COMPOSITION, CURED PRODUCT AND LAMINATE

Abstract

An object of the invention is to provide a composition having excellent heat resistance and excellent adhesiveness. Moreover, another object is to provide a cured product obtained by curing the composition and a laminate containing the cured product. Furthermore, another object is to provide a heat-resistant material, a heat-resistant member, an electronic material and an electronic member each containing the composition. The objects are achieved by providing a composition including: a (meth)allyl group-containing maleimide compound having a structure having one or more benzene rings, one or more groups having a (meth)allyl group and one or more groups having a maleimide group; and a hydroxy group-containing maleimide compound having a structure having one or more benzene rings, one or more groups having a hydroxy group and one or more maleimide groups.

Claims

1. A composition comprising a (meth)allyl group-containing maleimide compound represented by formula (1) below and a hydroxy group-containing maleimide compound represented by formula (4) below: ##STR00033## wherein n.sub.1 and m.sub.1 are each independently an integer of 1 to 5, Aly is a group having a (meth)allyl group represented by formula (2) below, MI is a group having a maleimide group represented by formula (3) below, and A.sub.1 is a structure having one or more benzene rings, ##STR00034## wherein Z.sub.1 is a direct bond or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R.sup.1 represents a hydrogen atom or a methyl group, ##STR00035## wherein Z.sub.2 is a direct bond or a hydrocarbon group having 1 or 2 carbon atoms which may have a substituent, and R.sup.2 and R.sup.3 each independently represent a hydrogen atom or a methyl group, ##STR00036## wherein n2 and m2 are each independently an integer of 1 to 5, MI is a group having a maleimide group represented by formula (3) above, and A.sub.2 is a structure having one or more benzene rings.

2. The composition according to claim 1, wherein in general formula (1) above, Al is any one of the structures shown in formula (5) below: ##STR00037## ##STR00038##

3. The composition according to claim 1, wherein in general formula (4) above, A.sub.2 is a benzene ring structure, and n.sub.2 and m.sub.2 are both 1.

4. The composition according to claim 1, further comprising an epoxy compound.

5. The composition according to claim 1, further comprising a filler.

6. The composition according to claim 1, further comprising a fibrous substrate.

7. A cured product comprising a product obtained by curing the composition according to claim 1.

8-17. (canceled)

18. A method for producing a composition comprising a (meth)allyl group-containing compound and a hydroxy group-containing maleimide compound, the method comprising: a step of producing an aromatic amino compound mixture by mixing a (meth)allyl group-containing amino compound represented by formula (6) below and a hydroxy group-containing amino compound represented by formula (9) below; and a step of maleimidating the aromatic amino compound mixture: ##STR00039## wherein n.sub.1 and m.sub.1 are each independently an integer of 1 to 5, Aly is a group having a (meth)allyl group represented by formula (7) below, B.sub.1 is a group having an amino group represented by formula (8) below, and A.sub.1 is a structure having one or more benzene rings, ##STR00040## wherein Z.sub.1 is a direct bond or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R.sup.1 represents a hydrogen atom or a methyl group,
[Chem. 8]
Z.sub.2NH.sub.2 (8) wherein Z.sub.2 is a direct bond or a hydrocarbon group having 1 or carbon atoms which may have a substituent, and R.sup.2 and R.sup.3 each independently represent a hydrogen atom or a methyl group, ##STR00041## wherein n.sub.2 and m.sub.2 are each independently an integer of 1 to 5, B2 is a group having an amino a malcimidc group represented by formula (8) above, and A.sub.2 is a structure having one or more benzene rings.

19. A method for producing a composition comprising a (meth)allyl group-containing compound and a hydroxy group-containing maleimide compound, the method comprising: a step of producing a mixture solution by mixing a (meth)allyl group-containing maleimide compound represented by formula (1) above, a hydroxy group-containing maleimide compound represented by formula (4) above and a solvent, and a step of removing the solvent from the obtained mixture solution.

