EP1399607B1 - Materiau a base de cellulose adapte a une coloration peu saline et a une impression a hauts rendements de couleur et a hautes solidites de couleur, a une impression par des procedes a jet d'encre et a une impression par transfert a l'etat humide - Google Patents

Materiau a base de cellulose adapte a une coloration peu saline et a une impression a hauts rendements de couleur et a hautes solidites de couleur, a une impression par des procedes a jet d'encre et a une impression par transfert a l'etat humide Download PDF

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Publication number
EP1399607B1
EP1399607B1 EP02748721A EP02748721A EP1399607B1 EP 1399607 B1 EP1399607 B1 EP 1399607B1 EP 02748721 A EP02748721 A EP 02748721A EP 02748721 A EP02748721 A EP 02748721A EP 1399607 B1 EP1399607 B1 EP 1399607B1
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EP
European Patent Office
Prior art keywords
printing
fabric
cellulosic
cellulose
dyeing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02748721A
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German (de)
English (en)
Other versions
EP1399607A2 (fr
Inventor
Frank GÄHR
Frank Hermanutz
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.)
Deutsche Institute fuer Textil und Faserforschung Stuttgart
Original Assignee
Deutsche Institute fuer Textil und Faserforschung Stuttgart
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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

  • the invention relates to a method for producing a cellulosic fiber or fabric by spinning or extruding a cellulosecarbamathigen spinning or extrusion solution and by conventional further processing to cellulosic fiber or fabric, wherein the carbamate groups in the cellulosic fiber or fabric are hydrolyzed so far that in the cellulosic fiber and sheet form 0.02 to 0.85 carbamate remain per anhydroglucose unit. Furthermore, it relates to advantageous uses of this process product. A comparable prior art is apparent from DE 38 20 415 A1.
  • a major drawback of the formulations used today for dyeing cellulosic fibers is the use of very high levels of salt to achieve good fixative yields.
  • the dye liquors are still added on average to about 50 g / l of sodium chloride or of sulfate.
  • Salt consumption in reactive dyeing is estimated to be 1.8 million tonnes per year worldwide.
  • the steps in wet-transfer printing with fiber-reactive dyes are the printing of a pattern onto a specially coated paper by means of rotary-film printing, intermediate drying and eventual storage of the printed paper, contacting this printed paper with a wet web of cellulosic material which is generally impregnated with some fixing alkali.
  • the fiber-reactive dye is transferred from the paper to the textile containing cellulosic fibers.
  • both steps i. both the printing of the paper and the dye transfer to the textile yield losses in yield by hydrolysis of the reactive dye or by incomplete transfer of the dye from the paper to the textile.
  • the first step about 10 to 15% dye is lost, in the second step about 20 to 30%.
  • the resulting dyed or printed substrates should have high fastnesses (washing, light and rubbing fastness).
  • these cellulose-based materials must be preparable by the conventional processes in the textile industry.
  • the chemicals for the production of these materials should be inexpensive.
  • This object is achieved in accordance with the invention by printing and / or dyeing the cellulosic fibrous or flat structures with the content of 0.02 to 0.85 carbamate groups per anhydroglucolysis unit.
  • the process according to the invention is preferably carried out in such a way that after the spinning or extrusion process the cellulose carbamates produced contain in particular 0.03 to 0.31 carbamate groups per anhydroglucose unit, corresponding to nitrogen contents of 0.17 to 6% by weight, in particular 0.23 to 2 , 5 wt .-%.
  • the preparation of the cellulose carbamate starting material is preferably carried out by the process described in DE 196 35 707, in which a small amount of a solvent-containing inclusion cellulose 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 conditions of the synthesis.
  • Cellulose carbamate solutions are prepared which preferably have a concentration of 7 to 12 wt .-%, based on ⁇ -cellulose. This can be done, for example, by dissolving the cellulose carbamate in an approximately 1 to 10% strength by weight, in particular approximately 4% strength by weight, sodium hydroxide solution.
  • this solution into a fibrous or flat structure takes place in a preferred embodiment by a wet spinning or wet extrusion process from alkaline solution in which the solution is introduced through a corresponding spinneret or extrusion orifice into a precipitation bath.
  • the precipitation bath contains a dilute acid, in particular dilute sulfuric acid.
  • a lower alcohol can be used, in particular methanol, which likewise triggers precipitation (coagulation) of the polymer.
  • the alcohol is selected such that the alcohol required for the preparation of the inclusion cellulose and the alcohol used as the precipitation medium are identical, so that a recovery of the alcohol, in particular by distillation processes, as well as the recovery of the alkali used is facilitated and cost is practicable.
  • the entrained acid from the precipitation bath is removed by washing in a bath with a weakly alkaline, aqueous medium, in particular in a bicarbonate-containing aqueous medium.
