JP6318885B2 - Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same - Google Patents

Description

  The present invention relates to a thermosetting resin composition, and a prepreg, laminate and printed wiring board using the same.

  In recent years, with the downsizing and thinning of electronic devices, there is a demand for miniaturization and thinning of semiconductor packages incorporated in electronic devices. The semiconductor package refers to a semiconductor package on which a semiconductor element is mounted. In the thinned semiconductor package, when mounting the semiconductor element on the semiconductor package wiring board and when assembling the semiconductor package mounted on the electronic device, it is caused by the difference in thermal expansion coefficient between the semiconductor package wiring board and the semiconductor element. Warping has become a major issue. For this reason, there is a demand for a material having both low thermal expansion and high elasticity for a semiconductor package wiring board.

  With the miniaturization and thinning of semiconductor packages, high-density mounting and multi-layered configurations are applied to laminated boards used for printed wiring boards such as semiconductor package wiring boards. As a laminated board for printed wiring boards, a resin composition mainly composed of an epoxy resin and a glass cloth are cured and integrally molded. Epoxy resins have an excellent balance of insulation, heat resistance, cost, and the like, but have a limit to meet the problem of improving heat resistance that occurs in high-density mounting and multi-layered configurations.

On the other hand, the bismaleimide resin is extremely superior in heat resistance as compared with the epoxy resin, and thus can be widely used for such high-density mounting and multi-layered laminated boards. However, the bismaleimide resin has high hygroscopicity and has a difficulty in adhesion. Further, in the case of an epoxy resin, it can be cured at a temperature of 180 ° C. or lower. However, when a bismaleimide resin is laminated, it takes a longer time than an epoxy resin to cure at a temperature of 220 ° C. or higher. Resins also have the disadvantage of poor productivity.
Patent Document 1 discloses that a thermosetting resin composition containing a maleimide compound, a silicone compound having an acidic substituent, and a thermosetting resin is excellent in low thermal expansion. However, in order to solve the problem of high elasticity, the thermosetting resin composition as in Patent Document 1 is difficult to press-mold when the filling rate of the inorganic filler is increased, which affects productivity and yield. There are things to do.
Thus, there has been no thermosetting resin composition that has both low thermal expansion and high elasticity and can satisfy the required moldability and productivity.

JP 2012-149155 A

  The present invention provides a thermosetting resin composition excellent in low thermal expansibility, high elasticity, and excellent in moldability during press molding of a laminated board, a prepreg using the same, a laminated board, and a printed wiring board. Let it be an issue.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific epoxy resin, a maleimide compound having at least two N-substituted maleimide groups in one molecule, and at least one molecule. The use of an amino compound having one amino group in the present invention found that a fluidity can be improved and a thermosetting resin composition having good moldability during press molding can be obtained, and the present invention has been completed. . The present invention has been completed based on such findings.

That is, the present invention provides the following thermosetting resin composition, prepreg, laminate and printed wiring board.
(1) (A) an epoxy resin having an ICI viscosity at 150 ° C. of 0.1 Pa · s or less, (B) a maleimide compound having at least two N-substituted maleimide groups in one molecule, and (C) in one molecule A thermosetting resin composition comprising an amino compound having at least one amino group.
(2) (B) The thermosetting resin composition according to (1), wherein the maleimide compound having at least two N-substituted maleimide groups in one molecule further has a phenoxy group.
(3) (C) The thermosetting resin composition according to (1) or (2), wherein the amino compound having at least one amino group in one molecule further has an acidic substituent.
(4) (C) The thermosetting resin composition according to any one of (1) to (3), wherein the amino compound having at least one amino group in one molecule has at least two amino groups.
(5) A prepreg produced by impregnating or coating the base material with the thermosetting resin composition according to any one of (1) to (4).
(6) A laminate obtained by laminating the prepreg according to (5).
(7) A printed wiring board manufactured using the laminated board according to (6).

  According to the present invention, there are provided a thermosetting resin composition having excellent low thermal expansion, high elasticity, and excellent moldability during press molding of a laminate, and a prepreg, laminate and printed wiring board using the same. can do.

