JP6238845B2 - Phenol resin, phenol resin mixture, epoxy resin, epoxy resin composition and cured products thereof - Google Patents

Description

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

  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.

  However, in recent years, with the development in the electric / electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler) as well as high purity of resin composition, There is a need for further improvements in various properties such as increased reactivity to shorten the molding cycle. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment. Especially in the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), as the semiconductor transitions, it becomes increasingly complex with thinning, stacking, systematization, and three-dimensionalization. Required characteristics such as heat resistance and high fluidity are required. 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. In order to improve the heat resistance of the epoxy resin, it is effective to improve the functional group density, but on the other hand, improvement of the water absorption rate and the dielectric constant is harmful.

  Thus, there has been a demand for an epoxy resin having both heat resistance and various properties such as water absorption and dielectric constant. As an epoxy resin having good heat resistance, a reaction between acetone and resorcin has been attempted, and phenol resins and epoxy resins having a flavan structure and a spirochroman structure as shown in Non-Patent Document 3, Patent Document 1, and Patent Document 2 have been developed. It was. However, while the flavan structure described in Patent Document 1 shows high heat resistance, the functional group density is still high, and it has been difficult to achieve the above-mentioned various physical properties. In the spirochroman structure described in Patent Document 2, since only the monomer component is isolated and used, the rigidity of the cured network due to the bond of the mother skeleton is not exhibited, and the heat resistance still remains insufficient. Further, Patent Document 3 discloses an epoxy resin having a spirochroman structure, but uses only a monomer component, does not disclose an oligomer component and a mixture, and its performance is unknown.

“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 P. Livant et al. Org. Chem. 1997, Vol. 62, 737-742

JP 2010-275221 A JP 2002-193970 A Japanese Patent Laid-Open No. 10-60091

In general, it is known that epoxy resins have a trade-off relationship between heat resistance and various physical properties such as water absorption and dielectric constant. This is because the crosslink density is improved and the ring opening structure of the epoxy group is increased. The present invention provides a phenolic resin, an epoxy resin, an epoxy resin composition, and a cured product thereof, which satisfy both of these physical properties in a semiconductor peripheral material that requires heat resistance, low water absorption, and low dielectric constant. Let it be an issue.

（式中、Ｒ_１、Ｒ_２、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４はそれぞれ独立して存在し、Ｒ_１、Ｒ_２は水素原子、炭素数１〜６のアルキル基、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、または置換又は無置換のフェニル基を表し、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４は水素原子または有機基を表し、少なくとも１つはヒドロキシル基又はヒドロキシル基で置換された有機基を表す。Ｘ_１とＸ_２、Ｘ_３とＸ_４は互いに結合して環状構造を形成しても良い。ｋは１〜４を示す。）
で表される構造を骨格中に含有するフェノール樹脂。
（２）前項（１）記載のフェノール樹脂と下記式（２）

（式中、Ｒ_１、Ｒ_２は水素原子または炭素数１〜６のアルキル基、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、または置換又は無置換のフェニル基を表す。ｋは１〜４を示す。）で表されるフェノール化合物を含有するフェノール樹脂混合物。
（３）下記式（３）

（式（３）中、Ｒ_２は水素原子または炭素数１〜６のアルキル基、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、または置換又は無置換のフェニル基を表し、ｋは１〜４を示す。）、
と下記式（４）

（式（４）中、Ｒ_１は、水素原子または炭素数１〜６のアルキル基、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、または置換又は無置換のフェニル基を表す。）
を反応させてなる前項（１）〜（２）のいずれかに記載のフェノール樹脂又はフェノール樹脂混合物。
（４）水酸基当量が１２０〜５００ｇ／ｅｑ．である前項（１）〜（３）のいずれか一項に記載のフェノール樹脂又はフェノール樹脂混合物。
（５）前項（１）〜（４）のいずれか一項に記載のフェノール樹脂又はフェノール樹脂混合物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。
（６）前項（１）〜（４）のいずれか一項に記載のフェノール樹脂又はフェノール樹脂混合物と、エポキシ樹脂を含有するエポキシ樹脂組成物。
（７）前項（５）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。
（８）前項（６）または（７）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。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention relates to the following (1) to (7).
(1) The following formula (1)

