldung.
    Nach dem Entgasen wird die Spinnmasse nach betriebsüblichen Viskosespinnverfahren in ein schwefelsaures, Natrium- und Zinksulfat-haltiges Bad zu Fasern versponnen, in sauren Bädern verstreckt, geschnitten, gewaschen, präpariert und getrocknet.
    Nach dem Weben erhält man so ein textiles Viskosegewebe, das direkt in einem Färbeprozeß nach dem Klotz-Verfahren weiterverarbeitet werden kann.     A spun viscose as described in Example 1 is a cellulose modified in accordance with the information in Example 1 of US Pat. No. 4,464,523 with a nitrogen content of 2.9%, a viscosity of 825 mPas (2% solution in water) and a DP -Value of approx. 700 mixed in. The procedure is as described in Example 1 of the present application.
    After degassing, the spinning mass is spun into fibers using a customary viscose spinning process in a sulfuric acid, sodium and zinc sulfate-containing bath, stretched in acidic baths, cut, washed, prepared and dried.
    After weaving, a textile viscose fabric is obtained which can be further processed directly in a dyeing process using the block method.

    Hierzu wird eine wäßrige Farbstofflösung, die in 1000 Vol.-Teilen 20 Teile des Farbstoffs der Formel,

    Figure 00130001
    bekannt aus der EP-A-0 158 233, Beispiel 1, und 3 Teile eines handelsüblichen nichtionogenen Benetzungsmittels gelöst enthält, mittels eines Foulards mit einer Flottenaufnahme von 80 %, bezogen auf das Gewicht des Gewebes, bei 25°C auf das Gewebe aufgebracht. Das mit der Farbstofflösung geklotzte Gewebe wird auf eine Docke aufgewickelt, in eine Plastikfolie gewickelt, während 4 Stunden bei 40 bis 50°C liegen gelassen und danach mit kaltem und heißem Wasser, das gegebenenfalls ein handelsübliches Tensid enthalten kann, gegebenenfalls anschließend nochmals mit kaltem Wasser gespült und getrocknet.
    Es wird eine farbstarke, gleichmäßig gefärbte gelbe Färbung erhalten, die gute Allgemeinechtheiten, insbesondere gute Reib- und Lichtechtheiten, besitzt.For this purpose, an aqueous dye solution containing 20 parts of the dye of the formula
    Figure 00130001
    known from EP-A-0 158 233, Example 1, and contains 3 parts of a commercially available nonionic wetting agent dissolved, applied to the fabric at 25 ° C. by means of a padder with a liquor absorption of 80%, based on the weight of the fabric. The fabric padded with the dye solution is wound onto a dock, wrapped in a plastic sheet, left to stand at 40 to 50 ° C. for 4 hours and then with cold and hot water, which may or may not contain a commercial surfactant, and then again with cold water, if necessary rinsed and dried.
    A strong, uniformly colored yellow coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.

    Beispiel 4Example 4

    In eine wie unter Beispiel 1 beschriebene Spinnviskose wird eine entsprechend den Angaben des Beispiels 28 der Offenlegungsschrift DE 41 25 752 A1 modifizierte Kartoffelstärke eingerührt. Dabei verfährt man entsprechend den Angaben des Beispiels 1 der vorliegenden Anmeldung.A spinning viscose as described in Example 1 is used accordingly the details of Example 28 of published patent application DE 41 25 752 A1 modified potato starch stirred in. The procedure is the same Information in Example 1 of the present application.

    Nach dem Entgasen, Verspinnen, Strecken, Schneiden, Waschen und Trocknen wird eine Faser erhalten, die nach einem üblichen Ausziehverfahren eingefärbt werden kann. Dazu werden 20 Teile der vorbehandelten Viskosefaser in einem Färbeapparat mit 200 Teilen einer wäßrigen Flotte behandelt, die - bezogen auf das Gewicht der trockenen Ware - 1,5 % des Reaktivfarbstoffs der Formel,

