JP2010047726A - Epoxy resin composition, cured product thereof, prepreg, copper-clad laminate, and resin composition for build-up adhesive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition giving a cured product excellent in both heat resistance and copper foil releasing properties to a high degree, the cured product, a prepreg, a copper-clad laminate, and a build-up adhesive film. <P>SOLUTION: The epoxy resin composition essentially comprises an epoxy resin (A) and a curing agent (B). The curing agent (B) is a modified phenol resin having a molecular structure, wherein 40-95% of phenolic hydroxy groups in a novolak type phenol resin is alkyl esterified or aryl esterified, and having a softening point within the range of 100-140°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to an epoxy resin composition that combines heat resistance of a cured product and copper foil peelability at a high level, and particularly suitable for a copper-clad laminate insulating material, and a cured product thereof.

  An epoxy resin composition containing an epoxy resin and a curing agent as an essential component exhibits excellent heat resistance and insulation in the cured product, and is therefore widely used in electronic component applications such as semiconductors and copper-clad laminates. Yes.

Among these electronic component applications, in the technical field of electronic component materials such as copper-clad laminate insulating materials and build-up adhesive films, in recent years, the speed of signals and the frequency of various electronic devices have been increasing. However, with the increase in signal speed and frequency, it is becoming difficult to obtain a low dielectric loss tangent while maintaining a sufficiently low dielectric constant.
Therefore, a thermosetting resin composition and a resin sheet capable of obtaining a cured body that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even with respect to high-speed and high-frequency signals It is desirable to provide a laminate. As a material capable of realizing these low dielectric constants and low dielectric loss tangents, a technique using an active ester compound obtained by aryl esterifying a phenolic hydroxyl group in a phenol novolac resin as a curing agent for an epoxy resin is known (patent) Reference 1).
However, due to the trend toward higher frequency and smaller size in electronic parts, copper-clad laminate insulating materials and build-up adhesive film materials are required to have extremely high heat resistance. The active ester compound obtained by aryl esterifying a hydroxyl group is one in which the heat resistance of the cured product is not sufficient. On the other hand, when a novolac resin is used as a curing agent for an epoxy resin, heat resistance can be improved by increasing the molecular weight of the novolak resin, but in this case, a copper-clad laminate or an adhesive film for build-up is used. Since the adhesiveness with the copper foil is inferior and cannot be practically used, it is difficult to achieve both heat resistance and adhesiveness.

JP 7-82348 A

  Therefore, the problem to be solved by the present invention is an epoxy resin composition having a high degree of both heat resistance and copper foil peelability in a cured product, the cured product, a prepreg, a copper clad laminate, and a build-up adhesive film. The object is to provide a resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have conducted the field of multilayer printed circuit boards by alkylating or arylesterifying a predetermined number of phenolic hydroxyl groups of a novolak type phenolic resin having a high molecular weight. The inventors have found that an insulating material having a combination of excellent heat resistance and copper foil peelability can be obtained, and the present invention has been completed.

That is, this invention is an epoxy resin composition which has an epoxy resin (A) and a hardening | curing agent (B) as an essential component, Comprising: The said hardening | curing agent (B) is 40 ~ of all phenolic hydroxyl groups of a novolak-type phenol resin. The present invention relates to an epoxy resin fat composition having a molecular structure in which 95% is alkylesterified or arylesterified, and a modified phenol resin having a softening point in the range of 100 to 140 ° C.
The present invention further relates to a cured product obtained by curing the epoxy resin composition.
The present invention further relates to a prepreg obtained by impregnating a fiber base material with the epoxy resin composition.
The present invention further relates to a structure formed by molding a prepreg.
The present invention further relates to a resin composition for a build-up adhesive film, characterized by comprising the epoxy resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition which combined heat resistance and copper foil peelability in hardened | cured material highly, the hardened | cured material, a prepreg, a copper clad laminated board, and the resin composition for buildup adhesive films can be provided. .

Examples of the epoxy resin (A) used in the epoxy resin composition of the present invention include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; biphenyl type epoxy resins and tetramethylbiphenyl type epoxy resins. Biphenyl type epoxy resin; phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, epoxidized product of condensate of phenol and aromatic aldehyde having phenolic hydroxyl group, biphenyl novolak type epoxy resin, etc. Novolac type epoxy resin; Triphenylmethane type epoxy resin; Tetraphenylethane type epoxy resin; Dicyclopentadiene-phenol addition reaction type epoxy resin; Phenol aralkyl type Epoxy resins; naphthol novolak type epoxy resin,
Naphthol aralkyl epoxy resin, naphthol-phenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, diglycidyloxynaphthalene, structural formula

