JP5344022B2 - Epoxy resin composition, prepreg, laminate, resin sheet, printed wiring board, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition having a high glass transition temperature and a low thermal expansion coefficient, suppressing the warpage of a printed wiring board overall when used for the printed wiring board, corresponding to the further thinning of the printed wiring board, and excelling in the reliability such as insulation reliability when applied to the thin printed wiring board, and to provide a prepreg, a laminated plate, a resin sheet, the printed wiring board, and a semiconductor device using the same. <P>SOLUTION: The epoxy resin composition includes a specific epoxy compound described in the specification, a bismaleimide compound, and an inorganic filler. <P>COPYRIGHT: (C)2013,JPO&amp;INPIT

Description

  The present invention relates to an epoxy resin composition suitably used for electronic component material applications, and a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device using the same.

  In recent years, with the demand for higher functionality of electronic devices, etc., the integration of electronic components and the mounting of high-density packaging have been progressing. In addition to this, miniaturization, thinning, and high density are progressing.

  Generally, when the printed wiring board is made thinner, there is a problem that the mounting reliability is lowered and the warpage of the printed wiring board is increased. Therefore, there is a method of lowering the thermal expansion coefficient of the resin composition used and raising the glass transition temperature. Various studies have been made.

  Patent Document 1 describes that an epoxy resin containing a naphthalene ring is used as a resin composition having a low coefficient of thermal expansion and a high glass transition temperature. According to Patent Document 1, by using such an epoxy resin, a prepreg, a laminated board, and a printed wiring board having high heat resistance during moisture absorption and a low coefficient of thermal expansion are provided.

JP 2001-302761 A

  Since the resin composition described in Patent Document 1 has a naphthalene ring in the molecule, the thermal expansion coefficient after curing can be reduced by the intermolecular interaction between the naphthalene rings. However, since the epoxy resin of patent document 1 has two or more epoxy groups couple | bonded from one naphthalene ring, the distance of epoxy groups is short and the crosslinking density after hardening becomes high. For this reason, the curing shrinkage of the resin composition increases, and as a result, the strain after curing increases. Therefore, even if the coefficient of thermal expansion of the cured product of the resin composition itself is low, the warp of the printed wiring board cannot be suppressed. In view of such a technical state, an object of the present invention is to provide an epoxy resin composition that can suppress warping of a printed wiring board and cope with further thinning of the printed wiring board.

The object is achieved by the present invention described in the following items [1] to [1 4 ].
[1] An epoxy resin composition comprising a naphthylene ether type epoxy compound represented by the following general formula (1), a bismaleimide compound, and an inorganic filler ,
An epoxy resin composition having a Young's modulus at 25 ° C. of 1 to 10 GPa of the epoxy resin composition after thermosetting.

(In the formula, n is an integer of 1 to 20. Each R is independently a hydrogen atom, a benzyl group, an alkyl group, or the following formula (2).)

(In the formula, Ar is each independently a phenylene group or a naphthylene group, and m is an integer of 1 or 2.)

[2] The epoxy resin composition according to item [1], wherein the epoxy resin composition after thermosetting has a glass transition temperature (Tg) of 160 ° C. or higher and 213 ° C. or lower .
[3] The linear expansion coefficient of less than the glass transition temperature (Tg) of the epoxy resin composition after heat curing is less than 40 ppm / ° C. [1] section or the [2] The epoxy resin composition according to item.
[4 ] The epoxy resin composition according to any one of [1] to [ 3 ], wherein the inorganic filler contains silica nanoparticles having an average particle diameter of 10 nm to 150 nm.
[ 5 ] The epoxy resin composition according to any one of [1] to [ 4 ], wherein the inorganic filler contains silicone rubber fine particles having an average particle diameter of 1 μm to 10 μm.
[6] The content of the bismaleimide compound in the epoxy resin composition is 35% to 55% by mass in the composition obtained by removing the inorganic filler from the entire epoxy resin composition. The epoxy resin composition according to any one of items [5].
[7] The content of the naphthylene ether type epoxy compound in the epoxy resin composition is within a range of 30 to 55 mass% with respect to the composition excluding the inorganic filler from the entire epoxy resin composition. The epoxy resin composition according to any one of [1] to [6].
[8] The content of the inorganic filler is any one of items [1] to [7], which is within a range of 30 to 75% by mass with respect to the total amount of the epoxy resin composition excluding the solvent. The epoxy resin composition described in 1.
[ 9 ] A prepreg obtained by impregnating a base material with the epoxy resin composition according to any one of items [1] to [ 8 ].
[ 10 ] A laminate obtained by disposing a metal layer on at least one surface of the prepreg according to the item [ 9 ].
[ 11 ] A laminate comprising a metal layer disposed on at least one surface of a prepreg laminate in which two or more prepregs according to the item [ 9 ] are laminated.
[1 2 ] A resin sheet obtained by disposing the epoxy resin composition according to any one of items [1] to [ 8 ] on a support film or a metal foil.
[1 3 ] A printed wiring board formed from the prepreg according to the item [ 9 ], the laminate according to the item [ 10 ] or [ 11 ], or the resin sheet according to the item [1 2 ]. .
[1 4 ] A semiconductor device in which a semiconductor element is mounted on the printed wiring board according to the item [1 3 ].

  The epoxy resin composition according to the present invention has a high glass transition temperature and a low coefficient of thermal expansion, and when used in a printed wiring board, it can comprehensively suppress warping of the printed wiring board.

(Epoxy resin composition)
First, the epoxy resin composition according to the present invention will be described. The epoxy resin composition according to the present invention comprises a naphthylene ether type epoxy compound represented by the following general formula (1), a bismaleimide compound, and an inorganic filler.

  The epoxy resin composition by this invention can contain the naphthylene ether type epoxy compound represented by following General formula (1).

(In the formula, n is an integer of 1 to 20, and more preferably an integer of 1 to 10. R is independently a hydrogen atom, a benzyl group, an alkyl group, or the following formula (2).)

(In the formula, Ar is each independently a phenylene group or a naphthylene group, and m is an integer of 1 or 2.)

  Since the naphthylene ether type epoxy compound represented by the general formula (1) has a naphthalene ring in the molecule, the molecular motion is suppressed by the intermolecular interaction between the naphthalene rings. The coefficient of thermal expansion after curing of the product is reduced. Moreover, since the epoxy compound represented by General formula (1) has only one epoxy group couple | bonded with respect to one naphthalene ring, the distance of epoxy groups is long, and the epoxy resin composition using this is long. The crosslinking density after curing does not become extremely high. For this reason, the curing shrinkage of the epoxy resin composition does not increase, and as a result, distortion after curing can be suppressed. Further, the naphthylene ether type epoxy compound represented by the general formula (1) has appropriate flexibility because the naphthalene structures are connected to each other by oxygen atoms, and at the time of molding an epoxy resin composition using the naphthylene ether type epoxy compound. Warping of the cured product is reduced.

