JP2011219674A - Thermosetting resin composition for circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition having a low coefficient of thermal expansion and excellent heat resistance and adhesion to a conductor circuit, and a prepreg, a laminated board, a resin sheet, a printed wiring board, and a semiconductor device using the same.SOLUTION: The thermosetting resin composition includes (A) a compound having at least two epoxy groups in one molecule, (B) a compound having at least two phenolic hydroxyl groups in one molecule, (C) a bismaleimide compound, and (D) a boron salt represented by general formula (1), wherein X, X, X, and Xare each independently hydrogen or a 1-12C substituted or unsubstituted hydrocarbon group; and Yis a monovalent cation.

Description

  The present invention relates to a thermosetting resin composition, 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, miniaturization and higher density are progressing.

  When the printed wiring board is thinned, there is a problem that the mounting reliability is lowered and the warpage of the printed wiring board is increased. Therefore, the low thermal expansion coefficient of the thermosetting resin composition or the thermosetting resin composition used is low. Studies have been actively conducted on the development of high-temperature, high glass transition temperature and high adhesion.

  For example, in Patent Document 1, (A) aromatic bismaleimide compound containing 3 or more aromatic rings in one molecule: 100 parts by weight, (B) aliphatic bismaleimide compound: 1 to 50 parts by weight, (C) An aromatic bismaleimide compound containing two or one aromatic ring in one molecule: 30 to 300 parts by weight and (D) a bisphenol compound represented by the following formula (1): 30 to 300 parts by weight System compositions are described. According to Patent Document 1, the bismaleimide composition is a matrix resin having heat resistance suitable for a CFRP robot hand for transporting liquid crystal glass, etc., and has no solvent impregnation, tackiness of prepreg, drape, and storage stability. It is stated that the matrix resin has reduced cracks in CFRP and has a small weight loss when placed under a high temperature for a long time, that is, heat resistance is further improved. For example, Patent Document 2 includes an epoxy resin curing agent (B) that is one selected from an epoxy resin (A), polyamine, polyphenol, or acid anhydride, and a quaternary phosphonium borate (C). And an epoxy resin composition for laminates that is uniformly dissolved in an organic solvent. According to Patent Document 2, the epoxy resin composition for laminates is excellent in curability, can be sufficiently cured even in a short laminate molding time, and has storage stability near room temperature, and moldability. It is also described that it can be suitably used for the production of a laminated board or a printed wiring board.

  In order to fully develop a further low coefficient of thermal expansion, high heat resistance, and high adhesion, it is necessary to completely react an epoxy resin, a phenol resin, and a bismaleimide compound. If the reaction does not proceed sufficiently, low thermal expansion, high heat resistance, and high adhesion cannot be achieved. In particular, if the adhesive force of the thermosetting resin composition is low, there is a problem that sufficient adhesiveness with a conductor circuit cannot be obtained when the composition is used for a printed wiring board or the like.

JP 2009-263624 A JP 2006-104337 A

  The present invention relates to a thermosetting resin composition having a low coefficient of thermal expansion and excellent heat resistance and adhesion to a conductor circuit (peel strength), and a prepreg, a laminate, a resin sheet, a printed wiring board, and a prepreg using the same. An object is to provide a semiconductor device.

その式中、Ｘ₁、Ｘ₂、Ｘ₃及びＸ₄は、各々独立に、水素又は炭素数１から１２の置換若しくは無置換の炭化水素基であり、Ｙ⁺は１価の陽イオンである。
（２）その（Ａ）エポキシ樹脂の粘度が、１５０℃条件下で、ＩＣＩ粘度計で測定して０．０５から３．５Ｐａ・ｓであり、かつ、その（Ａ）エポキシ樹脂のエポキシ当量が１６０から３２０である（１）に記載の熱硬化性樹脂組成物。
（３）その（Ｄ）一般式（１）で表されるホウ素塩が、テトラフェニルホスホニウムテトラフェニルボレート、テトラフェニルホスホニウムテトラ−ｐ−トリルボレート、テトラフェニルホスホニウムテトラ（ｐ−エチルフェニル）ボレート、テトラフェニルホスホニウムテトラ（ｐ−エトキシフェニル）ボレート、テトラフェニルホスホニウムｎ−ブチルトリフェニルボレート、テトラフェニルホスホニウムテトラ（４−フルオロフェニル）ボレート、ベンジルトリフェニルホスホニウムテトラフェニルボレート、トリ（ｐ−トリル）フェニルホスホニウムテトラ（ｐ−トリル）ボレート、テトラｎ−ブチルホスホニウムテトラフェニルボレート、ｎ−ブチルトリフェニルｎ−ブチルトリフェニルボレート、フェナシルトリフェニルホスホニウムテトラフェニルボレート、テトラエチルアンモニウムテトラフェニルボレート、ジアザビシクロウンデセニウムテトラフェニルボレート、ピリジニウムテトラフェニルボレート、及び2-エチル-4-メチルイミダゾリウムテトラフェニルボレートから選ばれる少なくとも１種である、（１）又は（２）に記載の熱硬化性樹脂組成物。
（４）（１）から（３）のいずれかに記載の熱硬化性樹脂組成物を基材に含浸させてなる、プリプレグ。
（５）（４）に記載のプリプレグの少なくとも片面上に金属箔を配置してなる、積層板。
（６）少なくとも２枚のそのプリプレグが積層されたプリプレグ積層体からなる、（５）に記載の積層板。
（７）（１）から（３）のいずれかに記載の熱硬化性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。
（８）（４）に記載のプリプレグ、（５）若しくは（６）に記載の積層板、又は（７）に記載の樹脂シートから形成されたプリント配線板。
（９）（８）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。 Means for achieving the above object are as follows.
(1) (A) a compound having at least two epoxy groups in one molecule, (B) a compound having at least two phenolic hydroxyl groups in one molecule, (C) a bismaleimide compound, (D ) A thermosetting resin composition comprising a boron salt represented by the following general formula (1).

