JP2010229203A - Phenolic resin composition, process for producing the resin composition and epoxy resin composition including the resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To industrially and safely obtain a phenolic resin composition which makes use of excellent properties of a triphenolmethane-type phenolic resin including, for example, a high glass transition temperature, low heat shrinkability, and low warpage and has a low melt viscosity and excellent curability as well. <P>SOLUTION: The phenolic composition includes 5-95 pts.wt. triphenolmethane-type phenolic resin and 95-5 pts.wt. methylene-crosslinked phenolic novolak resin. A process for producing the phenolic resin composition includes melt kneading 5-95 pts.wt. triphenolmethane-type phenolic resin with 95-5 pts.wt. methylene-crosslinked phenolic novolak resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a low melt viscosity phenol novolak resin useful for various binders, coating materials, laminated materials, molding materials, and the like, a production method thereof, and an epoxy cured product using the same. Low melt viscosity, high glass transition temperature, and handling, especially suitable for epoxy curing agents such as semiconductor sealing, printed circuit board insulation, electronic circuit copper clad laminates or fiber reinforced composite materials that can be preferably applied to aircraft structural materials The present invention relates to a low melt viscosity phenol novolac resin having excellent properties and a method for producing the same.

  Various phenolic polymers, such as phenol novolac resins and phenol aralkyl resins, are used as an epoxy resin curing agent for electronic materials, particularly for semiconductor encapsulation and printed circuit board insulation. However, in recent years, with the miniaturization and thinning of semiconductor packages, the increase in the number of pins, and the high density mounting, higher performance resins are required.

  On the other hand, carbon fiber reinforced composite materials that use carbon fibers with excellent specific strength and specific elastic modulus as reinforcing fibers and epoxy resins with good wettability and adhesion with the carbon fibers as matrix resins also have low viscosity and heat resistance. Resins having properties are demanded.

  An important physical property for using a phenol-based polymer for a semiconductor encapsulant is a high glass transition temperature. As a means for raising the glass transition temperature, it is effective to increase the hydroxyl group concentration, and so-called polyfunctional type is often used. A typical example is a phenol resin of triphenolmethane type. (For example, Patent Documents 1 and 2)

Japanese Patent Publication No. 7-121979, JP-A-2-173030

  These triphenolmethane type phenolic polymers have a high glass transition temperature, and thus have various features of excellent reliability. Further, when used in a single-side sealed package such as BGA (Ball GridArray), it has an excellent performance that the warpage of the package is small. However, in recent semiconductor packages, for example, in the case of BGA, it becomes a finer pitch or a batch sealing type, and it is required that the fluidity is high in addition to the small warpage and the adhesiveness with the substrate surface is good. ing. Further, even in packages such as SOP, QFP, and DIP, a reduction in viscosity is strongly desired in terms of extending the wire length, reducing the wire diameter, and reducing the size. Further, if the melt viscosity is low, the fluidity and adhesion are improved, and a large amount of filler can be added, which is advantageous in terms of solder heat resistance and water resistance. That is, in order to satisfy the required properties for these sealing materials, the appearance of a phenolic polymer (curing agent) having both a high glass transition temperature, a low melt viscosity, and excellent handling properties is strongly desired.

  In addition, epoxy resin compositions with excellent water resistance and high adhesiveness at high glass transition temperatures are also desired for interlayer insulation materials for build-up substrates. To achieve this, water resistance and storage stability are inherently improved. An excellent phenolic curing agent that has a high glass transition temperature, a low melt viscosity, and excellent handling properties is desired.

  However, when the hydroxyl group concentration is increased in order to increase the glass transition temperature, the melt viscosity increases due to hydrogen bonding between the hydroxyl groups. As a result, the fluidity is poor due to an increase in melt viscosity, which causes troubles in molding such as wire deformation. If the molecular weight is decreased or the hydroxyl group concentration is decreased in order to decrease the melt viscosity, the glass transition temperature is decreased, the curability at the time of molding is decreased, and the handleability of the phenol resin itself is also deteriorated. That is, it is considered that it is difficult in principle to satisfy both the high glass transition temperature, the low melt viscosity, and the handleability of the resin itself.

