Classifications

• • 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
  • D06P5/30—Ink jet printing
• • 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
  • 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
  • D06P3/6008—Natural or regenerated cellulose using acid dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/58—Material containing hydroxyl groups
  • D06P3/60—Natural or regenerated cellulose
  • D06P3/62—Natural or regenerated cellulose using direct 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
  • 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

• viscose fibers are essentially the same as those of cotton fibers.
• alkaline dispensing agents and electrolytes are necessary for dyeing cellulosic natural or regenerated fibers in order to achieve satisfactory fixing results with reactive dyes.
• precise these necessary additives represent unacceptable environmental impacts.
• regenerated cellulose fibers will therefore be of increasing importance, which previously had been converted into highly dye-affine, i.e. without additional process steps. salt- and alkali-free dyeable modifications were 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 Ausleschrift 1 469 062 also deals with "aminalized fibers". The additives are aminoethyl and diethylaminocelluloses in high concentrations, the coloring is done exclusively with acid dyes and in the presence of additional electrolyte salt.
• a viscose fiber can be produced which can be dyed in excellent quality with direct dyes even without the usual addition of electrolyte salt, but which can be colored in the otherwise desired form Properties hardly differ from the conventional viscose fibers.
• the present invention relates to a process for dyeing regenerated cellulose fibers with direct dyes or acid dyes, 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, processes the fibers into a woven or knitted fabric and dyes this with a direct dye or acid dye in the absence of additional electrolyte salt.
• 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 or N, N-diallyl-N, N-dimethylammonium halide, in particular N, N-diallyl-N, N-dimethylammonium chloride, to use.
• 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 consisting of carboxy, C1-C4-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 another ester group mentioned above instead of the sulfato group or N- (2-sulfatoethyl
• those compounds which have an ⁇ -chloro- ⁇ -hydroxy or epoxy substitution as a reactive residue on the amino component are also suitable for the modification of the prefabricated celluloses.
• reactive is generally to be understood as meaning those parts of the molecule which contain hydroxyl groups, for example cellulose, or amino and thiol groups, For example, wool and silk can react and are able to form 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 production of the aminated cellulose regenerated fibers is carried out either by alkalinizing cellulose (alkali cellulose), reacting with carbon disulfide and adding the amine-substituted cellulose derivatives to the viscose spinning solution obtained in this way, or by adding the amine-substituted cellulose derivatives directly to the alkali cellulose and then xanthating.
• the modified viscose fibers 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 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 implemented amine-substituted cellulose derivative and spun directly from the solution into fibers.
• a suitable organic solvent with which implemented amine-substituted cellulose derivative and spun directly from the solution into fibers.
• the best thing to do is to dose immediately before Spinning, where the mixing and homogeneous distribution can be carried out by known mixing systems with the help 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 otherwise there is a risk that the prefabricated aminated cellulose will be washed out of the fiber after spinning.
• 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 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 or printing fiber materials with direct dyes or acid dyes and using the temperature ranges and customary amounts of dye known for this purpose, but with the exception that for the dyebaths, padding liquors, printing pastes and ink Jet formulations can be dispensed with the addition of electrolyte salts.
• the salt content is usually from 0.01 to 0.5% by weight, based on the dye liquor. Without the modification of the cellulose fibers according to the invention, this salt content would be too low by a factor of 50 to 1000 for a successful dyeing process.
• Dyeing processes are, for example, the various pull-out processes, such as dyeing on the jigger and on the reel runner or dyeing from long and short liquors, dyeing in jet dyeing machines, dyeing according to the block-cold dwell process or a block-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.
• ink-jet or ink-jet process of the non-contact printing process is the only way to reproduce color images quickly, quietly and in high resolution.
• Ink jet processes typically use aqueous ink that is sprayed directly onto the substrate in small droplets.
• the textile is coated with a cationic polymer and then dyed with anionic dyes using the inkjet process.
• printing is carried out with reactive dyes and alkali is used to actually fix the dye on the fiber.
• the ink-jet process is particularly well suited for printing modified viscose fibers in a multicolor, sharply contoured and waste-free manner. Depending on the quality of the pretreatment, this happens more or less quantitatively, so that in most cases it is even possible to dispense with post-washing. In this way, waste-free dyeing is achieved by printing.
• the dyes that are used to dye the modified cellulose are the direct or acid dyes.
