EP0665311A1 - Aminated cellulosic synthetic fibers - Google Patents

Aminated cellulosic synthetic fibers Download PDF

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Publication number
EP0665311A1
EP0665311A1 EP95100299A EP95100299A EP0665311A1 EP 0665311 A1 EP0665311 A1 EP 0665311A1 EP 95100299 A EP95100299 A EP 95100299A EP 95100299 A EP95100299 A EP 95100299A EP 0665311 A1 EP0665311 A1 EP 0665311A1
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EP
European Patent Office
Prior art keywords
cellulose
group
substituted
synthetic fibers
sulfato
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95100299A
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German (de)
French (fr)
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EP0665311B1 (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
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Hoechst AG
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Priority claimed from DE19944402711 external-priority patent/DE4402711A1/en
Priority claimed from DE19944422758 external-priority patent/DE4422758A1/en
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0665311A1 publication Critical patent/EP0665311A1/en
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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 production and their use.
  • regenerated cellulose fibers are essentially the same as cotton fibers.
  • alkaline dispensing agents and electrolytes are required for dyeing cellulosic natural or regenerated fiber in order to achieve satisfactory fixing results with reactive dyes.
  • cellulose regenerated fibers will therefore be of increasing importance, which have previously been converted into highly dye-affine, i.e. without additional process steps. Salt and alkali-free dyeable modifications have been transferred.
  • the chemical behavior of fibers modified in this way is similar to that of animal fibers, such as wool or silk, and can be dyed under neutral conditions with anionic dyes, without further salt or alkali additives.
  • German Offenlegungsschrift 1 948 487 describes a process for producing viscose fibers with novel dyeing properties. The production is extremely complex and uneconomical. In addition, polyaminamides are used, which significantly disrupt the native character of the fiber. This is expressed, for example, by the use of disperse dyes in the later dyeing.
  • German Auslegeschrift 1 469 062 also deals with "mineralized fibers". The additives are aminoethyl and diethylaminocelluloses in high concentrations, the coloring is done exclusively with acid dyes.
  • This object is surprisingly achieved by adding an amine-substituted cellulose derivative to a viscose composition or alkali cellulose, or by adding it to a cellulose solution.
  • the monomers (A) are either 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 monomers (a), (c), (d), (e), (f), (g) and (h) are used, where (h) is maximum is used in an amount of up to 5% by weight, based on the total amount of all monomers (A).
  • N, N-diallyl-N, N-di (C1-C12) alkylammonium halides and cellulose 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.
  • amino group-containing compounds in which the ester group is a sulfato or phosphato group or a C1-C4-alkanoyl group, phenylsulfonyloxy or one on the benzene nucleus by substituents from the group carboxy, C1-C--alkyl, C1-C4-alkoxy and nitro substituted phenylsulfonyloxy group.
  • Particularly suitable amines are the compounds N- ( ⁇ -sulfatoethyl) piperazine, N- [ ⁇ - ( ⁇ '-sulfatoethoxy) ethyl] piperazine, N- ( ⁇ -sulfato- ⁇ -hydroxypropyl) piperidine, N- ( ⁇ -sulfato- ⁇ -hydroxy-propyl) pyrrolidine, N- ⁇ -sulfatoethyl-piperidine, 2-sulfato-3-hydroxy-1-aminopropane, 3-sulfato-2-hydroxy-1-amino propane, 1-sulfato-3-hydroxy-2-amino-propane, 3-hydroxy-1-sulfato-2-amino-propane, 2,3-disulfato-1-amino-propane, 1,3-disulfato-2- Amino-propane or a derivative of these compounds with one of the abovementioned ester groups instead of the sulfato group or N- (2-sulfat
  • those compounds which have an ⁇ -chloro- ⁇ -hydroxy or epoxy substitution as a reactive radical on the amino component are also suitable for the modification and preparation of the amine-substituted cellulose derivatives.
  • reactive is generally to be understood as meaning those parts of the molecule which can react with hydroxyl groups, for example of cellulose, or amino and thiol groups, for example of wool and silk, and which are capable of forming a covalent chemical bond.
  • Carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylhydroxyethylcellulose, sulfoethylcellulose, carboxymethylsulfoethylcellulose, hydroxypropylsulfoethylcellulose, hydroxyethylsulfoethylcellulose, methylsulfoethyluloseulose and cellulose have proven to be suitable as cellulose components for the production of the amine-substituted cellulose derivatives.
  • the process for the preparation of the aminated cellulosic synthetic fibers is carried out either by alkalinizing cellulose (alkali cellulose), reacting with carbon disulfide, dissolving the xanthate in sodium hydroxide solution and adding the amine-substituted cellulose derivatives to the viscose spinning solution thus obtained or by adding the amine-substituted cellulose derivatives directly to the alkali metal derivatives then xanthogenized.
