JP6284732B2 - Epoxy resin mixture and curable resin composition - Google Patents

Description

  The present invention provides a composition excellent in fluidity, and in the cured product, the cured product is excellent in heat resistance and flame retardancy, and at the same time has a high elastic modulus at high temperatures and provides a cured product excellent in strength. About.

  The present invention relates to an electrical and electronic material application that requires high functionality, particularly to an epoxy resin mixture, a curable resin composition, and a cured product thereof suitable as a semiconductor sealant and a thin film substrate material.

  Curable resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It is used.

However, in recent years, with the development in the electric / electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler) as well as high purity of resin composition, There is a need for further improvements in various properties such as increased reactivity to shorten the molding cycle. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment. Especially in the field of semiconductor encapsulation, substrates (substrate itself or its peripheral materials), the complexity of thinning, stacking, systematization, and three-dimensionalization has become more complex as the semiconductor has changed. Pitching and thinning are progressing more and more, and if there is no high fluidity, a wire sweep is induced. Furthermore, it has come to have a bad influence on the connection part of a wire, and the viscosity reduction of a system is needed.
As the thickness is reduced, the amount of warpage is increased during solder mounting, and the connection reliability is lowered. Therefore, development of a highly shrinkable epoxy resin having a high elastic modulus at a high temperature is required.

“Halogen-free high elastic low thermal expansion multilayer material MCL-E-700G (R)”, Hitachi Chemical Co., Ltd. [searched August 6, 2013], <http://www.hitachi-chem.co.jp/ japanese / report / 054 / 54_r8.pdf>

There are various methods for reducing the viscosity. Generally, the molecular weight reduction is used as the method for reducing the viscosity. However, since the shape at room temperature tends to have fluidity when the molecular weight is lowered, It is difficult to handle, the heat resistance of the cured product is lowered, and when it is made into a composition, it becomes sticky, making storage and handling difficult.
An object of this invention is to provide the phenol resin and epoxy resin which give the composition excellent in fluidity | liquidity, and give the hardened | cured material which has a high elasticity modulus at the same time high temperature, and was excellent in intensity | strength.

（式中、Ａｒはナフタレン核（ａ）またはベンゼン核（ｂ）を示し、かつ、（ａ）／（ｂ）＝０．１〜１００であり、Ｇはグリシジル基を示し、Ｒは水素原子またはメチル基を示し、ｍは１または２であり、ｎは０〜１５の整数である。）
で表されるフェノール・ナフトール混合ザイロック型エポキシ樹脂と置換もしくは無置換の４，４´−ビスグリシジルオキシビフェニル（ただし、置換基をその芳香環に有する場合、置換基の数は４以下、炭素数は４以下である。）を含有することを特徴とするエポキシ樹脂混合物、
（２）
前記式（Ｉ）で表されるフェノール・ナフトール混合ザイロック型エポキシ樹脂（Ａ）と置換もしくは無置換の４，４´−グリシジルオキシビフェニル（Ｂ）の重量比がＡ／Ｂ＝１〜１０であることを特徴とする前項（１）に記載のエポキシ樹脂混合物、
（３）
下記一般式（ＩＩ）

（式中、Ａｒはナフタレン核（ａ）またはベンゼン核（ｂ）を示し、かつ、（ａ）／（ｂ）＝０．１〜１００であり、Ｒは水素原子またはメチル基を示し、ｍは１または２であり、ｎは０〜１５の整数である。）
で表されるフェノール・ナフトール混合ザイロック型フェノール樹脂と置換もしくは無置換の４，４´−ビフェノール（ただし、置換基をその芳香環に有する場合、置換基の数は４以下、炭素数は４以下である。）を混合し、エピハロヒドリンと反応させ、得られることを特徴とする前項（１）に記載のエポキシ樹脂混合物、
（４）
前項（１）〜（３）に記載のエポキシ樹脂混合物、および硬化剤を含有することを必須とする硬化性樹脂組成物、
（５）
硬化剤がフェノールノボラックであることを特徴とする前項（４）に記載の硬化性樹脂組成物、
（６）
前項（１）〜（３）に記載のエポキシ樹脂混合物、および硬化促進剤を含有することを必須とする硬化性樹脂組成物、
（７）
前項（４）〜（６）に記載の硬化性樹脂組成物を硬化することを特徴とする硬化物、
（８）
前項（７）に記載の硬化物のうち、２５０℃における弾性率が２５００〜５０００ＭＰａであることを特徴とする硬化物、
を提供するものである。 As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
The following general formula (I)

(In the formula, Ar represents a naphthalene nucleus (a) or a benzene nucleus (b), and (a) / (b) = 0.1 to 100, G represents a glycidyl group, and R represents a hydrogen atom or Represents a methyl group, m is 1 or 2, and n is an integer of 0 to 15.)
And a substituted or unsubstituted 4,4′-bisglycidyloxybiphenyl (provided that the aromatic ring has a substituent, the number of substituents is 4 or less, and the number of carbon atoms) Is an epoxy resin mixture characterized by containing
(2)
The weight ratio of the phenol / naphthol mixed sylock type epoxy resin (A) represented by the formula (I) to the substituted or unsubstituted 4,4′-glycidyloxybiphenyl (B) is A / B = 1 to 10. The epoxy resin mixture as described in (1) above,
(3)
The following general formula (II)

(In the formula, Ar represents a naphthalene nucleus (a) or a benzene nucleus (b), and (a) / (b) = 0.1 to 100, R represents a hydrogen atom or a methyl group, and m represents 1 or 2 and n is an integer of 0 to 15.)
And a substituted or unsubstituted 4,4′-biphenol (provided that the aromatic ring has a substituent, the number of substituents is 4 or less and the number of carbons is 4 or less. The epoxy resin mixture according to item (1), which is obtained by mixing and reacting with epihalohydrin,
(4)
A curable resin composition essentially comprising an epoxy resin mixture according to the preceding items (1) to (3) and a curing agent;
(5)
The curable resin composition according to item (4), wherein the curing agent is phenol novolac,
(6)
A curable resin composition essentially comprising an epoxy resin mixture according to the preceding items (1) to (3) and a curing accelerator;
(7)
A cured product obtained by curing the curable resin composition according to any one of (4) to (6) above;
(8)
Of the cured product described in the preceding item (7), a cured product having an elastic modulus at 250 ° C. of 2500 to 5000 MPa,
Is to provide.

