Patent GB-1122117-A (GB)
Title: Epoxy resin sizing compositions
IPC: C08G59/44
Filed: 1966-11-18
Abstract: A composition for coating shaped polymeric structures to provide improved adhesion to rubber comprises (a) 2-pyrrolidone, (b) a polyepoxide having an average of at least 2 epoxy groups in each molecule, a melting point below 150 DEG  C., an average molecular weight below 3000 and an epoxy equivalent below 1500 and (c) an alkaline catalyst amounting to 0.005-2.0 wt. per cent of the 2-pyrrolidone, and optionally also formaldehyde and/or a blocked or polymerized polyisocyanate.  When the latter are present the preferred molar ratios are: pyrrolidone: formaldehyde = 1-10:1 and pyrrolidone: blocked polyisocyanate = 1-50:1.  The preferred weight ratio of polyepoxide: pyrrolidone is 1.5:1 to 1:10.  The blocked polyisocyanates are dimers and polymers of polyisocyanates and adducts of polyisocyanates with e.g. phenols, thiophenols, oximes and lactams. Suitable polyisocyanates are methylene-bis (4-phenyl isocyanate), m - phenylene diisocyanate, toluene - 2:4 - diisocyanate, (diphenyl ether)-2:4:41-triisocyanate, tetramethylxylylene diisocyanate and hexamethylene diisocyanate. The formaldehyde gives rise to N-methylol - 2 - pyrrolidone. Suitable catalysts (c) include NaOH, KOH, Na2CO3, K2CO3, NaOOC.CH3, KOOC.CH3, hexamethylene diamine and piperazine, or the catalyst may be formed in situ, e.g. by decomposition, during cure, of the blocked polyisocyanate. Structures treated with the composition are further treated with a resorcinol-formaldehyde-latex (RFL) composition, or these two compositions may be applied simultaneously in a single aqueous mixture. In this mixture the resorcinol: formaldehyde molar ratio is 0.6-1.35:1, the latex: RF solids weight ratio is 2-8:1, and the RFL solids constitute 12-25 wt. per cent of the total solids.  A butadiene-vinyl-pyridine latex is preferred.  In examples a mixture is used of 2-pyrrolidone, formalin and a glycerol polyglycidyl ether (molar ratio pyrrolidone: formaldehyde = 2:1, weight ratio pyrrolidone: polyepoxide = 5:1) and a minor amount of 10% aqueous NaOH.  In Example 5 this is combined with a resorcinol-formaldehyde-butadiene/styrene/vinylpyridine latex mixture which is applied separately in the other examples.  In Examples 6-9 there is also present in the solution acetone and a phenol adduct of methylene-bis (4-phenyl isocyanate) or of hexamethylene diisocyanate.ALSO:Shaped polymeric structures, e.g. tyre cords, are treated to improve their adhesion to rubber by coating with a composition comprising (a) 2-pyrrolidone, (b) a polyepoxide containing at least two epoxy groups per molecule, melting below 150 DEG C. and of molecular weight below 3000, and (c) an alkaline catalyst amounting to 0.005-2.0 wt. % of the 2-pyrrolidone, and optionally also formaldehyde and/or a blocked or polymerized poly-isocyanate.  Structures treated with the composition may be further treated with a resorcinol-formaldehyde-latex (RFL) composition, or the two compositions may be applied in a single aqueous mixture.  In Examples polyethylene terephthalate tyre cord, or yarn subsequently made up into tyre cord, is treated with a mixture of 2-pyrrolidone, formalin and a glycerol polyglycidyl ether, and a minor amount of 10% aqueous NaOH.  In Example 5 this is combined with a resorcinol-formaldehyde-butadiene/styrene/vinylpyridine latex which is applied separately in the other examples.  In Examples 6-9 there is also present in the composition acetone and a phenol adduct of methylene-bis-(4-phenyl isocyanate) or of hexamethylene diisocyanate. In Example 7 the cord is of a polymer of bis (4-amino-cyclohexyl) methane and dodecanedoic acid.