(In the formula, R ₁ , R ₂ , X ₁ , X ₂ , X ₃ and X ₄ are each independently present, and R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, Represents a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amino group, or a substituted or unsubstituted phenyl group, X ₁ , X ₂ , X ₃ , X ₄ represent a hydrogen atom or an organic group, and at least one of Represents a hydroxyl group or an organic group substituted with a hydroxyl group, X ₁ and X ₂ , X ₃ and X ₄ may be bonded to each other to form a cyclic structure.
A phenolic resin containing a structure represented by
(2) The phenol resin described in the preceding item (1) and the following formula (2)

(Wherein R ₁ and R ₂ represent a hydrogen atom or an alkyl 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, or a substituted or unsubstituted phenyl group. K represents 1 to 4.) A phenol resin mixture containing a phenol compound represented by:
(3) Following formula (3)

(In Formula (3), R ₂ represents a hydrogen atom or an alkyl 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, or a substituted or unsubstituted phenyl group. K represents 1 to 4).
And the following formula (4)

(In Formula (4), R ₁ represents a hydrogen atom or an alkyl 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, or a substituted or unsubstituted phenyl group. Represents.)
The phenol resin or the phenol resin mixture according to any one of the above items (1) to (2), wherein
(4) The hydroxyl group equivalent is 120 to 500 g / eq. The phenol resin or the phenol resin mixture according to any one of (1) to (3) above.
(5) An epoxy resin obtained by reacting the phenol resin or the phenol resin mixture according to any one of (1) to (4) with an epihalohydrin.
(6) An epoxy resin composition containing the phenol resin or the phenol resin mixture according to any one of (1) to (4) and an epoxy resin.
(7) An epoxy resin composition comprising the epoxy resin according to (5) above and a curing agent and / or a curing accelerator.
(8) A cured product obtained by curing the epoxy resin composition according to any one of (6) or (7).

  The phenol resin and epoxy resin of the present invention are a novel phenol resin and epoxy resin having a spirochroman oligomer structure. By obtaining such a phenol resin or epoxy resin, it is possible to obtain a resin having both heat resistance and conflicting characteristics such as low water absorption and low dielectric constant. Furthermore, the phenol resin and the epoxy resin of the present invention have high adhesion.

（式（３）中、Ｒ_２は水素原子または炭素数１〜６のアルキル基、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、または置換又は無置換のフェニル基を表し、ｋは１〜４を示す。）
で表される化合物である。
ジヒドロキシベンゼン類（a）の具体例としては、カテコール、３−メチルカテコール、４−ｔｅｒｔ−ブチルカテコール、３，５−Ｄｉ−ｔｅｒｔ−ブチルカテコール、レゾルシン、２−メチルレゾルシン、５−メチルレゾルシン、２，５−ジメチルレゾルシン、４−ブチルレゾルシン、４−ヘキシルレゾルシン、ハイドロキノン、２−メチルハイドロキノン、２，６−ジメチルハイドロキノン、２，３−ジメチルハイドロキノン、２，３，５−トリメチルハイドロキノン、２−ｔｅｒｔ−ブチルハイドロキノン、２，５−Ｄｉ−ｔｅｒｔ−ブチルハイドロキノンなどが例示されるが、これらには限定されない。カテコール、レゾルシン、ハイドロキノンが好ましく、レゾルシンが特に好ましい。ここで、式（１）においてオリゴマー構造を得るために、レゾルシンを特に好適に使用することができる。 The phenol resin represented by the general formula (1) of the present invention (hereinafter referred to as “the phenol resin of the present invention”) can be obtained by reacting dihydroxybenzenes (a) and carbonyls (b). .
First, dihydroxybenzenes (a) will be described. Dihydroxybenzenes (a) are represented by the following formula (3)

(In Formula (3), R ₂ represents a hydrogen atom or an alkyl 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, or a substituted or unsubstituted phenyl group. , K represents 1 to 4.)
It is a compound represented by these.
Specific examples of the dihydroxybenzenes (a) include catechol, 3-methylcatechol, 4-tert-butylcatechol, 3,5-Di-tert-butylcatechol, resorcin, 2-methylresorcin, 5-methylresorcin, 2 , 5-dimethylresorcin, 4-butylresorcin, 4-hexylresorcin, hydroquinone, 2-methylhydroquinone, 2,6-dimethylhydroquinone, 2,3-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, 2-tert- Examples include but are not limited to butyl hydroquinone and 2,5-Di-tert-butyl hydroquinone. Catechol, resorcin and hydroquinone are preferred, and resorcin is particularly preferred. Here, in order to obtain the oligomer structure in the formula (1), resorcin can be particularly preferably used.

