Thermosetting resin compositions and articles
The present invention generally relates to a resin composition, a cured resin, a sheet-like cured resin, a laminated body, a prepreg, electronic parts, single and multilayer circuit boards comprising a cyanate ester polymer and condensed phosphate ester, for use in single and multilayer circuit boards that are especially useful in the high-frequency range of above 100 MHz.
1. A thermosetting resin composition, comprising
a cyanate ester resin; and
a phosphate condensed ester of formula (I):
wherein R 1 to R 4 are the same or different, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, excluding the case where R 1 to R 4 are all hydrogen atoms; X is a bond, —CH 2 —, —C(CH 3 ) 2 —, —S—, —SO 2 —, —O—, —CO— or —N═N—; n is an integer of 0 or 1; and m is an integer of 0 to 5,
said composition having a dielectric dissipation factor (Df) of about 0.006 or less at 10 GHz.
2. The thermosetting resin composition of claim 1 , having a dielectric dissipation factor (Df) of about 0.006 or less at 1 GHz.
3. The thermosetting resin composition of claim 1 , having a dielectric dissipation factor (Df) of about 0.005 or less at 10 GHz.
4. The thermosetting resin composition of claim 2 , having a difference between the Df at 1 GHz and the Df at 10 GHz of 20% percent or less.
5. The thermosetting resin composition of claim 1 , having a dielectric constant (Dk) of 4 or less.
6. The thermosetting resin composition of claim 1 , wherein the cyanate ester resin is a monomer or prepolymer of a monomer selected from the group consisting of 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)ethane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, and α,α′-bis(4-cyanatophenyl)-m-diisopropylbenzene; or a dicyclopentadiene-based cyanate ester resin, a Bismaleimide-Triazine (BT) resin, or a Phenolic-Triazine (PT) resin.
7. The thermosetting resin composition of claim 6 , wherein the cyanate ester resin is a homopolymer of 2,2-bis(4-cyanatophenyl)propane.
8. The thermosetting resin composition of claim 1 , wherein the cyanate ester resin is present at between about 1 and about 95 percent by weight of said composition, and the phosphate condensed ester is present at between about 5 and about 30 percent by weight of said composition.
9. The thermosetting resin composition of claim 8 wherein the cyanate ester resin is present at between about 30 and about 40 percent by weight of said composition, and the phosphate condensed ester is present at between about 10 and about 30 by weight of said composition.
10. The thermosetting resin composition of claim 9 , comprising between about 30 and about 40 percent by weight of the cyanate ester polymer, and between about 15 and about 20 by weight of the phosphate condensed ester.
11. The thermosetting resin composition of claim 1 , further comprising one or more epoxy resins.
12. The thermosetting resin of claim 11 , wherein the epoxy resin is a member selected from the group consisting of dicyclopentadiene-containing polyepoxides, bisphenol A type epoxy resins, and bisphenol F type epoxy resins.
13. The thermosetting resin of claim 11 , comprising between about 0 and about 20 percent by weight of one or more epoxy resins.
14. The thermosetting resin of claim 13 , comprising between about 0 to about 15 percent by weight of one or more epoxy resins.
15. The thermosetting resin composition of claim 1 , further comprising a copolymer derived from at least one monomer selected from the group consisting of maleic anhydride, acrylonitrile, acrylic acid, ethyl acrylate, butyl acrylate, glycidyl acrylate, butadiene, ethyl methacrylate, butyl methacrylate and styrene.
16. The thermosetting resin composition of claim 15 , wherein the copolymer is a styrene maleic anhydride copolymer.
17. The thermosetting resin composition of claim 16 , wherein the styrene maleic anhydride copolymer comprises between about 0 and about 25 percent by weight of said composition.
18. The thermosetting resin composition of claim 17 , wherein the styrene maleic anhydride copolymer comprises between about 0 and about 20 percent by weight of said composition.
19. The thermosetting resin composition of claim 1 , wherein the phosphate condensed ester comprises resorcinol bis-(di-2,6-dimethylphenylphosphate).
20. The thermosetting resin composition of claim 1 , wherein the phosphate condensed ester is 4,4′-biphenyl bis-(di-2,6-dimethylphenylphosphate).
21. The thermosetting resin of claim 1 , further comprising at least one inorganic filler.
22. The thermosetting resin of claim 21 , wherein the inorganic filler is a member selected from inorganic hydrates, inorganic salts, metal oxides, inorganic phosphorus, or organo-phosphorous salts.
23. The thermosetting resin of claim 21 , wherein the inorganic filler is surface treated.
24. The thermosetting resin of claim 21 , wherein the inorganic filler is silica.
25. The thermosetting resin of claim 24 , wherein the silica is present at about 0 to about 50 percent by weight.
26. The thermosetting resin of claim 24 , wherein the silica is present at about 25 to about 35 percent by weight.
27. The thermosetting resin of claim 1 , further comprising at least one polyphenylene ether oligomer or polymer.
28. The thermosetting resin of claim 27 , wherein the polyphenylene ether oligomer or polymer is present at about 5 to about 50 percent by weight.
29. The thermosetting resin of claim 27 , wherein the polyphenylene ether oligomer or polymer is present at an amount of about 10 to about 30 percent by weight.
30. The thermosetting resin composition of claim 1 , further comprising a base material.
31. The thermosetting resin composition of claim 30 , wherein the base material is a woven or non-woven fabric.
32. The thermosetting resin composition of claim 30 , wherein the woven or non-woven fabric is a glass.
33. A prepreg comprising the thermosetting resin composition of claim 1 .
34. The prepreg of claim 33 , wherein the phosphate condensed ester is resorcinol bis-(di-2,6-dimethylphenylphosphate).
35. A printed circuit board comprising the thermosetting resin composition of claim 1 .
36. The printed circuit board of claim 35 , wherein the phosphate condensed ester is resorcinol bis-(di-2,6-dimethylphenylphosphate).
37. The printed circuit board of claim 35 , wherein the phosphate condensed ester is 4,4′-biphenyl bis-(di-2,6-dimethylphenylphosphate).
38. A printed circuit board of claim 35 , wherein the circuit board is a multilayer circuit board.
39. The thermosetting resin composition of claim 1 , wherein the phosphate condensed ester is Bisphenol A bis-(diphenylphosphate).
40. The thermosetting resin composition of claim 1 , having a dielectric dissipation factor (Df) in the range of about 0.001 to about 0.006.
41. A method of making a laminate having a dielectric dissipation factor (Df) of about 0.006 or less at 10 GHz which comprises
providing a thermosetting resin comprising a cyanate ester resin and a phosphate condensed ester of formula (I):
wherein R 1 to R 4 are the same or different, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, excluding the case where R 1 to R 4 are all hydrogen atoms; X is a bond, —CH 2 —, —C(CH 3 ) 2 —, —S—, —SO 2 —, —O—, —CO— or —N═N—; n is an integer of 0 or 1; and m is an integer of 0 to 5;
impregnating a substrate with said thermosetting resin; and
curing said impregnated substrate.
42. The method of claim 41 , which comprises laminating a sheet of electronically conductive metal to at least one side of the cured substrate.
43. The method of claim 41 , which comprises joining two or more of said impregnated substrates.
44. The method of claim 42 , wherein the electronically conductive metal comprises copper.
45. The method of claim 41 , wherein the substrate comprises a glass fiber.