JP6065437B2 - Thermosetting resin composition, prepreg, laminate and printed wiring board using the same - Google Patents

Description

  The present invention relates to a thermosetting resin composition suitable for semiconductor packages and printed wiring boards, and in particular, a thermosetting resin composition excellent in low thermal expansion while maintaining heat resistance, and a prepreg and a laminate using the same. The present invention relates to a board and a printed wiring board.

  With recent downsizing and higher performance of electronic equipment, printed wiring boards have advanced wiring density and higher integration, and accordingly, there has been an increasing demand for improved reliability of wiring laminates. In such applications, it is required to have both excellent heat resistance and low thermal expansion.

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 resins have an excellent balance of insulation, heat resistance, cost, etc., but in order to meet the demands for improved heat resistance due to recent high-density mounting of printed wiring boards and high-layer structures, the heat resistance is unavoidable. There is a limit to the improvement.

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, see Patent Document 1). . However, increasing the filling amount of the inorganic filler is known to cause a decrease in insulation reliability due to moisture absorption, insufficient adhesion of the resin-wiring layer, and poor press molding.
Polybismaleimide resins widely used for high-density packaging and highly multilayered laminates have difficulties in adhesion and low thermal expansion.

  A thermosetting resin composition containing epoxy resin, phenol resin and modified imide resin as main components is known (for example, see Patent Document 2). Although this modified imide resin-containing composition is improved in moisture resistance and adhesiveness, it is modified with a low molecular weight compound containing a hydroxyl group and an epoxy group to ensure solubility in a general-purpose solvent such as methyl ethyl ketone. There is a problem that the heat resistance of the resin is significantly inferior to that of the polybismaleimide resin.

  Furthermore, in recent years, with semiconductor package substrates, warping due to the difference in coefficient of thermal expansion between the chip and the substrate has become a major issue at the time of component mounting and package assembly as the size and thickness are reduced.

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

  In view of the current situation, an object of the present invention is to provide a resin composition particularly excellent in heat resistance and low thermal expansion, and a prepreg, a laminate and a printed wiring board using the resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that a resin composition containing a specific curing accelerator, a maleimide compound, and an amine compound meets the above object, The present invention has been reached.

That is, this invention provides the following thermosetting resin compositions, a prepreg, a laminated board, and a printed wiring board.
1. A compound (a) having at least one alkyl group in the phosphorus atom, an amine compound (b) having at least two primary amino groups in the molecular structure, an amine compound (c) having an acidic substituent, and a molecular structure A thermosetting resin composition comprising a maleimide compound (d) having at least two N-substituted maleimide groups.
2. An amine compound (b) having at least two primary amino groups in the molecular structure, an amine compound (c) having an acidic substituent, and a maleimide compound (d) having at least two N-substituted maleimide groups in the molecular structure ), An amino-modified resin having an amino group, an imide group and an N-substituted maleimide group, and a compound (a) having at least one alkyl group at the phosphorus atom. A thermosetting resin composition characterized by the above.
3. 3. The thermosetting resin composition according to 1 or 2 above, wherein the compound (a) having at least one alkyl group on a phosphorus atom is a compound having a quinone skeleton.
4). 4. The thermosetting resin composition according to 3 above, wherein the alkyl group of the compound (a) having at least one alkyl group on the phosphorus atom is an n-butyl group.
5. Furthermore, the said thermosetting resin composition of 1-4 containing at least 1 type of thermosetting resin (e) chosen from the epoxy resin and cyanate resin.
6). Furthermore, the thermosetting resin composition in any one of said 1-5 containing an inorganic filler.
7). A prepreg characterized by being B-staged after impregnating or coating the thermosetting resin composition of any one of 1 to 6 on a substrate.
8). An insulating resin layer is formed using the prepreg described in 7 above.
9. A printed wiring board obtained by circuit processing a metal foil disposed on one or both sides of an insulating resin layer in the laminated board described in 8 above.

  A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition of the present invention, a laminate produced by laminating the prepreg, and a multilayer print produced using the laminate The wiring board is particularly excellent in heat resistance, low thermal expansion and the like while maintaining the conventional performance, and is useful as a highly integrated printed wiring board for electronic equipment.

