JP3399774B2 - Thermosetting resin composition and prepreg and laminate using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition, a prepreg, and a laminate which are excellent in heat resistance, low moisture absorption, adhesiveness, workability, and solder heat resistance after moisture absorption.
That is, it relates to a resin composition for improving solder heat resistance after absorbing moisture, such as an electronic / electrical component, an insulating material for the semiconductor field, a resin encapsulating material, and a laminated board material, and particularly a printed wiring that is required to have heat resistance. TECHNICAL FIELD The present invention relates to a resin composition useful for a laminate for plates, a prepreg and a laminate using the same.

[0002]

2. Description of the Related Art With regard to printed wiring boards widely used in electric / electronic devices, communication devices, computing devices, etc., the wiring density has become more sophisticated and highly integrated.
There is an increasing demand for improved reliability by improving the heat resistance of laminated wiring boards. In addition, COB, PGA, BGA, MC
Applications for directly mounting a semiconductor chip on a substrate such as an M substrate are increasing, and in such a mounting process, high temperature is required and the substrate to be mounted is required to have heat resistance.
BACKGROUND ART Conventionally, epoxy resins, unsaturated polyester resins, polyimide resins, phenol resins, etc. have been used as resin materials for forming laminated boards for printed wiring boards. Of these resins, epoxy resins and bismaleimides have been used. The polyamino bismaleimide resin obtained by reacting a diamine with an aromatic diamine is widely used for high-density packaging and high-multilayer laminates.

[0003]

Although the epoxy resin has relatively good heat resistance, it has not been possible to meet the recent demand for higher heat resistance due to high-density mounting of printed wiring boards and high multilayer structure. However, there is a limit to the increase in heat resistance. Therefore, a polyamino bismaleimide resin or the like has been proposed as a laminate material for improving heat resistance (French Patent No. 1455514, JP-B-46-).
23250, JP-A-61-200149). In the case of this polyamino bismaleimide, although its heat resistance is very excellent, it has high hygroscopicity and has a problem in adhesiveness, and since it requires a high temperature and a long time as compared with an epoxy resin during lamination, There was a problem of high cost.
Further, in order to make up for the drawbacks of the polyamino bismaleimide resin, an imide-modified epoxy resin obtained by adding an epoxy resin to the polyamino bismaleimide resin (Japanese Patent Publication No. 47-4216).
However, there is a problem that the heat resistance is significantly inferior to the polyamino bismaleimide resin and the heat resistance is insufficient.

For this reason, it is possible to cope with the future progress of high-density mounting and multi-layering, and it is also applicable to the application of semiconductor chips directly. It has excellent heat resistance, low moisture absorption, and solder heat resistance after moisture absorption. There has been a strong demand for a resin material for laminated boards which is excellent in mechanical properties, has good mechanical properties such as adhesiveness and toughness, and is inexpensive, and which has a low cost. The present invention has been made in view of such circumstances, eliminating the drawbacks of conventional epoxy resins and polyimide resins, heat resistance, particularly excellent solder heat resistance after moisture absorption, mechanical properties such as toughness It is also an object of the present invention to provide a new resin material for laminated plates that can satisfy the above requirements.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve the above-mentioned problems, and as a result, obtained a polymaleimide compound and a phenol resin having dihydroxynaphthalene, dihydroxynaphthalene, dihydroxybiphenyl or dihydroxybiphenyl. By using the phenolic resin and the epoxy resin that have, by utilizing the characteristics such as heat resistance of polymaleimide resin, adhesiveness of epoxy resin, workability, succeeded in improving heat resistance, mechanical properties, solder heat resistance, The present invention has been completed. That is, the present invention provides 1) (a) a polymaleimide compound represented by the general formula (1) (chemical formula 3).

[0006]

[Chemical 3] (In the formula, R ₁ is an m-valent organic group, Xa and Xb are hydrogen atoms,
Same or different monovalent atom or group selected from halogen atom and organic group, m is an integer of 2 or more and 10 or less)
And (b) a phenol resin containing dihydroxynaphthalene or dihydroxynaphthalene represented by the formula (2) (chemical formula 4), a phenol resin containing dihydroxybiphenyl or dihydroxybiphenyl represented by the formula (3) (chemical formula 4), ( c) a thermosetting resin composition containing an epoxy resin having at least two epoxy groups in the molecule,

[0007]

[Chemical 4] (In the formula, R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms)

