JP5614048B2 - Thermosetting insulating resin composition, and prepreg, laminate and multilayer printed wiring board using the same - Google Patents

Description

  The present invention relates to a thermosetting insulating resin composition suitable for a semiconductor package or a printed wiring board, and a prepreg, a laminated board and a multilayer printed wiring board using the same.

  In recent years, with the trend toward miniaturization and high performance of electronic devices, the printed wiring board has been developed with higher wiring density and higher integration. With this, the reliability by improving the heat resistance of the laminated board for wiring boards There is an increasing demand for improvement. In such applications, it is required to combine excellent heat resistance and a low thermal expansion coefficient. In particular, in recent years, the above characteristics are particularly strongly required for semiconductor package substrates and the like.

As a laminated board for a printed wiring board, one obtained by curing and integrally molding a resin composition mainly composed of an epoxy resin and a glass woven fabric is generally used. Epoxy resin has an excellent balance of insulation, heat resistance, cost, etc., but there is a limit to meet the demand for improved heat resistance due to the recent high-density mounting of printed wiring boards and higher multi-layer configurations. .
In addition, since an epoxy resin has a large coefficient of thermal expansion, low thermal expansion is achieved by selecting an epoxy resin having an aromatic ring or by highly filling an inorganic filler such as silica (for example, Patent Document 1). reference). However, it is known that increasing the filling amount of the inorganic filler causes a decrease in insulation reliability due to moisture absorption, insufficient adhesion between the resin and the wiring material, and poor press molding.

On the other hand, the polybismaleimide resin widely used for high-density packaging and highly multilayered laminates is very excellent in heat resistance, but has high hygroscopicity and has difficulty in adhesion. Moreover, compared with an epoxy resin, there exists a fault that a high temperature and a long time are required for lamination and productivity is poor. That is, in general, the epoxy resin can be cured at a temperature of 180 ° C. or lower, but when a polybismaleimide resin is laminated, a high temperature of 220 ° C. or higher and a long time treatment are required.
For this reason, it has been proposed to use a modified imide resin obtained by modifying a polymaleimide resin with an epoxy resin having a naphthalene skeleton (for example, see Patent Document 2). Although this modified imide resin composition is improved in hygroscopicity and adhesiveness, it is modified with a low molecular weight compound containing a hydroxyl group and an epoxy group in order to impart solubility to general-purpose solvents such as methyl ethyl ketone. There was a problem that the heat resistance of the imide resin was significantly inferior to that of the polybismaleimide resin.

  Furthermore, storage stability is required for varnishes and prepregs of resin compositions for printed wiring boards, and curing agents and curing accelerators have high potential reactivity (latency), and the resin composition can be stored for a long time. It is essential to use possible materials. In particular, imidazole compounds are suitably used as curing accelerators in phenol curing systems, aromatic amine curing systems, and the like, but conventional imidazole compounds have insufficient potential and are difficult to store for a long time.

Japanese Patent Laid-Open No. 5-148343 JP-A-6-263843

  In view of the current situation, the object of the present invention is good resin curability, that is, it does not require high-temperature and long-time treatment at the time of prepreg lamination, has good curability and storage stability of varnish and prepreg, A thermosetting resin composition having excellent chemical properties, heat resistance, adhesiveness, and low warpage, and a prepreg, laminate, and multilayer printed wiring board using the same.

  As a result of intensive studies to solve the above-mentioned problems, the present invention provides a resin composition (A) having an unsaturated maleimide group produced by reacting a maleimide compound and an amine compound in an organic solvent, and a thermosetting resin. In (B), it discovered that said objective could be achieved by using a specific modified imidazole compound (C), and came to complete this invention. The present invention has been completed based on such knowledge.

That is, this invention provides the following thermosetting insulating resin compositions, and a prepreg, a laminated board, and a multilayer printed wiring board using the same.
1. A maleimide compound (a) having at least two N-substituted maleimide groups in a molecule and an amine compound (b) having at least two primary amino groups in one molecule are reacted in an organic solvent. The heat | fever characterized by including the modified imidazole compound (C) represented by the resin composition (A) which has an unsaturated maleimide group manufactured in this way, a thermosetting resin (B), and the following general formula (I). Curable resin composition.

In the formula, R ₁ and R ₂ each independently represents a hydrogen atom, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a hydroxymethyl group, or a phenyl group, and R ₃ represents a hydrogen atom or 1 to 20 carbon atoms. An aliphatic hydrocarbon group, a phenyl group, and an allyl group are shown.

2. Furthermore, said 1 thermosetting resin composition containing the amine compound (D) which has an acidic substituent represented by the following general formula (II).