  The epoxy resin mixture of the present invention is an epoxy resin that contributes to the fluidity of the composition with a very low viscosity, and is a highly shrinkable epoxy resin that exhibits a high elastic modulus at high temperatures. Therefore, it is useful for insulating materials for electrical and electronic parts, laminates (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, and the like. In particular, it is extremely useful for reducing the amount of warpage during solder mounting in a semiconductor sealing material for protecting a semiconductor element.

The epoxy resin mixture of the present invention is a phenol / naphthol mixed zyloc type epoxy resin and a substituted or unsubstituted 4,4′-bisglycidyloxybiphenyl (provided that the aromatic ring has a substituent, the number of substituents is 4 or less. , The number of carbon atoms is 4 or less).
Phenol / naphthol mixed sylock type epoxy resin is a reaction product of phenol / naphthol mixed sylock type phenol resin and epihalohydrin, or 4,4′-bisglycidyloxybiphenyl (provided that the substituent is a substituent in the aromatic ring) Is 4,4'-biphenol (provided that the aromatic ring has a substituent, the number of substituents is 4 or less, and the number of carbons is 4 or less.) .)

（式中、Ａｒはナフタレン核（ａ）またはベンゼン核（ｂ）を示し、（ａ）／（ｂ）＝０．１〜１００であり、Ｒは水素原子またはメチル基を示し、ｍは１または２であり、ｎは０〜１５の整数である。）
で表されるフェノール樹脂を使用する。
上記フェノール樹脂は、例えば特開２０１２−９７２２９号公報に記載の方法によって得ることができる。また、市販品としては、ＧＰＮＸ−７０ＨＮ（群栄化学社製）として入手することができる。
上記式（ＩＩ）において、ナフタレン核（ａ）とベンゼン核（ｂ）の割合（モル比）は、通常（ａ）／（ｂ）＝０．１〜１００であり、１．０〜２０がより好ましく、２．０〜１０が特に好ましい。ここで、（ａ）／（ｂ）の算出方法は、例えば、上記式（ＩＩ）のフェノール樹脂を反応させた後、残存しているナフタレン核を付与する原料とベンゼン核を付与する原料の未反応残存量をガスクロマトグラフィーで測定し、フェノール樹脂（ＩＩ）に取り込まれたナフタレン核、ベンゼン核のモル比を算出することで求めることができる。
尚、ナフタレン核（ａ）は、下記骨格

であり、Ａｒがナフタレン核である場合には上記骨格が上記式（ＩＩ）（式（Ｉ）も同様）に導入される。そして、Ａｒに結合する−（ＯＨ）ｍ基、Ｒ基、ないし連結基は上記骨格の炭素原子に結合する。
また、ベンゼン核（ｂ）は、下記骨格

であり、Ａｒがベンゼン核である場合には上記骨格が上記式（ＩＩ）（式（Ｉ）も同様）に導入される。そして、Ａｒに結合する−（ＯＨ）ｍ基、Ｒ基、ないし連結基は上記骨格の炭素原子に結合する。
また、ｎは繰り返し数を表し、通常０〜１５であるが、１〜１０がより好ましい。ｎが１５を超えると軟化点が高くなりすぎるため好ましくない。
軟化点としては３０〜８０℃が好ましく、４０〜７０℃がより好ましい。
水酸基当量としては、１８０〜２３０ｇ／ｅｑが好ましく、１９５〜２１５が特に好ましい。 In the present invention, the phenol / naphthol mixed zylock type phenol resin is represented by the following formula (II):

(In the formula, Ar represents a naphthalene nucleus (a) or a benzene nucleus (b), (a) / (b) = 0.1 to 100, R represents a hydrogen atom or a methyl group, and m represents 1 or 2 and n is an integer from 0 to 15.)
The phenol resin represented by is used.
The said phenol resin can be obtained by the method as described in Unexamined-Japanese-Patent No. 2012-97229, for example. Moreover, as a commercial item, it can be obtained as GPNX-70HN (manufactured by Gunei Chemical Co., Ltd.).
In the above formula (II), the ratio (molar ratio) of the naphthalene nucleus (a) to the benzene nucleus (b) is usually (a) / (b) = 0.1 to 100, and more preferably 1.0 to 20 Preferably, 2.0 to 10 is particularly preferable. Here, the calculation method of (a) / (b) is, for example, the reaction of the phenol resin of the above formula (II), and then the remaining raw material for imparting naphthalene nuclei and raw material for imparting benzene nuclei. The residual amount of the reaction can be determined by gas chromatography and calculating the molar ratio of naphthalene nuclei and benzene nuclei incorporated into the phenol resin (II).
The naphthalene nucleus (a) has the following skeleton

When Ar is a naphthalene nucleus, the skeleton is introduced into the above formula (II) (the same applies to formula (I)). The — (OH) m group, R group, or linking group bonded to Ar is bonded to the carbon atom of the skeleton.
The benzene nucleus (b) has the following skeleton

When Ar is a benzene nucleus, the skeleton is introduced into the above formula (II) (the same applies to formula (I)). The — (OH) m group, R group, or linking group bonded to Ar is bonded to the carbon atom of the skeleton.
Moreover, n represents the number of repetitions and is usually 0-15, but 1-10 is more preferable. If n exceeds 15, the softening point becomes too high, which is not preferable.
As a softening point, 30-80 degreeC is preferable and 40-70 degreeC is more preferable.
As a hydroxyl equivalent, 180-230 g / eq is preferable and 195-215 is especially preferable.