The invention will be described in detail below.
The thermosetting resin composition of the present invention comprises (A) an epoxy resin having an ICI viscosity of 0.1 Pa · s or less at 150 ° C. (hereinafter sometimes referred to as “component (A)”), and (B) in one molecule. A maleimide compound having at least two N-substituted maleimide groups (hereinafter sometimes referred to as component (B)), and (C) an amino compound having at least one amino group in one molecule (hereinafter referred to as (C A thermosetting resin composition containing (sometimes referred to as “component”).
The epoxy resin in the present invention is not particularly limited as long as the ICI viscosity at 150 ° C. is 0.1 Pa · s or less. For example, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol S type epoxy resin And bisphenol F type epoxy resin. When the ICI viscosity at 150 ° C. of the epoxy resin exceeds 0.1 Pa · s, the moldability is deteriorated.

A commercially available product may be used as the component (A) of the present invention. Commercially available products include, for example, naphthalene type epoxy resin, manufactured by DIC Corporation, trade name: EXA-731-G4 (ICI viscosity at 150 ° C .: 0.05 Pa · s), dicyclopentadiene type epoxy resin, DIC stock Product name: HP-7200L (ICI viscosity at 150 ° C .: 0.03 Pa · s), dicyclopentadiene type epoxy resin, product name: HP-7200 (ICI viscosity at 150 ° C .: 0 .06 Pa · s), naphthalene type epoxy resin, manufactured by DIC Corporation, trade names: HP-5000L, HP-5000 (ICI viscosity at 150 ° C .: 0.06 Pa · s), bisphenol S type epoxy resin, DIC stock Product name: EXA-1514 (ICI viscosity at 150 ° C : 0.08 Pa · s), as bisphenol F type epoxy resin, Nippon Steel Sumitomo Metal Chemical Co., Ltd., trade name: ICI viscosity at YSLV-70XY (150 ℃: 0.01Pa · s), and the like.
The ICI viscosity in the present invention measures a high shear rate known as an ICI viscometer, and is measured with a cone plate viscometer (manufactured by MS Engineering, apparatus name: ICI CONE AND PLATE VISCO METER). It is.

The component (B) in the present invention is not particularly limited as long as it has at least two N-substituted maleimide groups in one molecule. Examples of the component (B) of the present invention include N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N ′-(1,3-phenylene) bismaleimide, N, N ′. -[1,3- (2-methylphenylene)] bismaleimide, N, N ′-[1,3- (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-maleimide) Chlohexyl) 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-male Dophenoxy) 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′- (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] Sulfone, 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- ( -Maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimide) Phenoxy) -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, polyphenylmethanemaleimide (eg Daiwa Fine Chemicals Co., Ltd., trade name: BMI-2300), and the like. These may be used alone or in combination of two or more.
Among these, a maleimide compound having at least two N-substituted maleimide groups in one molecule and further having a phenoxy group is preferable from the viewpoint of solubility in an organic solvent. Examples of such maleimide compounds include 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane.
(B) As for the usage-amount of a component, 30-500 mass parts is preferable with respect to 100 mass parts of (A) component, and 75-200 mass parts is more preferable. Chemical resistance improves by setting it as 30 mass parts or more, and heat resistance improves by setting it as 500 mass parts or less.

