EP0779942B1 - Procede de fabrication de fibres de cellulose - Google Patents

Procede de fabrication de fibres de cellulose Download PDF

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Publication number
EP0779942B1
EP0779942B1 EP95931179A EP95931179A EP0779942B1 EP 0779942 B1 EP0779942 B1 EP 0779942B1 EP 95931179 A EP95931179 A EP 95931179A EP 95931179 A EP95931179 A EP 95931179A EP 0779942 B1 EP0779942 B1 EP 0779942B1
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EP
European Patent Office
Prior art keywords
polyisocyanates
diisocyanate
groups
compounds
nco
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
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EP95931179A
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German (de)
English (en)
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EP0779942A1 (fr
Inventor
Wolfgang Schrott
Wolfram Badura
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BASF SE
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BASF SE
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Priority to EP99123391A priority Critical patent/EP0985747B1/fr
Priority to EP99123392A priority patent/EP0984084B1/fr
Publication of EP0779942A1 publication Critical patent/EP0779942A1/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
    • 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
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/395—Isocyanates
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/419—Amides having nitrogen atoms of amide groups substituted by hydroxyalkyl or by etherified or esterified hydroxyalkyl groups
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance

Definitions

  • the present invention relates to a new method of manufacture of cellulose fibers spun from solvents reduced tendency to fibrillate by treating the fibers with certain reactive compounds.
  • GB-A-2 043 525 describes the production of cellulose fibers by spinning a cellulose solution in a suitable solvent, e.g. an N-oxide of a tertiary amine, such as N-methylmorpholine-N-oxide, known. In such a spinning process the Cellulose solution extruded through a suitable nozzle and the resulting fiber precursor washed in water and then dried. Such fibers are called “solvent spun Fibers ".
  • Such cellulose fibers spun from solvents offer many application advantages, but tend to fibrillate. This is the splicing of the finest fiber fibrils, the processing of cellulose fibers in textile production can lead to problems.
  • WO-A-92/07124 recommends the to solve this problem Treatment of the cellulose fibers with an aqueous solution or Dispersion of a polymer that has a variety of cationically ionizable Groups, e.g. a polyvinylimidazoline.
  • EP-A-538 977 teaches the use of compounds which have 2 to 6 functional groups with cellulose can react, e.g. Products based on dichlorotriazine, for this purpose.
  • the object of the present invention was to develop a new method for the production of cellulose fibers spun from solvents with reduced tendency to fibrillate, that comes from other chemical defibrillation reagents.
  • hydrophilically modified polyisocyanates are usually in the form of aqueous dispersions, which are essentially free of organic solvents and other emulsifiers are used in the method according to the invention.
  • Polyisocyanates serve the usual diisocyanates and / or usual higher functional polyisocyanates with a medium NCO functionality from 2.0 to 4.5. These components can alone or in a mixture.
  • Examples of common diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), Octamethylene diisocyanate, decamethylene diisocyanate, Dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic Diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (Isophorone diisocyanate) or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and aromatic di
  • Suitable, higher-functionality polyisocyanates are Triisocyanates such as 2,4,6-triisocyanatotoluene or 2,4,4'-triisocyanatodiphenyl ether or the mixtures of di-, Tri and higher polyisocyanates by phosgenation of corresponding aniline / formaldehyde condensates are obtained and Represent polyphenyl polyisocyanates having methylene bridges.
  • aliphatic diisocyanates are used and aliphatic, higher functional polyisocyanates in particular prefers.
  • the described diisocyanates and / or more functionalized Polyisocyanates become non-ionic hydrophilic for conversion modified polyisocyanates for use in the invention are particularly preferred with NCO-reactive compounds implemented the hydrophilic structural elements with nonionic Groups or with polar groups that are not in ion groups can be transferred. That’s it Diisocyanate or polyisocyanate in a stoichiometric excess before so the resulting hydrophilically modified polyisocyanate still has free NCO groups.
  • non-ionically hydrophilically modified polyisocyanates which contain the polyether VII built in therefore also a preferred embodiment.
  • ethylene oxide or propylene oxide polyethers started on C 1 to C 4 alkanol with average molecular weights of 250 to 7000, in particular 450 to 1500.
  • hydroxyl-terminated polyesters other hydroxyl-terminated polyethers or on polyols, e.g. Ethylene glycol, trimethylolpropane or butanediol
  • prepolymers generate and then these prepolymers or simultaneously with the polyethers VII in deficit to the hydrophilic implement modified polyisocyanates with free NCO groups.
  • non-ionically hydrophilically modified polyisocyanates from diisocyanate or polyisocyanate and polyalkylene glycols of the formula HO- (DO) n -H, in which D and n have the meanings given above. Both terminal OH groups of the polyalkylene glycol react with isocyanate.
  • non-ionic hydrophilic modified Polyisocyanates are described in DE-A 24 47 135, DE-A 26 10 552, DE-A 29 08 844, EP-A 0 13 112, EP-A 019 844, DE-A 40 36 927, DE-A 41 36 618, EP-B 206 059, EP-A 464 781 and EP-A 516 361 described in more detail.
  • the described diisocyanates and / or more functionalized Polyisocyanates become anionically hydrophilic for conversion modified polyisocyanates reacted with NCO-reactive compounds, the hydrophilizing anionic groups, in particular Acid groups such as carboxyl groups, sulfonic acid groups or Phosphonic acid groups.
  • the diisocyanate or Polyisocyanate in a stoichiometric excess, so that resulting hydrophilically modified polyisocyanate is still free Has NCO groups.
  • NCO-reactive compounds with anionic groups come especially hydroxycarboxylic acids like 2-hydroxyacetic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid or hydroxylpivalic acid and 2,2-bis- and 2,2,2-tris (hydroxymethyl) alkanoic acids, e.g. 2,2-bis (hydroxymethyl) acetic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid or 2,2,2-tris (hydroxymethyl) acetic acid.
  • the carboxyl groups can be partially or completely by a base be neutralized to in a water soluble or water dispersible Form.
