JP4474891B2 - Epoxy resin composition, cured product thereof and epoxy resin - Google Patents

Description

  The present invention is excellent in heat resistance, moisture resistance and dielectric properties (low dielectric constant, low dielectric loss tangent), resin composition for printed circuit boards, resin composition for encapsulants for electronic parts, resist ink, conductive paste, paint, The present invention relates to an epoxy resin composition that can be suitably used for adhesives, composite materials, and the like, a cured product obtained by using the composition, and an epoxy resin that can be suitably used for these applications.

  Epoxy resin compositions are suitable for use in semiconductor encapsulants, printed wiring boards, paints, casting materials, and the like because cured products with excellent heat resistance, adhesion, electrical insulation, and the like are obtained. . Among these, it is proposed to use a dicyclopentadiene type epoxy resin represented by the following general formula (4) in electrical / electronic applications particularly requiring high reliability (for example, see Patent Document 1). ).

（式中、各Ｒは独立に水素又は１〜４個の炭素原子を有するアルキル基であり、各Ｘは独立に水素、１〜１０個の炭素原子を有するヒドロカルビル基もしくは置換ヒドロカルビル基、ハロゲン原子、又はニトロ基であり、ｍは１．０１〜１２の値を有し、ｎは１〜１２の平均値を有する）

Wherein each R is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and each X is independently hydrogen, a hydrocarbyl group or substituted hydrocarbyl group having 1 to 10 carbon atoms, a halogen atom Or a nitro group, m has a value of 1.01 to 12, and n has an average value of 1 to 12)

  However, in recent years, in the field of electronic devices such as semiconductor encapsulants and printed circuit boards, epoxy resin compositions capable of imparting more excellent characteristics and higher performance such as high-density mounting and high-speed computation, and the composition Development of a novel epoxy resin that can be used as a main agent in the field is awaited.

Japanese Patent Laid-Open No. 3-188123 (pages 8-12)

  The present invention has been made in view of such circumstances, and the object of the present invention is to obtain a cured product having moisture resistance and dielectric properties superior to conventional materials typified by dicyclopentadiene type epoxy resins. , Epoxy resin compositions that can be suitably used for electrical and electronic applications that require high reliability, paints that require moisture resistance, adhesive applications, and composite materials that require high functionality, and curing thereof To provide things.

  Furthermore, it is providing the epoxy resin which can be used suitably as a main ingredient of the epoxy resin composition which has the said characteristic.

下記構造式（ａ１−２）、

及び下記構造式（ａ１−３）、

から成る群から選択される縮合多環脂肪族炭化水素基（ａ１）と所定のグリシジル基含有芳香族炭化水素基（ａ２）とを有し、且つ、前記構造式（ａ１−１）及び前記構造式（ａ１−２）から成る選択される縮合多環脂肪族炭化水素基（ｘ１）が縮合多環脂肪族炭化水素基（ａ１）中に２０モル％以上含有するエポキシ樹脂（Ａ）と硬化剤（Ｂ）とを含有することを特徴とするエポキシ樹脂組成物は、得られる硬化物の耐湿性、誘電特性が優れることを見出し、本発明を完成させた。 The present inventors have intensively studied to solve the above problems,
The following structural formula (a1-1),

The following structural formula (a1-2),

And the following structural formula (a1-3),

A condensed polycyclic aliphatic hydrocarbon group (a1) selected from the group consisting of: a predetermined glycidyl group-containing aromatic hydrocarbon group (a2), and the structural formula (a1-1) and the structure Epoxy resin (A) and hardener containing 20 mol% or more of condensed polycyclic aliphatic hydrocarbon group (x1) selected from formula (a1-2) in condensed polycyclic aliphatic hydrocarbon group (a1) The epoxy resin composition characterized by containing (B) was found to be excellent in moisture resistance and dielectric properties of the resulting cured product, and completed the present invention.

（Ｘ’は、下記構造式（ａ１−１）、

下記構造式（ａ１−２）、

及び下記構造式（ａ１−３）、

から成る群から選択される縮合多環脂肪族炭化水素基（ａ１）であり、かつ、前記構造式（ａ１−１）及び前記構造式（ａ１−２）から成る選択される縮合多環脂肪族炭化水素基（ｘ１）が縮合多環脂肪族炭化水素基（ａ１）中に２０モル％以上含有しており、かつ、ｎは１〜１０で表される繰り返しの平均値であり、Ｒは独立に水素原子、または炭素数１〜４のアルキル基であり、Ｇはグリシジル基であり、ｍは１〜３の整数である。）で表されることを特徴とするエポキシ樹脂は、前記エポキシ樹脂組成物中の主剤として用いることができる化合物であることを見出し、本発明を完成させた。 Furthermore, the present inventors have the following general formula (3 ′)

(X ′ is the following structural formula (a1-1),

The following structural formula (a1-2),

And the following structural formula (a1-3),

A condensed polycyclic aliphatic hydrocarbon group (a1) selected from the group consisting of: and a condensed polycyclic aliphatic group selected from the structural formula (a1-1) and the structural formula (a1-2) The hydrocarbon group (x1) is contained in the condensed polycyclic aliphatic hydrocarbon group (a1) in an amount of 20 mol% or more, and n is an average value represented by 1 to 10 and R is independent. Are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, G is a glycidyl group, and m is an integer of 1 to 3. The epoxy resin characterized by the above was found to be a compound that can be used as the main agent in the epoxy resin composition, and the present invention was completed.

