Laminates of polynorbornene and polyolefins derived from C2 -C4 monomers

Abstract

Printed wiring boards useful for high frequency applications are obtained by laminating a conductive foil pretreated with a silane to a polynorbornene prepreg wherein a sheet of polyolefin film derived from C 2 -C 4 monomers is laminated between the prepreg and the foil to the surfaces of each member. The prepreg is made by impregnating a fiberglass cloth with a ring-opening polymerized polymer. The conductive foil is pretreated with a silane which is capable of improving the bond strength between the conductive foil and a norbornene copolymer.

What is claimed is: 
     
       1. A printed wiring board produced by a process comprising: (a) providing a dipping solution comprising polynorbornene polymers dissolved within a solvent;   (b) impregnating a .[.non-cellulosic.]. .Iadd.glass .Iaddend.cloth with the dipping solution and drying the impregnated cloth to remove a substantial portion of solvent to form a substrate layer.   (c) pretreating the surface of a conductive film with a solution of silane compound suitable for increasing the bond strength between the substrate layer and the conductive film layer; and   (d) sandwiching .[.an.]. .Iadd.and .Iaddend.laminating a layer of polyolefin film derived from C 2  -C 4  monomer .Iadd.of up to about 10 mils in thickness .Iaddend.on the pretreated surface between the substrate layer and the .[.copper layer.]. .Iadd.conductive film .Iaddend.at a temperature above the glass transition temperature of the polynorbornene .[.and, when a curing agent is present, sufficiently high to activate said curing agent.]..   
     
     
       2. A printed wiring board of claim 1 wherein the cloth is a woven or non-woven fiberglass cloth. 
     
     
       3. A printed wiring board of claim 1 wherein the conductive film is copper. 
     
     
       4. A printed wiring board of claim 1 wherein the polyolefin is polyethylene. 
     
     
       5. A printed wiring board of claim 1 wherein the polynorbornene is derived from vinyl-norbornene monomer polymerized with either methyltetracyclododecene or dicyclopentadiene monomers. 
     
     
       6. A printed wiring board of claim 1 wherein the .[.polynorbornenes.]. .Iadd.polynorbornene polymers .Iaddend.are cross-linked with the aid of a curing agent and wherein step (b) is conducted at a temperature below the activation temperature of said curing agent. 
     
     
       7. A printed wiring board of claim 1 wherein the dipping solution further comprises an antioxidant. 
     
     
       8. A printed wiring board of claim .[.1.]. .Iadd.3 .Iaddend.wherein the copper film is the surface layer of a metallic film selected from the group consisting of copper, nickel, silver, gold, aluminum, platinum, titanium, zinc, bronze and chromium. 
     
     
       9. A printed wiring board of claim 1 wherein the silane suitable for increasing the bonding strength is selected from the group consisting of 3-methylacryloyloxypropyltrimethoxysilane,   3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride,   3-(N-allyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride,   N-(styrylmethyl)-3-aminopropyltrimethoxysilane hydrochloride,   N-2-aminoethyl-3-aminopropyltrimethoxysilane, and   3-(N-benzyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride.   
     
     
       10. A printed wiring board of claim 1 wherein then non-cellulosic cloth comprises glass fibers and is pretreated with a styryl diamino silane. 
     
     
       11. A printed .[.circuit.]. wiring board of claim 1, which exhibits a peel strength of at least about 6 lbs/inch, a dielectric constant below about 3.5 and a dissipation .[.faction of less 0.005..]. .Iadd.factor of less than 0.005 at 1 MHZ. .Iaddend. 
     
     
       12. A printed .[.circuit.]. wiring board of claim 1, which exhibits a peel strength of at least about 6 lbs/inch, a dielectric constant below about 3.1 and a dissipation .[.faction of less 0.003.]. .Iadd.factor of less than 0.003 at 1 MHZ. .Iaddend. 
     
     
       13. A laminate comprising at least one substrate layer comprising a .[.non-cellulosic.]. .Iadd.glass .Iaddend.cloth which has been impregnated with polynorbornene polymers laminated to at least one layer of conductive film which conductive film has been pretreated on at least one surface thereof with a silane compound suitable for increasing the bond strength between the substrate layer and the .[.copper.]. .Iadd.conductive .Iaddend.film layer, with a layer of polyolefin sandwiched therebetween. 
     