In the formula (II), each R ₄ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₅ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or Represents a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.

3. Furthermore, said 1 or 2 thermosetting resin composition containing an inorganic filler (E).
4). Furthermore, the thermosetting resin composition of any one of said 1-3 containing a molybdenum compound (F).
5. Thermosetting resin (B) is epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone The thermosetting resin composition according to any one of the above 1 to 4, which is at least one selected from a resin, a triazine resin, and a melamine resin.
6). 6. The thermosetting resin composition according to any one of 3 to 5, wherein the inorganic filler (E) is spherical silica and a metal hydrate having a thermal decomposition temperature of 300 ° C. or higher.
7). A prepreg obtained by applying the thermosetting resin composition according to any one of 1 to 6 above to a fiber sheet-like reinforcing base material and forming a B-stage.
8). A laminate obtained by laminating using the prepreg described in 7 above.
9. A multilayer printed wiring board produced using the laminate of 8 above.

  According to the present invention, good resin curability, that is, when prepreg lamination, high temperature and long time treatment is not required, and varnish and prepreg curability and storage stability are good, chemical resistance, heat resistance A thermosetting resin composition excellent in adhesiveness and low warpage, and a prepreg, laminate and multilayer printed wiring board using the same are provided.

Hereinafter, the present invention will be described in detail.
The thermosetting resin composition of the present invention comprises a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule and an amine compound having at least two primary amino groups in one molecule ( a resin composition (A) having an unsaturated maleimide group produced by reacting b) in an organic solvent, a thermosetting resin (B), and a modified imidazole compound (C) represented by the following general formula (I) It is a thermosetting resin composition characterized by containing.

In the formula, R ₁ and R ₂ each independently represents a hydrogen atom, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a hydroxymethyl group, or a phenyl group, and R ₃ represents a hydrogen atom or 1 to 20 carbon atoms. An aliphatic hydrocarbon group, a phenyl group, and an allyl group are shown.

  Examples of the maleimide compound (a) having at least two N-substituted maleimide groups in one molecule include N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, and N, N ′. -(1,3-phenylene) bismaleimide, N, N '-[1,3- (2-methylphenylene)] bismaleimide, N, N'-[1,3- (4-methylphenylene)] bismaleimide N, N ′-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3-dimethyl-5,5-diethyl- 4,4-diphenylmethane bismaleimide, 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, 2,2′-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, 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] Hong, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) -α, α-dimethyl Benzyl] 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-bi [4- (3-Maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α- Dimethylbenzyl] benzene, polyphenylmethanemaleimide (for example, product name: BMI-2300 manufactured by Daiwa Kasei Co., Ltd.) and the like. These maleimide compounds may be used alone or in combination of two or more. May be.

  Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, N, N ′-(1,3-phenylene) bismaleimide, which has a high reaction rate and can have higher heat resistance, 2 , 2-bis (4- (4-maleimidophenoxy) phenyl) propane and polyphenylmethanemaleimide are preferred, and bis (4-maleimidophenyl) methane is particularly preferred from the viewpoint of solubility in a solvent.

  The amine compound (b) having at least two primary amino groups in one molecule is not particularly limited, and examples thereof include m-phenylenediamine, p-phenylenediamine, 4,6-dimethyl-m. -Phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4-diaminomesitylene, m-xylene-2,5-diamine, m- Xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-bis (amino-tert-butyl) toluene, 2,4-diaminoxylene, 2,4-diamino Pyridine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminodurene, 4,5-diamino-6-hydroxy- -Mercaptopyrimidine, 3-bis (3-aminobenzyl) benzene, 4-bis (4-aminobenzyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (3-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3-bis (3- (3-aminophenoxy) phenoxy) benzene, 4-bis (4- (4-Aminophenoxy) phenoxy) benzene, 3-bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene, 4-bis (4- (4- (4-aminophenoxy) phenoxy) phenoxy) Benzene, 3-bis (α, α-dimethyl-3-aminobenzyl) benzene, 1,4-bis (α, α-dimethyl-3-aminobenzyl) ) Benzene, 3-bis (α, α-dimethyl-4-aminobenzyl) benzene,

Bis (4-methylaminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) benzene, 1,4-bis (3-aminopropyldimethylsilyl) benzene, bis [(4-aminophenyl) -2 -Propyl] 1,4-benzene, 2,5-diaminobenzenesulfonic acid, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3 , 3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl, 5,5′-diethyl-4 , 4′-diaminodiphenylmethane, 4,4′-methylene-bis (2-chloroaniline), 3,3′-diaminodiphenylethane, 4, 4'-diaminodiphenylethane, 2,2'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylpropane, 2,2'-bis [4- (4-aminophenoxy) phenyl ] Propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 3- (2 ′, 4′-diaminophenoxy) propanesulfonic acid, bis (4-aminophenyl) diethylsilane, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, bis (4 -Amino-t-butylphenyl) ether, 4,4'-diaminodipheny Ether-2,2′-disulfonic acid, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-amino Phenoxy) phenyl] sulfone, benzidine, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′- Diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl-6,6′-disulfonic acid,

