KR101889442B1 - Phenol novolak resin and epoxy resin composition using same - Google Patents

Abstract

(식 중, A는 각각 독립적으로 하기 일반식(2)의 1가 혹은 2가의 유닛, 또는 일반식(3)의 1가 혹은 2가의 유닛을 나타내고, n은 0~20의 정수이며, R1은 각각 독립적으로 탄소수 1~8의 알킬기를 나타내고, p 및 q는 각각 독립적으로 0~2의 정수이다.) An epoxy resin composition comprising a phenol novolac resin (more specifically, a phenol-naphthol novolak resin) and an epoxy resin, wherein the cured product obtained is remarkably improved in heat resistance and flammability, and an epoxy resin composition suitable for the epoxy resin composition To provide a phenolic novolak resin which can be used as a binder. A phenolic novolac resin comprising a chemical structure represented by the following general formula (1).
[Chemical Formula 1]

(Wherein A independently represents a monovalent or divalent unit of the following formula (2), or a monovalent or divalent unit of the formula (3), n is an integer of 0 to 20, and R1 is Each independently represent an alkyl group having 1 to 8 carbon atoms, and p and q are each independently an integer of 0 to 2.)

Description

PHENOL NOVOLAK RESIN AND EPOXY RESIN COMPOSITION USING SAME [0002]

The present invention relates to an epoxy resin composition and a phenol novolak resin suitably used in the epoxy resin composition. The epoxy resin composition of the present invention is improved in heat resistance and combustibility of the resulting cured product. Further, the epoxy resin composition of the present invention preferably has excellent solubility of the phenol novolak resin to be used, so that it is easy to dissolve uniformly in a solvent and can be suitably used, for example, for producing a laminated plate.

The epoxy resin composition is widely used in the fields of electric and electronic parts, structural materials, adhesives, paints and the like because of its good workability and its excellent electrical properties, heat resistance, adhesiveness, moisture resistance and the like.

However, in recent years, improvements in various properties of epoxy resin compositions have been demanded more and more in accordance with progress in the field of electric and electronic fields such as semiconductor encapsulating materials and laminated plates.

For example, since the reflow temperature becomes higher due to the adoption of lead-free solder, the epoxy resin composition used for a semiconductor package such as a laminated board, an interlayer insulating material, a sealing material, A higher heat resistance is required. In addition, as a countermeasure against environmental problems, it is required to improve flammability (flame retardancy) without using flame retardant such as halogen which may generate dioxin or antimony which is suspected of carcinogen in burning. In addition, when an epoxy resin composition is used as a matrix material or an interlayer insulating material of a laminate, since the epoxy resin composition is dissolved in a solvent and varnish is used, the epoxy resin composition is required to be soluble in a solvent.

Patent Document 1 discloses a phenol novolak obtained by reacting a phenol compound with a mixture of isomers of bis (methoxymethyl) biphenyl synthesized by a dehalogenation coupling reaction of a reaction product obtained by the halogenation reaction of methoxymethylbenzene, And an epoxy resin composition comprising the phenol novolac condensate and an epoxy resin. The phenol novolac condensate is an epoxy resin curing agent having excellent moisture absorption, heat resistance and flexibility. However, the phenol novolac condensate specifically disclosed herein is only a mixture of bis (methoxymethyl) biphenyl isomers, and the glass transition of the resulting cured product of an epoxy resin composition containing a phenol novolac condensate and an epoxy resin The temperature was about 140 캜 according to the examples, and there was room for improvement in heat resistance.

Patent Document 2 discloses a phenol-naphthol novolac condensate obtained by a condensation reaction of phenols and naphthols with a biphenyl compound such as bis (methoxymethyl) biphenyl, and a phenol-naphthol novolac condensate and an epoxy resin An epoxy resin composition is disclosed. However, the phenol-naphthol novolak condensate specifically disclosed herein has only used a mixture of isomers of bis (methoxymethyl) biphenyl as a biphenyl compound. This phenol-naphthol novolac condensate is improved in low water absorption and heat resistance as compared with the phenol novolak condensate of Patent Document 1. However, the phenol-naphthol novolac condensate is not limited to the phenol- novolak condensate of the cured product of the epoxy resin composition containing the phenol- The glass transition temperature was about 150 캜 according to the examples, and there was more room for improvement in heat resistance.

Patent Documents 1 and 2 describe the use of a mixture of isomers in a specific ratio, preferably as a biphenyl compound. However, the effect of the 4,4'-isomer such as 4,4'-bis (methoxymethyl) biphenyl as a biphenyl compound alone on the heat resistance, flammability, solubility and the like is not specifically described There was no suggestion.

Japanese Patent Application Laid-Open No. 8-143648 Japanese Patent Application Laid-Open No. 9-176262

The present invention relates to an epoxy resin composition comprising a phenol novolak resin (more specifically, a phenol-naphthol novolak resin) and an epoxy resin, wherein the cured product is remarkably improved in heat resistance and flammability, And to provide a phenol novolak resin which can be suitably used in a composition. Further, the present invention is preferably an epoxy resin composition which is excellent in solubility of a phenol novolac resin to be used, and is thus easily dissolved uniformly in a solvent and can be suitably used for producing, for example, a laminated plate, To provide a phenol novolak resin which can be suitably used in a resin composition.

The present invention relates to each of the following items.

(1) A phenol novolak resin comprising a chemical structure represented by the following general formula (1).

Formula 1

(Wherein A independently represents a monovalent or divalent unit of the following formula (2), or a monovalent or divalent unit of the formula (3), n is an integer of 0 to 20, and R1 is Each independently represent an alkyl group having 1 to 8 carbon atoms, and p and q are each independently an integer of 0 to 2.)

Provided that A is a monovalent or divalent unit represented by the following general formula (2), and a monovalent or divalent unit represented by the following general formula (3), in the phenol novolak resin as a whole.

(2)

(Wherein R 2 is each independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, i is an integer of 1 to 3, j is an integer of 0 to 2, and the sum of i and j is 4 or less.)

Formula 3

(Wherein R3 is independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, k is an integer of 1 to 3, 1 is an integer of 0 to 4, and the sum of k and l is 6 or less.)