20. A cured product comprising a product obtained by curing the composition according to claim 2.

21. A cured product comprising a product obtained by curing the composition according to claim 3.

22. A cured product comprising a product obtained by curing the composition according to claim 4.

23. A cured product comprising a product obtained by curing the composition according to claim 5.

24. A cured product comprising a product obtained by curing the composition according to claim 6.

Description

SYNTHESIS EXAMPLE 1

Synthesis of Allyl Group-Containing Maleimide Compound A

[0207] (1) Step of Protecting Amino Group

[0208] In a 3-L flask having a thermometer, a cooling tube and a stirrer, 150.21 g (0.58 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAPA, manufactured by Wakayama Seika Kogyo Co., Ltd.), 1 L of DMF (N,N-dimethylformamide) and 0.45 L of deionized water were put and stirred at room temperature. The reaction solution was heated to 60 C., and then 148.22 g (1.45 mol) of acetic anhydride was slowly dropped. After the completion of dropping, reaction was conducted at 60 C. for two hours, and then the resultant was air-cooled to room temperature. The precipitates were filtered, washed with 2 L of deionized water and then vacuum-dried at 80 C. for 10 hours, and 177.21 g (yield of 89.2%) of the reactant (a-1) in the chemical equation below as a solid was thus obtained. [0209] (2) Allylation Step

[0210] In a 3-L flask having a thermometer, a cooling tube and a stirrer, 150.00 g (0.438 mol) of the reactant (a-1) and 2.2 L of acetone were put and stirred. Then, 133.79 g (0.968 mol) of potassium carbonate was added, and the reaction solution was heated to a reflux state. After reflux for one hour, 116.60 g (0.964 mol) of allyl bromide was dropped over one hour. After the completion of dropping, reaction was conducted under reflux for 12 hours, and then the resultant was air-cooled to room temperature. After filtration, the reaction solution was concentrated under reduced pressure and further vacuum-dried at 80 C. for 10 hours, and 177.88 g (yield of 96.1%) of the reactant (a2) was thus obtained.

##STR00022## [0211] (3) Deprotection Step

[0212] In a 1-L flask having a thermometer, a cooling tube and a stirrer, 170.00 g (0.402 mol) of (a-2) and 330 mL of ethanol were put and stirred. Concentrated hydrochloric acid in an amount of 108.97 g was added, and the mixture was heated to 60 C. After reaction at 60 C. for 30 hours, the resultant was air-cooled to room temperature. The reaction solution was neutralized with an aqueous 20% sodium hydroxide solution, followed by extraction with 400 mL of ethyl acetate. The resultant was washed twice with 200 mL of deionized water, dried by adding sodium sulfate and then concentrated under reduced pressure. The obtained reactant was vacuum-dried at 80 C. for 10 hours, and 127.73 g (yield of 93.8%) of the reactant (a-3) as a liquid was thus obtained. [0213] (4) Maleimidation Step

[0214] In a 3-L flask having a thermometer, a cooling tube, a Dean-Stark trap and a stirrer, 76.49 g (0.780 mol) of maleic anhydride and 1.8 L of toluene were put and stirred at room temperature. Then, a mixture solution of 120.00 g (0.355 mol) of the reactant (a-3) and 200 mL of DMF was dropped over one hour. After the completion of dropping, the reaction was further conducted at room temperature for two hours. p-Toluenesulfonic acid monohydrate in an amount of 9.82 g was added, and the reaction solution was heated. After cooling and separating water and toluene which were generated as an azeotrope under reflux, only toluene was returned to the system, and dehydration reaction was conducted for eight hours. After air-cooling to room temperature, the resultant was concentrated under reduced pressure, and 274.58 g of a brown solution was thus obtained. The solution was dissolved in 800 mL of ethyl acetate, washed three times with 300 mL of deionized water and three times with 300 mL of an aqueous 2% sodium hydrogen carbonate solution, dried by adding sodium sulfate and then concentrated under reduced pressure. The obtained reactant was vacuum-dried at 80 C. for four hours, and 104.57 g of a crude product containing the allyl group-containing maleimide compound A was thus obtained. The purity of the obtained crude product was 75.0% (HPLC area %, detection wavelength of 275 nm).