  • the modified viscose fibers according to the invention are obtained by subsequent spinning in an acidic spinning bath.
  • the nitrogen-containing compounds used for the present process are incorporated into the viscose spinning material in an aqueous medium or, appropriately, also with the aid of emulsifiers and show good compatibility with the viscose.
  • the addition of the amine-substituted cellulose derivative takes place in an amount of 1 to 20%, preferably 1 to 12% by weight, based on the cellulose content of the dope before the precipitation and shaping.
  • the fibers according to the invention are produced from solution by other customary processes known to those skilled in the art for producing cellulosic fibers, such as, for example, the cupro process, the lyocell process and the process using low-substituted cellulose ethers, the cellulose is dissolved in a suitable organic solvent with which amine-substituted cellulose derivative and spun directly from the solution into fibers. It is most advantageous to meter in immediately before the spinning, and the mixing and homogeneous distribution can be carried out by known mixing systems with the aid of static or dynamic mixing systems. However, metering can also take place in any preliminary stage in the manufacture of spinning mass.
  • 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, since there is otherwise the risk that the prefabricated aminated cellulose the spinning is washed out of the fiber.
  • the prefabricated cellulose derivatives used to produce the modified viscose can, due to their solubility in water or in aqueous alkali solution, be stirred directly into the spinning mass in a good distribution.
  • the filterability of the viscose shows no deterioration in comparison with free samples, so that no clogging of the spinneret is observed in the course of the spinning process.
  • the viscose is deformed by customary and known methods, such as, for. B. with spinnerets, a subsequent precipitation bath, and optionally further post-treatment baths.
  • the present invention also relates to a process for producing a colored or printed textile material from regenerated cellulose fibers, characterized in that an amine-substituted cellulose derivative is added to a viscose composition or alkali cellulose and spun fibers by the viscose spinning process, or by adding said cellulose derivative to a cellulose solution and from the solution Fibers spins, the fibers are processed into a woven or knitted fabric and this is dyed or printed with one or more reactive dyes in the absence of additional electrolyte salt or alkali.
  • the textile-modified fiber material that is used in the dyeing process according to the invention can be present in all processing states, such as yarn, flake, sliver and piece goods (fabric).
  • the dyeing of the modified textile fiber materials according to the invention is carried out analogously to known dyeing methods and printing processes for dyeing and printing fiber materials with water-soluble textile dyes and using the temperature ranges and customary amounts of dye known to be used for this, but with the exception that for the dyebaths, padding processes, printing pastes and ink -Jet formulations an addition of alkaline compounds, such as are usually used for fixing fiber-reactive dyes, is not necessary and also to the usual Additions to electrolyte salts can be dispensed with. It is therefore dyed or printed at a 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 dyeing solution. Without the amination of the cellulose fibers according to the invention, this electrolyte content would be too low by a factor of 20 to 1000 for a successful dyeing process.
  • 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 used to dye the modified cellulose are generally anionic in nature.
  • the fiber-reactive textile dyes which can react with hydroxyl groups, for example of cellulose, or amino and thiol groups, for example of wool and silk, of synthetic polymers, such as polyamides, or also modified polymers, namely the aminated celluloses, and a covalent bond are particularly suitable able to enter.
  • the fiber-reactive component on the textile dyes in particular the sulfatoethylsulfonyl, vinylsulfonyl, chlorotriazinyl, fluorotriazinyl, and combinations of these "anchor systems" are mentioned. Unless otherwise stated, the parts given in the examples below are 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.
  • a potato starch modified in accordance with the information in Example 28 of published patent application DE 41 25 752 A1 is stirred into a spinning viscose as described in Example 1. The procedure is as described 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.
  • a hydroxyethyl cellulose modified in accordance with Example 2 of DE-A-1 593 657 is stirred into a spinning viscose as described in Example 1. The procedure is as described 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.

