JP5354309B2 - Epoxy resin composition, cured product thereof, semiconductor sealing material, novel polyvalent hydroxy compound, and production method thereof - Google Patents

Abstract

An epoxy resin composition that can be hardened rapidly, excelling in the flame retardance of a hardening product thereof obtainable even without the use of any halogen flame retardant, and that further excels in heat resistance. There are provided a hardening product thereof; a semiconductor sealing material comprising the epoxy resin composition; a novel epoxy resin and novel hydroxyl compound that can be used in the epoxy resin composition; and a process for producing the same.

Description

The present invention is excellent in curability, the cured product obtained has good flame retardancy and heat resistance, and can be suitably used for semiconductor encapsulants, printed circuit boards, paints, casting applications, etc. , A cured product thereof, a novel polyvalent hydroxy compound contained in the epoxy resin composition as a curing agent , and a method for producing the same.

  Conventionally, epoxy resin compositions have been widely used in various industrial fields such as paints, adhesive properties, and electrical and electronic properties because they are excellent in adhesion, corrosion resistance, electrical properties, and the like of the cured products obtained. Among these, in the field of electronic materials such as semiconductors and printed wiring boards, they are used as sealing materials and substrate materials, and demands for higher performance are increasing with technological innovation in these fields. .

  For example, semiconductor packages have been rapidly reduced in size and thickness, and BGA type semiconductor devices with excellent high-density mounting have been developed, and have become the mainstream of IC and LSI chip packages. In this package, warpage after molding has become a major problem, and as a solution to this problem, a technique for increasing the glass transition temperature of the package material has been adopted. Moreover, in order to shorten the molding cycle, the resin composition is required to have excellent curability.

  In addition, when the epoxy resin composition is used as a semiconductor sealing material, a halogen-based flame retardant such as bromine is blended together with an antimony compound 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.

  As a semiconductor package material that can cope with such a flame-retardant problem, for example, a technique using a thioether group-modified phenol resin is known (for example, see Patent Document 1). However, the cured product obtained using the resin reached the V-0 class of UL-94, which is a flame retardance index, but was inferior in curability and did not reach a satisfactory level.

  Moreover, what thioether-ized the aromatic nucleus of the phenol novolak is known as a thioether group modification phenol resin for semiconductor sealing materials which has a polymer structure similar to this (for example, refer patent document 2). However, although the effects of improving the moisture resistance and adhesion of the cured product obtained using the resin are recognized, the flame retardancy of the cured product and the rapid curability of the resin composition are not satisfactory.

  Furthermore, as a method for obtaining flame retardancy with a non-halogen epoxy resin composition, for example, it has been proposed to increase the aromaticity in the epoxy resin used (see, for example, Patent Document 3). However, the cured product obtained by using the epoxy resin composition described in Patent Document 1 reaches the V-0 class of UL-94, which is a flame retardant index, but is inferior in curability, and is also obtained. This glass transition temperature is low and cannot be applied to the aforementioned BGA, which requires a high glass transition temperature.

  An aromatic ring-modified phenol aralkyl resin is a resin material having excellent heat resistance (see, for example, Patent Document 4). However, the epoxy resin cured product using this aromatic ring-modified phenol aralkyl resin is also inferior in curability and sufficiently satisfactory in flame retardancy, although the effect of improving moisture resistance, heat resistance and impact resistance is recognized. It was something that was not reached.

  That is, a cured product capable of exhibiting sufficient flame retardancy can be obtained using a non-halogen epoxy resin composition, and the resin composition has all of the properties of quick curing and heat resistance of the cured product in a well-balanced manner. The current situation is that the composition has not yet been presented.

JP 2004-339277 A JP 2004-244526 A JP-A-11-140277 (page 3-4) JP-A-8-301980 (page 3-5)

The problem to be solved by the present invention has been made in view of the above-described circumstances, and is fast-curing, excellent in flame retardancy of a cured product obtained without using a halogen-based flame retardant, and heat resistant. It is in providing the epoxy resin composition which has favorable property, its hardened | cured material, the novel polyvalent hydroxy compound which this epoxy resin composition contains as a hardening | curing agent , and its manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyvalent hydroxy compound having the following specific structure solves the above problems, and further, hydroxy group-containing aromatic compounds and thioether groups. The present invention was completed by finding that a polyhydric hydroxy compound in which a thioether group-containing aromatic compound was efficiently introduced into the molecule could be obtained by carrying out a reaction using a compound containing an aromatic compound and a carbonyl group-containing compound. It came to do.

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

〔式中、Ａｒ^１は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ｘ^１はメチレン基、炭素原子数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上に更にアルキル基が芳香核置換したメチレン基であり、Ｇはグリシジル基又は置換基含有グリシジル基であり、ｍは１又は２である。〕
で表わされる構造単位と、

[In the formula, Ar ¹ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; X ¹ is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, a methylene group substituted with a biphenyl group, 9 A methylene group substituted with a fluorenyl group, or a methylene group in which an alkyl group is further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group, G is a glycidyl group or a substituent-containing glycidyl group, m is 1 or 2. ]
A structural unit represented by

The following general formula ( 2 )

〔式中、Ａｒ^２は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ｒ^１は炭素原子数１〜４のアルキル基又はフェニル基であり、Ｘ^２はメチレン基、炭素原子数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上に更にアルキル基が芳香核置換したメチレン基であり、ｎ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（Ｂ１）とエポキシ樹脂（Ａ）とを含有することを特徴とするエポキシ樹脂組成物（以下、これを「エポキシ樹脂組成物（Ｉ）」と略記する）に関する。

[In the formula, Ar ² is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X ² is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, or naphthyl. A methylene group substituted with a group, a methylene group substituted with a biphenyl group, a methylene group substituted with a 9-fluorenyl group, or an alkyl group further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group A methylene group and n is 1 or 2; ]
And an epoxy resin composition (hereinafter referred to as “epoxy resin composition ( I )”), which contains a polyvalent hydroxy compound (B 1 ) having a structural unit represented by formula ( I ) and an epoxy resin (A). Abbreviated).

The present invention further provides the following general formula ( 3 ) in one molecule.

〔式中、Ａｒ^１は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ａｒ^３はベンゼン骨格、ビフェニル骨格、ナフタレン骨格、またはこれらに炭化水素基が置換された芳香族骨格であり、Ｙ^１は同一でも異なっていてもよい水素原子又は炭素原子数１〜６の炭化水素基であり、ｍは１又は２である。〕
で表わされる構造単位と、

[In the formula, Ar ¹ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; Ar ³ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton in which a hydrocarbon group is substituted, and Y ¹ is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms And m is 1 or 2. ]
A structural unit represented by

The following general formula ( 4 )

〔式中、Ａｒ^２は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ａｒ^４はベンゼン骨格、ビフェニル骨格、ナフタレン骨格、またはこれらに炭化水素基が置換された芳香族骨格であり、Ｙ^２は同一でも異なっていてもよい水素原子又は炭素原子数１〜６の炭化水素基であり、Ｒ^１は炭素原子数１〜４のアルキル基又はフェニル基であり、ｎ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（Ｂ２）とエポキシ樹脂（Ａ）とを含有することを特徴とするエポキシ樹脂組成物（以下、これを「エポキシ樹脂組成物（ＩＩ）」と略記する）に関する。

[In the formula, Ar ² is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, Ar ⁴ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton having a hydrocarbon group substituted thereon, and Y ² is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is 1 or 2. ]
An epoxy resin composition (hereinafter, abbreviated as “epoxy resin composition (II)”), which contains a polyvalent hydroxy compound (B2) having a structural unit represented by formula (B2) and an epoxy resin (A). ).

The present invention relates to a semiconductor sealing material characterized by comprising the epoxy resin composition further be contained inorganic filler (C).

  The present invention further relates to an epoxy resin cured product obtained by curing the above-described epoxy resin composition.

The present invention further includes the following general formula ( 1 ) in one molecule.

〔式中、Ａｒ_１は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ｘ_１はメチレン基、炭素原子数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上に更にアルキル基が芳香核置換したメチレン基であり、ｍは１又は２である。〕
で表わされる構造単位と、

[In the formula, Ar ₁ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; X ₁ is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, a methylene group substituted with a biphenyl group, 9 -A methylene group substituted with a fluorenyl group, or a methylene group in which an alkyl group is further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group, and m is 1 or 2. ]
A structural unit represented by

The following general formula ( 2 )

〔式中、Ａｒ_２は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ｒ^１は炭素原子数１〜４のアルキル基又はフェニル基であり、Ｘ_２はメチレン基、炭素原子数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上に更にアルキル基が芳香核置換したメチレン基であり、ｎ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１００〜５００ｇ／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０．２〜５．０ｄＰａ・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（Ｂ１）に関する。

[In the formula, Ar ₂ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X ₂ is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, or naphthyl. A methylene group substituted with a group, a methylene group substituted with a biphenyl group, a methylene group substituted with a 9-fluorenyl group, or an alkyl group further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group A methylene group and n is 1 or 2; ]
The hydroxyl group equivalent is 100-500 g / eq. Further, the present invention relates to a novel polyvalent hydroxy compound (B 1 ) characterized in that the melt viscosity at 150 ° C. measured with an ICI viscometer is in the range of 0.2 to 5.0 dPa · s.

In the present invention, the hydroxy group-containing aromatic compound (a1), the thioether group-containing aromatic compound (a2), and the carbonyl group-containing compound (a3) are further reacted in the presence of an acid catalyst. The present invention relates to a method for producing a hydroxy compound (B 1 ).