2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-diaminodiphenyl sulfide, 4,4′-diamino-3,3′-biphenyldiol, 1,5-diaminonaphthalene, 1,4- Diaminonaphthalene, 2,6-diaminonaphthalene, 9,9′-bis (4-aminophenyl) fluorene, 9,9′-bis (4-aminophenyl) fluorene-2,7-disulfonic acid, 9,9′- Aromatic amines such as bis (4-aminophenoxyphenyl) fluorene, diaminoanthraquinone, 3,7-diamino-2,8-dimethyldibenzothiophenesulfone Ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, 2,5- Dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane , Diaminopolysiloxane, 2,5-diamino-1,3,4-oxadiazol, aliphatic amines such as bis (4-aminocyclohexyl) methane, melamine, benzoguanamine, acetogua 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-allyl-s-triazine, 2,4-diamino-6-acryloyloxyethyl-s-triazine, 2,4- And guanamine compounds such as diamino-6-methacryloyloxyethyl-s-triazine.

  Examples of the amine compound (b) having at least two primary amino groups in one molecule include m-phenylenediamine and p-phenylene, which are aromatic amines having good reactivity and heat resistance. Diamine, 1,4-bis (4-aminophenoxy) benzene, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'- Diaminodiphenylmethane, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, bis [4 -(4-Aminophenoxy) phenyl] sulfone, benzidine, 4,4'-bis (4-aminophenoxy) biphenyl 4,4′-diaminodiphenyl sulfide, 4,4′-diamino-3,3′-biphenyldiol and benzoguanamine which is a guanamine compound are preferable and p-phenylenediamine and 4,4′-diaminodiphenylmethane from the viewpoint of low cost. 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, benzoguanamine More preferred is 4,4′-diaminodiphenylmethane from the viewpoint of solubility in a solvent. These may be used alone or in combination of two or more.

The organic solvent used in the reaction between the maleimide compound (a) and the amine compound (b) is not particularly limited. For example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, acetone , Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, dimethylformamide, dimethyl Examples thereof include nitrogen atom-containing solvents such as acetamide and N-methylpyrrolidone, sulfur atom-containing solvents such as dimethyl sulfoxide, and the like.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility. Cyclohexanone, propylene glycol monomethyl ether are preferable because of low toxicity and high volatility and hardly remain as a residual solvent. Dimethylacetamide is particularly preferred.

Here, the use ratio of the maleimide compound (a) and the amine compound (b) is the equivalent ratio of the equivalent (Ta) of the maleimide group of the maleimide compound (a) to the equivalent (Tb) of the —NH ₂ group of the amine compound (b). (Ta / Tb) is preferably in the range of 1.0 to 10.0, and the relevant amount ratio (Ta / Tb) is more preferably in the range of 2.0 to 10.0. By setting the relevant amount ratio (Ta / Tb) within the above range, a thermosetting resin composition having excellent storage stability, solubility in organic solvents, copper foil adhesion, and heat resistance can be obtained.
Moreover, it is preferable to set it as 10-1000 mass parts per 100 mass parts of sum totals of a maleimide compound (a) and an amine compound (b), and, as for the usage-amount of an organic solvent, it is more preferable to set it as 100-500 mass parts, It is especially preferable to set it as 200-500 mass parts. By making the compounding quantity of an organic solvent into the said range, the solubility to an organic solvent is not insufficient, and it can react in a short time.

The reaction temperature of the maleimide compound (a) and the amine compound (b) is preferably 50 to 200 ° C, and particularly preferably 70 to 160 ° C. The reaction time is preferably from 0.1 to 10 hours, particularly preferably from 1 to 6 hours.
In this reaction, a reaction catalyst can be optionally used. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, and the like. Can be mixed and used.
Although the reaction method is not particularly limited, for example, the reaction can be carried out while refluxing using a reactor equipped with a stirrer and a reflux condenser, and a resin composition (A) having an unsaturated maleimide group is produced.

