Low Loss Pre-Pregs and Laminates and Compositions Useful for the Preparation Thereof

Abstract

In accordance with the present invention, compositions are described which are useful, for example, for the preparation of metal-clad laminate structures, methods for the preparation thereof, and various uses therefor. Invention metal-clad laminate structures are useful, for example, in the multi-layer board (MLB) industry, in the preparation of burn-in test boards and high reliability boards, in applications where low coefficient of thermal expansion (CTE) is beneficial, in the preparation of boards used in down-hole drilling, and the like.

What is claimed: 
     
         1 . A laminate comprising:
 at least one low loss dielectric layer formed from a composition comprising:
 a first resin that forms a triazine structure upon curing, 
 a second resin comprising at least one member selected from the group consisting of a polyphenylene oxide, a styrene-maleic anhydride copolymer, a carboxy-terminated butadiene nitrile resin, a multifunctional epoxy resin, a low-halogen epoxy resin and a bis-maleimide resin, 
 a substantially halogen-free, phosphorus-containing flame retardant having an atomic phosphorus content in the range of about 1-20 weight percent, based on the total weight of the resin components, and 
 a quantity of a particulate filler. 
   
     
     
         2 . The laminate of  claim 1  wherein the first resin is derived from a cyanate ester. 
     
     
         3 . The laminate of  claim 1  wherein the first resin is derived from a Novolac cyanate ester. 
     
     
         4 . The laminate of  claim 1  wherein said first resin is derived from a bisphenol-A cyanate ester, a hexafluorobisphenol-A cyanate ester, a bisphenol-E cyanate ester, a tetramethylbisphenol-F cyanate ester, a bisphenol-M cyanate ester, a phenol Novolac cyanate ester, a bisphenol-C cyanate ester, a dicyclopentadienyl-bisphenol cyanate ester, or a Novolac cyanate ester. 
     
     
         5 . The laminate of  claim 1  wherein said substantially halogen-free, phosphorus-containing compound is an organo-phosphate, a phosphonate, a phosphorus-based phenolic hardener, a phosphorus-containing cyanate ester, or a phosphorus-containing triazine. 
     
     
         6 . The laminate of  claim 5  wherein said organo-phosphate comprises at least one member selected from the group consisting of diphenyl phosphate and triphenyl phosphate. 
     
     
         7 . The laminate of  claim 1  wherein said flame retardant further comprises at least one nitrogen-containing synergist. 
     
     
         8 . The laminate of  claim 7  wherein said at least one nitrogen-containing synergist comprises at least one member selected from the group consisting of an iso cyanurate, a urea-containing compound, a melamine-containing compound, a phosphazene-containing compound, a nitrogen-containing phenolic resin, and a nitrogen-containing epoxy resin. 
     
     
         9 . The laminate of  claim 1  wherein said particulate filler is angular, platelet, spherical, amorphous, sintered, fired, powder, flake, crystalline, ground, crushed, milled, fumed or mixtures of any two or more thereof. 
     
     
         10 . The laminate of  claim 1  wherein said particulate filler is substantially spherical. 
     
     
         11 . The laminate of  claim 1  wherein the particle size of said particulate filler falls in the range of about 500 nm up to about 300 micron. 
     
     
         12 . The laminate of  claim 1  wherein said filler comprises at least one member selected from the group consisting of a naturally occurring mineral, a synthetic fused mineral, a treated filler, an organic polymer, a hollow sphere, a microsphere, or a powdered polymeric material. 
     
     
         13 . The laminate of  claim 1  wherein said filler comprises at least one member selected from the group consisting of talc, mica, calcium carbonate, calcium sulfate, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesia, silica, alumina, Ti0 2 , aluminum silicate, zirconium silicate, aluminum-zirconium-silicate, cordierite, silane treated mineral, polytetrafluoroethylene, and polyphenylene sulfide. 
     
     
         14 . The laminate of  claim 1  wherein the quantity of filler employed falls in the range of about 50 parts by weight up to about 400 parts by weight, relative to the total weight of the resin components of the composition. 
     
     
         15 . The laminate of  claim 1  wherein the weight ratio between the first resin and the second resin is in the range of about 1:1 to about 20:1. 
     
     
         16 . The laminate of  claim 1  wherein the atomic phosphorus content is in the range of about 1-10 wt %, based on the total weight of the first resin and the second resin. 
     
     
         17 . The laminate of  claim 1  wherein the low loss dielectric layer further comprises one or more agents selected from the group consisting of a flexibilizer, an anti-oxidant, a dye, a pigment, a surfactant, a defoamer, a silane coupling agent, a dispersing agent, a thixotropic agent, a flow modifier, a cure accelerator, a strength enhancer, a toughening agent, and a processing aid. 
     
     
         18 . The laminate of  claim 1  wherein said low loss dielectric layer has a peel strength of at least 3 pounds/inch. 
     
