JP5752574B2 - Phenol novolac resin and epoxy resin composition using the same - Google Patents

Description

  The present invention relates to an epoxy resin composition and a phenol novolac resin suitably used for the epoxy resin composition. The epoxy resin composition of the present invention is obtained by improving the heat resistance and combustion resistance of the resulting cured product. Furthermore, since the epoxy resin composition of the present invention preferably has excellent solubility of the phenol novolac resin used, it can be easily dissolved uniformly in a solvent, and is preferably used, for example, for the purpose of producing a laminate. Can do.

  Epoxy resin composition has good workability, and its cured product has excellent electrical properties, heat resistance, adhesion, moisture resistance, etc., so electrical / electronic parts, structural materials, adhesives, paints, etc. Widely used in the field.

  However, in recent years, with the advancement of technology in the electrical / electronic field such as semiconductor encapsulants and laminates, further improvements in various properties are required for epoxy resin compositions.

  For example, the use of lead-free solder has led to higher reflow temperatures, which means that epoxy resin compositions used in semiconductor packages such as laminates, interlayer insulation materials, and sealing materials can be compared to conventional products. High heat resistance is required. In addition, as a countermeasure to environmental problems, flame resistance (flame resistance) is improved without using halogens that may generate dioxins during combustion or antimony or other flame retardants that are suspected of causing carcinogenicity. It is demanded. Furthermore, when an epoxy resin composition is used as a matrix material or an interlayer insulating material for a laminated board, the epoxy resin composition is required to be soluble in a solvent for the epoxy resin composition because the epoxy resin composition is dissolved in a solvent and used as a varnish. ing.

  In Patent Document 1, a mixture of isomers of bis (methoxymethyl) biphenyl synthesized by a dehalogenation coupling reaction of a reaction product obtained by a halogenation reaction of methoxymethylbenzene is reacted with a phenol compound. A phenol novolac condensate obtained by the above-mentioned method and an epoxy resin composition containing the phenol novolac condensate and an epoxy resin are disclosed. This phenol novolac condensate is excellent in hygroscopicity, heat resistance and flexibility as an epoxy resin curing agent. However, the phenol novolac condensate specifically disclosed herein is only one using a mixture of isomers of bis (methoxymethyl) biphenyl, and an epoxy resin containing the obtained phenol novolac condensate and an epoxy resin According to the examples, the glass transition temperature of the cured product composed of the composition was about 140 ° C., and there was room for improvement in heat resistance.

  Patent Document 2 discloses a phenol-naphthol novolak condensate obtained by a condensation reaction of phenols and naphthols with a biphenyl compound such as bis (methoxymethyl) biphenyl, and the phenol-naphthol novolak condensate and an epoxy resin. An epoxy resin composition is disclosed. However, the phenol-naphthol novolak condensate specifically disclosed here is only one using a mixture of bis (methoxymethyl) biphenyl isomers as the biphenyl compound. This phenol-naphthol novolak condensate is obtained by improving low water absorption and heat resistance with respect to the phenol novolak condensate of Patent Document 1, but includes an epoxy resin containing a phenol-naphthol novolak condensate and an epoxy resin. According to the examples, the glass transition temperature of the cured product composed of the composition was about 150 ° C., and there was room for further improvement in heat resistance.

  Patent Documents 1 and 2 describe the use of a mixture of isomers in a specific proportion, preferably as a biphenyl compound. However, when a 4,4′-isomer such as 4,4′-bis (methoxymethyl) biphenyl is used alone as a biphenyl compound, it has any influence on heat resistance, combustion resistance, solubility, etc. There was no specific description or suggestion.

JP-A-8-143648 Japanese Patent Laid-Open No. 9-176262

  The present invention is an epoxy resin composition containing a phenol novolac resin (more specifically, a phenol-naphthol novolak resin) and an epoxy resin, and the resulting cured product has significantly improved heat resistance and combustion resistance. It is to provide an epoxy resin composition and a phenol novolac resin that can be suitably used for the epoxy resin composition. Furthermore, since the present invention preferably has excellent solubility of the phenol novolak resin used, it is easy to uniformly dissolve in a solvent, and for example, an epoxy resin composition that can be suitably used for the purpose of producing a laminated board And a phenol novolac resin that can be suitably used for the epoxy resin composition.

The present invention relates to the following items.
(1) A phenol novolac resin constituted by a chemical structure represented by the following general formula (1).

（式中、Ａは、それぞれ独立に、下記一般式（２）の１価若しくは２価のユニット、又は一般式（３）の１価若しくは２価のユニットを表し、ｎは０〜２０の整数であり、Ｒ１は、それぞれ独立に、炭素数１〜８のアルキル基を表し、ｐ及びｑは、それぞれ独立に、０〜２の整数である。）
但し、フェノールノボラック樹脂全体としては、Ａは、下記一般式（２）の１価若しくは２価のユニット、及び下記一般式（３）の１価若しくは２価のユニットの両者によって構成されている。

(In the formula, each A independently represents a monovalent or divalent unit of the following general formula (2) or a monovalent or divalent unit of the general formula (3), and n is an integer of 0 to 20. R1 represents each independently an alkyl group having 1 to 8 carbon atoms, and p and q are each independently an integer of 0 to 2.)
However, as a whole phenol novolac resin, A is composed of both monovalent or divalent units of the following general formula (2) and monovalent or divalent units of the following general formula (3).

（式中、Ｒ２は、それぞれ独立に、炭素数１〜８のアルキル基、又は炭素数１〜８のアルコキシ基を表し、ｉは１〜３の整数であり、ｊは０〜２の整数であり、ｉとｊとの合計は４以下である。）

(In the formula, each R2 independently represents 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, and j is an integer of 0 to 2). Yes, the sum of i and j is 4 or less.)

（式中、Ｒ３は、それぞれ独立に、炭素数１〜８のアルキル基、又は炭素数１〜８のアルコキシ基を表し、ｋは１〜３の整数であり、ｌは０〜４の整数であり、ｋとｌとの合計は６以下である。）

(In the formula, each R3 independently represents 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, and l is an integer of 0 to 4). Yes, the sum of k and l is 6 or less.)

(2) 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)] is 10/90 to 90/10. Item 2. The phenol novolac resin according to Item 1, which falls within the range.

