JP2015212356A - Phenolic resin, epoxy resin, epoxy resin composition, and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenolic resin, an epoxy resin, and an epoxy resin composition making it possible to provide a cured product having excellent heat resistance, flame retardancy and water absorption properties.SOLUTION: A phenolic resin is obtained by a reaction between: a phenolic compound having a benzopyran structure represented by formula (2) obtained by a reaction between dihydroxynaphthalene and aldehyde or ketone; and at least one selected from aldehyde, ketone, and a ring-containing organic compound. (Rand Rindependently represent H, a C1-6 alkyl group, a C1-6 alkoxy group, 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; and k is an integer of 0-4.)

Description

  The present invention relates to a phenol resin, an epoxy resin, an epoxy resin composition, and a cured product thereof, which give a cured product suitable for electric and electronic materials that are required to have 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 composite material, a material that is lightweight and excellent in mechanical properties is required for aerospace materials, leisure / sports equipment applications, and the like. 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, the demand for improvement in heat resistance has become more severe, and it is necessary to respond to solder reflow with high heat resistance and low linear expansion resin. At the same time, it is required to reduce or maintain the water absorption rate.

Japanese Patent Application No. 2013-213868

“2008 STRJ Report Semiconductor Roadmap Special Committee 2008 Report”, Chapter 8, p1-17, [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>

One of the characteristics particularly required for high functionality is heat resistance. Although heat resistance has been regarded as important conventionally, problems such as poor water absorption properties and poor flame retardance generally arise when heat resistance is raised. In the field of semiconductor peripheral materials, not only high heat resistance but also flame retardancy is required, and therefore development of a resin having such contradictory characteristics has been an urgent task.
The present inventors have been developing a phenol resin and an epoxy resin having a benzoxanthene structure that can be expected to have such characteristics (see Patent Document 1), and for further improvement, a new one having a benzoxanthene structure. We have made extensive studies with the aim of providing phenolic resins and epoxy resins.

（式中、Ｒ_１、Ｒ_２、Ｒ_３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、置換又は無置換のフェニル基、ナフチル基を表し、ｋ、ｐは０〜４の整数を示し、ｎは０〜１０の整数を示す。Ｘは結合基を表す。）
［２］下記一般式（２）で表されるフェノール化合物と下記一般式（３）で表される化合物との反応により得られる前項［１］に記載のフェノール樹脂、

（式中、Ｒ_１、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、置換又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。）

（式中、Ｒ_３は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、置換又は無置換のフェニル基、ナフチル基を表し、ｐは０〜４の整数を示す。）
［３］ジヒドロキシナフタレン類とケトン類と上記一般式（３）で表される化合物を反応させることにより得られる前項［１］または［２］に記載のフェノール樹脂、
［４］ジヒドロキシナフタレン類とアルデヒド類と上記一般式（３）で表される化合物を反応させることにより得られる前項［１］または［２］に記載のフェノール樹脂、
［５］前項［１］〜［４］のいずれか一項に記載のフェノール樹脂とエピハロヒドリンとの反応により得られるエポキシ樹脂、
［６］前記［１］〜［４］のいずれか一項に記載のフェノール樹脂を少なくとも１種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、
を、提供するものである。 In general, it is considered that an increase in the crosslink density is one of the factors that lower the flame resistance, water absorption, and dielectric properties when the heat resistance of the epoxy resin is improved. Therefore, the present inventors have found a new phenol resin and epoxy resin having a benzoxanthene structure and having the above characteristics without increasing the crosslinking density based on such knowledge, and have completed the present invention. . That is, the present invention
[1] A phenol resin represented by the following general formula (1):

(In the formula, R ₁ , R ₂ and R ₃ are each 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, and a naphthyl group are represented, k and p represent an integer of 0 to 4, n represents an integer of 0 to 10. X represents a bonding group. .)
[2] The phenol resin according to [1] above, obtained by a reaction between a phenol compound represented by the following general formula (2) and a compound represented by the following general formula (3):

(Wherein R ₁ and R ₂ are each 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 formula, R ₃ is 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, substituted or unsubstituted. Represents a phenyl group or a naphthyl group, and p represents an integer of 0 to 4.)
[3] The phenol resin according to [1] or [2], which is obtained by reacting dihydroxynaphthalenes, ketones, and the compound represented by the general formula (3),
[4] The phenol resin according to [1] or [2], obtained by reacting dihydroxynaphthalenes, aldehydes, and the compound represented by the general formula (3),
[5] An epoxy resin obtained by reacting the phenol resin according to any one of [1] to [4] with an epihalohydrin,
[6] An epoxy resin composition containing at least one phenol resin according to any one of [1] to [4] and an epoxy resin,
[7] An epoxy resin composition containing 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],
Is provided.

  The epoxy resin composition using the phenol resin of the present invention can provide 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_１、Ｒ_２、Ｒ_３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、置換又は無置換のフェニル基、ナフチル基を表し、ｋ、ｐは０〜４の整数を示し、ｎは０〜１０の整数を示す。Ｘは結合基を表す。） Hereinafter, the phenol resin (A) of the present invention will be described.
The phenol resin (A) of the present invention is a phenol resin represented by the following general formula (1).

(In the formula, R ₁ , R ₂ and R ₃ are each 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, and a naphthyl group are represented, k and p represent an integer of 0 to 4, n represents an integer of 0 to 10. X represents a bonding group. .)