The present invention further provides the following general formula ( 3 ) in one molecule.

〔式中、Ａｒ^１は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ａｒ^３はベンゼン骨格、ビフェニル骨格、ナフタレン骨格、またはこれらに炭化水素基が置換された芳香族骨格であり、Ｙ^１は同一でも異なっていてもよい水素原子又は炭素原子数１〜６の炭化水素基であり、ｍは１又は２である。〕
で表わされる構造単位と、

[In the formula, Ar ¹ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; Ar ³ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton in which a hydrocarbon group is substituted, and Y ¹ is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms And m is 1 or 2. ]
A structural unit represented by

The following general formula ( 4 )

〔式中、Ａｒ^２は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ａｒ^４はベンゼン骨格、ビフェニル骨格、ナフタレン骨格、またはこれらに炭化水素基が置換された芳香族骨格であり、Ｙ^２は同一でも異なっていてもよい水素原子又は炭素原子数１〜６の炭化水素基であり、Ｒ^１は炭素原子数１〜４のアルキル基又はフェニル基であり、ｎ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１５０〜５００ｇ／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０．２〜５．０ｄＰａ・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（Ｂ２）に関する。

[In the formula, Ar ² is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, Ar ⁴ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton having a hydrocarbon group substituted thereon, and Y ² is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is 1 or 2. ]
The hydroxyl group equivalent is 150-500 g / eq. In addition, the present invention relates to a novel polyvalent hydroxy compound (B2) characterized in that the melt viscosity at 150 ° C. measured with an ICI viscometer is in the range of 0.2 to 5.0 dPa · s.

In the present invention, the hydroxy group-containing aromatic compound (a1), the thioether group-containing aromatic compound (a2), and the aromatic crosslinking agent (a3) are further reacted in the presence of an acid catalyst. The present invention relates to a method for producing a monovalent hydroxy compound (B 2 ).

When the polyvalent hydroxy compound (B 1 ) or (B2) of the present invention is used as a curing agent for an epoxy resin, as can be seen from this example, compared with a conventional curing agent, the flame retardancy of a cured product, It can have both curability and high glass transition temperature of the cured product. Therefore, by using the polyvalent hydroxy compound (B), it is possible to obtain an epoxy resin material that is safe in an environment where high flame retardancy can be expressed without using a halogen-based flame retardant. Moreover, the high glass transition temperature of the hardened | cured material can suppress the curvature after shaping | molding in BGA. Furthermore, due to its excellent curability, the molding cycle can be shortened. In addition, the polyvalent hydroxy compounds (B 1 ) and (B2) can be easily and efficiently manufactured by the manufacturing method of the present invention, and a molecular design according to the target level of performance described above becomes possible. In addition to the above applications, it can also be suitably used for photosensitive material applications such as semiconductor photoresists and color developer materials.

  Hereinafter, the present invention will be described in detail.

The polyvalent hydroxy compound (B 1 ) used in the epoxy resin composition ( I ) of the present invention has the following general formula ( 1 ) in one molecule.

〔式中、Ａｒ^１は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ｘ^１はメチレン基、炭素原子数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上に更にアルキル基が芳香核置換したメチレン基であり、ｍは１又は２である。〕
で表わされる構造単位と、

[In the formula, Ar ¹ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; X ¹ is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, a methylene group substituted with a biphenyl group, 9 -A methylene group substituted with a fluorenyl group, or a methylene group in which an alkyl group is further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group, and m is 1 or 2. ]
A structural unit represented by

The following general formula ( 2 )

〔式中、Ａｒ^２は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ｒ^１は炭素原子数１〜４のアルキル基又はフェニル基であり、Ｘ^２はメチレン基、炭素原子数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上に更にアルキル基が芳香核置換したメチレン基であり、ｎ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。

[In the formula, Ar ² is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X ² is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, or naphthyl. A methylene group substituted with a group, a methylene group substituted with a biphenyl group, a methylene group substituted with a 9-fluorenyl group, or an alkyl group further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group A methylene group and n is 1 or 2; ]
It has a structural unit represented by these.

As Ar ¹ in the general formula ( 1 ), a benzene ring, a naphthalene ring, or carbon is preferable because it is easy to obtain industrial raw materials and is excellent in flame retardancy and curability of the obtained cured product. It is preferably a benzene ring or a naphthalene ring substituted with a C 1-3 alkyl group, aryl group, aralkyl group or C 1-3 alkoxy group. In the general formula (2), R ¹ is a methyl group, an ethyl group or a phenyl group, m is 1, and Ar ₂ may have a substituent, a benzene ring or a naphthalene ring, or a carbon atom It is preferable from the point which is excellent in the flame retardance of the hardened | cured material obtained that it is an aromatic hydrocarbon group substituted by the C1-C10 alkyl group, aryl group, aralkyl group, or C1-C10 alkoxy group.

Further, the following general formula in the formula (1) (1 ')

（式中、Ａｒ^１、ｍは前記一般式（１）と同義である。）
で表される構造単位と、

(In formula, Ar < ¹ >, m is synonymous with the said general formula ( 1 ).)
A structural unit represented by

The following general formula in the formula (2) (2 ')

（式中、Ａｒ^２、Ｒ^１、ｎは前記一般式（２）と同義である。）
で表される構造単位とのモル比率が前者／後者＝３０／７０〜９９／１の範囲であることが好ましく、特に５０／５０〜９９／１であることが好ましく、特に７０／３０〜９９／１であることが最も好ましい。

(In the formula, Ar ² , R ¹ and n have the same meanings as in the general formula ( 2 ).)
Is preferably in the range of the former / the latter = 30/70 to 99/1, particularly preferably 50/50 to 99/1, particularly 70/30 to 99. / 1 is most preferred.

As the hydroxyl group equivalent of polyvalent hydroxy compounds (B 1), from the viewpoint of excellent curability flame retardancy, 100 to 500 g / eq. In the range of 100 to 400 g / eq, 100 to 300 g / eq is most preferable. Furthermore, the thing whose melt viscosity in 150 degreeC measured with the ICI viscometer is the range of 0.2-5.0 dPa * s is preferable at the point which is excellent in the fluidity | liquidity at the time of shaping | molding, the heat resistance of hardened | cured material, etc.

Accordingly, a preferred polyvalent hydroxy compound (B 1 ) is the novel polyvalent hydroxy compound (B1) of the present invention, and the following general formula ( 1 ) is contained in one molecule.

〔式中、Ａｒ^１は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ｘ^１はメチレン基、炭素原子数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上に更にアルキル基が芳香核置換したメチレン基であり、ｍは１又は２である。〕
で表わされる構造単位と、

[In the formula, Ar ¹ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; X ¹ is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, a methylene group substituted with a biphenyl group, 9 -A methylene group substituted with a fluorenyl group, or a methylene group in which an alkyl group is further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group, and m is 1 or 2. ]
A structural unit represented by

The following general formula ( 2 )

〔式中、Ａｒ^２は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ｒ^１は炭素原子数１〜４のアルキル基又はフェニル基であり、Ｘ^２はメチレン基、炭素原子数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上に更にアルキル基が芳香核置換したメチレン基であり、ｎ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１００〜５００ｇ／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０．２〜５．０ｄＰａ・ｓの範囲にあることを特徴とするものが好ましい。

[In the formula, Ar ² is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X ² is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, or naphthyl. A methylene group substituted with a group, a methylene group substituted with a biphenyl group, a methylene group substituted with a 9-fluorenyl group, or an alkyl group further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group A methylene group and n is 1 or 2; ]
The hydroxyl group equivalent is 100-500 g / eq. It is preferable that the melt viscosity at 150 ° C. measured with an ICI viscometer is in the range of 0.2 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 formulas, but are not limited thereto.

In addition, when the polyvalent hydroxy compound (B 1 ) of the present invention described above pays attention to a binuclear component in a GPC (gel permeation chromatography) chart, 1) phenol and phenol are bonded via a crosslinking agent. Compound, 2) a compound in which phenol and thioether are bonded through a crosslinking agent, and 3) a compound in which a thioether group-containing skeleton and a thioether group-containing skeleton are bonded through a crosslinking agent can be confirmed. A binuclear compound may be included. However, among these, the non-functional component (3) a compound in which a thioether group-containing skeleton and a thioether group-containing skeleton are bonded via a crosslinking agent = does not have a phenolic hydroxyl group) The compound in which the containing skeleton is bonded via a crosslinking agent = has only one phenolic hydroxyl group), these components are in consideration of moldability (such as mold contamination and molding hardness) and heat resistance (glass transition temperature). Therefore, the polyfunctional hydroxy compound (B 1 ) of the present invention has a monofunctional component content of 0 to 10% by mass of 2) and a monofunctional component of 1 to 2 in the polyvalent hydroxy compound (B 1 ) of the present invention. It is preferably 20% by mass.

The polyvalent hydroxy compound (B1) can be easily obtained by the production method described in detail below. The obtained polyvalent hydroxy compound (B 1 ) may be used singly or as a mixture of two or more kinds, and can also be used for photosensitive material applications such as a photoresist for semiconductors, and for development material applications.

Hereinafter, this production method (hereinafter abbreviated as “production method (1)”) will be described in detail. The production method (1) is characterized by reacting a hydroxy group-containing aromatic compound (a1), a thioether group-containing aromatic compound (a2), and a carbonyl group-containing compound (a3) in the presence of an acid catalyst. Yes.

