JP6414845B2 - Phenolic resin, epoxy resin, epoxy resin composition, and cured products thereof - Google Patents

Description

  The present invention relates to a phenol resin, an epoxy resin, an epoxy resin composition, and a cured product thereof suitable for electrical and electronic material applications requiring heat resistance.

  Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.

  In recent years, with the development in the electrical and electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler), molding, etc., as well as high purity of resin composition There is a need for further improvements in various characteristics such as increased reactivity to shorten the cycle. In addition, as a structural material, a lightweight material with excellent mechanical properties is required for aerospace materials and leisure / sports equipment applications. Especially in semiconductor sealing applications and substrates (substrate itself or its peripheral materials), the process of semiconductors has become increasingly complex with thinning, stacking, systematization, and three-dimensionalization. Required characteristics such as heat resistance and high fluidity are required (Non-Patent Document 1). In particular, with the expansion of plastic packages to in-vehicle applications, demands for improving heat resistance are becoming more severe. Specifically, heat resistance of 150 ° C. or higher has been required due to an increase in semiconductor driving temperature (Non-patent Document 2).

As an epoxy resin having good heat resistance, an epoxy resin having a dibenzoxanthene structure as shown in Non-Patent Document 3 has been developed. However, the epoxy resin has many steps in the synthesis process when obtaining a phenol compound as a raw material, and there is a problem of using harmful sodium dichromate. Furthermore, there is a problem that the cyclic skeleton may be cleaved during the synthesis.
In general, when the heat resistance of an epoxy resin is increased, the flame retardancy decreases. This is due to an increase in crosslink density. However, while high heat resistance is required for semiconductor peripheral materials that require flame retardancy, it is an urgent task to develop a resin having these contradictory characteristics.

“2008 STRJ Report Semiconductor Roadmap Technical Committee 2008 Report”, Chapter 8, p1-1, [online], March 2009, JEITA Japan Electronics and Information Technology Industries Association Semiconductor Technology Roadmap Specialist Association, [May 30, 2012 search], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm> Nobuyuki Takakura et al., Matsushita Electric Engineering Technical Report Car-related device technology High-temperature operation IC for vehicles, 74, Japan, May 31, 2001, pp. 35-40 Ebe Abe et al., Polymer Preprints, Vol. 37, no. 3, 773 pages

  Therefore, it is an object to provide a phenol resin and an epoxy resin having a benzoxanthene structure that can be expected to improve heat resistance and flame retardancy, and a production method that can be produced with high yield by a simple and safe process.

（式中、Ｒ_２はそれぞれ独立して存在し、水素原子または炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、ヒドロキシル基、メトキシ基、エトキシ基、ニトロ基、ニトリル基、アミノ基、置換または無置換のフェニル基、ナフチル基を表し、ｋは０〜４の整数を示す。）
［２］前項［１］に記載のフェノール樹脂にエピハロヒドリンを反応させて得られるエポキシ樹脂、
［３］前項［１］に記載のフェノール樹脂と、エポキシ樹脂及び／または硬化促進剤を含有するエポキシ樹脂組成物、
［４］前項［２］に記載のエポキシ樹脂と、硬化剤及び／または硬化促進剤を含有するエポキシ樹脂組成物、
［５］前項［３］または［４］のいずれか一項に記載のエポキシ樹脂組成物を硬化して得られる硬化物、
を提供するものである。 The present inventors have found that, in a phenol resin having a benzoxanthene structure, when a certain amount of a compound having a specific structure is contained, not only heat resistance but also flame retardancy is improved, and the present invention is completed. It was.
That is, the present invention relates to the following [1] to [5].
[1] A phenol resin obtained by reacting dihydroxynaphthalenes with ketones or aldehydes, wherein the content ratio of the phenol compound represented by the following general formula (1) is a gel permeation chromatography (GPC) area ratio And a phenol resin that is 35 area% or less with respect to the phenol resin,

(In the formula, each R ₂ is independently present, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, An amino group, a substituted or unsubstituted phenyl group, or a naphthyl group is represented, and k represents an integer of 0 to 4.)
[2] An epoxy resin obtained by reacting an epihalohydrin with the phenol resin described in [1] above,
[3] An epoxy resin composition containing the phenol resin according to [1] above and an epoxy resin and / or a curing accelerator,
[4] An epoxy resin composition comprising the epoxy resin according to [2] above, and a curing agent and / or a curing accelerator,
[5] A cured product obtained by curing the epoxy resin composition according to any one of [3] or [4],
Is to provide.