（Ｘ’は、下記構造式（ａ１−１）、

下記構造式（ａ１−２）、

及び下記構造式（ａ１−３）、

から成る群から選択される縮合多環脂肪族炭化水素基（ａ１）であり、かつ、前記構造式（ａ１−１）及び前記構造式（ａ１−２）から成る選択される縮合多環脂肪族炭化水素基（ｘ１）が縮合多環脂肪族炭化水素基（ａ１）中に２０モル％以上含有しており、かつ、ｎは１〜１０で表される繰り返しの平均値であり、Ｒは独立に水素原子、または炭素数１〜４のアルキル基であり、Ｇはグリシジル基であり、ｍは１〜３の整数である。）で表されるエポキシ樹脂（Ａ）と硬化剤（Ｂ）とを含有することを特徴とするエポキシ樹脂組成物、及びこれを用いて得られる硬化物を提供するものである。 That is, the present invention provides the following general formula (3 ′)

(X ′ is the following structural formula (a1-1),

The following structural formula (a1-2),

And the following structural formula (a1-3),

A condensed polycyclic aliphatic hydrocarbon group (a1) selected from the group consisting of: and a condensed polycyclic aliphatic group selected from the structural formula (a1-1) and the structural formula (a1-2) The hydrocarbon group (x1) is contained in the condensed polycyclic aliphatic hydrocarbon group (a1) in an amount of 20 mol% or more, and n is an average value represented by 1 to 10 and R is independent. Are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, G is a glycidyl group, and m is an integer of 1 to 3. The epoxy resin composition characterized by containing the epoxy resin (A) represented by this, and the hardening | curing agent (B), and the hardened | cured material obtained using this are provided.

（Ｘ’は、下記構造式（ａ１−１）、

下記構造式（ａ１−２）、

及び下記構造式（ａ１−３）、

から成る群から選択される縮合多環脂肪族炭化水素基（ａ１）であり、かつ、前記構造式（ａ１−１）及び前記構造式（ａ１−２）から成る選択される縮合多環脂肪族炭化水素基（ｘ１）が縮合多環脂肪族炭化水素基（ａ１）中に２０モル％以上含有しており、かつ、ｎは１〜１０で表される繰り返しの平均値であり、Ｒは独立に水素原子、または炭素数１〜４のアルキル基であり、Ｇはグリシジル基であり、ｍは１〜３の整数である。）で表されることを特徴とするエポキシ樹脂を提供するものである。 Furthermore, the present invention provides the following general formula (3 ′)

(X ′ is the following structural formula (a1-1),

The following structural formula (a1-2),

And the following structural formula (a1-3),

A condensed polycyclic aliphatic hydrocarbon group (a1) selected from the group consisting of: and a condensed polycyclic aliphatic group selected from the structural formula (a1-1) and the structural formula (a1-2) The hydrocarbon group (x1) is contained in the condensed polycyclic aliphatic hydrocarbon group (a1) in an amount of 20 mol% or more, and n is an average value represented by 1 to 10 and R is independent. Are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, G is a glycidyl group, and m is an integer of 1 to 3. The epoxy resin characterized by being represented by this is provided.

  The epoxy resin composition of the present invention has a practical level of moldability and curability and is superior to conventional materials typified by dicyclopentadiene type epoxy resins, in particular, moisture resistance and dielectric properties, especially when absorbing moisture. Can be imparted to the cured product. For this reason, when used in the field of electronic materials such as printed circuit board resin compositions, electronic component encapsulant resin compositions, resist inks, and conductive pastes, high-density mounting, high-frequency compatibility, and high-speed computation It is extremely useful as a resin composition corresponding to the above. Further, the obtained molded cured product satisfies the requirements for the above-mentioned uses in terms of heat resistance, adhesion, and the like, and can cope with a field requiring high reliability. Furthermore, the epoxy resin of the present invention can be suitably used as a main agent in the epoxy resin composition, and is useful as a high-functional resin raw material such as an epoxy acrylate resin raw material and a photosensitive resin raw material such as a semiconductor photoresist. is there.

（Ｘ’は、下記構造式（ａ１−１）、

下記構造式（ａ１−２）、

及び下記構造式（ａ１−３）、

から成る群から選択される縮合多環脂肪族炭化水素基（ａ１）であり、かつ、前記構造式（ａ１−１）及び前記構造式（ａ１−２）から成る選択される縮合多環脂肪族炭化水素基（ｘ１）が縮合多環脂肪族炭化水素基（ａ１）中に２０モル％以上含有しており、かつ、ｎは１〜１０で表される繰り返しの平均値であり、Ｒは独立に水素原子、または炭素数１〜４のアルキル基であり、Ｇはグリシジル基であり、ｍは１〜３の整数である。）で表されるものである。前記構造式（ａ１−１）及び前記構造式（ａ１−２）から成る選択される縮合多環脂肪族炭化水素基（ｘ１）が縮合多環脂肪族炭化水素基（ａ１）中に２０モル％未満では、得られる硬化物の耐湿性、誘電特性が不足する為に好ましくない。 Hereinafter, the present invention will be described in detail.
The epoxy resin (A) used in the present invention is represented by the following general formula (3 ′)

(X ′ is the following structural formula (a1-1),

The following structural formula (a1-2),

And the following structural formula (a1-3),

A condensed polycyclic aliphatic hydrocarbon group (a1) selected from the group consisting of: and a condensed polycyclic aliphatic group selected from the structural formula (a1-1) and the structural formula (a1-2) The hydrocarbon group (x1) is contained in the condensed polycyclic aliphatic hydrocarbon group (a1) in an amount of 20 mol% or more, and n is an average value represented by 1 to 10 and R is independent. Are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, G is a glycidyl group, and m is an integer of 1 to 3. ). The condensed polycyclic aliphatic hydrocarbon group (x1) selected from the structural formula (a1-1) and the structural formula (a1-2) is 20 mol% in the condensed polycyclic aliphatic hydrocarbon group (a1). If it is less than 1, it is not preferable because the resulting cured product lacks moisture resistance and dielectric properties.

Examples of the condensed polycyclic aliphatic hydrocarbon group (a1), for example, a hydrocarbon group having a structure derived from dicyclopentadiene consisting of three 5-membered ring (a1-3), 5 pieces of 5-membered ring And hydrocarbon groups [(a1-1), (a1-2)] having a structure derived from tridicyclopentadiene . The molar ratio of the group represented by the condensed polycyclic aliphatic hydrocarbon group (x1) the structural formula (a1-1) a group with the formula represented in (a1-2) (a1- 1) / It is particularly preferable that ( a1-2 ) is 50/50 to 99/1 .

The method for introducing the condensed polycyclic aliphatic hydrocarbon group (a1) into the molecule is not particularly limited, but an unsaturated cyclic hydrocarbon (y1) such as dicyclopentadiene or tricyclopentadiene is used as a raw material. used, after reacting with hydroxy group-containing aromatic hydrocarbons, which will be described later this (y2), a method of epoxidizing the like, the condensed polycyclic aliphatic hydrocarbon group occupying in the desired epoxy resin (a) These unsaturated cyclic hydrocarbons (y1) are used alone or in combination depending on the content of (x1).

