JPH1045876A - Thermosetting resin composition and prepreg and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition comprising a polymaleimide compound, a specific OH group-containing compound, and an epoxy resin, capable of expressing excellent adhesivity, heat resistance, soldering heat resistance and mechanical characteristics, and useful for thermosetting resin laminates, etc. SOLUTION: This thermosetting resin composition comprises (A) a polymaleimide compound of formula I [(m) is 2-10; R1 is a m-valent organic group; X1 , Xb are each H, a halogen, an organic group], (B) an OH group- containing compound comprising (B1 ) a dihydroxynaphthalene of formula II, (B2 ) a phenolic resin containing the component B1 , (B3 ) a dihydroxybiphenyl of formula III or (B4 ) a phenolic resin containing the component B3 , (C) an epoxy resin having two or more epoxy groups in the molecule, and, if necessary, further (D) a modified imide resin modified with a compound having one or more active hydrogen atoms in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, a prepreg, and a laminate having excellent heat resistance, low moisture absorption, adhesion, workability, and resistance to soldering heat after moisture absorption.
In other words, it relates to a resin composition for improving solder heat resistance after absorbing moisture as an insulating material for electronic / electric parts and semiconductor fields, a resin sealing material, and a laminated board material. The present invention relates to a resin composition useful for a board laminate, a prepreg and a laminate using the same.

[0002]

2. Description of the Related Art As for printed wiring boards widely used for electric / electronic devices, communication devices, computing devices, etc., the wiring density has been advanced and the integration has been advanced.
There is a growing demand for improved reliability by improving the heat resistance of wiring laminates. COB, PGA, BGA, MC
Applications for directly mounting a semiconductor chip on a substrate, such as an M substrate, are increasing. In such a mounting process, a high temperature is required, and the substrate to be mounted is required to have heat resistance.
Conventionally, epoxy resins, unsaturated polyester resins, polyimide resins, phenolic resins, and the like have been used as resin materials constituting a laminate for a printed wiring board. Among these resins, epoxy resins and bismaleimides have been used. A polyaminobismaleimide resin obtained by reacting a resin with an aromatic diamine is widely used in high-density mounting and high-layer laminates.

[0003]

Although epoxy resin has relatively good heat resistance, it is necessary to respond to recent demands for improved 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, polyaminobismaleimide resin and the like have been proposed as a material for a laminated board for improving heat resistance (French Patent No. 1455514, Japanese Patent Publication No. 46-46).
No. 23250, JP-A-61-200149). In the case of this polyaminobismaleimide, although its heat resistance is very excellent, it has high hygroscopicity, has a problem in adhesiveness, and requires a high temperature and a long time compared to epoxy resin at the time of lamination, There was a problem that the cost was high.
In order to compensate for the disadvantage of the polyaminobismaleimide resin, an imide-modified epoxy resin obtained by adding an epoxy resin to a polyaminobismaleimide resin (Japanese Patent Publication No. 47-4216).
0), but there was a problem that the heat resistance was significantly lower than that of the polyaminobismaleimide resin, and the heat resistance was insufficient.

For this reason, it is possible to cope with the future progress of high-density mounting and multi-layering, and it is possible to cope with an application for directly mounting a semiconductor chip. It has excellent heat resistance, low moisture absorption, and solder heat resistance after moisture absorption. There has been a strong demand for a low-cost resin material for laminates which has excellent mechanical properties such as excellent adhesiveness and toughness, and is inexpensive. The present invention has been made in view of such circumstances, and solves the disadvantages of conventional epoxy resins and polyimide resins, and has excellent heat resistance, especially solder heat resistance after moisture absorption, and mechanical properties such as toughness. It is an object of the present invention to provide a new resin material for a laminate that can satisfy the above conditions.

[0005]

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

[0006]

Embedded image (Wherein, R ₁ is an m-valent organic group, Xa and Xb are hydrogen atoms,
The same or different monovalent atoms or groups selected from halogen atoms and organic groups, m is an integer of 2 or more and 10 or less)
And (b) a dihydroxynaphthalene represented by the formula (2) (formula 4), a phenol resin containing dihydroxynaphthalene, a phenol resin containing dihydroxybiphenyl or dihydroxybifunyl represented by the formula (3) (formula 4), c) a thermosetting resin composition containing an epoxy resin having at least two or more epoxy groups in a molecule;

[0007]

Embedded image (Wherein 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, dihydroxybiphenyl or a phenol resin containing dihydroxybiphenyl; A thermosetting resin composition comprising: an epoxy resin having at least two or more epoxy groups; and (d) a modified imide resin modified by a compound having at least one active hydrogen in the molecule; and 3) The thermosetting resin composition of the above 1) or 2) comprising a curing accelerator, a flame retardant, a filler, a linear polymer and / or an additive; 4) The above 1), 2) or 3) 5) A 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 polymaleimide compound (a) used in the present invention, any compound having two or more maleimide groups in one molecule can be used. Such polymaleimide compounds include, for example, 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) ether 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,
1,3,3,3-hexafluoropropane, 2,2-bis [4
-(4-maleimidophenoxy) phenyl] -1,1,1,1,
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, represented by the general formula (4)

[0011]

Embedded image Wherein n is an average of 0 to 10; and a polymaleimide compound represented by the general formula (5):

[0012]

Embedded image (Where k is an average of 0 to 10), and the like. These polymaleimide compounds may be used alone or as a mixture of two or more.

