JP5228758B2 - Epoxy resin composition, cured product thereof, and resin composition for electronic component substrate - Google Patents

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, electronic component materials such as copper-clad laminate insulating materials and build-up adhesive films have low dimensional stability due to differences in coefficient of linear expansion (CTE mismatch) with different materials such as copper wiring and solder. When the epoxy resin composition had a problem that cracks were likely to occur due to stress due to thermal shock, the introduction of the aryl ester structure lowered the crosslink density of the cured product and increased the linear expansion coefficient. Mismatches were likely to occur.

JP 7-82348 A

  Therefore, the problem to be solved by the present invention is to provide an epoxy resin composition having a low dielectric constant and dielectric loss tangent in a cured product and a sufficiently low linear expansion coefficient, a cured product thereof, and a resin composition for an electronic component substrate There is to do.

  As a result of intensive studies to solve the above problems, the present inventors have used an active ester compound obtained by alkylating or arylesterifying a polycondensate of bisphenol S and an aldehyde compound as an epoxy resin curing agent. The present inventors have found that the dielectric constant and dielectric loss tangent of the cured product can be reduced and the linear expansion coefficient is sufficiently low, and the present invention has been completed.

That is, the present invention is an epoxy resin composition comprising an epoxy resin (A) and a curing agent (B) as essential components, wherein the curing agent (B) is a polycondensate of bisphenol Ss and aldehydes ( The epoxy resin composition is characterized in that it is an active ester compound (b) having a molecular structure in which α) is alkylesterified or arylesterified.
The present invention further relates to a cured product obtained by curing the epoxy resin composition.
The present invention further relates to an electronic component substrate resin composition comprising the epoxy resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the dielectric constant and dielectric loss tangent in hardened | cured material can provide the epoxy resin composition which the dielectric constant and the coefficient of linear expansion are also low enough, its hardened | cured material, and the resin composition for electronic component boards | substrates.

  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 type epoxy resin, naphthol - phenol co-condensed novolak type epoxy resin, naphthol - cresol co-condensed novolac type epoxy resin, diglycidyl sulfopropyl the following 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。

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), bisphenol type epoxy resins are preferable, particularly from the viewpoint of excellent processability when used as an epoxy resin composition, and particularly excellent moldability in use for build-up adhesive films. Equivalent 160-200 g / eq. The bisphenol type epoxy resin is preferred.

  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. The epoxy equivalent of the epoxy resin having a naphthalene skeleton and the epoxy resin having a phosphorus primitive in the molecular structure is 1,000 g / equivalent or less, particularly 700 g / equivalent or less, particularly 500 g / equivalent or less from the viewpoint of heat resistance. preferable. On the other hand, for copper-clad laminate applications, novolac epoxy resins are preferred from the viewpoint of heat resistance.

  Next, as described above, the curing agent (B) used in the present invention is an active ester having a molecular structure in which a polycondensate (α) of bisphenol S and an aldehyde or ketone is alkylesterified or arylesterified. Compound (b). In the present invention, by using an active esterified product of a polycondensate (α) of bisphenol S and an aldehyde compound as a curing agent for an epoxy resin, a low dielectric constant and a low dielectric loss tangent are realized and an active ester is used. In spite of this, it was possible to reduce the linear expansion coefficient without causing an increase.

  The polycondensate (α) which is a precursor of the active ester compound (b) has a structure obtained by polycondensation of bisphenol Ss and aldehydes. Here, bisphenols include 2,4 The 2,4′-bis (hydroxyphenyl) sulfone compound of the “-bis (hydroxyphenyl) sulfone type is preferable because the compound itself has low crystallinity and good reactivity with the aldehyde compound.