Hereinafter, the present invention will be described in detail.
The thermosetting resin composition of the present invention comprises a compound (a) having at least one alkyl group in a phosphorus atom, an amine compound (b) having at least two primary amino groups in the molecular structure, and an acidic substituent. And an amine compound (c) having a molecular structure and a maleimide compound (d) having at least two N-substituted maleimide groups.

  In the thermosetting resin composition of the present invention, by using the compound (a) having at least one alkyl group in the phosphorus atom, curing is sufficiently advanced and low thermal expansion and heat resistance can be improved.

  Examples of the compound (a) having at least one alkyl group on the phosphorus atom include phosphines having an alkyl group such as butylphosphine, dibutylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, and triethylphosphine, and phosphines thereof. And the adducts of these phosphines and quinones. Among these, the adducts of phosphines and quinones are preferred.

The phosphine used in the adduct of phosphines and quinones may be any phosphine to which at least one alkyl group is bonded. For example, methylphosphine, dimethylphosphine, trimethylphosphine, triethylphosphine, tripropylphosphine , Trialkylphosphine such as tributylphosphine, trioctylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, diethylphenylphosphine, ethyldiphenylphosphine, dialkyl monoarylphosphine, alkyldiarylphosphine, tricyclohexylphosphine Examples thereof include phosphine to which a cyclic hydrocarbon is bonded.
In addition, examples of quinones used in adducts of phosphines and quinones include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, and the like. Among them, p-benzoquinone is moisture resistant and preserved. It is preferable from the viewpoint of stability.

  A method for producing an adduct of phosphines and quinones is not particularly limited, and examples thereof include a method in which both are mixed with stirring in a solvent in which tertiary phosphine and quinones as raw materials are dissolved. The production conditions in this case are from 1 hour to 12 in a solvent such as methyl isobutyl ketone, methyl ethyl ketone, and acetone such as acetone in the range of room temperature to 80 ° C. and high solubility of the raw material and low solubility of the adduct produced. It is preferable to stir for a period of time for the addition reaction.

一般式（Ｉ）中のＲは、水素原子または１価のアルキル基を表し、１価のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、オクチル基、シクロヘキシル基などが挙げられ、これらは単独で、あるいは２種類以上を組み合わせて用いてもよい。 Examples of the adduct of phosphines and quinones obtained in this manner include those represented by the following general formula (I).

R in the general formula (I) represents a hydrogen atom or a monovalent alkyl group, and examples of the monovalent alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, and a cyclohexyl group. These may be used alone or in combination of two or more.

  Specific adducts include adducts of trioctylphosphine and p-benzoquinone, adducts of tricyclohexylphosphine and p-benzoquinone, adducts of tri (n-butyl) phosphine and p-benzoquinone, etc. Among these, an adduct of tri (n-butyl) phosphine and p-benzoquinone is preferable, and particularly preferably used from the viewpoint of low thermal expansion. These may be used alone or in combination of two or more.

  As a compounding quantity, about 0.1-2.0 mass parts is preferable with respect to 100 mass parts of solid content conversion resin component total amount in a thermosetting resin composition, More preferably, it is 0.3-0.7. About mass parts. By using in this range, low thermal expansibility and heat resistance can be improved.

  As the amine compound (b) having at least two primary amino groups in the molecular structure, a commercially available product can be used. For example, “PAM-E” (functional group equivalent 130) having amino groups at both ends, “KF-8010” (functional group equivalent 430), “X-22-161A” (functional group equivalent 800), “X-22-161B” (functional group equivalent 1500), “KF-8012” (functional group equivalent 2200) ), "KF-8008" (functional group equivalent 5700) [above, manufactured by Shin-Etsu Chemical Co., Ltd.], "BY16-871" (functional group equivalent 130), "BY16-853U" (functional group equivalent 460) [above Manufactured by Toray Dow Corning Co., Ltd.], diaminobenzidine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenylsulfone, 3,3′-dichloro-4,4′-dia Nobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminobiphenyl-6,6'-disulfonic acid, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 4,4'-methylene-bis (2-chloroaniline), 1,3′-bis (4-aminophenoxy) benzene, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2′-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, 1,4′-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenyl sulfide, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino -3,3'-biphenyldiol, 9,9'-bis (4-aminophenyl) fluorene, o-tolidine sulfone, etc. may be mentioned, and these may be used alone or in admixture of two or more.