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 production and their 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.Regarding their dyeing behavior, regenerated cellulose fibers (hereinafter also referred to as viscose fibers) are essentially the same as cotton fibers. In the current state of the art, alkaline dispensing agents and electrolytes are required for dyeing cellulosic natural or regenerated fiber in order to achieve satisfactory fixing results with reactive dyes. For ecologically improved dyeing processes, it is precisely these necessary additives which are unacceptable environmental impacts. For the future, cellulose regenerated fibers will therefore be of increasing importance, which have previously been converted into highly dye-affine, i.e. without additional process steps. Salt and alkali-free dyeable modifications have been transferred. The chemical behavior of fibers modified in this way is similar to that of animal fibers, such as wool or silk, and can be dyed under neutral conditions with anionic dyes, without further salt or alkali additives.

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 "minalisierten 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. German Offenlegungsschrift 1 948 487 describes a process for producing viscose fibers with novel dyeing properties. The production is extremely complex and uneconomical. In addition, polyaminamides are used, which significantly disrupt the native character of the fiber. This is expressed, for example, by the use of disperse dyes in the later dyeing. The German Auslegeschrift 1 469 062 also deals with "mineralized fibers". The additives are aminoethyl and diethylaminocelluloses in high concentrations, the coloring is done exclusively with acid dyes.

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 process that provides a cellulosic synthetic fiber that is significantly more affine than conventional cellulosic fibers when it comes to dyeing with reactive dyes, and that otherwise has the desired properties, such as e.g. the handle of the goods.

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 an amine-substituted cellulose derivative to a viscose composition or alkali cellulose, or by adding it 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 imgb0001

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 imgb0002
 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 imgb0003
 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 imgb0001
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 imgb0002
 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,
R¹
Is hydrogen, methyl or ethyl,
R²
Is hydrogen, methyl or ethyl and
Z (-)
means an anion;
B
is the amino group of the formula H₂N or an amino or ammonium group of the general formula (d) or (e)
Figure imgb0003
 in which
R¹, R² and Z (-)
have one of the meanings mentioned above,
R³
Is methyl or ethyl and
R⁴
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 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) 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-C₁-C₁₂-alkylamines or their salts or diallyl-di (C₁-C₁₂-alkyl) ammonium compounds,
    where as further comonomers to (A)
    • f) monoethylenically unsaturated C₃-C₁₀ carboxylic acids and their alkali metal, alkaline earth metal or ammonium salts,
    • g) monoethylenically unsaturated C₃-C₁₀ 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.In many cases, it has proven useful to use polymers in which the monomers (A) are either 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 monomers (a), (c), (d), (e), (f), (g) and (h) are used, where (h) is maximum is used in an amount of up to 5% by weight, based on the total amount of all monomers (A).

Gute Ergebnisse werden auch erhalten, wenn als aminsubstituierte Cellulosederivate Polymerisate aus N,N-Diallyl-N,N-di(C₁-C₁₂)-alkylammoniumhalogeniden und Cellulose 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 (C₁-C₁₂) alkylammonium halides and cellulose 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 aminogruppenhaltigen 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 amino group-containing compounds in which the ester group is a sulfato or phosphato group or a C₁-C₄-alkanoyl group, phenylsulfonyloxy or one on the benzene nucleus by substituents from the group carboxy, C₁-C--alkyl, C₁-C₄-alkoxy and nitro substituted phenylsulfonyloxy group.

Als Amine haben sich besonders die Verbindungen N-(β-Sulfatoethyl)-piperazin, 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-amino-propan oder ein Derivat dieser Verbindungen mit einer der vorstehend genannten Estergruppe statt der Sulfatogruppe oder N-(2-Sulfatoethyl)-piperazinsulfat, im Sinne der vorliegenden Erfindung bewährt.Particularly suitable amines are the compounds N- (β-sulfatoethyl) piperazine, N- [β- (β'-sulfatoethoxy) ethyl] piperazine, N- (γ-sulfato-β-hydroxypropyl) piperidine, N- (γ-sulfato-β-hydroxy-propyl) pyrrolidine, N-β-sulfatoethyl-piperidine, 2-sulfato-3-hydroxy-1-aminopropane, 3-sulfato-2-hydroxy-1-amino propane, 1-sulfato-3-hydroxy-2-amino-propane, 3-hydroxy-1-sulfato-2-amino-propane, 2,3-disulfato-1-amino-propane, 1,3-disulfato-2- Amino-propane or a derivative of these compounds with one of the abovementioned ester groups instead of the sulfato group or N- (2-sulfatoethyl) piperazine sulfate, has proven itself in the context of the present invention.