  Such 2,4′-bis (hydroxyphenyl) sulfone compounds are specifically 2,4′-bisphenolsulfone, 4,6,2 ′, 3 ′, 5 ′, 6′-hexamethyl-2,4 ′. -Bisphenolsulfone, 4-methyl-2,4'-bisphenolsulfone, 3'-ethyl-2,4'-bisphenolsulfone, 3'-propyl-2,4'-bisphenolsulfone, 3'-t-butyl-2 , 4′-bisphenolsulfone, 3 ′, 5′-dibromo-2,4′-bisphenolsulfone, 3 ′, 5′-dichloro-2,4′-bisphenolsulfone, 3,3′-dimethyl-2,4 ′ -Bisphenol sulfone, 5-methyl-2,4'-bisphenol sulfone, 5-ethyl-2,4'-bisphenol sulfone, 5-propyl-2,4'-bisphenol sulfone 3,3′-dibromo-2,4′-bisphenolsulfone, 3,3′-dichloro-2,4′-bisphenolsulfone, 4,5,6,2 ′, 3 ′, 6′-hexamethyl-2 , 4′-bisphenolsulfone, 3,4,5,6,2 ′, 6′-hexamethyl-2,4′-bisphenolsulfone, 3,5-dimethyl-2,4′-bisphenolsulfone, 3,5-diethyl -2,4'-bisphenol sulfone, 3,5-dibromo-2,4'-bisphenol sulfone, 3,5-dichloro-2,4'-bisphenol sulfone and the like.

  Among these, 2,4′-bisphenolsulfone is obtained, and the solvent solubility of the active ester compound (b) obtained by esterifying the polycondensate (α) becomes good, and the film formation of the epoxy resin composition is easy. In addition, the cured product itself is preferable in that the linear expansion coefficient becomes lower and the cured product has better heat resistance and toughness.

  Next, as the aldehydes to be reacted with the bisphenol S, first, aldehydes specifically include formaldehyde, acetaldehyde, ethyl aldehyde, propyl aldehyde, t-butyraldehyde, benzaldehyde, 4-methylbenzaldehyde, 4- Examples thereof include ethylbenzaldehyde, 4-propylbenzaldehyde, 4-t-butylbenzaldehyde and the like. Among these, formaldehyde is preferable because it is excellent in workability and particularly in the cured product of the finally obtained active ester compound (b) and has high heat resistance.

  Among the polycondensates (α) having a structure obtained by polycondensation of bisphenol Ss and aldehydes, the 2,4′-bis (hydroxyphenyl) sulfone compound and aldehydes that are preferably used are polycondensates. The molecular structure is, for example, the following general formula (1)

（式中、ｎは繰り返し単位の平均で０〜５．０である。）
で表される分子構造を有し、かつ、該一般式（１）中、「Ｓ’」で表される構造部位が、下記構造式Ｓ’１で表される構造部位、

(In the formula, n is an average of repeating units of 0 to 5.0.)
And the structural moiety represented by “S ′” in the general formula (1) is a structural moiety represented by the following structural formula S′1,

下記構造式Ｓ’２で表される構造部位、

A structural moiety represented by the following structural formula S′2,

及び、下記構造式Ｓ’３で表される構造部位、

And a structural moiety represented by the following structural formula S′3,

（上記各構造式Ｓ’１〜Ｓ’３中、Ｒ^１、Ｒ^２、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸はそれぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、ハロゲン原子を表す。）
からなる群から選択されるものであり、かつ、
該一般式（１）中、「Ｘ」で表される構造部位が、下記構造式Ｘ１

(In each of the structural formulas S′1 to S′3, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom, carbon number 1 Represents an alkyl group of 4 or a halogen atom.)
Selected from the group consisting of:
In the general formula (1), the structural moiety represented by “X” is represented by the following structural formula X1

（Ｒ⁹は水素原子、炭素原子数１〜４のアルキル基、アリール基、又はアラルキル基を表す。）
で表されるものが挙げられる。

(R ⁹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group.)
The thing represented by is mentioned.

  Specific examples of the structural site derived from bisphenols represented by the above structural formulas S′1 to S′3 include those represented by the following structural formulas S′1-1 to S′1-8. .

  Examples of the structural portion represented by the structural formula S′2 include those represented by the following structural formulas S′2-1 to S′2-9.

  Examples of the structural portion represented by the structural formula S′3 include those represented by the following structural formulas S′3-1 to S′3-8.