（式（４）中、Ｒ_１は、水素原子または炭素数１〜６のアルキル基、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、または置換又は無置換のフェニル基を表す。）
で表される化合物である。
このようなカルボニル類（ｂ）の具体例としては、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、４−ヒドロキシベンズアルデヒド、アセトン、メチルエチルケトン、メチルブチルケトン、３−メチル−２−ブタノン、メチルイソブチルケトン、３−ペンタノン、２−メチル−３−ペンタノン、２，４−ジメチル−３−ペンタノン、アセトフェノン、ベンゾフェノン、４，４′−ジヒドロキシベンゾフェノン等が例示されるが、これらに限定されない。アセトン、メチルエチルケトンが好ましく、アセトンが特に好ましい。 Next, carbonyls (b) will be described. As the carbonyls (b), the following formula (4)

(In Formula (4), R ₁ represents a hydrogen atom or an alkyl 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, or a substituted or unsubstituted phenyl group. Represents.)
It is a compound represented by these.
Specific examples of such carbonyls (b) include formaldehyde, acetaldehyde, benzaldehyde, 4-hydroxybenzaldehyde, acetone, methyl ethyl ketone, methyl butyl ketone, 3-methyl-2-butanone, methyl isobutyl ketone, 3-pentanone, 2 -Methyl-3-pentanone, 2,4-dimethyl-3-pentanone, acetophenone, benzophenone, 4,4'-dihydroxybenzophenone and the like are exemplified, but not limited thereto. Acetone and methyl ethyl ketone are preferred, and acetone is particularly preferred.

The phenol resin of the present invention is obtained by a condensation reaction between one or more compounds represented by formula (3) and a compound represented by formula (4) under acidic conditions. The reaction can be carried out under basic conditions, but acidic conditions are preferred.
The compound represented by the formula (4) is usually used in an amount of 0.25 to 5.0 mol, preferably 0.3 to 2.5 mol, per 1 mol of the compound represented by the formula (3).

When the condensation reaction is carried out under acidic conditions, the acidic catalyst that can 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 normally with respect to 1 mol of compounds represented by Formula (3), 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. The solvent that can be used is not particularly limited as long as it does not have reactivity with the compound represented by the formula (4) such as carbonyls, but the compound represented by the formula (3) as a raw material can be easily used. It is preferable to use alcohols and aromatic hydrocarbons as the solvent in terms of dissolution in the solvent.
Specific examples of the solvent that can be used include alcohols such as methanol, ethanol, and isopropyl alcohol, aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, methyl ethyl ketone, and methyl isobutyl ketone, and toluene and xylene. Although aromatic hydrocarbon etc. are mentioned, it is not limited to these.
Although the usage-amount in particular when using a solvent is not restrict | limited, For example, 100-500 weight part can be used with respect to 1 mol of compounds represented by Formula (3).

  The reaction temperature is usually 10 to 150 ° C, preferably 30 to 130 ° C, particularly preferably 50 ° C to 100 ° C. The reaction time is usually 0.5 to 20 hours, but is not limited to this because the reactivity varies depending on the type of raw material compound.

