JP2010126693A - Asymmetric type multifunctional hydroxyl group-containing condensed ring structure compound and condensed ring structure-containing resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a functional multifunctional hydroxyl group-containing compound which gives cured products having optical characteristics, heat resistance and electric characteristics at high levels, has a low melting point, and is excellent in compatibility and flexibility, to provide an epoxy resin, to provide an epoxy ester resin, and to provide an alkali-soluble type resin. <P>SOLUTION: There are provided the multifunctional hydroxyl group-containing compound containing a condensed ring structure and further having an asymmetric structure; the epoxy resin; the epoxy ester resin, and the alkali-soluble type resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a novel polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound having heat and radiation curability, a condensed ring structure-containing asymmetric epoxy resin, a condensed ring structure-containing asymmetric epoxy ester resin, and a condensed ring structure-containing asymmetric alkali-soluble resin. The present invention relates to a method for producing the resin, and a thermosetting or radiation curable resin composition containing the resin. Furthermore, this invention relates to the molded object which is excellent in heat resistance, an electrical property, etc. obtained using this resin composition. Specifically, the present invention relates to a polyfunctional hydroxyl group-containing compound, an epoxy resin, an epoxy ester resin, and an alkali-soluble resin useful for preparing a resin composition having a high refractive index and excellent transparency. More specifically, the present invention relates to a polyfunctional hydroxyl group-containing compound, an epoxy resin, an epoxy ester resin, and an alkali-soluble resin useful for preparing a resin composition in which an organic pigment, inorganic fine particles, and the like are dispersed. Furthermore, the present invention is a thermosetting or radiation-sensitive resin composition containing the polyfunctional hydroxyl group-containing compound, epoxy resin, epoxy ester resin, and alkali-soluble resin, and includes a color filter, a liquid crystal display element, an integrated circuit element, The present invention relates to a composition useful for preparing a protective film or an interlayer insulating film in a solid-state imaging device or the like.

Generally, a polyfunctional hydroxyl group-containing compound or an epoxy resin is cured with various curing agents to form a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. Therefore, it is used in a wide range of fields such as adhesives, paints, laminates, molding materials and casting materials. Conventionally, bisphenol A is an industrially most used polyfunctional hydroxyl group-containing compound, and epoxy resins include liquid and solid bisphenol A type epoxy resins that are derivatives of bisphenol A. As an epoxy functional polymer material, an epoxy ester resin typified by an epoxy acrylate resin has been widely used. This resin is used in the field of, for example, a photosensitive material (for example, Non-Patent Document 1). However, these resins are insufficient in heat resistance, electrical characteristics and hardness, and are insufficient in, for example, the electronic material field where high level optical characteristics, electrical characteristics and heat resistance are required.
In response to these requirements, for example, epoxy resins and epoxy acrylate resins using a polyfunctional hydroxyl group-containing compound having a fluorene skeleton as a starting material have been proposed, and a high level of characteristics derived from the fluorene skeleton has been realized. (Patent Documents 1 and 2). However, since the fluorene skeleton has a rigid and highly crystalline property, the fluorene skeleton-containing polyfunctional hydroxyl group-containing compound, the fluorene skeleton-containing epoxy resin, etc. are particularly poorly compatible with various materials, and have a high melting point. Composition preparation, molding preparation, and various modifications may be difficult. In addition, since the fluorene skeleton is rigid and poor in polarity, various characteristics such as optical characteristics, heat resistance, and electrical characteristics improve as the ratio of introduction of the skeleton increases in resin production, but the obtained resin is flexible. There are problems with mechanical properties, such as poorness and brittleness. These may be improved by introducing other components at the time of resin production or compounding of various compositions, but as a result, the content of the fluorene skeleton is reduced, and optical properties, heat resistance and electrical properties are reduced. Good characteristics such as characteristics are lost. Therefore, there is a demand for a functional resin excellent in compatibility with optical properties, heat resistance, electrical properties, mechanical properties, and various materials that can meet higher level requirements in recent years.
Alkali-soluble resins and alkali-soluble radiation-polymerizable resins in which epoxy ester resins such as epoxy acrylate resins are modified with polybasic carboxylic acid anhydrides from bisphenol A type epoxy resins and cresol novolak type epoxy resins. Unsaturated resins have been studied as photosensitive and dispersing resins for color resists for producing solder resists and liquid crystal color filters (Patent Documents 3, 4, and 5). These are excellent in heat resistance, electrical characteristics, transparency and the like, but are insufficient for the higher level requirements in recent years.

JP-A 63-165378 JP 7-48424 A Japanese Patent Laid-Open No. 04-194492 Japanese Patent Laid-Open No. 06-93082 JP-A-7-207211 Akio Yamaoka and Hiroshi Morita "Photosensitive resin", Kyoritsu Shuppan, first published in March 1988, pp. 82-84

The object of the present invention is to solve the above-mentioned conventional problems, and the object is that the cured product has high-level optical characteristics, heat resistance and electrical characteristics, and has a low melting point and compatibility. The object is to provide a functional polyfunctional hydroxyl group-containing compound, an epoxy resin, an epoxy ester resin, and an alkali-soluble resin excellent in flexibility. Another object of the present invention is to provide a method for producing the resin and a thermosetting or radiation-sensitive composition containing the resin. Still another object of the present invention is to provide a molded article obtained by curing such a resin composition.

As a result of intensive studies, the present inventors have found that polyfunctional hydroxyl group-containing compounds, epoxy resins, epoxy ester resins, and alkali-soluble resins containing a certain condensed ring structure and asymmetric structure have a high refractive index. In addition to being excellent in heat resistance and transparency, it has been found that it has a low melting point and is excellent in compatibility and flexibility.
The polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound of the present invention is represented by the following general formula (1):

ここで一般式（１）のＸ_１は、各々独立して下記一般式（２）で示される基であり、ｒ_１〜２は各々独立して１から５までの整数である。

ここで前記一般式（１）のＺは、六員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つ以上の芳香環との縮環構造、または、五員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つの芳香環との縮環構造を含む二価基であり、Ｒ_１〜２は各々独立して炭素数１から１０の直鎖状、分岐状または環状のアルキル基若しくはアルケニル基、炭素数１から５のアルコキシ基、置換基を有していてもよいフェニル基、又はハロゲン原子、ｆ_１〜２は各々独立して０から４の整数である。さらに、前記一般式（２）のＲ_３は、水素原子またはメチル基、ｍ_１は０から１０の整数である。また、複数個のＲ_１〜３、Ｘ_１、ｍ_１は同一でも良いし、異なっていても良い。
但し、一般式（１）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、及び、（Ｘ_１）ｒ_１と（Ｘ_１）ｒ_２の置換位置のうち少なくとも１つが異なる。

Here, X ₁ in the general formula (1) is each independently a group represented by the following general formula (2), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z in the general formula (1) is a condensed structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings, or five-membered It is a divalent group containing a condensed ring structure of a ring alicyclic compound (which may contain atoms other than carbon on the ring) and one aromatic ring, and R _1-2 are each independently from 1 carbon atom. 10 linear, branched or cyclic alkyl groups or alkenyl groups, an alkoxy group having 1 to 5 carbon atoms, an optionally substituted phenyl group, or a halogen atom, and f _1-2 are each independently It is an integer from 0 to 4. Furthermore, R _{3 in the} general formula (2) is a hydrogen atom or a methyl group, and m ₁ is an integer of 0 to 10. Further, a plurality of _{R 1~3,} X _{1, m} 1 is may be the same or may be different.
However, the types of R ₁ and R ₂ in general formula (1), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (X ₁ ) r ₁ and (X ₁ ) r ₂ at least one of the substitution positions is different.

In a more preferred embodiment of the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound of the present invention, in the general formula (1), f ₁ is an integer of 1 or more, and at least one of f ₁ R ₁ is present. Is a polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound in which is a halogen atom, an alkyl or alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

In a more preferred embodiment of the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound of the present invention, Z in formula (1) contains a condensed ring structure selected from the group consisting of formulas (3) to (7). A valent group, more preferably a divalent group containing a condensed ring structure represented by formula (3). In another preferred embodiment, in Formulas (1) to (2), f _1-2 and m ₁ are each independently an integer of 0 to 2, and r 1-2 are each independently 1 to 2 Is an integer.

The present invention includes a resin composition containing the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound.

The present invention includes a molded article obtained by curing the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound.

The condensed ring structure-containing asymmetric epoxy resin of the present invention is represented by the following general formula (8).

ここで一般式（８）のＹ_１〜２は各々独立して、下記一般式（９）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで一般式（９）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（１１）で示される基である。さらに、一般式（９）のＹ_３〜４は、一般式（９）及び下記一般式（１１）から各々独立して選ばれる基であり、ｐ_１〜２は各々独立して０から４の整数である。

ここで前記一般式（８）、（９）のＺは、六員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つ以上の芳香環との縮環構造、または、五員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つの芳香環との縮環構造を含む二価基であり、Ｒ_１〜２は各々独立して、炭素数１から１０の直鎖状、分岐状または環状のアルキル基若しくはアルケニル基、炭素数１から５のアルコキシ基、置換基を有していてもよいフェニル基、又はハロゲン原子、ｆ_１〜２は各々独立して０から４の整数である。さらに、前記一般式（９）、（１０）、（１１）のＲ_４〜６は各々独立して水素原子またはメチル基、ｍ_２〜４、ｓ_１は各々独立して０から１０の整数である。また、複数個のＲ_１〜２、Ｙ_１〜５、Ａ_１、ｆ_１〜２、ｐ_１〜２、ｓ_１、Ｒ_４〜６、ｍ_２〜４は同一でも良いし、異なっていても良い。
但し、一般式（８）、（９）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、（Ｙ_１）ｒ_１と（Ｙ_２）ｒ_２の置換位置、ｐ_１とｐ_２の数値、及びＡ_１、（Ｙ_３）ｐ_１とＹ_５、（Ｙ_４）ｐ_２の置換位置うち少なくとも１つが異なる。

Here, Y _1-2 in the general formula (8) are each independently a group represented by the following general formula (9), and r _1-2 are each independently an integer of 1-5.

Here, A ₁ in the general formula (9) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (11). Furthermore, Y _{<3> -4} of General formula (9) is group respectively independently selected from General formula (9) and following General formula (11), and p _<1-2> is each independently _0-4 . It is an integer.

Here, Z in the general formulas (8) and (9) is a condensed ring structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings, Or a divalent group containing a condensed ring structure of a five-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one aromatic ring, and R _1-2 are each independently A linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an optionally substituted phenyl group, or a halogen atom, f _{1- 2} is an integer of 0 to 4 each independently. Further, R _{4 to 6 in the} general formulas (9), (10) and (11) are each independently a hydrogen atom or a methyl group, m _{2 to 4} and s ₁ are each independently an integer of 0 to 10. is there. A plurality of R _1-2 , Y _1-5 , A ₁ , f _1-2 , p _1-2 , s ₁ , R _4-6 , m _2-4 may be the same or different. good.
However, the types of R ₁ and R _{2 in} the general formulas (8) and (9), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , (R ₁ ) f ₁ and (R ₂ ) f ₂ substitution _{position, (Y 1) r} 1 and _(Y 2) substitution position of _{r 2,} numerical values of _{p 1} and _{p 2,} and _{a 1, (Y 3) p} 1 and _{Y 5,} substitution of _(Y 4) _{p 2} At least one of the positions is different.

The condensed ring structure-containing asymmetric epoxy resin of the present invention is obtained from a production method including a step of allowing an epihalohydrin to act on the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound represented by the general formula (1). The resin represented by the formula (8) is obtained by, for example, a process (manufacturing method) including this step.

One preferred embodiment of the condensed ring structure-containing asymmetric epoxy resin of the present invention is as follows. In the condensed ring structure-containing asymmetric epoxy resin of the general formula (8), r _1-2 is 1, and p _1-2 is 0. General formula (12) is mentioned.

ここで一般式（１２）のＹ_６〜７は各々独立して、下記一般式（１３）で示される基である。

ここで一般式（１３）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（１１）で示される基である。

ここで、一般式（１２）、（１３）、（１０）、（１１）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_４〜６、ｍ_２〜４、ｓ_１は前記と同じであり、複数個のＲ_１〜２、ｆ_１〜２、Ａ_１、ｓ_１、Ｒ_４〜６、ｍ_２〜４は同一でも良いし、異なっていても良い。
但し、一般式（１２）、（１３）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、（Ｒ_１）ｆ_２と（Ｒ_２）ｆ_２の置換位置、Ｙ_６とＹ_７の置換位置、及びＡ_１とＹ_５の置換位置のうち少なくとも１つが異なる。

Here, Y _6-7 in the general formula (12) are each independently a group represented by the following general formula (13).

Here, A ₁ in the general formula (13) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (11).

Here, Z, R _1-2 , f _1-2 , R _4-6 , m _2-4 , and s ₁ in the general formulas (12), (13), (10), and (11) are the same as described above. Yes, a plurality of R _1-2 , f _1-2 , A ₁ , s ₁ , R _4-6 , m _2-4 may be the same or different.
However, the types of R ₁ and R _{2 in} the general formulas (12) and (13), the numerical values of f ₁ and f ₂ , the substitution positions of (R ₁ ) f ₂ and (R ₂ ) f ₂ , Y ₆ and Y ₇ And at least one of the substitution positions of A ₁ and Y ₅ is different.

Another preferred embodiment of the condensed ring structure-containing asymmetric epoxy resin of the present invention includes the following general formula (14) in which s ₁ is 0 in the condensed ring structure-containing asymmetric epoxy resin of the general formula (8). It is done.

ここで一般式（１４）のＹ_５は各々独立して、下記一般式（１１）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで、一般式（１４）、（１１）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_６、ｍ_４は前記と同じであり、複数個のＲ_１〜２、Ｙ_５、Ｒ_６、ｍ_４は同一でも良いし、異なっていても良い。
但し、一般式（１４）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、及び、（Ｙ_５）ｒ_１と（Ｙ_５）ｒ_２の置換位置のうち少なくとも１つが異なる。

Here, Y ₅ in the general formula (14) is each independently a group represented by the following general formula (11), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z, R _<1-2> , f _<1-2> , R _{< 6 >} , m < _{4 > of} General formula (14), (11) is the same as the above, and several R _<1-2> , Y < _{5 >} , R _{< 6 >} . , M ₄ may be the same or different.
However, the types of R ₁ and R ₂ of the general formula (14), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (Y ₅ ) r ₁ and (Y ₅ ) r ₂ at least one of the substitution positions is different.

As one of the more preferable embodiments of the condensed ring structure-containing asymmetric epoxy resin of the present invention, there are a plurality of f _{1 in the} general formulas (8), (9), (12), (13), and (14). And f ₂ , at least one is an integer of 1 or more, and at least one of f ₁ R ₁ or f ₂ R ₂ is a halogen atom, an alkyl or alkenyl group having 2 to 5 carbon atoms, Or the condensed ring structure containing asymmetric epoxy resin which is a C1-C5 alkoxy group is mentioned.

In a more preferred embodiment of the condensed ring structure-containing asymmetric epoxy resin of the present invention, Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably a formula It is a bivalent group containing the condensed ring structure which is (3).

In another more preferred embodiment, in formulas (8) to (14), p _1-2 and f _1-2 are each independently an integer of 0 to 2, and m _1-4 are each independently. And an integer from 0 to 2, r _1-2 are each independently an integer from 1 to 2, and s ₁ are each independently an integer from 0 to 8.

The manufacturing method of the condensed ring structure containing asymmetric epoxy resin of this invention includes the process of making an epihalohydrin act on the polyfunctional hydroxyl group containing asymmetric condensed ring structure compound shown by the above-mentioned general formula (1).

Of the epihalohydrins, epichlorohydrin is preferably used.

The epoxy resin composition of the present invention contains the above condensed ring structure-containing asymmetric epoxy resin.

The present invention includes a molded product obtained by curing the epoxy resin composition.

The condensed ring structure-containing asymmetric epoxy ester resin of the present invention is represented by the following general formula (15).
In addition, the condensed ring structure containing asymmetric epoxy ester resin of this invention includes a condensed ring structure containing asymmetric epoxy acrylate resin.

ここで一般式（１５）のＹ_１〜２は各々独立して、下記一般式（１６）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで一般式（１６）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（１７）で示される基である。さらに、一般式（１６）のＹ_３〜４は、一般式（１６）及び下記一般式（１７）から各々独立して選ばれる基であり、ｐ_１〜２は各々独立して０から４の整数である。

ここで前記一般式（１５）、（１６）のＺは、六員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つ以上の芳香環との縮環構造、または、五員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つの芳香環との縮環構造を含む二価基であり、Ｒ_１〜２は各々独立して、炭素数１から１０の直鎖状、分岐状または環状のアルキル基若しくはアルケニル基、炭素数１から５のアルコキシ基、置換基を有していてもよいフェニル基、又はハロゲン原子、ｆ_１〜２は各々独立して０から４の整数である。さらに、前記一般式（１０）、（１７）のＲ_４〜６は各々独立して水素原子またはメチル基、Ｒ_７は単塩基性カルボン酸に由来する部位を含む基を示し、ｍ_２〜４、ｓ_１は各々独立して０から１０の整数である。また、複数個のＲ_１〜２、ｆ_１〜２、ｓ_１、Ｒ_４〜７、Ａ_１、Ｙ_１〜５、ｐ_１〜２、ｍ_２〜４は同一でも良いし、異なっていても良い。
但し、一般式（１５）、（１６）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、（Ｙ_１）ｒ_１と（Ｙ_２）ｒ_２の置換位置、ｐ_１とｐ_２の数値、及びＡ_１、（Ｙ_３）ｐ_１とＹ_５、（Ｙ_４）ｐ_２の置換位置のうち少なくとも１つが異なる。

Here, Y _1-2 in the general formula (15) are each independently a group represented by the following general formula (16), and r _1-2 are each independently an integer of 1-5.

Here, A ₁ in the general formula (16) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (17). Furthermore, Y _{<3> -4} of General formula (16) is group respectively independently selected from General formula (16) and following General formula (17), and p _<1-2> is respectively independently _0-4 . It is an integer.

Here, Z in the general formulas (15) and (16) represents a condensed ring structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings, Or a divalent group containing a condensed ring structure of a five-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one aromatic ring, and R _1-2 are each independently A linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an optionally substituted phenyl group, or a halogen atom, f _{1- 2} is an integer of 0 to 4 each independently. In the general formulas (10) and (17), R _{4 to 6} each independently represent a hydrogen atom or a methyl group, R ₇ represents a group containing a site derived from a monobasic carboxylic acid, and m _{2 to 4} , S ₁ are each independently an integer from 0 to 10. A plurality of R _1-2 , f _1-2 , s ₁ , R _4-7 , A ₁ , Y _1-5 , p _1-2 , m _2-4 may be the same _or different. good.
However, the types of R ₁ and R _{2 in} the general formulas (15) and (16), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , (R ₁ ) f ₁ and (R ₂ ) f ₂ substitution _{position, (Y 1) r} 1 and _(Y 2) substitution position of _{r 2,} numerical values of _{p 1} and _{p 2,} and _{a 1, (Y 3) p} 1 and _{Y 5,} substitution of _(Y 4) _{p 2} At least one of the positions is different.

The condensed ring structure-containing asymmetric epoxy ester resin of the present invention comprises a step of reacting a condensed ring structure-containing asymmetric epoxy resin represented by the general formulas (8), (12), and (14) with a monobasic carboxylic acid. The resin represented by the general formula (15) is obtained from, for example, a process (manufacturing method) including this step, or a polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound represented by the general formula (1). It is obtained by a process (manufacturing method) including a step of allowing glycidyl basic carboxylate to act.

In a preferred embodiment of the condensed ring structure-containing asymmetric epoxy ester resin obtained by the above process (production method), the general formulas (1), (8), (9), (12), Z in (13) and (14) includes a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably a condensed ring structure represented by formula (3). It is a divalent group.
In another preferred embodiment, p _1-2 and f _1-2 in the general formulas (1) to (14) in the above process (manufacturing method) are each independently an integer of 0 to 2, m _{1 -4} are each independently an integer from 0 to 2, and r _1-2 are each independently an integer from 1 to 2, and s ₁ is an integer from 0 to 8.

In one preferred embodiment of the condensed ring structure-containing asymmetric epoxy ester resin of the present invention, r _1-2 is 1 and p _1-2 is 0 in the condensed ring structure-containing asymmetric epoxy ester resin of the general formula (15). The following general formula (18) is mentioned.

ここで一般式（１８）のＹ_６〜７は各々独立して、下記一般式（１９）で示される基である。

ここで一般式（１９）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（１７）で示される基である。

ここで、一般式（１８）、（１９）、（１０）、（１７）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_４〜６、ｍ_２〜４、Ｒ_７、ｓ_１は前記と同じであり、複数個のＲ_１〜２、ｆ_１〜２、ｓ_１、Ａ_１、Ｙ_５、Ｒ_４〜６、ｍ_２〜４、Ｒ_７は同一でも良いし、異なっていても良い。
但し、一般式（１８）、（１９）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、（Ｒ_１）ｆ_２と（Ｒ_２）ｆ_２の置換位置、Ｙ_６とＹ_７の置換位置、及びＡ_１とＹ_５の置換位置のうち少なくとも１つが異なる。

Here, Y _6-7 in the general formula (18) are each independently a group represented by the following general formula (19).

Here, A ₁ in the general formula (19) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (17).

Here, Z, R _1-2 , f _1-2 , R _4-6 , m _2-4 , R ₇ , s ₁ in the general formulas (18), (19), (10), (17) A plurality of R _1-2 , f _1-2 , s ₁ , A ₁ , Y ₅ , R _4-6 , m _2-4 , R ₇ may be the same or different. .
However, the types of R ₁ and R _{2 in} the general formulas (18) and (19), the numerical values of f ₁ and f ₂ , the substitution positions of (R ₁ ) f ₂ and (R ₂ ) f ₂ , Y ₆ and Y ₇ And at least one of the substitution positions of A ₁ and Y ₅ is different.

As another preferred embodiment of the condensed ring structure-containing asymmetric epoxy ester resin of the present invention, s ₁ is 0 in the condensed ring structure-containing asymmetric epoxy ester resin of the general formula (15). Is mentioned.

ここで一般式（２０）のＹ_５は下記一般式（１７）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで、一般式（２０）、（１７）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_６、Ｒ_７、ｍ_４は前記と同じであり、複数個のＲ_１〜２、Ｙ_５、Ｒ_６、Ｒ_７、ｍ_４は同一でも良いし、異なっていても良い。
但し、一般式（２０）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、及び、（Ｙ_５）ｒ_１と（Ｙ_５）ｒ_２の置換位置のうち少なくとも１つが異なる。

Here, Y ₅ in the general formula (20) is a group represented by the following general formula (17), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z, R _1-2 , f _1-2 , R ₆ , R ₇ , m ₄ in the general formulas (20) and (17) are the same as described above, and a plurality of R _1-2 , Y ₅ , R ₆ , R ₇ and m ₄ may be the same or different.
However, the types of R ₁ and R _{2 in} the general formula (20), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (Y ₅ ) r ₁ and (Y ₅ ) r ₂ at least one of the substitution positions is different.

As one preferred embodiment of the condensed ring structure-containing asymmetric epoxy ester resin, the condensed ring structure-containing asymmetric epoxy ester resin has an unsaturated group at a site derived from a monobasic carboxylic acid, and has radiation polymerization properties. Examples thereof include an asymmetric epoxy ester resin having a condensed ring structure. These are particularly asymmetric epoxy acrylate resins containing a condensed ring structure, and are shown below.

The condensed ring structure-containing asymmetric epoxy acrylate resin of the present invention is represented by the following general formula (21).
This is an asymmetric epoxy ester resin containing a condensed ring structure in which R ₇ is a group having an unsaturated group in the general formula (15). Here, the unsaturated group is an ethenyl group or a 2-propenyl group.

ここで一般式（２１）のＹ_１〜２は、下記一般式（２２）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで一般式（２２）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（２３）で示される基である。さらに、一般式（２２）のＹ_３〜４は、一般式（２２）及び下記一般式（２３）から各々独立して選ばれる基であり、ｐ_１〜２は各々独立して０から４の整数である。

ここで前記一般式（２１）、（２２）、（１０）、（２３）のＺ、Ｒ_１〜２、Ｒ_４〜６、ｆ_１〜２、ｍ_２〜４、ｓ_１は前記と同じである。さらに、前記一般式（２３）のＲ_８は各々独立して水素原子またはメチル基を示す。また、複数個のＲ_１〜２、ｆ_１〜２、ｓ_１、ｐ_１〜２、Ｒ_４〜６、Ｒ_８、Ｙ_１〜５、ｍ_２〜４は同一でも良いし、異なっていても良い。
但し、一般式（２１）、（２２）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、（Ｙ_１）ｒ_１と（Ｙ_２）ｒ_２の置換位置、ｐ_１とｐ_２の数値、及びＡ_１、（Ｙ_３）ｐ_１とＹ_５、（Ｙ_４）ｐ_２の置換位置のうち少なくとも１つが異なる。

Here, Y _1-2 in the general formula (21) is a group represented by the following general formula (22), and r _1-2 are each independently an integer of 1-5.

Here, A ₁ in the general formula (22) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (23). Further, Y _3-4 in the general formula (22) are groups independently selected from the general formula (22) and the following general formula (23), and p _1-2 are each independently 0 to 4 It is an integer.

Here, Z, R _1-2 , R _4-6 , f _1-2 , m _2-4 , and s ₁ in the general formulas (21), (22), (10), and (23) are the same as described above. is there. Further, R _{8 in the} general formula (23) each independently represents a hydrogen atom or a methyl group. A plurality of R _1-2 , f _1-2 , s ₁ , p _1-2 , R _4-6 , R ₈ , Y _1-5 , m _2-4 may be the same or different. good.
However, the types of R ₁ and R _{2 in} the general formulas (21) and (22), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , (R ₁ ) f ₁ and (R ₂ ) f ₂ substitution _{position, (Y 1) r} 1 and _(Y 2) substitution position of _{r 2,} numerical values of _{p 1} and _{p 2,} and _{a 1, (Y 3) p} 1 and _{Y 5,} substitution of _(Y 4) _{p 2} At least one of the positions is different.

One preferred embodiment includes the following general formula (24) in which r _1-2 is 1 and p _1-2 is 0 in the condensed ring structure-containing asymmetric epoxy acrylate resin of the general formula (21).

ここで一般式（２４）のＹ_６〜７は各々独立して、下記一般式（２５）で示される基である。

ここで一般式（２５）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（２３）で示される基である。

ここで、一般式（２４）、（２５）、（１０）、（２３）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_４〜６、ｍ_２〜４、Ｒ_８、ｓ_１は前記と同じであり、複数個のＲ_１〜２、Ａ_１、Ｙ_５、ｆ_１〜２、ｓ_１、Ｒ_４〜６、ｍ_２〜４、Ｒ_８は同一でも良いし、異なっていても良い。
但し、一般式（２４）、（２５）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、（Ｒ_１）ｆ_２と（Ｒ_２）ｆ_２の置換位置、Ｙ_６とＹ_７の置換位置、及びＡ_１とＹ_５の置換位置のうち少なくとも１つが異なる。

Here, Y _6-7 in the general formula (24) are each independently a group represented by the following general formula (25).

Here, A ₁ in the general formula (25) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (23).

Here, Z, R _1-2 , f _1-2 , R _4-6 , m _2-4 , R ₈ , s ₁ in the general formulas (24), (25), (10), (23) The plurality of R _1-2 , A ₁ , Y ₅ , f _1-2 , s ₁ , R _4-6 , m _2-4 , R ₈ may be the same or different. .
However, the types of R ₁ and R _{2 in} the general formulas (24) and (25), the numerical values of f ₁ and f ₂ , the substitution positions of (R ₁ ) f ₂ and (R ₂ ) f ₂ , Y ₆ and Y ₇ And at least one of the substitution positions of A ₁ and Y ₅ is different.

Still another preferred embodiment is the following general formula (26) in which s ₁ is 0 in the condensed ring structure-containing asymmetric epoxy acrylate resin of the general formula (21).

ここで一般式（２６）のＹ_５は下記一般式（２３）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで、一般式（２６）、（２３）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_６、Ｒ_８、ｍ_４は前記と同じであり、複数個のＲ_１〜２、Ｙ_５、Ｒ_６、Ｒ_８、ｍ_４は同一でも良いし、異なっていても良い。
但し、一般式（２６）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、及び、（Ｙ_５）ｒ_１と（Ｙ_５）ｒ_２の置換位置のうち少なくとも１つが異なる。

Here, Y ₅ in the general formula (26) is a group represented by the following general formula (23), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z, R _1-2 , f _1-2 , R ₆ , R ₈ , m ₄ in the general formulas (26) and (23) are the same as described above, and a plurality of R _1-2 , Y ₅ , R ₆ , R ₈ and m ₄ may be the same or different.
However, the types of R ₁ and R _{2 in} the general formula (26), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (Y ₅ ) r ₁ and (Y ₅ ) r ₂ at least one of the substitution positions is different.

In a preferred embodiment of the condensed ring structure-containing asymmetric epoxy ester resin of the present invention, general formulas (15), (16), (18), (19), (20), (21), (22), ( In 24), (25), and (26), Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably Z is represented by formula (3). It is a divalent group containing a condensed ring structure.

In another preferred embodiment, in general formulas (15) to (26), p _1-2 and f _1-2 are each independently an integer of 0 to 2, and m _1-4 are each independently. And r _1-2 are each independently an integer of 1 to 2, and s ₁ is an integer of 0 to 8.

The first production method of the condensed ring structure-containing asymmetric epoxy ester resin of the present invention is the condensed ring structure-containing asymmetric epoxy resin represented by the general formulas (8), (12) and (14), or the general formula ( 1) It includes the step of allowing a monobasic carboxylic acid to act on the condensed structure-containing asymmetric epoxy resin obtained from the production method including the step of allowing epihalohydrin to act on the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound of 1).

