Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/54—Polycondensates of aldehydes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
  • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
  • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
  • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/14—Manufacture of cellular products
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
  • C08J3/095—Oxygen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1535—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• • 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
  • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/90—Applications
  • C08G2261/93—Applications in textiles, fabrics and yarns
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes
  • C08J2375/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• • 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
  • D06M2200/10—Repellency against liquids
  • D06M2200/12—Hydrophobic properties
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
  • Y10T428/24438—Artificial wood or leather grain surface
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
  • Y10T428/24496—Foamed or cellular component
  • Y10T428/24504—Component comprises a polymer [e.g., rubber, etc.]
  • Y10T428/24512—Polyurethane
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2164—Coating or impregnation specified as water repellent
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2213—Coating or impregnation is specified as weather proof, water vapor resistant, or moisture resistant
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2221—Coating or impregnation is specified as water proof

Definitions

• the invention relates to solutions of polyurethane ureas in ⁇ -butyrolactone or mixtures containing this with toxicologically harmless organic solvents, a process for coating substrates using these solutions of polyurethane ureas and the substrates coated in this way.
• the substrates coated in accordance with the invention are preferably textile products or leather, but also materials such as wood or concrete can be coated according to the invention.
• the coating of substrates for example textile fabrics, with polyurethane systems belongs to the state of the art. A distinction is made here between aqueous polyurethane dispersions and solvent-containing systems.
• aqueous polyurethane systems cover a wide range of applications and have the advantage of essentially being able to do without volatile organic substances.
• such coatings have lower water resistance than the corresponding polyurethane coatings made from organic solutions because the hydrophilizing groups remain in the coating film.
• polyurethane systems of organic solvents are preferable to the aqueous systems.
• the film-forming process is a physical process which, unlike the two-component polyurethanes, is not accompanied by any chemical reaction.
• One-component polyurethaneurea coatings based on organic solvents are highly valued by users for their hardness, elasticity and resistance and are used, for example, for the production of topcoats on textiles.
• Such systems are prepared by reacting an aliphatic or aromatic diisocyanate with a linear macrol diol (polyether, polyester or polycarbonate diol) to a prepolymer and then adjusted to the required molecular weight by reaction with an aliphatic diamine as a chain extender.
• linear polyurethane urea solutions which give particularly durable coatings, tend to associate and crystallize from organic solution because of their structure consisting of the urea hard segment and the soft macrodiol segment.
• toluene is a hazardous substance which should no longer be used in solvent mixtures for polyurethane ureas for textile coating.
• the amide- and urea-containing solvents customary in the textile coating such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or tetramethylurea, are likewise hazardous to health and, for these reasons, can likewise not be used despite their known good solubility.
• crystallization-interfering additives for example mixtures of different amines for chain extension
• crystallization-interfering additives for example mixtures of different amines for chain extension
• intentionally induced non-uniformity of the polymer so far disturbed in its composition that the desired properties of the product, the coating, lost.
• a suitable solvent system is preferable to this approach.
• These formulations or solutions must be stable, which means in particular that the dissolved polymers should not precipitate or crystallize out, ie the solutions have a high storage stability.
• the suitable solvent according to the invention is ⁇ -butyrolactone, preferably in admixture with other, toxicologically acceptable solvents.
• a solution according to the invention of polyurethaneurea if appropriate in a mixture of organic solvents, preferably contains 15-60% by weight of solid, more preferably 20-40% by weight of solid, and these solutions contain a proportion of ⁇ -butyrolactone, preferably 10%. 80 wt .-%, particularly preferably 15-50 wt .-%, based on the total solution, in addition to other solvents such as alcohols, esters and ketones.
• polyurethaneurea it is possible to use all polyurethaneureas which are known to be suitable for coating, in particular those whose usability for feeding textiles is known to the person skilled in the art or which appears prima facie suitable.
