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WO2007070904A1 - Procede de fabrication d’un corps moule cellulosique colore - Google Patents

Procede de fabrication d’un corps moule cellulosique colore Download PDF

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Publication number
WO2007070904A1
WO2007070904A1 PCT/AT2006/000521 AT2006000521W WO2007070904A1 WO 2007070904 A1 WO2007070904 A1 WO 2007070904A1 AT 2006000521 W AT2006000521 W AT 2006000521W WO 2007070904 A1 WO2007070904 A1 WO 2007070904A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulosic
starting material
dye
vat
vat dye
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.)
Ceased
Application number
PCT/AT2006/000521
Other languages
German (de)
English (en)
Inventor
Thomas Bechtold
Avinash Pradip Manian
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.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Priority to AT06817492T priority Critical patent/ATE462809T1/de
Priority to DE502006006611T priority patent/DE502006006611D1/de
Priority to CN2006800478248A priority patent/CN101389794B/zh
Priority to EP06817492A priority patent/EP1963552B1/fr
Publication of WO2007070904A1 publication Critical patent/WO2007070904A1/fr
Priority to EG2008061038A priority patent/EG26561A/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/06—Dyes
    • 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
    • D01F2/06—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
    • D01F2/16—Addition of dyes to the spinning solution

Definitions

  • the invention relates to the production of colored cellulose matrices from vat dyes dyed with vat dyes for the production of colored cellulosic molded bodies.
  • Shaped bodies can be fibers, films or other shapes.
  • the most important form of spinning pulp dyeing in the production of cellulosic molded bodies is based on the addition of finely dispersed, insoluble pigments to the spinning mass, which are fixed in the cellulose matrix during subsequent strand formation, and thus have good fastness properties, depending on the type of pigment used. Examples are given below:
  • a disadvantage of the addition of the insoluble dye pigments lies in the difficulty, on the one hand, of achieving the required fine distribution by grinding the pigments and also of maintaining these in the spinning mass. Accordingly, the addition of auxiliaries and additives is also described (Keil, A., Popp, P., and Krause, E. "Process for the production of pigmented regenerated cellulosic fibers” GB 872207 JuI 5, 1961; Eskridge, B. E. "Manufacture of pigmented viscose rayon” US 3033697 May 8, 1962; Gomm, AS, Morgan, LB, and Wood, L. "Process of incorporating aqueous pigment composition in viscose” US 3156574 Nov. 10, 1964; Ono, S., and Igase, T. "Dope dyeing of rayon” JP 54038919 Mar. 24, 1979, vide Chemical abstract no. 91: 40853).
  • the cause of dull, dull hues is, in particular, the presence of the color bodies in finely dispersed form, which implicitly causes matting effects due to the limited particle fineness.
  • the addition of finely dispersed pigments to the spinning solution and the problems resulting therefrom can be circumvented by using soluble dye systems to the dope.
  • the dyes can be pre-dissolved in polar, water-miscible solvents or added directly to the spinning mass (Soc. Pour l'ind., Chim. A BaIe. containing spinning masses "CH 212386 Mar 3, 1941; Phrix-Werke A.-G.” Spun-dyed regenerated cellulose "NL 6407087 Jan 18, 1965, vide Chemical Abstract No. 63: 63815; Ciba Ltd.” Dyeing of regenerated cellulosic fibers and films "FR 1417575 Nov 12, 1965, vide Chemical Abstract No.
  • a further variant recommends the reuse of dyed cellulose textiles with reactive dyestuffs for the production of dyed fibers by the viscose spinning process, the decisive disadvantage being that the dyeings obtained are undefined and not reproducible due to the composition of the raw materials, since some of the dyestuffs are reductively destroyed, while another part remains as a dye (from Eltz, A. "Recycling of dyed cellulosic wastes” EP 0717131 Jun 19, 1996.).
  • the excellent fastness properties of the vat dyes make them particularly interesting for use as pigments for the production of cellulosic molded bodies.
  • An important advantage, but at the same time a processing disadvantage is their insolubility in various media.
  • vat dyes are obtained as coarse-disperse pigments, for the preparation of which extensive finishing processes such as grinding and processing with adjusting agents, dispersants belong.
  • extensive finishing processes such as grinding and processing with adjusting agents, dispersants belong.
  • gefmishten pigments do not show the color characteristic of the respective vat dye, since the average particle size is still too large and for the color development of a fixed in the cellulose matrix molecular disperse form is needed.
  • vat dyes for producing cellulosic shaped bodies