  The naphthylene ether type epoxy compound represented by the general formula (1) can be synthesized by, for example, a method described in JP-A-2007-231083.

  Examples of the naphthylene ether type epoxy compound represented by the general formula (1) include those represented by the general formula (3).

(In the formula, n is an integer of 1 to 20, and more preferably an integer of 1 to 10. Each R is independently a hydrogen atom or the following formula (4).)

(In the formula, m is an integer of 1 or 2.)

Examples of the naphthylene ether type epoxy compound represented by the general formula (3) include those represented by the following formulas (5) to (8).

  In the present invention, other epoxy compounds may be used in combination as long as the desired effect of mixing the naphthylene ether type epoxy compound represented by the general formula (1) is not impaired. Examples of the epoxy compound that can be used in combination include a novolak type epoxy compound, a phenol aralkyl type epoxy compound having a phenylene skeleton, a phenol aralkyl type epoxy compound having a biphenylene skeleton, a naphthol type epoxy compound, an anthracene type epoxy compound, and an alkyl-modified triphenolmethane type. Examples thereof include, but are not limited to, epoxy compounds, triazine nucleus-containing epoxy compounds, dicyclopentadiene-modified phenol type epoxy compounds, and the like. When using these epoxy compounds together, it is preferable to suppress other epoxy compounds used together to 30 mass% or less with respect to the total amount of epoxy compounds so that the thermal expansion coefficient of the epoxy resin composition does not increase.

  Although the total content of the naphthylene ether type epoxy compound represented by the general formula (1) (the total content including the above-mentioned other epoxy compounds when including the other epoxy compounds) is not particularly limited, the entire epoxy resin composition Preferably it is 25-60 mass% with respect to the composition remove | excluding the inorganic filler from the range of 30-55 mass% more preferably. When the total content of the epoxy compound is less than the above lower limit, the thermal expansion coefficient (particularly, the linear expansion coefficient) after curing of the epoxy resin composition may be insufficiently reduced. On the contrary, when the total content of the epoxy compound exceeds the above upper limit, the heat resistance after curing of the epoxy resin composition may decrease.

  The epoxy resin composition according to the present invention may contain a bismaleimide compound. The bismaleimide compound contained in the epoxy resin composition according to the present invention is a compound having at least two maleimide groups in the molecule. The maleimide group of the bismaleimide compound has a five-membered planar structure, and since the double bond of the maleimide group easily interacts between molecules and has high polarity, the compound has a maleimide group, a benzene ring, and other planar structures. It shows strong intermolecular interaction and can suppress molecular motion. Therefore, the epoxy resin composition according to the present invention using the same can lower the coefficient of thermal expansion after curing, and further has excellent heat resistance.

  The bismaleimide compound contained in the epoxy resin composition according to the present invention is not particularly limited. For example, 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2, 2 ′-[4- (4-maleimidophenoxy) phenyl] propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, N, N ′ -Ethylene dimaleimide, N, N'-hexamethylene dimaleimide etc. are mentioned, As polymaleimide, polyphenyl methane maleimide etc. are mentioned.

  The bismaleimide compound contained in the epoxy resin composition according to the present invention is preferably a compound represented by the following general formula (9).

(In the formula, R ^{1 to} R ⁴ are hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms, and R ⁵ is —CH ₂ —, —O—, substituted or unsubstituted aromatic carbonization. (It is a hydrogen group or a structure represented by the following formula (10).)

(In the formula, R ^{6 to} R ⁹ are hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms.)

Among the compounds represented by the general formula (9), a bismaleimide compound in which R ^{1 to} R ⁴ are hydrogen is preferable because of its high reactivity with the curing agent.

  Specific examples of preferable bismaleimides contained in the epoxy resin composition according to the present invention are shown below, but the present invention is not limited to these compounds.

  Considering low water absorption, etc., 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane (Exemplary Compound 13), bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane (Exemplary Compound 12) is preferred.

  1 type may be used for the bismaleimide compound contained in the epoxy resin composition by this invention, and it may use it in combination of 2 or more type.

  The content of the bismaleimide compound in the epoxy resin composition according to the present invention is not particularly limited, but is preferably 30 to 60% by mass in the composition excluding the inorganic filler from the entire epoxy resin composition, 35 More preferably, it is -55 mass%.

  As described above, by appropriately containing the bismaleimide compound, the thermosetting resin composition according to the present invention can effectively exhibit a low coefficient of linear expansion. When the content of the bismaleimide compound is less than the above lower limit value, the linear expansion coefficient may not be sufficiently lowered, and the mounting reliability may be lowered or the warpage of the printed wiring board may be increased. And when said upper limit is exceeded, the peel strength regarding the adhesiveness of a conductor circuit and a resin layer may fall.

  The epoxy resin composition of this invention may contain the phenol resin type hardening | curing agent as needed. Examples of the phenol resin include phenol novolak resin, o-cresol novolak resin, p-cresol novolak resin, pt-butylphenol novolak resin, hydroxynaphthalene novolak resin, bisphenol A novolak resin, bisphenol F novolak resin, and terpene modified novolak resin. , Dicyclopentadiene-modified novolak resin, polybutadiene-modified phenol resin, phenol aralkyl resin, biphenyl aralkyl resin, and the like. The compounding amount of the phenol resin-based curing agent is an epoxy having the total content of the naphthylene ether type epoxy compound represented by the general formula (1) (the total content including the above-mentioned other epoxy compounds). It is preferable that the equivalent ratio with respect to the functionality falls within the range of 0.8 to 1.2.

  The content of the phenol resin-based curing agent is not particularly limited, but is preferably 0 to 25% by mass, particularly 0 to 15% by mass in the composition excluding the inorganic filler from the entire epoxy resin composition. It is preferable.

The epoxy resin composition of this invention may contain the aromatic diamine type hardening | curing agent as needed. The aromatic diamine curing agent is not particularly limited as long as it is a compound having two amino groups in the molecule and having an aromatic ring structure. Examples of aromatic diamine curing agents include m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, Examples include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4 ′-(p-phenylenediisopropylidene) dianiline, but are not limited thereto. . In particular, the use of 4,4′-diaminodiphenyl sulfone and 3,3′-diaminodiphenyl sulfone is preferable from the viewpoint of exhibiting a low coefficient of thermal expansion. The blending amount of the aromatic diamine-based curing agent is the total content of the naphthylene ether type epoxy compound represented by the general formula (1) (when the other epoxy compounds are included, the total content including them). It is preferable that the equivalent ratio with respect to the epoxy functionality is within the range of 0.8 to 1.2.