(2) The ratio of the unit of the general formula (2) to the unit of the general formula (3) (unit of the general formula (2) / unit of the general formula (3)) is within the range of 10/90 to 90/10 2. The phenol novolak resin according to claim 1,

(3) The resin composition according to any one of (1) to (4) above, wherein the component represented by the following general formula (4) in the whole components constituting the phenol novolac resin is 27% Phenol novolak resin.

Formula 4

(Wherein each R1 independently represents an alkyl group having 1 to 8 carbon atoms, p and q are each independently an integer of 0 to 2, R3 is independently an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms Alkoxy group, k is an integer of 1 to 3, 1 is an integer of 0 to 4, and the sum of k and l is 6 or less.

(4) A phenol novolak resin characterized by reacting a phenol represented by the following formula (5) and a naphthol represented by the following formula (6) with a biphenyl compound represented by the following formula (7) ≪ / RTI >

Formula 5

(Wherein R 2 is each independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, i is an integer of 1 to 3, j is an integer of 0 to 2, and the sum of i and j is 4 or less.)

Formula 6

(Wherein R3 is independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, k is an integer of 1 to 3, 1 is an integer of 0 to 4, and the sum of k and l is 6 or less.)

Formula 7

(Wherein each R1 independently represents an alkyl group having 1 to 8 carbon atoms, p and q each independently represent an integer of 0 to 2, and X represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom.)

(5) An epoxy resin composition comprising the phenol novolac resin (A) according to any one of claims 1 to 3 and an epoxy resin (B).

(6) The epoxy resin composition according to the above item (5), wherein the obtained cured product has a glass transition temperature of 155 占 폚 or higher, preferably 170 占 폚 or higher, more preferably 180 占 폚 or higher.

(7) The epoxy resin composition according to the above item (5) or (6), wherein the cured product obtained has UL-94 flame retardancy of V-0.

(8) A positive resist composition comprising the phenol novolak resin (A), the epoxy resin (B), and the solvent (C) according to any one of claims 1 to 3, Wherein the epoxy resin (B) is uniformly dissolved in the solvent (C).

(9) A cured product obtained by curing any one of the epoxy resin compositions according to any one of claims 5 to 8.

(10) A laminate formed by forming a matrix resin using the epoxy resin composition according to the above-mentioned 8.

Herein, "independently of each other" means that a plurality of substituents or each symbol representing a number can independently take other substituents or numbers when there are a plurality of symbols representing corresponding substituents or numbers. For example, the general formula (1) R1 of the in the (R1) R1 in the _p and (R1) _q is the contribution same alkyl, and the carbon number is the contribution other alkyl, and (R1) in R1 is a plurality of the _p , Each R < 1 > may each be the same alkyl group or may be an alkyl group having a different number of carbon atoms.

In the present invention, as a method of measuring the glass transition temperature, two kinds of methods are used for comparison. However, if there is a difference in measurement method, a method of measuring by a dynamic viscoelasticity measuring device do.

According to the present invention, there is provided an epoxy resin composition comprising a phenol novolac resin (more specifically, phenol-naphthol novolac resin) and an epoxy resin, wherein the cured product obtained is remarkably improved in heat resistance and flammability, A phenol novolac resin which can be suitably used for a resin composition can be provided. Further, since the phenol novolak resin preferably used in the present invention is excellent in solubility, it is easy to dissolve uniformly in a solvent. For example, an epoxy resin composition which can be suitably used for producing a laminate or an interlayer insulating material , And a phenol novolac resin that can be suitably used in the epoxy resin composition.

1 is a reaction mixture HPLC chart before the removal of unreacted raw material components at the end of the reaction in Example 1. Fig.
2 is an HPLC chart of the phenol novolak resin obtained in Example 1. Fig.
3 is a reaction mixture HPLC chart before the removal of unreacted raw material components at the end of the reaction in Example 2. Fig.
4 is a HPLC chart of the phenol novolac resin obtained in Example 2. Fig.

The phenol novolac resin of the present invention is preferably obtained by reacting a phenol represented by the following formula (5) and a naphthol represented by the following formula (6) with a biphenyl compound represented by the following formula (7) .

8

(Wherein R 2 is each independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, i is an integer of 1 to 3, j is an integer of 0 to 2, and the sum of i and j is 4 or less.)

9

(Wherein R3 is independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, k is an integer of 1 to 3, 1 is an integer of 0 to 4, and the sum of k and l is 6 or less.)

Formula 10

(Wherein each R1 independently represents an alkyl group having 1 to 8 carbon atoms, p and q each independently represent an integer of 0 to 2, and X represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom.)

The phenol represented by the general formula (5) is not particularly limited as long as it is a compound having at least one hydroxyl group in the benzene ring, and may have a substituent such as an alkyl group or an alkoxy group. For example, phenol, resorcinol, hydroquinone, cresol, ethylphenol, n-propylphenol, i-propylphenol, t-propylphenol, octylphenol, phenylphenol, guaiacol, guethol, Xylenol, methylethylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol, dibutylphenol and the like, preferably phenol. These phenols may be used singly or in combination.

The naphthol represented by the general formula (6) is not particularly limited as long as it is a compound having at least one hydroxyl group in the naphthalene ring, and may have a substituent such as an alkyl group or an alkoxy group. And examples thereof include aliphatic alcohols such as α-naphthol, β-naphthol, dihydroxynaphthalenes, trihydroxynaphthalenes, methylnaphthol, ethylnaphthol, propylnaphthol, allylnaphthol, t- , Methylbutylnaphthol, methylhexylnaphthol, dimethylnaphthol, diethylnaphthol, dibutylnaphthol and the like, preferably alpha -naphthol. These naphthols may be used singly or in a mixture of two or more thereof.

Examples of the biphenyl compound represented by the general formula (7) include 4,4'-bis (methoxymethyl) biphenyl, 4,4'-bis (ethoxymethyl) biphenyl, 4,4'- ) Biphenyl, 4,4'-bis (bromomethyl) biphenyl, 4,4'-bis (fluoromethyl) biphenyl and the like. These biphenyl compounds may have an alkyl group having 1 to 8 carbon atoms as a substituent. These biphenyl compounds may be used singly or in a mixture of two or more.

When a phenol and naphthol are reacted with a biphenyl compound, it is not necessary to use a catalyst, but an acid catalyst is usually used. As the acid catalyst, organic acids such as oxalic acid, formic acid and acetic acid, and friedel-crafts type catalysts such as sulfuric acid, p-toluenesulfonic acid and diethyl sulfate are suitable. In addition, when a biphenyl compound having a halogenomethyl group is used as the biphenyl compound, the reaction can be suitably carried out even in the absence of an acid catalyst.