The component (C) in the present invention is not particularly limited as long as it is a compound having one or more amino groups, but as an amino compound having at least one amino group in one molecule, further acidic substitution Those having a group and those having at least two amino groups are preferred, and it is particularly preferred to use these in combination.
Examples of compounds having at least one amino group in one molecule and further having an acidic substituent 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. It is done.
Among these, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline in terms of solubility and synthesis yield. Is preferred. Moreover, m-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance. Furthermore, p-aminophenol is particularly preferable from the viewpoint of low thermal expansion.
Examples of the amino compound having at least two amino groups in one molecule include m-phenylenediamine, p-phenylenediamine, 4,6-dimethyl-m-phenylenediamine, and 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-t-butyl) toluene, 2,4-diaminoxylene, 2,4-diaminopyridine, 2,6-diaminopyridine, 2,5-diamino Pyridine, 2,4-diaminodurene, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, 3-bis (3- Minobenzyl) benzene, 4-bis (4-aminobenzyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-amino) Phenoxy) 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′-diaminodiphenyl Ethane, 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-tert-butylphenyl) ether, 4,4′-diaminodiphenyl ether -2,2'-disulfonic acid, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamino Biphenyl, 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'-diaminodiphenylsulfur Fido, 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′-bis (4-aminophenoxyphenyl) fluorene, diaminoanthraquinone, 3,7-diamino-2,8 -Aromatic amines such as dimethyldibenzothiophene sulfone, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,5-dimethylhexamethylenediamine 3-methoxyhexamethylene di Min, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, 1,3-bis (3-amino Propyl) tetramethyldisiloxane, 2,5-diamino-1,3,4-oxadiazol, aliphatic amines such as bis (4-aminocyclohexyl) methane, melamine, benzoguanamine, acetoguanamine, 2,4-diamino -6-vinyl-s-triazine, 2,4-diamino-6-allyl-s-triazine, 2,4-diamino-6-acryloyloxyethyl-s-triazine, 2,4-diamino-6-methacryloyloxyethyl Examples include guanamine compounds of -s-triazine.
Among these, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenylmethane, which are aromatic amines having good reactivity and heat resistance, 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, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 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.
Among these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 3, More preferred are 3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, and benzoguanamine. From the viewpoint of toxicity and solubility in a solvent, 3,3′-diaminodiphenyl sulfone and 3,3′-diethyl-4,4′-diaminodiphenylmethane are particularly preferable.

Said (C) component may use 1 type, or may use 2 or more types together. Here, the amount of component (C) ₂ group and the sum of the equivalents of -NH, the relationship between the C = C group equivalent of the component (B), it is preferable that the range shown in the following equation.
0.1 ≦ [C = C group equivalent] / [-NH ₂ group equivalent] ≦ 10.0
More preferably, this relationship is within the range shown in the following equation.
1.0 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 9.0
Particularly preferably, this relationship is within the range shown in the following equation.
2.0 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 8.0
When the amount ratio is 0.1 or more, gelation of the thermosetting resin composition tends to be suppressed, and good heat resistance of the thermosetting resin composition is obtained. In addition, by setting the corresponding amount ratio to 10.0 or less, a decrease in solubility of the component (C) in the organic solvent tends to be suppressed, and good heat resistance of the thermosetting resin composition can be obtained. .

In the thermosetting resin composition of the present invention, the component (B) and the component (C) 1 may be reacted as necessary. A compound having an amino group, an imide group and an N-substituted maleimide group obtained by the reaction can be blended in the thermosetting resin composition of the present invention.
In this reaction, it is preferable that the blending amount of the maleimide compound (B) having at least two N-substituted maleimide groups in one molecule satisfies the above formula.
The reaction conditions are not particularly limited, but the reaction temperature is preferably 70 to 200 ° C., and the reaction time is preferably 0.5 to 10 hours.

Examples of the organic solvent used in the above reaction include alcohol solvents such as 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 ethyl ester and γ-butyrolactone, 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 sulfoxide And sulfur atom-containing solvents such as These may be used alone or in combination of two or more.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, γ-butyrolactone, and dimethylacetamide are preferable from the viewpoint of solubility, and have low toxicity and high volatility, so that they do not remain as residual solvents when producing prepregs. To cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are particularly preferred.

The blending amount of the organic solvent is preferably 25 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the component (B) and the component (C), from the viewpoint of solubility and reaction time, It is more preferable to set it as a mass part. After the reaction, it may be concentrated or diluted as necessary.
In the above reaction, a reaction catalyst can be used as necessary. 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. These may be used alone or in combination of two or more.

