JP2013064166A - Ring-fused structure-containing resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a ring-fused structure-containing epoxy ester resin which provides a cured product having high-level heat resistance, electrical characteristics, and optical characteristics, and excellent in dispersibility and patterning characteristics, a method for producing the same, a ring-fused structure-containing epoxy ester resin composition, and a molding.SOLUTION: The ring-fused structure-containing epoxy ester resin is an epoxy acrylate resin represented by general formula (17).

Description

The present invention relates to a novel condensed ring structure-containing epoxy resin having heat and radiation curability, a condensed ring structure-containing epoxy ester resin, a condensed ring structure-containing alkali-soluble resin, a method for producing the resin, and a heat containing the resin. The present invention relates to a curable or radiation curable resin composition. 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 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 an epoxy resin, an epoxy ester resin, and an alkali-soluble resin useful for preparing a resin composition in which organic pigments, inorganic fine particles, and the like are dispersed. Furthermore, the present invention is a thermosetting or radiation-sensitive resin composition containing the epoxy resin, epoxy ester resin, or alkali-soluble resin, and is used for protection in color filters, liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc. The present invention relates to a composition useful for preparing a film or an interlayer insulating film.

Generally, 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, there are liquid and solid bisphenol A type epoxy resins as epoxy resins most used industrially. 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 photosensitive materials, for example (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 field of electronic materials that require a high level of heat resistance.
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 1, 2, and 3). These are excellent in heat resistance, electrical properties, transparency and the like, but are insufficient for the higher level requirements in recent years. Further, in the use of photosensitive resin compositions for color filters, in recent years, there is a strong demand for increasing the concentration of pigments in order to increase color purity, but in conventional compositions, there is no choice but to add a large amount of dispersant. As a result, there has been a demand for a dispersion resin that is more excellent in dispersibility, such as sacrificing developability. In addition, for color inks used in the production of color filters by the inkjet method, a dispersion resin having excellent dispersibility and dispersion stability is required.

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 of the present invention is that the cured product has a high level of heat resistance and electrical characteristics, and has excellent patterning and dispersibility functions. It is to provide a conductive epoxy resin, an epoxy ester resin, and an alkali-soluble resin. 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 epoxy resins, epoxy ester resins, and alkali-soluble resins containing a certain condensed ring structure have a high refractive index, heat resistance, dispersibility, transparency, etc. The present invention was found to be superior to the present invention.
The condensed ring structure-containing epoxy resin of the present invention is represented by the following general formula (1):

Y _1-4 is a group independently selected from the following general formula (2) or the following general formula (3), and p _1-4 are each independently an integer of 0-4.

Here, Y _5-6 are groups independently selected from the general formula (2) or the following general formula (3), and p _5-6 are each independently an integer of 0-4.

Here, Z in the general formulas (1) and (2) 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 5-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one aromatic ring, and R _1-6 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, q _{1 -6} are each independently an integer of 0 to 4. Further, R _{7 to 14} in the above general formulas (1), (2) and (3) are each independently a hydrogen atom or a methyl group, m _{1 to 8} and s _{1 to 2} are each independently 0 to 10 It is an integer, and the structural formula may be symmetric or asymmetric. A plurality of R _1-14 and Y _1-6 may be the same or different.

Moreover, the condensed ring structure containing epoxy resin of this invention is obtained from the manufacturing method including the process of making an epihalohydrin act on the polyfunctional hydroxyl-containing condensed ring structure compound shown by following General formula (4), General formula (1) ) Is obtained by, for example, a process (manufacturing method) including this step.

Here, Z is the same as described above, and each of R _{15 to 16} is 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, A phenyl group which may have a substituent, or a halogen atom, f _1-2 are each independently an integer of 0 to 4, R _17-18 are each independently a hydrogen atom or a methyl group, m _9-10 Are each independently an integer from 0 to 10, and r _1-2 are each independently an integer from 1 to 5, and the structural formula may be symmetrical or asymmetrical. Moreover, several _R15-18 may be the same and may differ.

One preferred embodiment of the condensed ring structure-containing epoxy resin of the present invention includes the following general formula (5) in which p ₁ to ₄ are 0 in the condensed ring structure-containing epoxy resin of the general formula (1).

_{Here, Z, R 1~4, q 1~4} , R 7~10, m 1~4, s 1 is the same as defined above, even in the structural formula is symmetrical, it may be asymmetrical . Moreover, several R _{< 1 > -4} , R _{<7> -10} may be the same, and may differ.

In the condensed ring structure-containing epoxy resin of the present invention, another preferred embodiment includes the following general formula (6) in which s _1-2 is 0 in the condensed ring structure-containing epoxy resin of the general formula (1). It is done.

Here, Z, R _1-2 , q _1-2 , R ₇ , R ₁₀ , m ₁ , m ₄ are the same as above, and h _1-2 are each independently an integer from 1 to 5. The structural formula may be symmetrical or asymmetrical. Moreover, several R _<1-2 >, R _{< 7 >} , R _{< 10} > may be the same and may differ.

In a more preferred embodiment of the condensed ring structure-containing epoxy resin of the present invention, in the general formulas (1), (2), (4), (5), (6), Z is represented by the formulas (7) to (11). Is a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (9). In another preferred embodiment, in formulas (1) to (6), p _1-6 , q _1-6 , and f _1-2 are each independently an integer from 0 to 2, m _1-10. Are each independently an integer of 0 to 2, h _1-2 and r _1-2 are each independently an integer of 1 to 2, and s _1-2 are each independently an integer of 0 to 8.