    Figure 00140001
    bekannt aus der EP-A-0 061 151, Beispiel 4, in handelsüblicher Form und Beschaffenheit enthält. Man färbt die Faser mit dieser Flotte 30 min bei 80°C. Die Weiterbehandlung der so erzeugten Färbung erfolgt durch Spülen und Seifen in üblicher Weise. Es resultiert eine lebhafte Orangefärbung mit den für Reaktivfarbstoffe üblichen, guten Echtheiten.After degassing, spinning, stretching, cutting, washing and drying, a fiber is obtained which can be dyed using a conventional pull-out method. For this purpose, 20 parts of the pretreated viscose fiber are treated in a dyeing machine with 200 parts of an aqueous liquor which, based on the weight of the dry goods, contains 1.5% of the reactive dye of the formula
    Figure 00140001
    known from EP-A-0 061 151, example 4, in a commercially available form and composition. The fiber is dyed with this liquor at 80 ° C. for 30 minutes. The dyeing thus produced is further processed by rinsing and soaping in the customary manner. The result is a lively orange color with the good fastness properties customary for reactive dyes.

    Beispiel 5Example 5

    In eine wie unter Beispiel 1 beschriebene Spinnviskose wird eine entsprechend den Angaben des Beispiels 2 der DE-A-1 593 657 modifizierte Hydroxyethylcellulose eingerührt. Dabei verfährt man entsprechend den Angaben des Beispiels 1 der vorliegenden Anmeldung.A spinning viscose as described in Example 1 is used accordingly modified the details of Example 2 of DE-A-1 593 657 Hydroxyethylcellulose stirred in. The procedure is the same Information in Example 1 of the present application.

    Nach Weiterbearbeitung nach den für Spinnviskosen üblichen Prozeßschritten wird eine Faser aus modifizierter Viskose erhalten, die man in einem Ausziehverfahren ohne Salz- und Alkalizusätze einfärben kann. Dazu wickelt man 30 Teile Viskosegarn auf eine Kreuzspule und behandelt das Garn in einer Garnfärbeapparatur, die 450 Teile (bezogen auf das Gewicht der Ware) einer Flotte, die 0,6 Teile, bezogen auf das Warenanfangsgewicht, eines elektrolythaltigen Farbstoffs (überwiegend natriumchloridhaltig) der allgemeinen

    Figure 00140002
    Formel, bekannt aus der DE-A-28 40 380, Beispiel 1, enthält und heizt auf 80°C, auf, wobei die Flotte im Wechsel von innen nach außen und von außen nach innen gepumpt wird. Nach 60 min bei dieser Temperatur läßt man die Flotte ab, spült und wäscht nach den üblichen Konditionen die erhaltene Färbung nach. Man erhält eine egal gelb gefärbte Faser mit den allgemein guten Echtheiten für Reaktivfarbstoffe.After further processing according to the process steps customary for spinning viscose, a fiber made of modified viscose is obtained, which can be dyed in a pull-out process without salt and alkali additives. For this purpose, 30 parts of viscose yarn are wound on a cross-wound bobbin and the yarn is treated in a yarn dyeing machine, the 450 parts (based on the weight of the goods) of a liquor, the 0.6 parts, based on the initial weight of the goods, of an electrolyte-containing dye (predominantly containing sodium chloride) general
    Figure 00140002
    Formula, known from DE-A-28 40 380, example 1, contains and heats to 80 ° C., the liquor being pumped alternately from the inside to the outside and from the outside to the inside. After 60 minutes at this temperature, the liquor is drained off, rinsed and washed according to the usual conditions, the dyeing obtained. An irrespective yellow colored fiber with generally good fastness properties for reactive dyes is obtained.

    Weitere BeispieleFurther examples

    Man verfährt bei der Modifizierung der Viskose nach den Angaben des Beispiels 5 und färbt unter Verwendung der nachfolgend aufgeführten Reaktivfarbstoffe nach üblichen Verfahren, jedoch ohne Alkali- oder Salzzusätze und erhält vergleichbare Ergebnisse.

