JP6090784B2 - Epoxy resin varnish, epoxy resin composition, curable sheet, prepreg, laminate, printed wiring board, and semiconductor device - Google Patents

Description

  Provided are an epoxy resin composition, a prepreg, and a cured product thereof having high thermal conductivity and heat resistance, and having excellent solvent solubility.

Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials and casting materials. Conventionally, as an epoxy resin most used industrially, a compound obtained by reacting bisphenol A with epichlorohydrin is known. In applications such as semiconductor encapsulants, cresol novolac epoxy resins are widely used because heat resistance is required.
In recent years, in the electrical and electronic industry, which is a typical application of epoxy resin compositions, high-density mounting of semiconductors and high-density wiring of printed wiring boards for the purpose of multi-function, high performance, and compactness have been achieved. The demand for electrical reliability is increasing, such as package warpage due to heat shrinkage from the time of solder reflow, and malfunction due to heat generated from the inside of a semiconductor element or printed wiring board. As these measures, using a high heat-resistant resin to give high cured product Patent Documents 1 to 3 in the glass transition temperature, a method of narrowing the alpha ₂ domain of temperature shrinkage has been proposed. In Patent Document 4, a highly thermally conductive resin that improves molecular orientation and efficiently releases generated heat to the outside by introducing a mesogenic group into the structure has been developed.

JP 2006-213823 A JP-A-2-252724 JP-A-7-330645 JP 2006-63315 A

  However, since an epoxy resin that generally exhibits high thermal conductivity has a mesogenic group, there is a problem of high orientation and low solubility in a solvent. In particular, heat conductive sheets and heat-resistant substrates that require heat conduction characteristics cannot be molded unless they can be dissolved in a solvent. Further, even when dissolved, if crystals are precipitated during storage, the epoxy resin composition often cannot form a uniform cured product, and the crystal part can be a defective site such as a substrate. In addition, examples of fields that require thermal conductivity include automotive power devices, and in such fields, they are often exposed to high heat conditions, and high heat resistance is required. For this reason, the development of a resin that satisfies the thermal conductivity, heat resistance, and solvent solubility has been demanded.

  In view of such circumstances, the present inventors have intensively studied for an epoxy resin mixture, an epoxy resin composition, and a cured product thereof having excellent heat conduction characteristics and excellent heat resistance and solvent solubility, thereby completing the present invention. It came to. In the following description of the present specification, broken lines indicate that they may or may not exist.

（式中複数存在するＲ^１、Ｒ^２は同一であっても異なっていてもよく、Ｒ^１はそれぞれ独立して、水素原子、ヒドロキシル基、炭素数１〜１０のアルキル基、アルコキシ基、カルボキシル基又はその金属塩、アルコキシカルボニル基、アルキルカルボニルアミノ基、アルキルカルボニル基、ハロゲン原子、ニトロ基、シアノ基、又は置換基を有しても良いフェニル基を示す。ｍ、ｎは１〜５の正数を示す。）
で表されるエポキシ樹脂と溶剤を含有することを特徴とするエポキシ樹脂ワニス。
（２）（１）に記載のエポキシ樹脂が下記一般式（２）

（式中複数存在するＲ^１は前記と同じ意味を示す。）
で表されるフェノール化合物と、
下記一般式（３）

（式中複数存在するＲ^２、ｍ、ｎは前記と同じ意味を示す。）
で表されるポリホルミルポリフェニル誘導体を縮合させて得られるフェノール樹脂に、エピハロヒドリンを反応させて得られるエポキシ樹脂であるエポキシ樹脂ワニス。
（３）前記エポキシ樹脂の軟化点が９０℃以上である（１）または（２）のいずれか一項に記載のエポキシ樹脂ワニス。
（４）（１）または（２）のいずれか一項に記載のエポキシ樹脂ワニスと硬化剤および／または硬化促進剤を含有することを特徴とするエポキシ樹脂組成物。
（５）（４）に記載のエポキシ樹脂組成物を表面支持体に塗布、乾燥して得られる硬化性シート。
（６）（４）に記載のエポキシ樹脂組成物とガラスクロスおよび／または不織布からなるプリプレグ。
（７）（５）または（６）のいずれか一項に記載の硬化性シートおよび／またはプリプレグを貼り合わせて得られる積層板。
（８）（７）に記載の積層板を用いて製造されるプリント配線板。
（９）（８）に記載のプリント配線板に半導体素子を実装、封止した半導体装置。 That is, the present invention relates to the following (1) to (9).
(1) The following general formula (1)

(In the formula, a plurality of R ¹ and R ² may be the same or different, and each R ¹ is independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a carboxyl group. A group or a metal salt thereof, an alkoxycarbonyl group, an alkylcarbonylamino group, an alkylcarbonyl group, a halogen atom, a nitro group, a cyano group, or a phenyl group which may have a substituent, and m and n are 1 to 5. Indicates a positive number.)
The epoxy resin varnish characterized by containing the epoxy resin represented by these, and a solvent.
(2) The epoxy resin described in (1) is represented by the following general formula (2)

(R ¹ to plurality of wherein is as defined above.)
A phenolic compound represented by
The following general formula (3)

(In the formula, a plurality of R ^2, m, and n have the same meaning as described above.)
An epoxy resin varnish which is an epoxy resin obtained by reacting an epihalohydrin with a phenol resin obtained by condensing a polyformyl polyphenyl derivative represented by the formula:
(3) The epoxy resin varnish as described in any one of (1) or (2) whose softening point of the said epoxy resin is 90 degreeC or more.
(4) An epoxy resin composition comprising the epoxy resin varnish according to any one of (1) and (2), a curing agent and / or a curing accelerator.
(5) A curable sheet obtained by applying and drying the epoxy resin composition according to (4) on a surface support.
(6) A prepreg comprising the epoxy resin composition according to (4) and a glass cloth and / or nonwoven fabric.
(7) A laminate obtained by bonding the curable sheet and / or prepreg according to any one of (5) and (6).
(8) A printed wiring board manufactured using the laminated board according to (7).
(9) A semiconductor device in which a semiconductor element is mounted and sealed on the printed wiring board according to (8).

