Thermosetting resin composition, and prepreg, insulating film with support, laminate plate, and printed wiring board, each obtained using same

Abstract

A thermosetting resin composition containing: (A) a resin composition having an unsaturated maleimide group, produced by reacting (a) a maleimide compound having at least two N-substituted maleimide groups per one molecule and (b) an amine compound having at least two primary amino groups per one molecule, in an organic solvent; (B) a thermosetting resin; and (C) a modified imidazole compound, such as an isocyanate-masked imidazole and an epoxy-masked imidazole, and a prepreg, an insulating film with a support, a laminate plate and a printed wiring board, each containing the same.

Claims

1. A thermosetting resin composition comprising: (A) a resin composition having an unsaturated maleimide group, which is a reaction product produced by reacting (a) a maleimide compound having at least two N-substituted maleimide groups per one molecule and (b) an amine compound having at least two primary amino groups per one molecule, wherein in producing said reaction product, the maleimide compound (a) and the amine compound (b) are used in a ration that satisfies the equivalent ration (T.sub.a/T.sub.b) in a range of 1.0<T.sub.a/T.sub.b10.0, where (T.sub.a/T.sub.b) is the equivalent ratio of the equivalent (T.sub.a) of the maleimide group in the maleimide compound (a) to the equivalent (T.sub.b) of the NH.sub.2 group in the amine compound (b); (B) a thermosetting resin; (C) a modified imidazole compound represented by any one of the following general formulae (I) and (II): ##STR00010## wherein R.sub.3, R.sub.4, R.sub.5 and R.sub.6 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 20 carbon atoms or a phenyl group; and A represents an alkylene group or an aromatic hydrocarbon group, ##STR00011## wherein R.sub.3, R.sub.4, R.sub.5 and R.sub.6 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 20 carbon atoms or a phenyl group; and B represents a single bond, an alkylene group, an alkylidene group, an ether group or a sulfonyl group; and (D) an amine compound having an acidic substituent represented by the following general formula (IV): ##STR00012## wherein R.sub.1 each independently represent a hydroxyl group, a carboxyl group or a sulfonic acid group as the acidic substituent; R.sub.2 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 5 carbon atoms or a halogen atom; x represents an integer of from 1 to 5; and y represents an integer of from 0 to 4, provided that a sum of x and y is 5.

2. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises (E) an inorganic filler.

3. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises (F) a molybdenum compound.

4. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises (G) a phosphorus-containing compound that imparts flame retardancy.

5. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises (H) a compound that achieves chemical roughening.

6. The thermosetting resin composition according to claim 1, wherein the thermosetting resin (B) is at least one selected from the group consisting of an epoxy resin, a phenol resin, an unsaturated imide resin, a cyanate resin, an isocyanate resin, a benzoxazine resin, an oxetane resin, an amino resin, an unsaturated polyester resin, an allyl resin, a dicyclopentadiene resin, a silicone resin, a triazine resin and a melamine resin.

7. The thermosetting resin composition according to claim 2, wherein the inorganic filler (E) is fused spherical silica and/or a metal hydrate that has a thermal decomposition temperature of 300 C. or more.

8. An insulating film with a support comprising a support having formed on a surface thereof a film containing the thermosetting resin composition according to claim 1 in a semi-cured state.

9. A prepreg comprising the thermosetting resin composition according to claim 1 that is coated on a reinforcing substrate in a form of a fiber sheet, and is rendered into a B-stage.

10. A laminate plate comprising at least one sheet of the insulating film with a support according to claim 8.

11. A printed wiring board comprising the laminate plate according to claim 10.

12. A laminate plate comprising at least one sheet of the prepreg according to claim 9.

13. A printed wiring board comprising the laminate plate according to claim 12.

14. A laminate plate comprising (i) at least one sheet of an insulating film with a support comprising a support having formed on a surface thereof a film containing the thermosetting resin composition according to claim 1 in a semi-cured state, and (ii) at least one sheet of a prepreg comprising said thermosetting resin composition that is coated on a reinforcing substrate in a form of a fiber sheet and is rendered into a B-stage.

15. A printed wiring board comprising the laminate plate according to claim 14.

16. The thermosetting resin composition according to claim 1, wherein said modified imidazole compound (C) is the compound represented by the general formula (I).

17. The thermosetting resin composition according to claim 1, which contains 0.01 to 10 parts by mass of the modified imidazole compound (C) per 100 parts by mass of the thermosetting resin (B).

18. The thermosetting resin composition according to claim 1, wherein said modified imidazole compound (C) is the compound represented by the general formula (II).

19. A resin varnish comprising the thermosetting resin composition according to claim 1 and an organic solvent therefore.

20. The thermosetting resin composition according to claim 1, wherein said reaction product has been produced by reacting said maleimide compound and said amine compound in an organic solvent.

21. The thermosetting resin composition according to claim 1, wherein the amine compound (D) is at least one selected from the group consisting of m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline and 3,5-dicarboxyaniline.

22. The thermosetting resin composition according to claim 1, wherein the resin composition having an unsaturated maleimide group (A) and the amine compound (D) are used in a ratio that satisfies the equivalent ratio (T.sub.A/T.sub.D) in a range of 1.0<(T.sub.A/T.sub.D)10.0, where (T.sub.A/T.sub.D) is the equivalent ratio of the equivalent (T.sub.A) of the maleimide group of the resin composition (A) to the equivalent (T.sub.D) of the NH.sub.2 group in the amine compound (D).

Description

EXAMPLE

(1) The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the description thereof.

(2) The varnishes and the copper-clad laminate plates obtained in Examples and Comparative Examples were measured for the performance and evaluated in the following manners.