  As a compounding quantity, about 3-50 mass parts is preferable with respect to 100 mass parts of solid content conversion resin components in a thermosetting resin composition, More preferably, it is about 5-35 mass parts. The blending amount within this range is preferable because low thermal expansion and copper foil adhesiveness are improved.

  The amine compound (c) having an acidic substituent is, for example, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-amino. Benzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc., and among these, solubility and synthesis yield From the viewpoint, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable, and m-aminophenol and p are preferable from the viewpoint of heat resistance. -Aminophenol is more preferable, and p-aminophenol is particularly preferable from the viewpoint of low thermal expansion.

  As a compounding quantity, about 0.5-10 mass parts is preferable with respect to 100 mass parts of solid component conversion resin component total amount in a thermosetting resin composition, More preferably, about 0.7-3% mass part is preferable. It is. A blending amount in this range is preferable because heat resistance and low thermal expansion are improved.

  Examples of the maleimide compound (d) having at least two N-substituted maleimide groups in one molecular structure include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2- Bis (4- (4-maleimidophenoxy) phenyl) propane and the like can be mentioned, and one or two or more can be mixed and used.

  Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-, which has a high reaction rate and can have higher heat resistance. Diphenylmethane bismaleimide and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are preferable, and 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane is preferable from the viewpoint of solubility in a solvent. Bismaleimide and bis (4-maleimidophenyl) methane are more preferred, and bis (4-maleimidophenyl) methane is particularly preferred because it is inexpensive.

  In addition, as a compounding quantity, about 30-80 mass parts is preferable with respect to 100 mass parts of solid content conversion resin components in a thermosetting resin composition, More preferably, it is about 35-65 mass parts. The blending amount within this range is preferable because the elastic modulus and low thermal expansion are improved.

  The amine compound (b) having at least two primary amino groups in the molecular structure, the amine compound (c) having an acidic substituent, and at least two N-substituted maleimide groups in one molecular structure as described above Each of the maleimide compounds (d) having the above may be blended in the thermosetting resin composition, but these compounds (b), (c) and (d) are heated and kept warm as necessary to react in advance. It is also possible to add an amino-modified resin having an amino group, an imide group and an N-substituted maleimide group.

The amount of the maleimide compound (d) used here is such that the equivalent of the maleimide group of the maleimide compound (d) is equal to that of the primary amino group of the amine compounds (b) and (c), from the viewpoint of prevention of gelation and heat resistance. A range exceeding the equivalent is desirable. The amount of the amine compound (b) is preferably about 7 to 35 times the amount of the amine compound (c) from the viewpoint of heat resistance.
The reaction temperature of the maleimide compound (d) is preferably 70 to 200 ° C., and the reaction time is preferably 0.5 to 10 hours.

The organic solvent used in the above reaction is not particularly limited, but for example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. -Based solvents, ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, nitrogen atoms such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone A solvent, sulfur atom containing solvents, such as dimethyl sulfoxide, etc. are mentioned, It can use 1 type or in mixture of 2 or more types.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility, cyclohexanone, which has low toxicity and high volatility and does not easily remain as a residual solvent during prepreg production. Propylene glycol monomethyl ether and dimethylacetamide are particularly preferred.

  The amount of the organic solvent used is such that the amine compound (b) having at least two primary amino groups in the molecular structure, the amine compound (c) having an acidic substituent, and one molecular structure from the viewpoints of solubility and reaction time. It is preferable to set it as 25-1000 mass parts per 100 mass parts of total amounts of maleimide compound (d) which has an at least 2 N-substituted maleimide group in it, and it is more preferable to set it as 40-700 mass parts.