（上記式中、複数存在するＲ_１は各々独立して存在し、水素原子又は炭素数１〜４のアルキル基を示し、ｋは１〜４の整数を表す。）
で表される構造を表す。即ち、置換もしくは無置換の４，４’−ビフェノール（ただし、置換基をその芳香環に有する場合、置換基の数は４以下、炭素数は４以下である。）は４，４´−ビフェノールを基本骨格とする化合物であり、その具体例としては、４，４´−ビフェノール、３，３´，５，５´−テトラメチルビフェニル−４，４´−ジオール、３，３´−ジメチルビフェニル−４，４´−ジオール等が挙げられる。本発明においては入手のしやすさから、４，４´−ビフェノール、３，３´，５，５´−テトラメチルビフェニル−４，４´−ジオールが好ましく、エポキシ樹脂混合物のハンドリング性から４，４´−ビフェノールが好ましい。
Ｒ_１としては、全て水素原子が好ましい。 In the present invention, the substituted or unsubstituted 4,4′-biphenol is represented by the following formula (1):

(In the above formula, a plurality of R _{1 s} exist independently and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and k represents an integer of 1 to 4)
The structure represented by is represented. That is, substituted or unsubstituted 4,4′-biphenol (however, when the aromatic ring has a substituent, the number of substituents is 4 or less and the number of carbon atoms is 4 or less) is 4,4′-biphenol. Specific examples of such compounds include 4,4′-biphenol, 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diol, and 3,3′-dimethylbiphenyl. -4,4'-diol and the like. In the present invention, 4,4′-biphenol and 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diol are preferable from the viewpoint of easy availability, and 4,4′-diol is preferable from the handling property of the epoxy resin mixture. 4'-biphenol is preferred.
R ₁ is preferably all hydrogen atoms.

  In order to obtain the epoxy resin mixture of the present invention, each of the phenol and naphthol mixed sylock type phenol resins and the substituted or unsubstituted 4,4′-biphenol is uniformly mixed with the phenol and naphthol mixed zyloc type phenol resins. Alternatively, unsubstituted 4,4′-biphenol (however, when the aromatic ring has a substituent, the number of substituents is 4 or less and the number of carbon atoms is 4 or less) is mixed and reacted with epihalohydrin. You can get it. In the present invention, the latter is particularly preferred from the viewpoint of ease of production and molecular connections.

  Although it does not specifically limit as a method of reaction with epihalohydrin, An example of the synthesis | combining method of the epoxy resin mixture of this invention is described below.

  In the reaction to obtain the epoxy resin mixture of the present invention, a phenol / naphthol mixed sylock type phenol resin (AA) and a substituted or unsubstituted 4,4′-biphenol (however, when the aromatic ring has a substituent, The number is 4 or less and the carbon number is 4 or less.) (BB) is simultaneously reacted with epihalohydrin to obtain an epoxy resin mixture. Here, the ratio (weight ratio) of (AA) and (BB) is preferably AA / BB = 1 to 10, more preferably 1.5 to 7.5, and particularly preferably 2.0 to 6.0. . This range is preferable from the viewpoint of fluidity balance. Hereinafter, the mixture of (AA) and (BB) is referred to as the phenol resin mixture of the present invention.

In the reaction for obtaining the epoxy resin mixture of the present invention, the epihalohydrin is preferably epichlorohydrin which is industrially easily available. The amount of epihalohydrin used is usually 3.0 to 15 mol, preferably 3.0 to 10 mol, more preferably 3.5 to 8.5 mol, particularly preferably 1 mol per mol of the hydroxyl group of the phenol mixture of the present invention. 4.5 to 8.5 moles.
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.

In the above reaction, it is preferable to use an alkali metal hydroxide for the reaction with epihalohydrin. Examples of the alkali metal hydroxide that can be used 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 property and handling, it is preferable to use a solid material molded into a flake shape.
The amount of the alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, more preferably 0.99, based on 1 mol of the hydroxyl group of the phenol mixture of the present invention. ˜1.15 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 the hydroxyl group of the phenol mixture of the present invention.

In this reaction, in addition to the epihalohydrin, a nonpolar proton solvent (dimethyl sulfoxide, dioxane, dimethylimidazolidinone, etc. In the present invention, dimethyl sulfoxide and dioxane are preferred) and an alcohol having 1 to 5 carbon atoms may be used in combination. preferable. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol (methanol is preferred in the present invention). 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 there is a lot of moisture in the system, it is not preferable because the electrical reliability of the obtained epoxy resin mixture deteriorates, and it is preferable to synthesize by controlling the moisture to 5% or less. Moreover, when an epoxy resin mixture is obtained using a nonpolar proton solvent, an epoxy resin mixture having excellent 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. Furthermore, in order to obtain an epoxy resin mixture with less hydrolyzable halogen, the recovered epoxy resin mixture is a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). Is dissolved as a solvent, and the reaction is carried out by adding an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide 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 mixture of the present invention 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 mixture of the present invention. In addition, after distilling off the solvent under heating and decompression, after maintaining at 110 to 170 ° C., a plate shape (plate shape, sheet shape, belt shape, etc.) of 100 ° C. or less, more preferably 80 ° C. or less It is preferable to form it into a plate shape, a water droplet shape (marble shape), etc., and take it out by pouring or dropping. Note that a stepwise cooling method of cooling at 60 ° C. or lower after cooling at 80 ° C. or lower may be used.
In the present invention, the appearance of the most preferable epoxy resin mixture obtained has a turbid color with a crystallinity (specifically, it is not cloudy or amorphous).