In the thermosetting resin composition of the present invention, an inorganic filler may be blended, for example, silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, stannic acid. Examples thereof include zinc, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, glass powder such as E glass, T glass, and D glass, and hollow glass beads.
The blending amount of the inorganic filler is preferably 10 to 300 parts by mass, more preferably 100 to 250 parts by mass, and more preferably 150 to 250 parts by mass in terms of solid content with respect to 100 parts by mass of the thermosetting resin composition. It is particularly preferable to use parts by mass. If it is 10-300 mass parts, sufficient rigidity of a base material, moisture heat resistance, a flame retardance, the tolerance with respect to the erosion by a plating solution, etc. will be acquired.

  You may mix | blend a hardening accelerator with the thermosetting resin composition of this invention. The curing accelerator is not particularly limited, and examples thereof include imidazoles and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. . These may be used alone or in combination of two or more.

The thermosetting resin composition of the present invention contains a thermoplastic resin, an elastomer, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like. May be.
Examples of 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, poly Examples include ether ether ketone resins, polyether imide resins, silicone resins, and tetrafluoroethylene resins.
Examples of elastomers include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.
Examples of organic fillers include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resins, silicone resins, tetrafluoroethylene resins, acrylic ester resins, methacrylic ester resins, conjugated diene resins, etc. Examples thereof include a resin filler having a core-shell structure having a rubber-like core layer and a glass-like shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, or a vinyl cyanide resin.
Examples of flame retardants include halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphorous flame retardants such as red phosphorus, sulfamic acid Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate and melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide.
Examples of UV absorbers include benzotriazole UV absorbers, examples of antioxidants include hindered phenols and hindered amines, and examples of photopolymerization initiators include benzophenones, benzyl ketals, and thioxanthones. Examples of photopolymerization initiators and fluorescent brighteners include fluorescent brighteners of stilbene derivatives, and examples of adhesion improvers include urea compounds such as urea silane and silane, titanate, and aluminate coupling agents. Is mentioned.

  In addition, when blending the inorganic filler, it is also preferable that the inorganic filler is pretreated with a silane-based or titanate-based coupling agent, or a surface treatment agent such as a silicone oligomer, or an integral blend treatment.

  The thermosetting resin composition of the present invention is usually used as a varnish in which an organic solvent is used as a diluting solvent and each component is dissolved or dispersed in the organic solvent. The organic solvent is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohol solvents such as methyl cellosolve, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, and mesitylene. System solvents and the like. These may be used alone or in combination of two or more.

  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 coating properties and obtain a prepreg having an appropriate resin composition adhesion amount.

  The prepreg of the present invention is produced by impregnating or coating the base material with the thermosetting resin composition of the present invention. For example, after the thermosetting resin composition of the present invention is applied to a substrate by a method such as impregnation, spraying, or extrusion, the prepreg of the present invention is made into a semi-cured state (B stage state) by heating or the like. Can be manufactured. Hereinafter, the prepreg of the present invention will be described in detail.

As the base material used in the prepreg of the present invention, known materials used for various types of 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 substrate is not particularly limited. For example, a substrate having a thickness of about 0.03 to 0.5 mm can be used, and the substrate is surface-treated with a silane coupling agent or the like, or mechanically opened. Is suitable from the viewpoints of heat resistance, moisture resistance and processability.
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. The prepreg of the present invention can be obtained by heating and drying for 1 to 30 minutes to obtain a semi-cured state (B stage state).

  The laminate of the present invention is obtained by laminating the prepreg of the present invention. For example, a laminated board can be manufactured by laminating 1-20 sheets of the prepregs described above 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 the laminate for an electrical insulating material. The molding conditions may be, for example, a laminated plate for an electrical insulating material and a multilayer plate. For example, a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine or the like is used, and the temperature is 100 to 250 ° C. and the pressure is 0. It can be molded in a range of 2 to 10 MPa, a temperature increase rate of 1 to 10 ° C./min, and a heating time of 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 printed wiring board of the present invention is manufactured using the laminated board of the present invention. For example, the conductor layer provided on the laminated board of the present invention is processed by wiring by a normal etching method, and a plurality of laminated boards processed by wiring through the prepreg described above are stacked, and then multilayered by heating and pressing. After that, a multilayer printed wiring board can be manufactured through formation of through holes or blind via holes by drilling or laser processing and formation of interlayer wiring by plating or conductive paste.

  Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.

Each component used in the examples is as follows.
(A) Epoxy resin having an ICI viscosity at 150 ° C. of 0.1 Pa · s or less A-1: Naphthalene type epoxy resin [manufactured by DIC Corporation, trade name: EXA-7311-G4], ICI viscosity at 150 ° C .: 0. 05Pa · s
A-2: Bisphenol F type epoxy resin [manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YSLV-70XY], ICI viscosity at 150 ° C .: 0.01 Pa · s
A-3: Dicyclopentadiene type epoxy resin [manufactured by DIC Corporation, trade name: HP-7200L, ICI viscosity at 150 ° C .: 0.03 Pa · s]

(B) Maleimide compound having at least two N-substituted maleimide groups in one molecule B-1: 2,2-bis [(4- (4-maleimidophenoxy) phenyl)] propane [manufactured by Daiwa Kasei Kogyo Co., Ltd. ; Brand name BMI-4000]
(C) Amine compound having at least one amino group in one molecule C-1: p-aminophenol [manufactured by Kanto Chemical Co., Inc.]
C-2: 3,3′-diethyl-4,4′-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd .; trade name: KAYAHARD AA]

(D) Curing accelerator D-1: Isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd .; trade name: G-8809L]

(E) Epoxy resin having an ICI viscosity at 150 ° C. exceeding 0.1 Pa · s E-1: α-naphthol / cresol novolak type epoxy resin [manufactured by Nippon Kayaku Co., Ltd., trade name: NC-7000L], at 150 ° C. ICI viscosity: 0.25 Pa · s

Example 1
A 2 liter reaction vessel equipped with a thermometer, a stirrer, a moisture meter with a reflux condenser, and a 2 liter reaction vessel, 15.6 g of p-aminophenol (C-1 component) and 3,3′-diethyl -4,4'-diaminodiphenylmethane (C-2 component) 49.4 g, 2,2-bis [(4- (4-maleimidophenoxy) phenyl)] propane (B-1 component) 708.4 g and propylene glycol 1160.0 g of monomethyl ether (organic solvent) was added, reacted at 115 ° C. for 4 hours, and then concentrated to a solid content of 60% by mass. Thereafter, 173 g of a naphthalene type epoxy resin (component A-1) and 0.3 g of an isocyanate mask imidazole (component D-1) were mixed for 2 hours to prepare a varnish having a resin content of 60.5% by mass.
Next, the varnish was impregnated and applied to an S glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 3 minutes and 30 seconds to obtain a prepreg having a resin content of 39% by mass. Two pieces of this prepreg are stacked, 12 μm electrolytic copper foils are arranged on the top and bottom, and pressed for 60 minutes at a pressure of 0.5 MPa, a molding temperature of 240 ° C., and a heating rate of 3 ° C./min. I got a plate.
Example 2
It was produced in the same manner as in Example 1 except that the A-1 component was changed to A-2 component YSLV-70XY: 173 g.
Example 3
It was produced in the same manner as in Example 1 except that the A-1 component was changed to HP-7200L: 173 g of the A-3 component.