In this reaction, the molar ratio [(phenol and naphthol) / biphenyl compound] of the raw material biphenyl compound to the total amount of the phenols and naphthols as raw materials is preferably 20 to 1.5, more preferably 6.0 to 2.0 Is suitable. When the molar ratio is less than 1.5, the viscosity of the resin becomes excessively high and the handling property may be impaired. When the molar ratio exceeds 20, most of the products become low molecular weight and the glass transition temperature of the resulting cured product becomes insufficient. It remains large and becomes uneconomical.

The molar ratio [phenols / naphthols] of the phenols and naphthols as raw materials is preferably in the range of 10/90 to 90/10, more preferably 40/60 to 90/10. (2) derived from phenols of the obtained phenol novolak resin and the unit represented by the general formula (3) derived from naphthols due to the phenols of the resulting phenol novolac resin, by setting the molar ratio of the phenols and naphthols as raw materials within this range. Ratio can be set within the preferred range of the present invention. That is, when the naphthol component is too small, the unit of the general formula (3) introduced into the resin decreases, and it may be difficult to obtain sufficient heat resistance. If the naphthol component is too large, the unit of the general formula (3) introduced into the resin increases, and the unit represented by the general formula (4) also increases, which causes the solvent solubility to be impaired.

The reaction can be usually carried out in the absence of a solvent or in the presence of a solvent such as water and / or an organic solvent at 0 ° C to 150 ° C for 0.5 hours to 10 hours, The reaction conditions such as the reaction temperature, the reaction time and the like are appropriately controlled in order to control the ratio or the degree of polymerization.

After completion of the reaction, unreacted phenols, naphthols, and the like are suitably subjected to distillation under a reduced pressure or by heating while injecting an inert gas to remove them out of the system. Further, the acid catalyst can be removed by washing such as washing with water.

By this reaction, a biphenyl compound forms a crosslinked structure between a plurality of units made of phenols and / or naphthols, and a phenol novolac resin having a chemical structure represented by the general formula (1) is produced.

Therefore, when the phenol or naphthol represented by the general formula (5) and the general formula (6) in the general formula (1) constitute the molecular terminal, A in the general formula (1) Is a monovalent unit of the formula (3), and when contained in the molecule, A in the formula (1) is a divalent unit of the formula (2) and the formula (3).

In this reaction, first, a component in which n in the general formula (1) is 0 is produced. Subsequently, a part of the component in which n is 0 is also reacted with a biphenyl compound or a component in which n is 0 produced. In this way, components with n exceeding 1 and 1 are sequentially produced. Since the reaction for producing a component having n = 0 is continued while the reaction for producing a component in which n is more than 1 and 1 is proceeding, the phenol novolak resin of the present invention usually has a structure represented by the general formula (1) Is an aggregate of a plurality of components having different n values.

One of the characteristics of the phenol novolac resin of the present invention obtained by this reaction is that phenols and naphthols are combined with biphenyl compounds composed of 4,4'-isomers such as 4,4'-bis (chloromethyl) biphenyl To use. The cured product of the epoxy resin composition using the phenol novolac resin of the present invention is suitably improved in heat resistance and flammability.

In the present invention, the phenol novolac resin having the chemical structure represented by the general formula (1) has a ratio of the unit of the general formula (2) derived from the phenol and the unit of the general formula (3) derived from the naphthol [ (Unit of unit (2) / unit of formula (3)] is preferably within the range of 10/90 to 90/10, more preferably within the range of 10/90 to 60/40, Is in the range of 10/90 to 50/50, particularly preferably in the range of 10/90 to 40/60.

The ratio of the unit of the general formula (2) to the unit of the general formula (3) falls within this range, whereby the heat resistance and the combustibility of the cured product of the epoxy resin composition of the present invention can be suitably improved.

By introducing a unit represented by the general formula (3) in combination with a biphenyl compound composed of a 4,4'-isomer in the resin, the heat resistance of the obtained resin is efficiently improved, and combustion can be effectively suppressed, do. However, if the proportion of the unit represented by the general formula (3) is too high, the viscosity of the resin and the softening point may be increased to impair the handling property. In addition, the unit of the general formula (4) It becomes difficult to control.

Therefore, in the reaction for preparing the phenol novolak resin of the present invention, the proportion of the unit of the general formula (2) and the unit of the general formula (3) is preferably within the above range, And the proportion of the naphthol represented by the general formula (6) is controlled. Naphthol, and biphenyl are different from each other. However, since the reactivity of these phenols, naphthols, and biphenyl compounds is different from each other, the ratio of their reactivity and the ratio of phenols And the molar ratio of the biphenyl compound to the total of the naphthalene and the naphthol [(phenol and naphthol) / biphenyl compound] and the reaction conditions to be employed are adjusted to control the ratio. For those skilled in the art, the method of adjustment is self-explanatory, but can be found simply by carrying out a preliminary experiment if necessary.

One preferred embodiment of the phenol novolac resin in the present invention is one in which the component represented by the general formula (4) in the whole components of the aggregate represented by the general formula (1) constituting the phenol novolac resin is measured by HPLC Is not more than 27%, preferably not more than 20%. When the content of the component represented by the general formula (4) is controlled to be 27% or less in terms of the area ratio as measured by HPLC in all the components, the solubility in the organic solvent is improved and the resin / solvent is added to methyl ethyl ketone It becomes possible to uniformly dissolve even at a ratio of 50/50 by mass.

On the other hand, when the component represented by the general formula (4) in the total components exceeds 27% in terms of the area ratio as measured by HPLC, the solubility in an organic solvent is lowered and, for example, a resin / solvent is added to methyl ethyl ketone It becomes difficult to dissolve uniformly in a mass ratio of 50/50.

For example, if the resin / solvent can be uniformly dissolved in a high concentration ratio of 50/50 by mass using methyl ethyl ketone, the epoxy resin composition of the present invention is dissolved in methyl ethyl ketone to be varnishized to form a matrix It becomes easy to use it as a material or an interlayer insulating material. It is not easy to use it as a matrix material or an interlayer insulating material of a laminated board when the film can not be uniformly dissolved and can not be varnishized.

