JP2007297472A - Epoxy resin composition and cured product thereof - Google Patents

Abstract

で表されるメチロールアミノ基含有トリアジン骨格を分子構造内に有するフェノール樹脂であって、窒素原子含有率が５〜２６質量％であり、かつ、アミノメチロール当量が８０〜３５００ｇ／ｅｑであるフェノール樹脂（Ａ）、及び、エポキシ樹脂（Ｂ）を必須成分とする。
【選択図】 なし。
PROBLEM TO BE SOLVED: To provide an epoxy resin composition having excellent flame retardancy, moisture resistance and heat resistance, and a cured product thereof.
A triazine skeleton-containing phenol resin obtained by reacting phenol, melamine, and formaldehyde with a formalin further reacted with the following structural formula:

A phenol resin having a methylolamino group-containing triazine skeleton represented by the formula in a molecular structure, a nitrogen atom content of 5 to 26% by mass, and an aminomethylol equivalent of 80 to 3500 g / eq. (A) and an epoxy resin (B) are essential components.
[Selection figure] None.

Description

  The present invention relates to an epoxy resin composition that is excellent in flame retardancy, heat resistance, and moisture resistance of a cured product to be obtained, and that is suitable for materials for electronic and electrical parts.

  Epoxy resin compositions are suitable for use in semiconductor encapsulants, printed wiring boards, paints, casting materials, and the like because cured products with excellent heat resistance, adhesion, electrical insulation, and the like are obtained. . For example, in the printed wiring board field, materials using an epoxy resin composition are currently used in many printed wiring boards, and halogenated flame retardants such as brominated epoxy resins are blended to impart flame retardancy. Has been. However, in recent environmental and safety efforts, there is an increasing demand for the development of a new flame-retardant method that is friendly to the global environment and does not use halogen-based flame retardants that are likely to generate dioxins.

  As an epoxy resin composition that meets these requirements, a technology that dramatically improves the flame retardancy of a cured product by using a novolak type phenol resin containing a triazine ring in the molecule as a curing agent for the epoxy resin is known. (For example, refer to Patent Document 1).

  However, the novolak type phenol resin containing the triazine ring is excellent in flame retardancy, but has insufficient heat resistance and cannot exhibit high heat resistance corresponding to lead-free soldering. In other words, when using lead-free solder that has been widely used in recent years due to environmental pollution caused by lead elution from waste, the mounting temperature of semiconductor chips is higher than that of conventional lead-containing solder. When extremely high heat resistance capable of withstanding the mounting temperature is required, it has been extremely difficult to adjust a material having such high heat resistance in the above-described novolak type phenol resin containing a triazine ring.

  From such a viewpoint, a resol type phenol resin containing a triazine ring having a controlled molecular weight distribution is disclosed as a phenol resin type epoxy resin curing agent having both flame retardancy and heat resistance (for example, Patent Document 2). reference.). However, such a resol type phenolic resin has poor solubility in an organic solvent, and the presence of an aqueous solvent such as water or methanol is essential. However, the resol type phenolic resin contains a triazine ring as described above. Since the novolak type phenol resin is inferior in moisture resistance, there is a problem that the cured product is easily hydrolyzed by using an aqueous solvent. Furthermore, in the technical field of advanced printed wiring boards, high moisture resistance and solder resistance are required, and the problem of moisture resistance is extremely serious in this respect.

  Therefore, the present condition is that the material which has a good balance of a flame retardance, heat resistance, and moisture resistance as a resin material used for the electrical / electronic component field | area, especially the advanced printed wiring board field | area was not obtained.

JP 2001-226464 A JP 2004-59701 A

  The problem to be solved by the present invention is to provide an epoxy resin composition having excellent flame retardancy, moisture resistance and heat resistance in a cured product, and a cured product thereof.

  As a result of intensive studies to solve the above problems, the present inventors have adjusted the nitrogen atom content in a phenol resin having a triazine ring and introduced a predetermined amount of a methylolamino group into the triazine ring. In addition to the flame retardancy of the cured product, the present inventors have found that heat resistance and moisture resistance are drastically improved and have completed the present invention.

  That is, the present invention is a phenol resin having a methylolamino group-containing triazine skeleton in the molecular structure, the nitrogen atom content is 5 to 26% by mass, and the aminomethylol equivalent is 80 to 3500 g / eq. The present invention relates to an epoxy resin composition comprising a phenol resin (A) and an epoxy resin (B) as essential components.

  Furthermore, the present invention relates to a cured product obtained by curing the epoxy resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition which combined the flame retardance excellent in cured | curing material, moisture resistance, and heat resistance, and its hardened | cured material can be provided.