• chain extender per mole of macrodiol 0.5-2.0 mol of an aliphatic or cycloaliphatic diamine or hydrazine as a so-called chain extender
• the polyurethane ureas contained in the textile fabric coating compositions according to the invention are high molecular weight, but virtually uncrosslinked, thermoplastic polyurethane ureas which are prepared in solution or melt. They are characterized, inter alia, by the fact that they can be prepared and used without the concomitant use of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, tetramethylurea, toluene or other toxic highly polar solvents. These polyurethaneureas according to the invention can be prepared, dissolved and used in ⁇ -butyrolactone or the solvent mixtures based on ⁇ -butyrolactone and other toxicologically acceptable solvents such as alcohols, esters and ketones. It is also surprising that the coating compositions according to the invention are distinguished by excellent properties, such as adhesion and hardness of the dried film, despite the relatively high-boiling solvent ⁇ -butyrolactone.
• the structural components of the polyurethanes which form the basis of the coating compositions according to the invention are a large number of principally known polyurethane raw materials.
• a higher degree of branching of the macrodiols is to be avoided, since the resulting polyurethane solutions are given a very high viscosity by the high degree of crosslinking, which is disadvantageous for processing as a coating solution.
• the high level of cross-linking also prevents the resulting polyurethane solutions from being stable for several months, as the market demands.
• suitable are polyethers, polyesters and polycarbonates, preferably polyesters and polycarbonates.
• the candidate, hydroxyl-containing polyethers are those obtained by polymerization of cyclic ethers such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, z. B. in the presence of BF 3 , or by addition of these ring compounds, optionally in admixture or in succession, to starting components with reactive hydrogen atoms such as alcohols and amines, eg. For example, water, ethylene glycol, propylene glycol-1,2 or propylene glycol-1,3, are produced.
• the candidate, hydroxyl-containing polyesters are z. B. reaction products of polyhydric, preferably dihydric alcohols with polybasic, preferably dibasic carboxylic acids. Instead of the free carboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof can also be used to prepare the polyesters.
• the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally, e.g. be substituted by halogen atoms, and / or unsaturated. Examples include:
• polyhydric alcohols come z. Ethylene glycol, propylene glycol-1,2, propylene glycol-1,3, butylene glycol-1,4, butylene glycol-2,3, hexane-1,6-diol, octane-1,8-diol, neopentyl glycol or 2- Methyl-l, 3-propanediol in question.
• polyester from lactones, z. B. ⁇ -caprolactone can be used.
• Suitable hydroxyl-containing polycarbonates are those which, for. Example, by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol or di-, tri- or tetra-ethylene glycol with diaryl or dialkyl carbonates or with phosgene can be prepared. Preference is given to such polycarbonates based on 1,6-hexanediol, as well as modifying co-diols such. As butane-1,4-diol or ⁇ -caprolactone.
• Preferably used macrodiols are polyesters and polycarbonates, very particularly preferred macrodiols of the textile coating according to the invention are polycarbonates.
• Suitable short-chain aliphatic diols are, for example: ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, diethanolamine, 2-ethyl-1,3-hexanediol, N-methyldiisopropanolamine, 1,3-propanediol, 1,4-propanediol, butanediol -1,3, 1,4-butanediol or 1,6-hexanediol. 0.2 to 0.5 mol of the short-chain aliphatic diol are added per mole of macrodiol.
• chain extenders are also used.
• chain extenders are hydrazine or aliphatic diamines, eg ethylenediamine, propylenediamine, hexamethylenediamine-1,6 or other aliphatic diamines.
• cycloaliphatic diamines such as 1,4-bis (aminomethyl) -cyclohexane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane and other (C 1 -C 4 ) -di- and tetraalkyldicyclohexylmethanes, eg 4 , 4'-diamino-3,5-diethyl-3 ', 5'-diisopropyldicyclohexylmethan in question.
• Preference is given to 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophoronediamine) and 4,4'-diaminodicyclohexylmethane.
• chain extenders (b) are used per mole of macrodiol mixture (a), preferably 0.6-1.7 mol.
• chain extenders are used, based on the remaining isocyanate, with the subtraction of the isocyanate fraction reacted with the macrodiol mixture.
• less than the equivalent amount is used, down to about 30-80% of the NCO groups.
• the remaining NCO groups can be reacted with monofunctional terminators such as butylamine, stearylamine, trialkoxylsilylpropanamine, butanone oxime or morpholine. This prevents excessive growth of the molecular weight or of crosslinking and branching reactions.
• the alcohols contained in the solvent mixture can also act as chain extenders in this form.