The manufacturing method of the condensed ring structure containing epoxy resin of this invention includes the process of making an epihalohydrin act on the polyfunctional hydroxyl-containing condensed ring structure compound shown by the above-mentioned general formula (4).

Of the epihalohydrins, epichlorohydrin is particularly preferably used.

The epoxy resin composition of this invention contains the said condensed ring structure containing epoxy resin.

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

The condensed ring structure-containing epoxy ester resin of the present invention is represented by the following general formula (12).
In addition, the condensed ring structure containing epoxy ester resin of this invention includes a condensed ring structure containing epoxy acrylate resin.

Y _1-4 is a group independently selected from the following general formula (13) or the following general formula (14), and p _1-4 are each independently an integer of 0-4.

Y _5-6 is a group independently selected from the general formula (13) or the following general formula (14), and p _5-6 are each independently an integer of 0-4.

Here, Z, R _1-6 , q _1-6 , R _7-14 , m _1-8 , and s _1-2 in the general formulas (12), (13), and (14) are represented by the general formula (1). ), (2) and (3), R ₁₉ represents a group containing a site derived from a monobasic carboxylic acid, and the structural formula may be bilaterally symmetric or asymmetric. Further, a plurality of _R 1 to _14, R _19, to _{Y 1 to 6} may be the same or may be different.

Moreover, the condensed ring structure containing epoxy ester resin of this invention is a manufacturing method including the process of making the condensed ring structure containing epoxy resin and monobasic carboxylic acid shown by General formula (1), (5), (6) react. The resin represented by the general formula (12) can be obtained from, for example, a process (manufacturing method) including this step, or a polyfunctional hydroxyl group-containing condensed ring structure compound represented by the formula (4) and glycidyl monobasic carboxylate It is obtained by a process (manufacturing method) including a step of acting.

Furthermore, the condensed ring structure-containing epoxy ester resin of the present invention is obtained by adding a condensed ring structure-containing epoxy resin obtained from a production method including a step of allowing an epihalohydrin to act on a polyfunctional hydroxyl group-containing condensed ring structure compound of the general formula (4) It can be obtained from a production method including a step of allowing a basic carboxylic acid to act, and the resin represented by the general formula (12) can also be obtained, for example, by a process (manufacturing method) including this step.

In a preferred embodiment of the condensed ring structure-containing epoxy ester resin obtained by the above process (production method), the general formulas (1), (2), (4), (5), ( 6) Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably a condensed ring structure selected from the group consisting of formulas (7) to (9) Is a divalent group.
In another preferred embodiment, p _1-6 , q _1-6 , and f _1-2 in formulas (1) to (6) in the above process (production method) are each independently 0 to 2 , _{M 1-10} are each independently an integer of 0 to 2, and h _1-2 , r _1-2 are each independently an integer of 1 to 2, and s _1-2 are each independently 0 It is an integer of 8.

One preferred embodiment of the condensed ring structure-containing epoxy ester resin of the present invention includes the following general formula (15) in which p ₁ to ₄ are 0 in the condensed ring structure-containing epoxy ester resin of the general formula (12). It is done.

_{Here, Z, R 1~4, q 1~4} , R 7~10, m 1~4, R 19, s 1 are as defined for general formula (12), the structural formula is a symmetrical May be asymmetric. Moreover, several R _{< 1 > -4} , R _{<7> -10} , R _{< 19 >} may be the same and may differ.

In the condensed ring structure-containing epoxy ester resin of the present invention, as another preferred embodiment, in the condensed ring structure-containing epoxy ester resin of the general formula (12), s _1-2 is 0, and the following general formula (16) Is mentioned.

Here, Z, R _1-2 , q _1-2 , R ₇ , R ₁₀ , m ₁ , m ₄ , R ₁₉ are the same as in the general formula (12), and h _1-2 are each independently It is an integer from 1 to 5, and the structural formula may be symmetric or asymmetric. Moreover, several R _<1-2 >, R _{< 7 >} , R _{< 10 >} , R _{< 19} > may be the same and may differ.

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

The condensed ring structure-containing epoxy acrylate resin of the present invention is represented by the following general formula (17).
Note that this, R ₁₉ in the general formula (12) is a condensed ring structure-containing epoxy ester resin is a group having an unsaturated group. Here, the unsaturated group is an ethenyl group or a 2-propenyl group.

Y _1-4 is a group independently selected from the following general formula (18) or the following general formula (19), and p _1-4 are each independently an integer of 0-4.

Here, Y _5-6 is a group independently selected from General Formula (18) or the following General Formula (19), and p _5-6 are each independently an integer of 0-4.

Here, Z, R _1-6 , q _1-6 , R _7-14 , m _1-8 , and s _1-2 in the general formulas (17), (18), and (19) are the above general formula (1). , (2) and (3), R ₂₀ independently represents a hydrogen atom or a methyl group, and the structural formula may be bilaterally symmetric or asymmetric. Further, a plurality of _{R 1~14, R 20, Y 1~6} are may be the same or may be different.

One preferred embodiment includes the following general formula (20) in which p1 to ₄ are 0 in the condensed ring structure-containing epoxy acrylate resin of the general formula (17).

_{Here, Z, R 1~4, q 1~4} , R 7~10, m 1~4, R 20, s 1 are as defined for general formula (17), the structural formula is a symmetrical May be asymmetric. Moreover, several R _{< 1 > -4} , R _{<7> -10} , R _{< 20 >} may be the same and may differ.

As a further preferred embodiment, the following general formula (21) in which s _1-2 is 0 in the condensed ring structure-containing epoxy acrylate resin of the general formula (17) can be given.