  As the dicyclopentadiene, for example, Patent Document 1 shows an example in which 10% by weight is contained as a weight ratio of tricyclopentadiene that may be present in the raw material dicyclopentadiene. On the other hand, dicyclopentadiene can be obtained as a pure product as a reagent. As a result of intensive studies on an epoxy resin having a condensed polycyclic aliphatic hydrocarbon group (a1) using various raw materials, the present inventors have found that the condensed polycyclic aliphatic hydrocarbon is composed of the five 5-membered rings. By using the epoxy resin (A) containing 20 mol% or more of the group (x1) in the condensed polycyclic aliphatic hydrocarbon group (a1), the moisture resistance is higher than that of the conventionally used dicyclopentadiene type epoxy resin, It has been found that a cured product having excellent dielectric properties can be obtained. For example, a dicyclopentadiene type epoxy resin described in Patent Document 1 (= content of (x1) is 7 mol%), When compared with a dicyclopentadiene type epoxy resin obtained from a pure product of cyclopentadiene (= content of (x1) 0 mol%), the physical properties of the cured product obtained between them are large. Not observed, and they moisture resistance than a cured product obtained by using the epoxy resin used in the present invention, was poor in dielectric properties.

  The proportion of the five-membered condensed polycyclic aliphatic hydrocarbon group (x1) in the condensed polycyclic aliphatic hydrocarbon group (a1) is particularly preferably 50 to 100 mol%. .

Examples of the method for introducing the glycidyl group-containing aromatic hydrocarbon group (a2) in the general formula (3 ′) into the molecule include the unsaturated cyclic hydrocarbon (y1) and a hydroxy group having a desired structure. Examples include a method in which the aromatic hydrocarbon (y2) is reacted and a hydroxy group is converted into a glycidyl group (epoxidation).

Examples of the hydroxy group-containing aromatic hydrocarbon (y2) include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, and o-isopropylphenol. , M-propylphenol, p-propylphenol, p-sec-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, etc. mention may be made of a kind. In particular, phenol, o-cresol, m-cresol and the like are preferable from the viewpoints of economy and ease of production. These hydroxy group-containing aromatic hydrocarbons (y2) may be used alone or as a mixture of two or more.

  Although it does not specifically limit as a manufacturing method of the epoxy resin (A) used by this invention, For example, the above-mentioned unsaturated cyclic hydrocarbon (y1) and hydroxy containing aromatic hydrocarbons (y2) are acid catalysts. And a method of reacting with epihalohydrin.

  The molar ratio between the unsaturated cyclic hydrocarbon (y1) and the hydroxy group-containing aromatic hydrocarbon (y2) in this reaction is appropriately adjusted depending on the molecular weight and melt viscosity of the target epoxy resin (A). Usually, the molar ratio (y2) / (y1) = 1-20 of the hydroxy group-containing aromatic hydrocarbons (y2) and the unsaturated cyclic hydrocarbons (y1) is preferable. In particular, in order to lower the melt viscosity, the molar ratio (y2) / (y1) = 2 to 15 is preferable. An epoxy resin having a low melt viscosity is preferable because it can be filled with a high filler when used in a semiconductor encapsulating material, has a low coefficient of linear expansion, and has improved moisture resistance. It is preferably 10 dPa · s or less.

  Examples of the acid catalyst include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, organic acids such as toluenesulfonic acid, methanesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, and trifluoroacetic acid. Acid, Aluminum chloride, Iron chloride, Tin chloride, Gallium chloride, Titanium chloride, Aluminum bromide, Gallium bromide, Boron trifluoride, Boron trifluoride / ether complex, Boron trifluoride / phenol complex, Boron trifluoride A Lewis acid such as a water complex, boron trifluoride / alcohol complex, boron trifluoride / amine complex, or a mixture thereof is used. Among these, boron trifluoride, boron trifluoride / phenol complex, and boron trifluoride / ether complex are preferably used industrially from the viewpoint of catalytic activity and ease of catalyst removal, but are not limited thereto. It is not something. Moreover, it is preferable to use these addition amount in 10 ppm-5 weight% with respect to the total weight part of unsaturated cyclic hydrocarbon (y1) and hydroxy group containing aromatic hydrocarbon (y2).

  The reaction method is not particularly limited. For example, the reactor is charged with a predetermined amount of a hydroxy group-containing aromatic hydrocarbon (y2) and an acid catalyst, and then the unsaturated cyclic hydrocarbon (y2). The method of performing reaction by dripping is mentioned.

  In the reaction, the inside of the reactor is usually replaced with an inert gas such as nitrogen or argon. The reaction is preferably performed in a closed system substituted with an inert gas, but the reaction can also be performed in an open system while supplying the inert gas into the reactor.

  The reaction temperature may be adjusted as appropriate according to the degree of progress of the reaction, and is not particularly limited. Usually, the reaction is carried out in the range of 30 to 150 ° C., preferably 50 to 120 ° C. Progress can be preferably controlled. The degree of progress of the reaction here can be followed by, for example, analyzing the mixture in the middle of the reaction using GPC (gel permeation chromatography) or the like.

  The reaction time is not particularly limited as long as the reaction time is appropriately adjusted according to the degree of progress of the reaction. In particular, the monofunctional component in the mixture (unsaturated cyclic hydrocarbon has hydroxy group-containing aromatic hydrocarbons). The amount of the compound having a structure that has reacted at only one place is traced, and it is preferable to stop at a desired amount, usually 10 minutes to 60 hours, preferably 1 to 20 hours, more preferably 2 to 10 hours. By performing the reaction within the range, the reaction can be efficiently performed.

  The reaction is terminated by deactivating the catalyst. At that time, it is important to reliably stop the reaction. The means for deactivation is not particularly limited, but as a deactivator, alkali metals, alkaline earth metals or oxides thereof, hydroxides, carbonates, ammonium hydroxide, ammonia gas and other inorganic bases, triethylamine and the like Organic bases, hydrotalcite and the like can be used.

