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.

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• 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)

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Publications (2)

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Family Applications (1)

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Cited By (7)

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Citations (11)

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• 1995
  • 1995-01-11 DK DK95100299T patent/DK0665311T3/da active
  • 1995-01-11 AT AT95100299T patent/ATE174388T1/de not_active IP Right Cessation
  • 1995-01-11 DE DE59504452T patent/DE59504452D1/de not_active Expired - Fee Related
  • 1995-01-11 EP EP95100299A patent/EP0665311B1/fr not_active Expired - Lifetime
  • 1995-01-11 ES ES95100299T patent/ES2126794T3/es not_active Expired - Lifetime
  • 1995-01-26 US US08/378,600 patent/US5684141A/en not_active Expired - Fee Related
  • 1995-01-26 FI FI950343A patent/FI113281B/fi not_active IP Right Cessation
  • 1995-01-27 CA CA002141267A patent/CA2141267A1/fr not_active Abandoned
  • 1995-01-27 CN CN95101673A patent/CN1109925A/zh active Pending
  • 1995-01-27 JP JP7011863A patent/JPH07300719A/ja not_active Withdrawn
  • 1995-01-28 KR KR1019950001721A patent/KR950032755A/ko not_active Application Discontinuation
• 1997
  • 1997-10-31 US US08/963,683 patent/US5865858A/en not_active Expired - Fee Related

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