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

As the dihydroxynaphthalene, 1,3
-, 1,4-, 1,5-, 1,6-, 2,3-, 2,7
Examples of phenolic resins having dihydroxynaphthalene include dihydroxynaphthalene, such as phenols such as dihydroxynaphthalene and phenol, cresol, resorcinol, phenylphenol and dihydroxybiphenyl, or naphthols such as 1- and 2-naphthol and formaldehyde and acetaldehyde. Novolak resin which is a reaction product with aldehydes such as benzaldehyde, hydroxybenzaldehyde, gluoxal, and alkandial, and a reaction product of the above dihydroxynaphthalene, phenols, naphthols with an aralkyl alcohol derivative or an aralkyl halide derivative. An aralkyl resin is used, and one or a mixture of two or more 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'-
Examples of the phenolic resin having dihydroxybiphenyl include phenols such as phenol, cresol and resorcinol, and naphthols such as naphthol and dihydroxynaphthalene. And formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde,
Gluoxal, a novolak resin which is a reaction product with an aldehyde such as an alkanedial, and an aralkyl resin which is a reaction product of the above dihydroxybiphenyl, phenols and naphthols with an aralkyl alcohol derivative or an aralkyl halide derivative, One or a mixture of two or more of these phenolic resins is used.

The epoxy resin as the component (c) includes:
All epoxy compounds having two or more epoxy groups in the molecule can be used. Examples of such an epoxy compound include phenols such as phenol, cresol, resorcinol, and naphthol, or phenols obtained by halogenating them, and aldehydes such as formaldehyde, acetaldehyde, benzaldehyde, tolualdehyde, glyoxal, and alkandial. An epoxy resin obtained by a reaction of a reaction product obtained by condensation reaction with epichlorohydrin; an epoxy resin obtained by a reaction of a reaction product of the above phenols with an aralkyl alcohol derivative or an aralkyl halide derivative with epichlorohydrin; 2 in one molecule shown
Epoxy resins derived from compounds having two or more active hydrogens, for example, polyphenols 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, and polypropylene glycol; amines such as ethylenediamine, aniline, bis (4-aminophenyl) methane;
Epoxy resins obtained by reacting polychlorocarboxylic acids such as adipic acid, phthalic acid and isophthalic acid with epichlorohydrin are exemplified. One or a mixture of two or more of these epoxy resins can be used. In addition, various halogenated epoxy resins such as a brominated phenol novolak resin and a brominated bisphenol A type epoxy resin can be used.

In the composition of the present invention, the polymaleimide compound represented by the general formula (1) of the component (a) and (b)
The components of dihydroxynaphthalene, phenolic resin having dihydroxynaphthalene, phenolic resin having dihydroxybiphenyl or sihydroxybiphenyl, and epoxy resin of component (c) were added in an amount of 100 parts by weight of component (a) and 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) is based on the dihydroxynaphthalene, dihydroxybiphenyl or the phenol resin of the component (b). Is equivalent to 0.1 to 10
, Preferably in the range of 0.5 to 2.0.

The resin composition of the present invention may contain a phenol novolak resin, a naphthol novolak resin,
Phenol resins having no dihydroxynaphthalene or dihydroxybiphenyl such as phenol aralkyl resins and naphthol aralkyl resins, amines represented by diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, etc., and acid anhydrides such as phthalic anhydride and pyromellitic anhydride Can also be used in combination.

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

The method for producing the modified imide resin includes the following:
(A) a polymaleimide resin as a component, (b) a component,
The components (c) and (d) are simultaneously heated to 80 to 200 ° C.
In general, the mixture is heated and mixed for 0.1 to 10 hours, but may be further mixed by heating in an organic solvent. In the case of heating and mixing in an organic solvent, it is generally 50 to 200 ° C. and 0.1 to 2 depending on the boiling point of the organic solvent to be used.
0 hours. Although the content of the modified imide resin is not clear, it is considered to be mainly oligomerization of the polymaleimide resin. In the modification, it is difficult to produce a stable modified imide resin only with the component (b) and / or the component (c) or only the component (d) with respect to the component (a).