で表される４官能ナフタレン型エポキシ樹脂等の分子構造中にナフタレン骨格を有するエポキシ樹脂；リン原子含有エポキシ樹脂等が挙げられる。また、これらのエポキシ樹脂は単独で用いてもよく、２種以上を混合してもよい。
ここで、リン原子含有エポキシ樹脂としては、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド（以下、「ＨＣＡ」と略記する。）のエポキシ化物、ＨＣＡとキノン類とを反応させて得られるフェノール樹脂のエポキシ化物、フェノールノボラック型エポキシ樹脂をＨＣＡで変性したエポキシ樹脂、クレゾールノボラック型エポキシ樹脂をＨＣＡで変性したエポキシ樹脂、また、ビスフェノールＡ型エポキシ樹脂を、ＨＣＡとキノン類とを反応させて得られるフェノール樹脂で変成して得られるエポキシ樹脂、及びビスフェニールＡ型エポキシ樹脂を、ＨＣＡとキノン類とを反応させて得られるフェノール樹脂で変成して得られるエポキシ樹脂等が挙げられる。
上記したエポキシ樹脂（Ａ）のなかでも、特に耐熱性の点から、分子構造中にナフタレン骨格を有するエポキシ樹脂、分子構造中にリン原始を有するエポキシ樹脂であることが好ましい。

An epoxy resin having a naphthalene skeleton in a molecular structure such as a tetrafunctional naphthalene type epoxy resin represented by: a phosphorus atom-containing epoxy resin. Moreover, these epoxy resins may be used independently and may mix 2 or more types.
Here, as the phosphorus atom-containing epoxy resin, epoxidized product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as “HCA”), HCA and quinones Epoxy product of phenol resin obtained by reacting phenolic resin, epoxy resin obtained by modifying phenol novolac type epoxy resin with HCA, epoxy resin obtained by modifying cresol novolac type epoxy resin with HCA, and bisphenol A type epoxy resin using HCA and quinone Resin obtained by modification with a phenol resin obtained by reacting with a phenol, an epoxy resin obtained by modifying a bisphenyl A type epoxy resin with a phenol resin obtained by reacting an HCA with a quinone, etc. Is mentioned.
Among the above-described epoxy resins (A), particularly from the viewpoint of heat resistance, an epoxy resin having a naphthalene skeleton in the molecular structure and an epoxy resin having a phosphorus primitive in the molecular structure are preferable.

  Moreover, in order to raise the glass transition temperature of the hardened | cured material of an epoxy resin composition and to improve heat resistance, the epoxy group equivalent of an epoxy resin (B) is 1,000 g / equivalent or less, Especially 700 g / equivalent or less, Especially 500 g / It is preferable that it is below an equivalent.

  Of these, biphenyl type epoxy resins, naphthalene type epoxy resins, phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins and xanthene type epoxy resins are particularly preferred because of their excellent flame retardancy and dielectric properties.

  Next, as described above, the curing agent (B) used in the present invention has a molecular structure in which 40 to 95% of the phenolic hydroxyl group of the novolak type phenol resin is alkyl esterified or aryl esterified, and its softening. It is a modified phenolic resin having a point in the range of 100 to 140 ° C. Here, the softening point of the modified phenolic resin is a value measured by a ring and ball method (temperature increase rate: 5 ° C./min) in accordance with “JIS K7234-86”.

  In the present invention, since a modified phenol resin having a softening point in the range of 100 to 140 ° C., preferably in the range of 120 to 130 ° C. is used as a curing agent, excellent heat resistance is imparted to the cured product. Can do. Further, as described above, the target modified phenol resin can be obtained by alkyl esterifying or aryl esterifying the novolak type phenol resin. At this time, 40 to 95 of the phenolic hydroxyl group in the novolak type phenol resin can be obtained. %, Preferably 60 to 95% of the alkyl ester or aryl ester, the copper foil peel strength in copper-clad laminate applications and build-up adhesive film applications is good. Especially for copper clad laminates, not only the copper foil peel strength but also the interlayer strength in the multilayer laminate is dramatically improved. In this way, it is worth mentioning that the esterification of a predetermined amount of phenolic hydroxyl group in the novolak-type phenolic resin dramatically improves the copper foil peel strength, particularly the interlayer strength in copper clad laminate applications. As a result, heat resistance, copper foil peel strength, and interlayer strength can be combined at a high level. As described above, when novolak resin is used as a curing agent for epoxy resin, heat resistance and copper foil peel strength / interlaminar strength were mutually contradictory performances, so it was remarkable that both of these performances could be achieved. It can be said that it is an effect.

  Here, as the alkyl group or aryl group constituting the alkyl ester or aryl ester obtained by alkyl esterifying or aryl esterifying a phenolic hydroxyl group, specifically, methyl, ethyl, n-propyl, i-propyl, an alkyl group having 1 to 4 carbon atoms such as t-butyl, or a phenyl group, biphenyl group, methylphenyl group, ethylphenyl group, n-propylphenyl group, i-propylphenyl group, t-butylphenyl group, etc. And a phenyl group having a nucleus substituted with an alkyl group having 1 to 4 carbon atoms. Among these, an aryl group is preferable from the viewpoint of heat resistance.

