JP4706905B2 - Epoxy resin composition, cured product thereof, novel polyvalent hydroxy compound, and production method thereof - Google Patents

Description

  The present invention is excellent in flame retardancy and moldability of the resulting cured product, and can be suitably used for semiconductor encapsulants, printed circuit boards, paints, casting applications, etc., cured products thereof, and the The present invention relates to a novel polyvalent hydroxy compound that can be suitably used as a curing agent for an epoxy resin composition and a method for producing the same.

  The polyvalent hydroxy compound is a compound useful as an epoxy resin curing agent, an epoxy resin raw material, an adhesive, a molding material, a paint, a photoresist material, a color developing material, and the like. In particular, when used as a curing agent for epoxy resins, excellent heat resistance and moisture resistance of the obtained cured products are highly evaluated, and they are widely used in the fields of semiconductor encapsulants and printed circuit boards. In addition, a phenol novolac resin (phenol-formaldehyde resin) is generally used for that purpose.

  By the way, in recent electronics and high-performance paint fields, halogen-based flame retardants such as bromine are blended together with antimony compounds in order to impart flame retardancy. However, in recent environmental and safety efforts, environmentally and flame-resistant flame retardants that do not use halogen-based flame retardants that may cause dioxins and do not use antimony compounds that are suspected of carcinogenicity. There is a strong demand for the development of a conversion method. Further, non-halogenation of the semiconductor sealing material is expected to be a technology that greatly contributes to improvement of the reliability of the semiconductor device left at high temperature. On the other hand, in order to cope with advanced mounting methods in the semiconductor field, it is also necessary to have excellent moldability.

  As means for meeting these demands, for example, many modified polyhydroxy compounds containing an aralkyl skeleton have been proposed.

  For example, the following general formula (I)

（式中、Ａは炭素数１〜６のアルキル基が置換していても良いベンゼン環又はナフタレン環を示し、Ｂは芳香族環を示し、Ｒは水素原子又はメチル基を示す。）
で表される構造単位を有する芳香族環変性フェノールアラルキル樹脂が、耐湿性、耐熱性、耐衝撃性等の技術課題を解決するものとして開示されている（例えば、特許文献１参照）。これは一般的なフェノールアラルキル樹脂と異なり、フェノール類と芳香族系架橋剤とを反応させる際に、芳香族環含有化合物類を反応系に加えて得られる変性フェノールアラルキル樹脂の１種であり、一般的なフェノールアラルキル樹脂と比較して、芳香族性が上がり、水酸基当量も高まるために、エポキシ樹脂硬化物の難燃性の改良効果が認められるが、それでも要求レベルを十分満足できるレベルには至っていないばかりか、水酸基当量が高いために架橋密度が低くなり、成形性（成形時の硬度）が劣るものであった。

(In the formula, A represents a benzene ring or a naphthalene ring which may be substituted by an alkyl group having 1 to 6 carbon atoms, B represents an aromatic ring, and R represents a hydrogen atom or a methyl group.)
An aromatic ring-modified phenol aralkyl resin having a structural unit represented by the formula is disclosed as a solution to technical problems such as moisture resistance, heat resistance, and impact resistance (see, for example, Patent Document 1). Unlike general phenol aralkyl resins, this is one type of modified phenol aralkyl resin obtained by adding aromatic ring-containing compounds to the reaction system when reacting phenols with an aromatic crosslinking agent, Compared to general phenol aralkyl resins, the aromaticity increases and the hydroxyl equivalent also increases, so the effect of improving the flame retardancy of the cured epoxy resin is recognized, but still to the level that can sufficiently satisfy the required level Not only that, but the hydroxyl group equivalent was high, the crosslinking density was low, and the moldability (hardness during molding) was poor.

  The following general formula (II)

（式中、Ｒはメチル基またはエチル基を表し、Ｘは水素原子またはメチル基を表す。また、ｎは０〜３の整数を表し、ｍは１〜５の整数を表す。但し、ｎ＝０の化合物の含有率は１０％以下である。）
で表されるメトキシ基変性フェノールノボラック樹脂が、耐湿性と耐衝撃性の技術課題を解決するものとして開示されている（例えば、特許文献２参照。）。該樹脂の水酸基当量は一般的なフェノールノボラック樹脂と比較して高まるために、得られる硬化物の耐湿性と耐衝撃性の改良効果は認められるものの、難燃性と成形性を満足できるレベルにまで改良するものではなく、更なる改良が求められている。また、上記のメトキシ基変性フェノールノボラック樹脂は、フェノール類とホルムアルデヒドとの反応で得られるノボラック前駆体（ジメチロール化物）の段階で、フェノール水酸基をジメチル硫酸やハロゲン化アルキル等を用いてアルコキシ基化して得られるものであり、アニソール等のアルコキシ基含有芳香族系化合物を出発原料として用いたものではない。これは、フェノール性水酸基をアルコキシ化して得られるアルコキシ基が、フェノール性水酸基の保護技術として広く用いられている様に、一般的には、強酸性環境下では容易に分解することが知られていることによる。つまり、芳香族性ヒドロキシ化合物類の多核体化反応に、アルコキシ基含有芳香族系化合物を出発原料として使用すれば、反応中に容易に分解することが懸念され、それを該反応系で共重合させようといった発想は、通常、当業者は持ちえず、メトキシ基変性フェノールノボラック樹脂の出発原料としてアルコキシ基含有芳香族系化合物が、一切、具体的に記載されていない技術的背景である。

(In the formula, R represents a methyl group or an ethyl group, X represents a hydrogen atom or a methyl group, n represents an integer of 0 to 3, and m represents an integer of 1 to 5, provided that n = The content of 0 compound is 10% or less.)
A methoxy group-modified phenol novolac resin represented by the formula is disclosed as a solution to the technical problems of moisture resistance and impact resistance (see, for example, Patent Document 2). Since the hydroxyl equivalent of the resin is higher than that of a general phenol novolac resin, the effect of improving the moisture resistance and impact resistance of the resulting cured product is recognized, but the flame retardancy and moldability are satisfactory. There is a need for further improvements. The methoxy group-modified phenol novolac resin is obtained by alkoxylating a phenol hydroxyl group with dimethyl sulfate or alkyl halide at the stage of a novolak precursor (dimethylolated product) obtained by reaction of phenols with formaldehyde. It is obtained and not an alkoxy group-containing aromatic compound such as anisole as a starting material. This is because it is generally known that an alkoxy group obtained by alkoxylation of a phenolic hydroxyl group is easily decomposed in a strongly acidic environment, as is widely used as a protection technique for the phenolic hydroxyl group. Because it is. In other words, if an alkoxy group-containing aromatic compound is used as a starting material in the polynuclearization reaction of aromatic hydroxy compounds, there is a concern that it will be easily decomposed during the reaction, and it is copolymerized in the reaction system. An idea such as letting them usually cannot be possessed by those skilled in the art, and is a technical background in which no alkoxy group-containing aromatic compound is specifically described as a starting material for a methoxy group-modified phenol novolac resin.

JP-A-8-301980 JP 2004-10700 A

  In view of the above situation, an object of the present invention is to develop a polyvalent hydroxy compound used for a curing agent for epoxy resin capable of imparting excellent flame retardancy and moldability to a cured product, and an epoxy resin composition capable of solving the above problems It is to provide a product and a cured product thereof, and to provide a method for efficiently producing the polyvalent hydroxy compound.