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, those compounds which have an α-chloro-β-hydroxy or epoxy substitution as a reactive radical on the amino component are also suitable for the modification and preparation of the amine-substituted cellulose derivatives. Furthermore, reactive is generally to be understood as meaning those parts of the molecule which can react with hydroxyl groups, for example of cellulose, or amino and thiol groups, for example of wool and silk, and which are capable of forming 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.Carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylhydroxyethylcellulose, sulfoethylcellulose, carboxymethylsulfoethylcellulose, hydroxypropylsulfoethylcellulose, hydroxyethylsulfoethylcellulose, methylsulfoethyluloseulose and cellulose have proven to be suitable as cellulose components for the production of the amine-substituted cellulose derivatives.

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 the preparation of the aminated cellulosic synthetic fibers is carried out either by alkalinizing cellulose (alkali cellulose), reacting with carbon disulfide, dissolving the xanthate in sodium hydroxide solution and adding the amine-substituted cellulose derivatives to the viscose spinning solution thus obtained or by adding the amine-substituted cellulose derivatives directly to the alkali metal derivatives then xanthogenized. The modified viscose fibers according to the invention are obtained by subsequent spinning in an acidic spinning bath.

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 nitrogen-containing compounds used for the present process are incorporated into the viscose spinning material in an aqueous medium or, appropriately, also with the aid of emulsifiers and show good compatibility with the viscose. The addition of the amine-substituted cellulose derivative takes place in an amount of 1 to 20%, preferably 1 to 12% by weight, based on the cellulose content of the dope before the 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.If the fibers according to the invention are produced from solution by other customary processes known to those skilled in the art for producing cellulosic fibers, such as, for example, the cupro process, the lyocell process and the process using low-substituted cellulose ethers, the cellulose is dissolved in a suitable organic solvent with which amine-substituted cellulose derivative and spun directly from the solution into fibers. It is most advantageous to meter in immediately before the spinning, and the mixing and homogeneous distribution can be carried out by known mixing systems with the aid of static or dynamic mixing systems. However, metering can also take place in any preliminary stage in the manufacture of spinning mass.

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, since there is otherwise the risk that the prefabricated aminated cellulose 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 cellulose derivatives used to produce the modified viscose can, due to their solubility in water or in aqueous alkali solution, be stirred directly into the spinning mass in a good distribution. The filterability of the viscose shows no deterioration in comparison with free samples, so that no clogging of the spinneret is observed in the course of the spinning process. The viscose is deformed by customary and known methods, such as, for. B. with spinnerets, a subsequent precipitation bath, and optionally 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 process for producing a colored or printed textile material from regenerated cellulose fibers, characterized in that an amine-substituted cellulose derivative is added to a viscose composition or alkali cellulose and spun fibers by the viscose spinning process, or by adding said cellulose derivative to a cellulose solution and from the solution Fibers spins, the fibers are processed into a woven or knitted fabric and this is dyed or printed with one or more reactive dyes in the absence of additional electrolyte salt or alkali.

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 that is used in the dyeing process according to the invention can be present in all processing states, such as yarn, flake, sliver and piece goods (fabric).

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 dyeing of the modified textile fiber materials according to the invention is carried out analogously to known dyeing methods and printing processes for dyeing and printing fiber materials with water-soluble textile dyes and using the temperature ranges and customary amounts of dye known to be used for this, but with the exception that for the dyebaths, padding processes, printing pastes and ink -Jet formulations an addition of alkaline compounds, such as are usually used for fixing fiber-reactive dyes, is not necessary and also to the usual Additions to electrolyte salts can be dispensed with. It is therefore dyed or printed at a 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 dyeing solution. Without the amination of the cellulose fibers according to the invention, this electrolyte content would be too low by a factor of 20 to 1000 for a successful dyeing process.