  • the fiber structure obtained according to the invention is preferably processed into a woven, knitted or nonwoven fabric.
  • Such materials have not been used for dyeing purposes and textile printing.
  • the fibrous or flat structures containing carbamate groups show highly affine properties in comparison with reactive dyes, as a result of which dyeings and prints of hitherto unknown quality are obtained. 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 fibers or fabrics or the fabrics, knits or nonwovens made therefrom are subjected to dyeing or printing.
  • a particular advantage of the method is that the dye solutions used need not have a high electrolyte content, whereby the wastewater 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 used, for standard reactive dyes (eg CI Reactive Red 158) a salt concentration of less than 35 g / l, in particular less than 15 g / l, and for difficult to fix reactive dyes (eg CI Reactive Blue 21) of less than 50 g / l, in particular less than 25 g / l.
  • Another object of the present invention consists in cellulosic fiber or fabric produced by the above method and their use, in particular as outerwear or underwear, lining material, fabric, technical textile, hygiene or medical fleece, sponge cloth and film.
  • the color fastness in particular the surprisingly good lightfastnesses and the markedly improved wet scrub fastnesses compared to normal viscosity should be emphasized.
  • the necessary amount of salt in dyeing liquors can be greatly reduced. Due to these properties, these materials are particularly suitable for printing with fiber-reactive dyes by the inkjet and wet transfer methods.
  • the spinning solution is spun at 5 ° C in a precipitation bath with 10% sulfuric acid (room temperature), washed in a further, slightly acidified by bicarbonate bath, then washed again in a water bath and wound onto a bobbin.
  • the yarn withdrawal speed was 72 m / min, number of individual filaments: 40, titer: 110 dtex, nitrogen content: 1.5%, DS 0.18.
  • One knitted fabric made from this was dyed with the readily fixable reactive dye CI Reactive Red 158 as well as with the hard-fixable fiber-reactive turquoise dye CI Reactive Blue 21 by the exhaustion process in a closable dyeing cup made of stainless steel.
  • Table 4 shows the wet rub fastnesses for dyeings with CI Reactive Red 158 (3% dyeing concentration) on cellulose carbamate (CC1) and viscose (CV).
  • the wet rub fastnesses were determined according to DIN EN ISO 105 X12.
  • Table 4 shows the comparison between CC1 and CV.
  • the spun fibers of cellulose carbamate obtained in Example 2 are saponified by treatment with 60% warm 2% strength by weight sodium hydroxide solution 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 grammage of 120 g.
  • the fabric was impregnated with a solution containing 3% by weight of sodium bicarbonate, 10% by weight of urea and 0.5% by weight of sodium borohydride for 5 minutes between dried and printed analogously to Example 2.
  • the pressure is fixed by 10 minutes treatment in saturated steam at 102 ° C.
  • the fabric is washed twice with 95 ° C hot water and once with cold water.
  • Table 6 shows the color depth obtained for each of the 6 different colors on the basis of the K / S values in comparison to viscose fabric, which was impregnated and printed by an analogous method.
  • the cellulose carbamate CC 2 fabric prepared according to Example 2 was printed by the wet transfer method with CI Reactive Blue 21.
  • a paste was prepared which contained a thickener and 10 parts of liquid dye CI Reactive Blue 21.
  • the proportion of thickener was chosen so that a paste viscosity of 2000 mPa ⁇ s at a shear rate of 10 s -1 resulted.
  • the paste was left to evaporate in the refrigerator overnight, 5 parts (based on the weight of the paste) of sodium bicarbonate and 0.5 parts of sodium borohydride added and stirred briefly again.
  • This color paste was printed on a coated gp base paper at a printing speed of 60 m / min using a 125-mesh rotary stencil and a 1 cm squeegee. After drying by means of an IR dryer, the paint application was determined spectrophotometrically.
  • pretreated cotton fabric (135 g / m 2 ) or fabric made of cellulose carbamate according to Example 1 and 2 was used. The two fabrics were each impregnated with 5 wt .-% sodium hydroxide solution and squeezed by means of a padder to a moisture content of 60%. The transfer using the transfer paper was carried out by pressing the paper twice on the fabric on the padder.
  • the transfer prints were fixed for 16 hours at room temperature in the manner of the pad-cold paddling method.
  • the results of the printing are shown in Table 7 on the basis of the K / S values, the degree of exhaustion, the amount of dye transferred to the respective fabric [%] and the through-pressure.
  • a cellulose carbamate (nitrogen content 2.9 wt .-%) was prepared analogously to Example 1, washed and, similarly to Example 1, prepared a spinning solution. The spinning solution is spun at room temperature into a coagulation bath containing ordinary technical grade methanol. The thread is then washed and processed analogously to 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 dyed with the hard-to-fix fiber-reactive turquoise dye CI Reactive Blue 21 by the exhaustion process in a closable stainless steel dyeing cup. By comparison, a fabric of textile viscose was dyed under identical conditions.