(3) Varnish

(4) (1) Curing Property (Time to Gelation)

(5) A 0.5 mL portion as a specimen of each of the varnishes obtained in Examples and Comparative Examples was measured for the time from the input of the specimen to gelation (T.sub.0) of the specimen by using a gel timer, produced by Nisshin Kagaku Co., Ltd., set at 160 C.

(6) (2) Storage Stability

(7) The varnishes obtained in Examples and Comparative Examples were each stored at 40 C. for 3 days, and then measured for the time to gelation (T.sub.1) in the same manner as in the measurement of the curing property. The storage stability rate was obtained according to the following equation.
storage stability rate=T.sub.1/T.sub.0100(%)
Copper-Clad Laminate Plate
(1) Heat Resistance (Glass Transition Temperature Tg ( C.))

(8) The copper-clad laminate plates obtained in Examples and Comparative Examples were each immersed in a copper etching solution, thereby removing the copper foil, and a substrate for evaluation having a size of 5 mm square was prepared. The substrate for evaluation was measured for Tg by observing the thermal expansion characteristics in the z direction thereof with TMA tester (TMA2940, produced by DuPont Company), thereby evaluating the heat resistance.

(9) (2) Thermal Expansion Coefficient (Ppm/ C.)

(10) The copper-clad laminate plates obtained in Examples and Comparative Examples were each immersed in a copper etching solution, thereby removing the copper foil, and a substrate for evaluation having a size of 5 mm square was prepared. The substrate for evaluation was observed for the thermal expansion characteristics in the z direction thereof at a temperature lower than Tg with TMA tester (TMA2940, produced by DuPont Company), thereby evaluating the thermal expansion coefficient.

(11) (3) Copper Foil Adhesiveness (Copper Foil Peeling Strength (kN/m))

(12) The copper foil of each of the copper-clad laminate plates obtained in Examples and Comparative Examples was partially covered with a resist and immersed in a copper etching solution, thereby preparing a substrate for evaluation having the copper foil remaining with a width of 3 mm. The substrate for evaluation was measured for the adhesiveness (peeling strength) of the copper foil with a tensile tester.

(13) (4) Hygroscopicity (Water Absorption Coefficient (%))

(14) The copper-clad laminate plates obtained in Examples and Comparative Examples were each immersed in a copper etching solution, thereby removing the copper foil, and thereby a substrate for evaluation was prepared. The substrate for evaluation was subjected to a pressure cooker treatment under conditions of 121 C. and 2 atm for 5 hours with a pressure cooker tester, produced by Hirayama Manufacturing Corporation, and then the substrate for evaluation was measured for the water absorption coefficient.

(15) (5) Chemical Resistance (Rate of Change of Mass (% by Mass))

(16) The copper-clad laminate plates obtained in Examples and Comparative Examples were each immersed in a copper etching solution, thereby removing the copper foil, and thereby a substrate for evaluation was prepared. The substrate for evaluation was immersed in 18% by mass hydrochloric acid or a 10% by mass NaOH aqueous solution at 40 C. for 30 minutes, and then calculated for the rate of change of mass (((reduction of mass (g))/(mass of test piece before treatment (g)))100).

Example A

Production Example 1

(17) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-1)

(18) 569.30 g of bis(4-maleimidophenyl)methane, 59.04 g of 4,4-diaminodiphenylmethane and 350.00 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted for 5 hours under refluxing, thereby providing a solution of a resin composition having an unsaturated maleimide group (A-1).

Production Example 2

(19) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-2)

(20) 555.04 g of bis(4-maleimidophenyl)methane, 73.84 g of 3,3-diethyl-4,4-diaminodiphenylmethane and 350.00 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted for 5 hours under refluxing, thereby providing a solution of a resin composition having an unsaturated maleimide group (A-2).

Production Example 3

(21) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-3)

(22) 556.53 g of bis(4-maleimidophenyl)methane, 72.29 g of 3,3-diaminodiphenyl sulfone and 350.00 g of dimethylacetamide were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted at 100 C. for 5 hours, thereby providing a solution of a resin composition having an unsaturated maleimide group (A-3).

Production Example 4

(23) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-4)

(24) 562.69 g of polyphenylmethanemaleimide, 66.03 g of 3,3-dimethyl-4,4-diaminodiphenylmethane and 350.00 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted for 5 hours under refluxing, thereby providing a solution of a resin composition having an unsaturated maleimide group (A-4).

Production Example 5

(25) Production of Powder of Resin Composition Having Unsaturated Maleimide Group (A-5)

(26) 358.00 g of bis(4-maleimidophenyl)methane and 54.50 g of 4,4-diaminodiphenylmethane were placed in a kneader having a capacity of 1 L, equipped with a steam heating device, kneaded under heat at from 135 to 140 C. for 15 minutes, then cooled and pulverized, thereby providing powder of a resin composition having an unsaturated maleimide group (A-5).

Production Example 6

(27) Production of Powder of Resin Composition Having Unsaturated Maleimide Group (A-6)

(28) 358.00 g of polyphenylmethanemaleimide and 68.50 g of 3,3-dimethyl-4,4-diaminodiphenylmethane were placed in a kneader having a capacity of 1 L, equipped with a steam heating device, kneaded under heat at from 135 to 140 C. for 15 minutes, then cooled and pulverized, thereby providing powder of a resin composition having an unsaturated maleimide group (A-6).

Production Example 7

(29) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-7)

(30) 38.60 g of 4,4-bis(4-aminophenoxy) biphenyl, 478.50 g of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 22.90 g of p-aminophenol and 360.00 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted at the refluxing temperature for 2 hours, thereby providing a solution of a resin composition having an acidic substituent and an unsaturated maleimide group (A-7).