  Therefore, when the epoxy resin composition of the present invention is used in the field of electronic materials such as a resin composition for printed circuit boards, a resin composition for encapsulants for electronic parts, resist inks, conductive pastes, etc. In addition, it is extremely useful as a resin composition for high frequency and high speed computing. In addition, the obtained molded cured product satisfies the above-mentioned uses in moisture resistance, adhesion, and the like, and further high demands on adhesives, composite materials, and the like, and can respond to fields requiring high reliability.

  Hereinafter, the present invention will be described in detail.

  The phenol resin (A) used in the present invention is a phenol resin having a methylolamino group-containing triazine skeleton in the molecular structure. Specifically, the triazine has a molecular structure obtained by subjecting a phenol (x1), an amino group-containing triazine compound (x2), and an aldehyde (x3) to a condensation reaction, and the triazine It has a molecular structure in which a methylolamino group is bonded to the ring skeleton.

  The methylolamino group-containing triazine skeleton described above is a structure in which a methylolamino group is bonded to the triazine skeleton. For example, the following structural formula (1)

（式中、Ｒ^１は、アミノ基、アルキル基、フェニル基、ヒドロキシ基、ヒドロキシアルキル基、アルコキシ基、アルキルカルボニルオキシ基、アルキルオキシカルボニル基、酸基、ビニル基、シアノ基、ハロゲン原子のいずれかを表す。）
で表される構造、及び、下記構造式（２）

(In the formula, R ¹ represents any of an amino group, an alkyl group, a phenyl group, a hydroxy group, a hydroxyalkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, an acid group, a vinyl group, a cyano group, and a halogen atom. Represents.)
And the following structural formula (2)

で表される構造が挙げられる。

The structure represented by is mentioned.

  In the present invention, the structural moiety represented by the structural formula (1) or (2) is bonded to another triazine ring or a phenol structural moiety via a methylene group or an alkylidene group.

  And this invention is characterized by the nitrogen atom content rate being 5-26 mass% in the said phenol resin (A), and an aminomethylol equivalent being 80-3500 g / eq. That is, the phenol resin (A) is a phenol having a conventional triazine ring skeleton in the molecular structure by adjusting the nitrogen atom content to the above range and increasing the ratio of methylolamino groups bonded to the triazine ring skeleton. It has both excellent heat resistance and moisture resistance that cannot be expressed with resin. Here, the nitrogen atom content refers to the total mass of nitrogen atoms contained in the phenol resin (A) relative to the mass of the phenol resin (A), and the amino group content relative to the mass of the phenol resin (A). It can be calculated from the charged amount of the triazine compound (x2).

  Moreover, although the aminomethylol equivalent of the said phenol resin (A) is 80-3500 g / eq as above-mentioned, it is preferable that it is 100-1000 g / eq especially from the point of heat resistance and moisture resistance.

  The phenol resin (A) is specifically a resin structure obtained by condensation reaction of phenols (x1), amino group-containing triazine compounds (x2) and aldehydes (x3), specifically aldehydes. The amino group of the aminotriazine ring resulting from the amino group-containing triazine compound (x2) via the methylene group or alkylidene group resulting from the class (x3), or the aromatic nucleus of the phenol structure site resulting from the phenols (x1) The resin structure bonded to is a basic skeleton, and further has a structure in which a methylol group is bonded to an amino group resulting from the amino group-containing triazine compound (x2).

  In addition to the compound having the above resin structure, the phenol resin (A) is a condensate of phenols (x1) and aldehydes (x3), an amino group-containing triazine compound (x2) and aldehydes (x3). And a mixture containing an unreacted phenol (x1), an unreacted amino group-containing triazine compound (x2), and the like.

  Here, the phenol resin (A) preferably has a weight average molecular weight of 1,000 to 5,000 from the viewpoint of compatibility with an organic solvent when adjusting the varnish, fluidity of the varnish, and the like.

  As described above, the phenol resin (A) has a methylol amino group that has an essential methylolamino group bonded to the triazine ring skeleton. Usually, when a condensation reaction of a phenol (x1), an amino group-containing triazine compound (x2) and an aldehyde (x3) is carried out, it binds not only to such amino methylol but also to an aromatic nucleus having a phenol structure. Although so-called phenolic methylol may also be present, in the present invention, it is preferable that such phenolic methylol is as little as possible from the viewpoint of suppressing generation of volatile components during molding and obtaining a uniform cured product. Specifically, the ratio of the number of methylolamino groups to the total number of methylol groups present in the resin structure of the phenol resin (A) is 90% or more, particularly 95% or more. preferable. Furthermore, it is particularly preferable that the phenolic methylol is substantially undetectable.

  In the phenol resin (A), as described above, the phenols (x1) remaining unreacted may exist, but the content is 3 wt% in the phenol resin (A). % Or less is preferable. By making the content rate of phenols (x1) 3 weight% or less, the improvement effect of the heat resistance of the obtained hardened | cured material and moisture resistance becomes remarkable.