  Although content of an aromatic diamine type hardening | curing agent is not specifically limited, It is preferable that it is 0-25 mass% in the composition remove | excluding the inorganic filler from the whole epoxy resin composition, and it is 0-15 mass% especially. Preferably there is.

    The epoxy resin composition according to the present invention may contain an inorganic filler. As the inorganic filler contained in the epoxy resin composition according to the present invention, any material can be used as long as it does not impair the intended purpose and effect of the present invention. For example, silica, aluminum hydroxide , Magnesium hydroxide, alumina, talc, mica, boron nitride, alumina nitride and the like. It is preferable that content of an inorganic filler exists in the range of 30-75 mass% with respect to the total amount of the epoxy resin composition except a solvent. If the content of the inorganic filler is less than the above lower limit value, the coefficient of thermal expansion is not sufficiently low. On the contrary, if the content exceeds the upper limit value, the adhesion to the conductor circuit may be lowered.

  Examples of the inorganic filler that is particularly preferably used in the present invention include silica nanoparticles having an average particle diameter of 10 nm to 150 nm. Such silica nanoparticles can penetrate between the filaments of the base material, and the impregnation property of the epoxy resin composition into the base material is improved. In addition, since a fine rough surface can be formed on the surface of the laminated board as compared with the case where a conventional filler is used, a finer wiring can be formed than before. As such silica nanoparticles, for example, those produced by a combustion method such as VMC (Vaporized Metal Combustion) method, PVS (Physical Vapor Synthesis) method, a melting method in which crushed silica is flame-melted, a precipitation method, a gel method, etc. Is mentioned. Among these, the VMC method is particularly preferable. The VMC method is a method in which silica fine particles are formed by putting silicon powder into a chemical flame formed in an oxygen-containing gas, burning it, and then cooling it. In the VMC method, the particle diameter of the silica fine particles to be obtained can be adjusted by controlling the particle diameter of the silicon powder to be input, the input amount, the flame temperature, and the like. Moreover, as a silica nanoparticle, commercial items, such as NSS-5N (made by Tokuyama Co., Ltd.) and Sicastar 43-00-501 (made by Micromod), can also be used.

  Another inorganic filler particularly preferably used in the present invention includes silicone rubber fine particles having an average particle diameter of 1 μm to 10 μm. Such silicone rubber fine particles can further reduce the warpage of the printed wiring board because the rubber component causes stress relaxation. Further, when the drilling process is improved and a laminated board is produced, a stripe-like unevenness on the surface of the laminated board is eliminated, and a laminated board having a good appearance can be obtained. The silicone rubber fine particles are not particularly limited as long as they are rubber elastic fine particles formed of organopolysiloxane. For example, the fine particles made of silicone rubber (organopolysiloxane crosslinked elastomer) itself and the core portion made of silicone rubber are made of silicone resin. Examples include coated core-shell structured particles. As silicone rubber fine particles, KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil E-500, Trefil E-600 (manufactured by Toray Dow Corning Co., Ltd.), etc. Commercial products can be used.

The epoxy resin composition according to the present invention includes a brominated epoxy resin, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, as long as the intended purpose and effect of the present invention are not impaired. Flame retardants such as: natural waxes such as carnauba wax, synthetic waxes such as polyethylene wax, mold release agents such as higher fatty acids such as stearic acid and zinc stearate and their metal salts or paraffin; epoxy silane, mercaptosilane, aminosilane, alkyl Silane coupling agents such as silane, ureido silane, vinyl silane, titanate coupling agents, aluminum coupling agents, coupling agents such as aluminum / zirconium coupling agents; colorants such as carbon black and bengara; butadiene rubber, It can be blended inorganic ion exchangers such as for ionic impurities reduced, various additives as appropriate; Rironitoriru modified butadiene rubber, silicone oil, low-stress ingredients such as silicone rubber.

  As for the epoxy resin composition by this invention, it is preferable that the glass transition temperature (Tg) of the epoxy resin composition after the thermosetting is 160 degreeC or more. When this glass transition temperature (Tg) is 160 ° C. or higher, it is possible to comprehensively suppress the warpage of the printed wiring board in combination with the low linear expansion coefficient and Young's modulus described later. The glass transition temperature (Tg) of the epoxy resin composition after thermosetting according to the present invention is more preferably 170 ° C. or higher.

  The epoxy resin composition according to the present invention preferably has a linear expansion coefficient of less than 40 ppm / ° C. at less than the glass transition temperature (Tg) of the epoxy resin composition after heat curing. When the linear expansion coefficient in the glass state of the epoxy resin composition after thermosetting is less than 40 ppm / ° C., combined with the glass transition temperature (Tg) and Young's modulus described later, the printed wiring board is comprehensively warped. Can be suppressed. The linear expansion coefficient at a temperature lower than the glass transition temperature (Tg) of the epoxy resin composition after thermosetting according to the present invention is more preferably 35 ppm / ° C. or less.

  As for the epoxy resin composition by this invention, it is preferable that the elastic modulus (Young's modulus) in 25 degreeC of the epoxy resin composition after thermosetting exists in the range of 1-10 GPa. When this Young's modulus is 10 GPa or less, combined with the glass transition temperature (Tg) and the linear expansion coefficient, it is possible to comprehensively suppress warpage of the printed wiring board. The Young's modulus at 25 ° C. of the epoxy resin composition after thermosetting according to the present invention is more preferably in the range of 3 to 9 GPa.

  In the epoxy resin composition according to the present invention, the kind and content of the naphthylene ether type epoxy compound represented by the general formula (1), the kind and content of the bismaleimide compound, and the kind of inorganic filler By appropriately adjusting the content within the above-described range, the glass transition temperature, the linear expansion coefficient, and the Young's modulus of the epoxy resin composition after thermosetting can be set within the above-described range.

(Prepreg)
Next, the prepreg according to the present invention will be described. The prepreg according to the present invention is obtained by impregnating a base material with the epoxy resin composition. The substrate is not particularly limited. For example, a glass fiber substrate such as glass fiber cloth or glass non-woven cloth, an inorganic fiber substrate such as a fiber cloth or non-woven cloth containing an inorganic compound other than glass, an aromatic polyamide. Examples thereof include organic fiber base materials composed of organic fibers such as resins, polyamide resins, aromatic polyester resins, polyester resins, polyimide resins, and fluororesins. From the viewpoints of strength and water absorption, glass fiber base materials such as glass fiber cloth and glass fiber cloth are preferable.