  Next, as the thermosetting resin (B), for example, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, A dicyclopentadiene resin, a silicone resin, a triazine resin, a melamine resin, etc. are mentioned, These 1 type (s) or 2 or more types can be mixed and used. Among these, epoxy resins and cyanate resins are preferable from the viewpoint of moldability and electrical insulation.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin. , Stilbene type epoxy resin, Triazine skeleton containing epoxy resin, Fluorene skeleton containing epoxy resin, Triphenolphenol methane type epoxy resin, Biphenyl type epoxy resin, Xylylene type epoxy resin, Biphenyl aralkyl type epoxy resin, Naphthalene type epoxy resin, Dicyclopentadiene -Type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and diglycidyl ether compounds of polycyclic aromatics such as anthracene And phosphorus-containing epoxy resin obtained by introducing a phosphorus compounds thereto. Among these, biphenylaralkyl type epoxy resins and naphthalene type epoxy resins are preferred from the viewpoint of heat resistance and flame retardancy. These can be used alone or in combination of two or more.

  Examples of the cyanate resin include bisphenol type cyanate resins such as novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin, and prepolymers in which these are partially triazine. be able to. Among these, a novolak type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy. These can be used alone or in combination of two or more.

  The thermosetting resin composition of the present invention contains a specific modified imidazole compound (C) together with the above-described unsaturated maleimide group-containing resin composition (A) and thermosetting resin (B). It does not require high-temperature and long-time treatment during prepreg lamination, and the stability of varnish and prepreg is good, and a thermosetting resin excellent in chemical resistance, heat resistance and adhesion can be obtained. .

  In the thermosetting resin composition of the present invention, as the modified imidazole compound (C), the triazine ring-containing imidazole represented by the general formula (I) described above is used.

  Examples of the triazine ring-containing imidazole represented by the general formula (I) include Shikoku Kasei Kogyo Co., Ltd., trade names: 2MZ-A, 2MZA-PW, C11Z-A, and 2E4MZ-A.

  Any number of the above modified imidazole compounds may be used in combination. The blending amount of the modified imidazole compound is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the thermosetting resin (B). When the content is 0.01 parts by mass or more, good curability is obtained, and when the content is 10 parts by mass or less, good storage stability is obtained.

  The thermosetting resin composition of the present invention may further contain an amine compound (D) having an acidic substituent represented by the following general formula (II). In this case, the resin composition (A) having an unsaturated maleimide group and the amine compound (D) are preferably prepared as a prepolymer by reacting in an organic solvent before blending the thermosetting resin composition.

In the formula (II), each R ₄ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₅ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or Represents a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.

  Examples of the amine compound (D) having an acidic substituent represented by the general formula (II) include 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, 3,5-dicarboxyaniline, etc., among these, From the viewpoint of solubility and synthesis yield, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3,5-dihydroxyaniline are preferred, and heat resistance M-aminophenol and p-aminophenol are more preferred, and m-aminophenol is particularly preferred because of its low toxicity. Preferred.

  The organic solvent used in the reaction of the resin composition (A) having an unsaturated maleimide group and the amine compound (D) is the same as the solvent used in the reaction of the maleimide compound (a) and the amine compound (b). A resin composition (A) having an unsaturated maleimide group produced by reacting a maleimide compound (a) and an amine compound (b) in an organic solvent, and a compound represented by the general formula (II): It is preferable that the amine compound (D) having the acidic substituent shown is reacted to form a prepolymer and then blended into the thermosetting resin composition.

Here, the resin composition (A) having an unsaturated maleimide group and the amine compound (D) having an acidic substituent are used in an amount equivalent to the equivalent (TD) of the —NH ₂ group of the amine compound (D) (TD). The equivalent ratio (TA / TD) of equivalents (TA) of maleimide groups in A) is preferably in the range of 1.0 to 10.0, and the corresponding ratio (TA / TD) is 2.0 to 10.0. More preferably, it is the range. By setting the relevant amount ratio (TA / TD) within the above range, a thermosetting resin composition having excellent storage stability, solubility in organic solvents, copper foil adhesion, and heat resistance can be obtained.
The amount of the organic solvent used is preferably 10 to 1000 parts by mass per 100 parts by mass of the total of the resin composition (A) having an unsaturated maleimide group and the amine compound (D) having an acidic substituent. It is more preferable to set it as 100-500 mass parts, and it is especially preferable to set it as 200-500 mass parts. By making the compounding quantity of an organic solvent into the said range, reaction can be performed in a short time, without the solubility to an organic solvent being insufficient.

The reaction temperature of the resin composition (A) having an unsaturated maleimide group and the amine compound (D) having an acidic substituent is preferably 50 to 200 ° C, and particularly preferably 70 to 160 ° C. The reaction time is preferably from 0.1 to 10 hours, particularly preferably from 1 to 6 hours.
Moreover, a reaction catalyst can be arbitrarily used for this reaction. The reaction catalyst is not particularly limited, and examples thereof include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. The above can be mixed and used.