(3) Item 1 or 2 above, wherein the component represented by the following general formula (4) in all components constituting the phenol novolak resin is 27% or less in terms of area ratio when measured by HPLC The phenol novolac resin described in 1.

（式中、Ｒ１は、それぞれ独立に、炭素数１〜８のアルキル基を表し、ｐ及びｑは、それぞれ独立に、０〜２の整数であり、Ｒ３は、それぞれ独立に、炭素数１〜８のアルキル基、又は炭素数１〜８のアルコキシ基を表し、ｋは１〜３の整数であり、ｌは０〜４の整数であり、ｋとｌとの合計は６以下である。）

(In the formula, 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, and R3 is each independently an integer of 1 to 2 carbon atoms. 8 represents an alkyl group or an alkoxy group having 1 to 8 carbon atoms, k is an integer of 1 to 3, l is an integer of 0 to 4, and the sum of k and l is 6 or less.)

(4) A phenol represented by the following general formula (5) and a naphthol represented by the following general formula (6) are reacted with a biphenyl compound represented by the following general formula (7). A method for producing a phenol novolac resin.

（式中、Ｒ２は、それぞれ独立に、炭素数１〜８のアルキル基、又は炭素数１〜８のアルコキシ基を表し、ｉは１〜３の整数であり、ｊは０〜２の整数であり、ｉとｊとの合計は４以下である。）

(In the formula, each R2 independently represents 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, and j is an integer of 0 to 2). Yes, the sum of i and j is 4 or less.)

（式中、Ｒ３は、それぞれ独立に、炭素数１〜８のアルキル基、又は炭素数１〜８のアルコキシ基を表し、ｋは１〜３の整数であり、ｌは０〜４の整数であり、ｋとｌとの合計は６以下である。）

(In the formula, each R3 independently represents 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, and l is an integer of 0 to 4). Yes, the sum of k and l is 6 or less.)

（式中、Ｒ１は、それぞれ独立に、炭素数１〜８のアルキル基を表し、ｐ及びｑは、それぞれ独立に、０〜２の整数であり、Ｘは、炭素数１〜４のアルコキシル基、又はハロゲン原子を表す。）

(In the formula, 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, and X is an alkoxyl group having 1 to 4 carbon atoms. Or represents a halogen atom.)

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

(6) The epoxy resin composition as described in 5 above, wherein the obtained cured product has a glass transition temperature of 155 ° C. or higher, preferably 170 ° C. or higher, more preferably 180 ° C. or higher.

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

(8) The phenol novolac resin (A), the epoxy resin (B), and the solvent (C) according to any one of items 1 to 3, comprising the phenol novolac resin (A) and the epoxy resin (B) Is uniformly dissolved in the solvent (C).

(9) Hardened | cured material which hardened any one of the epoxy resin composition of the said items 5-8.
(10) A laminate in which a matrix resin is formed using the epoxy resin composition according to Item 8.

Here, “independently” means that when there are a plurality of symbols representing the corresponding substituents and numbers, each symbol representing a plurality of substituents and numbers is independently a different substituent or number. Means that you can take For example, R1 in (R1) _p and R1 in (R1) _q in the general formula (1) may be the same alkyl group or different alkyl groups, and R1 in (R1) _p is In a plurality of cases, each R1 may be the same alkyl group or may be an alkyl group having a different carbon number.
In the present invention, the glass transition temperature is measured by two methods for convenience of comparison. However, in the unlikely event that a difference due to the measurement method occurs, the measurement method by the dynamic viscoelasticity measuring device has priority.

  According to the present invention, an epoxy resin composition containing a phenol novolak resin (more specifically, a phenol-naphthol novolak resin) and an epoxy resin, the heat resistance and combustion resistance of the resulting cured product are remarkably improved. An epoxy resin composition and a phenol novolac resin that can be suitably used for the epoxy resin composition can be provided. Furthermore, the present invention preferably has excellent solubility of the phenol novolac resin used, and therefore can be easily dissolved in a solvent, and can be suitably used for, for example, the production of laminates and interlayer insulating materials. An epoxy resin composition that can be used, and a phenol novolac resin that can be suitably used for the epoxy resin composition can be provided.

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

  In the phenol novolac resin of the present invention, a phenol represented by the following general formula (5) and a naphthol represented by the following general formula (6) are reacted with a biphenyl compound represented by the following general formula (7). It can obtain suitably.

（式中、Ｒ２は、それぞれ独立に、炭素数１〜８のアルキル基、又は炭素数１〜８のアルコキシ基を表し、ｉは１〜３の整数であり、ｊは０〜２の整数であり、ｉとｊとの合計は４以下である。）

(In the formula, each R2 independently represents 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, and j is an integer of 0 to 2). Yes, the sum of i and j is 4 or less.)

（式中、Ｒ３は、それぞれ独立に、炭素数１〜８のアルキル基、又は炭素数１〜８のアルコキシ基を表し、ｋは１〜３の整数であり、ｌは０〜４の整数であり、ｋとｌとの合計は６以下である。）

(In the formula, each R3 independently represents 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, and l is an integer of 0 to 4). Yes, the sum of k and l is 6 or less.)

（式中、Ｒ１は、それぞれ独立に、炭素数１〜８のアルキル基を表し、ｐ及びｑは、それぞれ独立に、０〜２の整数であり、Ｘは、炭素数１〜４のアルコキシル基、又はハロゲン原子を表す。）

(In the formula, 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, and X is an alkoxyl group having 1 to 4 carbon atoms. Or represents a halogen atom.)

  The phenol represented by the general formula (5) is not particularly limited as long as it is a compound having one or more hydroxyl groups on 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, guetol, xylenol, methylethylphenol, methylbutylphenol, methylhexylphenol, di Propylphenol, dibutylphenol, etc., preferably phenol. These phenols may be used alone or as a mixture of a plurality of them.