The cured product using the phenol resin of the present invention has both high heat resistance and flame retardancy. Moreover, since it has a repeating structure and crystallinity is eased, solvent solubility becomes high and can be suitably used for an epoxy resin raw material, a cyanate resin raw material, and the like.

Here, R ₁ , R ₂ , and R ₃ are preferably alkyl groups having 1 to 6 carbon atoms because they are excellent in water absorption, and substituted or unsubstituted phenyl groups and naphthyl groups are preferable because they are excellent in heat resistance. k is preferably from 0 to 4, and particularly preferably from 0 to 2. p is preferably from 0 to 4, and particularly preferably from 0 to 2.

Moreover, in the phenol resin of this invention, the peak area of n = 0 by gel permeation chromatography (GPC) is 20-95 area% normally, Preferably it is 30-80 area%.
The average value of n is preferably 0.1 to 8.0, particularly preferably 0.4 to 7.0 phenol resin. Here, as for the content rate of the phenol compound in which n is not 0 in the obtained phenol resin, the content rate calculated by the measurement of gel permeation chromatography (GPC) is preferably 5 to 80 area%, and 20 to 70. Area% is more preferable.

It is preferable that the hydroxyl equivalent of the phenol resin of this invention is 125-450 g / eq, and 150-400 are more preferable. The softening point is preferably 50 to 250 ° C, more preferably 80 to 200 ° C.

  The phenol resin of the present invention is a polyfunctional phenol resin containing a benzopyran structure in the main chain, and is characterized by being connected by a bonding group (X) having an aromatic ring or a heterocyclic structure. Thereby, the hardened | cured material using the phenol resin which has both characteristics, such as heat resistance and a flame retardance, can be provided, without raising the crosslinking density of resin. In other words, connecting the benzopyran structure with a linking group not only improves the heat resistance because the molecular weight of the resin increases, but also increases the functional group equivalent and decreases the crosslink density, resulting in flame retardancy, dielectric properties, water absorption It is possible to suppress the deterioration of characteristics. Furthermore, when a group having a large molecular weight is used as a linking group, the functional group equivalent is increased, and the crosslinking density can be lowered. It is possible to cover the heat resistance that decreases due to the decrease in the crosslinking density by increasing the molecular weight, and to suppress the decrease in characteristics such as flame retardancy by increasing the functional group equivalent. In particular, by connecting with a bonding group (X) excellent in heat resistance such as an aromatic ring or a heterocyclic ring, it is possible to have not only a further improvement in heat resistance but also an effect excellent in flame retardancy, dielectric properties and water absorption.

As the bonding group (X), groups represented by the following general formulas (4) to (12) can be used.

（一般式（４）〜（１２）において、Ｒ_３、ｐは前記一般式（１）に記載のＲ_３、ｐと同じ意味を表す。）

(In General Formulas (4) to (12), R ₃ and p represent the same meaning as R ₃ and p described in General Formula (1).)

Although the specific example of a compound which has group represented by the general formula (4)-(12) mentioned above below is shown, it is not limited to these.

Examples of the compound represented by the general formula (4) include formaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5- Dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, syringaldehyde, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, isovanillin, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 3 , 4-dihydroxy-5-nitrobenzaldehyde, vanillin, o-vanillin, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-5-nitro-m-anisaldehyde, 2-hydroxy -5-methylisophthalaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 1-hydroxy-2-naphthaldehyde, 2-hydroxy-5-methoxybenzaldehyde, 5-nitrovanillin, 5-allyl-3-methoxysalicylaldehyde, 3 , 5-Di-tert-butylsalicylaldehyde, 3-ethoxysalicylaldehyde, 4-hydroxyisophthalaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5- Trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, acetone, 1,3-diphenyl-2-propanone, 2 Butanone, 1-phenyl-1,3-butanedione, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, acetylacetone, 2-hexanone, 3-hexanone, isoamyl methyl ketone, ethyl isobutyl ketone, 4-methyl- 2-hexanone, 2,5-hexanedione, 1,6-diphenyl-1,6-hexanedione, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-4-heptanone, 5-methyl-3- Heptanone, 6-methyl-2-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 4-octanone, 5-methyl-2-octanone, 2-nonanone, 3-nonanone, 4- Nonanone, 5-Nonanone, 2-decanone, 3-decanone, 4-decanone, 5-decanone, 2-undecane Non, 3-undecanone, 4-undecanone, 5-undecanone, 6-undecanone, 2-methyl-4-undecanone, 2-decanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 6-dodecanone, 2-tetradecanone, 3-tetradecanone, 8-pentadecanone, 10-nonadecanone, 7-tridecanone, 2-pentadecanone, 3-hexadecanone, 9-heptadecanone, 11-heneicosanone, 12-tricosanone, 14-heptacosanone, 16-hentriacontanone, 18-penta Triacontanone, 4-ethoxy-2-butanone, 4- (4-methoxyphenyl) -2-butanone, 4-methoxy-4-methyl-2-pentanone, 4-methoxyphenylacetone, methoxyacetone, phenoxyacetone, aceto Methyl acetate , Ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, isobutyl acetoacetate, sec-butyl acetoacetate, tert-butyl acetoacetate, 3-pentyl acetoacetate, amyl acetoacetate, isoamyl acetoacetate, hexyl acetoacetate, heptyl acetoacetate N-octyl acetoacetate, benzyl acetoacetate, dimethyl acetylsuccinate, dimethyl acetonylmalonate, diethyl acetonylmalonate, 2-methoxyethyl acetoacetate, allyl acetoacetate, 4-sec-butoxy-2-butanone, Benzyl butyl ketone, bisdemethoxycurcumin, 1,1-dimethoxy-3-butanone, 1,3-diacetoxyacetone, 4-hydroxyphenylacetone, 4- (4-hydroxyphenyl) -2-butanone, isoamylmethylketone, 4- Hydroxy-2-butanone, 5-hexen-2-one, acetonylacetone, 3,4-dimethoxyphenylacetone, piperonylmethylketone, piperonylacetone, phthalimidoacetone, 4-isopropoxy-2-butanone, 4 -Isobutoxy-2-butanone, acetoxy-2-propanone, N-acetoacetylmorpholine, 1-acetyl-4-piperidone and the like are preferable, and formaldehyde and acetone are more preferable.