  The thermosetting resin composition of the present invention may further contain a thermosetting resin. Examples of such a thermosetting resin (e) include an epoxy resin, a phenol resin, and an unsaturated imide resin. , Cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, etc., one or two of these The above 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 these phosphorus-containing epoxy resin obtained by introducing a phosphorus compound listed, among these, heat resistance, biphenyl aralkyl type epoxy resin from the viewpoint of flame retardancy, naphthalene type epoxy resins are preferred. These can be used alone or in combination of two or more.

  Examples of the cyanate resin include novolak-type cyanate resin, bisphenol A-type cyanate resin, bisphenol E-type cyanate resin, and bisphenol-type cyanate resin such as tetramethylbisphenol F-type cyanate resin, and prepolymers in which these are partially triazine. Can be mentioned. 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.

  In addition, as a compounding quantity of these thermosetting resins, about 5-50 mass parts is preferable with respect to 100 mass parts of solid content conversion resin components in a thermosetting resin composition, and 10-40 mass parts is preferable. More preferably, it is about.

  An inorganic filler can be arbitrarily blended in the thermosetting resin composition of the present invention. Inorganic fillers include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, and boron. Examples thereof include aluminum oxide, potassium titanate, glass powder such as E glass, T glass, and D glass, and hollow glass beads. These can be used alone or in combination.

  As the inorganic filler, 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.

  When fused spherical silica is used as the inorganic filler, the average particle size 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.

  It is preferable that the compounding quantity of an inorganic filler is 20-300 mass parts per 100 mass parts of solid content conversion resin component total amount in a thermosetting resin composition, and it is more preferable that it is 50-200 mass parts. By making the compounding quantity of an inorganic filler into 20-300 mass parts, the moldability and low thermal expansibility of a prepreg can be kept favorable.

  The thermosetting resin composition of the present invention includes a thermoplastic resin, an elastomer, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, and a photopolymerization as long as the thermosetting property is not impaired as the resin composition. Initiators, fluorescent brighteners and adhesion improvers can be used.

  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 the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.

  Examples of organic fillers include resin fillers of uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, acrylate ester resin, methacrylate ester resin, conjugated diene resin And a core-shell resin filler having a rubbery core layer and a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, etc. It is done.

  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.

Other 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 thioxanthone. Examples of photopolymerization initiators and fluorescent brighteners include stilbene derivative fluorescent brighteners, and adhesion improvers such as urea compounds such as urea silane and silane, titanate and aluminate cups. A ring agent is mentioned.
Further, at the time of blending, it is also preferable that the inorganic filler is pretreated with a silane-based or titanate-based coupling agent or a surface-treating 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 using an organic solvent as a diluting 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. A system solvent etc. are mentioned, 1 type (s) or 2 or more types can be mixed and used.

  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 formed by impregnating or coating the thermosetting resin composition of the present invention on a base material and then forming a B-stage. That is, the thermosetting resin composition of the present invention is applied to a substrate by a method such as impregnation, spraying, or extrusion, and then semi-cured (B-stage) by heating or the like to produce the prepreg of the present invention. To do. 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 base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface is treated with a silane coupling agent or the like or mechanically subjected to a fiber opening treatment. However, it is suitable from the aspects 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.

  In the laminated board of the present invention, the insulating resin layer is formed using the prepreg of the present invention, and the laminated board of the present invention can be formed by laminating using the prepreg described above. 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 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 obtained by circuit processing of a metal foil disposed on one or both surfaces of the insulating resin layer in the laminated board of the present invention. That is, the conductor layer of the laminated board of the present invention is processed by wiring by a normal etching method, a plurality of laminated boards processed by wiring through the above-mentioned prepreg, and after being multilayered by heating press processing, 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.
The copper clad laminate obtained in the following examples was measured and evaluated for performance by the following method.

(1) Glass transition temperature (Tg)
A 5 mm square evaluation board from which the copper foil was removed was prepared by immersing the copper clad laminate in a copper etching solution, and thermomechanical analysis was performed by a compression method using a TMA test apparatus (manufactured by DuPont, TMA2940). 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 load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of tangents with different thermal expansion curves in the second measurement was determined, and the heat resistance was evaluated.