  The naphthols represented by the general formula (6) are not particularly limited as long as they are compounds having one or more hydroxyl groups on the naphthalene ring, and may have a substituent such as an alkyl group or an alkoxy group. For example, α-naphthol, β-naphthol, dihydroxynaphthalene, trihydroxynaphthalene, methyl naphthol, ethyl naphthol, propyl naphthol, allyl naphthol, t-butyl naphthol, octyl naphthol, methyl ethyl naphthol, methyl propyl naphthol, methyl butyl naphthol, Examples include methylhexyl naphthol, dimethyl naphthol, diethyl naphthol, and dibutyl naphthol, and α-naphthol is preferable. These naphthols may be used alone or as a mixture of a plurality 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′-bis (chloromethyl) biphenyl, Preferred examples include 4,4′-bis (bromomethyl) biphenyl and 4,4′-bis (fluoromethyl) biphenyl. These biphenyl compounds may have an alkyl group having 1 to 8 carbon atoms as a substituent. These biphenyl compounds may be used alone or as a mixture of a plurality of them.

  When phenols and naphthols are reacted with a biphenyl compound, a catalyst may not be used, but an acid catalyst is usually used. As the acid catalyst, organic acids such as oxalic acid, formic acid and acetic acid, and Friedel-Craft type catalysts such as sulfuric acid, p-toluenesulfonic acid and diethyl sulfate are suitable. In particular, when a biphenyl compound having a halogenomethyl group is used as the biphenyl compound, the reaction can be suitably performed even in the absence of an acid catalyst.

In this reaction, the molar ratio of the raw material biphenyl compound to the total of the raw material phenols and naphthols [(phenols and naphthols) / biphenyl compound] is preferably 20 to 1.5, more preferably 6.0. A range of ~ 2.0 is preferred. If the molar ratio is less than 1.5, the viscosity of the resin may become too high and handling properties may be impaired. If the molar ratio exceeds 20, the cured product glass is obtained in the form of a low molecular weight product. The transition temperature becomes insufficient, and a large amount of unreacted raw material remains, making it uneconomical.
Further, 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. By making the molar ratio of the raw material phenols and naphthols within this range, it will be explained below, but it is caused by the unit of the general formula (2) and naphthols resulting from the phenols of the obtained phenol novolac resin. The ratio with the unit of General formula (3) can be made into the preferable range of this invention. That is, when there are too few naphthol components, the unit of General formula (3) introduce | transduced in resin may reduce, and it may become difficult to obtain sufficient heat resistance. Moreover, when there are too many naphthol components, the unit of General formula (3) introduce | transduced in resin will increase, and the unit shown by General formula (4) will also increase, It will become a cause by which solvent solubility is impaired.
The reaction can usually be 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 about 0.5 hours to 10 hours. In order to adjust the ratio of the constituent components, the degree of polymerization, and the like, reaction conditions such as reaction temperature and reaction time are appropriately adjusted.
After the reaction, unreacted phenols and naphthols are preferably distilled out of the system by heating under reduced pressure or blowing in an inert gas. The acid catalyst can be removed by washing such as water washing.

By this reaction, a biphenyl compound forms a cross-linked structure between a plurality of units composed of phenols and / or naphthols to form a phenol novolac resin having a chemical structure represented by the general formula (1). To do.
Therefore, in the general formula (1), when the phenols and naphthols represented by the general formula (5) and the general formula (6) constitute the molecular end, A in the general formula (1) is represented by the general formula ( 2) and a monovalent unit of the general formula (3), and when incorporated in the molecule, A in the general formula (1) is a divalent unit of the general formula (2) and the general formula (3). It becomes.
In this reaction, first, a component in which n in general formula (1) is 0 is generated. Next, a part of the produced n = 0 component further reacts with the biphenyl compound or the produced n = 0 component. In this way, components in which n exceeds 1 and 1 are sequentially generated. On the other hand, while the reaction for generating a component in which n exceeds 1 and 1 proceeds, the reaction for generating a component in which n is 0 continues. Therefore, the phenol novolac resin of the present invention is usually 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 novolak resin of the present invention obtained by this reaction is that a phenol and a naphthol are converted into a 4,4′-form biphenyl compound such as 4,4′-bis (chloromethyl) biphenyl. It is in place to use in combination. And the hardened | cured material which consists of an epoxy resin composition using the phenol novolak resin of this invention improves heat resistance and combustion resistance suitably.

In the present invention, the phenol novolac resin having the chemical structure represented by the general formula (1) is a ratio of the unit of the general formula (2) derived from phenols to the unit of the general formula (3) derived from naphthols. [Unit of general formula (2) / unit of general formula (3)] is preferably in the range of 10/90 to 90/10, more preferably in the range of 10/90 to 60/40, More preferably, it exists in the range of 10 / 90-50 / 50, Especially preferably, it exists in the range of 10 / 90-40 / 60.
When the ratio of the unit of the general formula (2) and the unit of the general formula (3) is within this range, the heat resistance and the combustion resistance of the cured product made of the epoxy resin composition of the present invention are preferably improved. can do.
By introducing a unit represented by the general formula (3) in combination with a biphenyl compound consisting of 4,4′-form into the resin, the heat resistance of the resulting resin is efficiently improved, and combustion is effectively performed. This makes it possible to improve the combustion resistance. However, if the proportion of the unit of the general formula (3) becomes too high, the viscosity and softening point of the resin may be increased, and the handling property may be impaired. Further, the unit of the general formula (4) in the resin It increases and it becomes difficult to control the solubility of the resin.

  Therefore, in the reaction for preparing the phenol novolac resin of the present invention, preferably, the general formula (2) of the raw material is used so that the ratio of the unit of the general formula (2) to the unit of the general formula (3) is within the above range. The use ratio of the phenols represented by 5) and the naphthols represented by the general formula (6) is adjusted. Of course, the ratio of the raw materials used in the unit to be introduced into the phenol novolac resin is increased, but the reactivity of these phenols, naphthols, and biphenyl compounds is different. The ratio is adjusted in consideration of the size, the molar ratio of the biphenyl compound to the total of phenols and naphthols [(phenols and naphthols) / biphenyl compound], the reaction conditions employed, and the like. For those skilled in the art, the adjustment method is self-explanatory, but can be easily found by conducting preliminary experiments if necessary.