  There is no particular limitation on the method of impregnating the base material with the epoxy resin composition. For example, the base material is immersed in the epoxy resin composition, the epoxy resin composition is applied to the base material with various coaters, or sprayed. The method of spraying etc. are mentioned. Especially, since the impregnation property of the composition with respect to a base material improves, the immersion method is preferable. In impregnating the base material with the epoxy resin composition, a normal impregnation coating facility can be used. Moreover, the impregnation property can be further improved by applying a reduced pressure.

(Laminated board)
Next, the laminated board by this invention is demonstrated. The laminated board by this invention is a molded article containing the said prepreg. For example, the laminate according to the present invention can be formed by disposing a metal layer on at least one surface of the prepreg. Moreover, the said laminated board may arrange | position a metal layer on the at least single side | surface of the prepreg laminated body which laminated | stacked two or more of the said prepregs. In the laminate according to the present invention, a metal foil and / or a support film may be laminated on one side or both upper and lower sides of the prepreg. Furthermore, in the laminate according to the present invention, a metal foil and / or a support film may be laminated on one side or the outermost upper and lower sides of a prepreg laminate in which at least two prepregs are laminated. The laminate according to the present invention has a low dielectric constant and dielectric loss tangent, and is excellent in heat resistance and adhesion.

  As the support film, one that can be easily handled can be selected. Specific examples of the support film include polyester resin films such as polyethylene terephthalate and polybutylene terephthalate, and thermoplastic resin films having heat resistance such as fluororesin and polyimide resin. Among these, polyester resin films such as polyethylene terephthalate and polybutylene terephthalate are preferable. Although there is no restriction | limiting in particular in the thickness of a support film, From the viewpoint of handleability, the inside of the range of 1-100 micrometers is preferable, and the inside of the range of 3-50 micrometers is more preferable.

  Examples of metal foils include copper and / or copper alloys, aluminum and / or aluminum alloys, iron and / or iron alloys, silver and / or silver alloys, gold and gold alloys, zinc and zinc alloys, Examples thereof include nickel and nickel-based alloys, tin and tin-based alloys. Although there is no restriction | limiting in particular in the thickness of metal foil, The inside of the range of 0.1-70 micrometers is preferable, The inside of the range of 1-35 micrometers is more preferable, Furthermore, the inside of the range of 1.5-18 micrometers is preferable. If the thickness of the metal foil is less than the above lower limit value, the metal foil is easily damaged, pinholes are easily generated, and when the metal foil is etched and used as a conductor circuit, variation in plating during circuit pattern molding, Circuit breakage, penetration of chemicals such as etching liquid and desmear liquid may occur. When the thickness of the metal foil exceeds the above upper limit value, the variation in the thickness of the metal foil and the variation in the surface roughness of the roughened metal foil may be increased.

The metal foil may be an ultrathin metal foil with a carrier foil. The ultrathin metal foil with a carrier foil is a metal foil obtained by laminating a peelable carrier foil and an ultrathin metal foil. Since an ultra-thin metal foil layer can be formed on both sides of a prepreg by using an ultra-thin metal foil with a carrier foil, for example, when forming a circuit by a semi-additive method, etc., an ultra-thin metal foil without performing electroless plating By directly electroplating as a power feeding layer, the ultrathin copper foil can be flash etched after the circuit is formed. By using an ultra-thin metal foil with a carrier foil, even with an ultra-thin metal foil having a thickness of 10 μm or less, for example, a reduction in handling properties of the ultra-thin metal foil in a pressing process, and cracking or cutting of the ultra-thin copper foil are prevented. Can do. The thickness of the ultrathin metal foil is preferably in the range of 0.1 to 10 μm, more preferably in the range of 0.5 to 5 μm, and still more preferably in the range of 1 to 3 μm. If the thickness of the ultra-thin metal foil is less than 0.1 μm, the ultra-thin metal foil is damaged after the carrier foil is peeled off, pinholes are generated in the ultrathin metal foil, Variations, disconnection of circuit wiring, penetration of chemicals such as etching liquid and desmear liquid may occur. When the thickness of the ultrathin metal foil is more than 10 μm, the variation in the thickness of the ultrathin metal foil or the variation in the surface roughness of the roughened surface of the ultrathin metal foil may increase. Usually, an ultrathin metal foil with a carrier foil peels off the carrier foil before forming a circuit pattern on the press-molded laminate.

  The laminated sheet of the present invention can be obtained by heating and pressurizing a laminate of a prepreg and a metal foil and / or a support film. The heating temperature is preferably 150 to 240 ° C, and more preferably 180 to 220 ° C. The applied pressure is preferably 2 to 5 MPa, more preferably 2.5 to 4 MPa.

(Resin sheet)
Next, the resin sheet according to the present invention will be described. The resin sheet by this invention arrange | positions the said epoxy resin composition on a support film or metal foil. The said resin sheet is obtained by forming the insulating layer which consists of solid content of the said epoxy resin composition on a support film or metal foil. When forming a resin sheet, the solid content of the epoxy resin composition is preferably in the range of 45 to 85 mass%, more preferably in the range of 55 to 75 mass%. The epoxy resin composition is coated on a support film and / or metal foil using various coating apparatuses and then dried, or the epoxy resin composition is sprayed onto the support film or metal foil by a spray device. A resin sheet can be produced by drying after coating. The support film and metal foil used for the resin sheet can be the same as those described for the laminate.

  The coating apparatus for producing the resin sheet is not particularly limited as long as it has no voids and can efficiently produce a resin sheet having a uniform insulating layer thickness. For example, a roll coater, a bar Examples include coaters, knife coaters, gravure coaters, die coaters, comma coaters, curtain coaters, and the like. Among these, a die coater, a knife coater, and a comma coater are preferable.

(Printed wiring board)
Next, the printed wiring board according to the present invention will be described. The printed wiring board by this invention is formed from the said prepreg, the said laminated board, or the said resin sheet. Although the manufacturing method of the printed wiring board by this invention is not specifically limited, For example, it can manufacture as follows.

  Prepare a laminated board with copper foil on both sides, form through-holes with a drill, etc., fill the through-holes with plating, and then form a predetermined conductor circuit (inner layer circuit) on both sides of the laminated board by etching etc. Then, the inner circuit board is produced by subjecting the conductor circuit to a roughening process such as a blackening process. When the epoxy resin composition of the present invention is used, fine through-holes can be formed with a good yield as compared with the prior art, and the unevenness of the wall after forming the through-hole is very small as compared with the conventional case.

  Next, the resin sheet of the present invention or the prepreg of the present invention is formed on the upper and lower surfaces of the inner layer circuit board, and is heated and pressed. Specifically, the resin sheet of the present invention, or the prepreg of the present invention and the inner circuit board are combined and vacuum-heated and pressure-molded using a vacuum-pressure laminator apparatus or the like. Thereafter, the insulating layer can be formed on the inner circuit board by heat-curing with a hot air drying device or the like. Although it does not specifically limit as conditions to heat-press form here, If an example is given, it can implement at the temperature of 60-160 degreeC, and the pressure of 0.2-3 MPa. Moreover, it is although it does not specifically limit as conditions to heat-harden, If an example is given, it can implement in temperature 140-240 degreeC and time 30-120 minutes.