  In the epoxy resin of the present invention, a phenol / naphthol mixed sylock type epoxy resin and a substituted or unsubstituted 4,4′-bisglycidyloxybiphenyl (provided that the number of substituents is 4 or less when the substituent is present in the aromatic ring) The number of carbon atoms is 4 or less.) Is not particularly limited as long as it is present at the same time, but in the reaction under the preferable conditions as described above, the phenol / naphthol mixed zylock type phenolic resin structure and the biphenol structure are connected by epihalohydrin. Structure (C) also exists. When only a phenol / naphthol mixed sylock type phenol resin is epoxidized, a structure (D) in which these are connected is formed. Since this molecular weight is large, the viscosity tends to increase. However, if the simultaneous epoxidation as described above is performed, the structure (C) is generated instead of the structure (D), so that the viscosity is relatively low. In the improvement of fluidity which is the object of the present invention, it is preferable.

  The epoxy resin mixture of the present invention thus obtained contains a phenol / naphthol mixed zylock type epoxy resin (A) and a substituted (or unsubstituted) 4,4′-bisglycidyloxybiphenyl (B). .

（式中、Ａｒはナフタレン核（ａ）またはベンゼン核（ｂ）を示し、かつ、（ａ）／（ｂ）＝０．１〜１００であり、Ｇはグリシジル基を示し、Ｒは水素原子またはメチル基を示し、ｍは１または２であり、ｎは０〜１５の整数である。）
で表される構造を有する。
上記式（ＩＩ）において、ナフタレン核（ａ）とベンゼン核（ｂ）の割合は、通常（ａ）／（ｂ）＝０．１〜１００であり、１．０〜２０がより好ましく、２．０〜１０が特に好ましい。ここで、（ａ）／（ｂ）は上記フェノール・ナフトール混合ザイロック型フェノール樹脂の際に算出した方法と同じ手法で算出可能である。
ここで、 ナフタレン核（ａ）は、下記骨格

であり、Ａｒがナフタレン核である場合には上記骨格が上記式（Ｉ）に導入される。そして、Ａｒに結合する−（ＯＧ）ｍ基、Ｒ基、ないし連結基は上記骨格の炭素原子に結合する。
また、ベンゼン核（ｂ）は、下記骨格

であり、Ａｒがベンゼン核である場合には上記骨格が上記式（Ｉ）に導入される。そして、Ａｒに結合する−（ＯＧ）ｍ基、Ｒ基、ないし連結基は上記骨格の炭素原子に結合する。
また、ｎは繰り返し数を表し、通常０〜１５であるが、１〜１０がより好ましい。 Phenol / naphthol mixed sylock type epoxy resin (A) has the following formula (I)

(In the formula, Ar represents a naphthalene nucleus (a) or a benzene nucleus (b), and (a) / (b) = 0.1 to 100, G represents a glycidyl group, and R represents a hydrogen atom or Represents a methyl group, m is 1 or 2, and n is an integer of 0 to 15.)
It has the structure represented by these.
In the above formula (II), the ratio of the naphthalene nucleus (a) to the benzene nucleus (b) is usually (a) / (b) = 0.1-100, more preferably 1.0-20, and 2. 0-10 are particularly preferred. Here, (a) / (b) can be calculated by the same method as the method calculated in the case of the above-mentioned phenol / naphthol mixed sylock type phenol resin.
Here, the naphthalene nucleus (a) has the following skeleton

When Ar is a naphthalene nucleus, the skeleton is introduced into the formula (I). The — (OG) m group, R group, or linking group bonded to Ar is bonded to the carbon atom of the skeleton.
The benzene nucleus (b) has the following skeleton

When Ar is a benzene nucleus, the skeleton is introduced into the formula (I). The — (OG) m group, R group, or linking group bonded to Ar is bonded to the carbon atom of the skeleton.
Moreover, n represents the number of repetitions and is usually 0-15, but 1-10 is more preferable.

（上記式中、複数存在するＲ_１は各々独立して存在し、水素原子又は炭素数１〜４のアルキル基を、Ｇはグリシジル基を示し、ｋは１〜４の整数を表す。）
で表される構造を有する。
Ｒ_１としては、全て水素原子が好ましい。 Substituted or unsubstituted 4,4′-bisglycidyloxybiphenyl is represented by the following formula (2):

(In the above formula, a plurality of R _{1 s} exist independently, each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, G represents a glycidyl group, and k represents an integer of 1 to 4).
It has the structure represented by these.
R ₁ is preferably all hydrogen atoms.

  In the epoxy resin mixture of the present invention, a phenol / naphthol mixed sylock type epoxy resin (A) and a substituted or unsubstituted 4,4′-bisglycidyloxybiphenyl (in the case where the aromatic ring has a substituent, The number is 4 or less and the carbon number is 4 or less.) The ratio (weight ratio) of (B) is preferably A / B = 1 to 10, more preferably 1.5 to 7.5, and particularly preferably 2. 0-6.0. This range is preferable from the viewpoint of fluidity.