  Since the epoxy resin varnish of the present invention is an epoxy resin varnish having excellent heat conduction characteristics and excellent heat resistance and solvent solubility, it is suitable for fields requiring heat conduction characteristics such as in-vehicle power devices. It is.

（式中複数存在するＲ^１、Ｒ^２は同一であっても異なっていてもよく、Ｒ^１はそれぞれ独立して、水素原子、ヒドロキシル基、炭素数１〜１０のアルキル基、アルコキシ基、カルボキシル基又はその金属塩、アルコキシカルボニル基、アルキルカルボニルアミノ基、アルキルカルボニル基、ハロゲン原子、ニトロ基、シアノ基、又は置換基を有しても良いフェニル基を示す。ｍ、ｎは１〜５の正数を示す。）
で表されるエポキシ樹脂（ａ）を成分として有し、溶剤（ｂ）を含有する。以下、本発明を詳細に説明する。本発明のエポキシ樹脂ワニスは高い熱伝導特性・耐熱性を有する硬化物を与える。
ここで、上記一般式（１）において、Ｒ^１、Ｒ^２として、好ましくは水素原子、ヒドロキシル基、炭素数１〜１０のアルキル基、アルコキシ基である。 The epoxy resin varnish of the present invention has the following general formula (1)

(In the formula, a plurality of R ¹ and R ² may be the same or different, and each R ¹ is independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a carboxyl group. A group or a metal salt thereof, an alkoxycarbonyl group, an alkylcarbonylamino group, an alkylcarbonyl group, a halogen atom, a nitro group, a cyano group, or a phenyl group which may have a substituent, and m and n are 1 to 5. Indicates a positive number.)
It has the epoxy resin (a) represented by this as a component, and contains a solvent (b). Hereinafter, the present invention will be described in detail. The epoxy resin varnish of the present invention gives a cured product having high heat conduction characteristics and heat resistance.
Here, in the above general formula ^(1), as R 1, ^{R 2,} is preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group.

（式中複数存在するＲ^１、Ｒ^２は同一であっても異なっていてもよく、Ｒ^１はそれぞれ独立して、水素原子、ヒドロキシル基、炭素数１〜１０のアルキル基、アルコキシ基、カルボキシル基又はその金属塩、アルコキシカルボニル基、アルキルカルボニルアミノ基、アルキルカルボニル基、ハロゲン原子、ニトロ基、シアノ基、又は置換基を有しても良いフェニル基を示す。ｍ、ｎは１〜５の正数を示す。）で表される。
上記一般式（２）で表されるフェノール化合物と一般式（３）で表されるポリホルミルポリフェニル誘導体を縮合させて得られるフェノール樹脂（ｃ）をエピハロヒドリンと反応させて得られるエポキシ樹脂においては、上記式（１）のエポキシ樹脂を含有する。このようなエポキシ樹脂において、上記式（１）の含有率は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）において通常５０面積％以上、好ましくは５５面積％、より好ましくは６０面積％以上含有する。一般式（１）で表される構造の含有率が５０％より低いと粘度が高すぎて、成型性が悪くなる恐れがある。尚、上記式（１）の含有率は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）を用いて、下記条件下測定できる。
ＧＰＣの各種条件
メーカー：島津製作所
カラム：ガードカラム ＳＨＯＤＥＸ ＧＰＣ ＫＦ−８０２．５（２本） ＫＦ−８０２ ＫＦ−８０３
流速：１．０ｍｌ／ｍｉｎ．
カラム温度：４０℃
使用溶剤：ＴＨＦ（テトラヒドロフラン）
検出器：ＲＩ（示差屈折検出器） The epoxy resin (a) used in the present invention has the general formula (1)

(In the formula, a plurality of R ¹ and R ² may be the same or different, and each R ¹ is independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a carboxyl group. A group or a metal salt thereof, an alkoxycarbonyl group, an alkylcarbonylamino group, an alkylcarbonyl group, a halogen atom, a nitro group, a cyano group, or a phenyl group which may have a substituent, and m and n are 1 to 5. It represents a positive number.)
In the epoxy resin obtained by reacting the phenol resin (c) obtained by condensing the phenol compound represented by the general formula (2) and the polyformyl polyphenyl derivative represented by the general formula (3) with epihalohydrin, And an epoxy resin of the above formula (1). In such an epoxy resin, the content of the above formula (1) is usually 50 area% or more, preferably 55 area%, more preferably 60 area% or more in GPC (gel permeation chromatography). If the content of the structure represented by the general formula (1) is lower than 50%, the viscosity is too high and the moldability may be deteriorated. In addition, the content rate of the said Formula (1) can be measured on condition of the following using GPC (gel permeation chromatography).
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC KF-802.5 (2) KF-802 KF-803
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

In the epoxy resin obtained by reacting the phenol resin obtained by condensing the phenol compound represented by the general formula (2) and the polyformyl polyphenyl derivative represented by the general formula (3) with epihalohydrin, the softening point Is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, and particularly preferably 100 ° C. or higher. This is because heat resistance can be improved, viscosity can be lowered, and storage stability is improved by being in the range of the softening point.
Here, in the general formula ^(2), as R 1, ^{R 2,} is preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group.