  The phenol resin and epoxy resin of the present invention are phenol resins containing a benzopyran structure, and are phenol resins or epoxy resins containing a specific amount of a specific structure. The epoxy resin composition using these can obtain a cured product having excellent heat resistance and flame retardancy. Therefore, it is useful for insulating materials for electrical and electronic parts, laminates (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, and the like.

（式中、Ｒ_２はそれぞれ独立して存在し、水素原子または炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、ヒドロキシル基、メトキシ基、エトキシ基、ニトロ基、ニトリル基、アミノ基、置換または無置換のフェニル基、ナフチル基を表し、ｋは０〜４の整数を示す。） Hereinafter, the phenol resin of the present invention will be described.
The phenol resin of the present invention can be obtained by reacting dihydroxynaphthalenes with ketones (b) or aldehydes (c). Dihydroxynaphthalene is a compound represented by the following general formula (2).

(In the formula, each R ₂ is independently present, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, An amino group, a substituted or unsubstituted phenyl group, or a naphthyl group is represented, and k represents an integer of 0 to 4.)

Specific examples of the dihydroxynaphthalene include 1,3-dihydroxynaphthalene, 1,4 dihydroxynaphthalene, 1,4-dihydroxy-5-alkyl-naphthalene, 1,4-dihydroxy-6-alkyl-naphthalene, 1,3- Preferred examples include dihydroxy-5-alkyl-naphthalene, 1,3-dihydroxy-6-alkyl-naphthalene, 1,3-dihydroxy-7-alkyl-naphthalene, 1,3-dihydroxy-8-alkyl-naphthalene, It is not limited to these. 1,3-dihydroxynaphthalene and 1,4 dihydroxynaphthalene are more preferable, and 1,4 dihydroxynaphthalene is particularly preferable.

（式中、Ｒ_１はそれぞれ独立して存在し、水素原子または炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、ヒドロキシル基、メトキシ基、エトキシ基、ニトロ基、ニトリル基、アミノ基、置換または無置換のフェニル基、ナフチル基を表す。） Ketones (b) and aldehydes (c) are compounds represented by the following general formula (3).

(In the formula, each R ₁ is independently present, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, Represents an amino group, a substituted or unsubstituted phenyl group, or a naphthyl group.)

Specific examples of the ketones (b) include acetone, cyclohexanone, bicyclohexanone, acetophenone, hydroxyacetophenone, furfural, methyl ethyl ketone, methyl isobutyl ketone, 3-methyl-butanone, 3-pentanone, 2-methyl-3-pentanone, 2 , 4-dimethyl-3-pentanone is preferred, and acetone, cyclohexanone, bicyclohexanone, acetophenone, hydroxyacetophenone, and furfural are more preferred, and acetone is particularly preferred.
Specific examples of the aldehydes (c) are preferably formaldehyde, hydroxybenzaldehyde, acetaldehyde, and benzaldehyde, more preferably formaldehyde and hydroxybenzaldehyde, and particularly preferably formaldehyde. Formaldehyde means a concept including synthetic equivalents of formaldehyde such as paraformaldehyde and formalin.

The phenol resin of the present invention is obtained by a condensation reaction between one or more compounds represented by the general formula (2) and one or more compounds represented by the general formula (3) under acidic conditions. In addition, although reaction can also be performed on basic conditions, the acidic condition is more preferable.
The compound represented by the general formula (3) is usually used in an amount of 0.25 to 5.0 moles, preferably 0.3 to 2.5 moles per 1 mole of the compound represented by the general formula (2). Use moles.

When the condensation reaction is performed under acidic conditions, the acidic catalyst to be used is not particularly limited, and examples thereof include organic acid catalysts such as toluenesulfonic acid, xylenesulfonic acid and oxalic acid, and inorganic acid catalysts such as hydrochloric acid and sulfuric acid. These may be used alone or in combination of a plurality of types. The usage-amount of an acidic catalyst is 0.001-15 mol with respect to 1 mol of compounds represented by the said General formula (2), Preferably it is 0.002-10 mol.
The condensation reaction can be performed in the same manner under basic conditions, and the basic catalyst used is not particularly limited as long as it is a known one.

In the reaction for obtaining the phenol resin of the present invention, a solvent may be used as necessary. Although there is no restriction | limiting in particular as a solvent which can be used, It is preferable to use alcohol and ketones as a solvent at the point which dissolves the compound represented with the said General formula (2) of a raw material easily.
Specific examples of the solvent that can be used include alcohols such as methanol, ethanol, isopropyl alcohol, and propylene glycol monomethyl acetate, aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, methyl ethyl ketone, and methyl isobutyl ketone. Aromatic hydrocarbons such as toluene, xylene, mesitylene and the like are preferably exemplified, but are not limited thereto, and may be used alone or in combination of two or more.
The amount used in the case of using a solvent is not particularly limited. For example, it is usually 5 to 500 parts by weight, preferably 10 to 400 parts by weight per 1 mol of the compound represented by the general formula (2). .