In the formula, X ₁ , X ₂ , X ₃ and X ₄ are each independently hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and Y ⁺ is a monovalent cation. .
(2) The viscosity of the (A) epoxy resin is 0.05 to 3.5 Pa · s as measured with an ICI viscometer under the condition of 150 ° C., and the epoxy equivalent of the (A) epoxy resin is The thermosetting resin composition according to (1), which is 160 to 320.
(3) The boron salt represented by (D) general formula (1) is tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetra (p-ethylphenyl) borate, tetra Phenylphosphonium tetra (p-ethoxyphenyl) borate, tetraphenylphosphonium n-butyltriphenylborate, tetraphenylphosphonium tetra (4-fluorophenyl) borate, benzyltriphenylphosphonium tetraphenylborate, tri (p-tolyl) phenylphosphonium tetra (P-tolyl) borate, tetra-n-butylphosphonium tetraphenylborate, n-butyltriphenyl n-butyltriphenylborate, phenacyltriphenylphospho Um tetraphenylborate, tetraethylammonium tetraphenylborate, diazabicycloundecenium tetraphenylborate, pyridinium tetraphenylborate, and 2-ethyl-4-methylimidazolium tetraphenylborate (1 ) Or (2) thermosetting resin composition.
(4) A prepreg obtained by impregnating a base material with the thermosetting resin composition according to any one of (1) to (3).
(5) A laminate comprising a metal foil disposed on at least one surface of the prepreg according to (4).
(6) The laminate according to (5), comprising a prepreg laminate in which at least two prepregs are laminated.
(7) A resin sheet obtained by disposing the thermosetting resin composition according to any one of (1) to (3) on a support film or a metal foil.
(8) The printed wiring board formed from the prepreg as described in (4), the laminated board as described in (5) or (6), or the resin sheet as described in (7).
(9) A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to (8).

  According to the present invention, a thermosetting resin composition for a circuit board having a low coefficient of thermal expansion, excellent heat resistance and adhesion to a conductor circuit (peel strength), and having a high glass transition temperature, and the same are used. A prepreg, a laminate, and a resin sheet are provided, and a printed wiring board and a semiconductor device using them are further provided.

  Hereinafter, the present invention will be described in more detail.

  The thermosetting resin composition of the present invention can be used for a prepreg or a laminate using a prepreg by impregnating a substrate such as a glass fiber substrate. Moreover, since the thermosetting resin composition of this invention has the outstanding insulation, it can be used for the insulating layer of a printed wiring board, for example. Furthermore, since the thermosetting resin composition of the present invention has low linear expansion and is excellent in heat resistance and adhesion to a conductor circuit, it 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 semiconductor package and the mother board and mounted on the mother board. The interposer may be used as a substrate on which a semiconductor package 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 substrate of a semiconductor package. In a semiconductor package, 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. There is a type that is connected by a method such as wire bonding and sealed with resin.

(1) Thermosetting resin composition The thermosetting resin composition according to the present invention comprises (A) a compound having at least two epoxy groups in one molecule and (B) at least two phenols in one molecule. Comprising a compound having a reactive hydroxyl group, (C) a bismaleimide compound, and (D) a boron salt represented by the following general formula (1). It has excellent heat resistance and adhesion to the conductor circuit.

  Here, the cured product means a product in which the reaction of the functional group of the curable component in the composition constituting the thermosetting resin composition is substantially completed. For example, differential scanning calorimetry (DSC) It can be evaluated by measuring the calorific value with an apparatus. Specifically, this indicates a state in which this calorific value is hardly detected. As a condition for obtaining a cured product, for example, it is preferably treated at 120 to 220 ° C. for 30 to 180 minutes, more preferably treated at 180 to 230 ° C. for 45 to 120 minutes.

  In addition, (A) a compound having at least two epoxy groups in one molecule is appropriately referred to as (A) “epoxy resin”, and (B) a compound having at least two phenolic hydroxyl groups in one molecule. As appropriate, it is referred to as (B) “phenolic resin”, and (D) a boron salt represented by the following general formula (1) is appropriately referred to as (D) “specific boron salt”.

In the formula, X ₁ , X ₂ , X ₃ and X ₄ are each independently hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and Y ⁺ is a monovalent cation. .

  The thermosetting resin composition according to the present invention comprises (A) an epoxy resin, (B) a phenol resin, (C) a bismaleimide compound, and (D) a specific boron salt. In the range which does not oppose, other resin, hardening | curing agent, hardening accelerator, a flame retardant, a coupling agent, an inorganic filler, other components, etc. may be included.

(A) Compound having at least two epoxy groups in one molecule (epoxy resin)
The (A) epoxy resin contained in the thermosetting resin composition according to the present invention is a compound having at least two epoxy groups in one molecule. Therefore, the (A) epoxy resin contained in the thermosetting resin composition according to the present invention is not subject to any restriction as long as it has at least two epoxy groups in one molecule.

  The epoxy resin contained in the thermosetting resin composition according to the present invention is not particularly limited as long as it is a compound having at least two epoxy groups in one molecule as described above. Bisphenol A, bisphenol F, biphenyl, novolac, polyfunctional phenol, naphthalene, alicyclic, alcoholic glycidyl ether, glycidylamine, glycidyl ester, etc. You may use, and may use them in combination of 2 or more types. Specifically, in terms of dielectric properties, heat resistance, moisture resistance and copper foil adhesion, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, Phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, phenol novolac type epoxy resins, and cresol novolac type epoxy resins are preferred, and they have good low thermal expansibility and high glass transition temperature, so that naphthalene ring-containing epoxy resins and anthracene types Epoxy resins, biphenyl type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, and phenol novolac type epoxy resins are more preferred.

  The (A) epoxy resin contained in the thermosetting resin composition according to the present invention is preferably a compound represented by the following general formula (2).

In the formula, R ¹ is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms, R ² is —CH ₂ —, —CH ₂ —Ph—Ph—CH ₂ — or —CH ₂ —Ph. —CH ₂ —, Ph is a divalent substituted or unsubstituted aromatic hydrocarbon group, and n is an integer of 1 to 10.

Among the compounds represented by the general formula (2), an epoxy resin in which R ¹ is CH ₃ and R ² is CH ₂ is more preferable, R ¹ is hydrogen, and R ² is —CH ₂ —Ph—. An epoxy resin that is Ph—CH ₂ — (Ph is a phenylene group) is more preferable.

  Although the specific exemplary compound of the preferable (A) epoxy resin contained in the thermosetting resin composition by this invention is shown below, this invention is not limited to these compounds.

  The viscosity of the (A) epoxy resin contained in the thermosetting resin composition according to the present invention is 0.05 to 3.5 Pa · s as measured with an ICI viscometer under the condition of 150 ° C. The epoxy equivalent of the resin is preferably 160 to 320, the viscosity is 0.07 to 2.0 Pa · s as measured with an ICI viscometer under the condition of 150 ° C., and the epoxy equivalent of the epoxy resin is More preferably, it is 180-300.

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

  The content of the epoxy resin (A) in the thermosetting resin composition according to the present invention is the same as that in the composition excluding silica, aluminum hydroxide, and other inorganic fillers from the entire thermosetting resin composition. It is preferably 20 to 55% by mass, more preferably 25 to 50% by mass, and still more preferably 30 to 45% by mass.