  The phenols (x1) are not particularly limited. For example, phenol; o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o- Alkylphenols such as isopropylphenol, m-propylphenol, p-propylphenol, p-sec-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol Halogenated phenols such as p-chlorophenol, o-bromophenol, m-bromophenol and p-bromophenol; mononaphthols such as α-naphthol and β-naphthol; divalent compounds such as resorcin, catechol and hydroquinone F Enols; bisphenols such as 2,2-bis (4′-hydroxyphenyl) propane, 1,1′-bis (dihydroxyphenyl) methane, 1,1′-bis (dihydroxynaphthyl) methane; biphenols, tetramethylbiphenol Biphenols such as hexamethylbiphenol; 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene , 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, naphthalenediols such as 2,7-dihydroxynaphthalene; and trivalent phenols such as trishydroxyphenylmethane. Kill.

  Among these, phenol, alkylphenols, mononaphthols, bisphenols, dihydric phenols, and naphthalenediols are preferable from the viewpoint of easy production of the phenol resin (A), and alkylphenols are particularly preferable for the phenol resin (A ) From the viewpoint of fluidity. In addition, the alkylphenol is an alkyl group having 1 to 4 carbon atoms in terms of fluidity of the phenol resin (A) and reactivity with the amino group-containing triazine compound (x2) and aldehydes (x3). From the viewpoint of superiority, o-cresol and m-cresol are particularly preferable.

  Next, the amino group-containing triazine compound (x2) is not particularly limited, but the following general formula (3)

(In the formula, R ¹ , R ² and R ³ are amino group, alkyl group, phenyl group, hydroxy group, hydroxyalkyl group, alkoxy group, alkylcarbonyloxy group, alkyloxycarbonyl group, acid group, vinyl group, cyano group. A group or a halogen atom, provided that at least one of R ¹ , R ² and R ³ is an amino group).

Specific examples of the compound represented by the general formula (1) include melamine; guanamine derivatives such as acetoguanamine, benzoguanamine, and guanamine benzoate.
Among these, guanamine derivatives such as melamine, acetoguanamine, benzoguanamine, and guanamine benzoate in which any two or three of R ¹ , R ² , and R ³ are amino groups are more preferable.

  The use of the amino group-containing triazine compound (x2) is not limited to one type, and two or more types can be used in combination.

  The aldehydes (x3) are compounds having one or more aldehyde groups in one molecule, and specific examples include formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde, and the like. Among these, formaldehyde is preferable from the viewpoint of excellent fluidity and curability of the resulting epoxy resin composition and heat resistance of the cured product.

  The phenol resin (A) having a triazine ring described in detail above can be industrially produced by the following production method.

  That is, the above-described phenols (x1), amino group-containing triazine compound (x2), and aldehydes (x3) are reacted in the absence of a catalyst or in the presence of a catalyst to obtain an aminotriazine skeleton-containing phenol resin (a1) (Step 1). Then, the phenol resin (A) having a methylolamino group-containing triazine skeleton in the molecular structure is obtained by reacting the aminotriazine skeleton-containing phenol resin (a1) with the aldehyde (x3) (Step 2). can get.

  In step 1, the phenols (x1) and aldehydes (x3) may be reacted first, and then the amino group-containing triazine compound (x2) may be added. Conversely, the amino group-containing triazine compound (x2) and the aldehydes may be added. The phenol (x1) may be added after reacting with (x3). Or you may make them react after mixing all the raw materials.

  In the present invention, it is preferable that the phenolic methylol group in the aminotriazine skeleton-containing phenol resin (a1) produced in Step 1 is reduced, and it is preferable that it is substantially absent. Therefore, the molar ratio of aldehydes (x3) to phenols (x1) is preferably in the range of aldehydes (x3) / phenols (x1) = 0.1 to 1.1. It is preferable that (x3) / phenols (x1) = 0.2 to 0.8.

  The molar ratio of the amino group-containing triazine compound (x2) to the phenols (x1) is such that the reaction system is uniform and the reaction product is uniform, and the crosslinking density of the resulting cured product is appropriate. From the viewpoint of excellent physical properties of the cured product, the amino group-containing triazine compound (x2) / phenols (x1) is preferably in the range of 0.05 to 1.50, particularly 0.10 to 0.50. It is preferable that it is the range.

  Moreover, although reaction of the process 1 can also be performed without a catalyst, you may use a catalyst suitably. Examples of the basic catalyst that can be used here include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, and barium hydroxide, and oxides thereof, ammonia, 1 to Tertiary amines, hexamethylenetetramine, sodium carbonate and the like can be mentioned. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and sulfonic acid, organic acids such as oxalic acid and acetic acid, Lewis acids, and zinc acetate. A divalent metal salt etc. are mentioned. When the epoxy resin composition of the present invention is used as a resin for electrical and electronic materials, it is not preferable that an inorganic substance such as a metal remains as a catalyst residue, so that basic catalysts include amines and acidic catalysts. Is preferably an organic acid, but most preferably a non-catalytic system. The reaction in step 1 is preferably performed under conditions where the pH in the reaction system is in the range of pH 3.0 to 9.0.