Among these, those in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ in the structural formulas S′1 to S′3 are a hydrogen atom, a methyl group, or an ethyl group Is preferable from the viewpoint of the solubility of the phenol resin in an organic solvent, and in particular, those in which all of R ^{1 to} R ⁸ in the structural formulas S′1 to S′3 are hydrogen atoms have a linear expansion coefficient of the cured product. It is preferable because it is low and the cured product has higher heat resistance and toughness.

On the other hand, R ⁹ in the structural formula X1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group or an aralkyl group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, ethyl Group, n-propyl group, i-propyl group, butyl group, t-butyl group and the like, and aryl group includes phenyl group, naphthyl group, biphenyl group, and these aromatic nuclei with methyl group, ethyl group, Examples thereof include an n-propyl group, an i-propyl group, a butyl group, a t-butyl group and the like.
Examples of the aralkyl group include a benzyl group.

  Therefore, the structural site represented by the structural formula X specifically includes the structures represented by the following X1 to X14.

こらのなかでも工業的製造法が簡便であり、その入手が容易であり、かつ、作業性に優れ、更に、特に最終的に得られる活性エステル化合物（ｂ）の硬化物における線膨張係数が低くなり、かつ、耐熱性も高くなる点から上記Ｘ１で表されるＲ^９が水素原子のものが好ましい。

Among these, the industrial production method is simple, easy to obtain, excellent in workability, and particularly low in the linear expansion coefficient in the cured product of the active ester compound (b) finally obtained. In view of increasing heat resistance, it is preferable that R ⁹ represented by X1 is a hydrogen atom.

  Further, the softening point of the polycondensate (α) is preferably in the range of 75 to 120 ° C. from the viewpoint that the linear expansion coefficient in the cured product of the finally obtained active ester compound (b) becomes lower. Here, the softening point is a value measured in accordance with “JIS K7234 (2001)”.

  The polycondensate (α) described above in detail is industrially produced, for example, by a production method in which bisphenol Ss and aldehydes are subjected to the following reaction steps 1 to 3 in the presence of a catalyst. be able to.

That is, the manufacturing method is
Step 1: Step of reacting the bisphenol S with the aldehyde in the presence of a catalyst Step 2: Step of washing the phenol resin solution obtained in Step 2 with water,
Step 3: Next, the step of obtaining the target phenol resin by removing the organic solvent from the phenol resin solution is an essential manufacturing step.

  Here, when formaldehyde is used as the aldehyde, it may be used as paraformaldehyde.

  Specific examples of the catalyst used in Step 1 include alkali hydroxides such as sodium hydroxide and potassium hydroxide, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, and tri-p-tolyl. Phosphorus compounds such as phosphine, tris (p-methoxyphenyl) phosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, tricyclohexylphosphine, tributylphosphine, tri-tert-butylphosphine, tri-n-octylphosphine, triethylamine, dimethylbenzylamine, Immune such as trisdimethylaminomethylphenol, tertiary amine compounds such as 1,8-diazabicyclo (5,4,0) undecane, 2-methylimidazole, 2-ethyl-4-methylimidazole, etc. Basic compound selected from tetrazole compounds.

  Among these, since the industrial production method is simple and the reaction progress is easy, alkali hydroxide such as sodium hydroxide and potassium hydroxide, triethylamine, benzyldimethylamine, trisdimethylaminomethylphenol, 1, Tertiary amine compounds such as 8-diazabicyclo (5,4,0) undecane are preferred.

  Here, the charging ratio of the bisphenol Ss and aldehydes is in the range of the former / the latter = 10/1 to 0.5 / 1 on a molar basis, and the softening point of the phenol resin obtained by the reaction. Is preferably in the range of 70 to 120 ° C., and particularly preferably in the range of 3/1 to 0.8 / 1 from the viewpoint of obtaining a phenol resin having a high softening point. In addition, when using formaldehyde as said aldehydes and using this as paraformaldehyde, these preparation ratios will be the molar ratio of a formaldehyde unit.

  Moreover, it is preferable to perform reaction of the process 1 in presence of water or an organic solvent. The organic solvent is not particularly limited, but alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, and aromatic hydrocarbons such as toluene and xylene And aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone.