  Specifically, the structure of the modified phenolic resin is represented by the following structural formula 1

（式中、Ｒ^１は、炭素原子数１〜４のアルキル基、フェニル基、炭素原子数１〜４のアルキル基で核置換されたフェニル基を表し、Ｒ^２は水素原子又は炭素原子数１〜４のアルキル基を表す。）
で表される構造部位Ｉと、下記構造式２

(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a phenyl group nucleus-substituted with an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ˜4.)
And a structural site I represented by the following structural formula 2

（式中、Ｒ^２は水素原子又は炭素原子数１〜４のアルキル基を表す。）
で表される構造部位IIとが、下記構造式３

(In the formula, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
Structural site II represented by the following structural formula 3

（式中、Ｒ^３は、メチル基又は水素原子を表し、Ｒ^４は、メチル基、フェニル基、水素原子を表す。）
で表されるアルキリデン構造部位IIIで結節された分子構造を有するものであることが、銅箔剥離強度、更に銅張積層板用途における層間強度が一層良好なものとなる点から好ましい。

(In the formula, R ³ represents a methyl group or a hydrogen atom, and R ⁴ represents a methyl group, a phenyl group, or a hydrogen atom.)
It is preferable that it has the molecular structure knotted by the alkylidene structure site III represented by the following, since the copper foil peel strength and the interlayer strength in the use of a copper clad laminate are further improved.

  Moreover, it is preferable that the average number of nuclei of the modified phenolic resin, that is, the total of the structural site I and the structural site II is present in an average of 6 to 9 per molecule, It is preferable that the structural site I is present in a proportion of 40 to 95%, preferably 60 to 95%, based on the total number of the structural site I and the structural site II.

Here, since the average number of nuclei of the modified phenol resin coincides with the average number of nuclei in the phenol resin as a raw material, the average number of nuclei of the phenol resin as a raw material is obtained by measuring by GPC. be able to. The method for obtaining the average number of nuclei of the phenol resin based on the GPC measurement is as follows.
[How to find the average number of nuclei]
According to GPC measurement performed under the following conditions, styrene equivalent molecular weights (α1, α2, α3, α4) corresponding to n = 1, n = 2, n = 3, and n = 4, and n = 1 and n = The ratios (β1 / α1, β2 / α2, β3 / α3, β4 / α4) to the respective theoretical molecular weights (β1, β2, β3, β4) of 2, n = 3, and n = 4 were determined, and these (β1 / The average value of α1 to β4 / α4) is obtained. The number of nuclei is calculated using the value obtained by multiplying the average value by the number average molecular weight (Mn) determined by GPC as the average molecular weight.

(GPC measurement conditions)
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

  The molecular structure in which 40 to 95% of the phenolic hydroxyl group of the novolak type phenol resin is alkylesterified or arylesterified is an esterifying agent (based on 1 mol of the phenolic hydroxyl group of the novolak type phenol resin used as a raw material). Benzoyl chloride) is a molecular structure obtained by reacting at a ratio of 0.40 to 0.95 mol, and the esterification ratio is determined from the hydroxyl equivalent value calculated from the average molecular weight by GPC measurement, and the raw material phenol The number of hydroxyl groups (number of moles) in the resin can be calculated and determined from the ratio of the number of moles of the esterifying agent (benzoyl chloride) subjected to the reaction to the number of moles of hydroxyl groups.

  Specifically, the curing agent (B) detailed above can be produced by reacting a novolac type phenol resin with an alkyl esterifying agent or an aryl esterifying agent.

  Here, as the novolac type phenol resin, specifically, the following structural formula 4

（式中、Ｒ^２は水素原子又は炭素原子数１〜４のアルキル基を表し、Ｒ^３は、メチル基又は水素原子を表し、Ｒ^４は、メチル基、フェニル基、水素原子を表し、ｎは繰り返し単位の平均で４〜７である。）
上記構造式４で表されるフェノール樹脂のなかでも特に銅箔剥離強度、更には層間強度の改善効果が顕著である点からフェノールノボラック樹脂、クレゾールノボラック樹脂であることが好ましい。

(In the formula, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ represents a methyl group or a hydrogen atom, R ⁴ represents a methyl group, a phenyl group, or a hydrogen atom, n Is an average of 4 to 7 repeating units.)
Among the phenol resins represented by the structural formula 4, a phenol novolac resin and a cresol novolac resin are preferable from the viewpoint that the effect of improving the copper foil peel strength and the interlayer strength is particularly remarkable.

  Examples of the alkyl esterifying agent or aryl esterifying agent to be reacted with the novolak type phenol resin include benzoic acid, phenyl benzoic acid, methyl benzoic acid, ethyl benzoic acid, n-propyl benzoic acid, i-propyl benzoic acid and Alkylbenzoic acids such as t-butylbenzoic acid, and acid halides such as acid fluorides, acid chlorides, acid bromides, and acid iodides are mentioned, and those having good reactivity with phenolic hydroxyl groups From this point, a benzoic acid chloride or an alkylbenzoic acid base is preferable.

And the method of making a novolak-type phenol resin react with an alkyl esterifying agent or an aryl esterifying agent can specifically make these each component react in presence of an alkali catalyst.
Examples of the alkali catalyst that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Of these, sodium hydroxide and potassium hydroxide are particularly preferred because they can be used in the form of an aqueous solution and the productivity is good.