  Next, the concentration step will be described. The reaction solution obtained by the above-mentioned method is treated in a concentration step after removing the deactivator and the like by washing with water, filtering and the like. In the concentration step, unreacted phenols are recovered and the content of the monofunctional component can be controlled. As a concentration condition, a certain condition is not determined from the relationship between the temperature in the concentration system, the pressure, and the vapor pressure. However, the most efficient concentration is possible by performing the following conditions. That is, the system temperature is not particularly limited as long as the resin does not decompose, but is preferably 250 ° C. or lower, more preferably 180 to 220 ° C. The system pressure may be carried out under normal pressure, reduced pressure, or increased pressure, but the system may be reduced under reduced pressure in order to smoothly and quickly concentrate in the above temperature range. preferable. Specifically, the range is preferably 66.5 kPa (500 torr) or less, and particularly preferably 40 kPa (300 torr) or less. Furthermore, in order to efficiently remove unreacted phenols in the resin, it is preferable to perform an operation of blowing nitrogen or high-pressure steam into the system under reduced pressure conditions. The pressure of water vapor or nitrogen introduced into the system is not particularly limited, but specifically, it is preferably in the range of 0.3 to 2.0 MPa, more preferably in the range of 0.5 to 1.5 MPa. Impurities can be efficiently removed when the blowing operation is performed.

  The epoxy resin of the present invention can be obtained by further reacting the hydroxy compound obtained as described above with epihalohydrin. The manufacturing method of an epoxy resin is described below.

An alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like is added to a dissolved mixture of the above hydroxy compound and an epihalohydrin such as epichlorohydrin, epibromohydrin, β-methylepichlorohydrin or the like, or 20 to 120 ° C. with addition. The epoxy resin used in the present invention can be obtained by reacting for 1 to 10 hours. The addition amount of epihalohydrins is usually in the range of 0.3 to 20 equivalents relative to 1 equivalent of hydroxyl group of the starting hydroxy compound. If epihalohydrin is 2.5 less than equivalent, since unreacted hydroxyl and epoxy groups is likely to react, groups unreacted hydroxyl and epoxy groups are generated by the addition reaction _{(-CH 2 CR (OH) CH} 2 - , R: a hydrogen atom or an organic carbon group). On the other hand, when it is more than 2.5 equivalents, the content of the theoretical structure (number of repeating units n = 1) becomes high. The amount of epihalohydrin may be appropriately adjusted according to desired characteristics.

  In the reaction for obtaining the epoxy resin, an aqueous solution of the alkali metal hydroxide may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and the reaction is performed under reduced pressure or at normal temperature. A method may be used in which water and epihalohydrin are continuously distilled under pressure, liquid separation is performed, water is removed, and epihalohydrin is continuously returned to the reaction system. In addition, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is added to the dissolved mixture of the hydroxy compound and epihalohydrin as a catalyst and reacted at 50 to 150 ° C. for 1 to 5 hours. A method of adding a solid or aqueous solution of an alkali metal hydroxide to the halohydrin etherified product of the hydroxy compound and reacting again at 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure) may be used.

  Furthermore, in order to make the reaction proceed smoothly, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, ethers such as 1,4-dioxane, aprotic such as dimethyl sulfone and dimethyl sulfoxide It is preferable to carry out the reaction by adding a polar solvent or the like. The amount of alcohols, ketones and ethers used in the solvent is usually 5 to 50% by weight, preferably 10 to 30% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 10-60 weight%.

  After the epoxidation reaction product is washed with water or without washing with water, epihalohydrin and other added solvents are removed at 110 to 250 ° C. under a pressure of 10 mmHg or less under reduced pressure. Furthermore, in order to obtain an epoxy resin with less hydrolyzable halogen, the crude epoxy resin obtained after recovering the epihalohydrin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal such as sodium hydroxide or potassium hydroxide. An aqueous solution of hydroxide can also be added and reacted further to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.5 to 10 mol, preferably 1.2 to 5.0 mol, per 1 mol of hydrolyzable chlorine remaining in the crude epoxy resin. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 3 hours. For the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present. The amount of the phase transfer catalyst used is preferably in the range of 0.1 to 3.0% by weight based on the crude epoxy resin.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and a solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain a high-purity epoxy resin.

  In addition, as the epoxy resin (A) used in the present invention, the compound obtained by the above-mentioned method from dicyclopentadiene alone and the compound obtained from tricyclopentadiene alone are synthesized and purified, respectively, and then the desired 5 It may be obtained by mixing so as to have a condensed polycyclic aliphatic hydrocarbon group (x1) content consisting of a single 5-membered ring, and dicyclohexane as an unsaturated cyclic hydrocarbon (y1) at the raw material stage. Pentadiene and tricyclopentadiene may be appropriately mixed to form an epoxy resin by the above-described method. In addition, if necessary, other unsaturated compounds such as 4-vinylcyclohexene, 5-vinylnorborna-2-ene, 3a, 4,7,7a-tetrahydroindene, α-pinene, β-pinene, limonene May be obtained by previously mixing with unsaturated cyclic hydrocarbon (y1), reacting with hydroxy group-containing aromatic hydrocarbons (y2) by the above-mentioned method, and further epoxidizing.

  The epoxy resin composition of the present invention can be used in combination with another epoxy resin (C) in addition to the epoxy resin (A). When used in combination, the proportion of the epoxy resin (A) in the total epoxy resin is preferably 20% by weight or more, and particularly preferably 40% by weight or more. As the other epoxy resin (C) that can be used in combination, various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type are exemplified. Epoxy resin derived from divalent phenols such as epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol Novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, dicyclopentadiene-phenol modified epoxy resin, pheno Ruaralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified Examples include, but are not limited to, epoxy resins derived from trivalent or higher phenols such as phenol resin type epoxy resins and biphenyl-modified novolak type epoxy resins, tetrabromobisphenol A type epoxy resins, brominated phenol novolak type epoxy resins and the like. Is not to be done. Moreover, these epoxy resins may be used independently and may mix 2 or more types.

  Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin , Cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol Aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolak Epoxy resins, it is particularly preferable to use a biphenyl-modified novolak type epoxy resin.