     
       14. A laminate of claim 13 wherein the conductive film is copper and the surface of the copper film which is pretreated has a bronze coating. 
     
     
       15. A laminate of claim 13 wherein the polynorbornene polymer is unsaturated and is derived from a cycloolefin monomer selected from methyltetracyclododecene, vinyl-norbornene and dicyclopentadiene. 
     
     
       16. A laminate of claim 13 wherein the monomers of the polynorbornene polymer are comprised in a weight to weight ratio of about 50-75 percent methyltetracyclododecene to 25-50 percent vinyl-norbornene. 
     
     
       17. A laminate of claim 13 wherein the monomers of the polynorbornene polymer are comprised in weight to weight ratio of about 75-90 percent dicyclopentadiene to about 10-25 percent vinyl-norbornene. 
     
     
       18. A laminate of claim 13 wherein the dipping solution further comprises a curing agent which initiates radical cross-linking. 
     
     
       19. A laminate of claim 13 wherein the silane is selected from the group consisting of 3-methylacryloyloxypropyltrimethoxysilane,   3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride,   3-(N-allyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride,   N-(styrylmethyl)-3-aminopropyltrimethoxysilane hydrochloride,   N-2-aminoethyl-3-aminopropyltrimethoxysilane, and   3-(N-benzyl-2-aminoethylamino)-propyltrimethoxy silane hydrochloride.   
     
     
       20. A laminate of claim .[.13.]. .Iadd.14 .Iaddend.further comprising placing two or more substrate layers in a stacking sequence with copper layers at the outside of the stack. 
     
     
       21. A laminate of claim 20 wherein a sheet of polyolefin is sandwiched between the substrate layers. 
     
     
       22. A laminate of claim 13 wherein the cloth is impregnated with from 30% to 80% by weight polynorbornene polymer. .[. 
     
     
       23.  A laminate of claim 13 wherein the thickness of the polyolefin sheet, prior to lamination, is less than or equal to about 10 mils..]. 
     
     
       24. A laminate of claim .[.23.]. .Iadd.1 .Iaddend.wherein the thickness of the polyolefin sheet, prior to lamination, .[.is less than or equal .]. .Iadd.has a thickness of up .Iaddend.to about 5 mils. 
     
     
       25. A laminate of claim 24 wherein the thickness of the polyolefin sheet, prior to lamination, .[.is less than or equal .]. .Iadd.has a thickness of up .Iaddend.to about 1.5 mils. 
     
     
       26. A laminate of claim 13 wherein the polyolefin is polyethylene. 
     
     
       27. A process for producing a laminate, comprising: (a) providing a dipping solution comprised of polynorbornene polymers dissolved within a solvent;   (b) impregnating .[.an on-cellulosic.]. .Iadd.a glass .Iaddend.cloth with the dipping solution and drying the impregnated cloth to remove a substantial portion of solvent to form a prepreg to function as a substrate layer;   (c) pretreating the surface of a conductive film with a solution of a silane compound suitable for increasing the bond strength between the substrate layer and the conductive film layer; and   (d) sandwiching and laminating a layer of polyolefin film derived from C 2  -C 4  monomers .Iadd.of up to about 10 mils thickness .Iaddend.on the pretreated surface between the substrate layer and the .[.copper layer, .]. .Iadd.conductive film .Iaddend.at a temperature above the glass transition temperature of the polynorbornene .[.and, when a curing agent is present, sufficiently high to activate said curing agent.]..   
     
     
       28. A process of claim 27 wherein the conductive film is copper and the surface of the copper film which is pretreated has a bronze coating. 
     
     
       29. A process of claim 27 wherein the polynorbornene polymer is unsaturated and is derived from a cycloolefin monomer selected from methyltetracyclododecene, vinyl-norbornene and dicyclopentadiene. 
     
     
       30. A process of claim 27 wherein the monomers of the polynorbornene polymer are comprised in a weight to weight ratio of about 50-75 percent methyltetracyclododecene to 25-50 percent vinyl-norbornene. 
     
     
       31. A process of claim 27 wherein the monomers of the polynorbornene polymer are comprised in weight to weight ratio of about 75-90 percent dicyclopentadiene to about 10-25 percent vinyl-norbornene. 
     
     
       32. A process of claim 27 wherein the dipping solution further comprises a curing agent which initiates radical cross-linking and wherein step (b) is conducted at a temperature below the activation temperature of said curing agent. 
     