The component (d) is preferably used in an amount of 1 to 100 parts by weight, based on 100 parts by weight of the polymaleimide resin. Particularly, for the purpose of maintaining heat resistance, it is preferable to use 5 to 30 parts by weight. .

The amount of the epoxy resin of the components (b) and (c) is preferably such that the total amount of the components (b) and (c) is 10 to 500 parts by weight, based on 100 parts by weight of the component (a). Is 25 to 300 parts by weight, and the equivalent ratio of the epoxy resin of 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 tolylphosphine. ;
Tetraphenylphosphonium tetraphenylborate,
Tetraphenylboron salts such as triethylammonium tetraphenylborate; and 1,8-diaza-bicyclo (5,4,0) undecene-7 and derivatives thereof. 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 parts by weight per 100 parts by weight of the resin.
Used in parts by weight.

The resin material of the present invention may be used, if necessary, with imide resins such as diallyl phthalate, triallyl isocyanurate, o, o'-diallylbisphenol A, bisphenol A diallyl ether, and bisphenol A dicyanate. Reactive diluents commonly used and used; various silicone oils; flame retardants such as bromo compounds, antimony, and phosphorus; fillers such as silica, talc, alumina, and aluminum nitride; polyether sulfone, polyphenylene ether, and aromatic polyester , Polysulfone,
Linear polymers such as polyphenylene sulfide, polyetheretherketone, polyimide, polyetherimide, polyamideimide, and polyparabanic acid; and other additives may be appropriately blended.

In order to produce a prepreg using the resin composition of the present invention as described above, the resin composition (a), (b), (c), a curing accelerator and other additives The agent is dissolved in a solvent to form a resin varnish. Or
A modified imide resin comprising the components (a), (b), (c) and (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
A range of 0 to 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 substrate, all known substrates such as glass cloth, carbon fiber, organic fiber cloth, glass non-woven fabric, and paper can be used. After applying and impregnating the varnish on the substrate, a prepreg is manufactured through a drying step, but the application 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. However, a high temperature is not preferable, and the amount of the residual solvent in the prepreg is desirably 1% by weight or less.

The laminate is manufactured by heating and pressing one or more of the above prepregs and integrating them. At this time, a metal foil or a metal plate is laminated on one or both surfaces which are the outermost layers. be able to. The heating temperature is 100-300 ° C and the pressure is 5-100kg
/ Cm ² is desirable. Copper as metal foil or metal plate,
Aluminum, iron, stainless steel, etc. can be used. Also,
A laminate for a multilayer printed wiring board may be formed by using the inner layer core material.

[0029]

The present invention will be described below in more detail with reference to examples. In addition, the test method of the performance in an Example is as follows. -Glass transition temperature: Dynamic viscoelasticity method-Copper foil peel test: JIS C-6481-Water absorption: JIS C-6481-Solder heat resistance: 120 ° C, 100% RH according to JIS C-6481 After the water absorption treatment for 3 hours under the conditions described above, the laminate was floated in a solder bath at 300 ° C. for 120 seconds, and the laminate was examined for any abnormality. The following materials were used in Examples and Comparative Examples.・ Polymaleimide compound; bis (4-maleimidophenyl) methane (manufactured by Mitsui Toatsu Chemicals, Inc.) ・ 1,6-dihydroxynaphthalene (manufactured by Kanto Chemical Co., Ltd.) ・ 4,4′-dihydroxybiphenyl; biphenol (Honshu・ Phenolic resin (1); dihydroxynaphthalene, cresol novolak resin (Synthesis example 1) ・ Phenol resin (2); dihydroxynaphthalene ziloc (Synthesis example 2) ・ Phenol resin (3); Dihydroxybiphenyl, phenol novolak resin (Synthesis example 3) Phenol resin (4); dihydroxybiphenyl ziloc (Synthesis example 4) Phenol resin (5); Cresol novolak resin (PN-80, Nippon Kayaku Co., Ltd.)・ Epoxy resin; bisphenol A type epoxy resin (Epicoat 1001, Yuka Shell Epoxy) Ltd.) glycidol; EPIOL OH (manufactured by NOF Corporation) Curing accelerator: 2 ethyl 4 methyl imidazole (2E4MZ
, Shikoku Chemicals Co., Ltd.) ・ Polyaminobismaleimide resin; Kelimide 601A (Rhone Poulin)

Synthesis Example 1 In a reaction vessel equipped with a thermometer, a stirrer and a cooler, 1012 g of dihydroxynaphthalene, 168 g of 4-methylphenol dimethylol and 0.3 g of sodium p-toluenesulfonate were charged and stirred at 150 ° C. For 6 hours. Then, after dissolving and washing in 1500 ml of toluene, toluene and unreacted monomer were distilled under reduced pressure (150 ml).
C., 5 mmHg) to obtain a 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 cooler.
Then, 0.35 g of methanesulfonic acid was charged, and the mixture was reacted at 150 to 160 ° C. for 4 hours while stirring. The generated water is sequentially trapped and removed out of the system, and the hydroxyl equivalent 160
To obtain a dihydroxynaphthalene aralkyl resin.