     
         19 . The laminate of  claim 1  wherein the low loss dielectric layer has a dielectric constant ≦4.5 when measured at 10 GHz. 
     
     
         20 . The laminate of  claim 1  wherein the low loss dielectric layer has a dielectric loss factor ≦0.02 when measured at 10 GHz. 
     
     
         21 . The laminate of  claim 19  wherein the composition has a dielectric loss factor ≦0.02 when measured at 10 GHz. 
     
     
         22 . The laminate of  claim 1  wherein the low loss dielectric layer comprises an epoxy component comprising at least one member selected from the group consisting of a multifunctional epoxy, a nitrogen-containing epoxy, a low-halogen epoxy, a non-halogenated epoxy and an epoxy silane. 
     
     
         23 . The laminate of  claim 1  wherein the low loss dielectric layer comprises a multifunctional epoxy component. 
     
     
         24 . The laminate of  claim 1  wherein the low loss dielectric layer comprises a styrene-maleic anhydride copolymer. 
     
     
         25 . The laminate of  claim 1  wherein the low loss dielectric layer comprises a carboxy-terminated butadiene nitrile resin. 
     
     
         26 . The laminate of  claim 1  further including a substrate, wherein the substrate is impregnated by the composition. 
     
     
         27 . The laminate of  claim 26  wherein the substrate is woven. 
     
     
         28 . The laminate of  claim 26  wherein the substrate is nonwoven. 
     
     
         29 . The laminate of  claim 26  wherein the substrate comprises at least one member selected from the group consisting of fiberglass, quartz, a polyester, a polyamide, a polyimide, a polyamide-imide, a liquid crystalline polymer (LCP), a polyphenylene sulfide (PPS), a polyalkylene, a polyphenylene oxide (PPO), a polybenzoxazoline (PBO), an Aramid, polytetrafluoroethylene, a copolymer of tetrafluoroethylene and perfluoromethylvinyl ether (MFA), and a conductive material. 
     
     
         30 . The laminate of  claim 1  wherein the low loss dielectric layer is formed on a substrate. 
     
     
         31 . The laminate of  claim 30 , wherein the substrate comprises a polymer. 
     
     
         32 . The laminate of  claim 30  wherein the substrate comprises at least one member selected from the group consisting of a polyester and a polyolefin. 
     
     
         33 . The laminate of  claim 30  wherein the substrate comprises at least one member selected from the group consisting of a polyester, a polyamide, a polyimide, a polyamide-imide, a liquid crystalline polymer (LCP), a polyphenylene sulfide (PPS), a polyphenylene oxide (PPO), a polybenzoxazoline (PBO), an Aramid, and a conductive material. 
     
     
         34 . The laminate of  claim 30  wherein the substrate comprises a conductive material. 
     
     
         35 . The laminate of  claim 30  wherein the conductive material includes at least one member selected from the group consisting of silver, nickel, golf, cobalt, copper, aluminum, and alloys thereof. 
     
     
         36 . An article comprising the laminate of  claim 1 . 
     
     
         37 . An article comprising the laminate of  claim 26 . 
     
     
         38 . An article comprising the laminate of  claim 30 . 
     
     
         39 . A method of making a laminate comprising:
 forming a low loss dielectric layer from a composition comprising:
 a first resin that forms a triazine structure upon curing, 
 a second resin comprising at least one member selected from the group consisting of a polyphenylene oxide, a styrene-maleic anhydride copolymer, a carboxy-terminated butadiene nitrile resin, a multifunctional epoxy resin, a low-halogen epoxy resin and a bis-maleimide resin, 
 a substantially halogen-free, phosphorus-containing flame retardant having an atomic phosphorus content in the range of about 1-20 weight percent, based on the total weight of the resin components, and 
 a quantity of a particulate filler, and 
 curing the low loss dielectric layer. 
   
     
     
         40 . The method of  claim 39  wherein a substrate is impregnated by the composition. 
     
     
         41 . The method of  claim 40  wherein the substrate comprises at least one member selected from the group consisting of fiberglass, quartz, a polyester, a polyamide, a polyimide, a polyamide-imide, a liquid crystalline polymer (LCP), a polyphenylene sulfide (PPS), a polyalkylene, a polyphenylene oxide (PPO), a polybenzoxazoline (PBO), an Aramid, polytetrafluoroethylene, a copolymer of tetrafluoroethylene and perfluoromethylvinyl ether (MFA), and a conductive material. 
     
     
         42 . The method of  claim 39  wherein the filler comprises at least one member selected from the group consisting of talc, mica, calcium carbonate, calcium sulfate, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesia, silica, alumina, Ti0 2 , aluminum silicate, zirconium silicate, aluminum-zirconium-silicate, cordierite, silane treated mineral, polytetrafluoroethylene, or polyphenylene sulfide. 
     