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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)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Paper (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Claims (10)

  1. Procédé de production d'un corps de fibres ou d'un corps plan cellulosique par filage ou extrusion d'une solution de filature ou solution d'extrusion contenant du carbamate de cellulose et par transformation ultérieure habituelle en corps de fibres ou corps plans cellulosiques, les groupes carbamate présents dans les corps de fibres ou les corps plans cellulosiques étant hydrolysés dans une mesure telle qu'il reste dans les corps de fibres et les corps plans cellulosiques 0,02 à 0,85 groupe carbamate par motif anhydroglucose, caractérisé en ce que les corps de fibres ou les corps plans cellulosiques ayant la teneur en 0,02 à 0,85 groupe carbamate par motif anhydroglucose sont imprimés et/ou teints.
  2. Procédé suivant la revendication 1, caractérisé en ce qu'il reste 0,03 à 0,31 groupe carbamate par motif anhydroglucose après l'hydrolyse.
  3. Procédé suivant la revendication 1 ou 2, caractérisé en ce que les corps plans cellulosiques sont imprimés et/ou teints sous forme d'un tissu, d'un tricot ou d'un voile.
  4. Procédé suivant la revendication 1 ou 2, caractérisé en ce que des fibres cellulosiques sont teintes.
  5. Procédé suivant l'une des revendications 1 à 3, caractérisé en ce que l'impression est effectuée par impression par jet d'encre ou par impression par transfert à l'humide.
  6. Procédé suivant l'une des revendications 1 à 5, caractérisé en ce qu'on utilise pour la teinture ou pour l'impression un colorant anionique pour matière textile.
  7. Procédé suivant l'une des revendications 1 à 5, caractérisé en ce qu'on utilise pour la teinture ou l'impression un colorant portant un groupe réactif avec la fibre.
  8. Procédé suivant la revendication 7, caractérisé en ce que la teinture est effectuée avec une solution de colorant qui présente une concentration en sel de moins de 50 g/l.
  9. Procédé suivant la revendication 8, caractérisé en ce que la solution de colorant présente une concentration en sel de moins de 25 g/l.
  10. Utilisation du corps de fibres ou corps plan cellulosique imprimé et/ou teint, obtenue par un procédé selon l'une au moins des revendications précédentes, comme étoffe pour vêtements de dessus ou pour sous-vêtements, étoffe pour doublures, tissu d'ameublement, matière textile technique, voile pour l'hygiène ou la médecine, tissu éponge ou film.
EP02748721A 2001-05-30 2002-05-28 Materiau a base de cellulose adapte a une coloration peu saline et a une impression a hauts rendements de couleur et a hautes solidites de couleur, a une impression par des procedes a jet d'encre et a une impression par transfert a l'etat humide Expired - Lifetime EP1399607B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10126244A DE10126244B4 (de) 2001-05-30 2001-05-30 Verfahren zur Herstellung eines cellulosischen Faser- oder Flächengebildes sowie die Verwendung des danach erhaltenen Gewebes, Gestricks oder Vliesstoffs
DE10126244 2001-05-30
PCT/EP2002/005858 WO2002097175A2 (fr) 2001-05-30 2002-05-28 Materiau a base de cellulose adapte a une coloration peu saline et a une impression a hauts rendements de couleur et a hautes solidites de couleur, a une impression par des procedes a jet d'encre et a une impression par transfert a l'etat humide