  Specifically, the reaction is carried out by mixing a novolak-type phenol resin with an alkyl esterifying agent or an aryl esterifying agent in the presence of an organic solvent, and dropping the alkali catalyst or an aqueous solution thereof continuously or intermittently. The method of making it react is mentioned. At that time, the concentration of the aqueous solution of the alkali catalyst is preferably in the range of 3.0 to 30%. Examples of the organic solvent that can be used here include toluene and dichloromethane.

  After completion of the reaction, if an aqueous solution of an alkali catalyst is used, the reaction solution is allowed to stand for separation, the aqueous layer is removed, and the remaining organic layer is repeated until the aqueous layer after washing becomes almost neutral, The target resin can be obtained.

  Since the modified phenolic resin thus obtained is usually obtained as an organic solvent solution, when used as a copper-clad laminate varnish or a build-up adhesive film, it is mixed with other ingredients as it is, The target epoxy resin composition can be produced by appropriately adjusting the amount of the organic solvent.

  In the epoxy resin composition of the present invention, the amount of the epoxy resin curing agent (B) is the sum of the epoxy group in the epoxy resin (A), the active hydrogen in the curing agent (B) and the ester bond. Is a blending ratio in which the molar ratio of the former epoxy group / the latter active hydrogen and the ester bond is 0.7 to 1.2, it is excellent in heat resistance, copper foil peel strength, and interlayer strength. It is preferable from the point.

In the epoxy resin composition of the present invention, in addition to the curing agent (B) as an epoxy resin curing agent, an amine compound, an amide compound, an acid anhydride compound, phenol as long as the effects of the present invention are not impaired. You may use together other hardening | curing agents for epoxy resins (B '), such as a system compound. In this case, the curing agent (B ′) can be used by replacing a part of the curing agent (B) with the curing agent (B ′). That is, when the curing agent (B ′) is used in combination, the total of the active hydrogen in the curing agent (B ′) and the active hydrogen and ester bond in the curing agent (B) is in the epoxy resin (A). The ratio is preferably 0.7 to 1.2 with respect to 1 mol of the epoxy group.
Moreover, a hardening | curing agent (B ') can be used in the ratio used as 50 mass% or less with respect to the total mass with a hardening | curing agent (B).

Examples of amine compounds that can be used here include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivatives.
Examples of the amide compounds include polyamide resins synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine.

  Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydroanhydride Examples include phthalic acid.

  Phenol compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, α-naphthol aralkyl resin, β-naphthol aralkyl resin, biphenyl aralkyl resin. , Trimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, aminotriazine-modified phenol resin, and the like. Specific examples of the aminotriazine-modified phenol resin include copolymers of formaldehyde and amino group-containing triazine compounds such as melamine and benzoguanamine, phenols such as phenol and cresol, and formaldehyde.

  Among these, polyhydric phenol compounds are particularly preferred because the linear expansion coefficient of the cured product is lower, and they are resistant to thermal and physical impacts and are excellent in toughness. Phenol novolac resins, cresol novolac resins, phenol aralkyl resins Α-naphthol aralkyl resin, β-naphthol aralkyl resin, biphenyl aralkyl resin, and aminotriazine-modified phenol resin are preferable.

  The epoxy resin composition of the present invention may further contain a curing accelerator (C) in addition to the components described above.

  Examples of the curing accelerator (C) that can be used here include imidazoles, tertiary amines, and tertiary phosphines.

  Specific examples of imidazoles include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2 -Phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1- Vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecyl Imi Tetrazole, another such 1-cyanoethyl-2-phenylimidazole, masking imidazoles and the like.

  Specific examples of the tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexadiamine, triethylenediamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-dimethylanisidine, pyridine, picoline, quinoline, N, N'-dimethylaminopyridine, N-methylpiperidine, N, N'-dimethylpiperazine, 1, And 8-diazabicyclo- [5,4,0] -7-undecene (DBU).

  Specific examples of the tertiary phosphines include trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, triphenylphosphine, dimethylphenylphosphine, and methyldiphenylphosphine. Among these, tertiary amines are preferable from the viewpoint of higher heat resistance of the cured product.

  Moreover, although the addition amount of a hardening accelerator (C) can be suitably adjusted with the target hardening time etc., with respect to the total mass of an above-described epoxy resin component, a hardening | curing agent component, and the said hardening accelerator (C). It is preferable that it is the range used as 0.1-2 mass%.

  The epoxy resin composition of the present invention can further use an organic solvent (D) in addition to the above-described components, depending on the intended use. For example, when the epoxy resin composition is used as a varnish for a copper clad laminate, the impregnation property to the base material is improved, and when used as a build-up adhesive film, the coating property to the base material sheet is good. become. Examples of the organic solvent (D) that can be used here include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , Ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate esters such as carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, Examples thereof include dimethylacetamide and N-methylpyrrolidone. When the organic solvent (D) is used as a varnish for a copper clad laminate, the impregnation property to the base material is improved and the nonvolatile content in the composition is in a range of 50 to 70% by mass. It is preferable. On the other hand, when using as a varnish for buildup adhesive films, it is preferable that the nonvolatile content in the composition is in a range of 30 to 60% by mass.

  The epoxy resin composition of the present invention may contain an inorganic filler, a modifier, a flame retardant, and the like as appropriate in addition to the components described above, depending on the intended use.

