JP2006063256A - Epoxy resin composition and laminate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition, having excellent flame retardance, heat resistance and moisture resistance, and suitably usable for a resin composition for a printed wiring board, a resin composition for a sealing material of an electronic component, a resist ink, an electroconductive paste, a coating material, an adhesive, a composite material or the like; and to provide a laminate using the composition. <P>SOLUTION: The epoxy resin composition comprises a modified epoxy resin obtained by reacting (A) an epoxy resin having an aromatic polycyclic skeleton obtained by bonding two aromatic hydrocarbons at two neighboring substitution positions on the aromatic rings in the aromatic hydrocarbons through carbon atoms and/or oxygen atoms, and glycidyloxy groups as substituents on the aromatic polycyclic skeletons, and (B) a phenolic compound having two aromatic hydroxy compounds directly bonded to each other, and a polyfunctional aromatic polyester resin. The laminate is obtained by using the epoxy resin composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides a cured product obtained with little variation in physical properties, low dielectric loss tangent, excellent flame retardancy, heat resistance, and moisture resistance, a resin composition for printed circuit boards, and a resin composition for encapsulants for electronic components. The present invention relates to an epoxy resin composition that can be suitably used for resist inks, conductive pastes, paints, adhesives, composite materials, and the like, and a laminate using the same.

  Epoxy resins are suitably used for semiconductor encapsulants, printed wiring boards, paints, casting materials applications, etc., because cured products with excellent heat resistance, adhesion, electrical insulation, etc. are obtained. With technological innovation, required levels such as heat resistance, moisture resistance, flame retardancy, and low dielectric constant are increasing year by year. Furthermore, with the recent increase in the amount of information communication, information communication in the high frequency band has been actively performed, and in order to reduce transmission loss in the higher frequency band, more excellent electrical characteristics, in particular, a low dielectric loss tangent. There is a need for an electrically insulating material having: In response to this demand, it has been proposed to use a polyfunctional polyester resin as a curing agent for an epoxy resin. (For example, refer to Patent Document 1). However, the composition described in Patent Document 1 has a problem inferior in flame retardancy.

  As an epoxy resin composition excellent in flame retardancy, for example, two aromatic hydrocarbons are bonded via carbon atoms and / or oxygen atoms at two adjacent substitution positions on an aromatic ring in aromatic hydrocarbons. An epoxy resin composition containing an epoxy resin having an aromatic polycyclic skeleton and a glycidyloxy group as a substituent on the aromatic polycyclic skeleton and a curing agent is also known (for example, patents) Reference 2). However, the epoxy resin in the epoxy resin composition does not have good solvent solubility. For example, a glass cloth is impregnated with a varnish prepared by dissolving a resin composition containing the epoxy resin composition in a solvent to produce a laminate. Then, since the epoxy resin is dissolved non-uniformly in the solvent, there is a problem that the physical properties are different depending on the portion of the obtained laminate.

JP 2004-169021 A JP 2003-201333 A

  An object of the present invention is to provide an epoxy resin composition capable of obtaining a cured product having a low dielectric loss tangent, excellent flame retardancy, heat resistance, moisture resistance, and little physical variation, and a laminate using the epoxy resin composition It is to provide.

As a result of intensive studies to solve the above problems, the present inventor has obtained a modified epoxy resin obtained by modifying the epoxy resin described in Patent Document 2 with a phenolic compound (B) in which two aromatic hydroxy compounds are directly bonded. Excellent solvent solubility, compatibility of the aromatic polyester resin with the modified epoxy resin and good use as a curing agent, epoxy resin composition containing the modified epoxy resin and the aromatic polyester resin is flame retardant A cured product having excellent heat resistance and moisture resistance can be obtained; a laminated board using the composition has a low dielectric loss tangent, excellent flame retardancy, heat resistance, and moisture resistance; and the laminated board has physical properties. The inventors have found that there is little variation and have completed the present invention.

  That is, the present invention provides an aromatic polycyclic skeleton in which two aromatic hydrocarbons are bonded via a carbon atom and / or an oxygen atom at two adjacent substitution positions on the aromatic ring in the aromatic hydrocarbon. And an epoxy resin (A) having a glycidyloxy group as a substituent on the aromatic polycyclic skeleton and a phenol compound (B) obtained by directly bonding two aromatic hydroxy compounds. An epoxy resin composition comprising a modified epoxy resin and a polyfunctional aromatic polyester resin (C) is provided.

  Moreover, this invention provides the laminated board characterized by being obtained using the said epoxy resin composition.

  The modified epoxy resin in the epoxy resin composition of the present invention is introduced with a rigid and symmetric structure, so that the aromatic content increases while the epoxy group concentration in the epoxy resin is lowered. As a result, the epoxy resin composition of the present invention can provide a cured product that is excellent in flame retardancy, heat resistance, moisture resistance, and dielectric properties and has little variation in physical properties. Therefore, when used in the field of electronic materials such as resin compositions for printed circuit boards, encapsulants for electronic components, resist inks, conductive pastes, etc., high-density mounting, high-frequency compatibility, high-speed computing, etc. It is extremely useful as a resin composition corresponding to the above. In addition to using a polyfunctional aromatic polyester resin as a curing agent, a cured product having a low dielectric loss tangent can be obtained, and the epoxy resin composition of the present invention can be used to cause environmental pollution such as halogen and phosphorus. A cured product excellent in flame retardancy, heat resistance, moisture resistance, and dielectric properties can be provided without using any of the above. Furthermore, the laminate of the present invention is excellent in low dielectric loss tangent, flame retardancy, heat resistance and moisture resistance. The epoxy resin composition of the present invention is also excellent in low thermal expansion. Furthermore, the laminate of the present invention has a low dielectric loss tangent, excellent flame retardancy, heat resistance, and moisture resistance, and little variation in physical properties.

  The epoxy resin (A) used in the present invention is an aromatic resin in which two aromatic hydrocarbons are bonded via a carbon atom and / or an oxygen atom at two adjacent substitution positions on the aromatic ring in the aromatic hydrocarbon. Epoxy resin having an aromatic polycyclic skeleton and a glycidyloxy group as a substituent on the aromatic polycyclic skeleton. The aromatic polycyclic skeleton in which two aromatic hydrocarbons are bonded via a carbon atom or an oxygen atom at two adjacent substitution positions on the aromatic ring in the aromatic hydrocarbon has a rigid and symmetric structure. Introducing this structure into the epoxy resin structure increases the aromatic content while lowering the epoxy group concentration in the epoxy resin, so that it not only has excellent moisture resistance and dielectric properties, but also excellent flame resistance An effect can be expressed. In addition, the heat resistance is dramatically improved due to the rigidity of the structure.