In a preferred embodiment, in General Formulas (1) to (14), Z is a divalent group containing a condensed ring structure selected from the group consisting of Formulas (3) to (7), more preferably, Z is a formula. (3) is a divalent group containing a condensed ring structure, p _1-2 and f _1-2 are each independently an integer of 0 to 2, m _1-4 are each independently 0 to 2 An integer, and r _1-2 are each independently an integer of 1 to 2, and s ₁ is an integer of 0 to 8.

In another preferred embodiment, the monobasic carboxylic acid is (meth) acrylic acid, whereby the condensed ring structure-containing asymmetric epoxy acrylate resin is obtained.

The second production method of the condensed ring structure-containing asymmetric epoxy ester resin of the present invention comprises a step of allowing a monobasic glycidyl carboxylate to act on the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound represented by the general formula (1). Include.

In a preferred embodiment, in the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound represented by the general formula (1), Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7). More preferably, Z is a divalent group containing a condensed ring structure represented by the formula (3), f _1-2 and m ₁ are each independently an integer of 0 to 2, and r _1-2 are each independently It is an integer from 1 to 2.

In another preferred embodiment, the monobasic carboxylic acid is glycidyl (meth) acrylate, whereby the condensed ring structure-containing asymmetric epoxy acrylate resin is obtained.

The epoxy ester resin composition of the present invention contains the above condensed ring structure-containing asymmetric epoxy ester resin, and is a thermosetting or radiation sensitive composition.

The present invention includes a molded product obtained by curing the epoxy ester resin composition.

The condensed ring structure-containing asymmetric alkali-soluble resin of the present invention is a condensed ring structure-containing asymmetric epoxy ester represented by the formula (15), (18), (20), (21), (24), or (26). It can be obtained by reacting a resin with a polybasic carboxylic acid or its anhydride.

In a preferred embodiment, in the above general formulas (15), (16), (18), (19), (20), (21), (22), (24), (25), (26) Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably a divalent group containing a condensed ring structure represented by formula (3).
In another preferred embodiment, in formulas (15) to (26), p _1-2 and f _1-2 are each independently an integer of 0 to 2, and m _1-4 are each independently And an integer from 0 to 2, and r _1-2 are each independently an integer from 1 to 2, and an integer from s ₁ 0 to 8.

One preferred embodiment of the condensed ring structure-containing asymmetric alkali-soluble resin of the present invention is a condensed ring structure-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin. The condensed ring structure-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin refers to a condensed ring-structure-containing asymmetric alkali-soluble resin having an unsaturated group having radiation polymerization in the molecule. For example, the condensed ring structure-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin is a polybasic carboxylic acid added to the condensed ring structure-containing asymmetric epoxy acrylate resin represented by the formulas (21), (24), and (26). Or it is obtained by making the anhydride react.

As a more preferred embodiment, there is a condensed ring structure-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin in which the radiation-polymerizable unsaturated group is an ethenyl group.

The method for producing the condensed ring structure-containing asymmetric alkali-soluble resin and the condensed ring structure-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin of the present invention has the general formulas (15), (18), (20), (21 ), (24), and (26), a step of reacting the condensed ring-containing asymmetric epoxy ester resin with a polybasic carboxylic acid or an anhydride thereof.

The radiation-sensitive alkali-soluble resin composition of the present invention contains the condensed ring structure-containing asymmetric alkali-soluble resin or the condensed ring structure-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin.

The present invention includes a molded product obtained by curing the radiation-sensitive alkali-soluble resin composition.

The epoxy resin composition, the condensed ring structure-containing asymmetric epoxy ester resin composition, and the radiation-sensitive alkali-soluble resin composition of the present invention preferably contain an organic pigment and / or inorganic fine particles.

The present invention includes a molded product obtained by curing the resin composition containing the organic pigment and / or inorganic fine particles.

The present invention is described in detail below.
D. Polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound

The polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound of the present invention is represented by the following general formula (1):

ここで一般式（１）のＸ_１は、各々独立して下記一般式（２）で示される基であり、ｒ_１〜２は各々独立して１から５までの整数である。

ここで前記一般式（１）のＺは、六員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つ以上の芳香環との縮環構造、または、五員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つの芳香環との縮環構造を含む二価基であり、Ｒ_１〜２は各々独立して炭素数１から１０の直鎖状、分岐状または環状のアルキル基若しくはアルケニル基、炭素数１から５のアルコキシ基、置換基を有していてもよいフェニル基、又はハロゲン原子、ｆ_１〜２は各々独立して０から４の整数である。さらに、前記一般式（２）のＲ_３は、水素原子またはメチル基、ｍ_１は０から１０の整数である。また、複数個のＲ_１〜３、Ｘ_１、ｍ_１は同一でも良いし、異なっていても良い。
但し、一般式（１）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、及び、（Ｘ_１）ｒ_１と（Ｘ_１）ｒ_２の置換位置のうち少なくとも１つが異なる。

Here, X ₁ in the general formula (1) is each independently a group represented by the following general formula (2), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z in the general formula (1) is a condensed structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings, or five-membered It is a divalent group containing a condensed ring structure of a ring alicyclic compound (which may contain atoms other than carbon on the ring) and one aromatic ring, and R _1-2 are each independently from 1 carbon atom. 10 linear, branched or cyclic alkyl groups or alkenyl groups, an alkoxy group having 1 to 5 carbon atoms, an optionally substituted phenyl group, or a halogen atom, and f _1-2 are each independently It is an integer from 0 to 4. Furthermore, R _{3 in the} general formula (2) is a hydrogen atom or a methyl group, and m ₁ is an integer of 0 to 10. Further, a plurality of _{R 1~3,} X _{1, m} 1 is may be the same or may be different.
However, the types of R ₁ and R ₂ in general formula (1), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (X ₁ ) r ₁ and (X ₁ ) r ₂ at least one of the substitution positions is different.

Examples of the divalent group containing a condensed ring structure of a 6-membered alicyclic compound and one or more aromatic rings in Z include, for example, a 6-membered alicyclic compound and 1 to 3 aromatic rings. Examples thereof include a divalent group containing a condensed ring structure. The six-membered alicyclic compound and the five-membered alicyclic compound may contain atoms other than carbon on the ring, and examples include those containing an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of Z include the following.

Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms in R _1-2 include, for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, sec-butyl group, n -Butyl group, tert-pentyl group, cyclohexyl group and the like. Examples of the linear, branched or cyclic alkenyl group having 1 to 10 carbon atoms include an ethylene group, a propylene group, a cyclohexenyl group, and the like. Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, and an isopropoxy group. Examples of the phenyl group that may have a substituent include a phenyl group, a tolyl group, a biphenyl group, and a cyclohexylphenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the present specification, the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound includes “hydroxy group-containing asymmetric condensed ring compound (D)”, “hydroxyl group-containing asymmetric compound (D)”, “hydroxyl group-containing compound (D)”, and the like. May be described. In the general formula (1), preferably Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably Z is a condensed group represented by formula (3). A divalent group containing a ring structure, f _1-2 are each independently an integer from 0 to 2, m ₁ are each independently an integer from 0 to 2, and r _1-2 are each independently from 1 It is an integer of 2.

When Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), high heat resistance, high refractive index and electrical properties derived from a condensed ring skeleton containing aromatics are imparted. Dispersion stability derived from a large surface structure can be obtained. Furthermore, when Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (5), it has higher levels of heat resistance, refractive index, electrical properties, and dispersion stability. In addition, good compatibility and flexibility can be obtained. On the other hand, when Z is a divalent group containing a condensed ring structure of formulas (3), (6), and (7), the melting point is particularly low and the compound is excellent in compatibility. From the balance between the high physical properties derived from these condensed ring skeletons, the melting point, compatibility, and flexibility, it can be said that the case where Z is a divalent group containing a condensed ring structure represented by formula (3) is a more preferable embodiment.

In general, a compound having a high density of an aromatic fused ring skeleton has high heat resistance, high refractive index, and high electrical properties, but does not dissolve in a solvent and melts only at a very high temperature. is there. In addition, since the molded product is weak, such as being brittle, there is a possibility that a problem may occur in the mechanical properties of the obtained molded product. In the hydroxyl group-containing asymmetric compound (D) of the present invention, the structure becomes asymmetric by making the position and number of substituents and the type of substituents asymmetric, resulting in a low melting point while retaining the characteristics derived from the aromatic condensed ring skeleton. In addition, high compatibility was achieved and handling and flexibility were dramatically improved.

Especially when it is a specific substituent, the effect becomes remarkable. In the general formula (1), f ₁ is an integer of 1 or more, and at least one of f ₁ R ₁ is a halogen atom, an alkyl or alkenyl group having 2 to 5 carbon atoms, or 1 to carbon atoms. The hydroxyl group-containing asymmetric compound (D) having a substituent such as an alkoxy group of 5 becomes more prominent in terms of solubility and flexibility and has a significantly lower melting point, and is therefore listed as one of preferred embodiments.

More specifically, the “asymmetric condensed ring structure compound” represented by the formula (1) can be made “asymmetric” by adopting at least one of the following (i) to (v).
(I) formula (1), a methyl group and _{R 1,} equal to an ethyl group and _{R 2, R 1} and making the type of the substituent of _{R 2} different.
(Ii) In formula (1), f ₁ and f ₂ are set to different numerical values, that is, the number of substituents R _{1 and} the number of substituents R ₂ are different (for example, _one R ₁ , R _{1 2} is 2).
In (iii) Formula _(1), and different numerical values r 1, _{r 2,} the number of _{X 1} of the aromatic ring of _{X 1} number and _{R 2} side of the aromatic ring of _{R 1} side, that formula (1) Be different (for example, _one X ₁ (R ₁ side) and two X ₂ (R ₂ sides)).
(Iv) In formula (1), R ₁ (f ₁ = 1) is the ortho position at the Z bond position, R ₂ (f ₂ = 1) is bonded to the meta position at the Z bond position, etc. , R ₁ and R ₂ should have different substitution positions. When f ₁ and f ₂ ≧ 2, the substitution positions of at least one pair of R ₁ and R ₂ out of f ₁ R ₁ and f ₂ R ₂ are different [for example, R ₁ (f ₁ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₂ (f ₂ = 2) is bonded to only the meta position (two positions) of the bonding position of Z. Etc.].
(V) In the formula (1), on the R ₁ side, X ₁ (r ₁ = 1) is in the ortho position of the bonding position of Z, and on the R ₂ side, X ₁ (r ₂ = 1) is present. etc. having the meta position of the bonding position of Z, making the X ₁ and the substitution position of X ₂ in the R ₂ side of the R ₁ side different. _In the case of r 1, _{r 2} ≧ 2, of _{R 1} side of the _{X 1} and _{r 2} or is _{X 1} of _{R 2} side with _{one r,} the substitution position of _{R 2} side with respect to _{R 1} side At least one point is different [for example, X ₁ (r ₁ = 2) is bonded to the para position and the ortho position of the Z bond position one by one, and X ₁ (r ₂ = 2) is a parameter of the Z bond position. Have one X ₁ each in the position and meta position].

本発明の多官能水酸基含有非対称縮環構造化合物（Ｄ）は、異なる２種のフェノールと反応させることにより得られるが、通常、下記反応式（２８）のごとく、目的の非対称化合物のほか、副生成物として対称型の化合物も同時に生成し得る。目的の非対称化合物は、これらの混合物を再結晶などの方法により精製を行うことで得ることが出来る。

本反応は、通常酸性条件下で行われ、酸としては、塩化水素、塩酸、硫酸、硝酸などのプロトン酸、塩化アルミニウム、塩化亜鉛、塩化鉄などのルイス酸などが用いられる。 For example, the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D) comprises a step of allowing two different phenol compounds to act on the condensed ring structure-containing ketone compound under acidic conditions as shown in the following reaction formula (27). Obtained from the process of including. This is an example and is not limited to these production methods.

The polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D) of the present invention can be obtained by reacting with two different types of phenols. Usually, as shown in the following reaction formula (28), Symmetric compounds can also be produced as products. The target asymmetric compound can be obtained by purifying the mixture by a method such as recrystallization.

This reaction is usually carried out under acidic conditions, and examples of the acid include proton acids such as hydrogen chloride, hydrochloric acid, sulfuric acid and nitric acid, and Lewis acids such as aluminum chloride, zinc chloride and iron chloride.

The polyfunctional hydroxyl group-containing composition of the present invention contains the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D). This polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D) can be used alone or in a mixture of two or more. The polyfunctional hydroxyl group-containing composition of the present invention preferably contains 10 to 90% by weight of the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D).

This composition may further comprise (i) a hydroxyl group-containing compound other than the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D), (ii) a reactive diluent, (iii) a curing agent, and (iv) Curing accelerators, (v) additives, (vi) solvents and the like may be included.

Examples of the hydroxyl group-containing compound (i) include bisphenol compounds such as bisphenol A, bisphenol S, and bisphenol F; polyfunctional phenol compounds such as phenol resins and cresol novolac resins; naphthalenediol compounds; biphenyl diols. Compound: Polyfunctional hydroxyl group-containing condensed ring structure compounds other than the above-mentioned hydroxyl group-containing asymmetric condensed ring compound (D) are exemplified.
The hydroxyl group-containing compound (i) is preferably contained in an amount of 5 to 70% by weight based on the hydroxyl group-containing asymmetric condensed ring compound (D) of the present invention.

The reactive diluent (ii) is a low-viscosity hydroxyl group-containing compound that is added for viscosity adjustment, and a bifunctional or higher-functional hydroxyl group-containing compound is particularly preferable. Examples of reactive diluents include butanediol, aniline, neopentyl glycol, cyclohexanedimethanol, polyglycol, polypropylene glycol, trimethylolpropane, glycerin, 4-vinylcyclohexene monooxide, vinylcyclohexene. Dioxide, methylated vinylcyclohexene dioxide, etc. These reactive diluents can be used alone or in combination of two or more.
The reactive diluent (ii) is preferably contained in an amount of 1 to 50% by weight based on the hydroxyl group-containing asymmetric condensed ring compound (D) of the present invention.

The curing agent of (iii) is not particularly limited, but epoxies, oxazolidines, nitroalcohols, nitroacetals, nitro-olefins, nitroamines, nitrohydropyrimidines, aminonitroalcohols, nitrones, Examples include hydroxylamines and imines.

Since the amount of the curing agent generally varies depending on the type of the curing agent, it cannot be generally specified. For example, in the case of epoxies, the epoxy group has an amount of 0.2-2. A proportion of 0 mol is preferred, more preferably 0.5 to 1.0 mol. In the case of other types of curing agents, those skilled in the art can appropriately use them with reference to the above values.

Examples of the curing accelerator (iv) include 1,8-diazabicyclo (5.4.0) undecene-7 and amines thereof (including tertiary amines) such as phenol salts, phenol novolac salts, carbonates, and formate salts. ) And derivatives thereof; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole; ethylphosphine, propylenephosphine, And organophosphines (first, second, and third phosphines) such as phenylphosphine, triphenylphosphine, and trialkylphosphine.

As for the compounding quantity of such a hardening accelerator, 0.05-5.0 weight part is preferable with respect to 100 weight part of hydroxyl-containing compounds, More preferably, it is 0.1-3.0 weight part.
The above-mentioned “hydroxyl group-containing compound” means all the hydroxyl group-containing compounds contained in the composition, and the hydroxyl group-containing asymmetric fused ring compound (D) of the present invention and the hydroxyl group-containing asymmetric fused ring compound (D) of the present invention. Other than the hydroxyl group-containing compound (i).

Examples of the additive (v) include reinforcing materials or fillers, colorants, flame retardants, curable compounds (curable monomers, oligomers, or resins), solid fine particles, and the like.
As the reinforcing agent or filler, a powdery or fibrous reinforcing agent or filler is used. Examples of the powdery reinforcing agent or filler include materials composed of the following materials: metal oxides such as aluminum oxide and magnesium oxide; metal carbonates such as calcium carbonate and magnesium carbonate; diatomaceous earth powder, basic Silicon compounds such as magnesium silicate, calcined clay, finely divided silica, fused silica and crystalline silica; metal hydroxides such as aluminum hydroxide; other kaolin, mica, quartz powder, graphite, molybdenum disulfide and the like. Examples of the fibrous reinforcing agent or filler include the following materials: glass fiber, ceramic fiber, carbon fiber, alumina fiber, silicon carbide fiber, boron fiber, polyester fiber, polyamide fiber, and the like.
Examples of the colorant or flame retardant include titanium dioxide, iron black, molybdenum red, bitumen, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, a bromine compound, and triphenyl phosphate.
The curable compound is used for the purpose of improving the properties of the resin in the final coating film, adhesive layer, molded article and the like. Examples thereof include alkyd resins, melamine resins, fluororesins, vinyl chloride resins, acrylic resins, silicone resins, and polyester resins.
Examples of the solid fine particles include organic pigments and inorganic fine particles. For example, the solid fine particles can be added for use in applications such as optical materials and display element materials. Specific examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), and the central metals are Cu, Mg, Al, Si, Examples thereof include dissimilar metal phthalocyanine pigments such as Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn. Specific examples of the inorganic fine particles include metal oxides such as titanium oxide, zirconium oxide, zinc oxide, aluminum oxide, cerium oxide, tin oxide, tantalum oxide, indium tin oxide, and barium oxide hafnium sulfate; calcium carbonate, chloride. Gold, gold bromide, silver chloride, silver bromide, silver iodide, palladium chloride, chloroplatinic acid, sodium chloroaurate, silver nitrate, platinum acetylacetonate, palladium acetylacetonate, etc .; gold, silver, platinum , Palladium, rhodium, ruthenium, iridium and other precious metals; zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber , Titanium black, synthetic iron black, carbon black, carbon nanotube, etc. . The particle size of these solid fine particles is, for example, 1 nm to 5 μm.
These (v) additives may be used alone or in combination of two or more.
When the additive (v) is added, the amount used is appropriately selected depending on the use and the kind of the additive, but is contained in an amount that does not impair the original properties of the resin composition of the present invention. It may be contained at a ratio of 1 to 300 parts by weight with respect to 100 parts by weight of the hydroxyl group-containing compound.

Examples of the solvent (vi) include the following solvents: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Glycol ethers such as dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, 3-methoxybutyl-1 -Ace Alkylene glycol monoalkyl ether acetates such as carbonate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone And ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3 -Esters such as methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate. These solvents may be used alone or in a combination of two or more.

When such a solvent is added, the blending amount is preferably 5 to 70% by weight of the entire composition.

The composition of the present invention is formed into a molded product according to the purpose. The molded body may be a product having a desired shape made of a cured product of the composition itself, or a coating film made of a cured product of the composition formed on a substrate. For example, the composition is heated and melted as necessary, poured into a predetermined mold and heated or cured by irradiation with radiation to obtain a molded article having a desired shape. Alternatively, a cured composition can be formed on the substrate by applying and drying a liquid composition containing a solvent on the substrate and then heating or irradiating with radiation.

The molding method and the curing conditions are not particularly limited. For example, when molding using a predetermined mold, a molding method by heating and pressurization or a low-temperature molding method called cold press is used. As a method by heating and pressing, for example, a method of filling the composition of the present invention in a mold at normal pressure by a method called hand lay-up or spray lay-up and then heat-curing; injection molding using a transfer press device And a continuous molding method such as a continuous lamination molding method, a continuous pultrusion molding method called pultrusion, and a filament winding molding method. In these molding methods, the above composition can be mixed with a reinforcing agent or impregnated into a reinforcing agent to obtain an intermediate molding material, which can be molded and cured. Examples of the reinforcing agent include woven fabric and nonwoven fabric made of resin, glass and the like. As an intermediate molding material obtained by using this, for example, a sheet-like intermediate molding material called SMC (Sheet Molding Compound); a liquid or solid intermediate molding material called BMC (Berg Molding Compound) or premix; glass Examples thereof include a prepreg obtained by impregnating the composition of the present invention in a cloth or a mat.

Since the hydroxyl group-containing asymmetric condensed ring compound (D) of the present invention is excellent in compatibility with other compounds and has a low melting temperature, the degree of freedom in composition and molding of the composition is very high. Further, the hydroxyl group-containing asymmetric condensed ring compound (D) has a high refractive index and excellent heat resistance, and a composition containing them is easily cured by heat or radiation irradiation. Since the resin composition containing this hydroxyl group-containing asymmetric condensed ring compound (D) is excellent in molding processability, as described above, it is easy to form into a predetermined shape by a mold or to form a thin film on a substrate. is there. Molded bodies (including thin films) obtained by curing these with heat or radiation have excellent heat resistance and environmental resistance (weather resistance), high mechanical strength such as bending properties, high toughness, and thermal shock resistance. And good moldability.

The molded product obtained from this hydroxyl group-containing asymmetric condensed ring compound (D) is excellent in flexibility and insulation, in addition to the above properties such as heat resistance, and has small curing shrinkage and excellent dimensional stability. The composition is useful for an electrical / electronic material sealant. Furthermore, since this composition is excellent in heat resistance, adhesiveness, curability, etc., it is suitably used for potting materials, coating materials, etc. for various electronic parts such as capacitors. When used as a sealing material for an electronic insulating material or a potting agent, it can be used in the same manner as a sealing resin using a hydroxyl group-containing compound generally used conventionally. Furthermore, since cured | curing material is excellent in transparency, it is useful also as a thermosetting resin composition for optical devices.

In addition, since the hydroxyl group-containing asymmetric condensed ring compound (D) of the present invention is excellent in dispersibility, it can be suitably used when an organic pigment or inorganic fine particles are dispersed in the composition. A molded body obtained by curing this composition is also one aspect of the present invention.

A. The condensed ring structure-containing asymmetric epoxy resin The condensed ring structure-containing asymmetric epoxy resin of the present invention is represented by the following general formula (8):

ここで一般式（８）のＹ_１〜２は各々独立して、下記一般式（９）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで一般式（９）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（１１）で示される基である。さらに、一般式（９）のＹ_３〜４は、一般式（９）及び下記一般式（１１）から各々独立して選ばれる基であり、ｐ_１〜２は各々独立して０から４の整数である。

ここで前記一般式（８）、（９）のＺ、Ｒ_１〜２、ｆ_１〜２は上記一般式（１）と同じであり、前記一般式（９）、（１０）、（１１）のＲ_４〜６は各々独立して水素原子またはメチル基、ｍ_２〜４、ｓ_１は各々独立して０から１０の整数である。また、複数個のＲ_１〜２、Ｙ_１〜５、Ａ_１、ｆ_１〜２、ｐ_１〜２、ｓ_１、Ｒ_４〜６、ｍ_２〜４は同一でも良いし、異なっていても良い。
但し、一般式（８）、（９）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、（Ｙ_１）ｒ_１と（Ｙ_２）ｒ_２の置換位置、ｐ_１とｐ_２の数値、及びＡ_１、（Ｙ_３）ｐ_１とＹ_５、（Ｙ_４）ｐ_２の置換位置のうち少なくとも１つが異なる。

Here, Y _1-2 in the general formula (8) are each independently a group represented by the following general formula (9), and r _1-2 are each independently an integer of 1-5.

Here, A ₁ in the general formula (9) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (11). Furthermore, Y _{<3> -4} of General formula (9) is group respectively independently selected from General formula (9) and following General formula (11), and p _<1-2> is each independently _0-4 . It is an integer.

Here, Z, R _1-2 and f _{1-2 in the} general formulas (8) and (9) are the same as those in the general formula (1), and the general formulas (9), (10) and (11). R _{4 to 6} are each independently a hydrogen atom or a methyl group, m _{2 to 4} and s ₁ are each independently an integer of 0 to 10. A plurality of R _1-2 , Y _1-5 , A ₁ , f _1-2 , p _1-2 , s ₁ , R _4-6 , m _2-4 may be the same or different. good.
However, the types of R ₁ and R _{2 in} the general formulas (8) and (9), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , (R ₁ ) f ₁ and (R ₂ ) f ₂ substitution _{position, (Y 1) r} 1 and _(Y 2) substitution position of _{r 2,} numerical values of _{p 1} and _{p 2,} and _{a 1, (Y 3) p} 1 and _{Y 5,} substitution of _(Y 4) _{p 2} At least one of the positions is different.

This condensed ring structure-containing asymmetric epoxy resin may be described as “condensed ring structure-containing asymmetric epoxy resin (A)”, “asymmetric epoxy resin (A)”, or the like in this specification. In the above general formulas (8) to (11), Z is preferably a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably Z is formula (3). In which p _1-2 and f _1-2 are each independently an integer of 0 to 2, m _2-4 are each independently an integer of 0 to 2, r _1-2 are each independently an integer from 1 to 2, and s ₁ are each independently an integer from 0 to 8.

When Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), high heat resistance, high refractive index, and electrical properties derived from a condensed ring skeleton containing aromatics are imparted. And dispersion stability derived from a large surface structure can be obtained. Furthermore, when Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (5), higher levels of heat resistance, refractive index, electrical properties, and dispersion stability can be obtained. .
When Z is a divalent group containing a condensed ring structure of formulas (3), (6) and (7), such an epoxy resin (A) is easy to handle and advantageous in terms of production cost. From the balance between the high physical properties derived from these condensed ring skeletons and the ease of handling, the case where Z is a divalent group containing a condensed ring structure represented by formula (3) is a more preferred embodiment.

In general, a compound having a high density of an aromatic fused ring skeleton has high heat resistance, high refractive index, and high electrical properties, but does not dissolve in a solvent and melts only at a very high temperature. is there. In addition, since the molded product is weak, such as being brittle, there is a possibility that a problem may occur in the mechanical properties of the obtained molded product. In the condensed ring structure-containing asymmetric epoxy resin (A) of the present invention, the structure becomes asymmetric by making the position and number of substituents and the type of substituents asymmetric, and as a result, the characteristics derived from the aromatic condensed ring skeleton remain. It has a low melting point and high compatibility, and has dramatically improved handling and flexibility.

Especially when it is a specific substituent, the effect becomes remarkable. In the general formulas (8) to (9), at least one of the plurality of f ₁ and f ₂ is an integer of 1 or more, and at least one of f ₁ R ₁ or f ₂ R ₂ is present. The condensed ring-containing asymmetric epoxy resin (A) having a substituent such as a halogen atom, an alkyl group or alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, has points of solubility and flexibility. Is more prominent and has a significantly lower melting point, and is therefore one of the preferred embodiments.

Further, the condensed ring structure-containing asymmetric epoxy resin (A) of the present invention has a condensed ring structure-containing asymmetric epoxy resin when s _{1 in the} general formula (9) is 1 or more and any _one of p _{1 and 2} is 1 or more. Has a branched structure. When all of p _1-2 are 0, the condensed ring structure-containing asymmetric epoxy resin (A) is a linear resin.

The condensed ring structure-containing asymmetric epoxy resin (A) having a branch is superior in, for example, curability, dispersion stability, heat resistance, etc., and the condensed ring structure-containing asymmetric epoxy resin (A) is linear For example, it is advantageous in that it is easy to handle and has a high degree of freedom in resin design.

With respect to the asymmetric epoxy resin represented by the formula (8), when s ₁ is 0, Y _1-2 is Y ₅ , that is, a group represented by the formula (11).

More specifically, the “asymmetric epoxy resin” represented by the formula (8) can be made “asymmetric” by adopting at least one of the following (i) to (v).
(I) In formula (8) or (9), a methyl group and _{R 1,} equal to an ethyl group and _{R 2, R 1} and making the type of the substituent of _{R 2} different.
(Ii) In formula (8) or (9), f ₁ and f ₂ are set to different numerical values, that is, the number of substituents R _{1 and} the number of substituents R ₂ are different (for example, R ₁ is 1 and ₂ R ₂ ).
(Iii) In Equation (8), r ₁ and r ₂ are set to different numerical values, that is, the number of Y _{1 and} the number of Y ₂ in Equation (8) are different (for example, _one Y ₁ , Y ₂ are two).
(Iv) In the formula (8) or (9), R ₁ (f ₁ = 1) is the ortho position of the bonding position of Z, and R ₂ (f ₂ = 1) is bonded to the meta position of the bonding position of Z The substitution positions of R ₁ and R ₂ should be different. When f ₁ and f ₂ ≧ 2, the substitution positions of at least one pair of R ₁ and R ₂ out of f ₁ R ₁ and f ₂ R ₂ are different [for example, R ₁ (f ₁ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₂ (f ₁ = 2) is bonded only to the meta position (two positions) of the bonding position of Z. Etc.].
(V) In Formula (8), Y ₁ (r ₁ = 1) is bonded to the para position of the bonding position of Z, Y ₂ (r ₂ = 1) is bonded to the meta position of the bonding position of Z, etc. , Y ₁ and Y ₂ should have different substitution positions. In addition, when r ₁ and r ₂ ≧ 2, at least one set of Y ₁ and Y ₂ is substituted at different positions among r ₁ Y ₁ and r ₂ Y ₂ [for example, Y ₁ (r ₁ = 2) is bonded to the para position and the meta position at the bonding position of Z one by one, and Y ₂ (r ₂ = 2) is bonded to the para position and the ortho position of the bonding position of Z one by one. It shall be.

