Epoxy resin compositions containing phosphorus, flame retardant resin sheet using said epoxy resin containing phosphorus, resin clad metal foil, prepreg and laminated board, multi layer board
View Patent ↗The present invention features phosphorus containing epoxy resin compositions useful for imparting flame retardant properties to prepregs, resin-clad metal foils, and laminate boards constructed therefrom. The phosphorus containing epoxy resin composition (a) comprises a phosphorus containing epoxy resin (A) and a hardener. The phosphorus containing epoxy resin (A) has an epoxy equivalent of 300-500 g/eq. and comprises the reaction product of a phosphorus containing organic compound (B) and at least one epoxy resin (C). Phosphorus containing compound (B) is the reaction product of organic phosphorus compounds (b) having one active hydrogen atom bonded to a phosphorus atom and a quinone compound, wherein the molar ratio of (b) to quinone is from 1.25:1 to 2:1. This molar excess of (b) yields a phosphorus containing compound (B) that comprises both the reaction product of (b) and quinone, as well as un-reacted (b). Epoxy resin (C) is selected from a group of specific aromatic-containing epoxy resins, and the content of epoxy resin (C) comprises from 20 to 45 wt. % of (A).
1. A phosphorus containing epoxy resin composition (a) comprising
a phosphorus containing epoxy resin (A) and
a hardener,
said phosphorus containing epoxy resin (A) comprising
the reaction product of a phosphorus containing organic compound (B) and
at least an epoxy resin (C);
wherein the epoxy equivalent of phosphorous containing epoxy resin (A) is 300-500 g/eq
wherein (B) is the reaction product of organic phosphorus compounds (b) having one active hydrogen atom bonded to a phosphorus atom and a quinone compound, said reaction product containing an unreacted component,
said reaction product formed with a molar ratio of (b) to quinone of 1.25:1 to 2:1 and containing an excess of organic phosphorous compounds (b) as said unreacted component,
wherein (C) is selected from the group, consisting of resins represented by formula 1, formula 2 and formula 3 wherein the content of said epoxy resins (C) comprises from 20 to 45 wt. % of (A),
wherein R 1 is a hydrogen atom and/or a phenyl group, m is an integer including 0,
wherein R 2 is a hydrogen atom and/or a phenyl group, n is an integer including 0,
wherein R 3 is a hydrogen atom and/or a phenyl group, l is an integer including 0,
wherein X is selected from the group consisting of —CH 2 —, —O—, —CO—, —SO 2 —, —S—, —CH(C 6 H 5 )—, —C(C 6 H 5 ) 2 —, a bond and a structure represented by formula 4
2. The phosphorus containing epoxy resin compositions in accordance with claim 1 , wherein the phosphorus content in phosphorous containing epoxy resin (A) is from 1.2 to 4 wt. %.
3. The phosphorus containing epoxy resin composition in accordance with claim 2 wherein the organic phosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom is 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide.
4. The phosphorus containing epoxy resin composition in accordance with claim 2 wherein the quinone compound is 1,4-benzoquinone and/or 1,4-naphthoquinone.
5. The phosphorus containing epoxy resin composition in accordance with claim 4 wherein the organic phosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom is 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide.
6. The phosphorus containing epoxy resin composition in accordance with claim 1 wherein the quinone compound is 1,4-benzoquinone and/or 1,4-naphthoquinone.
7. The phosphorus containing epoxy resin composition in accordance with claim 6 wherein the organic phosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom is 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide.
8. The phosphorus containing epoxy resin composition in accordance with claim 1 wherein the organic phosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom is 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide.
9. A flame retardant epoxy resin composition comprising the phosphorus containing epoxy resin composition of claim 1 and having a phosphorus content in epoxy resin composition (a) of from 0.5 to 4.0 wt %.
10. The flame retardant epoxy resin composition according to claim 9 , wherein the organic phosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom is 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide.
11. The flame retardant epoxy resin composition of claim 9 wherein the phosphorus containing epoxy resin (A) has a phosphorus content of from 1.2 to 4 wt %.
12. The flame retardant epoxy resin composition according to claim 11 , wherein the organic phosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom is 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide.
13. The flame retardant epoxy resin composition of claim 11 wherein the quinone compound is 1,4-benzoquinone and/or 1,4-naphthoquinone.
14. The flame retardant epoxy resin composition according to claim 13 , wherein the organic phosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom is 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide.
15. The flame retardant epoxy resin composition of claim 9 wherein the quinone compound is 1,4-benzoquinone and/or 1,4-naphthoquinone.
16. The flame retardant epoxy resin composition according to claim 15 , wherein the organic phosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom is 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide.
17. The flame retardant epoxy resin composition of claim 9 further comprising 10-150 weight parts of inorganic filler per 100 weight parts of solid epoxy resin.
18. The flame retardant epoxy resin composition of claim 17 wherein the inorganic filler is at least one of the group composed of aluminum hydroxide, magnesium hydroxide, talc, calcined talc, kaolin, titanium oxide, glass powder and silica balloon.
19. The phosphorus containing epoxy resin composition of claim 1 further comprising 10-150 weight parts of inorganic filler per 100 weight parts of solid epoxy resin.
20. The phosphorus containing epoxy resin composition of claim 19 wherein the inorganic filler is at least one of the group composed of aluminum hydroxide, magnesium hydroxide, talc, calcined talc, kaolin, titanium oxide, glass powder and silica balloon.
21. A resin sheet prepared from the phosphorus containing epoxy resin composition of claim 1 .
22. A resin clad metal foil prepared by coating a metal foil with the phosphorus containing epoxy resin composition of claim 1 .
23. A prepreg prepared by soaking a substrate in the phosphorus containing epoxy resin composition of claim 1 .
24. A laminated board prepared by bonding a plurality of sheets together, wherein the sheets comprise at least one of a resin sheet prepared from the phosphorus containing epoxy resin composition of claim 1 , a resin clad metal foil prepared by coating a metal foil with the phosphorus containing epoxy resin composition of claim 1 , or a prepreg prepared by soaking a substrate in the phosphorus containing epoxy resin composition of claim 1 .
25. A multi layer board prepared by coating a laminated substrate with the phosphorus containing epoxy resin composition of claim 1 .