Laminated polymeric articles and process for the production thereof

Abstract

A process is provided for bonding otherwise incompatible resin systems to form laminated resinous articles. A first resin layer is coated with a solvated coating which forms a surface solution with the surface of the first layer. Thereafter, a second resin layer is bonded to the coating. The coating contains a butadiene resin, a portion of the resin used in the second layer, and curing agent for the resin. The process is particularly adapted to bonding polyvinyl chloride pipe cores to epoxy-impregnated glass fiber overwrap to form improved laminated plastic pipe.

What is claimed is:  .[. 
     
       1.  In a process for bonding together a first resinous layer containing as a major component a first polymeric resin, said first polymeric resin being selected from the group consisting of poly(vinyl acetate), poly(methyl methacrylate), polystyrene, polybutene, poly(vinyl butyral) and the polymeric olefinic chlorides, and a second resinous layer containing as a major component a second polymeric resin, said second polymeric resin being thermosetting, dissimilar to and substantially chemically unbondable directly to said first polymeric resin and selected from the group consisting of epoxy resins, polyester resins and phenolic resins; which process comprises forming a surface solution, on the surface of said first resinous layer, of said first polymeric resin and a coating comprising a butadiene resin and a mutual solvent for said first polymeric resin and said butadiene resin, where said butadiene resin is substantially curable to said second polymeric resin and substantially chemically unbondable directly to and substantially incompatible with said first polymeric resin other than in a solvated state; at least partially fusing said surface solution; applying to said coating said second resinous layer containing said second polymeric resin in a substantially uncured form; and curing said second polymeric resin and simultaneously bonding said second resinous layer to said coating: the improvement which comprises incorporating into said coating said second polymeric resin and a curing agent for said second polymeric resin, and during the curing step bonding said second polymeric resin in said coating to said second polymeric resin in said second resinous layer..]. .[.2. The improved process of claim 1 wherein said first polymeric resin is a polymeric olefinic chloride selected from the group consisting of poly(vinylidine chloride), poly(vinyl chloride) and copolymers thereof..]. .[.3. The improved process of claim 1 wherein said second polymeric resin is an epoxy resin..]. .[.4. The improved process of claim 1 wherein said butadiene resin is selected from the group consisting of polybutadiene, butadiene-styrene resin, acrylonitrile-butadiene resin, acrylonitrile-butadiene-styrene resin, and mixtures thereof..]. .[.5. The improved process of claim 1 wherein said mutual solvent for said first polymeric resin and said butadiene resin is a solvent in which said second polymeric resin is also soluble..]. .[.6. In a process for bonding together a poly(vinyl chloride) layer and an epoxy-impregnated fiber glass layer, said process comprising forming a surface solution, on the surface of the poly(vinyl chloride) layer, a poly(vinyl chloride) and a coating containing a butadiene resin and a mutual solvent for said poly(vinyl chloride) and said butadiene resin; at least partially fusing said surface solution; applying to said coating said epoxy-impregnated fiber glass layer containing said epoxy resin in a substantially uncured form; and curing said epoxy resin and simultaneously bonding said epoxy-impregnated fiber glass layer to said coating:   the improvement which comprises incorporating said epoxy resin and a curing agent therefor into said coating and during the curing step bonding said epoxy resin in said coating to said epoxy resin in said epoxy-impregnated fiber glass layer..]. .[.7. The improved process of claim 6 wherein said butadiene resin is an acrylonitrile-butadiene-styrene resin..]. .[.8. The improved process of claim 7 wherein said mutual solvent is selected from the group consisting of tetrahydrofuran and methyl ethyl ketone..]. .[.9. The improved process of claim 1 wherein said second polymeric resin is present in said coating in an amount of 0.1 to 5 parts by weight per part of said butadiene resin..]. .[.10. The improved process of claim 9 wherein said second polymeric resin is present in said coating in an amount of from 1/6 to 3 parts of weight per part by weight of said butadiene resin..]. .[.11. The improved process of claim 1 wherein said curing agent is present in said coating in an amount of from 5 to 35 parts by weight per 100 parts by weight of said second polymeric resin in said coating..]. .