• Suitable acid or direct dyes for dyeing or printing cellulose fibers modified according to the invention are, for example, the diamine dyes, ®Sirius lightfast dyes, ®Alphanol dyes, ®Cotonerol dyes and ®Duasyn dyes, such as C.I. Acid Black 27 (C.I. No. 26 310), C.I. Acid Black 35 (C.I. No. 26 320), C.I. Acid Blue 113 (C.I. No. 26 360), C.I. Direct Orange 49 (C.I. No. 29 050), C.I. Direct Orange 69 (C.I. No. 29 055), C.I. Direct Yellow 34 (C.I. No. 29 060), C.I.
• Direct Red 79 (C.I. No. 29 065), C.I. Direct Yellow 67 (C.I. No. 29 080), C.I. Direct Brown 126 (C.I. No. 29085), C.I. Direct Red 84 (C.I. No. 35 760), C.I. Direct Red 80 (C.I. No. 35 780), C.I. Direct Red 194 (C.I. No. 35 785), C.I. Direct Red 81 (C.I. No. 28 160), C.I. Direct Red 32 (C.I. No. 35 790), C.I. Direct Blue 162 (C.I. No. 35 770), C.I. Direct Blue 159 (C.I. No. 35 775), C.I. Direct Black 162: 1 and C.I. Direct Violet 9 (C.I. No. 27 885).
• 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.
• a textile viscose fabric is obtained which can be further processed directly in a dyeing process using the exhaust process.
• 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, 2% of the acid dye of the formula (CI Direct Blue 108, CI No. 51320) contains dissolved.
• the pH of the liquor is previously adjusted to 4.5 with acetic acid.
• 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 strong blue dyeing with fastness properties that are far superior to conventional direct dyeings. This concerns above all the wash fastness.
• a potato starch modified in accordance with Example 28 of DE-A-41 25 752 is stirred into a spinning viscose as described in Example 1.
• the procedure is as described in Example 1 of the present application.
• a textile viscose fabric is obtained which can be further processed directly in a dyeing process using the block method.
• the dye solution was previously adjusted to a pH of 5 with acetic acid.
• the fabric padded with the dye solution is then steamed for 2 minutes.
• the dyeing thus produced is further processed by rinsing and soaping in the customary manner. The result is a strong turquoise color with very good general fastness properties.
• a viscose modified as in Example 2 is carried out by means of one or two rollers for guiding and tensioning the fabric under an ink-jet printing unit and printed with aqueous solutions of direct dyes.
• four-color printing is carried out with the basic colors for the subtractive color mixing (yellow, cyan, magenta and black).
• CI Direct Blue 199 was used as the cyan dye and CI Direct as the yellow dye Yellow 34 (CI No. 29060), as magenta dye CI Direct Red 79 (CI No. 29065) and as black component CI Direct Black 162: 1.
• the printer works according to the "drop on demand” process and the ink drop is generated thermally (bubble jet process).
• the printed fabric is then steamed for 2 minutes and then rinsed and soaped in the usual way.
• the resulting print has good general fastness properties.
• spinning viscose is one according to the data of Example 1 of US Patent 4,464,523 modified cellulose having 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.
• a viscose modified in this way is applied to a rotating roller.
• a print head based on the "continuous flow” technique now continuously delivers drops of direct dye, which, depending on the control by a computer, reach or deflect the viscose.
• a four-color print is carried out with the basic colors for the subtractive color mixing (yellow, cyan, magenta and black).
• C.I. Direct Blue 199 as a yellow dye
• C.I. Direct Yellow 34 as a magenta dye
• C.I. Direct Red 81 as a black component
• C.I. Acid Black 35 used.
• the printed fabric is then steamed for 2 minutes and then rinsed and soaped in the usual way.
• the resulting print has good general fastness properties.
• a spun viscose as described in Example 1 is modified in accordance with the information in Example 2 of DE-A-1 593 657 Hydroxyethylcellulose stirred in. The procedure is as described in Example 1 of the present application.
• a fiber of modified viscose is obtained, which is carried out by means of one or two rollers for guiding and tensioning the fabric under an ink jet printing unit and printed with aqueous solutions of direct dyes.
• the printer works according to the "drop on demand” process and the ink drop is generated by a pressure surge in the nozzle (piezo process).
• four-color printing is carried out with the basic colors for the subtractive color mixing (yellow, cyan, magenta and black).
• a cyan dye C.I. Direct Blue 199, as a yellow dye
• C.I. Direct Yellow 67 as magenta dye
• C.I. Direct Red 81 and as a black component C.I. Acid Black 27 used.
• the printed fabric is then steamed for 2 minutes and then rinsed and soaped in the usual way.
• the resulting print has good general fastness properties.
• Example 4 or 5 The procedure is as described in Example 4 or 5 and the modified viscose fiber is dyed in accordance with the information in Example 1 using the dyes listed below and similarly good results are obtained: CI Direct Violet 9 CI No. 27885 CI Direct Brown 126 CI No. 29085 CI Direct Orange 69 CI No. 29055 CI Acid Blue 113 CI No. 26360 CI Acid Blue 40 CI No. 62125

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Coloring (AREA)
• Artificial Filaments (AREA)

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• 1994
  • 1994-10-04 DE DE4435385A patent/DE4435385A1/de not_active Withdrawn
• 1995
  • 1995-09-22 EP EP95114951A patent/EP0705924A3/fr not_active Ceased
  • 1995-09-28 CN CN95117284A patent/CN1129269A/zh active Pending
  • 1995-09-29 US US08/538,503 patent/US5542955A/en not_active Expired - Fee Related
  • 1995-10-02 FI FI954683A patent/FI954683A/fi unknown
  • 1995-10-02 TR TR95/01203A patent/TR199501203A2/xx unknown
  • 1995-10-03 CA CA002159782A patent/CA2159782A1/fr not_active Abandoned
  • 1995-10-03 JP JP7256492A patent/JPH08188972A/ja not_active Withdrawn

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