In the present invention, one of the preferred embodiments of the phenol novolak resin is a component represented by the general formula (4) among all the components of the assembly represented by the general formula (1) constituting the phenol novolak resin. It is 27% or less, preferably 20% or less in terms of the area ratio when measured by. When the component represented by the general formula (4) is controlled to 27% or less by the area ratio when measured by HPLC in all the components, the solubility in an organic solvent is improved. For example, the resin / It is possible to uniformly dissolve the solvent even at a ratio of 50/50 by mass.
On the other hand, when the component represented by the general formula (4) in all the components exceeds 27% in terms of the area ratio when measured by HPLC, the solubility in an organic solvent is lowered, for example, a resin / solvent with respect to methyl ethyl ketone. If the ratio is 50/50 by mass , it will be difficult to dissolve uniformly.
For example, using methyl ethyl ketone, if the resin / solvent can be uniformly dissolved even at a high concentration ratio of 50/50 by mass, the epoxy resin composition of the present invention is dissolved in methyl ethyl ketone to form a varnish, and the matrix material or interlayer of the laminate It becomes easy to use as an insulating material. When it cannot be dissolved uniformly and cannot be varnished, it is not easy to use it as a matrix material or an interlayer insulating material of a laminated board.

The amount of the component represented by the general formula (4) in the component of the phenol novolac resin is adjusted by adjusting the molar ratio of the biphenyl compound to the total of phenols and naphthols used as raw materials [(phenols and naphthols) / biphenyl. Compound] and the molar ratio of phenols to naphthols [phenols / naphthols] are adjusted while taking into consideration the magnitude of their reactivity and the reaction conditions employed.
The molar ratio of the biphenyl compound to the sum of the phenols and naphthols [(phenols and naphthols) / biphenyl compound] should be a smaller value than normal (a value closer to 1). It is preferable because the component of the general formula (4) can be reduced by increasing the molecular weight. In addition, the molar ratio of phenols to naphthols is higher in reactivity of naphthols than phenols, so a relatively high proportion of naphthols can promote more reaction and increase the overall component. It is preferable because the component of the general formula (4) can be reduced by increasing the molecular weight. On the other hand, if the proportion of naphthols becomes too high, the component of the general formula (4) increases and the solubility is adversely affected. For example, when the naphthols are 100%, it is naturally difficult to increase the solubility by reducing the amount of the component of the general formula (4).
These ratios are adjusted in consideration of the magnitude of their reactivity and the reaction conditions employed. For those skilled in the art, the adjustment method is self-explanatory, but can be easily found by conducting preliminary experiments if necessary.

  The phenol novolac resin (A) constituted by the chemical structure represented by the general formula (1) of the present invention preferably has a softening point of 60 ° C to 150 ° C, more preferably 70 ° C to 140 ° C. If the softening point is less than 60 ° C., blocking or the like is likely to occur, and if it exceeds 150 ° C., there may be a problem in handling properties. Moreover, the weight average molecular weight of the phenol novolak resin (A) constituted by the chemical structure represented by the general formula (1) of the present invention is preferably in the range of 500 to 10,000, more preferably 500 to 5000, More preferably, it is the range of 500-2000.

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) that are constituted by a 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 type epoxy resin, bisphenol F type epoxy resin, phenol aralkyl type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, and triphenol. Examples include glycidyl ether type epoxy resins such as methane type epoxy resins and biphenyl type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, halogenated epoxy resins, and other epoxy resins having two or more epoxy groups in the molecule. . These epoxy resins may be used individually by 1 type, and may use 2 or more types together.
Among these, a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin, a triphenylmethane type epoxy resin, a cresol novolac type epoxy resin, and the like are particularly suitable for improving heat resistance and combustion resistance.

As an addition ratio of the epoxy resin (B) used in the epoxy resin composition of the present invention, the ratio of the hydroxyl equivalent of the curing agent to the epoxy equivalent in the epoxy resin [hydroxyl equivalent / epoxy equivalent] is 0.5 to 2.0. A range of about 0.8 is preferable, and a range of about 0.8 to 1.2 is more preferable . Outside this range, the curing reaction may not proceed sufficiently, and the effects 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) constituted by the chemical structure represented by the general formula (1) has a role of a curing agent for the epoxy resin in the epoxy resin composition of the present invention. The product may contain a curing agent other than the phenol novolac resin (A) constituted by the chemical structure represented by the general formula (1).
There are no particular limitations on the curing agent other than the phenol novolac resin (A), and various epoxy resin curing agents can be used depending on the intended use of the composition. For example, an amine-based curing agent, an amide-based curing agent, an acid anhydride-based curing agent, a phenol resin-based curing agent other than the phenol novolac resin (A) configured by the chemical structure represented by the general formula (1), etc. A normal epoxy resin curing agent can be suitably used.
Moreover, in the epoxy resin composition of the present invention, the ratio 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. In order to improve heat resistance and combustion resistance, a higher ratio is preferable, 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass, particularly preferably 100% by mass. is there.

The epoxy resin composition of the present invention preferably further contains a solvent (C), and the phenol novolac resin (A) and the epoxy resin (B) are uniformly dissolved in the solvent (C). Is preferred.
The epoxy resin composition in heat resistance and burning resistance of the resulting cured product is excellent, if it is possible to uniform varnish solution at high concentrations, so can be preferably used as the matrix material and interlayer dielectric material laminate Become.
The solvent (C) is not particularly limited as long as it dissolves the epoxy resin composition, but is preferably an organic solvent used for varnishing a matrix material or an interlayer insulating material of a normal laminate. Can be used. For example, ketones such as methyl ethyl ketone, acetone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, ethers such as propylene glycol monomethyl ether, amides such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethyl sulfoxide, γ-butyllactone, etc. Preferable examples include lactones, pyrrolidones such as N-methylpyrrolidone, and aromatic hydrocarbons such as toluene and xylene. Among these, methyl ethyl ketone and dimethylformamide are particularly preferable. These solvents can be used alone or in combination of two or more.
When the epoxy resin composition of the present invention is varnished, 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 ° C. .

In the epoxy resin composition of this invention, the other component used with a normal epoxy resin composition can be used suitably according to the use.
For example, a curing accelerator for curing an epoxy resin with a phenol resin can be used. Preferred examples of the curing accelerator include known organic phosphine compounds and their boron salts, tertiary amines, quaternary ammonium salts, imidazoles and tetraphenylboron salts. Among these, triphenylphosphine is preferable from the viewpoints of curability and moisture resistance. In addition, when high fluidity is required by the epoxy resin composition, a heat-latent curing accelerator that exhibits activity by heat treatment is preferable, and tetraphenylphosphonium, tetraphenylborate, and the like are particularly preferable. More preferred are phenylphosphonium derivatives. The addition amount of a hardening accelerator may be the same as the ratio in a well-known epoxy resin composition.