The amount of the component represented by the general formula (4) in the component of the phenol novolak resin can be controlled by adjusting the molar ratio of [(phenol and naphthol) / biphenyl compound] to the total amount of the phenols and naphthols used as raw materials, , And molar ratios of phenols and naphthols [phenols / naphthols] while adjusting the size of their reactivity, reaction conditions employed, and the like.

The molar ratio of [(phenol and naphthol) / biphenyl compound] to the total of phenols and naphthols is set to a smaller value (closer to 1 than usual) (4) can be reduced. Further, since the molar ratio of phenols and naphthols is higher than that of phenols, the reaction of naphthols is relatively increased, so that the reaction is further promoted to increase the molecular weight of the components as a whole, However, if the ratio of the naphthols is too high, the component of the general formula (4) increases and the solubility is adversely affected. For example, when naphthol is 100%, it is naturally difficult to increase the solubility by reducing the amount of the component of the general formula (4).

Their ratio control is carried out in consideration of their reactivity size, reaction conditions employed, and the like. For those skilled in the art, the method of adjustment is self-explanatory, but can be found simply by carrying out a preliminary experiment if necessary.

The phenol novolak resin (A) having the chemical structure represented by the general formula (1) of the present invention preferably has a softening point of 60 to 150 캜, more preferably 70 to 140 캜. When the softening point is less than 60 ° C, blocking or the like tends to occur. When the softening point is more than 150 ° C, there is a case where the handling property is problematic. The weight average molecular weight of the phenol novolac resin (A) composed of the chemical structure represented by the general formula (1) of the present invention is preferably in the range of 500 to 10000, more preferably 500 to 5000, And preferably in the range of 500 to 2000.

Next, the epoxy resin composition of the present invention will be described.

The epoxy resin composition of the present invention comprises a phenol novolac resin (A) and an epoxy resin (B) constituted of the chemical structure represented by the general formula (1).

Examples of the epoxy resin (B) used in the epoxy resin composition of the present invention include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol aralkyl epoxy resin, cresol novolak epoxy resin, phenol novolak type epoxy resin , Glycidyl ether type epoxy resins such as triphenol methane type epoxy resin and biphenyl type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin and halogenated epoxy resin, etc. Epoxy resin, and the like. These epoxy resins may be used singly or in combination of two or more.

Among them, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, triphenylmethane type epoxy resin, cresol novolak type epoxy resin and the like are particularly suitable for improving heat resistance and resistance to burning.

The addition ratio of the epoxy resin (B) to be used in the epoxy resin composition of the present invention is preferably such that the ratio of the hydroxyl equivalent of the curing agent to the epoxy equivalent in the epoxy resin [hydroxyl group equivalent / epoxy equivalent] is about 0.5 to 2.0, And more preferably about 0.8 to 1.2. Outside this range, the curing reaction does not proceed sufficiently, and the effect of the present invention may not be exhibited due to reasons such as unreacted curing agent or epoxy resin remaining.

The phenol novolac resin (A) having the chemical structure represented by the general formula (1) has a role as a curing agent of the epoxy resin in the epoxy resin composition of the present invention, but in the epoxy resin composition of the present invention, (A) other than the phenol novolac resin (A) composed of the chemical structure represented by the following formula (1).

The curing agent other than the phenol novolac resin (A) is not particularly limited, and various epoxy resin curing agents may be used depending on the intended use of the composition. For example, a conventional epoxy resin curing agent such as an amine curing agent, an amide curing agent, an acid anhydride curing agent, and a phenol resin curing agent other than the phenol novolac resin (A) having a chemical structure represented by the general formula (1) Can be suitably used.

In the epoxy resin composition of the present invention, the proportion of the phenol novolac resin (A) constituted by the chemical structure represented by the general formula (1) in the curing agent is not particularly limited. However, in order to improve the heat resistance and the combustibility of the cured product And more preferably 30 mass% or more, preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 90 mass% or more preferably 100 mass% or more.

It is preferable that the epoxy resin composition of the present invention further comprises a solvent (C), and the phenol novolak resin (A) and the epoxy resin (B) are uniformly dissolved in the solvent (C) .

If an epoxy resin composition excellent in heat resistance and flame resistance of the obtained cured product can be used as a highly concentrated and uniform varnish solution, it can be suitably used as a matrix material or an interlayer insulating material of a laminate.

The solvent (C) is not particularly limited as long as it dissolves the epoxy resin composition, but preferably a matrix material of a conventional laminate or an organic solvent used for varnishing an interlayer insulating material can be suitably used. Examples of the solvent include ketones such as methyl ethyl ketone, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as propylene glycol monomethyl ether, amides such as dimethyl formamide and dimethylacetamide, And the like; lactones such as? -Butyllactone; pyrrolidones such as N-methylpyrrolidone; aromatic hydrocarbons such as toluene and xylene. Of these, methyl ethyl ketone and dimethyl formamide are particularly preferable. These solvents may be used alone or in combination of two or more.

The concentration of the resin component is preferably about 10 to 90% by mass, and the solution viscosity is about 1 to 5000 cP at 30 캜, although it is not limited when the epoxy resin composition of the present invention is made into a varnish.

In the epoxy resin composition of the present invention, other components used as a conventional epoxy resin composition may be suitably used depending on the use thereof.

For example, a curing accelerator for curing an epoxy resin with a phenol resin can be used. As the curing accelerator, known organophosphine compounds and boron salts thereof, tertiary amines, quaternary ammonium salts, imidazoles and tetraphenylboron salts are suitably used. Of these, triphenylphosphine is preferable from the viewpoint of hardenability and moisture resistance. When high fluidity is required by the epoxy resin composition, a curing accelerator having thermal latency in which the activity is exhibited by heat treatment is preferable, and among these, a tetraphenylphosphonium derivative such as tetraphenylphosphonium tetraphenylborate Is more preferable. The addition amount of the curing accelerator may be the same as that in the known epoxy resin composition.

Fillers such as inorganic fillers can also be suitably used. As the inorganic filler, amorphous silica, crystalline silica, alumina, calcium silicate, calcium carbonate, talc, mica, barium sulfate and the like can be used, and more preferable are amorphous silica and crystalline silica. The particle size of the inorganic filler is not particularly limited, but it is preferably 0.01 탆 or more and 150 탆 or less considering the filling factor.