2) (a) a polymaleimide compound represented by the general formula (1) (b) dihydroxynaphthalene, a phenol resin containing dihydroxynaphthalene, a phenol resin containing dihydroxybiphenyl or dihydroxybiphenyl, and (c) in a molecule. A thermosetting resin composition containing an epoxy resin having at least two or more epoxy groups, and (d) a modified imide resin modified with a compound having at least one active hydrogen in the molecule, and 3). The thermosetting resin composition according to the above 1) or 2), which comprises a curing accelerator, a flame retardant, a filler, a linear polymer and / or an additive, 4) The above 1), 2) or 3). Prepreg characterized by impregnating a base material with the resin material of 5) 5) One or more prepregs of 4) above are laminated and formed. Thermosetting resin laminate wherein become Te, 6) is a thermosetting resin laminate of the above 5) formed by laminating integrally formed with the outermost metal foil.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As the (a) polymaleimide compound used in the present invention, any compound having two or more maleimide groups in one molecule can be used. Examples of such polymaleimide compounds include N, N '
-Ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N '-(1,3-phenylene) bismaleimide, N, N'-[1,3- (2-methylphenylene)] bismaleimide, N, N '-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4- Maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane,
1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane,
1,4-bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3
-Maleimidophenoxy) phenyl] methane, bis [4
-(4-maleimidophenoxy) phenyl] methane,
1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy)] Phenyl] ethane, 1,2-bis [4-
(4-maleimidophenoxy) phenyl] ethane, 2,2
-Bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy)
Phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-
Maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,
1,3,3,3-hexafluoropropane, 2,2-bis [4
-(4-maleimidophenoxy) phenyl] -1,1,1,
3,3,3-hexafluoropropane,

4,4'-bis (3-maleimidophenoxy)
Biphenyl, 4,4'-bis (4-maleimidophenoxy)
Biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4 -Maleimidophenoxy) phenyl] sulfide, bis [4-
(3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl]
Sulfoxide, bis [4- (3-maleimidophenoxy)
Phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4- Bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene,
1,4-bis [4- (3-maleimidophenoxy) -α, α
-Dimethylbenzyl] benzene, 1,3-bis [4- (3-
Maleimidophenoxy) -α, α-dimethylbenzyl]
Benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl]
Benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy)
-3,5-Dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy)-
3,5-Dimethyl-α, α-dimethylbenzyl] benzene, general formula (4)

[0011]

[Chemical 5] (In the formula, n is 0 to 10 on average), and a polymaleimide compound represented by the general formula (5)

[0012]

[Chemical 6] (In the formula, k has an average value of 0 to 10) and the like. These polymaleimide compounds may be used alone or in combination of two or more.

As the component (b), a dihydroxynaphthalene represented by the formula (2), a phenol resin having at least one dihydroxynaphthalene, a dihydroxybiphenyl represented by the formula (3) or a phenol having at least one dihydroxybiphenyl is represented. Any resin can be used.

As dihydroxynaphthalene, 1,3
-, 1,4-, 1,5-, 1,6-, 2,3-, 2,7
Examples of the phenol resin having dihydroxynaphthalene include phenols such as dihydroxynaphthalene and phenol, cresol, resorcinol, phenylphenol, and dihydroxybiphenyl, or naphthols such as 1- and 2-naphthol, and formaldehyde and acetaldehyde. Novolak resins which are reaction products with aldehydes such as benzaldehyde, hydroxybenzaldehyde, gluoxal, and alkanedials, and reaction products of the above dihydroxynaphthalene, phenols, naphthols with aralkyl alcohol derivatives or aralkyl halide derivatives. Aralkyl resins are mentioned, and one kind or a mixture of two or more kinds of these phenol resins is used.

Further, as dihydroxybiphenyl,
4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl, 4,4'dihydroxy-3,3', 5,5'-tetraethylbiphenyl, 4, 4'-dihydroxy-3,3
′, 5,5′-Tetrapropylbiphenyl, 4,4′-
Dihydroxy-3,3 ', 5,5'-tetrabutylbiphenyl and the like can be mentioned. Examples of the phenol resin having dihydroxybiphenyl include phenols such as dihydroxybiphenyl and phenol, cresol, resorcinol, or naphthols such as dihydroxynaphthalene. Formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde,
Gluoxal, a novolak resin that is a reaction product with aldehydes such as alkanedials, and the above dihydroxybiphenyl, phenols, aralkyl resin that is a reaction product of an aralkyl alcohol derivative or an aralkyl halide derivative, and the like. One kind or a mixture of two or more kinds of these phenolic resins is used.