  As another method, the resin sheet of the present invention or the prepreg of the present invention is overlaid on the inner circuit board, and this is heated and pressed using a flat plate press or the like to form an insulating layer on the inner circuit board. You can also. Although it does not specifically limit as conditions to heat-press form here, If an example is given, it can implement at the temperature of 140-240 degreeC, and the pressure of 1-4 MPa.

  The laminated body of the present invention can form a new conductive wiring circuit by metal plating after roughening the surface of the insulating layer with an oxidizing agent such as permanganate or dichromate.

  When the thermosetting composition of the present invention is used, it is excellent in fine wiring processing compared to the prior art, and the conductor width (line) when forming the conductor circuit and the wiring between the conductors (space) are formed with high yield. can do.

  Thereafter, the insulating layer is cured by heating. Although the temperature to harden | cure is not specifically limited, For example, you may harden | cure in the range of 160 to 240 degreeC, and it is preferable to harden in the range of 180 to 200 degreeC.

Next, an opening is provided in the insulating layer by using a carbonic acid laser device, and an outer layer circuit is formed on the surface of the insulating layer by electrolytic copper plating to achieve conduction between the outer layer circuit and the inner layer circuit. The outer layer circuit is provided with a connection electrode portion for mounting a semiconductor element. After that, a solder resist is formed on the outermost layer, the connection electrode part is exposed so that a semiconductor element can be mounted by exposure / development, nickel gold plating treatment is performed, and it is cut into a predetermined size to obtain a multilayer printed wiring board. Can do.

(Semiconductor device)
Next, a semiconductor device according to the present invention will be described. The semiconductor device according to the present invention is obtained by mounting a semiconductor element on the printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor element on the printed wiring board of the present invention. The mounting method and the sealing method of the semiconductor element are not particularly limited. For example, a semiconductor element and a printed wiring board are used, and the connection electrode part on the multilayer printed wiring board and the solder bump of the semiconductor element are aligned using a flip chip bonder or the like. Thereafter, the solder bump is heated to the melting point or higher by using an IR reflow device, a hot plate, or other heating device, and the printed wiring board and the solder bump are connected by fusion bonding. And a semiconductor device can be obtained by filling and hardening a liquid sealing resin between a printed wiring board and a semiconductor element.

  When the epoxy resin composition of the present invention is used, since the warpage of the printed wiring board can be suppressed even at a temperature of about 260 ° C. where the semiconductor element is mounted, the mounting property is excellent.

  In addition, this invention is not limited to the above-mentioned embodiment, The deformation | transformation in the range which can achieve the objective of this invention, improvement, etc. are included in this invention.

Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these. In addition, in an Example, unless otherwise specified, a part represents a mass part.
Example 1
[1] Preparation of resin varnish Naphthylene ether type epoxy compound represented by general formula (3) (manufactured by DIC, HP-6000, epoxy equivalent 273, in general formula (3), R is a hydrogen atom, n = 1 and n = 2) 24.4 parts by weight; 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane (Kay-Isei Chemical Co., Ltd.) as bismaleimide compound BMI-80) 14.9 parts by mass; phenol novolac resin (DIC, TD-2090, hydroxyl equivalent 105) 5.6 parts by mass as a phenolic resin curing agent; 2-phenylimidazole (Shikoku Chemicals) as a curing accelerator Manufactured by 2PZ) 0.1 parts by mass; as an inorganic filler, fused silica particles (manufactured by Admatex, SO-25R, average particle size 0.5 μm), 65.0 parts by mass, N -Methyl pyrrolidone was added and mixed so that solid content might be 65 mass%, and the resin varnish (500 grams) which consists of an epoxy resin composition was prepared.

[2] Manufacture of prepreg Using the above resin varnish, a glass fabric (length 530 mm, width 530 mm, thickness 0.18)
mm, manufactured by Nitto Boseki Co., Ltd.) 100 parts by mass of resin varnish is impregnated with 80 parts by mass of solid and dried in a drying oven at 190 ° C. for 7 minutes to produce a prepreg having a resin content of 44.4% by mass. did.

[3] Manufacture of Resin Sheet Copper foil (Mitsui Metal Mining Co., Ltd., Microcin Ex-3, carrier foil layer: copper foil (18 μm) obtained by bonding the above resin varnish to a peelable carrier foil layer and an electrolytic copper foil layer. ), Apply the electrolytic copper foil layer of the electrolytic copper foil layer (3 μm) using a comma coater so that the resin layer after drying is 40 μm, and dry it for 10 minutes with a drying apparatus at 150 ° C. A resin sheet was manufactured.

[4] Manufacture of laminated plate On the front and back of the prepreg laminate in which the two prepregs are stacked, an electrolytic copper foil (YGP-18 manufactured by Nippon Electrolytic Co., Ltd.) having a length of 560 mm, a width of 560 mm, and a thickness of 18 μm is stacked, and a pressure of 4 MPa, Heat pressing was performed at a temperature of 220 ° C. for 180 minutes to obtain a double-sided copper clad laminate having a thickness of 0.4 mm.

[5] Production of Printed Wiring Board After the through-hole processing was performed on the laminated board using a 0.1 mm drill bit, the through-hole was filled by plating. Further, a circuit was formed on both sides by etching and used as an inner layer circuit board. The resin sheet was superposed on the front and back of the inner layer circuit board, and this was subjected to vacuum heating and pressure molding at a temperature of 100 ° C. and a pressure of 1 MPa using a vacuum pressurizing laminator apparatus. This was heated and cured at 170 ° C. for 60 minutes in a hot air drying apparatus to obtain a laminate.

  Next, the surface electrolytic copper foil layer was subjected to blackening treatment, and a φ60 μm via hole for interlayer connection was formed by a carbon dioxide gas laser. Next, it is immersed in a swelling solution at 70 ° C. (Atotech Japan Co., Swelling Dip Securigant P) for 5 minutes, and further immersed in an aqueous solution of potassium permanganate at 80 ° C. (Concentrate Compact CP, manufactured by Atotech Japan) for 15 minutes. Then, it neutralized and the desmear process in a via hole was performed. Next, after the surface of the electrolytic copper foil layer is etched by about 1 μm by flash etching, electroless copper plating is performed with a thickness of 0.5 μm, a resist layer for electrolytic copper plating is formed with a thickness of 18 μm, and pattern copper plating is performed. The film was post-cured by heating at 60 ° C. for 60 minutes. Next, the plating resist was peeled off and the entire surface was flash etched to form a pattern of L / S = 20/20 μm. Finally, a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) having a thickness of 20 μm was formed on the circuit surface to obtain a printed wiring board.