  Examples of the inorganic filler used here include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and magnesium hydroxide. Among these, fused silica is particularly preferable from the viewpoint that the filling rate of the inorganic filler can be increased. Here, the fused silica can be used in either crushed or spherical shape, but in order to increase the blending amount of the fused silica and to suppress the increase in the melt viscosity of the molding material, it is preferable to mainly use the spherical one. preferable. 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 of the blending ratio of the inorganic filler varies depending on the application and desired characteristics. For example, when used for a semiconductor sealing material, a higher ratio is preferable in view of the linear expansion coefficient and flame retardancy, and the epoxy resin composition It is preferable that it is the range of 65-95 mass% with respect to the whole quantity, especially the range of 85-95 mass%. 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 types of thermosetting resins and thermoplastic resins can be used as the modifier. For example, phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether Examples thereof include resins, polyphenylene sulfide resins, polyester resins, polystyrene resins, and polyethylene terephthalate resins.

Examples of the flame retardant imparting agent include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and inorganic flame retardant compounds. Specifically, halogen compounds such as tetrabromobisphenol A type epoxy resin and brominated phenol novolak type epoxy resin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, Phosphate esters such as tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, resorcin diphenyl phosphate, ammonium polyphosphate, Condensation of polyphosphate amide, red phosphorus, guanidine phosphate, dialkylhydroxymethylphosphonate, etc. Phosphorus atom-containing compounds such as phosphate ester compounds, nitrogen-containing compounds such as melamine, aluminum hydroxide, magnesium hydroxide, zinc borate, and inorganic flame retardant compounds such as calcium borate.
However, the epoxy resin composition of the present invention is characterized by exhibiting an excellent flame retardant effect without using a halogen-based flame retardant having a high environmental load. It is preferable to use a phosphorus atom-containing compound, a nitrogen atom-containing compound, or an inorganic flame retardant compound.

  The conditions for thermosetting the epoxy resin composition of the present invention are not particularly limited, and can be cured under conditions for curing a normal phenol resin. Usually, it can carry out at the temperature of 120 to 250 degreeC. In particular, a temperature range of 170 to 220 ° C. is preferable from the viewpoint of good moldability.

  As described above, the epoxy resin composition of the present invention described in detail above is useful as a resin composition for copper-clad laminates, an interlayer insulating material for build-up printed boards, an adhesive film for build-up, and the like. It can also be used as a resin composition for encapsulants of electronic parts, a resin composition for resist ink, a binder for friction material, a conductive paste, a resin casting material, an adhesive, a coating material such as an insulating paint, and the like.

  The method for producing a resin composition for a copper clad laminate from the epoxy resin composition of the present invention specifically comprises the epoxy resin (A) and the curing agent (B) as essential components, and further if necessary. And a method of blending an organic solvent (D) and a curing accelerator (C) to form a varnish. Here, the varnish preferably has a nonvolatile content in a range of 50 to 70% by mass from the viewpoint of impregnation into a fiber base material and prepreg productivity.

  Next, specific examples of the method for producing a copper clad laminate from the above resin composition for copper clad laminate include the following methods.

  The varnish obtained by the above method is impregnated into a fiber substrate such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, 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. Under the present circumstances, it is preferable to adjust normally the compounding ratio of the epoxy resin composition to be used and a reinforcement base material so that the resin content in a prepreg may be 20-60 mass%.

  By laminating the obtained prepreg, further stacking copper foil, and heat-pressing it, a target copper-clad laminate can be obtained. Specific examples of the method of thermocompression bonding include a method of performing a temperature condition of 170 to 250 ° C. under a pressure of 1 to 10 MPa. The thermocompression bonding is preferably performed for 10 minutes to 3 hours.

Moreover, the epoxy resin composition of the present invention is extremely useful as an interlayer insulating material for build-up printed circuit boards.
Among the above-mentioned varnishing methods, the interlayer insulating material for such a build-up printed circuit board contains, in particular, the epoxy resin (A) and the curing agent (B) as essential components, and, if necessary, the organic solvent ( D), a hardening accelerator (C), and the method of mix | blending the said inorganic filler can adjust. Here, the varnish preferably has a nonvolatile content in the range of 30 to 60% by mass, particularly from the viewpoint of coating property and film formability. Specific examples of the method for producing a build-up substrate from the interlayer insulation material for a build-up substrate thus obtained include the following methods.

  That is, the interlayer insulating material for a build-up substrate is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then cured, and then, if necessary, a predetermined through-hole portion or the like After drilling, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, and a metal such as copper is plated. The plating method is preferably electroless plating or electrolytic plating, and examples of the roughening agent include oxidizing agents, alkalis, and organic solvents. Such operations are sequentially repeated as desired, and a build-up substrate can be obtained by alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern. However, it is preferable to drill the through-hole portion after the outermost resin insulation layer is formed, and a wiring board on which a circuit is formed from a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil. Further, it is possible to produce a build-up substrate by forming a roughened surface and omitting the plating process by thermocompression bonding at 170 to 250 ° C.