The curing agent (B) used in the epoxy resin composition of the present invention is not particularly limited, and various curing agents such as amine compounds, acid anhydride compounds, amide compounds, phenol compounds and the like. Can be used, but for example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid dimer and ethylenediamine, phthalic anhydride , Trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac resin, cresol no Rack resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol aralkyl resin, phenol trimethylol methane resin, tetraphenylol ethane resin , Naphthol novolac resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, aminotriazine-modified phenol resin, bisphenol A novolac resin, bisphenol F novolac resin and the like And modified products thereof, imidazole, BF ₃ -amine complexes, guanidine derivatives and the like. Moreover, these hardening | curing agents may be used independently and may mix 2 or more types. Among these curing agents, phenol novolak resin, bisphenol A novolak resin, naphthol novolak resin, and phenol trimethylol methane resin are particularly preferable in terms of excellent heat resistance, and phenol aralkyl resin and cresol in terms of excellent moisture resistance. Aralkyl resins, naphthol aralkyl resins, and biphenyl-modified phenol aralkyl resins are particularly preferable. From the viewpoint of excellent flame retardancy, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, biphenyl-modified phenol aralkyl resins, and aminotriazine-modified phenol resins are particularly preferable. .

  In the epoxy resin composition of the present invention, as a blending ratio of the epoxy resin (A), the curing agent (B), and other epoxy resins (C) blended as necessary, a good cured product can be obtained. The total amount of the active groups in the curing agent (B) is 0.5 to 2.0 equivalents relative to 1 equivalent of the total epoxy groups in the epoxy resin (A) and the other epoxy resin (C). preferable.

  Further, a curing accelerator can be used as appropriate, and examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. In addition, two or more types can be used in combination.

  Moreover, various compounding agents, such as an inorganic filler, a flame-retarding agent, a pigment, a silane coupling agent, a mold release agent, can be added to the epoxy resin composition of this invention as needed.

  Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. In order to increase the blending amount of the inorganic filler, it is common to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The desired range varies depending on the application and desired properties, but for example, when used in semiconductor encapsulant applications, it is preferably higher in view of the coefficient of linear expansion and flame retardancy. It is preferably 65% by weight or more, particularly preferably 85% by weight or more. Moreover, when using for uses, such as an electrically conductive paste and an electrically conductive film, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various flame retardants can be used as the flame retardant, and examples thereof include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and inorganic flame retardant compounds. Specific examples thereof include halogen compounds such as tetrabromobisphenol A type epoxy resin, phosphorus atom-containing compounds such as red phosphorus and phosphate compounds, nitrogen atom-containing compounds such as melamine, aluminum hydroxide, magnesium hydroxide, boric acid Examples thereof include inorganic flame retardant compounds such as zinc and calcium borate.

  The use of the epoxy resin composition of the present invention is not particularly limited, and for example, for printed circuit boards, electronic component sealing materials, resist inks, conductive pastes, resin casting materials, adhesives, and insulation. Examples include coating materials such as paints. Among these, from the point that the cured product obtained has excellent dielectric properties, it is suitable for resin compositions for printed circuit boards, resin compositions for encapsulants for electronic components, resist inks, and conductive pastes. It can be used suitably, can be used suitably for a paint and an adhesive from the point which is excellent in moisture resistance, and can be used suitably for a composite material from the point which is further highly functional.

  As the printed circuit board, it can be suitably used particularly for prepregs, copper-clad laminates, and interlayer insulation materials for build-up printed circuit boards.

  In order to make the epoxy resin composition of the present invention into a resin composition for a prepreg for a printed circuit board, it can be used without a solvent depending on the viscosity of the resin composition, but for prepreg by varnishing with an organic solvent. A resin composition is preferred. Examples of the organic solvent include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, non-alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethylformamide. Examples thereof include solvents having a boiling point of 160 ° C. or lower, such as a polar solvent, and can be appropriately used as a mixed solvent of two or more. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The weight ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 to 60% by weight.

  In order to obtain a resin composition for a copper-clad laminate from the epoxy resin composition of the present invention, it is the same as the method for preparing the resin composition for prepreg, and the obtained prepreg is disclosed in, for example, JP-A-7-41543. A copper-clad laminate can be obtained by laminating as described, stacking copper foils as appropriate, and thermocompression bonding at 170-250 ° C. for 10 minutes to 3 hours under a pressure of 1-10 MPa.

  Although it does not specifically limit as a method of obtaining the interlayer insulation material for buildup boards from the epoxy resin composition of the present invention, for example, Japanese Patent Publication No. 4-6116, Unexamined-Japanese-Patent No. 7-304931, Unexamined-Japanese-Patent No. 8-64960, Various methods described in JP-A-9-71762, JP-A-9-298369 and the like can be employed. More specifically, the resin composition appropriately blended with rubber, filler, and the like is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  As the electronic component sealing material, it can be suitably used for a semiconductor chip sealing material, underfill, and semiconductor interlayer insulating film.

  In order to adjust the epoxy resin composition of the present invention for a semiconductor sealing material, an epoxy resin (A), a curing agent (B), other epoxy resins (C) blended as necessary, a coupling agent A method of premixing additives such as mold release agents and inorganic fillers, and then sufficiently mixing until uniform using an extruder, kneader, roll, or the like. In the case of a melt mixed type (solvent-free) composition, the composition is cast or molded using a transfer molding machine, an injection molding machine, etc., and further heated at 50 to 200 ° C. for 2 to 10 hours. Thus, a cured product can be obtained, and semiconductor package molding corresponds to this.

  Moreover, when using as a tape-shaped sealing agent, after heating the resin composition obtained by the above-mentioned method and producing a semi-hardened sheet and using it as a sealing agent tape, this sealing agent tape is used as a semiconductor chip. Examples of the method include placing it on top, heating to 100 to 150 ° C, softening and molding, and completely curing at 170 to 250 ° C.

  Furthermore, when using as a potting type liquid sealing agent, the resin composition obtained by the above-mentioned method may be applied on a semiconductor chip or an electronic component and directly cured.

