JP5024605B2 - Curable resin composition, cured product thereof, novel phenolic resin, and production method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition providing a cured product exhibiting excellent flame retardancy, and to provide a new phenol-based resin. <P>SOLUTION: The curable resin composition contains a phenol resin containing a structural unit represented by structural formula (A-1) (wherein, X is a methoxynaphthalene skeleton; X' is a methoxynaphthalene skeleton or a cresol skeleton; and P is a cresol skeleton) as a main component, and &le;5 mass% compound corresponding to a structure represented by structural formula (2): P-CH<SB>2</SB>-P, and an epoxy resin as essential components. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention is excellent in flame retardancy of the obtained cured product, curable resin composition that can be suitably used for semiconductor encapsulant, printed circuit board, paint, casting application, the cured product, the cured product The present invention relates to a novel polyvalent hydroxy compound that can be suitably used as a curing agent for a conductive resin composition and a method for producing the same.

  Phenolic resins represented by phenol novolac resins (phenol-formaldehyde resins) are useful compounds as epoxy resin curing agents, epoxy resin raw materials, adhesives, molding materials, paints, photoresist materials, color developing materials, and the like. . In particular, when used as a curing agent for epoxy resins, excellent heat resistance and moisture resistance of the resulting cured products are highly evaluated, and they are widely used in fields such as semiconductor encapsulants and printed circuit boards. .

  In the field of electronics such as semiconductor encapsulating materials and printed circuit boards, or the field of high-performance paints, a halogen-based flame retardant such as bromine is usually blended with an antimony compound in order to impart flame retardancy. However, in recent environmental and safety initiatives, there are environmental and safety-friendly flame retardant methods that do not use halogen-based flame retardants that may cause dioxins and antimony compounds that are suspected of causing carcinogenicity. Development is strongly required.

In order to meet such a demand, as a technique for increasing the flame retardancy of the resin itself and using a halogen flame retardant and an antimony compound to express a practical flame retardant performance, for example,
A phenolic resin obtained by reacting methoxynaphthalene, cresol, and formaldehyde is known (for example, see Patent Document 1). Such a phenolic resin can certainly have a flame retardant effect in the cured product itself, and also has other characteristics such as a low dielectric constant and a low dielectric loss tangent. However, the present situation is that the flame resistance of the phenolic resin does not reach the level required from the background of remarkable downsizing, high integration, and high frequency of electronic components in the recent electronics field.

JP 2006-274236 A

  Therefore, the problem to be solved by the present invention is to provide a curable resin composition and a novel phenolic resin that exhibit excellent flame retardancy in the cured product.

  As a result of intensive studies to solve the above problems, the present inventors have a structure in which a phenol skeleton is knotted with a methylene group, and an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group is formed at the molecular end of the phenol skeleton. Introducing the phenolic resin with a reduced content of a low molecular weight substance having a specific molecular structure, the flame retardancy of the cured product is dramatically improved, and the present invention is completed. It came.

  That is, this invention is a curable resin composition which has a phenol resin (A) and an epoxy resin (B) as an essential component, Comprising: The said phenol resin (A) is following Structural formula (1).

（式中、Ｐはフェノール性水酸基含有芳香族炭化水素基を、Ｘはアルコキシ基含有縮合多環式芳香族炭化水素基、Ｘ’はアルコキシ基含有縮合多環式芳香族炭化水素基又はフェノール性水酸基含有芳香族炭化水素基を表し、ｎは１〜１００の整数である。）で表される化合物（ａ１）及び下記構造式（２）

(Wherein P is a phenolic hydroxyl group-containing aromatic hydrocarbon group, X is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group, and X ′ is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or phenolic. Represents a hydroxyl group-containing aromatic hydrocarbon group, and n is an integer of 1 to 100.) and the following structural formula (2)

（式中、Ｐはフェノール性水酸基含有芳香族炭化水素基を表す。）
で表される化合物（ａ２）を含有するものであって、フェノール樹脂（Ａ）中の前記化合物（ａ２）の含有率が５質量％以下となる割合であることを特徴とする硬化性樹脂組成物に関する。

(In the formula, P represents a phenolic hydroxyl group-containing aromatic hydrocarbon group.)
A curable resin composition containing the compound (a2) represented by the formula (A2), wherein the content of the compound (a2) in the phenol resin (A) is 5% by mass or less. Related to things.

  The present invention further relates to a cured resin product obtained by curing the curable resin composition.

  In addition to the phenol resin (A) and the epoxy resin (B), the present invention further contains an inorganic filler (C) at a ratio of 70 to 95% by mass in the composition. The present invention relates to a semiconductor sealing material.

  The present invention further includes the following structural formula (1):

（式中、Ｐはフェノール性水酸基含有芳香族炭化水素基を、Ｘはアルコキシ基含有縮合多環式芳香族炭化水素基、Ｘ’はアルコキシ基含有縮合多環式芳香族炭化水素基又はフェノール性水酸基含有芳香族炭化水素基を表し、ｎは１〜１００の整数である。）で表される化合物（ａ１）及び下記構造式（２）

(Wherein P is a phenolic hydroxyl group-containing aromatic hydrocarbon group, X is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group, and X ′ is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or phenolic. Represents a hydroxyl group-containing aromatic hydrocarbon group, and n is an integer of 1 to 100.) and the following structural formula (2)

（式中、Ｐはフェノール性水酸基含有芳香族炭化水素基を表す。）
で表される化合物（ａ２）を含有するフェノール樹脂であって、該フェノール樹脂（Ａ）中の前記化合物（ａ２）の含有率が５質量％以下となる割合であることを特徴とする新規フェノール樹脂に関する。

(In the formula, P represents a phenolic hydroxyl group-containing aromatic hydrocarbon group.)
A phenolic resin containing the compound (a2) represented by the formula (1), wherein the content of the compound (a2) in the phenolic resin (A) is 5% by mass or less. It relates to resin.