  The reaction temperature is usually 10 to 150 ° C, preferably 40 to 140 ° C. Although reaction time is 0.5 to 20 hours normally, since there is a difference in reactivity with the kind of raw material, it is not this limitation. Further, it is preferable to remove water by-produced by the reaction by azeotropic distillation or the like in order to complete the reaction.

  After completion of the reaction, the acid catalyst is neutralized with a base as necessary. Although it does not specifically limit as a base, Sodium hydroxide, sodium carbonate, trisodium phosphate 5 sodium, ammonia etc. are illustrated. At this time, in order to uniformly disperse the base, it is preferable to gradually drop it as an aqueous solution.

When taking out as a resin after completion | finish of reaction, an unreacted substance, a solvent, etc. are removed from a reaction liquid under heating and pressure reduction, after washing | cleaning a reaction substance without water washing. In order to efficiently remove unreacted substances, washing with water may be performed under basic conditions. When taking out with a crystal | crystallization, a crystal | crystallization is deposited by dripping a reaction liquid in a lot of water.

（式中、Ｒ_１、Ｒ_２、ｋは前記式（２）のＲ_２、ｋと、式（３）のＲ_１と同じ意味を表す。） The phenol resin (A) of the present invention thus obtained contains a phenol resin represented by the following general formula (4).

(In the formula, R ₁ , R ₂ and k represent the same meaning as R ₂ and k in the formula (2) and R _{1 in the} formula (3).)

R ₁ and R ₂ in the general formula (4) are preferably an alkyl group having 1 to 6 carbon atoms, and are preferably a substituted or unsubstituted phenyl group or naphthyl group because of excellent heat resistance. K is preferably 0 to 2.

（式中、Ｒ_２はそれぞれ独立して存在し、水素原子または炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、ヒドロキシル基、メトキシ基、エトキシ基、ニトロ基、ニトリル基、アミノ基、置換または無置換のフェニル基、ナフチル基を表し、ｋは０〜４の整数を示す。） Moreover, the phenol resin of this invention contains the phenol compound represented by following General formula (1).

(In the formula, each R ₂ is independently present, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, An amino group, a substituted or unsubstituted phenyl group, or a naphthyl group is represented, and k represents an integer of 0 to 4.)

In the phenol resin of the present invention, the content ratio of the phenol compound represented by the general formula (1) is a gel permeation chromatography (GPC) area ratio (each peak detected in a chromatogram obtained by GPC analysis). The area ratio is preferably 35 area% or less, more preferably 30 area% or less, and particularly preferably 25 area% or less with respect to the obtained phenol resin (A). When the content of the phenol compound represented by the general formula (1) is 35% by area or more, the flame retardancy of the obtained resin is lowered, which is not preferable.

The phenolic resin of the present invention has a hydroxyl group equivalent of 125 to 450 g / eq. Is more preferable, and 150-400 is more preferable. Further, the softening point of the phenol resin of the present invention is preferably 50 to 300 ° C, more preferably 80 to 250 ° C.

  The phenol resin of the present invention can be used as it is as a thermoplastic (or its raw material), or as an epoxy resin raw material and its curing agent as described later.

  Next, the epoxy resin of this invention is demonstrated. The epoxy resin of the present invention can be obtained by reacting the phenol resin of the present invention with epihalohydrin. Although it does not specifically limit as a method of reaction, An example of the synthesis | combining method of the epoxy resin of this invention is described below.

（式中、Ｒ_１、Ｒ_２、ｋは前記一般式（１）に記載のＲ_１、Ｒ_２、ｋと同じ意味を表す。）
で示される構造であることを特徴とするエポキシ樹脂であって、下記一般式（６）

（式中、Ｒ_２はそれぞれ独立して存在し、水素原子または炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、ヒドロキシル基、メトキシ基、エトキシ基、ニトロ基、ニトリル基、アミノ基、置換または無置換のフェニル基、ナフチル基を表し、ｋは０〜４の整数を示す。）
で表されるエポキシ樹脂を含有するエポキシ樹脂である。 As a specific structural formula of the epoxy resin of the present invention, the following general formula (5)

_{(Wherein, R 1,} R _2, k has the same meaning as _{R 1, R 2,} k according to the general formula (1).)
An epoxy resin having a structure represented by the following general formula (6)

(In the formula, each R ₂ is independently present, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, An amino group, a substituted or unsubstituted phenyl group, or a naphthyl group is represented, and k represents an integer of 0 to 4.)
It is an epoxy resin containing the epoxy resin represented by these.