Publications (2)

Publication Number Publication Date
EP1399607A2 EP1399607A2 (fr) 2004-03-24
EP1399607B1 true EP1399607B1 (fr) 2007-02-14

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Application Number Title Priority Date Filing Date
EP02748721A Expired - Lifetime EP1399607B1 (fr) 2001-05-30 2002-05-28 Materiau a base de cellulose adapte a une coloration peu saline et a une impression a hauts rendements de couleur et a hautes solidites de couleur, a une impression par des procedes a jet d'encre et a une impression par transfert a l'etat humide

Country Status (5)

Country Link
EP (1) EP1399607B1 (fr)
AT (1) ATE353989T1 (fr)
AU (1) AU2002319185A1 (fr)
DE (2) DE10126244B4 (fr)
WO (1) WO2002097175A2 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10339113A1 (de) * 2003-08-22 2005-03-10 Kalle Gmbh & Co Kg Eingefärbtes Schwammtuch und Verfahren zu dessen Herstellung
AT511002A1 (de) * 2011-02-08 2012-08-15 Univ Innsbruck Verfahren zur verformung von cellulosecarbamat und produkte, die nach diesem verfahren hergestellt werden
CN102691125B (zh) * 2012-06-19 2014-01-01 武汉大学 一种由纤维素氨基甲酸酯制备再生纤维素纤维的方法
CN104195662A (zh) * 2013-11-10 2014-12-10 湖北金环股份有限公司 半连续纺生产cc纤维素长丝的方法
CN104404797B (zh) * 2014-11-17 2016-08-24 浙江恒生印染有限公司 一种黑色再生纤维素纤维筒子纱的活性染料低碱染色方法
CN109575314B (zh) * 2018-12-27 2021-05-11 广西科技大学 一种溶解纤维素的方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI64605C (fi) * 1982-03-30 1983-12-12 Neste Oy Foerfarande foer behandling av fibrer av cellulosaderivat
AT384813B (de) * 1984-10-09 1988-01-11 Chemiefaser Lenzing Ag Verfahren zur herstellung von cellulosecarbamaten
FI77673C (fi) * 1987-07-07 1989-04-10 Neste Oy Foerfarande foer saenkning av karbamathalten i produkter som framstaellts ur cellulosakarbamat och produkter som framstaellts med foerfarandet.
DE19635707C1 (de) * 1996-09-03 1998-04-02 Inst Textil & Faserforschung Verfahren zur Herstellung von Cellulosecarbamat

Also Published As

Publication number Publication date
ATE353989T1 (de) 2007-03-15
DE10126244A1 (de) 2002-12-12
DE50209491D1 (de) 2007-03-29
WO2002097175A3 (fr) 2003-03-13
DE10126244B4 (de) 2005-05-12
EP1399607A2 (fr) 2004-03-24
AU2002319185A1 (en) 2002-12-09
WO2002097175A2 (fr) 2002-12-05

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