（式中複数存在するＲ^１は前記と同じ意味を表す。）
で表されるフェノール化合物と、 The epoxy resin (a) that can be used in the present invention is represented by the following general formula (2).

(In the formula, multiple R ^{1 s} represent the same meaning as described above.)
A phenolic compound represented by

（式中複数存在するＲ^２は前記と同じ意味を表す。）
で表されるポリホルミルポリフェニル誘導体を縮合させて得られるフェノール樹脂をエピハロヒドリンと反応させることにより得られる。 The following general formula (3)

(In the formula, a plurality of R ² have the same meaning as described above.)
It can be obtained by reacting a phenol resin obtained by condensing a polyformyl polyphenyl derivative represented by the following formula with epihalohydrin.

  Here, the phenol compound corresponds to a compound having at least one phenolic hydroxyl group. For example, various kinds of alkylphenols such as phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, etc. -Isomers, various omp-isomers of vinylphenol, allylphenol, propenylphenol, ethynylphenol, or cycloalkylphenols such as cyclopentylphenol, cyclohexylphenol, cyclohexylresole, etc. Examples thereof include, but are not limited to, substituted phenols, and naphthols such as α-naphthol and β-naphthol. Preferable examples include phenol, cresol, and xylenol. These phenols may be used alone or in combination of two or more. When the condensation reaction is performed, the amount of phenol used is usually 2 to 50 mol, preferably 2 to 20 mol, based on 1 mol of the formyl group of the polyformylpolyphenyl derivative represented by the formula (3). 2-10 mol is particularly preferred.

  Specific examples of polyformyl polyphenyl derivatives that can be used in the present invention include 2,2′-dichloromethylformyl diphenyl, 2,4′-diformyl diphenyl, 3,3′-diformyl diphenyl, and 4,4′-diformyl. Diphenyl, 3,3 ′, 4,4′-tetraformyldiphenyl, 3,3 ′, 5,5′-tetraformyldiphenyl, 3,3 ′, 5,5′-tetraformyl-4,4′-dihydroxydiphenyl 2,2′-diformyl-1,1′-binaphthyl and the like, but are not limited thereto. In particular, 4,4'-diformyldiphenyl is preferred.

  In the above condensation reaction, an acid catalyst is used if necessary. Various acid catalysts can be used, and examples include inorganic or organic acids such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Moreover, since the orientation of a phenol resin changes with kinds of acid, it should select suitably as needed. For example, if the ortho orientation is increased, the solubility in a solvent may be improved. Further, when the para-orientation increases, the molecular weight distribution tends to be lowered, and there is a possibility that the viscosity can be reduced. According to the knowledge of the present inventors, those having higher acidity tend to have stronger para-orientation. The amount of the acid catalyst used varies depending on the type of the catalyst, but an appropriate amount may be added within the range of 0.0005% to 200% by weight of the compound represented by the formula (2). Preferably, it selects in the range of 0.1-30 weight%.

  The reaction may be performed without a solvent or a solvent may be used. When the solvent is used, the amount of the solvent used is preferably 50 to 300% by weight, particularly preferably 100 to 250% by weight, based on the total weight of the charged raw materials. Examples of the solvent that can be used include alcohols, ketones, and alkyl-substituted phenyls that are inert to the reaction. Specifically, methanol, ethanol, isopropyl alcohol as the alcohols, acetone, methyl ethyl ketone, methyl isobutyl ketone as the ketones, and toluene, xylene, etc. are preferable as the alkyl-substituted phenyls, but are not limited thereto. An excessive amount of the phenol compound represented by the formula (2) may be charged to form a solvent. By arbitrarily selecting the amount of the phenol compound charged, the molecular weight distribution of the resulting phenol resin can be controlled. These solvents can be used alone or in combination of several kinds. It is preferable to distill off water or alcohols generated during the reaction out of the system by using a fractionating tube or the like in order to carry out the reaction quickly.

The reaction temperature is usually 40 to 200 ° C, preferably 50 to 150 ° C, more preferably 50 to 120 ° C. According to the knowledge of the present inventors, the para-orientation can be enhanced by reacting at a low temperature.
The reaction time is 0.5 to 20 hours, preferably 1 to 15 hours. The reaction may be carried out while charging all the raw materials at once or while raising the temperature, or may be carried out by sequentially adding them in portions, but it is preferable to add them all at once from the viewpoint of obtaining a constant molecular weight distribution.

  After completion of the reaction, washing with water is performed until the pH value of the washing liquid becomes 3 to 8, preferably 5 to 8. When washing with water, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate and diethylenetriamine are necessary. Various basic substances such as organic amines such as triethylenetetramine, aniline, and phenylenediamine may be used as the neutralizing agent. In some cases, a solvent may be added. The solvent that can be used is not particularly limited as long as it dissolves a high molecular weight substance and is well separated from the aqueous layer, and examples thereof include toluene, methyl ethyl ketone, and methyl isobutyl ketone. Washing with water may be performed according to a conventional method. For example, warm water in which the neutralizing agent is dissolved is added to the reaction mixture, and the liquid separation extraction operation is repeated.

