EP0783602B1 - Cellulosefaser - Google Patents

Cellulosefaser Download PDF

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Publication number
EP0783602B1
EP0783602B1 EP96926961A EP96926961A EP0783602B1 EP 0783602 B1 EP0783602 B1 EP 0783602B1 EP 96926961 A EP96926961 A EP 96926961A EP 96926961 A EP96926961 A EP 96926961A EP 0783602 B1 EP0783602 B1 EP 0783602B1
Authority
EP
European Patent Office
Prior art keywords
fibres
crosslinking agent
base
amine oxide
sulphonium
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
EP96926961A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0783602A1 (de
Inventor
Sigrid Seidl
Heinrich Firgo
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
Publication of EP0783602A1 publication Critical patent/EP0783602A1/de
Application granted granted Critical
Publication of EP0783602B1 publication Critical patent/EP0783602B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/272—Unsaturated compounds containing sulfur atoms
    • D06M13/278—Vinylsulfonium compounds; Vinylsulfone or vinylsulfoxide compounds

Definitions

  • the present invention relates to a new cellulose fiber and a process for producing this cellulose fiber.
  • Lyocell fibers A characteristic of Lyocell fibers is theirs pronounced tendency to fibrillate when wet. Under Fibrillation is breaking the wet fiber in Longitudinal direction with mechanical stress when wet understood, which gives the fiber a hairy, furry look receives. The reason for the fibrillation is believed to be the fiber consists of fibrils arranged in the direction of the fibers, only a small amount of cross-linking between them is available.
  • WO 92/14871 describes a method for producing a Fiber with reduced tendency to fibrillation. This is achieved by adding all the baths that hold the freshly spun fiber in front after the first drying, a pH of have a maximum of 8.5.
  • WO 92/07124 also describes a method for Production of a fiber with reduced tendency to fibrillation, according to which the freshly spun, i.e. not yet dried Fiber is treated with a cationizable polymer.
  • a cationizable polymer becomes a polymer with imidazole and Called azetidine groups.
  • Lyocell fibers can be improved by chemical crosslinking can.
  • EP-A-0 538 977 crosslinking of Lyocell fibers with chemical reagents using Cellulose can react, both never dried state, i.e. during fiber production, as well in the dried state, i.e. essentially during the textile finishing of the textile fabrics.
  • cross-linking reagents have as crosslinkable groups substituted with halogen, nitrogen-containing ring structures that are capable of alkaline conditions with the hydroxyl groups of cellulose to react. There are also compounds with vinyl sulfone groups or their predecessors. These connections too essentially only react with the addition of alkali or need alkali as neutralizing reagent for split off Acids.
  • a disadvantage is that in the reaction of the halogenated rings containing nitrogen or vinyl sulfones or their precursors form salts which then have to be washed out of the fiber, also have excess and not with the Washed out residual chemicals from cellulose fiber will. This means that in a continuous Another fiber manufacturing process Post-treatment step is necessary, the further one Investment and operating costs caused and additionally problems with polluted wastewater brings.
  • WO 94/20656 describes that the fibrillation of Lyocell fibers through networking with conventional ones Crosslinking chemicals that are commonly used to improve Crease angles used by cellulose textiles is reduced without the dyeability of the Fibers decrease when you crosslink at the same time Presence of flexible, linear polymers. in the conventional N-methylol resins become essential (Low formaldehyde) and the usual acidic catalysts used. The method is used both on the dried as well as on the never dried fiber described leading to success.
  • the crosslinker can with the Alkali applied from a bath and then one for crosslinking Treatment can be carried out at high temperature. Furthermore can be between treatment with crosslinker and treatment an intermediate drying can be carried out with alkali. As alkaline compounds become alkali metal hydroxides, Alkali metal carbonates and bicarbonates, and quaternary Ammonium bases, such as trimethylammonium hydroxide, are used. As Response times are 10 minutes at room temperature or shorter dwell times at higher temperatures, e.g. 3 minutes at 150 ° C. After the reaction has taken place The substrate can be washed free of alkali.
  • alkaline compounds such as e.g. Alkali metal bicarbonates
  • quaternary Ammonium bases such as trimethylammonium hydroxide
  • the present invention thus aims to Processes for making Lyocell fibers are available too with which fibers can be made, the have a predetermined tendency to fibrillate.
  • the process according to the invention for the production of cellulose fibers by the amine oxide process in which process a solution of cellulose in an aqueous tertiary amine oxide is spun into fibers and the fibers are brought into contact with a crosslinking agent, is characterized in that a sulfonium compound of the formula (I ) wherein R 1 is CH 2 CH 2 Z, alkyl, in particular C 1 -C 4 alkyl, aryl, substituted alkyl or a heterocycle, Z is halogen, sulfato, thiosulfato, phosphato or hydroxy, and Y - is an anion, and / or a sulfonium compound of the formula (II) in which OW is the residue of a polybasic acid in salt or acid form, and R 2 is CH 2 CH 2 OW, alkyl, in particular C 1 -C 4 alkyl, aryl, substituted alkyl or a heterocycle, is used.
  • Sulfonium compound of formula (II) an inner salt of Dialkali-tris- ( ⁇ -sulfatoethyl) sulfoniums, especially that inner salt of disodium tris ( ⁇ -sulfatoethyl) sulfonium, used.