The mixing ratio of the inorganic filler is not particularly limited, but is 70% by weight to 95% by weight, preferably 75% by weight to 90% by weight, and more preferably 80% by weight to 90% by weight in the epoxy resin composition. If the ratio of the inorganic filler is out of the above range, the water absorption of the cured product of the epoxy resin composition increases, which is not preferable. If the proportion of the inorganic filler is too large, the fluidity may be impaired.

In addition, the epoxy resin composition of the present invention may be added with a releasing agent, a colorant, a coupling agent, a flame retardant and the like, if necessary, or may be reacted in advance. The mixing ratio of these additives may be the same as that of the known epoxy resin composition. If necessary, a phosphorus-based flame retardant such as a nitrogen-based flame retardant such as melamine, isocyanuric acid compound or the like, a phosphoric acid compound, or an organic phosphorus compound may suitably be added to the epoxy resin composition of the present invention.

The epoxy resin composition of the present invention is prepared by uniformly mixing a phenol novolak resin (A), an epoxy resin (B), a curing accelerator, an inorganic filler, and other additives to be added, if necessary, using, for example, a mixer Kneading in a molten state using a mixing kneader such as a kneader, a kneader, a kneader, or an extruder, cooling the kneaded product, and optionally grinding the kneaded product.

Such an epoxy resin composition is not limited, but may be suitably used as a semiconductor encapsulating material or the like.

In addition, the epoxy resin composition of the present invention can be obtained by adding a phenol novolak resin (A) having a chemical structure represented by the general formula (1) to a solvent (C) such as methyl ethyl ketone, propylene glycol monomethyl ether or dimethyl formamide, (A) and the epoxy resin (B) are dissolved in a solvent (for example, a mixture of an epoxy resin (A) and an epoxy resin (B)), and if necessary, other curing agents, a curing accelerator, an inorganic filler, an additive, C) in the form of a solution.

The varnishized epoxy resin (solution) composition is not limited, but it can be suitably used as a matrix material or an interlayer insulating material of a laminate.

The epoxy resin composition of the present invention can suitably obtain a cured product by drying the solvent as required after the heat treatment.

The heat treatment conditions for obtaining the cured product depend on the presence or absence of the curing catalyst or the curing accelerator, the amount thereof to be added, and the like. Usually, the heat treatment is performed at a temperature of about 100 to 300 DEG C, preferably about 120 to 200 DEG C for about 1 to 10 hours It is preferable to carry out heat treatment.

The epoxy resin composition of the present invention can be suitably used as an encapsulating material for encapsulating semiconductor devices. For example, after a lead frame or the like on which the semiconductor element is mounted is placed in a metal cavity, the epoxy resin composition is molded by a molding method such as a transfer mold, a compression mold or an injection mold, The epoxy resin composition is cured by a heat treatment or the like at a temperature of 40 DEG C to obtain a semiconductor device suitably.

The epoxy resin composition of the present invention is preferably uniformly dissolved in a solvent such as methyl ethyl ketone to be varnish. The varnish solution is applied to a porous glass base material such as glass, glass fiber, paper aramid fiber, etc., ), And then subjected to heat treatment (semi-curing) to prepare a prepreg for a printed circuit board. Further, a laminate can be produced by laminating a plurality of prepregs obtained for the printed board, and optionally curing by heating under pressure.

Further, a metal plate is laminated on one side or both sides of the laminate or prepreg, and is subjected to heat treatment (for example, heat treatment at 180 캜 and 4 MPa pressure for 60 minutes) while pressurizing if necessary to form a metal sheet clad laminates can be obtained. The metal-clad laminate can be used suitably as a printed wiring board by forming a circuit pattern by etching.

The epoxy resin composition of the present invention is preferably uniformly dissolved in a solvent such as methyl ethyl ketone to be varnish, and the varnish solution is applied to the surface of a support such as a PET film or a copper foil by die coater , And the resulting coating film is heated and dried to obtain a laminated sheet having a resin layer and can be suitably used as an interlayer insulating material.

Example

Hereinafter, the present invention will be described in more detail by way of example. The present invention is not limited to these examples.

[1] preparation of phenolic novolak resins

The materials used in the following examples of preparing phenol novolak resins will be described.

(1) Phenol: product of Wako Pure Yakuko Co., Ltd.

(2)? -Naphthol (1-naphthol): manufactured by Wako Pure Chemical Industries, Ltd.

(3) 4,4'-bis (chloromethyl) biphenyl: manufactured by Wako Pure Chemical Industries, Ltd.

The analytical methods and evaluation methods used in the following examples of preparing phenol novolak resins will be described.

(1) Softening point: The softening point was measured by a ring method (ring method) based on JIS K6910.

(2) Hydroxyl equivalents: Hydroxyl equivalents according to JIS K0070 were measured.

(3) Measurement of the ratio of the unit of the general formula (2) to the unit of the general formula (3) (unit of the general formula (2) / unit of the general formula (3) The amount of phenol novolak resin produced, and the amount of by-product produced are measured, and the amount of unreacted starting material is calculated from the reaction resin. Since the biphenyl compound is reacted in its entirety, the unreacted raw material is composed of the phenols of the raw material constituting the unit of the formula (2) and the naphthols of the raw material constituting the unit of the formula (3). The ratio of the unreacted phenol and naphthol in the reaction mixture was determined from an HPLC chart obtained by HPLC measurement under the following conditions. The ratio (molar ratio) was taken as the area ratio. From the above data, the ratio of the unit of the general formula (2) to the unit of the general formula (3) (units of the general formula (2) / units of the general formula (3)) was calculated by the following equation.

Measurement conditions of HPLC

Device: Shimadzu Seisakusho Co., Ltd. HPLC

Column: STR ODS-H column (manufactured by Shin-Wakako Co., Ltd.)

Column oven temperature: 40 ° C

Mobile layer: acetonitrile, 5% phosphoric acid solution

The concentration of the mobile layer was adjusted by using a mixed solution having a volume ratio of acetonitrile / 5% phosphoric acid solution of 20/60 at the beginning of the measurement, and measuring the volume ratio of acetonitrile to a ratio of 60/40 linearly And then the ratio of acetonitrile was linearly increased up to 100/0 over a period of 5 minutes, and then acetonitrile was used as it was until the end of the measurement.

Flow rate (flow rate): 1.00 ml / min

Detected wavelength: 220 nm

(4) Ratio of components represented by general formula (4): The area ratio was obtained from an HPLC chart obtained by HPLC measurement under the following conditions.