Production Example 8

(31) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-8)

(32) 69.10 g of 4,4-bis(4-aminophenoxy) biphenyl, 429.90 g of bis(4-maleimidophenyl) sulfone, 41.00 g of p-aminophenol and 360.00 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted at the refluxing temperature for 2 hours, thereby providing a solution of a resin composition having an acidic substituent and an unsaturated maleimide group (A-8).

Production Example 9

(33) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-9)

(34) 32.20 g of 2,2-dimethyl-4,4-diaminobiphenyl, 475.20 g of 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 32.60 g of p-aminophenol and 360.00 g of dimethylacetamide were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted at 100 C. for 2 hours, thereby providing a solution of a resin composition having an acidic substituent and an unsaturated maleimide group (A-9).

Production Example 10

(35) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-10)

(36) 36.70 g of o-dianisidine, 471.10 g of 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 32.20 g of p-aminophenol and 360.00 g of dimethylacetamide were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted at 100 C. for 2 hours, thereby providing a solution of a resin composition having an acidic substituent and an unsaturated maleimide group (A-10).

Production Example 11

(37) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-11)

(38) 40.20 g of bis(4-aminophenyl) sulfone, 464.40 g of bis(4-maleimidophenyl)methane, 35.40 g of p-aminophenol and 360.00 g of dimethylacetamide were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted at 100 C. for 4 hours, thereby providing a solution of a resin composition having an acidic substituent and an unsaturated maleimide group (A-11).

Production Example 12

(39) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-12)

(40) 44.80 g of bis[4-(4-aminophenoxy)phenyl]sulfone, 472.60 g of 2,2-bis(4-(4-maleimidophenoxy)phenyl) propane, 22.60 g of p-aminophenol and 360.00 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted at the reflux temperature for 2 hours, thereby providing a solution of a resin composition having an acidic substituent and an unsaturated maleimide group (A-12).

Production Example 13

(41) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-13)

(42) 79.40 g of bis[4-(4-aminophenoxyl)phenyl]sulfone, 420.50 g of bis(4-maleimidophenyl) sulfone, 40.10 g of p-aminophenol and 360.00 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted at the reflux temperature for 2 hours, thereby providing a solution of a resin composition having an acidic substituent and an unsaturated maleimide group (A-13).

Production Example 14

(43) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-14)

(44) 44.10 g of o-tolidine sulfone, 460.80 g of bis(4-maleimidophenyl)methane, 35.10 g of p-aminophenol and 360.00 g of dimethylacetamide were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted at 100 C. for 2 hours, thereby providing a solution of a resin composition having an acidic substituent and an unsaturated maleimide group (A-14).

Production Example 15

(45) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-15)

(46) 358.00 g of bis(4-maleimidophenyl)methane, 54.50 g of p-aminophenol and 412.50 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted for 5 hours under refluxing, thereby providing a solution of a resin composition having an acidic substituent and an unsaturated maleimide group (A-15).

Production Example 16

(47) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-16)

(48) 358.0 g of polyphenylmethanemaleimide, 54.50 g of p-aminophenol and 412.50 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted for 5 hours under refluxing, thereby providing a solution of a resin composition having an acidic substituent and an unsaturated maleimide group (A-16).

Production Example 17

(49) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-17)

(50) 360.00 g of bis(4-maleimidophenyl) ether, 54.50 g of p-aminophenol and 414.50 g of dimethylacetamide were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted at 100 C. for 2 hours, thereby providing a solution of a resin composition having an acidic substituent and an unsaturated maleimide group (A-17).

Examples 1 to 31 and Comparative Examples 1 to 6

(51) Uniform varnishes having a resin content (i.e., a total amount of the resin components) of 65% by mass were produced by mixing the following ingredients according to the mixing ratios (by mass) shown in Tables 1 to 6:

(52) (1) as the curing agent, the solutions of the resin composition having an unsaturated maleimide group (A) obtained in Production Examples 1 to 17,

(53) (2) as the thermosetting resin (B), a novolak type cyanate resin (PT-30, a trade name, produced by Lonza Japan, Ltd.), a bisphenol A dicyanate prepolymer (BA230, a trade name, produced by Lonza Japan, Ltd.), a tetrafunctional naphthalene type epoxy resin (EXA-4710, a trade name, produced by Dainippon Ink And Chemicals, Inc.), a biphenyl aralkyl type epoxy resin (NC-3000-H, a trade name, produced by Nippon Kayaku Co., Ltd.), a bifunctional naphthalene type epoxy resin (HP-4032D, a trade name, produced by Dainippon Ink And Chemicals, Inc.), a naphthol aralkyl type epoxy resin (ESN-175, a trade name, produced by Tohto Kasei Co., Ltd.), a bifunctional naphthalene aralkyl type epoxy resin (ESN-375, a trade name, produced by Tohto Kasei Co., Ltd.), a biphenyl type epoxy resin (YX-4000, a trade name, produced by Japan Epoxy Resin Co., Ltd.), and an anthracene type epoxy resin (YX-8800, a trade name, produced by Japan Epoxy Resin Co., Ltd.),

(54) (3) as the modified imidazole (C), an isocyanate-masked imidazole (G8009L, a trade name, produced by Dai-ichi Kogyo Seiyaku Co., Ltd.) and an epoxy-masked imidazole (P200H50, a trade name, produced by Japan Epoxy Resin Co., Ltd.),

(55) (4) as the amine compound having an acidic substituent (D), p-aminophenol (produced by Ihara Chemical Industry Co., Ltd.),