    Figure 00150001
    Figure 00150002
    Figure 00150003
    Figure 00160001
    Figure 00160002
    Figure 00160003
    Figure 00160004
    Figure 00160005
    CuPc = Kupferphthalocyanin
    Figure 00170001
    NiPc = Nickelphthalocyanin
    Figure 00170002
    Figure 00170003
    Figure 00170004
    The procedure for modifying the viscose is as described in Example 5, and dyeing is carried out using the reactive dyes listed below by customary methods, but without additions of alkali metal or salt, and comparable results are obtained.
    Figure 00150001
    Figure 00150002
    Figure 00150003
    Figure 00160001
    Figure 00160002
    Figure 00160003
    Figure 00160004
    Figure 00160005
    CuPc = copper phthalocyanine
    Figure 00170001
    NiPc = nickel phthalocyanine
    Figure 00170002
    Figure 00170003
    Figure 00170004

    Claims (14)

    1. Aminated cellulosic synthetic fibers produced by adding an amine-substituted cellulose derivative to a viscose or an alkali cellulose and spinning fibers by the viscose spinning process, or by adding said cellulose derivative to a cellulose solution and spinning fibers from said solution, wherein the amine-substituted cellulose derivatives are polymers of olefinically unsaturated amines with cellulose or with cellulose components; or the amine-substituted cellulose derivatives are reaction products of cellulose or cellulose components with amines of the formula (1a) or (1b)
      Figure 00250001
      Figure 00250002
      where
      Y
      is an ester group;
      A and N
      together with 1 or 2 alkylene groups of 1 to 4 carbon atoms form the bivalent radical of a heterocyclic ring wherein
      A
      is an oxygen atom or a group of the formula (a), (b), or (c)
      Figure 00260001
      where
      R
      is a hydrogen atom or an amino group or is an alkyl group of 1 to 6 carbon atoms which may be substituted by 1 or 2 substituents selected from the group consisting of amino, sulfo, hydroxyl, sulfato, phosphato and carboxyl, or is an alkyl group of 3 to 8 carbon atoms which is interrupted by 1 or 2 groups of the formulae -O- and -NH- or a combination thereof and may be substituted by an amino, sulfo, hydroxyl, sulfato or carboxyl group,
      R1
      is hydrogen, methyl or ethyl,
      R2
      is hydrogen, methyl or ethyl, and
      Z(-)
      is an anion;
      B
      is an amino group of the formula H2N- or an amino or ammonium group of the formula (d) or (e)
      Figure 00260002
      where
      R1, R2 and Z(-)
      are each as defined above,
      R3
      is methyl or ethyl, and
      R4
      is hydrogen, methyl or ethyl;
      p
      is 1 or 2;
      alkylen
      is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms which may be substituted by 1 or 2 hydroxyl groups or is a straight-chain or branched alkylene radical of 3 to 8 carbon atoms which is interrupted by 1 or 2 groups of the formulae -O- and -NH- or a combination thereof;
      alk
      is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms or is a straight-chain or branched alkylene radical of 3 to 8 carbon atoms which is interrupted by 1 or 2 groups of the formulae -O- and -NH- or a combination thereof and is preferably a straight-chain or branched alkylene radical of 2 to 6 carbon atoms;
      m
      is 1 or 2;
      n
      is from 1 to 4;
      the amino, hydroxyl and ester groups can be attached to a primary, secondary or tertiary carbon atom of the alkylene radical.
    2. The aminated cellulosic synthetic fibers of claim 1 wherein the amine-substituted cellulose derivatives are polymers of A) and B) in a weight ratio of (A):(B) of from (95 to 20):(5 to 80) where
      A) comprises monomers or monomer mixtures from the group of the
      a) N-vinylimidazoles which can be substituted on the heterocyclic ring by up to three C1-C12-alkyl radicals and can be present in N-quaternized form or in salt form,
      b) five- to eight-membered N-vinyllactams which can be substituted on the ring by up to three C1-C12-alkyl radicals,
      c) dialkylaminoalkyl acrylates or methacrylates having in total up to 30 carbon atoms in the dialkylaminoalkyl radical, which can be present in N-quaternized form or in salt form,
      d) N-(dialkylaminoalkyl)-acrylamides or -methacrylamides having in total up to 30 carbon atoms in the dialkylaminoalkyl radical, which can be present in N-quaternized form or in salt form, and
      e) diallyl-C1-C12-alkylamines or their salts or diallyldi(C1-C12-alkyl)ammonium compounds,
      with or without further comonomers in addition to (A) comprising
      f) monoethylenically unsaturated C3-C10-carboxylic acids and their alkali metal, alkaline earth metal or ammonium salts,
      g) monoethylenically unsaturated C3-C10-carboxylic esters, and also
