WO1999046434A1 - Procede pour produire des corps moules cellulosiques - Google Patents

Procede pour produire des corps moules cellulosiques Download PDF

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Publication number
WO1999046434A1
WO1999046434A1 PCT/AT1999/000062 AT9900062W WO9946434A1 WO 1999046434 A1 WO1999046434 A1 WO 1999046434A1 AT 9900062 W AT9900062 W AT 9900062W WO 9946434 A1 WO9946434 A1 WO 9946434A1
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WO
WIPO (PCT)
Prior art keywords
dye
colorant
solution
cellulose
precursor
Prior art date
Application number
PCT/AT1999/000062
Other languages
German (de)
English (en)
Inventor
Peter Bartsch
Hartmut Rüf
Original Assignee
Lenzing Aktiengesellschaft
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 Aktiengesellschaft filed Critical Lenzing Aktiengesellschaft
Priority to AU28181/99A priority Critical patent/AU2818199A/en
Publication of WO1999046434A1 publication Critical patent/WO1999046434A1/fr

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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
    • 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
    • D01F1/04—Pigments
    • 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

Definitions

  • the present invention relates to a process for producing cellulosic moldings, in particular fibers, from solutions of cellulose in an aqueous tertiary amine oxide.
  • Synthetic fibers such as polyamide and polyester as well as viscose fibers are now routinely dyed with a dope. Only pigments are used for spin dyeing, which are usually sold in the form of granules or pasta. Generally, pigments are dispersed in the polymer melt or mass.
  • the pigment preparations are metered in either in portions (cellar process) or to the main viscose line (injection process).
  • a solution of cellulose is formed from a cellulose suspension in an aqueous tertiary amine oxide (preferably N-methyl-morpholine-N-oxide - NMMO) by evaporation of excess water and is extruded through a spinneret.
  • the filaments formed are passed through an air gap into a precipitation bath, washed and 2 dried. Fibers produced in this way are also called “solvent-spun” fibers or “Lyocell fibers”.
  • the circulation in the Lyocell process can lead to the accumulation of pigments, dyes and additives (e.g. from pigment preparations).
  • the thermal instability of the cellulose solution in NMMO also results in a very narrow selection of colorants. Spinning problems caused by undissolved pigment particles should also be taken into account.
  • WO 94/20653 describes the production of matted regenerated fibers by adding hollow bodies made of acrylate polymers or styrene-acrylate copolymers.
  • matting, pigmentation of cellulosic threads, films and membranes are made up of compositions which consist of solid particles which are embedded in a matrix of cellulose, NMMO, water and possibly other additives and are inert to this matrix .
  • inorganic or organic pigments for pigmenting cellulose threads is also described.
  • DE 195 19 024 describes a process for the spin dyeing of regenerated cellulose fibers by adding and spinning a formulation of canonized polysaccharide and an anionic dye to a viscose composition, alkali cellulose or a cellulose solution.
  • this document also describes the use of this process in solutions of cellulose in an amine oxide. According to the authors of this document, the use of a cationized polysaccharide is necessary to prevent washing out of the incorporated dye from a regenerated cellulose fiber.
  • the object of the present invention is to provide improved colored cellulosic moldings, in particular fibers, produced by the amine oxide process.
  • This object is achieved by adding a colorant and / or a colorant precursor to the solution of the cellulose in the tertiary amine oxide and / or the cellulose suspension in the tertiary amine oxide, which colorant or which colorant precursor in the cellulose solution is based on more than 95% by weight on originally used colorant or colorant precursor is insoluble.
  • the amount of colorants or colorant precursors used is chosen such that the content of colorant or colorant precursor in the resulting shaped body, based on cellulose, is 0.1 to 5% by weight, preferably 0.5 to 3% by weight.
  • the advantage of a spin dyeing of Lyocell fibers is that the problem of streaky dyeing due to the tendency of the fibers to fibrillate under mechanical stress is avoided.
  • spin dyeing all shades can be adjusted by mixing fewer starting dyes.
  • the dyeing process is independent of the usual dyeing parameters such as temperature, dyeing time, substantivity, reactivity, diffusion behavior, etc. In this way, large quantities of fibers can be produced with a constant depth of color and uniform dyeing across the fiber cross-section. 4
  • the dyes used have no negative influence on the quality of the solution (grade), the spinning safety and the fiber data.
  • metal-containing colorants should not be added to the suspension before solution preparation due to the thermal decomposability of the cellulose solution.