  Here, the use amount of the organic solvent specifically includes a range of 0.05 to 1.5 times the mass of the aldehydes.

  In the reaction in Step 1, it is preferable to use an organic solvent and water in combination from the viewpoint of excellent reactivity. Specifically, the reaction method in this case is as follows. First, bisphenol S, the aldehydes, an organic solvent, and water are charged into a reaction vessel equipped with a stirrer, and stirring is started in an inert gas atmosphere. To do. At this time, the amount of the organic solvent and water added to the reaction vessel is specifically 0.05 to 1.5 times the amount of organic solvent and 0.05 to 1 of water with respect to the mass of the aldehyde used. It is preferably 0.0 times the amount. After the reaction system is dispersed, a catalyst is added, the temperature is raised, and the reaction is held at a temperature not exceeding the reflux temperature (95 ° C.).

  In this step 1, among the reaction methods described above, in particular, an aliphatic ketone is used as the organic solvent in a ratio of 0.3 to 1.0 times the mass of the aldehyde used, and water is used. Used in a proportion of 0.1 to 0.3 times the mass of the aldehyde used, and the charge ratio of bisphenol S and aldehyde on a molar basis, the former / the latter = 1.2 / 1 It is preferable to use it at a ratio of 0.8 / 1 because the polycondensate (α) has a higher softening point.

  Moreover, you may add antioxidant and a reducing agent to this reaction system from the point which suppresses coloring of the polycondensate ((alpha)) obtained in reaction of this process 1. FIG. Although it does not specifically limit as antioxidant, For example, a hindered phenol type compound, such as a 2, 6- dialkylphenol derivative, a bivalent sulfur type compound, a phosphite type compound containing a trivalent phosphorus atom, etc. are mentioned. Can do. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, and salts thereof.

  Further, in the reaction of Step 1, when water is used excessively with respect to the organic solvent, 4.5 to 8 times the amount of the aldehyde used (mass basis) after the reaction of Step 1 is completed. It is preferable to add a polycondensate (α) as a target product from the reaction product. Among the organic solvents used here, aliphatic alcohols, aliphatic ethers, and aliphatic ketones are preferable because the extraction efficiency of the target polycondensate (α) is improved. Here, examples of the aliphatic alcohol include 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, 2-methoxyethanol, 2-ethoxyethanol, and diethylene glycol. Examples of aliphatic ethers include diethylene glycol diethyl ether. Examples of the aliphatic ketones include methyl isobutyl ketone and cyclohexanone. Among these, it is preferable that the boiling point is in the range of 100 to 130 ° C. from the viewpoint that the efficiency of this extraction operation is good, specifically, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol. 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, and methyl isobutyl ketone are preferred.

  Next, step 2 is a step of washing the phenol resin solution obtained in step 1 with water. The washing with water can be carried out according to a conventional method, but is preferably carried out until the pH of the phenol resin solution is 5 to 9, preferably 6 to 8. In Step 2, the catalyst used for the reaction may be preliminarily neutralized with a neutralizing agent before and during the water washing. Examples of the neutralizing agent used here include oxalic acid, monobasic sodium phosphate, and monobasic potassium phosphate.

  Next, step 3 is a step of obtaining the target polycondensate (α) by removing the organic solvent from the phenol resin solution. Specifically, the organic solvent may be removed from the phenol resin solution by removing the organic solvent by heating under reduced pressure. The conditions at this time are preferably in the range of 130 to 200 ° C. and 3 kPa or less.

  The target polycondensate (α) is obtained through the above steps 1 to 3.