Furthermore, 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 amorphous silica and crystalline silica are more preferable. Although there is no restriction | limiting in particular as a particle size of an inorganic filler, When a filling rate is considered, it is desirable that it is 0.01 micrometer or more and 150 micrometers or less.
Although there is no restriction | limiting in particular about the mixture ratio of an inorganic filler, It is 70 weight%-95 weight% in an epoxy resin composition, Preferably it is 75 weight%-90 weight%, More preferably, it is 80 weight%-90 weight%. . If the proportion of the inorganic filler is outside the above range, the water absorption rate of the cured product of the epoxy resin composition increases, which is not preferable. Moreover, when there is too much ratio of an inorganic filler, there exists a possibility that fluidity | liquidity may be impaired.

  Furthermore, a release agent, a coloring agent, a coupling agent, a flame retardant, etc. can be added to the epoxy resin composition of the present invention or reacted in advance if necessary. Moreover, the mixture ratio of these additives may be the same as the ratio in a known epoxy resin composition. In addition to this, the epoxy resin composition of the present invention contains a nitrogen-based flame retardant such as melamine or an isocyanuric acid compound, or a phosphorus-based flame retardant such as red phosphorus, a phosphoric acid compound or an organic phosphorus compound as a flame retardant aid. As appropriate.

The epoxy resin composition of the present invention uses a phenol novolak resin (A), an epoxy resin (B), a curing accelerator to be added as necessary, an inorganic filler, other additives, for example, using a mixer or the like. It can be produced by uniformly mixing, kneading in a molten state using a kneader such as a heating roll, a kneader, or an extruder, cooling, and pulverizing as necessary.
Although such an epoxy resin composition is not limited, it can be suitably used as a semiconductor sealing material.

In addition, the epoxy resin composition of the present invention is a phenol novolac resin (A) composed of a chemical structure represented by the general formula (1) in a solvent (C) such as methyl ethyl ketone, propylene glycol monomethyl ether or dimethylformamide. , Epoxy resin (B) and, if necessary, other curing agents, curing accelerators, inorganic fillers, additives and the like, and at least phenol novolac resin (A) by heating and stirring as necessary. ) And the epoxy resin (B) can be uniformly dissolved in the solvent (C) to produce a varnish solution.
Although this varnished epoxy resin (solution) composition is not limited, it can be suitably used as a matrix material or an interlayer insulating material of a laminated board.

As for the epoxy resin composition of this invention, after drying a solvent as needed, a hardened | cured material can be obtained suitably by heat-processing.
The heat treatment conditions for obtaining a cured product depend on the presence or absence of a curing catalyst and a curing accelerator, and the amount of addition thereof, but are usually about 100 to 300 ° C., preferably about 120 to 200 ° C. The heat treatment is preferably performed for about 10 minutes to about 10 minutes.

  The epoxy resin composition of the present invention can be suitably used as a sealing material for sealing a semiconductor element. For example, after a lead frame or the like on which the semiconductor element is mounted is placed in a metal cavity, an epoxy resin composition is molded by a molding method such as transfer molding, compression molding, or injection molding, and the temperature is about 120 ° C. to 300 ° C. A semiconductor device can be suitably obtained by curing the epoxy resin composition by heat treatment or the like.

  The epoxy resin composition of the present invention is preferably uniformly dissolved in a solvent such as methyl ethyl ketone to form a varnish, and the varnish solution is applied to a porous glass substrate such as glass, glass fiber, paper, aramid fiber, etc. Alternatively, a prepreg for a printed circuit board can be produced by impregnation and then heat treatment (semi-curing). Furthermore, a laminated board can be manufactured by laminating a plurality of obtained prepregs for a printed circuit board and curing them by applying heat treatment while applying pressure as necessary.

  In addition, a laminate or prepreg is a metal-clad laminate obtained by superposing a metal foil on one or both sides and performing heat treatment (for example, heat treatment at 180 ° C., 4 MPa for 60 minutes) while applying pressure as necessary. Can be obtained. This metal-clad laminate can be suitably used as a printed wiring board by forming a circuit pattern by etching.

  Furthermore, the epoxy resin composition of the present invention is preferably uniformly dissolved in a solvent such as methyl ethyl ketone to form a varnish, and the varnish solution is uniformly applied to a support surface such as a PET film or copper foil using a die coater or the like. The laminated film having a resin layer can be suitably used as an interlayer insulating material by applying to the substrate and drying the obtained coating film by heating.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

[1] Preparation of phenol novolac resin The materials used in the following examples of preparation of phenol novolac resin will be described.
(1) Phenol: manufactured by Wako Pure Chemical Industries, Ltd. (2) α-naphthol (1-naphthol): manufactured by Wako Pure Chemical Industries, Ltd. (3) 4, 4′-bis (chloromethyl) biphenyl: manufactured by Wako Pure Chemical Industries, Ltd.

The analysis method and evaluation method used in the following examples of preparing phenol novolac resins will be described.
(1) Softening point: Performed by ring and ball method softening point measurement based on JIS K6910.
(2) Hydroxyl equivalent: The hydroxyl equivalent was measured according to JIS K0070.
(3) Measurement of ratio of unit of general formula (2) and unit of general formula (3) [unit of general formula (2) / unit of general formula (3)]: In preparation of phenol novolac resin, The amount charged, the amount of phenol novolak resin produced, and the amount of by-products are measured, and the amount of unreacted raw material is calculated from the reaction balance. Since all of the biphenyl compound is reacted, the unreacted raw material consists of raw material phenols constituting the unit of the general formula (2) and raw material naphthols constituting the unit of the general formula (3). The ratio of unreacted phenols and naphthols in the reaction mixture was determined from an HPLC chart obtained by HPLC measurement under the following conditions. The ratio (molar ratio) was an area ratio. From the above data, 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)] was calculated by the following formula.