      h) compounds which contain at least two ethylenically unsaturated, nonconjugated double bonds in the molecule, and
      B) comprises monosaccharides, oligosaccharides, polysaccharides, thermally or mechanically treated, oxidatively, hydrolytically or enzymatically degraded polysaccharides, oxidized hydrolytically or enzymatically degraded polysaccharides, chemically modified mono-, oligo- and polysaccharides or mixtures thereof.
    3. The aminated cellulosic synthetic fibers of claim 2 wherein, in said polymers, the monomers (A) comprise either each of the compounds (a), (c), (d) and (e) alone or mixtures of 5 to 95 % by weight of a compound (b) and 95 to 5 % by weight of one or more of the compounds (a), (c), (d), (e), (f), (g) and (h), wherein (h) is present in an amount of not more than 5 % by weight, based on the total amount of all monomers (A).
    4. The aminated cellulosic synthetic fibers of claim 1 wherein the amine-substituted cellulose derivatives are polymers of N,N-diallyl-N,N-di(C1-C12)-alkylammonium halides and cellulose or cellulose components.
    5. The aminated cellulosic synthetic fibers of claim 4 wherein the N,N-diallyl-N,N-di(C1-C12)-alkylammonium halides are N,N-diallyl-N-methyl-N-dodecylammonium halide, N,N-diallyl-N-methyl-N-octylammonium halide, N,N-diallyl-N-methyl-N-decylamnonium halide, N,N-diallyl-N,N-dimethylammonium halide, especially N,N-diallyl-N,N-dimethylammonium chloride.
    6. The aminated cellulosic synthetic fibers of claim 1 wherein the ester group Y is a sulfato or phosphato group or is a C1-C4-alkanoyl group, a phenylsulfonyloxy group or a phenylsulfonyloxy group substituted at the benzene nucleus by substituents selected from the group consisting of carboxyl, C1-C4-alkyl, C1-C4-alkoxy and nitro.
    7. The aminated cellulosic synthetic fibers of claim 1 wherein the amines are a compound selected from the group consisting of N-(β-sulfatoethyl)piperazine, N-(2-sulfatoethyl)piperazine sulfate, N-[β-(β'-sulfatoethoxy)ethyl]piperazine, N-(γ-sulfato-β-hydroxypropyl)piperidine, N-(γ-sulfato-β-hydroxypropyl)pyrrolidine, N-(β-sulfatoethyl)piperidine, 2-sulfato-3-hydroxy-1-aminopropane, 3-suIfato-2-hydroxy-1-aminopropane, l-sulfato-3-hydroxy-2-aminopropane, 3-hydroxy-1-sulfato-2-aminopropane, 2,3-disulfato-1-aminopropane or 1,3-disulfato-2-aminopropane or a derivative of these compounds with a phosphato group, C1-C4-alkanoyl group, phenylsulfonyloxy group or with a phenylsulfonyloxy group substituted in the benzene nucleus by substituents selected from the group consisting of carboxyl, C1-C4-alkyl, C1-C4-alkoxy and nitro instead of the sulfato group.
    8. The aminated cellulosic synthetic fibers of claim 1 wherein the amines contain a reactive moiety capable of reacting with hydroxyl groups, especially a moiety with α-chloro-β-hydroxy or epoxy substitution.
    9. The aminated cellulosic synthetic fibers of at least one of claims 1 to 8 wherein the cellulose component used for producing the amine-substituted cellulose derivatives is carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylhydroxyethylcellulose, sulfoethylcellulose, carboxymethylsulfoethylcellulose, hydroxypropylsulfoethylcellulose, hydroxyethylsulfoethylcellulose, methylsulfoethylcellulose or ethylsulfoethylcellulose.
    10. The aminated cellulosic synthetic fibers of at least one of claims 1 to 9 wherein the amine-substituted cellulose derivatives have degrees of polymerization between 300 and 1000 anhydroglucose units and viscosities from 300 to 1500 mPas.
    11. The aminated cellulosic synthetic fibers of at least one of claims 1 to 10 wherein the regenerated cellulose fibers are spun by the cupro process or by the lyocell process.
    12. The aminated cellulosic synthetic fibers process of at least one of claims 1 to 11 wherein the amine-substituted cellulose derivative is added in a concentration of 1 to 20 % by weight, in particular 1 to 12 % by weight, based on the cellulose content of the spinning solution.
    13. A process for producing a dyed or printed textile material composed of cellulosic synthetic fibers of claim 1, which comprises adding an amine-substituted cellulose derivative to a viscose or an alkali cellulose and spinning fibers by the viscose spinning process, or by adding said cellulose derivative to a cellulose solution and spinning fibers from said solution, processing said fibers into a woven or knitted fabric and dyeing or printing said fabric with one or more reactive dyes in the absence of additional electrolyte salt or alkali.
    14. The process of claim 13 wherein the textile material is dyed or printed at a pH of between 4.5 and 8.5.
    EP95100299A 1994-01-29 1995-01-11 Aminated cellulosic synthetic fibers Expired - Lifetime EP0665311B1 (en)