  As mentioned above, the thermosetting resin composition by this invention can express adhesiveness and heat resistance effectively by containing (A) an epoxy resin appropriately. (A) If the content of the epoxy resin is less than the above lower limit (20% by mass), there is no problem in practical use, but the peel strength may be reduced, or the fine processing of the circuit board may be difficult. And if it exceeds the upper limit (55% by mass), there is no practical problem, but the solder heat resistance may deteriorate.

(B) Compound having at least two phenolic hydroxyl groups in one molecule (phenol resin))
The (B) phenol resin contained in the thermosetting resin composition according to the present invention is a compound having at least two phenolic hydroxyl groups in one molecule. Therefore, the (B) phenol resin contained in the thermosetting resin composition according to the present invention is not restricted at all as long as it has at least two phenolic hydroxyl groups in one molecule.

  The phenol resin contained in the thermosetting resin composition according to the present invention is not particularly limited as long as it is a compound having at least two phenolic hydroxyl groups in one molecule as described above. Examples of the phenol resin having two or more phenolic hydroxyl groups in one molecule include novolac type phenol resins, aralkyl type phenol resins, dicyclopentadiene modified phenol resins, polycyclic aromatic ring modified phenol resins, and the like. Resin may be used independently and may be used in combination of multiple types. Bifunctional compounds such as bisphenol A, bisphenol F, bisphenol S and the like are also exemplified.

  The (B) phenol resin contained in the thermosetting resin composition according to the present invention is preferably a compound represented by the following general formula (3).

In the formula, R ¹ is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms, R ² is —CH ₂ —, —CH ₂ —Ph—Ph—CH ₂ — or —CH ₂ —Ph. —CH ₂ —, Ph is a divalent substituted or unsubstituted aromatic hydrocarbon group, and n is an integer of 1 to 10.

  Although the specific exemplary compound of the preferable (B) phenol resin contained in the thermosetting resin composition by this invention is shown below, this invention is not limited to these compounds.

  The viscosity of the (B) phenol resin contained in the thermosetting resin composition according to the present invention is 0.05 to 3.5 Pa · s as measured with an ICI viscometer under the condition of 150 ° C., and phenol The phenolic hydroxyl group equivalent of the resin is preferably 95 to 240, the viscosity is 0.07 to 2.0 Pa · s as measured with an ICI viscometer under the condition of 150 ° C., and the phenolic hydroxyl group equivalent Is more preferably 100-220.

  1 type may be used for the (B) phenol resin contained in the thermosetting resin composition by this invention, and it may use it in combination of 2 or more type.

  The content of the (B) phenol resin in the thermosetting resin composition according to the present invention is such that the silica, aluminum hydroxide, and other inorganic fillers are excluded from the entire thermosetting resin composition. It is preferable that it is 10-50 mass%, and it is more preferable that it is 14-44 mass%.

  As mentioned above, the thermosetting resin composition by this invention can express heat resistance and adhesiveness effectively by containing (B) phenol resin appropriately. (B) When content of a phenol resin is less than said lower limit (10 mass%), although there is no problem in practical use, solder heat resistance may deteriorate or the reliability at the time of reflow work may fall. And if it exceeds the upper limit (50% by mass), there is no problem in practical use, but the peel strength may be lowered.

(C) Bismaleimide Compound The (C) bismaleimide compound contained in the thermosetting 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 thermosetting resin composition according to the present invention can lower the coefficient of thermal expansion of the cured product, and further has excellent heat resistance.

  The bismaleimide compound contained in the thermosetting resin composition according to the present invention is not particularly limited, and examples thereof include 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 and the like can be mentioned, and examples of the polymaleimide include polyphenylmethane maleimide and the like.

  The (C) bismaleimide compound contained in the thermosetting resin composition according to the present invention is preferably a compound represented by the following general formula (4).

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—, or a divalent substituted or unsubstituted aromatic group. It is a hydrocarbon group.

Among the compounds represented by the general formula (4), a bismaleimide compound in which R ¹ is hydrogen and R ² is hydrogen is more preferable.

  Although the specific exemplary compound of the preferable (C) bismaleimide contained in the thermosetting resin composition by this invention is shown below, this invention is not limited to these compounds.

  In consideration of low water absorption, etc., 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane (Exemplary Compound 4-3), bis- (3-ethyl-5-methyl-4-maleimidophenyl) ) Methane (Exemplary Compound 4-2) is preferred.

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

  The content of the (A) bismaleimide compound in the thermosetting resin composition according to the present invention is in the composition excluding silica, aluminum hydroxide, and other inorganic fillers from the entire thermosetting resin composition. Is preferably 15 to 70% by mass, more preferably 20 to 60% by mass, and still more preferably 25 to 50% by mass.

  As described above, by appropriately containing the (C) bismaleimide compound, the thermosetting resin composition according to the present invention can effectively exhibit a low linear expansion coefficient. (A) If the content of the bismaleimide compound is less than the above lower limit (15% by mass), the linear expansion coefficient may not be sufficiently low, and there is no practical problem, but the mounting reliability is reduced, or The warping of the wiring board may be large. And when it is above said upper limit (70 mass%), there is no problem practically, but the peel strength regarding the adhesiveness of a conductor circuit and a resin layer may fall.

(D) Specific boron salt The (D) specific boron salt contained in the thermosetting resin composition according to the present invention is a quaternary boron salt represented by the following general formula (1).

In the formula, X ₁ , X ₂ , X ₃ and X ₄ are each independently hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and Y ⁺ is a monovalent cation. .

It is preferable that at least three of X _{1 to} X ₄ in the compound represented by the general formula (1) are substituted or unsubstituted aromatic carbon groups, and all of X _{1 to} X ₄ are substituted or unsubstituted. More preferably, it is an aromatic carbon group.

Y ⁺ in the compound represented by the general formula (1) is not particularly limited as long as it is a monovalent cation, but it is not limited, but is substituted or unsubstituted quaternary ammonium ion, substituted or unsubstituted phosphonium ion. Is preferred.

  The (D) specific boron salt contained in the thermosetting resin composition according to the present invention is not particularly limited as long as it can be represented by the above general formula (1). For example, tetraphenylphosphonium tetra Phenylborate, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetra (p-ethylphenyl) borate, tetraphenylphosphonium tetra (p-ethoxyphenyl) borate, tetraphenylphosphonium n-butyltriphenylborate, tetraphenylphosphonium Tetra (4-fluorophenyl) borate, benzyltriphenylphosphonium tetraphenylborate, tri (p-tolyl) phenylphosphonium tetra (p-tolyl) borate, tetra n-butylphosphonium tetrafe Ruborate, n-butyltriphenyl n-butyltriphenylborate, phenacyltriphenylphosphonium tetraphenylborate, tetraethylammonium tetraphenylborate, diazabicycloundecenium tetraphenylborate, pyridinium tetraphenylborate, 2-ethyl-4- And methyl imidazolium tetraphenylborate.