HPLC measurement conditions Instrument: HPLC manufactured by Shimadzu Corporation
Column: STR ODS-H column (manufactured by Shinwa Kako)
Column oven temperature: 40 ° C
Moving bed: acetonitrile, 5% phosphoric acid solution
To adjust the concentration of the moving bed, use a mixed solution with a volume ratio of acetonitrile / 5% phosphoric acid solution of 20/60 at the start of measurement, and linearize the ratio of acetonitrile up to 60/40 over 10 minutes after the start of measurement. Then, the proportion of acetonitrile was linearly increased to 100/0 over 5 minutes, and then acetonitrile was used as it was until the measurement was completed.
Flow rate: 1.00 mL / min Detection wavelength: 220 nm

(4) Ratio of the component represented by the general formula (4): The area ratio was determined from the HPLC chart obtained by HPLC measurement under the following conditions.
HPLC measurement conditions Instrument: HPLC manufactured by Shimadzu Corporation
Column: STR ODS-H column (manufactured by Shinwa Kako)
Column oven temperature: 40 ° C
Moving bed: acetonitrile, 5% phosphoric acid solution
To adjust the concentration of the moving bed, use a 50/50 volume ratio of acetonitrile / 5% phosphoric acid solution at the start of measurement, and linearly adjust the ratio of acetonitrile to 75/25 over 20 minutes after the start of measurement. Then, the proportion of acetonitrile was linearly increased to 100/0 over 20 minutes, and thereafter acetonitrile was used as it was until the measurement was completed.
Flow rate: 1.00 mL / min Detection wavelength: 220 nm
(5) Solubility:
It evaluated by the solubility test by the method shown below.
Solvent: Methyl ethyl ketone Dissolution ratio (mass): Phenol novolac resin / Solvent = 50/50
Dissolution condition: Resin and solvent were added to an airtight container and dissolved by stirring at 60 ° C.
Evaluation: Visual observation was performed after dissolution and after standing at room temperature (23 ° C.) for 12 hours. It is possible to obtain a uniform solution by ◯ when the resin is uniformly dissolved and a uniform solution is retained after standing, and when the resin is uniformly dissolved but a part of the resin is deposited after standing. What was not made was set as x.

[Example 1]
Add 188.0 g (2.0 mol) of phenol and 123.4 g (0.9 mol) of α-naphthol to a 1000 mL glass flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, and a nitrogen stream Then, the raw material was dissolved by raising the internal temperature to 60 ° C. 4,4′-bis (chloromethyl) biphenyl (179.3 g, 0.7 mol) was added, and the mixture was reacted at an internal temperature of 60 ° C. to 100 ° C. for 4 hours and further at 165 ° C. for 3 hours. Unreacted components of the raw material were removed by the teaming process.
The phenol novolak resin thus obtained had a softening point of 113 ° C., a hydroxyl group equivalent of 263 g / eq, and a ratio of the unit of general formula (2) and the unit of general formula (3) measured by HPLC [general formula (2) Unit / unit of general formula (3)] was 30/70, and the proportion of the component represented by general formula (4) was 15%. The evaluation of solubility of this phenol novolac resin was ○.
In addition, the HPLC chart of the unreacted raw material of this reaction is shown in FIG. From this chart, the proportions of phenols and naphthols in the unreacted raw materials were calculated as 82% and 18%. Using this ratio, the ratio of the unit of general formula (2) and the unit of general formula (3) introduced into the resin according to the calculation method [unit of general formula (2) / unit of general formula (3) ] Was calculated.
Moreover, 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) (there is an isomer, so there are 3 peaks) was determined.

[Example 2]
Phenol 84.6 g (0.9 mol) and α-naphthol 129.6 g (0.9 mol) were added to a 1000 mL glass flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, and a nitrogen stream Then, the raw material was dissolved by raising the internal temperature to 60 ° C. After adding 180.7 g (0.7 mol) of 4,4′-bis (chloromethyl) biphenyl and reacting at an internal temperature of 60 ° C. to 100 ° C. for 4 hours and further at 165 ° C. for 3 hours, Unreacted components of the raw material were removed by the teaming process.
The obtained phenol novolac resin had a softening point of 131 ° C., a hydroxyl group equivalent of 256 g / eq, and a ratio of the unit of general formula (2) and the unit of general formula (3) measured by HPLC [general formula (2) Unit / unit of general formula (3)] was 20/80, and the proportion of the component represented by general formula (4) was 18%. The evaluation of solubility of this phenol novolac resin was ○.
In addition, the HPLC chart of the unreacted raw material of this reaction is shown in FIG. From this chart, the proportions of phenols and naphthols in the unreacted raw materials were calculated as 76% and 24%. Using this ratio, 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)] was calculated according to the calculation formula.
Moreover, the HPLC chart of the obtained phenol novolak resin is shown in FIG. The ratio of the component represented by the area ratio general formula (4) of this chart (the total of three peaks because there are isomers) was determined.

Example 3
Phenol 94.0 g (1.0 mol) and α-naphthol 144.0 g (1.0 mol) were added to a 1000 mL glass flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, and a nitrogen stream Then, the raw material was dissolved by raising the internal temperature to 60 ° C. After adding 161.9 g (0.7 mol) of 4,4′-bis (chloromethyl) biphenyl and reacting at an internal temperature of 60 ° C. to 100 ° C. for 4 hours and further at 165 ° C. for 3 hours, Unreacted components of the raw material were removed by the teaming process.
The obtained phenol novolac resin had a softening point of 117 ° C., a hydroxyl group equivalent of 247 g / eq, and the proportion of the component represented by the general formula (4) measured by HPLC was 24%. The evaluation of solubility of this phenol novolac resin was Δ.

Example 4
Add 188.0 g (2.0 mol) of phenol and 123.4 g (1.0 mol) of α-naphthol to a 1000 mL glass flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, and a nitrogen stream Then, the raw material was dissolved by raising the internal temperature to 60 ° C. After adding 119.5 g (0.5 mol) of 4,4′-bis (chloromethyl) biphenyl and reacting at an internal temperature of 60 ° C. to 100 ° C. for 4 hours and further at 165 ° C. for 3 hours, Unreacted components were removed by teaming treatment.
The obtained phenol novolac resin had a softening point of 97 ° C., a hydroxyl group equivalent of 238 g / eq, and the proportion of the component represented by the general formula (4) measured by HPLC was 30%. The evaluation of solubility of this phenol novolac resin was x.

