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
  • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
  • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of 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
  • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
• • 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
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/0032—Determining dye recipes and dyeing parameters; Colour matching or monitoring
• • 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

Definitions

• Cellulose-based material suitable for low-salt dyeing and printing in high color yields and fastness as well as for printing using the inkjet process and
• the invention relates to a process for producing a cellulosic fiber or sheet material containing carbamate groups, and to further processing, in particular by dyeing or printing.
• the present invention relates to cellulosic fiber or sheet-like structures produced by the method according to the invention and to their use as outer or undergarment material, lining material, upholstery material, technical textile, hygiene or medical fleece, sponge cloth and film.
• the cellulosic materials are suitable for significantly reducing the salt additives required for dyeing. This can significantly improve the quality of the wastewater and make it easier to reuse water through recycling.
• the cellulose materials are particularly suitable for special printing processes, such as printing with fiber-reactive dyes using inkjet or wet transfer technology in high color yields.
• a major disadvantage of the formulations used today for dyeing cellulose fibers is the use of very high amounts of salt in order to achieve good fixing yields.
• cellulose fibers eg cotton, viscose
• an average of approx. 50 g / 1 sodium chloride or sulfate is still added to the dye liquors.
• salt consumption in reactive dyeing is estimated at 1.8 million tons per year worldwide.
• Disadvantages in the printing area are the relatively long machine set-up times with conventional printing processes (film or rotary printing), unsatisfactory transferability of sample prints to production, the low flexibility and, especially when printing with reactive dyes, the high wastewater load and the accumulation of residual pastes that are disposed of have to.
• the steps in wet transfer printing with fiber-reactive dyes are the printing of a design on a specially coated paper using rotary film printing, intermediate drying and possible storage of the printed paper, contacting this printed paper with a moist web of cellulose material, which is usually impregnated with some fixing alkali.
• the fiber-reactive dye is transferred from the paper to the textile containing cellulose fibers.
• yield losses result from hydrolysis of the reactive dye or from incomplete transfer of the dye from the paper to the textile.
• the first step approx. 10 to 15% of the dye is lost, in the second step approx. 20 to 30%.
• the fixing yield in wet transfer printing with fiber-reactive dyes is 60 to 65%, which is not an improvement compared to established printing processes. It would therefore be of great advantage if, in particular in the second step, the dye transfer from paper to the textile goods, a significant improvement in the fixing yield was achieved.
• Ink jet printing uses only a fraction of the amount of dye compared to conventional direct printing. For this reason, dark shades are very difficult to achieve.
• the pressure drop is heavily dependent on the substrate, especially with ink-jet printing.
• the respective goods are therefore especially impregnated with certain substances.
• the impregnation of the printed matter with thickeners or quaternary nitrogen compounds is recommended in several patents (EP 534660, US 4702742, JP 268372). This pretreatment and impregnation of goods is based on empirical values and does not currently represent a satisfactory solution to the problem.
• the object of the present invention is therefore to provide a process for the production of a cellulosic fiber or sheet material with high affinity for dyes and high absorption capacity for dyes, so that as little dye as possible is lost through chemical hydrolysis or transfer losses.
• the resulting colored or printed substrates should have high fastness properties (wash, light and rub fastness).
• these cellulose-based materials must be able to be produced by the processes customary in the textile industry. The chemicals used to manufacture these materials are said to be inexpensive.
• a further object of the invention is to provide fiber and flat structures produced by the method according to the invention and to propose an advantageous use thereof.