  Moreover, you may perform reaction in presence of various solvents from the surface of reaction control. If necessary, impurities such as salts may be removed by neutralization and washing with water, but it is not necessary to use no catalyst or amines as a catalyst.

  After completion of the reaction, unreacted aldehydes (x3), phenols (x1), solvent and the like are removed according to a conventional method such as atmospheric distillation or vacuum distillation. At this time, in order to obtain a resin composition substantially free of methylol groups, it is preferable to perform a heat treatment at 120 ° C. or higher. Further, if the temperature is 120 ° C. or higher, the methylol group can be extinguished by taking a sufficient time, but it is preferable to perform heat treatment at a higher temperature, preferably 150 ° C. or higher, for efficient elimination. At this time, it is preferable to distill together with heating according to a conventional method for obtaining a novolac resin at a high temperature. At this time, as described above, the monofunctional phenols are preferably 3% by weight or less.

Next, in step 2, the aminotriazine skeleton-containing phenol resin (a1) obtained in step 1 is reacted with the aldehydes (x3). At this time, a plurality of aminotriazine skeleton-containing phenol resins (a1) obtained in the same manner using different raw materials in Step 1 may be mixed and used for the reaction in Step 2.
The reaction ratio of each component in step 2 is such that the molar ratio [(a1) / (a2)] of the amino group and the aldehydes (a2) in the aminotriazine skeleton-containing phenol resin (a1) from the viewpoint of heat resistance. It is preferably in a range of 1/10 to 10/1, and [(a1) / (a2)] is 2/3 to 3 in terms of a good balance of heat resistance, moisture resistance and flame retardancy. A range of 7/1 is particularly preferable.

  The reaction in step 2 is preferably carried out in the presence of a reaction catalyst, and the reaction solvent that can be used here is, for example, methanol or ethanol from the viewpoint of good solvent solubility of the phenol resin (A). Alcohol solvents such as isopropyl alcohol and normal butanol, methylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether Examples include solvents having a boiling point of 160 ° C. or lower, such as alkylene glycol alkyl ether solvents such as tellurium, aromatic hydrocarbon solvents such as toluene and xylene, and non-alcoholic polar solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and dimethylformamide. It is done. These can be used alone or as a mixed solvent of two or more kinds, and can be appropriately selected and used according to the intended use of the phenol resin composition, heat curing conditions, and the like. Among these, normal butanol, methyl isobutyl ketone, and cyclohexanone are particularly preferable because water in the reaction system can be azeotropically dehydrated. For this reason, when it is used as a reaction solvent, it is not necessary to take out the reactant from the system after the reaction, and the production process is simplified.

  Various epoxy resins can be used as the epoxy resin (B) used in the epoxy resin composition of the present invention. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type Epoxy resins derived from divalent phenols such as epoxy resins, resorcinol type epoxy resins, hydroquinone type epoxy resins, catechol type epoxy resins, dihydroxynaphthalene type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, phenol Novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol Aralkyl epoxy resin, biphenyl aralkyl epoxy resin, naphthol novolac epoxy resin, naphthol aralkyl epoxy resin, naphthol-phenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde resin modified Examples thereof include epoxy resins derived from trivalent or higher phenols such as phenol resin-type epoxy resins and biphenyl-modified novolak-type epoxy resins, and epoxy resins modified with organophosphorus compounds. These epoxy resins (B) may be used alone or in combination of two or more.

  Furthermore, among these, in order to improve the flame retardancy, bisphenol F type epoxy resin, bisphenol S type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol aralkyl type epoxy Resin, biphenyl aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, biphenyl-modified novolac type epoxy resin, or organic phosphorus In order to improve the heat resistance of an epoxy resin modified with a compound, a phenol novolac epoxy resin, a cresol novolac epoxy resin, triphenyl Methane type epoxy resin, tetraphenyl ethane epoxy resin, it is particularly preferable to use a polyfunctional epoxy resin such as naphthol novolak type epoxy resin.

  In the epoxy resin composition of the present invention, the phenol resin (A), the epoxy resin (B), and the blending ratio are usually the phenolic hydroxyl group in the phenol resin (A) and the epoxy in the epoxy resin (B). The equivalent ratio with the group is preferably in the range where the former / the latter = 1/1 to 1/2.

  In the epoxy resin composition of the present invention, a curing accelerator can be appropriately used in order to rapidly advance the curing reaction between the phenol resin (A) and the epoxy resin (B). Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like.