In addition, at least one of the following (vi) to (vii) can be the “asymmetric epoxy resin” of the present invention represented by the formula (8).
(Vi) In Equation (9), p ₁ and p ₂ are set to different numerical values, that is, the number of Y _{3 and} the number of Y ₄ are different (for example, one Y _{3 and} two Y ₄ ). In this case, s ₁ is 1 or more.
(Vii) In formula (9), the substitution positions of A ₁ , (Y ₃ ) p ₁ and Y ₅ , (Y ₄ ) p ₂ are different even at one place. Here, “the substitution positions of A ₁ , (Y ₃ ) p ₁ and Y ₅ , (Y ₄ ) p ₂ are different even at one place” means that when s ₁ is 2 or more, the formula (9) R ₁ side A ₁ , (Y ₃ ) p ₁ and R ₂ side A ₁ , (Y ₄ ) p ₂ may have different substitution positions at one position, or A ₁ on the R ₁ side of formula (9), It means that the substitution position of (Y ₃ ) p ₁ and Y ₅ on the R ₂ side and (Y ₄ ) p ₂ is different even at one place [for example, A ₁ and Y ₃ on the R ₁ side (p ₁ = 1) Are bonded to the para position and the meta position at the bonding position of Z, and A ₁ and Y ₄ (p ₂ = 1) on the R ₂ side are bonded to the para position and the ortho position at the bonding position of Z, respectively. In addition, when s ₁ is 1, R ₁ side A ₁ , (Y ₃ ) p ₁ and R ₂ side Y ₅ , (Y ₄ ) p ₂ of formula (9) The substitution position is different even at one place [Example If, _{A 1} and _Y 3 of _{R 1} side _(p 1 = 1) is attached by one place in the para position and meta-position of the bonding position of Z, the _{R 2} side _{Y 5} and _Y 4 _(p 2 = 1 ) Means one bond at each of the para and ortho positions of the Z bond position. In this case, s ₁ is 1 or more.

Moreover, " _Y3-4 of General formula (9) is a group each independently selected from General formula (9) and the following general formula (11)," means _{Y3-3 of} Formula (9). ₄ is the formula (11) or Y _3-4 is the formula (9). As a result, the group represented by the formula (9) becomes a structure (branched structure), and the terminal (Y _3-4 ) is It means that the group is represented by the formula (11). In this case, s ₁ is 1 or more.

Moreover, the condensed ring structure containing asymmetric epoxy resin (A) of this invention is obtained from the manufacturing method including the process of making an epihalohydrin act on the above-mentioned polyfunctional hydroxyl group containing asymmetric condensed ring structure compound shown by General formula (1). The resin represented by the general formula (8) is obtained by, for example, a process (manufacturing method) including this step.

In addition, the condensed ring structure-containing asymmetric epoxy resin may be described as “condensed ring structure-containing asymmetric epoxy resin (A1)”, “asymmetric epoxy resin (A1)”, or the like. This condensed ring structure-containing asymmetric epoxy resin (A1) is included in the aforementioned condensed ring structure-containing asymmetric epoxy resin (A). In the above general formulas (8) to (11), Z is preferably a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably Z is formula (3). In which p _1-2 and f _1-2 are each independently an integer of 0 to 2, m _2-4 are each independently an integer of 0 to 2, r _1-2 are each independently an integer from 1 to 2, and s ₁ are each independently an integer from 0 to 8.

Examples of the epihalohydrin include epichlorohydrin, epibromohydrin and the like, and epichlorohydrin is particularly preferred because it is easy to handle and inexpensive.

The reaction between the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D) and epichlorohydrin is usually performed in a temperature range of 50 to 120 ° C. for 1 to 10 hours. Preferably, it is performed for 3 to 6 hours in a temperature range of 70 to 110 ° C.
The ratio of the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D) and epichlorohydrin is 1 to 20 mol of epichlorohydrin with respect to 1 mol of the hydroxyl group of the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D). Is preferred.
Examples of the catalyst used in the reaction of the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D) with epichlorohydrin include phosphonium salts, quaternary ammonium salts, phosphine compounds, tertiary amine compounds, imidazole compounds, and the like. Is mentioned.

One preferred embodiment of the fused ring structure containing asymmetric epoxy resin of the present invention, p _{1 to 2} in condensed ring structure containing asymmetric epoxy resin of the general formula (8) is 0, r _{1 to 2} 1 below General formula (12) is mentioned.

ここで一般式（１２）のＹ_６〜７は各々独立して、下記一般式（１３）で示される基である。

ここで一般式（１３）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（１１）で示される基である。

ここで、一般式（１２）、（１３）、（１０）、（１１）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_４〜６、ｍ_２〜４、ｓ_１は前記と同じであり、複数個のＲ_１〜２、ｆ_１〜２、Ａ_１、ｓ_１、Ｒ_４〜６、ｍ_２〜４は同一でも良いし、異なっていても良い。
但し、一般式（１２）、（１３）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、（Ｒ_１）ｆ_２と（Ｒ_２）ｆ_２の置換位置、Ｙ_６とＹ_７の置換位置、及びＡ_１とＹ_５の置換位置のうち少なくとも１つが異なる。

Here, Y _6-7 in the general formula (12) are each independently a group represented by the following general formula (13).

Here, A ₁ in the general formula (13) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (11).

Here, Z, R _1-2 , f _1-2 , R _4-6 , m _2-4 , and s ₁ in the general formulas (12), (13), (10), and (11) are the same as described above. Yes, a plurality of R _1-2 , f _1-2 , A ₁ , s ₁ , R _4-6 , m _2-4 may be the same or different.
However, the types of R ₁ and R _{2 in} the general formulas (12) and (13), the numerical values of f ₁ and f ₂ , the substitution positions of (R ₁ ) f ₂ and (R ₂ ) f ₂ , Y ₆ and Y ₇ And at least one of the substitution positions of A ₁ and Y ₅ is different.

This condensed ring structure-containing asymmetric epoxy resin may be described as “condensed ring structure-containing asymmetric epoxy resin (A2)”, “asymmetric epoxy resin (A2)”, or the like in this specification. This condensed ring structure-containing asymmetric epoxy resin (A2) is included in the aforementioned condensed ring structure-containing asymmetric epoxy resin (A). In the general formulas (12), (13), and (10), Z is preferably a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably Z is A divalent group having a condensed ring structure represented by formula (3), wherein f _1-2 are each independently an integer of 0 to 2, m _2-4 are each independently an integer of 0 to 2, s ₁ Is an integer from 0 to 8.

Still one preferred embodiment, in the general formula (12) to (13), among a plurality is _{f 1} and _{f 2} of, at least one is an integer of 1 or more, there _{one f R 1} Or at least one of f ₂ R ₂ is a halogen atom, an alkyl or alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

With respect to the asymmetric epoxy resin represented by the formula (12), when s ₁ is 0, Y _{6 to 7} are Y ₅ , that is, a group represented by the formula (11).

More specifically, the “asymmetric epoxy resin” represented by the formula (12) can be made “asymmetric” by adopting at least one of the following (i) to (iv).
(I) formula (12) or (13), a methyl group and _{R 1,} equal to an ethyl group and _{R 2, R 1} and making the type of the substituent of _{R 2} different.
(Ii) In formula (12) or (13), f ₁ and f ₂ are set to different numerical values, that is, the number of substituents R _{1 and} the number of substituents R ₂ are different (for example, R ₁ is 1 and ₂ R ₂ ).
(Iii) In the formula (12) or (13), R ₁ (f ₁ = 1) is bonded to the ortho position of the bonding position of Z, and R ₂ (f ₂ = 1) is bonded to the meta position of the bonding position of Z The substitution positions of R ₁ and R ₂ are different from each other. When f ₁ and f ₂ ≧ 2, the substitution positions of at least one pair of R ₁ and R ₂ out of f ₁ R ₁ and f ₂ R ₂ are different [for example, R ₁ (f ₁ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₂ (f ₁ = 2) is bonded only to the meta position (two positions) of the bonding position of Z. Etc.].
(Iv) In formula (12), Y ₆ is different from the substitution position of Y ₆ and Y ₇ such that Y ₆ is bonded to the para position of the bonding position of Z, and Y ₇ is bonded to the meta position of the bonding position of Z. To be.

Further, also by (v) below, the “asymmetric epoxy resin” represented by the formula (12) can be made “asymmetric”.
(V) In formula (13), the substitution positions of A ₁ and Y ₅ are different. Here, "different substitution position of _{A 1} and _{Y 5",} when _{s 1} is 2 or more, the substitution position _{of A 1} is different from the _{A 1} and _{R 2} side of the _{R 1} side of Formula (13) it is bound to, or means that a ₁ and R ₂ side of Y ₅ of R ₁ side of formula (13) are bonded to different substitution position, and when s ₁ is 1, It means _{that Y 5} of _{a 1} and _{R 2} side of the _{R 1} side of formula (13) are attached to different substitution positions.

Another preferred embodiment of the condensed ring structure-containing asymmetric epoxy resin of the present invention includes the following general formula (14) in which s ₁ is 0 in the condensed ring structure-containing asymmetric epoxy resin of the general formula (8). It is done.

ここで一般式（１４）のＹ_５は各々独立して、下記一般式（１１）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで、一般式（１４）、（１１）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_６、ｍ_４は前記と同じであり、複数個のＲ_１〜２、Ｙ_５、Ｒ_６、ｍ_４は同一でも良いし、異なっていても良い。
但し、一般式（１４）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、及び、（Ｙ_５）ｒ_１と（Ｙ_５）ｒ_２の置換位置のうち少なくとも１つが異なる。

Here, Y ₅ in the general formula (14) is each independently a group represented by the following general formula (11), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z, R _<1-2> , f _<1-2> , R _{< 6 >} , m < _{4 > of} General formula (14), (11) is the same as the above, and several R _<1-2> , Y < _{5 >} , R _{< 6 >} . , M ₄ may be the same or different.
However, the types of R ₁ and R ₂ of the general formula (14), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (Y ₅ ) r ₁ and (Y ₅ ) r ₂ at least one of the substitution positions is different.

The condensed ring structure-containing asymmetric epoxy resin may be described as “condensed ring structure-containing asymmetric epoxy resin (A3)”, “epoxy asymmetric resin (A3)”, or the like in this specification. This condensed ring structure-containing asymmetric epoxy resin (A3) is included in the aforementioned condensed ring structure-containing asymmetric epoxy resin (A). In the general formula (14), preferably, Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably Z is a condensed group represented by formula (3). It is a divalent group containing a ring structure, f _1-2 and m ₄ are each independently an integer of 0 to 2, and r _1-2 are each independently an integer of 1 to 2.

As a further preferred embodiment, in the general formula (14), at least one of f ₁ and f ₂ is an integer of 1 or more, and f ₁ R ₁ or f ₂ R ₂ Among them, at least one is a halogen atom, an alkyl group or alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

In addition, as r _{1-2 in the} general formula (14) increases, the hardness and curability increase. On the other hand, as r _1-2 in general formula (14) decreases, the handling and design of the resin becomes easier.

More specifically, the “asymmetric epoxy resin” represented by the formula (14) can be made “asymmetric” by adopting at least one of the following (i) to (v).
(I) In formula (14), a methyl group and _{R 1,} equal to an ethyl group and _{R 2, R 1} and making the type of the substituent of _{R 2} different.
(Ii) In formula (14), f ₁ and f ₂ are set to different numerical values, that is, the number of substituents R _{1 and} the number of substituents R ₂ are different (for example, _one R ₁ , R _{1 2} is 2).
In (iii) Formula _(14), and different numerical values r 1, _{r 2,} the number of _{Y 5} number and _{R 2} side of the aromatic ring _{Y 5} aromatic rings of _{R 1} side, that formula (14) Be different (for example, one Y ₅ (R ₁ side) and two Y ₅ (R ₂ sides)).
(Iv) In Formula (14), R ₁ (f ₁ = 1) is bonded to the ortho position of the bonding position of Z, R ₂ (f ₂ = 1) is bonded to the meta position of the bonding position of Z, etc. , R ₁ and R ₂ should have different substitution positions. When f ₁ and f ₂ ≧ 2, the substitution positions of at least one pair of R ₁ and R ₂ out of f ₁ R ₁ and f ₂ R ₂ are different [for example, R ₁ (f ₁ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₂ (f ₂ = 2) is bonded to only the meta position (two positions) of the bonding position of Z. Etc.]. (V) In the formula (14), on the R ₁ side, Y ₅ (r ₁ = 1) is in the ortho position of the Z bonding position, and on the R ₂ side, Y ₅ (r ₂ = 1) is present. The substitution position of Y ₅ on the R ₁ side and Y ₅ on the R ₂ side is different, for example, it is in the meta position of the bonding position of Z. _In the case of r 1, _{r 2} ≧ 2, of _{R 1} side of _{Y 5} and _{r 2} pieces is _{R 2} side of _{Y 5} in _{one r,} the substitution position of _{R 2} side with respect to _{R 1} side At least one point is different [for example, Y ₅ (r ₁ = 2) is bonded to the para position and the ortho position of the bonding position of Z one by one, and Y ₅ (r ₂ = 2) is a parameter of the bonding position of Z Etc. having 1 Y ₅ each in the position and meta position].

The epoxy resin composition of the present invention contains the asymmetric epoxy resin (A). This asymmetric epoxy resin (A) can be used alone or as a mixture of two or more. The epoxy resin composition of the present invention preferably contains 10 to 90% by weight of the asymmetric epoxy resin (A).

The epoxy resin composition may further include (i) an epoxy resin other than the asymmetric epoxy resin (A), (ii) a reactive diluent, (iii) a curing agent, (iv) a curing accelerator, v) additives, (vi) solvents and the like may be included.

Examples of the epoxy resin (i) include bisphenol epoxy resins such as bisphenol A, bisphenol S, and bisphenol F; polyfunctional phenol epoxy resins such as phenol resin and cresol novolac resin; naphthalene epoxy such as naphthol epoxy resin Resin; Biphenyl type epoxy resin; Condensed ring structure type epoxy resin other than the above epoxy resin (A).
The epoxy resin (i) is preferably contained in an amount of 5 to 70% by weight based on the asymmetric epoxy resin (A) of the present invention.

The reactive diluent (ii) is a low-viscosity epoxy compound added for viscosity adjustment, and a bifunctional or higher-functional low-viscosity epoxy compound is particularly preferable. Examples of the reactive diluent include the following compounds: diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether, cyclohexane dimethanol diglycidyl ether, alkylene diglycidyl ether, polyglycol. Diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, and the like. These reactive diluents can be used alone or in combination of two or more.
The reactive diluent (ii) is preferably contained in an amount of 1 to 50% by weight based on the epoxy resin (A) of the present invention.

The curing agent of (iii) is not particularly limited, but amine compounds, imidazole compounds, carboxylic acids, acid anhydride compounds, phenols, quaternary ammonium salts, methylol group-containing compounds, triflic acid. Latent cations such as salts, boron trifluoride etherate compounds, boron trifluoride, diazonium salts, sulfonium salts, iodonium salts, benzothiazolium salts, ammonium salts, phosphonium salts that generate acid by light or heat A polymerization catalyst etc. are mentioned.

The amount of the curing agent generally varies depending on the type of the curing agent, and thus cannot be specified in general. For example, in the case of an acid anhydride compound or phenol, an acid anhydride with respect to 1 mol of an epoxy group The proportion of the group or phenolic hydroxyl group is preferably 0.2 to 2.0 mol, more preferably 0.5 to 1.0 mol. In the case of other types of curing agents, those skilled in the art can appropriately use them with reference to the above values.

Examples of the curing accelerator (iv) include 1,8-diazabicyclo (5.4.0) undecene-7 and amines thereof (including tertiary amines) such as phenol salts, phenol novolac salts, carbonates, and formate salts. ) And derivatives thereof; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole; ethylphosphine, propylenephosphine, And organophosphines (first, second, and third phosphines) such as phenylphosphine, triphenylphosphine, and trialkylphosphine.

As for the compounding quantity of such a hardening accelerator, 0.05-5.0 weight part is preferable with respect to 100 weight part of epoxy resins, More preferably, it is 0.1-3.0 weight part.
The above “epoxy resin” means all epoxy resins contained in the composition, and the asymmetric epoxy resin (A) of the present invention and the epoxy resin (i) other than the asymmetric epoxy resin (A) of the present invention. Including.

Examples of the additive (v) include reinforcing materials or fillers, colorants, flame retardants, curable compounds (curable monomers, oligomers, or resins), solid fine particles, and the like.
As the reinforcing agent or filler, a powdery or fibrous reinforcing agent or filler is used. Examples of the powdery reinforcing agent or filler include materials composed of the following materials: metal oxides such as aluminum oxide and magnesium oxide; metal carbonates such as calcium carbonate and magnesium carbonate; diatomaceous earth powder, basic Silicon compounds such as magnesium silicate, calcined clay, finely divided silica, fused silica and crystalline silica; metal hydroxides such as aluminum hydroxide; other kaolin, mica, quartz powder, graphite, molybdenum disulfide and the like. Examples of the fibrous reinforcing agent or filler include the following materials: glass fiber, ceramic fiber, carbon fiber, alumina fiber, silicon carbide fiber, boron fiber, polyester fiber, polyamide fiber, and the like.
Examples of the colorant or flame retardant include titanium dioxide, iron black, molybdenum red, bitumen, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, a bromine compound, and triphenyl phosphate.
The curable compound is used for the purpose of improving the properties of the resin in the final coating film, adhesive layer, molded article and the like. Examples thereof include alkyd resins, melamine resins, fluororesins, vinyl chloride resins, acrylic resins, silicone resins, and polyester resins.
Examples of the solid fine particles include organic pigments and inorganic fine particles. For example, the solid fine particles can be added for use in applications such as optical materials and display element materials. Specific examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), and the central metals are Cu, Mg, Al, Si, Examples thereof include dissimilar metal phthalocyanine pigments such as Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn. Specific examples of the inorganic fine particles include metal oxides such as titanium oxide, zirconium oxide, zinc oxide, aluminum oxide, cerium oxide, tin oxide, tantalum oxide, indium tin oxide, and barium oxide hafnium sulfate; calcium carbonate, chloride. Gold, gold bromide, silver chloride, silver bromide, silver iodide, palladium chloride, chloroplatinic acid, sodium chloroaurate, silver nitrate, platinum acetylacetonate, palladium acetylacetonate, etc .; gold, silver, platinum , Palladium, rhodium, ruthenium, iridium and other precious metals; zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber , Titanium black, synthetic iron black, carbon black, carbon nanotube, etc. . The particle size of these solid fine particles is, for example, 1 nm to 5 μm.
These (v) additives may be used alone or in combination of two or more.
When the additive (v) is added, the amount used is appropriately selected depending on the use and the kind of the additive, but is contained in an amount that does not impair the original properties of the resin composition of the present invention. It can contain in the ratio of 1-300 weight part with respect to 100 weight part of epoxy resins.

Examples of the solvent (vi) include the following solvents: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Glycol ethers such as dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, 3-methoxybutyl-1 -Ace Alkylene glycol monoalkyl ether acetates such as carbonate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone And ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3 -Esters such as methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate. These solvents may be used alone or in a combination of two or more.

When such a solvent is added, the blending amount is preferably 5 to 70% by weight of the entire composition.

The epoxy resin composition of the present invention is a molded product according to the purpose. The molded body may be a product having a desired shape made of a cured product of the composition itself, or a coating film made of a cured product of the composition formed on a substrate. For example, the composition is heated and melted as necessary, poured into a predetermined mold and heated or cured by irradiation with radiation to obtain a molded article having a desired shape. Alternatively, a cured composition can be formed on the substrate by applying and drying a liquid composition containing a solvent on the substrate and then heating or irradiating with radiation.

The molding method and the curing conditions are not particularly limited. For example, when molding using a predetermined mold, a molding method by heating and pressurization or a low-temperature molding method called cold press is used. As a method by heat and pressure, for example, a method in which the resin composition of the present invention is filled in a mold at normal pressure by a method called hand lay-up or spray lay-up, followed by heat-curing; injection using a transfer press device Examples thereof include a method of heating and compressing by molding; and a continuous molding method such as a continuous lamination molding method, a continuous drawing method called pultrusion, and a filament winding molding method. In these molding methods, an intermediate molding material can be obtained by mixing the resin composition with a reinforcing agent or impregnating the reinforcing agent, and then molding and curing the intermediate molding material. Examples of the reinforcing agent include woven fabric and nonwoven fabric made of resin, glass and the like. As an intermediate molding material obtained by using this, for example, a sheet-like intermediate molding material called SMC (Sheet Molding Compound); a liquid or solid intermediate molding material called BMC (Berg Molding Compound) or premix; glass Examples thereof include a prepreg obtained by impregnating a resin composition of the present invention in a cloth or a mat.

Since the condensed ring structure-containing asymmetric epoxy resin (A) of the present invention is excellent in compatibility with other compounds and has a low melting temperature, the degree of freedom in composition and molding of the composition is very high. The condensed ring structure-containing asymmetric epoxy resin (A) has a high refractive index, excellent heat resistance, and is easily cured by heat or radiation. Since the resin composition containing this epoxy resin (A) is excellent in molding processability, it is easy to form into a predetermined shape with a mold or form a thin film on a substrate as described above. Molded bodies (including thin films) obtained by curing these with heat or radiation have excellent heat resistance and environmental resistance (weather resistance), high mechanical strength such as bending properties, high toughness, and thermal shock resistance. And good moldability.

In addition to the properties such as heat resistance, the molded product obtained from this epoxy resin composition is excellent in flexibility and insulation, and has a small curing shrinkage and excellent dimensional stability. It is useful as an electrical / electronic material sealant. Furthermore, since this composition is excellent in heat resistance, adhesiveness, curability, etc., it is suitably used for potting materials, coating materials, etc. for various electronic parts such as capacitors. When used as a sealing material for an electronic insulating material or as a potting agent, it can be used in the same manner as a sealing resin using an epoxy resin that has been conventionally used. Furthermore, since cured | curing material is excellent in transparency, it is useful also as a thermosetting resin composition for optical devices.

In addition, since the asymmetric epoxy resin (A) of the present invention is excellent in dispersibility, it can be suitably used when an organic pigment or inorganic fine particles are dispersed in the composition. A molded body obtained by curing this composition is also one aspect of the present invention.

B. The condensed ring structure-containing asymmetric epoxy ester resin The condensed ring structure-containing asymmetric epoxy ester resin of the present invention is represented by the following general formula (15):

ここで一般式（１５）のＹ_１〜２は各々独立して、下記一般式（１６）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで一般式（１６）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（１７）で示される基である。さらに、一般式（１６）のＹ_３〜４は、一般式（１６）及び下記一般式（１７）から各々独立して選ばれる基であり、ｐ_１〜２は各々独立して０から４の整数である。

ここで前記一般式（１５）、（１６）のＺは、六員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つ以上の芳香環との縮環構造、または、五員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つの芳香環との縮環構造を含む二価基であり、Ｒ_１〜２は各々独立して、炭素数１から１０の直鎖状、分岐状または環状のアルキル基若しくはアルケニル基、炭素数１から５のアルコキシ基、置換基を有していてもよいフェニル基、又はハロゲン原子、ｆ_１〜２は各々独立して０から４の整数である。さらに、前記一般式（１０）、（１７）のＲ_４〜６は各々独立して水素原子またはメチル基、Ｒ_７は単塩基性カルボン酸に由来する部位を含む基を示し、ｍ_２〜４、ｓ_１は各々独立して０から１０の整数である。また、複数個のＲ_１〜２、ｆ_１〜２、ｓ_１、Ｒ_４〜７、Ａ_１、Ｙ_１〜５、ｐ_１〜２、ｍ_２〜４は同一でも良いし、異なっていても良い。
但し、一般式（１５）、（１６）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、（Ｙ_１）ｒ_１と（Ｙ_２）ｒ_２の置換位置、ｐ_１とｐ_２の数値、及びＡ_１、（Ｙ_３）ｐ_１とＹ_５、（Ｙ_４）ｐ_２の置換位置のうち少なくとも１つが異なる。

Here, Y _1-2 in the general formula (15) are each independently a group represented by the following general formula (16), and r _1-2 are each independently an integer of 1-5.

Here, A ₁ in the general formula (16) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (17). Furthermore, Y _{<3> -4} of General formula (16) is group respectively independently selected from General formula (16) and following General formula (17), and p _<1-2> is respectively independently _0-4 . It is an integer.

Here, Z in the general formulas (15) and (16) represents a condensed ring structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings, Or a divalent group containing a condensed ring structure of a five-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one aromatic ring, and R _1-2 are each independently A linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an optionally substituted phenyl group, or a halogen atom, f _{1- 2} is an integer of 0 to 4 each independently. In the general formulas (10) and (17), R _{4 to 6} each independently represent a hydrogen atom or a methyl group, R ₇ represents a group containing a site derived from a monobasic carboxylic acid, and m _{2 to 4} , S ₁ are each independently an integer from 0 to 10. A plurality of R _1-2 , f _1-2 , s ₁ , R _4-7 , A ₁ , Y _1-5 , p _1-2 , m _2-4 may be the same _or different. good.
However, the types of R ₁ and R _{2 in} the general formulas (15) and (16), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , (R ₁ ) f ₁ and (R ₂ ) f ₂ substitution _{position, (Y 1) r} 1 and _(Y 2) substitution position of _{r 2,} numerical values of _{p 1} and _{p 2,} and _{a 1, (Y 3) p} 1 and _{Y 5,} substitution of _(Y 4) _{p 2} At least one of the positions is different.

The condensed ring structure-containing asymmetric epoxy ester resin may be described as “condensed ring structure-containing asymmetric epoxy ester resin (B)”, “asymmetric epoxy ester resin (B)”, or the like. In the general formulas (15), (16), (10), and (17), Z is preferably a divalent group including a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably. Is a divalent group including a condensed ring structure represented by formula (3), p _1-2 and f _1-2 are each independently an integer of 0 to 2, and m _2-4 are each independently An integer from 0 to 2, and s ₁ is independently an integer from 0 to 8.

When Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), high heat resistance, high refractive index and electrical properties derived from a condensed ring skeleton containing aromatics are imparted. In addition, dispersion stability derived from a large surface structure can be obtained, and good compatibility and flexibility can be obtained. Furthermore, when Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (5), higher levels of heat resistance, refractive index, electrical properties, and dispersion stability can be obtained. .
When Z is a divalent group containing a condensed ring structure of formulas (3), (6), and (7), a compound having excellent compatibility is obtained. From the high physical properties, compatibility and flexibility balance derived from these condensed ring skeletons, it can be said that the case where Z is a divalent group containing a condensed ring structure represented by formula (3) is a more preferable embodiment.

In general, a compound having an aromatic fused ring skeleton at a high density has high heat resistance, a high refractive index, and high electrical properties, but has a large drawback in handling properties because it does not dissolve in a solvent. In addition, since the molded product is weak, such as being brittle, there is a possibility that a problem may occur in the mechanical properties of the obtained molded product. In the condensed ring structure-containing asymmetric epoxy ester resin (B) of the present invention, the structure becomes asymmetric by making the position and number of substituents and the type of substituents asymmetric, resulting in the characteristics derived from the aromatic condensed ring skeleton. However, it has a low melting point and high compatibility, and has dramatically improved handling and flexibility.

In the condensed ring structure-containing asymmetric epoxy ester resin of the present invention, when s _{1 in the} general formula (16) is 1 or more and any _one of p _{1 and 2} is 1 or more, the condensed ring structure-containing asymmetric epoxy ester resin is a branched structure. Have When all of p _1-2 are 0, the condensed ring structure-containing asymmetric epoxy ester resin is a linear resin.

The branched condensed ring-containing asymmetric epoxy ester resin having a branch is superior in, for example, heat resistance, curability, and dispersion stability. It is advantageous in that it is simple and increases the degree of freedom in resin design.

The condensed ring structure-containing asymmetric epoxy ester resin of the present invention can be obtained from a production method including a step of allowing a monobasic carboxylic acid to act on the condensed ring structure-containing asymmetric epoxy resin (A). ) Of the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound is obtained from a production method including a step of allowing a monobasic glycidyl carboxylate to act, and the resin represented by the general formula (15) is, for example, a process including this step. (Manufacturing method)

The condensed ring structure-containing asymmetric epoxy ester resin obtained by the above method is described as “condensed ring structure-containing asymmetric epoxy ester resin (B1)”, “asymmetric epoxy ester resin (B1)” or the like in this specification. There is a case. This condensed ring structure-containing asymmetric epoxy ester resin (B1) is included in the aforementioned condensed ring structure-containing asymmetric epoxy ester resin (B).

As a preferred embodiment, in the general formulas (15), (16), (10), (17), Z preferably includes a condensed ring structure selected from the group consisting of formulas (3) to (7). Divalent group, more preferably, Z is a divalent group containing a condensed ring structure represented by formula (3), and p _1-2 and f _1-2 are each independently an integer of 0 to 2, m _{2 -4} are each independently an integer from 0 to 2, r _1-2 are each independently an integer from 1 to 2, and s ₁ are each independently an integer from 0 to 8.

In another preferred embodiment, the monobasic carboxylic acid and the glycidyl monobasic carboxylate are (meth) acrylic acid and glycidyl (meth) acrylate, and thus have a condensed ring structure having radiation polymerizability. An asymmetric epoxy ester resin (B1) is obtained.

With respect to the asymmetric epoxy ester resin represented by the formula (15), when s ₁ is 0, Y _1-2 is Y ₅ , that is, a group represented by the formula (17).

More specifically, the “asymmetric epoxy ester resin” represented by the formula (15) can be made “asymmetric” by employing at least one of the following (i) to (v).
(I) formula (15) or (16), a methyl group and _{R 1,} equal to an ethyl group and _{R 2, R 1} and making the type of the substituent of _{R 2} different.
(Ii) In formula (15) or (16), f ₁ and f ₂ are set to different numerical values, that is, the number of substituents R _{1 and} the number of substituents R ₂ are different (for example, R ₁ is 1 and ₂ R ₂ ).
(Iii) In Expression (15), r ₁ and r ₂ are set to different numerical values, that is, the number of Y _{1 and} the number of Y ₂ in Expression (15) are different (for example, _one Y ₁ , ₂ Y ₂ ).
(Iv) In the formula (15) or (16), R ₁ (f ₁ = 1) is the ortho position of the bonding position of Z, and R ₂ (f ₂ = 1) is bonded to the meta position of the bonding position of Z The substitution positions of R ₁ and R ₂ are different from each other. When f ₁ and f ₂ ≧ 2, the substitution positions of at least one pair of R ₁ and R ₂ out of f ₁ R ₁ and f ₂ R ₂ are different [for example, R ₁ (f ₁ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₂ (f ₁ = 2) is bonded only to the meta position (two positions) of the bonding position of Z. Etc.].
(V) In Formula (15), Y ₁ (r ₁ = 1) is bonded to the para position of the bonding position of Z, Y ₂ (r ₂ = 1) is bonded to the meta position of the bonding position of Z, etc. , Y ₁ and Y ₂ should have different substitution positions. In addition, when r ₁ and r ₂ ≧ 2, at least one set of Y ₁ and Y ₂ is substituted at different positions among r ₁ Y ₁ and r ₂ Y ₂ [for example, Y ₁ (r ₁ = 2) is bonded to the para position and the meta position at the bonding position of Z one by one, and Y ₂ (r ₂ = 2) is bonded to the para position and the ortho position of the bonding position of Z one by one. It shall be.