  In the present invention, the hydroxy group-containing aromatic compound (x1) and formaldehyde are further reacted in the presence of an alkali catalyst, and then the alkali catalyst is neutralized, and then the alkoxy group-containing condensed polycyclic aromatic compound. The present invention relates to a method for producing a phenol resin, wherein (x2) is charged and reacted in the presence of an acid catalyst.

  According to the present invention, it is possible to provide a phenolic resin composition and a novel phenolic resin that exhibit excellent flame retardancy in the cured product.

Hereinafter, the present invention will be described in detail.
As described above, the phenol resin (A) used in the present invention has the following structural formula (1).

（式中、Ｐはフェノール性水酸基含有芳香族炭化水素基を、Ｘはアルコキシ基含有縮合多環式芳香族炭化水素基、Ｘ’はアルコキシ基含有縮合多環式芳香族炭化水素基又はフェノール性水酸基含有芳香族炭化水素基を表し、ｎは１〜１００の整数である。）で表される化合物（ａ１）及び下記構造式（２）

(Wherein P is a phenolic hydroxyl group-containing aromatic hydrocarbon group, X is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group, and X ′ is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or phenolic. Represents a hydroxyl group-containing aromatic hydrocarbon group, and n is an integer of 1 to 100.) and the following structural formula (2)

（式中、Ｐはフェノール性水酸基含有芳香族炭化水素基を表す。）
で表される化合物（ａ２）を含有するものであって、フェノール樹脂（Ａ）中の前記化合物（ａ２）の含有率が５質量％以下となる割合であることを特徴としている。

(In the formula, P represents a phenolic hydroxyl group-containing aromatic hydrocarbon group.)
The compound (a2) is represented by the formula (A2), and the content of the compound (a2) in the phenol resin (A) is 5% by mass or less.

  In the present invention, as the main component of the phenol resin (A), the following structural formula

（式中、Ｐはフェノール性水酸基含有芳香族炭化水素基を表す。）
で表される構造単位を繰り返し単位とする主骨格の末端にＸはアルコキシ基含有縮合多環式芳香族炭化水素基を導入すること、かつ、該フェノール樹脂（Ａ）中に含まれる前記化合物（ａ２）の含有率を低減させることにより、該フェノール樹脂（Ａ）の硬化物の難燃性を飛躍的に改善できたものである。

(In the formula, P represents a phenolic hydroxyl group-containing aromatic hydrocarbon group.)
X introduces an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group at the terminal of the main skeleton having the structural unit represented by the formula as a repeating unit, and the compound (A) contains the compound ( By reducing the content of a2), the flame retardancy of the cured product of the phenol resin (A) can be dramatically improved.

  Here, in the structural formula (1), in the compound (a1), X ′ is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or a phenolic hydroxyl group-containing aromatic hydrocarbon group, and Specifically, the compound (a1) has the following structural formulas (a1-1) and (a1-2)

で表される化合物が挙げられる。なお、上記構造式（ａ１−１）及び（ａ１−２）中、Ｘはアルコキシ基含有縮合多環式芳香族炭化水素基、Ｐは１価又は２価のフェノール性水酸基含有芳香族炭化水素基を表し、ｎは１〜１００の整数である。

The compound represented by these is mentioned. In the structural formulas (a1-1) and (a1-2), X is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group, and P is a monovalent or divalent phenolic hydroxyl group-containing aromatic hydrocarbon group. N is an integer of 1-100.

  The value of n in the structural formula (1) is the number of repeating units derived from GPC measurement. Here, the conditions for the GPC measurement are specifically as follows.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

  The value of n thus determined is in the range of 1 to 100 as described above. In particular, in the present invention, the content of the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group present at the molecular end is high. From the point that the flame retardant effect becomes remarkable, the range of 1 to 50 is particularly preferable.

  The phenolic hydroxyl group-containing aromatic hydrocarbon group (P) can have various structures, specifically, phenol, naphthol represented by the following structural formulas of P1 to P16, and these A compound having an alkyl group as a substituent on the aromatic nucleus is preferable in that it has excellent flame retardancy.

  Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end as described in the structural formula (a1-2). In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.

  The phenolic hydroxyl group-containing aromatic hydrocarbon group (P) described in detail above, particularly those having a methyl group as a substituent on the aromatic nucleus can impart particularly excellent flame retardancy to the cured product itself. This makes it possible to design halogen-free materials that are highly demanded in the parts field.

  Next, the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B) contained in the phenol resin structure is a monovalent aromatic hydrocarbon having an alkoxy group as a substituent on the condensed polycyclic aromatic nucleus. Specific examples thereof include an alkoxyquinephthalene structure represented by the following structural formulas B1 to B11 or an alkoxyanthracene represented by the following structural formula B12.