The cured product using the epoxy resin of the present invention has both high heat resistance and flame retardancy. R ₁ and R ₂ are more preferably an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, and a naphthyl group.

The epoxy equivalent of the epoxy resin of the present invention is 150 to 500 g / eq. It is preferable that it is 200-400 g / eq. It is particularly preferred that When the epoxy equivalent is in the above range, an epoxy resin excellent in heat resistance, electrical reliability and water absorption of the cured product can be obtained. Epoxy equivalent is 500 g / eq. In the case of exceeding the range, the epoxy ring is not completely closed, and it is expected that many compounds having no functional group are contained. In addition, many of these compounds that could not be ring-closed often contain chlorine, and as an electronic material application, there is concern about the release of chlorine ions under high-temperature and high-humidity conditions and the resulting corrosion of wiring. Absent.

The total chlorine remaining in the epoxy resin is preferably 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 2000 ppm or less.
The adverse effect of the chlorine amount is the same as described above. In addition, about chlorine ion and sodium ion, 5 ppm or less is preferable respectively, More preferably, it is 3 ppm or less. As described above, cation such as sodium ion is also a very important factor for chlorine ion, particularly in power device applications, and may contribute to a defective mode when a high voltage is applied.

  The epoxy resin of the present invention has a resinous form having a softening point. Here, as a softening point, 55-250 degreeC is preferable and it is especially preferable that it is 60-200 degreeC. If the softening point is too low, blocking during storage may become a problem, and there is a risk that it must be handled at a low temperature. On the other hand, if the softening point is too high, problems such as poor handling may occur during kneading with other resins.

The epoxy resin of the present invention is obtained by reacting the phenol resin of the present invention with epihalohydrin in a solvent and epoxidizing it. Here, a phenol compound other than the phenol resin may be used in combination with the phenol resin. As a phenol compound other than the phenol resin that can be used in combination, any phenol compound that is usually used as a raw material of an epoxy resin can be used without particular limitation.

In the reaction for obtaining the epoxy resin of the present invention, epichlorohydrin, α-methylepichlorohydrin, β-methylepichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin, and epichlorohydrin which is easily available industrially is preferable. The usage-amount of epihalohydrin is 1-20 mol normally with respect to 1 mol of hydroxyl groups of the phenol resin of this invention, Preferably it is 1.2-18 mol, More preferably, it is 1.5-15 mol, Most preferably 2 to 15 moles.
If the amount is less than 1 mol, the epoxy equivalent may be increased, and the workability of the resulting epoxy resin is likely to be poor, which is not preferable. If the amount exceeds 20 mol, the amount of solvent is large, which is not industrially preferable. .

Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide and the like, and a solid substance may be used, or an aqueous solution thereof may be used. From the viewpoint of moisture, solubility, and handling, it is preferable to use a solid material molded into a flake shape.
The usage-amount of an alkali metal hydroxide is 0.90-3.0 mol normally with respect to 1 mol of hydroxyl groups of the phenol resin of this invention, Preferably it is 0.95-2.5 mol, More preferably, it is 0.99. It is -2.0 mol, Most preferably, it is 0.99-1.5 mol.

  In order to accelerate the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, based on 1 mol of the hydroxyl group of the phenol resin of the present invention.

In this reaction, it is preferable to use a nonpolar proton solvent (dimethyl sulfoxide, dioxane, dimethylimidazolidinone, etc.) or an alcohol having 1 to 5 carbon atoms in addition to the epihalohydrin. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol. The usage-amount of a nonpolar protic solvent or a C1-C5 alcohol is 2-50 weight% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 4-25 weight%. Moreover, epoxidation may be performed while controlling the moisture in the system by a technique such as azeotropic dehydration.
When the amount of moisture in the system is large, it is not preferable because the electrical reliability of the obtained epoxy resin is deteriorated, and it is preferable to synthesize by controlling the moisture to 5% or less. Moreover, when an epoxy resin is obtained using a nonpolar proton solvent, an epoxy resin excellent in electrical reliability can be obtained, and therefore a nonpolar proton solvent can be suitably used.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. Especially, when an alcohol solvent is used, 50 to 90 ° C is preferable, 60 to 85 ° C is more preferable, and 70 to 80 ° C is particularly preferable. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is short, the reaction does not proceed, and if the reaction time is long, a by-product is formed, which is not preferable.
After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is a solvent containing a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). It can also be dissolved, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added to react to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the phenol resin of the present invention used for epoxidation. . The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  In the reaction with epihalohydrin, it is preferably substituted with an inert gas such as nitrogen from the beginning of the reaction, and the oxygen concentration in the cavity is preferably 10% or less. Oxygen residue affects coloration. As a method, an inert gas such as nitrogen is blown in the atmosphere (in the air or in the liquid) before the phenol resin of the present invention is charged, or after being evacuated under reduced pressure, the inert gas is replaced. If there is no substitution with an inert gas, the resulting resin may be colored. When the inert gas is blown, the amount varies depending on the volume of the kettle, but it is preferable to blow the inert gas in an amount that can replace 1 to 3 times the volume of the kettle in 0.5 to 10 hours. .