  A phenol resin (c) can be obtained by removing the solvent and unreacted phenols by heating and reducing the obtained organic layer with a rotary evaporator.

The para orientation ratio in the total orientation of the phenol resin (c) thus obtained is usually 50% or more, preferably 55%, more preferably 60% or more. When the para-orientation property is high, the molecules in the cured product are easily oriented, and the thermal conductivity tends to be good. In addition, the para orientation property calculated the ratio of para orientation and ortho orientation using < ¹³ > C-NMR (carbon nuclear magnetic resonance spectroscopy) under the following conditions.
¹³ C-NMR Various Conditions NMR Model: JEOL Ltd. JNM-ECS400
Solvent: DMSO-d ₆
Concentration: 100 mg / 0.5 mL
Frequency domain: 400MHz
Pulse interval: 3.7us
Integration count: 3000 times Measurement temperature: 9.4T

In the reaction for obtaining the epoxy resin (a) used in the present invention, the epihalohydrin is preferably an epichlorohydrin which is industrially easily available. The usage-amount of epihalohydrin is 3.0-15 mol normally with respect to 1 mol of hydroxyl groups of a phenol resin (c), Preferably it is 3.0-10 mol, More preferably, it is 3.5-8.5 mol, Most preferably 5.5 to 8.5 mol.
If the amount is less than 3.0 mol, the epoxy equivalent may be increased, and the workability of the resulting epoxy resin is likely to deteriorate. It is not preferable.

Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide and the like, and a solid substance may be used, or an aqueous solution thereof may be used. From the viewpoint of solubility and handling, it is preferable to use a solid material molded into a flake shape.
The amount of alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, more preferably 0.99 to 1, mol per mol of hydroxyl group in the raw material phenol mixture. .15 moles.

  In order to accelerate the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of hydroxyl group in the raw material phenol mixture.

In this reaction, it is preferable to use a nonpolar proton solvent (dimethyl sulfoxide, dioxane, dimethylimidazolidinone, etc.) or an alcohol having 1 to 5 carbon atoms in addition to the epihalohydrin. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol. The usage-amount of a nonpolar protic solvent or a C1-C5 alcohol is 2-50 weight% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 4-25 weight%. Moreover, epoxidation may be performed while controlling the moisture in the system by a technique such as azeotropic dehydration.
When the amount of moisture in the system is large, it is not preferable because the electrical reliability of the obtained epoxy resin is deteriorated, and it is preferable to synthesize by controlling the moisture to 5% or less. Moreover, when an epoxy resin is obtained using a nonpolar proton solvent, an epoxy resin excellent in electrical reliability can be obtained, and therefore a nonpolar proton solvent can be suitably used.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In particular, in the present invention, 60 ° C. or higher is preferable for higher-purity epoxidation, and reaction under conditions close to reflux conditions is particularly preferable. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is short, the reaction does not proceed, and if the reaction time is long, a by-product is formed, which is not preferable.
After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is a solvent containing a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). It can also be dissolved, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added to react to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the phenol resin (c) used for epoxidation. . The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin (a). The para orientation ratio in the total orientation of the epoxy resin (a) thus obtained is usually 40% or more, preferably 50%, more preferably 55% or more. When the para-orientation property is high, the molecules in the cured product are easily oriented, and the thermal conductivity tends to be good. In addition, the para orientation property measured the nuclear magnetic resonance peak of the carbon nucleus using < ¹³ > C-NMR (carbon nuclear magnetic resonance spectroscopy) on the following conditions, and computed the ratio of para orientation and ortho orientation.
¹³ C-NMR Various Conditions NMR Model: JEOL Ltd. JNM-ECS400
Solvent: DMSO-d ₆
Concentration: 100 mg / 0.5 mL
Frequency domain: 400MHz
Pulse interval: 3.7us
Integration count: 3000 times Measurement temperature: 9.4T
When this requirement is satisfied, the epoxy resin (a) is more excellent in solvent solubility and is useful as an epoxy resin varnish.

The solvent (b) that can be used in the present invention is not limited as long as it can dissolve the epoxy resin (a), and examples thereof include alkyl-substituted phenyls, ketones, and amides. Specific examples of alkyl-substituted phenyls include toluene, xylene, ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and amides include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. The amount of the solvent used is usually 10 to 90% by weight, preferably 15 to 90% by weight in the epoxy resin (a).
In the present invention, nonpolar solvents such as methyl ethyl ketone and methyl isobutyl ketone are preferred, and ketones are particularly preferred.

  The epoxy resin varnish of the present invention can give a cured product having excellent heat conduction characteristics and heat resistance, and is particularly useful in the fields of curable sheets, prepregs, substrates and the like.

  Next, the epoxy resin composition of the present invention will be described. The epoxy resin composition of the present invention is obtained by adding a curing agent and / or a curing accelerator to the aforementioned epoxy resin varnish.

