Phenolic-hydroxyl-containing resin, epoxy resin, curable resin composition, substance obtained by curing same, and semiconductor sealant

Patent metadata

Field	Value
Publication number	US-9580634-B2
Application number	US-201314439869-A
Country	US
Kind code	B2
Filing date	Nov 6, 2013
Priority date	Nov 12, 2012
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

Provided are a phenolic-hydroxyl containing resin, an epoxy resin, and a curable resin composition containing either resin that have high flowability and exhibit high heat resistance and flame retardancy after curing, a cured composition formed therefrom, and a sealant. A phenolic-hydroxyl containing resin is prepared by reacting a polycondensate of a phenolic compound (a) and formaldehyde with an aralkylating agent. The phenolic-hydroxyl containing resin contains as essential components a monoaralkylated derivative (x1) of the phenolic compound (a) having one aralkyl group on an aromatic nucleus thereof and a diaralkylated derivative (x2) of the phenolic compound (a) having two aralkyl groups on an aromatic nucleus thereof. An epoxy resin is prepared by converting the phenolic-hydroxyl containing resin into a polyglycidyl ether.

First claim

The invention claimed is:

1. A phenolic-hydroxyl containing resin prepared by reacting a polycondensate of a phenolic compound (a) and formaldehyde with an aralkylating agent, the phenolic-hydroxyl containing resin comprising as essential components:
a monoaralkylated derivative (x1) represented by structural formula (1):

(wherein R 1 is an alkyl or alkoxy group of 1 to 4 carbon atoms; R 2 is each independently a hydrogen atom or an alkyl or alkoxy group of 1 to 4 carbon atoms; and Ar 1 is phenyl or a structural unit derived therefrom and having at least one halogen atom or alkyl or alkoxy group of 1 to 4 carbon atoms on an aromatic nucleus thereof); and
a diaralkylated derivative (x2) represented by structural formula (2):

(wherein R 1 is an alkyl or alkoxy group of 1 to 4 carbon atoms; R 2 is each independently a hydrogen atom or an alkyl or alkoxy group of 1 to 4 carbon atoms; and Ar 1 is each independently phenyl or a structural unit derived therefrom and having at least one halogen atom or alkyl or alkoxy group of 1 to 4 carbon atoms on an aromatic nucleus thereof),
the monoaralkylated derivative (x1) being present in an amount of 0.5% to 15% in terms of area percentage as determined by GPC, the diaralkylated derivative (x2) being present in an amount of 3% to 20% in terms of area percentage as determined by GPC.

2. The phenolic-hydroxyl containing resin according to claim 1 , comprising, in addition to the monoaralkylated derivative (x1) and the diaralkylated derivative (x2), a polyfunctional compound (Y) represented by structural formula (3):

(wherein R 1 is an alkyl or alkoxy group of 1 to 4 carbon atoms; R 2 is each independently a hydrogen atom or an alkyl or alkoxy group of 1 to 4 carbon atoms; Ar 1 is each independently phenylene or a structural unit derived therefrom and having at least one halogen atom or alkyl or alkoxy group of 1 to 4 carbon atoms on an aromatic nucleus thereof; m is each independently 1 or 2; and n is an integer of 0 to 20).

3. The phenolic-hydroxyl containing resin according to claim 2 , wherein a difunctional derivative (y1) represented by structural formula (3) wherein n is 0 is present in an amount of 5% to 30% of the total amount of phenolic-hydroxyl containing resin in terms of area percentage as determined by GPC.

4. The phenolic-hydroxyl containing resin according to claim 2 , wherein the phenolic-hydroxyl containing resin has a melting point of 40° C. to 90° C. and a melt viscosity at 150° C. of 0.01 to 10.0 dPa·s.

5. The phenolic-hydroxyl containing resin according to claim 1 , wherein the phenolic-hydroxyl containing resin has a melting point of 40° C. to 90° C. and a melt viscosity at 150° C. of 0.01 to 10.0 dPa·s.