  • amine oxide or lyocell technology Various methods have been proposed in the literature for the use of the vat dyes for producing cellulosic shaped bodies, and a distinction can be made between techniques in the field of viscose technology and the so-called amine oxide or lyocell technology.
  • dye pigments can be added to the dope.
  • a prerequisite for this is an appropriate selection of the suitable pigments, taking into account the strongly oxidizing conditions which are caused by the solvent (N-methyl-N-morpholine-N-oxide - NMMO).
  • WO 01/11121 Ruf H., Lenzing AG, 08.03.2000
  • WO 99/46434 Bartsch P., Ruf H., "Method for producing cellulosic molded bodies", Lenzing AG, 10.03.1999
  • the Add suitable pigmentary dyes to the NMMO-Spirmmasse which the Add suitable pigmentary dyes to the NMMO-Spirmmasse.
  • the vat dyes are also mentioned as colorants which are added as insoluble pigments to the spinning mass, in particular the insolubility of more than 95% required by WO 99/46434 preventing the development of the required vat dye color.
  • a Farbmasterbatcb.es is described, which is to be understood as a color masterbatch according to the prior art, a preparation obtained by mixing colorant with cellulose and optionally NMMO.
  • the colorant available according to the prior art is then, for example, a pigment or a vat dye, which is mixed into cellulose.
  • the cellulose can thus have only a limited fine distribution of the pigment or the vat dye.
  • the resulting spin dyeings are by no means corresponding to the results of textile-chemical vat dyeings.
  • vat dyes into a cellulosic matrix by means of a dyeing process and to produce dyed fibers from them is not disclosed in the prior art.
  • the present invention is based on the surprising finding that a cellulosic starting material such as a pulp can serve as a solid matrix for molecularly dispersed vat dye.
  • the molecular disperse distribution of the dye can be effected by coloring the pulp according to the usual methods for the use of vat dyes, eg Ausziehverfahen, continuous process, wherein after completion of the dye, the dye is no longer present as an original pigment with particle sizes in the micrometer range, but molecularly dispersed in the cellulose is embedded.
  • this colored cellulose is particularly well suited for incorporation of the dye in molecularly disperse form in spinning masses.
  • the actual spinning masses can be produced by dissolving the cellulose by the viscose process or the amine oxide or lyocell process.
  • vat dyeing reduction / oxidation
  • the presence of the dye in molecularly disperse form achieves high dye yields with high brilliance.
  • pigments are no longer visible under the microscope.
  • the dyeing result therefore corresponds to a vat dyeing in hue, color depth and fastness properties, but may be based on the treatment of the fibers in strongly swelling alkaline baths, as is customary in dyeing with vat dyes, and also on the dyeing, which is difficult to color, e.g. Winding body, be waived.
  • the vat dye-containing cellulosic starting material when dyeing the pulp with high dye concentration, e.g. 20% by weight of dye based on the weight of the pulp, can be processed together with at least one further, optionally also a dye-containing starting material to formable solution.
  • the dyeing of the cellulosic starting material can according to the procedure according to the invention with vat dyes in a depth of 0.1 to 25% (mass of dye to mass cellulosic starting material), preferably from 1 to 20%, particularly preferably from 5 to 10% (each mass of dye to Mass cellulosic starting material).
  • the liquor ratio (mass of dyestuff to volume dyebath) can be between 1: 0.8 to 1:50, preferably between 1: 5 to 1:10.
  • the dyeing process may be carried out at temperatures of 20-80 ° C using conventional vat dyeing techniques. Also, continuous dyeing techniques, e.g. using modified screen belt equipment, can be applied.
  • dyeing processes employing dyeing techniques with dyebath recovery, e.g. Dyeing upstanding bath.
  • dyeing techniques with dyebath recovery, e.g. Dyeing upstanding bath.
  • the process-related emissions are significantly lower than with conventional vat dyeing processes.
  • vat dyes By avoiding the usual alkaline vat dyeing carried out under relatively severe conditions, it is also possible to produce sensitive substrates dyed without impairing the fiber properties with vat dyes.
  • the cellulosic starting material containing the vat dye can be mixed, depending on the desired color depth, with an optionally undyed cellulosic starting material, the mixing ratio of vat dye-containing starting material to the other starting material (s) being from 0.1: 10 to 10: 0.1, preferably from 1:10 to 10: 1 can be.
  • the mixing ratios depend on the dye content of the presented colored cellulosic starting material and the color depth of the spun-dyed material to be produced.
  • the cellulosic starting material and / or the at least one further starting material may in particular be selected from the group consisting of pulp, natural and man-made cellulose fibers and piecing material of a process for the production of cellulose fibers.