The epoxy resin composition of the present invention contains a curing agent. Specific examples of the curing agent include a phenol resin, a phenol compound, an amine compound, an acid anhydride compound, an amide compound, and a carboxylic acid compound. Specific examples of curing agents that can be used include phenolic resins, phenolic compounds; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydride Roxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1, Polycondensates with 1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene, and their modified products, and halogenated bisphenols such as tetrabromobisphenol A And polyphenols such as terpene and phenol condensates, but are not limited thereto. These may be used alone or in combination of two or more.
Preferred phenol resins include phenol aralkyl resins (resins having an aromatic alkylene structure) in terms of dielectric constant, and particularly preferred is a structure having at least one selected from phenol, naphthol, and cresol, and serves as the linker. A resin characterized in that the alkylene part is at least one selected from a benzene structure, a biphenyl structure, and a naphthalene structure (specifically, zylock, naphthol zylock, phenol biphenylene novolak resin, cresol-biphenylene novolak resin, phenol-naphthalene) And novolak resin.).
Amine-based compounds, amide-based compounds; diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, nitrogen-containing compound anhydride compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine , Carboxylic acid compounds; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl Hexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride , Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, acid anhydrides and the like; various alcohols, carbinol-modified silicone, a carboxylic acid resin obtained by the addition reaction of the aforementioned acid anhydride;
Others: Examples include imidazole, trifluoroborane-amine complexes, and guanidine derivative compounds, but are not limited thereto. These may be used alone or in combination of two or more.

The epoxy resin curing agent is used in an amount such that the phenolic hydroxyl group is usually 0.55 to 1.0 equivalent, preferably 0.6 to 0.95 equivalent, relative to the epoxy group of the epoxy resin. When the curing agent is less than 0.55 equivalent, the number of unreacted epoxy groups increases, and workability particularly during transfer molding is reduced. When it exceeds 1.0 equivalent, the amount of unreacted curing agent increases, and the thermal and mechanical properties deteriorate, which is not preferable.

If necessary, a curing accelerator may be added to the epoxy resin composition of the present invention. Specific examples of the curing accelerator include phosphines such as triphenylphosphine and bis (methoxyphenyl) phenylphosphine, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethylimidazole and 4-methylimidazole, Tertiary amines such as 2- (dimethylaminomethyl) phenol, trisdimethylaminomethylphenol, diazabicycloundecene, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc. Quaternary phosphonium salts such as quaternary ammonium salts, triphenylbenzyl phosphonium salts, triphenylethyl phosphonium salts, tetrabutyl phosphonium salts (the counter ions of quaternary salts are halogens) Organic acid ions, hydroxide ions, such as, but not particularly specified, in particular an organic acid ion, a hydroxide ion.), Metal compounds such as tin octylate and the like.

  The usage-amount of a hardening accelerator is 0.2-5.0 weight part normally per 100 weight part of epoxy resins, Preferably, it is 0.2-4.0 weight part.

The epoxy resin composition of the present invention can be used in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin (a) is preferably 30% by weight or more, particularly preferably 40% by weight or more.
Other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolak type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and dicyclopentadiene phenol additions. Examples include reactive epoxy resins. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, -Hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4-bis Polycondensates with (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, etc. and their modified products, halogenated bisphenols such as tetrabromobisphenol A, glycidyl ethers derived from alcohols, fats Cyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain, cyclic, ladder, or mixed siloxane structure of at least two kinds of glycidyl groups) And / or an epoxy resin having an epoxycyclohexane structure ) And other solid or liquid epoxy resins, but are not limited thereto.

  When used for electrical and electronic parts, those having a low hydrolyzable chlorine concentration are preferred. That is, it is preferable that hydrolyzable chlorine is 0.2% by weight or less as defined by the elimination chlorine when the epoxy resin is dissolved in dioxane and treated with 1N KOH for 30 minutes under reflux, 0.15% by weight The following are more preferable.

  The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

Furthermore, you may add antioxidant to the epoxy resin composition of this invention as needed. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part with respect to the resin component in the curable resin composition of this invention, Preferably it is 0.01-0.5 weight part. It is.
Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl) -6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) Propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t- Butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t- Butyl-4-hydroxybenzyl phosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methyl Enyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bisphenols such as bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) calcium 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 '-Hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1 , 3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, etc. Molecular type phenols are exemplified.
Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. .
Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. 9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxaphosphaphenanthrene oxides such as 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are exemplified.
These antioxidants can be used alone, but two or more of them may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable.

Furthermore, you may add a light stabilizer to the epoxy resin composition of this invention as needed.
As the light stabilizer, hindered amine-based light stabilizers, particularly HALS and the like are suitable. HALS is not particularly limited, but representative examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-pentamethyl-4-pi Peridyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), etc. Only one HALS is used. Two or more types may be used in combination.

  Furthermore, a binder resin can also be mix | blended with the epoxy resin composition of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.

  Furthermore, the epoxy resin composition of this invention can add an inorganic filler, a pigment, a mold release agent, a silane coupling agent, a softening agent, etc. as needed. In particular, the addition of non-flammable inorganic fillers has the effect of further improving the flame retardancy of the composition, and in terms of flame retardancy, it should be added in a large amount as long as there is no problem with workability and physical properties after curing. Is desirable. Non-combustible inorganic fillers include hydroxides such as aluminum hydroxide, magnesium hydroxide and iron hydroxide. Examples include zinc stannate, silica, alumina, calcium carbonate, aluminum nitride, and silicon nitride.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing each component at a predetermined ratio. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. In the epoxy resin composition of the present invention, for example, the epoxy resin and the curing agent are heated in advance to 100 to 200 ° C., at least one of the epoxy resin and the curing agent is melted, and the other is dissolved in the melt. Thereafter, it can be obtained by adding and mixing an inorganic filler, a pigment, a release agent, a flame retardant, a silane coupling agent and the like and a curing accelerator, if necessary, with an extruder, a roll, a kneader or the like. Moreover, you may mix said each component with an extruder, a roll, a kneader, etc. without passing through a melting process depending on the case. The obtained epoxy resin composition is usually molded and cured using a transfer molding machine or the like, and further performance is improved by post-curing at 80 to 200 ° C. for 2 to 10 hours. Moreover, when setting it as a liquid sealing material, a liquid epoxy resin is used and it can mix and manufacture the epoxy resin composition of this invention at room temperature.