  As the shape of the epoxy resin mixture of the present invention, when mixed homogeneously, it is preferable to have a solid resin shape with crystallinity, and the softening point at that time is a problem of handling properties and moldability at the time of curing, It is preferable that it is 30-80 degreeC, More preferably, it is 40-70 degreeC.

As a preferable resin characteristic of the epoxy resin mixture of the present invention, an epoxy equivalent is 200 to 450 g / eq. And more preferably 220 to 300 g / eq. It is. The epoxy resin excellent in the electrical reliability of hardened | cured material can be obtained because an epoxy equivalent exists in the said range. Epoxy equivalent is 450 g / eq. In the case of exceeding the range, the epoxy ring is not completely closed, and it is expected that many compounds having no functional group are contained. In addition, many of these compounds that could not be ring-closed often contain chlorine, and as an electronic material application, there is concern about the release of chlorine ions under high-temperature and high-humidity conditions and the resulting corrosion of wiring. Absent.
Further, the total chlorine remaining in the epoxy resin is preferably 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 2000 ppm or less. The adverse effect of the chlorine amount is the same as described above. In addition, about chlorine ion and sodium ion, 5 ppm or less is preferable respectively, More preferably, it is 3 ppm or less. Chlorine ions are described above. Needless to say, cations such as sodium ions are also very important factors particularly in power device applications, and contribute to a defective mode when a high voltage is applied.

  The epoxy resin of the present invention has a form on the resin having a softening point. Here, as a softening point, 30-80 degreeC is preferable, More preferably, it is 40-70 degreeC. When the softening point is too high, problems such as poor handling occur during kneading with other resins. The melt viscosity is preferably 2 Pa · s or less (ICI melt viscosity 150 ° C. cone plate method) or less. When mixing and using an inorganic material (filler etc.), the fluidity | liquidity is bad, and also the glass cloth etc. have the finer mesh | network, and the subject that inferior property is inferior arises.

Hereinafter, it describes about the curable resin composition of this invention containing the epoxy resin of this invention.
In the curable resin composition of the present invention, a curing agent or a curing accelerator is used as an essential component.

In the curable resin composition of this invention, it can classify | categorize roughly into 2 types, and is expressed as the curable resin composition A and the curable resin composition B below.
The curable resin composition A is a composition containing the epoxy resin mixture of the present invention and a curing agent as essential components.
The curable resin composition B is a composition containing the epoxy resin of the present invention and a curing accelerator as essential components.

  Hereinafter, each of the curable resin compositions A and B of the present invention will be described.

  In the curable resin composition A and the curable resin composition B, other epoxy resins than the epoxy resin of the present invention can be used in combination or alone. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more. However, when using the epoxy resin of this invention as a modifier of a curable resin composition, it adds in the ratio of 1 to 30 weight%.

  Specific examples of other epoxy resins include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. 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-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of them) Has glycidyl group and / or epoxycyclohexane structure Solid or liquid epoxy resin having an epoxy resin) and the like although not limited thereto.

Hereinafter, each curable resin composition will be referred to.
Thermal curing with a curing agent (curable resin composition A)
Specific examples of the curing agent contained in the curable resin composition A of the present invention include, for example, phenol resins, phenol compounds, amine compounds, acid anhydride compounds, amide compounds, carboxylic acid compounds, and the like. 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.
Preferable phenol resins include phenol aralkyl resins (resins having an aromatic alkylene structure), particularly preferably a structure having at least one selected from phenol, naphthol, and cresol, and the alkylene portion serving as the linker is benzene. A resin characterized by at least one selected from a structure, a biphenyl structure, and a naphthalene structure (specific examples include zylock, naphthol zylock, phenol biphenylene novolak resin, cresol-biphenylene novolak resin, phenol-naphthalene novolak resin, etc.) Is.)
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 Carboxylic acid resins obtained by addition reaction of acid anhydrides such as cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, various alcohols, carbinol-modified silicone, and the above acid anhydrides; Examples include imidazole, trifluoroborane-amine complexes, and guanidine derivative compounds. These may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a phenol resin from the viewpoint of reliability.

  In the curable resin composition A of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In the curable resin composition A of the present invention, a curing accelerator may be used in combination with the curing agent. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diaza. -Tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc. And quaternary ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, tetrabutylphosphonium salts, and the like. (The counter ion of the quaternary salt is not particularly specified, such as halogen, organic acid ion, hydroxide ion, etc., but organic acid ion and hydroxide ion are particularly preferable), metal compounds such as tin octylate, etc. It is done. When using a hardening accelerator, 0.01-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

  The curable resin composition A of the present invention may contain a phosphorus-containing compound as a flame retardant imparting 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 curable resin composition A 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- Til-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-tert-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-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5- Bisphenols such as (tilphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) ethyl 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'-tert-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -iso Anureate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol And the like.

  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.

Furthermore, you may add a light stabilizer to the curable resin composition A 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, binder resin can also be mix | blended with the curable resin composition A 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.

  An inorganic filler can be added to the curable resin composition A of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention. Furthermore, the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers. A compounding agent and various thermosetting resins can be added.

  The curable resin composition A of the present invention is obtained by uniformly mixing each component. The curable resin composition A of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are sufficient until uniform using an extruder, kneader, roll, etc. as necessary. To obtain a curable resin composition, potting the curable resin composition, melting (without melting in the case of a liquid), molding using a casting or transfer molding machine, and further 80 to 200 ° C. The cured product of the present invention can be obtained by heating for 2 to 10 hours.