  • the fibers can both never dried, as well as dried be brought into contact with the crosslinking agent, whereby it however, it is preferred that the fibers are never dried, e.g. e.g. freshly spun with the crosslinking agent in To get in touch.
  • the fibers are preferably treated with a base after being contacted with the crosslinking agent with the fibers before treatment with the base can be dried.
  • a particularly advantageous embodiment of the inventive method is that the fibers with a base treated and simultaneously with the Crosslinking agents are brought into contact, base and Crosslinking agents in a molar ratio of essentially 3: 1 (base: crosslinking agent). Then be the fibers dried. It has been shown that this Embodiment of the method according to the invention no washing of fibers is required. This is advantageous in that saved as one step in the manufacturing process can be.
  • aqueous solution Brought in contact which trisSS in a concentration of 0.3 to 25% by mass, preferably 0.5 to 5% by mass.
  • the Base is in 0.8 to 100 molar, preferably in 2.5 to 3.5 molar amount, based on trisSS, in the aqueous solution contain.
  • alkali metal hydroxides, Alkali metal carbonates and bicarbonates, quaternary Ammonium bases and polymeric amines are used.
  • buffer solutions with a pH in the range from 5 to 12, preferably from 7 to 9 can be.
  • Washing is not necessary even if one is used as the base potentially alkaline compound, e.g. a bicarbonate, is used.
  • the base potentially alkaline compound e.g. a bicarbonate
  • the invention also relates to cellulose fibers with predetermined Fibrillation tendency according to the inventive method are available.
  • the invention further relates to the use of a sulfonium compound of the formula (I) wherein R 1 , Z and Y - have the meaning given above, and / or a sulfonium compound of the formula (II) wherein OW and R 2 have the meaning given in claim 1, for treating fibers made by the amine oxide process and yarns and fabrics made from fibers made by the amine oxide process.
  • the invention also relates to the use of an inner Salt of the dialkali tris ( ⁇ -sulfatoethyl) sulfonium Treatment of fibers by the amine oxide process were made, and of yarns and woven fabrics made of fibers were produced by the amine oxide process.
  • an aqueous solution which is a base and an inner salt of the Dialkali-Tris ( ⁇ -sulfatoethyl) sulfoniums contains, with base and crosslinking agents in a molar ratio of im essential 3: 1 (base: crosslinking agent) are present.
  • the freshly spun, never dried fiber strand or the Never dried flakes of fiber can first be dissolved with trisSS impregnated and after squeezing onto one Moisture content from 100 to 150% with the base solution be impregnated, the order of treatment also can be reversed. After a dwell time of approximately 10 Minutes at room temperature can be washed and dried will.
  • the method according to the invention can have one stage be carried out, the fiber simultaneously with the Solution of trisSS and small amounts of base in one One-step procedure is dealt with.
  • alkaline compounds such as alkali metal bicarbonates, can be used, but also alkali in accordingly low concentration can be used.
  • the one-step process there is then one Heat treatment of the impregnated fiber required.
  • the Temperature treatment can be done by drying at temperatures of at least 60 ° C can be reached. If the molar ratio of Base to triSS is not greater than 3: 1 is a subsequent one Washing is not necessary.
  • sulfonium compounds can be alkaline Dye bath can be added.
  • the invention is illustrated in more detail with the following examples explained.
  • the trisSS is manufactured in Belgian Patent Applications No. 627 204 and No. 620 775.
  • a conventional cellulose fiber of the Lyocell genus has after this test about 50 fibrils on 0.276 mm fiber length on.
  • Flake Lyocell fibers were 100 at room temperature ml of an aqueous solution of trisSS impregnated for 3 minutes squeezed a water content of 140% and then 10 minutes at room temperature in 100 ml of an aqueous sodium hydroxide solution impregnated. Then the fibers were 3% Acetic acid and water washed free of alkali and over at 60 ° C Dried overnight.
  • Flake Lyocell fibers 1 g freshly spun and not yet dried Flake Lyocell fibers were 100 at room temperature ml of an aqueous solution of trisSS impregnated for 3 minutes, 2 Dried at 60 ° C for hours and then at 10 minutes Room temperature in 100 ml of an aqueous sodium hydroxide solution impregnated. Then the fibers were 3% Acetic acid and water washed free of alkali and over at 60 ° C Dried overnight.
  • Table 1 shows the trisSS concentrations in g / l.
  • the concentration of the sodium hydroxide solution is given in g NaOH / 1.
  • Examples 5 to 8 show that with increasing Concentration of sodium hydroxide the number of fibrils decreases produced fiber is less fibrillated. In the use of trisSS according to the invention is therefore possible the fibrillation tendency of the Control Lyocell fiber. When using high amounts of alkali it is of course necessary to wash the fibers free of alkali.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials For Medical Uses (AREA)
  • Artificial Filaments (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
EP96926961A 1995-08-18 1996-08-16 Cellulosefaser Expired - Lifetime EP0783602B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT0140295A AT402642B (de) 1995-08-18 1995-08-18 Cellulosefaser cellulosefaser
AT14029/59 1995-08-18
PCT/AT1996/000147 WO1997007267A1 (de) 1995-08-18 1996-08-16 Cellulosefaser