  • undyed cellulose fibers can also be dyed with vat dyes and serve as cellulosic matrix.
  • a particularly preferred embodiment uses for this purpose so-called piecing material, which arises when starting a fiber production plant and does not yet meet the quality requirements of the fibers, but is suitable as a cellulose matrix.
  • a preferred embodiment of the method according to the invention is characterized in that the starting material (s) is / are further processed by means of the viscose process or by means of the amine oxide process to give the shaped body.
  • the viscose process and the amine oxide process or lyocell process are well known to the person skilled in the art.
  • the amine oxide or lyocell process is described in more detail, for example, in EP 0 356 419 A or in WO 93/19230.
  • the invention further relates to the use of a cellulosic material which contains a vat dye in molecularly disperse form, as starting material for the production of a cellulosic shaped body.
  • the invention also relates to a cellulosic molding, in particular a cellulose fiber, which is obtainable by the process according to the invention.
  • the cellulose molded bodies according to the invention are completely through-dyed with the vat dye because of the process according to the invention. Due to the process according to the invention, moreover, an average particle size of the vat dye in the cellulose matrix of less than 0.1 ⁇ m can be achieved. The dye is thus no longer visible under a light microscope ordinary resolution at eg 400-fold magnification.
  • Celluloseformkörpem which can be obtained by adding an insoluble dye pigment to the dope and in which the particle size of the pigments in the fiber in the micrometer range.
  • the invention relates to a textile article, e.g. a yarn, a fabric or clothing containing a cellulosic shaped body according to the invention in the form of a fiber.
  • textile articles containing a cellulosic fiber according to the invention have excellent micro- and macroegalities, which is comparable to the level of levelness obtainable in conventional vat dyeing of textiles.
  • yarn dyeing by means of vat dyes often proves to be difficult, while using a cellulosic fiber according to the invention yarns can be produced with excellent uniform fategrochen.
  • the textile articles according to the invention are completely dyed due to the use of the cellulose fiber according to the invention. Complete staining is difficult to achieve with conventional vat dyeing of textiles.
  • Fiber pulp About 350 g of fiber pulp (Lenzing AG) are dyed by exhaustion with CI Vat Green 5 (Indanthrene Brilliant Green FFB, Dystar, Frankfurt, Germany) for 45 min at 50 ° C. in a liquor ratio of 1:15 in a dyebath which has the following composition : 10 g / L dye, 6.17 g / L NaOH, and 5 g / L Na 2 S 2 O 4 .
  • CI Vat Green 5 Indanthrene Brilliant Green FFB, Dystar, Frankfurt, Germany
  • the dye-cake and the residual dyebath containing the pulp are brought to dyeing temperature. After reaching the dyeing temperature, the solution containing the reduced dye and the pre-pulp containing bath mixed and the dyeing process is started. After 45 minutes at dyeing temperature, the dyeing process is terminated. The pulp is thoroughly rinsed and the oxidation step is carried out by air oxidation. Subsequently, the dyed pulp is dried. The dyed cellulose matrix is mixed with undyed pulp in a ratio of 1: 4 and processed into dyed fibers by the amine oxide or lyocell method. It is obtained a 2.5% color, which corresponds in color and fastness (wash fastness, light fastness) to the dyeings produced by conventional methods.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un corps moulé cellulosique coloré avec un colorant de cuve, notamment une fibre ou une feuille, ledit procédé comprenant les étapes suivantes : préparer un matériau de départ cellulosique contenant le colorant de cuve sous forme de dispersion moléculaire ; préparer une solution malléable à partir du matériau de départ cellulosique ; mettre en forme la solution en utilisant un outil de formage approprié; précipiter ou régénérer la cellulose dans la solution mise en forme.
PCT/AT2006/000521 2005-12-19 2006-12-18 Procede de fabrication d’un corps moule cellulosique colore Ceased WO2007070904A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AT06817492T ATE462809T1 (de) 2005-12-19 2006-12-18 Verfahren zur herstellung eines gefärbten cellulosischen formkörpers
DE502006006611T DE502006006611D1 (de) 2005-12-19 2006-12-18 Verfahren zur herstellung eines gefärbten cellulosischen formkörpers
CN2006800478248A CN101389794B (zh) 2005-12-19 2006-12-18 染色的纤维素模制体的制造方法
EP06817492A EP1963552B1 (fr) 2005-12-19 2006-12-18 Procede de fabrication d un corps moule cellulosique colore
EG2008061038A EG26561A (en) 2005-12-19 2008-06-18 Method of production of a pigmented cellulosic substance

