JP6186977B2 - Resin composition, resin sheet, prepreg, laminate, printed wiring board, and semiconductor device - Google Patents

Description

  The present invention relates to a resin composition, a resin sheet, a prepreg, a laminated board, a printed wiring board, and a semiconductor device.

  In recent years, with the demand for higher functionality of electronic devices, etc., high-density integration of electronic components, and further high-density mounting, etc. are progressing. Compared to the conventional technology, miniaturization and high density are progressing. As a countermeasure for increasing the density of this printed wiring board, a multilayer printed wiring board by a build-up method is often employed (for example, see Patent Document 1).

  In a multilayer printed wiring board by a build-up method, a thermosetting resin composition is usually used as an insulating layer. However, considering reliability and the like, the insulating layer has a low coefficient of thermal expansion and a high glass transition temperature. It is required to use a resin composition (for example, refer to Patent Document 2).

However, although the coefficient of thermal expansion can be lowered and the glass transition temperature can be raised by selecting an appropriate resin or increasing the inorganic filler, the width of the conductor circuit formed on the printed wiring board or between the conductor circuits A multilayer printed wiring board that requires the formation of a fine wiring circuit that further narrows the width cannot be accommodated.
The reason for this is that when the conductor circuit width becomes narrow, especially when the size is called a fine wiring circuit, the contact area between the conductor circuit and the insulating layer becomes small, and the adhesion of the conductor circuit to the insulating layer becomes worse. This is because peeling of a so-called conductor peel called a plating peel occurs.
By forming a fine roughened shape on the surface of the insulating layer formed by the resin composition and forming a fine wiring circuit on the insulating layer having such a fine roughened shape, the adhesion of the fine wiring circuit is improved. It is possible to increase. However, in order to sufficiently increase the adhesion of the fine wiring circuit, it is necessary to increase the roughness of the surface of the insulating layer. If the roughness of the surface of the insulating layer is too large, it becomes difficult to form the pattern accurately because the focus of exposure is lost when forming the pattern of the conductor circuit on the surface of the insulating layer by a photo process.
Therefore, there is a limit to a method for increasing the plating peel strength between the conductor circuit and the insulating layer by forming a fine roughened shape.

  A resin composition using a polyimide resin and an adhesion assistant (see, for example, Patent Document 3) containing a rubber particle as an adhesion layer on the surface of the insulating layer to form a fine roughened shape and sufficiently obtain a plating peel strength. (See, for example, Patent Document 4), but there is no insulating surface layer having a fine roughened shape and sufficient plating peel strength.

Japanese Patent Application Laid-Open No. 07-106767 JP 2006-191150 A JP 2006-159900 A JP 2006-196863 A

  The present invention relates to a resin composition used for an insulating layer of a multilayer printed wiring board by a build-up method, and a resin composition having an excellent balance of thermal expansion coefficient, glass transition temperature, plating peel strength, and the resin A prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device using the composition are provided.

（前記一般式（１）式において、ｎは１以上２０以下の整数であり、ｌは１または２の整数であり、Ｒ_１はそれぞれ独立に水素原子、ベンジル基、アルキル基または下記一般式（２）で表される構造であり、Ｒ_２はそれぞれ独立に水素原子またはメチル基である。）

（前記一般式（２）式において、Ａｒはそれぞれ独立にフェニレン基またはナフチレン基であり、Ｒ_２はそれぞれ独立に水素原子またはメチル基であり、ｍは１又は２の整数である。）
［２］前記（Ｃ）水酸基を少なくとも１つ含有する芳香族ポリアミド樹脂の含有量は、樹脂組成物の全固形分に対して５重量％以上１５重量％以下である［１］に記載の樹脂組成物。
［３］前記（Ｂ）シアネートエステル樹脂は、ノボラック型シアネートエステル樹脂である［１］または［２］に記載の樹脂組成物。
［４］前記（Ｄ）無機充填剤は、水酸化マグネシウム、水酸化アルミニウム、シリカ、溶融シリカ、タルク、焼成タルク、及びアルミナよりなる群から選ばれる少なくとも１種類以上である［１］ないし［３］のいずれか一項に記載の樹脂組成物。
［５］前記（Ｄ）無機充填剤の平均粒子径は、５．０μｍ以下である［１］ないし［４］のいずれか一項に記載の樹脂組成物。
［６］前記（Ｄ）無機充填剤が平均粒子径１０ｎｍ〜１５０ｎｍのシリカナノ粒子を含む［１］ないし［５］のいずれか一項に記載の樹脂組成物。
［７］［１］ないし［６］のいずれか一項に記載の樹脂組成物を基材に含浸させてなるプリプレグ。
［８］［７］に記載のプリプレグの少なくとも片面上に金属層を配置してなる積層板。
［９］［１］ないし［６］のいずれか一項に記載の樹脂組成物を支持フィルム又は金属箔上に配置してなる樹脂シート。
［１０］［７］に記載のプリプレグ、［８］に記載の積層板、［９］に記載の樹脂シートから形成されたプリント配線板。
［１１］［１０］に記載のプリント配線板に半導体素子を搭載してなる半導体装置。 Such an object is achieved by the following present invention [1] to [11].
[1] (A) A naphthylene ether type epoxy resin represented by the following general formula (1), (B) a cyanate ester resin, (C) an aromatic polyamide resin containing at least one hydroxyl group, and (D) inorganic A resin composition comprising a filler as an essential component.

(In the general formula (1), n is an integer of 1 or more and 20 or less, l is an integer of 1 or 2, and R ₁ is independently a hydrogen atom, a benzyl group, an alkyl group, or the following general formula ( 2), and each R ₂ is independently a hydrogen atom or a methyl group.)