  The active ester compound (b) used in the present invention has a molecular structure obtained by alkylating or arylesterifying the polycondensate (α) described above, and specifically, the following general formula (2)

（式中、ｎは繰り返し単位の平均で０〜５．０である。）
で表される分子構造を有し、かつ、該一般式（２）中、「Ｓ”」で表される構造部位が、
下記構造式Ｓ’１で表される構造部位、

(In the formula, n is an average of repeating units of 0 to 5.0.)
And a structural site represented by “S” ”in the general formula (2),
A structural moiety represented by the following structural formula S′1,

下記構造式Ｓ”２で表される構造部位、

A structural moiety represented by the following structural formula S ″ 2,

及び、下記構造式Ｓ”３で表される構造部位、

And a structural moiety represented by the following structural formula S ″ 3,

（上記各構造式Ｓ”１〜Ｓ”３中、Ａは水素原子、アルキルカルボニル基、又は、アリールカルボニル基を表し、Ｒ^１、Ｒ^２、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸はそれぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、ハロゲン原子を表す。但し、Ａのうち少なくとも１つはアルキルカルボニル基又はアリールカルボニル基である。）
からなる群から選択されるものであり、かつ、
該一般式（２）中、「Ｘ」で表される構造部位が、下記構造式Ｘ１

(In each of the structural formulas S ″ 1 to S ″ 3, A represents a hydrogen atom, an alkylcarbonyl group, or an arylcarbonyl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, provided that at least one of A is an alkylcarbonyl group or an arylcarbonyl group.
Selected from the group consisting of:
In the general formula (2), the structural moiety represented by “X” is represented by the following structural formula X1

（Ｒ⁹は水素原子、炭素原子数１〜４のアルキル基、アリール基、又はアラルキル基を表す。）で表されるものが挙げられる。

(R ⁹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group).

Examples of the alkyl group having 1 to 4 carbon atoms constituting R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ in each structural formula include a methyl group and an ethyl group. , An n-propyl group, an isopropyl group, a butyl group, a t-butyl group, and the like. Examples of the halogen atom include a chlorine atom and a bromine atom.

  More specifically, the 2,4′-bis (glycidyloxyphenylene) sulfone structure (S ″) represented by the above structural formulas S ″ 1 to S ″ 3 is more specifically represented by, for example, the structural formula S ″ 1. In addition to the above-described structural formulas S′1-1 to S′1-8, the structural portion S ″ 1 represented is represented by the following structural formulas S ″ 1-1 to S ″ 1-8 as essential structures. In each structural formula, “A ′” represents an alkylcarbonyl group or an arylcarbonyl group.

  Further, the structural site S ″ 2 represented by the structural formula S ″ 2 includes the following structural formulas S ″ 2-1 to S ″ 2 in addition to the following structural formulas S′2-1 to S′2-9. -9. In each structural formula, “A ′” represents an alkylcarbonyl group or an arylcarbonyl group.

  In addition to the above-described structural formulas S′3-1 to S′3-8, the structural site S ″ 3 represented by the structural formula S ″ 3 includes the following structural formulas S ″ 3-1 to S "3-8 is mentioned. In each structural formula, “A ′” represents an alkylcarbonyl group or an arylcarbonyl group.

Among these, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the structural formulas S ″ 1 to S ″ 3 are hydrogen from the viewpoint of solubility in organic solvents. Those which are atoms, methyl groups, and ethyl groups are preferred, and those in which all of R ^{1 to} R ^{8 in} the structural formulas S ″ 1 to S ″ 3 are hydrogen atoms have a low linear expansion coefficient of the cured product, And it is preferable from the point which hardened | cured material becomes higher heat resistance and toughness.

  On the other hand, the alkylidene group (X), which is a nodule group for linking the 2,4′-bis (glycidyloxyphenylene) sulfone structure (S ″), has the same meaning as in the general formula (1).

In addition, as described in detail regarding the polycondensate (α), R ^{1 to} R ⁸ and R ⁹ to R ^{9 in the} structural formulas S ″ 1 to S ″ 3 in terms of simple industrial production and excellent productivity. All of R ¹⁰ are preferably hydrogen atoms.

  The active ester compound (b) used in the present invention has a molecular structure in which 80 to 98% of the phenolic hydroxyl group in the polycondensate (α) is alkylesterified or arylesterified. It is preferable from the viewpoint that the property and moisture resistance are improved, and the copper foil peel strength in the use of the copper-clad laminate and the build-up adhesive film and the interlayer strength in the multilayer laminate are drastically improved. Moreover, it is preferable that the softening point is in the range of 85 to 130 ° C. from the viewpoint of lowering the linear expansion coefficient of the cured product. Here, the softening point of the active ester compound (b) is a value measured by a ring and ball method (temperature increase rate: 5 ° C./min) in accordance with “JIS K7234-86”.