  In order to solve the above problems, the present inventors have intensively studied for a polyvalent hydroxy compound having excellent characteristics as described above, and as a result, found that a polyvalent hydroxy compound having the following specific structure solves the above problem. Furthermore, when the reaction is carried out using an aromatic compound having 2 to 4 hydroxy groups, an alkoxy group-containing aromatic compound and an aromatic crosslinking agent, the alkoxy group is not decomposed in the molecule. The present inventors have found that a polyvalent hydroxy compound efficiently introduced into the product can be obtained, thereby completing the present invention.

  That is, the present invention provides the following general formula (1) in one molecule.

（式中、Ｘ_１は置換基を有していてもよい芳香環であり、Ａｒ_１は炭化水素基を置換基として有していてもよいベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^１は同一でも異なっていてもよい水素原子又は炭素数１〜６の炭化水素基であり、ｎは２〜４である。）
で表わされる構造単位と、下記一般式（２）

(Wherein, X ₁ is an aromatic ring which may have a substituent, Ar ₁ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ¹ Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, and n is 2 to 4.)
A structural unit represented by the following general formula (2)

（式中、Ｘ_２は置換基を有していてもよい芳香環であり、Ａｒ_２は炭化水素基を置換基として有していてもよいベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^２は同一でも異なっていてもよい水素原子又は炭素数１〜６の炭化水素基であり、Ｒ^３は炭素数１〜４のアルキル基であり、ｍは１又は２である。）
で表される構造単位を有する多価ヒドロキシ化合物とエポキシ樹脂とを含有することを特徴とするエポキシ樹脂組成物、及びその硬化物を提供するものである。

(Wherein, X ₂ is an aromatic ring which may have a substituent, Ar ₂ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ² Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and m is 1 or 2.)
The epoxy resin composition characterized by containing the polyvalent hydroxy compound which has the structural unit represented by this, and an epoxy resin, and its hardened | cured material are provided.

  Furthermore, the present invention provides the following general formula (1) per molecule.

（式中、Ｘ_１は置換基を有していてもよい芳香環であり、Ａｒ_１は炭化水素基を置換基として有していてもよいベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^１は同一でも異なっていてもよい水素原子又は炭素数１〜６の炭化水素基であり、ｎは２〜４である。）
で表わされる構造単位と、下記一般式（２）

(Wherein, X ₁ is an aromatic ring which may have a substituent, Ar ₁ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ¹ Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, and n is 2 to 4.)
A structural unit represented by the following general formula (2)

（式中、Ｘ_２は置換基を有していてもよい芳香環であり、Ａｒ_２は炭化水素基を置換基として有していてもよいベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^２は同一でも異なっていてもよい水素原子又は炭素数１〜６の炭化水素基であり、Ｒ^３は炭素数１〜４のアルキル基であり、ｍは１又は２である。）
で表される構造単位を有し、水酸基当量が１００〜２７０ｇ／ｅｑ．であり、且つＩＣＩ粘度計で測定した１５０℃における溶融粘度が０．３〜５．０ｄＰａ・ｓの範囲にあることを特徴とする新規多価ヒドロキシ化合物を提供するものである。

(Wherein, X ₂ is an aromatic ring which may have a substituent, Ar ₂ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ² Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and m is 1 or 2.)
The hydroxyl group equivalent is 100-270 g / eq. In addition, the present invention provides a novel polyvalent hydroxy compound characterized in that the melt viscosity at 150 ° C. measured with an ICI viscometer is in the range of 0.3 to 5.0 dPa · s.

  Furthermore, the present invention provides a polyvalent hydroxy compound obtained by reacting an aromatic compound having 2 to 4 hydroxy groups, an alkoxy group-containing aromatic compound and an aromatic crosslinking agent. A method for producing a monovalent hydroxy compound is also provided.

  When the polyvalent hydroxy compound of the present invention is used as a curing agent for an epoxy resin, as can be seen from this example, the flame retardancy and moldability of the cured product obtained are dramatically higher than conventional curing agents. Can be improved. Therefore, by using the polyvalent hydroxy compound, it is possible to obtain an epoxy resin material that is safe in an environment that can exhibit high flame retardancy without using a halogen-based flame retardant, and it is possible to achieve high productivity. . In addition, the polyvalent hydroxy compound can be easily and efficiently produced by the production method of the present invention, and the molecular design according to the target level of the aforementioned performance is possible. The present invention can also be suitably used for photosensitive material applications such as photoresists for color and for color developer materials.

Hereinafter, the present invention will be described in detail.
The polyvalent hydroxy compound (A) used in the epoxy resin composition of the present invention has the following general formula (1) in one molecule.

（式中、Ｘ_１は置換基を有していてもよい芳香環であり、Ａｒ_１は炭化水素基を置換基として有していてもよいベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^１は同一でも異なっていてもよい水素原子又は炭素数１〜６の炭化水素基であり、ｎは２〜４である。）
で表わされる構造単位と、下記一般式（２）

(Wherein, X ₁ is an aromatic ring which may have a substituent, Ar ₁ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ¹ Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, and n is 2 to 4.)
A structural unit represented by the following general formula (2)

（式中、Ｘ_２は置換基を有していてもよい芳香環であり、Ａｒ_２は炭化水素基を置換基として有していてもよいベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^２は同一でも異なっていてもよい水素原子又は炭素数１〜６の炭化水素基であり、Ｒ^３は炭素数１〜４のアルキル基であり、ｍは１又は２である。）
で表される構造単位を有するものである。

(Wherein, X ₂ is an aromatic ring which may have a substituent, Ar ₂ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ² Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and m is 1 or 2.)
It has a structural unit represented by these.

X ₁ in the general formula (1) may have a substituent from the viewpoint of easy industrial availability of raw materials and excellent flame retardancy and moldability of the resulting cured product. A benzene ring and a naphthalene ring which may have a substituent are preferable. In addition, R ³ in the general formula (2) is preferably a methyl group from the viewpoint of excellent flame retardancy of the resulting cured product, and similarly X ₂ is easily industrially available as a raw material. In view of the point and excellent flame retardancy and moldability of the resulting cured product, a benzene ring which may have a substituent and a naphthalene ring which may have a substituent are preferable.

  The following general formula (3) in the general formula (1) in the polyvalent hydroxy compound (A)

（式中、Ｘ_１、ｎは前記と同じである。）
で表される構造単位と、前記一般式（２）における下記一般式（４）

(Wherein X ₁ and n are the same as described above.)
And the following general formula (4) in the general formula (2):

（式中、Ｘ_２、Ｒ^３、ｍは前記と同じである。）
で表される構造単位とのモル比率が前者／後者＝３０／７０〜９８／２の範囲であることが、得られる硬化物の難燃性が一層優れるものになり、好ましいものである。

(Wherein X ₂ , R ³ and m are the same as above).
It is preferable that the molar ratio with the structural unit represented by the formula is in the range of the former / the latter = 30/70 to 98/2 because the flame retardancy of the obtained cured product is further improved.

  Moreover, as a hydroxyl equivalent of this polyhydric hydroxy compound (A), 100-270 g / eq. Those in the range are more preferable in terms of excellent flame retardancy and moldability. Furthermore, the thing whose melt viscosity in 150 degreeC measured with the ICI viscometer is the range of 0.3-5.0 dPa * s is preferable at the point which the fluidity | liquidity at the time of shaping | molding is excellent.