(In the general formula (2), Ar is each independently a phenylene group or a naphthylene group, R ₂ is each independently a hydrogen atom or a methyl group, and m is an integer of 1 or 2.)
[2] The resin according to [1], wherein the content of the aromatic polyamide resin (C) containing at least one hydroxyl group is 5% by weight to 15% by weight with respect to the total solid content of the resin composition. Composition.
[3] The resin composition according to [1] or [2], wherein the (B) cyanate ester resin is a novolak type cyanate ester resin.
[4] The inorganic filler (D) is at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide, silica, fused silica, talc, calcined talc, and alumina [1] to [3 ] The resin composition as described in any one of.
[5] The resin composition according to any one of [1] to [4], wherein the average particle diameter of the (D) inorganic filler is 5.0 μm or less.
[6] The resin composition according to any one of [1] to [5], wherein the (D) inorganic filler includes silica nanoparticles having an average particle diameter of 10 nm to 150 nm.
[7] A prepreg obtained by impregnating a base material with the resin composition according to any one of [1] to [6].
[8] A laminate comprising a metal layer disposed on at least one surface of the prepreg according to [7].
[9] A resin sheet obtained by disposing the resin composition according to any one of [1] to [6] on a support film or a metal foil.
[10] A printed wiring board formed from the prepreg according to [7], the laminate according to [8], and the resin sheet according to [9].
[11] A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to [10].

  Since the resin composition of the present invention has a low coefficient of thermal expansion and a high glass transition temperature, when used for an insulating layer of a multilayer printed wiring board by a build-up method, an insulating layer with less stress is formed, and the surface of the insulating layer A fine roughened shape is formed. The conductor circuit and the insulating layer are bonded with a sufficient plating peel strength. Furthermore, a prepreg, a resin sheet, a laminate, a multilayer printed wiring board, and a semiconductor device using the resin composition are excellent in reliability.

It is sectional drawing which shows an example of a structure of the prepreg in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor package in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor device in this embodiment.

  Hereinafter, the resin composition, prepreg, laminate, resin sheet, printed wiring board, and semiconductor device of the present invention will be described.

  First, the resin composition of the present invention will be described.

(Resin composition)
The resin composition used in the present invention includes (A) a naphthylene ether type epoxy resin represented by the following general formula (1), (B) a cyanate ester resin, and (C) an aromatic polyamide resin containing at least one hydroxyl group. And (D) an inorganic filler as an essential component. As a result, a resin composition having a small thermal expansion coefficient and high heat resistance can be obtained, and when the insulating layer is formed, a fine roughened shape can be formed on the surface of the insulating layer. High adhesion (plating peel strength) can be obtained. Further, when used in a multilayer printed wiring board, warpage of the multilayer printed wiring board can be suppressed.

  The epoxy resin composition according to the present invention contains a naphthylene ether type epoxy resin represented by the following general formula (1).

（式中、ｎは１以上２０以下の整数であり、１以上１０以下の整数がより好ましい。ｌは１または２の整数であり、Ｒ_１はそれぞれ独立に水素原子、ベンジル基、アルキル基または下記一般式式（２）で表される構造であり、Ｒ_２はそれぞれ独立に水素原子またはメチル基である。）

(In the formula, n is an integer of 1 or more and 20 or less, more preferably an integer of 1 or more and 10 or less. L is an integer of 1 or 2, and R ₁ is independently a hydrogen atom, a benzyl group, an alkyl group or (It is a structure represented by the following general formula (2), and each R ₂ is independently a hydrogen atom or a methyl group.)

（前記一般式（２）式において、Ａｒはそれぞれ独立にフェニレン基またはナフチレン基であり、Ｒ_２はそれぞれ独立に水素原子またはメチル基であり、ｍは１又は２の整数である。）

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

  Since the naphthylene ether type epoxy resin 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, and the epoxy resin composition using this The coefficient of thermal expansion after curing of the product is reduced. In addition, since the epoxy resin represented by the general formula (1) has only one epoxy group bonded to each naphthalene ring, the distance between the epoxy groups is long, and the epoxy resin composition using the epoxy resin has a long distance. 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. In addition, the naphthylene ether type epoxy resin represented by the general formula (1) has appropriate flexibility because the naphthalene structures are connected by oxygen atoms, and at the time of molding an epoxy resin composition using the naphthylene ether type epoxy resin. Warping of the cured product is reduced.

  The naphthylene ether type epoxy resin 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 resin represented by the general formula (1) include those represented by the following general formula (3).

（上記一般式（３）式において、ｎは１以上２０以下の整数であり、好ましくは１以上１０以下の整数であり、より好ましくは１以上３以下の整数である。Ｒはそれぞれ独立に水素原子または下記一般式（４）で表される構造であり、好ましくは水素原子である。）

(In the above general formula (3), n is an integer of 1 or more and 20 or less, preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 3 or less. R is independently hydrogen. (Atom or a structure represented by the following general formula (4), preferably a hydrogen atom)

（上記一般式（４）式において、ｍは１又は２の整数である。）

(In the above general formula (4), m is an integer of 1 or 2.)

  Examples of the naphthylene ether type epoxy resin represented by the general formula (3) include those represented by the following general formulas (5) to (9).

  The content of the naphthylene ether type epoxy resin represented by the general formula (1) is not particularly limited, but when the total solid content of the resin composition (that is, the component excluding the solvent) is 100% by mass, 5 The mass% is preferably 25% by mass or less, and more preferably 10% by mass or more and 20% by mass or less. By making content of a naphthylene ether type epoxy resin more than the said lower limit, the fall of the moisture resistance of the product obtained can be prevented. Moreover, the heat resistance fall can be prevented by setting it as the said upper limit or less.

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

  The (B) cyanate ester resin can impart to the resin composition a low thermal expansion coefficient and heat resistance that cannot be achieved by the epoxy resin alone. When (B) cyanate ester resin is not included, the coefficient of thermal expansion is high and the glass transition temperature is low, which is not preferable.

  Although the said cyanate ester resin is not specifically limited, For example, it can obtain by making a halogenated cyanide compound, phenols, and naphthol react, and prepolymerizing by methods, such as a heating, as needed. Moreover, the commercial item prepared in this way can also be used.