    Applications Claiming Priority (4)

    Application Number Priority Date Filing Date Title
    DE4402711 1994-01-29
    DE19944402711 DE4402711A1 (en) 1994-01-29 1994-01-29 Aminated viscose fibres, dyeable in absence of salt or alkali
    DE19944422758 DE4422758A1 (en) 1994-06-29 1994-06-29 Aminated viscose fibres, dyeable in absence of salt or alkali
    DE4422758 1994-06-29

    Publications (2)

    Publication Number Publication Date
    EP0665311A1 EP0665311A1 (en) 1995-08-02
    EP0665311B1 true EP0665311B1 (en) 1998-12-09

    Family

    ID=25933390

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP95100299A Expired - Lifetime EP0665311B1 (en) 1994-01-29 1995-01-11 Aminated cellulosic synthetic fibers

    Country Status (11)

    Country Link
    US (2) US5684141A (en)
    EP (1) EP0665311B1 (en)
    JP (1) JPH07300719A (en)
    KR (1) KR950032755A (en)
    CN (1) CN1109925A (en)
    AT (1) ATE174388T1 (en)
    CA (1) CA2141267A1 (en)
    DE (1) DE59504452D1 (en)
    DK (1) DK0665311T3 (en)
    ES (1) ES2126794T3 (en)
    FI (1) FI113281B (en)

    Families Citing this family (17)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE4435385A1 (en) * 1994-10-04 1996-04-11 Hoechst Ag Process for dyeing modified viscose fibers with acid or direct dyes
    DE4446540A1 (en) * 1994-12-24 1996-06-27 Hoechst Ag Process for the preparation of water-soluble aminoalkyl derivatives of polysaccharides
    DE19549408A1 (en) * 1995-05-24 1997-01-09 Hoechst Ag Aminated regenerated cellulose fibres prepn., have better affinity for reactive and direct dyes - by mixing viscose compsn., alkali cellulose or cellulose soln. with starch ether(s) which is etherified with alkylamine(s), useful for making dyed and printed textiles
    DE19519024A1 (en) * 1995-05-24 1996-11-28 Hoechst Ag Process for spin dyeing with colored salts
    AT402740B (en) * 1995-10-06 1997-08-25 Chemiefaser Lenzing Ag CELLULOSE FIBER
    DE19605578C2 (en) 1996-02-15 2001-03-29 Dystar Textilfarben Gmbh & Co Process for producing an anionic textile dye printed textile material
    CN1306081C (en) * 2005-07-26 2007-03-21 高明宝 Antibacterial and acarid-removing fiber product and preparing method thereof
    WO2009098073A1 (en) * 2008-02-08 2009-08-13 List Holding Ag Method and device for the production of molded bodies
    US9221963B2 (en) * 2008-11-27 2015-12-29 Speciality Fibres And Materials Ltd. Absorbent material
    CA2755586C (en) * 2009-03-20 2015-06-23 Fpinnovations Cellulose materials with novel properties
    US8399590B2 (en) * 2009-10-07 2013-03-19 Akzo Nobel Chemicals International B.V. Superhydrophilic amphiphilic copolymers and processes for making the same
    US8258250B2 (en) 2009-10-07 2012-09-04 Johnson & Johnson Consumer Companies, Inc. Compositions comprising superhydrophilic amphiphilic copolymers and methods of use thereof
    US11173106B2 (en) * 2009-10-07 2021-11-16 Johnson & Johnson Consumer Inc. Compositions comprising a superhydrophilic amphiphilic copolymer and a micellar thickener
    US9555558B2 (en) 2010-04-08 2017-01-31 List Holding Ag Process for producing a product
    JP5356582B2 (en) * 2011-12-28 2013-12-04 花王株式会社 Polyester resin composition
    CN104746161A (en) * 2013-12-31 2015-07-01 上海水星家用纺织品股份有限公司 Production process of medicine fibers and medicine home textile fibers
    CN108193310B (en) * 2017-12-30 2020-11-13 安徽宏祥丝绸织造有限公司 Preparation method of heat-resistant spandex fiber for elastic double-arbor