  Here, the alkyl group or the aryl group constituting the ester structure in the active ester compound (b) specifically includes 1 carbon atom such as methyl, ethyl, n-propyl, i-propyl, t-butyl and the like. Or an alkyl group having 1 to 4 carbon atoms, such as a phenyl group, a biphenyl group, a methylphenyl group, an ethylphenyl group, an n-propylphenyl group, an i-propylphenyl group, or a t-butylphenyl group. And a phenyl group substituted with a nucleus. Among these, an aryl group is preferable from the viewpoint of heat resistance.

In addition, n in the general formula (2) of the active ester compound (b) has an average repeating unit in the range of 0 to 5.0 as described above. The value of n in the general formula (2) Since this coincides with the value of n in the general formula (1) of the polycondensate (α), it can be determined by measuring the value of n of the polycondensate (α) as a raw material by GPC. 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 value of n is calculated using a value obtained by multiplying the average value by the number average molecular weight (Mn) obtained by GPC as an 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 obtained by alkylating or arylesterifying 80 to 98% of the phenolic hydroxyl group in the polycondensate (α) is based on 1 mol of the phenolic hydroxyl group of the polycondensate (α) used as a raw material. The esterification agent (benzoyl chloride) is a molecular structure obtained by reacting at a ratio of 0.80 to 0.98 mol, and the esterification ratio is a hydroxyl equivalent value calculated from the average molecular weight by GPC measurement. From the above, the number of hydroxyl groups (number of moles) in the charged raw material polycondensate (α) can be calculated and obtained from the ratio of the number of moles of the esterifying agent (benzoyl chloride) subjected to the reaction to the number of moles of this hydroxyl group. .

  Specifically, the active ester compound (b) described in detail above can be produced by reacting the polycondensate (α) with an alkyl esterifying agent or an aryl esterifying agent.

  Examples of the alkyl esterizing agent or aryl esterifying agent to be reacted with the polycondensate (α) include benzoic acid, phenylbenzoic acid, methylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, and i-propylbenzoic acid. Examples thereof include acid and alkyl benzoic acids such as t-butylbenzoic acid, and acid halides such as these acid fluorides, acid chlorides, acid bromides, and acid iodides, and the heat resistance of the cured product of the present invention is good. From the point of becoming a thing, it is preferable that it is a benzoic acid chloride or an alkyl benzoic acid chloride.

  In the method of reacting the polycondensate (α) with the alkyl esterifying agent or aryl esterifying agent, specifically, these components can be reacted in the 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 performed by mixing the polycondensate (α) 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. In that case, it is preferable that the density | concentration of the aqueous solution of an alkali catalyst is the range of 3.0-30 mass%. Examples of the organic solvent that can be used here include toluene, dichloromethane, and methyl isobutyl ketone.

  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 active ester compound (b) thus obtained is usually obtained as an organic solvent solution, when used as a copper-clad laminate varnish or build-up adhesive film, it is mixed as it is with other ingredients. Furthermore, 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 curing agent (B) is the ratio of the epoxy group in the epoxy resin (A) and the total of active hydrogen and ester bond in the curing agent (B). However, a blending ratio of 0.7 to 1.2 in terms of the molar ratio of the former epoxy group / the latter active hydrogen and ester bond is preferable from the viewpoint of excellent heat resistance, copper foil peel strength, and interlayer strength. .

  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 0.3 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). Alternatively, the other curing agent (B ′) may be used as a main curing agent, and the curing agent (B) may be used as a modifier for the purpose of reducing linear expansion coefficient and dielectric loss tangent / dielectric constant. In this case, the curing agent (B) can be used at a ratio of 20 to 50% by mass with respect to the total mass of the curing agent (B) and the 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, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydroanhydride Examples include phthalic acid.