  The method of using the epoxy resin composition of the present invention as an underfill resin is not particularly limited. However, Japanese Patent Application Laid-Open No. 9-266221 and “Plastics in the Electronics Field” (published by Industrial Research Council, 1999, pages 27 to 34). Can be used. More specifically, the epoxy resin composition of the present invention is injected into the gap between the semiconductor element with electrodes and the printed wiring board with solder during flip-chip mounting by a capillary flow method using a capillary phenomenon and cured. And a compression flow method in which the epoxy resin composition of the present invention is semi-cured on a substrate or a semiconductor element in advance, and then the semiconductor element and the substrate are brought into close contact with each other to be completely cured. In this case, the epoxy resin composition of the present invention is preferably used in the form of a liquid epoxy resin composition containing no organic solvent. In particular, when the capillary flow method is used, the viscosity needs to be low, and the viscosity is preferably 5000 mPa · s or less. If the said resin composition is a viscosity exceeding this, it can also inject | pour after heating to room temperature-100 degrees C or less.

  When the epoxy resin composition of the present invention is used as a semiconductor interlayer insulating material, for example, the method described in JP-A-6-85091 can be employed. When used as an interlayer insulating film, it will be in direct contact with the semiconductor, so it is required that the linear expansion coefficient of the insulating material be close to the linear expansion coefficient of the semiconductor so that cracks due to the difference in linear expansion coefficient do not occur in a high temperature environment. The In addition, in order to deal with the problem of signal delay due to miniaturization, multilayering, and high density of semiconductors, there is a demand for technology for reducing the capacity of insulating materials, and this problem can be solved by reducing the dielectric of insulating materials. be able to. The resin composition is preferable because it has characteristics satisfying these requirements.

  When the epoxy resin composition of the present invention is used as a resist ink, for example, according to the method described in JP-A No. 5-186567, a resist ink composition is prepared and then printed on a printed circuit board by a screen printing method. The method of making it a resist ink hardened | cured material after apply | coating to is mentioned.

  When using the epoxy resin composition of the present invention as a conductive paste, for example, fine conductive particles described in JP-A-3-46707 are dispersed in the resin composition, and the composition for anisotropic conductive film is used. And a paste resin composition for circuit connection which is liquid at room temperature as disclosed in JP-A-62-240183, JP-A-62-276215, JP-A-62-176139, etc. And an anisotropic conductive adhesive.

  When the epoxy resin composition of the present invention is used as a resin composition for coatings, for example, the epoxy resin (A) and other epoxy resins (C) used in combination as necessary may include pigments, colorants, and additives. Etc., add an organic solvent if necessary, and prepare in advance a pigment paste that is sufficiently kneaded and uniformly dispersed using an apparatus such as a mixing mixer or a ball mill. The curing agent (B) and curing acceleration are prepared in advance. A method of further blending an agent or the like to make it uniform and preparing it with an organic solvent or the like to have a desired viscosity can be mentioned. Moreover, as a method of obtaining a powder coating material, solid epoxy resin (A), solid curing agent (B), and, if necessary, other epoxy resin (C), curing accelerator, additive, pigment, etc. After coarsely pulverizing and blending, the mixture can be sufficiently pulverized and mixed using a pulverizer such as a Henschel mixer, melted and kneaded using a heated kneader, pulverized and classified after cooling.

  The resin composition prepared for the paint obtained by the above technique can be applied to various substrates by various coating methods, and the technique is not particularly limited. For example, a liquid paint resin Examples of the composition include a gravure coater, knife coater, roll coater, comma coater, spin coater, bar coater, brush coating, dipping coating, spray coating and the like, and powder coating includes electrostatic coating and the like. .

  Further, the curing method after coating the resin composition prepared for the paint is not particularly limited, and a cured coating film can be obtained by any of room temperature curing and heat curing.

  When using the epoxy resin composition of the present invention as a resin composition for an adhesive, for example, an epoxy resin (A), a curing agent (B), other epoxy resins (C) used in combination as necessary, Curing accelerators, additives, etc. can be obtained by uniformly mixing with a mixing mixer or the like at room temperature or under heating, and after being applied to various base materials, the base material is allowed to stand at room temperature or under heating. Can be bonded.

  In order to obtain a composite material from the epoxy resin composition of the present invention, the epoxy resin composition of the present invention can be used in a solvent-free system depending on the viscosity, but it is difficult to handle in a solvent-free system. After varnishing with an organic solvent, impregnating the varnish into a reinforcing base material and heating to obtain a prepreg, the direction of the fiber is changed little by little to make it pseudo-isotropic The method of carrying out hardening shaping | molding by laminating | stacking and heating after that is mentioned. Examples of the organic solvent include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, and the like. Non-alcoholic polar solvents and the like have a boiling point of 160 ° C. or lower, and can be used as a mixed solvent of two or more as appropriate. The heating temperature is determined in consideration of the type of solvent used, and is preferably 50 to 150 ° C. The type of the reinforcing substrate is not particularly limited, and examples thereof include carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The ratio of the resin component and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin component in the prepreg is adjusted to 20 to 60% by weight.

  The cured product of the present invention is obtained by molding and curing the above-described epoxy resin composition of the present invention, and can be used as a laminate, a cast product, an adhesive, a coating film, a film and the like. The curing method is not particularly limited. For example, the epoxy resin (A) and the curing agent (B), other epoxy resins (C) blended as necessary, various blending agents, etc. are uniformly mixed. Then, a method of heat curing at room temperature or 80 to 200 ° C. can be mentioned. Moreover, it is preferable to employ | adopt suitably the hardening method according to the use to which the epoxy resin composition prepared according to the above-mentioned various uses.

