EP0985747B1 - Process for manufacturing cellulosic fibres - Google Patents

Process for manufacturing cellulosic fibres Download PDF

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Publication number
EP0985747B1
EP0985747B1 EP99123391A EP99123391A EP0985747B1 EP 0985747 B1 EP0985747 B1 EP 0985747B1 EP 99123391 A EP99123391 A EP 99123391A EP 99123391 A EP99123391 A EP 99123391A EP 0985747 B1 EP0985747 B1 EP 0985747B1
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EP
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Prior art keywords
groups
polyisocyanates
compounds
diisocyanate
acid
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EP99123391A
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German (de)
French (fr)
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EP0985747A2 (en
EP0985747A3 (en
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Wolfgang Dr. Schrott
Wolfram Badura
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BASF SE
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BASF SE
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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 (C) are usually in the form of aqueous dispersions, which are essentially free of organic solvents and other emulsifiers are used. Your stake is not an object of the present invention.
  • Polyisocyanates serve the usual dizsocyanates 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.
  • the described diisocyanates and / or more functionalized Polyisocyanates become non-ionic hydrophilic for conversion modified polyisocyanates 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 built-in polyethers VII are particularly preferably ethylene oxide or propylene oxide polyethers with average molecular weights of 250 to 7000, in particular 450 to 1500, started on C 1 to C 4 alkanol.
  • 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 meanings given above 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 (C) mentioned in usually used in aqueous media is sufficient for To ensure dispersibility of the polyisocyanates.
  • the mixtures of polyurethanes and isocyanates (D) are like the compounds (C) usually in the form of aqueous Dispersions that are essentially free of organic solvents and in most cases are free of emulsifiers, used in the method according to the invention.
  • Polyurethanes are made from polyisocyanates (hereinafter also Called monomers I) and reactive towards polyisocyanates Compounds with at least one hydroxyl group and optionally Connections with at least one primary or secondary Understanding amino group built systems.
  • the polyurethanes generally no longer have any free isocyanate groups.
  • polyurethanes contained serve the usual diisocyanates and / or usual higher functional polyisocyanates such as those in the hydrophilic modified polyisocyanates (C) are described. Also here aliphatic diisocyanates and aliphatic become higher functional polyisocyanates preferred.
  • the other structural components of the polyurethane are concerned are initially polyols with a molecular weight of 400 to 6000 g / mol, preferably 600 to 4000 g / mol (monomers II).
  • Polyether polyols or polyester polyols are particularly suitable.
  • the polyester diols are in particular the known reaction products of dihydric alcohols with dibasic carboxylic acids.
  • the free polycarboxylic acids can also the corresponding polycarboxylic anhydrides or corresponding Polycarboxylic esters of lower alcohols or their Mixtures can be used to produce the polyester polyols.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic or be heterocyclic and optionally, e.g. by Halogen atoms, substituted and / or unsaturated.
  • succinic acid adipic acid, suberic acid, Azelaic acid, sebacic acid, phthalic acid, isophthalic acid, Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic Endomethylene tetrahydrophthalic anhydride, glutaric anhydride, Maleic acid, maleic anhydride, fumaric acid, dimeric fatty acids.
  • polyhydric alcohols are e.g.
  • Lactone-based polyester diols are also suitable homopolymers or copolymers of lactones, preferably terminal ones Addition products of lactones containing hydroxyl groups or lactone mixtures, e.g. ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -butyrolactone and / or methyl- ⁇ -caprolactone to suitable difunctional starter molecules, e.g. the above as a structural component for the low molecular weight polyester polyols, dihydric alcohols.
  • suitable difunctional starter molecules e.g. the above as a structural component for the low molecular weight polyester polyols, dihydric alcohols.
  • the corresponding polymers ⁇ -caprolactone are particularly preferred.
  • Even lower polyester diols or polyether diols can be used as starters for the preparation the lactone polymers can be used.
  • Lactones can also be chemically equivalent Polycondensates of the hydroxycarboxylic acids corresponding to the lactones be used.
  • the polyether diols which can also be used in a mixture with polyester diols, are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 or by addition of these compounds, optionally in a mixture or in succession
  • Starting components with reactive hydrogen atoms such as alcohols or amines, for example water, ethylene glycol, propylene glycol (1,3) or - (1,2), 4,4'-dihydroxydiphenylpropane, aniline, are available.
  • the proportion of monomer II described above is in generally 0.1 to 0.8 gram equivalent, preferably 0.2 to 0.7 Gram equivalent of the hydroxyl group of the monomer II based on 1 gram equivalent of isocyanate of the polyisocyanate.
  • polyurethane are concerned compared to chain extenders or crosslinkers with at least two Isocyanate-reactive groups selected from hydroxyl groups, primary or secondary amino groups.
  • Polyols in particular diols and triols, with a Molecular weight below 400 g / mol to 62 g / mol (monomers III).
  • polyester polyols diols and triols are used to manufacture the Suitable polyester polyols diols and triols, as well as higher than trifunctional alcohols such as pentaerythritol or sorbitol in Consideration.
  • the proportion of the monomers III is generally 0 to 0.8, in particular 0 to 0.7 gram equivalent based on 1 gram equivalent Isocyanate.
  • the monomers IV which may be used are are at least difunctional amine chain extenders or Crosslinker of the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which have at least two primary, two secondary or one primary and one secondary amino group contain.
  • Examples include diamines, such as diaminoethane, diaminopropanes, Diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, Amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, Aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as Diethylenetriamine or 1,8-diamino-4-aminomethyloctane.
  • diamines such as diaminoethane, diaminopropanes, Diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, Amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (
  • Chain extenders can also be blocked Shape, e.g. in the form of the corresponding ketimines (see e.g. CA-1 129 128), ketazines (see e.g. U.S.-A-4,269,748) or amine salts (see US-A-4,292,226).
  • Polyurethanes for chain extension of the prepolymers can be used.
  • When using such capped Polyamines are generally used with the prepolymers in Absence of water mixed and then this mixture with the water of dispersion or part of the water of dispersion mixed, so that the corresponding hydrolytically Polyamines are released.
  • Mixtures of di- and triamines are preferably used, especially preferably mixtures of isophoronediamine and diethylenetriamine.
  • Monomers V are amino alcohols with a Hydroxyl and a primary or secondary amino group such as Ethanolamine, isopropanolamine, methylethanolamine or aminoethoxyethanol.
  • the proportion of the monomers IV or V is in each case preferably 0 to 0.4, particularly preferably 0 to 0.2 gram equivalent to 1 gram equivalent of isocyanate of the polyisocyanate.
  • Connections can be used as a further structural component be at least one, preferably two over isocyanate groups reactive groups, i.e. hydroxyl, primary or secondary amino groups, and also in contrast to the Monomers described above or by ionic groups a simple neutralization or quaternization reaction in ionic groups convertible, potentially ionic groups.
  • (Monomers VI) By introducing the monomers VI the polyurethanes themselves dispersible, i.e. when dispersing in In this case, water is not used as a dispersing agent Protective colloids or emulsifiers are required.
  • the introduction of the cationic or anionic groups can by using (potential) cationic or (potential) compounds with anionic groups with opposite Isocyanate-reactive hydrogen atoms take place.
  • Groups of connections include e.g. tertiary nitrogen atoms containing polyethers with preferably two terminal hydroxyl groups, such as by alkoxylation of two on amine nitrogen bonded amine hydrogen atoms, e.g. Methylamine, aniline, or N, N'-dimethylhydrazine, in itself are accessible in the usual way.
  • Such polyethers have generally a molecular weight between 500 and 6000 g / mol on.
  • the ionic groups are preferred by concomitant use of comparatively low molecular weight compounds with (potential) ionic groups and towards isocyanate groups reactive groups introduced. Examples of this are in U.S. Patents 3,479,310 and 4,056,564 and GB 1,455,554. Also dihydroxyphosphonates, such as the sodium salt of 2,3-Dihydroxypropane-phosphonic acid ethyl ester or the corresponding Sodium salt of the non-esterified phosphonic acid can also be used as an ionic structural component.
  • Preferred (potential) ionic monomers VI are N-alkyl dialkanolamines, such as. N-methyldiethanolamine, N-ethyldiethanolamine, Diamino sulfonates, such as the Na salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid, Dihydroxysulfonates, dihydroxycarboxylic acids such as dimethylolpropionic acid, diaminocarboxylic acids or carboxylates such as lysine or the Na salt of N- (2-aminoethyl) -2-aminoethane carboxylic acid and diamines with at least one additional tertiary amine nitrogen, e.g. N-methyl bis (3-aminopropyl) -amine.
  • N-alkyl dialkanolamines such as. N-methyldiethanolamine, N-ethyldiethanolamine, Diamino sulfonates, such as the
  • Diamino- and dihydroxycarboxylic acids are particularly preferred, in particular the adduct of ethylenediamine with sodium acrylate or Dimethylolpropionic.
  • the transfer of the first optionally into the polyaddition product built-in potential ionic groups at least partly in ionic groups happens in a conventional manner by neutralizing the potential anionic or cationic Groups or by quaternization of tertiary amine nitrogen atoms.
  • Ammonium groups are inorganic or neutralizing agents organic acids, e.g. Salt, phosphorus, ants, vinegar, Fumaric, maleic, lactic, tartaric or oxalic acid or as quaternizing agent, e.g. Methyl chloride, methyl bromide, methyl iodide, Dimethyl sulfate, benzyl chloride, chloroacetic acid ester or bromoacetamide suitable.
  • Other neutralizing or quaternizing agents are e.g. in US-A 3,479,310 column 6.
  • This neutralization or quaternization of the potential ion groups can be before, during, but preferably after the isocanate polyaddition reaction respectively.
  • the amounts of the monomers VI, in the case of potential ion groups is suitably chosen so that the polyurethanes have a content of 0.05 to 2 meq / g polyurethane, preferably from 0.07 to 1.0 and particularly preferably from 0.1 to Have 0.7 meq / g of polyurethane on ionic groups.
  • monohydric polyether alcohols Molecular weight range 500 to 10,000 g / mol, preferably from 800 up to 5,000 g / mol.
  • Monohydric polyether alcohols are e.g. by Alkoxylation of monovalent starter molecules, e.g. methanol, Ethanol or n-butanol available, being used as an alkoxylating agent Ethylene oxide or mixtures of ethylene oxide with other alkylene oxides, especially propylene oxide. In case of use of alkylene oxide mixtures, however, preferably contain them at least 40, particularly preferably at least 65 mol% Ethylene oxide.
  • Monomers VII can thus optionally in the polyurethanes present in terminally arranged polyether chains
  • Polyethylene oxide segments to be installed in addition to the polyurethane influence the hydrophilic character of the ionic groups and ensure or improve dispersibility in water.
  • the compounds of the type mentioned are preferred, according to uses them in such quantities that they from 0 to 10, preferably from 0 to 5% by weight of polyethylene oxide units be introduced into the polyurethane.
  • Suitable monomers VIII which, in contrast to the above monomers, contain ethylenically unsaturated groups, are, for example, esters of acrylic or methacrylic acid with polyols, at least one OH group of the polyol remaining unesterified.
  • the adducts of (meth) acrylic acid with bisglycidyl ether of diols such as, for example, bisphenol A or butanediol are particularly suitable.
  • Adducts of (meth) acrylic acid with epoxidized can also be used Diolefins such as 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexane carboxylate.
  • the polyurethane can, if desired thermally or photochemically, optionally in the presence of an initiator, are subsequently hardened.
  • the proportion of ethylenically unsaturated is Groups under 0.2 mol per 100 g of polyurethane.
  • the proportion of the structural components is preferably so chosen that the sum of the hydroxyl groups reactive towards isocyanate and primary or secondary amino groups 0.9 to 1.2, particularly preferably 0.95 to 1.1, based on 1 isocyanate group, is.
  • the reaction temperature is generally between 20 and 160 ° C, preferably between 50 and 100 ° C.
  • the usual catalysts such as dibutyltin dilaurate, stannous octoate or diazabicyclo- (2,2,2) octane.
  • the polyurethane prepolymer obtained can, if appropriate, after (further) dilution with solvents of the type mentioned above, preferably with solvents with boiling points below 100 ° C, at a temperature between 20 and 80 ° C with amino functional Compounds of the monomers VI and optionally IV further implemented become.
  • the organic solvent After dispersion, the organic solvent, if its boiling point is below that of the water, distilled off become. Optionally used solvents with a higher boiling points can remain in the dispersion.
  • the content of the polyurethane in the dispersions can in particular between 5 and 70 percent by weight, preferably between 20 and 50 % By weight, based on the dispersions.
  • Customary auxiliaries e.g. Thickeners, Thixotropic agents, oxidation and UV stabilizers or Release agents can be added.
  • Hydrophobic aids that can be difficult to homogenize to be distributed in the finished dispersion can also be distributed the method described in US-A 4,306,998, the polyurethane or be added to the prepolymer before the dispersion.
  • isocyanates the second component in the mixtures (D), In principle, all connections with at least one are suitable free isocyanate group.
  • the usual ones are of particular importance here Diisocyanates, the usual higher functional polyisocyanates, as with the hydrophilically modified polyisocyanates (C) and those described under (C) Hydrophilically mofified polyisocyanates themselves. But also monoisocyanates such as phenyl isocyanate or tolyl isocyanates are suitable.
  • polyurethanes and isocyanates mentioned are in usually as mixtures in a weight ratio of 10:90 to 90:10, especially 25:75 to 75:25, especially 40:60 to 60:40.
  • the compounds (D) 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% by weight, which has compounds (A) to (D).
  • step 1 Dissolve the cellulose in a water-miscible solvent Level 2 Extrude the solution through a die to form the fiber precursor level 3 Treatment of the fiber precursor with water to remove solvents and form the cellulose fiber Level 4 Drying the fiber
  • 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 .-%.
  • Treatment according to the invention with the compounds (A) to (D) 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 (D) 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 carried out 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 the connections (D). 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 (D) can face 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.