  • the base is preferred here a tertiary amine, which is known to Isocyanate is inert.
  • the described diisocyanates and / or more functionalized Polyisocyanates can also be mixed with a non-ionic hydrophilically modifying and anionically hydrophobically modifying Compounds that are added sequentially or simultaneously are implemented, for example with a deficit the polyethers VII and the hydroxycarboxylic acids described.
  • anionically hydrophilically modified polyisocyanates are in the documents DE-A 40 01 783, DE-A 41 13 160 and DE-A 41 42 275 described in more detail.
  • the described diisocyanates and / or more functionalized Polyisocyanates become cationically hydrophilic for conversion modified polyisocyanates reacted with NCO-reactive compounds, the chemically built-in alkylatable or protonable Functions with the formation of a cationic center included.
  • such functions are tertiary nitrogen atoms, which are known to be inert to isocyanate and can be easily quaternized or protonated.
  • amino alcohols VIII are N-methyldiethanolamine, N-methyldi (iso) propanolamine, N-butyldiethanolamine, N-butyldi (iso) propanolamine, N-stearyldiethanolamine, N-stearyldi (iso) propanolamine, N, N-dimethylethanolamine, N, N-dimethyl (iso) propanolamine, N, N-diethylethanolamine, N, N-diethyl (iso) propanolamine, N, N-dibutylethanolamine, N, N-dibutyl (iso) propanolamine, triethanolamine, tri (iso) propanolamine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N- (2-hydroxyethyl) piperidine, N- (2-hydroxypropyl) piperidine, N-methyl-N '- (2-hydroxye
  • NCO-reactive compounds with tertiary nitrogen atoms are preferably diamines of the general formula IXa or IXb in which R 9 to R 11 have the abovementioned meanings and R 12 denotes C 1 to C 5 alkyl or forms a five- or six-membered ring, in particular a piperazine ring, with R 9 .
  • diamines IXa are N, N-dimethylethylenediamine, N, N-diethyl-ethylenediamine, N, N-dimethyl-1,3-diamino-2,2-dimethylpropane, N, N-diethyl-1,3-propylenediamine, N- (3-aminopropyl) morpholine, N- (2-aminopropyl) morpholine, N- (3-aminopropyl) piperidine, N- (2-aminopropyl) piperidine, 4-amino-1- (N, N-diethylamino) pentane, 2-amino-1- (N, N-dimethylamino) propane, 2-amino-1- (N, N-diethylamino) propane or 2-amino-1- (N, N-diethylamino) -2-methylpropane.
  • Particularly suitable diamines IXb are N, N, N'-trimethyl-ethylenediamine, N, N, N'-triethylethylenediamine, N-methylpiperazine or N-ethylpiperazine.
  • polyether (poly) oles can also be used as NCO-reactive compounds with built-in tertiary nitrogen atoms, the by propoxylation and / or ethoxylation of amine nitrogen having starter molecules can be used become.
  • Such polyether (poly) ole are, for example Propoxylation and ethoxylation products of ammonia, Ethanolamine, diethanolamine, ethylenediamine or N-methylaniline.
  • NCO-reactive compounds are tertiary nitrogen atoms containing polyester and polyamide resins, tertiary Polyols containing urethane groups and nitrogen atoms Polyhydroxypolyacrylates containing tertiary nitrogen atoms.
  • the described diisocyanates and / or more functionalized Polyisocyanates can also be mixed with a non-ionic hydrophilically modifying and cationically hydrophilically modifying Compounds that are added sequentially or simultaneously are implemented, for example with a deficit the polyethers VII and the amino alcohols VIII or the diamines IXa or IXb. Mixtures of non-ionic hydrophilic modifying and anionically hydrophilically modifying Connections are possible.
  • hydrophilically modified polyisocyanates mentioned in usually used in aqueous media is sufficient for To ensure dispersibility of the polyisocyanates.
  • the good results achieved with the hydrophilically modified Polyisocyanates in aqueous media are all the more surprising since it was to be expected that isocyanates would rapidly dissolve in an aqueous environment decompose. Nevertheless, the polyisocyanates used according to the invention have a pot life of several in the aqueous liquor Hours on, i.e. the present polyisocyanate dispersions are stable within the usual processing time. From one Dispersion is said to be stable when its components remain dispersed in each other without being discrete Separate layers.
  • pot life means the time during which the dispersions remain processable before they jell and set. Gel aqueous isocyanate dispersions and set because of a reaction between the water and the Isocyanate takes place, forming a polyurea.
  • the compounds can be used in the process according to the invention for the production of cellulose fibers generally in an aqueous System, preferably in aqueous solution or emulsion, for Application, the aqueous system in general, based on the weight of the aqueous system, 0.1 to 20% by weight, preferably 0.5 to 10 wt .-%, which has compounds.
  • the preferred solvent in stage 1 is N-methylmorpholine-N-oxide used.
  • the wet fiber obtained in Step 3 is called undried Fiber is usually referred to and referred to the dry weight of the fiber, 120 to 150 wt .-% water.
  • the water content of the dried fiber is generally based on the dry weight of the fiber, 60 to 80 wt .-%.
  • the treatment according to the invention with the compounds can either on the wet fiber (during or after level 3) or on the dried fiber (after step 4). It is but also a treatment in the fiber production stage (Level 2), e.g. in a precipitation bath, possible.
  • the treatment can for example by adding the aqueous system of the compounds happen to a circulating bath that is the fiber precursor contains.
  • the fiber precursor can e.g. as staple fiber available.
  • the treatment is done on the dried fiber, it can these e.g. as staple fiber, fleece, yarn, knitwear or fabric available.
  • the treatment of the fibers in this case can e.g. in aqueous liquor.
  • Treatment is usually at a temperature of 20 to 200 ° C, preferably 40 to 180 ° C, made.
  • the duration of treatment is usually 1 second to 20 minutes, preferably 5 to 60 seconds and in particular 5 to 30 seconds.
  • the treatment can be done both at room temperature (20 ° C) with subsequent drying up to 100 ° C as well Condensation at temperatures up to 200 ° C, in particular at 150 to 180 ° C.
  • the treatment of the moist or dried fiber can be 0.1 up to 10% by weight, preferably 0.2 to 5% by weight, in particular 0.2 up to 2% by weight, based in each case on the dry weight of the fiber, of connections. In some cases it can however, it may also be advantageous to increase the amounts mentioned, e.g. up to approx. 20% by weight.
  • connections can be made the compounds described in EP-A-538 977 pure can be fixed thermally (without alkali), making them optimal have it integrated into the fiber production process.
  • the dyeability the fibers treated in this way with all the usual cellulose fiber dyes, reactive dyes are generally also possible.