As the epoxy resin which is the component (c),
All epoxy compounds having two or more epoxy groups in the molecule can be used. Examples of such epoxy compounds include phenols such as phenol, cresol, resorcinol, and naphthol, or phenols obtained by halogenating these, and aldehydes such as formaldehyde, acetaldehyde, benzaldehyde, tolualdehyde, glyoxal, and alkanedial. Epoxy resin obtained by the reaction of the reaction product obtained by the condensation reaction with epichlorohydrin; an epoxy resin obtained by the reaction of the reaction product of the above phenols with an aralkyl alcohol derivative or an aralkyl halide derivative and epichlorohydrin; 2 in 1 molecule shown
Epoxy resins derived from compounds having one or more active hydrogens, for example, polyhydric phenols such as bisphenol A, bisphenol F, resorcinol, bishydroxydiphenyl ether, bishydroxybiphenyl, bishydroxynaphthalene, trihydroxyphenylmethane; ethylene glycol , Neopentyl glycol,
Polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, diethylene glycol, polypropylene glycol; amines such as ethylenediamine, aniline, bis (4-aminophenyl) methane;
An epoxy resin obtained by reacting a polycarboxylic acid such as adipic acid, phthalic acid or isophthalic acid with epichlorohydrin can be mentioned. These epoxy resins may be used alone or as a mixture of two or more. Also, the brominated flux
Various halogenated epoxy resins such as R> enol novolac resin and brominated bisphenol A type epoxy resin can be used.

In the composition of the present invention, the component (a), a polymaleimide compound represented by the general formula (1), and (b) are used.
Component dihydroxynaphthalene, phenolic resin having dihydroxynaphthalene, phenolic resin having dihydroxybiphenyl or cihydroxybiphenyl, and epoxy resin of component (c) are such that the component (b) is 100 parts by weight of the component (b). And the total amount of the component (c) is 10 to 500 parts by weight, preferably 25 to 300 parts by weight, and the epoxy resin of the component (c) with respect to the dihydroxynaphthalene, dihydroxybiphenyl or the phenolic resin of the component (b). Is an equivalent ratio of 0.1-10
Is in the range, preferably in the range of 0.5 to 2.0.

The resin composition of the present invention contains, if necessary, a phenol novolac resin, a naphthol novolac resin,
Dihydroxynaphthalene such as phenol aralkyl resin and naphthol aralkyl resin, phenol resin not containing dihydroxybiphenyl, amines represented by diaminodiphenylmethane, diaminodiphenysulfone, dicyandiamide, acid anhydrides such as phthalic anhydride and pyromellitic dianhydride Can also be used together.

As the component (d) used for producing the modified imide resin, any compound having at least one active hydrogen in the molecule can be used. Examples of compounds having at least one active hydrogen in the molecule include phenols such as phenol, bisphenol A, bisphenol F, cresol, resorcinol, naphthol and dihydroxynaphthol, aniline, aminophenol,
Phenylenediamine, ethylenediamine, bis (4-
Amines such as aminophenyl) methane, glycidol,
Glycerin diglycidyl ether, ethylene glycol monoglycidyl ether, resorcinol monoglycidyl ether, naphthresorcinol monoglycidyl ether, etc., compounds containing one alcoholic or phenolic OH group and one or more epoxy groups in one molecule, propargyl Examples thereof include compounds having an OH group such as alcohol and an acetylene group.

As a method for producing the modified imide resin,
(A) component polymaleimide resin, (b) component,
(C) component and (d) component at the same time 80-200 ℃
In general, the mixture is heated and mixed for 0.1 to 10 hours, but the mixture may be further heated and mixed in an organic solvent. When heating and mixing in an organic solvent, it generally depends on the boiling point of the organic solvent to be used, but is generally 50 to 200 ° C. and 0.1 to 2
It's 0 hours. Although the content of the modified imide resin is not clear, it is mainly considered to be oligomerization of the polymaleimide resin. At the time of modification, it is difficult to produce a stable modified imide resin with only the component (b) and / or the component (c) or the component (d) with respect to the polymaleimide resin (a) component.

The component (d) is preferably used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the polymaleimide resin, and particularly preferably 5 to 30 parts by weight for the purpose of maintaining heat resistance. .

The amount of the epoxy resin as the component (b) and the component (c) is preferably 10 to 500 parts by weight, preferably 10 to 500 parts by weight, based on 100 parts by weight of the component (a). Is from 25 to 300 parts by weight, and the equivalent ratio of the epoxy resin as the component (c) to the component (b) is in the range of 0.1 to 10, preferably 0.5 to 2.0.