Abstract

Prodn. of soln. of spun cellulose fibre with reduced fibrillation tendency is by treatment of the fibres with (A) a N-methylol ether of a carboxamide, urethane, urea or aminotriazine; (B) a cyclic hydroxy or alkoxy ethylene urea N-substd. by 1 or more alkyl gps.; (C) a hydrophilic modified polyisocyanate; and/or (D) a polyurethane/isocyanate mixt..

Description

Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von aus Lösungsmitteln gesponnenen Cellulosefasern mit verringerter Neigung zum Fibrillieren durch Behandlung der Fasern mit bestimmten reaktiven Verbindungen.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.

Aus der GB-A-2 043 525 ist die Herstellung von Cellulosefasern durch Spinnen einer Celluloselösung in einem geeigneten Lösungsmittel, z.B. einem N-Oxid eines tertiären Amins, wie N-Methylmorpholin-N-oxid, bekannt. In einem solchen Spinnprozeß wird die Celluloselösung durch eine geeignete Düse extrudiert und die resultierende Faservorstufe in Wasser gewaschen und danach getrocknet. Solche Fasern werden als "aus Lösungsmittel gesponnene Fasern" bezeichnet.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 ".

Solche aus Lösungsmitteln gesponnenen Cellulosefasern bieten viele anwendungstechnische Vorteile, neigen aber zum Fibrillieren. Darunter versteht man das Abspleißen feinster Faserfibrillen, die bei der Verarbeitung der Cellulosefasern in der Textilherstellung zu Problemen führen können.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.

Die WO-A-92/07124 empfiehlt zur Lösung dieses Problems die Behandlung der Cellulosefasern mit einer wäßrigen Lösung oder Dispersion eines Polymers, das über eine Vielzahl kationisch ionisierbarer Gruppen verfügt, z.B. ein Polyvinylimidazolin.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.

Weiterhin lehrt die EP-A-538 977 die Verwendung von Verbindungen, die 2 bis 6 funktionelle Gruppen aufweisen, die mit Cellulose reagieren können, z.B. Produkte auf Basis von Dichlortriazin, für diesen Zweck.Furthermore, 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.

Aufgabe der vorliegenden Erfindung war es, ein neues Verfahren zur Herstellung von aus Lösungsmitteln gesponnenen Cellulosefasern mit verringerter Neigung zum Fibrillieren bereitzustellen, das von anderen chemischen Defibrillierungsreagenzien ausgeht.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.

Es wurde nun gefunden, daß die Herstellung von aus Lösungsmitteln gesponnenen Cellulosefasern mit verringerter Neigung zum Fibrillieren vorteilhaft gelingt, wenn man die Fasern mit einer oder mehreren Verbindungen aus der Gruppe der

  • (D) Mischungen von Polyurethanen mit Isocyanaten
    • behandelt. It has now been found that the production of solvent-spun cellulose fibers with reduced tendency to fibrillate succeeds advantageously if the fibers are mixed with one or more compounds from the group of
  • (D) Mixtures of polyurethanes with isocyanates
    • treated.

    Hydrophil modifizierten Polyisocyanate (C) werden in der Regel in Form von wäßrigen Dispersionen, welche im wesentlichen frei von organischen Lösungsmitteln und weiteren Emulgatoren sind, eingesetzt. Ihr Einsatz ist kein Gegenstand der vorliegenden Erfindung.Hydrophilically modified polyisocyanates (C) are usually in the form of aqueous dispersions, which are essentially free of organic solvents and other emulsifiers are used. Your stake is not an object of the present invention.

    Als Basis für die verwendeten hydrophil modifizierten Polyisocyanate dienen übliche Dizsocyanate und/oder übliche höher funktionelle Polyisocyanate mit einer mittleren NCO-Funktionalität von 2,0 bis 4,5. Diese Komponenten können alleine oder im Gemisch vorliegen.As the basis for the hydrophilically modified used Polyisocyanates serve the usual dizsocyanates 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.

    Beispiele für übliche Diisocyanate sind aliphatische Diisocyanate wie Tetramethylendiisocyanat, Hexamethylendiisocyanat (1,6-Diisocyanatohexan), Octamethylendiisocyanat, Decamethylendiisocyanat, Dodecamethylendiisocyanat, Tetradecamethylendiisocyanat, Trimethylhexandiisocyanat oder Tetramethylhexandiisocyanat, cycloaliphatische Diisocyanate wie 1,4-, 1,3- oder 1,2-Diisocyanatocyclohexan, 4,4'-Di(isocyanatocyclohexyl)methan, 1-Isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexan (Isophorondiisocyanat) oder 2,4- oder 2,6-Diisocyanato-1-methylcyclohexan sowie aromatische Diisocyanate wie 2,4- oder 2,6-Toluylendiisocyanat, Tetramethylxylylendiisocyanat, p-Xylylendiisocyanat, 2,4'- oder 4,4'-Diisocyanatodiphenylmethan, 1,3- oder 1,4-Phenylendiisocyanat, 1-Chlor-2,4-phenylendiisocyanat, 1,5-Naphthylendiisocyanat, Diphenylen-4,4'-diisocyanat, 4,4'-Diisocyanato-3,3'-dimethyldiphenyl, 3-Methyldiphenylmethan-4,4'-diisocyanat oder Diphenylether-4,4'-diisocyanat. Es können auch Gemische der genannten Diisocyanate vorliegen. Bevorzugt werden hiervon aliphatische Diisocyanate, insbesondere Hexamethylendiisocyanat und Isophorondiisocyanat.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 diisocyanates such as 2,4- or 2,6-tolylene diisocyanate, Tetramethylxylylene diisocyanate, p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane, 1,3- or 1,4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, Diphenylene-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate or Diphenylether-4,4'-diisocyanate. Mixtures of mentioned diisocyanates are present. Of these, aliphatic are preferred Diisocyanates, especially hexamethylene diisocyanate and Isophorone.

    Als übliche höher funktionelle Polyisocyanate eignen sich beispielsweise Triisocyanate wie 2,4,6-Triisocyanatotoluol oder 2,4,4'-Triisocyanatodiphenylether oder die Gemische aus Di-, Tri- und höheren Polyisocyanaten, die durch Phosgenierung von entsprechenden Anilin/Formaldehyd-Kondensaten erhalten werden und Methylenbrücken aufweisende Polyphenylpolyisocyanate darstellen.Examples of 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.

    Von besonderem Interesse sind übliche aliphatische höher funktionelle Polyisocyanate der folgenden Gruppen:

  • (a) Isocyanuratgruppen aufweisende Polyisocyanate von aliphatischen und/oder cycloaliphatischen Diisocyanaten. Besonders bevorzugt sind hierbei die entsprechenden Isocyanato-Isocyanurate auf Basis von Hexamethylendiisocyanat und Isophorondiisocyanat. Bei den vorliegenden Isocyanuraten handelt es sich insbesondere um einfache Tris-isocyanatoalkyl- bzw. Triisocyanatocycloalkyl-Isocyanurate, welche cyclische Trimere der Diisocyanate darstellen, oder um Gemische mit ihren höheren, mehr als einen Isocyanuratring aufweisenden Homologen. Die Isocyanato-Isocyanurate haben im allgemeinen einen NCO-Gehalt von 10 bis 30 Gew.-%, insbesondere 15 bis 25 Gew.-%, und eine mittlere NCO-Funktionalität von 2,6 bis 4,5.
  • (b) Uretdiondiisocyanate mit aliphatisch und/oder cycloaliphatisch gebundenen Isocyanatgruppen, vorzugsweise von Hexamethylendiisocyanat oder Isophorondiisocyanat abgeleitet. Bei Uretdiondiisocyanaten handelt es sich um cyclische Dimersierungsprodukte von Diisocyanaten.
  • (c) Biuretgruppen aufweisende Polyisocyanate mit aliphatisch gebundenen Isocyanatgruppen, insbesondere Tris(6-isocyanatohexyl)biuret oder dessen Gemische mit seinen höheren Homologen. Diese Biuretgruppen aufweisenden Polyisocyanate haben im allgemeinen einen NCO-Gehalt von 18 bis 25 Gew.-% und eine mittlere NCO-Funktionalität von 3 bis 4,5.
  • (d) Urethan- und/oder Allophanatgruppen aufweisende Polyisocyanate mit aliphatisch oder cycloaliphatisch gebundenen Isocyanatgruppen, wie sie beispielsweise durch Umsetzung von überschüssigen Mengen an Hexamethylendiisocyanat oder an Isophorondiisocyanat mit einfachen mehrwertigen Alkoholen wie Trimethylolpropan, Glycerin, 1,2-Dihydroxypropan oder deren Gemischen erhalten werden können. Diese Urethan- und/oder Allophanatgruppen aufweisenden Polyisocyanate haben im allgemeinen einen NCO-Gehalt von 12 bis 20 Gew.-% und eine mittlere NCO-Funktionalität von 2,5 bis 3.
  • (e) Oxadiazintriongruppen enthaltende Polyisocyanate, vorzugsweise von Hexamethylendiisocyanat oder Isophorondiisocyanat abgeleitet. Solche Oxadiazintriongruppen enthaltenden Polyisocyanate sind aus Diisocyanat und Kohlendioxid herstellbar.
  • (f) Uretonimin-modifizierte Polyisocyanate.
    • Common aliphatic higher functional polyisocyanates of the following groups are of particular interest:
  • (a) Isocyanurate group-containing polyisocyanates of aliphatic and / or cycloaliphatic diisocyanates. The corresponding isocyanato-isocyanurates based on hexamethylene diisocyanate and isophorone diisocyanate are particularly preferred. The present isocyanurates are, in particular, simple tris-isocyanatoalkyl or triisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologues containing more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of 10 to 30% by weight, in particular 15 to 25% by weight, and an average NCO functionality of 2.6 to 4.5.
  • (b) uretdione diisocyanates with aliphatic and / or cycloaliphatic isocyanate groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimers of diisocyanates.
  • (c) Polyisocyanates containing biuret groups with aliphatically bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues. These polyisocyanates containing biuret groups generally have an NCO content of 18 to 25% by weight and an average NCO functionality of 3 to 4.5.
  • (d) Polyisocyanates containing urethane and / or allophanate groups with aliphatic or cycloaliphatic isocyanate groups, such as are obtained, for example, by reacting excess amounts of hexamethylene diisocyanate or isophorone diisocyanate with simple polyhydric alcohols such as trimethylolpropane, glycerol, 1,2-dihydroxypropane or mixtures thereof can. These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of 12 to 20% by weight and an average NCO functionality of 2.5 to 3.
  • (e) Polyisocyanates containing oxadiazinetrione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such polyisocyanates containing oxadiazinetrione groups can be prepared from diisocyanate and carbon dioxide.
  • (f) Uretonimine-modified polyisocyanates.