  In addition, the epoxy resin composition of the present invention includes, as necessary, an inorganic filler, a thermosetting and thermoplastic resin used as a modifier, a flame retardant, a pigment, a silane coupling agent, a release agent, and the like. Various compounding agents may be added.

  Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and magnesium 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.

  Examples of the modifier include phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyether sulfone resin, polyphenylene ether resin, polyphenylene sulfide resin, polyester resin, polystyrene resin, and polyethylene terephthalate resin.

  Examples of the flame retardant imparting agent include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and inorganic flame retardant compounds. Specific examples thereof include halogen compounds such as tetrabromobisphenol A type epoxy resin and brominated phenol novolak type epoxy resin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, tri Phosphate esters such as phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, resorcin diphenyl phosphate, polyphosphorus Ammonium acid, polyphosphoric acid amide, red phosphorus, guanidine phosphate, dialkylhydroxymethylphospho Phosphorus atom-containing compounds such as condensed phosphoric acid ester compounds such as chromatography bets, nitrogen atom-containing compound such as melamine, aluminum hydroxide, magnesium hydroxide, zinc borate, and inorganic flame retardant compounds such as calcium borate. Of these, non-halogen-based or non-antimony-based flame retardants are preferable from the viewpoint of environment and safety. Moreover, as above-mentioned, since the epoxy resin composition of this invention expresses the flame-retardant performance in which the hardened | cured material itself of the said phenol resin (A) was excellent, the usage-amount of a flame-retarding agent may be small.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above-mentioned phenol resin (A) and epoxy resin (B) with other compounding agents blended as necessary. At this time, the viscosity may be adjusted by adding an organic solvent depending on the purpose of improving workability, the application, and the heat curing conditions. Examples of the organic solvent that can be used at this time include any of those listed as the reaction solvents described above. Furthermore, the organic solvent used at the time of reaction may be the same as or different from that used for viscosity adjustment, and is appropriately selected according to the use, heat curing conditions, etc. when using the epoxy resin composition of the present invention. It is preferable to select and use.

  Moreover, even if the method of adjusting viscosity is a method in which an organic solvent is added in advance to the phenol resin (A) or the epoxy resin (B), and both are mixed, the phenol resin (A) and the epoxy are mixed. After mixing resin (B) and the various compounding agents mix | blended as needed, the method of adding a solvent as viscosity adjustment and making it uniform may be sufficient.

  The epoxy resin composition of the present invention can be used for coating materials such as printed circuit board materials, electronic component sealing materials, conductive pastes, resin casting materials, adhesives, and insulating paints. Among these, since it is excellent in the dielectric properties of the resulting cured product, it is preferably used for a resin composition for printed circuit boards, a resin composition for encapsulants for electronic components, resist inks, conductive pastes, and moisture resistance. It is also suitable for adhesives because of its excellent resistance. Furthermore, you may use suitably for a composite material from the point of being highly functional. Moreover, it is preferable that the organic solvent used here is fully dehydrated beforehand.

  Specifically, the printed board material can be suitably used for a prepreg material, a copper-clad laminate material, and an interlayer insulating material for a build-up printed board.

In order to make the epoxy resin composition of the present invention into a resin composition for a prepreg of a printed circuit board material, it is preferably made into a resin composition for 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. In addition, it is preferable that the organic solvent used here is fully dehydrated beforehand.
In order to produce a prepreg from the varnish, the 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 depending on the solvent type used. The prepreg as a cured product can be obtained by heating at a high heating temperature, preferably 50 to 170 ° C. 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 copper-clad laminate from the epoxy resin composition of the present invention, the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately laminated, and a pressure of 1 to 10 MPa is applied under a pressure of 170 to A copper-clad laminate can be obtained by thermocompression bonding at 250 ° C. for 10 minutes to 3 hours.

  As a method for obtaining a build-up substrate from the epoxy resin composition of the present invention, for example, the curable resin composition appropriately blended with rubber, filler or the like is applied to a wiring substrate on which a circuit is formed by a spray coating method, a curtain coating method, etc. After applying using, harden. 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 a sealing material for the electronic component, it can be suitably used for a tape-shaped sealing material for a semiconductor chip, a potting type liquid sealing agent, an underfill resin, and a semiconductor interlayer insulating film.

  In order to adjust the epoxy resin composition of the present invention for a semiconductor encapsulating material, the phenol resin (A), the epoxy resin (B), other coupling agents blended as necessary, and a release agent. For example, after pre-mixing additives such as inorganic fillers, etc., the mixture is sufficiently mixed 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 material can be obtained, for example, by semi-curing the epoxy resin composition of the present invention on a substrate or a semiconductor element in advance and then heating the semiconductor element and the substrate in close contact with each other. And a so-called compression flow method of complete curing.