In the thermosetting resin composition of this invention, in order to improve a moldability and to reduce a thermal expansion coefficient, it is preferable to contain an inorganic filler (E). Moreover, it is preferable to contain a molybdenum compound (F) in order to improve flame retardancy and to improve drill workability.

Inorganic fillers (E) include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, sulfuric acid Examples thereof include glass powder such as barium, aluminum borate, potassium titanate, E glass, T glass, and D glass, hollow glass beads, and the like, and these can be used alone or in combination.

Among these, silica is particularly preferable from the viewpoints of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include a precipitated silica produced by a wet method and having a high water content, and a dry method silica produced by a dry method and containing almost no bound water. The dry method silica further includes differences in production methods. Examples include crushed silica, fumed silica, and fused spherical silica. Among these, fused spherical silica is preferable because of its low thermal expansion and high fluidity when filled in a resin.
From the viewpoint of heat resistance, metal hydrates having a thermal decomposition temperature of 300 ° C. or higher are preferable among the above examples. For example, boehmite etc. are mentioned.

  When fused spherical silica is used as the inorganic filler (E), the average particle diameter is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by setting it to 10 μm or less, the mixing probability of coarse particles is reduced. Generation of defects due to coarse particles can be suppressed. Here, the average particle size is a particle size at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.

  When the inorganic filler (E) is contained in the thermosetting resin composition of the present invention, the content is preferably 10 to 60% by volume, and more preferably 20 to 50% by volume. By making content of an inorganic filler into 10-60 volume% of the whole resin composition, the moldability and low thermal expansibility of a thermosetting resin composition can be kept favorable.

  Examples of the molybdenum compound (F) include molybdenum trioxide, zinc molybdate, ammonium molybdate, magnesium molybdate, calcium molybdate, barium molybdate, sodium molybdate, potassium molybdate, phosphomolybdic acid, and phosphomolybdic acid. Inorganic molybdenum compounds such as ammonium, sodium phosphomolybdate, silicomolybdic acid, molybdenum disulfide, molybdenum diselenide, molybdenum ditelluride, molybdenum boride, molybdenum disilicide, molybdenum nitride, molybdenum carbide, molybdenum dialkyldithiophosphate, Organic molybdenum compounds such as molybdenum dialkyldithiocarbamate may be mentioned, and one or more of these may be used in combination.

  Among these, zinc molybdate, calcium molybdate, and magnesium molybdate are preferable from the viewpoints of low water solubility and toxicity, high electrical insulation, and good effect of preventing drill workability from being lowered. When zinc molybdate, calcium molybdate, and magnesium molybdate are used as the molybdenum compound, the resin composition can be obtained by supporting these molybdenum compounds on talc, silica, zinc oxide, calcium carbonate, magnesium hydroxide, etc. It is possible to prevent sedimentation and improve dispersibility when it is dissolved in an organic solvent to form a varnish. Examples of such molybdenum compounds include KEMGARD911C and KEMGARD1100 manufactured by Sherwin Williams.

  (F) It is preferable that content of a molybdenum compound is 0.02-20 volume% of the whole resin composition, and it is more preferable that it is 0.1-15 volume%. By making the content of the molybdenum compound 0.02 to 20% by volume of the entire resin composition, the adhesiveness of the resin composition can be kept good and the drilling workability can be sufficiently prevented from being lowered.

In addition to the above components, the thermosetting resin composition of the present invention includes a curing agent, a curing accelerator, a thermoplastic resin, an elastomer, an organic filler, a flame retardant, and an ultraviolet absorber as long as the object of the present invention is not adversely affected. Antioxidants, photopolymerization initiators, fluorescent brighteners, adhesion improvers, and the like can be used.
Examples of the curing agent include polyfunctional phenol compounds such as phenol novolak, cresol novolak, aminotriazine novolak resin, amine compounds such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, phthalic anhydride, pyromellitic anhydride, maleic anhydride, Examples thereof include acid anhydrides such as maleic anhydride copolymer, and these can be used alone or in combination.

  Examples of the curing accelerator include organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III), modified Examples include imidazoles other than imidazole compound (C) and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. Can be mixed and used.

The thermoplastic resins include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyetherether. Examples include ketone resins, polyetherimide resins, silicone resins, and tetrafluoroethylene resins.
Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.

  Organic fillers include resin fillers of uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc., acrylate ester resins, methacrylate ester resins, conjugated diene resins, etc. And a core-shell resin filler having a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like. .

  As flame retardants, halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphorous flame retardants such as red phosphorus, guanidine sulfamate, Nitrogen flame retardants such as melamine sulfate, melamine polyphosphate and melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide.