Here, Z, R _1-2 , q _1-2 , R ₇ , R ₁₀ , m ₁ , m ₄ , R ₂₀ are the same as in the general formula (17), and h _1-2 are each independently It is an integer from 1 to 5, and the structural formula may be symmetric or asymmetric. Moreover, several R _<1-2 >, R _{< 7 >} , R _{< 10 >} , R _{< 20} > may be the same and may differ.

In a preferred embodiment of the condensed ring structure-containing epoxy ester resin of the present invention, the general formulas (12), (13), (15), (16), (17), (18), (20), (21 ), Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably, Z is a condensed ring selected from the group consisting of formulas (7) to (9) A divalent group containing a structure.

In another preferred embodiment, in the general formulas (12) to (21), p _1-6 and q _1-6 are each independently an integer of 0 to 2, and m _1-8 are each independently And an integer from 0 to 2, h _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 1st manufacturing method of the condensed ring structure containing epoxy ester resin of this invention is the condensed ring structure containing epoxy resin represented by the said General formula (1), (5), (6), or General formula (4). A step of allowing a monobasic carboxylic acid to act on a condensed ring structure-containing epoxy resin obtained from a production method including a step of allowing an epihalohydrin to act on the polyfunctional hydroxyl group-containing condensed ring structure compound.

In a preferred embodiment, in the general formulas (1) to (6), Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably Z is a formula. (7) to (9) is a divalent group containing a condensed ring structure selected from the group consisting of p _1-6 , q _1-6 , and f _1-2 are each independently an integer of 0-2, m _{1 to 10} are each independently an integer from 0 to 2, and h _1-2 and r _1-2 are each independently an integer from 1 to 2, s _1-2 are each independently an integer from 0 to 8 is there.

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

The 2nd manufacturing method of the condensed ring structure containing epoxy ester resin of this invention includes the process of making monobasic glycidyl carboxylate act on the polyfunctional hydroxyl-containing condensed ring structure compound shown by the said General formula (4). .

In a preferred embodiment, in the polyfunctional hydroxyl group-containing condensed ring structure compound of the general formula (4), Z is a divalent group containing a condensed ring structure selected from the group consisting of the formulas (7) to (11), Preferably, Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (9), f _1-2 are each independently an integer of 0 to 2, and m _9-10 are Each is independently an integer from 0 to 2, and r _1-2 are each independently an integer from 1 to 2.

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

The epoxy ester resin composition of the present invention contains the above condensed ring structure-containing 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 alkali-soluble resin of the present invention is a condensed ring structure-containing epoxy ester resin represented by formulas (12), (15), (16), (17), (20), (21). It can be obtained by reacting a polybasic carboxylic acid or its anhydride.

In a preferred embodiment, in the above general formulas (12), (13), (15), (16), (17), (18), (20), (21), Z is the formula (7) to A divalent group containing a condensed ring structure selected from the group consisting of (11), more preferably a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (9).
As another preferred embodiment, in the general formulas (12) to (21), p _1-6 and q _1-6 are each independently an integer of 0 to 2, and m _1-8 are each independently And an integer from 0 to 2, and h _1-2 are each independently an integer from 1 to 2, and s _1-2 are each independently an integer from 0 to 8.

One preferred embodiment of the condensed ring structure-containing alkali-soluble resin of the present invention is a condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin. The condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin refers to one having a radiation-polymerizable unsaturated group in the molecule among the condensed ring-structure-containing alkali-soluble resin. For example, the condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin may be a polybasic carboxylic acid or an epoxy acrylate resin represented by formulas (17), (20), and (21). It can be obtained by reacting an anhydride.

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

The method for producing a condensed ring structure-containing alkali-soluble resin and a condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin of the present invention has the general formulas (12), (15), (16), (17), (20) The process of making polybasic carboxylic acid or its anhydride react with the condensed ring structure containing epoxy ester resin represented by (21) is included.

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

ADVANTAGE OF THE INVENTION According to this invention, the novel condensed ring structure containing epoxy resin, condensed ring structure containing epoxy ester resin, condensed ring structure containing alkali-soluble resin, and those simple manufacturing methods are provided. 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;

2 is a ¹ H-NMR chart of the condensed ring structure-containing epoxy resin of the present invention obtained in Example 1. FIG. 3 is a ¹ H-NMR chart of the condensed ring structure-containing epoxy resin of the present invention obtained in Example 3. FIG. 3 is a ¹ H-NMR chart of the condensed ring structure-containing epoxy resin of the present invention obtained in Example 4. FIG. 6 is a ¹ H-NMR chart of the condensed ring structure-containing epoxy resin of the present invention obtained in Example 5. FIG.

The present invention is described in detail below.
A. Condensed ring structure-containing epoxy resin The condensed ring structure-containing epoxy resin of the present invention is represented by the following general formula (1):

Y _1-4 is a group independently selected from the following general formula (2) or the following general formula (3), and p _1-4 are each independently an integer of 0-4.

Here, Y _5-6 are groups independently selected from the general formula (2) or the following general formula (3), and p _5-6 are each independently an integer of 0-4.

Here, Z in the general formulas (1) and (2) 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 _1-6 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, q _1- Each ₆ is independently an integer from 0 to 4. Further, R _{7 to 14} in the above general formulas (1), (2) and (3) are each independently a hydrogen atom or a methyl group, m _{1 to 8} and s _{1 to 2} are each independently 0 to 10 It is an integer, and the structural formula may be symmetric or asymmetric. A plurality of R _1-14 and Y _1-6 may be the same or 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 to 6} include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclohexyl group. 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.