(56) (5) as the inorganic filler (E), fused silica (SC2050-KC, a trade name, produced by Admatechs Co., Ltd.), aluminum hydroxide (HP-360, a trade name, produced by Showa Denko K.K.), and boehmite (BMT-3LV, a trade name, produced by Kawai Lime Industry Co., Ltd.),

(57) (6) as the molybdenum compound (F), zinc molybdate (KEMGARD 1100, a trade name, produced by Sherwin-Williams Company),

(58) (7) as the phosphorus-containing compound that imparts flame retardancy (G), a phosphorus-containing epoxy resin (Epotohto ZX-1548-3, a trade name, produced by Tohto Kasei Co., Ltd., phosphorus content: 3% by mass), a phosphorus-containing phenol resin (HCA-HQ, a trade name, produced by Sanko Co., Ltd., phosphorus content: 9.6% by mass), a condensation type phosphate ester compound (PX-200, a trade name, produced by Daihachi Chemical Industry Co., Ltd.), and aluminum dialkylphosphinate (OP-930, a trade name, produced by Clariant Japan Co., Ltd.),

(59) (8) as the compound that achieves chemical roughening (H), crosslinked acrylonitrile-butadiene rubber (NBR) particles (XER-91, produced by JSR Corporation), core-shell type rubber particles (Stafiloid AC3832, a trade name, produced by Ganz Chemical Co., Ltd.), a polyvinyl acetal resin (KS-23Z, a trade name, produced by Sekisui Chemical Co., Ltd.),

(60) (9) as the epoxy resin curing agent (I), an aminotriazine novolak resin (LA-3018, a trade name, produced by Dainippon Ink And Chemicals, Inc.), benzoguanamine (produced by Nippon Shokubai Co., Ltd.), and dicyandiamide (produced by Daieikagaku Co., Ltd.), and

(61) (10) as the diluent solvent, methyl ethyl ketone.

(62) In Comparative Examples, 2-phenylimidazole (2PZ, a trade name, produced by Shikoku Chemicals Corporation) and 2-ethyl-4-methylimidazole (2E4MZ, a trade name, produced by Shikoku Chemicals Corporation), which were each a curing accelerator (i.e., a non-modified imidazole), were used instead of the modified imidazole (C).

(63) The isocyanate-masked imidazole (G8009L) is the modified imidazole represented by the general formula (I), wherein R.sub.3 and R.sub.5 are each CH.sub.3, R.sub.4 and R.sub.6 are each C.sub.2H.sub.5, and A is CH.sub.4, and the epoxy-masked imidazole (P200H50) is the modified imidazole represented by the general formula (II), wherein R.sub.3 and R.sub.5 are each hydrogen, R.sub.4 and R.sub.6 are each a phenyl group, and B is C(CH.sub.3).sub.2.

(64) The varnishes thus produced were evaluated for the curing property (i.e., the time to gelation) and the storage stability of the varnishes according to the methods described above.

(65) The varnishes were each coated by impregnation on an E-glass cloth having a thickness of 0.1 mm and dried under heat at 160 C. for 10 minutes, thereby providing a prepreg having a resin content of 50% by mass. Four sheets of the prepreg were laminated with electrolytic copper foils having a thickness of 18 m disposed on both surfaces thereof, and the assembly was pressed at a pressure of 2.5 MPa and a temperature of 185 C. for 90 minutes, thereby producing a copper-clad laminate plate.

(66) The resulting copper-clad laminate plates were measured and evaluated for the heat resistance (i.e., the glass transition temperature), the thermal expansion coefficient, the copper foil adhesiveness, the hygroscopicity and the chemical resistance. The results are shown in Tables 1 to 6.

(67) TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Thermosetting Resin Composition (part by mass) (A) Resin composition having unsaturated maleimide group A-1 50 49 A-2 50 50 A-3 50 A-4 49 (B) Thermosetting resin Novolak type cyanate resin (PT-30) 49.5 49.5 Bisphenol A type dicyanate 49.5 prepolymer (BA230) Tetrafunctional naphthalene type 49.5 epoxy resin (EXA-4710) Biphenyl aralkyl type epoxy resin 49.5 49.5 (NC-3000-H) (C) Modified imidazole Isocyanate-masked imidazole 0.5 0.5 0.5 0.5 (G8009L) Epoxy-masked imidazole (P200H50) 0.5 0.5 (D) Amine compound having acidic substituent p-Aminophenol 1 1 (E) Inorganic filler Fused silica (SC2050-KC) 50 Aluminum hydroxide (HP-360) Boehmite (BMT-3LV) (F) Molybdenum compound Zinc molybdate (KEMGARD 1100) 10 Results of Measurement and Evaluation Varnish (1) Curing property (time to 420 450 500 470 400 450 gelation T.sub.0, sec) (2) Storage stability (after 415 446 498 466 398 445 storing at 40 C. for 3 days T.sub.1, sec) Storage stability (%) = T.sub.1/T.sub.0 98.8 99.1 99.6 99.1 99.5 98.9 Copper-clad laminate plate (1) Heat resistance (glass 220 210 220 220 220 210 transition temperature, C.) (2) Thermal expansion coefficient 50 50 50 50 50 28 (ppm/ C.) (3) Copper foil adhesiveness 1.3 1.2 1.3 1.3 1.2 1.2 (kN/m) (4) Hygroscopicity (water 0.6 0.6 0.6 0.6 0.5 0.5 absorption coefficient, %) (5) Chemical resistance (rate of change of mass, % by mass) 18% by mass hydrochloric acid 0.006 0.006 0.006 0.006 0.006 0.007 10% by mass NaOH aqueous solution 0.006 0.008 0.008 0.008 0.008 0.009