  Here, the hydroxy group-containing aromatic compound (a1) is, for example, unsubstituted phenols such as phenol, resorcinol, hydroquinone, cresol, ethylphenol, n-propylphenol, iso-propylphenol, t-butylphenol, octylphenol. Monosubstituted phenols such as nonylphenol and phenylphenol, disubstituted phenols such as xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol and dibutylphenol, mesitol, 2,3,5-trimethylphenol, 2 Trisubstituted phenols such as 1,3,6-trimethylphenol, naphthols such as 1-naphthol, 2-naphthol and methylnaphthol, hydroquinone, resorcinol Dihydroxybenzenes such as catechol, biphenol, tetramethyl biphenol, bisphenol A, bisphenol F, although bisphenols such as bisphenol S or the like can be exemplified, but the invention is not limited thereto. Two or more of these can also be mixed and used. Among these, from the viewpoint of particularly excellent curability of the resulting cured product, phenols or substituent-containing phenols, naphthols or substituent-containing naphthols are preferable, and a cured product particularly excellent in flame retardancy can be obtained. From the viewpoint, phenol having 1-naphthol, 2-naphthol, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a benzyl group as a substituent is preferable.

  The thioether group-containing aromatic compound (a2) is a thioanisole or a substituent-containing thioanisole, an ethylphenyl sulfide or a substituent-containing ethylphenyl sulfide, a diphenyl sulfide or a substituent-containing diphenyl sulfide (provided that Each of the substituents is an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or an alkoxy group having 1 to 10 carbon atoms.), For example, thioanisole, ethylphenyl sulfide, t-butylphenyl sulfide, 2-methylthioanisole, 3-methylthioanisole, 4-methylthioanisole, 2-ethylthioanisole, 3-ethylthioanisole, 4-ethylthioanisole, diphenyl sulfide, 1-methoxy-2- (methylthio) benzene, 1-methoxy − - (methylthio) benzene, 2-thio-methylnaphthalene, 2-thioethyl-naphthalene, 1,2-benzene dimethane thiol as exemplified, but not limited thereto. Two or more of these can also be mixed and used. Thus, the thioether group-containing aromatic compound (a2) used in the present invention has 1 to 2 thioether groups in one molecule, and has a hydroxy group and an aldehyde group on the aromatic ring having a thioether group. It is preferable that the aromatic compound does not. Of these, thioanisole, ethylthiosulfide, and diphenylsulfide are preferable from the viewpoint of excellent flame retardancy and curability of the obtained cured product, and thioanisole is particularly preferable.

  The carbonyl group-containing compound (a3) may have a chemical structure capable of crosslinking the compound (a1) and the compound (a2). For example, formaldehyde, acetaldehyde, benzaldehyde, 4-methylbenzaldehyde, 3,4 -Aldehyde compounds such as dimethylbenzaldehyde, 4-biphenylaldehyde and naphthylaldehyde, and ketone compounds such as benzophenone, fluorenone and indanone. Among these, formaldehyde, benzaldehyde, 4-biphenylaldehyde, and naphthylaldehyde are preferable because the cured product obtained has excellent flame retardancy.

  Further, the production method (1) of the present invention will be described in detail. The hydroxy group-containing aromatic compound (a1), the thioether group-containing aromatic compound (a2), and the carbonyl group-containing compound (a3) are converted into an acid catalyst. The target polyvalent hydroxy compound (B1) can be obtained by heating and stirring in the presence of. 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, Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. Is mentioned. 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.

  The reaction charge ratio of the hydroxy group-containing aromatic compound (a1), the thioether group-containing aromatic compound (a2), and the carbonyl group-containing compound (a3) is not particularly limited, but the hydroxy group-containing aromatic compound ( The molar ratio (a1) / (a2) between a1) and the thioether group-containing aromatic compound (a2) is 30/70 to 99/1, and the hydroxy group-containing aromatic compound (a1) and the thioether group The ratio {(a1) + (a2)} / (a3) of the total number of moles of the containing aromatic compound (a2) to the number of moles of the carbonyl group-containing compound (a3) is 51/49 to 97/3. It is preferable. By satisfying these conditions, it is possible to obtain a cured product that is further excellent in flame retardancy and curability.

When the reaction of the production method (1) is performed, 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. As usage-amount of an organic solvent, it is 10-500 mass% normally with respect to the total mass of a charging raw material, Preferably it is 30-250 mass%. 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.

  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, a thiosulfuric acid, a sulfurous acid, hydrosulfite, or 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, organic solvents and by-products mainly containing hydroxy group-containing aromatic compound (a1) and thioether group-containing aromatic compound (a2) are heated under reduced pressure. By distilling off the product, the product can be 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.

  Further, as described above, the hydroxy group-containing aromatic compound (a1), the thioether group-containing aromatic compound (a2), and the carbonyl group-containing compound (a3) are mixed in advance, and then the mixture is heated. In addition, the reaction may be carried out by adding 0.05 to 30 mol, preferably 2 to 30 mol, of the carbonyl group-containing compound (a3) with respect to 1 mol of the thioether group-containing aromatic compound (a2). A method in which the hydroxy group-containing aromatic compound (a1) is charged and reacted after substantially completely reacting can also be employed. In the latter method, when an excessive amount of a carbonyl group-containing compound is used relative to a thioether group-containing aromatic compound, the structure of the polyvalent hydroxy compound can be converted into an alternating copolymer, and the thioether group can be more efficiently converted. It can be introduced into the molecular structure. In the latter method, the meaning that the reaction is substantially complete does not mean that the thioether group-containing aromatic compound (a2) has disappeared quantitatively, but an excess of the carbonyl group-containing compound (a3). It means that sufficient reaction time and reaction temperature are applied.

In the epoxy resin composition ( I ) of the present invention, the polyvalent hydroxy compound (B 1 ) acts as a curing agent for the epoxy resin (A) described later. In this case, the polyvalent hydroxy compound (B1) of the present invention. 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 (B 1 ) of the present invention in the total curing agent is preferably 30% by mass or more, particularly preferably 40% by mass or more.

Examples of other curing agents that can be used in combination with the polyvalent hydroxy compound (B 1 ) used in the epoxy resin composition ( I ) of the present invention include amine compounds, amide compounds, acid anhydride compounds, and phenol compounds. Various curing agents such as 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. Polyamide resin synthesized from a monomer and ethylenediamine, and the like, and acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydroanhydride Examples thereof include phthalic acid, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Examples of phenolic compounds include phenol novolac resin, cresol novolac resin, 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 novolac 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 These modified products are exemplified. 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. From the viewpoint of flame retardancy and dielectric characteristics of the object it is excellent.

The epoxy resin (A) used in the epoxy resin composition ( I ) 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-condensed novolak type epoxy resin, Futoru - cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, a biphenyl novolak type epoxy resins and the like. Among these, biphenyl type epoxy resins, naphthalene type epoxy resins, phenol aralkyl type epoxy resin, a biphenyl novolak type epoxy resin, a xanthene-type epoxy resins are particularly preferred from the viewpoint of excellent flame retardancy and heat resistance.

Although the compounding quantity of the hardening | curing agent containing the said polyhydric hydroxy compound (B1) in the epoxy resin composition ( I ) of this invention and the said epoxy resin (A) is not restrict | limited in particular, Hardened | cured material obtained From the point that the characteristics are good, the active group in the curing agent containing the polyvalent hydroxy compound (B1) is 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of the epoxy groups of the epoxy resin (A). Is preferred.

Next, the epoxy resin composition ( II ) of the present invention will be described. The polyvalent hydroxy compound (B 2 ) used as a curing agent in the resin composition (II) is represented by the following general formula ( 3 ) in one molecule.

〔式中、Ａｒ^１は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ａｒ^３はベンゼン骨格、ビフェニル骨格、ナフタレン骨格、またはこれらに炭化水素基が置換された芳香族骨格であり、Ｙ^１は同一でも異なっていてもよい水素原子又は炭素原子数１〜６の炭化水素基であり、ｍは１又は２である。〕
で表わされる構造単位と、

[In the formula, Ar ¹ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; Ar ³ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton in which a hydrocarbon group is substituted, and Y ¹ is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms And m is 1 or 2. ]
A structural unit represented by

The following general formula ( 4 )

〔式中、Ａｒ^２は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ａｒ^４はベンゼン骨格、ビフェニル骨格、ナフタレン骨格、またはこれらに炭化水素基が置換された芳香族骨格であり、Ｙ^２は同一でも異なっていてもよい水素原子又は炭素原子数１〜６の炭化水素基であり、Ｒ^１は炭素原子数１〜４のアルキル基又はフェニル基であり、ｎ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。

[In the formula, Ar ² is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, Ar ⁴ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton having a hydrocarbon group substituted thereon, and Y ² is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is 1 or 2. ]
It has a structural unit represented by these.

Ar ¹ in the general formula (1) is a benzene ring, a naphthalene ring, or a carbon number from the viewpoint of easy industrial availability of raw materials and excellent flame retardancy and curability of the resulting cured product. A benzene ring or a naphthalene ring substituted with an alkyl group of 1 to 3, an aryl group, an aralkyl group or an alkoxy group of 1 to 3 carbon atoms is preferable.

In addition, R ¹ in the general formula (2) is preferably a methyl group, an ethyl group, or a phenyl group from the viewpoint of excellent flame retardancy of the obtained cured product. Similarly, X ² is a raw material industry. Benzene ring, naphthalene ring, or an alkyl group having 1 to 3 carbon atoms, aryl group, aralkyl group, or carbon number from the point of easy acquisition and the point of excellent curability and flame retardancy of the resulting cured product A benzene ring or a naphthalene ring substituted with 1 to 3 alkoxy groups is preferable.