[0215] By separating and purifying the obtained crude product by silica gel column chromatography (developing solvent: ethyl acetate/hexane =55/45, volume ratio),55.91g (yield of 31.5%) of the allyl group-containing maleimide compound (A) was obtained.

##STR00023##

[0216] .sup.1H-NMR: 7.22-7.16(8H), 7.07-7.05(2H), 5.94-5.84(2H), 5.27-5.15(4H), 4.54-4.51(4H), 1.61(6H)

[0217] .sup.13C-NMR: 169.97 ppm, 151.96 ppm, 142.39 ppm, 134.93 ppm, 133.19 ppm, 128.52 ppm, 128.09 ppm, 119.61 ppm, 116.65 ppm, 112.96 ppm, 68.26 ppm, 41.27 ppm, 30.60 ppm

[0218] Mass spectrum: M+=498

[0219] Melting point (DSC peak top): 134 C.

[0220] Purity: 96.7% (HPLC area %, detection wavelength of 275 nm)

SYNTHESIS EXAMPLE 2

Synthesis of Hydroxy Group-Containing Maleimide Compound (B)

[0221] According to the method described in the literature, Polymer Vol. 37 No. 16, 3721-3727; 1996, the hydroxy group-containing maleimide compound (B) was synthesized using 4-aminophenol as a starting material.

##STR00024##

[0222] .sup.1H-NMR: 9.69(1H), 7.13-7.07(4H), 6.85-6.82(2H)

[0223] .sup.13C-NMR: 170.26 ppm, 156.98 ppm, 134.48 ppm, 128.35 ppm, 122.47 ppm, 115.37 ppm

[0224] Mass spectrum: M.sup.+=189

[0225] Melting point (DSC peak top): 187 C.

[0226] Purity: 95.0% (HPLC area%, detection wavelength of 275 nm)

SYNTHESIS EXAMPLE 3

Synthesis of Hydroxy Group-Containing Maleimide Compound (C)

[0227] In a 3-L flask having a thermometer, a cooling tube, a Dean-Stark trap and a stirrer, 25.05 g (0.255 mol) of maleic anhydride and 520 mL of toluene were put and stirred at room temperature. Then, a mixture solution of 30.00 g (0.116 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAPA, manufactured by Wakayama Seika Kogyo Co., Ltd.) and 80 mL of DMF was dropped over one hour. After the completion of dropping, the reaction was further conducted at room temperature for two hours. p-Toluenesulfonic acid monohydrate in an amount of 2.75 g was added, and the reaction solution was heated. After cooling and separating water and toluene which were generated as an azeotrope under reflux, only toluene was returned to the system, and dehydration reaction was conducted for six hours. After air-cooling to room temperature, the resultant was concentrated under reduced pressure, and 113.77 g of an orange solution was thus obtained. The solution was dissolved in 400 mL of ethyl acetate, washed four times with 100 mL of deionized water and five times with 100 mL of an aqueous 2% sodium hydrogen carbonate solution, dried by adding sodium sulfate and then concentrated under reduced pressure. The obtained reactant was vacuum-dried at 80 C. for 10 hours, and 27.83 g of a crude product containing the hydroxy group-containing maleimide compound (C) was thus obtained.

##STR00025##

[0228] .sup.1H-NMR: 9.65 (1H), 7.12(4H), 7.05-7.02(4H), 6.85-6.83(2H), 1.54(6H)

[0229] .sup.13C-NMR: 170.18 ppm, 151.66 ppm, 141.05 ppm, 134.91 ppm, 128.58 ppm, 127.72 ppm, 117.82 ppm, 115.97 ppm, 41.04 ppm, 30.76 ppm

[0230] Mass spectrum: M+=418

[0231] Purity: 85.7% (HPLC area%, detection wavelength of 275 nm)

EXAMPLE 1

Synthesis of Maleimide Composition (D)