This condensed ring structure-containing epoxy resin may be described as “condensed ring structure-containing epoxy resin (A)”, “epoxy resin (A)” or the like in the present specification. In the above general formulas (1) to (3), Z is preferably a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably Z is formula (7). Is a divalent group including a condensed ring structure selected from the group consisting of (9), p _1-6 and q _1-6 are each independently an integer of 0 to 2, and m _1-8 are each independently Integers from 0 to 2, and s _1-2 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 (7) to (11), 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 (7) to (9), 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 represented by formulas (10) and (11), such an epoxy resin (A) is easy to handle and advantageous in terms of production cost.

In the condensed ring structure-containing epoxy resin of the present invention, when any of p1 to _{p4 in} the general formula (1) is 1 or more, the condensed ring structure-containing epoxy resin takes a branched structure, and any one of _{p5 to 6} If is 1 or more, it has a further branched structure. When all of p _{1 to 4} are 0, the condensed ring structure-containing epoxy resin is a linear resin.

The condensed ring structure-containing epoxy resin having a branch is superior in, for example, curability, dispersion stability, heat resistance, and the like. When the condensed ring structure-containing epoxy resin is linear, for example, handling is simple. This is advantageous in that the degree of freedom in resin design is increased.

Moreover, the condensed ring structure containing epoxy resin of this invention is obtained from the manufacturing method including the process of making an epihalohydrin act on the polyfunctional hydroxyl-containing condensed ring structure compound shown by following General formula (4), General formula (1) ) Is obtained, for example, by a process (manufacturing method) including this step.

Here, Z is the same as above, and R _{15 to 16} 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, A phenyl group which may have a substituent, or a halogen atom, f _1-2 are each independently an integer of 0 to 4, R _17-18 are each independently a hydrogen atom or a methyl group, m _9-10 Are each independently an integer from 0 to 10, and r _1-2 are each independently an integer from 1 to 5, and the structural formula may be symmetrical or asymmetrical. Moreover, several _R15-18 may be the same and may differ.

Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms in R _{15 to 16} include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclohexyl group. 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.

The polyfunctional hydroxyl group-containing condensed ring structure compound represented by the general formula (4) may be described as “polyfunctional hydroxyl group-containing condensed ring structure compound (D)” in the present specification.

In addition, this condensed ring structure-containing epoxy resin may be referred to as “condensed ring structure-containing epoxy resin (A1)”, “epoxy resin (A1)”, or the like in this specification. This condensed ring structure-containing epoxy resin (A1) is included in the aforementioned condensed ring structure-containing epoxy resin (A). In the general formula (4), preferably, Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably, Z is a formula (7) to (9). A divalent group containing a condensed ring structure selected from the group consisting of: f _1-2 are each independently an integer from 0 to 2, m _9-10 are each independently an integer from 0 to 2, and r _{1 ˜2} is each independently an integer of 1 to 2.

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

The polyfunctional hydroxyl group-containing condensed ring structure compound (D) can be prepared by a method known in the art. For example, it is known that it is produced by condensing phenols and ketones in the presence of an acidic catalyst (see, for example, JP-A-7-112949).

The reaction between the polyfunctional hydroxyl group-containing 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 condensed ring structure compound (D) and epichlorohydrin is preferably 1 to 20 mol of epichlorohydrin with respect to 1 mol of the hydroxyl group of the polyfunctional hydroxyl group-containing condensed ring structure compound (D). .
Examples of the catalyst used for the reaction of the polyfunctional hydroxyl group-containing condensed ring structure compound (D) and epichlorohydrin include phosphonium salts, quaternary ammonium salts, phosphine compounds, tertiary amine compounds, imidazole compounds, and the like. Can be mentioned.

One preferred embodiment of the condensed ring structure-containing epoxy resin of the present invention includes the following general formula (5) in which p ₁ to ₄ are 0 in the condensed ring structure-containing epoxy resin of the general formula (1).

_{Here, Z, R 1~4, q 1~4} , R 7~10, m 1~4, s 1 are as defined for general formula (1) may be the structural formula symmetrical, asymmetrical It may be. Moreover, several R _{< 1 > -4} , R _{<7> -10} may be the same, and may differ.

This condensed ring structure-containing epoxy resin may be described as “condensed ring structure-containing epoxy resin (A2)”, “epoxy resin (A2)”, or the like in this specification. This condensed ring structure-containing epoxy resin (A2) is included in the aforementioned condensed ring structure-containing epoxy resin (A). In the general formula (5), preferably, Z is a divalent group including a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably, Z is a formula (7) to (9). A bivalent group containing a condensed ring structure selected from the group consisting of q _{1 to 4} are each independently an integer of 0 to 2, m _{1 to 4} are each independently an integer of 0 to 2, and s ₁ Is an integer from 0 to 8.

In the condensed ring structure-containing epoxy resin of the present invention, another preferred embodiment includes the following general formula (6) in which s _1-2 is 0 in the condensed ring structure-containing epoxy resin of the general formula (1). It is done.

Here, Z, R _1-2 , q _1-2 , R ₇ , R ₁₀ , m ₁ , m ₄ are the same as in the above general formula (1), and h _1-2 are each independently 1 to 5 The structural formula may be bilaterally symmetric or asymmetrical. Moreover, several R _<1-2 >, R _{< 7 >} , R _{< 10} > may be the same and may differ.