Moreover, the following general formula (3 ′) in the general formula (3) in the polyvalent hydroxy compound ( B2 ).

（式中、Ａｒ^１、ｍは前記一般式（３）と同義である。）
で表される構造単位と、

(In formula, Ar < ¹ >, m is synonymous with the said general formula ( 3 ).)
A structural unit represented by

The following general formula in the formula (4) (4 ')

（式中、Ａｒ^２、Ｒ^１、ｎは前記一般式（４）と同義である。）
で表される構造単位とのモル比率が前者／後者＝３０／７０〜９９／１の範囲であることが好ましく、特に５０／５０〜９９／１であることが好ましく、６０／４０〜９９／１であることが最も好ましい。

(In the formula, Ar ² , R ¹ and n have the same meanings as in the general formula ( 4 ).)
Is preferably in the range of the former / the latter = 30/70 to 99/1, particularly preferably 50/50 to 99/1, and 60/40 to 99 /. Most preferred is 1.

The hydroxyl equivalent of the polyvalent hydroxy compound ( B2 ) is 150 to 500 g / eq. Those in the range are preferable in terms of excellent flame retardancy and curability, particularly preferably 170 to 400 g / eq, and most preferably 180 to 350 g / eq. Furthermore, the thing whose melt viscosity in 150 degreeC measured with the ICI viscometer is the range of 0.2-5.0 dPa * s is preferable at the point which is excellent in the fluidity | liquidity at the time of shaping | molding, the heat resistance of hardened | cured material, etc.

Therefore, polyhydroxy compound used in the epoxy resin composition of the present invention (B2) is a novel polyhydroxy compounds of the present invention (B2), the following formula in one molecule (3)

〔式中、Ａｒ^１は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ａｒ^３はベンゼン骨格、ビフェニル骨格、ナフタレン骨格、またはこれらに炭化水素基が置換された芳香族骨格であり、Ｙ^１は同一でも異なっていてもよい水素原子又は炭素原子数１〜６の炭化水素基であり、ｍは１又は２である。〕
で表わされる構造単位と、

[In the formula, Ar ¹ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; Ar ³ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton in which a hydrocarbon group is substituted, and Y ¹ is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms And m is 1 or 2. ]
A structural unit represented by

The following general formula ( 4 )

〔式中、Ａｒ^２は芳香族炭化水素基又は炭素原子数１〜１０のアルキル基、アリール基、アラルキル基又は炭素原子数１〜１０のアルコキシ基で置換された芳香族炭化水素基であり、Ａｒ^４はベンゼン骨格、ビフェニル骨格、ナフタレン骨格、またはこれらに炭化水素基が置換された芳香族骨格であり、Ｙ^２は同一でも異なっていてもよい水素原子又は炭素原子数１〜６の炭化水素基であり、Ｒ^１は炭素原子数１〜４のアルキル基又はフェニル基であり、ｎ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１５０〜５００ｇ／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０．２〜５．０ｄＰａ・ｓの範囲にあることを特徴とするものが最も好ましい。

[In the formula, Ar ² is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, Ar ⁴ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton having a hydrocarbon group substituted thereon, and Y ² is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is 1 or 2. ]
Wherein the hydroxyl group equivalent is 150 to 500 g / eq. Most preferably, the melt viscosity at 150 ° C. measured by an ICI viscometer is in the range of 0.2 to 5.0 dPa · s.

Specific examples of the general formula ( 3 ) include those represented by the following structural formulas, but are not limited thereto.

Specific examples of the general formula ( 4 ) include those represented by the following structural formula, but are not limited thereto.

In addition, when the polyvalent hydroxy compound (B 2 ) of the present invention described above focuses on a binuclear component in a GPC (gel permeation chromatography) chart, 1) phenol and phenol are bonded via a crosslinking agent. Compound, 2) a compound in which phenol and thioether are bonded through a crosslinking agent, and 3) a compound in which a thioether group-containing skeleton and a thioether group-containing skeleton are bonded through a crosslinking agent can be confirmed. A binuclear compound may be included. However, among these, the non-functional component (3) a compound in which a thioether group-containing skeleton and a thioether group-containing skeleton are bonded via a crosslinking agent = has no phenolic hydroxyl group), one functional component (2) phenol and thioether group The compound in which the containing skeleton is bonded via a crosslinking agent = has only one phenolic hydroxyl group), these components are in consideration of moldability (such as mold contamination and molding hardness) and heat resistance (glass transition temperature). Therefore, the content of the non-functional component of 3) is 0 to 10% by mass, and the content of the monofunctional component of 2) is 1 to 20 in the polyvalent hydroxy compound (B) of the present invention. It is preferable that it is mass%.

The polyvalent hydroxy compound (B2) can be easily obtained by the production method described in detail below. The obtained polyvalent hydroxy compound (B 2 ) may be used singly or as a mixture of two or more kinds, and can also be used for photosensitive materials such as a photoresist for semiconductors and for developers.

Hereinafter, this production method (hereinafter abbreviated as “production method (2)”) will be described in detail. The production method (2) comprises reacting a hydroxy group-containing aromatic compound ( b 1), a thioether group-containing aromatic compound ( b 2), and an aromatic crosslinking agent ( b 3) to produce a polyvalent hydroxy compound. It is characterized by comprising the step of obtaining

Wherein said hydroxy group-containing aromatic compound (b 1), the flame of the above hydroxy group-containing aromatic compound used in the production method (1) (a1) the like can be mentioned a cured product obtained especially From the viewpoint of being particularly excellent in flammability, phenols which may have a substituent and naphthols which may have a substituent are preferable, and from the viewpoint that a cured product having particularly excellent curability can be obtained. -Naphthol, 2-naphthol, phenols substituted with alkyl groups having 1 to 6 carbon atoms, phenyl groups or benzyl groups are particularly preferred.

The thioether group-containing aromatic compound (b 2), the flame retardant of the above-said thioether group-containing aromatic compound used in the production method (1) (a2) the same as the the like, the cured product obtained in particular From the viewpoint of excellent properties and curability, thioanisole, ethylthiosulfide, and diphenylsulfide are preferable, and thioanisole is particularly preferable.

As the aromatic crosslinking agent (b 3), but not in any way limited as long as the aromatic compound having a compound (b 1) and the compound (b 2) and capable of cross-linking structure represented by the following general Those represented by the formulas ( 5 ), ( 6 ) and ( 7 ) are preferable.

（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^２はハロゲン原子であり、Ｒ^３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 ² is a halogen atom, and R ³ 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 ( 5 ) 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 (chloromethyl) ) Biphenyl, 2,2′-bis (chloromethyl) biphenyl, 2,4′-bis (chloromethyl) biphenyl, 2,3′-bis (chloromethyl) biphenyl, 4,4′-bis (bromomethyl) biphenyl, 4,4′-bis (chloromethyl) diphenyl ether, 2,7-di (chloromethyl) naphthalene and the like can be mentioned.

Examples of the compound represented by the general formula ( 6 ) include p-xylylene glycol, 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.

Examples of the compound represented by the general formula ( 7 ) include bis (vinyl) biphenyl such as p-divinylbenzene, m-divinylbenzene, and 4,4′-bis (vinyl) biphenyl. It is not limited.

If specifically with respect to the reaction conditions of the production method (2), hydroxy group-containing aromatic compound (b 1) and a thioether group-containing aromatic compound (b 2) and an aromatic crosslinking agent and (b 3), The polyvalent hydroxy compound ( B2 ) of the present invention can be obtained by heating and stirring in the presence of a suitable polymerization catalyst. 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 mass with respect to the total mass of the charged raw materials.

The reaction charge ratio of the hydroxy group-containing aromatic compound ( b 1), the thioether group-containing aromatic compound ( b 2), and the aromatic cross-linking agent ( b 3) is not particularly limited. family compounds (b 1) and a thioether group containing aromatic compound (b2) and the molar ratio of (b 1) / (b 2 ) is 30 / 70-99 / 1, and a hydroxy group-containing aromatic Ratio of the total number of moles of the compound ( b 1) and the thioether group-containing aromatic compound ( b 2) to the number of moles of the aromatic crosslinking agent ( b 3) {( b 1) + ( b 2)} / (b 3) is preferably a 51 / 49-97 / 3. By satisfying these conditions, it is possible to obtain a cured product that is further excellent in flame retardancy and curability.

  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 mass, preferably 30 to 250% by mass, based on the total mass 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 ( 5 ) is used as the aromatic crosslinking agent ( b3 ), the reaction becomes a condensation reaction system, and a hydrogen halide gas such as hydrochloric acid as the reaction proceeds. Therefore, it is preferable to quickly discharge out of the system and trap outside the system by alkali treatment or the like. In addition, when the compound represented by the general formula ( 6 ) is used, a condensation system is formed, and water, methanol, and the like are generated as the reaction proceeds. It is preferable in speeding up In addition, when the compound represented by the general formula ( 7 ) is used, since it becomes an addition reaction system, it is not particularly necessary to treat by-products.

Further, when the obtained polyvalent hydroxy compound ( B2 ) 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 treatment under reduced pressure at a heating mainly unreacted starting material and organic solvent containing a hydroxy group-containing aromatic compound (b 1) and a thioether group-containing aromatic compound (b 2), sub The target polyvalent hydroxy compound ( B2 ) can be obtained by distilling off the organism and concentrating the product. 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.