  Further, the interlayer insulating material of the build-up printed board can be used as an adhesive film for build-up as well as the paint-like material described above. The epoxy resin composition of the present invention is particularly useful as an adhesive film for buildup because the resin component itself exhibits excellent heat resistance.

  The method for producing an adhesive film for buildup from the epoxy resin composition of the present invention is, for example, applied to the support film by forming the epoxy resin composition of the present invention on a support film to form a resin composition layer. The method of setting it as an adhesive film is mentioned.

  When the epoxy resin composition of the present invention is used for a build-up adhesive film, the adhesive film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and at the same time as laminating the circuit board, It is important to show fluidity (resin flow) capable of filling the via hole or through hole in the substrate, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like epoxy resin composition of the present invention, coating the varnish-like composition on the surface of the support film (Y), and further It can be produced by drying the organic solvent by heating or blowing hot air to form the layer (X) of the epoxy resin composition.

  The thickness of the formed layer (X) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the layer (X) in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is the range of 10-150 micrometers, Preferably it is used in the range of 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film is the range of 1-40 micrometers.

  The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (X) is protected by a protective film, after peeling these layers ( X) is laminated on one side or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C. and a pressure bonding pressure of preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ). Lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.

  In addition, in the above-described interlayer insulation material for build-up printed circuit boards and adhesive film for build-up, active components such as capacitors and passive components such as capacitors and active components such as IC chips are obtained due to the characteristic of exhibiting excellent heat resistance in the present invention. It is particularly useful as an insulating material in a so-called electronic component built-in substrate in which is embedded in a substrate.

  As described above, the epoxy resin composition of the present invention is useful as a resin composition for copper-clad laminates, an interlayer insulating material for build-up printed boards, an adhesive film for build-ups, and the like. It is particularly useful as an adhesive film for buildup. Furthermore, it is useful as a resin composition for copper clad laminates because it exhibits excellent interlayer strength. In addition to these, the epoxy resin composition of the present invention is excellent in heat resistance and adhesion to metal materials. In addition to these, a resin composition for encapsulants for electronic parts, a resin composition for resist ink, and a friction material It can also be used for binders, conductive pastes, adhesives, insulating paints, resin casting materials, and the like.

  Specific uses when the epoxy resin composition of the present invention is used as a resin composition for encapsulants of electronic components include semiconductor encapsulants, semiconductor tape encapsulants, potting liquid encapsulants, and underfill Examples thereof include resins and semiconductor interlayer insulating films.

  In order to adjust the epoxy resin composition of the present invention for a semiconductor sealing material, the epoxy resin (A), the curing agent (B), other coupling agents blended as necessary, and a mold release Examples thereof include a method in which an additive such as an agent or an inorganic filler is premixed and then sufficiently mixed until uniform using an extruder, a kneader, a roll or the like. When used as a semiconductor tape-like sealant, the resin composition obtained by the above-mentioned method is heated to prepare a semi-cured sheet, which is used as a sealant tape, and then this sealant tape is used as a semiconductor. A method of placing on a chip, heating to 100 to 150 ° C., softening and molding, and completely curing at 170 to 250 ° C. can be mentioned.

  As a method of using the epoxy resin composition of the present invention as a resist ink resin composition, for example, in addition to the epoxy resin (A) and the curing agent (B), an organic solvent (D), a pigment, talc, And a filler, and a composition for resist ink is applied to a printed circuit board by a screen printing method and then a resist ink cured product is used. Examples of the organic solvent (D) used here include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, dimethyl sulfoxide, dimethylformamide, dioxolane, tetrahydrofuran, propylene glycol monomethyl ether acetate, ethyl lactate and the like. Is mentioned.

  When the epoxy resin composition of the present invention is used as a binder for a friction material, in addition to the epoxy resin (I) and the curing agent (B), formaldehyde is further generated by heating hexamethylenetetramine, paraformaldehyde and the like. In addition, a binder for a friction material can be produced by using a substance and blending the curing accelerator. In order to adjust the friction material using such a binder for friction material, a method of adding a filler, an additive and the like to each of the above components and thermally curing, a method of impregnating each of the above components into a fiber substrate and thermosetting it Is mentioned. Fillers and additives used here are, for example, silica, barium sulfate, calcium carbonate, silicon carbide, cashew oil polymer, molybdenum disulfide, aluminum hydroxide, talc, clay, graphite, graphite, rubber particles, aluminum powder, copper Examples thereof include powder and brass powder.

  Further, when used as a potting type liquid sealant, the resin composition obtained by the above-mentioned method is dissolved in a solvent as necessary, and then applied onto a semiconductor chip or an electronic component and directly cured. That's fine.

  The method of using the epoxy resin composition of the present invention as an underfill resin is, for example, by previously applying a varnish-like epoxy resin composition on a substrate or a semiconductor element, then semi-curing it, and heating to form a semiconductor element. For example, a compression flow method in which the substrate is brought into close contact and completely cured can be used.

  The method of using the epoxy resin composition of the present invention as a semiconductor interlayer insulating material includes, for example, a composition comprising a curing accelerator and a silane coupling agent in addition to the epoxy resin (A) and the curing agent (B). There is a method in which an object is prepared and applied onto a silicon substrate by spin coating or the like. In this case, since the cured coating film is in direct contact with the semiconductor, it is preferable 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.