  When the epoxy resin composition of the present invention is used as a semiconductor interlayer insulating material, for example, an aluminum wiring on a silicon substrate is formed, and then the interlayer insulating film is applied and cured on the aluminum wiring by spin coating or the like. Can be formed. In this case, since the interlayer insulating material is in direct contact with the semiconductor, 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.

  When the epoxy resin composition of the present invention is used as a resist ink, a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst are blended, and further a pigment, talc, and filler are added to form a resist ink. A method of forming a resist ink cured product after coating on a printed circuit board by a screen printing method after preparing the composition for use.

  When the epoxy resin composition of the present invention is used as a conductive paste, for example, a method of dispersing fine conductive particles in the epoxy resin composition to form a composition for an anisotropic conductive film, which is liquid at room temperature Examples of the method include a paste resin composition for circuit connection and an anisotropic conductive adhesive.

  When using the epoxy resin composition of the present invention as a resin composition for an adhesive, for example, the aldehyde-modified phenol resin composition (A), the epoxy resin (B), and other curings blended as necessary. It can be obtained by uniformly mixing agents, resins, curing accelerators, solvents, additives, etc. using a mixing mixer etc. at room temperature or under heating, and after applying to various substrates, at room temperature or under heating The substrate can be adhered by leaving it to stand.

  In order to obtain a composite material from the epoxy resin composition of the present invention, a varnish was formed using an organic solvent in order to adjust the viscosity according to the application, the varnish was impregnated into a reinforcing substrate, and heated to obtain a prepreg. Thereafter, it is possible to include a method in which the direction of the fiber is changed little by little, the layers are laminated so as to have pseudo-isotropic properties, and then cured and cured by heating. 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. For example, the phenol resin (A), the epoxy resin (B), other curing agents blended as necessary, and various blending agents are uniformly mixed. Then, the method of heat-curing at room temperature or 80-200 degreeC can be mentioned. Moreover, it is preferable to employ | adopt suitably the hardening method according to the use to which the epoxy resin composition prepared according to the above-mentioned various uses.

  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.

The nitrogen atom content of the phenol resin (A) having a methylolamino group-containing triazine ring skeleton obtained in the following examples in the molecular structure is the amino group relative to the solid mass of the phenol resin solution finally obtained. It is calculated from the charged amount of the containing triazine compound (x2), and the amino methylol group equivalent is also calculated from the charged amount of each raw material.
Moreover, confirmation of the presence or absence of the phenolic methylol group, measurement of the amount of unreacted phenol monomer, and measurement of the weight average molecular weight (Mw) were performed as follows.
<Confirmation of the presence or absence of phenolic methylol groups>
The presence or absence of methylol groups present in the phenol resin (a1-1) obtained in Example 1 was measured using ¹³ C-NMR.
Apparatus: GSX270 proton made by JEOL Ltd .: 270 MHz, measurement solvent: heavy methanol or heavy acetone, heavy dimethyl sulfoxide, reference material: tetramethylsilane. In the obtained chart, it is in 60 to 70 ppm, and since amine methylol is observed in 70 to 80 ppm, it is clearly distinguished. This phenolic methylol group was used for determination using a peak that could be clearly distinguished from noise. The case where a peak was observed was “present”, and the case where a peak was not observed was “not present”.

<Measurement of the amount of unreacted phenol monomer>
Column: 30% Celite 545 carnauba wax 2 m × 3 mmΦ, column temperature: 170 ° C., inlet temperature: 230 ° C., detector: FID, carrier gas: N ₂ gas 1.0 kg / cm ² , measurement method: internal standard method Under the measurement conditions, the amount of monofunctional phenol in the aminotriazine skeleton-containing phenol resin (a1) was measured.

The presence or absence of unreacted formaldehyde in the phenol resin (A) obtained in the following synthesis example was determined as follows.
<Presence / absence of unreacted formaldehyde>
Column: 30% Celite 545 carnauba wax 2 m × 3 mmΦ, column temperature: 170 ° C., inlet temperature: 230 ° C., detector: FID, carrier gas: N ₂ gas 1.0 kg / cm ² , measurement method: internal standard method Under the measurement conditions, the amount of unreacted formaldehyde in the phenol resin (A) was measured. In the obtained chromatographic chart, the case where a peak of formaldehyde was observed was “present”, and the case where it was not recognized was “not present”.