[6] Manufacture of semiconductor device The printed wiring board is the above-mentioned printed wiring board, and has a size of 50 mm × 50 mm provided with a connection electrode portion subjected to nickel gold plating corresponding to the solder bump arrangement of the semiconductor element. It was cut and used. A semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 0.8 mm) has a solder bump formed of a eutectic of Sn / Pb composition, and a circuit protective film of the semiconductor element is a positive photosensitive resin (Sumitomo Bakelite). What was formed by company CRC-8300) was used. In assembling the semiconductor device, first, a flux material was uniformly applied to the solder bumps by a transfer method, and then mounted on a multilayer printed wiring board by thermocompression bonding using a flip chip bonder device. Next, after solder bumps were melt-bonded in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The curing condition of the liquid sealing resin was a temperature of 150 ° C. and 120 minutes.

Example 2
Resin in the same manner as in Example 1, except that 14.9 parts by mass of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70, manufactured by Kay Chemical Co., Ltd.) was used as the bismaleimide compound. A varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

Example 3
A resin varnish was prepared in the same manner as in Example 1 except that 5.6 parts by mass of bisphenol A novolak resin (manufactured by DIC, VH-4240, hydroxyl group equivalent 110) was used as a phenol resin-based curing agent, and a prepreg, a resin sheet, A laminated board, a printed wiring board, and a semiconductor device were obtained.

Example 4
12.2 parts by mass of a naphthylene ether type epoxy compound (manufactured by DIC, HP-6000) and 7.8 parts by mass of a phenol aralkyl resin (manufactured by Mitsui Chemicals, XLC-LL, hydroxyl group equivalent 175) as a phenol resin curing agent A resin varnish was prepared in the same manner as in Example 1 except that the prepreg was used, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

Example 5
16.3 parts by mass of a naphthylene ether type epoxy compound (manufactured by DIC, HP-6000); 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Kay Chemical Co., Ltd.) as a bismaleimide compound BMI-80) 14.9 parts by mass; 4,4′-diaminodiphenylsulfone (Mitsui Chemicals Fine, 4,4′-DAS, curing agent equivalent 62) as an aromatic diamine-based curing agent, 3.7 parts by mass; curing 0.1 parts by mass of 2-phenylimidazole (2PZ made by Shikoku Kasei) as an accelerator; 65.0 parts by mass of fused silica particles (manufactured by Admatechs, SO-25R, average particle size 0.5 μm) as an inorganic filler, N -Methyl pyrrolidone was added so as to have a solid content of 65% by mass and mixed to prepare a resin varnish (500 grams) made of an epoxy resin composition. Example 1 The resin varnish was prepared in the same manner as to give a prepreg, a resin sheet, a laminated board, printed wiring board, and a semiconductor device.

Example 6
16.9 parts by mass of a naphthylene ether type epoxy compound (manufactured by DIC, HP-6000) and 4,4′-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry, 49.5 curing agent equivalent) A resin varnish was prepared in the same manner as in Example 5 except that the content was 3.1 parts by mass to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

Example 7
16.2 parts by mass of a naphthylene ether type epoxy compound (manufactured by DIC, HP-6000) and an aromatic diamine-based curing agent of 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku) A resin varnish was prepared in the same manner as in Example 5 except that Kayahard AA, curing agent equivalent 63.5) 3.8 parts by mass, and a prepreg, resin sheet, laminate, printed wiring board, and semiconductor device were prepared. Got.

Example 8
32 parts by mass of fused silica particles (manufactured by Admatechs, SO-25R, average particle size 0.5 μm) and 3 parts by mass of silica nanoparticles (manufactured by Tokuyama Corporation, NSS-5N, average particle size 70 nm) and silicone A resin varnish was prepared in the same manner as in Example 1 except that it was combined with 30 parts by mass of rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-600, average particle size 5 μm), and a prepreg, resin sheet, and laminate were prepared. A board, a printed wiring board, and a semiconductor device were obtained.

Example 9
10.4 parts by mass of a naphthylene ether type epoxy compound (manufactured by DIC, HP-6000), and 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane (K-I Kasei) as a bismaleimide compound Manufactured, BMI-80) 22.6 parts by mass and the aromatic diamine-based curing agent was changed to 1.9 parts by mass of 4,4′-diaminodiphenylmethane (manufactured by Tokyo Kasei Co., Ltd., curing agent equivalent 49.5). A resin varnish was prepared in the same manner as in Example 6 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

Example 10
19.7 parts by mass of a naphthylene ether type epoxy compound (manufactured by DIC, HP-6000) and 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane (Kay-Isei Chemical) as a bismaleimide compound Manufactured, BMI-80) 11.6 parts by mass and the aromatic diamine-based curing agent was changed to 3.6 parts by mass of 4,4′-diaminodiphenylmethane (Tokyo Kasei Co., Ltd., curing agent equivalent 49.5). A resin varnish was prepared in the same manner as in Example 6 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

Comparative Example 1
Instead of the naphthylene ether type epoxy compound (DIC, HP-6000), 1,1-bis (2,7-diglycidyloxy-1-naphthyl) methane (DIC, HP-4700, epoxy equivalent 165) is used. The resin varnish was used in the same manner as in Example 1 except that the content was 12.5 parts by mass and the phenolic novolak resin (DIC, TD-2090, hydroxyl group equivalent 105) was 7.5 parts by mass as the phenol resin-based curing agent. The prepared prepreg, resin sheet, laminate, printed wiring board, and semiconductor device were obtained.

Comparative Example 2
Instead of the naphthylene ether type epoxy compound (DIC, HP-6000), 1,6-diglycidyloxynaphthalene (DIC, HP-4032, epoxy equivalent 140) is 11.4 parts by mass, and a phenol resin type A resin varnish was prepared in the same manner as in Example 1 except that 8.6 parts by mass of a phenol novolak resin (manufactured by DIC, TD-2090, hydroxyl group equivalent 105) was used as a curing agent, and a prepreg, a resin sheet, a laminate, a printed wiring A plate and a semiconductor device were obtained.

Comparative Example 3
14.7 parts by mass of 1,1-bis (2,7-diglycidyloxy-1-naphthyl) methane (manufactured by DIC, HP-4700) instead of naphthylene ether type epoxy compound (manufactured by DIC, HP-6000) And 4,5′-diaminodiphenylsulfone (Mitsui Chemicals Fine, 4,4′-DAS, curing agent equivalent 62) as an aromatic diamine-based curing agent was used in an amount of 5.3 parts by weight. A resin varnish was prepared in the same manner as described above to obtain a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device.