  Next, a method for preparing a conductive paste from the epoxy resin composition of the present invention is, for example, a method in which fine conductive particles are dispersed in the epoxy resin composition to form a composition for an anisotropic conductive film, which is liquid at room temperature. And a paste resin composition for circuit connection and an anisotropic conductive adhesive.

  The method for adjusting the epoxy resin composition of the present invention to a resin composition for an adhesive is, for example, the epoxy resin (A), the curing agent (B), and if necessary, resins, a curing accelerator, a solvent, and an addition Examples include a method in which an agent or the like is uniformly mixed using a mixing mixer or the like at room temperature or under heating. The base material can be adhered by applying it to various base materials and then leaving it under heating.

  The cured product of the present invention is obtained by molding and curing the epoxy resin composition of the present invention described in detail above, and is used as a laminate, cast product, adhesive, coating film, film, etc. depending on the application. it can. As described above, it is particularly useful as a copper-clad laminate for printed circuit boards and an adhesive film for buildup.

Hereinafter, the present invention will be described in detail by way of examples. The average number of nuclei in each synthesis example is a value determined as follows.
[Softening point measurement method]
It was measured by the ring and ball method (according to “JIS K7234-86”, heating rate 5 ° C./min).

[How to find the average number of nuclei]
According to GPC measurement performed under the following conditions, styrene equivalent molecular weights (α1, α2, α3, α4) corresponding to n = 1, n = 2, n = 3, and n = 4, and n = 1 and n = The ratios (β1 / α1, β2 / α2, β3 / α3, β4 / α4) to the respective theoretical molecular weights (β1, β2, β3, β4) of 2, n = 3, and n = 4 were determined, and these (β1 / The average value of α1 to β4 / α4) is obtained. The number of nuclei is calculated using the value obtained by multiplying the average value by the number average molecular weight (Mn) determined by GPC as the average molecular weight.

(GPC measurement conditions)
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

[How to find the ratio of esterification to the number of hydroxyl groups in raw phenolic resin]
From the hydroxyl group equivalent value calculated from the average molecular weight calculated by GPC measurement, the number of hydroxyl groups (number of moles) in the raw material phenol resin is calculated. The ratio of esterification was determined from the ratio between the number of moles of the hydroxyl group and the charged amount (number of moles) of the esterifying agent (benzoyl chloride).
[Synthesis Example 1]
A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was phenol novolac resin (“TD-2090” manufactured by DIC Corporation, hydroxyl equivalent: 105, softening point: 120 ° C., average number of nuclei: 8) 105.0 g and 627 g of methyl isobutyl ketone (hereinafter abbreviated as “MIBK”) were charged and the system was purged with nitrogen under reduced pressure to dissolve. Next, 126.5 g (0.90 mol) of benzoyl chloride was charged, and the inside of the system was purged with nitrogen under reduced pressure to be dissolved. Thereafter, 0.50 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while performing a nitrogen gas purge, and 181.8 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the MIBK layer in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanter dehydration, and subsequently MIBK was removed by vacuum dehydration to synthesize an active ester resin (A-1). Functional group equivalent of this resin (A-1) (equivalent based on the total of phenolic hydroxyl groups and ester bonds, hereinafter the same) 199, softening point is 127 ° C., average number of nuclear pairs is 8, relative to the number of hydroxyl groups of the raw material phenol novolac The rate of esterification was 90%.

[Synthesis Example 2]
A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was cresol novolak resin (“KA-1160” manufactured by DIC Corporation, hydroxyl equivalent: 117, softening point 126 ° C., average number of nuclei: 8) 117.0 g and MIBK 631.8 g were charged, and the inside of the system was purged with nitrogen under reduced pressure to be dissolved. Next, 126.5 g (0.90 mol) of benzoyl chloride was charged, and the inside of the system was purged with nitrogen under reduced pressure to be dissolved. Thereafter, 0.50 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while performing a nitrogen gas purge, and 181.8 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the MIBK phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanter dehydration, and subsequently MIBK was removed by vacuum dehydration to synthesize an active ester resin (A-2). This resin (A-2) had a functional group equivalent of 210.6, a softening point of 129 ° C., an average number of nuclear pairs of 8, and a ratio of esterification to the number of hydroxyl groups of the starting phenol novolac was 90%.

[Synthesis Example 3]
The active ester was reacted in the same manner as in Synthesis Example 1 except that 42.2 g (0.30 mol) of benzoyl chloride, 408 g of MIBK, 0.34 g of trabutylammonium bromide and 60.6 g of 20% aqueous sodium hydroxide solution were changed. Resin (A-3) was synthesized. This resin (A-3) had an esterification equivalent of 136, a softening point of 122 ° C., an average number of core pairs of 8, and a ratio of esterification to the number of hydroxyl groups of the starting phenol novolak was 30%.