Examples of the compound represented by the general formula (5) include adamantane-2-one, (1β, 3α, 5β, 7α) -4α-acetyloxytricyclo [3.3.1.13,7] decane- 2-one, (1β, 3α, 5β, 7α) -4β-acetyloxytricyclo [3.3.1.13,7] decan-2-one, (1β, 3α, 5β, 7α) -4β-acetyl Oxytricyclo [3.3.1.13,7] decan-2-one, (4S) -4-hydroxyadamantan-2-one, and the like are preferable.

As examples of the compound represented by the general formula (6), cyclopentadiene, 1-methylcyclopentadiene, 3,9-dimethyltricyclodeca-3,8-diene and the like are preferable.

Examples of the compound represented by the general formula (7) include o-dichloromethylbenzene, o-dibromomethylbenzene, o-xylylene glycol, o-dimethoxymethylbenzene, m-dichloromethylbenzene, m-dibromomethylbenzene. M-xylylene glycol, m-dimethoxymethylbenzene, p-dichloromethylbenzene, p-dibromomethylbenzene, p-xylylene glycol, p-dimethoxymethylbenzene, and the like are preferable, and p-dichloromethylbenzene, p is more preferable. -Xylylene glycol.

Examples of the compound represented by the general formula (8) include α, α′-dihydroxy-1,4-diisopropylbenzene, α, α′-dihydroxy-1,3-diisopropylbenzene, α, α′-dihydroxy- 1,2'-diisopropylbenzene and the like are preferable.

As an example of the structure containing the general formula (9) or (10), Nicanol G (manufactured by Fudou Co., Ltd.) is preferable.

Examples of the compound represented by the general formula (11) include 1,2-dibromomethylnaphthalene, 1,3-dibromomethylnaphthalene, 1,4-dibromomethylnaphthalene, 1,5-dibromomethylnaphthalene, 1,6 -Dibromomethylnaphthalene, 1,7-dibromomethylnaphthalene, 1,8-dibromomethylnaphthalene, 2,3-dibromomethylnaphthalene, 2,4-dibromomethylnaphthalene, 2,5-dibromomethylnaphthalene, 2,6-dibromo Methylnaphthalene, 2,7-dibromomethylnaphthalene, 2,8-dibromomethylnaphthalene, 1,2-dichloromethylnaphthalene, 1,3-dichloromethylnaphthalene, 1,4-dichloromethylnaphthalene, 1,5-dichloromethylnaphthalene 1,6-dichloromethylnaphthalene, 1,7-di Loromethylnaphthalene, 1,8-dichloromethylnaphthalene, 2,3-dichloromethylnaphthalene, 2,4-dichloromethylnaphthalene, 2,5-dichloromethylnaphthalene, 2,6-dichloromethylnaphthalene, 2,7-dichloromethyl Naphthalene, 2,8-dichloromethylnaphthalene, 1,2-dihydroxymethylnaphthalene, 1,3-dihydroxymethylnaphthalene, 1,4-dihydroxymethylnaphthalene, 1,5-dihydroxymethylnaphthalene, 1,6-dihydroxymethylnaphthalene, 1,7-dihydroxymethylnaphthalene, 1,8-dihydroxymethylnaphthalene, 2,3-dihydroxymethylnaphthalene, 2,4-dihydroxymethylnaphthalene, 2,5-dihydroxymethylnaphthalene, 2,6-dihydroxymethyl Naphthalene, 2,7-dihydroxymethylnaphthalene, 2,8-dihydroxymethylnaphthalene, 1,2-dimethoxymethylnaphthalene, 1,3-dimethoxymethylnaphthalene, 1,4-dimethoxymethylnaphthalene, 1,5-dimethoxymethylnaphthalene, 1,6-dimethoxymethylnaphthalene, 1,7-dimethoxymethylnaphthalene, 1,8-dimethoxymethylnaphthalene, 2,3-dimethoxymethylnaphthalene, 2,4-dimethoxymethylnaphthalene, 2,5-dimethoxymethylnaphthalene, 2, 6-dimethoxymethylnaphthalene, 2,7-dimethoxymethylnaphthalene, 2,8-dimethoxymethylnaphthalene and the like are preferable, 2,6-dichloromethylnaphthalene, 2,6-dihydroxymethylnaphthalene, 2,6-di Methoxymethylnaphthalene.