6. A curable resin composition comprising the phenolic-hydroxyl containing resin according to claim 2 and a curing agent.

7. A curable resin composition comprising the phenolic-hydroxyl containing resin according to claim 1 and a curing agent.

8. A cured composition prepared by curing the curable resin composition according to claim 7 .

9. A semiconductor sealant comprising the curable resin composition according to claim 7 and an inorganic filler.

10. An epoxy resin prepared by converting into a polyglycidyl ether a phenolic resin prepared by reacting a polycondensate of a phenolic compound (b) and formaldehyde with an aralkylating agent, the epoxy resin comprising as essential components:
a glycidyl ether (z1) of a monoaralkylated derivative represented by structural formula (4):

(wherein R 3 is an alkyl or alkoxy group of 1 to 4 carbon atoms; R 4 is each independently a hydrogen atom or an alkyl or alkoxy group of 1 to 4 carbon atoms; Ar 2 is phenyl or a structural unit derived therefrom and having at least one halogen atom or alkyl or alkoxy group of 1 to 4 carbon atoms on an aromatic nucleus thereof; and G is glycidyl), and
a glycidyl ether (z2) of a diaralkylated derivative represented by structural formula (5):

(wherein R 3 is an alkyl or alkoxy group of 1 to 4 carbon atoms; R 4 is each independently a hydrogen atom or an alkyl or alkoxy group of 1 to 4 carbon atoms; Ar e is each independently phenyl or a structural unit derived therefrom and having at least one halogen atom or alkyl or alkoxy group of 1 to 4 carbon atoms on an aromatic nucleus thereof; and G is glycidyl),
the glycidyl ether (z1) of the monoaralkylated derivative being present in an amount of 0.5% to 15% in terms of area percentage as determined by GPC, the glycidyl ether (z2) of the diaralkylated derivative being present in an amount of 3% to 20% in terms of area percentage as determined by GPC.

11. The epoxy resin according to claim 10 , comprising, in addition to the glycidyl ether (z1) of the monoaralkylated derivative and the glycidyl ether (z2) of the diaralkylated derivative, a polyfunctional compound (W) represented by structural formula (6):

(wherein R 3 is an alkyl or alkoxy group of 1 to 4 carbon atoms; R 4 is each independently a hydrogen atom or an alkyl or alkoxy group of 1 to 4 carbon atoms; Ar 2 is each independently phenylene or a structural unit derived therefrom and having at least one halogen atom or alkyl or alkoxy group of 1 to 4 carbon atoms on an aromatic nucleus thereof; G is glycidyl; p is each independently 1 or 2; and q is an integer of 0 to 20).

12. The epoxy resin according to claim 11 , wherein a difunctional derivative (w1) represented by structural formula (6) wherein n is 0 is present in an amount of 5% to 30% of the total amount of epoxy resin in terms of area percentage as determined by GPC.

13. The epoxy resin according to claim 11 , wherein the epoxy resin has a melting point of 40° C. to 80° C. and a melt viscosity at 150° C. of 0.01 to 10.0 dPa·s.

14. The epoxy resin according to claim 10 , wherein the epoxy resin has a melting point of 40° C. to 80° C. and a melt viscosity at 150° C. of 0.01 to 10.0 dPa·s.

15. A curable resin composition comprising the epoxy resin according to claim 10 and a curing agent.

16. A cured composition prepared by curing the curable resin composition according to claim 15 .

17. A semiconductor sealant comprising the curable resin composition according to claim 15 and an inorganic filler.

18. A curable resin composition comprising the epoxy resin according to claim 11 and a curing agent.

Assignees

• Dainippon Ink & Chemicals

Inventors

• Nagae Norio
• Hirota Yousuke
• Satou Yutaka
• Nakamura Nobuya

Classifications

• H10W74/47

  comprising organic materials, e.g. plastics or resins · CPC title

• C08L63/00

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C09J161/06

  of aldehydes with phenols · CPC title

• C08G8/28

  Chemically modified polycondensates · CPC title

• C08G8/12

  with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol · CPC title