In the present invention, when curing the resin composition, it is desirable to include a curing accelerator,
As such a curing accelerator, 2-methylimidazole,
Imidazoles such as 2-methyl-4-ethylimidazole and 2-heptadecylimidazole; amines such as triethanolamine, triethylenediamine and N-methylmorpholine; organic phosphines such as tributylphosphine, triphenylphosphine and tritolylphosphine ;
Tetraphenylphosphonium tetraphenylborate,
And tetraphenylboron salts such as triethylammonium tetraphenylborate; 1,8-diaza-bicyclo (5,4,0) undecene-7 and its derivatives. These curing accelerators may be used alone or in combination of two or more, and if necessary, an organic peroxide or an azo compound may be used in combination. The content of these curing accelerators is 0.005 to 10 relative to 100 parts by weight of the resin.
Used in the range of parts by weight.

In addition to the above various components, the resin material of the present invention may be used with imide resins such as diallyl phthalate, triallyl isocyanurate, o, o'-diallyl bisphenol A, bisphenol A diallyl ether and bisphenol A dicyanate, if necessary. Commonly used reactive diluents; various silicone oils; flame retardants such as bromine compounds, antimony, phosphorus, etc .; fillers such as silica, talc, alumina, aluminum nitride; polyether sulfones, polyphenylene ethers, aromatic polyesters , Polysulfone,
Linear polymers such as polyphenylene sulfide, polyether ether ketone, polyimide, polyether imide, polyamide imide and polyparabanic acid; other additives may be appropriately mixed.

To produce a prepreg using the resin composition of the present invention as described above, the resin composition (a) component, (b) component, (c) component, a curing accelerator and other additives are added. The agent is dissolved in a solvent to form a resin varnish. Or
A modified imide resin comprising the component (a), the component (b), the component (c) and the component (d), a curing accelerator and other additives are dissolved in a solvent to form a resin varnish.

The concentration of the thermosetting resin composition in the varnish is 4
The range of 0-80% by weight is desirable. As the solvent used at this time, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, dioxane, acetone, N-methyl-2- Pyrrolidone, dimethyl sulfoxide, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, 2-heptanone and the like can be used.

As the base material, all known base materials such as glass cloth, carbon fiber, organic fiber cloth, glass non-woven cloth and paper can be used. After coating and impregnating the base material with the varnish, a prepreg is manufactured through a drying step, but the coating method, impregnation method, and drying method are not particularly limited. The drying conditions are appropriately determined depending on the boiling point of the solvent used, but not too high a temperature, and the amount of the residual solvent in the prepreg is preferably 1% by weight or less.

The laminated plate is manufactured by heating and pressurizing one or a plurality of the above prepregs to be integrated, and at this time, a metal foil or a metal plate is laminated on one or both outermost layers. be able to. The heating temperature is 100 to 300 ° C, and the pressure is 5 to 100 kg.
/ Cm ² is desirable. Copper as metal foil or metal plate,
Aluminum, iron, stainless steel, etc. can be used. Also,
You may use it as a laminated board for multilayer printed wiring boards using an inner layer core material.

[0029]

EXAMPLES The present invention will be specifically described below with reference to examples. The test method of the performance in the examples is as follows.・ Glass transition temperature: Dynamic viscoelasticity method ・ Copper foil peel test: JIS C-6481 ・ Water absorption rate: JIS C-6481 ・ Solder heat resistance: 120 ° C, 100% RH of the test piece according to JIS C-6481 After the water absorption treatment for 3 hours under the above condition, it was floated in a solder bath at 300 ° C. for 120 seconds, and the presence or absence of abnormality of the laminated plate was examined. The following materials were used as the raw materials used in the examples and comparative examples.・ Polymaleimide compound; bis (4-maleimidophenyl) methane (manufactured by Mitsui Toatsu Chemicals, Inc.) ・ 1,6-dihydroxynaphthalene (manufactured by Kanto Chemicals, Inc.) ・ 4,4'-dihydroxybiphenyl; biphenol (Honshu) Chemical Industry Co., Ltd.)-Phenol resin (1); Dihydroxynaphthalene, cresol novolac resin (Synthesis example 1) -Phenol resin (2); Dihydroxynaphthalene zilock (Synthesis example 2) -Phenol resin (3); Dihydroxybiphenyl, phenol novolac resin (Synthesis example 3) -Phenol resin (4); Dihydroxybiphenyl Zyloc (synthesis example 4) -Phenol resin (5); Cresol novolac resin (PN-80, Nippon Kayaku Co., Ltd.)・ Epoxy resin; bisphenol A type epoxy resin (Epicoat 1001, oil-based shell epoxy Ltd.) glycidol; EPIOL OH (manufactured by NOF Corporation) Curing accelerator: 2 ethyl 4 methyl imidazole (2E4MZ
, Shikoku Kasei Co., Ltd. ・ Polyamino bismaleimide resin; Kelimide 601A (Rhone Poulenc Company)