  Further, the curable resin composition A of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone as necessary, and the curable resin composition varnish. The curable resin composition of the present invention is obtained by hot press-molding a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and drying by heating. It can be set as the hardened | cured material of the thing A. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, the epoxy resin hardened | cured material which contains a carbon fiber by the RTM system as it is can also be obtained as it is.

  Moreover, the curable resin composition A of this invention can be used also as a modifier of a film type composition. Specifically, it can be used to improve the flexibility of the B-stage. In such a film-type resin composition, the curable resin composition A of the present invention is applied onto a release film as the curable resin composition varnish, the solvent is removed under heating, and then B-stage is performed. Thus, it is obtained as a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

Curable resin composition B
The curing accelerator that can be contained in the curable resin composition B of the present invention can be used without limitation as long as it is a catalyst that is polymerized by heat or light. Specifically, a curing accelerator or an acidic curing accelerator is used. it can. Specific examples of the curing accelerator to be used include those described above. When using a hardening accelerator, 0.01-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

  The curable resin composition B of the present invention that is cured using an acidic curing accelerator contains a photopolymerization initiator or a thermal polymerization initiator as an acidic curing accelerator. Furthermore, you may contain various well-known compounds, materials, such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization start adjuvant, a photosensitizer. Moreover, you may contain various well-known additives, such as an inorganic filler, a color pigment, a ultraviolet absorber, antioxidant, a stabilizer, as needed.

  As the acidic curing accelerator, a cationic polymerization initiator is preferable, and a light or thermal cationic polymerization initiator is particularly preferable. It can be used as the curable resin composition B by blending a cationic polymerization initiator activated by active energy rays and / or a cationic polymerization initiator activated by heat.

  Cationic polymerization initiators that initiate cationic polymerization of the curable resin composition B of the present invention by irradiation with active energy rays include diazonium salts, iodonium salts, sulfonium salts, selenium salts, pyridinium salts, ferrocenium salts, phosphonium salts. And iodonium salts and sulfonium salts, more preferably diaryl iodonium salts and dialkylphenacyl sulfonium salts, and diaryl iodonium salts can be preferably used.

When photocationic polymerization initiators such as iodonium salts and sulfonium salts are used in the cationic curable resin composition of the present invention, BF ₄₋ , AsF ₆₋ , SbF ₆₋ , PF ₆₋ , and B (C ₆ F ₅ ) _{4- and the} like, preferably SbF ₆₋ , PF ₆₋ , or B (C ₆ F ₅ ) ₄₋ , particularly preferably SbF ₆₋ or B (C ₆ F ₅ ) _4−. It is.

  Specific examples of the cationic photopolymerization initiator include bis (dodecylphenyl) iodonium hexafluoroantimonate (manufactured by GE Toshiba Silicone, UV-9380C main component), tricumyliodonium tetrakis (pentafluorophenyl) borate (Rhodia) PHOTOINITIATOR 2074), bis (alkyl (C = 10-14) phenyliodonium) hexafluoroantimonate (Wcation Pure Chemicals photocationic polymerization initiator WPI-016), and the like.

  As the active energy rays for curing the curable resin composition B of the present invention, X-rays, electron beams, ultraviolet rays, visible light, and the like can be used, preferably ultraviolet rays or visible rays, particularly preferably. Is ultraviolet light. When ultraviolet rays are used, the wavelength range is not particularly limited, but is preferably 150 to 400 nm, and more preferably 200 to 380 nm. When ultraviolet rays are used, cationic polymerization can be efficiently started.

Further, in the curable resin composition B of the present invention, a sensitizer can be used in combination in order to further increase the activity of the photocationic polymerization initiator as necessary. As a sensitizer that can be used in the present invention, for example, a compound disclosed by Crivello in Advanced in Polymer Science (Adv. In Polymer Sci., 62, 1 (1984)) can be used. Specific examples include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavine. In addition, compounds widely used as photo radical polymerization initiators can also be used, and specifically, thioxanthones such as benzophenone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2,4-dichlorothioxanthone. Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-methyl-1 Α-hydroxyalkylphenones such as phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, α such as camphorquinone -Dicarbo Nil compounds and the like. In the present invention, thioxanthones and α-hydroxyalkylphenones can be particularly preferably used.

  The compounding quantity of the photocationic polymerization initiator to the curable resin composition B of this invention can be suitably adjusted according to the kind and irradiation amount of an active energy ray. For example, in the case of ultraviolet rays, the amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts, and still more preferably 1 to 3 parts relative to 100 parts by mass of the cation curable resin composition. Part. When the amount of the cationic polymerization initiator is less than 0.1 part, the curability may be inferior. On the other hand, when it exceeds 10 parts by mass, the properties necessary for the cured product are reduced to reduce the physical properties of the cured product. May decrease, or the coloring of the cured product may become intense.

  The compounding amount in the case of adding a sensitizer to the curable resin composition B of the present invention can be appropriately adjusted according to the type of active energy ray and the irradiation amount. For example, in the case of ultraviolet rays, the amount is preferably 5 parts by mass or less, more preferably 0.2 to 2 parts with respect to 100 parts by mass in total of the curable resin composition B. When the blending amount of the sensitizer is more than 5 parts by mass, the components that are truly necessary for the cured product may be reduced to deteriorate the physical properties of the cured product, or the cured product may be intensely colored.

  When the active energy ray is ultraviolet light or visible light, the cationic curable resin composition is exposed to air. At this time, the humidity of the atmosphere is preferably low, and preferably 80% humidity. H. 70% R.V. H. More preferably, it is as follows. Here, when ultraviolet rays or visible light is installed in the production line, a method of sending dry air in front of the light irradiation device or a method of reducing the humidity by attaching a heating device can be employed.