  A type of resin in which an allyl group is added to a triphenolmethane type phenolic resin has also been proposed (for example, Patent Document 3). Since these resins have a high glass transition temperature, the thermal shrinkage is small, and since the free volume of the resin skeleton is large, the cure shrinkage rate is also small, which is said to contribute to low warpage. However, this type of resin is still inadequate for the required level because the glass transition temperature actually decreases with increasing allyl group introduction amount and the curability also decreases.

JP-A-4-23824

In addition, as a means for improving fluidity, a resin that reacts phenols, salicylaldehydes, and formaldehyde has been proposed (for example, Patent Document 4). Since these resins have a low melt viscosity at 150 ° C., improvement in fluidity is expected.
However, since this type of resin is a reaction composed of three component raw materials, the reaction occurs by copolymerization. For this reason, the reaction conditions are complicated, and there has been a problem in stably producing in industrialization.

JP 2002-275228 A

  The present inventors made use of the above-mentioned phenolic resin composition having the excellent glass transition temperature, low heat shrinkage, low warpage and other physical properties of the above-described triphenolmethane type phenolic resin and having a low melt viscosity and excellent curability. It aims at obtaining stably industrially.

  As a result of intensive investigations to obtain the above-described objective phenol resin composition, the inventors have obtained a high glass transition by mixing triphenolmethane type phenol resin and phenol novolac resin in a specific range in the molecule. The inventors have found that a phenol resin composition that maintains temperature and has low melt viscosity and excellent handleability can be provided industrially and stably, thereby completing the present invention.

  That is, the following general formula (1):

（式中、ｎは繰り返し数を表し、０〜５の正数を示す。）
で表されるフェノール樹脂５〜９５重量部、および、
一般式（２）

(In the formula, n represents the number of repetitions and represents a positive number of 0 to 5.)
5 to 95 parts by weight of a phenol resin represented by:
General formula (2)

（式中ｍは繰り返し数を表し、０から５の正数を示す）
で表されるフェノール樹脂９５〜５重量部、
を含有するフェノール樹脂組成物により解決される。

(Where m represents the number of repetitions and represents a positive number from 0 to 5)
95 to 5 parts by weight of a phenol resin represented by
This is solved by a phenol resin composition containing

  Moreover, this invention is a manufacturing method of the phenol resin obtained by mixing the phenol resin of said (1) and (2).

  Furthermore, this invention is a hardening | curing agent for epoxy resins which consists of a phenol resin obtained by mixing the phenol resin of said (1) and (2).

  The phenol resin composition of the present invention has a high glass transition temperature and a low melt viscosity, and the cured product of the epoxy resin composition containing the phenol resin composition is excellent in heat resistance. It is extremely useful for a wide range of applications such as mold materials, laminate materials, paints, adhesives, and resists. Moreover, it can be manufactured stably industrially.

  Hereinafter, the present invention will be described in detail.

In the resin constituting one of the phenol resin compositions of the present invention, n represented by the general formula (1) represents a positive number of 0 to 5, preferably 1 to 3, and more preferably 1.3 to It is a triphenolmethane type phenolic resin showing a positive number of 2.5.
Although there is no restriction | limiting in particular as a weight average molecular weight, Preferably it is 500-1000, More preferably, it is 550 to 900, More preferably, it is 600-800, Most preferably, it is 600-700 resin. There is no problem even if a commercially available product is used. If a specific example is given as a commercial item, MEH-7500, MEH-7500H (made by Meiwa Kasei Co., Ltd.) etc. will be mentioned.

As for the phenol resin which comprises the other one of the phenol resin composition of this invention, m shown by the said General formula (2) is 0-5, Preferably it is 1-4, More preferably, it is 1.5-2.5. It is a phenol novolak resin represented by a positive number.
Although there is no restriction | limiting in particular as a weight average molecular weight, Preferably it is 300-1000, More preferably, it is 350-900, More preferably, it is 400-800, Most preferably, it is 450-750.
The softening point is a room temperature or higher, preferably 40 ° C. or higher, more preferably 45 ° C. or higher. The upper limit of the softening point is not particularly limited, but is usually 150 ° C. or lower.