  After completion of the reaction, the acid catalyst is neutralized with a base. 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, water washing may be performed under steam distillation or 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、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４はそれぞれ独立して存在し、Ｒ_１、Ｒ_２は水素原子または炭素数１〜６のアルキル基、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、またはこれらの置換基を有しても良いフェニル基を表し、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４は水素原子または有機基を表し、少なくとも１つはヒドロキシル基又はヒドロキシル基で置換された有機基を表す。Ｘ_１とＸ_２、Ｘ_３とＸ_４は互いに結合して環状構造を形成しても良い。ｋは１〜４を示す。）
で表される構造を骨格中に含有するフェノール樹脂となる。 The phenol resin of the present invention thus obtained has the following formula (1)

(In the formula, R ₁ , R ₂ , X ₁ , X ₂ , X ₃ and X ₄ are each independently present, and R ₁ and R ₂ are a hydrogen atom or an alkyl 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, or a phenyl group which may have these substituents is represented, and X ₁ , X ₂ , X ₃ and X ₄ represent a hydrogen atom or an organic group. , At least one represents a hydroxyl group or an organic group substituted with a hydroxyl group, X ₁ and X ₂ , X ₃ and X ₄ may combine with each other to form a cyclic structure. Show.)
It becomes the phenol resin which contains the structure represented by in the skeleton.

（式中、Ｒ_１、Ｒ_２、ｋは前述と同じ意味を表す。Ｐ_１、Ｐ_２、Ｐ_３、Ｐ_４は水素原子または炭素数１〜６のアルキル基、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、またはこれらの置換基を有しても良いフェニル基を表し、少なくとも１つ以上はヒドロキシル基を表し、ｎ、ｍは０以上の整数を表す。但し、ｎ＝ｍ＝０の場合を除く。）
下記式（６）、

（式中、Ａ、Ｂ、Ｒ_１、Ｒ_２、Ｐ_１、Ｐ_２、Ｐ_３、Ｐ_４、ｋは前述と同じ意味を表し、ｌ、ｎ、ｍは０以上の整数を表す。但し、ｎ＝ｍ＝０の場合を除く。）
下記式（７）、

（式中、Ａ、Ｂ、Ｒ_１、Ｒ_２、Ｐ_１、Ｐ_２、Ｐ_３、Ｐ_４、ｋは１〜４を示し、ｎ、ｍは０以上の整数を表す。但し、ｎ＝ｍ＝０の場合を除く。）
で表されるフェノール樹脂である。ただし、本発明の式（１）で表されるフェノール樹脂はこれらの具体例によって限定的に解釈されるべきものではない。 Specifically, the phenol resin represented by the formula (1) is represented by the following formula (5),

(Wherein R ₁ , R ₂ and k represent the same meaning as described above. P ₁ , P ₂ , P ₃ and P ₄ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a methoxy group, and ethoxy. Represents a group, a nitro group, a nitrile group, an amino group, or a phenyl group which may have these substituents, at least one represents a hydroxyl group, and n and m represent an integer of 0 or more. (Except when n = m = 0)
Following formula (6),

(In the formula, A, B, R ₁ , R ₂ , P ₁ , P ₂ , P ₃ , P ₄ , k represent the same meaning as described above, and l, n, m represent an integer of 0 or more, provided that (Except when n = m = 0)
Following formula (7),

(In the formula, A, B, R ₁ , R ₂ , P ₁ , P ₂ , P ₃ , P ₄ , k represent 1 to 4, n and m represent integers of 0 or more, provided that n = m. Except for = 0.)
It is the phenol resin represented by these. However, the phenol resin represented by the formula (1) of the present invention should not be construed as being limited by these specific examples.

（式中、Ｒ_１、Ｒ_２は水素原子または炭素数１〜６のアルキル基、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、またはこれらの置換基を有しても良いフェニル基を表し、ｋは１〜４を示す。）
で表される化合物が少なくとも一定量含有するフェノール樹脂混合物となる。式（２）で表される化合物の含有量は液体クロマトグラフィー（ＨＰＬＣ）の２７４ｎｍにおけるピーク面積において、通常１０〜９５面積％であり、好ましくは２０〜８０面積％、さらに好ましくは２５〜７０面積％である。式（２）で表される化合物の含有率が１０面積％より少ないとゲル化が懸念され、９５面積％より多いと耐熱性が劣る。 Further, the phenol resin of the present invention usually has the formula (2)

(In the formula, R ₁ and R ₂ may have a hydrogen atom or an alkyl 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, or a substituent thereof. Represents a good phenyl group, k represents 1-4.)
A phenol resin mixture containing at least a certain amount of the compound represented by The content of the compound represented by the formula (2) is usually 10 to 95 area%, preferably 20 to 80 area%, more preferably 25 to 70 area, in the peak area at 274 nm of liquid chromatography (HPLC). %. When the content of the compound represented by the formula (2) is less than 10% by area, gelation is a concern, and when it is more than 95% by area, the heat resistance is inferior.