(68) TABLE-US-00002 TABLE 2 Example Example Example Example 7 Example 8 Example 9 10 11 12 Thermosetting Resin Composition (part by mass) (A) Resin composition having unsaturated maleimide group A-2 49 48 A-3 49 49 A-4 49 A-5 49 (B) Thermosetting resin Novolak type cyanate resin (PT-30) Bisphenol A type dicyanate 20 prepolymer (BA230) Tetrafunctional naphthalene type 49.5 29.5 20 49 epoxy resin (EXA-4710) Biphenyl aralkyl type epoxy resin 29.5 49.5 49 (NC-3000-H) (C) Modified imidazole Isocyanate-masked imidazole 0.5 0.5 0.5 0.5 1.0 1.0 (G8009L) Epoxy-masked imidazole (P200H50) (D) Amine compound having acidic substituent p-Aminophenol 1 1 1 2 1 1 (E) Inorganic filler Fused silica (SC2050-KC) 50 50 50 50 50 50 Aluminum hydroxide (HP-360) 50 50 Boehmite (BMT-3LV) 50 50 50 50 (F) Molybdenum compound Zinc molybdate (KEMGARD 1100) 10 10 10 10 10 Results of Measurement and Evaluation Varnish (1) Curing property (time to 450 450 440 440 400 400 gelation T.sub.0, sec) (2) Storage stability (after 447 447 436 435 396 396 storing at 40 C. for 3 days T.sub.1, sec) Storage stability (%) = T.sub.1/T.sub.0 99.3 99.3 99.1 98.9 99.0 99.0 Copper-clad laminate plate (1) Heat resistance (glass 210 230 230 220 220 230 transition temperature, C.) (2) Thermal expansion coefficient 24 23 21 23 22 22 (ppm/ C.) (3) Copper foil adhesiveness 1.2 1.3 1.3 1.4 1.4 1.2 (kN/m) (4) Hygroscopicity (water 0.5 0.5 0.5 0.5 0.5 0.5 absorption coefficient, %) (5) Chemical resistance (rate of change of mass, % by mass) 18% by mass hydrochloric acid 0.007 0.007 0.006 0.007 0.006 0.007 10% by mass NaOH aqueous solution 0.008 0.008 0.008 0.009 0.007 0.008

(69) TABLE-US-00003 TABLE 3 Comp. Comp. Comp. Comp. Comp. Comp. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Thermosetting Resin Composition (part by mass) (A) Resin composition having unsaturated maleimide group A-1 50 50 A-2 49 49 A-5 50 A-6 49 (B) Thermosetting resin Novolak type dicyanate resin 50 (PT-30) Bisphenol A type cyanate 49.5 prepolymer (BA230) Tetrafunctional naphthalene 49.5 49.5 type epoxy resin (EXA-4710) Biphenyl aralkyl type epoxy resin 49.5 49 (NC-3000-H) (D) Amine compound having acidic substituent p-Aminophenol 1 1 1 (E) Inorganic filler Fused silica (SC2050-KC) 50 50 50 50 Aluminum hydroxide (HP-360) 50 Boehmite (BMT-3LV) 50 50 (F) Molybdenum compound Zinc molybdate (KEMGARD 1100) 10 10 10 10 10 Curing accelerator (non-modified imidazole) 2-Phenylimidazole (2PZ) 0.5 0.5 2-Ethyl-4-methyl- 0.5 0.5 0.5 imidazole (2E4MZ) Results of Measurement and Evaluation Varnish (1) Curing property (time to 600 400 550 400 350 350 gelation T.sub.0, sec) (2) Storage stability (after 550 250 500 220 200 180 storing at 40 C. for 3 days T.sub.1, sec) Storage stability (%) = (T.sub.0 T.sub.1)/T.sub.0 91.7 62.5 90.9 50.0 57.1 51.4 Copper-clad laminate plate (1) Heat resistance (glass 180 180 170 180 140 150 transition temperature, C.) (2) Thermal expansion 66 59 40 35 40 40 coefficient (ppm/ C.) (3) Copper foil adhesiveness 1.0 1.2 1.2 1.1 0.8 1.0 (kN/m) (4) Hygroscopicity (water 0.7 0.6 0.5 0.5 0.8 0.7 absorption coefficient, %) (5) Chemical resistance (rate of change of mass, % by mass) 18% by mass hydrochloric acid 0.015 0.007 0.015 0.007 0.020 0.015 10% by mass NaOH aqueous solution 0.020 0.008 0.040 0.009 0.040 0.032

(70) TABLE-US-00004 TABLE 4 Example Example Example Example Example Example 13 14 15 16 17 18 Thermosetting Resin Composition (part by mass) (A) Resin composition having unsaturated maleimide group A-7 50 A-8 50 50 A-9 50 70 A-10 50 (B) Thermosetting resin Biphenyl aralkyl type epoxy resin 30 (NC-3000-H) HP-4032D 49.5 HSN-175 30 EP-806 20 N-770 30 YX-8800 30 (C) Modified imidazole Isocyanate-masked imidazole 0.5 0.5 0.5 0.5 0.5 0.5 (G8009L) (E) Inorganic filler Fused silica (SC2050-KC) 40 40 40 40 40 40 (G) Phosphorus- containing compound HCA-HQ 3 3 3 3 3 3 (H) Compound achieving chemical roughening XER-91 1 1 1 1 1 1 (I) Epoxy curing agent LA-3018 15 19.5 18.5 4.5 4.5 Dicyandiamide 1 Benzoguanamine 4.5 5 5 Phosphorus atom content 0.3 0.3 0.3 0.3 0.3 0.3 Results of Measurement and Evaluation Varnish (1) Curing property (time to 480 530 500 550 580 560 gelation T.sub.0, sec) (2) Storage stability (after 479 528 497 549 578 559 storing at 40 C. for 3 days T.sub.1, sec) Storage stability (%) = T.sub.1/T.sub.0 99.6 99.6 99.4 99.8 99.7 99.8 Copper-clad laminate plate (1) Heat resistance (glass 240 260 260 260 270 240 transition temperature, C.) (2) Thermal expansion 20 26 28 30 31 33 coefficient (ppm/ C.) (3) Copper foil adhesiveness 1.3 1.3 1.3 1.3 1.2 1.3 (kN/m) (4) Hygroscopicity (water 0.5 0.5 0.5 0.5 0.5 0.5 absorption coefficient, %) (5) Chemical resistance (rate of change of mass, % by mass) 18% by mass hydrochloric acid 0.008 0.009 0.008 0.008 0.008 0.009 10% by mass NaOH aqueous solution 0.025 0.020 0.020 0.015 0.025 0.020