  Although the specific exemplary compound of the preferable (D) specific boron salt contained in the thermosetting resin composition by this invention is shown below, this invention is not limited to these compounds.

  The (D) specific boron salt contained in the thermosetting resin composition according to the present invention may be used singly or in combination of two or more.

  Content of (D) specific boron salt in the thermosetting resin composition by this invention is 0.05 in the composition remove | excluding the silica and other inorganic fillers from the whole thermosetting resin composition. It is preferable that it is -2.5 mass%, It is more preferable that it is 0.20-2.0 mass%, It is still more preferable that it is 0.4 mass%-1.0 mass%.

  As mentioned above, the thermosetting resin composition by this invention can express high adhesiveness effectively by containing (D) specific boron salt appropriately. (D) When the content of the specific boron salt is less than the above lower limit (0.05% by mass), there is no practical problem, but the peel strength may be reduced, or the fine processing of the circuit board may be difficult. is there. And if it exceeds the upper limit (2.5% by mass), there is no problem in practical use, but the storability of the prepreg may not be sufficient.

(2) Prepreg The prepreg according to the present invention is obtained by impregnating a base material with the thermosetting resin composition of the present invention. The prepreg according to the present invention is excellent in characteristics such as heat resistance.

  The base material used in the prepreg according to the present invention is not particularly limited. For example, glass fiber base materials such as glass fine cloth and glass non-woven cloth, inorganic cloth such as fine cloth and non-woven cloth containing inorganic compounds other than glass as components. Examples thereof include fiber base materials, aromatic polyamide resins, polyamide resins, aromatic polyester resins, polyester resin, polyimide resins, organic fiber base materials composed of organic fibers such as fluorine resins, and the like.

  From the viewpoints of strength and water absorption, glass fiber base materials such as glass fiber cloth and glass fiber cloth are preferable.

  The method for impregnating the base material with the thermosetting resin composition of the present invention is not particularly limited. For example, the thermosetting resin composition is made into a resin varnish using a solvent, and the base material is made into a resin varnish. Examples include a dipping method, a coating method using various coaters, and a spraying method.

  From the viewpoint of impregnation, a method of immersing the substrate in the resin varnish is preferable. Thereby, it is possible to further improve the impregnation property of the thermosetting resin composition to the substrate. In addition, when a base material is immersed in a resin varnish, a normal impregnation coating equipment can be used.

  The solvent used in the resin varnish preferably exhibits good solubility in the thermosetting resin composition of the present invention, but a poor solvent may be used as long as it does not have an adverse effect. Although it will not specifically limit if it is a solvent which shows favorable solubility, For example, N-methylpyrrolidone etc. are mentioned.

  Although solid content in a resin varnish is not specifically limited, 40-80 mass% of solid content of the thermosetting resin composition of this invention is preferable, and 50-65 mass% is more preferable. Thereby, the impregnation property to the base material of the resin varnish can further be improved.

  A prepreg can be obtained by impregnating the base material with the thermosetting resin composition of the present invention and drying at a predetermined temperature, for example, 80 to 200 ° C.

(3) Laminate The laminate according to the present invention is formed by arranging a metal foil on at least one surface of the prepreg of the present invention, or at least one surface of a prepreg laminate in which at least two prepregs of the present invention are laminated. A metal foil is arranged on the top. The laminate of the present invention has a low dielectric constant and dielectric loss tangent, and is excellent in heat resistance and adhesion.

  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 surfaces of the prepreg of the present invention. Furthermore, in the laminate according to the present invention, the metal foil and / or the support film may be laminated on one side or the outermost upper and lower surfaces of the prepreg laminate in which at least two prepregs of the present invention are laminated.

  As the support film, one that can be easily handled can be selected. The support film is not particularly limited, and examples thereof include polyester resin films such as polyethylene terephthalate and polybutylene terephthalate, thermoplastic resin films having heat resistance such as fluororesin and polyimide resin, and the like. Polyester resin films such as terephthalate and polybutylene terephthalate are preferred.

  The thickness of the support film is not particularly limited as long as it is easy to handle, but is preferably 1 to 100 μm, and more preferably 3 to 50 μm.

  The metal foil is not particularly limited. For example, copper and / or copper-based alloy, aluminum and / or aluminum-based alloy, iron and / or iron-based alloy, silver and / or silver-based alloy, gold and gold-based alloy, zinc And zinc-based alloys, nickel and nickel-based alloys, tin and tin-based alloys.

  Although the thickness of metal foil is not specifically limited, It is preferable that they are 0.1 micrometer or more and 70 micrometers or less, More preferably, they are 1 micrometer or more and 35 micrometers or less, More preferably, they are 1.5 micrometers or more and 18 micrometers or less. When the thickness of the metal foil is less than 0.1 μm (lower limit), there is no practical problem. However, when the metal foil is damaged, pinholes are generated, and the metal foil is etched and used as a conductor circuit, a circuit pattern is formed. Sometimes plating variation, circuit disconnection, penetration of chemicals such as etching liquid and desmear liquid may occur. If the thickness of the metal foil is more than 70 μm (upper limit), the thickness variation of the metal foil may increase, or the surface roughness variation of the metal foil roughened surface may increase.

  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 from 0.1 μm to 10 μm, more preferably from 0.5 μm to 5 μm, still more preferably from 1 μm to 3 μm. When the thickness of the ultrathin metal foil is less than 0.1 μm (lower limit), there is no practical problem, but the ultrathin metal foil is damaged after the carrier foil is peeled off, the pinhole of the ultrathin metal foil is generated, the pinhole Occurrence of plating pattern variations during circuit pattern formation, disconnection of circuit wiring, penetration of chemicals such as etching liquid and desmear liquid may occur. If the thickness of the ultrathin metal foil exceeds 10 μm (upper limit), there is no practical problem, but the thickness variation of the ultrathin metal foil increases or the roughness of the roughened surface of the ultrathin metal foil increases. May be larger. 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. Although the temperature to heat is not specifically limited, 150-240 degreeC is preferable and 180-220 degreeC is more preferable. The pressure to be pressurized is not particularly limited, but is preferably 2 to 5 MPa, and more preferably 2.5 to 4 MPa.