Examples of the compound represented by the general formula (12) include 2,2′-dichloromethyldiphenyl, 2,2′-dibromomethyldiphenyl, 2,2′-dimethoxymethyldiphenyl, and 2,2′-dimethyloldiphenyl. 2,4′-dichloromethyldiphenyl, 2,4′-dibromomethyldiphenyl, 2,4′-dimethoxymethyldiphenyl, 2,4′-dimethyloldiphenyl, 3,3′-dichloromethyldiphenyl, 3,3 ′ -Dibromomethyldiphenyl, 3,3'-dimethoxymethyldiphenyl, 3,3'-dimethyloldiphenyl, 4,4'-dichloromethyldiphenyl, 4,4'-dibromomethyldiphenyl, 4,4'-dimethoxymethyldiphenyl, 4,4′-dimethyloldiphenyl, 3,3 ′, 4,4′-tetrachloromethyldipheny 3,3 ′, 4,4′-tetrabromomethyldiphenyl, 3,3 ′, 4,4′-tetramethoxymethyldiphenyl, 3,3 ′, 4,4′-tetramethyloldiphenyl, 3,3 ′, 5,5′-tetrachloromethyldiphenyl, 3,3 ′, 5,5′-tetrabromomethyldiphenyl, 3,3 ′, 5,5′-tetramethoxymethyldiphenyl, 3,3 ′, 5,5′- Tetramethylol diphenyl, 3,3 ′, 5,5′-tetrachloromethyl-4,4′-dihydroxydiphenyl, 3,3 ′, 5,5′-tetrabromomethyl-4,4′-dihydroxymethyldiphenyl, 3, , 3 ′, 5,5′-tetramethoxymethyl-4,4′-dihydroxydiphenyl, 3,3 ′, 5,5′-tetramethylol-4,4′-dihydroxymethyldiphenyl, etc. Preferred, more preferably 4,4'-dichloromethyl-diphenyl, 4,4'-dimethoxymethyl diphenyl.

Specific examples of the phenol resin of the present invention include the following formulas (13) to (21). However, the phenol resin represented by the general formula (1) of the present invention should not be construed as being limited by these specific examples.

（式中のうちＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋは前記式（１）に記載のＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋとそれぞれ同じ意味を表す。） A phenolic resin represented by the following formula (13):

_{(. R 1, R 2,} R 3, n, k of the formula is representative of the _{R 1, R 2, R 3} , n, k and the respective same meaning as defined in the formula (1))

（式中のうちＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐは前記式（１）に記載のＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐとそれぞれ同じ意味を表す。） A phenolic resin represented by the following formula (14):

(In the formula, R ₁ , R ₂ , R ₃ , n, k, and p have the same meanings as R ₁ , R ₂ , R ₃ , n, k, and p described in the formula (1), respectively.)

（式中のうちＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐは前記式（１）に記載のＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐとそれぞれ同じ意味を表す。） A phenolic resin represented by the following formula (15):

(In the formula, R ₁ , R ₂ , R ₃ , n, k, and p have the same meanings as R ₁ , R ₂ , R ₃ , n, k, and p described in the formula (1), respectively.)

（式中のうちＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐは前記式（１）に記載のＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐとそれぞれ同じ意味を表す。） A phenol resin represented by the following formula (16):

(In the formula, R ₁ , R ₂ , R ₃ , n, k, and p have the same meanings as R ₁ , R ₂ , R ₃ , n, k, and p described in the formula (1), respectively.)

（式中のうちＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐは前記式（１）に記載のＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐとそれぞれ同じ意味を表す。） A phenol resin represented by the following formula (17);

(In the formula, R ₁ , R ₂ , R ₃ , n, k, and p have the same meanings as R ₁ , R ₂ , R ₃ , n, k, and p described in the formula (1), respectively.)

（式中のうちＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋは前記式（１）に記載のＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋとそれぞれ同じ意味を表す。） A phenolic resin represented by the following formula (18):

_{(. R 1, R 2,} R 3, n, k of the formula is representative of the _{R 1, R 2, R 3} , n, k and the respective same meaning as defined in the formula (1))

（式中のうちＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋは前記式（１）に記載のＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋとそれぞれ同じ意味を表す。） A phenol resin represented by the following formula (19);

_{(. R 1, R 2,} R 3, n, k of the formula is representative of the _{R 1, R 2, R 3} , n, k and the respective same meaning as defined in the formula (1))

（式中のうちＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐは前記式（１）に記載のＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐとそれぞれ同じ意味を表す。） A phenolic resin represented by the following formula (21):

(In the formula, R ₁ , R ₂ , R ₃ , n, k, and p have the same meanings as R ₁ , R ₂ , R ₃ , n, k, and p described in the formula (1), respectively.)

（式中のうちＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐは前記式（１）に記載のＲ_１、Ｒ_２、Ｒ_３、ｎ、ｋ、ｐとそれぞれ同じ意味を表す。） It is a phenol resin represented by the following formula (22).

(In the formula, R ₁ , R ₂ , R ₃ , n, k, and p have the same meanings as R ₁ , R ₂ , R ₃ , n, k, and p described in the formula (1), respectively.)

（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。）

（式中、Ｒ_３、ｐは前記一般式（１）に記載のＲ_３、ｐと同じ意味を表す。） Next, the manufacturing method of the phenol resin (A) of this invention is demonstrated.
The phenol resin (A) of the present invention condenses at least one of the benzopyran type phenol resin (a) represented by the following general formula (2) and the compound represented by the following general formula (3). Can be obtained.

_{(Wherein, R 1,} R _2, k has the same meaning as _{R 1, R 2,} k according to the general formula (1).)

(In the formula, R ₃ and p have the same meaning as R ₃ and p described in the general formula (1).)