  A compound that is activated by heat to initiate cationic polymerization, that is, a thermal cationic polymerization initiator, can also be used in the curable resin composition B of the present invention. Examples of this include various onium salts such as quaternary ammonium salts, phosphonium salts and sulfonium salts, combinations of alkoxysilanes and aluminum complexes, and the like. Available products include Adeka Opton CP-66 and Adeka Opton CP-77 (both trade names, manufactured by Asahi Denka Kogyo Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, and Sun-Aid SI-100L (both trade names) , Sanshin Chemical Industry Co., Ltd.), and CI series (Nihon Soda Co., Ltd.).

  The blending ratio of the thermal cationic polymerization initiator to the curable resin composition B of the present invention is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the cation curable resin composition, more preferably. Is 0.1 to 5 parts, more preferably 0.5 to 3 parts. When the blending ratio is less than 0.01 parts by mass, the ring-opening reaction of the ring-opening polymerizable group may not be allowed to proceed sufficiently even if it is activated by the action of heat. Moreover, even if it mixes exceeding 10 mass parts, since the effect | action which advances superposition | polymerization does not increase any more and the physical property of hardened | cured material may fall, it is unpreferable.

  Furthermore, the curable resin composition B of the present invention is added with various compounding agents such as the above inorganic fillers, silane coupling materials, mold release agents, pigments, and various thermosetting resins as necessary. can do.

  The curable resin composition B of the present invention can be obtained by uniformly mixing each component. It is also possible to dissolve in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone and make it uniform, and then use it after removing the solvent by drying. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition B of the present invention and the solvent. The curable resin composition B of the present invention can be cured by irradiating with ultraviolet rays, but the amount of ultraviolet irradiation varies depending on the curable resin composition, and therefore is determined by the respective curing conditions. What is necessary is just the irradiation amount which a photocurable curable resin composition hardens | cures, and should just satisfy | fill the curing conditions with favorable adhesive strength of hardened | cured material. Since it is necessary for light to be transmitted through the details during the curing, the epoxy resin and the curable resin composition B of the present invention are highly transparent. Moreover, it is difficult for these epoxy resin-based photocuring to be completely cured only by light irradiation, and in applications where heat resistance is required, it is necessary to complete reaction curing by heating after light irradiation.

  The heating after the light irradiation may be performed in the normal curing temperature range of the curable resin composition B. For example, the range of 30 minutes to 7 days at room temperature to 150 ° C. is suitable. Although it changes depending on the blending of the curable resin composition B, the higher the temperature range, the more effective the curing is after light irradiation, and the short heat treatment is effective. Further, the lower the temperature, the longer the heat treatment. By performing such heat after-curing, an effect of aging treatment is obtained.

  Moreover, since the shape of the cured product obtained by curing these curable resin compositions B can be variously selected depending on the application, it is not particularly limited. For example, it may be a film shape, a sheet shape, a bulk shape, or the like. . The molding method varies depending on the applicable part and member. For example, a casting method, a casting method, a screen printing method, a spin coating method, a spray method, a transfer method, a dispenser method, or the like can be applied. Although it is mentioned, it is not limited to these. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied. In addition, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be applied in order to improve releasability from the mold.

  For example, when used for a cation curable resist, first, the photo cation curable resin composition B of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone is used as a copper-clad laminate, The composition of the present invention is applied to a film thickness of 5 to 160 μm on a substrate such as a ceramic substrate or a glass substrate by a method such as screen printing or spin coating to form a coating film. The coating film is preliminarily dried at 60 to 110 ° C., and then irradiated with ultraviolet rays (for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film having a desired pattern. Then, post-exposure baking is performed at 70 to 120 ° C. Thereafter, the unexposed part is dissolved and removed (developed) with a solvent such as polyethylene glycol monoethyl ether, and if necessary, sufficient by irradiation with ultraviolet rays and / or heating (for example, at 100 to 200 ° C. for 0.5 to 3 hours). Curing is performed to obtain a cured product. In this way, it is also possible to obtain a printed wiring board.

  The hardened | cured material formed by hardening | curing curable resin composition A and curable resin composition B of this invention can be used for various uses.

  Examples include general uses in which the curable resin composition A or the curable resin composition B is used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials ( In addition to the sealing agent, the additive to other resins, etc. are mentioned. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agent and substrate, potting sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, ICs, LSIs for COB, COF, TAB, etc. Examples include underfill for flip chip, sealing (including reinforcing underfill) and package substrate when mounting IC packages such as QFP, BGA, and CSP. Moreover, it is suitable also for the board | substrate use with which functionality, such as a network board | substrate and a module board, is calculated | required.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
The various analysis methods used in the examples are described below.
Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001)
ICI melt viscosity: compliant with JIS K 7117-2 (ISO 3219) Softening point: compliant with JIS K 7234 GPC:
Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)
The coupled eluent is tetrahydrofuran. The flow rate is 0.5 ml / min.
Column temperature is 40 ° C
Detection: RI (differential refraction detector)

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

Example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, and a phenol / naphthol mixed sylock type phenol resin (based on GPC measurement results (a) / (b) = 2.3) 200 parts ( (Manufactured by Gunei Chemical Industry Co., Ltd.), 23 parts of 4,4′-biphenol, 456 parts of epichlorohydrin and 114 parts of dimethyl sulfoxide were added, dissolved under stirring, and heated to 45 ° C. Next, 51 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 75 minutes. After completion of the reaction, excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. The residue was dissolved by adding 584 parts of methyl isobutyl ketone, washed with water, and heated to 75 ° C. Under stirring, 14 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water of the oil layer became neutral. From the resulting solution, the pressure was reduced using a rotary evaporator. Methyl isobutyl ketone and the like were distilled off below to obtain 263 parts of the epoxy resin (EP1) of the present invention. The epoxy equivalent of the obtained epoxy resin was 231 g / eq. The ICI melt viscosity at a softening point of 55 ° C. and 150 ° C. was 0.09 Pa · s.