Comparative Example 4
12.5 mass of 1,1-bis (2,7-diglycidyloxy-1-naphthyl) methane (manufactured by DIC, HP-4700) instead of naphthylene ether type epoxy compound (manufactured by DIC, HP-6000) The resin varnish was prepared in the same manner as in Example 2 except that 7.5 parts by mass of phenol novolac resin (manufactured by DIC, TD-2090, hydroxyl group equivalent 105) was used as the phenol resin-based curing agent. Sheets, laminates, printed wiring boards, and semiconductor devices were obtained.

Comparative Example 5
Without using a bismaleimide compound, 25.2 parts by mass of a naphthylene ether type epoxy compound (manufactured by DIC, HP-6000) and a phenol novolac resin (manufactured by DIC, TD-2090, hydroxyl equivalent of 105) as a phenol resin-based curing agent. ) A resin varnish was prepared in the same manner as in Example 1 except that the amount was 9.7 parts by mass to obtain a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device.

Comparative Example 6
Without using a bismaleimide compound, 28.4 parts by mass of a naphthylene ether type epoxy compound (manufactured by DIC, HP-6000) and 4,4′-diaminodiphenylsulfone (Mitsui Chemical Fine) as an aromatic diamine-based curing agent Resin varnish was prepared in the same manner as in Example 5 except that it was made except for 4,4'-DAS, curing agent equivalent 62) 6.5 parts by mass, and a prepreg, resin sheet, laminate, print A wiring board and a semiconductor device were obtained.

Comparative Example 7
9.5 parts by mass of 1,1-bis (2,7-diglycidyloxy-1-naphthyl) methane (manufactured by DIC, HP-4700) instead of naphthylene ether type epoxy compound (manufactured by DIC, HP-6000) As a bismaleimide compound, 22.6 parts by mass of 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Kay Chemical Co., Ltd., BMI-80) and an aromatic diamine-based curing agent A resin varnish was prepared in the same manner as in Example 6 except that 2.8 parts by mass of 4,4′-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd., curing agent equivalent 49.5) was prepared, and a prepreg, a resin sheet, a laminate, A printed wiring board and a semiconductor device were obtained.

  The following evaluation was performed about the resin varnish and laminated board which were obtained by each Example and the comparative example. Each evaluation is shown below together with the evaluation method. The obtained results are shown in Tables 1 and 2.

[Evaluation method]
(1) Glass transition temperature of resin composition after curing Two resin sheets having a thickness of 40 μm obtained in the above examples and comparative examples are stacked and pressed at 220 ° C. for 180 minutes to obtain a resin plate with copper foil. It was. The entire surface of the resin sheet with copper foil is etched to prepare a 6 mm × 25 mm test piece, and the temperature is raised at 5 ° C./min using a DMA device (Dynamic Viscoelasticity Measuring Device DMA983 manufactured by TA Instruments). The peak position of tan δ was defined as the glass transition temperature (° C.).

(2) Linear expansion coefficient of resin composition after curing Two resin sheets with a thickness of 40 μm obtained in the above examples and comparative examples were stacked and pressed at 220 ° C. for 180 minutes to obtain a resin plate with copper foil. It was. The entire surface of this resin sheet with copper foil is etched to prepare a test piece of 5 mm × 20 mm, and a glass in the thickness direction (Z direction) is used under the condition of 5 ° C./min using a TMA apparatus (manufactured by TA Instruments). The linear expansion coefficient in the region below the transition temperature was measured.

(3) Elastic modulus at 25 ° C. (Young's modulus) of the cured resin composition
Two resin sheets with a thickness of 40 μm obtained in the above Examples and Comparative Examples were stacked and pressed at 220 ° C. for 180 minutes to obtain a resin plate with copper foil. The entire surface of the resin sheet with copper foil is etched to prepare a 6 mm × 25 mm test piece, and the temperature is raised at 5 ° C./min using a DMA device (Dynamic Viscoelasticity Measuring Device DMA983 manufactured by TA Instruments). The tensile elastic modulus at 25 ° C. was measured.

(4) Solder heat resistance of laminated plate After the laminated plates obtained in the above examples and comparative examples were cut into 50 mm x 50 mm with a grinder saw, a sample was prepared by leaving only 1/4 of the copper foil by etching. Evaluation was performed according to C 6481. The evaluation was performed by performing PCT moisture absorption treatment at 121 ° C., 100% for 2 hours, and then immersing in a solder bath at 288 ° C. for 30 seconds, and then checking for an appearance abnormality.

(5) Coefficient of linear expansion of laminated plate The double-sided copper-clad laminate of 0.4 mm thickness obtained in the above examples and comparative examples was etched entirely, and a test piece of 5 mm × 20 mm was prepared from the obtained laminate. The linear expansion coefficient in the plane direction (X direction) was measured using a TMA apparatus (manufactured by TA Instruments) at 5 ° C./min.

(6) Warpage of printed wiring board in semiconductor device After leaving the semiconductor devices obtained in the examples and comparative examples in an atmosphere of temperature 30 ° C. and humidity 70% for 196 hours, and performing 260 ° C. reflow three times. The warpage of the printed wiring board in the semiconductor device was evaluated. The reflow conditions are preheating (160 to 200 ° C., raising temperature in 50 to 60 seconds), heating (200 to 260 ° C., raising temperature in 65 to 75 seconds), reflow (260 to 262 ° C., 5 to 10 seconds) and cooling. (262-30 degreeC, 15 minutes) was made into 1 cycle. Using a temperature variable laser three-dimensional measuring machine (manufactured by Hitachi Technology & Service, model LS220-MT100MT50), the semiconductor device surface of the semiconductor device obtained above is placed in the sample chamber of the measuring machine, and multilayer printing is performed. The displacement in the height direction of the wiring board was measured, and the largest value of the displacement difference was taken as the warpage amount. Regarding the warpage amount, if it exceeds 150 μm, there is a high possibility of causing a connection failure when the mother board is mounted.