    • Die beschriebenen Diisocyanate und/oder höher funktionalisierten Polyisocyanate werden zur Überführung in nicht-ionisch hydrophil modifizierte Polyisocyanate mit NCO-reaktiven Verbindungen umgesetzt, die hydrophil machende Strukturelemente mit nichtionischen Gruppen oder mit polaren Gruppen, die nicht in Ionengruppen übergeführt werden können, enthalten. Dabei liegt das Diisocyanat bzw. Polyisocyanat im stöchiometrischen Überschuß vor, damit das resultierende hydrophil modifizierte Polyisocyanat noch freie NCO-Gruppen aufweist.The described diisocyanates and / or more functionalized Polyisocyanates become non-ionic hydrophilic for conversion modified polyisocyanates 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.

    Als solche NCO-reaktive Verbindungen mit hydrophil machenden Strukturelementen kommen vor allem hydroxylgruppenterminierte Polyether der allgemeinen Formel VII R8-E-(DO)n-H in der

    R8
    für C1- bis C20-Alkyl, insbesondere C1- bis C4-Alkyl, oder C2-bis C20-Alkenyl, Cyclopentyl, Cyclohexyl, Glycidyl, Oxethyl, Phenyl, Tolyl, Benzyl, Furfuryl oder Tetrahydrofurfuryl steht,
    E
    Schwefel oder insbesondere Sauerstoff bezeichnet,
    D
    Propylen oder vor allem Ethylen bedeutet, wobei auch insbesondere blockweise gemischt ethoxylierte und propoxylierte Verbindungen auftreten können, und
    n
    für eine Zahl von 5 bis 120, insbesondere 10 bis 25 steht,
    in Betracht.Hydroxyl group-terminated polyethers of the general formula VII in particular come as such NCO-reactive compounds with hydrophilicizing structural elements R 8 -E- (DO) n -H in the
    R 8
    represents C 1 to C 20 alkyl, in particular C 1 to C 4 alkyl, or C 2 to C 20 alkenyl, cyclopentyl, cyclohexyl, glycidyl, oxethyl, phenyl, tolyl, benzyl, furfuryl or tetrahydrofurfuryl,
    e
    Denotes sulfur or especially oxygen,
    D
    Propylene or especially ethylene means, and in particular mixed ethoxylated and propoxylated compounds can also occur in blocks, and
    n
    represents a number from 5 to 120, in particular 10 to 25,
    into consideration.

    Bei nicht-ionisch hydrophil modifizierten Polyisocyanaten, welche die Polyether VII eingebaut enthalten, handelt es sich besonders bevorzugt um auf C1- bis C4-Alkanol gestartete Ethylenoxid- oder Propylenoxid-Polyether mit mittleren Molekulargewichten von 250 bis 7000, insbesondere 450 bis 1500.Non-ionically hydrophilically modified polyisocyanates which contain the built-in polyethers VII are particularly preferably ethylene oxide or propylene oxide polyethers with average molecular weights of 250 to 7000, in particular 450 to 1500, started on C 1 to C 4 alkanol.

    Man kann aus den beschriebenen Diisocyanaten und/oder höher funktionalisierte Polyisocyanaten auch zuerst durch Umsetzung mit einem Unterschuß an hydroxylgruppenterminierten Polyestern, an anderen hydroxylgruppenterminierten Polyethern oder an Polyolen, z.B. Ethylenglykol, Trimethylolpropan oder Butandiol, Präpolymere erzeugen und diese Präpolymere dann anschließend oder auch gleichzeitig mit den Polyethern VII im Unterschuß zu den hydrophil modifizierten Polyisocyanaten mit freien NCO-Gruppen umsetzen.One can from the described diisocyanates and / or more functionalized Polyisocyanates also first by reaction with a deficit of 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.

    Es ist auch möglich, nicht-ionisch hydrophil modifizierte Polyisocyanate aus Diisocyanat bzw. Polyisocyanat und Polyalkylenglykolen der Formel HO-(DO)n-H, in der D und n die oben genannten Bedeutungen haben, herzustellen. Dabei reagieren beide endständigen OH-Gruppen des Polyalkylenglykols mit Isocyanat ab.It is also possible to prepare 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.

    Die aufgezählten Arten nicht-ionisch hydrophil modifizierter Polyisocyanate sind in den Schriften 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 und EP-A 516 361 näher beschrieben.The enumerated types of 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.

    Die beschriebenen Diisocyanate und/oder höher funktionalisierten Polyisocyanate werden zur Überführung in anionisch hydrophil modifizierte Polyisocyanate mit NCO-reaktiven Verbindungen umgesetzt, die hydrophil machende anionische Gruppen, insbesondere Säuregruppen wie Carboxylgruppen, Sulfonsäuregruppen oder Phosphonsäuregruppen, enthalten. Dabei liegt das Diisocyanat bzw. Polyisocyanat im stöchiometrischen Überschuß vor, damit das resultierende hydrophil modifizierte Polyisocyanat noch freie NCO-Gruppen aufweist.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.

    Als solche NCO-reaktiven Verbindungen mit anionischen Gruppen kommen vor allem Hydroxycarbonsäuren wie 2-Hydroxyessigsäure, 3-Hydroxypropionsäure, 4-Hydroxybuttersäure oder Hydroxylpivalinsäure sowie 2,2-Bis- und 2,2,2-Tris(hydroxymethyl)alkansäuren, z.B. 2,2-Bis(hydroxymethyl)essigsäure, 2,2-Bis(hydroxymethyl)propionsäure, 2,2-Bis(hydroxymethyl)buttersäure oder 2,2,2-Tris(hydroxymethyl)essigsäure, in Betracht. Die Carboxylgruppen können teilweise oder vollständig durch eine Base neutralisiert sein, um in einer wasserlöslichen oder wasserdispergierbaren Form vorzuliegen. Als Base tritt hierbei vorzugsweise ein tertiäres Amin auf, welches bekanntermaßen gegenüber Isocyanat inert ist.As such, 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.

    Die beschriebenen Diisocyanate und/oder höher funktionalisierten Polyisocyanate können auch mit einer Mischung aus nicht-ionisch hydrophil modifizierenden und anionisch hydrophobil modifizierenden Verbindungen, welche nacheinander oder gleichzeitig zugegeben werden, umgesetzt werden, beispielsweise mit einem Unterschuß aus den Polyethern VII und den beschriebenen Hydroxycarbonsäuren.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.

    Die aufgezählten Arten anionisch hydrophil modifizierter Polyisocyanate sind in den Schriften DE-A 40 01 783, DE-A 41 13 160 und DE-A 41 42 275 näher beschrieben.The enumerated types of 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.

    Die beschriebenen Diisocyanate und/oder höher funktionalisierten Polyisocyanate werden zur Überführung in kationisch hydrophil modifizierte Polyisocyanate mit NCO-reaktiven Verbindungen umgesetzt, die chemisch eingebaute alkylierbare oder protonierbare Funktionen unter Ausbildung eines kationischen Zentrums enthalten. Insbesondere sind solche Funktionen tertiäre Stickstoffatome, welche bekanntermaßen gegenüber Isocyanat inert sind und sich leicht quaternieren oder protonieren lassen. Bei der Umsetzung von Diisocyanat bzw. Polyisocyanat mit diesen NCO-reaktiven Verbindungen liegen erstere im Überschuß vor, damit das resultierende hydrophil modifizierte Polyisocyanat noch freie NCO-Gruppen aufweist.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. In particular, such functions are tertiary nitrogen atoms, which are known to be inert to isocyanate and can be easily quaternized or protonated. When implementing of diisocyanate or polyisocyanate with these NCO-reactive Connections exist in excess so that the resulting hydrophilically modified polyisocyanate is still free Has NCO groups.

    Als derartige NCO-reaktive Verbindungen mit tertiären Stickstoffatomen kommen vorzugsweise Aminoalkohole der allgemeinen Formel VIII

    Figure 00080001
    in der

    R9 und R10
    lineares oder verzweigtes C1- bis C20-Alkyl, insbesondere C1- bis C5-Alkyl, bedeuten oder zusammen mit dem N-Atom einen fünf- oder sechsgliedrigen Ring bilden, der noch ein O-Atom oder ein tertiäres N-Atom enthalten kann, insbesondere einen Piperidin-, Morpholin-, Piperazin-, Pyrrolidin-, Oxazolin- oder Dihydrooxazin-Ring, wobei die Reste R2 und R3 noch zusätzlich Hydroxylgruppen, insbesondere jeweils eine Hydroxylgruppe, tragen können, und
    R11
    eine C2- bis C10-Alkylengruppe, insbesondere eine C2- bis C6-Alkylengruppe, die linear oder verzweigt sein kann, bezeichnet,
    in Betracht.Such NCO-reactive compounds with tertiary nitrogen atoms are preferably amino alcohols of the general formula VIII
    Figure 00080001
    in the
    R 9 and R 10
    are linear or branched C 1 - to C 20 -alkyl, in particular C 1 - to C 5 -alkyl, or together with the N atom form a five- or six-membered ring which also contains an O atom or a tertiary N atom may contain, in particular a piperidine, morpholine, piperazine, pyrrolidine, oxazoline or dihydrooxazine ring, where the radicals R 2 and R 3 may additionally carry hydroxyl groups, in particular in each case one hydroxyl group, and
    R 11
    denotes a C 2 to C 10 alkylene group, in particular a C 2 to C 6 alkylene group, which may be linear or branched,
    into consideration.