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 used to dye the modified cellulose are generally anionic in nature. The fiber-reactive textile dyes, which can react with hydroxyl groups, for example of cellulose, or amino and thiol groups, for example of wool and silk, of synthetic polymers, such as polyamides, or also modified polymers, namely the aminated celluloses, and a covalent bond are particularly suitable able to enter. The fiber-reactive component on the textile dyes, in particular the sulfatoethylsulfonyl, vinylsulfonyl, chlorotriazinyl, fluorotriazinyl, and combinations of these "anchor systems" are mentioned. Unless otherwise stated, the parts given in the examples below are 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 imgb0004

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 imgb0004
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 imgb0005

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 imgb0005
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 imgb0006

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 imgb0006
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 potato starch modified in accordance with the information in Example 28 of published patent application DE 41 25 752 A1 is stirred into a spinning viscose as described in Example 1. The procedure is as described 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 imgb0007

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 imgb0007
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 hydroxyethyl cellulose modified in accordance with Example 2 of DE-A-1 593 657 is stirred into a spinning viscose as described in Example 1. The procedure is as described 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 imgb0008

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 imgb0008
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 imgb0009
Figure imgb0010
Figure imgb0011
 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 imgb0009
Figure imgb0010
Figure imgb0011

Claims (14)

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 imgb0012
 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 imgb0013
 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 imgb0014
 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.Aminated cellulosic synthetic fibers, produced by adding an amine-substituted cellulose derivative to a viscose mass 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 cellulose-derived, unsaturated polymerized olefin-derived polymers Are 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 imgb0012
 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 bivalent radical of a heterocyclic ring, in which A is an oxygen atom or a group of the general formula (a), (b) or (c)
Figure imgb0013
 is in which R is a hydrogen atom or an amino group or an alkyl group of 1 to 6 carbon 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 Is C atoms which is interrupted by 1 or 2 groups of the formulas -O- and -NH- or a combination thereof and can be substituted by an amino, sulfo, hydroxyl, sulfato or carboxy group, R¹ is hydrogen, methyl or ethyl, R² is hydrogen, methyl or ethyl and Z (-) represents an anion; B is the amino group of the formula H₂N or an amino or ammonium group of the general formula (d) or (e)
Figure imgb0014
 in which R¹, R² and Z (-) have one of the meanings given above, R³ is methyl or ethyl and R⁴ 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 represented 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 is 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. Aminierte cellulosische Synthesefasern nach Anspruch 1, dadurch gekennzeichnet, daß die aminsubstituierten Cellulosederivate Polymerisate von A) und B) im Gewichtsverhältnis (A):(B) von (95 bis 20):(5 bis 80) sind, wobei A) Monomere 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 achtgliedrige 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, sind und B) Monosaccharide, Oligosaccharide, Polysaccharide, thermisch oder mechanisch behandelte, oxidativ, hydrolytisch oder enzymatisch abgebaute Polysaccharide, oxidierte hydrolytisch oder enzymatisch abgebaute Polysaccharide, chemisch modifizierte Mono-, Oligo- und Polysaccharide oder Mischungen der genannten Verbindungen (B) sind. Aminated cellulosic synthetic fibers according to claim 1, characterized in that the amine-substituted cellulose derivatives are polymers of A) and B) in the weight ratio (A) :( B) of (95 to 20) :( 5 to 80), wherein A) monomers or monomer mixtures from the group of a) N-vinylimidazoles which are 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-vinyl lactams, which can be substituted on the ring by up to three C₁-C₁₂ 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 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, and e) diallyl-C₁-C₁₂-alkylamines or their salts or diallyl-di (C₁-C₁₂-alkyl) ammonium compounds, where as further comonomers to (A) f) monoethylenically unsaturated C₃-C₁₀ carboxylic acids and their alkali metal, alkaline earth metal or ammonium salts, g) monoethylenically unsaturated C₃-C₁₀ carboxylic acid esters and h) at least two ethylenically unsaturated, non-conjugated double bonds may be present in the molecule containing compounds, and B) are 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. Aminierte cellulosische Synthesefasern nach Anspruch 2, dadurch gekennzeichnet, daß in den genannten Polymerisaten die 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 Verbindungen (a), (c), (d), (e), (f), (g) und (h), wobei (h) maximal in einer Menge bis zu 5 Gew.