  Among the alkoxy group-containing condensed polycyclic aromatic hydrocarbon groups (B) described in detail above, those having an alkoxynaphthalene type structure are particularly preferred from the point that the flame retardancy of the cured product is good, In recent years, it has become possible to design a halogen-free material that is highly demanded in the field of electronic components, and therefore, a naphthalene structure represented by the structural formulas B1 to B10 having a methoxy group or an ethoxy group as a substituent, and further to them An aromatic hydrocarbon group formed from a structure having a methyl group as a substituent is preferable.

  The phenol resin (A) is mainly composed of the compound (a1-1) and the compound (a1-2), and various other by-products at the time of producing the phenol resin (A). For example, the following structural formula (3)

（式中、Ｐはフェノール性水酸基含有芳香族炭化水素基を表し、ｎは０〜１００の整数である。）
で表される化合物の他、下記構造式（４）及び（５）

(In the formula, P represents a phenolic hydroxyl group-containing aromatic hydrocarbon group, and n is an integer of 0 to 100.)
In addition to the compounds represented by the following structural formulas (4) and (5)

（式（４）及び（５）中、Ｐはフェノール性水酸基含有芳香族炭化水素基を、Ｘはアルコキシ基含有縮合多環式芳香族炭化水素基を表す。）
で表される化合物が挙げられる。更に、前記構造式（ａ１−１）及び（ａ１−２）において、アルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）中のアルコキシ基が、メチレンを介して結合するフェノール性水酸基含有芳香族炭化水素基（Ｐ）中のフェノール水酸基と脱アルコール反応して環状構造を形成した化合物（ａ１−３）などを含み得る。かかる化合物（ａ１−３）としては、例えば、前記フェノール性水酸基含有芳香族炭化水素基（Ｐ）として、前記構造式Ｐ６を用い、かつ、前記アルコキシ基含有縮合多環式芳香族炭化水素基（Ｂ）として前記構造式Ｂ１を用いた場合には、例えば下記構造式（６）

(In formulas (4) and (5), P represents a phenolic hydroxyl group-containing aromatic hydrocarbon group, and X represents an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group.)
The compound represented by these is mentioned. Furthermore, in the structural formulas (a1-1) and (a1-2), the phenolic hydroxyl group-containing fragrance in which the alkoxy group in the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) is bonded via methylene. The compound (a1-3) etc. which formed the cyclic structure by the dealcoholization reaction with the phenol hydroxyl group in aromatic hydrocarbon group (P) may be included. As such a compound (a1-3), for example, as the phenolic hydroxyl group-containing aromatic hydrocarbon group (P), the structural formula P6 is used, and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group ( When the structural formula B1 is used as B), for example, the following structural formula (6)

で表される化合物や、下記構造式（７）

And the following structural formula (7)

で表される化合物が挙げられる。

The compound represented by these is mentioned.

In the present invention, among such various compounds, in particular, in the compound represented by the structural formula (3), particularly a compound having n = 0, that is, the following structural formula (2)

で表される化合物に着目し、この化合物のフェノール樹脂（Ａ）中の含有率を５質量％以下に低減させることで硬化物の難燃性を飛躍的に改善することができたものである。このような難燃効果の改善が顕著なものとなる点から、特に１．０〜３．５質量％なる範囲であることが好ましい。

The flame retardancy of the cured product can be drastically improved by reducing the content of this compound in the phenolic resin (A) to 5% by mass or less. . From the point that such improvement of the flame retardant effect becomes remarkable, the range of 1.0 to 3.5% by mass is particularly preferable.

  The phenol resin (A) may contain various compounds as described above. In the structural formula (1), the compound of n = 1, the compound of n = 2, the compound of n = 3, and n = The value obtained by dividing the total mass of the compounds of 4 by the total mass of all the compounds represented by the structural formula (1) is 0.3 to 0.8. This is preferable from the standpoint of good dielectric properties such as low dielectric constant and low dielectric loss tangent in the cured product as well as flammability. In the present invention, in particular, in the structural formula (1), all of the compound of n = 1, the compound of n = 2, the compound of n = 3, and the compound of n = 4 are all represented by the structural formula (a1- It is preferable from the point which the flame retardance of hardened | cured material becomes further better that it is represented by 1).

  Further, the phenol resin (A) is 40% by mass or less, preferably 10 to 30% by mass of the alkoxy group-containing condensed polycyclic aromatic compound (x2) charged when the phenol resin (A) is synthesized. The compound (a1-3) is preferably contained in such a ratio that the compound (a1-3) is formed.

  The phenol resin (A) has a hydroxyl group equivalent of 120 to 500 g / eq. The thing of this range is preferable from the point from which the flame retardance of hardened | cured material becomes still better. Moreover, in this invention, what comprises the conditions of such a hydroxyl equivalent and melt viscosity becomes the novel phenol resin of this invention here. The hydroxyl equivalent is particularly 200 to 450 g / eq. The balance between the flame retardancy of the cured product and the curability of the composition is particularly excellent.

  Further, the phenol resin (A) has a molar ratio of the abundance ratio of the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B). / The latter = 30/70 to 98/2 is preferable because the flame retardancy of the cured product is further improved.

  The phenol resin (A) detailed above can be produced by reacting a hydroxy group-containing aromatic compound (x1), an alkoxy group-containing condensed polycyclic aromatic compound (x2), and formaldehyde.

Specific examples of the hydroxy group-containing aromatic compound (x1) used in the above production method include unsubstituted phenols such as phenol, resorcinol and hydroquinone, cresol, phenylphenol, ethylphenol, n-propylphenol and iso-propyl. Monosubstituted phenols such as phenol and t-butylphenol, disubstituted phenols such as xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol and dibutylphenol, mesitol, 2,3,5-trimethylphenol, 2 , 3,6-trimethylphenol and the like, and naphthols such as 1-naphthol, 2-naphthol and methylnaphthol.
Two or more of these may be used in combination.