（式中、Ｒ_３、ｋは前記一般式（１）に記載のＲ_３、ｋと同じ意味を表す。） First, the benzopyran type phenol resin (a) represented by the general formula (2) will be described. The phenol resin (a) represented by the general formula (2) can be obtained by reacting dihydroxynaphthalenes with ketones (b) or aldehydes (c). Dihydroxynaphthalene is a compound represented by the following general formula (22).

(In the formula, R ₃ and k represent the same meaning as R ₃ and k described in the general formula (1).)

Specific examples of dihydroxyaphthalenes include 1,3-dihydroxynaphthalene and 1,4 dihydroxynaphthalene. Also, 1,4-dihydroxy-5-alkyl-naphthalene, 1,4-dihydroxy-6-alkyl-naphthalene, 1,3-dihydroxy-5-alkyl-naphthalene, 1,3-dihydroxy-6-alkyl-naphthalene, Examples include, but are not limited to, 1,3-dihydroxy-7-alkyl-naphthalene, 1,3-dihydroxy-8-alkyl-naphthalene, and the like. 1,3-dihydroxynaphthalene and 1,4 dihydroxynaphthalene are preferred, and 1,4 dihydroxynaphthalene is particularly preferred.

（式中、Ｒ_１は前記一般式（１）に記載のＲ_１と同じ意味を表す。） Ketones (b) and aldehydes (c) are compounds represented by the following formula (23).

(In the formula, R ₁ represents the same meaning as R ₁ described in the general formula (1).)

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 and the like, and acetone, cyclohexanone, bicyclohexanone, acetophenone, hydroxyacetophenone, and furfural are preferable, and acetone is particularly preferable. Specific examples of the aldehydes (c) include formaldehyde, hydroxybenzaldehyde, acetaldehyde, benzaldehyde and the like. Formaldehyde and hydroxybenzaldehyde are preferable, and formaldehyde is particularly preferable. Formaldehyde is a concept including synthetic equivalents of formaldehyde such as paraformaldehyde and formalin.

The benzopyran type phenol resin (a) is obtained by a condensation reaction between one or more compounds represented by the formula (22) and the compound represented by the formula (23) under acidic conditions. Although the reaction can be carried out under basic conditions, acidic conditions are preferred.
The compound represented by the formula (23) is 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 (22).

When the condensation reaction is carried out under acidic conditions, the acidic catalyst used is not particularly limited, but in addition to organic acid catalysts such as toluenesulfonic acid, xylenesulfonic acid and oxalic acid, inorganic acid catalysts such as hydrochloric acid and sulfuric acid, and phosphotungstic acid And heteropolyacids such as silicotungstic acid, phosphomolybdic acid, sodium phosphomolybdate, phosphotungstomolybdic acid, and phosphovanadomolybdic 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 Formula (22), 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 benzopyran type phenol resin (a), 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 (23) such as ketones, but the compound represented by the formula (22) as a raw material. Alcohols are preferably used as a solvent from the viewpoint of easily dissolving.
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. Although aromatic hydrocarbons, such as toluene, xylene, mesitylene, etc. are mentioned, it is not limited to these, You may use individually or in combination of 2 or more types.
Although the usage-amount in the case of using a solvent is not restrict | limited in particular, For example, it is 5-500 weight part with respect to 1 mol of compounds represented by Formula (22), Preferably it is the range of 10-400 weight part.

  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は前記一般式（１）に記載の、Ｒ_１、Ｒ_２、ｋと同じ意味を表す。）
ここで、Ｒ_１、Ｒ_２は炭素数１〜６のアルキル基であると吸水性に優れ、置換又は無置換のフェニル基、ナフチル基であると耐熱性に優れるため好ましい。
また、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）の測定により算出されるベンゾピラン型フェノール樹脂（ａ）の含有割合は、６０〜１００面積％が好ましく、７５〜９９面積％がより好ましい。
また、水酸基当量は１００〜５００ｇ／ｅｑであることが好ましく、１２０〜４５０ｇ／ｅｑであることが特に好ましい。軟化点は３０〜３００℃であることが好ましく、７０〜２５０℃であることが特に好ましい。 The benzopyran type phenol resin (a) thus obtained is a compound represented by the following formula (2).

_(Wherein, R _{1, R} 2, k is described in the above general formula _(1), the same meanings as R _{1, R} 2, k.)
Here, R ₁ and R ₂ are preferably alkyl groups having 1 to 6 carbon atoms because they are excellent in water absorption, and substituted or unsubstituted phenyl groups and naphthyl groups are preferable because they are excellent in heat resistance.
Moreover, 60-100 area% is preferable and, as for the content rate of the benzopyran type phenol resin (a) calculated by the measurement of a gel permeation chromatography (GPC), 75-99 area% is more preferable.
Moreover, it is preferable that a hydroxyl equivalent is 100-500 g / eq, and it is especially preferable that it is 120-450 g / eq. The softening point is preferably 30 to 300 ° C, particularly preferably 70 to 250 ° C.

Next, the phenol resin (A) of the present invention is obtained by adding at least one of the compounds represented by the general formulas (4) to (12) to the benzopyran-type phenol resin (a) obtained by the above-described method. It can be obtained by condensing more than one kind.
Alternatively, after reacting the general formula (22) and the general formula (23), at least one of the compounds represented by the general formula (3) is reacted without performing purification and extraction such as washing with water. Can also be obtained.
Moreover, when performing a condensation reaction, an acidic or basic catalyst can also be used as needed.