[0232] In a 3-L flask having a thermometer, a cooling tube, a Dean-Stark trap and a stirrer, 132.48 g (1.351 mol) of maleic anhydride and 1.53 L of toluene were put and stirred at room temperature. The flask was placed in an ice bath, and a mixture solution of 109.14 g (0.322 mol) of the reactant (a-3), 63.76 g (0.584 mol) of 4-aminophenol and 280 mL of DMF was dropped. After the completion of dropping, the reaction was further conducted at room temperature for two hours. p-Toluenesulfonic acid monohydrate in an amount of 15.27 g was added, and the reaction solution was heated. After cooling and separating water and toluene which were generated as an azeotrope under reflux, only toluene was returned to the system, and dehydration reaction was conducted for nine hours. After air-cooling to room temperature, the resultant was concentrated under reduced pressure, and 553.22 g of a brown solution was thus obtained. The solution was dissolved in 1.4 L of ethyl acetate, washed four times with 400 mL of deionized water and five times with 400 mL of an aqueous 2% sodium hydrogen carbonate solution, dried by adding sodium sulfate and then concentrated under reduced pressure. The obtained reactant was vacuum-dried at 80 C. for 11 hours, and 192.55 g of the maleimide composition (D) containing an allyl group-containing maleimide compound and a hydroxy group-containing maleimide compound was thus obtained.

##STR00026##

[0233] Because the mass spectrum of the obtained maleimide composition (D) exhibited the peaks of M+=498 and 189, it was found that the aimed maleimidation progressed. Moreover, by .sup.1H-NMR, it was found that the ratio of the maleimide components was allyl group-containing maleimide/hydroxy group-containing maleimide=57:43 (weight ratio). To calculate the ratio, the signal derived from the allyl groups of the allyl group-containing maleimide and the signal derived from the aromatic ring of the hydroxy group-containing maleimide in .sup.1-NMR were used.

EXAMPLE 2

Synthesis of Maleimide Composition (E)

[0234] In a 3-L flask having a thermometer, a cooling tube, a Dean-Stark trap and a stirrer, 76.49 g (0.780 mol) of maleic anhydride and 1.8 L of toluene were put and stirred at room temperature. Then, a mixture solution of 120.00 g (0.355 mol) of the reactant (a-3) and 200 mL of DMF was dropped over one hour. After the completion of dropping, the reaction was further conducted at room temperature for two hours. p-Toluenesulfonic acid monohydrate in an amount of 9.82 g was added, and the reaction solution was heated. After cooling and separating water and toluene which were generated as an azeotrope under reflux, only toluene was returned to the system, and dehydration reaction was conducted for eight hours. After air-cooling to room temperature, the resultant was concentrated under reduced pressure, and 274.58 g of a brown solution was thus obtained. The solution was dissolved in 800 mL of ethyl acetate and washed three times with 300 mL of deionized water and three times with 300 mL of an aqueous 2% sodium hydrogen carbonate solution, and 815.4 g of a resin solution (e-1) containing the allyl group-containing maleimide compound (A) was thus obtained. The hydroxy group-containing maleimide compound (B) obtained in Synthesis Example (2) in an amount of 75.7 g (0.400 mol) was added thereto and stirred, and thus a resin solution in which the allyl group-containing maleimide compound and the hydroxy group-containing maleimide compound were uniformly mixed was obtained. The resin solution was dried by adding sodium sulfate and then concentrated under reduced pressure. The obtained reactant was vacuum-dried at 80 C. for four hours, and 175.2 g of the maleimide composition (E) containing the allyl group-containing maleimide compound and the hydroxy group-containing maleimide compound was thus obtained.

##STR00027##

[0235] Because the mass spectrum of the obtained maleimide composition (E) exhibited the peaks of M.sup.+=498 and 189, it was found that the aimed maleimidation progressed. Moreover, by .sup.1H-NMR, it was found that the ratio of the maleimide components was allyl group-containing maleimide/hydroxy group-containing maleimide=58:42 (weight ratio). To calculate the ratio, the signal derived from the allyl groups of the allyl group-containing maleimide and the signal derived from the aromatic ring of the hydroxy group-containing maleimide in .sup.1-NMR were used.