  The aromatic polycyclic skeleton of the epoxy resin (A) used in the present invention has two aromatic carbon atoms via carbon atoms or oxygen atoms at two adjacent substitution positions on the aromatic ring in the aromatic hydrocarbon. It suffices to have an aromatic polycyclic skeleton to which hydrogen is bonded. Examples of such a skeleton include an aromatic polycyclic skeleton in which two phenol skeletons are bonded through one carbon atom at each of two adjacent substitution positions. An aromatic polycyclic skeleton in which a ring skeleton and two phenol skeletons are bonded via one carbon atom and one oxygen atom at two adjacent substitution positions, and two substitution positions at which two phenol skeletons are adjacent An aromatic polycyclic skeleton bonded via one oxygen atom each, and one carbon atom at each of two substitution positions adjacent to each other by two naphthalene skeletons Aromatic polycyclic skeleton bonded via two aromatic nuclei skeletons bonded via one carbon atom and one oxygen atom at two adjacent substitution positions of two naphthalene skeletons adjacent to each other An aromatic polycyclic skeleton bonded through one oxygen atom at each of the two substitution positions is mentioned. Among them, the aromatic polycyclic skeletons represented by the following general formulas (I) and (II) are mentioned. A ring skeleton can be preferably used. In addition, the line segment drawn from the aromatic ring in the following general formula shows a covalent bond with another structural part.

（式中、Ｘは酸素原子または置換基を有してもよいメチレン基を表す。ｍ及びｎは同一でも異なっていてもよく０〜３の整数である。）

(In the formula, X represents an oxygen atom or a methylene group which may have a substituent. M and n may be the same or different and are integers of 0 to 3.)

  X is more preferably a methylene group which may have a substituent. m and n may be the same or different, and an integer of 1 to 3 is more preferable.

  Examples of the methylene group which may have a substituent include a methylene group, a methylene group substituted with an alkyl group, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, and a biphenyl group. And methylene group substituted with 9-fluorenyl group. The phenyl group, naphthyl group, and biphenyl group may be further substituted with a substituent such as an alkyl group.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group.

  Specific examples of the aromatic polycyclic skeleton represented by the general formula (I) include aromatic polycyclic skeletons represented by the following 1 to 17. The line drawn from the aromatic ring in the following general formula indicates a covalent bond with another structural part.

  Examples of the aromatic polycyclic skeleton represented by the general formula (II) include aromatic polycyclic skeletons represented by the following 18 to 20. The line drawn from the aromatic ring in the following general formula indicates a covalent bond with another structural part.

  Moreover, the aromatic polycyclic skeleton shown by the following 21-22 can be mentioned as an aromatic polycyclic skeleton which the epoxy resin (A) used by this invention has. “T-Bu” in the aromatic polycyclic skeleton represented by 21 below represents a tertiary butyl group (t-butyl group).

  The epoxy resin (A) used in the present invention is preferably an epoxy resin having a methyl group as a substituent on the aromatic polycyclic skeleton. Examples of the aromatic polycyclic skeleton possessed by such an epoxy resin include the aromatic polycyclic skeletons shown in 9 to 17 above.

  The epoxy resin (A) used in the present invention may be, for example, an epoxy resin having an aromatic polycyclic skeleton represented by the general formula (I) or the general formula (II) alone, or a plurality of types of aromatic resins. An epoxy resin having a ring skeleton may be used, but an epoxy resin represented by the following general formula (1) or (2) is more preferable.

（式中、Ｘは酸素原子または置換基を有してもよいメチレン基を表す。ｍ及びｎは同一でも異なっていてもよく０〜３の整数である。Ｐは平均繰り返し単位数で０〜１０である。）

(In the formula, X represents an oxygen atom or a methylene group which may have a substituent. M and n may be the same or different and each is an integer of 0 to 3. P is an average number of repeating units of 0 to 3. 10)

  X is more preferably a methylene group which may have a substituent, m and n may be the same or different, more preferably an integer of 1 to 3, and P is more preferably 0 to 5.

  Examples of the methylene group which may have a substituent include a methylene group, a methylene group substituted with an alkyl group, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, and a biphenyl group. And methylene group substituted with 9-fluorenyl group. The phenyl group, naphthyl group, and biphenyl group may be further substituted with an alkyl group.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group.

  Moreover, the epoxy resin (A) used by this invention may contain the aromatic polycyclic skeleton shown below to such an extent that the effect of this invention is not impaired.

  The method for obtaining the epoxy resin (A) is not particularly limited. For example, a method of glycidyl etherification of the polyvalent hydroxy compound having the aromatic polycyclic skeleton disclosed in JP-A-2003-201333, etc. Is mentioned.

  The phenolic compound (B) used in the present invention is a phenolic compound in which two aromatic hydroxy compounds are directly bonded. As such a compound, for example, a compound represented by the following general formula (3) or general formula (4) can be preferably used.

（ｍ及びｎは同一でも異なっていてもよく０〜３の整数である。）

(M and n may be the same or different and are integers of 0 to 3.)

  Specific examples of the general formula (3) include compounds shown in the following 25 to 29. Specific examples of the general formula (4) include compounds shown in the following 30 to 32.

  The phenol compound (B) used in the present invention is preferably a phenol compound having a methyl group as a substituent on the aromatic hydroxy compound. In the general formulas (3) and (4), n and m are more preferably 1 to 3.

  The modified epoxy resin used in the present invention is obtained by reacting the epoxy resin (A) with the phenol compound (B). As a method for producing a modified epoxy resin, for example, it is preferable to appropriately select reaction conditions in which an appropriate grafting rate is obtained and gelation does not occur, for example, in the presence of a catalyst as necessary, for example, Examples include a method of reacting the epoxy resin (A) and the phenol compound (B) at 20 to 200 ° C.

  Here, the catalyst that can be used is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; tertiary amines such as triethylamine and benzyldimethylamine; tetramethylammonium. Examples include quaternary ammonium salts such as chloride; imidazole compounds; triphenylphosphine and the like.

  Moreover, it is preferable to perform the said reaction in presence of an organic solvent as needed from the point which becomes easy to control reaction. As an organic solvent that can be used, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, n-butanol, methoxypropanol, methyl cellosolve, ethyl carbitol, acetic acid from the point of inertness to the epoxy resin. Ethyl, xylene, toluene, cyclohexanol, N, N-dimethylformamide and the like are preferable.

  The use ratio of the phenol compound (B) to the epoxy resin (A) is determined based on all the epoxy resin components in the final composition.

  That is, it is preferable that an epoxy equivalent that can be preferably used as the epoxy resin (A) is 200 to 300 g / eq from the viewpoint that the epoxy equivalent of the modified epoxy resin can be easily adjusted to an appropriate range.

  Thus, the finally obtained modified epoxy resin preferably has an epoxy equivalent of 200 to 1000 g / eq, but more preferably 300 to 800 g / eq from the viewpoint of the mechanical performance and heat resistance of the cured product. .