Also, the “asymmetric epoxy ester resin” represented by the formula (15) can be made “asymmetric” by at least one of the following (vi) to (vii).
(Vi) In Equation (16), p ₁ and p ₂ are set to different numerical values, that is, the number of Y _{3 and} the number of Y ₄ are different (for example, one Y _{3 and} two Y ₄ ). ). In this case, s ₁ is 1 or more.
(Vii) In formula (16), the substitution positions of A ₁ , (Y ₃ ) p ₁ and Y ₅ , (Y ₄ ) p ₂ are different even at one place. Here, “the substitution positions of A ₁ , (Y ₃ ) p ₁ and Y ₅ , (Y ₄ ) p ₂ are different even at one place” means that when s ₁ is 2 or more, the formula (16) _a 1 in R _{1 side, (Y} 3) _{p 1} and _a 1 of the _{R 2 side, (Y} 4) or the substitution position of _{p 2} are different even in one place, or _a 1 in _{R 1} side of formula (16), It means that the substitution position of (Y ₃ ) p ₁ and Y ₅ on the R ₂ side and (Y ₄ ) p ₂ is different even at one place [for example, A ₁ and Y ₃ on the R ₁ side (p ₁ = 1) Are bonded to the para position and the meta position at the bonding position of Z, and A ₁ and Y ₄ (p ₂ = 1) on the R ₂ side are bonded to the para position and the ortho position at the bonding position of Z, respectively. In addition, when s ₁ is 1, R ₁ side A ₁ , (Y ₃ ) p ₁ and R ₂ side Y ₅ , (Y ₄ ) p ₂ in formula (16) The replacement position may be different even at one place. [For example, _{A 1} and _Y 3 of _{R 1} side _(p 1 = 1) is attached by one place in the para position and meta-position of the bonding position of Z, the _{R 2} side _{Y 5} and _Y 4 _(p 2 = 1) means one bond at each of the para and ortho positions of the bond position of Z, etc.]. In this case, s ₁ is 1 or more.

Moreover, " _Y3-4 of General formula (16) is group respectively independently selected from General formula (16) and the following general formula (17)," means _{Y3-3 of} Formula (16). ₄ is the formula (17) or Y _3-4 is the formula (16). As a result, the group represented by the formula (16) is a structure (branched structure), and the terminal (Y _3-4 ) is It means that the group is represented by the formula (17). In this case, s ₁ is 1 or more.

In one preferred embodiment of the condensed ring structure-containing asymmetric epoxy ester resin of the present invention, all p _1-2 are 0 and r _1-2 are 0 in the condensed ring structure-containing asymmetric epoxy ester resin of the general formula (15). The following linear general formula (18), which is 1, is exemplified.

ここで一般式（１８）のＹ_６〜７は各々独立して、下記一般式（１９）で示される基である。

ここで一般式（１９）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（１７）で示される基である。

ここで、一般式（１８）、（１９）、（１０）、（１７）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_４〜６、ｍ_２〜４、Ｒ_７、ｓ_１は前記と同じであり、複数個のＲ_１〜２、ｆ_１〜２、ｓ_１、Ａ_１、Ｙ_５、Ｒ_４〜６、ｍ_２〜４、Ｒ_７は同一でも良いし、異なっていても良い。
但し、一般式（１８）、（１９）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、（Ｒ_１）ｆ_２と（Ｒ_２）ｆ_２の置換位置、Ｙ_６とＹ_７の置換位置、及びＡ_１とＹ_５の置換位置のうち少なくとも１つが異なる。

Here, Y _6-7 in the general formula (18) are each independently a group represented by the following general formula (19).

Here, A ₁ in the general formula (19) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (17).

Here, Z, R _1-2 , f _1-2 , R _4-6 , m _2-4 , R ₇ , s ₁ in the general formulas (18), (19), (10), (17) A plurality of R _1-2 , f _1-2 , s ₁ , A ₁ , Y ₅ , R _4-6 , m _2-4 , R ₇ may be the same or different. .
However, the types of R ₁ and R _{2 in} the general formulas (18) and (19), the numerical values of f ₁ and f ₂ , the substitution positions of (R ₁ ) f ₂ and (R ₂ ) f ₂ , Y ₆ and Y ₇ And at least one of the substitution positions of A ₁ and Y ₅ is different.

The condensed ring structure-containing asymmetric epoxy ester resin may be described as “condensed ring structure-containing asymmetric epoxy ester resin (B2)”, “asymmetric epoxy ester resin (B2)”, or the like in this specification. This condensed ring structure-containing asymmetric epoxy ester resin (B2) is included in the aforementioned condensed ring structure-containing asymmetric epoxy ester resin (B). In the general formula (18), preferably, Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably, Z is a condensed group represented by formula (3). A divalent group containing a ring structure, f _1-2 are each independently an integer from 0 to 2, m _2-4 are each independently an integer from 0 to 2, and s ₁ are each independently from 0 It is an integer of 8.

With respect to the asymmetric epoxy ester resin represented by the formula (18), when s ₁ is 0, Y _{6 to 7} are Y ₅ , that is, a group represented by the formula (17).

More specifically, the “asymmetric epoxy ester resin” represented by the formula (18) can be made “asymmetric” by adopting at least one of the following (i) to (iv).
(I) formula (18) or (19), a methyl group and _{R 1,} equal to an ethyl group and _{R 2, R 1} and making the type of the substituent of _{R 2} different.
(Ii) In formula (18) or (19), f ₁ and f ₂ are set to different numerical values, that is, the number of substituents R _{1 and} the number of substituents R ₂ are different (for example, R ₁ is 1 and ₂ R ₂ ).
(Iii) In the formula (18) or (19), R ₁ (f ₁ = 1) is bonded to the ortho position of the bonding position of Z, and R ₂ (f ₂ = 1) is bonded to the meta position of the bonding position of Z. The substitution positions of R ₁ and R ₂ should be different. When f ₁ and f ₂ ≧ 2, the substitution positions of at least one pair of R ₁ and R ₂ out of f ₁ R ₁ and f ₂ R ₂ are different [for example, R ₁ (f ₁ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₂ (f ₁ = 2) is bonded only to the meta position (two positions) of the bonding position of Z. Etc.].
(Iv) In formula (18), Y ₆ is different from the substitution position of Y ₆ and Y ₇ , such as Y ₆ is bonded to the para position of the bonding position of Z, and Y ₇ is bonded to the meta position of the bonding position of Z. To be.

Further, also by the following (v), the “asymmetric epoxy ester resin” represented by the formula (18) can be made “asymmetric”.
(V) In formula (19), the substitution positions of A ₁ and Y ₅ are different. Here, "different substitution position of _{A 1} and _{Y 5",} when _{s 1} is 2 or more, the substitution position _{of A 1} is different from the _{A 1} and _{R 2} side of the _{R 1} side of Formula (19) it is bound to, or means that a ₁ and R ₂ side of Y ₅ of R ₁ side of formula (19) are bonded to different substitution position, and when s ₁ is 1, It means _{that Y 5} of _{a 1} and _{R 2} side of the _{R 1} side of formula (19) are attached to different substitution positions.

As another preferred embodiment of the condensed ring structure-containing asymmetric epoxy ester resin of the present invention, s ₁ is 0 in the condensed ring structure-containing asymmetric epoxy ester resin of the general formula (15). Is mentioned.

ここで一般式（２０）のＹ_５は下記一般式（１７）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで、一般式（２０）、（１７）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_６、Ｒ_７、ｍ_４は前記と同じであり、複数個のＲ_１〜２、Ｙ_５、Ｒ_６、Ｒ_７、ｍ_４は同一でも良いし、異なっていても良い。
但し、一般式（２０）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、及び、（Ｙ_５）ｒ_１と（Ｙ_５）ｒ_２の置換位置のうち少なくとも１つが異なる。

Here, Y ₅ in the general formula (20) is a group represented by the following general formula (17), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z, R _1-2 , f _1-2 , R ₆ , R ₇ , m ₄ in the general formulas (20) and (17) are the same as described above, and a plurality of R _1-2 , Y ₅ , R ₆ , R ₇ and m ₄ may be the same or different.
However, the types of R ₁ and R _{2 in} the general formula (20), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (Y ₅ ) r ₁ and (Y ₅ ) r ₂ at least one of the substitution positions is different.

The condensed ring structure-containing asymmetric epoxy ester resin may be described as “condensed ring structure-containing asymmetric epoxy ester resin (B3)”, “asymmetric epoxy ester resin (B3)”, or the like in this specification. This condensed ring structure-containing asymmetric epoxy ester resin (B3) is included in the aforementioned condensed ring structure-containing asymmetric epoxy ester resin (B). In the general formula (18), preferably, Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably Z is a condensed group represented by formula (3). It is a divalent group containing a ring structure, f _1-2 and m ₄ are each independently an integer of 0 to 2, and r _1-2 are each independently an integer of 1 to 2.

In addition, as r _{1-2 in the} general formula (20) increases, hardness, curability, and the like increase. On the other hand, as _{r 1 to 2} of the general formula (20) is reduced, thereby facilitating the resin handling and design.

More specifically, the “asymmetric epoxy ester resin” represented by the formula (20) can be made “asymmetric” by adopting at least one of the following (i) to (iv).
(I) In the formula (20), the types of substituents of R ₁ and R ₂ are different, for example, R ₁ is a methyl group and R ₂ is an ethyl group.
(Ii) In formula (20), f ₁ and f ₂ are set to different numerical values, that is, the number of substituents R _{1 and} the number of substituents R ₂ are different (for example, _one R ₁ , R _{1 2} is 2).
In (iii) Formula _(20), and different numerical values r 1, _{r 2,} the number of _{Y 5} number and _{R 2} side of the aromatic ring _{Y 5} aromatic rings of _{R 1} side, that formula (20) Be different (for example, one Y ₅ (R ₁ side) and two Y ₅ (R ₂ sides)).
(Iv) In Formula (20), R ₁ (f ₁ = 1) is bonded to the ortho position of the bonding position of Z, R ₂ (f ₂ = 1) is bonded to the meta position of the bonding position of Z, etc. , R ₁ and R ₂ should have different substitution positions. When f ₁ and f ₂ ≧ 2, the substitution positions of at least one pair of R ₁ and R ₂ out of f ₁ R ₁ and f ₂ R ₂ are different [for example, R ₁ (f ₁ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₂ (f ₂ = 2) is bonded to only the meta position (two positions) of the bonding position of Z. Etc.]. In (v) Formula (20), the _{R 1 side, Y 5 (r 1 = 1} ) to have the ortho-position of the bonding positions of Z, the _{R 2 side,} Y 5 a _(r 2 = 1) The substitution position of Y ₅ on the R ₁ side and Y ₅ on the R ₂ side is different, for example, it is in the meta position of the bonding position of Z. _In the case of r 1, _{r 2} ≧ 2, of _{R 1} side of _{Y 5} and _{r 2} pieces is _{R 2} side of _{Y 5} in _{one r,} the substitution position of _{R 2} side with respect to _{R 1} side At least one point is different [for example, Y ₅ (r ₁ = 2) is bonded to the para position and the ortho position of the bonding position of Z one by one, and Y ₅ (r ₂ = 2) is a parameter of the bonding position of Z Etc. having 1 Y ₅ each in the position and meta position].

One preferred embodiment of the condensed ring structure-containing asymmetric epoxy ester resin is that the portion derived from the monobasic carboxylic acid of the condensed ring structure-containing asymmetric epoxy ester resin is a group having an unsaturated group. It is done. These are particularly asymmetric epoxy acrylate resins containing a condensed ring structure, and are shown below.
The asymmetric epoxy acrylate resin containing a condensed ring structure has a radiation polymerizable functional group.

The condensed ring structure-containing asymmetric epoxy acrylate resin of the present invention is represented by the following general formula (21).
This is an asymmetric epoxy ester resin containing a condensed ring structure in which R ₇ is a group having an unsaturated group in the general formula (15). Here, the unsaturated group is an ethenyl group or a 2-propenyl group.

ここで一般式（２１）のＹ_１〜２は、下記一般式（２２）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで一般式（２２）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（２３）で示される基である。さらに、一般式（２２）のＹ_３〜４は、一般式（２２）及び下記一般式（２３）から各々独立して選ばれる基であり、ｐ_１〜２は各々独立して０から４の整数である。

ここで前記一般式（２１）、（２２）、（１０）、（２３）のＺ、Ｒ_１〜２、Ｒ_４〜６、ｆ_１〜２、ｍ_２〜４、ｓ_１は前記と同じである。さらに、前記一般式（２３）のＲ_８は各々独立して水素原子またはメチル基を示す。また、複数個のＲ_１〜２、ｆ_１〜２、ｓ_１、ｐ_１〜２、Ｒ_４〜６、Ｒ_８、Ｙ_１〜５、ｍ_２〜４は同一でも良いし、異なっていても良い。
但し、一般式（２１）、（２２）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、（Ｙ_１）ｒ_１と（Ｙ_２）ｒ_２の置換位置、ｐ_１とｐ_２の数値、及びＡ_１、（Ｙ_３）ｐ_１とＹ_５、（Ｙ_４）ｐ_２の置換位置のうち少なくとも１つが異なる。

Here, Y _1-2 in the general formula (21) is a group represented by the following general formula (22), and r _1-2 are each independently an integer of 1-5.

Here, A ₁ in the general formula (22) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (23). Further, Y _3-4 in the general formula (22) are groups independently selected from the general formula (22) and the following general formula (23), and p _1-2 are each independently 0 to 4 It is an integer.

Here, Z, R _1-2 , R _4-6 , f _1-2 , m _2-4 , and s ₁ in the general formulas (21), (22), (10), and (23) are the same as described above. is there. Further, R _{8 in the} general formula (23) each independently represents a hydrogen atom or a methyl group. A plurality of R _1-2 , f _1-2 , s ₁ , p _1-2 , R _4-6 , R ₈ , Y _1-5 , m _2-4 may be the same or different. good.
However, the types of R ₁ and R _{2 in} the general formulas (21) and (22), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , (R ₁ ) f ₁ and (R ₂ ) f ₂ substitution _{position, (Y 1) r} 1 and _(Y 2) substitution position of _{r 2,} numerical values of _{p 1} and _{p 2,} and _{a 1, (Y 3) p} 1 and _{Y 5,} substitution of _(Y 4) _{p 2} At least one of the positions is different.

In this specification, the condensed ring structure-containing asymmetric epoxy ester resin is referred to as “condensed ring structure-containing asymmetric epoxy ester resin (B4)”, “asymmetric epoxy ester resin (B4)”, “condensed ring structure-containing asymmetric epoxy acrylate resin”. (B4) ”,“ asymmetric epoxy acrylate resin (B4) ”and the like. This condensed ring structure-containing asymmetric epoxy ester resin (B4) is included in the aforementioned condensed ring structure-containing asymmetric epoxy ester resin (B). In the general formulas (21), (22), (10), and (23), Z is preferably a divalent group including a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably Z. Is a divalent group containing a condensed ring structure represented by Formula (3), p _1-2 and f _1-2 are each independently an integer of 0 to 2, and m _2-4 are each independently 0 An integer of 2 and s ₁ are each independently an integer of 0 to 8.

Condensed ring structures containing asymmetric epoxy acrylate resin of the present invention, the above general formula (22) condensed ring structures containing asymmetric epoxy acrylate resin when either p _{1 to 2} is one or more of a branched structure. When all of p _{1 and 2} are 0, the condensed ring structure-containing asymmetric epoxy acrylate resin is a linear resin.

The branched condensed ring structure-containing asymmetric epoxy acrylate resin having a branch is superior in, for example, heat resistance, curability, and dispersion stability. It is advantageous in that it is simple and increases the degree of freedom in resin design.

With respect to the asymmetric epoxy acrylate resin represented by the formula (21), when s ₁ is 0, Y _1-2 is Y ₅ , that is, a group represented by the formula (23).

More specifically, the “asymmetric epoxy acrylate resin” represented by the formula (21) can be made “asymmetric” by adopting at least one of the following (i) to (iv).
(I) formula (21) or (22), a methyl group and _{R 1,} equal to an ethyl group and _{R 2, R 1} and making the type of the substituent of _{R 2} different.
(Ii) In formula (21) or (22), f ₁ and f ₂ are set to different numerical values, that is, the number of substituents R _{1 and} the number of substituents R ₂ are different (for example, R ₁ is 1 and ₂ R ₂ ).
(Iii) In formula (21), r ₁ and r ₂ are set to different numerical values, that is, the number of Y _{1 and} the number of Y ₂ in formula (21) are different (for example, _one Y ₁ , Y ₂ are two).
(Iv) In the formula (21) or (22), R ₁ (f ₁ = 1) is bonded to the ortho position of the bonding position of Z, and R ₂ (f ₂ = 1) is bonded to the meta position of the bonding position of Z. The substitution positions of R ₁ and R ₂ should be different. When f ₁ and f ₂ ≧ 2, the substitution positions of at least one pair of R ₁ and R ₂ out of f ₁ R ₁ and f ₂ R ₂ are different [for example, R ₁ (f ₁ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₂ (f ₁ = 2) is bonded only to the meta position (two positions) of the bonding position of Z. Etc.]. (V) In the formula (21), Y ₁ (r ₁ = 1) is the para position at the bonding position of Z, Y ₂ (r ₂ = 1) is bonded to the meta position at the bonding position of Z, etc. , Y ₁ and Y ₂ should have different substitution positions. Further, in the case of f ₁ and f ₂ ≧ 2, at least one pair of Y ₁ and Y ₂ is substituted at different positions among r ₁ Y ₁ and r ₂ Y ₂ [for example, Y ₁ (r ₁ = 2) is bonded to the para position and the meta position at the bonding position of Z one by one, and Y ₂ (r ₂ = 2) is bonded to the para position and the ortho position of the bonding position of Z one by one. It shall be.

Also, the “asymmetric epoxy acrylate resin” represented by the formula (21) can be made “asymmetric” by at least one of the following (vi) to (vii).
(Vi) In formula (22), p ₁ and p ₂ are set to different numerical values, that is, the number of Y _{3 and} the number of Y ₄ are different (for example, one Y _{3 and} two Y ₄ ). ). In this case, s ₁ is 1 or more.
(Vii) In formula (22), the substitution positions of A ₁ , (Y ₃ ) p ₁ and Y ₅ , (Y ₄ ) p ₂ are different even at one place. Here, “the substitution positions of A ₁ , (Y ₃ ) p ₁ and Y ₅ , (Y ₄ ) p ₂ are different even at one place” means that when s ₁ is 2 or more, the formula (22) R ₁ side A ₁ , (Y ₃ ) p ₁ and R ₂ side A ₁ and (Y ₄ ) p ₂ have different substitution positions at one place, or A ₁ on the R ₁ side of the formula (22), It means that the substitution position of (Y ₃ ) p ₁ and Y ₅ on the R ₂ side and (Y ₄ ) p ₂ is different even at one place [for example, A ₁ and Y ₃ on the R ₁ side (p ₁ = 1) Are bonded to the para position and the meta position at the bonding position of Z, and A ₁ and Y ₄ (p ₂ = 1) on the R ₂ side are bonded to the para position and the ortho position at the bonding position of Z, respectively. In addition, when s ₁ is 1, R ₁ side A ₁ , (Y ₃ ) p ₁ and R ₂ side Y ₅ , (Y ₄ ) p _{2 in} the formula (22) The replacement position is different even at one place And [for example, _{A 1} and _Y 3 of _{R 1} side _(p 1 = 1) is attached by one place in the para position and meta-position of the bonding position of Z, the _{R 2} side _{Y 5} and _Y 4 _{(p 2} = 1) means that one bond is bonded to each of the para position and the ortho position of the bond position of Z. In this case, s ₁ is 1 or more.

Moreover, " _Y3-4 of General formula (22) is a group each independently selected from General formula (22) and the following general formula (23)," means _{Y3-3 of} Formula (22). ₄ is the formula (23) or Y _3-4 is the formula (22). As a result, the group represented by the formula (22) becomes a structure (branched structure), and the terminal (Y _3-4 ) is It means that the group is represented by the formula (23). In this case, s ₁ is 1 or more.

One preferred embodiment includes the following general formula (24) in which all the p _1-2 are 0 and r _1-2 are 1 in the condensed ring structure-containing asymmetric epoxy acrylate resin of the general formula (21). .

ここで一般式（２４）のＹ_６〜７は各々独立して、下記一般式（２５）で示される基である。

ここで一般式（２５）のＡ_１は、下記一般式（１０）で示される二価基であり、Ｙ_５は、下記一般式（２３）で示される基である。

ここで、一般式（２４）、（２５）、（１０）、（２３）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_４〜６、ｍ_２〜４、Ｒ_８、ｓ_１は前記と同じであり、複数個のＲ_１〜２、Ａ_１、Ｙ_５、ｆ_１〜２、ｓ_１、Ｒ_４〜６、ｍ_２〜４、Ｒ_８は同一でも良いし、異なっていても良い。
但し、一般式（２４）、（２５）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、（Ｒ_１）ｆ_２と（Ｒ_２）ｆ_２の置換位置、Ｙ_６とＹ_７の置換位置、及びＡ_１とＹ_５の置換位置のうち少なくとも１つが異なる。

Here, Y _6-7 in the general formula (24) are each independently a group represented by the following general formula (25).

Here, A ₁ in the general formula (25) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (23).

Here, Z, R _1-2 , f _1-2 , R _4-6 , m _2-4 , R ₈ , s ₁ in the general formulas (24), (25), (10), (23) The plurality of R _1-2 , A ₁ , Y ₅ , f _1-2 , s ₁ , R _4-6 , m _2-4 , R ₈ may be the same or different. .
However, the types of R ₁ and R _{2 in} the general formulas (24) and (25), the numerical values of f ₁ and f ₂ , the substitution positions of (R ₁ ) f ₂ and (R ₂ ) f ₂ , Y ₆ and Y ₇ And at least one of the substitution positions of A ₁ and Y ₅ is different.

This condensed ring structure-containing asymmetric epoxy ester resin is referred to as “condensed ring structure-containing asymmetric epoxy ester resin (B5)”, “asymmetric epoxy ester resin (B5)”, “condensed ring structure-containing asymmetric epoxy acrylate resin”. (B5) ”,“ asymmetric epoxy acrylate resin (B5) ”and the like. This condensed ring structure-containing asymmetric epoxy ester resin (B5) is included in the aforementioned condensed ring structure-containing asymmetric epoxy ester resin (B). In the general formula (24), preferably, Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), more preferably Z is a condensed group represented by formula (3). A divalent group containing a ring structure, f _1-2 are each independently an integer from 0 to 2, m _2-4 are each independently an integer from 0 to 2, and s ₁ are each independently from 0 It is an integer of 8.

With respect to the asymmetric epoxy acrylate resin represented by the formula (24), when s ₁ is 0, Y _{6 to 7} are Y ₅ , that is, a group represented by the formula (23).

More specifically, the “asymmetric epoxy acrylate resin” represented by the formula (24) can be made “asymmetric” by adopting at least one of the following (i) to (iv).
(I) formula (24) or (25), a methyl group and _{R 1,} equal to an ethyl group and _{R 2, R 1} and making the type of the substituent of _{R 2} different.
(Ii) In formula (24) or (25), f ₁ and f ₂ are set to different numerical values, that is, the number of substituents R _{1 and} the number of substituents R ₂ are different (for example, R ₁ is 1 and ₂ R ₂ ).
(Iii) In Formula (24) or (25), R ₁ (f ₁ = 1) is bonded to the ortho position of the bonding position of Z, and R ₂ (f ₂ = 1) is bonded to the meta position of the bonding position of Z. The substitution positions of R ₁ and R ₂ are different from each other. When f ₁ and f ₂ ≧ 2, the substitution positions of at least one pair of R ₁ and R ₂ out of f ₁ R ₁ and f ₂ R ₂ are different [for example, R ₁ (f ₁ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₂ (f ₁ = 2) is bonded only to the meta position (two positions) of the bonding position of Z. Etc.].
(Iv) In formula (24), Y ₆ is different in the substitution position of Y ₆ and Y ₇ such that Y ₆ is bonded to the para position of the bonding position of Z and Y ₇ is bonded to the meta position of the bonding position of Z To be.

Further, also by (v) below, the “asymmetric epoxy acrylate resin” represented by the formula (24) can be made “asymmetric”.
(V) In formula (25), the substitution positions of A ₁ and Y ₅ are different. Here, "different substitution position of _{A 1} and _{Y 5",} when _{s 1} is 2 or more, the substitution position _{of A 1} is different from the _{A 1} and _{R 2} side of the _{R 1} side of Formula (25) it is bound to, or means that a ₁ and R ₂ side of Y ₅ of R ₁ side of formula (25) are bonded to different substitution position, and when s ₁ is 1, It means _{that Y 5} of _{a 1} and _{R 2} side of the _{R 1} side of formula (25) are attached to different substitution positions.

Still another preferred embodiment includes the following general formula (26) in which all s ₁ are 0 in the condensed ring-containing asymmetric epoxy acrylate resin of the general formula (21).

ここで一般式（２６）のＹ_５は下記一般式（２３）で示される基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで、一般式（２６）、（２３）のＺ、Ｒ_１〜２、ｆ_１〜２、Ｒ_６、Ｒ_８、ｍ_４は前記と同じであり、複数個のＲ_１〜２、Ｙ_５、Ｒ_６、Ｒ_８、ｍ_４は同一でも良いし、異なっていても良い。
但し、一般式（２６）のＲ_１とＲ_２の種類、ｆ_１とｆ_２の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、及び、（Ｙ_５）ｒ_１と（Ｙ_５）ｒ_２の置換位置のうち少なくとも１つが異なる。

Here, Y ₅ in the general formula (26) is a group represented by the following general formula (23), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z, R _1-2 , f _1-2 , R ₆ , R ₈ , m ₄ in the general formulas (26) and (23) are the same as described above, and a plurality of R _1-2 , Y ₅ , R ₆ , R ₈ and m ₄ may be the same or different.
However, the types of R ₁ and R _{2 in} the general formula (26), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (Y ₅ ) r ₁ and (Y ₅ ) r ₂ at least one of the substitution positions is different.

This condensed ring structure-containing asymmetric epoxy acrylate resin is referred to herein as "condensed ring structure-containing asymmetric epoxy ester resin (B6)", "asymmetric epoxy ester resin (B6)", "condensed ring structure-containing asymmetric epoxy acrylate resin". (B6) ”,“ asymmetric epoxy acrylate resin (B6) ”and the like. This condensed ring structure-containing asymmetric epoxy ester resin (B6) is included in the aforementioned condensed ring structure-containing asymmetric epoxy ester resin (B). In the general formula (26), preferably, Z is a divalent group including a condensed ring structure selected from the group consisting of the above formulas (3) to (7), more preferably Z is represented by the above formula (3). Each of f _1-2 and m ₄ is independently an integer from 0 to 2, and r _1-2 is each independently an integer from 1 to 2.

In addition, as r _{1-2 in the} general formula (26) increases, hardness, curability, and the like increase. On the other hand, as r _1-2 in general formula (26) decreases, the handling and design of the resin becomes easier.

More specifically, the “asymmetric epoxy acrylate resin” represented by the formula (26) can be made “asymmetric” by adopting at least one of the following (i) to (iv).
(I) formula (26), a methyl group and _{R 1,} equal to an ethyl group and _{R 2, R 1} and making the type of the substituent of _{R 2} different.
(Ii) In the formula (26), f ₁ and f ₂ are set to different numerical values, that is, the number of substituents R _{1 and} the number of substituents R ₂ are different (for example, _one R ₁ , R _{1 2} is 2).
In (iii) Formula _(26), and different numerical values r 1, _{r 2,} the number of number and _{R 2} of the side of the aromatic ring _{Y 5} of _{Y 5} aromatic rings of _{R 1} side, that formula (26) Be different (for example, one Y ₅ (R ₁ side) and two Y ₅ (R ₂ sides)).
(Iv) In the formula (26), R ₁ (f ₁ = 1) is bonded to the ortho position of the bonding position of Z, R ₂ (f ₂ = 1) is bonded to the meta position of the bonding position of Z, etc. , R ₁ and R ₂ should have different substitution positions. When f ₁ and f ₂ ≧ 2, the substitution positions of at least one pair of R ₁ and R ₂ out of f ₁ R ₁ and f ₂ R ₂ are different [for example, R ₁ (f ₁ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₂ (f ₂ = 2) is bonded to only the meta position (two positions) of the bonding position of Z. Etc.]. (V) In the formula (26), on the R ₁ side, Y ₅ (r ₁ = 1) is in the ortho position of the Z bonding position, and on the R ₂ side, Y ₅ (r ₂ = 1) is present. The substitution position of Y ₅ on the R ₁ side and Y ₅ on the R ₂ side is different, for example, it is in the meta position of the bonding position of Z. _In the case of r 1, _{r 2} ≧ 2, of _{R 1} side of _{Y 5} and _{r 2} pieces is _{R 2} side of _{Y 5} in _{one r,} the substitution position of _{R 2} side with respect to _{R 1} side At least one point is different [for example, Y ₅ (r ₁ = 2) is bonded to the para position and the ortho position of the bonding position of Z one by one, and Y ₅ (r ₂ = 2) is a parameter of the bonding position of Z Etc. having 1 Y ₅ each in the position and meta position].