Example 5
Phenol 141.0 g (1.5 mol) and α-naphthol 216.0 g (1.5 mol) were added to a 1000 mL glass flask equipped with a thermometer, a charging / distilling outlet, a condenser and a stirrer, and a nitrogen stream Then, the raw material was dissolved by raising the internal temperature to 60 ° C. After adding 125.5 g (0.5 mol) of 4,4′-bis (chloromethyl) biphenyl and reacting at an internal temperature of 60 ° C. to 100 ° C. for 4 hours and further at 165 ° C. for 3 hours, Unreacted components were removed by teaming treatment.
The obtained phenol novolac resin had a softening point of 94 ° C., a hydroxyl group equivalent of 238 g / eq, and a proportion of the component represented by the general formula (4) measured by HPLC of 49%. The evaluation of solubility of this phenol novolac resin was x.

  The phenol novolak resins of Examples 1 to 5 are summarized in Table 1. From the solubility evaluation results in this table, in order to uniformly dissolve the epoxy resin composition using the phenol novolak resin of the present invention in a solvent, the proportion of the component represented by the general formula (4) is 27% or less, It can be seen that it is preferably 20% or less.

[2] Comparison of Preparation of Epoxy Resin Composition of the Present Invention and Patent Document 2 Materials used in the examples relating to the epoxy resin composition will be described below.
(1) Epoxy resin Orthocresol type 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): manufactured by Hokuko Chemical Co., Ltd.

Below, the evaluation method which concerns on an epoxy resin composition is demonstrated.
(1) Heat resistance (glass transition temperature (Tg))
It carried out according to the measuring method of patent document 2. That is, using a test piece made of a cured product having dimensions of 4 mm × 6 mm × 10 mm, the temperature was increased at a rate of temperature increase of 5 ° C./min, and measurement was performed by the TMA method (Thermal Mechanical Analysis).

Example 6
The phenol novolac resin obtained in Example 1, orthocresol type epoxy resin EOCN-1020-70, and a curing accelerator TPP were added in the formulation shown in Table 2 to obtain an epoxy resin composition, which was treated at 150 ° C. The mixture is heated, melted and mixed, and vacuum degassed, then poured into a 150 ° C. mold (thickness 4 mm), cured at 150 ° C. for 5 hours, and further cured at 180 ° C. for 8 hours to cure. A molded body was obtained.
With respect to this cured molded body, the glass transition temperature was measured and found to be 175 ° C.

  In Example 6, an epoxy resin composition was prepared by the same operation 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. It is what I did. The evaluation results of Example 6 are shown in Table 2 in comparison with the data of Example 7 of Patent Document 2.

  Table 2 shows that the glass transition temperature of the cured product of the epoxy resin composition is remarkably improved by using the phenol novolac resin of the present invention.

[3] Preparation of epoxy resin composition of the present invention and evaluation by EMC test piece The materials used in the examples relating to the epoxy resin composition will be described below.
(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): Hokuko Chemical Co., Ltd. (3) Inorganic filler Silica “MSR-2212”: Tatsumori Co., Ltd.

Below, the evaluation method which concerns on an epoxy resin composition is demonstrated.
(1) Flammability Measured according to UL-94.
(2) Heat resistance (glass transition temperature (Tg))
Using an EMC test piece having dimensions of 40 mm × 12 mm × 1 mm, a dynamic viscoelasticity measuring device (RSA-G2 manufactured by TA Instruments) was used and the temperature was increased at a rate of 3 ° C./min.
(3) Mechanical properties: Mechanical strength: Measured according to JIS K 7171.

Example 7
The phenol novolac resin obtained in Example 1, YX-4000 of biphenyl type epoxy resin, TPP of curing accelerator, and silica MSR-2212 of inorganic filler were added in the formulation shown in Table 2, and these were added at 80 ° C. After kneading using two rolls at -100 ° C, the mixture was pulverized to obtain the epoxy resin composition of the present invention.
A tablet is prepared using the obtained epoxy resin composition, and this is injected into a mold using a low-pressure transfer molding machine under conditions of a mold temperature of 175 ° C., an injection pressure of 6.8 MPa, and a holding time of 600 seconds. Then, after taking out from the mold and post-curing at 180 ° C. for 8 hours, an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition was obtained.
The results of evaluating this are shown in Table 3.

Example 8
Except that the phenol novolac resin obtained in Example 2 was used, the same operation as in Example 7 was performed to obtain an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition.
The results of evaluating this are shown in Table 3.

Example 9
Except for using the phenol novolac resin obtained in Example 3, the same operation as in Example 7 was performed to obtain an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition.
The results of evaluating this are shown in Table 3.

Example 10
Except for using the phenol novolac resin obtained in Example 4, the same operation as in Example 7 was performed to obtain an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition.
The results of evaluating this are shown in Table 3.

Except that the phenol novolac resin obtained in Example 5 was used, the same operation as in Example 7 was performed to obtain an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition.
The results of evaluating this are shown in Table 3.

Except for using the phenol novolac resin obtained in Example 6, the same operation as in Example 7 was performed to obtain an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition.
The results of evaluating this are shown in Table 3.

[Reference Example 1]
Phenol 470.0 g (5.0 mol) was added to a 1000 mL glass flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, and the temperature was raised to an internal temperature of 60 ° C. under a nitrogen stream to dissolve the raw material I let you. After adding 313.8 g (1.3 mol) of 4,4′-bischloromethylbiphenyl and reacting at an internal temperature of 60 ° C. to 100 ° C. for 4 hours and further at 165 ° C. for 3 hours, vacuum-steaming treatment To remove unreacted components. The obtained phenol novolac resin E had a softening point of 68 ° C. and a hydroxyl group equivalent of 202 g / eq.

[Comparative Example 1]
Except that the phenol novolac resin obtained in Reference Example 1 was used, the same operation as in Example 6 was performed, and an EMC (Epoxy Molding Compound) test piece having dimensions of 40 mm × 12 mm × 1 mm made of a cured product of the epoxy resin composition. Got.
The results of evaluating this are shown in Table 3.