（Ｘ’は、下記構造式（ａ１−１）、

下記構造式（ａ１−２）、

及び下記構造式（ａ１−３）、

から成る群から選択される縮合多環脂肪族炭化水素基（ａ１）であり、かつ、前記構造式（ａ１−１）及び前記構造式（ａ１−２）から成る選択される縮合多環脂肪族炭化水素基（ｘ１）が縮合多環脂肪族炭化水素基（ａ１）中に２０モル％以上含有しており、かつ、ｎは１〜１０で表される繰り返しの平均値であり、Ｒは独立に水素原子、または炭素数１〜４のアルキル基であり、Ｇはグリシジル基であり、ｍは１〜３の整数である。）で表されることを特徴とする。これらのなかでも、前記一般式（３’）中、Ｘが前記構造式（ａ１−１）及び前記構造式（ａ１−２）から成る選択される縮合多環脂肪族炭化水素基（ｘ１）である、下記一般式（３）

ｎは１〜１０で表される繰り返しの平均値であり、Ｒは独立に水素原子、または炭素数１〜４のアルキル基であり、Ｇはグリシジル基であり、ｍは１〜３の整数である。）で表されるものが好ましい。
The epoxy resin of the present invention has the following general formula (3 ′)

(X ′ is the following structural formula (a1-1),

The following structural formula (a1-2),

And the following structural formula (a1-3),

A condensed polycyclic aliphatic hydrocarbon group (a1) selected from the group consisting of: and a condensed polycyclic aliphatic group selected from the structural formula (a1-1) and the structural formula (a1-2) The hydrocarbon group (x1) is contained in the condensed polycyclic aliphatic hydrocarbon group (a1) in an amount of 20 mol% or more, and n is an average value represented by 1 to 10 and R is independent. Are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, G is a glycidyl group, and m is an integer of 1 to 3. ). Among these, in the general formula (3 ′), X is a condensed polycyclic aliphatic hydrocarbon group (x1) selected from the structural formula (a1-1) and the structural formula (a1-2). The following general formula (3)

n is an average value of repetitions represented by 1 to 10, R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, G is a glycidyl group, and m is an integer of 1 to 3. is there. ) Is preferred.

  As a synthesis method of the compound represented by the general formula (3), tricyclopentadiene as a raw material and a hydroxy group-containing aromatic hydrocarbon having a desired structure (for example, phenol, cresol, xylenol, pt-butylphenol, etc.) ) Using an acid catalyst in the same manner as the hydroxy compound described above, and further epoxidized using epihalohydrin. In addition, the glycidyl group in the said General formula (3) is 1 or more types of groups chosen from the following by the structure of the epihalohydrin to be used.

（Ｒ２は水素原子、または炭素数１〜４のアルキル基を表す）

(R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

  As the use of the epoxy resin represented by the general formula (3), as a main component of the epoxy resin composition of the present invention, a high-functional resin such as an epoxy acrylate resin raw material, a photosensitive resin raw material such as a semiconductor photoresist It can be used as a raw material and contributes to improvement of physical properties such as moisture resistance, dielectric properties, heat resistance and the like of the cured product.

  Next, the present invention will be specifically described with reference to synthesis examples, examples and comparative examples. In the following, “parts” and “%” are based on weight unless otherwise specified.

  Of the unsaturated cyclic hydrocarbons used in the synthesis, tricyclopentadiene is a tricyclopentadiene manufactured by Maruzen Petrochemical Co., Ltd. (85% having the structure of the structural formula (1), of the structural formula (2) (Containing 15% of those having a structure), and a commercially available reagent (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was used as dicyclopentadiene.

In addition, the cured-material physical-property evaluation method of the epoxy resin composition obtained by this invention is shown to (1)-(3).
(1) Glass transition temperature: The glass transition temperature was measured by the DMA method (temperature increase rate 3 ° C./min).
(2) Moisture absorption rate: The change in weight (wt%) before and after being treated for 300 hours in a constant temperature and humidity device at 85 ° C./85% RH was measured as the moisture absorption rate (test piece size 75 × 25 × 2 mm).
(3) Dielectric properties: Dielectric constant and dielectric loss tangent at frequencies of 10 MHz, 100 MHz, and 1 GHz were measured using a dielectric property evaluator (test piece size 75 × 25 × 2 mm). For the dielectric properties after moisture absorption, the dielectric constant and dielectric loss tangent were measured using a test piece treated by the method described in (2) above.

Example 1
940 g (10 mol) of phenol was charged into a reactor equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, heated to 70 ° C., and 9.4 g of boron trifluoride-ether complex was added, followed by reaction. While controlling the temperature at 70 ° C., 198 g (1 mol) of tricyclopentadiene was gradually added dropwise over 1.5 hours, and after completion of the addition, reaction was performed at 100 ° C. for 5 hours. After completion of the reaction, 7.4 g of triethylamine was added to the obtained reaction product and stirred for 30 minutes to deactivate the catalyst. Then, the unreacted phenol was concentrated and recovered to obtain a crude polyvalent hydroxy compound. Next, the obtained crude polyvalent hydroxy compound containing the catalyst residue was dissolved in 600 g of methyl isobutyl ketone, and then washed with 200 g of water three times. The solvent was concentrated and recovered to obtain 372 g of hydroxy compound (1). The obtained hydroxy compound (1) has a melt viscosity at 150 ° C. of 15 dPa · s, a softening point of 115 ° C., and a phenolic hydroxyl group equivalent of 206 g / eq. Met. Moreover, n which is the number of repeating units was 1.3 from GPC, and each peak of M ⁺ = 386, 678, 971, 1262 was confirmed by MS spectrum.

  While purging the reactor equipped with a thermometer, a dropping funnel, a condenser, and a stirrer with nitrogen gas, 206 g of hydroxy compound (1) (hydroxyl equivalent 206), 463 g of epichlorohydrin, 53 g of n-butanol, 2.3 g of tetraethylbenzylammonium chloride Was charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 82 g of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours, and then stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled azeotropically was separated by a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 550 g of methyl isobutyl ketone and 55 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 15 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. After that, washing with 100 g of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 254 g of the desired epoxy resin (A-1). As a result of measuring the free phenol content in the obtained epoxy resin using a method of coloring with 4-aminoantipyrine, no color development was observed, and 50 ppm or less was confirmed. Moreover, the epoxy equivalent of the obtained epoxy resin is 296 g / eq. It was confirmed that it was epoxidized. The melt viscosity at 150 ° C. of the obtained resin was 3.0 dPa.s. s and the softening point was 81 ° C.

Example 2
Except having changed the phenol to be used into 1080 g (10 mol) of o-cresol, the same operation as in Example 1 was performed to obtain 392 g of a hydroxy compound (2). The obtained hydroxy compound (2) has a melt viscosity of 11 dPa · s, a softening point of 125 ° C., and a phenolic hydroxyl group equivalent of 234 g / eq. Met. From GPC, it confirmed each peak of n = 1.3 and MS spectrum M ⁺ = 415, 721, 1027, 1333.