The weight average molecular weight of the phenol resin or phenol resin mixture of the present invention (hereinafter referred to as “the phenol resin of the present invention”) is usually 300 to 2,000, preferably 320 to 1,500, more preferably 340 to 1, 000. The hydroxyl equivalent is usually 120 to 500 g / eq, preferably 130 to 400 g / eq, more preferably 140 to 300 g / eq. A softening point is 70-200 degreeC normally, Preferably it is 80-180 degreeC, More preferably, it is 100-160 degreeC.
The phenol resin of the present invention is useful as a raw material for resins such as cyanate resin and epoxy resin.

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 obtained by the above-mentioned method with epihalohydrin in a solvent and epoxidizing it. Here, a phenol compound other than the phenol resin of the present invention may be used in combination with the phenol resin of the present invention.
As the phenolic compound other than the phenolic resin of the present invention that can be used in combination, any phenolic compound that is usually used as a raw material for the epoxy resin can be used without particular limitation.
As the epoxy resin of the present invention, a cured product having an excellent melting point and high heat resistance can be obtained.

  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, but epichlorohydrin which is easily available industrially is preferable. The usage-amount of epihalohydrin is 2-20 mol normally with respect to 1 mol of hydroxyl groups, such as a phenol resin of this invention, Preferably it is 2-15 mol, Most preferably, it is 2-8 mol. Usually, an epoxy resin is obtained by a reaction in which a phenol compound and an epihalohydrin are added in the presence of an alkali metal oxide, and then the resulting 1,2-halohydrin ether group is opened to epoxidize. At this time, by using epihalohydrin in an amount significantly smaller than usual as described above, the molecular weight of the epoxy resin can be increased and the molecular weight distribution can be broadened. As a result, the resulting epoxy resin can be removed from the system as a resinous material having a relatively low softening point, and exhibits excellent solvent solubility.

  In addition, during the epoxidation, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane. Among these, alcohols are preferable, and the ionic reaction during epoxidation can be efficiently advanced depending on the polarity of the alcohol solvent, and an epoxy resin can be obtained with high purity. As the alcohol solvent that can be used, methanol, ethanol, and isopropyl alcohol are preferable. Among these, it is particularly preferable to use methanol from the viewpoint of compatibility with the epoxy resin.

  When using the said alcohol, the usage-amount is 2-50 mass% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 4-35 mass%. Moreover, when using an aprotic polar solvent, it is 5-100 mass% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 mass%.

Examples of the alkali metal hydroxide that can be used for the epoxidation reaction include sodium hydroxide, potassium hydroxide, and the like, and these may be used as they are, or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and separated from a mixture of water and epihalohydrin distilled continuously under reduced pressure or normal pressure. Alternatively, water may be removed and only the epihalohydrin is continuously returned to the reaction system. The amount of the alkali metal hydroxide used is usually 0.9 to 3.0 mol, preferably 1.0 to 2.5 mol, more preferably 1.0 to 1 mol of the hydroxyl group of the phenol resin of the present invention. It is -2.0 mol, Most preferably, it is 1.0-1.3 mol.
In addition, in the epoxidation reaction, by using flaky sodium hydroxide in particular, the amount of halogen contained in the epoxy resin obtained can be significantly reduced as compared with using sodium hydroxide as an aqueous solution. Further, the flaky sodium hydroxide is preferably added in portions in the reaction system. By performing divided addition, it is possible to prevent a rapid decrease in the reaction temperature, thereby preventing the formation of 1,3-halohydrin and halomethylene as impurities.