Further, as described above, the hydroxy group-containing aromatic compound ( b 1), the thioether group-containing aromatic compound ( b 2), and the aromatic crosslinking agent ( b 3) are mixed in advance, may be performed and the reaction by heating the mixture, also a thioether group-containing aromatic compound (b 2) with respect to 1 mol of reacted 2 to 30 moles of an aromatic crosslinking agent (b 3) Further, after the thioether group-containing aromatic compound ( b2 ) is substantially completely reacted and consumed, the hydroxy group-containing aromatic compound ( b1 ) is charged and reacted. According to the latter method, the structure of the polyvalent hydroxy compound can be converted into an alternating copolymer, and a thioether group can be more efficiently introduced into the molecular structure. In the latter method, the meaning that the reaction is substantially complete does not mean that the thioether group-containing aromatic compound ( b2 ) has disappeared quantitatively, but an excess of the aromatic crosslinking agent ( b 3) means that sufficient reaction time and reaction temperature are applied.

The polyvalent hydroxy compound (B 2 ) in the epoxy resin composition ( II ) of the present invention acts as a curing agent for the epoxy resin (A) described later. In this case, the polyvalent hydroxy compound (B2 ) of the present invention It 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 ( B2 ) of the present invention in the total curing agent is preferably 30% by mass or more, and particularly preferably 40% by mass or more.

The other curing agent that can be used in combination with the polyvalent hydroxy compound (B 2 ) of the present invention is not particularly limited, and examples thereof include amine compounds, amide compounds, acid anhydride compounds, phenol compounds. Various curing agents such as can be used. Examples of amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complexes, guanidine derivatives, and the like, and 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 novolac 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. From the viewpoint of flame retardancy and curing of the objects it is excellent.

The epoxy resin (A) used in the epoxy resin composition ( II ) 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, tetramethylbiphenyl 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-condensed novolak type epoxy resin Fat, 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. Among these, biphenyl type epoxy resins, naphthalene type epoxy resins, phenol aralkyl type epoxy resin, a xanthene-type epoxy resins of the biphenyl novolac type epoxy resin and JP 2003-201333 Patent described, excellent flame retardancy and curing It is particularly preferable from the viewpoint.

The blending amount of the epoxy resin (A) and the curing agent (B) in the epoxy resin composition (II) of the present invention is not particularly limited. The amount of active groups in the curing agent (B) containing the polyvalent hydroxy compound (B1) is preferably 0.7 to 1.5 equivalents relative to a total of 1 equivalent of epoxy groups in the resin (A).

The epoxy resin composition ( I ) or ( II ) of the present invention described in detail above can be used in combination with a curing accelerator as appropriate. 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 sealing material application, triphenylphosphine, tetraphenylphosphonium tetrakisphenylborate, tetraphenylphosphonium are used as phosphorus compounds because of their excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc. For tetrakis (4-methylphenyl) borate, an adduct of a phosphine compound and a quinone compound, and a tertiary amine, 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is preferred.

The epoxy resin composition ( I ) or ( II ) of the present invention has a flame retardancy imparting effect because the polyvalent hydroxy compound (A) itself used as a curing agent has an effect of imparting flame retardancy. Even if a conventionally used flame retardant is not blended for imparting, the cured product has good flame retardancy. However, in order to exhibit a higher degree of flame retardancy, a non-halogen flame retardant (C) that substantially does not contain a halogen atom is used as long as the moldability in the sealing process and the reliability of the semiconductor device are not deteriorated. It can mix | blend with an epoxy resin composition ( I ) or ( II ), and the said fat composition can be utilized as a non-halogen-type flame-retardant resin composition.

  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.

  Examples of the phosphonic acid compound include diphenylphosphinic acid, methylethylphosphinic acid, 9,10-dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydroxyphenyl) -10H. Cyclic organic phosphorus compounds such as -9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and A derivative obtained by reacting it with a compound such as an epoxy resin or a phenol resin can be used.

  Specific examples of the phosphine oxide compound include triphenylphosphine oxide, tris (3-hydroxypropyl) phosphine oxide, diphenylphosphinyl hydroquinone and the like.

  Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds.

  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 mass 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 mass 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 mass, particularly in the range of 0.5 to 6.0 parts by mass. Is preferred.

  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, and 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 mass, especially in the range of 0.05 to 10 parts by mass, in 100 parts by mass 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 mass.

  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 mass in 100 parts by mass of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives.

  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 composite metal hydroxide. it can.

  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 the range of 0.05 to 20 parts by mass in 100 parts by mass of the epoxy resin composition in which all of the agent, non-halogen flame retardant and other fillers and additives are blended. It is preferable to mix in the range of 15 parts by mass.

  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 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 naphthidylline 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.

  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 mass in 100 parts by mass of the epoxy resin composition containing all of the epoxy resin, the curing agent, the non-halogen flame retardant, and other fillers and additives.

An inorganic filler can be mix | blended with the epoxy resin composition ( I ) or ( II ) of this invention as needed. 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 mass 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 ( I ) or ( II ) of the present invention as necessary.

Epoxy resin composition ( I ) or ( II ) of this invention is obtained by mixing each component uniformly. The epoxy resin composition of the present invention, in which the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator are 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.

The epoxy resin composition ( I ) or ( II ) of the present invention can be used as a semiconductor sealing material, a resin composition used for a laminated board or an electronic circuit board, a resin casting material, an adhesive, and a build-up board. Interlayer insulating materials for coating, coating materials such as insulating paints, and the like can be mentioned. Among these, it can be suitably used for semiconductor sealing materials. Hereinafter, the semiconductor sealing material of the present invention will be described in detail.

That is, the semiconductor encapsulating material of the present invention, in addition to the epoxy resin composition (I) or (II) in the epoxy resin (A) and the curing agent (B), further or composition containing an inorganic filler It is characterized by

  In order to produce such a semiconductor encapsulant, the above-described components are sufficiently mixed until uniform using an extruder, kneader, roll, etc. to obtain a melt-mixed epoxy resin composition. Just do it. At that time, silica is usually used as the inorganic filler, and the filler is preferably used in a range of 30 to 95% by mass per 100 parts by mass of the epoxy resin composition. 70 parts by mass or more is particularly preferable in order to improve the moisture resistance and solder crack resistance and decrease the linear expansion coefficient, and 80 parts by mass or more is more effective in order to significantly increase these effects. Can be increased. 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 the semiconductor sealing material of the present invention, a coupling agent may be used as necessary in order to improve the adhesion between the resin component and the inorganic filler. Examples of the coupling agent include various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum compounds, zirconium compounds, and aluminum chelates.

  The amount of the coupling agent is preferably 0.01 to 5% by mass and more preferably 0.05 to 2.5% by mass with respect to the inorganic filler. If it is less than 0.01% by mass, the adhesiveness with various package components tends to decrease, and if it exceeds 5% by mass, molding defects such as voids tend to occur.

  Furthermore, in the semiconductor sealing material of the present invention, as other additives, a mold release agent, a colorant, a stress relaxation agent, an adhesion improver, a surfactant and the like can be blended as necessary.

  Examples of the mold release agent include carnauba wax, hydrocarbon, aliphatic, amide, ester, higher alcohol, and higher fatty acid metal salt.

  Examples of the hydrocarbon type include paraffin wax and polyolefin wax. Polyolefin waxes are roughly classified into non-polarized non-polar polyolefin waxes and oxidized polyolefin waxes, and there are polyethylene-based, polypropylene-based, and vinyl acetate-ethylene copolymer systems, respectively.

  As the fatty acid system, montanic acid, stearic acid, hebenic acid, 12-hydroxystearic acid, as the amide system, stearic acid amide, oleic acid amide, methylenebisstearic acid amide, as the ester system, butyl stearate, stearic acid Examples of acid monoglycerides, stearyl stearate, and higher alcohols include stearyl alcohol, and examples of higher fatty acid metal salts include calcium stearate, zinc stearate, and magnesium stearate.

  As the colorant, inorganic colorants such as bengara, carbon black, glass compositions, and phthalocyanine-based compounds, anthraquinone-based, methine-based, indigoid-based, and azo-based organic compound pigments can be used. Carbon black is preferred because of its excellent effect.

  There is no restriction | limiting in particular as a low stress agent (stress relaxation agent), For example, silicone oil, liquid rubber, rubber powder, a methyl acrylate-butadiene-styrene copolymer, such as a thermoplastic resin, methyl methacrylate-butadiene- Examples include butadiene copolymer rubbers such as styrene copolymers and those described in silicone compounds.

  Further, hydrotalcites and ion trapping agents such as bismuth hydroxide may be blended for the purpose of improving the reliability in the moisture resistance reliability test. The adhesion improver is not particularly limited, and examples thereof include N-cyclohexyl-2-benzothiazolylsulfanamide, N-oxydiethylene-2-benzothiazolylsulfanamide, N, N-dicyclohexyl-2-benzo Examples thereof include thiazolylsulfanamide, Nt-butyl-2-benzothiazolylsulfanamide, a compound having a benzothiazole skeleton, an indene resin, a crosslinked diallyl phthalate resin powder, and butadiene rubber particles.

  Examples of the surfactant include polyethylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride and the like.

  The semiconductor encapsulating material of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general method, however, a predetermined amount of raw materials are sufficiently mixed by a mixer or the like. And a method of cooling and pulverizing after melt-kneading with a mixing roll, an extruder or the like. It is easy to use if it is tableted with dimensions and mass that match the molding conditions.