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.

  Hereinafter, the epoxy resin composition of the present invention will be described. The epoxy resin composition of the present invention contains at least one of the epoxy resin of the present invention and the phenol resin of the present invention as an essential component.

  In the epoxy resin composition of the present invention, the epoxy resin of the present invention can be used alone or in combination with other epoxy resins.

Specific examples of other epoxy resins that can be used in combination include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, bisphenol I, etc.) and phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, Alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene and dihydroxynaphthalene) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde and cinnamaldehyde Etc.), aromatic compounds such as xylene and formal Polycondensates of hydrides and phenols, phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, Polymers with butadiene and isoprene), polycondensates with phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzene dimethanol and biphenyldi) Polycondensates with methanol, etc., polycondensates of phenols with aromatic dichloromethyls (such as α, α'-dichloroxylene and bischloromethylbiphenyl), phenols with aromatic bisalkoxy Polycondensates with cymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, and glycidyl ether epoxy resins obtained by glycidylation of alcohols, etc. A cyclic epoxy resin, a glycidylamine epoxy resin, a glycidyl ester epoxy resin, and the like can be mentioned, but the epoxy resin is not limited to these as long as it is a commonly used epoxy resin. These may be used alone or in combination of two or more.
When other epoxy resins are used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin component in the epoxy resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and 70% by mass. The above is more preferable, and 100% by mass (when no other epoxy resin is used in combination) is particularly preferable. However, when using the epoxy resin of this invention as a modifier of an epoxy resin composition, it adds in the ratio used as 1-30 mass% in all the epoxy resins.

Examples of the curing agent that can be used in the epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Specific examples of these other curing agents are shown in the following (a) to (e).
(A) Amine-based compounds diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, etc. (b) acid anhydride-based compounds phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride , Tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. (c) Amide compounds Dicyandiamide or linolenic acid dimer and ethylenediamine Polyamide resin, etc.

(D) Phenol compound polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 3,3 ′, 5, 5'-tetramethyl- (1,1'-biphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane and 1,1,2,2-tetrakis (4 -Hydroxyphenyl) ethane and the like; phenols (eg, phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene and dihydroxynaphthalene) and aldehydes (formaldehyde, acetaldehyde, benzaldehyde, p-hydro) Phenol resins obtained by condensation with benzaldehyde, o-hydroxybenzaldehyde, furfural, etc.), ketones (p-hydroxyacetophenone, o-hydroxyacetophenone, etc.), or dienes (dicyclopentadiene, tricyclopentadiene, etc.); Phenols and substituted biphenyls (such as 4,4′-bis (chloromethyl) -1,1′-biphenyl and 4,4′-bis (methoxymethyl) -1,1′-biphenyl), or substituted phenyls ( Phenol resins obtained by polycondensation with 1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, 1,4-bis (hydroxymethyl) benzene and the like; Or a modified product of the phenol resin; Lumpur A and halogenated phenols such as brominated phenol resin (e) Other imidazoles, BF ₃ ^- amine complex, guanidine derivatives

Among these other curing agents, active hydrogen such as amine compounds such as diaminodiphenylmethane, diaminodiphenylsulfone and naphthalenediamine, and condensates of catechol with aldehydes, ketones, dienes, substituted biphenyls or substituted phenyls. A curing agent having a structure in which groups are adjacent is preferable because it contributes to the arrangement of the epoxy resin.
Other curing agents may be used alone or in combination. When another curing agent is used in combination, the proportion of the phenolic compound of the present invention in the total curing agent component in the epoxy resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 70% by mass. The above is more preferable, and 100% by mass (when no other curing agent is used in combination) is particularly preferable.
In the epoxy resin composition of the present invention, the use amount of the total curing agent containing the phenol resin of the present invention is preferably 0.5 to 2.0 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins, 0.6 to 1.5 equivalents are particularly preferred.