EXAMPLE 3

Synthesis of Maleimide Composition (F)

[0236] The maleimide composition (F) was obtained by conducting the same operations as those in Example 1 using 3-aminophenol instead of 4-aminophenol in Example 1.

##STR00028##

[0237] Because the mass spectrum of the obtained maleimide composition (F) exhibited the peaks of M.sup.+=498 and 189, it was found that the aimed maleimidation progressed. Moreover, by .sup.1H-NMR, it was found that the ratio of the maleimide components was allyl group-containing maleimide/hydroxy group-containing maleimide=60:40 (weight ratio). To calculate the ratio, the signal derived from the allyl groups of the allyl group-containing maleimide and the signal derived from the aromatic ring of the hydroxy group-containing maleimide in .sup.1H-NMR were used.

EXAMPLE 4

Synthesis of Maleimide Composition (G)

[0238] In a 3-L flask having a thermometer, a cooling tube, a Dean-Stark trap and a stirrer, 118.65 g (1.210 mol) of maleic anhydride and 1.0 L of toluene were put and stirred at room temperature. The flask was placed in an ice bath, and a mixture solution of 122.97 g (0.363 mol) of the reactant (a-3), 40.86 g (0.374 mol) of 4-aminophenol and 190 mL of DMF was dropped. After the completion of dropping, the reaction was further conducted at room temperature for two hours. p-Toluenesulfonic acid monohydrate in an amount of 14.12 g was added, and the reaction solution was heated. After cooling and separating water and toluene which were generated as an azeotrope under reflux, only toluene was returned to the system, and dehydration reaction was conducted for nine hours. The same separation step as that in Example 1 was conducted, and 169.92 g of a maleimide composition (G) was thus obtained.

[0239] Because the mass spectrum of the obtained maleimide composition (G) exhibited the peaks of M+=498 and 189, it was found that the aimed maleimidation progressed. Moreover, by .sup.1H-NMR, it was found that the ratio of the maleimide components was allyl group-containing maleimide/hydroxy group-containing maleimide=70:30 (weight ratio). To calculate the ratio, the signal derived from the allyl group of the allyl group-containing maleimide and the signal derived from the aromatic ring of the hydroxy group-containing maleimide in .sup.1H-NMR were used.

EXAMPLE 5

Synthesis of Maleimide Composition (H)

[0240] The reactant (h-1) was synthesized according to the method described in the literature, Proceedings of the National Academy of Sciences, India, Section A: Physical Sciences, 71(1), 5-12; 2001.

##STR00029##

[0241] In a 3-L flask having a thermometer, a cooling tube and a stirrer, 60.00 g (0.232 mol) of the reactant (h-1), 800 mL of acetic acid and 800 mL of hydrobromic acid (47%) were put and heated to a reflux state while stirring. After reaction under reflux for 12 hours, the resultant was air-cooled to room temperature. The reaction solution was neutralized with an aqueous 20% sodium hydroxide solution, followed by extraction with 600 mL of ethyl acetate. The resultant was washed three times with 200 mL of deionized water, dried by adding sodium sulfate and then concentrated under reduced pressure, and 43.01 g (yield of 80.5%) of the reactant (h-2) was thus obtained.

##STR00030##

[0242] The allyl group-containing amine compound (h-3) was obtained by conducting the same operations as those in Synthesis Example 1(1) to (3) using the reactant (h-2) instead of BAPA in Synthesis Example 1.

##STR00031##

[0243] The maleimide composition (G) was obtained by conducting the same operations as those in Example 1 using the reactant (h-3) instead of the reactant (a-3) in Example 1.

##STR00032##

[0244] Because the mass spectrum of the obtained maleimide composition (H) exhibited the peaks of M.sup.+=470 and 189, it was found that the aimed maleimidation progressed. Moreover, by .sup.1H-NMR, it was found that the ratio of the maleimide components was allyl group-containing maleimide/hydroxy group-containing maleimide=72:28 (weight ratio). To calculate the ratio, the signal derived from the allyl groups of the allyl group-containing maleimide and the signal derived from the aromatic ring of the hydroxy group-containing maleimide in .sup.1H-NMR were used.