  As an electronic component device including an element sealed with a semiconductor sealing material obtained in the present invention, a lead frame, a wired tape carrier, a wiring board, glass, a support member such as glass, a silicon wafer, a semiconductor chip, a transistor, Examples include an electronic component device in which active elements such as diodes and thyristors, and passive elements such as capacitors, resistors, and coils are mounted and necessary portions are sealed with the semiconductor sealing material of the present invention. As such an electronic component device, specifically, 1) a semiconductor element is fixed on a lead frame, a terminal part of an element such as a bonding pad and a lead part are connected by wire bonding or bump, DIP, PLCC, QFP, SOP, SOJ, TSOP, TQFP, and other general resin-encapsulated ICs that are encapsulated by transfer molding using a semiconductor encapsulation material, and 2) connected to the tape carrier by bumps A semiconductor chip in which a semiconductor chip is sealed with a semiconductor sealing material of the present invention, a wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, or the like. 3) Transistor, diode, thyristor Active elements such as capacitors or passive elements such as capacitors, resistors, and coils are sealed with the semiconductor sealing material of the present invention. OB module, 4) A semiconductor chip is mounted on an interposer substrate on which terminals for connecting a hybrid IC, a multi-chip module, and a mother board are formed, and after connecting the semiconductor chip and the wiring formed on the interposer substrate by bump or wire bonding, One-side sealed packages such as BGA, CSP, MCP, etc., in which the semiconductor chip mounting side is sealed with the semiconductor sealing material of the invention, can be mentioned. Among these, a single-side sealed package including an element sealed with a semiconductor sealing material obtained by the present invention has a feature that the amount of warpage is small.

  As the lead frame, a copper (including copper alloy) lead frame, a Ni-plated lead frame in which a Ni layer is formed on the surface of a copper plate or the like by a method such as plating, or a 42 alloy lead frame should be used. Can do.

  As a method for sealing an element using the semiconductor sealing material of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.

Next, in order to process the epoxy resin composition ( I ) or ( II ) of the present invention into a printed circuit board composition, for example, a resin composition for prepreg can be obtained. 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. Although it does not specifically limit as a mass ratio of the epoxy resin composition ( I ) or ( II ) used here and a reinforcement base material, Usually, it prepares so that the resin content in a prepreg may be 20-60 mass%. preferable. Moreover, when manufacturing a copper clad laminated board using this epoxy resin composition, the prepreg obtained as mentioned above is laminated | stacked, copper foil is laminated | stacked suitably, 170-250 degreeC under the pressure of 1-10 MPa. A copper-clad laminate can be obtained by heating and pressure bonding for 10 minutes to 3 hours.

When the epoxy resin composition ( I ) or ( II ) of the present invention is used as a resist ink, a resist ink composition is prepared by a conventional method, and then applied to a printed circuit board by a screen printing method. The method of using an ink cured product is mentioned.

When using the epoxy resin composition ( I ) or ( II ) of the present invention as a conductive paste, a method of dispersing fine conductive particles in the resin composition to obtain a composition for anisotropic conductive film, room temperature And a liquid paste resin composition for circuit connection 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 ( I ) or ( II ) of this invention, Specifically, the said curable resin composition which mix | blended rubber | gum, a filler, etc. suitably. An object 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 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.

  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. For example, the method of heating the composition obtained by the said method in the temperature range of about room temperature-250 degreeC is mentioned. A general method of the epoxy resin composition can also be used as the molding method.

An ion trap agent (ion exchanger, ion scavenger) can be blended in the epoxy resin composition (I) or ( II ) of the present invention. Examples of the ion trapping agent include hydrotalcites and hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, and bismuth. The amount of the ion trapping agent is not particularly limited as long as it is a sufficient amount capable of trapping anions such as halogen ions, but from the viewpoint of fluidity and bending strength, 0.1 to 30 mass with respect to (A) the epoxy resin. % Is preferable, 0.5 to 10% by mass is more preferable, and 1 to 5% by mass is more preferable.

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 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 GSAR270 manufactured by JEOL Ltd.
5) MS: Double Density Mass Spectrometer AX505H (FD505H) manufactured by JEOL Ltd.

Example 1 [Synthesis of polyvalent hydroxy compound ( B- 1)]
A flask equipped with a thermometer, condenser, fractionator, and stirrer was charged with 376.4 g (4.00 mol) of phenol, 248.38 g (2.00 mol) of thioanisole, and 7.2 g of oxalic acid at 70 ° C. The temperature was raised to. While increasing the temperature from 70 ° C. to 100 ° C. in 60 minutes, 90.1 g of 92% paraform (2.76 mol in terms of formaldehyde) was added in 5 portions. After the addition, the mixture was reacted at 100 ° C. for 1 hour, heated to 150 ° C. in 60 minutes, and further reacted for 1 hour. After completion of the reaction, 700 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, thioanisole, 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（Ｂ−１）３２８ｇを得た。これの軟化点は８３℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は３．１ｄＰａ・ｓ、水酸基当量は１１５ｇ／ｅｑ．であった。回収した未反応のフェノール及びチオアニソールの質量測定の結果、及び得られた多価ヒドロキシ化合物の水酸基当量の測定結果から、化合物中における前記一般式（１’）で表される構造単位と前記一般式（２’）で表される構造単位とのモル比率は、前者／後者＝９５／５であった。

328 g of a polyvalent hydroxy compound (B-1) having a structural unit represented by The softening point is 83 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 3.1 dPa · s, and the hydroxyl equivalent is 115 g / eq. Met. From the results of mass measurement of the recovered unreacted phenol and thioanisole and the measurement results of the hydroxyl equivalent of the obtained polyvalent hydroxy compound, the structural unit represented by the general formula (1 ′) in the compound and the general The molar ratio with the structural unit represented by the formula (2 ′) was the former / the latter = 95/5.

Example 2 [Synthesis of polyvalent hydroxy compound (B-2)]
In a flask equipped with a thermometer, condenser, fractionator, and stirrer, 188.2 g (2.00 mol) of phenol, 124.2 g (1.00 mol) of thioanisole, and 49.0 g of 92% paraformaldehyde (formaldehyde) 1.50 mol) was charged, 7.2 g of oxalic acid was added, and the temperature was raised to 100 ° C. over 1 hour. After raising the temperature, the reaction was carried out at 100 ° C. for 1 hour and further at 150 ° C. for 1 hour. After completion of the reaction, 500 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, thioanisole, and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure, and the following structural formula

160 g of a polyvalent hydroxy compound (B-2) having a structural unit represented by From the results of mass measurement of the recovered unreacted phenol and thioanisole, and the measurement results of the hydroxyl group of the obtained polyvalent hydroxy compound, the structural unit represented by the general formula ( 1 ′ ) in the compound and the general formula The molar ratio with the structural unit represented by ( 2 ′ ) was the former / the latter = 95/5. The softening point is 78 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 2.1 dPa · s, and the hydroxyl equivalent is 114 g / eq. Met. FIG. 1 shows the GPC chart, FIG. 2 shows the ¹³ C-NMR chart, and FIG. 3 shows the MS spectrum.

Example 3 [Synthesis of polyvalent hydroxy compound (B-3)]
In a flask equipped with a thermometer, condenser, fractionator, and stirrer, 564.7 g (6.00 mol) of phenol, 372.6 g (3.00 mol) of thioanisole, and 97.9 g of 92% paraformaldehyde (formaldehyde) 3.00 mol) was added, 20.7 g of oxalic acid was added, and the temperature was raised to 100 ° C. over 1 hour. After raising the temperature, the reaction was carried out at 100 ° C. for 1 hour and further at 150 ° C. for 1 hour. After completion of the reaction, 500 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, thioanisole, 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（Ｂ−３）３３２ｇを得た。回収した未反応のフェノール及びチオアニソールの質量測定の結果、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（１’）で表される構造単位と前記一般式（２’）で表される構造単位とのモル比率は、前者／後者＝９６／４であった。これの軟化点は６１℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は０．５ｄＰａ・ｓ、水酸基当量は１０７ｇ／ｅｑ．であった。これのＧＰＣチャートを図４に示す。

332 g of a polyvalent hydroxy compound (B-3) having a structural unit represented by From the results of mass measurement of the recovered unreacted phenol and thioanisole, and the measurement results of the hydroxyl group of the obtained polyvalent hydroxy compound, the structural unit represented by the general formula ( 1 ′ ) in the compound and the general formula The molar ratio with the structural unit represented by ( 2 ′ ) was the former / the latter = 96/4. The softening point thereof is 61 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 0.5 dPa · s, and the hydroxyl group equivalent is 107 g / eq. Met. A GPC chart of this is shown in FIG.

Example 4 [Synthesis of polyvalent hydroxy compound (B-4)]
In a flask equipped with a thermometer, condenser, fractionator, and stirrer, 94.1 g (1.00 mol) of phenol, 248.4 g (2.00 mol) of thioanisole, and 49.0 g of 92% paraformaldehyde (formaldehyde) 1.50 mol) was charged, 7.8 g of oxalic acid was added, and the temperature was raised to 100 ° C. over 1 hour. After raising the temperature, the reaction was carried out at 100 ° C. for 1 hour and further at 150 ° C. for 1 hour. After completion of the reaction, 300 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, thioanisole, 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（Ｂ−４）１１０ｇを得た。回収した未反応のフェノール及びチオアニソールの質量測定の結果、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（１’）で表される構造単位と前記一般式（２’）で表される構造単位とのモル比率は、前者／後者＝８９／１１であった。これの軟化点は５８℃（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１２４ｇ／ｅｑ．であった。これのＧＰＣチャートを図５に示す。

110 g of a polyvalent hydroxy compound (B-4) having a structural unit represented by From the results of mass measurement of the recovered unreacted phenol and thioanisole, and the measurement results of the hydroxyl group of the obtained polyvalent hydroxy compound, the structural unit represented by the general formula (1 ′) in the compound and the general formula The molar ratio with the structural unit represented by (2 ′) was the former / the latter = 89/11. The softening point was 58 ° 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 124 g / eq. Met. A GPC chart of this is shown in FIG.