  Accordingly, the most preferred polyvalent hydroxy compound (A) is the novel hydroxy compound of the present invention, and the following general formula (1) is contained in one molecule.

（式中、Ｘ_１は置換基を有していてもよい芳香環であり、Ａｒ_１は炭化水素基を置換基として有していてもよいベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^１は同一でも異なっていてもよい水素原子又は炭素数１〜６の炭化水素基であり、ｎは２〜４である。）
で表わされる構造単位と、下記一般式（２）

(Wherein, X ₁ is an aromatic ring which may have a substituent, Ar ₁ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ¹ Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, and n is 2 to 4.)
A structural unit represented by the following general formula (2)

（式中、Ｘ_２は置換基を有していてもよい芳香環であり、Ａｒ_２は炭化水素基を置換基として有していてもよいベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^２は同一でも異なっていてもよい水素原子又は炭素数１〜６の炭化水素基であり、Ｒ^３は炭素数１〜４のアルキル基であり、ｍは１又は２である。）
で表される構造単位を有し、水酸基当量が１００〜２７０ｇ／ｅｑ．であり、且つＩＣＩ粘度計で測定した１５０℃における溶融粘度が０．３〜５．０ｄＰａ・ｓの範囲にある化合物である。

(Wherein, X ₂ is an aromatic ring which may have a substituent, Ar ₂ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ² Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and m is 1 or 2.)
The hydroxyl group equivalent is 100-270 g / eq. And a compound having a melt viscosity at 150 ° C. measured with an ICI viscometer in the range of 0.3 to 5.0 dPa · s.

  Specific examples of the general formula (1) include those represented by the following structural formula, but are not limited thereto.

  Specific examples of the general formula (2) include those represented by the following structural formula, but are not limited thereto.

  Although it does not specifically limit as a manufacturing method of the said polyvalent hydroxy compound (A), It can obtain easily by the manufacturing method of this invention explained in full detail below of this invention.

Hereinafter, the manufacturing method of the present invention will be described.
In the production method of the present invention, an aromatic compound (a1) having 2 to 4 hydroxy groups, an alkoxy group-containing aromatic compound (a2), and an aromatic crosslinking agent (a3) are reacted to produce a polyvalent compound. A hydroxy compound is obtained.

  In particular, the aromatic compound (a1) having 2 to 4 hydroxy groups is a compound represented by the following general formula (5), and the alkoxy group-containing aromatic compound (a2) is represented by the following general formula (6). It is preferable to use a compound represented by the following general formula (7) after the crosslinking reaction of the aromatic crosslinking agent (a3).

（式中、Ｘ_１、Ｘ_２は置換基を有していてもよい芳香環であり、Ａｒは炭化水素基を置換基として有していてもよいベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒは同一でも異なっていてもよい水素原子又は炭素数１〜６の炭化水素基であり、Ｒ^３は炭素数１〜４のアルキル基であり、ｎは２〜４であり、ｍは１又は２である。）

(Wherein X ₁ and X ₂ are aromatic rings which may have a substituent, Ar is a benzene skeleton, biphenyl skeleton and naphthalene skeleton which may have a hydrocarbon group as a substituent; R is a hydrocarbon group having 1 to 6 carbon good hydrogen atom or a C be the same or different, R ³ is an alkyl group having 1 to 4 carbon atoms, n is 2 to 4, m is 1 or 2)

  As the aromatic compound (a1) having 2 to 4 hydroxy groups, any aromatic compound having 2 to 4 aromatic hydroxy groups in one molecule can be used. For example, unsubstituted diphenols such as catechol, resorcinol, hydroquinone; unsubstituted triphenols such as phloroglicinol; substituted diphenols such as monomethylhydroquinone, 4-ethylresorcinol, dimethylhydroquinone, dimethylresorcinol; Unsubstituted dinaphthols such as dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; substitution such as 1,6-dihydroxy-7-methylnaphthalene Examples include dinaphthols It is, but is not limited thereto. Two or more of these can also be mixed and used. Among these, unsubstituted diphenols and unsubstituted dinaphthols are preferable from the viewpoint of particularly excellent flame retardancy of the obtained cured product.

  As the alkoxy group-containing aromatic compound (a2), any aromatic compound having one or more alkoxy groups in one molecule can be used, for example, monoalkoxy such as anisole and ethoxybenzene. Benzenes, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, 1,4-diethoxybenzene, dialkoxybenzenes such as 1-methoxy-2-isopropoxybenzene, 1- Monoalkoxynaphthalenes such as methoxynaphthalene and 2-methoxynaphthalene, dialkoxynaphthalenes such as 1,4-dimethoxynaphthalene, 2,6-dimethoxynaphthalene and 2,7-dimethoxynaphthalene, 1-methoxy-4-propylbenzene, 1-methoxypropynylbenzene, 1- (4-methyl Examples thereof include, but are not limited to, substituted alkoxybenzenes such as xylphenyl) -1-propane and 1-propyl-2-methoxy-4-methylbenzene, 1,2-methylenedioxybenzene, anisaldehyde and the like. . Two or more of these can also be mixed and used. Among these, from the viewpoint of particularly excellent flame retardancy of the resulting cured product, methoxybenzene optionally having a substituent, dimethoxybenzene optionally having a substituent, having a substituent It is preferable to use an optionally substituted methoxynaphthalene or an optionally substituted dimethoxynaphthalene. Anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, 1 -Methoxynaphthalene and 2-methoxynaphthalene are particularly preferred. In addition, anisole, 1-methoxynaphthalene, 2-methoxynaphthalene, and 1-methoxy-4-propylbenzene are particularly preferable from the viewpoint that a cured product having particularly excellent dielectric characteristics can be obtained.

  The aromatic crosslinking agent (a3) is not limited as long as it is an aromatic compound having a structure capable of crosslinking the compound (a1) and the alkoxy group-containing aromatic compound (a2). Those represented by the following general formulas (8), (9) and (10) are preferred.

（式中、Ａｒは炭化水素基を置換基として有していてもよいベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^４はハロゲン原子であり、Ｒ^５は水素原子又は炭素数１〜６の炭化水素基である。）

(In the formula, Ar is a benzene skeleton, biphenyl skeleton or naphthalene skeleton which may have a hydrocarbon group as a substituent, R ⁴ is a halogen atom, and R ⁵ is a hydrogen atom or a C 1-6 carbon atom. It is a hydrocarbon group.)