  Examples of the cyanate ester resins include novolak type cyanate ester resins, bisphenol A type cyanate ester resins, bisphenol E type cyanate ester resins, tetramethylbisphenol F type cyanate ester resins, and the like; naphthol aralkyl type phenol resins, Examples thereof include naphthol aralkyl type cyanate ester resin obtained by reaction with cyanogen halide; dicyclopentadiene type cyanate ester resin; biphenylalkyl type cyanate ester resin. Among these, novolak type cyanate ester resins and naphthol aralkyl type cyanate ester resins are preferable, and novolak type cyanate ester resins are more preferable. By using the novolac type cyanate ester resin, the crosslink density of the obtained insulating layer is increased, and the heat resistance is improved.

The reason for this is that the novolak cyanate ester resin forms a triazine ring after the curing reaction. Furthermore, it is considered that novolak-type cyanate ester resin has a high benzene ring ratio due to its structure and is easily carbonized. Moreover, the insulating layer containing a novolac-type cyanate ester resin has excellent rigidity. Therefore, the heat resistance of the insulating layer can be further improved.
As the novolac-type cyanate ester resin, for example, those represented by the following general formula (I) can be used.

  The average repeating unit n of the novolak-type cyanate ester resin represented by the general formula (I) is an arbitrary integer. The average repeating unit n is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. When the average repeating unit n is not less than the above lower limit, the heat resistance of the novolak-type cyanate ester resin is improved, and it is possible to suppress desorption and volatilization of the low-mer during heating. The average repeating unit n is not particularly limited, but is preferably 10 or less, more preferably 7 or less. It can suppress that melt viscosity becomes it high that n is below the said upper limit, and can improve the moldability of a prepreg.

  As the cyanate ester resin, a naphthol aralkyl type cyanate ester resin represented by the following general formula (II) is also preferably used. The naphthol aralkyl type cyanate ester resin represented by the following general formula (II) includes, for example, naphthols such as α-naphthol or β-naphthol, p-xylylene glycol, α, α′-dimethoxy-p-xylene, 1, It is obtained by condensing a naphthol aralkyl type phenolic resin obtained by reaction with 4-di (2-hydroxy-2-propyl) benzene or the like and cyanogen halide. The repeating unit n of the general formula (II) is preferably an integer of 10 or less. When the repeating unit n is 10 or less, a more uniform insulating layer can be obtained. In addition, intramolecular polymerization hardly occurs at the time of synthesis, the liquid separation property at the time of washing with water tends to be improved, and the decrease in yield tends to be prevented.

（式中、Ｒは水素原子またはメチル基を示し、ｎは１以上１０以下の整数を示す。）

(In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 10.)

Although the weight average molecular weight (Mw) of cyanate ester resin is not specifically limited, Mw500 or more is preferable and Mw600 or more is more preferable. When Mw is equal to or more than the above lower limit, it is possible to suppress the occurrence of tackiness when producing prepregs, and to prevent the prepregs from adhering to each other or the transfer of the prepregs. Mw is not particularly limited, but is preferably Mw 4,500 or less, and more preferably Mw 3,000 or less. When Mw is not more than the above upper limit, it is possible to suppress the cyclization reaction of the cyanate ester resin from being accelerated, and it is possible to suppress the occurrence of defects in the insulating layer and the decrease in peel strength between the insulating layer and the metal layer. can do.
The Mw of the cyanate ester resin can be measured by, for example, GPC (gel permeation chromatography, standard substance: converted to polystyrene).

  Moreover, cyanate ester resin may be used individually by 1 type, may use together 2 or more types which have different Mw, and may use 1 type or 2 types and those prepolymers together. .

  The content of the cyanate ester resin is not particularly limited, but when the total solid content of the resin composition (that is, the component excluding the solvent) is 100% by mass, 7% by mass to 27% by mass is preferable, and 12% by mass. More preferred is 22% by mass or less.

(C) The aromatic polyamide resin containing at least one hydroxyl group is not particularly limited. By including an aromatic amide structure in the resin skeleton, high adhesion to the conductor circuit can be obtained. Furthermore, by including a hydroxyl group, a crosslinked structure can be formed with the epoxy resin, and a cured product having excellent mechanical properties can be obtained.
In addition, it preferably has a segment in which at least four carbon chains having a diene skeleton are connected, and includes a diene skeleton that is easy to be roughened. A modified shape can be formed.

  Examples of the aromatic polyamide resin having at least one hydroxyl group include those represented by the following formula (11).

（上記一般式（１１）において、ｍ、ｎは繰り返し単位数を表し、５０以上５，０００以下の整数である。Ａｒ_１、Ａｒ_２は２価の芳香族基を示し、それぞれ同じでも異なっていてもよい。Ｘは、ジエン骨格を有する少なくとも４つ以上の炭素鎖が繋がったセグメントを有する基であり、たとえば１，３−ブタジエンの重合体、イソプレンの重合体を示す。）

(In the above general formula (11), m and n represent the number of repeating units and are integers of 50 or more and 5,000 or less. Ar ₁ and Ar ₂ represent a divalent aromatic group, and are the same or different. X is a group having a segment in which at least four carbon chains having a diene skeleton are connected, and examples thereof include a polymer of 1,3-butadiene and a polymer of isoprene.)

(C) The weight average molecular weight (Mw) of the aromatic polyamide resin containing at least one hydroxyl group is preferably 2.0 × 10 ⁵ or less. Thereby, adhesiveness with a conductor circuit can be obtained. When the weight average molecular weight (Mw) is higher than 2.0 × 10 ⁵ , the fluidity of the prepreg or the resin sheet may be lowered when the prepreg or the resin sheet is produced from the resin composition. It may become impossible to embed or the solvent solubility may deteriorate.

  (C) The content of the aromatic polyamide resin containing at least one hydroxyl group is not particularly limited. When the total solid content (that is, the portion excluding the solvent) of the resin composition is 100% by mass, 5% by mass to 15% by mass is preferable, and 6% by mass to 12% by mass is more preferable. When the content is not less than the lower limit, a sufficient peel strength can be maintained. Moreover, by setting it as the said upper limit or less, a heat resistant fall can be prevented and it can prevent that a thermal expansion coefficient becomes large.