  Among these, as described above, 1-naphthol, 2-naphthol, cresol, and phenol are particularly preferable from the viewpoint of flame retardancy of the cured product.

Next, the alkoxy group-containing condensed polycyclic aromatic compound (x2) specifically includes 1-methoxynaphthalene, 2-methoxynaphthalene, 1-methyl-2-methoxynaphthalene, 1-methoxy-2-methylnaphthalene. 1,3,5-trimethyl-2-methoxynaphthalene, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 1-ethoxynaphthalene, 1,4-dimethoxynaphthalene, 1-t-butoxynaphthalene, 1-methoxy And anthracene.
Among these, 2-methoxynaphthalene is particularly preferable from the viewpoint of excellent flame retardancy.

The above-mentioned hydroxy group-containing aromatic compound (x1), alkoxy group-containing condensed polycyclic aromatic compound (x2) and formaldehyde can be reacted via the following two-stage reaction. .
First stage: A hydroxy group-containing aromatic compound (x1) and formaldehyde are charged, and a methylolation reaction is carried out in the presence of an alkali catalyst.
Second stage: After neutralizing the alkali catalyst with a neutralizing agent, an alkoxy group-containing condensed polycyclic aromatic compound (x2) is charged and reacted under an acid catalyst to obtain a phenol resin.

  The alkali catalyst used in the first step is preferably an alkali metal or alkaline earth metal hydroxide, and examples thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide. . The amount used is preferably in the range of 0.1 to 3.0 times the number of moles of the charged hydroxy group-containing aromatic compound (x1).

  The first stage reaction can be carried out, for example, with stirring under a temperature condition of 0 to 80 ° C.

  Examples of the neutralizing agent used in the second stage include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, boron trifluoride and anhydrous aluminum chloride. And Lewis acids such as zinc chloride.

  Examples of the acid catalyst used in the second stage include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, Examples include Lewis acids such as zinc chloride. The amount used is preferably in the range of 0.1 to 5% by mass with respect to the total mass of the charged raw materials.

  In the above reaction, the reaction charge ratio of the hydroxy group-containing aromatic compound (x1), the alkoxy group-containing condensed polycyclic aromatic compound (x2), and formaldehyde is the hydroxy group-containing aromatic compound (x1) and the alkoxy group. The molar ratio (x1) / (x2) to the condensed polycyclic aromatic compound (x2) is 30/70 to 98/2, and the hydroxy group-containing aromatic compound (x1) and the alkoxy group-containing condensation The ratio of the total number of moles of the polycyclic aromatic compound (x2) and the number of moles of formaldehyde is preferably 40/60 to 97/3.

  In carrying out the second stage reaction, water or an organic solvent can be used as necessary. Specific examples of the organic solvent that can be used include, but are not limited to, methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is usually 10 to 500% by mass, preferably 30 to 250% by mass, based on the total mass of the charged raw materials. The reaction temperature of the first-stage methylolation reaction is usually 20 to 150 ° C., more preferably 30 to 100 ° C., and the reaction time is usually 1 to 10 hours. Subsequently, the reaction temperature in the second stage is usually from 40 to 250 ° C, and more preferably from 100 to 200 ° C. The reaction time is usually 1 to 10 hours.

  Further, when the resulting polyvalent hydroxy compound is highly colored, an antioxidant or a reducing agent may be added to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. be able to. Although it does not specifically limit as said reducing agent, For example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, these salts, zinc, etc. are mentioned.

  After completion of the reaction, the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 4 to 7. What is necessary is just to perform a neutralization process and a water washing process according to a conventional method. For example, when an acid catalyst is used, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, and aniline can be used as the neutralizing agent. At the time of neutralization, a buffer such as phosphoric acid may be added in advance, or the pH may be adjusted to 3 to 7 with oxalic acid after the base side is once used. After the neutralization or water washing treatment, an unreacted raw material or organic solvent mainly containing a hydroxy group-containing aromatic compound (x1) and an alkoxy group-containing condensed polycyclic aromatic compound (x2) under reduced pressure heating, By-products are distilled off and the product is concentrated to obtain the target polyvalent hydroxy compound. The unreacted raw material recovered here can be reused. Introducing a microfiltration step into the processing operation after the completion of the reaction is a more preferable method because inorganic salts and foreign substances can be purified and removed.

  In the curable resin composition of the present invention, the phenol resin (A) may be used alone as a curing agent for the epoxy resin (B), or may be cured for other epoxy resins as long as the effects of the present invention are not impaired. An agent may be used. Specifically, other curing agents can be used in combination so that the phenol resin (A) is 30% by mass or more, preferably 40% by mass or more with respect to the total mass of the epoxy resin curing agent.

  The other curing agent that can be used in combination with the phenol resin of the present invention is not particularly limited, and examples thereof include amine compounds, amide compounds, acid anhydride compounds, and phenol compounds other than the above-described phenol resins. And polyphenolic compounds of aminotriazine-modified phenolic resins (polyhydric phenolic compounds in which phenolic nuclei are linked with melamine, benzoguanamine or the like).