    Als Aminoalkohole VIII eignen sich vor allem N-Methyldiethanolamin, N-Methyldi(iso)propanolamin, N-Butyldiethanolamin, N-Butyldi(iso)propanolamin, N-Stearyldiethanolamin, N-Stearyldi(iso)propanolamin, N,N-Dimethylethanolamin, N,N-Dimethyl(iso)propanolamin, N,N-Diethylethanolamin, N,N-Diethyl(iso)propanolamin, N,N-Dibutylethanolamin, N,N-Dibutyl(iso)propanolamin, Triethanolamin, Tri(iso)propanolamin, N-(2-Hydroxyethyl)morpholin, N-(2-Hydroxypropyl)morpholin, N-(2-Hydroxyethyl)piperidin, N-(2-Hydroxypropyl)piperidin, N-Methyl-N'-(2-hydroxyethyl)piperazin, N-Methyl-N'-(2-hydroxypropyl)piperazin, N-Methyl-N'-(4-hydroxybutyl)piperazin, 2-Hydroxyethyl-oxazolin, 2-Hydroxypropyl-oxazolin, 3-Hydroxypropyl-oxazolin, 2-Hydroxyethyl-dihydrooxazin, 2-Hydroxypropyl-dihydrooxazin oder 3-Hydroxypropyl-dihydrooxazin.Particularly suitable 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-hydroxyethyl) piperazine, N-methyl-N' - (2-hydroxypropyl) piperazine, N-methyl-N '- (4-hydroxybutyl) piperazine, 2-hydroxyethyl oxazoline, 2-hydroxypropyl oxazoline, 3-hydroxypropyl oxazoline, 2-hydroxyethyl dihydrooxazine, 2-hydroxypropyl dihydrooxazine or 3-hydroxypropyl dihydrooxazine.

    Weiterhin kommen als derartige NCO-reaktive Verbindungen mit tertiären Stickstoffatomen vorzugsweise Diamine der allgemeinen Formel IXa oder IXb

    Figure 00080002
    in der R9 bis R11 die oben genannten Bedeutungen haben und R12 C1bis C5-Alkyl bezeichnet oder mit R9 einen fünf- oder sechsgliedrigen Ring, insbesondere einen Piperazin-Ring, bildet, in Betracht.Furthermore, such NCO-reactive compounds with tertiary nitrogen atoms are preferably diamines of the general formula IXa or IXb
    Figure 00080002
    in which R 9 to R 11 have the meanings given above 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 .

    Als Diamine IXa eigenen sich vor allem N,N-Dimethyl-ethylendiamin, N,N-Diethyl-ethylendiamin, N,N-Dimethyl-1,3-diamino-2,2-dimethylpropan, N,N-Diethyl-1,3-propylendiamin, N-(3-Aminopropyl)morpholin, N-(2-Aminopropyl)morpholin, N-(3-Aminopropyl)piperidin, N-(2-Aminopropyl)piperidin, 4-Amino-1-(N,N-diethylamino)pentan, 2-Amino-1-(N,N-dimethylamino)propan, 2-Amino-1-(N,N-diethylamino)propan oder 2-Amino-1-(N,N-diethylamino)-2-methylpropan.Particularly suitable 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.

    Als Diamine IXb eignen sich vor allem N,N,N'-Trimethyl-ethylendiamin, N,N,N'-Triethyl-ethylendiamin, N-Methylpiperazin oder N-Ethylpiperazin.Particularly suitable diamines IXb are N, N, N'-trimethyl-ethylenediamine, N, N, N'-triethylethylenediamine, N-methylpiperazine or N-ethylpiperazine.

    Weiterhin können als NCO-reaktive Verbindungen auch Polyether(poly)ole mit eingebauten tertiären Stickstoffatomen, die durch Propoxylierung und/oder Ethoxylierung von Aminstickstoff aufweisenden Startermolekülen herstellbar sind, eingesetzt werden. Derartige Polyether(poly)ole sind beispielsweise die Propoxylierungs- und Ethoxylierungsprodukte von Ammoniak, Ethanolamin, Diethanolamin, Ethylendiamin oder N-Methylanilin.Furthermore, 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.

    Andere verwendbare NCO-reaktive Verbindungen sind tertiäre Stickstoffatome aufweisende Polyester- und Polyamidharze, tertiäre Stickstoffatome aufweisende urethangruppenhaltige Polyole sowie tertiäre Stickstoffatome aufweisende Polyhydroxypolyacrylate.Other usable 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.

    Die beschriebenen Diisocyanate und/oder höher funktionalisierten Polyisocyanate können auch mit einer Mischung aus nicht-ionisch hydrophil modifizierenden und kationisch hydrophil modifizierenden Verbindungen, welche nacheinander oder gleichzeitig zugegeben werden, umgesetzt werden, beispielsweise mit einem Unterschuß aus den Polyethern VII und den Aminoalkoholen VIII oder den Diaminen IXa bzw. IXb. Auch Mischungen aus nicht-ionisch hydrophil modifizierenden und anionisch hydrophil modifizierenden Verbindungen sind möglich.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.

    Die aufgezählten Arten kationisch hydrophil modifizierter Polyisocyanate sind in den Schriften DE-A 42 03 510 und EP-A 531 820 näher beschrieben. The listed types of cationically hydrophilic modified polyisocyanates are in the documents DE-A 42 03 510 and EP-A 531 820 described in more detail.

    Da die genannten hydrophil modifizierten Polyisocyanate (C) in der Regel in wäßrigen Medien eingesetzt werden, ist für eine ausreichende Dispergierbarkeit der Polyisocyanate zu sorgen. Vorzugsweise wirken innerhalb der Gruppe der beschriebenen hydrophil modifizierten Polyisocyanaten bestimmte Umsetzungsprodukte aus Di- bzw. Polyisocyanaten und hydroxylgruppenterminierten Polyethern (Polyetheralkoholen) wie den Verbindungen VII als Emulgatoren für diesen Zweck.Since the hydrophilically modified polyisocyanates (C) mentioned in usually used in aqueous media is sufficient for To ensure dispersibility of the polyisocyanates. Preferably act hydrophilic within the group of described modified polyisocyanates from certain reaction products Di- or polyisocyanates and hydroxyl-terminated polyethers (Polyether alcohols) such as compounds VII as emulsifiers for this purpose.

    Die erzielten guten Ergebnisse mit den hydrophil modifizierten Polyisocyanaten (C) in wäßrigen Medien sind um so überraschender, da zu erwarten war, daß Isocyanate sich in wäßrigem Milieu rasch zersetzen. Trotzdem weisen die eingesetzten Polyisocyanate in der wäßrigen Flotte eine Topfzeit von mehreren Stunden auf, d.h. die vorliegenden Polyisocyanat-Dispersionen sind im Rahmen der üblichen Verarbeitungsdauer stabil. Von einer Dispersion wird gesagt, daß sie stabil ist, wenn ihre Komponenten ineinander dispergiert bleiben, ohne daß sie sich in diskrete Schichten trennen. Mit dem Ausdruck "Topfzeit" ist die Zeit gemeint, während der die Dispersionen verarbeitbar bleiben, bevor sie gelieren und abbinden. Wäßrige Isocyanat-Dispersionen gelieren und binden ab, weil eine Reaktion zwischen dem Wasser und dem Isocyanat stattfindet, wobei ein Polyharnstoff entsteht.The good results achieved with the hydrophilically modified Polyisocyanates (C) 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 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. The term "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.

    Die Mischungen aus Polyurethanen und Isocyanaten (D) werden wie die Verbindungen (C) in der Regel in Form von wäßrigen Dispersionen, welche im wesentlichen frei von organischen Lösungsmitteln und in den meisten Fällen frei von Emulgatoren sind, beim erfindungsgemäßen Verfahren eingesetzt.The mixtures of polyurethanes and isocyanates (D) are like the compounds (C) usually in the form of aqueous Dispersions that are essentially free of organic solvents and in most cases are free of emulsifiers, used in the method according to the invention.

    Unter Polyurethanen sind aus Polyisocyanaten (im weiteren auch Monomere I genannt) und gegenüber Polyisocyanaten reaktiven Verbindungen mit mindestens einer Hydroxylgruppe und gegebenenfalls Verbindungen mit mindestens einer primären oder sekundären Aminogruppe aufgebaute Systeme zu verstehen. Die Polyurethane weisen in aller Regel keine freien Isocyanatgruppen mehr auf.Polyurethanes are made from polyisocyanates (hereinafter also Called monomers I) and reactive towards polyisocyanates Compounds with at least one hydroxyl group and optionally Connections with at least one primary or secondary Understanding amino group built systems. The polyurethanes generally no longer have any free isocyanate groups.

    Als Polyisocyanate zur Herstellung der in den Mischungen (D) enthaltenen Polyurethane dienen übliche Diisocyanate und/oder übliche höher funktionelle Polyisocyanate wie sie bei den hydrophil modifizierten Polyisocyanaten (C) beschrieben sind. Auch hier werden aliphatische Diisocyanate und aliphatische höher funktionelle Polyisocyanate bevorzugt. As polyisocyanates for the production of the mixtures (D) Polyurethanes contained serve the usual diisocyanates and / or usual higher functional polyisocyanates such as those in the hydrophilic modified polyisocyanates (C) are described. Also here aliphatic diisocyanates and aliphatic become higher functional polyisocyanates preferred.

    Bei den weiteren Aufbaukomponenten des Polyurethans handelt es sich zunächst um Polyole mit einem Molekulargewicht von 400 bis 6000 g/mol, vorzugsweise 600 bis 4000 g/mol (Monomere II).The other structural components of the polyurethane are concerned are initially polyols with a molecular weight of 400 to 6000 g / mol, preferably 600 to 4000 g / mol (monomers II).

    In Betracht kommen insbesondere Polyetherpolyole oder Polyesterpolyole.Polyether polyols or polyester polyols are particularly suitable.

    Bei den Polyesterdiolen handelt es sich insbesondere um die an sich bekannten Umsetzungsprodukte von zweiwertigen Alkoholen mit zweiwertigen Carbonsäuren. Anstelle der freien Polycarbonsäuren können auch die entsprechenden Polycarbonsäureanhydride oder entsprechende Polycarbonsäureester von niederen Alkoholen oder deren Gemische zur Herstellung der Polyesterpolyole verwendet werden. Die Polycarbonsäuren können aliphatisch, cycloaliphatisch, aromatisch oder heterocyclisch sein und gegebenenfalls, z.B. durch Halogenatome, substituiert und/oder ungesättigt sein. Als Beispiele hierfür seien genannt: Bernsteinsäure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, Phthalsäure, Isophthalsäure, Phthalsäureanhydrid, Tetrahydrophthalsäureanhydrid, Hexahydrophthalsäureanhydrid, Tetrachlorphthalsäureanhydrid, Endomethylentetrahydrophthalsäureanhydrid, Glutarsäureanhydrid, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, dimere Fettsäuren. Als mehrwertige Alkohole kommen z.B. Ethylenglykol, Propylenglykol-(1,2) und -(1,3), Butandiol-(1,4), -(1,3), Butendiol-(1,4), Butindiol-(1,4), Pentandiol-(1,5), Hexandiol-(1,6), Octandiol-(1,8), Neopentylglykol, Cyclohexandimethanol (1,4-Bis-hydroxymethylcyclohexan), 2-Methyl-1,3-propandiol, Pentandiol-(1,5), ferner Diethylenglykol, Triethylenglykol, Tetraethylenglykol, Polyethylenglykol, Dipropylenglykol, Polypropylenglykol, Dibutylenglykol und Polybutylenglykole in Frage.The polyester diols are in particular the known reaction products of dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids can also the corresponding polycarboxylic anhydrides or corresponding Polycarboxylic esters of lower alcohols or their Mixtures can be used to produce the polyester polyols. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic or be heterocyclic and optionally, e.g. by Halogen atoms, substituted and / or unsaturated. As examples the following are mentioned: succinic acid, adipic acid, suberic acid, Azelaic acid, sebacic acid, phthalic acid, isophthalic acid, Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic Endomethylene tetrahydrophthalic anhydride, glutaric anhydride, Maleic acid, maleic anhydride, fumaric acid, dimeric fatty acids. As polyhydric alcohols are e.g. Ethylene glycol, propylene glycol- (1,2) and - (1,3), butanediol- (1,4), - (1,3), butenediol- (1,4), Butynediol- (1.4), pentanediol- (1.5), hexanediol- (1.6), octanediol- (1.8), Neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, pentanediol- (1,5), also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, Dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycols in question.