(4) Resin sheet The resin sheet by this invention arrange | positions the thermosetting thermosetting resin composition of this invention on a support film or metal foil. The resin sheet using the thermosetting resin composition of the present invention is obtained by forming an insulating layer made of a resin varnish on a support film or a metal foil.

  Although content of the thermosetting resin composition of this invention in a resin varnish is not specifically limited, 45-85 mass% is preferable and 55-75 mass% is more preferable.

  Next, the resin varnish is coated on the support film and / or metal foil using various coating devices and then dried, or the resin varnish is spray-coated on the support film and / or metal foil by a spray device. And then dry. A resin sheet can be produced by either method.

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

  Since the support film forms an insulating layer on the support film, it is preferable to select a support film that is easy to handle. In addition, since the support film is peeled off after laminating the insulating layer of the resin sheet on the inner circuit board surface, it is preferable that the resin sheet is easily peeled off after being laminated on the inner circuit board. Accordingly, the support film is not particularly limited as long as it can be easily peeled off from the insulating layer with an appropriate strength. For example, a polyester resin film such as polyethylene terephthalate or polybutylene terephthalate, or a fluorine resin. And thermoplastic resin films having heat resistance such as polyimide resin, and among these, polyester resin films are preferable.

  The thickness of the support film is not particularly limited as long as it is easy to handle and has excellent flatness on the surface of the insulating layer, but is preferably 1 to 100 μm, more preferably 3 to 50 μm.

  Similar to the support film, the metal foil may be used after being peeled after laminating a resin sheet on the inner circuit board, or may be used by etching the metal foil as a conductor circuit. The metal foil is not particularly limited. For example, copper and / or copper-based alloy, aluminum and / or aluminum-based alloy, iron and / or iron-based alloy, silver and / or silver-based alloy, gold and / or Alternatively, a gold alloy, zinc and / or a zinc alloy, nickel and / or a nickel alloy, tin and / or a tin alloy, and the like can be given.

  Although the thickness of metal foil is not specifically limited, It is preferable that they are 0.1 micrometer or more and 70 micrometers or less, More preferably, they are 1 micrometer or more and 35 micrometers or less, More preferably, they are 1.5 micrometers or more and 18 micrometers or less. When the thickness of the metal foil is less than 0.1 μm (lower limit), there is no practical problem, but the metal foil is damaged, pinholes are generated, and further, when the metal foil is etched and used as a conductor circuit, a circuit pattern Plating variation during molding, circuit disconnection, penetration of chemicals such as etching liquid and desmear liquid may occur. If the thickness of the metal foil exceeds 70 μm (upper limit), there is no practical problem, but the thickness variation of the metal foil may increase or the surface roughness variation of the roughened metal foil surface may increase.

  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 ultrathin metal foil layer can be formed on both surfaces of the insulating layer by using an ultrathin metal foil with a carrier foil, for example, when forming a circuit by a semi-additive method, etc. By electroplating the metal foil directly as the 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 from 0.1 μm to 10 μm, more preferably from 0.5 μm to 5 μm, still more preferably from 1 μm to 3 μm. When the thickness of the ultrathin metal foil is less than 0.1 (lower limit), there is no practical problem, but the ultrathin metal foil is damaged after peeling the carrier foil, pinholes are generated in the ultrathin metal foil, There are cases in which plating variations during circuit pattern formation due to the generation of holes, disconnection of circuit wiring, penetration of chemicals such as etching liquid and desmear liquid, etc. may occur. When the thickness of the ultrathin metal foil is more than 10 μm (upper limit), the thickness variation of the ultrathin metal foil may increase or the surface roughness of the ultrathin metal foil roughened surface 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.

(5) Printed wiring board The printed wiring board by this invention is formed from the prepreg of this invention, the laminated board of this invention, or the resin sheet of this invention.

  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, 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 Then, the inner circuit board is produced by subjecting the conductor circuit to a roughening process such as a blackening process.

  When the thermosetting resin composition of the present invention is used, fine through-holes can be formed with better yield than before, and the unevenness of the wall after through-hole formation is much smaller than before. .

  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 layer circuit board, and this is heated and pressed using a flat plate press or the like to form an insulating layer on the inner layer circuit board. It can also be formed. 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 resin composition of the present invention is used, it is excellent in fine wiring processing as compared with the prior art, and the conductor width (line) when the conductor circuit is formed and the wiring with a very narrow space between the conductors (space) have a good yield. Can be formed.

  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.

  When the thermosetting resin composition of the present invention is used, since metal atoms such as nickel do not remain in the insulating layer compared to the case of using a conventional epoxy thermosetting resin composition during nickel gold plating, Excellent in properties.

(6) Semiconductor Device 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 thermosetting 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, an example for explaining the present invention more concretely is provided. In addition, this invention is not limited to a following example in the range which does not deviate from the objective and the main point.

Example 1
(1) Preparation of resin varnish 13.5 parts by mass of cresol novolac epoxy resin (Exemplary Compound 2-2) (N-690, DIC Corporation, epoxy equivalent: 220, 2 Pa · s (ICI viscometer, 150 ° C.)) 6.5 parts by mass of phenol novolak resin (Exemplary Compound 3-1) (TD-2093 manufactured by DIC Corporation, phenolic hydroxyl group equivalent: 105, 1.5 Pa · s (ICI viscometer, 150 ° C.)), 15 parts by mass of tetraphenylphosphonium tetraphenylborate (Hokuko Chemical Co., Ltd.), 15.0 parts by mass of 2,2′-bis- [4- (4-maleimidophenoxy) phenylpropane (Exemplary Compound 4-3) (KAI Kasei BMI-80, double bond equivalent 285) and 0.5 parts by mass of 3-glycidyloxypropyltrimethoxysilane (Shin-Etsu Silicone KBM-403) 4.5 parts by mass of fused silica particles (Admatics SO-25R, average particle size 0.5 μm) was added to cyclohexanone and adjusted to a non-volatile content of 65% to obtain a resin varnish.

(2) Manufacture of prepreg Using the resin varnish described above, 100 parts by mass of glass fiber cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts by mass of resin varnish in a solid content, and 190 ° C. The prepreg having a resin content of 44.4% by mass was produced by drying in a drying oven for 7 minutes.

(3) Manufacture of laminated board Two prepregs above are stacked, and 18 μm thick electrolytic copper foil (YGP-18 manufactured by Nihon Electrolytic Co., Ltd.) is stacked on top and bottom, and heated and pressed at a pressure of 4 MPa and a temperature of 220 ° C. for 180 minutes. A double-sided copper-clad laminate with a thickness of 0.4 mm was obtained.