This condensed ring structure-containing epoxy resin may be described as “condensed ring structure-containing epoxy resin (A3)”, “epoxy resin (A3)”, or the like in this specification. This condensed ring structure-containing epoxy resin (A3) is included in the aforementioned condensed ring structure-containing epoxy resin (A). In the general formula (6), preferably, Z is a divalent group including a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably, Z is a formula (7) to (9). A divalent group containing a condensed ring structure selected from the group consisting of: q _1-2 are each independently an integer from 0 to 2, m ₁ and m ₄ are each independently an integer from 0 to 2, and h _{1 and 2} are each independently an integer of 1 to 2.

Incidentally, as the above general formula h _{1 to 2} of (6) increases, such as hardness and curability becomes high. On the other hand, as h _1-2 in general formula (6) decreases, the handling and design of the resin becomes easier.

The epoxy resin composition of the present invention contains the epoxy resin (A). This epoxy resin (A can be used alone or in a mixture of two or more. The epoxy resin composition of the present invention comprises 10 to 90% by weight of the epoxy resin (A). It is preferable to contain.

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

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 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 includes the epoxy resin (A) of the present invention and the epoxy resin (i) other than the epoxy resin (A) of the present invention.

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 comprising 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.
The (v) additive may be contained in an amount within a range that does not impair the original properties of the resin composition of the present invention.

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 -AS 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; by injection molding using a transfer press device Examples thereof include a method of heat compression; 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 the composition of the present invention in a cloth or a mat.

The condensed ring structure-containing epoxy resin (A) of the present invention has a high refractive index, is excellent in heat resistance, and is easily cured by heat or radiation irradiation. 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 above properties such as heat resistance, the molded product obtained from this epoxy resin composition is excellent in insulation, has small curing shrinkage and excellent dimensional stability. Useful for electronic material sealants. 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.

Moreover, since the epoxy resin (A) of this invention is excellent in a dispersibility, it can be used suitably when an organic pigment and an inorganic fine particle are disperse | distributed in a composition. A molded body obtained by curing this composition is also one aspect of the present invention.

B. Condensed ring structure-containing epoxy ester resin The condensed ring structure-containing epoxy ester resin of the present invention is represented by the following general formula (12):

Y _1-4 is a group independently selected from the following general formula (13) or the following general formula (14).

Here, Y _5-6 are groups independently selected from the general formula (13) or the following general formula (14).

Here, Z, p _1-6 , R _1-6 , q _1-6 , R _7-14 , m _1-8 , s _1-2 are the same as the above general formulas (1)-(3), R ₁₉ represents a group containing a site derived from a monobasic carboxylic acid. The structural formula may be symmetric or asymmetric. Further, a plurality of _R 1 to _14, R _19, to _{Y 1 to 6} may be the same or may be different.

This condensed ring structure-containing epoxy ester resin may be described as “condensed ring structure-containing epoxy ester resin (B)”, “epoxy ester resin (B)”, or the like in this specification. In the above general formulas (12) to (14), Z is preferably a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably Z is formula (7). Is a divalent group including a condensed ring structure selected from the group consisting of (9), p _1-6 and q _1-6 are each independently an integer of 0 to 2, and m _1-8 are each independently Integers from 0 to 2, and s _1-2 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 (7) to (11), 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 (7) to (9), 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 the formulas (10) and (11), such an epoxy ester resin (B) is easy to handle and advantageous in terms of production cost.

The condensed ring structure-containing epoxy ester resin of the present invention has a branched structure when any one of p1 to _p4 of the above general formulas (12) and (13) is 1 or more, and further has p If any of _5-6 is 1 or more, it has a further branched structure. When all of p _{1 to 4} are 0, the condensed ring structure-containing epoxy ester resin is a linear resin.

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

Moreover, the condensed ring structure containing epoxy ester resin of this invention is obtained from the manufacturing method including the process of making a monobasic carboxylic acid act on the said condensed ring structure containing epoxy resin (A), or General formula (4) The resin represented by the general formula (12) can be obtained from a production method including a step of allowing a monobasic glycidyl carboxylate to act on a polyfunctional hydroxyl group-containing condensed ring structure compound. ).

The condensed ring structure-containing epoxy ester resin obtained by the above method may be described as “condensed ring structure-containing epoxy ester resin (B1)”, “epoxy ester resin (B1)” or the like in the present specification. is there. This condensed ring structure-containing epoxy ester resin (B1) is included in the aforementioned condensed ring structure-containing epoxy ester resin (B).

As a preferred embodiment, in the general formulas (1) to (6), preferably Z is a divalent group containing a condensed ring structure selected from the group consisting of the formulas (7) to (11), more preferably Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (9), and p _1-6 , q _1-6 , and f _1-2 are each independently 0 to 2 An integer, m _1-10 are each independently an integer from 0 to 2, h _1-2 , r _1-2 are each independently an integer from 1 to 2, and s _1-2 are each independently 0 to 8 Is an integer.

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 epoxy ester resin (B1) is obtained.

One preferred embodiment of the condensed ring structure-containing epoxy ester resin of the present invention is a linear general formula represented by the following general formula, wherein p ₁ to ₄ are 0 in the condensed ring structure-containing epoxy ester resin of the general formula (12). (15).

_{Z, R 1~4, q 1~4,} R 7~10, m 1~4, R 19, s 1 is the same as in the general formula (12). The structural formula may be symmetric or asymmetric. Moreover, several R _{< 1 > -4} , R _{<7> -10} , R _{< 19 >} may be the same and may differ.