(2) Coefficient of thermal expansion A 5 mm square evaluation board from which the copper foil has been removed by immersing a copper clad laminate in a copper etching solution is prepared and heated by a compression method using a TMA test apparatus (manufactured by DuPont, TMA2940). Mechanical analysis was performed. 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 load of 5 g and a heating 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.

(3) Measurement of flexural modulus A copper-clad laminate was dipped in a copper etching solution to produce a 50 mm × 25 mm evaluation board from which the copper foil was removed, using a 5-ton tensilon manufactured by Orientec Co., Ltd., and a crosshead speed of 1 mm. / Min Measured at a span distance of 20 mm. In addition, as a wiring board, the bending elastic modulus of about 28 GPa or more is normally calculated | required.

(4) Copper foil adhesion (copper foil peel strength)
A copper foil having a width of 3 mm was formed by immersing the copper-clad laminate in a copper etching solution to produce an evaluation substrate, and the adhesiveness (90 ° peel strength) of the copper foil was measured using a tensile tester. In addition, as a wiring board, the peel strength of about 0.6 KN / m or more is normally calculated | required.

(5) Evaluation of desmear resistance The 40 mm x 40 mm evaluation board | substrate which removed the copper foil by immersing a copper clad laminated board in a copper etching liquid was desmeared by the process shown in the following Table 1. A chemical manufactured by Atotech was used. The evaluation of desmear resistance was calculated from the weight difference after desmear treatment with respect to the dry weight before desmear treatment. The smaller the amount, the better the desmear resistance, but the wiring board is usually required to be about 3.0 g / m ² or less.

Examples 1-10, Comparative Examples 1-4
Each component shown below was mixed at a blending ratio (parts by mass) shown in Tables 2 to 4, and a uniform varnish having a resin content of 65% by mass was prepared using methyl ethyl ketone as a solvent. Next, this 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 48 mass%.
Four prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate. Tables 2 to 4 show the results of tests and evaluations of the obtained copper-clad laminate.

Adduct of tertiary phosphine and quinones (a)
(A-1) Adduct of trioctylphosphine and p-benzoquinone (a-2) Adduct of tricyclohexylphosphine and p-benzoquinone (a-3) Adduct of tri (n-butyl) phosphine and p-benzoquinone The production method (a) can be synthesized by stirring and mixing both in a solvent in which tertiary phosphine and p-benzoquinone as raw materials are dissolved. The production conditions are those in which stirring is performed for 1 hour to 12 hours in methyl isobutyl ketone in the range of room temperature to 80 ° C., in which the solubility of the raw material is high and the generated adduct is low in solubility.

An amine compound (b) having at least two primary amino groups in the molecular structure;
(B-1) Both-ends diamine-modified siloxane [manufactured by Shin-Etsu Chemical Co., Ltd .; trade name: X-22-161A]
(B-2) Both-ends diamine-modified siloxane [manufactured by Shin-Etsu Chemical Co., Ltd .; trade name: X-22-161B]
(B-3) 3,3′-diethyl-4,4′-diaminodiphenylmethane [manufactured by Nippon Kayaku; trade name: KAYAHARD AA]
(B-4) 2,2′-bis [4- (4-aminophenoxy) phenyl] propane [manufactured by Wakayama Seika; trade name: BAPP]

Amine compound (c) having an acidic substituent
(C-1) Aromatic amine [manufactured by Kanto Chemical Co., Inc .; p-aminophenol]
(C-2) Aromatic amine [manufactured by Kanto Chemical Co., Inc .; m-aminophenol]

Maleimide compound (d) having at least two N-substituted maleimide groups
(D-1) Bis (4-maleimidophenyl) methane [manufactured by Kei-I Kasei Co., Ltd .; trade name: BMI]
(D-2) 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane [manufactured by Daiwa Kasei Kogyo Co., Ltd .; trade name: BMI-4000]

Production Example 1: Amino-modified resin (X-1)
In a reaction vessel with a capacity of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture quantifier with a reflux condenser, X-22-161A: 99.2 g and 3,3′-diethyl-4,4 '-Diaminodiphenylmethane: 54.4 g, p-aminophenol: 4.8 g, bis (4-maleimidophenyl) methane: 125.3 g and propylene glycol monomethyl ether: 250.0 g were added and reacted at 100 ° C. for 3 hours. To obtain an amino-modified resin (X-1) -containing solution having an acidic substituent.