〔式（ｃ１−１）及び（ｃ１−２）中、ｋ、ｌはそれぞれ０〜１．５の繰り返し単位の平均値であり、式（ｃ１−３）中、ｑは０〜４の繰り返し単位の平均値で、Ｋ、Ｍ、Ｐ、Ｒは置換基で、各々独立にハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基で、ｋ、ｍ、ｐ、ｒは各々独立に０〜４の整数であり、式（ｃ１−８）中、ｓ、ｔは各々独立に０〜３の整数で、Ｙは酸素原子、メチレン基、アルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上にさらにアルキル基が芳香族置換したメチレン基である。〕
から選ばれる１種以上の芳香族多価ヒドロキシ化合物残基（ｃ１）と芳香族多価カルボン酸残基（ｃ２）とからなり、且つ分子末端がアリールオキシカルボニル基（ｃ３）であるポリエステル樹脂（Ｃ１）が、溶媒溶解性に優れるエポキシ樹脂組成物が得られ、硬化時に極性の高い水酸基が生成せず、誘電正接の低い硬化物を得ることができるので好ましい。 The polyfunctional aromatic polyester resin (C) used in the present invention is not particularly limited as long as it has an aromatic group in the resin skeleton, for example, by gun condensation using aromatic dicarboxylic acid or aromatic diol as an essential component. Obtainable. Here, the polyfunctionality means a property that has two or more ester bonds that react with an epoxy group and can react with a plurality of epoxy groups. The polyfunctional aromatic polyester resin (C) includes the following structural formulas (c1-1) to (c1-7) and the following general formula (c1-8).

[In formulas (c1-1) and (c1-2), k and l are average values of 0 to 1.5 repeating units, respectively, and in formula (c1-3), q is 0 to 4 repeating units. Where K, M, P, and R are substituents, each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and k, m, p, and r are Each independently represents an integer of 0 to 4, and in formula (c1-8), s and t each independently represents an integer of 0 to 3, Y represents a methylene group substituted with an oxygen atom, a methylene group or an alkyl group, A methylene group substituted with a phenyl group, or a methylene group in which an alkyl group is further aromatically substituted on the phenyl group, the naphthyl group or the biphenyl group. ]
A polyester resin comprising at least one aromatic polyvalent hydroxy compound residue (c1) and an aromatic polyvalent carboxylic acid residue (c2) selected from the group consisting of an aryloxycarbonyl group (c3) C1) is preferable because an epoxy resin composition excellent in solvent solubility is obtained, and a highly polar hydroxyl group is not generated during curing, and a cured product having a low dielectric loss tangent can be obtained.

  The ester bond in the polyfunctional aromatic polyester resin (C1) has a high reaction activity with respect to the epoxy group, and does not generate a highly polar hydroxyl group by the curing reaction with the epoxy resin, and the mobility of the molecular skeleton. Therefore, a cured product having a low dielectric loss tangent can be obtained from the epoxy resin composition using the polyfunctional aromatic polyester resin (C1) as a curing agent. Further, since the polyfunctional aromatic polyester resin (C1) has an aryloxycarbonyl group at the molecular chain end, it has a low molecular weight that increases the dielectric loss tangent even if the ester bond at the crosslinking point of the cured product is hydrolyzed by moisture absorption. This carboxylic acid is not liberated, and a low dielectric loss tangent can be maintained even under high humidity conditions. Moreover, since this polyfunctional aromatic polyester resin (C1) has many ester bonds which have reaction activity with respect to an epoxy group in one molecule, the crosslinked density of the cured product is high and the glass transition temperature is high. Moreover, since all the groups represented by the formulas (a1-1) to (a1-8) have a plurality of bulky aromatic rings and alicyclic structures in the molecule, aggregation of molecular chains can be suppressed and organic groups can be suppressed. Excellent solubility in solvent, less amount of solvent to use when dissolving epoxy resin composition containing polyfunctional aromatic polyester resin (C1) in solvent or preparing varnish, work It is also excellent in properties.

As the polyfunctional aromatic polyester resin (C1), the inherent viscosity of the polyester resin (C1) is 0 from the viewpoint that a cured product having excellent solvent solubility, a high glass transition temperature, and a low dielectric loss tangent can be obtained. It is preferably 0.02 to 0.42 dl / g. When the inherent viscosity is in the above range, it has good solubility when dissolved in methyl ethyl ketone (MEK) or toluene, which is widely used as a solvent for epoxy resin compositions, and the polyfunctionality in the solution. Crystallization and aggregation of the aromatic polyester resin (C1) can be prevented. Moreover, when it exists in the said inherent viscosity range, the fluidity | liquidity at the time of a fusion | melting will also become favorable, and the high filling of a filler will be attained.

  In particular, when the inherent viscosity of the polyfunctional aromatic polyester resin (C1) is in the range of 0.03 to 0.15 dL / g, the solubility in MEK or toluene is further improved. For example, MEK or toluene Can be dissolved in an amount of 50% by weight or more. A 50% by weight solution is uniformly transparent and stable at room temperature. For example, even if a cooling cycle in which it is allowed to stand at 25 ° C. for 5 hours and then allowed to stand at −20 ° C. for 11 hours is repeated for 2 months or more, no solid precipitates. It is stable.

Further, the polystyrene-reduced number average molecular weight of the polyfunctional aromatic polyester resin (C1) is not particularly limited, but a cured product having a high glass transition temperature and a low dielectric loss tangent is obtained, and the solution viscosity is suitable. From the viewpoint of excellent workability, it is preferably 550 to 7000, particularly preferably 550 to 2500.

In addition, the polyfunctional aromatic polyester resin (C1) is softened or melted at 200 ° C. or less without using a solvent, and thus can be suitably used for processing by heating.

By using the polyfunctional aromatic polyester resin (C1), specifically, the dielectric loss tangent at 1 GHz is less than 8.0 × 10 −3, which is preferably used for recent high frequency electrical and electronic components. Can do. In addition, the rate of change of dielectric loss tangent due to moisture absorption after pressure cooker test at 121 ° C. for 2 hours is 40% or less, and shows a stable low dielectric loss tangent even when the humidity in the usage environment changes.

Among the aromatic polyvalent hydroxy compound residues (c1), a polyfunctional aromatic polyester resin having a group represented by the following general formula (c1-1), (c1-2) or (c1-3) When used, it is preferable in terms of exhibiting excellent low water absorption and moisture resistance in addition to heat resistance and dielectric properties, and is also suitable for electrical insulating materials such as semiconductor sealing materials.

  When a polyfunctional aromatic polyester resin having a naphthalene skeleton represented by the structural formulas (c1-4) to (c1-6) is used, the machine has excellent toughness in addition to the heat resistance of the cured product. From the point that the mechanical strength is good and the fluidity of the epoxy resin composition is excellent, the inorganic filler can be highly filled especially in the field of semiconductor sealing materials. In particular, those obtained by using a polyfunctional aromatic polyester resin having a group represented by the structural formula (c1-5) are particularly preferable because these properties are remarkable.