The asymmetric epoxy ester resin (B) can be obtained, for example, by allowing a monobasic carboxylic acid to act on the asymmetric epoxy resin (A) described above.
Alternatively, it can be obtained by allowing glycidyl monobasic carboxylate to act on the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D) represented by the general formula (1).

Examples of the monobasic carboxylic acid used for the preparation of the asymmetric epoxy ester resin (B) include, but are not limited to, the following compounds having one carboxyl group: (meth) acrylic acid, cyclopropanecarboxylic acid 2,2,3,3-tetramethyl-1-cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, 2-cyclopentenylcarboxylic acid, 2-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid, cyclohexanecarboxylic acid, 4-propyl Cyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-heptylcyclohexanecarboxylic acid, 4-cyanocyclohexane-1-carboxylic acid, 4-hydroxycyclohexanecarbo Acid, 1,3,4,5-tetrahydroxycyclohexane-1-carboxylic acid, 2- (1,2-dihydroxy-4-methylcyclohexyl) propionic acid, shikimic acid, 3-hydroxy-3,3-diphenylpropionic acid 3- (2-oxocyclohexyl) propionic acid, 3-cyclohexene-1-carboxylic acid, alkyl 4-cyclohexene-1,2-dicarboxylate, hydrogen, cycloheptanecarboxylic acid, norbornenecarboxylic acid, tetracyclododecenecarboxylic acid, 1-adamantanecarboxylic acid, (4-tricyclo [5.2.1.0 ^2.6 ] dec-4-yl) acetic acid, p-methylbenzoic acid, p-ethylbenzoic acid, p-octylbenzoic acid, p- Decylbenzoic acid, p-dodecylbenzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, p-propoxy Benzoic acid, p-butoxybenzoic acid, p-pentyloxybenzoic acid, p-hexyloxybenzoic acid, p-fluorobenzoic acid, p-chlorobenzoic acid, p-chloromethylbenzoic acid, pentafluorobenzoic acid, pentachlorobenzoic acid 4-acetoxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-di-t-butyl-4-hydroxybenzoic acid, o-benzoylbenzoic acid, o-nitrobenzoic acid, o- (acetoxybenzoyloxy) Benzoic acid, terephthalic acid monomethyl ester, isophthalic acid monomethyl ester, isophthalic acid monocyclohexyl ester, phenoxyacetic acid, chlorophenoxyacetic acid, phenylthioacetic acid, phenylacetic acid, 2-oxo-3-phenylpropionic acid, o-bromophenylacetic acid, o- Iodophenylacetic acid, methoxypheny Acetic acid, 6-phenylhexanoic acid, biphenylcarboxylic acid, α-naphthoic acid, β-naphthoic acid, anthracenecarboxylic acid, phenanthrenecarboxylic acid, anthraquinone-2-carboxylic acid, indanecarboxylic acid, 1,4-dioxo-1,4 -Dihydronaphthalene-2-carboxylic acid, 3,3-diphenylpropionic acid, nicotinic acid, isonicotinic acid, cinnamic acid, 3-methoxycinnamic acid, 4-methoxycinnamic acid, quinolinecarboxylic acid, etc. You may use independently and may combine 2 or more types.
Particularly preferred monobasic carboxylic acids are those containing an unsaturated group capable of introducing a radiation-polymerizable functional group. For example, (meth) acrylic acid is preferred.
Incidentally, R ₇ of the general formula (17) is a part formed in the single basic carboxylic acids described above.

Moreover, the monobasic carboxylic acid used for preparation of the asymmetric epoxy ester resins (B4) to (B6) is selected from (meth) acrylic acid.

Examples of monobasic glycidyl carboxylates used for the preparation of the asymmetric epoxy ester resin (B) include, but are not limited to: glycidyl (meth) acrylate, glycidyl acetate, glycidyl butyrate, benzoic acid Glycidyl, glycidyl p-ethylbenzoate, glycidyl (tere) phthalate, and the like may be used alone or in combination of two or more.
Particularly preferred monobasic glycidyl carboxylates are those containing an unsaturated group capable of introducing a radiation-polymerizable functional group. For example, glycidyl (meth) acrylate is preferred.
Incidentally, R ₇ of the general formula (17) is a part formed in the above-mentioned monobasic carboxylic acids glycidyl.

Moreover, the monobasic glycidyl carboxylate used for preparation of the asymmetric epoxy ester resins (B4) to (B6) is selected from glycidyl (meth) acrylate.

The reaction between the asymmetric epoxy resin (A) and the monobasic carboxylic acid, and the reaction between the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (D) and the monobasic glycidyl carboxylate are all appropriate as necessary. For 5 to 30 hours in a temperature range of 50 to 120 ° C. Examples of the solvent that can be used include methyl cellosolve acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and 3-methoxybutyl-1-acetate. Alkylene monoalkyl ether acetates such as; alkylene monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dibutyl ether; ketones such as methyl ethyl ketone and methyl amyl ketone; dimethyl succinate, diethyl succinate, diethyl adipate , Marron Diethyl, and the like esters such as dibutyl oxalate. Of these, propylene glycol monomethyl ether acetate and 3-methoxybutyl-1-acetate are preferred. Furthermore, a catalyst and a polymerization inhibitor can be used as necessary. Examples of the catalyst used include phosphonium salts, quaternary ammonium salts, phosphine compounds, tertiary amine compounds, imidazole compounds, and the like, and usually used in a range of 0.01 to 10% by weight of the total reaction product. It is preferred that Examples of the polymerization inhibitor to be used include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 4-methylquinoline, phenothiazine, and the like, and can be usually added in the following range of 5% by weight of the whole reaction product.

Among the asymmetric epoxy ester resins (B), those having an unsaturated group in the molecule, for example, asymmetric epoxy acrylate resins (B4) to (B6), have thermosetting properties and radiation curable properties. Here, the radiation is a generic term for visible light, ultraviolet rays, electron beams, X-rays, α rays, β rays, γ rays, and the like. Therefore, the epoxy acrylate resin composition containing the asymmetric epoxy acrylate resins (B4) to (B6) functions as a thermosetting or radiation sensitive resin composition.
Further, among the asymmetric epoxy ester resins (B) of the present invention, those having no radiation curability can be contained in the radiation-sensitive resin composition, and the radiation-sensitive resin composition containing them. Can be imparted with heat resistance, dispersibility, optical properties and the like derived from the condensed ring structure.
In any composition, the asymmetric epoxy ester resin (B) may be contained alone or as a mixture of two or more.

When the epoxy ester resin composition containing the asymmetric epoxy ester resin (B) is a radiation sensitive resin composition, the composition includes (I) light in addition to the asymmetric epoxy acrylate resin (B). A polymerization initiator may be contained, and in the case of a thermosetting resin composition, (II) a radical initiator may be contained. Further, in any of these compositions, (III) a photocurable or thermosetting acrylate compound other than the asymmetric epoxy ester resin (B), (IV) additive, (V) solvent, (VI) solid fine particles Etc. may be contained.

The photopolymerization initiator of (I) that can be contained in the radiation-sensitive resin composition containing the asymmetric epoxy ester resin (B) of the present invention is the asymmetric epoxy ester resin (B) and the above-mentioned if necessary. A compound having an effect of initiating photopolymerization of a photocurable acrylate compound and / or a compound having a sensitizing effect. Examples of such a photopolymerization initiator include the following compounds: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert. -Acetophenones such as butyl acetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzyldimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropyl Sulfur compounds such as ruthioxanthene; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, etc. Organic peroxides; and thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole.

The blending amount of such a photopolymerization initiator is preferably 0.05 to 5.0 parts by weight, more preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the radiation curable unsaturated group-containing compound. Part.
The “radiation curable unsaturated group-containing compound” means all the radiation curable unsaturated group-containing compounds contained in the radiation-sensitive resin composition, and is an asymmetric epoxy ester resin (B) of the present invention. Including those having radiation curability and photocurable or thermosetting acrylate compounds other than the asymmetric epoxy ester resin (B) of the present invention.

These compounds may be used individually by 1 type, and can also be used in combination of 2 or more type. In addition, a compound that does not act as a photopolymerization initiator per se, but that can increase the ability of the photopolymerization initiator by using it in combination with the above-mentioned compound can also be added. Examples of such compounds include tertiary amines such as triethanolamine which are effective when used in combination with benzophenone.

The radical initiator (II) that can be contained in the thermosetting resin composition includes ketone peroxide compounds, diacyl peroxide compounds, hydroperoxide compounds, dialkyl peroxide compounds, and peroxyketal compounds. , Radical initiators composed of alkyl perester compounds, percarbonate compounds, azobis compounds, and the like are used. In particular, diacyl peroxide type or azobis type radical initiators are suitable, and for example, benzoyl peroxide, α, α'-azobis (isobutyronitrile), etc. are widely used. These compounds may be used individually by 1 type, and can also be used in combination of 2 or more type.

As for the compounding quantity of such a radical initiator, 0.05-10.0 weight part is preferable with respect to 100 weight part of radiation-curable unsaturated group containing compounds, More preferably, it is 0.1-5.0 weight part. It is.

A photocurable or thermosetting acrylate compound other than the asymmetric epoxy ester resin (B) of (III) is used as a viscosity modifier or a photocrosslinking agent depending on the physical properties required for the composition, The compound is contained in the composition within a predetermined range. Examples of such acrylate compounds include the following compounds: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. Monovalent acrylate having a hydroxyl group such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyhydric such as glycerol (meth) acrylate (meth) acrylate.

These compounds can be used alone or in combination of two or more.

These compounds can be contained within a range that does not impair the properties of the resin composition of the present invention. Usually, these compounds are contained at a ratio of 50 parts by weight or less per 100 parts by weight of the condensed ring structure-containing asymmetric epoxy ester resin. When the amount exceeds 50 parts by weight, cracking is likely to occur when the composition containing the component is cured, and the adhesion tends to be lowered.
However, this is not the case when the condensed ring structure-containing asymmetric epoxy ester resin having no radiation curability is used.

As the additive (IV), a thermal polymerization inhibitor, an adhesion assistant, an antifoaming agent, a surfactant, a plasticizer and the like are used depending on the purpose of use of the composition.

Among these, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like. These compounds can be used alone or in combination of two or more. The blending amount of such a thermal polymerization inhibitor can be contained in a proportion of 5 parts by weight or less with respect to 100 parts by weight of the radiation curable unsaturated group-containing compound.

The adhesion assistant is added for the purpose of improving the adhesion to the substrate when the liquid composition containing the asymmetric epoxy ester resin (B) is applied to the substrate. As the adhesion assistant, a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanato group, or an epoxy group is preferably used. Specific examples of such functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ -Glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

Such compounding amount of the adhesion assistant can be usually contained at a ratio of 5 parts by weight or less with respect to 100 parts by weight of the epoxy ester resin.

Examples of antifoaming agents include silicone compounds, fluorine compounds, acrylic compounds, and the like.

The surfactant is contained for the purpose of facilitating application of the liquid composition and improving the flatness of the resulting coating film. Examples of the surfactant include silicone-based, fluorine-based, and acrylic compounds. Specifically, for example, BM-1000 [manufactured by BM Hemy Co.]; Megafuck F142D, Megafuck F172, Megafuck F173, Megafuck F183 [manufactured by Dainippon Ink & Chemicals, Inc.]; Fluorard FC-135, Fluorard FC-170C, Florard FC-430, Florard FC-431 [manufactured by Sumitomo 3M Limited]; Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 [Asahi Glass Co., Ltd. SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 [manufactured by Toray Silicone Co., Ltd.] and the like.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl.

Examples of the solvent (V) include the following solvents: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Glycol ethers such as dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate Carbonate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, alkylene glycol monoalkyl ether acetates such as 3-methoxybutyl-1-acetate; aroma such as toluene and xylene Group hydrocarbons; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; and ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid Methyl, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydro Methyl 2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, succinic acid Esters such as dimethyl, diethyl succinate, diethyl adipate, diethyl malonate, and dibutyl oxalate. These solvents may be used alone or in a combination of two or more. When such a solvent is added, the blending amount is preferably 5 to 70% by weight of the entire composition.

Examples of the solid fine particles (VI) include organic pigments and inorganic fine particles, which can be added for use in applications such as optical materials and display element materials. Specific examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), and the central metals are Cu, Mg, Al, Si, Examples thereof include dissimilar metal phthalocyanine pigments such as Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn. Specific examples of the inorganic fine particles include titanium oxide, zirconium oxide, zinc oxide, aluminum oxide, cerium oxide, tin oxide, tantalum oxide, indium tin oxide, and hafnium barium sulfate metal oxides; or calcium carbonate, Metal salts such as gold chloride, gold bromide, silver chloride, silver bromide, silver iodide, palladium chloride, chloroplatinic acid, sodium chloroaurate, silver nitrate, platinum acetylacetonate, palladium acetylacetonate; gold, silver, Noble metals such as platinum, palladium, rhodium, ruthenium, iridium; zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, List amber, titanium black, synthetic iron black, carbon black, carbon nanotube, etc. It can be. These solid fine particles can be used alone or in combination of two or more. The particle size of these solid fine particles is, for example, 1 nm to 5 μm.
In addition, when such solid fine particles are added, the amount used is appropriately selected depending on the application and the type of the solid fine particles, but is contained in an amount that does not impair the original properties of the resin composition of the present invention. , And can be contained at a ratio of 1 to 300 parts by weight with respect to 100 parts by weight of the epoxy ester resin.

Examples of the radiation used for curing the radiation-sensitive resin composition of the present invention include visible light, ultraviolet light, electron beam, X-ray, α-ray, β-ray, and γ-ray in order from the longest wavelength. Of these, ultraviolet rays are the most preferable radiation from the viewpoint of economy and efficiency. As the ultraviolet light used in the present invention, ultraviolet light oscillated from a lamp such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an arc lamp, a metal halide lamp, or a xenon lamp can be preferably used. The above radiation having a shorter wavelength than ultraviolet rays is theoretically superior to ultraviolet rays because of its high chemical reactivity, but ultraviolet rays are practical from the viewpoint of economy.

The composition of the present invention is formed into a molded product according to the purpose. A molded body obtained by curing the asymmetric epoxy ester resin composition of the present invention is also one aspect of the present invention.
The molded body may be a product having a desired shape made of a cured product of the composition itself, or a coating film made of a cured product of the composition formed on a substrate.

For example, a cured film can be formed on a substrate by applying and drying a liquid composition containing a solvent on the substrate and then irradiating or heating with radiation (for example, light). Alternatively, the radiation-curable or thermosetting composition is heated and melted as necessary, poured into a predetermined mold, heated, or irradiated with radiation to obtain a molded article having a desired shape.

A molded body (including a coating film) formed of the composition of the present invention has high flexibility and hardness, extremely excellent heat resistance, and has a high refractive index.

Since the condensed ring structure-containing asymmetric epoxy ester resin (B) of the present invention is excellent in compatibility with other compounds and has a low melting temperature, the degree of freedom in blending and molding the composition is very high. The condensed ring structure-containing asymmetric epoxy ester resin (B) is excellent in heat resistance and optical characteristics. The thermosetting or radiation-sensitive composition containing this asymmetric epoxy ester resin is used for various applications. Specifically, for example, it is useful as various coating agents, particularly coating agents that require high hardness and heat resistance. Or a resist ink material for a color filter; a material for a protective film of an electronic component (for example, a material for forming a protective film used for a liquid crystal display element, an integrated circuit element, a solid-state image sensor including a color filter); Alternatively, it is suitably used as a photosensitive composition suitable for forming a planarizing film; a solder resist used in the production of a printed wiring board; or a columnar spacer used as a substitute for a bead spacer in a liquid crystal display element. Furthermore, the composition of the present invention comprises materials for various optical parts (lenses, LEDs, plastic films, substrates, optical disks, etc.); a coating agent for forming a protective film for the optical parts; an adhesive for optical parts (adhesive for optical fibers) Etc.); a coating agent for producing a polarizing plate; a photosensitive resin composition raw material for hologram recording, and the like.

Since the condensed ring structure-containing asymmetric epoxy ester resin (B) of the present invention is excellent in dispersibility, it can be suitably used when an organic pigment or inorganic fine particles are dispersed in the composition. A molded body obtained by curing this composition is also one aspect of the present invention.

C. Condensed ring structure-containing asymmetric alkali-soluble resin The condensed ring structure-containing asymmetric alkali-soluble resin of the present invention is a condensed ring-structure-containing asymmetric epoxy ester resin represented by the general formulas (15) to (26), etc. ) And a polybasic carboxylic acid or anhydride thereof. The condensed ring structure-containing asymmetric alkali-soluble resin is described herein as “condensed ring structure-containing asymmetric alkali-soluble resin (C)”, “asymmetric alkali-soluble resin (C)”, and the like. There is a case.

An example of the condensed ring structure-containing asymmetric alkali-soluble resin (C) is, for example, a resin represented by the following general formula (29):

ここで一般式（２９）のＹ_１〜２は各々独立して、下記一般式（３０）、（３３）若しくは、下記一般式（３４）から選ばれる基であり、ｒ_１〜２は各々独立して１から５の整数である。

ここで一般式（３０）のＡ_１、Ａ_３は各々独立して、下記一般式（３１）で示される二価基、Ａ_２は、下記一般式（３２）で示される二価基であり、Ｙ_５は下記一般式（３３）若しくは、下記一般式（３４）で示される基である。さらに、一般式（３０）のＹ_３〜４、Ｙ_６〜９は、一般式（３０）、下記一般式（３３）若しくは、下記一般式（３４）から各々独立して選ばれる基であり、ｐ_１〜６は各々独立して０から４の整数である。

ここで前記一般式（２９）、（３０）のＺは、六員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つ以上の芳香環との縮環構造、または、五員環の脂環式化合物（環上に炭素以外の原子を含んでもよい）と１つの芳香環との縮環構造を含む二価基であり、Ｒ_１〜２、Ｒ_{１３〜１８}は各々独立して、炭素数１から１０の直鎖状、分岐状または環状のアルキル基若しくはアルケニル基、炭素数１から５のアルコキシ基、ハロゲン原子、又は置換基を有していてもよいフェニル基、ｆ_１〜８は各々独立して０から４の整数である。さらに、前記一般式（３０）、（３１）、（３２）、（３３）、（３４）のＲ_４〜６、Ｒ_９〜１０は各々独立して水素原子またはメチル基、Ｒ_７及びＲ_{１１〜１２}は単塩基性カルボン酸に由来する部位を含む基を示し、ｍ_２〜６、ｓ_１〜２は各々独立して０から１０の整数であり、ｕ_１は１から６０の整数である。そして、Ｌ_１〜２は各々独立して多塩基性カルボン酸又は多塩基性カルボン酸無水物の残基である。また、複数個のＲ_１〜２、Ｒ_４〜７、Ｒ_９〜１８、Ｙ_１〜９、Ａ_１〜３、Ｌ_１〜２、ｆ_１〜８、ｐ_１〜６、ｓ_１〜２、ｕ_１、ｍ_２〜６は同一でも良いし、異なっていても良い。
但し、Ｒ_１とＲ_２の種類、Ｒ_１３とＲ_１４の種類、Ｒ_１５とＲ_１６の種類、Ｒ_１７とＲ_１８の種類、ｆ_１とｆ_２の数値、ｆ_３とｆ_４の数値、ｆ_５とｆ_６の数値、ｆ_７とｆ_８の数値、ｒ_１とｒ_２の数値、（Ｒ_１）ｆ_１と（Ｒ_２）ｆ_２の置換位置、（Ｒ_１３）ｆ_３と（Ｒ_１４）ｆ_４の置換位置、（Ｒ_１５）ｆ_５と（Ｒ_１６）ｆ_６の置換位置、（Ｒ_１７）ｆ_７と（Ｒ_１８）ｆ_８の置換位置、（Ｙ_１）ｒ_１と（Ｙ_２）ｒ_２の置換位置、ｐ_１とｐ_２の数値、ｐ_３とｐ_４の数値、ｐ_５とｐ_６の数値、及び一般式（３０）におけるＡ_１、（Ｙ_３）ｐ_１とＡ_２、（Ｙ_４）ｐ_２の置換位置、、Ａ_２、（Ｙ_６）ｐ_３とＡ_３、（Ｙ_７）ｐ_４の置換位置、Ａ_３、（Ｙ_８）ｐ_５とＹ_５、（Ｙ_９）ｐ_６の置換位置のうち少なくとも１つが異なる。

Here, Y _1-2 in the general formula (29) are each independently a group selected from the following general formula (30), (33) or the following general formula (34), and r _1-2 are each independently It is an integer from 1 to 5.

Here, A ₁ and A ₃ in the general formula (30) are each independently a divalent group represented by the following general formula (31), and A ₂ is a divalent group represented by the following general formula (32). Y ₅ is a group represented by the following general formula (33) or the following general formula (34). Furthermore, Y _{3-4 and} Y _6-9 in the general formula (30) are groups independently selected from the general formula (30), the following general formula (33), or the following general formula (34). p _{1 to 6} are each independently an integer of 0 to 4.

Here, Z in the general formulas (29) and (30) is a condensed ring structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings, Or it is a bivalent group containing the condensed ring structure of a 5-membered alicyclic compound (it may contain atoms other than carbon on a ring) and one aromatic ring, and R _{< 1-2 >} , R _{<13> -18} Are each independently a linear, branched or cyclic alkyl or alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, or an optionally substituted phenyl The groups f _1-8 are each independently an integer from 0 to 4. Further, R _4-6 and R _9-10 in the general formulas (30), (31), (32), (33), (34) are each independently a hydrogen atom or a methyl group, R ₇ and R _{11. 12} represents a group containing a site derived from monobasic carboxylic _acids, m _{2~6, s 1~2} are each independently an integer from 0 to 10, _{u 1} is an integer from 1 to 60 . L ₁ and ₂ are each independently a residue of a polybasic carboxylic acid or polybasic carboxylic acid anhydride. Further, a plurality of _{R 1~2, R 4~7, R 9~18} , Y 1~9, A 1~3, L 1~2, f 1~8, p 1~6, s 1~2, u ₁ and m _{2 to 6} may be the same or different.
However, the kind of _{R 1} and _{R 2,} the kind of _{R 13} and _{R 14,} the type of _{pair of R 15} and _{R 16,} the kind of _{R 17} and _{R 18,} numerical values of _{f 1} and _{f 2,} numerical values of _{f 3} and _{f 4,} figures f ₅ and _{f 6,} numerical values of _{f 7} and _{f 8,} numerical values of _{r 1} and _{r 2, (R 1) f} 1 and _(R 2) substitution position of _{f 2,} and _(R 13) _{f 3 (R 14)} substitution position of _{f 4, (R 15) f} 5 _(the substitution position of R 16) _{f 6, (and} R 17) _{f 7 (substitution} position of _{R 18) f 8, (Y} 1) r 1 (the Y ₂ ) substitution position of r ₂ , numerical values of p ₁ and p ₂ , numerical values of p ₃ and p ₄ , numerical values of p ₅ and p ₆ , and A ₁ in general formula (30), (Y ₃ ) p ₁ and A ₂ , (Y ₄ ) p ₂ substitution position, A ₂ , (Y ₆ ) p ₃ and A ₃ , (Y ₇ ) p ₄ substitution position, A ₃ , (Y ₈ ) p ₅ and Y ₅ , _(Y 9) substituted position of _{p 6} At least one different of.

In the above general formulas (29) to (34), Z is preferably a divalent group containing a condensed ring structure selected from the group consisting of the above formulas (3) to (7), more preferably the above formula (3). It is a bivalent group containing the condensed ring structure shown by these. When Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), high heat resistance, high refractive index, and electrical properties derived from a condensed ring skeleton containing aromatics are imparted. And dispersion stability derived from a large surface structure can be obtained. Furthermore, when Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (5), higher levels of heat resistance, refractive index, electrical properties, and dispersion stability can be obtained. . When Z is a divalent group containing a condensed ring structure of formula (3), such a condensed ring structure-containing asymmetric alkali-soluble resin (C) has good solubility in various solvents. For example, when preparing a low-viscosity radiation-sensitive resin composition, a dilute solution is obtained. However, a resin having poor solubility may cause turbidity due to the resin in such a dilute state. . From the balance between the high physical properties derived from these condensed ring skeletons and the solvent solubility, it can be said that the case where Z is a divalent group containing a condensed ring structure represented by formula (3) is a more preferred embodiment.
In another preferred embodiment, p _1-6 and f _1-8 are each independently an integer from 0 to 2, m _2-6 are each independently an integer from 0 to 2, and r _1-2 are each Independently an integer from 1 to 2, and s _1-2 are each independently an integer from 0 to 8.

The weight average molecular weight of the condensed ring structure-containing asymmetric alkali-soluble resin (C) of the present invention varies depending on the use, but is preferably from 1,000 to 100,000, more preferably from the viewpoint of fluidity, solubility, dispersibility, and the like. 2000 to 20000.

R ₇ and R _{11 to 12} in the general formulas (32), (33), and (34) are sites derived from a monobasic carboxylic acid. For example, the monobasic carboxylic acid includes a carboxyl group. Examples include, but are not limited to, (meth) acrylic acid, cyclopropanecarboxylic acid, 2,2,3,3-tetramethyl-1-cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, 2-cyclopentenylcarboxylic acid, 2-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid, cyclohexanecarboxylic acid, 4-propylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid 4-heptylcyclohexanecarboxylic acid, 4-cyanosi Rhohexane-1-carboxylic acid, 4-hydroxycyclohexanecarboxylic acid, 1,3,4,5-tetrahydroxycyclohexane-1-carboxylic acid, 2- (1,2-dihydroxy-4-methylcyclohexyl) propionic acid, shikimic acid , 3-hydroxy-3,3-diphenylpropionic acid, 3- (2-oxocyclohexyl) propionic acid, 3-cyclohexene-1-carboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid hydrogen alkyl, cycloheptanecarboxylic acid , Norbornene carboxylic acid, tetracyclododecene carboxylic acid, 1-adamantane carboxylic acid, (4-tricyclo [5.2.1.0 ^2.6 ] dec-4-yl) acetic acid, p-methylbenzoic acid, p- Ethylbenzoic acid, p-octylbenzoic acid, p-decylbenzoic acid, p-dodecylbenzoic acid Acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, p-propoxybenzoic acid, p-butoxybenzoic acid, p-pentyloxybenzoic acid, p-hexyloxybenzoic acid, p-fluorobenzoic acid, p-chlorobenzoic acid Acid, p-chloromethylbenzoic acid, pentafluorobenzoic acid, pentachlorobenzoic acid, 4-acetoxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-di-t-butyl-4-hydroxybenzoic acid, o- Benzoylbenzoic acid, o-nitrobenzoic acid, o- (acetoxybenzoyloxy) benzoic acid, terephthalic acid monomethyl ester, isophthalic acid monomethyl ester, isophthalic acid monocyclohexyl ester, phenoxyacetic acid, chlorophenoxyacetic acid, phenylthioacetic acid, phenylacetic acid, 2 -Oxo-3-phenylpropionic acid o-Bromophenylacetic acid, o-iodophenylacetic acid, methoxyphenylacetic acid, 6-phenylhexanoic acid, biphenylcarboxylic acid, α-naphthoic acid, β-naphthoic acid, anthracenecarboxylic acid, phenanthrenecarboxylic acid, anthraquinone-2-carboxylic acid , Indanecarboxylic acid, 1,4-dioxo-1,4-dihydronaphthalene-2-carboxylic acid, 3,3-diphenylpropionic acid, nicotinic acid, isonicotinic acid, cinnamic acid, 3-methoxycinnamic acid, 4 -Methoxycinnamic acid, quinoline carboxylic acid and the like.