Example 5 [Synthesis of polyvalent hydroxy compound (B-5)]
In a flask equipped with a thermometer, condenser, fractionator, nitrogen gas inlet, and stirrer, 314.3 g (3.34 mol) of phenol, 206.2 g (1.66 mol) of thioanisole and paraxylene dimethoxy were added. After charging 332.4 g of side (2.00 mol in terms of formaldehyde), adding 8.5 g (0.045 mol) of toluenesulfonic acid, raising the temperature to 150 ° C., and collecting methanol as a by-product with a fractionating tube. The reaction was performed for 6 hours while collecting. After completion of the reaction, 5000 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, thioanisole, 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（Ｂ−５）３９７ｇを得た。これの軟化点は６８℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は１．９ｄＰａ・ｓ、水酸基当量は２０４ｇ／ｅｑ．であった。回収した未反応のフェノール及びチオアニソールの質量測定の結果、及び得られた多価ヒドロキシ化合物の水酸基当量の測定結果から、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＝８８／１２であった。

397 g of a polyvalent hydroxy compound (B-5) having a structural unit represented by Its softening point is 68 ° C. (B & R method), melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 1.9 dPa · s, and hydroxyl equivalent is 204 g / eq. Met. From the results of mass measurement of the recovered unreacted phenol and thioanisole, and the measurement results of the hydroxyl equivalent of the obtained polyvalent hydroxy compound, the structural unit represented by the general formula (3 ′) in the compound and the general formula The molar ratio with the structural unit represented by the formula (4 ′) was the former / the latter = 88/12.

Example 6 [Synthesis of polyvalent hydroxy compound (B-6)]
A flask equipped with a thermometer, condenser, fractionator, nitrogen gas inlet, and stirrer was charged with 157.2 g (1.67 mol) of phenol, 103.08 g (0.83 mol) of thioanisole and paraxylene dimethoxy. 166.2 g (1.00 mol) of side was added, 4.3 g (0.023 mol) of toluenesulfonic acid was added, the temperature was raised to 150 ° C., and methanol produced as a by-product was collected with a fractionating tube. The reaction was performed for 6 hours. 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, thioanisole, and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure, and the following structural formula

198 g of a polyvalent hydroxy compound (B-6) having a structural unit represented by the formula: From the results of mass measurement of the recovered unreacted phenol and thioanisole, 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 formula The molar ratio with the structural unit represented by (4 ′) was the former / the latter = 88/12. The softening point thereof is 67 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 1.8 dPa · s, and the hydroxyl group equivalent is 212 g / eq. Met. FIG. 6 shows the GPC chart, FIG. 7 shows the C ¹³ NMR chart, and FIG. 8 shows the MS spectrum. The residual thioether group confirmed that the thioether group in the compound was not decomposed from the signal of the thioether group observed at 15 ppm in NMR and the hydroxyl group equivalent.

Example 7 [Synthesis of polyvalent hydroxy compound (B-7)]
A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer was charged with 141.2 g (1.50 mol) of phenol, 186.3 g (1.50 mol) of thioanisole and paraxylene dimethoxy. 166.2 g (1.00 mol) of side was added, 4.9 g (0.023 mol) of toluenesulfonic acid was added, the temperature was raised to 150 ° C., and methanol produced as a by-product was collected with a fractionating tube. The reaction was performed for 6 hours. 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, thioanisole, and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure, and the following structural formula

209 g of a polyvalent hydroxy compound (B-7) having a structural unit represented by From the results of mass measurement of the recovered unreacted phenol and thioanisole, 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 formula The molar ratio with the structural unit represented by (4 ′) was the former / the latter = 80/20. The softening point is 70 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 2.0 dPa · s, and the hydroxyl equivalent is 252 g / eq. Met. A GPC chart of this is shown in FIG.

Synthesis example 1
In accordance with Example 1 of JP 2004-244526 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（Ｂ’−１）を得た。これの軟化点は７５℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法，測定温度：１５０℃）は２．６ｄＰａ・ｓ、水酸基当量は１５３ｇ／ｅｑ．であった。

The polyvalent hydroxy compound (B'-1) which has a structural unit represented by this was obtained. The softening point is 75 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 2.6 dPa · s, and the hydroxyl group equivalent is 153 g / eq. Met.

Synthesis example 2
In accordance with Example 1 of JP 2004-339277 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（Ｂ’−２）を得た。これの軟化点は９２℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法，測定温度：１５０℃）は３．４ｄＰａ・ｓ、水酸基当量は１７３ｇ／ｅｑ．であった。

The polyvalent hydroxy compound (B'-2) which has a structural unit represented by this was obtained. The softening point is 92 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 3.4 dPa · s, and the hydroxyl group equivalent is 173 g / eq. Met.

Synthesis example 3
While subjecting a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer to nitrogen gas purge, Mitsui Chemicals Co., Ltd. Millex XLC-4L168 parts, epichlorohydrin 463 g (5.0 mol), n-butanol 139 g, tetraethylbenzyl 2 g of ammonium 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.

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

Synthesis example 4
A flask equipped with a thermometer, condenser, fractionator, and stirrer was charged with 470.5 g (5.0 mol) of phenol and 242.3 of 4,4′-bis (methoxymethyl) biphenyl, and paratoluenesulfonic acid. After 2.5 g was added and the temperature was raised to 140 ° C., the reaction was carried out for 3 hours while collecting by-product methanol with a fractionating tube. 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 and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure, and the following structural formula

360 g of a polyvalent hydroxy compound (B′-3) having a structural unit represented by The softening point thereof is 61 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 1.0 dPa · s, and the hydroxyl equivalent is 200 g / eq. Met.

Synthesis example 5
In accordance with Example 1 of JP-A-8-301980, the following structural formula

The polyvalent hydroxy compound (B'-4) 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 6
In accordance with Example 4 of JP-A-8-301980, the following structural formula

The polyvalent hydroxy compound (B'-5) 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 7
In accordance with Example 1 and Example 7 of JP-A-8-301980, the following structural formula

The epoxy resin ( A-2 ) which has a structural unit represented by this was obtained. The softening point of this was 61 ° C. (B & R method), and the epoxy equivalent was 324 g / eq. Met.

Synthesis example 8
In accordance with Example 4 and Example 10 of JP-A-8-301980, the following structural formula

The epoxy resin ( A-3 ) which has a structural unit represented by this was obtained. The softening point is 79 ° C. (B & R method), and the epoxy equivalent is 421 g / eq. Met.

Comparative Examples 1 and 2
Patent Document 1 as a d epoxy resin, examples Nippon Kayaku Co., Ltd. NC-3000 having the same structure as those described in 1 (a biphenyl aralkyl type epoxy resin, epoxy equivalent: 274 g / eq), a curing agent ( B) and to Mitsui chemical Co., Ltd. XLC-3L (phenol aralkyl resin, hydroxyl equivalent: 176 g / eq), Meiwa Kasei Co., Ltd. MEH-7851SS (biphenyl novolac resin, hydroxyl equivalent: 200 g / eq) using the curing Triphenylphosphine (TPP) as an accelerator, condensed phosphate ester (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.), magnesium hydroxide (Echo Mug Z-10 manufactured by Air Water Co., Ltd.), spherical as an inorganic filler Silica (S-COL manufactured by Micron Corporation), γ- as silane coupling agent Compounded in the composition shown in Table 1 using lysidoxytriethoxyxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), carnauba wax (PEARL WAX No.1-P manufactured by Celarica Noda Co., Ltd.), carbon black, It melt-kneaded for 5 minutes at the temperature of 85 degreeC using 2 rolls, and obtained the target composition. The physical properties of the cured product were prepared by using the above composition to prepare a sample for evaluation by the following method, measuring flame retardancy, curability (gel time), and glass transition temperature by the following method, and the results are shown in Table 1. It was.

Curability (gel time)
0.15 g of the epoxy resin composition is placed on a cure plate (made by THERMO ELECTRIC) heated to 150 ° C., and time measurement is started with a stopwatch. Stir the sample evenly with the tip of the rod and stop the stopwatch when the sample breaks into a string and remains on the plate. The time until this sample was cut and remained on the plate was defined as the gel time.

Glass transition temperature Viscoelasticity was measured using a viscoelasticity measuring device (solid viscoelasticity measuring device RSAII manufactured by Rheometric Co., Ltd., double currant lever method; frequency 1 Hz, temperature rising rate 3 ° C./min).

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.