  Among these, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, Biphenyl-modified phenolic resin, biphenyl-modified naphthol resin, aminotriazine-modified phenolic resin are preferred because of excellent flame retardancy, especially high aromaticity such as phenol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, Using a compound such as a phenolic resin having a high hydroxyl equivalent or an aminotriazine-modified phenolic resin containing a nitrogen atom, From the viewpoint of retardancy and dielectric properties superior.

  Next, as the epoxy resin (B) used in the curable resin composition of the present invention, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type Epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type Epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon Formaldehyde resin-modified phenol resin type epoxy resin, a biphenyl novolak type epoxy resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types.

  Of these, biphenyl type epoxy resins, naphthalene type epoxy resins, phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins and xanthene type epoxy resins are particularly preferred because of their excellent flame retardancy and dielectric properties.

  Although it does not restrict | limit especially as a compounding quantity of the epoxy resin (B) and hardening | curing agent in the curable resin composition of this invention, From the point that the hardened | cured material characteristic obtained is favorable, of an epoxy resin (B). The amount of active groups in the curing agent containing the phenol resin (A) is preferably 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of epoxy groups.

  Moreover, a hardening accelerator can also be suitably used together with the curable resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.

  Since the curable resin composition of the present invention described in detail above has an excellent flame retardancy imparting effect depending on the selection of the molecular structure of the phenol resin, it is difficult to use conventionally. Even if no flame retardant is blended, the flame retardancy of the cured product is good. However, in order to exert a higher degree of flame retardancy, for example, in the field of semiconductor sealing materials, it contains substantially halogen atoms in a range that does not reduce the moldability in the sealing process and the reliability of the semiconductor device. Non-halogen flame retardants that do not work may be blended.

  The curable resin composition containing such a non-halogen flame retardant contains substantially no halogen atom, but does not contain a halogen atom due to a trace amount of impurities of about 5000 ppm or less derived from an epihalohydrin contained in an epoxy resin, for example. It may be.

  Examples of the non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. The flame retardants may be used alone or in combination, and a plurality of flame retardants of the same system may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7- Examples thereof include cyclic organophosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, phenol resin, phenol resin, In 100 parts by mass of curable resin composition containing all of halogen-based flame retardant and other fillers and additives, 0.1 to 2.0 parts by mass of red phosphorus is used as a non-halogen flame retardant. It is preferable to mix in the range, and when using an organophosphorus compound, it is preferably mixed in the range of 0.1 to 10.0 parts by mass, particularly in the range of 0.5 to 6.0 parts by mass. It is preferable to do.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenolic resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) and (iii) with paulownia oil, isomerized linseed oil, etc. It is.

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, a phenol resin, It is preferable to mix in the range of 0.05 to 10 parts by mass in 100 parts by mass of the curable resin composition containing all of epoxy resin, non-halogen flame retardant and other fillers and additives. It is preferable to mix | blend in the range of 1-5 mass parts.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, a phenol resin, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable resin composition containing all of epoxy resin, non-halogen flame retardant and other fillers and additives. It is preferable to mix | blend in 5-15 mass parts.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organic metal salt flame retardant is appropriately selected depending on the type of the organic metal salt flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. , Phenol resin, epoxy resin, non-halogen flame retardant, and other fillers and additives are preferably blended in a range of 0.005 to 10 parts by mass in 100 parts by mass of the curable resin composition. .

  An inorganic filler (C) can be blended with the curable resin composition of the present invention as necessary. Examples of the inorganic filler (C) include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 65% by mass or more with respect to the total amount of the curable resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, can be added to the curable resin composition of this invention as needed.

  The curable resin composition of the present invention can be obtained by uniformly mixing the above-described components. The curable resin composition of the present invention, in which the phenol resin of the present invention, the epoxy resin, and, if necessary, the curing accelerator is blended, can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Applications in which the curable resin composition of the present invention is used include semiconductor sealing materials, resin compositions used for laminates and electronic circuit boards, resin casting materials, adhesives, build-up substrate interlayer insulation materials, Examples thereof include a coating material such as an insulating paint, and among these, it can be suitably used as a semiconductor sealing material.

  In order to use the curable resin composition of the present invention as a semiconductor encapsulant, a compounding agent such as a phenol resin (A), an epoxy resin (B), and an inorganic filler (C) is optionally used as an extruder, A melt-mixing type curable resin composition may be obtained by sufficiently mixing with a kneader or a roll until uniform. Here, as the inorganic filler (C), silica is usually used, but the filling rate is preferably in the range of 30 to 95% by mass of the filler per 100 parts by mass of the curable resin composition. Among them, 70 parts by mass or more is particularly preferable in order to improve flame retardancy, moisture resistance, solder crack resistance, and decrease in linear expansion coefficient, and 80 parts by mass or more in order to significantly increase these effects. However, the effect can be further enhanced. For semiconductor package molding, the composition is molded by casting, using a transfer molding machine, an injection molding machine or the like, and further heated at 50 to 200 ° C. for 2 to 10 hours to form a semiconductor device which is a molded product. There is a way to get it.

  In order to process the curable resin composition of the present invention into a printed circuit board composition, for example, a prepreg resin composition can be used. Depending on the viscosity of the curable resin composition, the curable resin composition can be used without a solvent, but it is preferable to obtain a prepreg resin composition by varnishing using an organic solvent. As the organic solvent, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it can be used alone or as a mixed solvent of two or more kinds. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Moreover, when manufacturing a copper clad laminated board using this curable resin composition, the prepreg obtained as mentioned above is laminated | stacked by a conventional method, copper foil is laminated | stacked suitably, and it is under pressure of 1-10 MPa. A copper-clad laminate can be obtained by thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours.

