Patent GB-1233932-A (GB)
IPC: C08J9/28
Filed: 1968-07-19
Abstract: 1,233,932. Making polyurethane microporous films. FARBENFABRIKEN BAYER A.G. 19 July, 1968 [22 July, 1967], No. 34490/68. Heading B5B. [Also in Division C3] Microporous films (and other sheet structures) which are permeable to water vapour are made by mixing (a) 90 to 70 parts by weight of one or more polyurethane-ureas which are free from NCO groups and which have been obtained by reacting high molecular weight linear polyhydroxy compounds which are not miscible with water and which have terminal OH groups and have a molecular weight of 500 to 5000, and, if desired, diols of low molecular weight, with diisocyanates to form a prepolymer containing at least 0À75% by weight of free NCO groups, followed by chain lengthening in highly polar, water miscible solvents having a boiling point above 100‹ C., with water and/or a bifunctional compound which contains reactive hydrogen atoms linked to nitrogen atoms, and (b) 10 to 30% by weight (based on dry substance) of one or more high molecular weight linear cationic polyurethanes which are free from NCO groups and which contain 8 to 35% by weight of urethane, and, if desired, urea groups, and 0À5 to 2À0% of quaternary ammonium nitrogen atoms, the cationic polyurethane composition being present in the form of an aqueous dispersion or colloidal solution which has a concentration such that the proportion of water introduced with it into the finished mixture is below 7% by weight, and dissolving the mixture in (c) 200 to 2000 parts by weight of a water-soluble, strongly polar solvent for polyurethane-urea (a) having a boiling point above 100‹ C., so that the viscosity of the solution is 1 to 30 minutes, measured in a Ford viscometer with 6 mm. outflow nozzle at 20‹ C.; (d) shaping the mixture to form a film or sheet, by applying the solution to a substrate and after exposing the coated substrate to moist air until the coating of the solution gels, dipping the coated substrate in at least one mixture of a solvent and a liquid which is a non-solvent for the polymer and miscible with the solvent and drying the coated substrate. The non-solvent used may be water and the solvent may be dimethylformamide. The polyurethaneurea may be prepared from a prepolymer obtained by reacting a polyester of adipic acid with a diisocyanate such as diphenylmethane- 4,4<SP>1</SP>-diisocyanate or one or more of the isomeric toluylene diisocyanates. The diisocyanate used may contain hexane-1,4-diisocyanate or dicyclohexane-4,4<SP>1</SP>-diisocyanate. The chain lengthening agent may be ethylene diamine, m-xylylene diamine, hydrazine carbohydrazide and/or water used in a proportion of at least 50 mols. per cent of chain lengthening agents used. The mixture obtained in step (c) may be heated to 40‹ to 60‹ C. for 60 minutes before gelling. At least 2À5% (as dry substance based on dry substance (b)) of an anionic synthetic tanning agent may be added to the mixture before any gelling sets in, or the completely coagulated film obtained from components (a) and (b) may be treated with an aqueous solution of the synthetic tanning agent, which tanning agent has been obtained from substituted or unsubstituted aryl sulphonic acids, aryl carboxylic acids or phenols, and formaldehyde, if desired with sulphurous acid or its salts and other compounds which react with formaldehyde.