• AIs diisocyanates (c) are all known in the art aliphatic, cycloaliphatic and / or aromatic isocyanates having an average NCO functionality> 1, preferably> 2 used individually or in any mixtures with each other, it is irrelevant whether these are phosgene or phosgene -free process were made.
• Isocyanates from the series of aliphatic or cycloaliphatic representatives are preferably used, these having a carbon skeleton (without the NCO groups contained) of 3 to 30, preferably 4 to 20 carbon atoms.
• Particularly preferred compounds of component (c) correspond to the abovementioned type with aliphatically and / or cycloaliphatically bonded NCO groups, for example bis (isocyanatoalkyl) ethers, bis- and tris (isocyanatoalkyl) -benzenes, -toluenes, and -xylols, Propane diisocyanates, butane diisocyanates, pentane diisocyanates, hexane diisocyanates (eg hexamethylene diisocyanate, HDI), heptane diisocyanates, octane diisocyanates, nonane diisocyanates (eg trimethyl-HDI (TMDI) generally as a mixture of the 2,4,4- and 2,2,4-diisocyanates).
• TMDI trimethyl-HDI
• nonane triisocyanates eg 4-isocyanatomethyl-1, 8-octane diisocyanate
• decane diisocyanates decane triisocyanates
• undecanediisocyanates undecane diisocyanates
• dodecane diisocyanates dodecane triisocyanates
• 1,3- and 1,4-bis isocyanatomethyl) cyclohexanes
• HeXDI 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate
• IPDI isophorone diisocyanate
• Hi 2 MDI bis (4-isocyanatocyclohexyl) methane
• NBDI bis (isocyanatomethyl) norbornane
• Very particularly preferred compounds of component (c) are hexamethylene diisocyanate (HDI), trimethyl-HDI (TMDI), 2-methylpentane-l, 5-diisocyanate (MPDI), isophorone diisocyanate (IPDI), 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane (H 6 XDI), bis (isocyanatomethyl) norbornene (NBDI), 3 (4) isocyanatomethyl-1-methylcyclohexylisocyanate (IMCI) and / or 4,4'-bis (isocyanatocyclohexyl) methane ( HnMDI) or mixtures of these isocyanates.
• HDI hexamethylene diisocyanate
• TMDI trimethyl-HDI
• MPDI 2-methylpentane-l
• MPDI 5-diisocyanate
• IPDI isophorone diisocyanate
• diisocyanate component (c) are used per mole of macrodiol mixture (a), preferably 1.7-2.8 mol.
• macrodiol optionally a low molecular weight aliphatic diol, and also diisocyanate are reacted with one another in the melt or in solution until all the hydroxyl groups have been consumed. Then further solvents are added and the optionally dissolved Kettenverinrungsdiamin added. After reaching the target viscosity, the remaining residues of NCO are blocked by a monofunctional aliphatic amine or by butanone oxime.
• AIs solvent for the preparation and the application of polyurethane urea coatings according to the invention are mixtures of alcohols with ⁇ -butyrolactone into consideration, wherein the proportion of ⁇ -butyrolactone, based on the total weight of the polyurethane solution, between 10 wt .-% and 80 wt .-%, preferably between 15 wt .-% and 50 wt .-%.
• the alcohols which are used together with the ⁇ -butyrolactone are ethanol, n-propanol, isopropanol and 1-methoxy-2- ⁇ ropanol.
• esters and ketones such as, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone and methyl isobutyl ketone can also be used.
• the polyurethane ureas according to the invention have melting points above 100 0 C, preference, from 130 0 C to 220 0 C. They have high adhesion and surface hardness, high elongation and tear strength.
• They can be used in any desired concentration or concentration for the particular application or type of substrate to be coated; it is preferable to use 15-60% strength by weight solutions, particularly preferably from 20 to 40% strength by weight solutions.
• the polyurethaneurea solutions according to the invention are preferably used for coating textile fabrics and leather.
• the job can be done directly by printing, spraying, knife coating or transfer coating.
• the polyurethaneurea solutions according to the invention for the production of coating articles on textile substrates by the transfer process.
• the polyurethane urea solutions according to the invention are used as topcoats, which produce an overlay of 5 to 60 g / m 2 on the carrier fabric.