(71) TABLE-US-00005 TABLE 5 Example Example Example Example Example Example 19 20 21 22 23 24 Thermosetting Resin Composition (part by mass) (A) Resin composition having unsaturated maleimide group A-10 50 70 A-11 50 A-12 50 A-13 50 A-14 50 (B) Thermosetting resin HP-4032D 35 HSN-175 30 HSN-375 20 30 YX-4000 30 YX-8800 30 (C) Modified imidazole Isocyanate-masked imidazole (G8009L) 0.5 0.5 0.5 0.5 0.5 0.5 (E) Inorganic filler Fused silica (SC2050-KC) 40 40 40 40 40 40 (G) Phosphorus- containing compound HCA-HQ 3 3 5 3 3 ZX-1548-3 10 (H) Compound achieving chemical roughening XER-91 1 1 1 1 1 1 AC3832 1 (I) Epoxy curing agent LA-3018 13.5 9.5 19.5 19.5 15 Dicyandiamide 1 5 4.5 Benzoguanamine 5 Phosphorus atom content 0.3 0.3 0.3 0.5 0.3 0.3 Results of Measurement and Evaluation Varnish (1) Curing property (time to gelation 530 600 530 470 500 480 T.sub.0, sec) (2) Storage stability (after storing 528 597 526 468 497 477 at 40 C. for 3 days T.sub.1, sec) Storage stability (%) = T.sub.1/T.sub.0 99.6 99.5 99.2 99.6 99.4 99.4 Copper-clad laminate plate (1) Heat resistance (glass transition 240 260 260 260 260 240 temperature, C.) (2) Thermal expansion coefficient 32 28 28 26 26 32 (ppm/ C.) (3) Copper foil adhesiveness (kN/m) 1.3 1.2 1.3 1.3 1.3 1.3 (4) Hygroscopicity (water absorption 0.5 0.5 0.5 0.5 0.5 0.5 coefficient, %) (5) Chemical resistance (rate of change of mass, % by mass) 18% by mass hydrochloric acid 0.010 0.009 0.009 0.008 0.008 0.008 10% by mass NaOH aqueous solution 0.020 0.025 0.025 0.020 0.020 0.020

(72) TABLE-US-00006 TABLE 6 Example Example Example Example Example Example Example 25 26 27 28 29 30 31 Thermosetting Resin Composition (part by mass) (A) Resin composition having unsaturated maleimide group A-14 90 A-15 50 50 50 A-16 50 70 A-17 50 (B) Thermosetting resin Biphenyl aralkyl type epoxy resin 49.5 30 (NC-3000-H) HP-4032D 5 35 20 HSN-175 30 30 HSN-375 (C) Modified imidazole Isocyanate-masked imidazole 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (G8009L) (E) Inorganic filler Fused silica (SC2050-KC) 40 40 40 40 40 40 (G) Phosphorus-containing compound HCA-HQ 3 5 3 3 ZX-1548-3 10 OP-930 3 3 (H) Compound achieving chemical roughening XER-91 1 1 1 1 KS-23Z 1 1 (I) Epoxy curing agent LA-3018 19.5 19.5 19.5 Benzoguanamine 4.5 4.5 Phosphorus atom content 0.3 0.7 0.3 0.7 0.5 0.3 0.3 Results of Measurement and Evaluation Varnish (1) Curing property (time to 560 400 390 370 380 400 370 gelation T.sub.0, sec) (2) Storage stability (after 556 396 386 366 377 398 365 storing at 40 C. for 3 days T.sub.1, sec) Storage stability (%) = 99.3 99.0 99.0 98.9 99.2 99.5 98.6 T.sub.1/T.sub.0 Copper-clad laminate plate (1) Heat resistance (glass 290 210 230 220 230 240 220 transition temperature, C.) (2) Thermal expansion 24 38 38 39 37 35 40 coefficient (ppm/ C.) (3) Copper foil adhesiveness 1.1 1.0 1.0 1.1 1.1 1.2 1.1 (kN/m) (4) Hygroscopicity (water 0.5 0.5 0.5 0.5 0.5 0.6 0.5 absorption coefficient, %) (5) Chemical resistance (rate of change of mass, % by mass) 18% by mass hydrochloric acid 0.010 0.009 0.010 0.010 0.008 0.009 0.008 10% by mass NaOH aqueous solution 0.030 0.025 0.020 0.025 0.020 0.025 0.015

(73) It is apparent from Tables 1, 2 and 4 to 6 that Examples according to the present invention are all excellent in curing property and storage stability of the varnishes. On the other hand, Comparative Examples in Table 3 are considerably poor in at least one of curing property and storage stability since the modified imidazole compound (C) is not contained.