Comparative Example 1
A 2 liter reaction vessel equipped with a thermometer, a stirrer, a moisture meter with a reflux condenser, and a 2 liter reaction vessel, 15.6 g of p-aminophenol (C-1 component) and 3,3′-diethyl -4,4'-diaminodiphenylmethane (C-2 component) 49.4 g, 2,2-bis [(4- (4-maleimidophenoxy) phenyl)] propane (B-1 component) 708.4 g and propylene glycol 1160.0 g of monomethyl ether (organic solvent) was added, reacted at 115 ° C. for 4 hours, and then concentrated to a solid content of 60% by mass. Thereafter, 173 g of α-naphthol / cresol novolac type epoxy resin (E-1 component) and 0.3 g of isocyanate mask imidazole (D-1 component) were mixed for 2 hours to prepare a varnish having a resin content of 60.5% by mass.
Next, the varnish was impregnated and applied to an S glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 3 minutes and 30 seconds to obtain a prepreg having a resin content of 39% by mass. Two pieces of this prepreg are stacked, 12 μm electrolytic copper foils are arranged on the top and bottom, and pressed for 60 minutes at a pressure of 0.5 MPa, a molding temperature of 240 ° C., and a temperature increase rate of 3 ° C./min. I got a plate.

The characteristics of the copper clad laminates obtained in Examples 1 to 3 and Comparative Example 1 were evaluated by the methods shown below. Table 1 shows the evaluation results.
(1) Measurement of coefficient of thermal expansion Press temperature: A 5-mm square evaluation board from which copper foil was removed by immersing a copper-clad laminate molded at 240 ° C. in a copper etching solution was prepared, and a TMA test apparatus (manufactured by TA Instruments) was prepared. , TMAQ400EM) was used for thermomechanical analysis by the compression method. After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a temperature increase rate of 10 ° C./min. The average coefficient of thermal expansion from 30 ° C. to 100 ° C. in the second measurement was calculated and used as the value of the coefficient of thermal expansion.
(2) Measurement of flexural modulus A copper-clad laminate molded at a press temperature of 240 ° C. was immersed in a copper etching solution to produce a 25 × 40 mm square evaluation board, from which a flexural modulus test apparatus ( (Orientec Co., Ltd., 5 ton tensilon) was used, and the crosshead speed was 1 mm / min and the span distance was 20 mm.
(3) Confirmation of formability The formability of the copper clad laminate obtained at a heating rate of 3 ° C / min was confirmed, and the molding temperature limit was observed. Moreover, the moldability confirmation method removes copper foil by immersing a copper clad laminated board in a copper etching solution, and evaluates by the difference in thickness between a central portion and a portion 10 mm from the end, and the difference is 0.05 mm or less. It was sometimes molded. When it was able to be molded, it was marked as ◯, and when it could not be marked as x.

  From the results of Table 1, it can be seen that the thermosetting resin composition according to the present invention can improve the moldability while maintaining the thermal expansion coefficient and the flexural modulus. The thermosetting resin composition according to the present invention has both low thermal expansibility and high elasticity, and can meet the required productivity.

  A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition according to the present invention, a laminate produced by laminating the prepreg, and a print produced using the laminate The wiring board is useful for highly integrated printed wiring boards for electronic devices because of its excellent low thermal expansion, high elasticity, and good press moldability.

Claims (7)

(A) an epoxy resin having an ICI viscosity at 150 ° C. of 0.03 Pa · s or less, (B) a maleimide compound having at least two N-substituted maleimide groups in one molecule, and (C) at least in one molecule. A prepreg produced by impregnating or coating a base material with a thermosetting resin composition containing an amino compound having one amino group. (B) The prepreg according to claim 1, wherein the maleimide compound having at least two N-substituted maleimide groups in one molecule further has a phenoxy group. (C) The prepreg according to claim 1 or 2, wherein the amino compound having at least one amino group in one molecule further has an acidic substituent. (C) The prepreg according to any one of claims 1 to 3, wherein the amino compound having at least one amino group in one molecule has at least two amino groups. (B) The compounding quantity of a component is 30-500 mass parts with respect to 100 mass parts of (A) component,
  (C) Component blending amount is derived from (C) component-NH ₂ The prepreg according to any one of claims 1 to 4, wherein the relationship between the sum of the group equivalents and the C = C group equivalent derived from the component (B) is in a range represented by the following formula.
  0.1 ≦ [C = C group equivalent] / [— NH ₂ Sum of group equivalents] ≦ 10.0 A laminate obtained by laminating the prepreg according to any one of claims 1 to 5 .   The printed wiring board manufactured using the laminated board of Claim 6.