• auxiliaries such as handle auxiliaries, pigments, dyes, matting agents, UV stabilizers, phenolic antioxidants, light stabilizers, water repellents and / or leveling agents may also be used.
• the coatings obtained with the polyurethaneurea solutions according to the invention have very high fastness properties despite the use of the relatively high-boiling solvent ⁇ -butyrolactone. Particularly advantageous are the high adhesion, hardness and tear resistance.
• the dynamic viscosities of the polyisocyanate solutions were determined at 23 ° C. with the viscometer VT 550, plate-cone measuring arrangement PK 100, from Haake (Karlsruhe, Germany). Measurements at different shear rates ensured that the flow behavior of the polyisocyanate mixtures used as well as the comparative products corresponded to the ideal Newtonian liquids. The specification of the shear rate can therefore be omitted.
• the determination of the NCO content of the resins described in the examples and comparative examples was carried out by titration in accordance with DIN 53 185.
• the NCO values indicated in the examples always refer to the initial weight of the considered synthesis stage of the reaction mixture and not to the total solution.
• This example describes the preparation of a polyurethaneurea solution according to the invention.
• n-butylamine are added to block the remaining residual NCO content. This gives 909 g of a 30% polyurethaneurea solution in 1-methoxypropyl acetate / ⁇ -butyrolactone / isopropanol / 1-methoxy-2-propanol having a viscosity of 21,500 mPas at 22 ° C.
• This example describes the preparation of a polyurethaneurea solution according to the invention.
• 200 g of a polycarbonate diol with an average molecular weight of 2,000, prepared from dimethyl carbonate and 1,6-hexanediol are mixed diisocyanate with 63.3 g of 1-methoxypropyl acetate and 52.3 g of isophorone and constant at 110 0 C to a NCO content of 3.60% implemented. It is cooled and diluted with 211.2 g of ⁇ -butyrolactone and 188.9 g of isopropanol. At room temperature, a solution of 21.2 g of 4,4'-diaminodicyclohexylmethane in 161.8 g of 1-methoxy-2-propanol are added.
• the resulting solution is completely stable to crystallization. Even after 6 months storage at room temperature, no turbidity can be detected.
• This example describes the preparation of a polyurethaneurea solution using toluene.
• Example 2 For this one proceeds as described in example 2. Instead of ⁇ -butyrolactone, the same amount of toluene is used, otherwise all starting materials and reaction parameters remain as described in Example 2. This gives 909 g of a 30% polyurethaneurea solution having a viscosity of 30,000 mPas, which is stable for 6 months at room temperature.
• Example 4 Comparative Example without using toluene or ⁇ -butyrolactone
• This example is a comparative example of Inventive Example 1.
• Example 1 The preparation of this polyurethane urea solution is carried out as described in Example 1, the following changes being made to Example 1:
• a 30% strength polyurethane urea solution in 1-methoxypropyl acetate / methyl ethyl ketone / isopropanol / 1-methoxypropanol-2 having a viscosity of 30400 mPas at 22 ° C. is obtained. After 2 weeks of storage at room temperature, increasing turbidity of the solution is noted.
• This example is a comparative example of Inventive Example 1.
• Example 1 The preparation of this polyurethane urea solution is carried out as described in Example 1, the following changes being made to Example 1:
• This example is a comparative example of Inventive Example 1.
• Example 1 The preparation of this polyurethane urea solution is carried out as described in Example 1, the following changes being made to Example 1:
• a 30% strength polyurethane urea solution in 1-methoxypropyl acetate / propylene carbonate / isopropanol / 1-methoxy-2-propanol having a viscosity of 33,000 mPas is obtained. After 4 days of storage at room temperature, the solution becomes cloudy.
• This example is a comparative example of Inventive Example 1.
• Example 1 The preparation of this polyurethane urea solution is carried out as described in Example 1, the following changes being made to Example 1: Instead of ⁇ -butyrolactone, a mixture of 111.2 g of 1-Methoxypro ⁇ ylacetat and 100 g of butyl acetate are used
• the batch gels upon addition of 80% of the total amount of 4,4'-diaminodicyclohexylmethane in 1-methoxy-2-propanol.
• This example is a comparative example of Inventive Example 1.