  Benzotriazole UV absorbers as UV absorbers, hindered phenol and hindered amine antioxidants as antioxidants, benzophenones, benzyl ketals, thioxanthone photopolymerization initiators, fluorescent as photopolymerization initiators Examples of the whitening agent include fluorescent whitening agents of stilbene derivatives, and examples of the adhesion improver include urea compounds such as urea silane, coupling agents such as silane, titanate, and aluminate.

Since the thermosetting resin composition of the present invention is used for the preparation of a prepreg, it is finally preferable that each component is in a varnish state in which each component is dissolved or dispersed in an organic solvent.
Examples of the organic solvent used in this case include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and acetic acid. Ester solvents such as butyl and propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl Examples include sulfur atom-containing solvents such as sulfoxides, and one or two or more of them can be used in combination.

  Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.

Further, at the time of blending, the inorganic filler is preferably pretreated or integral blended with a surface treatment agent such as a silane or titanate coupling agent or a silicone oligomer.
It is preferable that the resin composition in the varnish finally obtained is 40 to 90 mass% of the whole varnish, and it is more preferable that it is 50 to 80 mass%. By setting the content of the resin composition in the varnish to 40 to 90% by mass, it is possible to maintain good coatability and obtain a prepreg having an appropriate resin composition adhesion amount.

  The prepreg of the present invention is obtained by applying the thermosetting resin composition described above to a fiber sheet-like reinforcing base material and forming a B-stage. Hereinafter, the prepreg of the present invention will be described in detail.

The prepreg of the present invention is obtained by applying a thermosetting resin composition to a fiber sheet-like reinforcing substrate by impregnation, spraying, extrusion, or the like, and semi-curing (B-stage) by heating or the like. Prepreg can be manufactured.
As the prepreg fiber sheet reinforcing substrate, known materials used for various laminates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and tetrafluoroethylene, and mixtures thereof. These base materials have, for example, shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, A single material or two or more materials and shapes can be combined.

  The thickness of the fiber sheet-shaped reinforcing substrate is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface treatment with a silane coupling agent or the like or mechanical fiber opening treatment Those subjected to are suitable from the viewpoints of heat resistance, moisture resistance and workability. After impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. Can be heated and dried for 1 to 30 minutes and semi-cured (B-stage) to obtain the prepreg of the present invention.

  The laminate of the present invention is obtained by laminate molding using the above-described prepreg. For example, a laminated board can be manufactured by laminating 1 to 20 prepregs and laminating them with a structure in which a metal foil such as copper and aluminum is disposed on one or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material applications.

  The molding conditions can be applied to a laminate for an electrical insulating material and a multilayer board. For example, a multistage press, a multistage vacuum press, a continuous molding, an autoclave molding machine, etc. are used, and a temperature is 100 to 250 ° C., a pressure is 2 to 100 kg / cm 2. It can be molded in the range of heating time 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.

The multilayer printed wiring board of the present invention is manufactured using the above-mentioned laminated board, and is manufactured by forming a circuit on the surface of the printed wiring board.
That is, the conductor layer of the laminated board of the present invention is subjected to wiring processing by a normal etching method, a plurality of laminated boards subjected to wiring processing through the above-described prepreg are laminated, and then multilayered by heating press processing. Then, a multilayer printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing and formation of an interlayer wiring by plating or conductive paste.

  Next, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these descriptions. In addition, the performance measurement and evaluation of the varnish and copper clad laminated board obtained by each Example and the comparative example were performed with the following method.

(varnish)
・ Curing property (Time to gel)
Using 0.5 ml of the varnish obtained in each Example and Comparative Example as a sample, a time (T0) from sample introduction to gelation was measured using a gel timer manufactured by Nissin Kagaku Co., Ltd. set at 160 ° C.
・ Storage stability (storage stability rate)
After storing the varnishes obtained in each Example and Comparative Example at 40 ° C. for 3 days, the time until gelation (T1) was measured in the same manner as in the above “curability” test, and the storage stability was obtained by the following formula. The rate was determined.
Storage stability rate = T1 / T0 x 100 (%)