-%, bezogen auf die Gesamtmenge aller Monomeren (A), vorhanden ist, sind.Aminated cellulosic synthetic fibers according to claim 2, characterized in that in the polymers mentioned, the monomers (A) either the compounds (a), (c), (d) and (e) each alone or mixtures of 5 to 95% by weight. a compound (b) and 95 to 5% by weight of one or more of the compounds (a), (c), (d), (e), (f), (g) and (h), where (h) is present in a maximum of up to 5% by weight, based on the total amount of all monomers (A). Aminierte cellulosische Synthesefasern nach Anspruch 1, dadurch gekennzeichnet, daß die aminsubstituierten Cellulosederivate Polymerisate aus N,N-Diallyl-N,N-di(C₁-C₁₂)-alkylammoniumhalogeniden und Cellulose oder Cellulosekomponenten sind.Aminated cellulosic synthetic fibers according to claim 1, characterized in that the amine-substituted cellulose derivatives are polymers of N, N-diallyl-N, N-di (C₁-C₁₂) alkylammonium halides and cellulose or cellulose components. Aminierte cellulosische Synthesefasern nach Anspruch 4, dadurch gekennzeichnet, daß die N,N-Diallyl-N,N-di(C₁-C₁₂)-alkylammoniumhalogenide 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, sind.Aminated cellulosic synthetic fibers according to claim 4, characterized in that the N, N-diallyl-N, N-di (C₁-C₁₂) alkylammonium halides 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. Aminierte cellulosische Synthesefasern nach Anspruch 1, dadurch gekennzeichnet, daß die Estergruppe Y 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.Aminated cellulosic synthetic fibers according to claim 1, characterized in that the ester group Y is a sulfato or phosphato group or a C₁-C₄ alkanoyl group, phenylsulfonyloxy or one on the benzene nucleus by substituents from the group consisting of carboxy, C₁-C₄-alkyl, C₁-C₄ -Alkoxy and nitro substituted phenylsulfonyloxy group. Aminierte cellulosische Synthesefasern nach Anspruch 1, dadurch gekennzeichnet, daß die Amine eine Verbindung aus der Gruppe 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-amino-propan oder ein Derivat dieser Verbindungen mit einer Phosphatogruppe, C₁-C₄-Alkanoylgruppe, Phenylsulfonyloxygruppe oder mit einer am Benzolkern durch Substituenten aus der Gruppe Carboxy, C₁-C₄-Alkyl, C₁-C₄-Alkoxy und Nitro substituierten Phenylsulfonyloxygruppe statt der Sulfatogruppe sind.Aminated cellulosic synthetic fibers according to claim 1, characterized in that the amines are a compound from the group 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-amino -propane, 2,3-disulfato-1-aminopropane, 1,3-disulfato-2-aminopropane or a derivative of these compounds with a phosphato group, C₁-C₄alkanoyl group, phenylsulfonyloxy group or with one on the benzene nucleus by substituents the group carboxy, C₁-C₄-alkyl, C₁-C₄-alkoxy and nitro substituted phenylsulfonyloxy group instead of the sulfato group. Aminierte cellulosische Synthesefasern nach Anspruch 1, dadurch gekennzeichnet, daß die Amine einen reaktiven Molekülteil enthalten, der mit Hydroxygruppen reagieren kann, insbesondere eine α-Chlor-β-hydroxy- oder Epoxy-Substitution aufweist.Aminated cellulosic synthetic fibers according to claim 1, characterized in that the amines contain a reactive part of the molecule which can react with hydroxyl groups, in particular has an α-chloro-β-hydroxy or epoxy substitution. Aminierte cellulosische Synthesefasern nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß als Cellulosekomponente für die Herstellung der aminsubstituierten Cellulosederivate Carboxymethylcellulose, Hydroxyethylcellulose, Hydroxypropylcellulose, Carboxymethylhydroxyethylcellulose, Sulfoethylcellulose, Carboxymethylsulfoethylcellulose, Hydroxypropylsulfoethylcellulose, Hydroxyethylsulfoethylcellulose, Methylsulfoethylcellulose oder Ethylsulfoethylcellulose verwendet wird.Aminated cellulosic synthetic fibers according to at least one of Claims 1 to 8, characterized in that carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, sulfoethyl cellulose, carboxymethylsulfoethyl cellulose, hydroxypropylsulfoethyl cellulose, hydroxypropylsulfoethyl cellulose, hydroxypropylsulfoethyl cellulose, hydroxypropylsulfoethyl cellulose, hydroxypropylsulfoethylsulfoethyl cellulose, hydroxypropylsulfoethylsulfoethylcellulose, hydroxypropylsulfoethylsulfoethylsulfoethylsulfoethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxethylsulfoxylsulfoxethylsulfo Aminierte cellulosische Synthesefasern nach mindestens einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die aminsubstituierten Cellulosederivate Polymerisationsgrade zwischen 300 und 1000 Anhydroglucoseeinheiten und Viskositäten von 300 bis 1500 mPas besitzen.Aminated cellulosic synthetic fibers according to at least one of claims 1 to 9, characterized in that the amine-substituted cellulose derivatives have degrees of polymerization between 300 and 1000 anhydroglucose units and viscosities from 300 to 1500 mPas. Aminierte cellulosische Synthesefasern nach mindestens einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Cellulose-Regeneratfasern nach dem Cuproverfahren oder dem Lyocellverfahren ersponnen werden.Aminated cellulosic synthetic fibers according to at least one of Claims 1 to 10, characterized in that the regenerated cellulose fibers are spun using the cupro process or the lyocell process. Aminierte cellulosische Synthesefasern Verfahren nach mindestens einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß das aminsubstituierte Cellulosederivat in einer Konzentration von 1 bis 20 Gew.-%, insbesondere 1 bis 12 Gew.-%, bezogen auf den Cellulosegehalt der Spinnmasse, zugegeben wird.Aminated cellulosic synthetic fibers Process according to at least one of Claims 1 to 11, characterized in that 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 mass . Verfahren zur Herstellung eines gefärbten oder bedruckten Textilmaterials aus cellulosischen Synthesefasern, 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 Elektrolytsalz oder Alkali färbt oder bedruckt.A process for producing a dyed or printed textile material from cellulosic synthetic fibers, characterized in that an amine-substituted cellulose derivative is added to a viscose mass or alkali cellulose and fibers are spun by the viscose spinning process, or by adding said cellulose derivative to a cellulose solution and spinning fibers from the solution into fibers a tissue processed or knitted and dyed or printed with one or more reactive dyes in the absence of additional electrolyte salt or alkali. Verfahren nach Anspruch 13, dadurch gekennzeichnet, daß man das Textilmaterial bei einem pH-Wert zwischen 4,5 und 8,5 färbt oder bedruckt.A method according to claim 13, characterized in that the textile material is dyed or printed at a pH between 4.5 and 8.5.
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Cited By (7)