Measurement conditions of HPLC

Device: Shimadzu Seisakusho Co., Ltd. HPLC

Column: STR ODS-H column (manufactured by Shin-Wakako Co., Ltd.)

Column oven temperature: 40 ° C

Mobile layer: acetonitrile, 5% phosphoric acid solution

The concentration of the mobile layer was adjusted by using a mixed solution having a volume ratio of acetonitrile / 5% phosphoric acid solution of 50/50 at the start of the measurement and a volume ratio of acetonitrile to a ratio of 75/25 , Followed by increasing the proportion of acetonitrile linearly up to a volume ratio of 100/0 over 20 minutes, and thereafter using acetonitrile until the end of the measurement in its original state.

Flow rate: 1.00 ml / min

Detected wavelength: 220 nm

(5) Solubility:

Was evaluated by a dissolution test by the following method.

Solvent: methyl ethyl ketone

Solubility ratio (mass): phenol novolac resin / solvent = 50/50

Dissolution condition: A resin and a solvent were added to a sealed container, and the solution was stirred and dissolved at 60 캜.

Evaluation Judgment: After dissolution and after standing for 12 hours at room temperature (23 占 폚), the sample was visually observed. The resin was uniformly dissolved and uniformly maintained even after standing; the resin was uniformly dissolved, but a part of the resin was precipitated after standing; and a case where a uniform solution could not be obtained was evaluated as X.

[Example 1]

188.0 g (2.0 mol) of phenol and 123.4 g (0.9 mol) of? -Naphthol were added to a 1000 ml glass flask equipped with a thermometer, a charging / discharging outlet, a condenser and a stirrer, And the temperature was raised to 60 DEG C to dissolve the raw material. 179.3 g (0.7 mol) of 4,4'-bis (chloromethyl) biphenyl was added and reacted at an internal temperature of 60 ° C to 100 ° C for 4 hours and further at 165 ° C for 3 hours, followed by a reduced pressure-steaming treatment To remove unreacted components of the raw material.

The obtained phenol novolac resin had a softening point of 113 ° C and a hydroxyl group equivalent of 263 g / eq. The ratio of the unit of the general formula (2) to the unit of the general formula (3) (unit of general formula (2) The unit of the formula (3)] was 30/70, and the proportion of the component represented by the general formula (4) was 15%. The evaluation of the solubility of the phenol novolac resin was & cir &

An HPLC chart of unreacted raw materials of this reaction is shown in Fig. From this chart, the proportions of phenols and naphthols in unreacted raw materials were calculated to be 82% and 18%. The ratio of the unit of the general formula (2) and the unit of the general formula (3) (unit of the general formula (2) / unit of the general formula (3)) introduced into the resin is Respectively.

The HPLC chart of the obtained phenol novolak resin is shown in Fig. From the area ratio of this chart, the ratio of the component represented by the general formula (4) (the sum of three peaks in the presence of isomers) was obtained.

[Example 2]

84.6 g (0.9 mol) of phenol and 129.6 g (0.9 mol) of? -Naphthol were added to a 1000 ml glass flask equipped with a thermometer, inlet / outlet, cooler and stirrer and the internal temperature was raised to 60 ° C To dissolve the raw material. (0.7 mol) of 4,4'-bis (chloromethyl) biphenyl was added and reacted at an internal temperature of 60 ° C to 100 ° C for 4 hours and further at 165 ° C for 3 hours, followed by decompression- Unreacted components were removed.

The phenol novolak resin thus obtained had a softening point of 131 ° C and a hydroxyl group equivalent of 256 g / eq. The ratio of the unit of the general formula (2) to the unit of the general formula (3) as measured by HPLC (unit of the general formula (2) (Unit of (3)] was 20/80, and the proportion of the component represented by general formula (4) was 18%. The evaluation of the solubility of the phenol novolac resin was & cir &

An HPLC chart of unreacted raw materials of this reaction is shown in Fig. From this chart, the proportions of phenols and naphthols in unreacted raw materials were calculated to be 76% and 24%, respectively. Using this ratio, the ratio of units of the general formula (2) to units of the general formula (3) (units of the general formula (2) / units of the general formula (3)) was calculated according to the above calculation formula.

A HPLC chart of the obtained phenol novolak resin is shown in Fig. From the area ratio of this chart, the ratio of the component represented by the general formula (4) (the sum of three peaks in the presence of isomers) was obtained.

[Example 3]

94.0 g (1.0 mol) of phenol and 144.0 g (1.0 mol) of? -Naphthol were added to a 1000 ml glass flask equipped with a thermometer, inlet / outlet, cooler and stirrer, To dissolve the raw material. (0.7 mol) of 4,4'-bis (chloromethyl) biphenyl was added and reacted at an internal temperature of 60 ° C to 100 ° C for 4 hours and further at 165 ° C for 3 hours, followed by decompression- Unreacted components were removed.

The resulting phenol novolac resin had a softening point of 117 ° C, a hydroxyl equivalent of 247 g / eq, and a proportion of the component represented by the general formula (4) measured by HPLC to 24%. The evaluation of the solubility of the phenol novolak resin was?.

[Example 4]

18.0.0 g (2.0 mol) of phenol and 123.4 g (1.0 mol) of? -Naphthol were added to a 1000 ml glass flask equipped with a thermometer, an inlet and an outlet, a condenser and a stirrer, To dissolve the raw material. 119.5 g (0.5 mol) of 4,4'-bis (chloromethyl) biphenyl was added and reacted at an internal temperature of 60 ° C. to 100 ° C. for 4 hours and further at 165 ° C. for 3 hours. The ingredients were removed.

The resulting phenol novolac resin had a softening point of 97 ° C, a hydroxyl equivalent of 238 g / eq, and a proportion of the component represented by the general formula (4) as measured by HPLC was 30%. The evaluation of the solubility of the phenol novolak resin was X.

[Example 5]

141.0 g (1.5 mol) of phenol and 216.0 g (1.5 mol) of? -Naphthol were added to a 1000 ml glass flask equipped with a thermometer, inlet / outlet, cooler and stirrer, To dissolve the raw material. 125.5 g (0.5 mol) of 4,4'-bis (chloromethyl) biphenyl was added and reacted at an internal temperature of 60 ° C to 100 ° C for 4 hours and further at 165 ° C for 3 hours, followed by decompression- The ingredients were removed.