Publications (2)

Publication Number Publication Date
EP0783602A1 EP0783602A1 (de) 1997-07-16
EP0783602B1 true EP0783602B1 (de) 1998-01-28

Family

ID=3513120

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96926961A Expired - Lifetime EP0783602B1 (de) 1995-08-18 1996-08-16 Cellulosefaser

Country Status (10)

Country Link
EP (1) EP0783602B1 (ja)
JP (1) JPH10507497A (ja)
CN (1) CN1165544A (ja)
AT (2) AT402642B (ja)
AU (1) AU712681B2 (ja)
BR (1) BR9606586A (ja)
CA (1) CA2202141A1 (ja)
DE (1) DE59600086D1 (ja)
NO (1) NO971754D0 (ja)
WO (1) WO1997007267A1 (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10043297B4 (de) * 2000-09-02 2005-12-08 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Verfahren zur Herstellung von Cellulosefasern und Cellulosefilamentgarnen

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3446686B2 (ja) 1999-10-21 2003-09-16 セイコーエプソン株式会社 インクジェット式記録装置
AT507051B1 (de) * 2008-06-27 2015-05-15 Chemiefaser Lenzing Ag Cellulosefaser und verfahren zu ihrer herstellung

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1186440B (de) * 1963-08-27 1965-02-04 Basf Ag Verfahren zum Veredeln von Textilien
DE1469249A1 (de) * 1964-05-09 1969-02-27 Basf Ag Praeparieren,Avivieren und antistatisches Ausruesten von Textilgut
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
US4246221A (en) * 1979-03-02 1981-01-20 Akzona Incorporated Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent
AT403296B (de) * 1995-08-11 1997-12-29 Chemiefaser Lenzing Ag Verfahren zur herstellung eines celluloseformkörpers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10043297B4 (de) * 2000-09-02 2005-12-08 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Verfahren zur Herstellung von Cellulosefasern und Cellulosefilamentgarnen

Also Published As

Publication number Publication date
EP0783602A1 (de) 1997-07-16
CA2202141A1 (en) 1997-02-27
ATE162858T1 (de) 1998-02-15
AU6695596A (en) 1997-03-12
DE59600086D1 (de) 1998-03-05
AT402642B (de) 1997-07-25
ATA140295A (de) 1996-11-15
CN1165544A (zh) 1997-11-19
AU712681B2 (en) 1999-11-11
JPH10507497A (ja) 1998-07-21
NO971754L (no) 1997-04-17
WO1997007267A1 (de) 1997-02-27
NO971754D0 (no) 1997-04-17
BR9606586A (pt) 1997-10-28

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