(4) Manufacture of resin sheet Copper foil (Mitsui Metal Mining Co., Ltd., manufactured by bonding the resin varnish obtained above with a peelable carrier foil layer and an electrolytic copper foil layer having a thickness of 0.5 to 5.0 μm. Apply to the electrolytic copper foil layer of micro thin Ex-3, carrier foil layer: copper foil (18 μm), electrolytic copper foil layer (3 μm) using a comma coater so that the resin layer after drying is 40 μm. This was dried for 10 minutes with a drying apparatus at 150 ° C. to produce a resin sheet.

(5) Production of Printed Wiring Board After the through-hole processing was performed on the laminated board obtained above 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 prepreg obtained above was superposed on the front and back of the inner layer circuit board, and this was subjected to vacuum heating and press 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 a printed wiring board obtained as described above, and is provided with a connection electrode portion that has been subjected to nickel gold plating treatment corresponding to the solder bump arrangement of the semiconductor element. It cut | disconnected and used for the magnitude | size of * 50mm. 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)
Except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used in place of 0.15 parts by mass of tetraphenylphosphonium tetra-p-tolylborate (manufactured by Hokuko Chemical), Example A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 3)
Except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.17 parts by mass of tetraphenylphosphonium tetra (p-ethylphenyl) borate (manufactured by Hokuko Chemical), A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

Example 4
Except for using 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 in place of 0.18 parts by mass of tetraphenylphosphonium tetra (p-ethoxyphenyl) borate (made by Hokuko Chemical), A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 5)
Except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used in place of 0.15 parts by mass of tetraphenylphosphonium n-butyltriphenylborate (manufactured by Hokuko Chemical), Example A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 6)
Except for using 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 in place of 0.25 parts by mass of tetraphenylphosphonium tetra (4-fluorophenyl) borate (manufactured by Hokuko Chemical), A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 7)
The same as Example 1 except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.25 parts by mass of benzyltriphenylphosphonium tetraphenylborate (manufactured by Aldrich). A resin varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 8)
The 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.18 parts by mass of tri (p-tolyl) phenylphosphonium tetra (p-tolyl) borate (manufactured by Hokuko Chemical). Except that, a resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

Example 9
Example 1 except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.20 parts by mass of tetra n-butylphosphonium tetraphenylborate (manufactured by Aldrich). Similarly, a resin varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 10)
Except for using 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 in place of 0.18 parts by mass of n-butyltriphenyl n-butyltriphenylborate (made by Hokuko Chemical), A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 11)
Example 1 except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.20 parts by mass of phenacyltriphenylphosphonium tetraphenylborate (made by Hokuko Chemical). A resin varnish was prepared in the same manner as described above to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 12)
The same procedure as in Example 1 was conducted except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.25 parts by mass of tetraethylammonium tetraphenylborate (manufactured by Aldrich). A resin varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 13)
Except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.25 parts by mass of diazabicycloundecenium tetraphenylborate (manufactured by Hokuko Chemical Co., Ltd.) A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 14)
Resin in the same manner as in Example 1 except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.25 parts by mass of pyridinium tetraphenylborate (manufactured by Aldrich). A varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 15)
Except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.25 parts by mass of 2-ethyl-4-methylimidazolium tetraphenylborate (made by Hokuko Chemical). A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 16)
15.0 parts by mass of 2,2′-bis- [4- (4-maleimidophenoxy) phenylpropane (Exemplary Compound 4-3) used in Example 1 was replaced with 15.0 parts by mass of bis (3-ethyl). Resin varnish was prepared in the same manner as in Example 1 except that it was used instead of -5-methyl-4-maleimidophenyl) methane (Exemplary Compound 4-2) (KMI Kasei BMI-70, double bond equivalent 221). The prepreg, laminate, resin sheet, printed wiring board, and semiconductor device were prepared.

(Example 17)
15.0 parts by mass of 2,2′-bis- [4- (4-maleimidophenoxy) phenylpropane (Exemplary Compound 4-3) used in Example 1 was replaced with 15.0 parts by mass of N, N′— A resin varnish was prepared in the same manner as in Example 1 except that (4′4′-diphenylmethane) bismaleimide (KMI Kasei BMI-H, double bond equivalent: 175) was used. A resin sheet, a printed wiring board, and a semiconductor device were obtained.

(Example 18)
13.5 parts by mass of a cresol novolac epoxy resin (Exemplary Compound 2-2) and 6.5 parts by mass of a phenol novolac resin (Exemplary Compound 3-1) used in Example 1 were converted into 12.9 parts by mass of a phenol novolac. Epoxy resin (Exemplary Compound 2-1) (N-770, DIC Corporation, epoxy equivalent: 190, 0.5 Pa · s (ICI viscometer, 150 ° C.)) and 7.1 parts by mass of phenol novolac resin (Exemplary Compound) A resin varnish was prepared in the same manner as in Example 1 except that it was used instead of 3-1) to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 19)
13.5 parts by mass of cresol novolac epoxy resin (Exemplary Compound 2-2) and 6.5 parts by mass of phenol novolac resin (Exemplary Compound 3-1) used in Example 1 were mixed with 11.0 parts by mass of biphenyl aralkyl. Type epoxy resin (Exemplified Compound 2-3) (Nippon Kayaku Co., Ltd. NC-3000H, epoxy equivalent: 285, 0.3 Pa · s (ICI viscometer, 150 ° C.)) and 9.0 parts by mass of biphenyl aralkyl type Resin varnish in the same manner as in Example 1 except that it was used instead of phenol resin (MEH-7851H, Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent: 220, 0.5 Pa · s (ICI viscometer, 150 ° C.)) Were prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 20)
13.5 parts by mass of the cresol novolac epoxy resin (Exemplary Compound 2-2) and 6.5 parts by mass of the phenol novolac resin (Exemplary Compound 3-1) used in Example 1 were 10.0 parts by mass of methoxynaphthalene. Type epoxy resin (Exemplified Compound 2-4) (EXA-9900 manufactured by DIC Corporation, epoxy equivalent: 275, 2.7 Pa · s (ICI viscometer, 150 ° C.)) and 10.0 parts by mass of a biphenyl aralkyl type phenol resin A resin varnish was prepared in the same manner as in Example 1 except that MEH-7785H (Maywa Kasei Co., Ltd., phenolic hydroxyl group equivalent: 220, 0.5 Pa · s (ICI viscometer, 150 ° C.)) was used. Thus, a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device were obtained.