  The epoxy resin composition of the present invention can be used for various applications such as molding materials, adhesives, composite materials and paints. In particular, since the cured epoxy resin of the present invention exhibits excellent heat resistance and heat conduction characteristics, it is useful in the electrical and electronic fields such as IC sealing materials, laminated materials, and electrical insulating materials.

  The curable sheet of the present invention is formed by forming an insulating layer made of the resin composition on a surface support such as a metal foil or a film and forming a B-stage. Here, the method for forming the curable sheet is not particularly limited. For example, a resin varnish is prepared by adding a solvent or the like to the above-described epoxy resin composition as necessary, and resin is prepared using various coating apparatuses. A method of drying the varnish after coating the varnish on the substrate, a method of spraying the epoxy resin composition varnish on the substrate with a spray device and then drying the varnish are exemplified.

  The solvent used in the above-described epoxy resin composition varnish desirably exhibits good solubility with respect to the resin component in the resin composition, but a poor solvent may be used as long as it does not have an adverse effect. . Examples of the solvent exhibiting good solubility include alkyl-substituted phenyls, ketones, amides and the like. Specific examples of alkyl-substituted phenyls include toluene, xylene, ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and amides include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

  Although it does not specifically limit as solid content in the above-mentioned epoxy resin composition varnish, 10 to 70 weight% is preferable and 20 to 55 weight% is especially preferable.

  When the curable sheet of the present invention has two or more insulating layers, it is preferable that at least one of them is the resin composition of the present invention. Moreover, it is preferable that the insulating layer which consists of a resin composition for printed wiring boards of this invention forms the resin layer which consists of an epoxy resin composition of this invention directly on metal foil or a film. By doing so, the insulating layer made of the epoxy resin composition of the present invention can exhibit high plating peel strength with the outer layer circuit conductor during the production of the printed wiring board.

  The insulating layer made of the epoxy resin composition of the present invention preferably has a thickness of 0.5 μm to 10 μm. By setting the thickness of the insulating layer within the above range, high adhesion with the conductor circuit can be obtained.

  Although the film used for the curable sheet of the present invention is not particularly limited, for example, a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, a thermoplastic resin film having heat resistance such as a fluorine resin, or a polyimide resin is used. Can do.

Although the metal foil used for the curable sheet of this invention is not specifically limited, For example, copper and / or a copper-type alloy, aluminum, and / or
Or metal alloy such as aluminum alloy, iron and / or iron alloy, silver and / or silver alloy, gold and gold alloy, zinc and zinc alloy, nickel and nickel alloy, tin and tin alloy, etc. Can be used. In manufacturing the resin sheet of the present invention, the surface roughness (Rz) of the irregularities on the surface of the metal foil on which the insulating layer is laminated is preferably 2 μm or less. By forming an insulating layer made of the resin composition of the present invention on the surface of a metal foil having a surface roughness (Rz) of 2 μm or less, the surface roughness is small and adhesion (plating peel strength) is excellent. Can be. The curable sheet of the present invention is particularly useful for applications such as a substrate adhesive sheet, an interlayer insulating film, and a semiconductor element sheet sealing.

  The method for producing a prepreg according to the present invention is obtained by impregnating a base material with the aforementioned epoxy resin composition varnish.

  The base material used in the prepreg is not particularly limited, and examples thereof include 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, and aromatics. 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. Among these base materials, glass fiber base materials represented by glass woven fabric are preferable in terms of strength and water absorption.

  The method of impregnating the base material with the epoxy resin composition is not particularly limited. For example, the resin composition is prepared as a resin varnish using a solvent, and the base material is immersed in the resin varnish. Examples thereof include a method of applying with a coater and a method of spraying a resin varnish by spraying. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material improves. As a solvent used when preparing a resin varnish, it is desirable to show favorable solubility with respect to a resin composition. Such solvents include alkyl substituted phenyls, ketones, amides and the like. Specific examples of alkyl-substituted phenyls include toluene, xylene, ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and amides include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

  The prepreg is obtained by heating and drying a base material impregnated with the epoxy resin composition varnish.

The method for producing a laminate according to the present invention is characterized in that the above-mentioned curable sheet or prepreg is heat-press molded as the whole layer or a part of the layer, and if necessary, one-sided by the above-mentioned heat-pressure molding Or it can obtain by arranging metal foils, such as copper foil and aluminum foil, on both surfaces, and carrying out lamination molding by well-known methods, such as a multistage press, a multistage vacuum press, a continuous molding machine, and an autoclave. The curing condition is usually performed by heating at about 80 to 250 ° C. for 30 seconds to 15 hours. Moreover, although the pressure of 2-100 kgf / cm < ² > is applied as needed, you may change conditions suitably.

  The printed wiring board of the present invention is manufactured using the above-described laminated board.