で表される基を挙げることができる。これらのジベンゾピラン構造を有する多官能性芳香族ポリエステル樹脂から得られる硬化物は耐熱性、誘電特性に加え、優れた難燃性を有し電気絶縁材料用途に好適に用いることができる。 Specific examples of the product represented by the general formula (c1-8) include the following structural formulas (c1-8-1) to (c1-8-8).

The group represented by these can be mentioned. Cured products obtained from these polyfunctional aromatic polyester resins having a dibenzopyran structure have excellent flame resistance in addition to heat resistance and dielectric properties, and can be suitably used for electrical insulating material applications.

Among these, in particular, a cured product obtained using the polyfunctional aromatic polyester resin having the group represented by the structural formula (c1-1) has a remarkable performance that the dielectric loss tangent is low even in a high humidity atmosphere. And is the most preferred.

  The aromatic polyvalent carboxylic acid residue (c2) may have a structure in which two or more carboxyl groups are directly bonded to an aromatic hydrocarbon nucleus containing an aromatic nucleus such as a benzene ring and a naphthalene ring. Even if the structure contains an ether bond, a methylene group, an ethylidene group or a 2,2-propylene group, the aromatic nucleus has a halogen atom such as a chlorine atom or a bromine atom, a methyl group, etc. Also good. Further, two or more carboxyl groups may be bonded to one aromatic nucleus, or a structure in which the carboxyl groups are bonded to different aromatic nuclei may be used.

（式中Ａ、Ｂ、Ｄ、Ｅ及びＧは各々独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、またはハロゲン原子であり、ａ、ｅ及びｇは各々独立に０〜４の整数であり、ｂ及びｄは各々独立に０〜３の整数であり、Ｘは単結合、−Ｓ−、−Ｏ−、−ＣＯ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、または−ＳＯ_２−である。）で表される基である事が好ましく、特に前記多官能性ポリエステル樹脂（Ｃ１）の製造が容易で、且つ溶媒溶解性に優れる点から、イソフタロイル基及びテレフタロイル基であることが好ましい。 As the aromatic polyvalent carboxylic acid residue (c2), the following general formulas (c2-1) to (c2-3)

Wherein A, B, D, E and G are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and a, e and g are each Each independently represents an integer of 0 to 4, b and d are each independently an integer of 0 to 3, and X represents a single bond, —S—, —O—, —CO—, —CH ₂ —, —C ( CH ₃ ) ₂ — or —SO ₂ —) is preferable. From the viewpoint of easy production of the polyfunctional polyester resin (C1) and excellent solvent solubility. An isophthaloyl group and a terephthaloyl group are preferable.

（式中、Ｊ、Ｑ、Ｔ、Ｕ及びＶは各々独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ニトロ基、またはハロゲン原子であり、ｊ及びｖは０〜５の整数であり、ｔ及びｕは０〜４の整数であり、ｑは０〜３の整数であり、Ｚは単結合、−Ｏ−、−ＣＯ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）２−、または−ＳＯ_２−である。）で表される基であることが耐熱性と誘電特性に優れた硬化物が得られる点で好ましく、例えば、下記構造式（ｃ３−１−１）〜（ｃ３−３−６）

で表される物が好ましい。 The aryloxycarbonyl group (c3) is not particularly limited, and the structure includes a halogen atom such as a chlorine atom or a bromine atom as a substituent on an aromatic ring such as a benzene ring or a naphthalene ring, or a methyl group. , 2-propyl group, phenoxy group and the like, for example, the following general formulas (c3-1) to (c3-3)

Wherein J, Q, T, U and V are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, or a halogen atom, and j and v Is an integer of 0 to 5, t and u are integers of 0 to 4, q is an integer of 0 to 3, Z is a single bond, —O—, —CO—, —CH ₂ —, — C (CH ₃ ) 2− or —SO ₂ —) is preferable in that a cured product having excellent heat resistance and dielectric properties can be obtained. For example, the following structural formula (c3 -1-1) to (c3-3-6)

The thing represented by these is preferable.

  Since the molecular terminal of the aryloxycarbonyl group (c3) does not form an intermolecular bridge in the curing reaction with the epoxy resin, the smaller the content of the group (c3), that is, the polyfunctional aromatic polyester resin (C1). The higher the molecular weight, the higher the crosslink density of the resulting cured product, and the higher the glass transition temperature.

（式中、Ｐｈはフェニル基であり、ｎ’は繰り返しの平均値で０．４〜２０である。尚、式中の縮合多環脂肪族炭化水素基は、原料としてジシクロペンタジエンを用い、これとフェノール類とを付加させて得られる基である。）
で表されるものである。 As a specific example of the polyfunctional aromatic polyester resin (C1) having the three types of structures described above, the structural formula (c1-1) as an aromatic polyvalent hydroxy compound residue (c1) is aromatic. The polyfunctional aromatic having the general formula (c2-1) as the polyvalent carboxylic acid residue (c2) and the group represented by the general formula (c3-1) as the terminal aryloxycarbonyl group (c3) Polyester resin (C-1)

(In the formula, Ph is a phenyl group, and n ′ is an average of repetitions of 0.4 to 20. In addition, the condensed polycyclic aliphatic hydrocarbon group in the formula uses dicyclopentadiene as a raw material, This is a group obtained by adding this and phenols.)
It is represented by

（式中、Ｐｈ及びｎ’は前記と同じである。）で表される物である。 The polyfunctional aromatic polyester resin (C-2) having a group represented by the structural formula (c1-6) as the aromatic hydroxy compound residue (c1),

(Wherein Ph and n ′ are the same as above).

（式中、Ｐｈ及びｎ’は前記と同じである。）で表される物である。 The polyfunctional aromatic polyester resin (C-3) having a group represented by the structural formula (c1-8-5) as the aromatic hydroxy compound residue (c1),

(Wherein Ph and n ′ are the same as above).

  Among these, the aromatic polyvalent hydroxy compound residue (c1) is a group represented by the structural formula (c1-1), and the aromatic polyvalent carboxylic acid residue (c2) is the structural formula (c2- Polyester aromatic polyester resin (C-1) which is a group represented by 1) and a polyester resin having a number average molecular weight of 550 to 2500 are particularly excellent in terms of the balance of physical properties of the resulting cured product. It is preferable.

  The method for producing the polyfunctional aromatic polyester resin (C1) is not particularly limited, and for example, an aromatic polyvalent hydroxy compound (x1) and an aromatic polyvalent carboxylic acid (x2) having a desired structure. And a polyester resin having a carboxyl group at both ends of the molecule is synthesized, and the carboxyl group is converted into an aromatic monohydroxy compound (x3) [a compound having a desired terminal aryloxycarbonyl group (a3)]. Further, dehydration esterification reaction for esterification, aromatic polyvalent hydroxy compound (x2) and aromatic monohydroxy compound (x3) having a desired structure are acetylated with acetic anhydride, and then aromatic polyvalent carboxylic acid (x2) And so-called transesterification reaction for acidolysis, and the Schotten-Baumann reaction described later. Among the methods, generally aromatic reactive low that transesterification of the reaction of the hydroxy compound, a method of utilizing the Schotten-Baumann reaction preferably.

