Patent GB-1049868-A (GB)
Title: Improvements in laminated and coated articles and materials
IPC: C09J123/08
Filed: 1963-05-29
Abstract: A thermoplastic compound usable as an adhesive or a coating comprises a copolymer having from 99.5 to 50% ethylene and from 0.5 to 50% of at least one vinyl amide having the formula <FORM:1049868/C3/1> where R is an alkyl group containing 1-4 carbon atoms, and each R1 is hydrogen or a hydrocarbon radical free of aliphatic unsaturation having 1-6 carbon atoms, e.g. an alkyl, phenyl or cycloaliphatic group.  Suitable vinyl amides are acrylamide, N-methyl acrylamide, N-hexyl acrylamide, N-cyclohexyl acrylamide, N-phenyl acrylamide, N,N-dihexyl acrylamide, N,N-dicyclohexyl acrylamide, N,N-diphenylacrylamine, N-vinyl acetamide, N-vinyl propionamide, N-vinyl valeramide, N-methyl-N-vinyl acetamide, N-hexyl-N-vinyl acetamide, N-cyclohexyl-N-vinyl acetamide, N-phenyl-N-vinyl acetamide, N-ethyl-N-vinyl acetamide, N-propyl-N-vinyl acetamide, N-isopropyl-N-vinyl acetamide, N-butyl-N-vinyl acetamide, N-ethyl acrylamide, N-propyl acrylamide N-isopropyl acrylamide,N,N-dimethyl acrylamide, N,N-diisopropyl acrylamide. Organic isocyanates may be added to the copolymer and may be represented by the formula Z(NCO)x, where x is an integer of at least 1 and preferably 2 or 3, and Z is any organic radical having a valence of x and in which the valence bonds are from carbon atoms, e.g. an aliphatic moiety, an alicyclic moiety, an aromatic moiety or other hydrocarbon moiety containing 2-40 carbon atoms.  Z can also include radicals of the formula [-Z1-Y-]nZ1--, where n is an integer of from 1 to 10, Y is a divalent moiety such as <FORM:1049868/C3/2> and Z1 is a divalent hydrocarbon moiety having 2-40 carbon atoms.  The hydrocarbon moieties can be substituted with one or more inert groups such as alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkanoyl, aroyl, alkanoyloxy or aroyloxy. Preferred polyisocyanates are those wherein the -N = C = O groups are on different ring carbon atoms of the same or different aromatic ring, e.g. 2:4-diisocyanatotoluene and dianisidine diisocyanate (3-methoxy-4-isocyanatobiphenyl). Up to 20% isocyanate may be added, preferably 0.5 to 2%, e.g. by milling or kneading or by adding it to a solution of the copolymer in a solvent.  The isocyanate may react with the copolymer and, if it is a polyisocyanate, may cause it to cross-link.  The copolymer may be applied to a substrate in a solvent or may be formed into a film and bonded to the substrate by heating. Dies, pigments, tints and plasticizers may be added. In Example V, an ethylene/N-methyl-N-vinyl acetamide copolymer containing 25% of the N-methyl-N-vinyl acetamide is blended with 1% of tolylene diisocyanate and formed into a film suitable for uniting glass sheets.  The following isocyanates were also used:  bitolylene diisocyanate, dianisidine diisocyanate, a 60 : 40 adduct of tolylene diisocyanate and polyethylene oxide having a reduced viscosity, a 60:40 adduct of bis(2-isocyanatoethyl) carbonate and polyethylene oxide, meta-xylylene diisocyanate, polymethylene polyphenyl isocyanate, bis-(4-isocyanatophenyl)-methane, and bis - (3 - methyl - 4 - isocyanatophenyl) - methane. In Examples VI and VII the copolymer contained 15% and 25% N-methyl-N-vinyl acetamide and various percentages of dianisidine diisocyanate. The copolymers have melt indices according to A.S.T.M. D1238-577 of from 0.01 to 1000 dgm/min.ALSO:A thermoplastic compound usable as an adhesive or a coating comprises a copolymer having from 99.5 to 50% of polymerized ethylene and from 0.5 to 50% of at least one polymerized vinyl amide having the formula:  <FORM:1049868/B1-B2/1> or <FORM:1049868/B1-B2/2> Wherein R is an alkyl group containing from 1-4 carbon atoms, and each R1 is hydrogen or a hydrocarbon radical free of aliphatic unsaturation having from 1 to 6 carbon atoms, e.g. an alkyl, phenyl or cycloaliphatic group.  Examples of suitable vinyl amides are given, the preferred compounds being the N-substituted-N-vinyl acetamides of the formula:  <FORM:1049868/B1-B2/3> where R3 is an alkyl radical from 1 to 6 carbon atoms or phenyl, and the acrylamides of the formulae:  <FORM:1049868/B1-B2/4> Where R4 is an hydrogen atom, an alkyl radical of from 1 to 6 carbon atoms, or phenyl.  Up to 20% of an organic isocyanate may be incorporated, preferred materials being the aromatic diisocyanates wherein the -N=C=O groups are on different ring carbon atoms of the same or different aromatic ring, e.g. 2, 4-diisocyanatotoluene and dianisidine diisocyanate (3-methoxy-4-isocyanatobiphenyl).  The isocyanate may react with the copolymer and, if it is a polyisocyanate, may cause it to cross link. A list is given of materials with which the copolymer forms strong bonds, the list including metals, cellulosic materials, plastics, glass, rubbers, cements and masonry.  The article to which the copolymer is applied may be plane or shaped, e.g. in the form of a rod, cylinder or bottle. The copolymer may be applied by dip coating, solvent spray coating or extrusion coating in solution with subsequent evaporation of the solvent or by melting while in contact with the receiving surface; alternatively, a sheet of the copolymer is hot pressed on to the receiving surface, the latter or the sheet having first been coated with a layer of isocyanate.  The copolymer is suitable as an acid or water-proof coating for structural materials, as grease-and water-proofing materials for paper or cloth, and as an adhesive interlayer in plywood or safetypanes.  Dyes, pigments and tints may be incorporated in the copolymer together with plasticizers, if desired.  In Example IX, various films are bonded to kraft paper or 30/70 methyl methacrylate/styrene copolymer to form an oxygen barrier, the free surfaces of the films being coated with an epoxy resin or polyvinylidene chloride.  In Examples XXI-XXVI, a copolymer containing 16.9% N-methyl -N-vinyl acetamide is heated to 80 DEG C. in heptane to provide a dipping solution for iron strip, polyvinyl alcohol and cotton cloth.  In Example XXII, particles of the copolymer are used to form a fluidized bed in which heated iron is dipped.