     
         43 . The method of  claim 39  wherein the cured low loss dielectric layer has a dielectric constant ≦4.5 when measured at 10 GHz. 
     
     
         44 . The method of  claim 39  wherein the cured low loss dielectric layer has a dielectric loss factor ≦0.02 when measured at 10 GHz. 
     
     
         45 . The method of  claim 43  wherein the cured low loss dielectric layer has a dielectric loss factor ≦0.02 when measured at 10 GHz. 
     
     
         46 . The method of  claim 39  wherein the composition is applied onto a substrate. 
     
     
         47 . The method of  claim 46  wherein the substrate comprises at least one member selected from the group consisting of fiberglass, quartz, a polyester, a polyamide, a polyimide, a polyamide-imide, a liquid crystalline polymer (LCP), a polyphenylene sulfide (PPS), a polyalkylene, a polyphenylene oxide (PPO), a polybenzoxazoline (PBO), an Aramid, polytetrafluoroethylene, a copolymer of tetrafluoroethylene and perfluoromethylvinyl ether (MFA), and a conductive material. 
     
     
         48 . The method of  claim 46  wherein the filler comprises at least one member selected from the group consisting of talc, mica, calcium carbonate, calcium sulfate, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesia, silica, alumina, Ti0 2 , aluminum silicate, zirconium silicate, aluminum-zirconium-silicate, cordierite, silane treated mineral, polytetrafluoroethylene, or polyphenylene sulfide. 
     
     
         49 . The method of  claim 46  wherein the cured low loss dielectric layer has a dielectric constant ≦4.5 when measured at 10 GHz. 
     
     
         50 . The method of  claim 46  wherein the cured low loss dielectric layer has a dielectric loss factor ≦0.02 when measured at 10 GHz. 
     
     
         51 . The method of  claim 49  wherein the cured low loss dielectric layer has a dielectric loss factor ≦0.02 when measured at 10 GHz. 
     
     
         52 . A pre-preg comprising:
 a porous substrate impregnated with a composition comprising:
 a first resin that forms a triazine structure upon curing, 
 a second resin comprising at least one member selected from the group consisting of a polyphenylene oxide, a styrene-maleic anhydride copolymer, a carboxy-terminated butadiene nitrile resin, a multifunctional epoxy resin, a low-halogen epoxy resin and a bis-maleimide resin, 
 a substantially halogen-free, phosphorus-containing flame retardant having an atomic phosphorus content in the range of about 1-20 weight percent, based on the total weight of the resin components, and 
 a quantity of a particulate filler. 
   
     
     
         53 . The pre-preg of  claim 52  wherein said substrate is woven or non-woven. 
     
     
         54 . A laminated sheet produced by layering and molding a prescribed number of sheets of the pre-preg of  claim 52 . 
     
     
         55 . The laminated sheet of  claim 54  further comprising one or more conductive layers. 
     
     
         56 . The laminated sheet of  claim 55  wherein said one or more conductive layers are selected from the group consisting of a metal foil, a metal plate, and an electrically conductive polymeric layer. 
     
     
         57 . A printed wiring board layer produced by forming conductive patterns on the surface of the laminated sheet of  claim 54 . 
     
     
         58 . A multilayer printed wiring board produced by layering and molding a prescribed number of sheets of the patterned laminate layers of  claim 58 , bonded together with one or more layers of pre-preg from which the printed wiring board layer was prepared. 
     
     
         59 . A resin coated electrical component comprising:
 a substrate,   a coating formed on the substrate, the coating being formed from a composition comprising:   a first resin that forms a triazine structure upon curing,
 a second resin comprising at least one member selected from the group consisting of a polyphenylene oxide, a styrene-maleic anhydride copolymer, a carboxy-terminated butadiene nitrile resin, a multifunctional epoxy resin, a low-halogen epoxy resin and a bis-maleimide resin, 
 a substantially halogen-free, phosphorus-containing flame retardant having an atomic phosphorus content in the range of about 1-20 weight percent, based on the total weight of the resin components, and 
 a quantity of a particulate filler. 
   
     
     
         60 . The electrical component of  claim 59  wherein said substrate comprises a metal foil. 
     
     
         61 . A laminated sheet produced by layering and molding a prescribed number of sheets of the electrical component of  claim 59 . 
     
     
         62 . The laminated sheet of  claim 61  further comprising one or more conductive layers. 
     
     
         63 . The laminated sheet of  claim 62  wherein said one or more conductive layers are selected from the group consisting of a metal foil, a metal plate, and an electrically conductive polymeric layer. 
     
     
         64 . A printed wiring board layer produced by forming conductive patterns on the surface of the laminated sheet of  claim 61 . 
     
     
         65 . A multilayer printed wiring board produced by layering and molding a prescribed number of sheets of patterned laminated sheets of  claim 64 , bonded together with one or more layers of pre-preg from which the printed wiring board layer was prepared.