Claims (4)

  1. Procédé de fabrication de fibres de cellulose filées à partir de solvants et présentant une tendance à la fibrillation abaissée, caractérisé en ce que l'on traite les fibres avec un ou plusieurs composés choisis dans le groupe des polyisocyanates hydrophiles modifiés.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise en tant que composés, des polyisocyanates modifiés hydrophiles non ioniques comprenant des polyéthers à terminaison hydroxyle de formule générale VII R8-E-(DO)n-H dans laquelle
    R8
    représente un groupement alkyle en C1-C20, ou alcényle en C2-C20, cyclopentyle, cyclohexyle, glycidyle, oxéthyle, phényle, tolyle, benzyle, furfuryle ou tétrahydrofurfuryle,
    E
    représente du soufre ou de l'oxygène,
    D
    représente un groupement propylène ou éthylène et
    n
    est mis pour un nombre de 5 à 120.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on traite les fibres avec 0,1 à 10% en poids des composés, par rapport au poids sec des fibres.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'on effectue le traitement à une température de 20 à 200°C.
EP95931179A 1994-09-06 1995-08-22 Procede de fabrication de fibres de cellulose Expired - Lifetime EP0779942B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP99123391A EP0985747B1 (fr) 1994-09-06 1995-08-22 Procédé de fabrication de fibres de cellulose
EP99123392A EP0984084B1 (fr) 1994-09-06 1995-08-22 Procédé de fabrication de fibres de cellulose