     
       33. A process of claim 27 wherein the silane is selected from the group consisting of 3-methylacryloyloxypropyltrimethoxysilane,   3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride,   3-(N-allyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride,   N-(styrylmethyl)-3-aminopropyltrimethoxysilane hydrochloride,   N-2-aminoethyl-3-aminopropyltrimethoxysilane, and   3-(N-benzyl-2-aminoethylamino)-propyltrimethoxy silane hydrochloride. .[.34. A process of claim 27 wherein the lamination is performed at a temperature above the glass transition temperature of the   
     
     
        polynorbornene..]. 35. A process of claim 27 wherein the lamination is performed at temperatures between about ambient and about 250° C. 
     
     
        and at a pressure of from about 1000 to about 1100 SI. 36. A process of claim .[.27.]. .Iadd.28 .Iaddend.further comprising placing two or more substrate layers in a stacking sequence with copper layers at the outside 
     
     
        of the stack. 37. A process of claim 36 wherein a sheet of polyolefin is 
     
     
        sandwiched between the substrate layers. 38. A process of claim 27 wherein the cloth is impregnated with from 30% to 90% by weight polynorbornene polymer. .[.39. A process of claim 27 wherein the thickness of the polyolefin sheet prior to lamination, is less than or equal to about 10 
     
     
        mils..]. 40. A process of claim .[.39.]. .Iadd.27 .Iaddend.wherein the .[.thickness of the.]. polyolefin sheet, prior to lamination, .[.is less than or equal.]. .Iadd.has a thickness of up .Iaddend.to about 5 mils. 
     
     
            A process of claim 40 wherein the .[.thickness of the.]. polyolefin sheet, prior to lamination, .[.is less than or equal.]. .Iadd.has a 
     
     
        thickness of up .Iaddend.to about 1.5 mils. 42. A process of claim 27 
     
     
        wherein the polyolefin is polyethylene. 43. A process of claim .[.27.]. .Iadd.28 .Iaddend.further comprising the steps of: (e) exposing the surface of the copper layer of step (d) to photoresist imaging conditions and etching the copper layer to form a copper pattern on the surface of the laminate;   (f) repeating steps (b) and (c) to produce a prepreg layer and a treated film layer;   (g) arranging the pattern laminate from step (e), one or more prepreg layers and treated film layer from step (f) in the sequence laminate/prepreg layer(s)/copper film layer, optionally with a layer of polyolefin derived from a C 2  -C 4  monomer .Iadd.of up to about 10 mils in thickness .Iaddend.between the laminate/prepreg layer(s) and optionally between the prepreg layer(s)/ and the copper film layer; and   
     
     
       (h) laminating the sequence of step (g). 44. A process of claim 43 wherein the copper-patterned surface of step (e) is oxidized with an oxidizing 
     
     
        agent. 45. A process for producing a laminate, comprising: (a) providing a .Iadd.dipping .Iaddend.solution comprised of polynorbornene polymers selected from copolymers comprising, in a weight-to-weight ratio of about (i) 50-75% methyltetracyclododecene .Iadd.: .Iaddend.25-50% vinylnorborene.Iadd., .Iaddend.or (ii) about 75-90% dicyclopentadiene: about 10-25% vinyl-norbornene;     (b) impregnating a .[.non-cellulosic.]. .Iadd.glass .Iaddend.cloth with the dipping solution;   (c) drying the impregnated cloth to remove a substantial portion of solvent to form a substrate layer;   (d) pretreating the surface of a conductive film with a solution of a silane compound suitable for increasing the bond strength between the substrate layer and the .[.copper.]. .Iadd.conductive .Iaddend.film layer; and   (e) sandwiching and laminating a layer of polyolefin film derived from C 2  -C 4  monomers .Iadd.of up to about 10 mils in thickness .Iaddend.on the pretreated surface between the substrate layer and the conductive layer at a temperature above the glass transition temperature of the polynorbornene .[.and, where a curing agent is present,   
     
     
        sufficiently high to activate said curing agent.].. 46. A printed circuit 
     
     
        wiring board prepared by the process of claim 45. .Iadd.47.  A printed wiring board of claim 1 wherein said dipping solution of (a) further comprises a curing agent which initiates radical cross-linking..Iaddend. 
     
     
        .Iadd.48.  A printed wiring board of claim 45 wherein said dipping solution of (a) further comprises a curing agent which initiates radical cross-linking.