Phosphine oxide hydroxyarl mixtures with novolac resins for co-curing epoxy resins
View Patent ↗There is disclosed a novel mixture of polyhydroxy phenolic curing agents, such as novolac resins blended with a mixture of mono, bis and tris hydroxyaryl phosphine oxides for co-curing epoxy resins and imparting flame resistance thereto. A preferred composition includes a mixture of monohydroxyaryl, bishydroxyaryl and trishydroxyaryl phosphine oxide and a benzoguanamine/phenol/formaldehyde terpolymer which is used along with an epoxy resin to produce flame-resistant printed wiring boards without the use of halogens.
1. A polyhydroxy mixture for co-crosslinking an epoxy resin and imparting flame resistance comprising,
(a) a mixture of phosphine oxides including hydroxyaryl phosphine oxides of the formulae:
(i) a mono(hydroxyaryl)phosphine oxide of the formula:
wherein R 1 is a divalent, substituted or unsubstituted arylene moiety and R 2 is a monovalent, substituted or unsubstituted aryl moiety or is an alkyl moiety or is an aralkyl moiety; and
(ii) a bis(hydroxyaryl)phosphine oxide of the formula:
wherein R 1 and R 2 are defined as above; and
(iii) a tris(hydroxyaryl)phosphine oxide of the formula:
wherein R 1 is defined as above; and
(iv) optionally containing minor amounts of a pentavalent phosphine oxide of the formula:
wherein R 2 is defined as above; and
(b) a phenolic co-crosslinking composition comprising a phenolic component having a hydroxy functionality of two or more.
2. The polyhydroxy mixture according to claim 1 , wherein R 1 is derived from an alkyl aryl ether.
3. The polyhydroxy mixture according to claim 1 , wherein the phosphine oxide mixture consists essentially of diphenyl(4-hydroxyphenyl)phosphine oxide, bis(4-hydroxyphenyl)phenylphosphine oxide and tris(4-hydroxyphenyl)phosphine oxide, optionally including minor amounts of triphenylphosphine oxide.
4. The polyhydroxy mixture according to claim 1 , wherein the phosphine oxide mixture consists essentially of bis(4-methylphenyl)(4-hydroxyphenyl)phosphine oxide, bis(4-hydroxyphenyl)(4-methylphenyl)phosphine oxide and tris(4-hydroxyphenyl)phosphine oxide, said mixture optionally including minor amounts of tris(4-methylphenyl)phosphine oxide.
5. The polyhydroxy mixture according to claim 1 , wherein the phosphine oxide mixture consists essentially of bis(1-naphthyl)(4-hydroxyphenyl)phosphine oxide, bis(4-hydroxyphenyl)(1-naphthyl)phosphine oxide and tris(4-hydroxyphenyl)-phosphine oxide, optionally including minor amounts of tris(1-naphthyl)-phosphine oxide.
6. The polyhydroxy mixture according to claim 1 , wherein the phosphine oxide mixture consists essentially of bis(2-naphthyl)(4-hydroxyphenyl)phosphine oxide, bis(4-hydroxyphenyl)(2-naphthyl)phosphine oxide and tris(4-hydroxyphenyl)-phosphine oxide, optionally including minor amounts of tris(2-naphthyl)-phosphine oxide.
7. The polyhydroxy mixture according to claim 1 , wherein the phosphine oxide mixture consists essentially of bis(4-phenoxyphenyl)(4-hydroxyphenyl)phosphine oxide, bis(4-hydroxyphenyl)(4-phenoxyphenyl)phosphine oxide and tris(4-hydroxyphenyl)phosphine oxide, optionally including minor amounts of tris(4-phenoxyphenyl)phosphine oxide.
8. The polyhydroxy mixture according to claim 1 , wherein the phosphine oxide mixture consists essentially of bis(2,4,5-trimethylphenyl)(4-hydroxyphenyl)phosphine oxide, bis(4-hydroxyphenyl)(2,4,5-trimethylphenyl)phosphine oxide and tris(4-hydroxyphenyl)phosphine oxide, optionally including minor amounts of tris(2,4,5-trimethylphenyl)phosphine oxide.
9. The polyhydroxy mixture according to claim 1 , wherein the phosphine oxide mixture consists essentially of bis(tert-butyl)(4-hydroxyphenyl)phosphine oxide, bis(4-hydroxyphenyl)(tert-butyl)phosphine oxide and tris(4-hydroxyphenyl)-phosphine oxide, optionally including minor amounts of tris(tert-butyl)phosphine oxide.
10. The polyhydroxy mixture according to claim 1 , wherein said phosphine oxide mixture comprises from about 5 to about 40 mole percent of the mono(hydroxyaryl)phosphine oxide of the formula (I), from about 5 to about 60 mole percent of the bis(hydroxyaryl)phosphine oxide of the formula (II), from about 10 to 90 mole percent of the tris(hydroxyaryl)phosphine oxide of the formula (III) and from about 0 up to about 10 mole percent of the pentavalent phosphine oxide of the formula (IV), based on the moles of compounds of the formulae (I), (II), (III) and (IV) present in the polyhydroxy mixture.
11. The polyhydroxy mixture according to claim 1 , wherein said phenolic co-crosslinking composition comprises a novolac resin.
12. The polyhydroxy mixture according to claim 11 , wherein said phenolic co-crosslinking composition comprises a resin selected from the group consisting of phenol formaldehyde resins, cresol formaldehyde resins and mixtures thereof.
13. The polyhydroxy mixture according to claim 11 , wherein said novolac resin is a polymer of a phenol, a nitrogen heteroaryl compound and an aldehyde.
14. The polyhydroxy mixture according to claim 13 , wherein said novolac resin is selected from the group consisting of benzoguanamine phenol formaldehyde resins, acetoguanamine phenol formaldehyde resins, melamine phenol formaldehyde resins, benzoguanamine cresol formaldehyde resins, acetoguanamine cresol formaldehyde resins, melamine cresol formaldehyde resins, and mixtures thereof.