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

Examples 8 to 13 and Comparative Examples 3 and 4
The above A-1 as an epoxy resin and NC-3000 manufactured by Nippon Kayaku Co., Ltd. (biphenylaralkyl type epoxy resin, epoxy equivalent: 274 g / eq), (B-2) to (B-4) as polyhydric phenol compounds, (B′-1) to (B′-2) were used as comparative curing agents, triphenylphosphine (TPP) as a curing accelerator, and condensed phosphate ester (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) as a flame retardant. ), Magnesium hydroxide (Echo Mug Z-10 manufactured by Air Water Co., Ltd.), spherical silica (S-COL manufactured by Micron Co., Ltd.) as the inorganic filler, and γ-glycidoxytriethoxyxysilane (Shin-Etsu Chemical Co., Ltd.) as the silane coupling agent. KBM-403 manufactured by Kogyo Co., Ltd., Carnauba wax (Pearl Wax No. 1-P manufactured by Celalica Noda Co., Ltd.), With over carbon black were blended in the composition shown in Table 1, to obtain the desired composition was 5 minutes melt-kneaded at a temperature of 85 ° C. using two rolls. The physical properties of the cured product were prepared by preparing a sample for evaluation by the following method using the above composition and measuring the flame retardancy, curability (gel time), and glass transition temperature in the same manner as in Example 8. It is shown in Table 1.

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

Ratio Comparative Examples 5 and 6
A-2 to A-3 are used as epoxy resins, XLC-3L manufactured by Mitsui Chemicals as a curing agent (Zylock resin, hydroxyl group equivalent: 176 g / eq), triphenylphosphine (TPP) as a curing accelerator, and condensation as a flame retardant. Phosphoric ester (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.), magnesium hydroxide (Echo Mug Z-10 manufactured by Air Water Co., Ltd.), spherical silica (S-COL manufactured by Micron Co., Ltd.) as an inorganic filler, silane coupling Composition shown in Table 1 using γ-glycidoxytriethoxyxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), carnauba wax (PEARL WAX No. 1-P manufactured by Celerica Noda Co., Ltd.) and carbon black as agents. And then melted and kneaded for 5 minutes at a temperature of 85 ° C. using two rolls. A resin composition was obtained. For the physical properties of the cured product, a sample for evaluation was prepared by the following method using the above composition, and the flame retardancy and curability were measured by the following method.

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

Comparative Example 14 to 18 cases 7-9
The above A-1 as an epoxy resin, NC-3000 manufactured by Nippon Kayaku Co., Ltd. (biphenylaralkyl type epoxy resin, epoxy equivalent: 274 g / eq), B-5 to B-6 as a polyvalent hydroxy compound, and comparative curing B′-3 to B′-5 are used as agents, triphenylphosphine (TPP) as a curing accelerator, condensed phosphate ester (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.), magnesium hydroxide (air Echo Mug Z-10 manufactured by Water Co., Ltd., spherical silica (S-COL manufactured by Micron Co., Ltd.) as an inorganic filler, and γ-glycidoxytriethoxyxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent , Carnauba wax (Pearl Wax No. 1-P manufactured by Celalica Noda Co., Ltd.), carbon black Used were blended at the composition shown in Table 1, to obtain the desired composition was 5 minutes melt-kneaded at a temperature of 85 ° C. using two rolls. Regarding the physical properties of the cured product, an evaluation sample was prepared by the following method using the above composition, the flame retardancy and curability were measured by the following method, and the results are shown in Table 4.

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

1 is a GPC chart of the polyvalent hydroxy compound obtained in Example 2. FIG. FIG. 2 is a ¹³ C-NMR spectrum of the polyvalent hydroxy compound obtained in Example 2. FIG. 3 is a mass spectrum of the polyvalent hydroxy compound obtained in Example 2. 4 is a GPC chart of the polyvalent hydroxy compound obtained in Example 3. FIG. FIG. 5 is a GPC chart of the polyvalent hydroxy compound obtained in Example 4. 6 is a GPC chart of the polyvalent hydroxy compound obtained in Example 6. FIG. FIG. 7 is a ¹³ C-NMR spectrum of the polyvalent hydroxy compound obtained in Example 6. FIG. 8 is a mass spectrum of the polyvalent hydroxy compound obtained in Example 6. FIG. 9 is a GPC chart of the polyvalent hydroxy compound obtained in Example 7.

Claims (15)

The following general formula (1) per molecule

[In the formula, Ar ¹ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; X ¹ is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, a methylene group substituted with a biphenyl group, 9 -A methylene group substituted with a fluorenyl group, or a methylene group in which an alkyl group is further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group, and m is 1 or 2. ]
A structural unit represented by the following general formula (2)

[In the formula, Ar ² is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X ² is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, or naphthyl. A methylene group substituted with a group, a methylene group substituted with a biphenyl group, a methylene group substituted with a 9-fluorenyl group, or an alkyl group further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group A methylene group and n is 1 or 2; ]
An epoxy resin composition comprising a polyvalent hydroxy compound (B1) having a structural unit represented by formula (B1) and an epoxy resin (A). The following general formula (1 ′) in the general formula (1) in the polyvalent hydroxy compound (B1)

(In formula, Ar < ¹ >, m is synonymous with the said General formula (1).)
And the following general formula (2 ′) in the general formula (2)

(In the formula, Ar ² , R ¹ and n have the same meanings as in the general formula (2).)
The epoxy resin composition according to claim 1, wherein the molar ratio of the structural unit represented by the formula is in the range of the former / the latter = 30/70 to 99/1. The following general formula (3) per molecule

[In the formula, Ar ¹ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; Ar ³ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton in which a hydrocarbon group is substituted, and Y ¹ is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms And m is 1 or 2. ]
A structural unit represented by the following general formula (4):

[In the formula, Ar ² is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, Ar ⁴ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton having a hydrocarbon group substituted thereon, and Y ² is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is 1 or 2. ]
An epoxy resin composition comprising a polyvalent hydroxy compound (B2) having a structural unit represented by formula (B2) and an epoxy resin (A). The following general formula (3 ′) in the general formula (3) in the polyvalent hydroxy compound (B2)

(In the formula, Ar ¹ and m have the same meaning as in the general formula (3).)
And the following general formula (4 ′) in the general formula (4):

(In the formula, Ar ² , R ¹ and n have the same meanings as in the general formula (4).)
The epoxy resin composition according to claim 3, wherein the molar ratio with the structural unit represented by the formula is in the range of the former / the latter = 30/70 to 99/1. Furthermore, the epoxy resin composition as described in any one of Claims 1-4 containing a non-halogen-type flame retardant.   Furthermore, the semiconductor sealing material which consists of an epoxy resin composition as described in any one of Claims 1-4 containing an inorganic filler. A cured product obtained by curing the epoxy resin composition according to claim 1. The following general formula (1) per molecule

[In the formula, Ar ₁ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; X ₁ is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, a methylene group substituted with a biphenyl group, 9 -A methylene group substituted with a fluorenyl group, or a methylene group in which an alkyl group is further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group, and m is 1 or 2. ]
A structural unit represented by the following general formula (2)

[In the formula, Ar ₂ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X ₂ is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, or naphthyl. A methylene group substituted with a group, a methylene group substituted with a biphenyl group, a methylene group substituted with a 9-fluorenyl group, or an alkyl group further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group A methylene group and n is 1 or 2; ]
The hydroxyl group equivalent is 100-500 g / eq. And having a melt viscosity at 150 ° C. measured by an ICI viscometer in the range of 0.2 to 5.0 dPa · s, a novel polyvalent hydroxy compound (B1). The polyvalent hydroxy compound (B1), wherein the hydroxy group-containing aromatic compound (a1), the thioether group-containing aromatic compound (a2), and the carbonyl group-containing compound (a3) are reacted in the presence of an acid catalyst. Manufacturing method. The molar ratio (a1) / (a2) between the hydroxy group-containing aromatic compound (a1) and the thioether group-containing aromatic compound (a2) is 30/70 to 99/1, and the hydroxy group-containing aromatic The ratio {(a1) + (a2)} / (a3) of the total number of moles of the compound (a1) and the thioether group-containing aromatic compound (a2) to the number of moles of the carbonyl group-containing compound (a3) is 50. The production method according to claim 9, which is / 50 to 97/3. 11. The hydroxy group-containing aromatic compound (a1), the thioether group-containing aromatic compound (a2), and the carbonyl group-containing compound (a3) are mixed, and then the mixture is heated to react. Manufacturing method. The following general formula (3) per molecule

[In the formula, Ar ¹ is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms; Ar ³ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton in which a hydrocarbon group is substituted, and Y ¹ is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms And m is 1 or 2. ]
A structural unit represented by the following general formula (4):

[In the formula, Ar ² is an aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or an alkoxy group having 1 to 10 carbon atoms, Ar ⁴ is a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic skeleton having a hydrocarbon group substituted thereon, and Y ² is the same or different hydrogen atom or hydrocarbon having 1 to 6 carbon atoms R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is 1 or 2. ]
The hydroxyl group equivalent is 150-500 g / eq. And having a melt viscosity at 150 ° C. measured with an ICI viscometer in the range of 0.2 to 5.0 dPa · s, a novel polyvalent hydroxy compound (B2). The polyvalent hydroxy compound (B2), wherein the hydroxy group-containing aromatic compound (a1), the thioether group-containing aromatic compound (a2), and the aromatic crosslinking agent (a3) are reacted in the presence of an acid catalyst. ) Manufacturing method. The molar ratio (a1) / (a2) between the hydroxy group-containing aromatic compound (a1) and the thioether group-containing aromatic compound (a2) is 30/70 to 99/1, and the hydroxy group-containing aromatic The ratio {(a1) + (a2)} / (a3) of the total number of moles of the aromatic compound (a1) and the thioether group-containing aromatic compound (a2) and the number of moles of the aromatic crosslinking agent (a3) is The production method according to claim 13, which is 51/49 to 97/3. The hydroxy group-containing aromatic compound (a1), the thioether group-containing aromatic compound (a2), and the aromatic crosslinking agent (a3) are mixed, and then the mixture is heated to react. The manufacturing method as described.

Images