Production Example 2: Amino-modified resin (X-2)
2-22 g of X-22-161B: 3,3′-diethyl-4,4 ′ in a reaction vessel with a capacity of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. -Diaminodiphenylmethane: 15.0 g, p-aminophenol: 4.7 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane: 123.2 g and propylene glycol monomethyl ether: 250.0 g It was allowed to react at 115 ° C. for 3 hours to obtain an amino-modified resin (X-2) -containing solution having an acidic substituent.

Thermosetting resin (e)
(E-1) α-naphthol / cresol novolac type epoxy resin [manufactured by Nippon Kayaku Co., Ltd .; trade name: NC-7000L]
(E-2) Biphenyl aralkyl type epoxy resin [Nippon Kayaku Co., Ltd .; trade name: NC-3000H]

Curing accelerator (f)
(F-1) 1-cyanoethyl-2-methylimidazole [manufactured by Shikoku Kasei Co., Ltd .; trade name: 2MZ-CN]
(F-2) 2-phenyl-imidazole [manufactured by Shikoku Kasei Co., Ltd .; trade name: 2PZ]

  Inorganic filler: fused silica (manufactured by Admatechs Co., Ltd .: trade name: SC2050-KNK)

  As is apparent from Tables 2 to 3, the Examples of the present invention are excellent in all of glass transition temperature (Tg), low thermal expansibility, elastic modulus, copper foil adhesion and desmear resistance. On the other hand, as is clear from Table 4, none of the comparative examples satisfies all the characteristics of glass transition temperature (Tg), low thermal expansion, elastic modulus, copper foil adhesion and desmear resistance at the same time, and particularly low thermal expansion. Inferior in rate and heat resistance characteristics. Therefore, the thermosetting resin composition of the present invention has a laminated sheet excellent in low thermal expansion coefficient and heat resistance while having properties such as elastic modulus, copper foil adhesion and desmear resistance. I understand.

  The thermosetting resin composition of the present invention can produce a laminated board having a particularly low coefficient of thermal expansion and excellent heat resistance. Therefore, a printed wiring board having a high density and a high multilayer can be produced. It is suitably used for a wiring board of an electronic device such as a computer or an information device terminal that processes data at high speed.

Claims (9)

  A compound (a) having at least one alkyl group in the phosphorus atom, an amine compound (b) having at least two primary amino groups in the molecular structure, an amine compound (c) having an acidic substituent, and a molecular structure A thermosetting resin composition comprising a maleimide compound (d) having at least two N-substituted maleimide groups.   An amine compound (b) having at least two primary amino groups in the molecular structure, an amine compound (c) having an acidic substituent, and a maleimide compound (d) having at least two N-substituted maleimide groups in the molecular structure ), An amino-modified resin having an amino group, an imide group and an N-substituted maleimide group, and a compound (a) having at least one alkyl group at the phosphorus atom. A thermosetting resin composition characterized by the above.   The thermosetting resin composition according to claim 1 or 2, wherein the compound (a) having at least one alkyl group at a phosphorus atom is a compound having a quinone skeleton.   The thermosetting resin composition according to claim 3, wherein the alkyl group of the compound (a) having at least one alkyl group on a phosphorus atom is an n-butyl group.   Furthermore, the thermosetting resin composition of Claims 1-4 containing the at least 1 type of thermosetting resin (e) chosen from the epoxy resin and cyanate resin.   Furthermore, the thermosetting resin composition in any one of Claims 1-5 containing an inorganic filler.   A prepreg characterized by being B-staged after impregnating or coating the thermosetting resin composition according to any one of claims 1 to 6 on a substrate.   An insulating resin layer is formed using the prepreg according to claim 7.   A printed wiring board obtained by circuit processing a metal foil disposed on one or both sides of an insulating resin layer in the laminated board according to claim 8.