  Examples of the compound represented by the general formula (8) include 1,2-di (chloromethyl) benzene, 1,2-di (bromomethyl) benzene, 1,3-di (chloromethyl) benzene, 1, 3-di (fluoromethyl) benzene, 1,4-di (chloromethyl) benzene, 1,4-di (bromomethyl) benzene, 1,4-di (fluoromethyl) benzene, 1,4-di (chloromethyl) -2,5-dimethylbenzene, 1,3-di (chloromethyl) -4,6-dimethylbenzene, 1,3-di (chloromethyl) -2,4-dimethylbenzene, 4,4'-bis (chloro Methyl) biphenyl, 2,2′-bis (chloromethyl) biphenyl, 2,4′-bis (chloromethyl) biphenyl, 2,3′-bis (chloromethyl) biphenyl, 4,4′-bis (bromomethyl) Phenyl, 4,4′-bis (chloromethyl) diphenyl ether, 2,7-di (chloromethyl) naphthalene, and the like. Examples of the general formula (9) include p-xylylene glycol and m-xylene glycol. 1,4-di (2-hydroxy-2-ethyl) benzene, 4,4′-bis (dimethylol) biphenyl, 2,4′-bis (dimethylol) biphenyl, 4,4′-bis (2-hydroxy-) 2-propyl) biphenyl, 2,4′-bis (2-hydroxy-2-propyl) biphenyl, 1,4′-di (methoxymethyl) benzene, 1,4′-di (ethoxymethyl) benzene, 1,4 '-Di (isopropoxy) benzene, 1,4'-di (butoxy) benzene, 1,3'-di (methoxymethyl) benzene, 1,3'-di (ethoxymethyl) ) Benzene, 1,3′-di (isopropoxy) benzene, 1,3′-di (butoxy) benzene, 1,4-di (2-methoxy-2-ethyl) benzene, 1,4-di (2- Hydroxy-2-ethyl) benzene, 1,4-di (2-ethoxy-2-ethyl) benzene, 4,4′-bis (methoxymethyl) biphenyl, 2,4′-bis (methoxymethyl) biphenyl, 2, 2′-bis (methoxymethyl) biphenyl, 2,3′-bis (methoxymethyl) biphenyl, 3,3′-bis (methoxymethyl) biphenyl, 3,4′-bis (methoxymethyl) biphenyl, 4,4 ′ -Bis (ethoxymethyl) biphenyl, 2,4'-bis (ethoxymethyl) biphenyl, 4,4'-bis (isopropoxy) methylbiphenyl, 2,4'-bis (isopropoxy) Methylbiphenyl, bis (1-methoxy-1-ethyl) biphenyl, bis (1-methoxy-1-ethyl) biphenyl, bis (1-isopropoxy-1-ethyl) biphenyl, bis (2-hydroxy-2-propyl) Biphenyl, bis (2-methoxy-2-propyl) biphenyl, bis (2-isopropoxy-2-propyl) biphenyl and the like can be mentioned. Examples of the general formula (10) include p-divinylbenzene and m-divinyl. Examples thereof include, but are not limited to, benzene, bis (vinyl) biphenyl such as 4,4′-bis (vinyl) biphenyl, and the like.

  This reaction condition will be described in detail. The aromatic compound (a1) having 2 to 4 hydroxy groups, the alkoxy group-containing aromatic compound (a2), and the aromatic crosslinking agent (a3) are heated and stirred in the presence of a suitable polymerization catalyst. Thus, the target polyvalent hydroxy compound can be obtained. The polymerization catalyst is not particularly limited, but an acid catalyst is preferable. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Can be mentioned. The amount used is preferably in the range of 0.1 to 5% by weight with respect to the total weight of the charged raw materials.

  The reaction charge ratio of the aromatic compound (a1) having 2 to 4 hydroxy groups, the alkoxy group-containing aromatic compound (a2), and the aromatic crosslinking agent (a3) is not particularly limited. The molar ratio (a1) / (a2) of the aromatic compound (a1) having 4 hydroxy groups and the alkoxy group-containing aromatic compound (a2) is 30/70 to 98/2, and Ratio between the total number of moles of the aromatic compound (a1) having 2 to 4 hydroxy groups and the alkoxy group-containing aromatic compound (a2) and the number of moles of the aromatic crosslinking agent (a3) {(a1 ) + (A2)} / (a3) is preferably 51/49 to 97/3. By satisfying these conditions, it is possible to obtain a cured product that is further excellent in flame retardancy and moldability.

  In carrying out this reaction, 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 weight, preferably 30 to 250% by weight, based on the total weight of the charged raw materials. Moreover, as reaction temperature, it is 40-250 degreeC normally, and the range of 100-200 degreeC is more preferable. The reaction time is usually 1 to 10 hours.

  When the compound represented by the general formula (8) is used as the aromatic crosslinking agent (a3), the reaction becomes a condensation reaction system, and hydrogen halide gas such as hydrochloric acid is generated as the reaction proceeds. Since it occurs, it is preferable to quickly discharge out of the system and trap outside the system by alkali treatment or the like. Further, when the compound represented by the general formula (9) is used, it becomes a condensation system, and water, methanol and the like are generated as the reaction proceeds. It is preferable for speeding up the process. In addition, when the compound represented by the general formula (10) is used, it becomes an addition reaction system, so that no by-product treatment is particularly necessary.

  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 in accordance with 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 neutralization or washing with water, unreacted raw materials mainly containing an aromatic compound (a1) having 2 to 4 hydroxy groups and an alkoxy group-containing aromatic compound (a2) under reduced pressure heating, The organic solvent and 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 addition, as described above, the aromatic compound (a1) having 2 to 4 hydroxy groups, the alkoxy group-containing aromatic compound (a2), and the aromatic crosslinking agent (a3) are charged substantially simultaneously. The reaction may be carried out. Further, 2 to 30 mol of the aromatic crosslinking agent (a3) is reacted with 1 mol of the alkoxy group-containing aromatic compound (a2), and the alkoxy group-containing aromatic compound ( It is also possible to employ a method in which the aromatic compound (a1) having 2 to 4 hydroxy groups is charged and reacted after substantially completely reacting and consuming a2). According to the latter method, the structure of the polyvalent hydroxy compound can be converted into an alternating copolymer, and an alkoxy group can be more efficiently introduced into the molecular structure. The meaning of “substantially simultaneous” here means that all raw materials are charged until the reaction is accelerated by heating, and that the reaction is substantially complete means quantitatively. It does not mean that the alkoxy group-containing aromatic compound (a2) has disappeared, but means that a sufficient reaction time and reaction temperature have been applied using an excess aromatic crosslinking agent (a3). It is.

  In the epoxy resin composition of the present invention, the polyvalent hydroxy compound (A) obtained by the production method of the present invention acts as a curing agent for the epoxy resin (B) described later, and in this case, the polyvalent hydroxy compound of the present invention. The compound can be used alone or in combination with other curing agents as long as the effects of the present invention are not impaired. When used in combination, the proportion of the polyvalent hydroxy compound (A) of the present invention in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.

Other curing agents that can be used in combination are not particularly limited, and various curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds can be used. Examples of amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complexes, guanidine derivatives, and the like. Examples of amide compounds include dicyandiamide and linolenic acid. And polyamide resins synthesized from ethylenediamine. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyl Examples include tetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Examples of phenolic compounds include phenol novolac resins, cresol novolac resins, Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (commonly known as zylock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol Condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group) ), Polyphenol compounds such as aminotriazine-modified phenol resins (polyphenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.), and Examples of these modified products include, but are not limited to, these. These may be used alone or in combination of two or more.

  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, The use of a compound such as a polyhydroxy compound having a high hydroxyl equivalent weight or an aminotriazine-modified phenol resin containing a nitrogen atom results in a hard resin obtained. Flame retardancy of a product, from the viewpoint of formability is excellent.