Synthesis Example 3 In a reaction vessel equipped with a thermometer, a stirrer and a cooler, 1176 g of dihydroxybiphenyl, 168 g of 4-methylphenol dimethylol and 0.3 g of sodium p-toluenesulfonate were charged and stirred at 150 ° C. For 6 hours. Then, after dissolving and washing in 1500 ml of toluene, toluene and unreacted monomers were distilled under reduced pressure (150 ml).
C., 5 mmHg) to obtain a dihydroxybiphenyl / 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 cooler. While charging and stirring, 150
The reaction was performed at -160 ° C for 4 hours. The generated water was sequentially trapped and removed outside the system to obtain a dihydroxybiphenylaralkyl resin having a hydroxyl equivalent of 160.

Production Example of Modified Imide Resin (1) In a reaction vessel equipped with a stirrer, thermometer and 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 Imide Resin (2) 100 parts by weight of polymaleimide resin and phenol resin (2) were placed in a reaction vessel equipped with a stirrer, thermometer and cooler.
30 parts by weight, epoxy resin 50 parts by weight, glycidol 2
0 parts by weight and 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 Imide Resin (3) 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 were placed in a reaction vessel equipped with a stirrer, thermometer and cooler. And react at 130 ° C. for 30 minutes.
A modified imide resin (3) was obtained.

Production Example of Modified Imide Resin (4) 100 parts by weight of a polymaleimide resin and a phenol resin (4) were placed in a reaction vessel equipped with a stirrer, a thermometer and a cooler.
30 parts by weight, 50 parts by weight of epoxy resin, and 20 parts by weight of 1,6-dihydroxynaphthalene
The reaction was performed 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 obtained in this way was 104 g / m
² and dried at 140 ° C. for 5 minutes to obtain about 190 g / m ² of prepreg. 16 prepregs are stacked, and 18 μm
Of copper foil at a pressure of 40 kg / cm ² ,
Molding was performed at 200 ° C. for 120 minutes to obtain a 1.6 mm-thick copper-clad laminate. Tables 1 and 2 show the test results of the obtained laminates. For comparison, a prepreg and a laminate were also manufactured for the composition different from the example and the phenolic resin, a polyaminobismaleimide resin, dihydroxynaphthalene, a mixed resin of dihydroxybiphenyl and an epoxy resin, and the resin properties were similarly evaluated. . In the case of the polyaminobismaleimide resin of Comparative Example 3, molding was performed under heating conditions of 200 to 220 ° C. for 120 minutes.

[0039]

[Table 1]

[0040]

[Table 2]

As compared with Examples 1 to 8 of the present invention, the polyaminobismaleimide resin has a high water absorption and is inferior in solder heat resistance. When no polymaleimide resin is contained, T
g is low and solder heat resistance is poor. Also, when a cresol novolak resin is used, the Tg is low and the solder heat resistance is poor. As described above, as compared with this example, the moisture absorption, the adhesiveness, and the solder heat resistance were not all at a level satisfying the requirements.

[0042]

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

Continued on the front page (72) Inventor Kenji Shima 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Kotaro Asahina 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Toatsu Chemical Co., Ltd.

Claims (6)

[Claims] (A) A polymaleimide compound represented by the general formula (1): (Wherein, R ₁ is an m-valent organic group, Xa and Xb are hydrogen atoms,
The same or different monovalent atoms or groups selected from halogen atoms and organic groups, m is an integer of 2 or more and 10 or less)
And (b) a dihydroxynaphthalene represented by the formula (2) (formula 2), a phenol resin containing dihydroxynaphthalene, a phenol resin containing dihydroxybiphenyl or dihydroxybifunyl represented by the formula (3) (formula 2), c) A thermosetting resin composition containing an epoxy resin having at least two or more epoxy groups in a molecule. Embedded image (Wherein R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) 2. A polymaleimide compound represented by the following general formula (1): (b) dihydroxynaphthalene, a phenolic resin containing dihydroxynaphthalene, dihydroxybiphenyl or a phenolic resin containing dihydroxybiphenyl; And (d) a modified imide resin modified by a compound having at least one active hydrogen in the molecule. 3. The thermosetting resin composition according to claim 1, further comprising 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, wherein one or more prepregs according to claim 4 are laminated. 6. The thermosetting resin laminate according to claim 5, which is formed by laminating and integrating with the outermost metal foil.