    Geeignet sind auch Polyesterdiole auf Lacton-Basis, wobei es sich um Homo- oder Mischpolymerisate von Lactonen, bevorzugt um endständige Hydroxylgruppen aufweisende Anlagerungsprodukte von Lactonen bzw. Lactongemischen, wie z.B. ε-Caprolacton, β-Propiolacton, υ-Butyrolacton und/oder Methyl-ε-caprolacton an geeignete difunktionelle Startermoleküle, z.B. die vorstehend als Aufbaukomponente für die Polyesterpolyole genannten niedermolekularen, zweiwertigen Alkohole handelt. Die entsprechenden Polymerisate des ε-Caprolactons sind besonders bevorzugt. Auch niedere Polyesterdiole oder Polyetherdiole können als Starter zur Herstellung der Lacton-Polymerisate eingesetzt sein. Anstelle der Polymerisate von Lactonen können auch die entsprechenden, chemisch äquivalenten Polykondensate der den Lactonen entsprechenden Hydroxycarbonsäuren eingesetzt werden. Lactone-based polyester diols are also suitable homopolymers or copolymers of lactones, preferably terminal ones Addition products of lactones containing hydroxyl groups or lactone mixtures, e.g. ε-caprolactone, β-propiolactone, υ-butyrolactone and / or methyl-ε-caprolactone to suitable difunctional starter molecules, e.g. the above as a structural component for the low molecular weight polyester polyols, dihydric alcohols. The corresponding polymers ε-caprolactone are particularly preferred. Even lower polyester diols or polyether diols can be used as starters for the preparation the lactone polymers can be used. Instead of the polymers Lactones can also be chemically equivalent Polycondensates of the hydroxycarboxylic acids corresponding to the lactones be used.

    Die - gegebenenfalls auch im Gemisch mit Polyesterdiolen - einsetzbaren Polyetherdiole, sind insbesondere durch Polymerisation von Ethylenoxid, Propylenoxid, Butylenoxid, Tetrahydrofuran, Styroloxid oder Epichlorhydrin mit sich selbst, z.B. in Gegenwart von BF3 oder durch Anlagerung dieser Verbindungen gegebenenfalls im Gemisch oder nacheinander, an Startkomponenten mit reaktionsfähigen Wasserstoffatomen, wie Alkohole oder Amine, z.B. Wasser, Ethylenglykol, Propylenglykol-(1,3) oder -(1,2), 4,4'-Dihydroxydiphenylpropan, Anilin erhältlich.The polyether diols, which can also be used in a mixture with polyester diols, are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 or by addition of these compounds, optionally in a mixture or in succession Starting components with reactive hydrogen atoms, such as alcohols or amines, for example water, ethylene glycol, propylene glycol (1,3) or - (1,2), 4,4'-dihydroxydiphenylpropane, aniline, are available.

    Der Anteil des vorstehend beschriebenen Monomeren II beträgt im allgemeinen 0,1 bis 0,8 Grammäquivalent, vorzugsweise 0,2 bis 0,7 Grammäquivalent der Hydroxylgruppe des Monomeren II bezogen auf 1 Grammäquivalent Isocyanat des Polyisocyanats.The proportion of monomer II described above is in generally 0.1 to 0.8 gram equivalent, preferably 0.2 to 0.7 Gram equivalent of the hydroxyl group of the monomer II based on 1 gram equivalent of isocyanate of the polyisocyanate.

    Bei weiteren Aufbaukomponenten des Polyurethans handelt es sich um Kettenverlängerer oder Vernetzer mit mindestens zwei gegenüber Isocyanat reaktiven Gruppen, ausgewählt aus Hydroxylgruppen, primären oder sekundären Aminogruppen.Other structural components of the polyurethane are concerned compared to chain extenders or crosslinkers with at least two Isocyanate-reactive groups selected from hydroxyl groups, primary or secondary amino groups.

    Genannt seien Polyole, insbesondere Diole und Triole, mit einem Molekulargewicht unter 400 g/mol bis 62 g/mol (Monomere III).Polyols, in particular diols and triols, with a Molecular weight below 400 g / mol to 62 g / mol (monomers III).

    Insbesondere kommen die oben aufgeführten zur Herstellung der Polyesterpolyole geeigneten Diole und Triole, sowie höher als trifunktionelle Alkohole wie Pentaerythrit oder Sorbit in Betracht.In particular, those listed above are used to manufacture the Suitable polyester polyols diols and triols, as well as higher than trifunctional alcohols such as pentaerythritol or sorbitol in Consideration.

    Der Anteil der Monomeren III beträgt im allgemeinen 0 bis 0,8, insbesondere 0 bis 0,7 Grammäquivalent, bezogen auf 1 Grammäquivalent Isocyanat.The proportion of the monomers III is generally 0 to 0.8, in particular 0 to 0.7 gram equivalent based on 1 gram equivalent Isocyanate.

    Bei den gegebenenfalls einzusetzenden Monomeren IV handelt es sich um mindestens difunktionelle Amin-Kettenverlängerer bzw. -vernetzer des Molgewichtsbereiches von 32 bis 500 g/mol, vorzugsweise von 60 bis 300 g/mol, welche mindestens zwei primäre, zwei sekundäre oder eine primäre und eine sekundäre Aminogruppe enthalten.The monomers IV which may be used are are at least difunctional amine chain extenders or Crosslinker of the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which have at least two primary, two secondary or one primary and one secondary amino group contain.

    Beispiel hierfür sind Diamine, wie Diaminoethan, Diaminopropane, Diaminobutane, Diaminohexane, Piperazin, 2,5-Dimethylpiperazin, Amino-3-aminomethyl-3,5,5-trimethyl-cyclohexan (Isophorondiamin, IPDA), 4,4'-Diaminodicyclohexylmethan, 1,4-Diaminocyclohexan, Aminoethylethanolamin, Hydrazin, Hydrazinhydrat oder Triamine wie Diethylentriamin oder 1,8-Diamino-4-aminomethyloctan. Die aminogruppenhaltigen Kettenverlängerer können auch in blockierter Form, z.B. in Form der entsprechenden Ketimine (siehe z.B. CA-1 129 128), Ketazine (vgl. z.B. die US-A-4 269 748) oder Aminsalze (s. US-A-4 292 226) eingesetzt sein. Auch Oxazolidine, wie sie beispielsweise in der US-A-4 192 937 verwendet werden, stellen verkappte Polyamine dar, die für die Herstellung der erfindungsgemäßen Polyurethane zur Kettenverlängerung der Prepolymeren eingesetzt werden können. Bei der Verwendung derartiger verkappter Polyamine werden diese im allgemeinen mit den Prepolymeren in Abwesenheit von Wasser vermischt und diese Mischung anschließend mit dem Dispersionswasser oder einem Teil des Dispersionswassers vermischt, so daß intermediär hydrolytisch die entsprechenden Polyamine freigesetzt werden.Examples include diamines, such as diaminoethane, diaminopropanes, Diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, Amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, Aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as Diethylenetriamine or 1,8-diamino-4-aminomethyloctane. Those containing amino groups Chain extenders can also be blocked Shape, e.g. in the form of the corresponding ketimines (see e.g. CA-1 129 128), ketazines (see e.g. U.S.-A-4,269,748) or amine salts (see US-A-4,292,226). Even oxazolidines, like they are used, for example, in US-A-4 192 937 masked polyamines used for the preparation of the invention Polyurethanes for chain extension of the prepolymers can be used. When using such capped Polyamines are generally used with the prepolymers in Absence of water mixed and then this mixture with the water of dispersion or part of the water of dispersion mixed, so that the corresponding hydrolytically Polyamines are released.

    Bevorzugt werden Gemische von Di- und Triaminen verwendet, besonders bevorzugt Gemische von Isophorondiamin und Diethylentriamin.Mixtures of di- and triamines are preferably used, especially preferably mixtures of isophoronediamine and diethylenetriamine.

    Bei den gegebenenfalls ebenfalls als Kettenverlängerer einzusetzenden Monomeren V handelt es sich um Aminoalkohole mit einer Hydroxyl- und einer primären oder sekundären Aminogruppe wie Ethanolamin, Isopropanolamin, Methylethanolamin oder Aminoethoxyethanol.For those that may also be used as chain extenders Monomers V are amino alcohols with a Hydroxyl and a primary or secondary amino group such as Ethanolamine, isopropanolamine, methylethanolamine or aminoethoxyethanol.

    Der Anteil der Monomeren IV oder V beträgt jeweils vorzugsweise 0 bis 0,4, besonders bevorzugt 0 bis 0,2 Grammäquivalent, bezogen auf 1 Grammäquivalent Isocyanat des Polyisocyanats.The proportion of the monomers IV or V is in each case preferably 0 to 0.4, particularly preferably 0 to 0.2 gram equivalent to 1 gram equivalent of isocyanate of the polyisocyanate.

    Als weitere Aufbaukomponente können Verbindungen eingesetzt werden, die mindestens eine, vorzugsweise zwei gegenüber Isocyanatgruppen reaktionsfähige Gruppen, also Hydroxyl-, primäre oder sekundäre Aminogruppen, und außerdem im Gegensatz zu den voranstehend beschriebenen Monomeren ionische Gruppen oder durch eine einfache Neutralisations- oder Quaternisierungsreaktion in ionische Gruppen überführbare, potentiell ionische Gruppen aufweisen. (Monomere VI). Durch Einführung der Monomeren VI werden die Polyurethane selbst dispergierbar, d.h. beim Dispergieren in Wasser werden in diesem Fall keine Dispergierhilfsmittel wie Schutzkolloide oder Emulgatoren benötigt.Connections can be used as a further structural component be at least one, preferably two over isocyanate groups reactive groups, i.e. hydroxyl, primary or secondary amino groups, and also in contrast to the Monomers described above or by ionic groups a simple neutralization or quaternization reaction in ionic groups convertible, potentially ionic groups. (Monomers VI). By introducing the monomers VI the polyurethanes themselves dispersible, i.e. when dispersing in In this case, water is not used as a dispersing agent Protective colloids or emulsifiers are required.