• the object is achieved according to the invention by a process for producing a cellulosic fiber or sheet by spinning or extruding a cellulose-carbamate-containing spinning or extrusion solution, in which the carbamate groups in the cellulosic fiber or sheet not after the spinning or extrusion process be completely hydrolyzed.
• the process according to the invention gives fibrous or sheetlike structures which are particularly suitable for textile uses and which, when dyeing, in particular with anionic textile dyes, provide high color depths, fixation yields and fastness properties.
• the process is preferably carried out in such a way that the cellulose carbamates produced contain 0.02 to 0.85, in particular 0.03 to 0.31, carbamate groups per anhydroglucose unit after the spinning or extrusion process, corresponding to nitrogen contents of 0.17 to 6% by weight. -%, in particular 0.23 to 2.5 wt .-%.
• the cellulose carbamate starting material is preferably produced by the process described in DE 196 35 707, in which a small amount of inclusion cellulose containing a solvent is reacted with a urea melt.
• the fibrous cellulose carbamate starting material typically has nitrogen contents of 2.0 to 6.0%, depending on the synthesis conditions.
• Cellulose carbamate solutions are produced which preferably have a concentration of 7 to 12% by weight, based on ⁇ -cellulose. This can be done, for example, by dissolving the cellulose carbamate in about 1 to 10% by weight, in particular about 4% by weight. -%, sodium hydroxide solution.
• this solution is processed into a fibrous or sheet-like structure by a wet spinning or wet extrusion process from an alkaline solution, in which the solution is introduced into a precipitation bath through a corresponding spinneret or extrusion opening.
• the precipitation bath preferably contains a dilute acid, in particular dilute sulfuric acid.
• a lower alcohol, in particular methanol can be used in the precipitation bath (coagulation bath) according to the method described in Lenzinger reports 59 (1985), 111-117, which likewise triggers precipitation (coagulation) of the polymer.
• the alcohol is selected such that the alcohol required for the production of the inclusion cellulose and the alcohol used as the precipitation medium are identical, so that recovery of the alcohol, in particular by destiUative processes, and also recovery of the alkali used is facilitated and is practicable at low cost.
• the acid carried along from the precipitation bath is advantageously removed by washing out in a bath with a weakly alkaline, aqueous medium, in particular in an aqueous medium containing hydrogen carbonate.
• the fiber structure obtained according to the invention preferably becomes a woven fabric,
• Knitted or nonwoven processed Such materials have not previously been used for dyeing and textile printing.
• the fiber or sheet-like structures containing carbamate groups have highly affine properties with respect to reactive dyes, as a result of which dyeings and prints are obtained in a previously unknown quality. It has been found that a high content of carbamate groups leads to a high affinity of the material for textile dyes. This means that a high degree of substitution leads to high achievable color yields or color depths.
• the cellulosic fiber or flat structures or the woven, knitted or nonwoven fabrics produced therefrom are subjected to dyeing or printing.
• a particular advantage of the process is that the dye solutions used do not have to have a high electrolyte content, as a result of which the waste water quality and the possibility of water recycling are significantly improved. Particularly good results are achieved when using anionic textile dyes.
• a particularly preferred embodiment consists in the use of fiber-reactive dyes with which very high color yields can be achieved.
• a reactive dye solution is preferably used which has a salt concentration of less than 35 g / 1, in particular less than 15 g / 1, for standard reactive dyes (for example CI Reactive Red 158) and less than for reactive dyes which are difficult to fix (for example CI Reactive Blue 21) 50 g / 1, in particular less than 25 g / 1.
• the present invention furthermore relates to cellulosic fiber or sheetlike structures produced by the preceding method and their use, in particular as outer or undergarment material, lining material, cover material, technical textile, hygiene or medical fleece, sponge cloth and film.
• the spinning solution is spun at 5 ° C. in a precipitation bath with 10% sulfuric acid (room temperature), washed in a further bath which has been made slightly alkaline by hydrogen carbonate, then washed again in a water bath and wound onto a bobbin.
• the thread take-off speed was 72 m / min, number of individual filaments: 40, titer: 110 dtex, nitrogen content: 1.5%, DS 0.18.
• On knitted fabric made from this was both with the easily fixable reactive dye
• Glauber's salt variable (see tables 1 and 2)