Synthesis Example 1 A reaction vessel equipped with a thermometer, a stirrer and a condenser was charged with 1012 g of dihydroxynaphthalene, 168 g of 4-methylphenol dimethylol and 0.3 g of sodium p-toluenesulfonate and stirred at 150 ° C. While reacting for 6 hours. Then, after dissolving in 1500 ml of toluene and washing, toluene and unreacted monomer are distilled under reduced pressure (150
It was removed at 5 ° C., 5 mmHg) to obtain dihydroxynaphthalene and cresol novolak resin having a hydroxyl equivalent of 90.

Synthesis Example 2 207 g of α, α-dihydroxy-p-xylene and 480 g of dihydroxynaphthalene were placed in a reaction vessel equipped with a stirrer, a thermometer, a Dean Stark azeotropic trap and a condenser.
Then, 0.35 g of methanesulfonic acid was charged, and the reaction was carried out at 150 to 160 ° C. for 4 hours while stirring. The generated water is sequentially trapped and removed to the outside of the system to give a hydroxyl equivalent of 160
To obtain a dihydroxynaphthalene aralkyl resin.

Synthesis Example 3 A reaction vessel equipped with a thermometer, a stirrer and a condenser was charged with 1176 g of dihydroxybiphenyl, 168 g of 4-methylphenol dimethylol and 0.3 g of sodium p-toluenesulfonate and stirred at 150 ° C. While reacting for 6 hours. Then, after dissolving in 1500 ml of toluene and washing, toluene and unreacted monomer are distilled under reduced pressure (150
It was removed at 5 ° C., 5 mmHg) to obtain a dihydroxybiphenyl and cresol novolak resin having a hydroxyl equivalent of 90.

Synthesis Example 4 207 g of α, α'-dihydroxy-p-xylene, 558 g of dihydroxybiphenyl and 0.35 g of methanesulfonic acid were placed in a reaction vessel equipped with a stirrer, a thermometer, a Dean Stark azeotropic trap and a condenser. While charging and stirring, 150
The reaction was carried out at ~ 160 ° C for 4 hours. The generated water was sequentially trapped and removed to the outside of the system to obtain a dihydroxybiphenylaralkyl resin having a hydroxyl equivalent of 160.

Production Example of Modified Imido Resin (1) In a reaction vessel equipped with a stirrer, a thermometer and a cooler, 100 parts by weight of polymaleimide resin, 30 parts by weight of dihydroxynaphthalene, 50 parts by weight of epoxy resin, 20 parts by weight of glycidol. , And react at 130 ° C for 30 minutes,
A modified imide resin (1) was obtained.

Production Example of Modified Imido Resin (2) 100 parts by weight of polymaleimide resin and phenol resin (2) were placed in a reaction vessel equipped with a stirrer, a thermometer and a cooler.
30 parts by weight, epoxy resin 50 parts by weight, glycidol 2
Insert 0 parts by weight, 100 parts by weight of methyl ethyl ketone,
The reaction was carried out at 80 ° C. for 10 hours to obtain a modified imide resin (2).

Production Example of Modified Imido Resin (3) In a reaction vessel equipped with a stirrer, thermometer and cooler, 100 parts by weight of polymaleimide resin, 30 parts by weight of dihydroxybiphenyl, 50 parts by weight of epoxy resin, 20 parts by weight of glycidol. , And react at 130 ° C for 30 minutes,
A modified imide resin (3) was obtained.

Production Example of Modified Imido Resin (4) 100 parts by weight of polymaleimide resin and phenol resin (4) were placed in a reaction vessel equipped with a stirrer, a thermometer and a cooler.
Insert 30 parts by weight, 50 parts by weight of epoxy resin, and 20 parts by weight of 1,6-dihydroxynaphthalene at 130 ° C. and 3
The reaction was carried out for 0 minutes to obtain a modified imide resin (4).