(74) It is apparent from Tables 1, 2 and 4 to 6 that Examples according to the present invention are all excellent in heat resistance (Tg), copper foil adhesiveness, moisture resistance and chemical resistance. On the other hand, Comparative Examples in Table 3 are considerably poor in at least one of these characteristics since the modified imidazole compound (C) is not contained.

Example B

Production Example 1

(75) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-1)

(76) 569.30 g of bis(4-maleimidophenyl)methane, 59.04 g of 4,4-diaminodiphenylmethane and 350.00 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted for 5 hours under refluxing, thereby providing a solution of a resin composition having an unsaturated maleimide group (A-1).

Production Example 2

(77) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-2)

(78) 555.04 g of bis(4-maleimidophenyl)methane, 73.84 g of 3,3-diethyl-4,4-diaminodiphenylmethane and 350.00 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted for 5 hours under refluxing, thereby providing a solution of a resin composition having an unsaturated maleimide group (A-2).

Production Example 3

(79) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-3)

(80) 556.53 g of bis(4-maleimidophenyl)methane, 72.29 g of 3,3-diaminodiphenyl sulfone and 350.00 g of dimethylacetamide were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted at 100 C. for 5 hours, thereby providing a solution of a resin composition having an unsaturated maleimide group (A-3).

Production Example 4

(81) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-4)

(82) 562.69 g of polyphenylmethanemaleimide, 66.03 g of 3,3-dimethyl-4,4-diaminodiphenylmethane and 350.00 g of propylene glycol monomethyl ether were placed in a reaction vessel having a capacity of 2 L capable of being heated and cooled, equipped with a thermometer, an agitator and a water quantity meter having a reflux condenser, and were reacted for 5 hours under refluxing, thereby providing a solution of a resin composition having an unsaturated maleimide group (A-4).

Comparative Production Example 1

(83) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-5)

(84) 358.00 g of bis(4-maleimidophenyl)methane and 54.50 g of 4,4-diaminodiphenylmethane were placed in a kneader having a capacity of 1 L, equipped with a steam heating device, kneaded under heat at from 135 to 140 C. for 15 minutes, then cooled and pulverized, thereby providing powder of a resin composition having an unsaturated maleimide group (A-5).

Comparative Production Example 2

(85) Production of Solution of Resin Composition Having Unsaturated Maleimide Group (A-6)

(86) 358.00 g of polyphenylmethanemaleimide and 68.50 g of 3,3-dimethyl-4,4-diaminodiphenylmethane were placed in a kneader having a capacity of 1 L, equipped with a steam heating device, kneaded under heat at from 135 to 140 C. for 15 minutes, then cooled and pulverized, thereby providing powder of a resin composition having an unsaturated maleimide group (A-6).

Examples 1 to 7 and Comparative Examples 1 to 6

(87) Uniform varnishes having a resin content (i.e., a total amount of the resin components) of 65% by mass were produced by mixing the following ingredients according to the mixing ratios (by mass) shown in Tables 1 to 3:

(88) as the curing agent, the solutions of the resin composition having an unsaturated maleimide group (A) obtained in Production Examples 1 to 5 and Comparative Production Examples 1 and 2,

(89) as the thermosetting resin (B), a novolak type cyanate resin (PT-30, a trade name, produced by Lonza Japan, Ltd.), a bisphenol A dicyanate prepolymer (BA230, a trade name, produced by Lonza Japan, Ltd.), a tetrafunctional naphthalene type epoxy resin (EXA-4710, a trade name, produced by Dainippon Ink And Chemicals, Inc.), and a biphenyl aralkyl type epoxy resin (NC-3000-H, a trade name, produced by Nippon Kayaku Co., Ltd.),

(90) as the modified imidazole (C), 2,4-diamino-6-[2-undecylimidazolyl-(1)]-ethyl-S-triazine (C11Z-A, a trade name, produced by Shikoku Chemicals Corporation), and 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-S-triazine (2E4MZ-A, a trade name, produced by Shikoku Chemicals Corporation),

(91) as the amine compound having an acidic substituent (D), p-aminophenol (produced by Ihara Chemical Industry Co., Ltd.),

(92) as the inorganic filler (E), fused silica (SC2050-KC, a trade name, produced by Admatechs Co., Ltd.), aluminum hydroxide (HP-360, a trade name, produced by Showa Denko K. K.), and boehmite (BMT-3LV, a trade name, produced by Kawai Lime Industry Co., Ltd.), and

(93) as the diluent solvent, methyl ethyl ketone.

(94) In Comparative Examples, 2-undecylimidazole (C11Z, a trade name, produced by Shikoku Chemicals Corporation) and 2-ethyl-4-methylimidazole (2E4MZ, a trade name, produced by Shikoku Chemicals Corporation), which were each a curing accelerator (i.e., a non-modified imidazole), were used instead of the modified imidazole (C).

(95) The varnishes thus produced were evaluated for the curing property (i.e., the time to gelation) and the storage stability of the varnishes according to the methods described above.

(96) The varnishes were each coated by impregnation on an E-glass cloth having a thickness of 0.1 mm and dried under heat at 160 C. for 10 minutes, thereby providing a prepreg having a resin content of 50% by mass. Four sheets of the prepreg were laminated with electrolytic copper foils having a thickness of 18 m disposed on both surfaces thereof, and the assembly was pressed at a pressure of 2.5 MPa and a temperature of 185 C. for 90 minutes, thereby producing a copper-clad laminate plate.

(97) The resulting copper-clad laminate plates were measured and evaluated for the heat resistance, the thermal expansion coefficient, the copper foil adhesiveness, the hygroscopicity, the chemical resistance and the maximum warpage. The results are shown in Tables 1 to 3.