  When utilizing the Schotten-Baumann reaction, there are an interfacial polycondensation method in which the reaction is carried out at the interface and a solution polycondensation method in which the reaction is carried out in a homogeneous solution. The interfacial polycondensation method includes an organic solution phase containing an acid halide of an aromatic polyvalent carboxylic acid (x2), and an aqueous phase containing an aromatic polyvalent hydroxy compound (x1) and an aromatic monohydroxy compound (x3). And polyfunctional aromatic polyester resin (C1) is obtained by interfacial polycondensation in the presence of an acid scavenger, and the solution polycondensation method comprises aromatic polycarboxylic acid (x2). By mixing a solution containing the acid halide of the above, a solution containing the aromatic polyhydroxy compound (x1) and the aromatic monohydroxy compound (x3) in the presence of an acid scavenger, and dehydrohalogenating the mixture. A polyfunctional aromatic polyester resin (C1) is obtained.

〔式（ｘ１−１）及び（ｘ１−２）中、ｋ、ｌはそれぞれ０〜１．５の繰り返し単位の平均値であり、式（ｘ１−３）中、ｑは０〜４の繰り返し単位の平均値で、Ｋ、Ｍ、Ｐ、Ｒは置換基で、各々独立にハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基で、ｋ、ｍ、ｐ、ｒは各々独立に０〜４の整数であり、式（ｘ１−８）中、ｓ、ｔは各々独立に０〜３の整数で、Ｙは酸素原子、メチレン基、アルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上にさらにアルキル基が芳香族置換したメチレン基である。〕
で表される芳香族多価ヒドロキシ化合物等が挙げられる。 Hereinafter, the production method using the Schotten-Baumann reaction will be described in detail.
Examples of the aromatic polyvalent hydroxy compound (x1) include compounds that give groups represented by the above formulas (c1-1) to (c1-8). 1) to (x1-8)

[In formulas (x1-1) and (x1-2), k and l are average values of 0 to 1.5 repeating units, respectively, and in formula (x1-3), q is 0 to 4 repeating units. Where K, M, P, and R are substituents, each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and k, m, p, and r are Each independently represents an integer of 0 to 4, and in formula (x1-8), s and t each independently represents an integer of 0 to 3, Y represents a methylene group substituted with an oxygen atom, a methylene group or an alkyl group, A methylene group substituted with a phenyl group, or a methylene group in which an alkyl group is further aromatically substituted on the phenyl group, the naphthyl group or the biphenyl group. ]
An aromatic polyvalent hydroxy compound represented by

  Among these, the cured product obtained using the polyfunctional aromatic polyester resin (C1) derived from the compound represented by the structural formula (x1-1) is excellent in moisture resistance, and even in a high humidity environment. This is preferable from the viewpoint of showing stable dielectric characteristics. In particular, from the viewpoint of preventing gelation when synthesizing the polyfunctional aromatic polyester resin (C1) in a solution, k, which is an average value of the number of repeating units in the formula, is in the range of 0 to 0.2. Is preferred. However, even when a k value exceeding 0.2 is used, gelation hardly occurs when the molecular weight of the resulting polyfunctional aromatic polyester resin (C1) is 3000 or less. The polyfunctional aromatic polyester resin (C1) can be obtained even when the value of k is 0 to 1.5. Furthermore, even if the value of k exceeds 0.2, the polyfunctional aromatic polyester resin (C1) can be obtained without causing gelation by using other aromatic polyvalent hydroxy compounds in combination. In this case, for example, when an aromatic polyvalent hydroxy compound (x1-1) having k = 1 is used, the aromatic occupying in the wholly aromatic polyvalent hydroxy compound (x1) The ratio of the polyvalent hydroxy compound (x1-1) is preferably 20 mol% or less.

  Moreover, the hardened | cured material obtained using the polyfunctional aromatic polyester resin (C1) induced | guided | derived from the aromatic polyvalent hydroxy compound (x1) represented by the said structural formula (x1-4)-(x1-6). Has good heat resistance and dielectric properties.

で表される化合物が挙げられ、これから誘導される多官能性芳香族ポリエステル樹脂（Ｃ１）を用いて得られる硬化物は低誘電正接である。 Specific examples of the compound having a dipenzopyran skeleton represented by the general formula (x1-8) include, for example, the following structural formulas (x1-8-1) to (x1-8-8)

The hardened | cured material obtained using polyfunctional aromatic polyester resin (C1) induced | guided | derived from this is a low dielectric loss tangent.

（式中Ａ、Ｂ、Ｄ、Ｅ及びＧは各々独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、またはハロゲン原子であり、ａ、ｅ及びｇは各々独立に０〜４の整数であり、ｂ及びｄは各々独立に０〜３の整数であり、Ｘは単結合、−Ｓ−、−Ｏ−、−ＣＯ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、または−ＳＯ_２−である。）
で表される芳香族多価カルボン酸等が挙げられる。 When the polyfunctional aromatic polyester resin (C1) is produced using the Schotten-Baumann reaction, the aromatic polyvalent carboxylic acid (x2) is used in the form of an acid halide. As the halogen of the acid halide used here, chlorine or bromine is generally used. The aromatic polycarboxylic acid (x2) used in the form of acid halide is trimesic acid, trimellitic acid, pyromellitic acid, or the following general formulas (x2-1) to (x2-3)

Wherein A, B, D, E and G are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and a, e and g are each Each independently represents an integer of 0 to 4, b and d are each independently an integer of 0 to 3, and X represents a single bond, —S—, —O—, —CO—, —CH ₂ —, —C ( CH ₃ ) ₂ —, or —SO ₂ —.)
An aromatic polyvalent carboxylic acid represented by

  Among the polyvalent aromatic carboxylic acids, the polyfunctional aromatic polyester resin obtained from the acid halide of the aromatic polyvalent carboxylic acid represented by the general formulas (x2-1) to (x2-3). (C1) exhibits excellent solubility in various solvents, and is obtained using an epoxy resin composition obtained by blending a polyfunctional aromatic polyester resin (C1) as a curing agent for the modified epoxy resin described later. The resulting cured product exhibits a high glass transition temperature and a low dielectric loss tangent. Examples of the aromatic polycarboxylic acid represented by the general formulas (x2-1) to (x2-3) include isophthalic acid, terephthalic acid, 1,4-, 2,3-, and 2,6- And naphthalenedicarboxylic acid. Of these, polyfunctional aromatic polyester resins obtained by using isophthalic acid or a mixture of isophthalic acid and terephthalic acid are particularly preferable because of their excellent solubility in various solvents.