If necessary, a curing accelerator may be added to the epoxy resin composition of the present invention. Specific examples of the curing accelerator include phosphines such as triphenylphosphine and bis (methoxyphenyl) phenylphosphine, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethylimidazole and 4-methylimidazole, Tertiary amines such as 2- (dimethylaminomethyl) phenol, trisdimethylaminomethylphenol, diazabicycloundecene, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc. Quaternary phosphonium salts such as quaternary ammonium salts, triphenylbenzyl phosphonium salts, triphenylethyl phosphonium salts, tetrabutyl phosphonium salts (the counter ions of quaternary salts are halogens) , Organic acid ions, hydroxide ions and the like are not particularly specified, but organic acid ions and hydroxide ions are particularly preferable.), Metal compounds such as tin octylate, etc. are exemplified.
The usage-amount of a hardening accelerator is 0.2-5.0 weight part normally per 100 weight part of epoxy resins, Preferably, it is 0.2-4.0 weight part.

The epoxy resin composition of the present invention can contain an inorganic filler as required.
If the inorganic filler which the epoxy resin composition of this invention contains is a well-known thing, there will be no restriction | limiting at all. Specific examples of the inorganic filler include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, alumina, and magnesium oxide, and fibers such as synthetic fibers and ceramic fibers. A filler, a coloring agent, etc. are mentioned. The shape of these inorganic fillers may be any of powder (lump shape, spherical shape), single fiber, long fiber and the like.
The usage-amount of the inorganic filler in the epoxy resin composition of this invention is 2-1000 mass parts normally with respect to 100 mass parts of resin components in an epoxy resin composition. These inorganic fillers may be used alone or in combination of two or more.

  If necessary, various compounding agents such as a silane coupling agent, a release agent and a pigment, various thermosetting resins, various thermoplastic resins, and the like can be added to the epoxy resin composition of the present invention. Specific examples of thermosetting resins and thermoplastic resins include vinyl ester resins, unsaturated polyester resins, maleimide resins, cyanate resins, isocyanate compounds, benzoxazine compounds, vinyl benzyl ether compounds, polybutadiene and its modified products, and acrylonitrile. Examples include modified polymers, indene resins, fluororesins, silicone resins, polyetherimides, polyethersulfones, polyphenylene ethers, polyacetals, polystyrenes, polyethylenes, and dicyclopentadiene resins. The thermosetting resin or thermoplastic resin is used in an amount occupying 60% by mass or less in the epoxy resin composition of the present invention.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components, and preferred applications thereof include semiconductor encapsulants and printed wiring boards.
The epoxy resin composition of the present invention can be easily made into a cured product by the same method as conventionally known. For example, an epoxy resin that is an essential component of the epoxy resin composition of the present invention, a curing agent, and, if necessary, a curing accelerator, a compounding agent, various thermosetting resins and various thermoplastic resins, an extruder, if necessary. The epoxy resin composition of the present invention obtained by sufficiently mixing until uniform using a kneader or a roll is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, etc. The cured product of the epoxy resin composition of the present invention can be obtained by heating at the melting point or higher for 2 to 10 hours. By sealing the semiconductor element mounted on the lead frame or the like by the above-described method, the epoxy resin composition of the present invention can be used for semiconductor sealing applications.

Moreover, the epoxy resin composition of this invention can also be made into the varnish containing a solvent. The varnish includes, for example, at least one of the epoxy resin of the present invention or the phenol resin of the present invention in at least one of an epoxy resin and a curing agent, and if necessary, has a thermal conductivity of 20 W / m · K or more. Mixtures containing other components such as inorganic fillers, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, N, N′-dimethylformamide, N, N′-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether Glycol ethers such as Tell, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, It can be obtained by mixing with a cyclic ester such as γ-butyrolactone, an organic solvent such as petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. The amount of the solvent is usually 10 to 95% by mass, preferably 15 to 85% by mass with respect to the whole varnish.
The varnish obtained as described above is impregnated into a fiber substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber and paper, and then the solvent is removed by heating, and the epoxy resin composition of the present invention By making a semi-cured state, the prepreg of the present invention can be obtained. Here, the “semi-cured state” means a state in which an epoxy group which is a reactive functional group partially remains unreacted. The prepreg can be hot press molded to obtain a cured product.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the synthesis examples, examples, and comparative examples, “part” means “part by mass”.
The hydroxyl group equivalent, epoxy equivalent, softening point, and ICI melt viscosity were measured under the following conditions.
-Hydroxyl equivalent: Measured by the method described in JIS K-7236, the unit is g / eq. It is.
-Epoxy equivalent Measured by the method described in JIS K-7236, the unit is g / eq. It is.
-Softening point It measures by the method based on JISK-7234, and a unit is (degreeC).
-ICI melt viscosity It measures by the method based on JISK7117-2, and a unit is Pa * s.