<Evaluation of Resin Cured Product>

[0245] (1) Production of Composition

[0246] The allyl group-containing maleimide compound and the hydroxy group-containing maleimide compounds obtained in Synthesis Examples 1 to 3, the maleimide compositions obtained in Examples 1 to 5, epoxy resins, a phenolic resin, bismaleimide for comparison and a catalyst were blended at the proportions shown in Table 2 to Table 5 by pulverizing and mixing with a mortar, and compositions were prepared.

<Melt Viscosity of Maleimide Component>

[0247] Regarding the melt viscosity of a maleimide component, the viscosity at 150 C. was measured using a dynamic viscoelasticity measuring device (ARES manufactured by TA instruments).

<Gel Time of Resin Composition>

[0248] The gel times (tack disappearing times) of the compositions blended at the proportions shown in Table 2 to Table 5 were measured at 200 C. [0249] (2) Production of Cured Product

[0250] The prepared compositions were heated under the following conditions, and resin cured products were thus obtained.

[0251] Curing conditions: A resin composition was put into a form to which copper foil having a thickness of 18 m (JTCSLC-18 manufactured by JX Nippon Mining & Metals Corporation, untreated surface) had been placed, and a cured product was obtained by press forming by heating at 200 C. for two hours and at 250 C. for two hours.

[0252] Thickness of cured product: 2 mm

[0253] The physical properties of the cured products were evaluated by the following methods. The results are shown in Tables 2 and 3.

<Glass Transition Temperature>

[0254] A piece having a size of a width of 5 mm and a length of 50 mm was cut out of a cured product having a thickness of 2 mm and used as a test piece. Regarding the test piece, the temperature at which the change in the elastic modulus was the largest (the tan change rate was the largest) was measured using a viscoelasticity measuring device (DMA: a solid viscoelasticity measuring device DMS7100 manufactured by Hitachi High-Tech Science Corporation, deformation mode: dual cantilever bending, measurement mode: sinusoidal oscillation, frequency .sup.1Hz, heating rate 3 C./minute) and determined as the glass transition temperature.

<Resistance to Thermal Decomposition>

[0255] A cured product having a thickness of 2 mm was cut into fine pieces, and the measurement was conducted using a thermogravimetric analyzer (TG/DTA6200 manufactured by SII Nanotechnology Inc.) at a heating rate of 5 C./minute in a nitrogen atmosphere. The temperature at which the weight decreased by 5% (Td5) was determined.

<Metal Adhesiveness>

[0256] A piece having a size of a width of 10 mm and a length of 70 mm was cut out of a cured product having a thickness of 2 mm to which copper foil was adhered, and this piece was used as a test piece. The peeling strength of the test piece in the 90 direction was evaluated (test speed: 50 mm/min) with a tensile tester (Tensilon RTC manufactured by A&D Company, Limited).

TABLE-US-00002 TABLE 2 Example Example Example 6 Example 7 Example 8 Example 9 10 11 Allyl group-containing 45 maleimide compound (A) Hydroxy group-containing 30 maleimide compound (B) Hydroxy group-containing maleimide compound (C) Maleimide composition (D) 100 75 Maleimide composition (E) 75 Maleimide composition (F) 75 Maleimide composition (G) 81 Maleimide composition (H) HP-4700 25 25 25 25 19 N-655-EXP-S HP-6000 TPP 0.5 0.5 0.5 0.5 0.4 Maleimide content of 100 75 75 75 75 81 composition (%) Evaluation of resin Maleimide component 0.4 Did not 0.4 0.5 0.4 0.6 150 C. melt viscosity (dPa .Math. s) melt. Gel time of composition at >600 108 76 82 62 107 200 C. (sec) Evaluation of cured product Glass transition temperature >360 >360 >360 >360 >360 >360 ( C.) Temperature of thermal 435 376 385 381 375 392 decomposition resistance (Td5, C.) Copper foil adhesiveness 0.3 1.1 1.7 1.7 2.4 1.7 (N/10 mm)