  (D) The inorganic filler is not particularly limited. For example, talc, fired talc, fired clay, unfired clay, mica, silicates such as glass, oxides such as titanium oxide, alumina, silica, and fused silica, Carbonates such as calcium carbonate, magnesium carbonate and hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, zinc borate , Borate salts such as barium metaborate, aluminum borate, calcium borate and sodium borate, nitrides such as aluminum nitride, boron nitride, silicon nitride and carbon nitride, titanates such as strontium titanate and barium titanate Etc. As the inorganic filler, one of these can be used alone, or two or more can be used in combination. Among these, magnesium hydroxide, aluminum hydroxide, silica, fused silica, talc, calcined talc, and alumina are preferable, and fused silica is particularly preferable in terms of excellent low thermal expansion.

  (D) Content of an inorganic filler is not specifically limited. When the total solid content of the resin composition (that is, the component excluding the solvent) is 100% by mass, it is preferably 30% by mass or more and 70% by mass or less, and more preferably 35% by mass or more and 65% by mass or less. (D) By making content of an inorganic filler more than the said lower limit, a coefficient of thermal expansion becomes low enough, and the adhesiveness with respect to a conductor circuit becomes sufficient by making it below the said upper limit. .

  (D) Although the shape of an inorganic filler has crushed shape, spherical shape, etc., it can be selected according to a use. For example, when impregnating a substrate such as glass fiber during prepreg production, it is necessary to lower the melt viscosity of the resin composition in order to ensure impregnation, and it is preferable to use a spherical one. A shape can be selected according to the use and purpose of using the resin composition.

  (D) The particle size of the inorganic filler is not particularly limited. The particle size can be selected according to the use and purpose of using the resin composition. Preferably, the average particle size is 5.0 μm or less, more preferably 1.0 μm or less. When the average particle size is 5.0 μm or less, the roughness of the insulating layer is sufficiently small in the desmear treatment step when a multilayer printed wiring board is produced using a resin sheet or prepreg produced from the resin composition. Thus, the surface of the insulating layer can be formed smoothly. In addition, an average particle diameter can be calculated | required by measuring an average particle diameter with a particle size distribution analyzer (Shimadzu make, SALD-7000), for example.

  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.

  The resin composition of this invention can use a hardening | curing agent and / or a hardening catalyst as needed. Although it does not specifically limit as a hardening | curing agent, For example, a phenol novolak resin, a biphenyl aralkyl type phenol resin, an alkylphenol novolak resin, a naphthol type phenol resin having a naphthalene skeleton, a bisphenol A type novolak resin, a dicyclopentadiene type phenol resin, a zylock type Known and commonly used curing agents such as phenol resins, terpene-modified phenol resins, and polyvinylphenols can be used alone or in combination of two or more.

  Although content of the said hardening | curing agent is not specifically limited, (A) Equivalent ratio (phenolic hydroxyl group equivalent / epoxy group equivalent) with an epoxy resin is less than 1.0 and 0.1 or more are preferable. As a result, there remains no unreacted phenolic curing agent, and the moisture absorption heat resistance is improved. Furthermore, when severe moisture absorption heat resistance is required, the range of 0.2 to 0.9 is particularly preferable. In addition, the phenolic curing agent not only acts as a curing agent, but can promote curing of a cyanate group and an epoxy group.

  Although the said curing catalyst is not specifically limited, For example, amine compounds, such as a phenolic compound, primary, secondary, or a tertiary amine, a dicyandiamide compound, an imidazole compound etc. can be used. Among these, an imidazole compound is particularly preferable because it has at least excellent curability and insulation reliability. Moreover, when an imidazole compound is used, a laminate having a high glass transition temperature and excellent moisture absorption heat resistance can be obtained.

  The imidazole compound is not particularly limited, and examples thereof include 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, Examples include 2-phenyl-4,5-dihydroxyimidazole and 2,3-dihydro-1H-pyrrolo (1,2-a) benzimidazole. Further, one type of curing catalyst or a plurality of two or more types may be used.

  The epoxy resin composition according to the present invention includes a flame retardant such as brominated epoxy resin, antimony trioxide, zinc borate, zinc molybdate, phosphazene, carnauba wax, etc., unless the intended purpose and effect of the present invention are impaired. Natural waxes, synthetic waxes such as polyethylene waxes, higher fatty acids such as stearic acid and zinc stearate and release agents such as metal salts or paraffins thereof; epoxy silanes, mercapto silanes, amino silanes, alkyl silanes, ureido silanes, vinyl silanes, etc. Silane coupling agents, titanate coupling agents, aluminum coupling agents, coupling agents such as aluminum / zirconium coupling agents; colorants such as carbon black and bengara; butadiene rubber, acrylonitrile modified butadiene rubber, silico It can be blended inorganic ion exchangers such as for ionic impurities reduced, various additives as appropriate; N'oiru, stress reduction components such as silicone rubber.

(Prepreg)
Next, the prepreg 100 according to the present invention will be described. FIG. 1 is a cross-sectional view showing an example of the configuration of the prepreg 100 in the present embodiment. The prepreg according to the present invention is obtained by impregnating the base material 101 with the resin composition. The base material is not particularly limited, but for example, glass fiber base materials such as glass fiber cloth and glass non-woven cloth, inorganic fiber base materials such as fiber cloth and non-fiber cloth containing inorganic compounds other than glass, aromatic Examples thereof include organic fiber base materials composed of organic fibers such as polyamide resin, polyamide resin, aromatic polyester resin, polyester resin, polyimide resin, and fluorine resin. From the viewpoints of strength and water absorption, glass fiber base materials such as glass fiber cloth and glass fiber cloth are preferable.

  Examples of the glass constituting the glass fiber substrate include one or more of E glass, C glass, A glass, S glass, D glass, NE glass, T glass, H glass, and the like. Among these, S glass or T glass is preferable. Thereby, the thermal expansion coefficient of a glass fiber base material can be made small, and, thereby, the thermal expansion coefficient of a prepreg can be made small.