The charged amount of the benzopyran-type phenol resin (a) is usually 1.2 to 20 mol, preferably 1.5 to 15 mol with respect to 1 mol of the total amount of the compounds represented by the formulas (4) to (12). It is. If the amount of the benzopyran-type phenol resin (a) is too large, the amount of benzopyran-type phenol resin (a) that does not participate in the reaction increases, and the crystallinity is high and the solvent solubility is poor.

In the condensation reaction, a catalyst can be used as necessary.
As a catalyst that can be used, an acidic catalyst is basically preferable. When the catalyst is used, specific examples of the acidic catalyst include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as oxalic acid, toluenesulfonic acid, and acetic acid; heteropolyacids such as tungstic acid, activated clay, and inorganic acids. , Stannic chloride, zinc chloride, ferric chloride and the like, and other acidic catalysts usually used for the production of novolak resins such as organic and inorganic acid salts showing acidity. These catalysts are not limited to those mentioned above, and may be used alone or in combination of two or more. The amount of the catalyst used is usually 0.005 to 2.0 times mol, preferably 0.01 to 1.1 times mol for the phenol compound (a), or 0.1 to 0.1 g for the phenol compound (a). 1-10 g, more preferably 0.3-7 g. If the amount of catalyst is small, the progress of the reaction is slow. Moreover, problems such as the need for a reaction at a high temperature and the reaction not proceeding to the end are not preferable. On the other hand, when the amount of catalyst is too large, it is not preferable because much work is required in post-treatment such as neutralization and purification.
In addition, when corrosive gas produces | generates by reaction, it is preferable to make it exhaust from the inside of a system by sending inactive gas, such as drawing pressure or nitrogen.

  The reaction may be performed without a solvent or a solvent may be used. When the solvent is used, the amount of the solvent used is preferably 50 to 300% by weight, particularly preferably 100 to 250% by weight, based on the total weight of the charged raw materials. Specific examples of solvents that can be used include, but are not limited to, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, toluene, xylene, mesitylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like. Methyl isobutyl ketone is preferred because of the solubility of the benzopyran type phenol resin (a). These solvents can be used alone or in combination of several kinds. Further, it is preferable to distill off water or alcohols generated during the reaction out of the system using a fractionating tube or the like in order to carry out the reaction quickly.

  The reaction time is preferably 5 to 150 hours, and the reaction temperature is preferably 40 to 150 ° C.

  After completion of the reaction, washing with water is carried out until the pH value of the washing liquid becomes 3 to 7, preferably 5 to 7. When washing with water, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate and diethylenetriamine are necessary. Various basic substances such as organic amines such as triethylenetetramine, aniline, and phenylenediamine may be used as the neutralizing agent. In some cases, a solvent may be added. The solvent that can be used is not particularly limited as long as it dissolves a high molecular weight substance and is well separated from the aqueous layer, and examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Washing with water may be performed according to a conventional method. For example, warm water in which the neutralizing agent is dissolved is added to the reaction mixture, and the liquid separation extraction operation is repeated.

  The phenol resin (A) of the present invention can be obtained by removing the solvent and unreacted phenols from the obtained organic layer with a rotary evaporator under heating under reduced pressure or by crystallization.

The phenol resin (A) of the present invention may be used alone. Usually, the benzopyran-type phenol resin (a), which is a raw material, is 1 to 90 with respect to the phenol resin (A) obtained by the reaction at a GPC area ratio. It is contained in an area%, more preferably 5 to 80 area%, particularly preferably 20 to 70 area%. When the content of the dibenzopyran-type phenol resin (a) is less than 1 area%, the viscosity of the resulting resin becomes very high, making it difficult to take out, handling during composition, and composition. This greatly affects the subsequent formability and makes molding difficult. When the content of the dibenzopyran type phenol resin (a) is less than 1 area%, it is preferable to coexist other phenol resin instead.
Moreover, when the dibenzopyran type phenol resin (a) exceeds 90%, the high heat resistance, which is a feature of the present invention, is impaired, which is not preferable.

  The phenol resin (A) 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 (A) 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.

  As a specific structural formula of the epoxy resin of the present invention, the following formula (24)

（式中、Ｒ_１、Ｒ_２、Ｒ_３、ｋ、ｐ、ｎは前記と同じ意味を表す。）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り、その硬化物は高い耐熱性と難燃性を両立する。また、繰り返し構造を有し、結晶性が緩和されるため、溶剤溶解性が高くなる。
Ｒ_１、Ｒ_２、Ｒ_３は炭素数１〜６のアルキル基であると吸水性に優れ、置換又は無置換のフェニル基、ナフチル基であると耐熱性に優れるため好ましい。ｋは０〜４が好ましく、特に０〜２が好ましい。ｐは０〜４が好ましく、特に０〜２が好ましい。

(Wherein R ₁ , R ₂ , R _3, k, p, n represent the same meaning as described above) is an epoxy resin characterized in that the cured product has high heat resistance. And flame retardancy. Moreover, since it has a repeating structure and crystallinity is eased, solvent solubility becomes high.
R ₁ , R ₂ and R ₃ are preferably alkyl groups having 1 to 6 carbon atoms because they are excellent in water absorption, and substituted or unsubstituted phenyl groups and naphthyl groups are excellent in heat resistance. k is preferably from 0 to 4, and particularly preferably from 0 to 2. p is preferably from 0 to 4, and particularly preferably from 0 to 2.