[Evaluation results]
As is apparent from Table 1, Examples 1 to 10 are the epoxy resin composition according to the present invention, and a laminated board, printed wiring board and semiconductor device using the same, and a high glass transition temperature after curing and low. As a synergistic effect of the linear expansion coefficient and the elastic modulus, it can be seen that the warpage of the printed wiring board in the semiconductor device is suppressed. In all the examples, there was no problem in solder heat resistance. On the other hand, as is clear from Table 2, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) methane was used without using a naphthylene ether type epoxy compound (manufactured by DIC, HP-6000). Comparative Examples 1, 3, and 4 increase the glass transition temperature of the cured resin composition, but also increase the linear expansion coefficient and elastic modulus of the cured resin composition, and the linear expansion coefficient of the laminate, As a whole, the warpage of the printed wiring board in the semiconductor device was significantly increased. In Comparative Example 7 using 1,1-bis (2,7-diglycidyloxy-1-naphthyl) methane and using a large amount of bismaleimide, the warp of the printed wiring board in the semiconductor device was good. However, the heat resistance of the laminated board deteriorated. On the other hand, Comparative Example 2 using 1,6-diglycidyloxynaphthalene as an epoxy compound is the same as in Examples 1 to 4 regarding the linear expansion coefficient and elastic modulus of the cured resin composition, and the linear expansion coefficient of the laminate. Although it is equivalent to 10, the glass transition temperature was low, and the warpage of the substrate as a whole could not be suppressed. Further, in Comparative Examples 5 and 6 in which no bismaleimide compound was used, the linear expansion coefficient of the cured resin composition and the linear expansion coefficient of the laminated plate were not lowered, and it was not possible to suppress the warpage of the substrate as a whole. .
Hereinafter, examples of the reference form will be added.
[1] An epoxy resin composition comprising a naphthylene ether type epoxy compound represented by the following general formula (1), a bismaleimide compound, and an inorganic filler.
(In the formula, n is an integer of 1 to 20. Each R is independently a hydrogen atom, a benzyl group, an alkyl group, or the following formula (2).)
(In the formula, Ar is each independently a phenylene group or a naphthylene group, and m is an integer of 1 or 2.)
[2] The epoxy resin composition according to item [1], wherein the epoxy resin composition after thermosetting has a glass transition temperature (Tg) of 160 ° C. or higher.
[3] The epoxy resin composition according to item [1] or [2], wherein a linear expansion coefficient at less than a glass transition temperature (Tg) of the epoxy resin composition after thermosetting is less than 40 ppm / ° C.
[4] The epoxy according to any one of items [1] to [3], wherein the epoxy resin composition after thermosetting has an elastic modulus (Young's modulus) at 25 ° C. of 1 to 10 GPa. Resin composition.
[5] The epoxy resin composition according to any one of [1] to [4], wherein the inorganic filler includes silica nanoparticles having an average particle diameter of 10 nm to 150 nm.
[6] The epoxy resin composition according to any one of [1] to [5], wherein the inorganic filler contains silicone rubber fine particles having an average particle diameter of 1 μm to 10 μm.
[7] A prepreg obtained by impregnating a base material with the epoxy resin composition according to any one of items [1] to [6].
[8] A laminate comprising a metal layer disposed on at least one surface of the prepreg according to item [7].
[9] A laminate comprising a metal layer disposed on at least one surface of a prepreg laminate in which two or more prepregs according to the item [7] are laminated.
[10] A resin sheet obtained by disposing the epoxy resin composition according to any one of items [1] to [6] on a support film or a metal foil.
[11] A printed wiring board formed from the prepreg according to item [7], the laminate according to item [8] or [9], or the resin sheet according to item [10].
[12] A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to the item [11].

The epoxy resin composition of the present invention can be used as a prepreg by impregnating a substrate such as a glass fiber substrate, and further as a laminate using the prepreg. Moreover, since the hardened | cured material of the epoxy resin composition of this invention has the outstanding insulation, it can be used suitably for the insulating layer of a printed wiring board, for example. Furthermore, the cured product of the epoxy resin composition of the present invention has a low linear expansion and is excellent in heat resistance and adhesion to a conductor circuit, and therefore can be used as an interposer of a semiconductor device. As a printed wiring board of a semiconductor device, a mother board and an interposer are known. The interposer is a printed wiring board similar to the mother board, but is interposed between the semiconductor element (bare chip) or the printed wiring board and the mother board and mounted on the mother board. The interposer may be used as a substrate on which a printed wiring board is mounted in the same manner as a mother board. However, the interposer is used as a package substrate or a module substrate as a specific usage method different from the mother board. The package substrate means that an interposer is used as a printed wiring board substrate. In the printed wiring board, a semiconductor element is mounted on a lead frame, both are connected by wire bonding and sealed with resin, and an interposer is used as a package substrate, and a semiconductor element is mounted on the interposer. Are connected by a method such as wire bonding and sealed with resin.

Claims (14)

An epoxy resin composition comprising a naphthylene ether type epoxy compound represented by the following general formula (1), a bismaleimide compound, and an inorganic filler ,
An epoxy resin composition having a Young's modulus at 25 ° C. of 1 to 10 GPa of the epoxy resin composition after thermosetting.
(In the formula, n is an integer of 1 to 20. Each R is independently a hydrogen atom, a benzyl group, an alkyl group, or the following formula (2).)
(In the formula, Ar is each independently a phenylene group or a naphthylene group, and m is an integer of 1 or 2.) The epoxy resin composition according to claim 1, wherein the epoxy resin composition after thermosetting has a glass transition temperature (Tg) of 160 ° C or higher and 213 ° C or lower .   The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin composition after thermosetting has a linear expansion coefficient of less than 40 ppm / ° C at a glass transition temperature (Tg) of less than 40 ppm / ° C. The epoxy resin composition according to any one of claims 1 to 3 , wherein the inorganic filler includes silica nanoparticles having an average particle diameter of 10 nm to 150 nm. The epoxy resin composition according to any one of claims 1 to 4 , wherein the inorganic filler contains silicone rubber fine particles having an average particle diameter of 1 µm to 10 µm. The content of the bismaleimide compound in the epoxy resin composition is 35% to 55% by mass in the composition excluding the inorganic filler from the entire epoxy resin composition. The epoxy resin composition according to item. The content of the naphthylene ether type epoxy compound in the epoxy resin composition is in the range of 30 to 55 mass% with respect to the composition obtained by removing the inorganic filler from the entire epoxy resin composition. The epoxy resin composition according to any one of 1 to 6. The epoxy resin composition according to any one of claims 1 to 7, wherein the content of the inorganic filler is in the range of 30 to 75 mass% with respect to the total amount of the epoxy resin composition excluding the solvent. A prepreg obtained by impregnating a base material with the epoxy resin composition according to any one of claims 1 to 8 . A laminate comprising a metal layer disposed on at least one surface of the prepreg according to claim 9 . A laminate comprising a metal layer disposed on at least one surface of a prepreg laminate in which two or more prepregs according to claim 9 are laminated. The resin sheet formed by arrange | positioning the epoxy resin composition of any one of Claims 1-8 on a support film or metal foil. The prepreg according to claim 9, the laminate according to claim 10 or 11, or claim 1 second printed circuit board formed from a resin sheet according to. Semiconductor device comprising a semiconductor element mounted on a printed wiring board according to claim 1 3.