  • the colorant used is essentially insoluble in the cellulose solution, as required by the invention, it is possible to add the colorant to the solution.
  • the colorant or the precursor of a colorant can be added in powder or granule form or as a liquid brand (pasta) or in the form of a masterbatch (cellulose / colorant) for NMMO / cellulose suspension preparation or for solution preparation.
  • a preferred embodiment of the process according to the invention is characterized in that a vat or a sulfur dye in the oxidized form is added to the cellulose suspension or the cellulose solution.
  • the dye can already be added in the oxidized and thus coloring form.
  • a further preferred embodiment of the method according to the invention is characterized in that the dye precursor of a development dye is added.
  • Coupling reaction with the dye precursor can form the finished dye.
  • This dyeing step can be carried out immediately after the fiber has been washed out.
  • a dye precursor such as a naphthol component (e.g. 2-hydroxy-3-naphthoic acid anilide)
  • a naphthol component e.g. 2-hydroxy-3-naphthoic acid anilide
  • the dye development (coupling) on the never dried fiber takes place in a post-treatment step immediately after the washout process.
  • the staple fibers or staple fibers primed with a Naphtol AS component are passed through a solution which contains a dye-fast salt or a diazonium salt solution of a dye base. This is due to the choice among different
  • Dye-proofing salts with the same primer, enable a very quick change of shades.
  • the fiber then contains the dye precursor and can be used in any further processing stage, e.g. to a fabric that is ready-dyed according to the customer's requirements.
  • Organic pigments and pigment preparations such as e.g. Azo pigments, carbonyl pigments such as Anthraquinones, quinacridones, as well as polymethines, sulfur dyes and phthalocyanines in question.
  • Anthraquinone dyes are particularly suitable.
  • the pigments or dyes were suspended or dissolved in an NMMO / water mixture, after which the cellulose was added.
  • the suspension was made into a spinnable mass by evaporating excess water in a known manner. 1-3% dye based on cellulose was used.
  • lg fibers were spun in a known precipitation bath volume (450 ml), wound onto a godet (0.6 m / min) and washed out at the same time (150 ml). The spinning time was 33 minutes in each case. The threads were then washed for 15 minutes in a post-treatment bath (200 ml) at room temperature. The washed-out dye content can then be determined by VIS spectroscopic examination of the precipitation and washing baths and is a measure of the solubility of the dye in the cellulose solution.
  • the cellulose solutions are composed as follows (data in% by weight):
  • NMMO solubility of different pigment classes a mixture of 3.8 g of NMMO monohydrate, 0.45 g of H 2 O and 15 mg of pigment was heated in a test tube at 100 ° C. for two hours.
  • the pigments that are soluble in NMMO are primarily azo pigments and mostly color lacquers, i.e. metal complexes containing sulfo or carboxyl groups (Ni ++ , Mn ++ , Sr ++ , Ca ++ ). 9
  • azo pigment molecules mainly shades of blue but also red, can be spun in without any problems. They are insoluble in NMMO and are not washed out of the fiber in the precipitation bath.
  • Anthraquinone (indanthrene) and indigoide (indigo, thioindigo) vat dyes also proved to be insoluble.
  • Oxidized vat dyes e.g. indigo, indanthrene
  • indigo indanthrene
  • fine pigment particles of approx. 10 ⁇ m in size can be seen under the microscope.
  • Dioxazines, quinacridones and blue phthalocyanines were also found to be insoluble.
  • 1% Naphtol AS® (based on cellulose) was suspended in the NMMO / water mixture. After kneading with pulp, the Naphtol AS® was distributed homogeneously. The spinning mass was spun in a precipitation bath and then passed through a 20 diazonium salt solution (dyeing fast salt solution). The water-insoluble development dye forms in the fiber. The short residence time in the developing bath is sufficient to dye the fiber. Small amounts of Naphtol AS® are washed out in the development bath and form insoluble dye particles there. This offers the possibility of using less water-soluble naphthols as primers and thus preventing the formation of a sediment from water-insoluble development dye. The advantage of the development dyes is that several colors can be achieved with one primer simply by the choice of dye fastness salts in the aftertreatment. This enables a quick color change by simply replacing the dye salt in the aftertreatment.
  • Vat dyes in the oxidized form e.g. indanthrene, indigo, thioindigo
  • dioxazines e.g. quinacridones
  • blue phthalocyanines were NMMO-insoluble.
  • Dye yield and color properties can be influenced by adjusting the conditions in the air gap.
  • Copper-containing metal complex pigments such.
  • Color strengths and brilliance reduce the thermal activity of the cellulose solution if they are added to the cellulose suspension before the production of the cellulose solution.