（式中、Ｊ、Ｑ、Ｔ、Ｕ及びＶは各々独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ニトロ基、またはハロゲン原子であり、ｊ及びｖは０〜５の整数であり、ｔ及びｕは０〜４の整数であり、ｑは０〜３の整数であり、Ｚは単結合、−Ｏ−、−ＣＯ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、または−ＳＯ_２−である。）で表される芳香族モノヒドロキシ化合物が挙げられる。 The aromatic monohydroxy compound (x3) may have a substituent such as a halogen atom such as a chlorine atom or a bromine atom, a methyl group, a 2-propyl group, or a phenoxy group on a benzene ring or naphthalene ring. Well, for example, the following general formulas (x3-1) to (x3-3)

Wherein J, Q, T, U and V are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, or a halogen atom, and j and v Is an integer of 0 to 5, t and u are integers of 0 to 4, q is an integer of 0 to 3, Z is a single bond, —O—, —CO—, —CH ₂ —, — An aromatic monohydroxy compound represented by C (CH ₃ ) ₂ — or —SO ₂ —.

で表される物が好ましい。 Among these, the following structural formulas (x3-1-1) to (x3-3-6)

The thing represented by these is preferable.

  Among these, a substance represented by (x3-2-1), (x3-2-2), (x3-3-1), or (x3-3-2) having a naphthalene skeleton or a biphenyl skeleton is used. In this case, the dielectric loss tangent of the obtained cured product is particularly low, and when the product represented by (x3-2-2) is used, the resulting polyfunctional aromatic polyester resin (C1) or the same is contained. The epoxy resin composition is most preferable because of its excellent solvent solubility.

  As the solvent used in the organic solution phase when the polyfunctional aromatic polyester resin (C1) is produced by the interfacial polycondensation method of the Schotten-Baumann reaction, an acid halide of an aromatic polyvalent carboxylic acid is dissolved, and an acid Any solvent that is inert to the halide and incompatible with water may be used, and examples thereof include toluene and dichloromethane. In the aqueous phase, an aromatic polyhydroxy compound (x1), an aromatic monohydroxy compound (x3), and an alkali as an acid scavenger are dissolved.

  Moreover, as a solvent used when manufacturing the said polyfunctional aromatic polyester resin (C1) by a solution polymerization method, the acid halide of aromatic polyvalent carboxylic acid (x2), aromatic polyvalent hydroxy compound (x1) And an aromatic monohydroxy compound (x3) and a solvent inert to the acid halide, such as toluene and dichloromethane. Moreover, pyridine, triethylamine, etc. can be used as an acid scavenger used for a polycondensation reaction.

  The mixing ratio of each raw material is appropriately selected depending on the structure of each raw material to be used, the inherent viscosity of the target polyfunctional aromatic polyester resin (C1), the number average molecular weight, and the like. As a method for suitably obtaining a polyfunctional aromatic polyester resin (C1) of 0.02 to 0.43 dl / g, an aromatic polyvalent hydroxy compound (x1), an aromatic polyvalent carboxylic acid (x2), an aromatic As an equivalent ratio of the monohydroxy compound (x3), [(x1) / (x2)] is 0.28 to 0.95, and [(x1) / (x3)] is 0.20 to 10. It is preferable.

  The obtained polyfunctional aromatic polyester resin (C1) is preferably purified by operations such as washing and reprecipitation to reduce the impurity content. If impurities such as monomers, halogen ions, alkali metal ions, alkaline earth metal ions, or salts remain in the polyfunctional aromatic polyester resin (C1), the dielectric loss tangent and other physical properties are deteriorated.

  As the compounding ratio of the modified epoxy resin and the polyfunctional aromatic polyester resin (C1), the curing reaction is good, and the resulting cured product is excellent in heat resistance (glass transition temperature) and dielectric properties. A blending amount such that the aryloxycarbonyl group (c3) in the polyfunctional aromatic polyester resin (C1) is 0.15 to 5 mol is preferable with respect to 1 mol of the epoxy group in the epoxy resin, and 0.5 to 2.5 mol. It is more preferable that the amount is as follows.

  The epoxy resin composition of the present invention can be used in combination with a curing accelerator as necessary. The curing accelerator that can be used is not particularly limited, and various types can be used, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-hepta. Imidazole compounds such as decylimidazole and 2-undecylimidazole, organic phosphine compounds such as triphenylphosphine and tributylphosphine, organic phosphite compounds such as trimethylphosphite and triethylphosphite, ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenyl Phosphonium salts such as borate, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylamine) Nomine) phenol, amine compounds such as 1,8diazabicyclo (5,4,0) -undecene-7 (hereinafter abbreviated as DBU), and salts of DBU with terephthalic acid or 2,6-naphthalenedicarboxylic acid, tetraethyl Quaternary ammonium salts such as ammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrahexylammonium bromide, benzyltrimethylammonium chloride, 3-phenyl-1,1-dimethylurea, 3- (4 -Methylphenyl) -1,1-dimethylurea, chlorophenylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, etc. Urea compound, sodium hydroxide And salts of crown ether such as an alkali such as potassium hydroxide, potassium phenoxide and potassium acetate and the like, which may be used alone or plural. Among these, imidazole compounds and 4-dimethylaminopyridine are preferably used.

  If necessary, the epoxy resin composition of the present invention includes inorganic fillers, thermosetting and thermoplastic resins used as modifiers, flame retardants, pigments, silane coupling agents, mold release agents, etc. Various compounding agents can be added.

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

  Various thermosetting and thermoplastic resins can be used as the modifier. For example, phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether resin. And polyphenylene sulfide resin, polyester resin, polystyrene resin, polyethylene terephthalate resin and the like.

  Moreover, you may use together epoxy resins other than the said modified epoxy resin used by this invention in the range which does not impair the effect of invention. Various epoxy resins can be used as the epoxy resin other than the modified epoxy resin. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type Epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, epoxy resin derived from divalent phenols such as tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, Cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenolic Rukiru type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified Examples include, but are not limited to, epoxy resins derived from trivalent or higher phenols such as phenol resin type epoxy resins and biphenyl-modified novolak type epoxy resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types. These epoxy resins that can be used in combination are preferably 20% by mass or less based on the total epoxy resin components in the composition.

  The use of the epoxy resin composition of the present invention is not particularly limited. For example, for printed circuit boards, electronic component sealing materials, conductive pastes, resin casting materials, adhesives, insulating paints, etc. Coating materials, etc. are mentioned, and among these, it can be suitably used for resin compositions for printed circuit boards, resin compositions for encapsulants for electronic components, and conductive pastes because of the excellent dielectric properties of the resulting cured products. From the point of being excellent in moisture resistance, it can be suitably used for an adhesive, and since it is excellent in flame retardancy, moisture resistance and heat resistance, it can be suitably used for a composite material.

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

  In order to use the epoxy resin composition of the present invention as a prepreg for a printed circuit board, it is preferable to form a prepreg by varnishing using an organic solvent. Examples of the organic solvent include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide and the like. Non-alcoholic polar solvents and the like have a boiling point of 160 ° C. or lower, and can be used as a mixed solvent of two or more as appropriate. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The weight ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 to 60% by weight.