[.12. The improved process of claim 11 wherein said curing agent is present in the coating composition as 11 to 25 parts by weight per 100 parts by weight of said second polymeric resin in said coating..]. .[.13. A laminated article having improved bonding between the laminae comprising a first resinous layer containing as the principal component a polymeric olefinic chloride resin selected from the group consisting of polyvinyl chloride and copolymers of vinyl chloride and vinylidene chloride, and a second resinous layer containing as the principal component an epoxy resin, said first and second polymeric resins being bonded into a laminate by a coating therebetween and in intimate contact therewith, said coating initially comprising:   a a butadiene resin, which is thermoplastic, substantially curable to said epoxy resin and substantially chemically unbondable directly to and substantially incompatible with said polymeric olefinic chloride resin other than in a solvated state:   b said epoxy polymeric resin:   c a mutual solvent for at least said polymeric olefinic chloride resin and said butadiene resin: and   d a curing agent for said epoxy resin; said coating and said polymeric olefinic chloride resin forming a fused surface solution on the surface of said first resinous layer and said coating and said second resinous layer being chemically bonded; and     said epoxy resin and said butadiene resin being present in said coating in a weight ratio of epoxy resin to butadiene resin in the range of 0.175:1 to 0.70:1..]. .[.14. The laminated article of claim 13 wherein said second resinous layer comprises an epoxy resin matrix containing glass fiber reinforcement..]. .[.15. The laminated article of claim 13 wherein said butadiene resin is selected from the group consisting of polybutadiene, butadiene-styrene resin, acrylonitrile-butadiene resin, acrylonitrile-butadienestyrene resin and mixtures thereof..]. .[.16. A laminated article having improved bonding between the laminae, which consists essentially of a poly(vinyl chloride) layer and an epoxy resin impregnated fiber glass layer, said layers being bonded into a laminate by a coating there-between and in intimate contact therewith, said coating initially comprising:   a. an acrylonitrile-butadiene-styrene resin:   b. epoxy resin:   c. a mutual solvent for at least said poly(vinyl chloride) and said acrylonitrile-butadiene-styrene resins; and   d. a curing agent for said epoxy resin; with said coating and said poly(vinyl chloride) forming a surface solution of said poly(vinyl chloride) layer and said coating and said epoxy resin impregnated fiber glass layer being chemically bonded, and said epoxy resin and said acrylonitrile-butadienestyrene resin being present in said coating in a weight ratio of epoxy resin to acrylonitrile-butadiene-styrene resin in the range of 0.175:1 to 0.70:1..]. .[.17. The laminated article of claim 16 wherein said mutual solvent is selected from the group consisting of tetrahydrofuran and methyl ethyl ketone..].  .[.18. The laminated article of claim 16 wherein said laminae comprise a poly(vinyl chloride) hollow inner cylinder and an outer layer thereupon of epoxy resin matrix reinforced with glass fiber, and said coating bonding said inner cylinder and said outer layer comprises acrylonitrile-butadienestyrene resin, epoxy resin, methyl ethyl ketone, and a curing agent comprising an equimolar complex of diacetoneacrylamide and diethylenetriamine..]. .[.19. The improved laminated article of claim 13 wherein said curing agent is present in said coating in an amount of from 5 to 35 parts by weight per 100 parts by weight of said epoxy resin in said coating..]. .[.20. The improved laminated article of claim 19 wherein said curing agent is present in the coating composition as 11 to 25 parts by weight per 100 parts by weight of said epoxy resin in said coating..]. .[.21. The laminated article of claim 13 comprising a pipe..]. .Iadd. 22. In a process for bonding together a plastic layer comprising a thermoplastic poly(vinyl acetate), poly(methyl methacrylate), polystyrene, polybutene, poly(vinyl butyral) or polymeric olefinic chloride resin and a thermosetting layer comprising a liquid thermosetting epoxy, phenolic, or polyester resin, which layers are substantially chemically unbondable to each other;   which process comprises forming a surface solution, on the surface of said thermoplastic layer, of said thermoplastic resin and a coating comprising a butadiene resin and a mutual solvent for said butadiene resin and said thermoplastic resin; at least partially fusing said surface solution; applying to said coating said thermosetting layer in a substantially uncured state; and curing said thermosetting layer and simultaneously bonding said thermosetting layer to said coating;   the improvement which comprises increasing the strength of the bond formed in said curing step between said coating and said thermosetting layer by incorporating into said coating a solid thermosetting epoxy, phenolic or   
     