[Synthesis Example 4]
The reaction was carried out in the same manner as in Synthesis Example 1 except that 140.5 g (1.00 mol) of benzoyl chloride, 627 g of MIBK, 0.52 g of trabutylammonium bromide and 202.0 g of 20% aqueous sodium hydroxide solution were used. Resin (A-3) was synthesized. This resin (A-3) had an esterification equivalent of 206, a softening point of 129 ° C., an average number of nuclear pairs of 8, and a ratio of esterification to the number of hydroxyl groups of the starting phenol novolak was 100%.

Examples 1 to 6 and Comparative Examples 1 to 4 (Adjustment of epoxy resin composition and evaluation of physical properties)
In accordance with the formulation shown in Table 1 below, an epoxy resin and an ester compound were blended, and methyl ethyl ketone was blended and adjusted so that the nonvolatile content (NV) of each composition was finally 58% by mass.

Subsequently, it was hardened on the following conditions, the laminated board was made as an experiment, and various evaluation was performed. The results are shown in Table 1.
[Laminate production conditions]
Base material: Nitto Boseki Co., Ltd. glass cloth “WEA 2116”
Number of plies: 6 Pre-pregation conditions: 160 ° C., copper foil: 18 μm (Furukawa Sakit Foil, Inc.)
Curing conditions: 200 ° C., 40 kg / cm ² for 1.5 hours, thickness after molding: 0.8 mm
[Physical property test conditions]
Glass transition temperature: Measured by DMA method after removing copper foil by etching. Temperature rising speed 3 ° C / min.
Copper foil peelability: The peel strength was measured according to JIS-K6481.
Interlaminar peel strength: Conforms to JIS-K6481.
Dielectric constant and dielectric loss tangent: A test piece was cut into a size of 50 × 25 × 2 mm by a method in accordance with JIS-C-6481, using an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, Inc. and a fixture. After drying completely, the sample was stored in a room at 23 ° C. and 50% humidity for 24 hours, and then the dielectric constant and dielectric loss tangent of the test piece at 1 GHz were measured.

表１の各成分は、以下の通りである。
「ＨＰ−４０３２」：ジグリジシルオキシナフタレン
「ＨＰ−４７００」：下記構造式

Each component of Table 1 is as follows.
“HP-4032”: Diglycidyloxynaphthalene “HP-4700”: Structural formula shown below

で表される４官能ナフタレン型エポキシ樹脂
「リン含有エポキシ」：ＨＣＡ及びハイドロキノンの反応物と、ビスフェノール型エポキシ樹脂との反応生成物であるエポキシ樹脂（エポキシ当量４７５ｇ／ｅｑ．、リン原子含有率３質量％）
「ＴＤ−２０９０」：フェノールノボラック樹脂６０質量％ＭＥＫ溶液
水酸基当量：１０５ｇ／ｅｑ、軟化点１２０℃

A “phosphorus-containing epoxy”: an epoxy resin that is a reaction product of a reaction product of HCA and hydroquinone and a bisphenol-type epoxy resin (epoxy equivalent 475 g / eq., Phosphorus atom content 3) mass%)
“TD-2090”: phenol novolac resin 60 mass% MEK solution
Hydroxyl equivalent: 105 g / eq, softening point 120 ° C

Claims (11)

An epoxy resin composition comprising an epoxy resin (A) and a curing agent (B) as essential components, wherein the curing agent (B) alkylates 40 to 95% of the phenolic hydroxyl group of the novolac type phenol resin. An epoxy resin composition comprising a modified phenolic resin having an aryl esterified molecular structure and a softening point in the range of 100 to 140 ° C. The modified phenolic resin has the following structural formula 1

(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a phenyl group nucleus-substituted with an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ˜4.)
And a structural site I represented by the following structural formula 2

(In the formula, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
Structural site II represented by the following structural formula 3

(In the formula, R ³ represents a methyl group or a hydrogen atom, and R ⁴ represents a methyl group, a phenyl group, or a hydrogen atom.)
The epoxy resin composition according to claim 1, which has a molecular structure knotted at an alkylidene structure site III represented by: The modified phenolic resin has a molecular structure obtained by alkylesterifying or arylesterifying 60 to 95% of the phenolic hydroxyl group of the novolak type phenolic resin, and has a softening point in the range of 120 to 130 ° C. The epoxy resin composition according to claim 1 or 2. The epoxy resin composition according to claim 1, 2, or 3, wherein the modified phenolic resin is obtained by reacting a phenol novolac resin or a cresol novolac resin with a benzoic acid chloride or an alkylbenzoic acid base. The epoxy resin composition according to any one of claims 1 to 4, wherein the epoxy resin (A) has a naphthalene skeleton in the molecular structure. The epoxy resin composition according to any one of claims 1 to 4, wherein the epoxy resin (A) has a phosphorus atom in the molecular structure. The epoxy resin composition according to any one of claims 1 to 6, further comprising a curing accelerator (C) in addition to the epoxy resin (A) and the active ester compound (B). Hardened | cured material formed by hardening | curing the epoxy resin composition of Claims 1-7. A prepreg obtained by impregnating a fiber base material with the epoxy resin composition according to claim 1. A copper-clad laminate obtained by laminating the prepreg according to claim 9 and further laminating a copper foil, followed by thermocompression bonding. A resin composition for a build-up adhesive film, comprising the epoxy resin composition according to claim 1.