  The method for impregnating the substrate with the resin composition is not particularly limited. For example, the method of immersing the substrate in the resin composition, the method of applying the resin composition to the substrate with various coaters, or spraying with a sprayer, etc. Is 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 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 concerning this invention is demonstrated. The laminate according to the present invention is a molded product including the prepreg 100. 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 equal to or more than the above lower limit value, the metal foil is not damaged, and when the metal foil is etched and used as a conductor circuit, the plating variation at the time of forming the circuit pattern, circuit disconnection, etching solution or desmear Infiltration of chemicals such as liquid does not occur. When the thickness of the metal foil is not more than the above upper limit value, the variation in the thickness of the metal foil and the variation in the surface roughness of the roughened surface of the metal foil are reduced, and the workability is excellent.

  The metal foil may be an ultrathin metal foil with a carrier foil. The ultrathin metal foil with carrier foil is a metal foil obtained by bonding 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. When the thickness of the ultra-thin metal foil is 0.1 μm or more, when the metal foil is etched and used as a conductor circuit without damaging the metal foil, plating variation, circuit disconnection, and etching solution when forming the circuit pattern No penetration of chemicals such as desmear liquid. When the thickness of the ultrathin metal foil is 10 μm or less, the variation in the thickness of the metal foil and the variation in the surface roughness of the roughened metal foil surface are reduced, and the workability is excellent. 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 concerning this invention is demonstrated. The resin sheet according to the present invention is obtained by arranging the resin composition on a support film or a metal foil. The said resin sheet is obtained by forming the insulating layer which consists of solid content of the said resin composition on a support film or metal foil. When forming a resin sheet, the solid content of the resin composition is preferably in the range of 45 to 85 mass%, more preferably in the range of 55 to 75 mass%. The 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 spray-coated on the support film or metal foil with a spray device. A resin sheet can be produced by drying after processing. 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 boards and semiconductor packages)
Next, the printed wiring board and the semiconductor package 200 according to the present invention will be described. The printed wiring board concerning this invention is formed from the said prepreg, the said laminated board, or the said resin sheet. The method for manufacturing the printed wiring board and the semiconductor package 200 according to the present invention is not particularly limited, and can be manufactured as follows, for example.

  A laminated board 213 having copper foil on both sides is prepared, a through hole is formed by a drill or the like, and after filling the through hole by plating, a predetermined conductor circuit (inner layer circuit) is formed on both sides of the laminated board by etching or the like. An inner layer circuit board is produced by forming and roughening the conductor circuit such as blackening treatment. When the 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.

  In the laminate of the present invention, a new conductive wiring circuit can be formed by metal plating after roughening the surface of the insulating layer with an oxidizing agent such as permanganate or dichromate.

  When the resin composition of the present invention is used, it is excellent in fine wiring processing as compared with the prior art, and a conductor width (line) when a conductor circuit is formed and a wiring with a very narrow space between conductors (space) should be 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. Thereafter, a solder resist 201 is formed on the outermost layer, the connection electrode part is exposed so that a semiconductor element can be mounted by exposure and development, nickel gold plating treatment is performed, and a predetermined size is obtained to obtain a multilayer printed wiring board be able to.

  Subsequently, by performing a reflow process, the semiconductor element 203 is fixed to the connection terminal 205 which is a part of the wiring pattern via the solder bump 207. Thereafter, the semiconductor package 203 as shown in FIG. 2 can be obtained by sealing the semiconductor element 203, the solder bump 207, and the like with the sealing material 211.

(Semiconductor device)
Next, the semiconductor device 300 in this embodiment will be described.
The semiconductor package 200 can be used in a semiconductor device 300 as shown in FIG. A method for manufacturing the semiconductor device 300 is not particularly limited, and examples thereof include the following methods.
First, the solder bump 301 is formed by supplying a solder paste to the opening 209 of the solder resist layer 201 of the obtained semiconductor package 200 and performing a reflow process. The solder bump 301 can also be formed by attaching a solder ball prepared in advance to the opening 209.

  Next, the semiconductor package 200 is mounted on the mounting substrate 303 by bonding the connection terminals 305 and the solder bumps 301 of the mounting substrate 303, and the semiconductor device 300 shown in FIG. 3 is obtained.

  When the 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.

  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 resin represented by general formula (3) (manufactured by DIC, HP-6000, epoxy equivalent 273, in general formula (3), each R is a hydrogen atom, (mixture of component where n = 1 and component where n = 2) 16.2 parts by mass; 14.3 parts by mass of phenol novolac-type cyanate ester resin (manufactured by LONZA, PT-30); containing at least one hydroxyl group 9.1 parts by mass of aromatic polyamide resin (Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent 4000); 0.2 parts by mass of 1-benzyl-2-phenylimidazole (1B2PZ, Shikoku Kasei Co., Ltd.) as a curing accelerator ; 0.2 parts by weight of an epoxy silane coupling agent (M187, manufactured by Momentive Performance Materials, Inc.) as a coupling agent; As a filler, fused silica particles (manufactured by Admatechs, SO-25R, average particle size 0.5 μm) 56.0 parts by mass, silica nanoparticles (manufactured by Tokuyama, NSS-5N, average particle size 70 nm) 4.0 parts by mass N-methylpyrrolidone was added and mixed so that the solid content was 65% by mass to prepare a resin varnish (500 grams) made of an epoxy resin composition.

[2] Manufacture of prepreg Using the resin varnish, the resin varnish is solid in 100 parts by weight of glass fabric (T glass, length 530 mm, width 530 mm, thickness 0.05 mm, manufactured by Nittobo Co., Ltd.). 80 parts by mass, impregnated by a varnish dip method, and dried in a drying furnace at 190 ° C. for 7 minutes to prepare a prepreg having a resin content of 44.4% by mass.

[3] Manufacture of resin sheet Copper foil (Mitsui Metal Mining Co., Ltd., Microcin Ex-3, Carrier foil layer: Copper foil) in which the above-mentioned resin varnish is bonded to a peelable carrier foil layer and an electrolytic copper foil layer. 18 [mu] m), and the electrolytic copper foil layer (3 [mu] m)) is coated with a comma coater so that the resin layer after drying is 40 [mu] m, and this is dried for 10 minutes with a 150 [deg.] C. drying apparatus. Thus, a resin sheet was manufactured.