  The epoxy resin (B) used in the epoxy resin composition of the present invention is not particularly limited, and various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, Biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac 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-compacted novolak 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. In particular, biphenyl type epoxy resin, naphthalene type epoxy resin, phenol aralkyl type epoxy resin, biphenyl novolac type epoxy resin and xanthene type epoxy resin described in JP-A No. 2003-201333 are excellent in flame retardancy, moldability and dielectric properties. Particularly preferred.

  The amount of the curing agent containing the epoxy resin (B) and the polyvalent hydroxy compound (A) in the epoxy resin composition of the present invention is not particularly limited, but the obtained cured product has good characteristics. Therefore, the amount of the active group in the curing agent containing the polyvalent hydroxy compound (A) is preferably 0.7 to 1.5 equivalents with respect to 1 equivalent of the total epoxy groups of the epoxy resin (B).

  Moreover, a hardening accelerator can also be suitably used together with the epoxy 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.

  The epoxy resin composition of the present invention is conventionally used for imparting flame retardancy of a cured product because the polyvalent hydroxy compound (A) itself used as a curing agent has an effect of imparting flame retardancy. Even if the flame retardant used is not added, the cured product has good flame retardancy, but the moldability in the sealing process and the reliability of the semiconductor device are reduced in order to exhibit higher flame retardancy. It is also possible to obtain a non-halogen flame retardant resin composition by blending the non-halogen flame retardant (C) which does not substantially contain a halogen atom within a range not to be allowed to occur.

  The flame retardant resin composition substantially not containing a halogen atom as used herein means a resin composition exhibiting sufficient flame retardancy without blending a halogen-based compound for the purpose of imparting flame retardancy. For example, halogen atoms due to a small amount of impurities of about 5000 ppm or less derived from epihalohydrin contained in an epoxy resin may be contained.

  The non-halogen flame retardant (C) is a compound that does not substantially contain a halogen atom such as chlorine or bromine and has a function as a flame retardant or a flame retardant aid. For example, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organometallic salt-based flame retardants, and the like are not limited in any way. Even if it is used alone, a plurality of flame retardants of the same type may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, both inorganic and organic compounds can be used as long as they are compounds containing phosphorus atoms. Examples of the inorganic compound include phosphoric acids such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, which may be surface-treated for the purpose of preventing hydrolysis and the like. Examples thereof include inorganic nitrogen-containing phosphorus compounds such as ammonium and phosphoric acid amide.

  Examples of the surface treatment method of red phosphorus include (i) coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof. A method of treating, (ii) a method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide and titanium hydroxide, and a thermosetting resin such as a phenol resin, (iii) magnesium hydroxide And a method of double coating with a thermosetting resin such as phenol resin on a coating of an inorganic compound such as aluminum hydroxide, zinc hydroxide or titanium hydroxide, and any of (i) to (iii) What was processed by the method of can also be used.

  Examples of the organic phosphorus compounds include phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, and organic nitrogen-containing phosphorus compounds.

  Specific examples of the phosphoric ester compound include triphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis (di-2,6-xylenol phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl). Phosphate), resorcinyl diphenyl phosphate, and the like.

  Specific examples of the phosphonic acid compound include phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, and phosphonic acid metal salts described in JP-A No. 2000-226499.

  Specific examples of the phosphinic acid compound include diphenylphosphinic acid, methylethylphosphinic acid, a compound described in JP-A-2001-55484, 9,10-dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phospha Examples thereof include cyclic organophosphorus compounds such as phenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  Specific examples of the phosphine oxide compound include triphenylphosphine oxide, tris (3-hydroxypropyl) phosphine oxide, diphenylphosphinyl hydroquinone, JP-A No. 2000-186186, JP-A No. 2002-080484, JP-A No. 2002. -097248 gazette etc. are mentioned.

  Specific examples of the phosphorane compound include compounds described in JP-A No. 2000-281871.

  Examples of organic nitrogen-containing phosphorus compounds include JP 2002-60720, JP 2001-354686, JP 2001-261792, JP 2001-335703, JP 2000-103939, and the like. And the phosphazene compounds described.

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

  Further, the method of using the phosphorus-based flame retardant is not particularly limited. For example, JP 2002-080566 A, JP 2002-053734 A, JP 2000-248156 A, and JP 9-9 A. No. 235449, etc., hydrotalcite used together, Japanese Patent Application Laid-Open No. 2001-329147, etc., magnesium hydroxide used together, Japanese Patent Application Laid-Open No. 2002-23989, Japanese Patent Application Laid-Open No. 2001-323134, etc. Compound combination, zirconium oxide combination described in JP-A No. 2002-069271, etc., black dye combination described in JP-A No. 2001-123047, etc., calcium carbonate described in JP-A No. 2000-281873, etc. Combined use, combined use of zeolite described in JP-A-2000-281873, etc., JP-A-200 Used in combination with zinc molybdate described in JP-A No. -248155, etc., used in combination with activated carbon described in JP-A No. 2000-212392, JP-A No. 2002-348440, JP-A No. 2002-265758, and JP-A No. 2002-180053. Conventional methods such as surface treatment methods described in JP-A No. 2001-329147, JP-A No. 2001-226564, JP-A No. 11-269345, and the like can be applied.

  The nitrogen-based flame retardant is not particularly limited as long as it is a compound containing a nitrogen atom. Examples thereof include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like. Triazine compounds, cyanuric acid compounds An isocyanuric acid compound is preferred.

  Specific examples of the triazine compound include, for example, melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and derivatives thereof. For example, (i) aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, melam sulfate, (ii) phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, melamine, benzoguanamine, acetoguanamine, formguanamine, etc. A co-condensate of melamines and formaldehyde, (iii) a mixture of the co-condensate of (ii) and a phenol resin such as a phenol formaldehyde condensate, (iv) the above (ii), (iii) Furthermore tung, such as those modified with isomerized linseed oil, and the like.

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

  Specific examples of the isocyanuric acid compound include tris (β-cyanoethyl) isocyanurate, diallyl monoglycidyl isocyanuric acid, monoallyl diglycidyl isocyanuric acid, and the like.

Further, the compound containing a nitrogen atom has a functional group such as —OH, —NH ₂ , —NCO, —COOH, —CHO, —SH, methylol, acrylate, methacrylate, silyl, glycidyl group or epoxy group. May be.

  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 epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 10 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix in the range of 5 parts by weight.

  Further, the method of using the nitrogen-based flame retardant is not particularly limited. For example, the metal hydroxide described in JP-A-2001-234036 and the like, JP-A-2002-003577, JP-A Conventional methods such as combined use of molybdenum compounds described in JP 2001-098144 A can be applied.

  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.

  Specific examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, polyether-modified silicone oil, and the like.

  Specific examples of the silicone rubber include methyl silicone rubber and methylphenyl silicone rubber.

  Specific examples of the silicone resin include methyl silicone, methyl phenyl silicone, and phenyl silicone.

The organic compound containing a silicon atom has a functional group such as —OH, —NH ₂ , —NCO, —COOH, —CHO, —SH, methylol, acrylate, methacrylate, silyl, glycidyl group or epoxy group. You may do it.

  The amount of the silicone flame retardant is appropriately selected according to the type of the silicone flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 20 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives.

  Further, the method of using the silicone-based flame retardant is not particularly limited. For example, a combination of molybdenum compounds described in JP 2001-011288 A, alumina described in JP 10-182941 A, and the like. A conventional method such as a combination of these can be applied.