  Hereinafter, although an example of the manufacturing method of a printed wiring board is demonstrated, the manufacturing method of a printed wiring board is not limited to the following manufacturing method.

First, metal layers (copper foil) on both sides
Is prepared, and through holes are formed in the laminated plate by a drill or the like. Next, a conductive post is formed by filling the through hole with plating or the like. Next, the metal layers formed on both sides of the laminated board are patterned into a predetermined pattern by etching or the like to conduct a conductor circuit (inner layer circuit)
Form. Next, the conductor circuit is subjected to a roughening process such as a blackening process. Thereby, an inner layer circuit board is obtained.

Next, the above-described prepreg is stacked on both surfaces of the inner layer circuit board, and this is heated and pressed using a vacuum pressure laminator device. Thereafter, an insulating layer formed by completely curing the resin composition in the prepreg is formed on both surfaces of the inner circuit board by heat-curing with a hot air dryer or the like. The conditions for heat and pressure molding are not particularly limited. For example, the temperature is 60 to 160 ° C.
And a pressure of 0.2 to 3 MPa. Moreover, it is although it does not specifically limit as conditions to carry out heat hardening, For example, it can implement in temperature 140-240 degreeC and time 30-120 minutes.

Next, through holes are formed in each insulating layer by laser irradiation, and the through holes are filled with plating or the like to form conductor posts. Next, a metal layer is formed on the surface of each insulating layer, and this metal layer is patterned into a desired pattern, whereby a conductor circuit (outer layer circuit) is formed on the surface of each insulating layer.
Form. The outer layer circuit is provided with a connection electrode portion for mounting a semiconductor element.

  Next, a solder resist is formed on the outermost layer, and the connection electrode portion is exposed so that the semiconductor element can be mounted by exposure and development. Next, it is cut into a predetermined size. Thereby, a multilayer printed wiring board is obtained.

  Such a printed wiring board has excellent heat conduction characteristics and heat resistance, and the warpage of the printed wiring board is suppressed.

  The semiconductor device of the present invention is obtained by mounting and sealing a semiconductor element on the printed wiring board described above. The mounting method and the sealing method of the semiconductor element are not particularly limited. For example, a flip chip bonder or the like is used to align the connection electrode portions on the multilayer printed wiring board and the solder bumps of the semiconductor element. Thereafter, the solder bumps are heated to the melting point or more, and the printed wiring board and the solder bumps are connected by fusion bonding. Next, a liquid sealing resin is filled between the printed wiring board and the semiconductor element and cured. Thereby, a semiconductor device is obtained.

  Since the semiconductor device thus obtained has excellent heat conduction characteristics and heat resistance, it is particularly useful for in-vehicle power devices.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples. Below, a part is a weight part unless there is particular notice. The hydroxyl group equivalent, epoxy equivalent, softening point, ICI viscosity, DMA, and thermal conductivity were measured under the following conditions.
-Hydroxyl equivalent: Measured by the method described in JIS K-7236, the unit is g / eq. It is.
-Epoxy equivalent Measured by the method described in JIS K-7236, the unit is g / eq. It is.
-Softening point Measured by a method based on JIS K-7234.
-ICI viscosity Measured by a method based on JIS K-7117-2.
・ DMA
Dynamic viscoelasticity measuring device: DMA-2980 manufactured by TA-instruments
Temperature increase rate: 2 ° C / min.TMA
TMA thermomechanical measuring device: TM-7000 manufactured by Vacuum Riko Co., Ltd.
Temperature increase rate: 2 ° C./min.
Thermal conductivity thermal conductivity measuring device: Uniter 2022 manufactured by Anter
Conforms to ASTME-1530 ・ Various conditions of ¹³ C-NMR NMR model: JNM-ECS400, JEOL Ltd.
Solvent: DMSO-d ₆
Concentration: 100 mg / 0.5 mL
Frequency domain: 400MHz
Pulse interval: 3.7us
Integration count: 3000 times Measurement temperature: 9.4T

Synthesis Example 1 Synthesis of Phenol-Diformyldiphenyl Type Phenolic Resin
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, add 1506 parts of phenol, 84 parts of 4,4′-diformyldiphenyl, and 25 parts of p-toluenesulfonic acid while purging with nitrogen, and raise the temperature to 100 ° C. The reaction was carried out for 8 hours while maintaining the temperature as it was. After completion of the reaction, 300 parts of methyl isobutyl ketone (MIBK) was added and washed with water until the aqueous layer became neutral. Excess phenol was distilled off from the resulting organic layer under reduced pressure at 180 ° C. using a rotary evaporator to obtain 202 parts of a phenol resin. The obtained phenol resin was red solid, and the hydroxyl equivalent was 145 g / eq. The softening point was 130 ° C. and the para orientation ratio was 74% (lower chart 1- (a)).
Chart 1:
(A) Carbon nuclear magnetic resonance of phenol resin

Synthesis Example 2 Synthesis of Phenol-Diformyldiphenyl Type Epoxy Resin
To a flask equipped with a stirrer, a reflux condenser, and a stirrer was added 202 parts of the phenolic resin obtained in Example 1, 773 parts of epichlorohydrin, 50 parts of methanol, and 7.8 parts of water while purging with nitrogen. The temperature was raised to 75 ° C. Next, 58 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the organic layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue, 532 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 6.3 parts of methanol and 18 parts of 30% aqueous sodium hydroxide solution were added and reacted for 1 hour. Then, the organic layer was washed with water until the washing water became neutral. The solvent was distilled off at 180 ° C. under reduced pressure to obtain 257 parts of the desired epoxy resin. The obtained epoxy resin was a yellow solid, and the epoxy equivalent was 217 g / eq. The softening point was 99 ° C., the viscosity at 150 ° C. was 2.7 Pa · s, and the para orientation ratio was 55% (Another chart 1- (b)).
Chart 1:
(B) Carbon nuclear magnetic resonance of epoxy resin

Example 1 and Comparative Examples 1 to 4
Various epoxy resins were dissolved in methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and toluene by heating to 50 ° C. at a concentration of 50 wt% and 70 wt%. The resulting varnish was allowed to stand at room temperature, and the period until crystals were obtained is shown in Table 1.