Example 1
To a flask equipped with a stirrer, reflux condenser, and stirrer, add 32 parts of dihydroxynaphthalene, 10 parts of acetone, 50 parts of methyl isobutyl ketone, and 3.8 parts of p-toluenesulfonic acid while purging with nitrogen. It melt | dissolved and it heated up to 100 degreeC. After heating and refluxing for 12 hours, washing with water is carried out until the washing water becomes neutral, and from the resulting solution, the methyl isobutyl ketone and the like are distilled off under reduced pressure using a rotary evaporator. -1) 24 parts were obtained. Among the obtained phenol resins, the content percentage of the phenol resin represented by the general formula (4) in GPC area% is 79 area%, and the content ratio of the phenol compound represented by the general formula (1) is 17 area%. Met.

(Example 2)
To a flask equipped with a stirrer, reflux condenser, and stirrer, add 150 parts of dihydroxynaphthalene, 54 parts of acetone, 234 parts of methyl isobutyl ketone, and 1.8 parts of p-toluenesulfonic acid while purging with nitrogen. After dissolving and heating to reflux at 70 ° C. for 3 hours and at 110 ° C. for 15 hours, washing with water until the washing water becomes neutral, and using a rotary evaporator, methyl isobutyl ketone and the like are removed from the resulting solution under reduced pressure. By distilling off, 129 parts of the phenolic resin (P-2) of the present invention was obtained. Among the obtained phenol resins, the content percentage of the phenol resin represented by the general formula (4) in terms of area% of GPC is 75 area%, and the content ratio of the phenol compound represented by the general formula (1) is 13 area%. Met.

(Example 3)
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, add 50 parts of dihydroxynaphthalene, 36 parts of acetone, 100 parts of methyl isobutyl ketone, and 0.6 parts of p-toluenesulfonic acid while purging with nitrogen. Dissolve and heat to reflux at 40 ° C. for 8 hours and 110 ° C. for 15 hours, and then wash with water until the washing water becomes neutral. From the resulting solution, use a rotary evaporator to remove methyl isobutyl ketone and the like under reduced pressure. By distilling off, 50 parts of the phenol resin (P-3) of the present invention was obtained. Among the obtained phenol resins, the content percentage of the phenol resin represented by the general formula (4) in area% of GPC is 65 area%, and the content ratio of the phenol compound represented by the general formula (1) is 28 area%. Met.

(Comparative Example 1)
To a flask equipped with a stirrer, reflux condenser, and stirrer, add 250 parts of dihydroxynaphthalene, 45 parts of acetone, 500 parts of methyl isobutyl ketone, and 5.9 parts of p-toluenesulfonic acid while purging with nitrogen. Dissolve and heat to reflux for 5 hours at room temperature and 15 hours at 110, then wash with water until the wash water becomes neutral, and remove methyl isobutyl ketone and the like from the resulting solution under reduced pressure using a rotary evaporator. As a result, 267 parts of phenol resin (P-4) was obtained. Among the obtained phenol resins, the content percentage of the phenol resin represented by the general formula (4) in GPC area% is 57 area%, and the content ratio of the phenol compound represented by the general formula (1) is 37 area%. Met.

Example 4
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 24 parts of the phenol resin (P-1) of the present invention, 93 parts of epichlorohydrin (7 molar equivalents to phenol resin), methanol 28 Part was added and dissolved under stirring, and the temperature was raised to 70 to 75 ° C. Next, 6.4 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, the reaction mixture was washed with 19 parts of water, and excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. 61 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 75 ° C. Under stirring, 2.3 parts of 30% by weight sodium hydroxide aqueous solution was added and reacted for 1 hour, followed by washing with water until the washing water of the oil layer became neutral. 28 parts of epoxy resin (EP-1) of this invention was obtained by distilling off methyl isobutyl ketone etc. under reduced pressure using the rotary evaporator. The epoxy equivalent of the obtained epoxy resin was 207 g / eq. The softening point was 135 ° C.

(Example 5)
129 parts of phenol resin (P-2) of the present invention, 314 parts of epichlorohydrin (5 molar equivalents to phenol resin), methanol 94 while purging nitrogen in a flask equipped with a stirrer, reflux condenser, and stirrer Part was added and dissolved under stirring, and the temperature was raised to 70 to 75 ° C. Next, 30 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, water was washed with 91 parts of water, and excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. To the residue, 317 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 11 parts of a 30% by weight aqueous sodium hydroxide solution was added and reacted for 1 hour, followed by washing with water until the washing water of the oil layer became neutral. 144 parts of epoxy resins (EP-2) of this invention were obtained by distilling off methyl isobutyl ketone etc. under reduced pressure using the rotary evaporator. The epoxy equivalent of the obtained epoxy resin was 239 g / eq. The softening point was 65 ° C.