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA2029/2005 2005-12-19
AT0202905A AT502993B1 (de) 2005-12-19 2005-12-19 Verfahren zur herstellung eines gefärbten cellulosischen formkörpers

Publications (1)

Publication Number Publication Date
WO2007070904A1 true WO2007070904A1 (fr) 2007-06-28

Family

ID=37864525

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT2006/000521 Ceased WO2007070904A1 (fr) 2005-12-19 2006-12-18 Procede de fabrication d’un corps moule cellulosique colore

Country Status (6)

Country Link
EP (1) EP1963552B1 (fr)
CN (1) CN101389794B (fr)
AT (2) AT502993B1 (fr)
DE (1) DE502006006611D1 (fr)
EG (1) EG26561A (fr)
WO (1) WO2007070904A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016123643A1 (fr) 2015-02-06 2016-08-11 Lenzing Ag Recyclage de fibres cellulosiques artificielles
CN109181360A (zh) * 2018-07-03 2019-01-11 张华娟 一种还原染料
US10316467B2 (en) 2013-11-26 2019-06-11 Lenzing Aktiengesellschaft Process for pretreating reclaimed cotton fibers to be used in the production of molded bodies from regenerated cellulose

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1253864B (de) * 1962-02-26 1967-11-09 British Cellophane Ltd Verfahren zum Massefaerben von nach Nassspinn- bzw. Nassgussmethoden hergestellten Faeden oder Filmen
EP0717131A1 (fr) * 1994-12-13 1996-06-19 Hoechst Aktiengesellschaft Procédé de recyclage de produits cellulosiques teints
WO1999046434A1 (fr) * 1998-03-12 1999-09-16 Lenzing Aktiengesellschaft Procede pour produire des corps moules cellulosiques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1253864B (de) * 1962-02-26 1967-11-09 British Cellophane Ltd Verfahren zum Massefaerben von nach Nassspinn- bzw. Nassgussmethoden hergestellten Faeden oder Filmen
EP0717131A1 (fr) * 1994-12-13 1996-06-19 Hoechst Aktiengesellschaft Procédé de recyclage de produits cellulosiques teints
WO1999046434A1 (fr) * 1998-03-12 1999-09-16 Lenzing Aktiengesellschaft Procede pour produire des corps moules cellulosiques

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10316467B2 (en) 2013-11-26 2019-06-11 Lenzing Aktiengesellschaft Process for pretreating reclaimed cotton fibers to be used in the production of molded bodies from regenerated cellulose
WO2016123643A1 (fr) 2015-02-06 2016-08-11 Lenzing Ag Recyclage de fibres cellulosiques artificielles
JP2018505973A (ja) * 2015-02-06 2018-03-01 レンツィング アクチェンゲゼルシャフト 人工セルロース系繊維の再利用
US10370778B2 (en) 2015-02-06 2019-08-06 Lenzing Aktiengesellschaft Recycling of man-made cellulosic fibers
CN109181360A (zh) * 2018-07-03 2019-01-11 张华娟 一种还原染料

Also Published As

Publication number Publication date
ATE462809T1 (de) 2010-04-15
DE502006006611D1 (de) 2010-05-12
EP1963552B1 (fr) 2010-03-31
AT502993A1 (de) 2007-07-15
AT502993B1 (de) 2008-07-15
EG26561A (en) 2014-02-18
CN101389794A (zh) 2009-03-18
EP1963552A1 (fr) 2008-09-03
CN101389794B (zh) 2012-06-06

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