[4] Manufacture of laminated plate On the front and back of the prepreg laminate in which the above four 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. Heat-press molding was carried out at a temperature of 220 ° C. for 180 minutes to obtain a double-sided copper-clad laminate having a thickness of 0.2 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. Furthermore, after forming circuits on both surfaces by etching, the surface electrolytic copper foil layer was subjected to blackening treatment 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, a φ60 μm via hole for interlayer connection was formed with 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
18.4 parts by mass of naphthylene ether type epoxy resin (manufactured by DIC, HP-6000), 16.1 parts by mass of phenol novolac type cyanate ester resin (manufactured by LONZA, PT-30); contains at least one hydroxyl group A resin varnish was prepared in the same manner as in Example 1 except that 5.2 parts by mass of an aromatic polyamide resin (manufactured by Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent 4000) was prepared, and a prepreg, a resin sheet, a laminate, A printed wiring board and a semiconductor device were obtained.

Example 3
13.2 parts by mass of a naphthylene ether type epoxy resin (manufactured by DIC, HP-6000), 11.6 parts by mass of a phenol novolac type cyanate ester resin (manufactured by LONZA, PT-30); containing at least one hydroxyl group A resin varnish was prepared in the same manner as in Example 1 except that aromatic polyamide resin (manufactured by Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent 4000) was 14.8 parts by mass, and a prepreg, resin sheet, laminate, A printed wiring board and a semiconductor device were obtained.

Example 4
19.5 parts by mass of naphthylene ether type epoxy resin (manufactured by DIC, HP-6000), 12.2 parts by mass of phenol novolac type cyanate ester resin (manufactured by LONZA, PT-30); contains at least one hydroxyl group A resin varnish was prepared in the same manner as in Example 1 except that 7.8 parts by mass of an aromatic polyamide resin (manufactured by Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent: 4000), and a prepreg, a resin sheet, a laminate, A printed wiring board and a semiconductor device were obtained.

Example 5
8.6 parts by mass of a naphthylene ether type epoxy resin (manufactured by DIC, HP-6000), 18.9 parts by mass of a phenol novolac type cyanate ester resin (manufactured by LONZA, PT-30); contains at least one hydroxyl group A resin varnish was prepared in the same manner as in Example 1 except that aromatic polyamide resin (manufactured by Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent 4000) 12.1 parts by mass was prepared, and a prepreg, resin sheet, laminate, A printed wiring board and a semiconductor device were obtained.

Example 6
13.0 parts by mass of naphthylene ether type epoxy resin (manufactured by DIC, HP-6000), 3.2 parts by mass of biphenylaralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000, epoxy equivalent 285); phenol novolac Type cyanate ester resin (manufactured by LONZA, PT-30) 14.3 parts by mass; aromatic polyamide resin containing at least one hydroxyl group (Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent 4000) 9.1 parts by mass Except that, a resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device.

(Synthesis example 1) Cyanate ester resin (naphthol aralkyl type cyanate ester resin)
A naphthol aralkyl type phenolic resin (manufactured by Nippon Steel Chemical Co., Ltd., SN485N, hydroxyl group equivalent: 215 g / eq) (101 g, 0.47 mol hydroxyl group) was charged in 400 g of methyl isobutyl ketone (hereinafter MIBK) and dissolved at room temperature with stirring. After dissolution, it was cooled to -10 ° C. At −10 ° C., 110 g of cyanogen bromide (hereinafter BrCN) was added (purity 95%, 0.987 mol), and when the internal temperature reached −15 ° C., 100 g (0.99 mol) of triethylamine (hereinafter TEA) and 600 g of MIBK The mixture was added dropwise over 1 hour. After dropping, the reaction was further aged for 30 minutes and further aged for about 2 hours to complete the reaction.
To the obtained solution, 400 ml of pure water was added for liquid separation, and further 1000 ml of 5% aqueous hydrogen chloride solution (HCl) was added for liquid separation. Furthermore, it was washed and separated twice with 500 g of 10% saline and washed twice with 500 ml of pure water.
The organic layer was dehydrated with anhydrous sodium sulfate, and then the solvent was removed under reduced pressure to obtain a solid resin. The obtained solid was washed with hexane and then dried under reduced pressure to obtain a naphthol aralkyl-type cyanate ester resin. The naphthol aralkyl-type cyanate ester resin thus obtained was analyzed by infrared absorption spectrum measurement (IR Prestige-21, KBr transmission method manufactured by Shimadzu Corporation), and 3200 to 3600 cm ⁻ which is an absorption band of a phenolic hydroxyl group. The peak of ¹ disappeared, and a peak around 2264 cm ^−1, which is an absorption band of nitrile cyanate ester, was confirmed.

Example 7
11.7 parts by mass of naphthylene ether type epoxy resin (manufactured by DIC, HP-6000); 21.3 parts by mass of naphthol aralkyl type cyanate ester resin obtained in Synthesis Example 1; aromatic containing at least one hydroxyl group A resin varnish was prepared in the same manner as in Example 1 except that 7.0 parts by mass of a polyamide resin (manufactured by Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent 4000) was prepared, and a prepreg, a resin sheet, a laminate, a printed wiring A plate and a semiconductor device were obtained.

Example 8
12.5 parts by mass of naphthylene ether type epoxy resin (manufactured by DIC, HP-6000); 20.1 parts by mass of bisphenol A type cyanate ester resin (manufactured by LONZA, BA230); aromatic containing at least one hydroxyl group A resin varnish was prepared in the same manner as in Example 1 except that 7.0 parts by mass of a polyamide resin (manufactured by Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent 4000) was prepared, and a prepreg, a resin sheet, a laminate, a printed wiring A plate and a semiconductor device were obtained.