<Measurement of weight average molecular weight (Mw)>
Using the polystyrene standard method, the weight average molecular weight (Mw) was measured in the following apparatus and measurement conditions.
Equipment: “HLC-8220GPC” manufactured by Tosoh Corporation
Column: G2000HXLx2, G3000HXL, G4000HXL7.8 mmφ × 300 mm,
Column temperature: 40 ° C
Detector: RI, carrier solvent: tetrahydrofuran, flow rate: 1.0 ml / min,

Example 1 (Step 1: Synthesis of aminotriazine skeleton-containing phenol resin (a1))
A reactor equipped with a condenser and an atmospheric pressure and vacuum distillation apparatus was charged with 940 parts of phenol, 188 parts of melamine, and 361 parts of 41.5% formalin, heated to 100 ° C., and allowed to react for 2 hours. Next, the temperature was raised to 135 ° C. during atmospheric distillation, and the reflux reaction was continued for 2 hours, and the temperature was raised to 180 ° C. again under atmospheric distillation, followed by distillation under reduced pressure at 180 ° C. to remove unreacted monomers, water, etc. Low boiling point components were removed to obtain 670 parts of a resin having a softening point of 136 ° C. The nitrogen atom content in this resin was 24.9% by mass. This phenol resin is referred to as “phenol resin (a1-1)”. The solid content in the obtained phenol resin did not contain methylol groups, the amount of unreacted phenol monomer was 0.9% by weight, and the hydroxyl group equivalent was 146 g / eq. The amino group equivalent is 151 g / eq. The weight average molecular weight was 1,100.

Example 2 (Step 2: Methylolation of amino group)
A reactor equipped with a condenser and a vacuum water distillation separation apparatus was charged with 151 parts of the phenol resin (a1-1) obtained in Example 1, 100 parts of cyclohexanone, and 87 parts of 41.5% formalin. After stirring for a period of time, the temperature was raised to 100 ° C. and decanter dehydration was performed under reduced pressure. After confirming the disappearance of unreacted formalin, the solution was cooled to room temperature, and this solution was adjusted to a non-volatile content of 60% with methyl ethyl ketone. 300 parts of a phenol resin solution having a group-containing triazine ring skeleton in the molecular structure was obtained. The nitrogen atom content in the solid content of this resin solution was 20.6% by mass, and the aminomethylol equivalent was 171 g / eq. Further, the phenolic methylol group of this resin solution was “none” and the unreacted formaldehyde was “none”. This resin solution is designated as “A-1”. (Formalin 1.2 equivalent product with respect to amino group equivalent)

Example 3 (Step 2: methylolation of amino group)
A reactor equipped with a condenser and a vacuum water distillation separation apparatus was charged with 151 parts of the phenol resin (a1-1) obtained in Synthesis Example 1, 100 parts of cyclohexanone, and 72 parts of 41.5% formalin. After stirring for a period of time, the temperature was raised to 100 ° C. and decanter dehydration was performed under reduced pressure. After confirming the disappearance of unreacted formalin, the solution was cooled to room temperature, and this solution was adjusted to a non-volatile content of 60% with methyl ethyl ketone. As a result, 292 parts of a phenol resin solution having a group-containing triazine ring skeleton in the molecular structure was obtained. The nitrogen atom content in the solid content of this resin solution was 21.1% by mass, and the aminomethylol equivalent was 199 g / eq.
The phenolic methylol group of this resin solution was “none” and the unreacted formaldehyde was “none”. This resin solution is designated as “A-2”. (Formalin 1.0 equivalent product with respect to amino group equivalent)

Example 4 (Step 2: methylolation of amino group)
In a reactor equipped with a condenser and a reduced-pressure water distillation separator, 151 parts of the phenol resin (a1-1) obtained in Synthesis Example 1, 100 parts of cyclohexanone, and 54 parts of 41.5% formalin were charged. After stirring for a period of time, the temperature was raised to 100 ° C. and decanter dehydration was performed under reduced pressure. After confirming the disappearance of unreacted formalin, the solution was cooled to room temperature, and this solution was adjusted to a non-volatile content of 60% with methyl ethyl ketone. As a result, 280 parts of a phenol resin solution having a group-containing triazine ring skeleton in the molecular structure was obtained. The nitrogen atom content in the solid content of the resin solution was 22.0% by mass, and the aminomethylol equivalent was 262 g / eq. Further, the phenolic methylol group of this resin solution was “none” and the unreacted formaldehyde was “none”. This resin solution is designated as “A-3”. (Formalin 0.75 equivalent product with respect to amino group equivalent)

Example 5 (Step 2: methylolation of amino group)
A reactor equipped with a condenser and a vacuum water distillation separation apparatus was charged with 151 parts of the phenol resin (a1-1) obtained in Example 1, 100 parts of cyclohexanone, and 36 parts of 41.5% formalin. After stirring for a period of time, the temperature was raised to 100 ° C. and decanter dehydration was performed under reduced pressure. After confirming the disappearance of unreacted formalin, the solution was cooled to room temperature, and this solution was adjusted to a non-volatile content of 60% with methyl ethyl ketone. As a result, 269 parts of a phenol resin solution having a group-containing triazine ring skeleton in the molecular structure was obtained. The nitrogen atom content in the solid content of this resin solution was 22.8% by mass, and the aminomethylol equivalent was 368 g / eq. Further, the phenolic methylol group of this resin solution was “none” and the unreacted formaldehyde was “none”. This resin solution is designated as “A-4”. (Formalin 0.5 equivalent product with respect to amino group equivalent)