The condensed ring structure-containing epoxy ester resin may be described as “condensed ring structure-containing epoxy ester resin (B2)”, “epoxy ester resin (B2)”, or the like in this specification. This condensed ring structure-containing epoxy ester resin (B2) is included in the aforementioned condensed ring structure-containing epoxy ester resin (B). In the general formula (15), preferably, Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably, Z is a formula (7) to (9). A bivalent group containing a condensed ring structure selected from the group consisting of q _{1 to 4} are each independently an integer of 0 to 2, m _{1 to 4} are each independently an integer of 0 to 2, and s ₁ Are each independently an integer of 0 to 8.

In the condensed ring structure-containing epoxy ester resin of the present invention, as another preferred embodiment, in the condensed ring structure-containing epoxy ester resin of the general formula (12), s _1-2 is 0, and the following general formula (16) Is mentioned.

Z, R _1-2 , q _1-2 , R ₇ , R ₁₀ , m ₁ , m ₄ , R ₁₉ are the same as in the general formula (12), and h _1-2 are each independently 1 to 5 It is an integer up to. The structural formula may be symmetric or asymmetric. Moreover, several R _<1-2 >, R _{< 7 >} , R _{< 10 >} , R _{< 19} > may be the same and may differ.

The condensed ring structure-containing epoxy ester resin may be described as “condensed ring structure-containing epoxy ester resin (B3)”, “epoxy ester resin (B3)”, or the like in this specification. This condensed ring structure-containing epoxy ester resin (B3) is included in the aforementioned condensed ring structure-containing epoxy ester resin (B). In the general formula (16), preferably, Z is a divalent group including a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably, Z is a formula (7) to (9). A divalent group containing a condensed ring structure selected from the group consisting of: q _1-2 are each independently an integer from 0 to 2, and m ₁ and m ₄ are each independently an integer from 0 to 2. , H _1-2 are each independently an integer of 1 to 2.

Incidentally, as the _{h 1 to 2} in the general formula (16) is increased, such as hardness and curability becomes high. On the other hand, as h _1-2 in general formula (16) decreases, the handling and design of the resin becomes easier.

One preferred embodiment of the condensed ring structure-containing epoxy ester resin is one in which the site derived from the monobasic carboxylic acid of the condensed ring structure-containing epoxy ester resin is a group having an unsaturated group. These are especially epoxy ring acrylate resins containing a condensed ring structure, and are shown below.
The condensed ring structure-containing epoxy acrylate resin is characterized by having a radiation polymerizable functional group.

The condensed ring structure-containing epoxy acrylate resin of the present invention is represented by the following general formula (17).
Note that this, R ₁₉ in the general formula (12) is a condensed ring structure-containing epoxy ester resin is a group having an unsaturated group. Here, the unsaturated group is an ethenyl group or a 2-propenyl group.

Y _1-4 is a group independently selected from the following general formula (18) or the following general formula (19).

Here, Y _5-6 are groups independently selected from the general formula (18) or the following general formula (19).

Here, Z, p _1-6 , R _1-6 , q _1-6 , R _7-14 , m _1-8 , s _1-2 are the same as the above general formulas (12), (13), (14). And R ₂₀ is independently a hydrogen atom or a methyl group. The structural formula may be symmetric or asymmetric. Further, a plurality of _{R 1~14, R 20, Y 1~6} are may be the same or may be different.

The condensed ring structure-containing epoxy ester resin is referred to as “condensed ring structure-containing epoxy ester resin (B4)”, “epoxy ester resin (B4)”, or “condensed ring structure-containing epoxy acrylate resin (B4)”. And “epoxy acrylate resin (B4)”. This condensed ring structure-containing epoxy ester resin (B4) is included in the aforementioned condensed ring structure-containing epoxy ester resin (B). In the above general formulas (17) to (19), preferably, Z is a divalent group containing a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably Z is formula (7). Is a divalent group including a condensed ring structure selected from the group consisting of (9), p _1-6 and q _1-6 are each independently an integer of 0 to 2, and m _1-8 are each independently Integers from 0 to 2, and s _1-2 are each independently an integer from 0 to 8.

The condensed ring structure-containing epoxy acrylate resin of the present invention has a branched structure when any one of p1 to _p4 of the above general formulas (12) and (13) is 1 or more, and further has p If any of _5-6 is 1 or more, it has a further branched structure. When all of p _{1 to 4} are 0, the condensed ring structure-containing epoxy acrylate resin is a linear resin.

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

One preferred embodiment includes the following general formula (20) in which p1 to ₄ are 0 in the condensed ring structure-containing epoxy acrylate resin of the general formula (17).

_{Z, R 1~4, q 1~4,} R 7~10, m 1~4, R 20, s 1 is the same as in the general formula (17). The structural formula may be symmetric or asymmetric. Moreover, several R _{< 1 > -4} , R _{<7> -10} , R _{< 20 >} may be the same and may differ.

This condensed ring structure-containing epoxy ester resin is referred to as “condensed ring structure-containing epoxy ester resin (B5)”, “epoxy ester resin (B5)”, “condensed ring structure-containing epoxy acrylate resin (B5)”. And “epoxy acrylate resin (B5)”. This condensed ring structure-containing epoxy ester resin (B5) is included in the aforementioned condensed ring structure-containing epoxy ester resin (B). In the general formula (20), preferably, Z is a divalent group including a condensed ring structure selected from the group consisting of formulas (7) to (11), more preferably Z is a formula (7) to (9). A bivalent group containing a condensed ring structure selected from the group consisting of q _{1 to 4} are each independently an integer of 0 to 2, m _{1 to 4} are each independently an integer of 0 to 2, and s ₁ Are each independently an integer of 0 to 8.