Example 9
12.1 parts by mass of naphthylene ether type epoxy resin (manufactured by DIC, HP-6000), 10.7 parts by mass of phenol novolac type cyanate ester resin (manufactured by LONZA, PT-30); contains at least one hydroxyl group Aromatic polyamide resin (Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent 4000) 6.8 parts by mass; fused silica particles as inorganic filler (manufactured by Admatechs, SO-25R, average particle size 0.5 μm) 66 A resin varnish was prepared in the same manner as in Example 1 except that 0.0 part by mass and 4.0 parts by mass of silica nanoparticles (manufactured by Tokuyama Corporation, NSS-5N, average particle diameter: 70 nm) were prepared. A prepreg, a resin sheet, and a laminate A board, a printed wiring board, and a semiconductor device were obtained.

Example 10
20.3 parts by mass of a naphthylene ether type epoxy resin (manufactured by DIC, HP-6000), 17.9 parts by mass of a phenol novolac type cyanate ester resin (manufactured by LONZA, PT-30); containing at least one hydroxyl group Aromatic polyamide resin (Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent 4000) 11.4 parts by mass; fused silica particles (manufactured by Admatechs, SO-25R, average particle size 0.5 μm) 46 as an inorganic filler A resin varnish was prepared in the same manner as in Example 1 except that 0.0 part by mass and 4.0 parts by mass of silica nanoparticles (manufactured by Tokuyama Corporation, NSS-5N, average particle diameter: 70 nm) were prepared. A prepreg, a resin sheet, and a laminate A board, a printed wiring board, and a semiconductor device were obtained.

Example 11
As an inorganic filler, fused silica particles (manufactured by Admatechs, SO-25R, average particle size 0.5 μm) 46.0 parts by mass, talc (manufactured by Fuji Talc, LMS-300, average particle size 4.8 μm) 10. A resin varnish was prepared in the same manner as in Example 1 except that 0 part by mass and 4.0 parts by mass of silica nanoparticles (manufactured by Tokuyama Corporation, NSS-5N, average particle diameter 70 nm) were prepared. A prepreg, a resin sheet, and a laminate A printed wiring board and a semiconductor device were obtained.

Example 12
A resin varnish was prepared in the same manner as in Example 1 except that 60.0 parts by mass of fused silica particles (manufactured by Admatechs, SO-25R, average particle size 0.5 μm) were used as the inorganic filler, and the prepreg and resin Sheets, laminates, printed wiring boards, and semiconductor devices were obtained.

Example 13
12.4 parts by mass of naphthylene ether type epoxy resin (manufactured by DIC, HP-6000), phenol novolac type cyanate ester resin (manufactured by LONZA, PT-30) 10.9 parts by mass; containing at least one hydroxyl group Aromatic polyamide resin (manufactured by Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent 4000) 7.0 parts by mass; biphenyl aralkyl type phenol resin (Maywa Kasei Co., Ltd., MEH-7851-3H, hydroxyl group equivalent 220) as a curing agent 9 A resin varnish was prepared in the same manner as in Example 1 except that the content was 6 parts by mass to obtain a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device.

Comparative Example 1
Resin in the same manner as in Example 1 except that naphthylene ether type epoxy resin was not used and instead, biphenylaralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000, epoxy equivalent 285) was 16.2 parts by mass. A varnish was prepared to obtain a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device.

Comparative Example 2
A resin varnish was prepared in the same manner as in Example 1 except that an aromatic polyamide resin containing at least one hydroxyl group was not used and 9.1 parts by mass of a polyamideimide resin (DIC, V-8000) was used instead. Thus, a prepreg, a resin sheet, a laminated board, a printed wiring board, and a semiconductor device were obtained.

Comparative Example 3
Without using an aromatic polyamide resin containing at least one hydroxyl group, 21.1 parts by mass of naphthylene ether type epoxy resin (manufactured by DIC, HP-6000), phenol novolac type cyanate ester resin (manufactured by LONZA, PT- 30) A resin varnish was prepared in the same manner as in Example 1 except that 18.5 parts by mass was obtained, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

Comparative Example 4
Without using an inorganic filler, 40.8 parts by mass of naphthylene ether type epoxy resin (manufactured by DIC, HP-6000), 35.8 parts by mass of phenol novolac type cyanate ester resin (manufactured by LONZA, PT-30); A resin varnish was prepared in the same manner as in Example 1 except that 22.9 parts by mass of an aromatic polyamide resin (Nippon Kayaku Co., Ltd., BPAM-155, hydroxyl group equivalent 4000) containing at least one hydroxyl group was prepared. A resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

Comparative Example 5
Without using a cyanate ester resin, 18.8 parts by mass of a naphthylene ether type epoxy resin (manufactured by DIC, HP-6000) and an aromatic polyamide resin containing at least one hydroxyl group (manufactured by Nippon Kayaku Co., Ltd., BPAM-155) , Hydroxyl group equivalent 4000) 7.0 parts by mass, and biphenylaralkyl type phenolic resin (Maywa Kasei Co., Ltd., MEH-7851-3H, hydroxyl group equivalent 220) 13.8 parts by mass as the curing agent. A resin varnish was prepared to obtain a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device.

  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 Table 1.

[Evaluation method]
(1) Linear expansion coefficient
The metal foil of the metal-clad laminate obtained in [4] was removed by etching, and a 4 mm × 20 mm test piece was produced from the insulating layer from which the metal foil was removed. About this test piece, using a TMA (thermomechanical analysis) apparatus (TA Instrument Co., Ltd., Q400), a temperature range of 30 to 300 ° C., 10 ° C./min, and a load of 5 g, 50 to 50 in the second cycle. The linear expansion coefficient (CTE) in the plane direction (XY direction) at 150 ° C. was measured.

(2) Glass transition temperature
The metal foil of the metal-clad laminate obtained in [4] was removed by etching, and a 6 mm × 25 mm test piece was produced from the insulating layer from which the metal foil was removed. About this test piece, it heated up at 5 degree-C / min (frequency 1Hz) using DMA apparatus (The dynamic viscoelasticity measuring apparatus DMA983 by TA Instruments), and made the peak position of tan-delta the glass transition temperature.