  When the curable resin composition of the present invention is used as a conductive paste, for example, a method of dispersing fine conductive particles in the curable resin composition to obtain a composition for anisotropic conductive film, liquid at room temperature And a paste resin composition for circuit connection and an anisotropic conductive adhesive.

  As a method for obtaining an interlayer insulating material for a build-up substrate from the curable resin composition of the present invention, for example, the curable resin composition appropriately blended with rubber, filler, etc., spray coating method on a wiring board on which a circuit is formed, After applying using a curtain coating method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  In the method for obtaining the cured product of the present invention, the heating temperature condition may be appropriately selected depending on the type and use of the curing agent, but the composition obtained by the above method is heated in a temperature range of room temperature to about 250 ° C. A method is mentioned.

  Therefore, by using the phenol resin, it is possible to obtain a resin material with a low environmental load that can exhibit high flame retardancy without using a halogen-based flame retardant. In addition, the phenol resin can be easily and efficiently produced by the production method of the present invention, and a molecular design corresponding to the target level of performance described above becomes possible.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. The melt viscosity and GPC measurement at 150 ° C. were measured under the following conditions.
1) Melt viscosity at 150 ° C .: according to ASTM D4287 2) Softening point measurement method: according to “JIS K7234”.
3) GPC:
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
4) NMR: “NMR GSX270” manufactured by JEOL Ltd.
5) MS: Double Density Gravimetric Analyzer AX505H (FD505H) manufactured by JEOL Ltd.

Example 1 [Synthesis of phenol resin (A-1)]
In a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 324.42 g (3.00 mol) of o-cresol, 300.00 g of water, and a 49 mass% sodium hydroxide aqueous solution 210. 00 g (2.57 mol) was charged and the temperature was raised to 40 ° C. 486.97 g (6.00 mol) of 37% by mass aqueous formaldehyde solution was added dropwise over 1 hour, and the mixture was kept at 40 ° C. for 4 hours. Thereafter, neutralization was performed using an appropriate amount of 98% sulfuric acid. Subsequently, 15.98 g of oxalic acid and 474.60 g (3.00 mol) of 2-methoxynaphthalene were added, and the temperature was raised to 130 ° C. and reacted at 130 ° C. for 1 hour. During this time, the outflowing water was collected by a fractionating tube. After completion of the reaction, 1500 g of methyl isobutyl ketone was added, transferred to a separatory funnel and washed with water. After washing with water until the washing water shows neutrality, unreacted o-cresol, 2-methoxynaphthalene, and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure, and the following structural formula (A-1)

（式中、Ｘはメトキシナフタレン骨格、Ｘ’はメトキシナフタレン骨格又はクレゾール骨格、Ｐはクレゾール骨格である。）
で表される分子構造を有する化合物を主成分とするフェノール樹脂（Ａ−１）７５１．６ｇを得た。
フェノール樹脂（Ａ−１）は構造式（Ａ−１）におけるｎ＝１〜１７の化合物を含有するものであった。また、フェノール樹脂（Ａ−１）において、前記構造式（Ａ−１）中、ｎ＝１〜４で表される化合物は全てＸ’がメトキシナフタレン骨格のものであり、ｎ＝１〜４の化合物の合計質量を、構造式（Ａ−１）で表される全ての化合物の全質量で除した値は０．６７７であった。
また、フェノール樹脂（Ａ−１）は、の軟化点は１１１℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１３．０ｄＰａ・ｓ、水酸基当量は３６３ｇ／ｅｑ．であった。更に、フェノール樹脂（Ａ−１）の理論水酸基当量と実測の水酸基当量との比較から、反応に用いたメトキシナフタレンの２２質量％がｏ−クレゾール構造部位との脱メタノール反応による環状構造を形成していることが確認できた。
得られたフェノール樹脂（Ａ−１）のＧＰＣチャートを図１に、Ｃ^１３−ＮＭＲチャートを図２に示す。ＧＰＣ分析の結果、フェノール樹脂（Ａ−１）中の下記構造式(２)

(Wherein, X is a methoxynaphthalene skeleton, X ′ is a methoxynaphthalene skeleton or a cresol skeleton, and P is a cresol skeleton.)
The phenol resin (A-1) 751.6g which has as a main component the compound which has the molecular structure represented by this was obtained.
The phenol resin (A-1) contained the compound of n = 1-17 in Structural formula (A-1). Moreover, in the phenol resin (A-1), in the structural formula (A-1), all of the compounds represented by n = 1 to 4 have a methoxynaphthalene skeleton, and n = 1 to 4 A value obtained by dividing the total mass of the compounds by the total mass of all the compounds represented by the structural formula (A-1) was 0.677.
The phenol resin (A-1) has a softening point of 111 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 13.0 dPa · s, and a hydroxyl group equivalent of 363 g. / Eq. Met. Furthermore, from a comparison between the theoretical hydroxyl group equivalent of phenol resin (A-1) and the measured hydroxyl group equivalent, 22% by mass of methoxynaphthalene used in the reaction formed a cyclic structure by demethanol reaction with the o-cresol structure site. It was confirmed that
A GPC chart of the obtained phenol resin (A-1) is shown in FIG. 1, and a C ¹³ -NMR chart is shown in FIG. As a result of GPC analysis, the following structural formula (2) in the phenol resin (A-1)

で表される構造に該当する化合物の含有率は１．４質量％であった。回収した未反応のο-クレゾール及び２−メトキシナフタレンの質量測定の結果から、該フェノール樹脂（Ａ−１）中のクレゾール骨格の構造単位と、メトキシナフタレン骨格の構造単位とのモル比率は、前者／後者＝５０／５０であった。

The content rate of the compound corresponding to the structure represented by was 1.4 mass%. From the results of mass measurement of the recovered unreacted ο-cresol and 2-methoxynaphthalene, the molar ratio between the structural unit of the cresol skeleton and the structural unit of the methoxynaphthalene skeleton in the phenol resin (A-1) is / The latter = 50/50.