Examples 6 to 9 and Comparative Example 1
A varnish was prepared by the following method according to the formulation shown in Table 1, and cured under the following conditions to produce a double-sided copper-clad laminate, and various evaluations were performed. The results are shown in Table 1.
[Adjustment of varnish]
The varnish is prepared by mixing the phenol resin solution of A-1 to A-4, or the phenol resin (a1-1) and the epoxy resin (B), and finally using an organic solvent, the nonvolatile content of the composition ( N.V.) was adjusted to 55%.
[Laminate production conditions]
Substrate: 180 μm; glass cloth “WEA 7628 H258” manufactured by Nitto Boseki Co., Ltd.
Number of plies: 8
Prepregation conditions: 160 ° C / 3 minutes
Copper foil: 35 μm; manufactured by Furukawa Circuit Kit Co., Ltd. Curing conditions: 170 ° C., 40 kg / cm ² for 1.0 hour
Thickness after molding: 1.6mm Resin content: 40%
[Physical property test conditions]
Molding state: After performing etching treatment and removing the copper foil, visual inspection was carried out, and those that were uniformly molded without defects, scumming, and mising were marked as ◯.

  Glass transition temperature: Measured by DMA method after removing copper foil by etching. Temperature rising speed 3 ° C / min.

  Moisture absorption: Using a pressure cooker tester, a test piece (25 mm × 50 mm) was held for 2 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.

Combustion test: After removing the copper foil by etching, a varnish was prepared by dispersing and adding 30% by weight of aluminum hydroxide to the solid content in the epoxy resin composition for the combustion test. In addition, a laminate was prepared. The test method conforms to the UL-94 vertical test.
Oven heat resistance: Using a thermostat with an air circulation device, test pieces (50 mm x 50 mm x 3 sheets) were treated for 1 hour under the conditions of 220 ° C, 240 ° C, 260 ° C, and the test piece side and end face were blistered and peeled off. A sample without blistering was blistered on one of the three test pieces, a sample with flaking occurred was marked with Δ, a blistering on two or more samples of three samples, and a sample with flaking was marked with ×.

  Resistance to solder float: Float a test piece (25 mm x 25 mm x 3 sheets) using a solder bath at 260 ° C, 280 ° C, and 288 ° C until blistering occurs on one side and end face of the test piece Was measured.

尚、表１中の各原料及び略号は以下の通りである。
「Ｎ−６７３−８０Ｍ」 ：クレゾールノボラック型エポキシ樹脂メチルエチルケトン溶液（大日本インキ化学工業株式会社製、商品名［ＥＰＩＣＬＯＮ Ｎ−６７３−８０Ｍ］、エポキシ当量２１１ｇ／ｅｑ．、不揮発分８０％）
「ＭＥＫ」 ：メチルエチルケトン。

In addition, each raw material and abbreviation in Table 1 are as follows.
“N-673-80M”: Cresol novolak-type epoxy resin methyl ethyl ketone solution (Dainippon Ink Chemical Co., Ltd., trade name [EPICLON N-673-80M], epoxy equivalent 211 g / eq., Nonvolatile content 80%)
“MEK”: methyl ethyl ketone.

Claims (8)

Phenol resin (A) having a methylolamino group-containing triazine ring skeleton in the molecular structure, having a nitrogen atom content of 5 to 26% by mass and an aminomethylol equivalent of 80 to 3500 g / eq And an epoxy resin (B) as an essential component. The phenol resin (A) is obtained by reacting the phenols (x1), the compound (x2) having a triazine ring with the aldehydes (x3) to obtain a condensate (a1), and then adding the aldehydes (a2) to the condensate. The epoxy resin composition according to claim 1, which is obtained by reacting The epoxy resin composition according to claim 2, wherein the compound (x2) having a triazine ring is one or more compounds selected from the group consisting of melamine, acetoguanamine and benzoguanamine. The epoxy resin composition according to claim 1, 2 or 3, wherein the phenol resin (A) has a ratio of the number of methylolamino groups to 90% or more with respect to the total number of methylol groups present in the resin structure. The said phenol resin (A) is a thing of the ratio from which the content rate of the monofunctional phenols which remain | survives in this phenol resin (A) will be 3 weight% or less, Any one of Claims 1-4. Epoxy resin composition. Molar ratio when reacting the aldehyde (a2) with the condensate (a1) obtained by reacting the phenol (x1), the compound (x2) having a triazine ring and the aldehyde (x3) [(a1) / The epoxy resin composition according to claim 2, wherein (a2)] is 1/10 to 10/1. The epoxy resin composition according to any one of claims 1 to 6, further comprising an organic solvent in addition to the phenol resin (A) and the epoxy resin (B). A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 7.