TABLE-US-00003 TABLE 3 Example Example Example Example 12 13 14 15 Allyl group-containing maleimide 34 49 45 compound (A) Hydroxy group-containing maleimide 34 29 compound (B) Hydroxy group-containing maleimide 30 compound (C) Maleimide composition (D) Maleimide composition (E) Maleimide composition (F) Maleimide composition (G) Maleimide composition (H) 81 HP-4700 19 25 N-655-EXP-S 32 HP-6000 22 TPP 0.4 0.6 0.5 0.5 Maleimide content of composition (%) 81 68 71 75 Evaluation of resin Maleimide component 0.9 Did not Did not Did not 150 C. melt viscosity (dPa .Math. s) melt. melt. melt. Gel time of composition at 200 C. (sec) 40 82 167 88 Evaluation of cured product Glass transition temperature ( C.) >360 288 311 >360 Temperature of thermal decomposition 380 375 395 379 resistance (Td5, C.) Copper foil adhesiveness (N/10 mm) 1.7 1.5 1.7 0.9

TABLE-US-00004 TABLE 4 Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Allyl group-containing 100 maleimide compound (A) Hydroxy group-containing 100 33 maleimide compound (B) BMI-1000 100 67 HP-4700 N-655-EXP-S TD-2131 TPP Maleimide content of 100 100 100 100 composition (%) Evaluation of resin Maleimide component Did not melt. 1.3 Did not melt. Did not melt. 150 C. melt viscosity (dPa .Math. s) Gel time of composition at >600 >600 >600 200 C. (sec) Evaluation of cured product Glass transition temperature >360 >360 >360 ( C.) Temperature of thermal 481 432 430 decomposition resistance (Td5, C.) Copper foil adhesiveness Did not 0.1> Did not (N/10 mm) adhere. adhere.

TABLE-US-00005 TABLE 5 Comparative Comparative Comparative Comparative Example 5 Example 6 Example 7 Example 8 Allyl group-containing 60 50 maleimide compound (A) Hydroxy group-containing 53 30 maleimide compound (B) BMI-1000 45 HP-4700 40 47 25 N-655-EXP-S 33 TD-2131 17 TPP 1 0.6 0.5 Maleimide content of 60 53 75 50 composition (%) Evaluation of resin Maleimide component 1.3 Did not melt. Did not melt. 1.3 150 C. melt viscosity (dPa .Math. s) Gel time of composition at >600 168 158 75 200 C. (sec) Evaluation of cured product Glass transition temperature 250 334 358 194 ( C.) Temperature of thermal 340 362 365 377 decomposition resistance (Td5, C.) Copper foil adhesiveness 0.3 Did not Did not 0.2 (N/10 mm) adhere. adhere.

[0257] The materials used in the tables are as follows.

[0258] BMI-1000: 4,4-diphenylmethane bismaleimide (manufactured by Daiwa Kasei Industry Co., Ltd.)

[0259] N-655-EXP-S: cresol novolak-type epoxy resin (manufactured by DIC Corporation)

[0260] HP-4700: naphthalene-type epoxy resin (manufactured by DIC Corporation)

[0261] HP-6000: naphthylene ether-type epoxy resin (manufactured by DIC Corporation)

[0262] TD-2131: phenol novolak (manufactured by DIC Corporation)

[0263] TPP: triphenylphosphine (manufactured by Hokko Chemical Industry Co., Ltd.)

[0264] As shown by Comparative Example 1 and Comparative Example 2, sufficient adhesiveness could not be obtained with the cured products obtained from one maleimide compound alone. In particular, as shown by Comparative Example 1, when the cured product was obtained from only one maleimide compound containing no allyl group, the copper foil peeled off immediately after the production of the cured product, and the adhesiveness could not be measured.

[0265] In Comparative Example 3, the resin volatilized during curing, and a cured product could not be produced.