[4] Manufacture and evaluation of copper-clad laminate using the epoxy resin composition of the present invention The materials used in the examples relating to the production of copper-clad laminate are described below.
(1) Epoxy resin Bisphenol A type epoxy resin “828EL”: manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / eq
(2) Curing accelerator (curing catalyst)
2-ethyl-4-methylimidazole (2E4MZ): manufactured by Shikoku Chemicals Co., Ltd. (3) solvent (methyl ethyl ketone): manufactured by Wako Pure Chemical Industries, Ltd. (4) glass cloth (non-alkali treated glass cloth) “M7628-105”: Arisawa Manufacturing Co., Ltd. (5) Copper foil (electrolytic copper foil) “CF-T9B-THE”: manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., thickness 35 μ

Below, the evaluation method which concerns on a copper clad laminated board is demonstrated.
(1) Adhesiveness (peel strength)
Using a dynamic viscoelasticity measuring apparatus (“AG-5000D” manufactured by Shimadzu Corporation), the 90 ° copper foil 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 at a rate of temperature increase of 3 ° C / min using a dynamic viscoelasticity measuring device ("RSA-G2" manufactured by TA Instruments).
(3) Water absorption Measured according to JIS C6481.

Example 12
To 231.2 parts by mass of methyl ethyl ketone as a diluent solvent, 131 parts by mass of the phenol novolac resin obtained in Example 1, 100 parts by mass of a bisphenol type epoxy resin, and 0.1 parts by mass of 2E4MZ of a curing accelerator were added to form a varnish. A varnish solution having a resin concentration of 50% by mass dissolved in was obtained.
The obtained varnish solution was impregnated with M7628-105 of glass cloth and then dried at 130 ° C. for 15 minutes to obtain a prepreg. 8 sheets of this prepreg were stacked, and CF-T9B-THE of copper foil was stacked on both sides of the prepreg, and pressed using a press machine at 170 ° C. and 30 kg / cm ² for 15 minutes. After taking out the tension laminate from the press machine, it was further cured at 200 ° C. for 5 hours to obtain a double-sided copper clad laminate.
The obtained copper-clad laminate had a glass transition temperature of 159 ° 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]
In a glass flask with a capacity of 1000 mL equipped with a thermometer, charging / distilling outlet, condenser and stirrer, phenol 470.0 g (5.0 mol), 92% paraformaldehyde 110.9 g (3.4 mol), oxalic acid 0 .3 g was added and reacted at 100 ° C. for 5 hours. After completion of the reaction, unreacted components were removed by reduced pressure-steaming treatment. The obtained phenol novolac resin E had a softening point of 96 ° C. and a hydroxyl group equivalent of 107 g / eq.

[Comparative Example 2]
Instead of the phenol novolak resin obtained in Example 1, the general phenol novolak resin prepared in Reference Example 2 was used, and the formulation was as shown in Table 4, and the double-sided copper was prepared in the same manner as in Example 9. A tension laminate was obtained.
The obtained copper-clad laminate had a glass transition temperature of 147 ° C., a peel strength of 1.6 N / mm, and a water absorption of 0.09% by mass. The results are shown in Table 4.

  According to the present invention, an epoxy resin composition containing a phenol novolak resin (more specifically, a phenol-naphthol novolak resin) and an epoxy resin, the heat resistance and combustion resistance of the resulting cured product are remarkably improved. An epoxy resin composition and a phenol novolac resin that can be suitably used for the epoxy resin composition can be provided. Furthermore, the present invention preferably has excellent solubility of the phenol novolac resin used, and therefore can be easily dissolved in a solvent, and can be suitably used for, for example, the production of laminates and interlayer insulating materials. An epoxy resin composition that can be used, and a phenol novolac resin that can be suitably used for the epoxy resin composition can be provided.

Claims (10)

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

(In the formula, each A independently represents a monovalent or divalent unit of the following general formula (2) or a monovalent or divalent unit of the general formula (3), and n is an integer of 0 to 20. R1 represents each independently an alkyl group having 1 to 8 carbon atoms, and p and q are each independently an integer of 0 to 2.)
However, as a whole phenol novolac resin, A is composed of both monovalent or divalent units of the following general formula (2) and monovalent or divalent units of the following general formula (3).

(In the formula, each R2 independently represents 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, and j is an integer of 0 to 2). Yes, the sum of i and j is 4 or less.)

(In the formula, each R3 independently represents 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, and l is an integer of 0 to 4). Yes, the sum of k and l is 6 or less.)   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 in the range of 10/90 to 90/10. The phenol novolac resin according to claim 1, wherein the phenol novolac resin is present. The component represented by the following general formula (4) in all components constituting the phenol novolac resin is 27% or less in terms of an area ratio when measured by HPLC. Phenol novolac resin.

(In the formula, 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, and R3 is each independently an integer of 1 to 2 carbon atoms. 8 represents an alkyl group or an alkoxy group having 1 to 8 carbon atoms, k is an integer of 1 to 3, l is an integer of 0 to 4, and the sum of k and l is 6 or less.) A phenol novolak resin characterized by reacting a phenol represented by the following general formula (5) and a naphthol represented by the following general formula (6) with a biphenyl compound represented by the following general formula (7) Manufacturing method.

(In the formula, each R2 independently represents 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, and j is an integer of 0 to 2). Yes, the sum of i and j is 4 or less.)

(In the formula, each R3 independently represents 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, and l is an integer of 0 to 4). Yes, the sum of k and l is 6 or less.)

(In the formula, 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, and X is an alkoxyl group having 1 to 4 carbon atoms. Or represents a halogen atom.)   An epoxy resin composition comprising the phenol novolac resin (A) according to any one of claims 1 to 3 and an epoxy resin (B).   The epoxy resin composition according to claim 5, wherein the obtained cured product has a glass transition temperature of 155 ° C or higher.   The epoxy resin composition according to claim 5 or 6, wherein the obtained cured product has flame retardancy according to UL-94 of V-0.   The phenol novolac resin (A), the epoxy resin (B), and the solvent (C) according to any one of claims 1 to 3, comprising the phenol novolac resin (A) and the epoxy resin (B). An epoxy resin composition, which is uniformly dissolved in the solvent (C).   Hardened | cured material which hardened the epoxy resin composition of any one of Claims 5-8.   The laminated board which formed matrix resin using the epoxy resin composition of Claim 8.

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