(3) Plating peel strength
The copper foil was removed from the metal-clad laminate obtained in [4] by etching, immersed in a swelling solution at 60 ° C. (Swelling Dip Seligant P, manufactured by Atotech Japan) for 10 minutes, and further permanganic acid at 80 ° C. After immersion in an aqueous potassium solution (Atotech Japan Co., Ltd., Concentrate Compact CP) for 5 minutes, neutralization and roughening treatment were performed. After passing through the steps of degreasing, applying a catalyst, and activating this, an electroless copper plating film was formed to have a thickness of about 1 μm and electroplated copper was formed to 30 μm, and annealed at 200 ° C. for 60 minutes in a hot air drying apparatus. A 100 mm × 20 mm test piece was prepared based on JIS-C-6481, and the plating peel strength at 23 ° C. was measured.

(4) Solder heat resistance of laminated board
After cutting the metal-clad laminate obtained in [4] to 50 mm × 50 mm with a grinder saw, a sample in which only 1/4 of the copper foil was left by etching was prepared and evaluated in accordance with JIS 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.
The criteria are as follows.
◎: No peeling, no blistering ○: Small peeling, blistering, but practically no problem ×: peeling, blistering

(5) Thin wire workability evaluation
In [5], the printed wiring board after forming a fine circuit pattern of L / S = 20/20 μm was evaluated by a thin wire appearance inspection and a continuity check with a laser microscope. The evaluation criteria are as follows.
◎: No problem in both shape and continuity ○: Wiring width varies, but there is no short circuit or wiring breakage, no problem ×: Short circuit, wiring breakage

(6) Insulation reliability evaluation
A test sample in which a build-up material (BLA-3700GS manufactured by Sumitomo Bakelite Co., Ltd.) is laminated and cured on the fine circuit pattern of L / S = 20/20 μm of the printed wiring board obtained in [5] instead of the solder resist. Was made. Using this test sample, the continuous humidity insulation resistance was evaluated under the conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 3.3 V. A resistance value of 106Ω or less was regarded as a failure. The evaluation criteria are as follows.
◎: No failure for 300 hours or more ○: Failure for 150 hours or more and less than 300 hours ×: Failure for less than 150 hours

(7) Warpage evaluation of semiconductor devices
The warpage at normal temperature (23 ° C.) and 260 ° C. of the semiconductor package obtained in [6] was evaluated using a temperature variable laser three-dimensional measuring machine (manufactured by Hitachi Technology and Service, model LS220-MT100MT50). The semiconductor element surface was placed in the sample chamber of the measuring machine, the displacement in the height direction was measured, and the largest value of the displacement difference was taken as the amount of warpage. The evaluation criteria are as follows.
Normal temperature (23 ℃)
A: Warpage amount is less than 150 μm B: Warpage amount is 150 μm or more and less than 200 μm ×: Warpage amount is 200 μm or more and 260 ° C.
A: Warpage amount is less than 100 μm B: Warpage amount is 100 μm or more and less than 150 μm ×: Warpage amount is 150 μm or more

[Evaluation results]
As is clear from Table 1, Examples 1 to 13 are the resin composition according to the present invention, and a laminate, a printed wiring board and a semiconductor device using the resin composition, and have a high glass transition temperature and low after curing. 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. In addition, all the examples had sufficient plating peel strength, and there was no problem in fine wire workability. On the other hand, as is clear from Table 1, in Comparative Example 1 in which the naphthylene ether type epoxy compound (manufactured by DIC, HP-6000) was not used, the warpage of the printed wiring board in the semiconductor device was significantly increased. In Comparative Example 2 in which an aromatic polyamide resin containing at least one hydroxyl group was not used, the solder heat resistance deteriorated, and in Comparative Example 3, the plating peel strength deteriorated. In Comparative Example 4 in which the inorganic filler was not used, the linear expansion coefficient of the laminated plate was not lowered, and the warpage of the substrate as a whole could not be suppressed.

  The 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 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 resin composition of the present invention has a low linear expansion and is excellent in solder heat resistance and adhesiveness with 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.

DESCRIPTION OF SYMBOLS 100 Prepreg 101 Fiber base material 103 Resin layer 200 Semiconductor package 201 Solder resist layer 203 Semiconductor element 205 Connection terminal 207 Solder bump 209 Opening 211 Sealing material 213 Laminated plate 215 Through hole 300 Semiconductor device 301 Solder bump 303 Mounting substrate 305 Connection terminal

Claims (11)

(A) a naphthylene ether type epoxy resin represented by the following general formula (1), (B) a cyanate ester resin, (C) an aromatic polyamide resin containing at least one hydroxyl group, and (D) an inorganic filler. A resin composition comprising as an essential component.

(In the general formula (1), n is an integer of 1 or more and 20 or less, l is an integer of 1 or 2, and R ₁ is independently a hydrogen atom, a benzyl group, an alkyl group, or the following general formula ( 2), and each R ₂ is independently a hydrogen atom or a methyl group.)

(In the general formula (2), Ar is each independently a phenylene group or a naphthylene group, R ₂ is each independently a hydrogen atom or a methyl group, and m is an integer of 1 or 2.)   2. The resin composition according to claim 1, wherein the content of the aromatic polyamide resin (C) containing at least one hydroxyl group is 5 wt% or more and 15 wt% or less with respect to the total solid content of the resin composition.   The resin composition according to claim 1, wherein the (B) cyanate ester resin is a novolac-type cyanate ester resin.   4. The inorganic filler (D) is at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide, silica, fused silica, talc, calcined talc, and alumina. The resin composition according to item.   The resin composition according to any one of claims 1 to 4, wherein an average particle size of the (D) inorganic filler is 5.0 µm or less.   The resin composition according to any one of claims 1 to 5, wherein the (D) inorganic filler contains silica nanoparticles having an average particle diameter of 10 nm to 150 nm.   A prepreg obtained by impregnating a base material with the resin composition according to any one of claims 1 to 6.   A laminate comprising a metal layer disposed on at least one surface of the prepreg according to claim 7.   The resin sheet formed by arrange | positioning the resin composition as described in any one of Claim 1 thru | or 6 on a support film or metal foil.   A printed wiring board formed from the prepreg according to claim 7, the laminate according to claim 8, or the resin sheet according to claim 9.   A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to claim 10.

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