The “one example of the condensed ring structure-containing asymmetric alkali-soluble resin (C)” represented by the formula (29) will be described more specifically. At least one of the following (i) to (xx) is adopted. It can be made “asymmetric”.
(I) formula (29), a methyl group and _{R 1,} equal to an ethyl group and _{R 2, R 1} and making the type of the substituent of _{R 2} different.
(Ii) In the formula _(30), a methyl group and _{R 13,} equal to ethyl and _{R 14, R 13} and _{R 14} in making the different types of substituents. In this case, s ₁ is 1 or more.
(Iii) In the formula (30), the types of substituents of R ₁₅ and R ₁₆ are different, for example, R ₁₅ is a methyl group and R ₁₆ is an ethyl group.
(Iv) In the formula (30), the types of substituents of R ₁₇ and R ₁₈ are different, for example, R ₁₇ is a methyl group and R ₁₈ is an ethyl group. In this case _{s 2} is 1 or more.
(V) In Formula (29), f ₁ and f ₂ are set to different numerical values, that is, the number of substituents R _{1 and} the number of substituents R ₂ are different (for example, _one R ₁ , R _{1 2} are two).
(Vi) In Formula (30), f ₃ and f ₄ are set to different numerical values, that is, the number of substituents R _{13 and} the number of substituents R ₁₄ are different (for example, one R ₁₃ is R, ₁₄ is 2). In this case, s ₁ is 1 or more.
(Vii) In formula (30), f ₅ and f ₆ are set to different numerical values, that is, the number of substituents R _{15 and} the number of substituents R ₁₆ are different (for example, one R ₁₅ is R, ₁₆ is 2).
(Viii) In formula (30), f ₇ and f ₈ are set to different numerical values, that is, the number of substituents R _{17 and} the number of substituents R ₁₈ are different (for example, one R ₁₇ is R, ₁₈ is 2). In this case _{s 2} is 1 or more.
(Ix) In Equation (29), r ₁ and r ₂ are set to different numerical values, that is, the number of Y _{1 and} the number of Y ₂ in Equation (29) are different (for example, _one Y ₁ , Y ₂ are two).
(X) In the formula _(30), and the p 1, _{p 2} different numerical values, be different the number of the number and _{Y 4} of _{Y 3} clogging formula (30) (e.g., _{Y 3} is one, Y ₄ is two). In this case, s ₁ is 1 or more.
(Xi) In Expression (30), p ₃ and p ₄ are set to different numerical values, that is, the number of Y _{6 and} the number of Y ₇ in Expression (30) are different (for example, one Y ₆ , 2 Y ₇ ).
(Xii) In formula (30), p ₅ and p ₆ are set to different numerical values, that is, the number of Y _{8 and} the number of Y ₉ in formula (30) are different (for example, one Y ₈ is Y ₉ are two). In this case _{s 2} is 1 or more.
(Xiii) In the formula (29), R ₁ (f ₁ = 1) is bonded to the ortho position of the bonding position of Z, R ₂ (f ₂ = 1) is bonded to the meta position of the bonding position of Z, etc. , R ₁ and R ₂ should have different substitution positions. When f ₁ and f ₂ ≧ 2, the substitution positions of at least one pair of R ₁ and R ₂ out of f ₁ R ₁ and f ₂ R ₂ are different [for example, R ₁ (f ₁ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₂ (f ₁ = 2) is bonded only to the meta position (two positions) of the bonding position of Z. Etc.].
(Xiv) In the formula (30), R ₁₃ (f ₃ = 1) is bonded to the ortho position of the bonding position of Z, R ₁₄ (f ₄ = 1) is bonded to the meta position of the bonding position of Z, etc. , it is different substitution positions of _{R 13} and _{R 14.} When f ₃ and f ₄ ≧ 2, the substitution positions of at least one set of R ₁₃ and R ₁₄ out of f ₃ R ₁₃ and f ₄ R ₁₄ are different [for example, R ₁₃ (f ₃ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₁₄ (f ₄ = 2) is bonded to only the meta position (two positions) of the bonding position of Z. Etc.]. In this case, s ₁ is 1 or more.
(Xv) In the formula (30), R ₁₅ (f ₅ = 1) is bonded to the ortho position of the bonding position of Z, R ₁₆ (f ₆ = 1) is bonded to the meta position of the bonding position of Z, etc. , R ₁₅ and R ₁₆ should have different substitution positions. When f ₅ and f ₆ ≧ 2, the substitution positions of at least one pair of R ₁₅ and R ₁₆ out of f ₅ R ₁₅ and f ₆ R ₁₆ are different [for example, R ₁₅ (f ₅ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₁₆ (f ₆ = 2) is bonded to only the meta position (two positions) of the bonding position of Z. Etc.].
(Xvi) In the formula (30), R ₁₇ (f ₇ = 1) is bonded to the ortho position of the bonding position of Z, R ₁₈ (f ₈ = 1) is bonded to the meta position of the bonding position of Z, etc. , R ₁₇ and R ₁₈ must have different substitution positions. When f ₇ and f ₈ ≧ 2, the substitution positions of at least one pair of R ₁₇ and R ₁₈ out of f ₇ R ₁₇ and f ₈ R ₁₈ are different [for example, R ₁₇ (f ₇ = 2) is bonded to the ortho position and the meta position of the bonding position of Z one by one, and R ₁₈ (f ₈ = 2) is bonded to only the meta position (two positions) of the bonding position of Z. Etc.]. In this case _{s 2} is 1 or more.
(Xvii) In formula (29), Y ₁ (r ₁ = 1) is linked to the para position of the bonding position of Z, Y ₂ (r ₂ = 1) is bonded to the meta position of the bonding position of Z, etc. , R ₁ and R ₂ should have different substitution positions. Further, in the case of f ₁ and f ₂ ≧ 2, at least one pair of Y ₁ and Y ₂ is substituted at different positions among r ₁ Y ₁ and r ₂ Y ₂ [for example, Y ₁ (r ₁ = 2) is bonded to the para position and the meta position at the bonding position of Z one by one, and Y ₂ (r ₂ = 2) is bonded to the para position and the ortho position of the bonding position of Z one by one. It shall be.
(Xviii) In formula (30), the substitution positions of A ₁ , (Y ₃ ) p ₁ and A ₂ , (Y ₄ ) p ₂ are different even at one place. Here, “the substitution positions of A ₁ , (Y ₃ ) p ₁ and A ₂ , (Y ₄ ) p ₂ are different even at one place” means that when s ₁ is 2 or more, the formula (30) _a 1 in R _{13 side, (Y} 3) _{p 1} and _a 1 of the _{R 14 side, (Y} 4) or the substitution position of _{p 2} are different even in one place, or _a 1 in _{R 13} side of the equation (30), It means that the substitution position of (Y ₃ ) p ₁ and A ₂ on the R ₁₄ side and (Y ₄ ) p ₂ is different even at one place [for example, A ₁ and Y ₃ on the R ₁₃ side (p ₁ = 1) Are bonded to the para position and the meta position at the bonding position of Z, and A ₁ and Y ₄ (p ₂ = 1) on the R ₁₄ side are bonded to the para position and the ortho position at the bonding position of Z, respectively. etc. are bound to], and when _{s 1} is 1, _a 1 in _{R 13} side of the equation _{(30), (Y 3)} p 1 and _{R 14} side of the _{a 2,} the _(Y 4) _{p 2} One replacement position Differ even at _{[e.g., A 1} and _Y 3 of the _{R 13} side _(p 1 = 1) is attached by one place in the para position and meta-position of the bonding position of _Z, the _{R 14} side _{A 2} and _{Y 4} (p 2 _{= 1)} means a constant] bound by one position para and ortho bonding positions of Z. In this case, s ₁ is 1 or more.
(Xiv) In formula (30), the substitution positions of A ₂ , (Y ₆ ) p ₃ and A ₃ , (Y ₇ ) p ₄ are different even at one place. Here, “the substitution positions of A ₂ , (Y ₆ ) p ₃ and A ₃ , (Y ₇ ) p ₄ are different even at one place” means that when s ₂ is 1 or more, the formula (30) _a 2 of the R _{15 side, (Y} 6) _{p 3} and _{R 16} side of the _{a 3, (Y} 7) substitution position of _{p 4} is means may differ in one place _[e.g., the _{R 15} side _{a 2} and Y ₆ (p ₃ = 1) is bonded to the para position and the meta position of the Z bond position one by one, and A ₃ and Y ₇ (p ₄ = 1) on the R ₁₆ side are the para positions of the Z bond position. Etc.), and when s ₂ is 0, A ₂ on the R ₁₅ side of Formula (30), (Y ₆ ) p ₃ and Y ₅ on the R ₁₆ side, (Y ₇ ) The substitution position of p ₄ is different even at one place [for example, A ₂ on the R ₁₅ side and Y ₆ (p ₃ = 1) are bonded to the para position and the meta position of the bonding position of Z one by one. And R Y ₅ and Y ₇ (p ₄ = 1) on the ₁₆ side are bonded to the para position and the ortho position of the bonding position of Z, etc.].
(Xx) In formula (30), the substitution positions of A ₃ , (Y ₈ ) p ₅ and Y ₅ , (Y ₉ ) p ₆ are different even at one place. Here, “the substitution positions of A ₃ , (Y ₈ ) p ₅ and Y ₅ , (Y ₉ ) p ₆ are different even at one place” means that when s ₂ is 2 or more, the formula (30) R ₁₇ side of the _{a 3, (Y} 8) _{p 5} and _{R 18} side of the _{a 3, (Y} 9) or the substitution position of _{p 6} are different even in one place, _{R 17} side of the _a 3 of formula (30), ( Y _{8) p 5} and _{R 18} side of _{Y 5, (Y} 9) the substitution position of _{p 6} is means may differ in one place _{[e.g., a 3} of the _{R 17} side and _Y 8 _(p 5 = 1) is , Z is bonded to the para position and the meta position at the bonding position of Z, and A ₃ and Y ₉ (p ₆ = 1) on the R ₁₈ side are bonded to the para position and the ortho position at the bonding position of Z, respectively. If equal] with that, and also _{s 2} is 1, _{R 17} side of the _a 3 of formula _{(30), (Y 8)} p 5 and _{R 18} side of _{Y 5,} substitution of _(Y 9) _{p 6} Even at one location Made it _{[e.g., A 3} and _Y 8 of _{R 17} side _(p 5 = 1) binds one piece at the para-position and meta-position of the bonding position of _Z, the _{R 18} side _{Y 5} and _Y 9 (p ₆ = 1) means that one bond is formed at each of the para position and the ortho position of the bond position of Z. In this case _{s 2} is 1 or more.

Further, “Y _{3-4 and} Y _6-9 in the general formula (30) are groups independently selected from the following general formula (30), (33) or the following general formula (34)”. Is Y _3-4, Y _6-9 in formula (30) is formula (33), or is formula (34), or Y _3-4, Y _6-9 is further in formula (30). As a result, the group represented by the formula (30) becomes a structure (branched structure), and the terminal (Y _3-4, Y _6-9 ) becomes the group represented by the formula (33) or the formula (34). Means.

More specific examples of the condensed ring structure-containing asymmetric alkali-soluble resin (C) include, for example, a resin represented by the following general formula (35):

Here, Z, R _1-2 , R _15-16 , f _1-2 , f _5-6 , u ₁ in the general formula (35) are the same as described above, and a plurality of R _1-2 , R _{15-16 are used. , f} 5~6 is may be the same, may be different. However, R ₁ and R ₂ types, R ₁₅ and R ₁₆ types, f ₁ and f ₂ values, f ₅ and f ₆ values, and (R ₁ ) f ₁ and (R ₂ ) f ₂ substitution positions And at least one of the substitution positions of (R ₁₅ ) f ₅ and (R ₁₆ ) f ₆ is different. In the general formula (35), Y ₁ is the general formula (33), Y ₂ is the general formula (30), and Y ₅ in the formula (30) is the general formula (33). Wherein r _1-2 = 1, s _1-2 = 0, p _3-4 = 0, m _4-6 = 0, R ₇ and R _11-12 are derived from p-methylbenzoic acid. A group containing a moiety, L ₁ is a residue of pyromellitic dianhydride, and L ₂ is a specific example of a condensed alkali-containing resin (C) containing a condensed ring structure that is a residue of tetrahydrophthalic anhydride. .

The condensed ring structure-containing asymmetric alkali-soluble radiation polymerizable unsaturated resin of the present invention is included in the condensed ring structure-containing asymmetric alkali-soluble resin. Those having a functional group having a property, specifically, those having an unsaturated group in the molecule are referred to as a condensed ring-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin.

In the present specification, the condensed ring structure-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin is referred to as “condensed ring structure-containing asymmetric alkali-soluble resin (C1)” or “asymmetric alkali-soluble resin (C1)”. "A condensed alkali-soluble radiation-polymerizable unsaturated resin (C1)", "Asymmetric alkali-soluble radiation-polymerizable unsaturated resin (C1)", "Asymmetric radiation-polymerizable unsaturated resin (C1)" ) "Or the like. This condensed ring structure-containing asymmetric alkali-soluble resin (C1) is included in the above-mentioned condensed ring structure-containing asymmetric alkali-soluble resin (C).

The condensed ring structure-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin (C1) is a condensed ring structure-containing asymmetric epoxy ester resin (B) having an unsaturated group in the molecule, for example, a condensed ring structure. It can be obtained by reacting the contained asymmetric epoxy acrylate resins (B4) to (B6) with a polybasic carboxylic acid or its anhydride. In the general formula (29), at least one of R ₇ , R ₁₁ , and R _{12 in} the general formulas (32), (33), and (34) is an unsaturated group such as (meth) acrylic acid. It is a site derived from the contained monobasic carboxylic acid.

In addition, since the condensed ring structure-containing asymmetric alkali-soluble resin represented by the general formula (35) does not have an unsaturated group, it is an example of a condensed ring-structure-containing asymmetric alkali-soluble resin having no radiation polymerizability. It can be said.

On the other hand, as specific examples of the condensed ring structure-containing asymmetric alkali-soluble resin having radiation-polymerizable property and the above-mentioned condensed ring-structure-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin (C1), for example, Examples of the resin represented by the formula (36) include:

Here, Z, R _1-2 , R _15-16 , f _1-2 , f _5-6 , u ₁ in the general formula (36) are the same as described above, and a plurality of R _1-2 , R _{15-16 are used.} , F _5-6 may be the same _or different. However, R ₁ and R ₂ types, R ₁₅ and R ₁₆ types, f ₁ and f ₂ values, f ₅ and f ₆ values, and (R ₁ ) f ₁ and (R ₂ ) f ₂ substitution positions And at least one of the substitution positions of (R ₁₅ ) f ₅ and (R ₁₆ ) f ₆ is different. In the general formula (36), Y ₁ is the general formula (33), Y ₂ is the general formula (30), and Y ₅ in the formula (30) is the general formula (33). a group _{represented, r 1~2 = 1, s 1~2} = 0, p 3~4 = 0, m 4~6 = 0, R 7 and _{R 11 to 12} includes a site derived from acrylic acid A group, L ₁ is a residue of biphenyltetracarboxylic dianhydride, and L ₂ is a specific example of a condensed ring-containing asymmetric alkali-soluble resin (C) that is a residue of trimellitic anhydride.

The asymmetric alkali-soluble resin (C) can be obtained by reacting a condensed ring structure-containing asymmetric epoxy ester resin (B) with a polybasic carboxylic acid or an anhydride thereof. Here, the condensed ring structure-containing asymmetric epoxy ester resin (B) may be used alone or in combination of two or more. The polybasic carboxylic acid is a carboxylic acid having a plurality of carboxyl groups such as dicarboxylic acid and tetracarboxylic acid. Examples of such polybasic carboxylic acid or anhydride thereof include the following compounds: Named: Dicarboxylic acids such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, glutaric acid Acids and anhydrides thereof; trimellitic acid or anhydride thereof; tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, and acid dianhydrides thereof. These may be used alone or in combination of two or more. In addition, L _<1-2> of general formula (32)-(33) becomes a residue of said polybasic carboxylic acid or polybasic carboxylic acid anhydride. For example, when L ₁ is a dicarboxylic acid or an anhydride thereof, the residue does not include a carboxyl group. When L ₂ is a dicarboxylic acid or an anhydride thereof, the residue contains one carboxyl group. On the other hand, when L ₁ is a tetracarboxylic acid and their anhydrides, the residue contains up to two carboxyl groups, and when L ₂ is a tetracarboxylic acid and their anhydrides, the residue has up to 3 carboxyl groups. Included. Since the number of carboxyl groups contained in the residue particularly affects developability, dispersibility, solubility, etc., the type and ratio of the polybasic carboxylic acid used can be selected according to the purpose.

In this reaction, the reaction can be carried out in the presence of polyhydric alcohols in order to improve the heat resistance and heat yellowing of the resulting resin.

Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2 -Aliphatic diols such as methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,6-nonanediol, 1,9-nonanediol, 1,4 -Cyclohexanedimethanol, tricyclodecane dimethanol, alicyclic diols such as hydrogenated bisphenol A, aromatic diols such as ethylene oxide and propylene oxide adducts of bisphenol A, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, Sorbitol Trihydric or higher alcohols such as dipentaerythritol, and the like.

In this reaction, the addition order of the condensed ring structure-containing asymmetric epoxy ester resin (B), the polyhydric alcohols, and the polybasic carboxylic acid or its anhydride is not particularly limited. For example, a method in which these are mixed and reacted at the same time, a condensed ring structure-containing epoxy ester resin (B) and a polyhydric alcohol are mixed, and then a polybasic carboxylic acid or its anhydride is added, mixed and reacted. There are methods. Further, a polybasic carboxylic acid may be further added to these reaction products for reaction.

By appropriately selecting the type and number of the polybasic carboxylic acid or its anhydride, various condensed ring structure-containing asymmetric alkali-soluble resins having different condensed structures and different structures (Ca) Furthermore, a condensed ring-containing asymmetric alkali-soluble resin (Cb) obtained by reacting a polyhydric alcohol can be produced. Specifically, for example, the first to sixth condensed rings shown in the following (C-a-i) to (C-a-iii) and (C-b-i) to (C-b-iii): The structure-containing asymmetric alkali-soluble resin (C) is prepared, but these are exemplary.

(C-ai) First condensed ring structure-containing asymmetric alkali-soluble resin: a condensed ring structure-containing asymmetric epoxy ester resin and one kind of polybasic carboxylic acid or anhydride thereof are mixed and reacted. (C-a-ii) second condensed ring structure-containing asymmetric alkali-soluble resin: condensed ring structure-containing asymmetric epoxy ester resin (B) and two or more polybasic carboxylic acids Or a resin obtained by mixing and reacting with a mixture of anhydrides thereof (for example, a mixture of dicarboxylic anhydride and tetracarboxylic dianhydride); and (C-a-iii) a third condensed ring structure Containing asymmetric alkali-soluble resin: a reaction between the condensed ring-containing asymmetric epoxy ester resin (B) and tetracarboxylic acid or its dianhydride, and the resulting reaction product with dicarboxylic acid or its anhydride Resins obtained by reacting and.

(C-bi) Fourth condensed ring structure-containing asymmetric alkali-soluble resin: condensed ring structure-containing asymmetric epoxy ester resin (B), polyhydric alcohol, one kind of polybasic carboxylic acid or its anhydride (C-b-ii) Fifth condensed ring structure-containing asymmetric alkali-soluble resin: condensed ring structure-containing asymmetric epoxy ester resin (B) and polyhydric alcohol A resin obtained by mixing and reacting with a mixture of two or more polybasic carboxylic acids or anhydrides thereof (eg, a mixture of dicarboxylic anhydride and tetracarboxylic dianhydride); and (C-b-iii) Sixth condensed ring structure-containing asymmetric alkali-soluble resin: condensed ring structure-containing asymmetric epoxy ester resin (B), polyhydric alcohol, tetracarboxylic acid or dianhydride thereof The reacted, obtained by reacting the reaction product obtained with a dicarboxylic acid or anhydride resin.

The thus obtained condensed ring structure-containing asymmetric alkali-soluble resin (Ca) or (Cb) having a different structure is used depending on the intended use.

The “polybasic carboxylic acid or anhydride thereof” means “at least one of a specific polybasic carboxylic acid and an anhydride corresponding thereto”. For example, the polybasic carboxylic acid is phthalic acid. An acid refers to at least one of phthalic acid and phthalic anhydride.

Further, “a mixture of two or more polybasic carboxylic acids or anhydrides thereof” means that at least two types of polybasic carboxylic acids or anhydrides thereof are simultaneously present. Therefore, in the methods (C-a-ii) and (Cb-ii), at least two types of polybasic carboxylic acids or anhydrides are involved in the reaction.

In any of the above methods, the condensed ring structure-containing asymmetric alkali-soluble resin can be obtained by changing the condensed ring structure-containing asymmetric epoxy ester resin (B), polyhydric alcohol, polybasic carboxylic acid, or anhydride thereof to the method exemplified above. In (order), for example, it is prepared by dissolving (suspending) in a cellosolve solvent such as ethyl cellosolve acetate or butyl cellosolve acetate and reacting by heating. Furthermore, a catalyst can be added as needed. Examples of the catalyst used include phosphonium salts, quaternary ammonium salts, phosphine compounds, tertiary amine compounds, and imidazole compounds, and are usually used in the range of 0.01 to 10% by weight of the total reaction product. It is preferable.

In the production of the condensed ring structure-containing asymmetric alkali-soluble resin, the condensed ring structure-containing asymmetric epoxy ester resin (B) and the polyhydric alcohol are the hydroxyl group and the polyhydric alcohol of the condensed ring structure-containing asymmetric epoxy ester resin (B). Is preferably adjusted so that the molar ratio of the hydroxyl group to the hydroxyl group (the hydroxyl group of the condensed ring structure-containing asymmetric epoxy ester resin (B) / the hydroxyl group of the polyhydric alcohol) is from 99/1 to 50/50. More preferably, it is 60/40. When the molar ratio of the hydroxyl group of the polyhydric alcohol exceeds 50%, the molecular weight of the resulting resin increases rapidly and there is a risk of gelation. Moreover, if it is less than 1%, it tends to be difficult to improve heat resistance and heat discoloration.

The polybasic carboxylic acid or an anhydride thereof is preferably 0.3 in terms of an acid anhydride group with respect to a total of 1 equivalent (mol) of the condensed ring structure-containing asymmetric epoxy ester resin (B) and the hydroxyl group of the polyhydric alcohol. ˜1 equivalent, more preferably 0.4-1 equivalent. If the polybasic carboxylic acid or its anhydride is less than 0.3 equivalent in terms of acid anhydride group, the molecular weight of the resulting alkali-soluble resin may not be sufficiently high. Therefore, when exposure and development are performed using such a radiation-sensitive resin composition containing an alkali-soluble resin, the resulting film may have insufficient heat resistance or the film may remain on the substrate. is there. When the polybasic carboxylic acid or its anhydride exceeds 1 equivalent in terms of acid anhydride group, unreacted acid or acid anhydride remains, and the molecular weight of the resulting alkali-soluble resin becomes low, and the resin In some cases, the developability of the radiation-sensitive resin composition containing is poor.

In addition, acid anhydride group conversion shows the quantity when all the carboxyl groups and acid anhydride groups contained in the polybasic carboxylic acid to be used or its anhydride are converted into acid anhydride.

In the production of the second, third, fifth, and sixth condensed ring structure-containing asymmetric alkali-soluble resins (C), two or more polybasic carboxylic acids or anhydrides thereof are used. Generally, dicarboxylic anhydride and tetracarboxylic dianhydride are used. The ratio of dicarboxylic anhydride to tetracarboxylic dianhydride (dicarboxylic anhydride / tetracarboxylic dianhydride) is preferably 1/99 to 90/10 in molar ratio, and 5/95 to 80. More preferably, it is / 20. When the proportion of dicarboxylic acid anhydride is less than 1 mol% of the total acid anhydride, the resin viscosity increases and workability may be reduced. Furthermore, since the molecular weight of the obtained resin becomes too large, when the thin film is formed on the substrate using the radiation-sensitive resin composition containing the resin and the exposure is performed, the exposed portion is in contact with the developer. It tends to be difficult to dissolve and difficult to obtain the desired pattern. When the proportion of dicarboxylic acid anhydride exceeds 90 mol% of the total acid anhydride, the molecular weight of the resulting resin becomes too small, so when a coating film is formed on the substrate using the composition containing the resin, Problems such as sticking remaining in the coating film after pre-baking tend to occur.

In any of the above cases, during the reaction of the condensed ring structure-containing asymmetric epoxy ester resin (B), polyhydric alcohol and polybasic carboxylic acid or anhydride thereof, the reaction temperature is preferably 50 to 130 ° C., more preferably 70 ~ 120 ° C. When the reaction temperature exceeds 130 ° C., some condensation of carboxyl groups and hydroxyl groups occurs, and the molecular weight increases rapidly. On the other hand, if it is less than 50 ° C., the reaction does not proceed smoothly, and unreacted polybasic carboxylic acid or its anhydride remains.

The thus obtained condensed ring structure-containing asymmetric alkali-soluble resin (C) of the present invention is suitably used as the main component of the radiation-sensitive alkali-soluble resin composition.

The radiation-sensitive alkali-soluble resin composition of the present invention contains the above-mentioned condensed ring structure-containing asymmetric alkali-soluble resin.
Usually, the radiation-sensitive alkali-soluble resin composition contains the condensed ring structure-containing asymmetric alkali-soluble resin (C) and a radiation-reactive compound. When this composition is a positive radiation sensitive resin composition, for example, a quinonediazide compound is used as the radiation reactive compound, and usually the condensed ring structure-containing asymmetric alkali-soluble resin (C) 100 is used. The radiation-reactive compound is preferably contained in an amount of 0.5 to 50 parts by weight with respect to parts by weight. In the case of a negative-type radiation-sensitive alkali-soluble resin composition, for example, a photopolymerization initiator or acrylate is used as the radiation-reactive compound, and usually the condensed ring structure-containing asymmetric alkali-soluble resin 100 is used. For example, the photopolymerization initiator is preferably contained in an amount of 0.1 to 30 parts by weight, and more preferably in the range of 0.4 to 10 parts by weight with respect to parts by weight. Moreover, in the case of an acrylate, it is preferable to contain 0.1-50 weight part normally with respect to 100 weight part of said condensed ring structure containing asymmetric alkali-soluble resins.
The radiation sensitive resin composition of the present invention further contains other components as necessary.
As the negative radiation-sensitive alkali-soluble resin composition, a condensed ring structure-containing asymmetric alkali-soluble resin having radiation polymerization properties, for example, an asymmetric alkali-soluble resin (C1) is preferable. The condensed ring-containing asymmetric alkali-soluble resin having no radiation polymerizability contained in (C) can also be suitably used by blending with another compound having radiation polymerizability.
Hereinafter, the radiation-sensitive alkali-soluble resin composition of the present invention will be described by taking a negative radiation-sensitive alkali-soluble resin composition as an example.

The radiation-sensitive alkali-soluble resin composition containing the condensed ring structure-containing asymmetric alkali-soluble resin (C) of the present invention includes the condensed ring structure-containing asymmetric alkali-soluble resin (C), and, if necessary, (A) a photopolymerization initiator, (b) a polymerizable monomer or oligomer other than the condensed ring structure-containing asymmetric alkali-soluble resin (C), (c) a compound having an epoxy group, (d) an additive, ( e) contains solvent, (f) solid fine particles and the like.

The photopolymerization initiator (a) refers to a compound having a photopolymerization initiating action and / or a compound having a sensitizing effect. Examples of such compounds include the following compounds: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone. Benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzyldimethyl ketal Thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthione Sulfur compounds such as xanthene; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; organics such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide Peroxides; and thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole.

The blending amount of such a photopolymerization initiator is preferably 0.05 to 10.0 parts by weight, more preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the radiation curable unsaturated group-containing compound. Part.

The “radiation curable unsaturated group-containing compound” means all the radiation curable unsaturated group-containing compounds contained in the radiation-sensitive alkali-soluble resin composition, and the asymmetric alkali-soluble resin of the present invention. (C) includes those having radiation curability, and photocurable or thermosetting acrylate compounds other than the asymmetric alkali-soluble resin (C) of the present invention.

These compounds may be used individually by 1 type, and may be used in combination of 2 or more type. Furthermore, a compound which does not act as a photopolymerization initiator itself but can increase the ability of the photopolymerization initiator by using it in combination with the above compound can also be added. Examples of such compounds include tertiary amines such as triethanolamine which are effective when used in combination with benzophenone.

The polymerizable monomer or oligomer other than the condensed ring structure-containing asymmetric alkali-soluble resin (C) in (b) above is a monomer or oligomer that can be polymerized by radiation, and depends on the intended use of the composition. It can be contained according to physical properties. Examples of such monomers or oligomers that can be polymerized by radiation include the following monomers or oligomers: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and the like. (Meth) acrylic acid esters having the following hydroxyl groups: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaeryth Torutori (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acrylic acid esters such as glycerol (meth) acrylate. These monomers or oligomers may be used alone or in combination of two or more.

These monomers or oligomers can be contained as long as they act as a viscosity modifier or a photocrosslinking agent and do not impair the properties of the resin composition of the present invention. Usually, at least one of the above monomers and oligomers is contained in the composition in a range of 50 parts by weight or less with respect to 100 parts by weight of the asymmetric alkali-soluble resin (C). When the content of the monomer or oligomer exceeds 50 parts by weight, a problem arises in sticking property after pre-baking.

As the compound having an epoxy group (c), a polymer or monomer having at least one epoxy group is used. Examples of the polymer having at least one epoxy group include a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a biphenyl epoxy resin, and an alicyclic ring. There is an epoxy resin such as an epoxy resin.
Examples of the monomer having at least one epoxy group include phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, and glycidyl methacrylate. These compounds may be used alone or in combination of two or more.

The compound which has these epoxy groups may be contained in the range which does not impair the property of the resin composition of this invention. Usually, the compound having an epoxy group is contained in a proportion of 50 parts by weight or less per 100 parts by weight of the condensed ring structure-containing asymmetric alkali-soluble resin (C). When the amount exceeds 50 parts by weight, cracking is likely to occur when the composition containing the component is cured, and the adhesion tends to be lowered.

Examples of the additive (d) include thermal polymerization inhibitors, adhesion assistants, epoxy group curing accelerators, surfactants, antifoaming agents, etc., and these are in amounts that do not impair the purpose of the present invention. Contained in the composition.

Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like.

The adhesion aid is contained in order to improve the adhesion of the resulting composition. As the adhesion assistant, a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanato group, and an epoxy group is preferable. Specific examples of this functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.

Examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol group-containing compounds. By containing a small amount of an epoxy group curing accelerator, various properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical properties and hardness of the cured film obtained by heating are improved.

The surfactant is included, for example, to facilitate application of a liquid composition on a substrate, and the flatness of the resulting film is also improved. Surfactants include, for example, BM-1000 (manufactured by BM Hemy), MegaFuck F142D, MegaFuck F172, MegaFuck F173 and MegaFuck F183 (Dainippon Ink and Chemicals), Florard FC-135, Fluorard FC-170C, Fluorard FC-430 and Fluorard FC-431 (manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141 and Surflon S-145 (Asahi Glass Co., Ltd.) )), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 (manufactured by Toray Silicone Co., Ltd.).

Examples of the antifoaming agent include silicone, fluorine, and acrylic compounds.

The solvent of the above (e) that can be contained in the radiation-sensitive resin composition of the present invention is used for uniformly dissolving each component in the composition, for example, for facilitating coating on a substrate. Such a solvent is not particularly limited as long as it is an organic solvent that does not react with each component in the composition and can dissolve or disperse them. Examples include the following compounds: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and diethylene glycol ethyl methyl ether; diethylene glycol monomethyl ether, diethylene glycol Diethylene glycol monoalkyl ethers such as no ethyl ether and diethylene glycol monobutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Alkylene glycol monoalkyl ether acetates such as 3-methoxybutyl-1-acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc. Ketones; and 2 Ethyl hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3-methoxypropionic acid Methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, dimethyl succinate, diethyl succinate, diethyl adipate, diethyl malonate Esters such as dibutyl oxalate.