Examples 1 to 8 and Comparative Examples 1 to 4 The compositions (parts by weight) shown in Tables 1 and 2 were dissolved in a flask to obtain a thermosetting resin varnish. The thermosetting resin varnish thus obtained was treated with 104 g / m 2.
² glass cloth was impregnated and dried at 140 ° C. for 5 minutes to obtain about 190 g / m ² of prepreg. 16 pieces of this prepreg are piled up, and 18μ is further placed on the upper and lower outermost layers
180 kg of copper foil is placed at a pressure of 40 kg / cm ^2.
Molding was carried out at 200 ° C. for 120 minutes to obtain a copper-clad laminate having a thickness of 1.6 mm. The test results of the obtained laminated plate are shown in Tables 1 and 2. For comparison, different compositions of the example and the phenolic resin, polyamino bismaleimide resin, dihydroxynaphthalene, also for mixed resin of dihydroxybiphenyl and epoxy resin, a prepreg, a laminated board was manufactured, and the resin characteristics were evaluated in the same manner. . In the case of the polyamino bismaleimide resin of Comparative Example 3, it was molded under heating conditions of 200 to 220 ° C. and 120 minutes.

[0039]

[Table 1]

[0040]

[Table 2]

Compared with Examples 1 to 8 of the present invention, the polyamino bismaleimide resin has a high water absorption rate and poor solder heat resistance. If it does not contain polymaleimide resin, T
g is low and solder heat resistance is poor. Further, even when cresol novolac resin is used, Tg is low and solder heat resistance is poor. As described above, the levels were not satisfied with all of the hygroscopicity, the adhesiveness, and the solder heat resistance as compared with the present example.

[0042]

As described in Examples and Comparative Examples, the thermosetting resin composition according to the present invention has a high Tg, a low hygroscopicity, a good adhesiveness, and a solder heat resistance after moisture absorption. It is an excellent new thermosetting resin composition and is effective as a resin material for laminated boards.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08G 73/12 C08G 73/12 C08J 5/24 CFC C08J 5/24 CFC C08L 63/00 C08L 63/00 (72) Inventor Shima Kenji 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor, Hitoshi Sakuraba 1190, Kasama-cho, Sakae-ku, Yokohama, Yokohama, Kanagawa Mitsui Toatsu Chemicals (72) Inventor, Kotaro Asahina Yokohama, Kanagawa Mitsui Toatsu Chemical Co., Ltd., 1190 Kasama-cho, Sakae-ku, Japan (56) References JP-A-8-225668 (JP, A) JP-A-8-259668 (JP, A) JP-A-6-263844 (JP, A) ) JP-A-6-263843 (JP, A) JP-A-3-723 (JP, A) JP-A-58-65718 (JP, A) JP-A-56-109219 (JP, A) (58) Field (Int.Cl . ^7, DB name) C08G 59/00 - 59/72 B32B 15/08 C08G 65/38 - 65/44 C08G 73/12 C08J 5/24 C08L 63/00 - 63/10

Claims (6)

(57) [Claims] (A) A polymaleimide compound represented by the general formula (1) (Chemical Formula 1): (In the formula, R ₁ is an m-valent organic group, Xa and Xb are hydrogen atoms,
Same or different monovalent atom or group selected from halogen atom and organic group, m is an integer of 2 or more and 10 or less)
And (b) a phenol resin containing dihydroxynaphthalene or dihydroxynaphthalene represented by formula (2) (formula 2), a phenol resin containing dihydroxybiphenyl or dihydroxybiphenyl represented by formula (3) (formula 2), c) A thermosetting resin composition containing an epoxy resin having at least two epoxy groups in the molecule. [Chemical 2] (In the formula, R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) 2. (a) a polymaleimide compound represented by the general formula (1), (b) a phenol resin containing dihydroxynaphthalene, dihydroxynaphthalene, a phenol resin containing dihydroxybiphenyl or dihydroxybiphenyl, and (c) a molecule A thermosetting resin composition containing an epoxy resin having at least two epoxy groups, and a modified imide resin obtained by modifying (d) a compound having at least one active hydrogen in the molecule. 3. The thermosetting resin composition according to claim 1, which comprises a curing accelerator, a flame retardant, a filler, a linear polymer and / or an additive. 4. A prepreg characterized in that a base material is impregnated with the resin material according to claim 1, 2 or 3. 5. A thermosetting resin laminate comprising one or a plurality of the prepregs according to claim 4 laminated. 6. The thermosetting resin laminate according to claim 5, which is integrally formed with the outermost metal foil.