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

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

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

  In order to adjust the epoxy resin composition of the present invention for a semiconductor sealing material, after pre-mixing other coupling agents, additives such as mold release agents, inorganic fillers, etc., which are blended as necessary And a method of sufficiently mixing until uniform using an extruder, kneader, roll or the like. When used as a tape-like sealant, the resin composition obtained by the above-described method is heated to produce a semi-cured sheet, which is used as a sealant tape, and then this sealant tape is applied to a semiconductor chip. And a method of softening by heating to 100 to 150 ° C. and completely curing at 170 to 250 ° C. can be 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 not particularly limited, but the semiconductor element and the substrate are heated by semi-curing the epoxy resin composition of the present invention on a substrate or semiconductor element in advance. The compression flow method etc. which are made to adhere | attach and fully harden | cure are mentioned.

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

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

  When the epoxy resin composition of the present invention is used as a resin composition for an adhesive, other curing agents, curing accelerators, solvents, additives, and the like blended as necessary are mixed at room temperature or under heating. Etc. can be obtained by uniformly mixing, etc., and after being applied to various base materials, the base materials can be adhered by allowing them to stand at room temperature or under heating.

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

  The cured product of the present invention is obtained by molding and curing the above-described epoxy resin composition of the present invention, and can be used as a laminate, a cast product, an adhesive, a coating film, a film and the like. The curing method is not particularly limited, and examples include a method in which other curing agents blended as necessary, various blending agents, and the like are uniformly mixed and then heated and cured at room temperature or 80 to 200 ° C. Can do. Moreover, it is preferable to employ | adopt suitably the hardening method according to the use to which the epoxy resin composition prepared according to the above-mentioned various uses.

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

Synthesis Example 1 (Synthesis of modified epoxy resin)
100 g of a benzopyran-type epoxy resin having an epoxy equivalent of 240 and 16 g of 4,4′-biphenol represented by the following structural formula synthesized by the method disclosed in JP-A-2003-201333 were dissolved in 30 g of cyclohexanone. 0.1 g of triphenylphosphine was added as a catalyst and reacted at 150 ° C. for 5 hours to obtain a target modified epoxy resin having an epoxy equivalent of 490. Hereinafter, this is abbreviated as resin (A-1). In addition, P in the following structural formula is 0.1.

Synthesis example 2 (same as above)
A target modified epoxy resin having an epoxy equivalent of 350 was obtained in the same manner as in Synthesis Example 1 except that 11 g of 2,2 ′, 6,6′-tetramethylbiphenol was used instead of 16 g of 4,4′-biphenol. Hereinafter, this is abbreviated as resin (A-2).

Synthesis example 3 (same as above)
A target epoxy resin having a modified epoxy equivalent of 430 was obtained in the same manner as in Synthesis Example 2 except that 16 g of 2,2 ′, 6,6′-tetramethylbiphenol was used. Hereinafter, this is abbreviated as resin (A-3).

Synthesis Example 4 (Synthesis of polyfunctional aromatic polyester resin)
Into a reaction vessel, 1000 ml of water and 20 g of sodium hydroxide were charged, and 5.2 g of α-naphthol and 52.8 g of dicyclopentadienyl diphenol “DPP-6085” (manufactured by Nippon Petrochemical Co., Ltd.) were charged in a nitrogen stream. Then, the mixture was stirred for 1 hour at 300 rpm with a Ferdler blade. Next, a solution prepared by dissolving 20.3 g of isophthalic acid chloride and 20.3 g of terephthalic acid chloride in 1000 ml of methylene chloride was dropped into the reaction vessel kept at 30 ° C. over 15 seconds, and stirring was continued for 4 hours. The resulting mixture is allowed to stand and remove to remove the aqueous phase, and the remaining methylene chloride phase is washed with a 0.5% strength aqueous sodium hydroxide solution and the aqueous phase is removed three times. Washing with ionic water and removal of the aqueous phase were repeated three times. After the methylene chloride phase after washing was concentrated to 400 ml, 1000 ml of heptane was added dropwise over 15 seconds, and then the precipitate was washed with methanol, filtered and dried to obtain a polyfunctional aromatic polyester resin (C-1). Obtained.

Synthesis example 5 (same as above)
A polyfunctional aromatic polyester resin (C-2) was obtained in the same manner as in Synthesis Example 4 except that 44.0 g of dicyclopentadienyl diphenol was used.

Synthesis example 6 (same as above)
Instead of using 52.8 g of dicyclopentadienyl diphenol, a polyfunctional aromatic is used in the same manner as in Synthesis Example 4 except that 52.0 g of dihydroxybenzopyran represented by the structural formula (x1-8-5) is used. A polyester resin (C-2) was obtained.

Synthesis example 7 (same as above)
In the same manner as in Synthesis Example 4, except that 6.2 g of O-phenylphenol was used instead of 5.2 g of α-naphthol and 52.0 g of dihydroxynaphthalene was used instead of 52.8 g of dicyclopentadienyl diphenol. A functional aromatic polyester resin (C-4) was obtained.

Example 1
The modified epoxy resin obtained in Synthesis Examples 1 to 3, the polyfunctional aromatic polyester resin obtained in Synthesis Examples 4 to 7, the curing accelerator and the inorganic filler are mixed in the ratio shown in Table 1, The epoxy resin composition of the present invention was produced. A varnish was produced using the epoxy resin composition, and a double-sided copper-clad laminate was produced using the varnish. Using this double-sided copper-clad laminate, physical properties tests (combustion test, glass transition temperature, peel strength, moisture absorption rate, moisture resistance solder resistance, delamination strength, dielectric constant and dielectric loss tangent) were performed. The manufacturing method of a varnish, the manufacturing method of a double-sided copper clad laminated board, and the method of each physical property test are shown below, respectively. The test results are shown in Table 1.

  [Adjustment of varnish]: It was obtained by adjusting the epoxy resin composition of the present invention with methyl ethyl ketone so that the final nonvolatile content (NV) of the composition was 55%.

[Laminate production conditions]
Base material: 180 μm; glass cloth “WEA 7628 H258” manufactured by Nitto Boseki Co., Ltd.
Number of plies: 8 prepreg conditions: 160 ° C./4 minutes Copper foil: 35 μm; Furukawa-Sakito Foil Co., Ltd. Curing conditions: 200 ° C., 40 kg / cm 2 for 1.0 hour Mold thickness after molding: 1.6 mm Resin content Amount: 40%

[Physical property test conditions]
Combustion test: Conforms to UL-94 vertical test.
Glass transition temperature: Measured by DMA method after removing copper foil by etching. Temperature rising speed 3 ° C / min.
Peel strength: compliant with JIS-K6481.
Interlaminar peel strength: Conforms to JIS-K6481.
Moisture absorption: Using a pressure cooker tester, a test piece (25 mm × 50 mm) was held for 2 to 6 hours under the conditions of 121 ° C., 2.1 atm and 100% RH, and the weight change before and after the test piece was measured.