(98) TABLE-US-00007 TABLE 7 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 (A) Resin composition having unsaturated maleimide group A-1 50 49 A-2 50 50 A-3 50 A-4 49 (B) Thermosetting resin PT-30 49.5 49.5 BA230 49.5 EXA-4710 49.5 NC-3000-H 49.5 49.5 (C) Modified imidazole 2E4MZ-A 0.5 0.5 0.5 0.5 0.5 C11Z-A 0.5 (D) Amine compound having acidic substituent p-Aminophenol 1 1 (E) Inorganic filler SC2050-KC 50 HP-360 BMT-3LV (E) Molybdenum compound KEMGARD 1100 10 Results of Measurement and Evaluation Time to gelation (sec) 410 440 490 450 390 450 Time to gelation after storing 405 436 488 446 388 445 at 40 C. for 3 days (sec) (1) Heat resistance (Tg) 220 210 220 220 220 210 (2) Thermal expansion 50 50 50 47 50 28 coefficient (ppm/ C.) (3) Copper foil adhesiveness 1.4 1.3 1.4 1.4 1.4 1.2 (kN/m) (4) Hygroscopicity (water 0.6 0.6 0.6 0.6 0.6 0.5 absorption coefficient, %) (5) Chemical resistance (rate of change of mass, % by weight) 18% by weight hydrochloric 0.006 0.006 0.006 0.006 0.006 0.007 acid 10% by weight NaOH aqueous 0.008 0.008 0.008 0.008 0.008 0.009 solution (6) Maximum warpage (mm) 2 2 2 2 2 1

(99) TABLE-US-00008 TABLE 8 Example Example Example Example 7 Example 8 Example 9 10 11 12 (A) Resin composition having unsaturated maleimide group A-2 49 48 A-3 49 49 A-4 49 A-5 49 (B) Thermosetting resin PT-30 BA230 20 EXA-4710 49.5 29.5 20 49 NC-3000-H 29.5 49.5 49 (C) Modified imidazole 2E4MZ-A 0.5 0.5 0.5 0.5 0.5 C11Z-A 0.5 0.5 0.5 (D) Amine compound having acidic substituent p-Aminophenol 1 1 1 2 1 1 (E) Inorganic filler SC2050-KC 50 50 50 50 50 60 HP-360 50 50 BMT-3LV 50 50 50 50 (E) Molybdenum compound KEMGARD 1100 10 10 10 10 10 Results of Measurement and Evaluation Time to gelation (sec) 440 440 430 430 380 380 Time to gelation after storing 437 437 426 425 374 375 at 40 C. for 3 days (sec) (1) Heat resistance (Tg) 210 230 230 220 220 210 (2) Thermal expansion 24 23 21 46 49 27 coefficient (ppm/ C.) (3) Copper foil adhesiveness 1.3 1.4 1.4 1.4 1.4 1.4 (kN/m) (4) Hygroscopicity (water 0.5 0.5 0.5 0.6 0.6 0.5 absorption coefficient, %) (5) Chemical resistance (rate of change of mass, % by weight) 18% by weight hydrochloric 0.007 0.007 0.006 0.006 0.006 0.007 acid 10% by weight NaOH aqueous 0.008 0.008 0.008 0.008 0.008 0.009 solution (6) Maximum warpage (mm) 1 1 0.5 2 2 0.5

(100) TABLE-US-00009 TABLE 9 Comp. Comp. Comp. Comp. Comp. Comp. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 (A) Resin composition having unsaturated maleimide group A-1 50 50 A-2 49 49 A-6 50 A-7 49 (B) Thermosetting resin PT-30 50 BA230 49.5 EXA-4710 49.5 49.5 NC-3000-H 49.5 49 (D) Amine compound having acidic substituent p-Aminophenol 1 1 1 (E) Inorganic filler SC2050-KC 50 50 50 50 HP-360 50 BMT-3LV 50 50 (E) Molybdenum compound KEMGARD 1100 10 10 10 10 10 Curing accelerator (non-modified imidazole) 2E4MZ 0.5 0.5 C11Z 0.5 0.5 0.5 Results of Measurement and Evaluation Time to gelation (sec) 600 400 550 400 350 350 Time to gelation after 550 250 500 220 200 180 storing at 40 C. for 3 days (sec) (1) Heat resistance (Tg) 180 180 170 180 140 150 (2) Thermal expansion 66 59 40 35 40 40 coefficient (ppm/ C.) (3) Copper foil 1.0 1.2 1.2 1.1 0.8 1.0 adhesiveness (kN/m) (4) Hygroscopicity (water 0.7 0.6 0.5 0.5 0.8 0.7 absorption coefficient, %) (5) Chemical resistance (rate of change of mass, % by weight) 18% by weight hydrochloric 0.015 0.007 0.015 0.007 0.020 0.015 acid 10% by weight NaOH aqueous 0.020 0.008 0.040 0.009 0.040 0.032 solution (6) Maximum warpage (mm) 6 4 5 4 8 8

(101) It is apparent from Tables 7 and 8 that Examples according to the present invention are all excellent in curing property and storage stability of the varnishes. On the other hand, Comparative Examples in Table 9 are considerably poor in at least one of curing property and storage stability since the modified imidazole compound (C) is not contained.

(102) It is apparent from Tables 7 and 8 that Examples according to the present invention are all excellent in heat resistance (Tg), copper foil adhesiveness, moisture resistance, chemical resistance and low warpage property. On the other hand, Comparative Examples in Table 9 are considerably poor in at least one of these characteristics since the modified imidazole compound (C) is not contained.