Polyphenylene ether derivative having N-substituted maleimide group, and heat curable resin composition, resin varnish, prepreg, metal-clad laminate, and multilayer printed wiring board using same

1. A polyphenylene ether derivative (A) having at least one N-substituted maleimide group represented by the following general formula (I) in a molecule:

wherein R 1 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, R 2 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A 1 represents a residual group represented by one of the following general formulas (II), (Ill), (IV), or (V), m is an integer of 1 or more as the number of the structural unit, and x and y are each an integer of 1 to 4,

wherein R 3 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and p is an integer of 1 to 4,

wherein R 4 and R 5 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A 2 represents an alkylene group or alkylidene group having 1 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a ketone group, a single bond, or a residual group represented by the following general formula (III-1), and q and r are each an integer of 1 to 4,

wherein R 6 and R 7 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A 3 represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a ketone group, or a single bond, and s and t are each an integer of 1 to 4,

wherein n is an integer of 1 to 10,

wherein R 8 and R 9 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and u is an integer of 1 to 8.

2. The polyphenylene ether derivative (A) according to claim 1 , wherein the N-substituted maleimide group comprises at least one represented by the following formulas (I-1), (I-2), or (I-3):

wherein m is as defined for the general formula (I),

wherein m is as defined for the general formula (I),

wherein m is as defined for the general formula (I).

3. A heat curable resin composition comprising the polyphenylene ether derivative (A) according to claim 1 and a thermosetting resin (B).

4. The heat curable resin composition according to claim 3 , wherein the polyphenylene ether derivative (A) has a number average molecular weight of 5,000 to 12,000.

5. The heat curable resin composition according to claim 3 , wherein the thermosetting resin (B) is at least one selected from the group consisting of an epoxy resin, a cyanate ester resin, and a maleimide compound.

6. The heat curable resin composition according to claim 5 , wherein the maleimide compound as the thermosetting resin (B) comprises a bismaleimide compound (a) having at least two N-substituted maleimide groups in a molecule, or a polyaminobismaleimide compound (c) represented by the following general formula (VI):

wherein A 4 is a residual group represented by one of the following general formulas (VII), (VIII), (IX), or (X), and A 5 is a residual group represented by the following general formula (XI):

wherein R 10 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom,

wherein R 11 and R 12 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and A 6 represents an alkylene group or alkylidene group having 1 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a ketone group, a single bond, or a residual group represented by the following general formula (VIII-1):

wherein R 13 and R 14 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and A 7 represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a ketone group, or a single bond,

wherein i is an integer of 1 to 10,

wherein R 15 and R 16 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and j is an integer of 1 to 8,

wherein R 17 and R 18 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom, and As represents an alkylene group or alkylidene group having 1 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a ketone group, a fluorenylene group, a single bond, or a residual group represented by one of the following general formulas (XI-1) or (XI-2):

wherein R 19 and R 20 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and A 9 represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, a m- or p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a ketone group, or a single bond,

wherein R 21 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and A 10 and A 11 each represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a ketone group, or a single bond.

7. The heat curable resin composition according to claim 3 , wherein the ratio of the polyphenylene ether derivative (A) and thermosetting resin (B) contained is in the range of: (A):(B) =(5 to 80% by mass):(95 to 20% by mass).

8. The heat curable resin composition according to claim 3 , which further comprises an inorganic filler (C).

9. The heat curable resin composition according to claim 3 , which further comprises a flame retardant (D).

10. The heat curable resin composition according to claim 3 , which further comprises a curing accelerator (E).

11. The heat curable resin composition according to claim 3 , which further comprises a phenolic antioxidant (F).

12. The heat curable resin composition according to claim 3 , wherein the resin composition after being cured has a glass transition temperature of 200° C. or higher.

13. A resin varnish comprising the heat curable resin composition according to claim 3 and an organic solvent.

14. A prepreg obtained by applying the resin varnish according to claim 13 to a sheet-form fiber reinforced substrate, and drying the applied resin varnish.

15. A laminate obtained by stacking one sheet or more of the prepreg according to claim 14 , and disposing a metal foil or foils on one side or both sides of the stacked material, and subjecting the resultant material to hot pressing.

16. A multilayer printed wiring board formed using the laminate according to claim 15 by performing circuit formation processing and bonding processing for forming a multilayer.

17. A method for producing the polyphenylene ether derivative (A) according to claim 1 , the method comprising the steps of: reacting a phenol compound having at least one primary amino group in a molecule and being represented by the following general formula (XII) with a polyphenylene ether having a structure represented by the following general formula (XIII) and having a number average molecular weight of 15,000 to 25,000 in an organic solvent to produce a polyphenylene ether compound having a primary amino group; and reacting the obtained polyphenylene ether compound with a bismaleimide compound having at least two N-substituted maleimide groups in a molecule and being represented by the following general formula (XIV):

wherein R 1 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and x is an integer of 1 to 4,

wherein R 2 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, y is an integer of 1 to 4, and k is an integer of 1 or more,

wherein A 1 is as defined for the general formula (I).