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EP0705924A3 (en) * 1994-10-04 1996-10-23 Hoechst Ag Process for dyeing modified viscose fibers with direct or acid dyes
WO1996037643A1 (en) * 1995-05-24 1996-11-28 Dystar Textilfarben Gmbh & Co. Deutschland Kg Spin dyeing process with dyeing salts
WO1996037642A1 (en) * 1995-05-24 1996-11-28 Dystar Textilfarben Gmbh & Co. Deutschland Kg Amination of regenerated cellulose with highly substituted starches and use of the thus modified fibres
WO1997013893A1 (en) * 1995-10-06 1997-04-17 Lenzing Aktiengesellschaft Cellulose fibres
EP0790348A1 (en) 1996-02-15 1997-08-20 DyStar Textilfarben GmbH & Co. Deutschland KG Process for washing-off textile printed fabrics from aminated cotton or regenerated cellulose and silk fibers
EP0719793B1 (en) * 1994-12-24 2001-10-10 Clariant GmbH Process for preparing water-soluble aminoalkyl derivatives of polysachariden
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

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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
US8871922B2 (en) * 2009-03-20 2014-10-28 Fpinnovations Cellulose materials with novel properties
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
US8399590B2 (en) * 2009-10-07 2013-03-19 Akzo Nobel Chemicals International B.V. Superhydrophilic amphiphilic copolymers and processes for making the same
EP2556186B1 (en) 2010-04-08 2017-01-04 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
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