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 within 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.
Further, 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. Chlorine ions are described above. Needless to say, cations such as sodium ions are also very important factors particularly in power device applications, and 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 becomes a problem, and there are many problems such as handling at low temperatures. On the other hand, when the softening point is too high, problems such as poor handling occur during kneading with other resins.

The epoxy resin of the present invention is obtained by reacting the phenol resin (A) of the present invention with epihalohydrin in a solvent and epoxidizing it. Here, a phenol compound other than the phenol resin (A) may be used in combination with the phenol resin (A). As a phenol compound other than the phenol resin (A) that can be used in combination, any phenol compound that is usually used as a raw material for 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, but 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 (A) of this invention, Preferably it is 1.2-18 mol, More preferably, it is 1.5-15 mol, Most preferably, it is 2-15 mol.
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 (A) of this invention, Preferably it is 0.95-2.5 mol, More Preferably it is 0.99-2.0 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 with moisture controlled 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-based compounds 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.

(Synthesis example)
To a flask equipped with a stirrer, reflux condenser, stirrer, and Dean Stark, was added 150 parts of dihydroxynaphthalene, 49 parts of acetone, 235 parts of methyl isobutyl ketone, and 1.78 parts of p-toluenesulfonic acid while purging with nitrogen. It melt | dissolved under stirring and heated up to 120 degreeC, spin-dry | dehydrating. After heating to reflux for 10 hours, cooling and washing with water until the washing water becomes neutral, the methyl isobutyl ketone and the like are distilled off from the resulting solution under reduced pressure using a rotary evaporator. 145 parts were obtained. The obtained phenol resin (a) has a hydroxyl equivalent of 167 g / eq. Met.

Example 1
To a flask equipped with a stirrer, reflux condenser, stirrer, and hydrochloric acid trap, add 20 parts of phenol resin (a) (hydroxyl equivalent: 167 g / eq.), 20 parts of methanol, and 30 parts of toluene while purging with nitrogen, and stir. It melt | dissolved under and heated up to 50 degreeC. Thereto, 2 parts of p-xylylene glycol was added and reacted at 50 ° C. for 5 hours, then heated to 110 ° C. and heated to reflux for 5 hours while dehydrating. Thereafter, it is cooled to room temperature and washed until the washing water becomes neutral, and the phenol resin (A) (P) of the present invention is distilled off from the resulting solution using a rotary evaporator under reduced pressure. 17 parts of -1) were obtained. The obtained phenol resin has a hydroxyl group equivalent of 213 g / eq. Met.

(Example 2)
To a flask equipped with a stirrer, reflux condenser, stirrer, and hydrochloric acid trap, add 20 parts of phenol resin (a) (hydroxyl equivalent: 167 g / eq.), 20 parts of methanol, and 30 parts of toluene while purging with nitrogen, and stir. It melt | dissolved under and heated up to 50 degreeC. Thereto was added 3 parts of 4,4′-bischloromethylbiphenyl, and the mixture was heated to reflux at 50 ° C. for 10 hours while removing hydrochloric acid. Then, it cools to room temperature and performs washing with water until the washing water becomes neutral, and the phenol resin (A) of the present invention is obtained by distilling off toluene and the like from the resulting solution under reduced pressure using a rotary evaporator. I got a part. The obtained phenol resin has a hydroxyl group equivalent of 274 g / eq. Met.

(Example 3)
To a flask equipped with a stirrer, reflux condenser, stirrer, and hydrochloric acid trap, add 20 parts of phenol resin (a) (hydroxyl equivalent: 167 g / eq.), 22 parts of methanol, and 90 parts of toluene while purging with nitrogen, and stir. It melt | dissolved under and heated up to 70 degreeC. Thereto was added 1 part of 4,4′-bischloromethylbiphenyl, and the mixture was heated to reflux at 70 ° C. for 10 hours while removing hydrochloric acid. Thereafter, it is cooled to room temperature and washed until the washing water becomes neutral, and the phenol resin (A) (P) of the present invention is distilled off from the resulting solution using a rotary evaporator under reduced pressure. -2) was obtained 16 parts. The obtained phenol resin has a hydroxyl group equivalent of 219 g / eq. Met.

Example 4
To a flask equipped with a stirrer, reflux condenser, stirrer, and hydrochloric acid trap, add 20 parts of dihydroxynaphthalene, 11 parts of acetone, 50 parts of methyl isobutyl ketone, and 1 part of p-toluenesulfonic acid while purging with nitrogen. Then, the temperature was raised to 70 ° C. and heated to reflux for 10 hours. Thereafter, the reaction temperature was raised to 110 ° C., and the mixture was further refluxed for 6 hours while dehydrating. Thereafter, 0.8 part of p-xylylene glycol was added, and the mixture was heated to reflux at 110 ° C. for 6 hours while dehydrating. Thereafter, it is cooled to room temperature, washed with water until the washing water becomes neutral, and methyl isobutyl ketone and the like are distilled off from the obtained solution under reduced pressure using a rotary evaporator. 25 parts were obtained. The obtained phenol resin has a hydroxyl group equivalent of 197 g / eq. Met.