The resulting phenol novolac resin had a softening point of 94 占 폚, a hydroxyl group equivalent of 238 g / eq, and a proportion of the component represented by the general formula (4) as measured by HPLC was 49%. The evaluation of the solubility of the phenol novolak resin was X.

Table 1 summarizes the phenol novolac resins of Examples 1 to 5. From the results of the evaluation of the solubility in this table, it is preferable that the proportion of the component represented by the general formula (4) is not more than 27%, preferably not more than 20%, in order to uniformly dissolve the epoxy resin composition using the phenol novolac resin of the present invention in a solvent Is preferable.

[2] Preparation of the epoxy resin composition of the present invention and comparison of Patent Document 2

Hereinafter, the materials used in the examples according to the epoxy resin composition will be described.

(1) Epoxy resin

Ortho cresol epoxy resin "EOCN-1020-70" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 200 g / eq, softening point: 70 ° C.

(2) Curing accelerator (curing catalyst)

Triphenylphosphine (TPP): product of Hokkokagakusa

The evaluation method according to the epoxy resin composition will be described below.

(1) Heat resistance (glass transition temperature (Tg))

The measurement was carried out in accordance with the measurement method of Patent Document 2. That is, the temperature was raised at a heating rate of 5 ° C / minute by using a test piece made of a cured product having dimensions of 4 mm × 6 mm × 10 mm and measured by the TMA method (Thermal Mechanical Analysis, Thermal Mechanical Analysis).

[Example 6]

EOCN-1020-70, which is an isocresol type epoxy resin, and TPP, which is a curing accelerator, were added in the formulations shown in Table 2 to obtain an epoxy resin composition. The epoxy resin composition was heat-melted The resultant mixture was vacuum-defoamed and then cast into a mold (thickness: 4 mm) at 150 DEG C and cured at 150 DEG C for 5 hours and further cured at 180 DEG C for 8 hours to obtain a cured molded article .

The glass transition temperature of this cured molded article was measured and found to be 175 ° C.

In Example 6, an epoxy resin composition was prepared by the same procedure as in Examples 5 to 6 of Patent Document 2 except that the phenol novolak resin used was changed, and the cured product was evaluated in the same manner. The evaluation results of this Example 6 are shown in Table 2 in comparison with the data of Example 7 of Patent Document 2.

From Table 2, it can be seen that by using the phenol novolak resin of the present invention, the glass transition temperature of the cured product of the epoxy resin composition is remarkably improved.

[3] Preparation of epoxy resin composition of the present invention and evaluation by EMC test piece

Hereinafter, the materials used in the examples according to the epoxy resin composition will be described.

(1) Epoxy resin

Biphenyl-type epoxy resin "YX-4000" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 187 g / eq

(2) Curing accelerator (curing catalyst)

Triphenylphosphine (TPP): product of Hokkokagakusa

(3) Inorganic fillers

Silica "MSR-2212 ": manufactured by Tatsumori

The evaluation method according to the epoxy resin composition will be described below.

(1) Flammability

And measured according to UL-94.

(2) Heat resistance (glass transition temperature (Tg))

An EMC specimen having dimensions of 40 mm x 12 mm x 1 mm was measured at a heating rate of 3 DEG C / min using a dynamic viscoelasticity measuring apparatus (RSA-G2 manufactured by TA Instruments).

(3) Mechanical properties: Mechanical strength: Measured according to JIS K 7171.

[Example 7]

The phenol novolac resin obtained in Example 1, YX-4000 as a biphenyl type epoxy resin, TPP as a curing accelerator, and silica MSR-2212 as an inorganic filler were added in the form shown in Table 2, , The mixture was kneaded using two rolls and pulverized to obtain an epoxy resin composition of the present invention.

A tablet was prepared using the obtained epoxy resin composition and injected into a mold under the conditions of a mold temperature of 175 캜, an injection pressure of 6.8 MPa, and a pressure holding time of 600 seconds using a low pressure transfer molding machine to prepare a test piece, And then postcured at 180 DEG C for 8 hours to obtain an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition.

The evaluation results are shown in Table 3.

[Example 8]

(Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition was obtained in the same manner as in Example 7 except that the phenol novolak resin obtained in Example 2 was used.

The evaluation results are shown in Table 3.

[Example 9]

(Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition was obtained in the same manner as in Example 7 except that the phenol novolak resin obtained in Example 3 was used.

The evaluation results are shown in Table 3.

[Example 10]

(Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition was obtained in the same manner as in Example 7 except that the phenol novolak resin obtained in Example 4 was used.

The evaluation results are shown in Table 3.

(Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition was obtained in the same manner as in Example 7 except that the phenol novolak resin obtained in Example 5 was used.

The evaluation results are shown in Table 3.

(Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition was obtained in the same manner as in Example 7 except that the phenol novolak resin obtained in Example 6 was used.

The evaluation results are shown in Table 3.

[Referential Example 1]

470.0 g (5.0 moles) of phenol was added to a glass flask having a capacity of 1000 ml equipped with a thermometer, a charging / discharging port, a condenser and a stirrer and the internal temperature was raised to 60 ° C in a nitrogen stream to dissolve the raw material. (1.3 mol) of 4,4'-bischloromethylbiphenyl was added and reacted at an internal temperature of 60 ° C to 100 ° C for 4 hours and further at 165 ° C for 3 hours, followed by decompression-steaming treatment to remove unreacted components Respectively. The resulting phenol novolac resin E had a softening point of 68 占 폚 and a hydroxyl group equivalent of 202 g / eq.

[Comparative Example 1]

An epoxy (Epoxy Molding Compound) test piece having a size of 40 mm x 12 mm x 1 mm and made of a cured product of the epoxy resin composition was obtained, except that the phenol novolak resin obtained in Reference Example 1 was used .

The evaluation results are shown in Table 3.

[4] Production and Evaluation of Copper Clad Laminate Using the Epoxy Resin Composition of the Present Invention

Hereinafter, the materials used in the examples of manufacturing the copper clad laminate will be described.

(1) Epoxy resin

Bisphenol A type epoxy resin "828EL ": product of Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / eq

(2) Curing accelerator (curing catalyst)

2-ethyl-4-methylimidazole (2E4MZ): manufactured by Shikoku Kasei Co., Ltd.