(Copper clad laminate)
(1) Heat resistance (glass transition temperature Tg: ° C)
A copper-clad laminate obtained in each example and comparative example was immersed in a copper etching solution to prepare a 5 mm square evaluation substrate from which the copper foil was removed, and a TMA test apparatus (manufactured by DuPont, TMA2940) was used. Tg was determined by observing the thermal expansion characteristics in the Z direction of the evaluation substrate, and the heat resistance was evaluated.
(2) Thermal expansion coefficient (ppm / ° C)
A copper-clad laminate obtained in each example and comparative example was immersed in a copper etching solution to prepare a 5 mm square evaluation substrate from which the copper foil was removed, and a TMA test apparatus (manufactured by DuPont, TMA2940) was used. It evaluated by observing the thermal expansion characteristic below Tg of the Z direction of an evaluation board | substrate.
(3) Copper foil adhesion (copper foil peel strength: kN / m)
A part of the copper foil part of the copper clad laminate obtained in each Example and Comparative Example was coated with a resist and immersed in a copper etching solution to prepare an evaluation board that left a 3 mm wide copper foil, The adhesion (peel strength) of the copper foil was measured using a tensile tester.
(4) Hygroscopicity (Water absorption rate:%)
The evaluation board | substrate which removed the copper foil was produced by immersing the copper clad laminated board obtained by each Example and the comparative example in the copper etching liquid, and using the pressure cooker test apparatus by Hirayama Manufacturing Co., Ltd., 121 After performing the pressure-cooker treatment for 5 hours under the conditions of 2 ° C. at 2 ° C., the water absorption rate of the evaluation substrate was measured.
(5) Chemical resistance (mass change rate: mass%)
The evaluation board | substrate which removed the copper foil was produced by immersing the copper clad laminated board obtained by each Example and the comparative example in copper etching liquid, and 30 minutes at 40 degreeC to 18 mass% hydrochloric acid or 10 mass% NaOH aqueous solution. The mass change rate after immersion (mass loss (g) / pre-treatment specimen mass (g) × 100) was calculated.
(6) Maximum warpage (mm)
An evaluation board from which the copper foil was removed by immersing the copper-clad laminate obtained in each example and comparative example in a copper etching solution was prepared from room temperature to 260 ° C. using ThreMoire manufactured by Thermotronics Trading Co., Ltd. Thereafter, the maximum amount of warpage in a measurement region of 12 mm × 12 mm was measured at a temperature change of 50 ° C.

Production Example 1 [Production of Solution of Resin Composition (A-1) Having Unsaturated Maleimide Group]
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, bis (4-maleimidophenyl) methane: 563.30 g and 4,4′-diaminodiphenylmethane : 59.04 g and propylene glycol monomethyl ether: 350.00 g were added and reacted for 5 hours while refluxing to obtain a solution of the resin composition (A-1) having an unsaturated maleimide group.

Production Example 2 [Production of Solution of Resin Composition (A-2) Having Unsaturated Maleimide Group]
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture quantifier with a reflux condenser, bis (4-maleimidophenyl) methane: 555.04 g and 3,3′-diethyl- 4,4′-Diaminodiphenylmethane: 73.84 g and propylene glycol monomethyl ether: 350.00 g were added and reacted for 5 hours while refluxing to obtain a solution of a resin composition (A-2) having an unsaturated maleimide group. It was.

Production Example 3 [Production of Solution of Resin Composition (A-3) Having Unsaturated Maleimide Group]
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, bis (4-maleimidophenyl) methane: 556.53 g and 3,3′-diaminodiphenyl Sulfone: 72.29 g and dimethylacetamide: 350.00 g were added and reacted at 100 ° C. for 5 hours to obtain a solution of a resin composition (A-3) having an unsaturated maleimide group.

Production Example 4 [Production of Solution of Resin Composition (A-4) Having Unsaturated Maleimide Group]
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, polyphenylmethane maleimide: 562.69 g, 3,3′-dimethyl-4,4 ′ -Diaminodiphenylmethane: 66.03 g and propylene glycol monomethyl ether: 350.00 g were added and reacted for 5 hours while refluxing to obtain a solution of a resin composition (A-4) having an unsaturated maleimide group.

Comparative Production Example 1 [Production of Solution of Resin Composition (A-5) Having Unsaturated Maleimide Group]
Bis (4-maleimidophenyl) methane: 358.00 g and 4,4′-diaminodiphenylmethane: 54.50 g were placed in a 1 liter kneader equipped with a steam heating device, and heated and kneaded at 135 to 140 ° C. for 15 minutes. After cooling and pulverizing, a powder of a resin composition (A-5) having an unsaturated maleimide group was obtained.

Comparative Production Example 2 [Production of Solution of Resin Composition (A-6) Having Unsaturated Maleimide Group]
Polyphenylmethane maleimide: 358.00 g and 3,3′-dimethyl-4,4′-diaminodiphenylmethane: 68.50 g were placed in a 1 liter kneader equipped with a steam heating device, and the temperature was 135 to 140 ° C. for 15 minutes. The mixture was heated and kneaded, cooled, and pulverized to obtain a resin composition (A-6) powder having an unsaturated maleimide group.