  In order to accelerate the epoxidation reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol resin of the present invention.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. 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.
After completion of the reaction, the reaction product is washed with water or without washing with water, and the epihalohydrin, the solvent and the like are removed from the reaction solution under heating and reduced pressure. In order to further reduce the amount of halogen contained in the obtained epoxy resin, the recovered epoxy resin of the present invention is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal such as sodium hydroxide or potassium hydroxide. The reaction can be carried out by adding an aqueous solution of hydroxide to ensure ring closure. In this case, the usage-amount of an alkali metal hydroxide is 0.01-0.3 mol normally with respect to 1 mol of hydroxyl groups, such as a phenol resin of this invention, Preferably it is 0.05-0.2 mol. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

After completion of the reaction, the produced salt is removed by filtration, washing with water, and the like, and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention. Moreover, when the epoxy resin of this invention precipitates as a crystal | crystallization, after melt | dissolving the salt produced | generated in a lot of water, you may collect the crystal | crystallization of the epoxy resin of this invention by filtration.
The epoxy resin of the present invention thus obtained has a structure in which the hydroxyl group contained in the phenol resin of the present invention represented by the formula (1) is glycidylated, but the phenol represented by the formula (2) A certain amount of the glycidylated compound may also be mixed. Here, in the obtained epoxy resin, the glycidylated product of the phenol compound represented by the formula (2) in the resin is usually 10 to 95% by area, preferably at a peak area at 274 nm of liquid chromatography (HPLC), preferably It contains 20 to 80 area%, more preferably 25 to 70 area%. When the content of the glycidylated product of the phenol compound of the present invention represented by the formula (2) is less than 10 area%, gelation is concerned, and when it is more than 95 area%, the heat resistance is inferior.

  The weight average molecular weight of the epoxy resin of the present invention is usually 300 to 2,000, preferably 320 to 1,500, and more preferably 340 to 1,000. The epoxy equivalent is usually 180 to 550 g / eq, preferably 190 to 450 g / eq, more preferably 200 to 350 g / eq. A softening point is 50-180 degreeC normally, Preferably it is 60-160 degreeC, More preferably, it is 70-150 degreeC.

  As described above, the total halogen content of the epoxy resin of the present invention obtained by using flaky sodium hydroxide is usually 1800 ppm or less, preferably 1600 ppm or less, more preferably 1300 ppm or less. If the total halogen content is too large, the cured product properties of the cured product will be adversely affected, and it will remain as uncrosslinked terminals, so the orientation of molecules in the molten state during curing will not progress and the cured product properties will deteriorate. Leads to.

  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 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, cinnamaldehyde, etc.) Of polycondensates with benzene, aromatic compounds such as xylene and formaldehyde Polycondensates of compounds and phenols, phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene and isoprene Etc.), polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.) Polycondensates, phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl etc.), phenols and aromatic bisalkoxymethyls Polycondensates with bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc., polycondensates of bisphenols and various aldehydes, and glycidyl ether epoxy resins obtained by glycidylation of alcohols, alicyclic An epoxy resin, a glycidylamine-based epoxy resin, a glycidyl ester-based 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). However, the curing agent that can be used in the present invention should not be limitedly interpreted by these specific examples.
(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 compounds Polyphenols (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) Phenolic resins obtained by condensation with xybenzaldehyde, 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 other curing agents are used in combination, the proportion of the phenolic resin 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. % Or more 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 amount of the total curing agent including 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 -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, such as, but not particularly specified, in particular an organic acid ion, a hydroxide ion.), Metal compounds such as tin octylate and the like.
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.

  The epoxy resin composition of the present invention may contain a curing accelerator. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, triethylenediamine, Tertiary amines such as triethanolamine and 1,8-diazabicyclo (5,4,0) undecene-7, organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine, metal compounds such as tin octylate, Tetrasubstituted phosphonium tetrasubstituted borates such as tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium ethyltriphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate and N Such as tetraphenyl boron salts such methylmorpholine tetraphenylborate and the like. 0.01-15 mass parts is used for a hardening accelerator as needed with respect to 100 mass parts of epoxy resins.

