Patent GB-681494-A (GB)
Title: Anti-sticking cellulose films
IPC: C08J7/046
Filed: 1950-07-28
Abstract: Regenerated cellulose films, pellicles and sheets, are rendered resistant to sticking by treating them while in the wet gel state with an aqueous bath containing an acylated polyalkylene polyamine or a salt thereof.  The preferred acylated polyamines are those of the formula: R1.(R2).N.(CH2)n.N.(R3).R4 where n is an integer from 1 to 10, R1 is an acyl group of 2-18 C atoms, preferably 12-18 C atoms, R2 and R4 are H, alkyl radicals of 1-7 C atoms, acyl groups of 2-7 C atoms, or o -amino polyalkylene polyamino groups of the formula: (CxH2xNR5)y.CxH2x.N.(R6) R7 (where x is an integer from 1-10, y is an integer from 1-100, R5 is H or an alkyl radical of 1-7 C atoms, R6 and R7 are H, alkyl radicals of 1-7 C atoms, or acyl groups of 2-7 C atoms), and R3 is H, an alkyl radical of 1-7 C atoms, or an acyl radical of 2-7 C atoms.  These compounds may be obtained from ethylene diamine, diethylene triamine, triethylene tetramine, tripropylene tetramine, tributylene tetramine, or hexamethylene diamine, and butyric, caproic, caprylic, capric, lauric, myristic, palmitic, stearic, oleic, or linoleic acid.  The unreacted amine groups may be neutralized by means of an organic acid.  The solution or stable emulsion of the acylated polyalkylene polyamine or its salt may be added to the plasticizer bath on the casting machine in a quantity sufficient to produce a concentration in the bath of 0.05-2.0 per cent of solids.  The regenerated cellulose wet gel film is then impregnated by passage through the bath, the excess of solution being removed by squeeze rolls or wiper blades. Alternatively the anti-sticking agent may be applied subsequently to the plasticizer.  In this case the solids content of the solution should be higher, e.g. 1.0-2.0 per cent.  If desired, the anti-sticking agent may be applied after the film has been partially dried to a stage where the moisture content is still not less than 60 per cent.  The film is reconverted to the wet gel state while passing through the aqueous solution.  In an example, 1 mol. of triethylene tetramine is condensed with 1.3 mols. of stearic acid.  The initial condensation is carried out in xylene at 140 DEG  C. till the theoretical amount of water has been removed. The xylene is distilled off and the resulting compound N-(b -aminoethyl), N1-(b -stearamidoethyl) ethylene diamine is added to water containing 2 mols. of succinic acid.  A 5-10 per cent aqueous dispersion is formed and is added to the plasticizer bath.  In another example, 1 mol. of stearic acid is condensed with 1 mol. of diethylene triamine and the compound is reacted with acetic acid to form the acetylated amide.  A 5-10 per cent aqueous dispersion of the amide is added to the plasticizer bath with which the regenerated cellulose wet gel film is treated.ALSO:Acylated polyalkylene polyamines or their salts for use in imparting an anti-sticking finish to regenerated cellulose films (see Group IV (a)), have the generic formula: R1.(R2).N.(CH2)n.N.(R3).R4 where n is an integer from 1-10, R1 is an acyl group of 2-18 C atoms, preferably 12-18 C atoms, R2 and R4 are H, alkyl radicals of 1-7 C atoms, acyl groups of 2-7 C atoms, or o -amino polyalkylene polyamino groups of the formula: (CxH2xNR5)y.CxH2x.N. (R6).R7 (where #c is an integer from 1-10, y is an integer from 1-100, R5 is H or an alkyl radical of 1-7 C atoms, R6 and R7 are H, alkyl radicals of 1-7 C atoms, or acyl groups of 2-7 C atoms), and R3 is H, an alkyl radical of 1-7 C atoms, or an acyl radical of 2-7 C atoms. These compounds may be obtained by heating a polyalkylene polyamine with a fatty acid in the molecular ratio range of 1 to 1-1.7, preferably at 105-140 DEG  C.  The reaction may be carried out in an inert solvent such as toluene or xylene until an equivalent molecular proportion of water has been removed.  The solvent, if any, is then removed, e.g. by distillation.  Ethylene diamine, diethylene triamine, triethylene tetramine, tripropylene tetramine, tributylene tetramine, or hexamethylene diamine may be heated with butyric, caproic, caprylic, capric, lauric, myristic, palmitic, stearic, oleic, or linoleic acid.  The resulting compound may be added with stirring to water containing an organic acid such as acetic, propionic, maleic, fumaric, lactic, or succinic acid to neutralize a major portion of the unreacted amine groups.  In an example, 1 mol. of triethylene tetramine is condensed with 1.3 mols. of stearic acid, the initial condensation taking place in xylene at 140 DEG  C. until the theoretical amount of water has been removed. The xylene is removed by distillation.  The resulting compound N(b -aminoethyl), N1(b  stearamidoethyl)ethylene diamine is added to water containing 2 mols. of succinic acid.  In another example, 1 mol. of stearic acid is condensed with 1 mol. of diethylene triamine and the resulting compound is reacted with acetic acid to form the acetylated amide.  Triethylene tetramine may be condensed with lauric acid, and the compound obtained may be converted into the succinate, or acetate.