Examples 1 11 Comparative Example 1-5
As a curing agent, a solution of a resin composition (A) having an unsaturated maleimide group obtained in Production Examples 1 to 4 and Comparative Production Examples 1 and 2,
As the thermosetting resin (B), novolak-type cyanate resin [Lonza Japan Co., Ltd., product name: PT-30], bisphenol A dicyanate prepolymer [Lonza Japan Co., Ltd., product name: BA230], 4 Functional naphthalene type epoxy resin [Dainippon Ink Chemical Co., Ltd., trade name, EXA-4710], biphenyl aralkyl type epoxy resin [Nippon Kayaku Co., Ltd., trade name: NC-3000-H],
As the modified imidazole compound (C), 2,4-diamino-6- [2′-undecylimidazolyl- (1) ′]-ethyl-S-triazine [manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: C11Z-A ], 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1) ′]-ethyl-S-triazine [manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2E4MZ-A],
P-aminophenol (produced by Ihara Chemical Co., Ltd.) as the amine compound (D) having an acidic substituent,
As the inorganic filler (E), fused silica [manufactured by Admatech Co., Ltd., trade name: SC2050-KC], aluminum hydroxide [manufactured by Showa Denko KK, trade name: HP-360], boehmite [Kawai Lime Industry Co., Ltd. ), Product name: BMT-3LV],
Methyl ethyl ketone was used as a diluent solvent and mixed at a blending ratio (parts by mass) shown in Tables 1 to 3 to prepare a uniform varnish having a resin content (total of resin components) of 65% by mass.
In the comparative example, in place of the modified imidazole (C), 2-undecylimidazole [trade name: C11Z manufactured by Shikoku Kasei Co., Ltd.], which is a curing accelerator (unmodified imidazole), and 2-ethyl-4- Methylimidazole [manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ] was used.

The varnish curability (time until gelation) and storage stability were evaluated by the above method using each varnish thus prepared.
Next, the varnish was impregnated and applied to an E glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 50 mass%. Next, four sheets of this prepreg were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 185 ° C. for 90 minutes to produce a copper clad laminate.
The obtained copper-clad laminate was measured and evaluated for heat resistance, coefficient of thermal expansion, copper foil adhesion, hygroscopicity, chemical resistance, and maximum warpage by the methods described above. The results are shown in Tables 1 to 3.

As is apparent from Tables 1 and 2, all the examples of the present invention are excellent in varnish curability and storage stability. On the other hand, in the comparative example of Table 3, since either the modified imidazole compound (C) is not included, either curability or storage stability is remarkably inferior.
Further, as is apparent from Tables 1 and 2, all of the examples of the present invention are excellent in heat resistance (Tg), copper foil adhesion, moisture absorption resistance, chemical resistance and low warpage. On the other hand, in the comparative example of Table 3, since any modified imidazole compound (C) is not included, any of these characteristics is remarkably inferior.

Claims (6)

Manufactured by reacting a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule with an amine compound (b) having at least two primary amino groups in one molecule in an organic solvent. Containing unsaturated maleimide group (A), thermosetting resin (B) and modified imidazole compound (C) represented by the following general formula (I), The equivalent of the unsaturated maleimide group of the resin composition having a maleimide group is 0.32 to 0.83 with respect to the equivalent of the reactive group of the thermosetting resin of the component (B), and the modification of the component (C) The thermosetting resin composition, wherein the imidazole compound is 0.01 to 10 parts by mass with respect to 100 parts by mass of the thermosetting resin of the component (B).

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a hydroxymethyl group, or a phenyl group, and R ₃ represents a hydrogen atom or 1 to 20 carbon atoms. Represents an aliphatic hydrocarbon group, a phenyl group or an allyl group) Furthermore, the thermosetting resin composition of Claim 1 containing the amine compound (D) which has an acidic substituent represented by the following general formula (II).

(In the formula (II), each R ₄ independently represents a hydroxyl group, carboxyl group or sulfonic acid group which is an acidic substituent, and each R ₅ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)   Furthermore, the thermosetting resin composition of Claim 1 or 2 containing an inorganic filler (E).   Furthermore, the thermosetting resin composition of any one of Claims 1-3 containing a molybdenum compound (F).   Thermosetting resin (B) is epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone The thermosetting resin composition according to any one of claims 1 to 4, wherein the thermosetting resin composition is at least one selected from a resin, a triazine resin, and a melamine resin.   The thermosetting resin composition according to any one of claims 3 to 5, wherein the inorganic filler (E) is spherical silica or a metal hydrate having a thermal decomposition temperature of 300 ° C or higher.