  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. A mixture containing other components such as inorganic fillers of 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 Glycol ethers such as ether, esters such as 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. The following materials, processing details, processing procedures, and the like can be changed as appropriate without departing from the spirit of the present invention. 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, a reflux condenser, and a stirrer, 253 parts of resorcin, 387 parts of toluene, and 113 parts of 98% sulfuric acid were added while purging with nitrogen, and the temperature was raised to 80 ° C. with stirring. In this, 134 parts of acetone was dripped over 1 hour, and reaction was continued for 3 hours with the same temperature. After completion of the reaction, the mixture was neutralized with 10% sodium hydroxide, and 500 parts of methyl isobutyl ketone was added to dissolve the resin. Subsequently, washing with water is carried out until the washing water becomes neutral, and 238 parts (P1) of the phenol resin of the present invention are obtained by distilling off methyl isobutyl ketone and the like from the resulting solution under reduced pressure using a rotary evaporator. It was. The obtained phenol resin has a hydroxyl group equivalent of 212 g / eq. The softening point was 108 ° C. and the weight average molecular weight was 586.

Example 2
To a flask equipped with a stirrer, a reflux condenser and a stirrer, 435 parts of resorcin, 664 parts of toluene, and 20 parts of phosphotungstic acid were added while purging with nitrogen, and the temperature was raised to 80 ° C. with stirring. When 229 parts of acetone was dropped into the reaction solution, the reaction solution generated intense heat. When the reaction was continued for 5 hours at the same temperature, white crystals were precipitated. Subsequently, Dean Stark was placed in the flask, and the temperature was raised to 120 ° C. while dehydrating by azeotropy. As a result, the white crystals dissolved and became uniform, and the reaction was continued for 10 hours in this state. After completion of the reaction, the mixture was neutralized with 0.2 parts of sodium dihydrogen phosphate and 2.5 parts of 30% sodium hydroxide, and further 500 parts of methyl isobutyl ketone was added to dissolve the resin. Subsequently, washing with water is carried out until the washing water becomes neutral, and 390 parts of the phenol resin (P2) of the present invention is obtained by distilling off methyl isobutyl ketone and the like from the resulting solution under reduced pressure using a rotary evaporator. It was. The obtained phenol resin P2 has a hydroxyl group equivalent of 190 g / eq. The softening point was 111 ° C. and the weight average molecular weight was 530.

Comparative Example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 300 parts of resorcin, 78 parts of acetone, and 0.3 part of paratoluenesulfonic acid, and reacted at 80 ° C. for 2 hours. Subsequently, 78 parts of acetone was added and reacted at 80 ° C. for 2 hours. Next, washing was performed with pure water until the washing water became neutral, and the distillate was removed from the obtained solution under reduced pressure using a rotary evaporator to obtain 228 parts of white crystalline phenol resin (P3). . The obtained phenol resin P3 has a melting point of 200 ° C. and a hydroxyl group equivalent of 118 g / eq. The weight average molecular weight was 509.

Example 3
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while 238 parts of the phenol resin (P1) of the present invention, 953 parts of epichlorohydrin (9.2 molar equivalents to phenol resin), methanol 62 Part was added and dissolved under stirring, and the temperature was raised to 70 to 75 ° C. Next, after 46.4 parts of flaky sodium hydroxide was added in portions over 90 minutes, the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, water was washed with 150 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, 570 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 14.9 parts of a 30% by weight aqueous sodium hydroxide solution and 6.8 parts of methanol were added and reacted for 1 hour, followed by washing with water until the washing water of the oil layer became neutral, and the resulting solution Then, 296 parts of the epoxy resin (E1) of the present invention was 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 276 g / eq. The ICI melt viscosity at a softening point of 71 ° C. and 150 ° C. was 0.15 Pa · s, and the weight average molecular weight was 594.

Comparative Example 2
To a flask equipped with a stirrer, reflux condenser, and stirrer, add 336 parts of phenolic resin (P3), 1082 parts of epichlorohydrin (4 molar equivalents to phenolic resin), and 70 parts of methanol while purging with nitrogen. It melt | dissolved under and heated up to 70-75 degreeC. Next, 121.1 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 75 ° C. for 75 minutes. After completion of the reaction, washing was performed, and excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. To the residue, 950 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 39.0 parts of a 30% by weight aqueous sodium hydroxide solution and 11.4 parts of methanol were added and reacted for 1 hour, followed by washing with water until the washing water of the oil layer became neutral, and the resulting solution Then, 466 parts of epoxy resin (E3) was 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 E3 is 207 g / eq. The ICI melt viscosity at a softening point of 79 ° C. and 150 ° C. was 0.57 Pa · s, and the weight average molecular weight was 1,375.