• Dyeing temperature 40 ° C for C.I. Reactive Red 158 80 ° C for C.I. Reactive Blue 21
• Reactive Blue 21 15 g / 1 soda and 1.5 ml / 1 sodium hydroxide solution 32.5% by weight staining time from the addition of alkali: 60 min
• Table 4 shows the wet rub fastness for dyeings with CI Reactive Red 158 (3% dye concentration) on cellulose carbamate (CC1) and viscose (CV).
• the wet fastness properties were determined in accordance with DIN EN ISO 105 X12.
• Table 4 shows the comparison between CC1 and CV.
• this material is produced in the colors black, turquoise, blue, red, orange and yellow, which were taken from the Cibacron range (salt-free) from Ciba-Geigy , printed.
• the printing inks are characterized by the following parameters: pH 7.7; Conductivity 3.7 mS / cm; Surface tension 51.3 mN / m; Viscosity approx. 1 mPas.
• the pressure is fixed in saturated steam at 102 ° C for 10 minutes.
• Tissue is rinsed twice with hot water at 95 ° C and once with cold water.
• a fabric made from normal viscose was treated, printed and washed according to identical conditions.
• Table 5 shows the color depth obtained for the 6 different colors based on the K / S values. In particular, the colors yellow and red appear much more brilliant on CC2 compared to CV.
• the staple fibers of cellulose carbamate obtained in Example 2 are saponified by treatment with 2% by weight sodium hydroxide solution at a temperature of 60 ° C. to a nitrogen content of 0.24% by weight, corresponding to a DS of 0.03. These filaments were processed into a fabric (CC3) with a square meter weight of 120 g.
• the fabric was impregnated with a solution containing 3% by weight sodium hydrogen carbonate, 10% by weight urea and 0.5% by weight sodium borohydride, 5 minutes intermediate dried and printed as in Example 2.
• the pressure is fixed in saturated steam at 102 ° C for 10 minutes.
• the fabric is washed twice with hot water at 95 ° C and once with cold water.
• Table 6 shows the color depth obtained for each of the 6 different colors using the K S values in comparison to viscose fabric, which was impregnated and printed using an analogous process.
• the fabric made of cellulose carbamate CC 2 produced according to Example 2 was printed with CI Reactive Blue 21 by the wet transfer process.
• a paste was prepared that contained a thickener and 10 parts of CI Reactive Blue 21 liquid dye.
• the proportion of thickener was chosen so that a paste viscosity of 2000 mPa s with a shear rate of 10 s "1 resulted.
• the paste was left to swell overnight in the refrigerator, 5 parts (based on the weight of the paste) sodium hydrogen carbonate and 0.
• a cellulose carbamate (nitrogen content 2.9% by weight) was produced, washed and, likewise analogously to example 1, a spinning solution was prepared.
• the spinning solution is spun at room temperature in a coagulation bath containing ordinary technical methanol.
• the thread is then washed and processed as in Example 1.
• the nitrogen content of the carbamate thread (CC4) was 2.1%, corresponding to a DS of 0.26.
• a knitted fabric made from this was made with the difficult to fix fiber-reactive turquoise dye C.I. Reactive Blue 21 dyed using the pull-out method in a sealable stainless steel staining cup.
• a knitted fabric made of textile viscose was dyed according to identical conditions. Liquor ratio: 1:20 dye concentration: 3% Glauber's salt: 10 g / 1
• Heating rate 1.5 ° C alkali addition 30 min after reaching the dyeing temperature: 15 g / 1 soda and 1.5 ml / 1 sodium hydroxide solution 32.5% by weight
• Table 8 shows the color depths obtained, degrees of exhaustion [%] and lightfastness notes for the corresponding dyeings on viscose (CV) and cellulose carbamate (CC4).
• Table 5 K / S values for 6 different reactive dyes in ink-jet printing on viscose (CV) and cellulose carbamate (CC2)
• Table 8 Color depths, degree of exhaustion [%] and light fastness rating for 3% staining with C.I. Reactive Blue 21 on viscose (CV) and cellulose carbamate (CC4)

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Coloring (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)
• Paper (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=7686589

Family Applications (1)

Country Status (5)

Families Citing this family (6)

Family Cites Families (4)

• 2001
  • 2001-05-30 DE DE10126244A patent/DE10126244B4/de not_active Expired - Fee Related
• 2002
  • 2002-05-28 AU AU2002319185A patent/AU2002319185A1/en not_active Abandoned
  • 2002-05-28 DE DE50209491T patent/DE50209491D1/de not_active Expired - Lifetime
  • 2002-05-28 EP EP02748721A patent/EP1399607B1/fr not_active Expired - Lifetime
  • 2002-05-28 AT AT02748721T patent/ATE353989T1/de active
  • 2002-05-28 WO PCT/EP2002/005858 patent/WO2002097175A2/fr active IP Right Grant

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events