(3) Solvent (methyl ethyl ketone): product of Wako Junyaku Corporation

(4) Glass cloth (glass cloth without alkali treatment) "M7628-105": manufactured by Arisawa Seisakusho Co., Ltd.

(5) Copper foil (electrolytic copper foil) "CF-T9B-THE ": Fukuda Kinshoku

The evaluation method according to the copper-clad laminate will be described below.

(1) Adhesion (peel strength)

Using a dynamic viscoelasticity measuring device ("AG-5000D" manufactured by Shimadzu Seisakusho Co., Ltd.), 90 ° copper peel strength was measured at a load of 1 kN / 100 kgf and a test speed of 50 mm / min.

(2) Heat resistance

The glass transition temperature (Tg) was measured using a dynamic viscoelasticity measuring device ("RSA-G2" manufactured by TA Instruments) at a heating rate of 3 ° C / min.

(3) Absorption rate (water absorption rate)

Measured according to JIS C6481.

[Example 12]

131 parts by mass of the phenol novolac resin obtained in Example 1, 100 parts by mass of the bisphenol-type epoxy resin and 0.1 part by mass of 2E4MZ as a curing accelerator were added to 231.2 parts by mass of methyl ethyl ketone as a diluting solvent to obtain a uniformly dissolved resin component To obtain a varnish solution having a concentration of 50 mass%.

The obtained varnish solution was impregnated with M7628-105 of glass cloth and dried at 130 DEG C for 15 minutes to obtain a prepreg. The overlap of 8 prepreg rolled up in CF-T9B-THE copper foil on both sides, and pressed by using a press machine for 15 minutes with 170 ℃, 30kg / cm ^2. The copper-clad laminate was taken out from the press machine, and further subjected to after-curing at 200 DEG C for 5 hours to obtain a double-side copper clad laminate.

The obtained copper clad laminate had a glass transition temperature of 159 DEG C, a peel strength of 2.0 N / mm, and a water absorption of 0.05% by mass. The results are shown in Table 4.

[Reference Example 2]

470.0 g (5.0 mol) of phenol, 110.9 g (3.4 mol) of 92% paraformaldehyde and 0.3 g of oxalic acid were added to a 1000 ml glass flask equipped with a thermometer, an inlet and an outlet, a condenser and a stirrer. Lt; / RTI > After the completion of the reaction, unreacted components were removed by vacuum-steaming. The resulting phenol novolac resin E had a softening point of 96 占 폚 and a hydroxyl group equivalent of 107 g / eq.

[Comparative Example 2]

A double-sided copper clad laminate was obtained in the same manner as in Example 9, except that the general phenol novolac resin prepared in Reference Example 2 was used in place of the phenol novolak resin obtained in Example 1, and the blending was carried out as shown in Table 4.

The obtained copper clad laminate had a glass transition temperature of 147 캜, a fill strength of 1.6 N / mm, and a water absorption rate of 0.09% by mass. The results are shown in Table 4.

According to the present invention, there is provided an epoxy resin composition comprising a phenol novolac resin (more specifically, phenol-naphthol novolac resin) and an epoxy resin, wherein the cured product obtained is remarkably improved in heat resistance and flammability, A phenol novolac resin which can be suitably used for a resin composition can be provided. Further, according to the present invention, since the phenol novolak resin used is preferably excellent in solubility, it is easy to dissolve uniformly in a solvent. For example, an epoxy resin which can be suitably used for producing a laminate or an interlayer insulating material A resin composition, and a phenol novolak resin that can be suitably used in the epoxy resin composition can be provided.

Claims (10)

A phenol novolak resin characterized by comprising a chemical structure represented by the following general formula (1).

(Wherein A independently represents a monovalent or divalent unit of the following formula (2), or a monovalent or divalent unit of the formula (3), n is an integer of 0 to 20, and R1 is Each independently represent an alkyl group having 1 to 8 carbon atoms, and p and q are each independently an integer of 0 to 2.)
With the proviso that A is a monovalent or divalent unit represented by the following general formula (2) and a monovalent or divalent unit represented by the following general formula (3) in the phenol novolak resin as a whole,

(Wherein R 2 is each independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, i is an integer of 1 to 3, j is an integer of 0 to 2, and the sum of i and j is 4 or less.)

(Wherein R3 is independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, k is an integer of 1 to 3, 1 is an integer of 0 to 4, and the sum of k and l is 6 or less.)
And the component represented by the following general formula (4) in all the components constituting the phenol novolac resin is 27% or less in terms of the area ratio measured by HPLC.

(Wherein each R1 independently represents an alkyl group having 1 to 8 carbon atoms, p and q are each independently an integer of 0 to 2, R3 is independently an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms Alkoxy group, k is an integer of 1 to 3, 1 is an integer of 0 to 4, and the sum of k and l is 6 or less. The method according to claim 1,
The unit of the unit of the general formula (2) and the unit of the general formula (3) (unit of the general formula (2) / unit of the general formula (3)) is in the range of 10/90 to 90/10 Phenolic novolak resin. delete A process for producing a phenol compound represented by the formula (1) or (2), wherein the phenol represented by the following formula (5) and the naphthol represented by the following formula (6) are reacted with the biphenyl compound represented by the following formula (Preparation method of phenol novolak resin).

(Wherein R 2 is each independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, i is an integer of 1 to 3, j is an integer of 0 to 2, and the sum of i and j is 4 or less.)

(Wherein R3 is independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, k is an integer of 1 to 3, 1 is an integer of 0 to 4, and the sum of k and l is 6 or less.)

(Wherein each R1 independently represents an alkyl group having 1 to 8 carbon atoms, p and q each independently represent an integer of 0 to 2, and X represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom.) An epoxy resin composition comprising the phenol novolak resin (A) according to any one of claims 1 to 3 and an epoxy resin (B). 6. The method of claim 5,
And the resulting cured product has a glass transition temperature of 155 占 폚 or higher. 6. The method of claim 5,
And the flame retardancy of the obtained cured product by UL-94 is V-0. An epoxy resin composition comprising the phenol novolak resin (A), the epoxy resin (B) and the solvent (C) according to any one of claims 1 to 5, wherein the phenol novolac resin (A) Wherein the epoxy resin composition is uniformly dissolved in the solvent (C). A cured product obtained by curing the epoxy resin composition according to claim 5. A laminate characterized in that a matrix resin is formed using the epoxy resin composition according to claim 8.

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