Of these, ethylene glycol ethers, alkylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferred, and in particular, ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate and methyl amyl ketone are preferred. These solvents may be used alone or in a combination of two or more.
When such a solvent is added, the blending amount is preferably 5 to 70% by weight of the entire composition.

Examples of the solid fine particles (f) include organic pigments and inorganic fine particles, which can be added for use in applications such as optical materials and display element materials. Specific examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), and the central metals are Cu, Mg, Al, Si, Examples thereof include dissimilar metal phthalocyanine pigments such as Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn. Specific examples of the inorganic fine particles include titanium oxide, zirconium oxide, zinc oxide, aluminum oxide, cerium oxide, tin oxide, tantalum oxide, indium tin oxide, hafnium barium sulfate, and other metal oxides; calcium carbonate, Metal salts such as gold chloride, gold bromide, silver chloride, silver bromide, silver iodide, palladium chloride, chloroplatinic acid, sodium chloroaurate, silver nitrate, platinum acetylacetonate, palladium acetylacetonate; gold, silver, Noble metals such as platinum, palladium, rhodium, ruthenium, iridium; and zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green , Amber, titanium black, synthetic iron black, carbon black, carbon nanotube, etc. Can. These solid fine particles can be used alone or in combination of two or more. The particle size of these solid fine particles is, for example, 1 nm to 5 μm.
In addition, when such solid fine particles are added, the amount used is appropriately selected depending on the application and the type of the solid fine particles, but is contained in an amount that does not impair the original properties of the resin composition of the present invention. , And may be contained in a proportion of 1 to 300 parts by weight with respect to 100 parts by weight of the alkali-soluble resin

The condensed ring structure-containing asymmetric alkali-soluble resin (C) of the present invention is soluble in alkali. The radiation-sensitive alkali-soluble resin composition containing this alkali-soluble resin is molded into a desired shape, cured by radiation, and used for various purposes. In particular, it is used for the purpose of forming a thin film having a predetermined pattern by forming a thin film on the substrate with the composition, irradiating with radiation, and developing.

For example, as described above, in the case where a thin film is formed on a substrate and radiation curing and development are performed, usually, each component of the composition containing a solvent is first mixed to obtain a liquid composition. For example, it is more preferable to filter this with a Millipore filter having a pore diameter of about 1.0 to 0.2 μm to obtain a uniform liquid. Next, this liquid composition is applied onto a substrate to obtain a coating film. Examples of the coating method include a dipping method, a spray method, a roller coating method, a slit coating method, a bar coating method, and a spin coating method. In particular, a spin coating method is widely used. By applying the liquid resin composition to a thickness of about 1 to 30 μm by these methods and then removing the solvent, a thin film is formed. Usually, a pre-bake treatment is performed to sufficiently remove the solvent. Usually, prebaking is performed at 70 to 140 ° C. for several minutes.

After placing a mask having a desired pattern on the thin film of the substrate, irradiation with radiation is performed. Examples of the radiation used include visible light, ultraviolet light, electron beam, X-ray, α-ray, β-ray, and γ-ray in order from the longest wavelength. Of these, ultraviolet rays are the most preferable radiation from the viewpoint of economy and efficiency. Ultraviolet light oscillated from a lamp such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an arc lamp, or a xenon lamp can be preferably used as the ultraviolet light used in the present invention. Radiation having a shorter wavelength than ultraviolet rays has high chemical reactivity and is theoretically superior to ultraviolet rays, but ultraviolet rays are practical from the viewpoint of economy.

By the irradiation, the exposed part is cured by a polymerization reaction. Unexposed portions are developed with a developer. Thereby, the non-irradiated part of the radiation is removed, and a thin film having a desired pattern is obtained. Examples of the developing method include a liquid piling method, a dipping method, and a rocking dipping method.

Examples of the developer include an alkaline aqueous solution, a mixed solution of the alkaline aqueous solution and a water-soluble organic solvent and / or a surfactant, an organic solvent in which the composition of the present invention can be dissolved, and preferably an alkaline aqueous solution and an interface. It is a liquid mixture with an active agent.

Examples of the base used for preparing the alkaline aqueous solution suitable for developing the radiation-sensitive asymmetric alkali-soluble resin composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia. , Ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1, Examples include 8-diazabicyclo (5.4.0) -7-undecene and 1,5-diazabicyclo (4.3.0) -5-nonane, preferably sodium carbonate and tetramethylammonium. Such as hydroxide is used.

An appropriate amount of a water-soluble organic solvent such as methanol, ethanol, acetone, propanol, or ethylene glycol, or a surfactant such as a sulfonate, phosphate ester, or polyoxyalkylene derivative is added to the alkaline aqueous solution as necessary. The

The development of the resin composition of the present invention can be usually performed at a temperature of 10 to 50 ° C., preferably 20 to 40 ° C., using a commercially available developing machine or ultrasonic cleaner. The development time can be appropriately adjusted depending on the development method, developer, temperature, coating film thickness, and the like.

After alkali development, in order to improve alkali resistance, it is desirable to apply an epoxy curing treatment by heating (post-bake treatment). In the resin composition of the present invention, by performing heat treatment, not only the durability against strong alkaline water is remarkably improved, but also various properties such as adhesion to metals such as copper or glass, heat resistance, surface hardness, etc. improves. About the heating temperature and heating time in this heat-hardening conditions, 80-250 degreeC and 10-120 minutes are mentioned, for example. A preferable heating temperature is 100 to 200 ° C. In this way, a cured thin film having a desired pattern can be obtained.

Since the condensed ring structure-containing asymmetric alkali-soluble resin of the present invention is excellent in compatibility with various solvents, it has a very high degree of freedom regarding applications.

Furthermore, the cured film obtained by curing the composition of the present invention has flexibility, heat resistance, transparency, adhesion to the substrate, acid resistance, alkali resistance, chemical resistance, solvent resistance, surface hardness, etc. Excellent. Furthermore, since this cured film is an organic coating film, it has a low dielectric constant. Therefore, the composition of the present invention includes, for example, a material for a protective film of an electronic component (for example, a material for forming a protective film used for a liquid crystal display element such as a color filter, an integrated circuit element, a solid-state imaging element); an interlayer insulating film and // Forming material of planarization film; Binder for color resist: Solder resist used for production of printed wiring board; Alkali-soluble photosensitive composition suitable for forming columnar spacer as an alternative to bead spacer in liquid crystal display device It is suitably used as an object. Furthermore, the composition of the present invention comprises materials for various optical parts (lenses, LEDs, plastic films, substrates, optical disks, etc.); a coating agent for forming a protective film for the optical parts; an adhesive for optical parts (adhesive for optical fibers) Etc.); a coating agent for producing a polarizing plate; a photosensitive resin composition for hologram recording, and the like.
A molded article obtained by curing the radiation-sensitive alkali-soluble resin composition of the present invention is also one aspect of the present invention.

Moreover, since the condensed ring structure-containing asymmetric alkali-soluble resin of the present invention is excellent in dispersibility, it can be suitably used when an organic pigment or inorganic fine particles are dispersed in the composition. A molded body obtained by curing this composition is also one aspect of the present invention.

According to the present invention, a polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound, a novel condensed ring structure-containing asymmetric epoxy resin, a condensed ring structure-containing asymmetric epoxy ester resin, and a condensed ring structure-containing asymmetric alkali-soluble resin are thus obtained. As well as a simple production method thereof. These resins can be polymerized and cured by heat or radiation. A resin composition containing these is excellent in fine particle dispersibility. Further, a cured molded article or thin film obtained using a resin composition containing these has high transparency, high level of heat resistance and electrical characteristics, and low degree of curing shrinkage. Furthermore, when the alkali-soluble resin of the present invention is used, a thin film having the above-mentioned excellent properties with a desired pattern can be accurately formed on the substrate. Therefore, the resin or resin composition of the present invention is a protective film forming material for various electronic components (liquid crystal display elements including color filters, integrated circuit elements, solid-state imaging elements, etc.); interlayer insulating film forming materials, for color resists. Binder composition; Solder resist used in the production of printed wiring board; Coating agent;

Hereinafter, based on an Example, this invention is demonstrated concretely.

Example 1
(Synthesis of polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound)
In a 5 L flask equipped with a stirrer, a reflux condenser, and a thermometer, 363.5 g (3.85 mol) of phenol, 580.3 g (3.85 mol) of 2-tert-butylphenol, and 15.6 g (0. 08 mol) and 250.0 g (1.3 mol) of xanthone were added and stirred. While stirring, 13.3 g of concentrated sulfuric acid was added dropwise at 70 to 80 ° C. over 1 hour. And reaction temperature was further raised to 90-100 degreeC, and it stirred as it was for 20 hours. Thereafter, excess phenol was distilled off at about 90 to 100 ° C. under a reduced pressure of about 1 torr to substantially remove it. To the residue, 1500 g of diisopropyl ether (IPE) was added and dissolved, and with 300 g of 5% aqueous sodium hydroxide solution per time, phenol and 2-tert-butylphenol remaining in the organic layer were not detected by HPLC analysis. Repeated washing was performed. After washing with an aqueous sodium hydroxide solution, the organic layer was washed with 300 g of 1% hydrochloric acid. 50 g of anhydrous sodium sulfate was added to the organic layer, the organic layer was dried, the crystal was removed by filtration, and then the solvent was removed until the solid content reached 60%. After removing the solvent, the residue is cooled to 10 ° C. over 1 hour to precipitate crystals, and the crystals are collected by filtration. In the general formula (1), Z is a divalent group containing the formula (3). R ₁ = tert-butyl group, f ₁ = 1, f ₂ = 0, r ₁ = 1, r ₂ = 1, m ₁ = 0, and a polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a ) 210 g was obtained.

The obtained polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound was purified by preparative GPC (apparatus: LC-908 manufactured by Nihon Analytical Industrial Co., Ltd.), and structural analysis was performed on the obtained purified compound. The results are shown below. A chart of ¹ H-NMR is shown in FIG.

[1] ¹ H-NMR (solvent: CDCl ₃ , internal standard: TMS)
Peak δ, ppm
j 1.2 9H
k 4.7 2H
c, d 6.4-6.7 2H
a, b, e 6.6-6.9 5H
f, g, h, i 6.9-7.3 8H

[2] MS m / n = 422 (M−H) − (apparatus: alliance ZQ4000 manufactured by Waters)

Example 2
(Synthesis of polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound)
To a 1 L flask equipped with a stirrer, reflux condenser and thermometer, 72.7 g (0.77 mol) of phenol, 103.7 g (0.77 mol) of 2-allylphenol, 3.1 g of dodecanethiol (0.016) Mol) and 50.0 g (0.25 mol) of xanthone were added and stirred. While stirring, 2.7 g of concentrated sulfuric acid was added dropwise at 70 to 80 ° C. over 1 hour. And reaction temperature was further raised to 90-100 degreeC, and it stirred as it was for 20 hours. Thereafter, excess phenol was distilled off at about 90 to 100 ° C. under a reduced pressure of about 1 torr to substantially remove it. 200 g of IPE was added to the residue and dissolved, and washed repeatedly with 60 g of a 5% aqueous sodium hydroxide solution until phenol and 2-allylphenol remaining in the organic layer were not detected by HPLC analysis. After washing with an aqueous sodium hydroxide solution, the organic layer was washed with 60 g of 1% hydrochloric acid. To the organic layer, 10 g of anhydrous sodium sulfate was added, the organic layer was dried, the crystals were removed by filtration, and the solvent was removed until the solid content was 65%. After removing the solvent, the residue is cooled to 5 ° C. over 1 hour to precipitate crystals, and the crystals are collected by filtration. In the general formula (1), Z is a divalent group containing the formula (3). R ₁ = allyl group, f ₁ = 1, f ₂ = 0, r ₁ = 1, r ₂ = 1, m ₁ = 0, polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (2.a) 32 g Got.

The obtained polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound was purified by preparative GPC (apparatus: LC-908 manufactured by Nihon Analytical Industrial Co., Ltd.), and structural analysis was performed on the obtained purified compound. The results are shown below. ^{A 1} H-NMR chart is shown in FIG.

(1) ¹ H-NMR (solvent: CDCl _3, internal standard: TMS)
Peak δ, ppm
j 3.3 2H
l, m 5.0-5.1 2H
k 5.9 1H
a, b, c, d, e 6.7-6.9 7H
f, g, h, i 6.9-7.3 8H

[2] MS m / n = 405 (M−H) − (apparatus: alliance ZQ4000 manufactured by Waters)

Example 3
(Synthesis of polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound)
In a 1 L flask equipped with a stirrer, reflux condenser, and thermometer, 95.6 g (0.77 mol) of 2-methoxyphenol, 115.7 g (0.77 mol) of 2-sec-butylphenol, 3.1 g of dodecanethiol. (0.016 mol) and 50.0 g (0.25 mol) of xanthone were added and stirred. While stirring, 2.7 g of concentrated sulfuric acid was added dropwise at 70 to 80 ° C. over 1 hour. And reaction temperature was further raised to 90-100 degreeC, and it stirred as it was for 20 hours. Thereafter, 200 g of IPE was added and washed repeatedly with 60 g of 5% aqueous sodium hydroxide solution until 2-methoxyphenol and 2-sec-butylphenol remaining in the organic layer were not detected by HPLC analysis. It was. After washing with an aqueous sodium hydroxide solution, the organic layer was washed with 60 g of 1% hydrochloric acid. To the organic layer, 10 g of anhydrous sodium sulfate was added, the organic layer was dried, the crystals were removed by filtration, and the solvent was removed until the solid content was 65%. After removing the solvent, the residue is cooled to 5 ° C. over 1 hour to precipitate crystals, and the crystals are collected by filtration. In the general formula (1), Z is a divalent group containing the formula (3). A polyfunctional hydroxyl group-containing asymmetric condensed ring in which R ₁ = methoxy group, f ₁ = 1, R ₂ = sec-butyl group, f ₂ = 1, r ₁ = 1, r ₂ = 1, m ₁ = 0 41 g of structural compound (3.a) was obtained.

The obtained polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound was purified by preparative GPC (apparatus: LC-908 manufactured by Nihon Analytical Industrial Co., Ltd.), and structural analysis was performed on the obtained purified compound. The results are shown below. ^{The 1} H-NMR chart is shown in FIG.

[1] ¹ H-NMR (solvent: CDCl ₃ , internal standard: TMS)
Peak δ, ppm
o 0.7 3H
l 1.0 3H
n 1.4 2H
m 2.9 1H
k 3.6 3H
q 4.6 1H
p 5.5 1H
a, b, c, d, e, f 6.3-6.8 6H
g, h, i, j 6.9-7.3 8H

[2] MS m / n = 451 (M−H) − (apparatus: alliance ZQ4000 manufactured by Waters)

Example 4
(Handling evaluation of polyfunctional hydroxyl group-containing asymmetric condensed ring structure compounds)
Using the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a), the following items were evaluated.

[1] Melting point:
The melting point is measured by DSC (DSC210 type: manufactured by SII Nano Technology Co., Ltd.).

[2] Melt viscosity:
The melt viscosity at 180 ° C. is measured with a high shear array viscometer CAP-2000 manufactured by Brookfield.

[3] Solvent solubility:
The polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound and the organic solvent are mixed and stirred so that the solid content becomes 20%, and the degree of solubility is visually judged and evaluated according to the following criteria.
○: Completely dissolves at room temperature.
(Triangle | delta): Although it does not melt | dissolve at room temperature, it melt | dissolves completely by heating.
X: Even if heated to the boiling point of the solvent, there remains undissolved.
In addition, the solvent to be used shall be three types, xylene, methyl isobutyl ketone (MIBK), and isopropanol (IPA).

The evaluation results are shown in Table 1. Table 1 also shows examples and comparative examples described later.

Example 5
Evaluation was performed in the same manner as in Example 4 except that the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a) was changed to the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (2.a).

Example 6
Evaluation was performed in the same manner as in Example 4 except that the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a) was changed to the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (3.a).

Comparative Example 1
Evaluation was performed in the same manner as in Example 4 except that the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a) was changed to bisphenolfluorene (4.a).

Comparative Example 2
Evaluation was performed in the same manner as in Example 4 except that the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a) was changed to bisphenol A.

As is apparent from the results in Table 1, the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound of the present invention has a low melting point and melt viscosity, and has good compatibility with various solvents. It can be seen that it can have a variety of uses.

Example 7
(Preparation and Evaluation of Molded Body Using Thermosetting Resin Composition Containing Polyfunctional Hydroxyl-Containing Asymmetric Condensed Ring Structure Compound)
100 parts by weight of a polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a) and 94 parts by weight of a bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.) were mixed and dissolved by heating, and then triphenylphosphine (TPP) as a catalyst. 2 parts by weight were mixed, and the resulting mixture was put into a stainless steel mold having a size of 100 mm × 100 mm and a thickness of 3 mm, and heated in a 120 ° C. oven for 1 hour and then at 180 ° C. for 4 hours to be thermally cured. Using the obtained molded body (test piece), the following items were evaluated.

[1] Raw material melting temperature:
A predetermined amount of a polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound and a bisphenol A type epoxy resin were charged, and the temperature was increased stepwise by 10 ° C. while stirring. At the same temperature, stirring was continued for 10 minutes, and the temperature when the raw material was completely dissolved was recorded.

[2] Formability:
The state of the composition in the molding step and the appearance of the molded body (test piece) were visually judged on the following criteria to evaluate the moldability. .
○: A test piece containing no bubbles can be prepared.
Δ: Viscosity increases when the catalyst is dissolved, and bubbles remain in the test piece.
X: Gelation occurs when the catalyst is dissolved, and a test piece cannot be prepared.

[3] Heat resistance:
Tg is measured by DSC (DSC210 type: manufactured by SII Nano Technology Co., Ltd.).

Table 2 shows the composition of the composition used in this example, and Table 3 shows the evaluation result of the obtained test piece. Tables 2 and 3 also show comparative examples described later.

Comparative Example 3
The polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a) was changed to bisphenolfluorene (4.a), and the bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.) was changed to 125 parts by weight. Evaluation was performed in the same manner as in Example 7.

Comparative Example 4
The polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a) is changed to bisphenol A, except that bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.) is changed to 173 parts by weight and TPP is changed to 3 parts by weight. Evaluation was performed in the same manner as in Example 7.

As is apparent from the results in Tables 2 and 3, it can be seen that the resin composition containing the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound of the present invention can be dissolved at low temperature and has excellent moldability. Moreover, it turns out that the molded article using the polyfunctional hydroxyl-containing asymmetric condensed ring structure compound of this invention has a high level of heat resistance.

Example 8
(Preparation and Evaluation of Film Using Thermosetting Resin Composition Containing Polyfunctional Hydroxyl-Containing Asymmetric Condensed Ring Structure Compound)
100 parts by weight of a polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a), 94 parts by weight of a bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.), and 2 parts by weight of triphenylphosphine (TPP) are mixed. The solution was diluted and dissolved with cyclohexanone so that the solid content was 70%. The obtained composition was applied to a Teflon (registered trademark) substrate so as to have a thickness of 100 to 200 μm. Heating was carried out in an oven at 120 ° C. for 1 hour and then at 180 ° C. for 4 hours to be thermally cured. The obtained molded body (film) was peeled off from the substrate, and the following items were evaluated.

[1] Refractive index:
About the obtained molded object (film), the refractive index in 632.8 nm is measured with an ABBE refractometer.

[2] Light transmittance:
About the obtained molded object (film), the spectral transmittance in a visible light region (400 nm) is measured with Hitachi spectrophotometer U-2000.

[3] Flexibility The molded body (film) obtained above is cut into a size of 15 mm × 30 mm, the long side of 30 mm is slowly bent, the bending angle until breaking is measured, and the flexibility is evaluated according to the following criteria. .
○: Bending angle is 90 ° or more Δ: Bending angle is more than 45 ° to less than 90 ° ×: Bending angle is 45 ° or less

Table 4 shows the composition of the composition used in this example, and Table 5 shows the evaluation result of the obtained test piece. Tables 4 and 5 also show the comparative examples described later.

Comparative Example 5
The polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a) was changed to bisphenolfluorene (4.a), and the bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.) was changed to 113 parts by weight. Evaluation was performed in the same manner as in Example 8.

Comparative Example 6
The same as Example 8 except that the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a) was changed to bisphenol A and the bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.) was changed to 137 parts by weight. Was evaluated.

As is apparent from the results in Tables 4 to 5, it is understood that when the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound of the present invention is used, a film having flexibility and high optical properties can be easily obtained. .

Example 9
(Synthesis of asymmetric epoxy resin containing a condensed ring structure)
A polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound represented by the following formula (1.a) (in the above general formula (1), Z is a divalent group containing the formula (3), and R ₁ = tert-butyl group _{, f 1 = 1, f 2} = 0, m 1 = 0, r 1 = 1, r 2 = 1) the 200g was dissolved in epichlorohydrin 640 g, further added benzyltriethylammonium chloride 1.3 g, 100 ° C. For 5 hours. Next, 114 g of a 40% aqueous sodium hydroxide solution was added dropwise at 70 ° C. under reduced pressure (150 mmHg) over 3 hours. Meanwhile, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropping, the reaction was continued for another 30 minutes. Then, after removing the salt produced | generated by filtration and further washing with water, epichlorohydrin is distilled off, methanol is added, In the said General formula (8), Z is a bivalent group containing Formula (3), Condensed ring structure-containing asymmetric epoxy resin (1.b) in which s ₁ = 0, R ₁ = tert-butyl group, f ₁ = 1, f ₂ = 0, r ₁ = 1, r ₂ = 1, m ₄ = 0. ) 220 g was obtained. The epoxy equivalent of this resin was 276 g / eq.

The obtained epoxy resin was purified by preparative GPC (apparatus: LC-908 manufactured by Nippon Analytical Industrial Co., Ltd.), and structural analysis was performed on the obtained purified epoxy resin. The results are shown below. ^{The 1} H-NMR chart is shown in FIG.

[1] ¹ H-NMR (solvent: CDCl ₃ , internal standard: TMS)
Peak δ, ppm
d 1.2 9H
a 2.7-3.0 4H
b 3.4 2H
c 3.9-4.3 4H
e 6.7 1H
f, g, h, i 6.7-6.9 6H
j, k, l, m 6.9-7.3 8H

[2] MS m / n = 535 M ⁺ (apparatus: alliance ZQ4000 manufactured by Waters)

Example 10
(Handling evaluation of asymmetric epoxy resin containing a condensed ring structure)
Using the condensed ring structure-containing asymmetric epoxy resin (1.b), the following items were evaluated.

[1] Melting point:
The melting point is measured by DSC (DSC210 type: manufactured by SII Nano Technology Co., Ltd.).

[2] Melt viscosity:
The melt viscosity at 180 ° C. is measured with a high shear array viscometer CAP-2000 manufactured by Brookfield.

[3] Solvent solubility:
The condensed ring structure-containing asymmetric epoxy resin and the organic solvent are mixed and stirred so that the solid content is 20%, and the degree of solubility is visually judged and evaluated according to the following criteria.
○: Completely dissolves at room temperature.
(Triangle | delta): Although it does not melt | dissolve at room temperature, it melt | dissolves completely by heating.
X: Even if heated to the boiling point of the solvent, there remains undissolved.
In addition, the solvent to be used shall be three types, xylene, methyl isobutyl ketone (MIBK), and isopropanol (IPA).

The evaluation results are shown in Table 6. The comparative examples are also shown in Table 6.

Comparative Example 7
Evaluation was performed in the same manner as in Example 10 except that the condensed ring structure-containing asymmetric epoxy resin (1.b) was changed to bisphenolfluorene epoxy resin (2.b).

Comparative Example 8
Evaluation was performed in the same manner as in Example 10 except that the condensed ring structure-containing asymmetric epoxy resin (1.b) was changed to a bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.).

As is clear from the results in Table 6, the condensed ring structure-containing asymmetric epoxy resin of the present invention has a low handling point such as a low melting point and melt viscosity and good compatibility with various solvents. It can be understood that it can be used for various purposes.

Example 11
(Preparation and Evaluation of Molded Body Using Thermosetting Resin Composition Containing Asymmetric Epoxy Resin Containing Fused Ring Structure)
100 parts by weight of the condensed ring structure-containing asymmetric epoxy resin (1.b) obtained in Example 9 and 60 parts by weight of a methylhexahydrophthalic anhydride type curing agent (Rikacid MH-700 manufactured by Shin Nippon Rika Co., Ltd.) 2 parts by weight of 2-ethyl-4-methylimidazole (2E4MZ) as a catalyst is mixed with the mixture of No. 1 and the obtained mixture is put into a stainless steel mold having a size of 100 mm × 100 mm and a thickness of 1 mm, and is then left in an oven at 100 ° C. for 1 hour. Then, it was heated at 180 ° C. for 4 hours to be thermally cured. Using the obtained molded body (test piece), the following items were evaluated.

[1] Heat resistance:
Tg is measured by DSC (DSC210 type: manufactured by SII Nano Technology Co., Ltd.).

[2] Dielectric constant and dielectric loss tangent:
A DIELECTRIC TEST FIXTURE 16451B is attached to a PRECISION LCR METER 4284A type manufactured by Agilent Technologies, Inc. and measured at a frequency of 1 MHz.

[3] Elastic modulus:
Using a dynamic viscoelasticity measuring device DMS6100 (manufactured by SII Nano Technology Co., Ltd.), in the temperature range of −50 to 250 ° C., the response when a 1 Hz sine wave is given in the double-end bending mode is measured, The storage elastic modulus E ′ is obtained.

Table 7 shows the composition of the composition used in this example, and Table 8 shows the evaluation result of the obtained test piece. Tables 7 and 8 also show examples and comparative examples described later.

Comparative Example 9
Except that the epoxy resin (1.b) was changed to bisphenolfluorene epoxy resin and the methylhexahydrophthalic anhydride type curing agent (Rikacid MH-700 manufactured by Shin Nippon Rika Co., Ltd.) was changed to 71 parts by weight. A test piece was prepared and evaluated in the same manner as in Example 11.

Comparative Example 10
Epoxy resin (1.b) was changed to bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.), and methylhexahydrophthalic anhydride type curing agent (New Japan Rika Co., Ltd. Rikacid MH-700) was replaced with 86 A test piece was prepared and evaluated in the same manner as in Example 11 except that the weight was changed to parts by weight.

As is apparent from the results of Tables 7 to 8, when the condensed ring structure-containing asymmetric epoxy resin of the present invention is used, a molded product having mechanical strength and high heat resistance and electrical properties at a high level is obtained. I understand that

Example 12
(Preparation and Evaluation of Thin Film Using Thermosetting Resin Composition Containing Asymmetric Epoxy Resin Containing Fused Ring Structure)
100 parts by weight of the condensed ring structure-containing asymmetric epoxy resin (1.b) obtained in Example 9 and 1 part by weight of an aromatic sulfonium salt (Sun Aid SI-60 manufactured by Sanshin Chemical Industry Co., Ltd.) as a catalyst were used as a solvent. Dissolved in a certain cyclohexanone to give a solution having a concentration of 30% by weight. Next, the obtained mixture was applied onto a glass substrate and a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to obtain a coating film having a thickness of about 2 μm. Subsequently, it was heat-cured by post-baking in an oven at 240 ° C. for 1 hour. The obtained cured film was evaluated for the following items. Table 9 shows the composition of the composition used in this example, and Table 10 shows the evaluation results of the obtained cured film. Tables 9 and 10 also show examples and comparative examples described later.

(1) Film forming property:
The surface of the obtained cured film is visually confirmed, and the film forming property is evaluated according to the following criteria.
○: No precipitate ×: There is a precipitate

(2) Refractive index:
About the obtained cured film, the refractive index in 632.8 nm is measured with an optical interference type film quality measuring machine.

(3) Light transmittance:
With respect to the obtained cured film, the spectral transmittance in the visible light region (400 nm) is measured with a Hitachi spectrophotometer U-2000.

(4) Adhesion According to JIS-K-5400, evaluation is made by a cross-cut peel test.

Example 13
Example 12 except that 100 parts by weight of epoxy resin (1.b) was changed to a mixture of 50 parts by weight of epoxy resin (1.b) and 50 parts by weight of bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.) A cured film was prepared and evaluated under the same conditions as those described above.

Comparative Example 11
A cured film was prepared and evaluated under the same conditions as in Example 12 except that the epoxy resin (1.b) was changed to bisphenolfluorene epoxy resin.

Comparative Example 12
A cured film was prepared and evaluated under the same conditions as in Example 13 except that the epoxy resin (1.b) was changed to a bisphenolfluorene epoxy resin.

Comparative Example 13
A cured film was prepared and evaluated under the same conditions as in Example 12 except that the epoxy resin (1.b) was changed to a bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.).

As is clear from the results of Tables 9 to 10, when the condensed ring structure-containing asymmetric epoxy resin of the present invention is used, a thin film can be easily obtained, and a cured thin film having high transparency and a high level of refractive index can be obtained. I understand that.

Example 14
(Synthesis of an asymmetric epoxy ester resin containing a condensed ring structure)
In a 300 ml four-necked flask, 200 g of the asymmetric epoxy resin (1.b) obtained in Example 9 (epoxy equivalent 276 g / eq), 520 mg of triethylbenzylammonium chloride as a catalyst, and 2,6-diisobutylphenol as a polymerization inhibitor 45 mg and 63 g of acrylic acid were charged and dissolved by heating at 90 to 100 ° C. while blowing air at a rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. Although the solution became clear and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 17 hours for the acid value to reach the target. In the general formula (15), Z is a divalent group including the formula (3), R ₁ = tert-butyl group, f ₁ = 1, f ₂ = 0, r ₁ = 1, r ₂ = 1, A light yellow transparent and solid condensed ring structure-containing asymmetric epoxy ester resin (1.c) in which s ₁ = 0, m ₄ = 0, and R ₇ = ethenyl group was obtained.