(Example 6)
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 100 parts of the phenol resin (P-3) of the present invention, 434 parts of epichlorohydrin (7 molar equivalents to phenol resin), methanol 130 Part was added and dissolved under stirring, and the temperature was raised to 70 to 75 ° C. Next, 30 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, water was washed with 90 parts of water, and excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. To the residue, 261 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 10 parts of a 30% by weight aqueous sodium hydroxide solution was added and reacted for 1 hour, followed by washing with water until the washing water of the oil layer became neutral. 121 parts of epoxy resins (EP-3) of this invention were obtained by distilling off methyl isobutyl ketone etc. under pressure reduction using the rotary evaporator. The epoxy equivalent of the obtained epoxy resin is 227 g / eq. Met.

(Comparative Example 2)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, and 106 parts of phenol resin (P-4) for comparison, 362 parts of epichlorohydrin (7 molar equivalents to phenol resin), methanol 109 Part was added and dissolved under stirring, and the temperature was raised to 70 to 75 ° C. Next, 25 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, water was washed with 75 parts of water, and excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. To the residue, 261 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 9 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was performed for 1 hour, followed by washing with water until the washing water of the oil layer became neutral. 110 parts of epoxy resins (EP-4) for comparison were obtained by distilling off methyl isobutyl ketone and the like under reduced pressure using a rotary evaporator. The epoxy equivalent of the obtained epoxy resin is 256 g / eq. Met.

(Examples 7 to 9, Comparative Example 3)
The epoxy resins (EP-1, EP-2, EP-3, EP-4) obtained above were used as curing agents (P-5), fillers, waxes, coupling agents, and curing accelerators in the proportions shown in Table 1 ( Equivalent) and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer molded (175 ° C. × 60 seconds), and after demolding, was cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation. The test results are also shown in Table 1. The physical property values were measured by the following methods.
<Heat resistance test>
Glass transition temperature (DMA): Conforms to JIS K-7244 Dynamic viscoelasticity measuring instrument: DMA-2980, manufactured by TA-instruments
Measurement temperature range: -30 ° C to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm).
Analysis condition Tg: Tanδ peak point (tanδMAX) in DMA measurement was defined as Tg.
<Flame retardance test>
・ Flame retardancy: Conforms to UL94. The sample size was 12.5 mm wide × 150 mm long, and the thickness was 0.8 mm.
・ Afterflame time: Total afterflame time of 0.8mm test piece (cured product)

Ｐ−５：三井化学社製 ミレックスＸＬＣ−３Ｌ
Ｃ１：トリフェニルフォスフィン（北興化学株式会社製 ＴＰＰ）
溶融シリカ：瀧森工業社製 ＭＳＲ−２２１２
硬化促進剤使用量：1phr対エポキシ樹脂
エポキシ樹脂・硬化剤比率：１．０等当量

P-5: Millex XLC-3L manufactured by Mitsui Chemicals, Inc.
C1: Triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.)
Fused silica: MSR-2212 manufactured by Kashimori Kogyo Co., Ltd.
Curing accelerator usage: 1 phr to epoxy resin epoxy resin / curing agent ratio: 1.0 equivalent

It turns out that the epoxy resin of this invention can give the hardened | cured material which has high heat resistance.

Moreover, it turns out that a flame retardance level changes with content of the phenolic compound represented by the said General formula (1). Therefore, the hardened | cured material which made high heat resistance and high flame retardance compatible can be given by restraining content of the phenolic compound represented by the said General formula (1).

Claims (5)

A phenol resin obtained by reacting 1,4-dihydroxy-naphthalenyl emissions and ketones or aldehydes, the content is gel permeation chromatography of the phenol compound represented by the following general formula (1) (GPC) A phenol resin having an area ratio of 13 area% to 35 area% with respect to the phenol resin.

An epoxy resin obtained by reacting the phenol resin according to claim 1 with an epihalohydrin. The epoxy resin composition containing the phenol resin of Claim 1, and an epoxy resin and / or a hardening accelerator. An epoxy resin composition comprising the epoxy resin according to claim 2 and a curing agent and / or a curing accelerator. Hardened | cured material obtained by hardening | curing the epoxy resin composition as described in any one of Claim 3 to Claim 4.