  The phenol resin represented by the formula (2) has no problem even if a synthetic product or a commercial product is used. Specific examples of commercially available products include PN-152 (M) and H-5 (manufactured by Meiwa Kasei Co., Ltd.). H-5 has a low melting point and is a semi-solid phenol resin at room temperature, and is available as PN-152 (M) in a solution diluted with an organic solvent for easy handling, and can be used as it is. .

Below, the synthesis | combining method of the phenol resin of General formula (1) is described easily.
The phenol novolak resin represented by the general formula (1) can be obtained by a condensation reaction of salicylaldehyde and phenol in the presence of an acid catalyst.
Usually, phenol is used in a range of 7 to 20 moles, preferably 10 to 13 moles per mole of salicylaldehyde, and the reaction of phenol and salicylaldehyde at a low reaction temperature (for example, around 110 ° C). To obtain a phenolic resin.
The acid catalyst to be used is not particularly limited, and known ones such as hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid can be used alone or in combination of two or more. Toluenesulfonic acid is particularly preferred.

Next, a method for synthesizing the phenol resin of the general formula (2) will be briefly described.
The phenol novolac resin represented by the general formula (2) can be obtained by a condensation reaction of formaldehyde and phenol in the presence of an acid catalyst.
Usually, phenol is used in the range of 1 to 10 times mol, preferably 2 to 5 times mol for 1 mol of formaldehyde, and the reaction of phenol and formaldehyde is carried out at a low reaction temperature (for example, around 100 ° C.). A phenolic resin is obtained.
The acid catalyst to be used is not particularly limited, and known ones such as hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, and paratoluenesulfonic acid can be used alone or in combination of two or more. Toluenesulfonic acid is particularly preferred.
Formaldehyde is not a problem as long as it is a compound that forms formaldehyde in a condensation reaction system, such as a commercially available formalin aqueous solution or paraformaldehyde.

  The phenol resin composition of the present invention can usually be obtained by melt-mixing a predetermined amount of the phenol resin of the formula (1) and a predetermined amount of the phenol resin of the formula (2). However, when the melting point of the phenol resin itself of the formula (2) is low and semisolid and difficult to handle, it can be melt-mixed by the following method.

For example, it is also possible to synthesize a semi-solid phenol resin represented by the formula (2) in a synthesis kettle in advance and melt-mix the phenol resin represented by the formula (1) therein.
In some cases, the phenol resin composition of the present invention can be obtained by synthesizing the phenol resin represented by the formula (1) and mixing the phenol resin represented by the formula (2).

The phenol resin composition of the present invention is obtained by melt mixing of the phenol resin represented by the formula (1) and the phenol resin represented by the formula (2), and the ratio is 5 to 95 by weight ratio: 95-5, preferably 20-80: 80-20, more preferably 30-70: 70-30, most preferably 40-60: 60-40.
When the proportion of the phenolic resin of the formula (1) is less than 5% by weight, the effect of reducing the viscosity is reduced, whereas when it exceeds 95% by weight, the resulting phenolic resin composition (the phenolic resin of the formula (1)) And a mixture of phenolic resins of formula (2)) are too low in handling.

[Hardened epoxy resin]
The phenol resin composition of the present invention can be used as a curing agent for epoxy resins.
Therefore, it can be used as an epoxy resin composition by being contained in an epoxy resin. The usage method as a hardened | cured material for epoxy resins mixes the phenol resin composition of this invention, an epoxy resin, and a hardening accelerator, and it makes it harden | cure in a 100-250 degreeC temperature range.
The obtained cured product is used as a semiconductor sealant or the like.
On the other hand, an epoxy resin composition containing the phenol resin composition can also be cured by the above method.