  Epoxidation was carried out in the same manner as in Example 1 except that 234 g of the hydroxy compound (2) was used instead of 206 g of the hydroxy compound (1) to obtain the target epoxy resin (A-2). Using the same method as in the example, it was confirmed that the phenolic hydroxyl group was epoxidized. The epoxy equivalent of the obtained epoxy resin is 322 g / eq. The melt viscosity at 150 ° C. is 5.8 dPa.s. s and the softening point was 86 ° C.

Example 3
Except that the unsaturated cyclic hydrocarbon used was changed to a mixture of 99 g (0.5 mol) of tricyclopentadiene and 66 g (0.5 mol) of dicyclopentadiene, the same operation as in Example 1 was carried out to obtain a hydroxy compound ( 3) 334 g was obtained. The obtained hydroxy compound (3) had a melt viscosity at 150 ° C. of 4.0 dPa · s, a softening point of 102 ° C., and a phenolic hydroxyl group equivalent of 188 g / eq. Met.

  Except for using 188 g of hydroxy compound (3) (hydroxyl equivalent 188 g / eq.) Instead of 206 g of hydroxy compound (1), the same operation as in Example 1 was carried out to obtain 241 parts of epoxy resin (A-3). . The epoxy equivalent of the obtained epoxy resin was 274 g / eq. The melt viscosity at 150 ° C. was 1.4 dPa · s, and the softening point was 80 ° C.

Comparative Example 1
Except that the unsaturated cyclic hydrocarbon used was changed to a mixture of 30 g (0.15 mol) of tricyclopentadiene and 112 g (0.85 mol) of dicyclopentadiene, the same operation as in Example 1 was carried out to obtain a hydroxy compound ( 4) 320 g was obtained. The obtained hydroxy compound (4) has a melt viscosity at 150 ° C. of 1.5 dPa · s, a softening point of 88 ° C., and a phenolic hydroxyl group equivalent of 172 g / eq. Met.

  Except using 172 g of hydroxy compound (4) (hydroxyl equivalent 172 g / eq.) Instead of 206 g of hydroxy compound (1), the same operation as in Example 1 was performed to obtain 217 g of epoxy resin (A-4). The epoxy equivalent of the obtained epoxy resin is 255 g / eq. The melt viscosity at 150 ° C. is 0.6 dPa.s. s and the softening point was 61 ° C.

Examples 4-6, Comparative Examples 2-4
An epoxy resin composition was prepared at a blending ratio shown in Table 1, and was heat-cured (175 ° C. × 5 hours; press molding), cut into a predetermined size, and a test piece was obtained. A phenol novolak resin (Phenolite TD-2131, manufactured by Dainippon Ink & Chemicals, Inc., hydroxyl equivalent: 104 g / eq.) Was used as the curing agent (B), and Examples 1 to 3 and Comparative Example 1 were used as the epoxy resin. The epoxy resins (A-1) to (A-4) obtained in (1) were used. Further, as Comparative Example 3, dicyclopentadiene-phenol-modified epoxy resin (EPICLON HP-7200, manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent 259 g / eq.), As Comparative Example 4, orthocresol type epoxy resin (Dainippon Ink) Chemical Industry Co., Ltd. EPICLON N-665-EXP, epoxy equivalent 203g / eq.) Was used.

Claims (14)

The following general formula (3 ')

(X ′ is the following structural formula (a1-1),

The following structural formula (a1-2),

And the following structural formula (a1-3),

A condensed polycyclic aliphatic hydrocarbon group (a1) selected from the group consisting of: and a condensed polycyclic aliphatic group selected from the structural formula (a1-1) and the structural formula (a1-2) The hydrocarbon group (x1) is contained in the condensed polycyclic aliphatic hydrocarbon group (a1) in an amount of 20 mol% or more, and n is an average value represented by 1 to 10 and R is independent. Are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, G is a glycidyl group, and m is an integer of 1 to 3. The epoxy resin composition characterized by containing the epoxy resin (A) represented by this, and a hardening | curing agent (B). The molar ratio of the group represented by the condensed polycyclic aliphatic hydrocarbon group (x1) the structural formula (a1-1) a group with the formula represented in (a1-2) (a1- 1) / (a1- 2) is 50 / 50-99 / 1 in a claim 1 epoxy resin composition. Epoxy resin (A), a compound obtained by reacting a tri-cyclopentadiene and monohydric phenols, further claim 1 epoxy resin composition according containing the compound obtained by epoxidizing with Epiharohidoron. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) has a melt viscosity at 150 ° C. of 10 dPa · s or less. Claim 1 any one epoxy resin composition according 4 which is prepared in the printed circuit board resin composition. The epoxy resin composition according to any one of claims 1 to 4, which is prepared as a resin composition for an electronic component sealing material. The epoxy resin composition according to claim 1, which is prepared as a resist ink. The epoxy resin composition according to claim 1, which is prepared into a conductive paste. The epoxy resin composition according to any one of claims 1 to 4, which is prepared into a paint. The epoxy resin composition according to any one of claims 1 to 4, which is prepared as an adhesive. The epoxy resin composition according to claim 1, which is prepared into a composite material. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 4 . The following general formula (3 ')

(X ′ is the following structural formula (a1-1),

The following structural formula (a1-2),

And the following structural formula (a1-3),

A condensed polycyclic aliphatic hydrocarbon group (a1) selected from the group consisting of: and a condensed polycyclic aliphatic group selected from the structural formula (a1-1) and the structural formula (a1-2) The hydrocarbon group (x1) is contained in the condensed polycyclic aliphatic hydrocarbon group (a1) in an amount of 20 mol% or more, and n is an average value represented by 1 to 10 and R is independent. Are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, G is a glycidyl group, and m is an integer of 1 to 3. Epoxy resin, characterized by being represented by). 14. In the general formula (3 ′), X is a condensed polycyclic aliphatic hydrocarbon group (x1) selected from the structural formula (a1-1) and the structural formula (a1-2). Epoxy resin.