Example 15
(Handling evaluation of asymmetric epoxy ester resin containing a condensed ring structure)
Using the condensed ring structure-containing asymmetric epoxy ester resin (1.c), the following items were evaluated.

[1] Solution viscosity:
Diluted and dissolved the condensed ring structure-containing asymmetric epoxy ester resin (1.c) with propylene glycol monomethyether acetate (PGMEA) so that the solid content is 50%, and with a rotational viscometer (B type viscometer) The solution viscosity at 25 ° C. was measured.

[2] Solvent solubility:
The condensed ring structure-containing asymmetric epoxy ester resin (1.c) and the organic solvent are mixed and stirred so that the solid content is 20%, and the degree of solubility is visually judged and evaluated according to the following criteria.
○: Completely dissolves at room temperature.
(Triangle | delta): Although it does not melt | dissolve at room temperature, it melt | dissolves completely by heating.
X: Even if heated to the boiling point of the solvent, there remains undissolved.
In addition, the solvent to be used shall be three types, xylene, methyl isobutyl ketone (MIBK), and isopropanol (IPA).

The evaluation results are shown in Table 11. The comparative examples described later are also shown in Table 11.

Comparative Example 14
Evaluation was performed in the same manner as in Example 15 except that the condensed ring structure-containing asymmetric epoxy ester resin (1.c) was changed to the bisphenol fluorene epoxy acrylate resin (2.c).

Comparative Example 15
Evaluation was performed in the same manner as in Example 15 except that the condensed ring structure-containing asymmetric epoxy ester resin (1.c) was changed to a bisphenol A type epoxy acrylate resin (3.c).

As is clear from the results in Table 11, the asymmetric epoxy ester resin containing a condensed ring structure of the present invention has a low viscosity and a high handling property such as good compatibility with various solvents. It can be used for various purposes.

Example 16
(Preparation and Evaluation of Cured Film Using Photocurable Resin Composition Containing Asymmetric Epoxy Ester Resin Containing Fused Ring Structure)
100 parts by weight of the condensed ring structure-containing asymmetric epoxy ester resin (1.c) obtained in Example 14 and 3 parts by weight of Irgacure 907 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) as a solvent to obtain a concentration. The solution was 30% by weight. The solution containing the epoxy acrylate resin was applied on a glass substrate and a silicon substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 120 seconds to obtain a coating film having a thickness of about 2 μm. Further, for the evaluation of flexibility, the above solution was applied to a PET film with a bar coater and then pre-baked in an oven at 90 ° C. for 120 seconds to obtain a coating film having a thickness of about 2 μm. Next, they were irradiated with 300 mJ / cm ² of light with a high-pressure mercury lamp (400 W) to cure the coating film. The obtained cured film was evaluated for the following items. The composition of the composition used in this example is shown in Table 12, and the evaluation results of the obtained cured film are shown in Table 13. Tables 12 and 13 also show examples and comparative examples described later.

(1) Film forming property:
The surface of the obtained cured film is visually confirmed, and the film forming property is evaluated according to the following criteria.
○: No precipitate ×: There is a precipitate

(2) Refractive index:
About the obtained cured film, the refractive index in 632.8 nm is measured with an optical interference type film quality measuring machine.

(3) Light transmittance:
With respect to the obtained cured film, the spectral transmittance in the visible light region is measured with a Hitachi spectrophotometer U-2000.

(4) Adhesiveness The cured film obtained above is evaluated by a cross-cut peel test according to JIS-K-5400.

(5) Heat resistance The cured film obtained above is placed in an oven at 250 ° C. for 3 hours and cured and baked. Film thickness change rate before and after cure baking [(film thickness before cure baking−film thickness after cure bake) / (film thickness before cure bake)] × 100. In this evaluation, the smaller the value, the better the heat resistance.

(6) Film shrinkage rate The film thickness change rate before and after exposure and curing is calculated.
Film thickness change rate before and after exposure curing [(film thickness before exposure−film thickness after exposure) / (film thickness before exposure)] × 100.

(7) Flexibility:
The cured thin film coated on the PET film is slowly folded together with the PET film having a long side of 3 cm, the angle when the thin film is cracked is measured, and the flexibility is evaluated according to the following criteria.
○: Bending angle is 90 ° or more Δ: Bending angle is more than 45 ° to less than 90 ° ×: Bending angle is 45 ° or less

Example 17
Example 100 except that 100 parts by weight of the epoxy ester resin (1.c) in Example 16 was changed to a mixture of 60 parts by weight of the epoxy ester resin (1.c) and 40 parts by weight of dipentaerythritol hexaacrylate (DPHA). A thin film was prepared under the same conditions as in No. 16, and evaluated.

Comparative Example 16
A thin film was prepared and evaluated under the same conditions as in Example 16 except that the epoxy ester resin (1.c) in Example 16 was changed to a bisphenolfluorene epoxy acrylate resin (2.c).

Comparative Example 17
A thin film was prepared and evaluated under the same conditions as in Example 17 except that the epoxy ester resin (1.c) in Example 17 was changed to a bisphenolfluorene epoxy acrylate resin (2.c).

Comparative Example 18
A thin film was prepared and evaluated under the same conditions as in Example 16 except that the epoxy ester resin (1.c) in Example 16 was changed to a bisphenol A type epoxy acrylate resin (3.c).

As is clear from the results of Tables 12 to 13, when the condensed ring structure-containing asymmetric epoxy ester resin of the present invention is used, it has high flexibility, high transparency, high refractive index and heat resistance, It can be seen that a cured thin film having a low degree of curing shrinkage can be easily obtained.

Example 18
(Synthesis of an asymmetric alkali-soluble resin containing a condensed ring structure)
After 87 g of 3-methoxybutyl acetate (PGMEA) was added to 100 g of the condensed asymmetric epoxy ester resin (1.c) prepared in Example 14 and dissolved, 21 g of biphenyltetracarboxylic dianhydride (BPDA) and catalyst were added. As a mixture, 0.1 g of tetraethylammonium bromide was mixed, and this was gradually heated and reacted at 110 to 115 ° C. for 14 hours. Subsequently, 10.9 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and the reaction was carried out at 90 to 95 ° C. for 4 hours.
In this manner, a PGMEA solution of the condensed ring structure-containing asymmetric alkali-soluble resin (1.e) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.
The condensed ring structure-containing asymmetric alkali-soluble resin (1.e) can be classified as a condensed ring structure-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin.

Here, a plurality of R ₁ and R ₂ are not all the same, but _one of R ₁ and R _{2 in} a pair is a tert-butyl group and the other is a hydrogen atom. The average t is 7.5.

Example 19
(Preparation and evaluation of thin film using composition containing a condensed alkali-soluble resin containing a condensed ring structure)
30 parts by weight of the alkali-soluble resin (1.e) obtained in Example 18 as solids, 20 parts by weight of dipentaerythritol hexaacrylate (DPHA), and 3 parts by weight of Irgacure 907, in PGMEA as a solvent To obtain a solution having a concentration of 30% by weight. This solution was applied onto a glass substrate and a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of about 2 μm. A glass substrate having this coating film and a mask having a predetermined pattern are placed on the coating film surface of the silicon substrate, and a light intensity of 9.5 mW / cm at a wavelength of 405 nm using a 250 W high-pressure mercury lamp in a nitrogen atmosphere. ² ultraviolet rays were irradiated so as to have an energy amount of 1000 mJ / cm ² . Subsequently, the development process for 120 second was performed at 23 degreeC using 0.1 weight% sodium carbonate aqueous solution, and the unexposed part of the coating film was removed. Then, the rinse process was performed with the ultrapure water. The substrate having the obtained thin film was placed in an oven at 200 ° C., post-baking was performed for 30 minutes, and the thin film was heat-cured (hereinafter, the film thus cured is referred to as a heat-cured film).

The evaluation at the time of preparation of the heat-cured thin film in this example and the evaluation of the obtained cured film were performed for the following items.

<1> Dilution Resistance The adjusted PGMEA solution having a concentration of 30% by weight is diluted with each solvent so that the concentration becomes 5% by weight, and the degree of occurrence of turbidity is visually determined according to the following criteria.
In addition, the solvent to be used shall be four types, toluene, methyl isobutyl ketone (MIBK), ethylene glycol monobutyl ether acetate (BMGAC), and diethylene glycol monobutyl ether acetate (BDGAC).
○: No turbidity or precipitation occurs ×: Turbidity or precipitation occurs

The above results are shown in Table 14. Table 14 also shows the results of Examples 20 to 21 and Comparative Examples 19 to 20 described later.

<2> Drying property of coating film The drying property of the coating film after the pre-baking is evaluated according to JIS-K-5400. The rank of evaluation is as follows.
○: No sticking is observed Δ: Slight sticking is recognized ×: Remarkably sticking is recognized

<3> Developability with respect to alkaline aqueous solution The glass substrate having the pre-baked coating film is immersed in a 0.1% by weight aqueous sodium carbonate solution for 120 seconds without exposure treatment.
Film thickness change rate before and after development [(film thickness before development−film thickness after development) / (film thickness before development)] × 100 is obtained. In this evaluation, the larger the value, the better the developability.

<4> Exposure sensitivity As a mask, a step tablet (negative mask with 12 steps of optical density) is adhered to the coating film after the pre-baking, and exposure and development are performed. Thereafter, the number of steps of the remaining step tablet is examined (in this evaluation method, the higher the sensitivity, the larger the number of remaining steps).

<5> Adhesiveness with substrate The heat-cured film obtained above is evaluated by a cross-cut peel test according to JIS-K-5400.

<6> Heat resistance The obtained heat-cured film is placed in an oven at 250 ° C. for 3 hours and cured and baked. Film thickness change rate before and after cure baking [(film thickness before cure baking−film thickness after cure bake) / (film thickness before cure bake)] × 100. In this evaluation, the smaller the value, the better the heat resistance.

<7> Refractive Index The refractive index at 632.8 nm is measured for the heat-cured film obtained above with a light interference film quality measuring machine.

<8> Light transmittance With respect to the heat-cured film obtained above, the spectral transmittance in the visible light region is measured with a Hitachi spectrophotometer U-2000.

<9> Chemical resistance The substrate having the heat-cured film obtained above is immersed in the following chemicals under the following conditions.
(I) Acidic solution: immersed in 5 wt% HCl aqueous solution at room temperature for 24 hours (ii) Alkaline solution ii-1: immersed in 5 wt% NaOH aqueous solution at room temperature for 24 hours ii-2: in 4 wt% KOH aqueous solution Immersion at 50 ° C. for 10 minutes ii-3: Immersion in 1% by weight NaOH aqueous solution at 80 ° C. for 5 minutes (iii) Solvent iii-1: Immersion in N-methylpyrrolidone at 40 ° C. for 10 minutes iii-2: N-methyl The film thickness change rate (%) before and after immersion for 5 minutes at 80 ° C. in pyrrolidone ((film thickness before immersion−film thickness after immersion) / (film thickness before immersion)) × 100 is obtained. The obtained results were evaluated according to the following evaluation criteria.
A: Excellent in chemical resistance (thickness change rate in all solutions is less than 5%)
○: Excellent chemical resistance (change rate of film thickness in all solutions 5% to less than 10%)
Δ: Chemical resistance is slightly inferior (the film thickness change rate in any solution is 10% or more to less than 20%)
X: Inferior in chemical resistance (film thickness change rate in any solution of 20% or more)

The results are shown in Table 15. Table 15 also shows the results of Examples 20 to 21 and Comparative Examples 19 to 20 described later.

Example 20
A thin film was prepared and evaluated under the same conditions as in Example 19 except that dipentaerythritol hexaacrylate was changed to trimethylolpropane triacrylate (TMPTA).

Example 21
Furthermore, a thin film was prepared and evaluated under the same conditions as in Example 19 except that a composition containing 6 parts by weight of tetramethylbiphenyl type epoxy resin (Epicoat Yx-4000, manufactured by Japan Epoxy Resin Co., Ltd.) was used. .

Comparative Example 19
In Example 19, a thin film was formed under the same conditions as in Example 19 except that the alkali-soluble resin (1.e) was changed to a bisphenolfluorene-type photopolymerizable unsaturated resin (2.e) represented by the following formula. Was created and evaluated.

ここで平均のｔ_２は６．９である。

Here, the average t ₂ is 6.9.

Comparative Example 20
In Example 19, the thin film was formed under the same conditions as in Example 19 except that the alkali-soluble resin (1.e) was changed to a bisphenol A photopolymerizable unsaturated resin (3.e) represented by the following formula. Was created and evaluated.

ここでｖは約０．５、平均のｗは４．９である。

Here, v is about 0.5 and the average w is 4.9.

As is clear from the results of Tables 14 to 15, when the condensed ring structure-containing asymmetric alkali-soluble resin of the present invention is used, the compatibility with various solvents, the dilution resistance is good, the refractive index and the transparency are high, It turns out that the cured thin film excellent in coating-film drying property, heat resistance, and chemical resistance is obtained. Furthermore, it is clear that a thin film having the above-mentioned excellent properties with a desired pattern is formed with high precision on the substrate by exposure and development.

According to the present invention, a novel polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound, a condensed ring structure-containing asymmetric epoxy resin, a condensed ring structure-containing asymmetric epoxy ester resin, and a condensed ring structure-containing asymmetric alkali-soluble resin are thus obtained. As well as a simple production method thereof. These resins can be polymerized and cured by heat or radiation. When these resins are used, various cured molded bodies or thin films can be easily obtained. Furthermore, these cured molded bodies or thin films have mechanically strong flexibility, high transparency, high levels of heat resistance and electrical properties, and a low degree of curing shrinkage. Furthermore, when the alkali-soluble radiation-polymerizable unsaturated resin of the present invention is used, a thin film having a desired pattern and having the above-mentioned excellent properties can be accurately formed on a substrate. Therefore, the resin or resin composition of the present invention is a protective film forming material for various electronic components (liquid crystal display elements including color filters, integrated circuit elements, solid-state imaging elements, etc.); interlayer insulating film forming materials, for color resists. Binder composition; Solder resist used in the production of printed wiring board; Coating agent;

1 is a ¹ H-NMR chart of the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (1.a) obtained in Example 1. FIG. 2 is a ¹ H-NMR chart of the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (2.a) of the present invention obtained in Example 2. FIG. 3 is a ¹ H-NMR chart of the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound (3.a) of the present invention obtained in Example 3. FIG. ^{1 is} a ¹ H-NMR chart of the asymmetric epoxy resin (1.b) containing a condensed ring structure of the present invention obtained in Example 9.

Claims (38)

A polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound represented by the following general formula (1).

Here, X ₁ in the general formula (1) is each independently a group represented by the following general formula (2), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z in the general formula (1) is a condensed structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings, or five-membered It is a divalent group containing a condensed ring structure of a ring alicyclic compound (which may contain atoms other than carbon on the ring) and one aromatic ring, and R _1-2 are each independently from 1 carbon atom. 10 linear, branched or cyclic alkyl groups or alkenyl groups, an alkoxy group having 1 to 5 carbon atoms, an optionally substituted phenyl group, or a halogen atom, and f _1-2 are each independently It is an integer from 0 to 4. Furthermore, R _{3 in the} general formula (2) is a hydrogen atom or a methyl group, and m ₁ is an integer of 0 to 10. Further, a plurality of _{R 1~3,} X _{1, m} 1 is may be the same or may be different.
However, the types of R ₁ and R ₂ in general formula (1), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (X ₁ ) r ₁ and (X ₁ ) r ₂ at least one of the substitution positions is different. In the general formula (1), f ₁ is an integer of 1 or more, and at least one of f ₁ R ₁ is a halogen atom, an alkyl group or alkenyl group having 2 to 5 carbon atoms, or 1 to carbon atoms. The polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound according to claim 1, which is an alkoxy group of 5. Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7), The polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound according to any one of claims 1 to 2.

Z is a bivalent group containing the condensed ring structure shown by Formula (3), The polyfunctional hydroxyl group containing asymmetric condensed ring structure compound as described in any one of Claims 1-2.

The resin composition containing the polyfunctional hydroxyl-containing asymmetric condensed ring structure compound as described in any one of Claims 1-4. The molded object obtained by hardening the resin composition of Claim 5. A condensed epoxy-containing asymmetric epoxy resin represented by the following general formula (8).

Here, Y _1-2 in the general formula (8) are each independently a group represented by the following general formula (9), and r _1-2 are each independently an integer of 1-5.

Here, A ₁ in the general formula (9) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (11). Furthermore, Y _{<3> -4} of General formula (9) is group respectively independently selected from General formula (9) and following General formula (11), and p _<1-2> is each independently _0-4 . It is an integer.

Here, Z in the general formulas (8) and (9) is a condensed ring structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings, Or a divalent group containing a condensed ring structure of a five-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one aromatic ring, and R _1-2 are each independently A linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an optionally substituted phenyl group, or a halogen atom, f _{1- 2} is an integer of 0 to 4 each independently. Further, R _{4 to 6 in the} general formulas (9), (10) and (11) are each independently a hydrogen atom or a methyl group, m _{2 to 4} and s ₁ are each independently an integer of 0 to 10. is there. A plurality of R _1-2 , Y _1-5 , A ₁ , f _1-2 , p _1-2 , s ₁ , R _4-6 , m _2-4 may be the same or different. good.
However, the types of R ₁ and R _{2 in} the general formulas (8) and (9), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , (R ₁ ) f ₁ and (R ₂ ) f ₂ substitution _{position, (Y 1) r} 1 and _(Y 2) substitution position of _{r 2,} numerical values of _{p 1} and _{p 2,} and _{a 1, (Y 3) p} 1 and _{Y 5,} substitution of _(Y 4) _{p 2} At least one of the positions is different. The condensed ring structure containing asymmetric epoxy resin of Claim 7 obtained from the manufacturing method including the process of making an epihalohydrin act on the polyfunctional hydroxyl group containing asymmetric condensed ring structure compound as described in any one of Claims 1-4. The condensed ring-containing asymmetric epoxy resin according to claim 7 or 8, which is represented by the following general formula (12).

Here, Y _6-7 in the general formula (12) are each independently a group represented by the following general formula (13).

Here, A ₁ in the general formula (13) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (11).

Here, Z, R _1-2 , f _1-2 , R _4-6 , m _2-4 , and s ₁ in the general formulas (12), (13), (10), and (11) are the same as described above. Yes, a plurality of R _1-2 , f _1-2 , A ₁ , s ₁ , R _4-6 , m _2-4 may be the same or different.
However, the types of R ₁ and R _{2 in} the general formulas (12) and (13), the numerical values of f ₁ and f ₂ , the substitution positions of (R ₁ ) f ₂ and (R ₂ ) f ₂ , Y ₆ and Y ₇ And at least one of the substitution positions of A ₁ and Y ₅ is different. The condensed ring-containing asymmetric epoxy resin according to claim 7 or 8, which is represented by the following general formula (14).

Here, Y ₅ in the general formula (14) is each independently a group represented by the following general formula (11), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z, R _<1-2> , f _<1-2> , R _{< 6 >} , m < _{4 > of} General formula (14), (11) is the same as the above, and several R _<1-2> , Y < _{5 >} , R _{< 6 >} . , M ₄ may be the same or different.
However, the types of R ₁ and R ₂ of the general formula (14), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (Y ₅ ) r ₁ and (Y ₅ ) r ₂ at least one of the substitution positions is different. In the general formulas (8), (9), (12), (13), and (14), at least one of a plurality of f ₁ and f ₂ is an integer of 1 or more, and there is f ₁ R of ₁ or f ₂ pieces is R _2, at least one halogen atom, an alkyl group or an alkenyl group having 2 to 5 carbon atoms, or any one of claims 7 to 10 carbon atoms of 1 to a 5 alkoxy group The condensed ring structure-containing asymmetric epoxy resin described in 1. The condensed ring-containing asymmetric epoxy resin according to any one of claims 7 to 11, wherein Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7).

Z is a divalent group containing the condensed ring structure shown by Formula (3), The condensed ring structure containing asymmetric epoxy resin as described in any one of Claims 7-11.

It is a manufacturing method of the condensed ring structure containing asymmetric epoxy resin as described in any one of Claims 7-13, Comprising: In the polyfunctional hydroxyl group containing asymmetric condensed ring structure compound as described in any one of Claims 1-4. A method comprising the step of acting an epihalohydrin. 15. The method of claim 14, wherein the epihalohydrin is epichlorohydrin. The epoxy resin composition containing the condensed ring structure containing asymmetric epoxy resin as described in any one of Claims 7-13. The molded object obtained by hardening the epoxy resin composition of Claim 16. A condensed epoxy structure-containing asymmetric epoxy ester resin represented by the following general formula (15).

Here, Y _1-2 in the general formula (15) are each independently a group represented by the following general formula (16), and r _1-2 are each independently an integer of 1-5.

Here, A ₁ in the general formula (16) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (17). Furthermore, Y _{<3> -4} of General formula (16) is group respectively independently selected from General formula (16) and following General formula (17), and p _<1-2> is respectively independently _0-4 . It is an integer.

Here, Z in the general formulas (15) and (16) represents a condensed ring structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings, Or a divalent group containing a condensed ring structure of a five-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one aromatic ring, and R _1-2 are each independently A linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an optionally substituted phenyl group, or a halogen atom, f _{1- 2} is an integer of 0 to 4 each independently. In the general formulas (10) and (17), R _{4 to 6} each independently represent a hydrogen atom or a methyl group, R ₇ represents a group containing a site derived from a monobasic carboxylic acid, and m _{2 to 4} , S ₁ are each independently an integer from 0 to 10. A plurality of R _1-2 , f _1-2 , s ₁ , R _4-7 , A ₁ , Y _1-5 , p _1-2 , m _2-4 may be the same _or different. good.
However, the types of R ₁ and R _{2 in} the general formulas (15) and (16), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , (R ₁ ) f ₁ and (R ₂ ) f ₂ substitution _{position, (Y 1) r} 1 and _(Y 2) substitution position of _{r 2,} numerical values of _{p 1} and _{p 2,} and _{a 1, (Y 3) p} 1 and _{Y 5,} substitution of _(Y 4) _{p 2} At least one of the positions is different. The manufacturing method including the process with which the condensed ring structure asymmetric epoxy resin as described in any one of Claims 7-13 is made to react with monobasic carboxylic acid, or as described in any one of Claims 1-4. 19. The condensed ring structure-containing asymmetric epoxy ester resin according to claim 18, obtained from a production method comprising a step of allowing a monobasic glycidyl carboxylate to act on a polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound. The condensed ring structure containing asymmetric epoxy ester resin of Claim 18 or 19 shown by following General formula (18).

Here, Y _6-7 in the general formula (18) are each independently a group represented by the following general formula (19).

Here, A ₁ in the general formula (19) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (17).

Here, Z, R _1-2 , f _1-2 , R _4-6 , m _2-4 , R ₇ , s ₁ in the general formulas (18), (19), (10), (17) A plurality of R _1-2 , f _1-2 , s ₁ , A ₁ , Y ₅ , R _4-6 , m _2-4 , R ₇ may be the same or different. .
However, the types of R ₁ and R _{2 in} the general formulas (18) and (19), the numerical values of f ₁ and f ₂ , the substitution positions of (R ₁ ) f ₂ and (R ₂ ) f ₂ , Y ₆ and Y ₇ And at least one of the substitution positions of A ₁ and Y ₅ is different. The condensed ring structure containing asymmetric epoxy ester resin of Claim 18 or 19 shown by following General formula (20).

Here, Y ₅ in the general formula (20) is a group represented by the following general formula (17), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z, R _1-2 , f _1-2 , R ₆ , R ₇ , m ₄ in the general formulas (20) and (17) are the same as described above, and a plurality of R _1-2 , Y ₅ , R ₆ , R ₇ and m ₄ may be the same or different.
However, the types of R ₁ and R _{2 in} the general formula (20), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (Y ₅ ) r ₁ and (Y ₅ ) r ₂ at least one of the substitution positions is different. The condensed ring structure-containing asymmetric epoxy ester resin according to claim 18 or 19, which is an epoxy acrylate resin represented by the following general formula (21).

Here, Y _1-2 in the general formula (21) is a group represented by the following general formula (22), and r _1-2 are each independently an integer of 1-5.

Here, A ₁ in the general formula (22) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (23). Further, Y _3-4 in the general formula (22) are groups independently selected from the general formula (22) and the following general formula (23), and p _1-2 are each independently 0 to 4 It is an integer.

Here, Z, R _1-2 , R _4-6 , f _1-2 , m _2-4 , and s ₁ in the general formulas (21), (22), (10), and (23) are the same as described above. is there. Further, R _{8 in the} general formula (23) each independently represents a hydrogen atom or a methyl group. A plurality of R _1-2 , f _1-2 , s ₁ , p _1-2 , R _4-6 , R ₈ , Y _1-5 , m _2-4 may be the same or different. good.
However, the types of R ₁ and R _{2 in} the general formulas (21) and (22), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , (R ₁ ) f ₁ and (R ₂ ) f ₂ substitution _{position, (Y 1) r} 1 and _(Y 2) substitution position of _{r 2,} numerical values of _{p 1} and _{p 2,} and _{a 1, (Y 3) p} 1 and _{Y 5,} substitution of _(Y 4) _{p 2} At least one of the positions is different. The condensed ring-containing asymmetric epoxy ester resin according to claim 22, which is an epoxy acrylate resin represented by the following general formula (24).

Here, Y _6-7 in the general formula (24) are each independently a group represented by the following general formula (25).

Here, A ₁ in the general formula (25) is a divalent group represented by the following general formula (10), and Y ₅ is a group represented by the following general formula (23).

Here, Z, R _1-2 , f _1-2 , R _4-6 , m _2-4 , R ₈ , s ₁ in the general formulas (24), (25), (10), (23) The plurality of R _1-2 , A ₁ , Y ₅ , f _1-2 , s ₁ , R _4-6 , m _2-4 , R ₈ may be the same or different. .
However, the types of R ₁ and R _{2 in} the general formulas (24) and (25), the numerical values of f ₁ and f ₂ , the substitution positions of (R ₁ ) f ₂ and (R ₂ ) f ₂ , Y ₆ and Y ₇ And at least one of the substitution positions of A ₁ and Y ₅ is different. The condensed ring structure-containing asymmetric epoxy ester resin according to claim 22, which is an epoxy acrylate resin represented by the following general formula (26).

Here, Y ₅ in the general formula (26) is a group represented by the following general formula (23), and r ₁ and ₂ are each independently an integer of 1 to 5.

Here, Z, R _1-2 , f _1-2 , R ₆ , R ₈ , m ₄ in the general formulas (26) and (23) are the same as described above, and a plurality of R _1-2 , Y ₅ , R ₆ , R ₈ and m ₄ may be the same or different.
However, the types of R ₁ and R _{2 in} the general formula (26), the numerical values of f ₁ and f ₂ , the numerical values of r ₁ and r ₂ , the substitution positions of (R ₁ ) f ₁ and (R ₂ ) f ₂ , and , (Y ₅ ) r ₁ and (Y ₅ ) r ₂ at least one of the substitution positions is different. The condensed ring-containing asymmetric epoxy ester resin according to any one of claims 18 to 24, wherein Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (3) to (7).

Z is a divalent group containing the condensed ring structure shown by Formula (3), The condensed ring structure containing asymmetric epoxy ester resin as described in any one of Claims 18-24.

It is a manufacturing method of the condensed ring structure containing asymmetric epoxy ester resin as described in any one of Claims 18-26, Comprising: The condensed ring structure containing asymmetric epoxy resin as described in any one of Claims 7-13, and single. A method comprising a step of reacting a basic carboxylic acid, or a step of reacting the polyfunctional hydroxyl group-containing asymmetric condensed ring structure compound according to any one of claims 1 to 4 with glycidyl monobasic carboxylate. . 28. The method of claim 27, wherein the monobasic carboxylic acid is (meth) acrylic acid and the monobasic glycidyl carboxylic acid is glycidyl (meth) acrylate. The condensed ring structure containing asymmetric epoxy ester resin composition containing the condensed ring structure containing asymmetric epoxy ester resin as described in any one of Claims 18-26. A molded product obtained by curing the condensed ring structure-containing asymmetric epoxy ester resin composition according to claim 29. A condensed ring-containing asymmetric alkali-soluble resin obtained by reacting a condensed basic structure-containing asymmetric epoxy ester resin according to any one of claims 18 to 26 with a polybasic carboxylic acid or an anhydride thereof. 32. The condensed ring according to claim 31, wherein the condensed ring structure-containing asymmetric alkali-soluble resin is a condensed ring structure-containing asymmetric alkali-soluble radiation-polymerizable unsaturated resin having a radiation-polymerizable unsaturated group in the molecule. An asymmetric alkali-soluble resin containing a ring structure. The condensed ring-containing asymmetric alkali-soluble resin according to claim 32, wherein the radiation-polymerizable unsaturated group is an ethenyl group. It is a manufacturing method of the condensed ring structure containing asymmetric alkali-soluble resin as described in any one of Claims 31-33, Comprising: The condensed ring structure containing asymmetric epoxy ester as described in any one of Claims 18-26 A method comprising a step of reacting a resin with a polybasic carboxylic acid or an anhydride thereof. The radiation sensitive alkali-soluble resin composition containing the condensed ring structure containing asymmetric alkali-soluble resin as described in any one of Claims 31-33. A molded product obtained by curing the radiation-sensitive alkali-soluble resin composition according to claim 35. The resin composition according to any one of claims 5, 16, 29, and 35, comprising an organic pigment and / or inorganic fine particles. A molded product obtained by curing the resin composition according to claim 37.

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