  Examples of the epoxy resin containing the phenol resin composition of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, triphenolmethane type epoxy resin, and biphenyl type epoxy. Examples thereof include epoxy resins having two or more epoxy groups in the molecule, such as glycidyl ether type epoxy resins such as resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and halogenated epoxy resins. These epoxy resins may be used alone or in combination of two or more.

(Curing accelerator)
A well-known hardening accelerator can be used for the hardening accelerator in the case of obtaining hardened | cured material from the phenol resin composition and epoxy resin of this invention. Examples of such curing accelerators include organic phosphine compounds and their boron salts, tertiary amines, quaternary ammonium salts, imidazoles and their tetraphenylboron salts, and among them, curability and moisture resistance. From this point, triphenylphosphine and 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) are preferable. In order to achieve higher fluidity, a heat-latent curing accelerator that exhibits activity by heating is more preferable, and tetraphenylphosphonium derivatives such as tetraphenylphosphonium and tetraphenylborate are preferable.

(Other additives)
In the epoxy resin composition containing the phenol resin composition of the present invention, an inorganic filler, a release agent, a colorant, a flame retardant, a low stress agent, or the like may be added or reacted in advance as necessary. Can do. Especially when used for semiconductor encapsulation, the addition of inorganic fillers is essential. Examples of such inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay, talc, mica, magnesia, barium sulfate and the like. However, amorphous silica, crystalline silica and the like are particularly preferable. The usage-amount of these additives may be the same as the usage-amount in the conventional epoxy resin composition for semiconductor sealing.

Comparative Example 1
A glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube was charged with 2086.8 g (22.2 mol) of phenol, 244 g (2.0 mol) of salicylaldehyde, and 2.9 g of paratoluenesulfonic acid at 110 ° C. The condensed liquid was neutralized and washed with water, and then heat-treated under reduced pressure to remove unreacted phenol and water out of the system, thereby obtaining 460 g of phenol resin A.

Comparative Example 2
A glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube was charged with 1184.4 g (12.6 mol) of phenol, 244 g (2.0 mol) of salicylaldehyde, and 1.65 g of paratoluenesulfonic acid at 110 ° C. The reaction mixture was reacted for 7 hours, neutralized and washed with water, and then heat-treated under reduced pressure to remove unreacted phenol and water out of the system to obtain 416 g of phenol resin B.

Comparative Example 3
A glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube was charged with 1,880 g (20.0 mol) of phenol, 174.78 g (5.36 mol) of 92% paraformaldehyde, and 1.25 g of oxalic acid, Reaction was carried out at 100 ° C. for 5 hours, followed by washing with water, and then heat treatment under reduced pressure to remove unreacted phenol and water out of the system, thereby obtaining 870 g of phenol resin C.

Comparative Example 4
A glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube was charged with 940 g (10.0 mol) of phenol, 163.1 g (5.0 mol) of 92% paraformaldehyde, and 0.7 g of oxalic acid at 100 ° C. The mixture was reacted for 5 hours, washed with water, and then heat-treated under reduced pressure to remove unreacted phenol and water out of the system to obtain 675 g of phenol resin D.

A glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube was charged with 2086.8 g (22.2 mol) of phenol, 244 g (2.0 mol) of salicylaldehyde, and 2.9 g of paratoluenesulfonic acid at 110 ° C. For 7 hours to neutralize the condensate (up to this point under the same production conditions as in Comparative Example 1), and 115 g of phenol resin C is added. Thereafter, washing with water and heat treatment under reduced pressure were performed to remove unreacted phenol and water out of the system to obtain 575 g of a phenol resin composition E. (The ratio of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 80 parts by weight to 20 parts by weight.)

  Synthesis was performed in the same manner as in Example 1, except that the amount of phenol resin C was changed to 307 g, and 767 g of phenol resin composition F was obtained. (The proportion of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 60 parts by weight to 40 parts by weight.)

  Synthesis was performed in the same manner as in Example 1, except that the amount of phenol resin C charged was changed to 690 g, and 1150 g of phenol resin composition G was obtained. (The proportion of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 40 parts by weight to 60 parts by weight.)