(Synthesis Example 1)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 235 parts of a phenol / naphthol mixed sylock type phenol resin, 429 parts of epichlorohydrin (4 molar equivalents to phenol resin) and 129 parts of methanol while purging with nitrogen. In addition, it melt | dissolved under stirring and heated up to 70-75 degreeC. Next, 52 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, 155 parts of water was washed with water, and excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. To the residue, 570 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 19 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water of the oil layer became neutral. From the resulting solution, the pressure was reduced using a rotary evaporator. 270 parts of epoxy resin (EP2) was obtained by distilling off methyl isobutyl ketone and the like below. The epoxy equivalent of the obtained epoxy resin is 261 g / eq. The ICI melt viscosity at a softening point of 55 ° C. and 150 ° C. was 0.08 Pa · s.

Examples 2 and 3 and Comparative Examples 1 and 2
<Heat resistance test, flame retardancy test>
The epoxy resin obtained above and a phenol novolak resin (P1, softening point 80 ° C., hydroxyl group equivalent 105 g / eq) as a curing agent are blended in the proportions (parts by weight) shown in Table 1 and mixed uniformly using a mixing roll. -It knead | mixed and the curable resin composition for sealing was obtained. The curable resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted curable resin composition was transfer molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways.
・ Heat resistance (DMA)
Dynamic viscoelasticity measuring device: TA-instruments, DMA-2980
Measurement temperature range: -30 to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm)
Tg: Tan-δ peak point is defined as Tg

実施例２と比較例１、実施例３と比較例２を比較すると本発明のエポキシ樹脂混合物を用いることで、２５０℃における弾性率が向上することがわかる。特に硬化剤としてフェノールノボラックを用いたときに特異的に弾性率が高くなった。

When Example 2 is compared with Comparative Example 1 and Example 3 is compared with Comparative Example 2, it can be seen that the elastic modulus at 250 ° C. is improved by using the epoxy resin mixture of the present invention. In particular, when phenol novolac was used as a curing agent, the elastic modulus increased specifically.

フィラーを含有しない硬化物である実施例４とフィラーを含有させた硬化物である実施例５を比較すると急激な弾性率の向上が見られた。これより、本発明のエポキシ樹脂はフィラーを含有させることで極めて高い弾性率を示すことが明らかとなった。

When Example 4 which is a cured product not containing a filler and Example 5 which is a cured product containing a filler were compared, an abrupt improvement in elastic modulus was observed. From this, it became clear that the epoxy resin of this invention shows a very high elasticity modulus by containing a filler.

From the above results, it is clear that the composition using the epoxy resin mixture of the present invention is excellent in fluidity, and that the cured product is particularly excellent in flame retardancy and heat resistance, and a semiconductor that requires high functionality is required. It can be seen that it is useful for a sealing material and a thin film substrate material (including an interlayer insulating film) that requires high filler filling.
Moreover, it is clear that the elastic modulus is increased and the strength is increased by including a combination with a phenol novolac or a filler and curing it, which proves that it is useful for reducing warpage during solder mounting.

Claims (7)

The following general formula (I)

(In the formula, Ar represents a naphthalene nucleus (a) or a benzene nucleus (b), and (a) / (b) = 1.0 to 20, G represents a glycidyl group, and R represents a hydrogen atom or Represents a methyl group, m is 1 or 2, and n is an integer of 0 to 15.)
Phenol / naphthol mixed sylock type epoxy resin represented by the following general formula (2)

(In the above formula, a plurality of R _{1 s} exist independently, each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, G represents a glycidyl group, and k represents an integer of 1 to 4).
In epoxy resin mixture, characterized in that it contains a substituted or unsubstituted 4,4'-bis glycidyloxy biphenyl simultaneously represented.
  The weight ratio of the phenol / naphthol mixed sylock type epoxy resin (A) represented by the formula (I) to the substituted or unsubstituted 4,4′-glycidyloxybiphenyl (B) is A / B = 1 to 10. The epoxy resin mixture according to claim 1. The following general formula (II)

(In the formula, Ar represents a naphthalene nucleus (a) or a benzene nucleus (b), and (a) / (b) = 1.0 to 20, R represents a hydrogen atom or a methyl group, and m represents 1 or 2 and n is an integer of 0 to 15.)
Phenol / naphthol mixed sylock type phenol resin represented by the following general formula (1)

(In the above formula, a plurality of R _{1 s} exist independently and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and k represents an integer of 1 to 4)
In the substituted or unsubstituted 4,4'-biphenol represented mixed and reacted with an epihalohydrin, an epoxy resin mixture according to claim 1, characterized in that it is obtained.
  The curable resin composition which makes it essential to contain the epoxy resin mixture as described in any one of Claims 1-3, and a hardening | curing agent.   The curable resin composition which makes it essential to contain the epoxy resin mixture as described in any one of Claims 1-3, and a hardening accelerator.   The curable resin composition according to claim 4, wherein the curing agent is phenol novolac.   Hardened | cured material characterized by hardening | curing the curable resin composition as described in any one of Claims 4-6.