    Die Einführung der kationischen oder anionischen Gruppen kann durch Mitverwendung von (potentielle) kationische oder (potentielle) anionische Gruppen aufweisende Verbindungen mit gegenüber Isocyanat reaktionsfähigen Wasserstoffatomen erfolgen. Zu diesen Gruppen von Verbindungen gehören z.B. tertiäre Stickstoffatome aufweisende Polyether mit vorzugsweise zwei endständigen Hydroxylgruppen, wie sie z.B. durch Alkoxylierung von zwei an Aminstickstoff gebundene Wasserstoffatome aufweisenden Aminen, z.B. Methylamin, Anilin, oder N,N'-Dimethylhydrazin, in an sich üblicher Weise zugänglich sind. Derartige Polyether weisen im allgemeinen ein zwischen 500 und 6000 g/mol liegendes Molgewicht auf.The introduction of the cationic or anionic groups can by using (potential) cationic or (potential) compounds with anionic groups with opposite Isocyanate-reactive hydrogen atoms take place. To this Groups of connections include e.g. tertiary nitrogen atoms containing polyethers with preferably two terminal hydroxyl groups, such as by alkoxylation of two on amine nitrogen bonded amine hydrogen atoms, e.g. Methylamine, aniline, or N, N'-dimethylhydrazine, in itself are accessible in the usual way. Such polyethers have generally a molecular weight between 500 and 6000 g / mol on.

    Vorzugsweise werden jedoch die ionischen Gruppen durch Mitverwendung von vergleichsweise niedermolekularen Verbindungen mit (potentiellen) ionischen Gruppen und gegenüber Isocyanatgruppen reaktionsfähigen Gruppen eingeführt. Beispiele hierfür sind in der US-A 3 479 310 und 4 056 564 sowie der GB-1 455 554 aufgeführt. Auch Dihydroxyphosphonate, wie das Natriumsalz des 2,3-Dihydroxypropan-phosphonsäure-ethylesters oder das entsprechende Natriumsalz der nichtveresterten Phosphonsäure, können als ionische Aufbaukomponente mitverwendet werden.However, the ionic groups are preferred by concomitant use of comparatively low molecular weight compounds with (potential) ionic groups and towards isocyanate groups reactive groups introduced. Examples of this are in U.S. Patents 3,479,310 and 4,056,564 and GB 1,455,554. Also dihydroxyphosphonates, such as the sodium salt of 2,3-Dihydroxypropane-phosphonic acid ethyl ester or the corresponding Sodium salt of the non-esterified phosphonic acid can also be used as an ionic structural component.

    Bevorzugte (potentielle) ionische Monomere VI sind N-Akyldialkanolamine, wie z.B. N-Methyldiethanolamin, N- Ethyldiethanolamin, Diaminosulfonate, wie das Na-Salz der N-(2-Aminoethyl)-2-aminoethansulfonsäure, Dihydroxysulfonate, Dihydroxycarbonsäuren wie Dimethylolpropionsäure, Diaminocarbonsäuren bzw.carboxylate wie Lysin oder das Na-Salz der N-(2-Aminoethyl)-2-aminoethancarbonsäure und Diamine mit mindestens einem zusätzlichen tertiären Aminstickstoffatom, z.B. N-Methylbis-(3-aminopropyl)-amin.Preferred (potential) ionic monomers VI are N-alkyl dialkanolamines, such as. N-methyldiethanolamine, N-ethyldiethanolamine, Diamino sulfonates, such as the Na salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid, Dihydroxysulfonates, dihydroxycarboxylic acids such as dimethylolpropionic acid, diaminocarboxylic acids or carboxylates such as lysine or the Na salt of N- (2-aminoethyl) -2-aminoethane carboxylic acid and diamines with at least one additional tertiary amine nitrogen, e.g. N-methyl bis (3-aminopropyl) -amine.

    Besonders bevorzugt werden Diamino- und Dihydroxycarbonsäuren, insbesondere das Addukt von Ethylendiamin an Natriumacrylat oder Dimethylolpropionsäure.Diamino- and dihydroxycarboxylic acids are particularly preferred, in particular the adduct of ethylenediamine with sodium acrylate or Dimethylolpropionic.

    Die Überführung der gegebenenfalls zunächst in das Polyadditionsprodukt eingebauten potentiellen ionischen Gruppen zumindest teilweise in ionische Gruppen geschieht in an sich üblicher Weise durch Neutralisation der potentiellen anionischen oder kationischen Gruppen oder durch Quaternierung von tertiären AminStickstoffatomen.The transfer of the first optionally into the polyaddition product built-in potential ionic groups at least partly in ionic groups happens in a conventional manner by neutralizing the potential anionic or cationic Groups or by quaternization of tertiary amine nitrogen atoms.

    Zur Neutralisation von potentiellen anionischen Gruppen, z.B. Carboxylgruppen, werden anorganische und/oder organische Basen eingesetzt wie Alkalihydroxide, -carbonate oder -hydrogencarbonate, Ammoniak oder primäre, sekundäre und besonders bevorzugt tertiäre Amine wie Triethylamin oder Dimethylaminopropanol.For the neutralization of potential anionic groups, e.g. Carboxyl groups, become inorganic and / or organic bases used like alkali metal hydroxides, carbonates or bicarbonates, Ammonia or primary, secondary and particularly preferred tertiary amines such as triethylamine or dimethylaminopropanol.

    Zur Überführung der potentiellen kationischen Gruppen, z.B. der tertiären Amingruppen in die entsprechenden Kationen, z.B. Ammoniumgruppen, sind als Neutralisationsmittel anorganische oder organische Säuren, z.B. Salz-, Phosphor-, Ameisen-, Essig-, Fumar-, Malein-, Milch-, Wein- oder Oxalsäure oder als Quaternierungsmittel, z.B. Methylchlorid, Methylbromid, Methyljodid, Dimethylsulfat, Benzylchlorid, Chloressigsäureester oder Bromacetamid geeignet. Weitere Neutralisations- oder Quaternierungsmittel sind z.B. in der US-A 3 479 310, Spalte 6, beschrieben.To transfer the potential cationic groups, e.g. the tertiary amine groups into the corresponding cations, e.g. Ammonium groups are inorganic or neutralizing agents organic acids, e.g. Salt, phosphorus, ants, vinegar, Fumaric, maleic, lactic, tartaric or oxalic acid or as quaternizing agent, e.g. Methyl chloride, methyl bromide, methyl iodide, Dimethyl sulfate, benzyl chloride, chloroacetic acid ester or bromoacetamide suitable. Other neutralizing or quaternizing agents are e.g. in US-A 3,479,310 column 6.

    Diese Neutralisation oder Quaternierung der potentiellen Ionengruppen kann vor, während, jedoch vorzugsweise nach der Isocanat-Polyadditionsreaktion erfolgen.This neutralization or quaternization of the potential ion groups can be before, during, but preferably after the isocanate polyaddition reaction respectively.

    Die Mengen der Monomeren VI, bei potentiellen ionengruppenhaltigen Komponenten unter Berücksichtigung des Neutralisationsoder Quaternierungsgrades, ist geeigneterweise so zu wählen, daß die Polyurethane einen Gehalt von 0,05 bis 2 mÄqu/g Polyurethan, vorzugsweise von 0,07 bis 1,0 und besonders bevorzugt von 0,1 bis 0,7 mÄqu/g Polyurethan an ionischen Gruppen aufweisen.The amounts of the monomers VI, in the case of potential ion groups Components taking into account the neutralization or Degree of quaternization, is suitably chosen so that the polyurethanes have a content of 0.05 to 2 meq / g polyurethane, preferably from 0.07 to 1.0 and particularly preferably from 0.1 to Have 0.7 meq / g of polyurethane on ionic groups.

    Gegebenenfalls werden auch monofunktionelle Amin- oder Hydroxylverbindungen als Aufbaukomponenten mitverwendet (Monomere VII). Es handelt sich bevorzugt um einwertige Polyetheralkohole des Molgewichtsbereiches 500 bis 10 000 g/mol, vorzugsweise von 800 bis 5 000 g/mol. Einwertige Polyetheralkohole sind z.B. durch Alkoxylierung von einwertigen Startermolekülen,wie z.B. Methanol, Ethanol oder n-Butanol erhältlich, wobei als Alkoxylierungsmittel Ethylenoxid oder Gemische von Ethylenoxid mit anderen Alkylenoxiden, besonders Propylenoxid, eingesetzt werden. Im Falle der Verwendung von Alkylenoxidgemischen enthalten diese jedoch vorzugsweise mindestens 40, besonders bevorzugt mindestens 65 mol-% Ethylenoxid.If necessary, monofunctional amine or hydroxyl compounds also used as structural components (monomers VII). It is preferably monohydric polyether alcohols Molecular weight range 500 to 10,000 g / mol, preferably from 800 up to 5,000 g / mol. Monohydric polyether alcohols are e.g. by Alkoxylation of monovalent starter molecules, e.g. methanol, Ethanol or n-butanol available, being used as an alkoxylating agent Ethylene oxide or mixtures of ethylene oxide with other alkylene oxides, especially propylene oxide. In case of use of alkylene oxide mixtures, however, preferably contain them at least 40, particularly preferably at least 65 mol% Ethylene oxide.

    Durch die Monomeren VII können in den Polyurethanen somit gegebenenfalls in endständig angeordneten Polyetherketten vorliegende Polyethylenoxidsegmente eingebaut sein, die im Polyurethan neben den ionischen Gruppen den hydrophilen Charakter beeinflussen und eine Dispergierbarkeit in Wasser gewährleisten oder verbessern.Monomers VII can thus optionally in the polyurethanes present in terminally arranged polyether chains Polyethylene oxide segments to be installed in addition to the polyurethane influence the hydrophilic character of the ionic groups and ensure or improve dispersibility in water.

    Die Verbindungen der genannten Art werden bevorzugt, so man von ihnen Gebrauch macht, in solchen Mengen eingesetzt, daß von ihnen von 0 bis 10, vorzugsweise von 0 bis 5 Gew.-% Polyethylenoxideinheiten in das Polyurethan eingebracht werden.The compounds of the type mentioned are preferred, according to uses them in such quantities that they from 0 to 10, preferably from 0 to 5% by weight of polyethylene oxide units be introduced into the polyurethane.

    Weitere Beispiele von bei der Herstellung der beschriebenen Polyurethane als Monomere I bis VII einsetzbaren Verbindungen sind z.B. in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", von Saunders-Frisch, Interscience Publishers, New York, London, Band I, 1962, Seiten 32 bis 42 und Seiten 44 bis 54 und Band II, Seiten 5 bis 6 und 198 bis 199, beschrieben. Further examples of in the manufacture of the polyurethanes described Compounds which can be used as monomers I to VII e.g. in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology "by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32 to 42 and pages 44 to 54 and Volume II, pages 5 to 6 and 198 to 199.