  Synthesis was performed in the same manner as in Example 1, except that the amount of phenol resin C charged was changed to 1,073 g, and 1,533 g of phenol resin composition H was obtained. (The ratio of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 30 parts by weight to 70 parts by weight.)

  Synthesis was performed in the same manner as in Example 1, and the same synthesis was performed except that the input amount of the phenol resin D was changed to 115 g, to obtain 575 g of a phenol resin composition I. (The ratio of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 80 parts by weight to 20 parts by weight.)

  Synthesis was performed in the same manner as in Example 1, except that the amount of phenol resin D charged was changed to 307 g. Thus, 767 g of phenol resin composition J was obtained. (The proportion of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 60 parts by weight to 40 parts by weight.)

  Synthesis was performed in the same manner as in Example 1, except that the amount of phenol resin D charged was changed to 690 g, and 1150 g of phenol resin composition K was obtained. (The proportion of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 40 parts by weight to 60 parts by weight.)

  Synthesis was performed in the same manner as in Example 1, except that the amount of phenol resin D charged was changed to 1,073 g, and 1,533 g of phenol resin composition L was obtained. (The ratio of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 30 parts by weight to 70 parts by weight.)

A glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube was charged with 940 g (10.0 mol) of phenol, 87.24 g (2.68 mol) of 92% paraformaldehyde, and 0.63 g of oxalic acid at 100 ° C. The mixture is reacted for 5 hours, washed with water (reaction on 1/2 scale of Comparative Example 3), and 2175 g of phenol resin B is added. Then, 2610 g of phenol resin composition M was obtained by removing unreacted phenol and water out of the system by heat treatment under reduced pressure. (The ratio of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 80 parts by weight to 20 parts by weight.)

  Synthesis was performed in the same manner as in Example 9, and the same synthesis was performed except that the input amount of phenol resin B was changed to 653 g, and 1088 g of phenol resin composition N was obtained. (The proportion of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 60 parts by weight to 40 parts by weight.)

  Synthesis was performed in the same manner as in Example 9, and the same synthesis was performed except that the input amount of phenol resin B was changed to 290 g, and 725 g of phenol resin composition O was obtained. (The proportion of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 40 parts by weight to 60 parts by weight.)

  Synthesis was performed in the same manner as in Example 9, and the same synthesis was performed except that the input amount of the phenol resin D was changed to 109 g, and 543 g of the phenol resin composition P was obtained. (The proportion of the phenol resin of the general formula (1) and the phenol resin of the general formula (2) is equivalent to 20 parts by weight to 80 parts by weight.)

Comparative Example 5
In a glass reaction kettle equipped with a stirrer, a condenser and a nitrogen gas inlet tube, 94 g (1 mol) of phenol, 19.5 g of a 37% formalin aqueous solution (0.24 mol in terms of formaldehyde), oxalic acid dihydrate 34 g was charged and reacted at 95 ° C. for 4 hours. Thereafter, 106.2 g (1.13 mol) of phenol, 29.3 g (0.24 mol) of salicylaldehyde, and 7.1 g of 35% hydrochloric acid aqueous solution were further added and reacted at 90 ° C. for 4 hours. Neither unreacted formaldehyde nor salicylaldehyde was detected in the condensate after the reaction (reaction rate 100%). This condensate was further heat-treated under reduced pressure to remove unreacted phenol, water, oxalic acid and HCl out of the system, thereby obtaining 98.0 g of phenol resin Q.

The production conditions of the phenol resins of Examples 1 to 12 and Comparative Examples 1 to 5 and the physical property values of the obtained phenol resins are shown in Table 1. Further, Table 2 summarizes the composition of the epoxy resin composition prepared by the following method and the properties of the cured product obtained from the composition.