  Phenol compounds include phenol novolak 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. Acid ester compounds, other, phosphorus atom-containing compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenoxyphosphazene, nitrogen atom-containing compounds such as melamine, aluminum hydroxide, Examples include inorganic flame retardant compounds such as magnesium hydroxide, zinc borate, and calcium borate.

  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 material for electronic component substrates such as a resin composition for copper-clad laminates, an interlayer insulating material for build-up printed boards, and an adhesive film for build-up. In addition to these, for resin compositions for electronic component sealing materials, resin compositions for resist inks, binders for friction materials, conductive pastes, resin casting materials, adhesives, coating materials such as insulating paints, etc. It can also be used.

  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 material for electronic component substrates such as a resin composition for copper-clad laminates, an interlayer insulating material for build-up printed boards, and an adhesive film for build-up. It is particularly useful as a laminate resin composition and build-up adhesive film. 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.

  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 of uniformly mixing an agent or the like using a mixing mixer or the like at room temperature or under heating. After coating on various base materials, the base material can be adhered by 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 value of n in the general formula (1)]
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 value obtained by multiplying the number average molecular weight (Mn) determined by GPC by this average value was used as the average molecular weight, and the value of n in the general formula (1) was determined, which was used as the average value of n.

(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]
2,4′-bisphenol S novolak resin (polycondensate of 2,4′-bisphenol sulfone and formaldehyde, general formula (1) ) Is 0.2, hydroxyl equivalent: 126 (solid content value), softening point 83 ° C. (solid content value) 126 g and methyl isobutyl ketone (hereinafter abbreviated as “MIBK”) 659 g. Then, the system was purged with nitrogen under reduced pressure and dissolved, and then 126.5 g (0.90 mol) of benzoyl chloride was charged and the system was purged with nitrogen under reduced pressure, after which 0.55 g of tetrabutylammonium bromide was dissolved. While dissolving and performing nitrogen gas purging, the inside of the system was controlled to 60 ° C. or lower, and 181.8 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was continued for 1.0 hour under the conditions, and after the completion of the reaction, the solution was allowed to stand for liquid separation, the aqueous layer was removed, and water was added to the MIBK phase in which the reactant was dissolved, followed by stirring and mixing for about 15 minutes. This operation was repeated until the pH of the aquarium reached 7. After that, water was removed by decanter dehydration, MIBK was then removed by vacuum dehydration, and an active ester resin ( The active ester resin (A-1) had a functional group equivalent of 220 and a softening point of 94 ° C. The esterification rate of 2,4′-bisphenol S novolac resin to the phenolic hydroxyl group was obtained. Was 90%.

Example 1 and Comparative Examples 1 to 3 (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 0.5 phr of dimethylaminopyridine was further added as a curing catalyst. Finally, the nonvolatile content (NV) of each composition was 58% by mass. It adjusted by mix | blending methyl ethyl ketone so that it might become. This was transferred to an aluminum petri dish and dried at 120 ° C. to remove methyl ethyl ketone to obtain a semi-cured product. Next, the semi-cured product is put into a 15 cm × 15 cm × 2 mm mold and vacuum press-molded (temperature conditions: 200 ° C., pressure: 40 kg / cm ² , molding time: 1.5 hours) to obtain a plate-shaped cured product. Obtained. Using this as a test piece, the following various evaluations were performed. The results are shown in Table 1.

[Heat resistance test]
Glass transition temperature: The test piece was measured by the DMA method. Temperature rising speed 3 ° C / min.
[Measurement of dielectric constant and dissipation factor]
In accordance with JIS-C-6481, the dielectric material at 1 GHz of the test piece after being stored in an indoor room at 23 ° C. and 50% humidity for 24 hours after absolutely dry using an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, Inc. The rate and dielectric loss tangent were measured.

[Linear expansion coefficient]
The cured product film was used as a test piece having a width of about 3 mm and a length of about 15 mm, and thermomechanical analysis was performed in a tensile mode using a thermomechanical analyzer (TMA: SS-6100 manufactured by Seiko Instruments Inc.) (measurement weight) : 30 mN, temperature rising rate: twice at 3 ° C / min, measuring temperature range: 20 ° C to 250 ° C). The linear expansion coefficient in the glass region (50 ° C.) in the second measurement was evaluated.