  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, for example, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide, JP 2002-212391 A, and JP 2001. Examples thereof include composite metal hydroxides described in JP-A No. 335681 and JP-A No. 2001-32050.

  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 epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, cured It is preferable to mix in an amount of 0.05 to 20 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives, and particularly 0.5 to 20 parts by weight. It is preferable to mix in the range of 15 parts by weight.

  Further, the method of using the inorganic flame retardant is not particularly limited. For example, the method for controlling the specific surface area described in JP-A-2001-226564, JP-A-2000-19595, JP-A-2000. 191886, JP-A-2000-109647, JP-A-2000-038776, etc., methods for controlling the shape, particle size, and particle size distribution, JP-A-2001-32050, JP-A-2000-095956 JP, 10-279813, JP 10-251486, a method for performing surface treatment, JP 2002-030200, JP 2001-279063, etc. Combined use, combined use of zinc borate described in JP 2001-049084 A, etc., JP 2000-195994 A A combination of inorganic powders described in JP-A-2000-156437, a butadiene rubber described in JP-A-2000-156437, a high acid value polyethylene wax described in JP-A-2000-053875 and a long-chain alkyl phosphate ester compound Conventional methods such as combined use can be applied.

  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.

  Specific examples of the acetylacetonate metal complex include compounds described in JP-A No. 2002-265760.

  Specific examples of the organometallic carbonyl compound include compounds described in JP-A No. 2002-371169.

  Specific examples of the organic cobalt salt compound include, for example, a cobalt naphthenic acid complex, a cobalt ethylenediamine complex, a cobalt acetoacetonate complex, a cobalt piperidine complex, a cobalt cyclohexanediamine complex, a cobalt tetraazacyclotetradodecane complex, and a cobalt ethylenediaminetetraacetic acid complex. , Cobalt tetraethylene glycol complex, cobalt aminoethanol complex, cobalt cyclohexadiamine complex, cobalt glycine complex, cobalt triglycine complex, cobalt naphthidirine complex, cobalt phenanthroline complex, cobalt pentanediamine complex, cobalt pyridine complex, cobalt salicylic acid complex, cobalt Salicylaldehyde complex, cobalt salicylideneamine complex, cobalt complex porphyrin, cobalt thiourea complex And the like can be given.

  Specific examples of the organic sulfonic acid metal salt include potassium diphenylsulfone-3-sulfonate.

  Specific examples of the compound in which the metal atom and the aromatic compound or heterocyclic compound are ion-bonded or coordinate-bonded include compounds described in JP-A-2002-226678.

  The amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of the organometallic salt-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.005 to 10 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the epoxy resin, curing agent, non-halogen flame retardant and other fillers and additives.

  An inorganic filler can be blended in the epoxy resin composition of the present invention as necessary. Examples of the inorganic filler 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 weight or more with respect to the total amount of the epoxy 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 epoxy resin composition of this invention as needed.

  The epoxy resin composition of the present invention is obtained by uniformly mixing each component, and 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 of the epoxy resin composition of the present invention include semiconductor sealing materials, resin compositions used for laminates and electronic circuit boards, resin casting materials, adhesives, interlayer insulation materials for build-up substrates, insulation paints Among these, it can be suitably used for a semiconductor sealing material.

  In order to produce an epoxy resin composition prepared for a semiconductor encapsulant, an epoxy resin, a curing agent (including a polyvalent hydroxy compound), a compounding agent such as a filler, and the like are used as necessary. -A melt-mixed epoxy resin composition may be obtained by sufficiently mixing with a da, roll or the like until uniform. At that time, silica is usually used as the filler, and the filling rate is preferably in the range of 30 to 95% by weight per 100 parts by weight of the epoxy resin composition. In order to improve moisture resistance and solder crack resistance and to reduce the linear expansion coefficient, it is particularly preferably 70 parts by weight or more, and in order to significantly increase these effects, 80 parts by weight or more further enhances the effect. be able to. 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 epoxy resin composition of the present invention into a printed circuit board composition, for example, a resin composition for a prepreg can be used. Although it can be used without a solvent depending on the viscosity of the epoxy resin composition, it is preferable to obtain a resin composition for prepreg 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 weight 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 weight. When producing a copper-clad laminate using the epoxy resin composition, the prepreg obtained as described above is laminated as described in, for example, JP-A-7-41543, and copper is appropriately added. A copper-clad laminate can be obtained by stacking the foils and thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

  When the epoxy resin composition of the present invention is used as a resist ink, for example, according to the method described in JP-A No. 5-186567, a resist ink composition is prepared and then printed on a printed circuit board by a screen printing method. The method of making it a resist ink hardened | cured material after apply | coating to is mentioned.

  When using the epoxy resin composition of the present invention as a conductive paste, for example, fine conductive particles described in JP-A-3-46707 are dispersed in the resin composition, and the composition for anisotropic conductive film is used. And a paste resin composition for circuit connection which is liquid at room temperature as disclosed in JP-A-62-240183, JP-A-62-276215, JP-A-62-176139, etc. And an anisotropic conductive adhesive.

  Although it does not specifically limit as a method of obtaining the interlayer insulation material for buildup boards from the epoxy resin composition of the present invention, for example, Japanese Patent Publication No. 4-6116, Unexamined-Japanese-Patent No. 7-304931, Unexamined-Japanese-Patent No. 8-64960, Various methods described in JP-A-9-71762, JP-A-9-298369 and the like can be employed. More specifically, the curable resin composition appropriately blended with rubber, filler, and the like is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, or the like, and then 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 substrate 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.

  The method for obtaining the cured product of the present invention may be based on a general method for curing an epoxy resin composition. For example, the heating temperature condition may be appropriately selected depending on the type and application of the curing agent to be combined, What is necessary is just to heat the composition obtained by the said method in the temperature range of room temperature-about 250 degreeC. As the molding method and the like, a general method of the epoxy resin composition is used, and a condition specific to the epoxy resin composition of the present invention is not particularly required.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on weight unless otherwise specified. The melt viscosity at 150 ° C., GPC measurement, NMR, and MS spectrum were measured under the following conditions.
1) Melt viscosity at 150 ° C .: in accordance with ASTM D4287 2) Softening point measurement method: JIS K7234
3) GPC:
・ Device: HLC-8220 GPC manufactured by Tosoh Corporation, Column: TSK-GEL G2000HXL + G2000HXL + G3000HXL + G4000HXL manufactured by Tosoh Corporation
・ Solvent: Tetrahydrofuran ・ Flow rate: 1 ml / min
・ Detector: RI
4) NMR: NMR GSX270 manufactured by JEOL Ltd.
5) MS: Double Density Mass Spectrometer AX505H (FD505H) manufactured by JEOL Ltd.