ＰＮ：フェノールノボラック（明和化成工業株式会社製 Ｈ−１）
ＯＣＮ：ｏ−クレゾールノボラック型エポキシ樹脂（日本化薬株式会社製 ＥＯＣＮ−１０２０−５５）
ＴＰＰ：トリフェニルホスフィン（純正化学株式会社製） Example 4, Comparative Examples 3, 4
Various components are blended in the proportions (parts) shown in Table 1, kneaded with a mixing roll, converted into a tablet, a resin molded product is prepared by transfer molding, and heated at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours. Hardened | cured material of the epoxy resin composition of invention and the resin composition for a comparison was obtained. The results of measuring the physical properties of these cured products under the following conditions are shown in Table 1.
・ TMA
TMA thermomechanical measuring device: TM-7000 manufactured by Vacuum Riko Co., Ltd.
Temperature increase rate: 2 ° C./min.
・ Peel strength Conforms to JISK-6911 ・ After boiling water-absorbing diameter 5 cm x 4 mm thick disc-shaped test piece for 24 hours under conditions of 100 ° C-immersion, 85 ° C-85%, 121 ° C-100% Weight increase rate (%)
・ Measured at 1 GHz in accordance with dielectric K6991

PN: Phenol novolak (M-1 Kasei Kogyo H-1)
OCN: o-cresol novolac type epoxy resin (EOCN-1020-55 manufactured by Nippon Kayaku Co., Ltd.)
TPP: Triphenylphosphine (manufactured by Junsei Chemical Co., Ltd.)

  As is apparent from the results in Table 1, the cured product of the present invention is superior in heat resistance, low water absorption, and low dielectric constant compared to the cured product using the epoxy resin currently used (Comparative Example 4). Can be confirmed. Moreover, it can confirm that the low water absorption and the low dielectric constant are further excellent compared with the hardened | cured material (comparative example 3) using the epoxy resin which has the same frame | skeleton.

The phenol resin of the present invention, such as an epoxy resin, an epoxy resin composition, and a cured product, are compatible with these physical properties in semiconductor peripheral materials that require heat resistance, low water absorption, and low dielectric constant. It is useful as a stopper or printed wiring board.

Claims (7)

Following formula (1)

(In the formula, R ₁ , R ₂ , X ₁ , X ₂ , X ₃ and X ₄ are each independently present, and R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, Represents a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amino group, or a substituted or unsubstituted phenyl group, X ₁ , X ₂ , X ₃ , X ₄ represent a hydrogen atom or an organic group, and at least one of A hydroxy group or an organic group substituted with a hydroxy group, X ₁ and X ₂ , X ₃ and X ₄ may combine with each other to form a cyclic structure; Phenolic resin containing the structure to be formed in the skeleton and the following formula (2)

(In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl 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, or a substituted or unsubstituted phenyl group. k shows 1-4.) The phenol resin mixture containing the phenol compound represented by this. (3) Following formula (3)

(In Formula (3), R ₂ represents a hydrogen atom or an alkyl 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, or a substituted or unsubstituted phenyl group. K represents 1 to 4).
And the following formula (4)

(In Formula (4), R ₁ represents a hydrogen atom or an alkyl 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, or a substituted or unsubstituted phenyl group. Represents.)
The phenol resin mixture according to claim 1 , which is obtained by reacting. Hydroxyl equivalent weight is 120-500 g / eq. The phenol resin mixture according to claim 1 or 2 , wherein The epoxy resin obtained by making an epihalohydrin react with the phenol resin mixture as described in any one of Claim 1 to Claim 3 . A phenolic resin mixture according to the phenolic resin or any one of claims 1及至claim 3 according to claim 1, epoxy resin compositions containing an epoxy resin. The epoxy resin composition containing the epoxy resin of Claim 4 , and a hardening | curing agent and / or a hardening accelerator. Hardened | cured material obtained by hardening | curing the epoxy resin composition of Claim 5 or Claim 6 .