Example 2 [Synthesis of phenol resin (A-2)]
In Example 1, except that 316.4 g (2.00 mol) of 2-methoxynaphthalene was used, the following structural formula (A-2)

で表される分子構造を有する化合物を主成分とするフェノール樹脂（Ａ−２）６０５．０ｇを得た。
フェノール樹脂（Ａ−２）は構造式（Ａ−２）におけるｎ＝１〜４１の化合物を含有するものであった。また、フェノール樹脂（Ａ−２）において、前記構造式（Ａ−２）中、ｎ＝１〜４で表される化合物は全てＸ’がメトキシナフタレン骨格のものであり、ｎ＝１〜４の化合物の合計質量を、構造式（Ａ−２）で表される全ての化合物の全質量で除した値は０．４９２であった。
また、フェノール樹脂（Ａ−２）の軟化点は１１１℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１１０．０ｄＰａ・ｓ、水酸基当量は２９４ｇ／ｅｑ．であった。更に、フェノール樹脂（Ａ−２）の理論水酸基当量と実測の水酸基当量との比較から、反応に用いたメトキシナフタレンの２１質量％がｏ−クレゾール構造部位との脱メタノール反応による環状構造を形成していることが確認できた。得られたフェノール樹脂のＧＰＣチャートを図３に示す。ＧＰＣ分析の結果、フェノール樹脂（Ａ−２）中の下記構造式(２)

The phenol resin (A-2) 605.0g which has as a main component the compound which has the molecular structure represented by this was obtained.
The phenol resin (A-2) contained a compound having n = 1 to 41 in the structural formula (A-2). Moreover, in the phenol resin (A-2), in the structural formula (A-2), all compounds represented by n = 1 to 4 are those in which X ′ is a methoxynaphthalene skeleton, and n = 1 to 4 A value obtained by dividing the total mass of the compounds by the total mass of all the compounds represented by the structural formula (A-2) was 0.492.
The softening point of the phenol resin (A-2) is 111 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 110.0 dPa · s, and the hydroxyl group equivalent is 294 g / eq. . Met. Furthermore, from the comparison between the theoretical hydroxyl equivalent of the phenol resin (A-2) and the actually measured hydroxyl equivalent, 21% by mass of the methoxynaphthalene used in the reaction forms a cyclic structure by demethanol reaction with the o-cresol structure site. It was confirmed that The GPC chart of the obtained phenol resin is shown in FIG. As a result of GPC analysis, the following structural formula (2) in the phenol resin (A-2)

で表される構造に該当する化合物の含有率は３．３質量％であった。回収した未反応のｏ−クレゾール及び２−メトキシナフタレンの質量測定の結果から、該フェノール樹脂中のフェノール性水酸基含有芳香族炭化水素基の構造単位と、アルコキシ基含有縮合多環式芳香族炭化水素基の構造単位とのモル比率は、前者／後者＝６０／４０であった。

The content rate of the compound corresponding to the structure represented by this was 3.3 mass%. From the results of mass measurement of the recovered unreacted o-cresol and 2-methoxynaphthalene, the structural unit of the phenolic hydroxyl group-containing aromatic hydrocarbon group in the phenol resin and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon The molar ratio of the group to the structural unit was the former / the latter = 60/40.

Synthesis Example 1 (Synthesis of Compound of Example 1 of JP 2006-274236 A)
In a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, ο-cresol 432.4 g (4.00 mol) and 2-methoxynaphthalene 158.2 g (1.00 mol) 419.3 mass% paraformaldehyde 179.3g (2.45mol) was prepared, oxalic acid 9.0g was added, and it heated up to 100 degreeC, and was made to react at 100 degreeC for 3 hours. Subsequently, 73.2 g (1.00 mol) of 41 mass% paraform was added dropwise over 1 hour while collecting water with a fractionating tube. After completion of the dropwise addition, the temperature was raised to 150 ° C. over 1 hour and further reacted at 150 ° C. for 2 hours. After completion of the reaction, 1500 g of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. After washing with water until the washing water shows neutrality, unreacted o-cresol, 2-methoxynaphthalene and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure, and the following structural formula

で表される各構造単位を交互に結合した分子構造を有するフェノール樹脂（Ａ−３）５３１ｇを得た。得られたフェノール樹脂の軟化点は７６℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１．０ｄＰａ・ｓ、水酸基当量は１６４ｇ／ｅｑ．であった。ＧＰＣ分析の結果、ＧＰＣ分析の結果、フェノール樹脂（Ａ−３）中の下記構造式(２)

531 g of a phenol resin (A-3) having a molecular structure in which the structural units represented by The softening point of the obtained phenol resin was 76 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) was 1.0 dPa · s, and the hydroxyl group equivalent was 164 g / eq. Met. As a result of GPC analysis, as a result of GPC analysis, the following structural formula (2) in phenol resin (A-3)

で表される構造に該当する化合物の含有率は６．９質量％であった。

The content of the compound corresponding to the structure represented by 6.9% was 6.9% by mass.