     
        polyester resin and a curing agent therefor. .Iaddend..Iadd. 23.  The improved process of claim 22 wherein said thermoplastic resin is a polymeric olefinic chloride selected from the group consisting of poly(vinylidine chloride), poly(vinyl chloride) and copolymers thereof. .Iaddend..Iadd. 24. The improved process of claim 22 wherein both of said thermosetting resins are epoxy resins. .Iaddend..Iadd. 25. The improved process of claim 22 wherein said butadiene resin is selected from the group consisting of polybutadiene, butadiene-styrene resin, acrylonitrile-butadiene-styrene resin, and mixtures thereof. .Iaddend..Iadd. 26. The improved process of claim 22 wherein said mutual solvent for said thermoplastic resin and said butadiene resin is a solvent in which said solid thermosetting resin is also soluble. .Iaddend..Iadd. 27. The improved process of claim 22 wherein said thermosetting resin is present in said coating in an amount of 0.1 to 5 parts by weight per part of said butadiene resin. .Iaddend..Iadd. 28. The improved process of claim 27 wherein said solid thermosetting resin is present in said coating in an amount of from 1/6 to 3 parts of weight per part by weight of said butadiene resin. .Iaddend..Iadd. 29. The improved process of claim 22 wherein said curing agent is present in said coating in an amount of from 5 to 35 parts by weight per 100 parts by weight of said solid thermosetting resin in said coating. .Iaddend. .Iadd. 30. The improved process of claim 29 wherein said curing agent is present in the coating composition as 11 to 25 parts by weight per 100 parts by weight of said solid thermosetting resin in said coating. .Iaddend..Iadd. 31. In a process for bonding together a poly(vinyl chloride) layer and an epoxy-impregnated fiber glass layer; said process comprising forming a surface solution, on the surface of the poly(vinyl chloride) layer of poly(vinyl chloride) and a coating containing a butadiene resin and a mutual solvent for said poly(vinyl chloride) and said butadiene resin; at least partially fusing said surface solution; applying to said coating said epoxy-impregnated fiber glass layer containing said epoxy resin in a substantially liquid uncured form; and curing said epoxy resin and simultaneously bonding said epoxy-impregnated fiber glass layer to said coating; the improvement which comprises increasing the strength of the bond formed in the curing step between the epoxy-impregnated fiber glass layer and the coating by incorporating into said coating a solid epoxy resin and a curing agent thereof. .Iaddend..Iadd. 32. The improved process of claim 31 wherein said butadiene resin is an acrylonitrile-butadiene-styrene resin. .Iaddend..Iadd. 33. The improved process of claim 32 wherein said mutual solvent is selected from the group consisting of tetrahydrofuran and methyl ethyl ketone. .Iaddend..Iadd. 34. A laminated article having improved bonding between the laminae comprising a thermoplastic layer containing as the principal component a polymeric olefinic chloride resin selected from the group consisting of polyvinyl chloride and copolymers of vinyl chloride and vinylidene chloride, and a thermosetting layer containing as the principal component an epoxy resin, said layers being bonded into a laminate by a coating therebetween and an intimate contact therewith, said coating initially comprising:   a. a butadiene resin, which is thermoplastic, substantially curable to said epoxy resin and substantially chemically unbondable directly to and substantially incompatible with said polymeric olefinic chloride resin other than in a solvated state;   b. a solid epoxy resin;   c. a mutual solvent for at least said polymeric olefinic chloride resin and said butadiene resin; and   d. a curing agent for said solid epoxy resin; said coating and said polymeric olefinic chloride resin forming a fused surface solution on the surface of said thermoplastic layer and said coating and said thermosetting layer being chemically bonded; and   said solid epoxy resin and said butadiene resin being present in said coating in a weight ratio of epoxy resin to butadiene resin in the range of 0.175:1 to 0.70:1. .Iaddend..Iadd. 35. The laminated article of claim 34 wherein said thermosetting layer comprises an epoxy resin matrix containing glass fiber reinforcement. .Iaddend..Iadd. 36. The laminated article of claim 34 wherein said butadiene resin is selected from the group consisting of polybutadiene, butadiene-styrene resin, acrylonitrile-butadiene resin, acrylonitrile-butadiene-styrene resin and mixtures thereof. .Iaddend. .Iadd. 37. The improved laminated article of claim 34 wherein said curing agent is present in said coating in an amount of from 5 to 35 parts by weight per 100 parts by weight of said solid epoxy resin in said coating. .Iaddend..Iadd. 38. The improved laminated article of claim 37 wherein said curing agent is present in the coating composition as 11 to 25 parts by weight per 100 parts by weight of said solid epoxy resin in said coating. .Iaddend..Iadd. 39. The laminated article of claim 34 comprising a pipe. .Iaddend..Iadd. 40. A laminated article having improved bonding between the laminae, which consists essentially of a poly(vinyl chloride) layer and an epoxy resin impregnated fiber glass layer, said layers being bonded into a laminate by a coating therebetween and in intimate contact therewith, said coating initially comprising:     a. an acrylonitrile-butadiene-styrene resin;   b. a solid epoxy resin;   c. a mutual solvent for at least said poly(vinyl chloride) and said acrylonitrile-butadiene-styrene resins; and   d. a curing agent for said solid epoxy resin; with said coating and said poly(vinyl chloride) forming a surface solution of said poly(vinyl chloride) layer and said coating and said epoxy resin impregnated fiber glass layer being chemically bonded, and   said solid epoxy resin and said acrylonitrile-butadiene-styrene resin being present in said coating in a weight ratio of solid epoxy resin to acrylonitrile-butadiene-styrene resin in the range of 0.175:1 to 0.70:1. .Iaddend. .Iadd. 41. The laminated article of claim 40 wherein said mutual solvent is selected from the group consisting of tetrahydrofuran and methyl ethyl ketone. .Iaddend..Iadd. 42. The laminated article of claim 40 wherein said laminae comprise a poly(vinyl chloride) hollow inner cylinder and an outer layer thereupon of epoxy resin matrix reinforced with glass fiber, and said coating bonding said inner cylinder and said outer layer comprises acrylonitrile-butadiene-styrene resin, solid epoxy resin, methyl ethyl ketone, and a curing agent comprising an equimolar complex of diacetoneacrylamide and diethylenetriamine. .Iaddend.