表１の各成分は、以下の通りである。
「エポキシ樹脂」：ビスフェノールＡ型エポキシ樹脂（ＤＩＣ(株)製「エピクロン８５０Ｓ」、エポキシ当量１８８ｇ／ｅｑ．）
「フェノールノボラック樹脂」：フェノールノボラック樹脂（水酸基当量：１０５ｇ／ｅｑ、軟化点１２０℃、平均核体数８）
「フェノールノボラック型活性エステル」：フェノールノボラック樹脂（水酸基当量：１０５ｇ／ｅｑ、軟化点１２０℃）のポリフェニルエステル（フェノール性水酸基に対するエステル化率９０％、軟化点１２５℃）
「ビスフェノールＳノボラック樹脂」：合成例１で用いた２，４’−ビスフェノールＳノボラック樹脂（２,４’−ビスフェノールスルホンとホルムアルデヒドとの重縮合体、前記一般式（１）中のｎの平均は０．２、水酸基当量：１２６（固形分値）、軟化点８３℃（固形分値））

Each component of Table 1 is as follows.
“Epoxy resin”: bisphenol A type epoxy resin (“Epiclon 850S” manufactured by DIC Corporation, epoxy equivalent 188 g / eq.)
“Phenol novolac resin”: phenol novolac resin (hydroxyl equivalent: 105 g / eq, softening point 120 ° C., average number of nuclei 8)
“Phenol novolac-type active ester”: polyphenyl ester of phenol novolac resin (hydroxyl equivalent: 105 g / eq, softening point 120 ° C.) (esterification rate to phenolic hydroxyl group 90%, softening point 125 ° C.)
“Bisphenol S novolak resin”: 2,4′-bisphenol S novolak resin used in Synthesis Example 1 (polycondensate of 2,4′-bisphenol sulfone and formaldehyde, the average of n in the general formula (1) is 0.2, hydroxyl equivalent: 126 (solid content value), softening point 83 ° C. (solid content value))

Claims (8)

An epoxy resin composition comprising an epoxy resin (A) and a curing agent (B) as essential components, wherein the curing agent (B) alkylates a polycondensate (α) of bisphenol Ss and aldehydes. An epoxy resin composition characterized by being an active ester compound (b) having an aryl esterified molecular structure. The epoxy resin composition according to claim 1, wherein the active ester compound (b) is a modified phenol resin having a softening point in the range of 85 to 130 ° C. The active ester compound (b) is represented by the following general formula (2)

(In the formula, n is an average of repeating units of 0 to 5.0.)
And the structural moiety represented by “S ″” in the general formula (1) is a structural moiety represented by the following structural formula S ″ 1;

A structural moiety represented by the following structural formula S ″ 2,

And a structural moiety represented by the following structural formula S ″ 3,

(In each of the structural formulas S ″ 1 to S ″ 3, A represents a hydrogen atom, an alkylcarbonyl group, or an arylcarbonyl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, provided that at least one of A is an alkylcarbonyl group or an arylcarbonyl group.
Selected from the group consisting of:
In the general formula (1), the structural moiety represented by “X” is represented by the following structural formula X1

(R ⁹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group.)
The epoxy resin composition according to claim 1, which is represented by the formula: The active ester resin (b) has a molecular structure obtained by alkylesterifying or arylesterifying 80 to 98% of the phenolic hydroxyl group of the polycondensate (α). Epoxy resin composition. The epoxy resin composition according to claim 1, 2 or 3, wherein the active ester resin (b) is obtained by reacting the polycondensate (α) with a benzoic acid chloride or an alkyl benzoic acid chloride. The epoxy resin composition according to any one of claims 1 to 5 , further comprising a curing accelerator (C) in addition to the epoxy resin (A) and the curing agent (B). Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-6 . The resin composition for electronic component base materials which consists of an epoxy resin composition of Claims 1-6 .