(Example 5)
To a flask equipped with a stirrer, reflux condenser, stirrer, and hydrochloric acid trap, add 50 parts of dihydroxynaphthalene, 18 parts of acetone, 50 parts of methyl isobutyl ketone and 6 parts of p-toluenesulfonic acid while purging with nitrogen. Then, the temperature was raised to 70 ° C. and heated to reflux for 10 hours. Thereafter, the reaction temperature was raised to 110 ° C., and the mixture was further refluxed for 6 hours while dehydrating. Thereafter, 2 parts of p-xylylene glycol was added, and the mixture was heated to reflux at 110 ° C. for 6 hours while dehydrating. Thereafter, it is cooled to room temperature, washed with water until the washing water becomes neutral, and methyl isobutyl ketone and the like are distilled off from the obtained solution under reduced pressure using a rotary evaporator. 55 parts were obtained. The obtained phenol resin has a hydroxyl group equivalent of 225 g / eq. Met.

(Example 6)
To a flask equipped with a stirrer, reflux condenser, stirrer, and hydrochloric acid trap, 20 parts of dihydroxynaphthalene, 11 parts of acetone, 50 parts of methyl isobutyl ketone and 1.2 parts of p-toluenesulfonic acid were added while purging with nitrogen. It melt | dissolved under stirring, heated up to 70 degreeC, and heated and refluxed for 10 hours. Thereafter, the reaction temperature was raised to 110 ° C., and the mixture was further refluxed for 6 hours while dehydrating. After cooling to 70 ° C., 1 part of 4,4′-bischloromethylbiphenyl was added, and the mixture was heated to reflux at 70 ° C. for 10 hours while removing hydrochloric acid. Thereafter, it is cooled to room temperature, washed with water until the washing water becomes neutral, and methyl isobutyl ketone and the like are distilled off from the obtained solution under reduced pressure using a rotary evaporator. 21 parts were obtained. The obtained phenol resin has a hydroxyl group equivalent of 230 g / eq. Met.

(Example 7)
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, 63 parts of the phenol resin of the present invention (P-1 hydroxyl equivalent 213 g / eq.), 190 parts epichlorohydrin (7 molar equivalents) Phenol resin) and 57 parts of methanol were added, dissolved under stirring, and the temperature was raised to 70 to 75 ° C. Next, 13 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, washing with 40 parts of water was carried out, and excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. To the residue, 150 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 4.7 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. 70 parts of epoxy resins (EP-1) of this invention were obtained by distilling methyl isobutyl ketone etc. off under reduced pressure using the rotary evaporator. The epoxy equivalent of the obtained epoxy resin is 318 g / eq. The softening point was 121 ° C.
(Example 8)
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, 20 parts of the phenol resin of the present invention (P-2 hydroxyl equivalent 219 g / eq.), 59 parts epichlorohydrin (7 molar equivalents) Phenol resin) and 18 parts of methanol were dissolved under stirring, and the temperature was raised to 70 to 75 ° C. Next, 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, water was washed with 12 parts of water, and excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. 48 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 75 ° C. Under stirring, 1.5 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. 22 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 is 312 g / eq. The softening point was 114 ° C.

(Examples 9 to 10, Comparative Example 1)
The epoxy resins (EP-1, EP-2) obtained above and the comparative epoxy resin (EP-3) are shown in Table 1 as curing agents (P-3), fillers, waxes, coupling agents, and curing accelerators. Were mixed at a ratio (equivalent) and uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition. The curable resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted curable resin composition was transfer molded (175 ° C. × 60 seconds), and after demolding, 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.
・ Glass transition temperature (DMA): Conforms to JIS K-7244

ＥＰ−３：日本化薬社製 ＮＣ−３０００
Ｐ−３：三井化学社製 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

EP-3: Nippon Kayaku NC-3000
P-3: Millex XLC-3L manufactured by Mitsui Chemicals
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 can be confirmed that the cured product of the epoxy resin composition using the phenol resin of the present invention has high heat resistance.

Moreover, the epoxy resin (EP-1, EP-2) of this invention has a large functional group equivalent (epoxy equivalent) compared with a comparative example (EP-3). That is, the crosslinking density of the epoxy resin (EP-1, EP-2) of the present invention is smaller than that of the comparative example (EP-3). Therefore, it turns out that the epoxy resin of this invention is resin which has high heat resistance irrespective of the improvement of a crosslinking density.
Since the heat resistance is increased without increasing the crosslink density, it is understood that the epoxy resin of the present invention does not have the flame retardancy, water absorption, and dielectric properties that are normally decreased when the Tg is increased by improving the crosslink density. Therefore, it turns out that the epoxy resin of this invention is excellent in heat resistance, a flame retardance, water absorption, and a dielectric characteristic.

Claims (8)

A phenol resin represented by the following general formula (1).

(In the formula, R ₁ , R ₂ and R ₃ are each 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, and a naphthyl group are represented, k and p represent an integer of 0 to 4, and n represents an integer of 0 to 10). The phenol resin of Claim 1 obtained by reaction of the phenol compound represented by following General formula (2), and the compound represented by following General formula (3).

(Wherein R ₁ and R ₂ are each 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 formula, R ₃ is 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, substituted or unsubstituted. Represents a phenyl group or a naphthyl group, and p represents an integer of 0 to 4.) The phenol resin according to claim 1 or 2, which is obtained by reacting dihydroxynaphthalene, ketones and the compound represented by the general formula (3). The phenol resin according to claim 1 or 2, which is obtained by reacting dihydroxynaphthalenes, aldehydes, and the compound represented by the general formula (3). The epoxy resin obtained by reaction of the phenol resin as described in any one of Claim 1 to Claim 4, and an epihalohydrin. An epoxy resin composition comprising at least one phenol resin according to any one of claims 1 to 4 and an epoxy resin. An epoxy resin composition comprising the epoxy resin according to claim 5 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 6 or Claim 7.