    Family Cites Families (16)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    NL298982A (en) * 1962-10-09
    NL6506343A (en) * 1964-06-01 1965-12-02
    US3472840A (en) * 1965-09-14 1969-10-14 Union Carbide Corp Quaternary nitrogen-containing cellulose ethers
    GB1243194A (en) * 1967-12-13 1971-08-18 Courtaulds Ltd The manufacture of more dyeable regenerated cellulose filaments
    FR1581593A (en) * 1968-06-25 1969-09-19
    CH508060A (en) * 1968-10-01 1971-05-31 Ciba Geigy Ag Process for the production of modified viscose fibers
    US4464523A (en) * 1983-05-16 1984-08-07 National Starch And Chemical Corporation Process for the preparation of graft copolymers of cellulose derivatives and diallyl, dialkyl ammonium halides
    SE452448B (en) * 1985-02-04 1987-11-30 Hyco Hydraulic Ab LIFTING EQUIPMENT FOR LIFTING OF VEHICLES
    DE3709766A1 (en) * 1987-03-25 1988-10-06 Hoechst Ag METHOD FOR ALKALI-FREE DYEING WITH REACTIVE DYES
    DE3831464A1 (en) * 1988-09-16 1990-03-29 Hoechst Ag METHOD FOR ALKALI-FREE DYEING AND PRINTING OF CELLULOSE FIBERS
    TW201803B (en) * 1991-04-15 1993-03-11 Hoechst Ag
    TW223134B (en) * 1991-05-11 1994-05-01 Hoechst Ag
    DE4125752A1 (en) * 1991-08-03 1993-02-04 Basf Ag POLYMERISATES FROM ETHYLENICALLY UNSATURATED, N-CONTAINING COMPOUNDS, POLYMERIZED IN THE PRESENCE OF MONOSACCHARIDES, OLIGOSACCHARIDES, POLYSACCHARIDES OR THEIR DERIVATIVES
    TW211595B (en) * 1991-12-07 1993-08-21 Hoechst Ag
    JP3234270B2 (en) * 1992-03-19 2001-12-04 富士通株式会社 Surface discharge type plasma display panel
    DE4435385A1 (en) * 1994-10-04 1996-04-11 Hoechst Ag Process for dyeing modified viscose fibers with acid or direct dyes

    Also Published As

    Publication number Publication date
    KR950032755A (en) 1995-12-22
    DE59504452D1 (en) 1999-01-21
    ATE174388T1 (en) 1998-12-15
    FI113281B (en) 2004-03-31
    FI950343A (en) 1995-07-30
    FI950343A0 (en) 1995-01-26
    CN1109925A (en) 1995-10-11
    US5684141A (en) 1997-11-04
    CA2141267A1 (en) 1995-07-30
    US5865858A (en) 1999-02-02
    JPH07300719A (en) 1995-11-14
    ES2126794T3 (en) 1999-04-01
    DK0665311T3 (en) 1999-08-16
    EP0665311A1 (en) 1995-08-02