Examples 3 and 4 and Comparative Example 1
As epoxy resin, Nippon Kayaku Co., Ltd. NC-3000 (biphenyl novolac type epoxy resin, epoxy equivalent: 274 g / eq), phenol resin (A-1) and (A-2), and comparative phenol resin ( A-3), triphenylphosphine (TPP) as a curing accelerator, spherical silica (S-COL manufactured by Micron Corporation) as an inorganic filler, and γ-glycidoxytriethoxyxysilane (Shin-Etsu Chemical) as a silane coupling agent “KBM-403” manufactured by Kogyo Co., Ltd.), Carnauba wax (“Pearl Wax No. 1-P” manufactured by Celalica Noda Co., Ltd.), carbon black, and the composition shown in Table 1 were blended. To obtain the desired composition by melting and kneading at 85 ° C. for 5 minutes, and preparing a sample for evaluation by the following method. The results measured retardance by the following method shown in Table 1.

<Flame retardance>
A sample for evaluation having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm was formed by molding at a temperature of 175 ° C. for 90 seconds using a transfer molding machine and then post-curing at a temperature of 175 ° C. for 5 hours. A combustion test was performed using five test pieces having a thickness of 1.6 mm in accordance with the UL-94 test method using the prepared test pieces.

Footnotes in Table 1:
* 1: Maximum combustion time (seconds) in one flame contact
* 2: Total burning time of 5 test pieces (seconds)

FIG. 1 is a GPC chart of the phenol resin obtained in Example 1. 2 is a C ¹³ -NMR chart of the phenol resin obtained in Example 1. FIG. FIG. 3 is a GPC chart of the phenol resin obtained in Example 2.

Claims (10)

A curable resin composition comprising a phenol resin (A) and an epoxy resin (B) as essential components, wherein the phenol resin (A) has the following structural formula (1):

(Wherein P is a phenolic hydroxyl group-containing aromatic hydrocarbon group, X is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group, and X ′ is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or phenolic. Represents a hydroxyl group-containing aromatic hydrocarbon group, and n is an integer of 1 to 100.) and the following structural formula (2)

(In the formula, P represents a phenolic hydroxyl group-containing aromatic hydrocarbon group.)
A curable resin composition containing the compound (a2) represented by the formula (A2), wherein the content of the compound (a2) in the phenol resin (A) is 5% by mass or less. object.   The curable resin composition according to claim 1, wherein the content of the compound (a2) in the phenol resin is 1.0 to 3.5% by mass.   In the structural formula (1), the phenol resin (A) represents the total mass of the compound of n = 1, the compound of n = 2, the compound of n = 3, and the compound of n = 4 in the structural formula (1). The curable resin composition according to claim 1 or 2, wherein the compound (a1) is contained at a ratio of 0.3 to 0.8 when the value divided by the total mass of all the compounds represented by . P in the phenol resin (A) is selected from the following formulas P6 to P9, X is selected from the following formulas B1 to B8 and B10 , and X ′ is the following formulas P6 to P9 and the following formulas The curable resin composition according to claim 1, which is selected from B1 to B8 and B10 .

  A cured resin obtained by curing reaction of the curable resin composition according to any one of claims 1 to 4. In addition to the phenol resin (A)及beauty et epoxy resin (B), further, a semi-conductive sealing material you content ratio to form inorganic filler (C) and composition 70 to 95 wt%, the The phenol resin (A) has the following structural formula (1)

(Wherein P is a phenolic hydroxyl group-containing aromatic hydrocarbon group, X is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group, and X ′ is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or phenolic. Represents a hydroxyl group-containing aromatic hydrocarbon group, and n is an integer of 1 to 100.) and the following structural formula (2)

(In the formula, P represents a phenolic hydroxyl group-containing aromatic hydrocarbon group.)
The compound (a2) represented by this, Comprising: It is a ratio from which the content rate of the said compound (a2) in a phenol resin (A) will be 5 mass% or less, The semiconductor sealing material characterized by the above-mentioned. .

. The following structural formula (1)

(Wherein P is a phenolic hydroxyl group-containing aromatic hydrocarbon group, X is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group, and X ′ is an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or phenolic. Represents a hydroxyl group-containing aromatic hydrocarbon group, and n is 0 to 50 on the average of the repeating units.) And the following structural formula (2)

(In the formula, P represents a phenolic hydroxyl group-containing aromatic hydrocarbon group.)
In a phenol resin containing a compound (a2) represented, novel phenol resin which is a percentage content of the compound of the phenolic trees in fat (a2) is 5 mass% or less. P is, those selected from the formula P6～P9, which X is selected from the front above formula B1 to B8 and B10, X 'previous following formula P6～P9, before following formula B1 to B8 and B10 The novel phenol resin of Claim 7 which is chosen from these.   Hydroxy group-containing aromatic compound (x1) and formaldehyde are reacted in the presence of an alkali catalyst, and after neutralizing the alkali catalyst, an alkoxy group-containing condensed polycyclic aromatic compound (x2) is charged. A method for producing a phenol resin, wherein the reaction is carried out in the presence of an acid catalyst.   The method for producing a phenol resin according to claim 9, wherein the hydroxy group-containing aromatic compound (x1) is cresol, and the alkoxy group-containing condensed polycyclic aromatic compound (x2) is methoxynaphthalene.

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