[0266] As shown by Comparative Example 4, Comparative Example 6 and Comparative Example 7, when the maleimides in the compositions contained no allyl group, the copper foil peeled off immediately after the production of the cured products, and the adhesiveness could not be measured.

[0267] As shown by Comparative Example 5 and Comparative Example 8, when the compositions did not contain any hydroxy group-containing maleimide compound, the results were with a low glass transition temperature and a low temperature of thermal decomposition resistance.

<Production of Laminated Plate>

[0268] Compositions were prepared by blending compounds and a catalyst at the proportions shown in Table 6. The nonvolatile contents of the compositions were adjusted to 58 mass% with methyl ethyl ketone, and resin composition solutions were thus obtained. Laminated plates were produced under the following conditions.

[0269] Substrate: glass cloth #2116 manufactured by Nitto Boseki Co., Ltd. (210280 mm)

[0270] Number of plies: 6

[0271] Conditions for prepreg formation: 160 C., 3 minutes

[0272] Curing conditions: 1.5 hours at 200 C. at 40 kg/cm2, thickness after molding: 0.8 mm

<Gel Time of Resin Composition>

[0273] The gel times (tack disappearing times) of the resin compositions blended at the proportions shown in Table 6 were measured at 160 C.

<Glass Transition Temperature>

[0274] A cured product having a thickness of 0.8 mm with a size of a width of 5 mm and a length of 50 mm was cut out of each laminated plate and used as a test piece. Regarding the test piece, the temperature at which the change in the elastic modulus was the largest (the tan change rate was the largest) was measured using a viscoelasticity measuring device (DMA: a solid viscoelasticity measuring device DMS7100 manufactured by Hitachi High-Tech Science Corporation, deformation mode: dual cantilever bending, measurement mode: sinusoidal oscillation, frequency .sup.1Hz, heating rate 3 C./minute) and determined as the glass transition temperature.

<Bending Strength>

[0275] A cured product having a thickness of 0.8 mm with a size of a width of 15 mm and a length of 100 mm was cut out of each laminated plate, and the piece was used as a test piece and evaluated in accordance with JIS-K7107.

<Tensile Strength>

[0276] A cured product having a thickness of 0.8 mm with a size of a width of 15 mm and a length of 120 mm was cut out of each laminated plate, and the piece was used as a test piece and evaluated in accordance with JIS-K7165.

TABLE-US-00006 TABLE 6 Comparative Example 16 Example 9 Maleimide composition (D) 75 HP-4700 25 N-680 67 TD-2090 33 2E4MZ 0.2 0.04 Evaluation of resin Gel time of composition at 160 C. (sec) 392 397 Evaluation of cured product Glass transition temperature ( C.) 341 220 Bending strength Maximum point stress 590 420 (MPa) Maximum distortion 2.9 2.9 (%) Elastic modulus (GPa) 23.33 16.52 Tensile strength Maximum point stress 350 250 (MPa) Maximum distortion 3.3 3.3 (%) Elastic modulus (GPa) 13.89 11.35

[0277] The materials used in the table are as follows.

[0278] HP-4700: naphthalene-type epoxy resin (manufactured by DIC Corporation)

[0279] N-680: cresol novolak-type epoxy resin (manufactured by DIC Corporation)

[0280] TD-2090: phenol novolak (manufactured by DIC Corporation) 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Corporation)

[0281] As shown by Example 12, regarding both of the bending strength and the tensile strength, the glass transition temperature and the mechanical strength were higher than those of the conventional epoxy cured product.

INDUSTRIAL APPLICABILITY

[0282] The composition of the invention has a low viscosity, and a cured product thereof has a high glass transition temperature, excellent resistance to thermal decomposition and high adhesiveness. Therefore, the composition can be suitably used for a heat-resistant member and an electronic member. The composition can be particularly suitably used for a semiconductor encapsulating material, a circuit board, a buildup film, a buildup board and the like as well as an adhesive and a resist material. Moreover, the composition can be suitably used also for a matrix resin of a resin and is particularly suitable as a highly heat-resistant prepreg.