Moisture resistance / solder resistance: Using a pressure cooker tester, hold the test piece (25 mm × 50 mm) for 2 to 6 hours under the conditions of 121 ° C., 2.1 atm and 100% RH, and then solder the test piece to 260 ° C. It was immersed in a bath for 30 seconds, and the state change before and after that was observed.
○: No change in appearance, Δ: No more than 5 blisters with a diameter of 5 mm or less, X: No more than 5 mm in diameter, or 6 or more blisters with a diameter of 5 mm or less.

Measurement of dielectric constant and dielectric loss tangent By the method according to JIS-C-6481, it was stored in an indoor room at 23 ° C. and 50% humidity after being completely dried by using impedance material analyzer “HP4291B” manufactured by Agilent Technologies. The dielectric constant and dielectric loss tangent at 1 GHz of the subsequent double-sided copper-clad laminate were measured.

Examples 2-9 and Comparative Examples 1-4
A varnish was prepared in the same manner as in Example 1 except that a modified epoxy resin, a curing agent, and a curing accelerator were used in the formulations shown in Tables 1 to 2, and a double-sided copper-clad laminate using these varnishes. Manufactured. Each physical property test was conducted in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

The raw materials and abbreviations in Tables 1 and 2 are as follows.
DMAP: curing accelerator. 4-dimethylaminopyridine.
2E4MZ: curing accelerator. 2-Ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name [CURESOL 2E4MZ]).
HP-7200H: dicyclopentadiene type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name [EPICLON HP-7200H], epoxy equivalent 280 g / eq.).
N-695: Cresol novolak type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name [EPICLON N-690], epoxy equivalent 220 g / eq.).
TD-2090: Phenol novolac resin (Dainippon Ink Chemical Co., Ltd., trade name [PHENOLITE TD-2090], hydroxyl group equivalent 105 g / eq.).

Test example 1
The modified epoxy resin produced in Synthesis Example 1 was diluted with methyl ethyl ketone so as to have a nonvolatile content of 55% to prepare a resin solution. This resin solution was left in an environment of 25 ° C. for 24 hours. A sample was randomly collected from this resin solution and the epoxy equivalent of this sample was measured. The measurement results are shown in Table 3. A smaller variation in this value indicates a more uniform resin solution.

Test example 2
A sample was taken in the same manner as in Test Example 1 except that HP-7200H used in Comparative Example 3 was used, and the epoxy equivalent was measured. The measurement results are shown in Table 3.

Test example 3
A sample was taken in the same manner as in Example 1 except that the benzopyran type epoxy resin used in Synthesis Example 1 was used, and the epoxy equivalent was measured. The measurement results are shown in Table 3.

Claims (12)

The aromatic hydrocarbon has an aromatic polycyclic skeleton in which two aromatic hydrocarbons are bonded via a carbon atom and / or an oxygen atom at two adjacent substitution positions on the aromatic ring in the aromatic hydrocarbon; and A modified epoxy resin obtained by reacting an epoxy resin (A) having a glycidyloxy group as a substituent on an aromatic polycyclic skeleton with a phenol compound (B) in which two aromatic hydroxy compounds are directly bonded, and a polyfunctional An epoxy resin composition comprising a functional aromatic polyester resin (C). The epoxy resin (A) has an aromatic polycyclic skeleton in which two aromatic hydrocarbons are bonded via a carbon atom or an oxygen atom at two adjacent substitution positions on the aromatic ring in the aromatic hydrocarbon. The epoxy resin composition according to claim 1, which is an epoxy resin having a glycidyloxy group as a substituent on the aromatic polycyclic skeleton. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) is an epoxy resin having a methyl group as a substituent on the aromatic polycyclic skeleton. The epoxy resin (A) is represented by the following general formula (1) or (2)

(In the formula, X represents an oxygen atom or a methylene group which may have a substituent. M and n may be the same or different and each is an integer of 0 to 3. P is an average number of repeating units of 0 to 3. 10)
The epoxy resin composition according to claim 1, wherein the epoxy resin composition is represented by the formula: The epoxy resin composition according to claim 4, wherein the phenol compound (B) is a phenol compound having a methyl group as a substituent on the aromatic hydroxy compound. The phenol compound (B) is represented by the following general formula (3) or (4)

(M and n may be the same or different and are integers of 0 to 3.)
The epoxy resin composition of Claim 4 which is a phenol compound represented by these. The polyfunctional aromatic polyester resin (C) has the following structural formulas (c1-1) to (c1-7) and the following general formula (c1-8).

[In formulas (c1-1) and (c1-2), k and l are average values of 0 to 1.5 repeating units, respectively, and in formula (c1-3), q is 0 to 4 repeating units. Where K, M, P, and R are substituents, each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and k, m, p, and r are Each independently represents an integer of 0 to 4, and in formula (c1-8), s and t each independently represents an integer of 0 to 3, Y represents a methylene group substituted with an oxygen atom, a methylene group or an alkyl group, A methylene group substituted with a phenyl group, or a methylene group in which an alkyl group is further aromatically substituted on the phenyl group, the naphthyl group or the biphenyl group. ]
2. The aromatic polyvalent hydroxy compound residue (c1) and aromatic polyvalent carboxylic acid residue (c2) selected from the group consisting of an aryloxycarbonyl group (c3). The epoxy resin composition of any one of -7. The aromatic polyvalent carboxylic acid residue (c2) is represented by the following general formulas (c2-1), (c2-2) and (c2-3)

(In the formula, A, B, D, E and G are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and a, e and g are each Each independently represents an integer of 0 to 4, b and d are each independently an integer of 0 to 3, and X represents a single bond, —S—, —O—, —CO—, —CH ₂ —, —C ( CH ₃ ) ₂ — or —SO ₂ —.)
The epoxy resin composition according to claim 7, which is at least one group selected from the group consisting of: The epoxy resin composition according to claim 7, wherein the aromatic polycarboxylic acid residue (c2) is an isophthaloyl group or a terephthaloyl group. The aryloxycarbonyl group (c3) is represented by the following general formulas (c3-1), (c3-2) and (c3-3)

(Wherein J, Q, T, U and V are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, or a halogen atom; j and v Is an integer of 0 to 5, t and u are integers of 0 to 4, q is an integer of 0 to 3, Z is a single bond, —O—, —CO—, —CH ₂ —, -C _{(CH 3) 2} -, or -SO ₂ - and a).
The epoxy resin composition according to claim 7, which is at least one group selected from the group consisting of: The aryloxycarbonyl group (c3) is a group consisting of α-naphthyloxycarbonyl group, Β-naphthyloxycarbonyl group, biphenyl-2-oxycarbonyl group, biphenyl-4-oxycarbonyl group and p-cumyloxycarbonyl group. The epoxy resin composition according to claim 10, which is at least one group selected from the group consisting of: A laminate obtained by using the epoxy resin composition according to any one of claims 1 to 11.