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4431635A DE4431635A1 (de) 1994-09-06 1994-09-06 Verfahren zur Herstellung von Cellulosefasern
DE4431635 1994-09-06
PCT/EP1995/003327 WO1996007780A1 (fr) 1994-09-06 1995-08-22 Procede de fabrication de fibres de cellulose

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP99123391A Division EP0985747B1 (fr) 1994-09-06 1995-08-22 Procédé de fabrication de fibres de cellulose
EP99123392A Division EP0984084B1 (fr) 1994-09-06 1995-08-22 Procédé de fabrication de fibres de cellulose

Publications (2)

Publication Number Publication Date
EP0779942A1 EP0779942A1 (fr) 1997-06-25
EP0779942B1 true EP0779942B1 (fr) 2000-06-21

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Application Number Title Priority Date Filing Date
EP99123392A Expired - Lifetime EP0984084B1 (fr) 1994-09-06 1995-08-22 Procédé de fabrication de fibres de cellulose
EP99123391A Expired - Lifetime EP0985747B1 (fr) 1994-09-06 1995-08-22 Procédé de fabrication de fibres de cellulose
EP95931179A Expired - Lifetime EP0779942B1 (fr) 1994-09-06 1995-08-22 Procede de fabrication de fibres de cellulose

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EP99123392A Expired - Lifetime EP0984084B1 (fr) 1994-09-06 1995-08-22 Procédé de fabrication de fibres de cellulose
EP99123391A Expired - Lifetime EP0985747B1 (fr) 1994-09-06 1995-08-22 Procédé de fabrication de fibres de cellulose

Country Status (8)

Country Link
US (1) US5776394A (fr)
EP (3) EP0984084B1 (fr)
JP (1) JPH10505389A (fr)
AT (3) ATE194018T1 (fr)
DE (4) DE4431635A1 (fr)
DK (1) DK0779942T3 (fr)
ES (2) ES2148552T3 (fr)
WO (1) WO1996007780A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276732B (zh) 2003-11-28 2016-01-20 伊士曼化工公司 纤维素共聚体和氧化方法
US9410292B2 (en) 2012-12-26 2016-08-09 Kimberly-Clark Worldwide, Inc. Multilayered tissue having reduced hydrogen bonding
US9416494B2 (en) 2012-12-26 2016-08-16 Kimberly-Clark Worldwide, Inc. Modified cellulosic fibers having reduced hydrogen bonding
US8980054B2 (en) * 2012-12-26 2015-03-17 Kimberly-Clark Worldwide, Inc. Soft tissue having reduced hydrogen bonding
KR102440861B1 (ko) * 2020-05-26 2022-09-05 오영세 라이오셀 섬유의 제조방법 및 이로부터 제조된 라이오셀 섬유

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0516361A1 (fr) * 1991-05-29 1992-12-02 Imperial Chemical Industries Plc Composition de polyisocyanate
EP0531820A1 (fr) * 1991-09-10 1993-03-17 Bayer Ag Mélanges de polyisocyanate, procédé de leur préparation et leur utilisation
EP0538977A1 (fr) * 1991-10-21 1993-04-28 Courtaulds Plc Traitement de fibre
DE4142275A1 (de) * 1991-12-20 1993-06-24 Bayer Ag Isocyanatocarbonsaeuren, ein verfahren zu ihrer herstellung und ihrer verwendung

Family Cites Families (8)

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WO1996007780A1 (fr) 1996-03-14
EP0779942A1 (fr) 1997-06-25
EP0985747A3 (fr) 2000-04-19
DE59508498D1 (de) 2000-07-27
DE59510440D1 (de) 2002-12-05
EP0984084A2 (fr) 2000-03-08
ATE226985T1 (de) 2002-11-15
US5776394A (en) 1998-07-07
JPH10505389A (ja) 1998-05-26
EP0985747A2 (fr) 2000-03-15
DE4431635A1 (de) 1996-03-07
EP0984084B1 (fr) 2003-01-02
ATE194018T1 (de) 2000-07-15
ES2148552T3 (es) 2000-10-16
ATE230447T1 (de) 2003-01-15
DK0779942T3 (da) 2000-08-28
ES2190169T3 (es) 2003-07-16
EP0984084A3 (fr) 2000-04-19
DE59510523D1 (de) 2003-02-06
EP0985747B1 (fr) 2002-10-30

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