(Example 21)
13.5 parts by mass of a cresol novolac epoxy resin (Exemplary Compound 2-2) and 6.5 parts by mass of a phenol novolac resin (Exemplary Compound 3-1) used in Example 1 were converted into 13.9 parts by mass of a phenol aralkyl. Type epoxy resin (Exemplified Compound 2-5) (YL-7303, JER Corporation, epoxy equivalent: 240, 0.15 Pa · s (ICI viscometer, 150 ° C.)) and 6.1 parts by mass of phenol novolac resin (Exemplary) A resin varnish was prepared in the same manner as in Example 1 except that it was used in place of Compound 3-1) to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 22)
13.5 parts by mass of a cresol novolac epoxy resin (Exemplary Compound 2-2) (Exemplary Compound 2-2) and 6.5 parts by mass of a phenol novolac resin (Exemplary Compound 3-1) used in Example 1 .7 parts by mass of a naphthol aralkyl type epoxy resin (Exemplary Compound 2-6) (NC-7000L, Nippon Kayaku Co., Ltd., epoxy equivalent: 230, 0.7 Pa · s (ICI viscometer, 150 ° C.)) and 6. A resin varnish was prepared in the same manner as in Example 1 except that 3 parts by mass of phenol novolac resin (Exemplary Compound 3-1) was used, and a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device were prepared. Got.

(Example 23)
13.5 parts by mass of cresol novolac epoxy resin (Exemplary Compound 2-2) and 6.5 parts by mass of phenol novolac resin (Exemplary Compound 3-1) used in Example 1 were mixed with 11.0 parts by mass of biphenyl aralkyl. Type epoxy resin (Exemplary Compound 2-3) (NC-3000H, Nippon Kayaku Co., Ltd., epoxy equivalent: 285, 0.3 Pa · s (ICI viscometer, 150 ° C.)) and 9.0 parts by mass of phenol aralkyl resin (Exemplary Compound 3-5) Example 1 except that it was used instead of MEH-7800H (Maywa Kasei Co., Ltd., phenolic hydroxyl group equivalent: 180, 0.5 Pa · s (ICI viscometer, 150 ° C.)). Similarly, a resin varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Example 24)
13.5 parts by mass of a cresol novolac epoxy resin (Exemplary Compound 2-2) and 6.5 parts by mass of a phenol novolac resin (Exemplary Compound 3-1) used in Example 1 were replaced with 12.5 parts by mass of a cresol novolac. Resin in the same manner as in Example 1 except that the epoxy resin (Exemplary Compound 2-2) and 7.5 parts by mass of bisphenol S (BPS-N manufactured by Nikka Chemical Co., Ltd., phenolic hydroxyl group equivalent: 125) were used. A varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Comparative Example 1)
Except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.15 parts by mass of 2-phenylimidazole (manufactured by Shikoku Chemicals), the same procedure as in Example 1 was performed. A resin varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Comparative Example 2)
Example 1 except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.15 parts by mass of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei). A resin varnish was prepared in the same manner as described above to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Comparative Example 3)
The same procedure as in Example 1 was conducted except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.15 parts by mass of diazabicycloundecene (manufactured by Tokyo Chemical Industry). A resin varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Comparative Example 4)
The same procedure as in Example 1 was conducted except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.15 parts by mass of tetraphenylphosphonium chloride (made by Hokuko Chemical). A resin varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Comparative Example 5)
The same procedure as in Example 1 was conducted except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.15 parts by mass of tetraphenylphosphonium bromide (made by Hokuko Chemical). A resin varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Comparative Example 6)
The same procedure as in Example 1 was conducted except that 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 was used instead of 0.15 parts by mass of benzyltriphenylphosphonium chloride (manufactured by Hokuko Chemical). A resin varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Comparative Example 7)
15.0 parts by mass of 2,2′-bis- [4- (4-maleimidophenoxy) phenylpropane (Exemplary Compound 4-3) and 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 Except that 15.0 parts by mass of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane (Exemplary Compound 4-2) and 0.15 parts by mass of 2-phenylimidazole were used. A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Comparative Example 8)
15.0 parts by mass of 2,2′-bis- [4- (4-maleimidophenoxy) phenylpropane (Exemplary Compound 4-3) and 0.15 parts by mass of tetraphenylphosphonium tetraphenylborate used in Example 1 Resin in the same manner as in Example 1 except that 15.0 parts by mass of N, N ′-(4,4′-diphenylmethane) bismaleimide and 0.15 parts by mass of 2-phenylimidazole were used. A varnish was prepared to obtain a prepreg, a laminate, a resin sheet, a printed wiring board, and a semiconductor device.

(Comparative Example 9)
13.5 parts by mass of cresol novolac epoxy resin (Exemplary Compound 2-2), 6.5 parts by mass of phenol novolac resin (Exemplary Compound 3-1), and 0.15 parts by mass of tetraphenyl used in Example 1 Replacing phosphonium tetraphenylborate with 11.0 parts by mass of biphenyl aralkyl type epoxy resin (Exemplary Compound 2-3), 9.0 parts by mass of biphenyl aralkyl type phenol resin, and 0.15 parts by mass of 2-phenylimidazole A resin varnish was prepared in the same manner as in Example 1 except that the prepreg, laminate, resin sheet, printed wiring board, and semiconductor device were obtained.

(Comparative Example 10)
13.5 parts by mass of cresol novolac epoxy resin (Exemplary Compound 2-2), 6.5 parts by mass of phenol novolac resin (Exemplary Compound 3-1), and 0.15 parts by mass of tetraphenyl used in Example 1 The phosphonium tetraphenylborate is replaced with 10.0 parts by mass of a methoxynaphthalene type epoxy resin (Exemplary Compound 2-4), 10.0 parts by mass of a biphenylaralkyl type phenolic resin, and 0.15 parts by mass of 2-phenylimidazole. A resin varnish was prepared in the same manner as in Example 1 except that the prepreg, laminate, resin sheet, printed wiring board, and semiconductor device were obtained.

(Comparative Example 11)
13.5 parts by mass of cresol novolac epoxy resin (Exemplary Compound 2-2) and 6.5 parts by mass of phenol novolac resin (Exemplary Compound 3-1) and 0.15 parts by mass of tetraphenyl used in Example 1 Other than using phosphonium tetraphenylborate instead of 12.5 parts by mass of cresol novolac epoxy resin (Exemplary Compound 2-2), 7.5 parts by mass of bisphenol S, and 0.15 parts by mass of 2-phenylimidazole. Prepared the resin varnish like Example 1, and obtained the prepreg, the laminated board, the resin sheet, the printed wiring board, and the semiconductor device.

