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

• US 20140138128A1
• Filed: 01/24/2014
• Published: 05/22/2014
• Est. Priority Date: 06/11/2009
• Status: Abandoned Application

• Current Assignee: Arlon Incorporated
• Original Assignee: Arlon Incorporated
• Inventors: Chang, Daniel, Najjar, Sam
• Application Number:
  US14/163,527
• Publication Number:
  US 20140138128A1
• Time in Patent Office: Days
• US Class Current: 174/255
• CPC Class Codes: C08J 2379/04 Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08J 5/249 characterised by the additives used in the prepolymer mixture
• CPC Class Codes: C08K 3/36 Silica
• CPC Class Codes: C08K 5/523 with hydroxyaryl compounds
• CPC Class Codes: C08L 79/04 Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: H01B 3/40 epoxy resins
• CPC Class Codes: H05K 1/0298 Multilayer circuits
• CPC Class Codes: H05K 1/03 Use of materials for the substrate
• CPC Class Codes: H05K 1/0353 consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
• CPC Class Codes: H05K 1/0373 containing additives, e.g. fillers H05K1/036 takes precedence
• CPC Class Codes: H05K 2201/012 Flame-retardant; Preventing of inflammation
• CPC Class Codes: Y10T 428/249955 Void-containing component partially impregnated with adjacent component
• CPC Class Codes: Y10T 428/31511 Of epoxy ether
• CPC Class Codes: Y10T 428/31525 Next to glass or quartz
• CPC Class Codes: Y10T 428/31529 Next to metal
• CPC Class Codes: Y10T 428/31721 Of polyimide
• CPC Class Codes: Y10T 428/31725 Of polyamide
• CPC Class Codes: Y10T 428/31786 Of polyester [e.g., alkyd, etc.]
• CPC Class Codes: Y10T 428/31931 Polyene monomer-containing
• CPC Class Codes: Y10T 442/20 Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
• CPC Class Codes: Y10T 442/2475 : Coating or impregnation is electrical insulation-providing, -improving, or -increasing, or conductivity-reducing

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.

Claims

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, Ti0₂, 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, Ti0₂, 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, Ti0₂, 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.