エポキシ樹脂１：合成例２で得られたエポキシ樹脂
エポキシ樹脂２：フェノール−グリオキザール型エポキシ樹脂（日本化薬（株）製ＧＴＲ−１８００ エポキシ当量：１７０ｇ／ｅｑ．）
エポキシ樹脂３：ビフェノール型エポキシ樹脂とテトラメチルビフェノール型エポキシ樹脂の混合物（日本化薬（株）製ＹＬ６１２１Ｈ エポキシ当量：１７１ｇ／ｅｑ．）
エポキシ樹脂４：トリスフェノールメタン型エポキシ樹脂（日本化薬（株）製ＥＰＰＮ−５０１ＨＹ エポキシ当量：１６７ｇ／ｅｑ．）
エポキシ樹脂５：２−ターシャリーブチル−５−メチルフェノール−サリチルアルデヒド型エポキシ樹脂（日本化薬（株）製 エポキシ当量：２１４ｇ／ｅｑ．）
硬化剤１：フェノールノボラック（明和化成工業株式会社製 Ｈ−１）
硬化剤２：ジフェニルジアミノメタン（東京化成工業株式会社製）
触媒：トリフェニルホスフィン（純正化学株式会社製） Test Examples 1-5
Various components were blended in the proportions (parts) shown in Table 2, kneaded with a mixing roll, and tableted, and then a resin molded product was prepared by transfer molding, followed by 160 ° C. for 2 hours and further 180 ° C.
Was heated for 8 hours to obtain a cured product of the epoxy resin composition of the present invention and the comparative resin composition. Table 2 shows the physical properties of these cured products.
It was shown to.

Epoxy resin 1: Epoxy resin obtained in Synthesis Example 2 Epoxy resin 2: Phenol-glyoxal type epoxy resin (Nippon Kayaku Co., Ltd. GTR-1800 epoxy equivalent: 170 g / eq.)
Epoxy resin 3: A mixture of a biphenol type epoxy resin and a tetramethyl biphenol type epoxy resin (YL6121H epoxy equivalent by Nippon Kayaku Co., Ltd .: 171 g / eq.)
Epoxy resin 4: Trisphenol methane type epoxy resin (EPPN-501HY manufactured by Nippon Kayaku Co., Ltd. Epoxy equivalent: 167 g / eq.)
Epoxy resin 5: 2-tertiary butyl-5-methylphenol-salicylaldehyde type epoxy resin (Epoxy equivalent: 214 g / eq. Manufactured by Nippon Kayaku Co., Ltd.)
Curing agent 1: phenol novolak (M-1 Kasei Kogyo H-1)
Hardener 2: Diphenyldiaminomethane (manufactured by Tokyo Chemical Industry Co., Ltd.)
Catalyst: Triphenylphosphine (Pure Chemical Co., Ltd.)

From the above results, since the epoxy resin (a) used in the present invention is excellent in solvent solubility, it can be made into an epoxy resin varnish and an epoxy resin composition, and can be a curable sheet, prepreg, laminated board, printed wiring board, semiconductor device. This is particularly useful for power devices for vehicles and the like because it can be molded into a molded product and can provide a cured product having higher heat conduction characteristics and heat resistance.

Claims (8)

An epoxy resin varnish containing an epoxy resin represented by the following general formula (1) and a solvent, and having a softening point of 95 ° C. or higher .

(In the formula, a plurality of R ¹ and R ² may be the same or different, and R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group) A group, a carboxyl group or a metal salt thereof, an alkoxycarbonyl group, an alkylcarbonylamino group, an alkylcarbonyl group, a halogen atom, a nitro group, a cyano group, or a phenyl group which may have a substituent. Shows a positive number from 1 to 5. The broken line may or may not exist. ) Epihalohydrin is added to a phenol resin obtained by condensing a phenol compound represented by the following general formula (2) and a polyformyl polyphenyl derivative represented by the following general formula (3). Epoxy resin varnish, which is an epoxy resin obtained by reaction.

(A plurality of R ¹ and broken lines in the formula have the same meaning as described above.)

(A plurality of R ² , m, n, and broken lines in the formula have the same meaning as described above.) An epoxy resin composition comprising the epoxy resin varnish according to claim 1 or 2, a curing agent and / or a curing accelerator. A curable sheet obtained by applying and drying the epoxy resin composition according to claim 3 on a surface support. A prepreg comprising the epoxy resin composition according to claim 3 and a glass cloth and / or a nonwoven fabric. A laminate obtained by bonding the curable sheet according to claim 4 and / or the prepreg according to claim 5 . The printed wiring board manufactured using the laminated board of Claim 6 . A semiconductor device in which a semiconductor element is mounted and sealed on the printed wiring board according to claim 7 .