Still another preferred embodiment includes the following general formula (21) in which s _1-2 is 0 in the condensed ring-containing epoxy acrylate resin of the general formula (17).

Z, R _1-2 , q _1-2 , R ₇ , R ₁₀ , m ₁ , m ₄ , R ₂₀ are the same as in the general formula (17), and h _1-2 are each independently 1 to 5 It is an integer up to. The structural formula may be symmetric or asymmetric. Moreover, several R _<1-2 >, R _{< 7 >} , R _{< 10 >} , R _{< 20} > may be the same and may differ.

In this specification, this condensed ring structure-containing epoxy acrylate resin is referred to as “condensed ring structure-containing epoxy ester resin (B6)”, “epoxy ester resin (B6)”, or “condensed ring structure-containing epoxy acrylate resin (B6)”. And “epoxy acrylate resin (B6)”. This condensed ring structure-containing epoxy ester resin (B6) is included in the aforementioned condensed ring structure-containing epoxy ester resin (B). In the general formula (21), preferably, Z is a divalent group including a condensed ring structure selected from the group consisting of the above formulas (7) to (11), more preferably Z is the above formulas (7) to ( 9) is a divalent group containing a condensed ring structure selected from the group consisting of q), q _1-2 are each independently an integer from 0 to 2, m ₁ and m ₄ are each independently an integer from 0 to 2, H ₁ and ₂ are each independently an integer of 1 to 2.
When Z is a divalent group containing a condensed ring structure represented by formulas (10) and (11), such an epoxy acrylate resin (B6) is easy to handle and advantageous in terms of production cost.

Incidentally, as the above general formula _{h 1 to 2} of (21) increases, such as hardness and curability becomes high. On the other hand, as h _1-2 in general formula (21) decreases, the handling and design of the resin becomes easier.

The said epoxy ester resin (B) is obtained by making monobasic carboxylic acid act on the above-mentioned epoxy resin (A), for example.
Alternatively, it can be obtained by allowing glycidyl monobasic carboxylate to act on the polyfunctional hydroxyl group-containing condensed ring structure compound (D) represented by the general formula (4).

The monobasic carboxylic acid used for the preparation of the epoxy ester resin (B) includes, but is 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-propylcyclohexane Carboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-heptylcyclohexanecarboxylic acid, 4-cyanocyclohexane-1-carboxylic acid, 4-hydroxycyclohexanecarboxylic acid, , 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, hydrogen alkyl 4-cyclohexene-1,2-dicarboxylate, cycloheptanecarboxylic acid, norbornenecarboxylic acid, tetracyclododecenecarboxylic 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, p-methoxybenzoic acid, p-ethoxybenzoic acid, p-propoxybenzoic acid 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 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-iodo Phenylacetic 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-dihydro Naphthalene-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 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.
In addition, R < ₁₉ > of General formula (12)-(16) becomes a site | part originating in said monobasic carboxylic acid.

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

Examples of monobasic glycidyl carboxylates used in the preparation of the epoxy ester resin (B) include, but are not limited to: glycidyl (meth) acrylate, glycidyl acetate, glycidyl butyrate, glycidyl benzoate , Glycidyl p-ethylbenzoate, glycidyl (tere) phthalate, etc., and these 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.
In addition, R < ₁₉ > of General formula (12)-(16) becomes a site | part originating in said monobasic carboxylic acid glycidyl.

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

For the reaction between the epoxy resin (A) and the monobasic carboxylic acid, and the reaction between the polyfunctional hydroxyl group-containing condensed ring structure compound (D) and the monobasic carboxylic acid glycidyl, an appropriate solvent is used as necessary. Used for 5-30 hours in a temperature range of 50-120 ° 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 and 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 epoxy ester resins (B), those having an unsaturated group in the molecule, for example, 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 these epoxy acrylate resins (B4) to (B6) functions as a thermosetting or radiation sensitive resin composition.
Moreover, about the thing which does not have radiation curability among the epoxy ester resin (B) of this invention, it is possible to make it contain in a radiation sensitive resin composition, and to the radiation sensitive resin composition containing them. Can be imparted with heat resistance, dispersibility, optical properties and the like derived from an almost resin-fused ring structure.
In any composition, the epoxy ester resin (B) may be contained singly or as a mixture of two or more.

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

The photopolymerization initiator (I) that can be contained in the radiation-sensitive resin composition containing the epoxy ester resin (B) of the present invention includes the epoxy ester resin (B) and the photocuring agent that is optionally contained. A compound having an effect of initiating photopolymerization of a functional 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 the epoxy ester resin (B) of the present invention emits radiation. It includes those having curability and photo-curing or thermosetting acrylate compounds other than the 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.

Examples of the radical initiator (II) that can be contained in the thermosetting resin composition include 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.

The photocurable or thermosetting acrylate compound other than the 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. 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 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 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.

When the liquid composition containing the epoxy ester resin (B) is applied to the substrate, the adhesion assistant is added for the purpose of improving the adhesion with 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 Salts, alkylene 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; aromatics 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.
Moreover, these solid fine particles may be contained in an amount within a range that does not impair the original properties of the resin composition of the present invention.

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 article obtained by curing the 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 from the composition of the present invention has high hardness, extremely excellent heat resistance, and further has a high refractive index.

The condensed ring structure-containing epoxy ester resin (B) of the present invention is excellent in heat resistance and optical properties. The thermosetting or radiation-sensitive composition containing this 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 fused ester structure-containing 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 alkali-soluble resin The condensed ring structure-containing alkali-soluble resin of the present invention includes a condensed ring structure-containing epoxy ester resin (B) represented by the general formulas (12) to (21) and the like, It can be obtained by reacting a polybasic carboxylic acid or its anhydride.