• Example 1 The preparation of this polyurethane urea solution is carried out as described in Example 1, the following changes being made to Example 1:
• a 30% strength polyurethaneurea solution in 1-methoxypropyl acetate / butyl acetate / isopropanol / 1-methoxypropanol-2 having a viscosity of 36,000 mPas at 22 ° C. is obtained. After 8 days of storage at room temperature, a significant turbidity of the solution is detected.
• This example is a comparative example of Inventive Example 1.
• Example 1 The preparation of this polyurethane urea solution is carried out as described in Example 1, the following changes being made to Example 1:
• a 30% strength polyurethaneurea solution in 1-methoxypropyl acetate / butyl acetate / isopropanol / 1-methoxypropanol-2 having a viscosity of 39200 mPas at 22 ° C. is obtained. After 4 days of storage at room temperature, a strong turbidity of the solution is detected.
• This example is a comparative example of Inventive Example 1.
• Example 1 The preparation of this polyurethane urea solution is carried out as described in Example 1, the following changes being made to Example 1: Instead of ⁇ -butyrolactone, a mixture of 161.2 g of butyl acetate and 50 g of propylene carbonate is used.
• a 30% strength polyurethane urea solution in 1-methoxypropyl acetate / butyl acetate / propylene carbonate / isopropanol / 1-methoxy-propanol having a viscosity of 39200 mPas at 22 ° C. is obtained. After 6 days of storage at room temperature, a turbidity of the solution is detected.
• This example is a comparative example of Inventive Example 1.
• Example 1 The preparation of this polyurethane urea solution is carried out as described in Example 1, the following changes being made to Example 1:
• This example describes the preparation of a polyurethaneurea solution according to the invention.
• the resulting solution is completely stable to crystallization. After 6 months storage at room temperature, no turbidity can be detected.
• This example describes the preparation of a polyurethaneurea solution according to the invention.
• the resulting solution is completely stable to crystallization. After 6 months storage at room temperature, no turbidity can be detected.
• This example describes the preparation of a polyurethaneurea solution using toluene.
• Example 13 For this one proceeds as described in the example 13. Instead of ⁇ -butyrolactone using equal amounts of toluene, otherwise all reactants and reaction parameters remain as described in Example 13. This gives 1322.5 g of a 38% polyurethane urea solution having a viscosity of 48,000 mPas, which is stable for 6 months at room temperature.
• This example is a comparative example of Inventive Example 1.
• Example 1 The preparation of this polyurethane urea solution is carried out as described in Example 1, the following changes being made to Example 1: Instead of ⁇ -butyrolactone, equal amounts of butyl acetate are used.
• This example describes the preparation of a polyurethane-urea solution according to the invention.
• the resulting solution is free from turbidity and crystallization stable over 6 months.
• This example describes the preparation of a polyurethaneurea solution according to the invention.
• the resulting solution is free from turbidity and crystallization stable over 6 months.
• This example describes the preparation of a polyurethaneurea solution according to the invention.
• the resulting solution is free from turbidity and crystallization stable over 6 months.
• This example describes the preparation of a polyurethaneurea according to the invention in solution.
• This example describes the preparation of a polyurethaneurea solution using toluene, but without the use of ⁇ -butyrolactone, as a comparative example to Examples 16, 17, 18 and 19 according to the invention.
• Example 17 To do this, proceed as described in Example 17. Instead of butyl acetate and ⁇ -butyrolactone using equal amounts of toluene, otherwise all reactants and reaction parameters remain as described in Example 17.
• Example 21 Comparative Example without using toluene or ⁇ -butyrolactone
• This example is a comparative example of Inventive Examples 16-19.
• the resulting solution contains gel particles and is therefore already slightly cloudy. After one week of storage at room temperature, a significant increase in the turbidity of the solution can be seen.
• coating films in a layer thickness of 0.15 mm were prepared and tested from the polyurethane solutions according to Example 1, Example 2 and Comparative Example 3 (product according to the prior art with toluene as solvent).
• coating films in a layer thickness of 0.15 mm were prepared and tested from the polyurethane solutions according to Example 12 and Comparative Example 3 (product according to the prior art with toluene as solvent).
• coating films in a layer thickness of 0.15 mm were prepared and tested from the polyurethane solutions according to Example 16, Example 17 and Comparative Example 18 (toluene-containing).

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