Example 1 [Synthesis of polyvalent hydroxy compound (A-1)]
In a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 440.4 g (4.00 mol) of resorcinol, 316.4 g (2.00 mol) of 2-methoxynaphthalene and paraxy 166.2 g (1.00 mol) of rangemethoxide was added, 8.6 g (0.045 mol) of paratoluenesulfonic acid was added, and the temperature was raised to 150 ° C., and methanol produced as a by-product was captured by a fractionation tube. The reaction was performed for 2 hours while collecting. After completion of the reaction, 1500 g of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. Next, after washing with water until the washing water shows neutrality, unreacted phenol, 2-methoxynaphthalene, and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure, and the following structural formula

で表される構造単位を有する多価ヒドロキシ化合物（Ａ−１）を得た。回収した未反応のレゾルシノール及び２−メトキシナフタレンの重量測定の結果、及び得られた多価ヒドロキシ化合物の水酸基の測定結果から、化合物中における前記一般式（３）で表される構造単位と前記一般式（４）で表される構造単位とのモル比率は、前者／後者＝７６／２４であった。これの軟化点は６３℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は０．９ｄＰａ・ｓ、水酸基当量は１１５ｇ／ｅｑ．であった。これのＭＳスペクトルを図１に示す。メトキシ基の残存は、ＮＭＲにおける５５ｐｐｍに観測されるメトキシ基のシグナル、及び水酸基当量から確認し、得られた化合物中のメトキシ基は分解していないことを確認した。

The polyvalent hydroxy compound (A-1) which has a structural unit represented by this was obtained. From the results of the weight measurement of the recovered unreacted resorcinol and 2-methoxynaphthalene and the measurement results of the hydroxyl group of the obtained polyvalent hydroxy compound, the structural unit represented by the general formula (3) in the compound and the general The molar ratio with the structural unit represented by the formula (4) was the former / the latter = 76/24. The softening point thereof is 63 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 0.9 dPa · s, and the hydroxyl group equivalent is 115 g / eq. Met. The MS spectrum of this is shown in FIG. The remaining methoxy group was confirmed from the signal of the methoxy group observed at 55 ppm in NMR and the hydroxyl group equivalent, and it was confirmed that the methoxy group in the obtained compound was not decomposed.

Example 2 [Synthesis of polyvalent hydroxy compound (A-2)]
In Example 1, except that resorcinol was changed to 251.2 g (2.67 mol) and 2-methoxynaphthalene was changed to 294.0 g (1.33 mol), the following structural formula was obtained.

で表される構造単位を有する多価ヒドロキシ化合物（Ａ−２）を得た。回収した未反応のレゾルシノール及び２−メトキシナフタレンの重量測定の結果、及び得られた多価ヒドロキシ化合物の水酸基の測定結果から、化合物中における一般式（３）で表される構造単位と前記一般式（４）で表される構造単位とのモル比率は、前者／後者＝６７／３３であった。これの軟化点は９０℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は５．０ｄＰａ・ｓ、水酸基当量は１２０ｇ／ｅｑ．であった。

The polyvalent hydroxy compound (A-2) which has a structural unit represented by this was obtained. From the result of the weight measurement of the recovered unreacted resorcinol and 2-methoxynaphthalene and the result of the measurement of the hydroxyl group of the obtained polyvalent hydroxy compound, the structural unit represented by the general formula (3) in the compound and the above general formula The molar ratio with the structural unit represented by (4) was the former / the latter = 67/33. The softening point is 90 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 5.0 dPa · s, and the hydroxyl equivalent is 120 g / eq. Met.

Synthesis example 1
In accordance with Example 1 of JP-A-8-301980, the following structural formula

で表される構造単位を有する多価ヒドロキシ化合物（Ａ’−１）を得た。これの軟化点は８４℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法，測定温度：１５０℃）は４．４ｄＰａ・ｓ、水酸基当量は２５２ｇ／ｅｑ．であった。

The polyvalent hydroxy compound (A'-1) which has a structural unit represented by this was obtained. The softening point thereof is 84 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 4.4 dPa · s, and the hydroxyl group equivalent is 252 g / eq. Met.

Synthesis example 2
In accordance with Example 4 of JP-A-8-301980, the following structural formula

で表される構造単位を有する多価ヒドロキシ化合物（Ａ’−２）を得た。これの軟化点は１００℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１９ｄＰａ・ｓ、水酸基当量は２４９ｇ／ｅｑ．であった。

The polyvalent hydroxy compound (A'-2) which has a structural unit represented by this was obtained. The softening point is 100 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 19 dPa · s, and the hydroxyl group equivalent is 249 g / eq. Met.

Synthesis example 3
In accordance with Example 1 of JP 2004-010700 A, the following structural formula

で表される構造単位を有する多価ヒドロキシ化合物（Ａ’−３）を得た。これの軟化点は７７℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法，測定温度：１５０℃）は０．８ｄＰａ・ｓ、水酸基当量は１６０ｇ／ｅｑ．であった。

The polyvalent hydroxy compound (A'-3) which has a structural unit represented by this was obtained. The softening point is 77 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 0.8 dPa · s, and the hydroxyl equivalent is 160 g / eq. Met.

Synthesis example 4
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas, while Mitex Chemical Co., Ltd. Mirex XLC-4L168 g, epichlorohydrin 463 g (5.0 mol), n-butanol 139 g, tetraethylbenzylammonium 2 g of chloride was charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 590 g of methyl isobutyl ketone and 177 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water 150 g was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain the following structural formula.

で表される構造単位を有するエポキシ樹脂（Ｂ−１）を得た。該エポキシ樹脂のエポキシ当量は２４１ｇ／ｅｑであった。

The epoxy resin (B-1) which has a structural unit represented by this was obtained. The epoxy equivalent of the epoxy resin was 241 g / eq.

Synthesis example 5
In accordance with Examples 3 and 4 in JP-A-2003-201333, the following structural formula

で表されるエポキシ樹脂（Ｂ−２）を得た。このもののエポキシ当量は２６２ｇ／ｅｑであった。

The epoxy resin (B-2) represented by these was obtained. The epoxy equivalent of this was 262 g / eq.

Examples 3 to 10 and Comparative Examples 1 to 3
As the epoxy resin, the above B-1 to B-2, and YX-4000H (tetramethylbiphenol type epoxy resin, epoxy equivalent: 188 g / eq) manufactured by Japan Epoxy Resin Co., Ltd., NC-3000 manufactured by Nippon Kayaku Co., Ltd. (biphenylaralkyl) Type epoxy resin, epoxy equivalent: 274 g / eq), EXA-4700 (naphthalene type epoxy resin, epoxy equivalent: 164 g / eq) manufactured by Dainippon Ink & Chemicals, Inc., A-1 to A-2 as polyvalent hydroxy compounds, A′-1 to A′-3 are used as comparative curing agents, triphenylphosphine (TPP) is used as a curing accelerator, condensed phosphate ester (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) is used as a flame retardant, hydroxylation Magnesium (Echo Mug Z-10, manufactured by Air Water Co., Ltd.) (S-COL manufactured by Micron Co., Ltd.), γ-glycidoxytriethoxyxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, Carnauba wax (PEARL WAX No. 1 manufactured by Celerica Noda Co., Ltd.) -P), the composition shown in Tables 1 and 2 using carbon black, and melt-kneading for 5 minutes at a temperature of 85 ° C using two rolls to obtain an epoxy resin composition. Regarding the physical properties of the cured product, samples for evaluation were prepared by the following method using the above composition, flame retardancy and moldability were measured by the following methods, and the results are shown in Tables 1 and 2.

Flame Retardancy Create a sample for evaluation with a width of 12.7mm, a length of 127mm, and a thickness of 1.6mm by molding for 90 seconds at a temperature of 175 ° C using a transfer molding machine and then post-curing at a temperature of 175 ° C for 5 hours. did. 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.