    Als Monomere VIII, welche im Gegensatz zu den voranstehenden Monomeren ethylenisch ungesättigte Gruppen enthalten, kommen z.B. Ester von Acryl- oder Methacrylsäure mit Polyolen, wobei mindestens eine OH-Gruppe des Polyols unverestert bleibt, in Betracht. Besonders geeignet sind Hydroxyalkyl(meth)acrylate der Formel HO(CH2)mOOC(R12)C=CH2 (m = 2 bis 8; R12 = H, CH3) und ihre Stellungsisomeren, Mono(meth)acrylsäureester von Polyetherdiolen, wie z.B. bei den Monomeren II aufgeführt, Trimethylolpropanmono- und di(meth)acrylat, Pentaerythritdi- und -tri(meth)acrylat oder Reaktionsprodukte von Epoxidverbindungen mit (Meth)acrylsäure, wie sie z.B. in der US-A-357 221 genannt sind. Besonders geeignet sind die Addukte von (Meth)acrylsäure an Bisglycidylether von Diolen wie z.B. Bisphenol A oder Butandiol.Suitable monomers VIII, which, in contrast to the above monomers, contain ethylenically unsaturated groups, are, for example, esters of acrylic or methacrylic acid with polyols, at least one OH group of the polyol remaining unesterified. Hydroxyalkyl (meth) acrylates of the formula HO (CH 2 ) m OOC (R 12 ) C = CH 2 (m = 2 to 8; R 12 = H, CH 3 ) and their positional isomers, mono (meth) acrylic acid esters of Polyether diols, such as those listed for the monomers II, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol di- and tri (meth) acrylate or reaction products of epoxy compounds with (meth) acrylic acid, as mentioned, for example, in US Pat. No. 357,221 are. The adducts of (meth) acrylic acid with bisglycidyl ether of diols such as, for example, bisphenol A or butanediol are particularly suitable.

    Verwendbar sind auch Addukte von (Meth)acrylsäure an epoxidierte Diolefine wie z.B. 3,4-Epoxycyclohexylmethyl-3', 4'-epoxycyclohexancarboxylat.Adducts of (meth) acrylic acid with epoxidized can also be used Diolefins such as 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexane carboxylate.

    Durch Einbau der Monomeren VIII kann, falls gewünscht, das Polyurethan thermisch oder photochemisch, gegebenenfalls in Gegenwart eines Initiators, nachträglich gehärtet werden.By incorporating the monomers VIII, the polyurethane can, if desired thermally or photochemically, optionally in the presence of an initiator, are subsequently hardened.

    Im allgemeinen liegt der Anteil der ethylenisch ungesättigten Gruppen unter 0,2 mol pro 100 g Polyurethan.In general, the proportion of ethylenically unsaturated is Groups under 0.2 mol per 100 g of polyurethane.

    Insgesamt wird der Anteil der Aufbaukomponenten vorzugsweise so gewählt, daß die Summe der gegenüber Isocyanat reaktiven Hydroxylgruppen und primären oder sekundären Aminogruppen 0,9 bis 1,2, besonders bevorzugt 0,95 bis 1,1, bezogen auf 1 Isocyanatgruppe, beträgt.Overall, the proportion of the structural components is preferably so chosen that the sum of the hydroxyl groups reactive towards isocyanate and primary or secondary amino groups 0.9 to 1.2, particularly preferably 0.95 to 1.1, based on 1 isocyanate group, is.

    Die Herstellung der beschriebenen Polyurethane, insbesondere als Dispersionen, kann nach den üblichen Methoden, wie sie z.B. in den oben angeführten Schriften beschrieben sind, erfolgen.The production of the polyurethanes described, especially as Dispersions can be prepared using the usual methods, e.g. in described above are done.

    Bevorzugt wird in einem inerten, mit Wasser mischbaren Lösungsmittel, wie Aceton, Tetrahydrofuran, Methylethylketon oder N-Methylpyrrolidon aus den Monomeren I und II und gegebenenfalls III, V, VI, VII und VIII, falls VI keine Aminogruppen enthält, das Polyurethan oder, falls eine weitere Umsetzung mit aminofunktionellen Monomeren IV oder VI beabsichtigt ist, ein Polyurethanprepolymer mit noch endständigen Isocyanatgruppen hergestellt.In an inert, water-miscible solvent, preference is given to such as acetone, tetrahydrofuran, methyl ethyl ketone or N-methylpyrrolidone from the monomers I and II and optionally III, V, VI, VII and VIII, if VI contains no amino groups, the polyurethane or, if a further reaction with amino-functional Monomers IV or VI is intended to be a polyurethane prepolymer prepared with terminal isocyanate groups.

    Die Reaktionstemperatur liegt im allgemeinen zwischen 20 und 160°C, vorzugsweise zwischen 50 und 100°C. The reaction temperature is generally between 20 and 160 ° C, preferably between 50 and 100 ° C.

    Zur Beschleunigung der Reaktion der Diisocyanate können die üblichen Katalysatoren, wie Dibutylzinndilaurat, Zinn-II-octoat oder Diazabicyclo-(2,2,2)-octan, mitverwendet sein.To accelerate the reaction of the diisocyanates, the usual catalysts, such as dibutyltin dilaurate, stannous octoate or diazabicyclo- (2,2,2) octane.

    Das erhaltene Polyurethanprepolymer kann, gegebenenfalls nach (weiterer) Verdünnung mit Lösungsmitteln der oben genannten Art, bevorzugt mit Lösungsmitteln mit Siedepunkten unter 100°C, bei einer Temperatur zwischen 20 und 80°C mit aminofunktionellen Verbindungen der Monomeren VI und gegebenenfalls IV weiter umgesetzt werden.The polyurethane prepolymer obtained can, if appropriate, after (further) dilution with solvents of the type mentioned above, preferably with solvents with boiling points below 100 ° C, at a temperature between 20 and 80 ° C with amino functional Compounds of the monomers VI and optionally IV further implemented become.

    Die Überführung potentieller Salzgruppen, z.B. Carboxylgruppen, oder tertiärer Aminogruppen, welche über die Monomeren VI in das Polyurethan eingeführt wurden, in die entsprechenden Ionen erfolgt durch Neutralisation mit Basen oder Säuren oder durch Quaternisierung der tertiären Aminogruppen vor oder während dem Dispergieren des Polyurethans in Wasser.The transfer of potential salt groups, e.g. carboxyl groups, or tertiary amino groups, which via the monomers VI in the Polyurethane has been introduced into the corresponding ions is carried out by neutralization with bases or acids or by Quaternization of the tertiary amino groups before or during the Disperse the polyurethane in water.

    Nach der Dispergierung kann das organische Lösungsmittel, falls sein Siedepunkt unterhalb dem des Wasser liegt, abdestilliert werden. Gegebenenfalls mitverwendete Lösungsmittel mit einem höheren Siedepunkt können in der Dispersion verbleiben.After dispersion, the organic solvent, if its boiling point is below that of the water, distilled off become. Optionally used solvents with a higher boiling points can remain in the dispersion.

    Der Gehalt des Polyurethans in den Dispersionen kann insbesondere zwischen 5 und 70 Gewichtsprozent, bevorzugt zwischen 20 bis 50 Gew.-%, bezogen auf die Dispersionen, liegen.The content of the polyurethane in the dispersions can in particular between 5 and 70 percent by weight, preferably between 20 and 50 % By weight, based on the dispersions.

    Den Dispersionen können übliche Hilfsmittel, z.B. Verdicker, Thixotropiermittel, Oxidations- und UV- Stabilisatoren oder Trennmittel, zugesetzt werden.Customary auxiliaries, e.g. Thickeners, Thixotropic agents, oxidation and UV stabilizers or Release agents can be added.

    Hydrophobe Hilfsmittel, die unter Umständen nur schwierig homogen in der fertigen Dispersion zu verteilen sind, können auch nach der in US-A 4 306 998 beschriebenen Methode dem Polyurethan oder dem Prepolymer bereits vor der Dispergierung zugesetzt werden.Hydrophobic aids that can be difficult to homogenize to be distributed in the finished dispersion can also be distributed the method described in US-A 4,306,998, the polyurethane or be added to the prepolymer before the dispersion.

    Als Isocyanate, der zweiten Komponente in den Mischungen (D), eignen sich im Prinzip alle Verbindungen mit mindestens einer freien Isocyanatgruppe. Besondere Bedeutung haben hier die üblichen Diisocyanate, die üblichen höher funktionellen Polyisocyanate, wie sie bei den hydrophil modifizierten Polyisocyanaten (C) beschrieben sind, sowie die unter (C) beschriebenen hydrophil mofifizierten Polyisocyanate selbst. Aber auch Monoisocyanate wie Phenylisocyanat oder Tolylisocyanate sind geeignet. As isocyanates, the second component in the mixtures (D), In principle, all connections with at least one are suitable free isocyanate group. The usual ones are of particular importance here Diisocyanates, the usual higher functional polyisocyanates, as with the hydrophilically modified polyisocyanates (C) and those described under (C) Hydrophilically mofified polyisocyanates themselves. But also monoisocyanates such as phenyl isocyanate or tolyl isocyanates are suitable.

    Die genannten Polyurethane und die genannten Isocyanate liegen in der Regel als Mischungen im Gew.-Verhältnis von 10:90 bis 90:10, insbesondere 25:75 bis 75:25, vor allem 40:60 bis 60:40, vor.The polyurethanes and isocyanates mentioned are in usually as mixtures in a weight ratio of 10:90 to 90:10, especially 25:75 to 75:25, especially 40:60 to 60:40.

    In einer bevorzugten Ausführungsform setzt man als Verbindungen (D) Mischungen aus Polyesterurethanen und aliphatischen Diisocyanaten, aliphatischen höher funktionellen Polyisocyanaten oder hydrophil modifizierten Polyisocyanaten im Gew.-Verhältnis von 10:90 bis 90:10 ein.In a preferred embodiment, one sets as Compounds (D) mixtures of polyester urethanes and aliphatic Diisocyanates, aliphatic higher functional polyisocyanates or hydrophilically modified polyisocyanates in the weight ratio from 10:90 to 90:10.

    Die Verbindungen (D) können beim erfindungsgemäßen Verfahren zur Herstellung von Cellulosefasern generell in einem wäßrigen System, vorzugsweise in wäßriger Lösung oder Emulsion, zur Anwendung gelangen, wobei das wäßrige System im allgemeinen, bezogen auf das Gewicht des wäßrigen Systems, 0,1 bis 20 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-%, der Verbindungen (A) bis (D) aufweist.The compounds (D) 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% by weight, which has compounds (A) to (D).

    Die Herstellverfahren für aus Lösungsmittel gesponnene Cellulosefasern laufen in der Regel in 4 Stufen ab. Stufe 1 Lösen der Cellulose in einem mit Wasser mischbaren Lösungsmittel Stufe 2 Extrudieren der Lösung durch eine Düse unter Bildung der Faservorstufe Stufe 3 Behandlung der Faservorstufe mit Wasser um Lösungsmittel zu entfernen und die Cellulosefaser auszubilden Stufe 4 Trocknung der Faser The manufacturing processes for cellulose fibers spun from solvents generally run in 4 stages. step 1 Dissolve the cellulose in a water-miscible solvent Level 2 Extrude the solution through a die to form the fiber precursor level 3 Treatment of the fiber precursor with water to remove solvents and form the cellulose fiber Level 4 Drying the fiber

    Als Lösungsmittel in Stufe 1 wird vorzugsweise N-Methylmorpholin-N-oxid verwendet.The preferred solvent in stage 1 is N-methylmorpholine-N-oxide used.

    Die feuchte Faser, die in Stufe 3 erhalten wird, wird als nichtgetrocknete Faser bezeichnet und weist in der Regel, bezogen auf das Trockengewicht der Faser, 120 bis 150 Gew.-% Wasser auf.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.