    Similar Documents

    Publication Publication Date Title
    EP0665311B1 (en) Aminated cellulosic synthetic fibers
    DE69223305T2 (en) Treatment of cellulosic fibers to reduce their tendency to fibrillate
    EP0692559B1 (en) Synthetic cellulosic fibres modified with polymeric amine compounds
    DE19519025C1 (en) Starch etherified to a high degree with alkyl sulfonic acid residues
    EP0828868B1 (en) Amination of regenerated cellulose with highly substituted starches and use of the thus modified fibres
    EP0683251B1 (en) Amination of cellulosic synthetic fibres
    AT409144B (en) METHOD FOR TREATING CELLULOSE FIBERS AND FORMS OF THESE FIBERS
    EP0703305A1 (en) Process for the production of aminated regenerated cellulose
    EP0692558A1 (en) Process for the production of aminated fibres from regenerated cellulose
    EP0705924A2 (en) Process for dyeing modified viscose fibers with direct or acid dyes
    DE69600639T2 (en) Anthraquinone reactive dye compositions and dyeing or printing processes using them
    DE4402711A1 (en) Aminated viscose fibres, dyeable in absence of salt or alkali
    DE4422758A1 (en) Aminated viscose fibres, dyeable in absence of salt or alkali
    DE69226834T2 (en) Reactive dye mixtures and their use
    DE19519023C1 (en) Strengths highly substituted with amino groups
    DE3141082A1 (en) METHOD FOR CONTINUOUSLY DYEING FIBER GOODS FROM GEL STATE ACRYLNITRILE POLYMERISATS SPORN FROM ORGANIC SOLVENTS
    DE4421740A1 (en) Modified cellulose@ synthetic fibres with affinity for reactive dyes
    CH687355B5 (en) A process for dyeing cellulosic textile material.
    AT205654B (en) Process for the production of colored structures, in particular fibers and films, from viscose
    DE4417211A1 (en) Modified cellulose@ synthetic fibres with affinity for reactive dyes
    DE2023179C (en) Process for coloring and printing textile fibers
    DE29520890U1 (en) Highly substituted starches and regenerated cellulose aminated with highly substituted starches
    DE2438543B2 (en) Process for the production of dyed threads from fully aromatic polyamides
    DE2023179A1 (en) Process for dyeing and printing textile fibers
    DE2442553C2 (en) Dye preparations for the production of deep yellow tones with reactive dyes, their production and their use

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE CH DE DK ES FR GB IT LI SE

    17P Request for examination filed

    Effective date: 19960202

    17Q First examination report despatched

    Effective date: 19970722

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: DYSTAR TEXTILFARBEN GMBH & CO. DEUTSCHLAND KG

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH DE DK ES FR GB IT LI SE

    REF Corresponds to:

    Ref document number: 174388

    Country of ref document: AT

    Date of ref document: 19981215

    Kind code of ref document: T

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REF Corresponds to:

    Ref document number: 59504452

    Country of ref document: DE

    Date of ref document: 19990121

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 19990112

    ET Fr: translation filed
    ITF It: translation for a ep patent filed

    Owner name: ING. C. GREGORJ S.P.A.

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2126794

    Country of ref document: ES

    Kind code of ref document: T3

    REG Reference to a national code

    Ref country code: DK

    Ref legal event code: T3

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed
    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DK

    Payment date: 20011221

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: CH

    Payment date: 20011224

    Year of fee payment: 8

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: IF02

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20030131

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20030131

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20030131

    REG Reference to a national code

    Ref country code: DK

    Ref legal event code: EBP

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20051222

    Year of fee payment: 12

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: ES

    Payment date: 20060113

    Year of fee payment: 12

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: SE

    Payment date: 20060120

    Year of fee payment: 12

    Ref country code: FR

    Payment date: 20060120

    Year of fee payment: 12

    Ref country code: AT

    Payment date: 20060120

    Year of fee payment: 12

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20060123

    Year of fee payment: 12

    Ref country code: BE

    Payment date: 20060123

    Year of fee payment: 12

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20060131

    Year of fee payment: 12

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20070112

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20070801

    EUG Se: european patent has lapsed
    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20070111

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20070930

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20070111

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20070111

    BERE Be: lapsed

    Owner name: *DYSTAR TEXTILFARBEN G.M.B.H. & CO. DEUTSCHLAND K.

    Effective date: 20070131

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20070131

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20070112

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20070131

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20070112

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20070111