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)

Abstract

L'invention concerne un procédé permettant de produire des corps moulés cellulosiques, notamment des fibres, à partir de solutions de cellulose dans un oxyde d'amine tertiaire aqueux, par préparation de la solution à partir d'une suspension cellulosique dans l'oxyde d'amine tertiaire aqueux, extrusion de la solution par un outil de moulage, acheminement de la solution moulée par l'intermédiaire d'un entrefer dans un bain de précipitation et lavage et séchage du corps moulé obtenu. L'invention se caractérise en ce qu'un colorant et/ou un précurseur de colorant sont ajoutés à la solution et/ou à la suspension cellulosique. Plus de 95 % en poids dudit colorant ou précurseur de colorant, par rapport au colorant ou au précurseur de colorant utilisé initialement, sont insolubles dans la solution cellulosique.
PCT/AT1999/000062 1998-03-12 1999-03-10 Procede pour produire des corps moules cellulosiques WO1999046434A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU28181/99A AU2818199A (en) 1998-03-12 1999-03-10 Method for producing cellulosic moulded bodies

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT15598U AT2207U1 (de) 1998-03-12 1998-03-12 Verfahren zur herstellung cellulosischer formkörper
ATGM155/98 1998-03-12

Publications (1)

Publication Number Publication Date
WO1999046434A1 true WO1999046434A1 (fr) 1999-09-16

Family

ID=3483011

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT1999/000062 WO1999046434A1 (fr) 1998-03-12 1999-03-10 Procede pour produire des corps moules cellulosiques

Country Status (3)

Country Link
AT (1) AT2207U1 (fr)
AU (1) AU2818199A (fr)
WO (1) WO1999046434A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007070904A1 (fr) * 2005-12-19 2007-06-28 Lenzing Aktiengesellschaft Procede de fabrication d’un corps moule cellulosique colore
WO2012116384A1 (fr) * 2011-03-01 2012-09-07 Lenzing Ag Tissus lavables par blanchissage industriel et résistant au rétrécissement en fibres en viscose, en lyocell ou en modal contenant des additifs particulaires
WO2021199058A1 (fr) * 2020-03-31 2021-10-07 Aditya Birla Science and Technology Company Private Limited Procédé de préparation de fibre lyocell teintée par dopage

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT407997B (de) 1999-08-10 2001-07-25 Chemiefaser Lenzing Ag Gefärbte cellulosische formkörper

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB211446A (en) * 1923-02-16 1925-03-26 Cellophane Sa Improved manufacture of cellulose films, threads, tubes or the like
GB395864A (en) * 1932-06-21 1933-07-27 Kenneth Stewart Low The production of multi-coloured artificial cellulosic materials in the form of sheets, bands or films
US3053678A (en) * 1960-03-23 1962-09-11 Cassella Farbwerke Mainkur Ag Spundyed regenerated cellulose products
DE1224869B (de) * 1963-07-16 1966-09-15 Phrix Werke Ag Herstellen von Faeden aus Viskose
DE1245032B (de) * 1963-05-11 1967-07-20 Hoechst Ag Verfahren zur Herstellung gefaerbter Gebilde
DE1806199A1 (de) * 1967-11-10 1971-04-29 Ciba Geigy Ag Verfahren zur Herstellung transparent gefaerbter Formkoerper auf Basis regenerierter Cellulose mit organischen schwerloeslichen Farbstoffen
DE19519024A1 (de) * 1995-05-24 1996-11-28 Hoechst Ag Verfahren zur Spinnfärbung mit Farbsalzen
WO1997023552A1 (fr) * 1995-12-22 1997-07-03 Lenzing Aktiengesellschaft Eponge en cellulose et son procede de production

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3752646A (en) * 1971-07-30 1973-08-14 Du Pont Water swollen cellulose and blends dyed with insoluble, non-vattable anthraquinone dyed in a glycol ether solution
US4416698A (en) * 1977-07-26 1983-11-22 Akzona Incorporated Shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent and a process for making the article
USH1592H (en) * 1992-01-17 1996-09-03 Viskase Corporation Cellulosic food casing

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB211446A (en) * 1923-02-16 1925-03-26 Cellophane Sa Improved manufacture of cellulose films, threads, tubes or the like
GB395864A (en) * 1932-06-21 1933-07-27 Kenneth Stewart Low The production of multi-coloured artificial cellulosic materials in the form of sheets, bands or films
US3053678A (en) * 1960-03-23 1962-09-11 Cassella Farbwerke Mainkur Ag Spundyed regenerated cellulose products
DE1245032B (de) * 1963-05-11 1967-07-20 Hoechst Ag Verfahren zur Herstellung gefaerbter Gebilde
DE1224869B (de) * 1963-07-16 1966-09-15 Phrix Werke Ag Herstellen von Faeden aus Viskose
DE1806199A1 (de) * 1967-11-10 1971-04-29 Ciba Geigy Ag Verfahren zur Herstellung transparent gefaerbter Formkoerper auf Basis regenerierter Cellulose mit organischen schwerloeslichen Farbstoffen
DE19519024A1 (de) * 1995-05-24 1996-11-28 Hoechst Ag Verfahren zur Spinnfärbung mit Farbsalzen
WO1996037643A1 (fr) * 1995-05-24 1996-11-28 Dystar Textilfarben Gmbh & Co. Deutschland Kg Procede de coloration dans la masse avec des sels colorants
WO1997023552A1 (fr) * 1995-12-22 1997-07-03 Lenzing Aktiengesellschaft Eponge en cellulose et son procede de production

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007070904A1 (fr) * 2005-12-19 2007-06-28 Lenzing Aktiengesellschaft Procede de fabrication d’un corps moule cellulosique colore
WO2012116384A1 (fr) * 2011-03-01 2012-09-07 Lenzing Ag Tissus lavables par blanchissage industriel et résistant au rétrécissement en fibres en viscose, en lyocell ou en modal contenant des additifs particulaires
WO2021199058A1 (fr) * 2020-03-31 2021-10-07 Aditya Birla Science and Technology Company Private Limited Procédé de préparation de fibre lyocell teintée par dopage

Also Published As

Publication number Publication date
AU2818199A (en) 1999-09-27
AT2207U1 (de) 1998-06-25

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