Production method [Examples 1 to 12, Comparative Examples 1 to 5] of an epoxy resin composition [EMC (Synthesis of Epoxy Molding Compound)]
The epoxy resin composition was manufactured with the compounding ratio shown in Table 2. That is, the phenol resin of the present invention is used as a curing agent, biphenyl epoxy resin (manufactured by JER; YX-4000, epoxy equivalent 188 g / eq) is used as an epoxy resin, and the hydroxyl group equivalent and the epoxy equivalent ratio are 1: 1. Then, TPP (triphenylphosphine) catalyst was charged in an amount of 3.2 wt% based on the weight of the epoxy resin of the blend. The filler was added to 83 wt%, and these were kneaded with a biaxial kneader under conditions of 100 ° C to 110 ° C and pulverized to prepare EMC powder.
In addition, Tatsumori silica (MSR-2212) was used as a filler.
A tablet was prepared using the obtained EMC powder, and spiral flow measurement was performed.
Moreover, the test piece was created with the transfer molding machine, TMA and the test piece were obtained for 180 degreeC 8 hours postcure.
The test methods for various physical properties are as follows.

Hydroxyl equivalent measurement of hydroxyl equivalent according to JIS K0070

Softening point
Ring and ball softening point based on JIS K2207

ICI viscosity ICI cone plate viscometer MODEL CV-1S TOA Industrial Co., Ltd.
The plate temperature of the ICI viscometer is set to 150 ° C., and a predetermined amount of the sample is weighed.
Place the weighed resin on the plate, press it with the cone from the top, and leave it for 90 seconds.
The cone is rotated and its torque value is read as ICI viscosity.

  Glass transition temperature: Measured using TMA method (Thermal Mechanical Analysis, thermomechanical analysis method) (temperature rising rate 3 ° C./min).

Spiral flow Using a mold for spiral flow measurement according to EMMI-I-66, measurement was performed at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa, and a curing time of 2 minutes. This spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity.

  Handling property Blocking property: In a polypropylene cup having a diameter of 7.5 cm and a height of 8.0 cm, 100 g of the granular phenol resin and phenol resin compositions (A) to (Q) synthesized in the following examples are placed, and 27 ° C. Leave for 2 hours. After that, if the (A) to (Q) are taken out and returned to the original granular shape (flakes), ◎, leaving the shape of the cup, but if it can be easily loosened by hand, ○, leaving the shape of the cup by hand. When it was difficult to unravel easily, Δ, and when it was not unraveled in the shape of the cup, x.

Physical properties of phenolic resin

Physical properties of cured epoxy resin

  Thus, the phenolic resin and epoxy resin composition of the present invention are phenolic resins that have a low melt viscosity and excellent handling properties while maintaining a high glass transition temperature and can be stably provided industrially.

Claims (7)

The following general formula (1):

(In the formula, n represents the number of repetitions and represents a positive number of 0 to 5.)
5 to 95 parts by weight of a phenol resin represented by:
General formula (2)

(Where m represents the number of repetitions and represents a positive number from 0 to 5)
95 to 5 parts by weight of a phenol resin represented by
A phenolic resin composition containing   The phenol resin composition according to claim 1, wherein the melt viscosity at 150 ° C. is 10 to 100 mPa · s.   The phenol resin composition according to claim 1 or 2, wherein the phenol resin of the general formula (1) has a weight average molecular weight of 500 to 1,000, and the phenol resin of the general formula (2) has a weight average molecular weight of 300 to 1,000. object. The following general formula (1):

(In the formula, n represents the number of repetitions and represents a positive number of 0 to 5.)
With respect to 5 to 95 parts by weight of the phenol resin represented by
General formula (2)

(Where m represents the number of repetitions and represents a positive number from 0 to 5)
95 to 5 parts by weight of a phenol resin represented by
A method for producing a phenol resin composition, comprising melting and mixing the components.   At least one phenol resin composition and epoxy resin selected from the group consisting of the phenol resin composition according to any one of claims 1 to 3 and the phenol resin composition obtained by the production method according to claim 4. An epoxy resin composition comprising:   The epoxy resin composition of Claim 5 containing a hardening accelerator and / or an inorganic filler.   Hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 5 or 6.