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EP0359188A2 (en) * 1988-09-16 1990-03-21 Hoechst Aktiengesellschaft Dyeing and printing process of cellulose fibres in the absence of alkali or reducing agents
EP0509397A1 (en) * 1991-04-15 1992-10-21 Hoechst Aktiengesellschaft Process for dyeing modified with N-containing, basic polymers cellulosic fibrous material with anionic dyestuffs and the modified cellulosic fibrous material by itself
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
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DE1469062A1 (en) * 1962-10-09 1969-03-13 Courtaulds Ltd Process for the production of aminalized fibers from regenerated cellulose
DE1494547A1 (en) * 1964-06-01 1969-04-24 Algemene Kunstzijde Unie Nv Process for the production and dyeing of threads and staple fibers from regenerated cellulose
DE1593657A1 (en) * 1965-09-14 1970-10-22 Union Carbide Corp Process for the production of cellulose ethers
DE1814565A1 (en) * 1967-12-13 1969-07-24 Courtaulds Ltd Process for the production of regenerated cellulose threads
FR1581593A (en) * 1968-06-25 1969-09-19
DE1948487A1 (en) * 1968-10-01 1970-04-09 Ciba Geigy Process for the production of viscose fibers with novel coloring properties
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
EP0359188A2 (en) * 1988-09-16 1990-03-21 Hoechst Aktiengesellschaft Dyeing and printing process of cellulose fibres in the absence of alkali or reducing agents
EP0509397A1 (en) * 1991-04-15 1992-10-21 Hoechst Aktiengesellschaft Process for dyeing modified with N-containing, basic polymers cellulosic fibrous material with anionic dyestuffs and the modified cellulosic fibrous material by itself
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
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EP0546476A1 (en) * 1991-12-07 1993-06-16 Hoechst Aktiengesellschaft Process for making a modified fiber material and process for dyeing the modified fiber material with anionic dyestuffs

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DR. U. EINSELE: "Über die Aminierung von Cellulosefasern bei der Textilveredlung und deren physikalisches und chemisches Verhalten bei der Textilveredlung", MELLIAND TEXTILBERICHTE, no. 6, HEIDELBERG, BRD, pages 641 - 647 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0705924A3 (en) * 1994-10-04 1996-10-23 Hoechst Ag Process for dyeing modified viscose fibers with direct or acid dyes
EP0719793B1 (en) * 1994-12-24 2001-10-10 Clariant GmbH Process for preparing water-soluble aminoalkyl derivatives of polysachariden
WO1996037643A1 (en) * 1995-05-24 1996-11-28 Dystar Textilfarben Gmbh & Co. Deutschland Kg Spin dyeing process with dyeing salts
WO1996037642A1 (en) * 1995-05-24 1996-11-28 Dystar Textilfarben Gmbh & Co. Deutschland Kg Amination of regenerated cellulose with highly substituted starches and use of the thus modified fibres
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
US5851239A (en) * 1995-05-24 1998-12-22 Dystar Textilfarben Gmbh & Co. Spin dyeing process with dyeing salts
US6001995A (en) * 1995-05-24 1999-12-14 Dystar Textilfarben Gmbh & Co. Deutschland Kg Water-soluble etherified starches
WO1997013893A1 (en) * 1995-10-06 1997-04-17 Lenzing Aktiengesellschaft Cellulose fibres
EP0790348A1 (en) 1996-02-15 1997-08-20 DyStar Textilfarben GmbH & Co. Deutschland KG Process for washing-off textile printed fabrics from aminated cotton or regenerated cellulose and silk fibers
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

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CA2141267A1 (en) 1995-07-30
KR950032755A (en) 1995-12-22
US5684141A (en) 1997-11-04
ES2126794T3 (en) 1999-04-01
FI950343A0 (en) 1995-01-26
DK0665311T3 (en) 1999-08-16
DE59504452D1 (en) 1999-01-21
US5865858A (en) 1999-02-02
FI113281B (en) 2004-03-31
EP0665311B1 (en) 1998-12-09
FI950343A (en) 1995-07-30
ATE174388T1 (en) 1998-12-15
JPH07300719A (en) 1995-11-14
CN1109925A (en) 1995-10-11

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