Measurement of moldability (hardness during molding) A composition prepared using two rolls was filled in a mold of φ90 mm, thickness 2.0 mm for 90 seconds at a temperature of 175 ° C. using a transfer molding machine, and molded for 90 seconds. After opening the mold, the hardness of the cured product was measured with a Shore hardness D meter.

Footnotes in Tables 1 and 2:
* 1: Maximum combustion time (seconds) in one flame contact
* 2: Total burning time of 5 test pieces (seconds)
* 3: Although the flame retardancy required for V-1 (ΣF ≦ 250 seconds and F _max ≦ 30 seconds) is not satisfied, it does not reach combustion (flame clamp arrival) and extinguishes.

2 is a mass spectrum of the polyvalent hydroxy compound obtained in Example 1. FIG.

Claims (27)

The following general formula (1) per molecule

(Wherein, X ₁ is an aromatic ring which may have a substituent, Ar ₁ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ¹ Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, and n is 2 to 4.)
A structural unit represented by the following general formula (2)

(Wherein, X ₂ is an aromatic ring which may have a substituent, Ar ₂ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ² Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and m is 1 or 2.)
An epoxy resin composition comprising a polyvalent hydroxy compound (A) having a structural unit represented by formula (A) and an epoxy resin (B). A polyvalent hydroxy compound (A) reacts an aromatic compound (a1) having 2 to 4 hydroxy groups, an alkoxy group-containing aromatic compound (a2), and an aromatic crosslinking agent (a3). The epoxy resin composition according to claim 1, which is a polyvalent hydroxy compound obtained. The following general formula (3) in the general formula (1) in the polyvalent hydroxy compound (A)

(Wherein X ₁ and n are the same as described above.)
And the following general formula (4) in the general formula (2):

(Wherein X ₂ , R ³ and m are the same as above).
2. The epoxy resin composition according to claim 1, wherein the molar ratio with the structural unit represented by the formula is in the range of the former / the latter = 30/70 to 98/2. The hydroxyl group equivalent of the polyvalent hydroxy compound (A) is 100 to 270 g / eq. The epoxy resin composition according to claim 3, which is in the range of The epoxy resin composition according to claim 3, wherein the melt viscosity at 150 ° C. of the polyvalent hydroxy compound (A) measured with an ICI viscometer is in the range of 0.3 to 5.0 dPa · s. The epoxy resin composition according to claim 1, wherein X ₁ in the general formula (1) is a benzene ring or a naphthalene ring which may have a substituent. The epoxy resin composition according to claim 1, wherein R ³ in the general formula (2) is a methyl group, m is 1 or 2, and X ₂ is a benzene ring or a naphthalene ring which may have a substituent. object. The epoxy resin (B) is at least one selected from the group consisting of biphenyl type epoxy resins, naphthalene type epoxy resins, phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins and xanthene type epoxy resins. The epoxy resin composition according to claim 1. The epoxy resin composition according to claim 8, further comprising a non-halogen flame retardant (C). The non-halogen flame retardant (C) is one or more flame retardants selected from the group consisting of phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants and organometallic salt flame retardants. Item 10. The epoxy resin composition according to Item 9. The epoxy resin composition according to claim 9 or 10, which is used for a semiconductor encapsulant. The epoxy resin composition according to claim 9 or 10, which is for a printed circuit board. The epoxy resin composition according to claim 9 or 10, which is used for resist ink. The epoxy resin composition according to claim 9 or 10, which is used for a conductive paste. The epoxy resin composition according to claim 9 or 10, which is used for an interlayer insulating material. A cured product obtained by curing the epoxy resin composition according to claim 1. The cured product according to claim 16, which is a semiconductor device. The cured product according to claim 16, which is a printed circuit board device. The following general formula (1) per molecule

(Wherein, X ₁ is an aromatic ring which may have a substituent, Ar ₁ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ¹ Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, and n is 2 to 4.)
A structural unit represented by the following general formula (2)

(Wherein, X ₂ is an aromatic ring which may have a substituent, Ar ₂ is a benzene skeleton which may have a hydrocarbon group as a substituent, a biphenyl skeleton, a naphthalene skeleton, R ² Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and m is 1 or 2.)
The hydroxyl group equivalent is 100-270 g / eq. And a melt viscosity at 150 ° C. measured with an ICI viscometer is in the range of 0.3 to 5.0 dPa · s. Polyhydroxy obtain an aromatic compound (a1) and an alkoxy group-containing aromatic compound (a2) and an aromatic crosslinking agent (a3) and is reacted polyhydroxy compound with 2-4 hydroxy groups A method for producing a compound comprising:
The molar ratio (a1) / (a2) of the aromatic compound (a1) having 2 to 4 hydroxy groups and the alkoxy group-containing aromatic compound (a2) is 30/70 to 98/2, and The ratio between the total number of moles of the aromatic compound (a1) having 2 to 4 hydroxy groups and the alkoxy group-containing aromatic compound (a2) and the number of moles of the aromatic crosslinking agent (a3) {( a1) + (a2)} / (a3) is 51/49 to 97/3 , A method for producing a polyvalent hydroxy compound, The aromatic compound (a1) having 2 to 4 hydroxy groups is a compound represented by the following general formula (5), and the alkoxy group-containing aromatic compound (a2) is represented by the following general formula (6). 21. The production method according to claim 20, wherein the compound has a structure represented by the following general formula (7) after the aromatic crosslinking agent (a3) undergoes a crosslinking reaction.

(Wherein X ₁ and X ₂ are aromatic rings which may have a substituent, Ar is a benzene skeleton, biphenyl skeleton or naphthalene skeleton which may have a hydrocarbon as a substituent; Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, n is 2 to 4, and m is 1 or 2 .) 21. An acid catalyst is used when the aromatic compound (a1) having 2 to 4 hydroxy groups, the alkoxy group-containing aromatic compound (a2), and the aromatic crosslinking agent (a3) are reacted. The manufacturing method as described. The production method according to claim 20, wherein the aromatic compound (a1) having 2 to 4 hydroxy groups is a phenol and / or a naphthol which may have a substituent. The alkoxy group-containing aromatic compound (a2) is one or more compounds selected from the group consisting of optionally substituted methoxybenzenes, dimethoxybenzenes, methoxynaphthalenes, and dimethoxynaphthalenes. Item 21. The production method according to Item 20. The aromatic crosslinking agent (a3) is represented by the following general formulas (8), (9) and (10)

(In the formula, Ar is a benzene skeleton, biphenyl skeleton or naphthalene skeleton which may have a hydrocarbon group as a substituent, R ⁴ is a halogen atom, and R ⁵ is a hydrogen atom or a C 1-6 carbon atom. It is a hydrocarbon group.)
The production method according to claim 20, which is one or more compounds selected from the group consisting of: The aromatic compound (a1) having 2 to 4 hydroxy groups, the alkoxy group-containing aromatic compound (a2), and the aromatic crosslinking agent (a3) are charged substantially simultaneously to carry out the reaction. 26. The production method according to any one of 25 . An aromatic compound (a1) having 2 to 4 hydroxy groups after reacting 2 to 30 mol of the aromatic crosslinking agent (a3) with respect to 1 mol of the alkoxy group-containing aromatic compound (a2). The production method according to any one of claims 20 to 25 , wherein:

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