Halogen-free resin composition

• US 20040147640A1
• Filed: 04/11/2003
• Published: 07/29/2004
• Est. Priority Date: 01/16/2003
• Status: Active Grant

• Current Assignee: Chang CHUN Plastics Company Limited (C.C.P. Contact Probes Co., Ltd.)
• Original Assignee: Chang CHUN Plastics Company Limited (C.C.P. Contact Probes Co., Ltd.)
• Inventors: Tu, An-Pang, Hwang, Kuen-Yuan, Liang, Mong, Wu, Sheng-Yen, Ju, Chi-Yi, Kao, Chun-Hsiung, Su, Fang-Shian
• Granted Patent: US 6,900,269 B2
• Time in Patent Office: Days
• US Class Current: 523/400
• CPC Class Codes: C08G 59/304 containing phosphorus
• CPC Class Codes: C08G 59/5046 heterocyclic
• CPC Class Codes: C08L 2666/22 Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 71/12 Polyphenylene oxides
• CPC Class Codes: H05K 1/0326 containing O

Abstract

Disclosed is a halogen-free resin composition comprising: (A) one or more phosphorus-containing epoxy resins; (B) a hardener; (C) a hardening accelerator; (D) a polyphenylene oxide resin; and (E) a filling material, wherein the hardener of component B has the structure represented by the following formula (I):

wherein each symbol is as defined above. The halogen-free resin composition of the present invention without adding halogen has excellent heat resistance and flame retardant property, and excellent dielectric property. The halogen-free resin composition of the present invention is particularly useful in the application of bonding sheets, composite materials, laminated plates, printed circuit boards, copper foil adhesives, inks used for build-up process, semiconductor packaging materials and the like.

Claims

1. A halogen-free resin composition, comprising the following components:

(A) one or more phosphorus-containing epoxy resins;

(B) a hardener;

(C) a hardening accelerator;

(D) a polyphenylene oxide resin; and

E) a filling material, wherein the hardener of component (B) has the structure represented by the following formula (I);

 

wherein R¹ is one selected from the group consisting of an alkyl group, an alkenyl group, an alkoxyl group, a hydroxy group and an amino group;

R² is one selected from the group consisting of a bond, an alkylene group, O, S and SO₂;

R³ is H or an alkyl group; and

m and n are independently an integer of 0 to 4.

2. The composition according to claim 1, wherein R¹ is t-butyl;

R² is methylene; and

m is 0 and n is 1.

3. The composition according to claim 1, wherein the hardener having the structure represented by the formula (I) is one prepared by the reaction of a phenolic compound, an aromatic diamine compound, and a aldehyde compound in the presence of a solvent.

4. The composition according to claim 3, wherein the phenolic compound is phenol;

the aromatic diamine compound is 4,4′

-diaminodiphenylmethane;

the aldehyde compound is paraformaldehyde; and

the solvent is aromatic hydrocarbon solvent.

5. The composition according to claim 1, wherein the phosphorus-containing epoxy resin is a side chain type phosphorus-containing epoxy resin represented by the following formula (III):

6. The composition according to claim 5, wherein the side chain type phosphorus-containing epoxy resin is one prepared by introducing 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide into the structure of the epoxy resin.

7. The composition according to claim 1, wherein the phosphorus-containing epoxy resin is a side chain type phosphorus-containing epoxy resin represented by the following formula (IV):

8. The composition according to claim 7, wherein the side chain type phosphorus-containing epoxy resin is one prepared by undergoing the additive reaction of 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide and an aromatic aldehyde compound, and then undergoing the condensation reaction with an aromatic compound having reactive hydrogens to produce a phosphorus-containing compound, and subsequently reacting the phosphorus-containing compound with an epoxy resin.

9. The composition according to claim 8, wherein the aromatic aldehyde compound is 4-hydroxybenzaldehyde;

and the aromatic compound having reactive hydrogens is phenol.

10. The composition according to claim 6 or 8, wherein the epoxy resin is one derived from monomers selected from the group consisting of bisphenol glycidyl ether, biphenyol glycidyl ether, benzenediol glycidyl ether, nitrogen-containing hetero-ring glycidyl ether, dihydroxynaphthalene glycidyl ether, phenolic glycidyl ether, and polyhydric phenol glycidyl ether.

11. The composition according to claim 1, wherein the one or more phosphorus-containing epoxy resins of component A are used in an amount of 40 to 80 percent by weight based on the total amount of the phosphorus-containing epoxy resins of component A and the hardener of component B.

12. The composition according to claim 1, wherein the hardening accelerator of component C is one selected from the group consisting of tertiary amine, tertiary phosphine, quaternary ammonium salt, quaternary phosphonium salt, boron trifluoride complex salt, lithium-containing compound, imidazole compound and mixtures thereof.

13. The composition according to claim 1, wherein the hardening accelerator is used in an amount of 0.01 to 1 percent by weight relative to the total weight of the resin composition.

14. The composition according to claim 1, wherein the polyphenylene oxide resin of component D has the structure unit represented by the following formula (V):

15. The composition according to claim 14, wherein R⁹ is methyl;

and x is 2.

16. The composition according to claim 1, wherein the polyphenylene oxide resin of component D is used in an amount of 10 to 50 percent by weight based on the total solid amount of the phosphorus-containing epoxy resins of component A and the hardener of component B.

17. The composition according to claim 1, wherein the filling material of component E is one selected from the group consisting of silicon dioxide powder, quartz glass powder, talc powder, alumina powder, aluminum hydroxide powder, magnesium hydroxide powder, calcium carbonate powder, zinc borate, aluminum nitride compound, boron nitride compound and mixtures thereof.

18. The composition according to claim 17, wherein the filling material of component E is silicon dioxide powder.

19. The composition according to claim 1, wherein the filling material of component E is used in an amount of 20 to 150 percent by weight based on the total solid amount of components (A), (B), and (C) in the resin composition.

20. The composition according to claim 1, wherein the composition is useful in the application of bonding sheets, composite materials, laminated plates, printed circuit boards, copper foil adhesives, inks used for build-up process, and semiconductor packaging materials.