(Comparative Example 12)
13.5 parts by mass of the cresol novolac epoxy resin (Exemplary Compound 2-2) and 6.5 parts by mass of the phenol novolac resin (Exemplary Compound 3-1) used in Example 1 were converted into 24.0 parts by mass of the cresol novolac. 15.0 parts by mass of 2,2′-bis used in Example 1 were used instead of epoxy resin (Exemplary Compound 2-2) and 11.0 parts by mass of phenol novolac resin (Exemplary Compound 3-1). A resin varnish was prepared in the same manner as in Example 1 except that-[4- (4-maleimidophenoxy)] phenylpropane (Exemplary Compound 4-3) was not used, and a prepreg, laminate, resin sheet, and printed wiring were prepared. A plate 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 Table 1.

1. Evaluation Method (1) Glass Transition Temperature The 0.4 mm thick double-sided copper clad laminate obtained in the above examples and comparative examples was etched on the whole surface to produce a 6 mm × 25 mm test piece, and a DMA device (TA-in) The temperature was raised at 5 ° C./min using a dynamic viscoelasticity measuring apparatus DMA983 manufactured by Strument Co., and the peak position of tan δ was defined as the glass transition temperature.

(2) Linear expansion coefficient The 0.4 mm-thick double-sided copper-clad laminate obtained in the examples and comparative examples was etched all over, and a test piece of 5 mm × 20 mm was produced from the obtained laminate, and a TMA apparatus The linear expansion coefficient in the plane direction (X direction) was measured under the condition of 5 ° C./min using (TA Instruments).

(3) Solder heat resistance After the obtained laminate was cut into a 50 mm × 50 mm grinder saw, a sample in which only a quarter of the copper foil was left by etching was prepared, and evaluated according to 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 260 ° C. and 288 ° C. for 30 seconds, and then checking for the presence or absence of an abnormality in appearance. The evaluation method was implemented in the following three stages.
◎ Evaluation method: No abnormality
: There is a bulge (there is an overall bulge)
: Small balloon (small balloon on glass cloth, initial stage)

(4) Peel strength A test piece of 100 mm x 20 mm was prepared from a double-sided copper clad laminate having a thickness of 0.4 mm obtained in Examples and Comparative Examples, and the peel strength at 23 ° C was measured. The peel strength measurement was performed according to JIS C 6481.

(5) Warpage of substrate The warpage evaluation was conducted by leaving the semiconductor device obtained above in an atmosphere of 30 ° C. and 70% humidity for 196 hours, and then performing reflow at 260 ° C. three times to evaluate the warpage of the substrate. 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 (model LS220-MT100MT50, manufactured by Hitachi Technology & Service Co., Ltd.), install the semiconductor device obtained above in the sample chamber of the measuring machine with the semiconductor element side down, and multilayer printed wiring The displacement in the height direction of the plate was measured, and the largest value of the displacement difference was taken as the amount of warpage. 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.

2. Evaluation results As is apparent from Table 1, the laminates using the thermosetting resin compositions of the present invention of Examples 1 to 24 have a high glass transition temperature and a low coefficient of thermal expansion, and are solder heat resistant. There was no problem, and the adhesion (peel strength) was excellent. And the semiconductor device using the thermosetting resin composition of this invention of Examples 1-24 had no problem in the curvature of a board | substrate.

  The laminated board of Comparative Examples 1-11 which did not use (D) specific boron salt contained in the thermosetting resin composition of this invention compared with the laminated board of Examples 1-24, adhesiveness (peel) (Strength) was not sufficient. Furthermore, the laminated plates of Comparative Examples 3 to 6 are inferior in adhesion (peel strength) to the laminated plates of Examples 1 to 24, and inferior in glass transition temperature and solder heat resistance. It became the result. And the semiconductor device of Comparative Examples 3-6 had a big problem of the curvature of a board | substrate.

  The laminated plate of Comparative Example 12 that did not use the bismaleimide compound was inferior in glass transition temperature and linear expansion coefficient as compared with the laminated plates of Examples 1 to 24, resulting in a problem. And the semiconductor device of the comparative example 12 had a big problem of the curvature of a board | substrate.

  For the resin sheet, the same experiment was performed and the same result could be obtained.

  Furthermore, the printed wiring board formed using the laminated board and resin sheet of this invention became favorable. And the semiconductor device which mounts a semiconductor on the printed wiring board formed using the resin sheet also became favorable.

Claims (9)

(A) a compound having at least two epoxy groups in one molecule, (B) a compound having at least two phenolic hydroxyl groups in one molecule, (C) a bismaleimide compound, (D) A thermosetting resin composition comprising a boron salt represented by formula (1).

In the formula, X ₁ , X ₂ , X ₃ and X ₄ are each independently hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and Y ⁺ is a monovalent cation. .   The viscosity of the compound (A) having at least two epoxy groups in one molecule is 0.05 to 3.5 Pa · s as measured with an ICI viscometer under the condition of 150 ° C., and ( The thermosetting resin composition according to claim 1, wherein the epoxy equivalent of A) the epoxy resin is 160 to 320.   The boron salt represented by the general formula (1) is tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetra (p-ethylphenyl) borate, tetraphenylphosphonium tetra. (P-ethoxyphenyl) borate, tetraphenylphosphonium n-butyltriphenylborate, tetraphenylphosphonium tetra (4-fluorophenyl) borate, benzyltriphenylphosphonium tetraphenylborate, tri (p-tolyl) phenylphosphonium tetra (p- Tolyl) borate, tetra-n-butylphosphonium tetraphenylborate, n-butyltriphenyl n-butyltriphenylborate, phenacyltriphenylphosphonium 2. At least one selected from traphenyl borate, tetraethylammonium tetraphenyl borate, diazabicycloundecenium tetraphenyl borate, pyridinium tetraphenyl borate, and 2-ethyl-4-methylimidazolium tetraphenyl borate. Or the thermosetting resin composition of 2.   A prepreg obtained by impregnating a base material with the thermosetting resin composition according to any one of claims 1 to 3.   The laminated board formed by arrange | positioning metal foil on the at least single side | surface of the prepreg of Claim 4.   The laminated board of Claim 5 which consists of a prepreg laminated body in which the said prepreg of at least 2 sheets was laminated | stacked.   The resin sheet formed by arrange | positioning the thermosetting resin composition of any one of Claim 1 to 3 on a support film or metal foil.   The printed wiring board formed from the prepreg of Claim 4, the laminated board of Claim 5 or Claim 6, or the resin sheet of Claim 7.   A semiconductor device in which a semiconductor element is mounted on the printed wiring board according to claim 8.