    Der Wassergehalt der getrockneten Faser beträgt im allgemeinen, bezogen auf das Trockengewicht der Faser, 60 bis 80 Gew.-%.The water content of the dried fiber is generally based on the dry weight of the fiber, 60 to 80 wt .-%.

    Die erfindungsgemäße Behandlung mit den Verbindungen (A) bis (D) kann entweder an der feuchten Faser (während oder nach Stufe 3) oder an der getrockneten Faser (nach Stufe 4) erfolgen. Es ist aber auch eine Behandlung im Stadium der Faserherstellung (Stufe 2), z.B. in einem Fällbad, möglich.Treatment according to the invention with the compounds (A) to (D) 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.

    Wenn die Behandlung an der feuchten Faser erfolgt, so kann dies beispielsweise durch Zugabe des wäßrigen Systems der Verbindungen (D) zu einem zirkulierenden Bad geschehen, das die Faservorstufe enthält. Die Faservorstufe kann dabei z.B. als Stapelfaser vorliegen.If the treatment is done on the moist fiber, it can for example by adding the aqueous system of the compounds (D) happen to a circulating bath that is the fiber precursor contains. The fiber precursor can e.g. as staple fiber available.

    Wenn die Behandlung an der getrockneten Faser erfolgt, so kann diese z.B. als Stapelfaser, Vlies, Garn, Maschenware oder Gewebe vorliegen. Die Behandlung der Fasern in diesem Fall kann z.B. in wäßriger Flotte erfolgen.If 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.

    Im Gegensatz zu der in der EP-A-538 977 beschriebenen Methode kann im erfindungsgemäßen Verfahren auf die Anwesenheit von Alkali verzichtet werden.In contrast to the method described in EP-A-538 977 can in the process of the invention to the presence of Alkali should be avoided.

    Die Behandlung wird in der Regel bei einer Temperatur von 20 bis 200°C, vorzugsweise 40 bis 180°C, vorgenommen. Dabei erfolgt eine chemische Reaktion der Verbindungen (D) mit den Hydroxygruppen der Cellulose, wobei auch eine chemische Verknüpfung zwischen Hydroxygruppen verschiedener Cellulose-Fibrillen möglich ist. Dadurch wird die Stabilität der Faser erhöht.Treatment is usually at a temperature of 20 to 200 ° C, preferably 40 to 180 ° C, made. There is a chemical reaction of the compounds (D) with the hydroxyl groups of cellulose, with a chemical link between Hydroxy groups of different cellulose fibrils possible is. This increases the stability of the fiber.

    Die Zeitdauer der Behandlung beträgt üblicherweise 1 Sekunde bis 20 Minuten, vorzugsweise 5 bis 60 Sekunden und insbesondere 5 bis 30 Sekunden.The duration of treatment is usually 1 second to 20 minutes, preferably 5 to 60 seconds and in particular 5 to 30 seconds.

    Beim Imprägnierverfahren kann die Behandlung sowohl bei Raumtemperatur (20°C) mit anschließender Trocknung bis 100°C als auch bei Durchführung von Kondensationen bei Temperaturen bis zu 200°C, insbesondere bei 150 bis 180°C, erfolgen.In the impregnation process, the treatment can be carried out 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.

    Die Behandlung der feuchten oder getrockneten Faser kann mit 0,1 bis 10 Gew.-%, vorzugsweise 0,2 bis 5 Gew.-%, insbesondere 0,2 bis 2 Gew.-%, jeweils bezogen auf das Trockengewicht der Faser, der Verbindungen (D) erfolgen. In manchen Fällen kann es jedoch auch vorteilhaft sein, die genannten Mengen noch zu erhöhen, z.B. bis auf ca. 20 Gew.-%.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 the connections (D). In some cases it can however, it may also be advantageous to increase the amounts mentioned, e.g. up to approx. 20% by weight.

    Bei der Behandlung können weitere hierbei übliche Hilfsmittel in den hierfür üblichen Mengen mitverwendet werden. Insbesondere sind hier Antimigrationsmittel, beispielsweise auf Basis von Oxethylierungsprodukten, zu erwähnen. In the treatment, other aids that are customary here can be used in the usual quantities used for this purpose. In particular are anti-migration agents, for example based on oxethylation products, to mention.

    Wie bereits ausgeführt, können die Verbindungen (D) gegenüber den in der EP-A-538 977 beschriebenen Verbindungen rein thermisch (ohne Alkali) fixiert werden, wodurch sie sich optimal in den Faserherstellungsprozeß integrieren lassen. Die Anfärbbarkeit der so behandelten Fasern mit allen üblichen Cellulosefaserfarbstoffen, auch Reaktivfarbstoffen, ist in der Regel möglich.As already stated, the connections (D) can face 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.

    Unter Anwendung der in der EP-A-538 977 beschriebenen Testmethoden, auf die hier ausdrücklich Bezug genommen wird, können vorteilhafte Ergebnisse erzielt werden.Using the test methods described in EP-A-538 977, to which express reference is made here can be advantageous Results are achieved.

    Claims (4)

    1. A process for producing solvent-spun cellulosic fibers having a reduced tendency to fibrillate, which comprises treating the fibers with one or more compounds from the group of the
      (D) mixtures of polyurethanes with isocyanates.
    2. A process as claimed in claim 1, wherein compounds (D) comprise mixtures of polyesterurethanes and aliphatic diisocyanates, aliphatic higher functional polyisocyanates or hydrophilic modified polyisocyanates in a weight ratio of from 10:90 to 90:10.
    3. A process as claimed in claim 1 or 2, wherein the fibers are treated with from 0.1 to 10% by weight, based on the dry weight of the fibers, of compounds (D).
    4. A process as claimed in claim 1 to 3, wherein the treatment is carried out at from 20 to 200°C.
    EP99123391A 1994-09-06 1995-08-22 Process for manufacturing cellulosic fibres Expired - Lifetime EP0985747B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE4431635A DE4431635A1 (en) 1994-09-06 1994-09-06 Process for the production of cellulose fibers
    DE4431635 1994-09-06
    EP95931179A EP0779942B1 (en) 1994-09-06 1995-08-22 Process for manufacturing cellulose fibres

    Related Parent Applications (1)

    Application Number Title Priority Date Filing Date
    EP95931179A Division EP0779942B1 (en) 1994-09-06 1995-08-22 Process for manufacturing cellulose fibres

    Publications (3)

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    EP0985747A2 EP0985747A2 (en) 2000-03-15
    EP0985747A3 EP0985747A3 (en) 2000-04-19
    EP0985747B1 true EP0985747B1 (en) 2002-10-30

    Family

    ID=6527487

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    Application Number Title Priority Date Filing Date
    EP99123391A Expired - Lifetime EP0985747B1 (en) 1994-09-06 1995-08-22 Process for manufacturing cellulosic fibres
    EP95931179A Expired - Lifetime EP0779942B1 (en) 1994-09-06 1995-08-22 Process for manufacturing cellulose fibres
    EP99123392A Expired - Lifetime EP0984084B1 (en) 1994-09-06 1995-08-22 Process for manufacturing cellulosic fibres

    Family Applications After (2)

    Application Number Title Priority Date Filing Date
    EP95931179A Expired - Lifetime EP0779942B1 (en) 1994-09-06 1995-08-22 Process for manufacturing cellulose fibres
    EP99123392A Expired - Lifetime EP0984084B1 (en) 1994-09-06 1995-08-22 Process for manufacturing cellulosic fibres

    Country Status (8)

    Country Link
    US (1) US5776394A (en)
    EP (3) EP0985747B1 (en)
    JP (1) JPH10505389A (en)
    AT (3) ATE194018T1 (en)
    DE (4) DE4431635A1 (en)
    DK (1) DK0779942T3 (en)
    ES (2) ES2148552T3 (en)
    WO (1) WO1996007780A1 (en)

    Families Citing this family (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2005054297A2 (en) 2003-11-28 2005-06-16 Eastman Chemical Company Cellulose interpolymers and method of oxidation
    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
    US9410292B2 (en) 2012-12-26 2016-08-09 Kimberly-Clark Worldwide, Inc. Multilayered tissue having reduced hydrogen bonding
    KR102440861B1 (en) * 2020-05-26 2022-09-05 오영세 Method for manufacturing lyocell fiber and lyocell fiber therefrom

    Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0516361A1 (en) * 1991-05-29 1992-12-02 Imperial Chemical Industries Plc Polyisocyanate composition
    EP0531820A1 (en) * 1991-09-10 1993-03-17 Bayer Ag Polyisocyanate mixtures, process for their preparation and their use
    EP0538977A1 (en) * 1991-10-21 1993-04-28 Courtaulds Plc Fibre treatment
    DE4142275A1 (en) * 1991-12-20 1993-06-24 Bayer Ag ISOCYANATOCARBONIC ACIDS, A METHOD FOR THE PRODUCTION AND USE THEREOF

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    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
    DE3831093A1 (en) * 1988-09-13 1990-03-15 Basf Ag METHOD FOR EQUIPMENT CARE OF TEXTILE MATERIALS
    DE3912084A1 (en) * 1989-04-13 1990-10-25 Basf Ag METHOD FOR PRODUCING AQUEOUS SOLUTIONS OF N-METHYLOLETHERS
    GB9022175D0 (en) * 1990-10-12 1990-11-28 Courtaulds Plc Treatment of fibres
    JP3130148B2 (en) * 1992-10-30 2001-01-31 日清紡績株式会社 Method for preventing fibrillation of solvent-spun cellulosic fibers
    GB9304887D0 (en) * 1993-03-10 1993-04-28 Courtaulds Plc Fibre treatment
    DE4313262A1 (en) * 1993-04-23 1994-10-27 Pfersee Chem Fab Process for the easy care of cellulose-containing fiber materials
    GB9313128D0 (en) * 1993-06-24 1993-08-11 Courtaulds Fibres Ltd Fabric treatment

    Patent Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0516361A1 (en) * 1991-05-29 1992-12-02 Imperial Chemical Industries Plc Polyisocyanate composition
    EP0531820A1 (en) * 1991-09-10 1993-03-17 Bayer Ag Polyisocyanate mixtures, process for their preparation and their use
    EP0538977A1 (en) * 1991-10-21 1993-04-28 Courtaulds Plc Fibre treatment
    DE4142275A1 (en) * 1991-12-20 1993-06-24 Bayer Ag ISOCYANATOCARBONIC ACIDS, A METHOD FOR THE PRODUCTION AND USE THEREOF

    Also Published As

    Publication number Publication date
    EP0984084A2 (en) 2000-03-08
    US5776394A (en) 1998-07-07
    ATE230447T1 (en) 2003-01-15
    ATE226985T1 (en) 2002-11-15
    ATE194018T1 (en) 2000-07-15
    DE59510523D1 (en) 2003-02-06
    EP0985747A2 (en) 2000-03-15
    EP0984084B1 (en) 2003-01-02
    ES2190169T3 (en) 2003-07-16
    ES2148552T3 (en) 2000-10-16
    DE59510440D1 (en) 2002-12-05
    JPH10505389A (en) 1998-05-26
    EP0984084A3 (en) 2000-04-19
    EP0779942B1 (en) 2000-06-21
    DE4431635A1 (en) 1996-03-07
    WO1996007780A1 (en) 1996-03-14
    EP0779942A1 (en) 1997-06-25
    EP0985747A3 (en) 2000-04-19
    DK0779942T3 (en) 2000-08-28
    DE59508498D1 (en) 2000-07-27

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