In the present specification, the condensed ring structure-containing alkali-soluble resin is sometimes referred to as “condensed ring structure-containing alkali-soluble resin (C)”, “alkali-soluble resin (C)”, or the like. is there.

Further, the condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin of the present invention is included in the condensed ring-structure-containing alkali-soluble resin, and among the condensed ring structure-containing alkali-soluble resins, radiation-polymerizable A compound having a functional group having an aromatic group, specifically, a compound having an unsaturated group in the molecule is defined as an alkali-soluble radiation-polymerizable unsaturated resin containing a condensed ring structure.

In the present specification, the condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin is referred to as “condensed ring structure-containing alkali-soluble resin (C1)”, “alkali-soluble resin (C1)”, “ The condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin (C1) ”,“ alkali-soluble radiation-polymerizable unsaturated resin (C1) ”,“ radiation-polymerizable unsaturated resin (C1) ”, etc. There is a case. This condensed ring structure-containing alkali-soluble resin (C1) is included in the aforementioned condensed ring structure-containing alkali-soluble resin (C).

The condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin (C1) is a condensed ring structure-containing epoxy ester resin (B) having an unsaturated group in the molecule, for example, a condensed ring structure-containing epoxy. It can be obtained by reacting acrylate resins (B4) to (B6) with a polybasic carboxylic acid or its anhydride.

The polybasic carboxylic acid used for preparing the alkali-soluble resin (C) is a carboxylic acid having a plurality of carboxyl groups such as dicarboxylic acid and tetracarboxylic acid, and such polybasic carboxylic acid. Or its anhydrides include the following compounds: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorend Acids, dicarboxylic acids such as methyltetrahydrophthalic acid and glutaric acid and anhydrides thereof; trimellitic acid or anhydride thereof; tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and biphenylethertetracarboxylic acid Acids and their acids Anhydrous and the like.

An example of the condensed ring structure-containing alkali-soluble resin (C) is, for example, a resin represented by the following general formula (22):

Z 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 five-membered alicyclic compound ( A divalent group containing a condensed ring structure of one aromatic ring, which may contain atoms other than carbon on the ring), A ₃ is the residue of tetracarboxylic dianhydride, and A ₄ is the residue of dicarboxylic anhydride It is a group. Here, the average u ₂ is 0 to 130 on average.

In the general formula (22), Z is preferably a divalent group including a condensed ring structure selected from the group consisting of the above formulas (7) to (11), more preferably the above formulas (7) to (9). A divalent group containing a condensed ring structure selected from the group consisting of:
When Z is a divalent group containing a condensed ring structure of formulas (10) and (11), such a condensed ring structure-containing alkali-soluble resin (C) is easy to handle and advantageous in terms of production cost. It is.

The condensed ring structure-containing alkali-soluble resin represented by the general formula (22) does not have an unsaturated group, and thus can be said to be an example of a condensed ring-structure-containing alkali-soluble resin having no radiation polymerizability. .

On the other hand, examples of the condensed ring structure-containing alkali-soluble resin having radiation polymerizability and the above-mentioned condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin (C1) include, for example, the following general formula (23): Resins represented include:

Z 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 five-membered alicyclic compound ( A divalent group containing a condensed ring structure of one aromatic ring, which may contain atoms other than carbon on the ring), A ₁ is the residue of tetracarboxylic dianhydride, and A ₂ is the residue of dicarboxylic anhydride It is a group. Here, the average u is 0 to 130 on average.

In the general formula (23), Z is preferably a divalent group containing a condensed ring structure selected from the group consisting of the above formulas (7) to (11), more preferably the above formulas (7) to (9). A divalent group containing a condensed ring structure selected from the group consisting of:
When Z is a divalent group containing a condensed ring structure of formulas (10) and (11), such a condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin (C1) is easy to handle and manufactured. This is advantageous in terms of cost.

The condensed ring structure-containing alkali-soluble resin (C) is obtained by reacting the condensed ring structure-containing epoxy ester resin (B) with a polybasic carboxylic acid or an anhydride thereof. 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 order of addition of the condensed ring structure-containing epoxy ester resin (B), polyhydric alcohols, and polybasic carboxylic acid 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 alkali-soluble resins (C-a) having a condensed ring structure skeleton and different structures Can produce a condensed ring structure-containing alkali-soluble resin (Cb) obtained by reacting a polyhydric alcohol. 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 alkali-soluble resin (C) is prepared, but these are examples.

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

(C-bi) Fourth condensed ring structure-containing alkali-soluble resin: condensed ring structure-containing epoxy ester resin (B, polyhydric alcohol and one kind of polybasic carboxylic acid or anhydride thereof. Resin obtained by mixing and reacting; (Cb-ii) Fifth condensed ring structure-containing alkali-soluble resin: condensed ring structure-containing epoxy ester resin (B), polyhydric alcohol, A resin obtained by mixing and reacting with a mixture of a further polybasic carboxylic acid or anhydride thereof (for example, a mixture of dicarboxylic anhydride and tetracarboxylic dianhydride); and (Cb- iii) Sixth condensed ring structure-containing alkali-soluble resin: a reaction product obtained by reacting a condensed ring structure-containing epoxy ester resin (B) with a polyhydric alcohol and tetracarboxylic acid or a dianhydride thereof. And Zika Bon acids or resins obtained by reacting an anhydride thereof.

The thus obtained condensed ring-containing alkali-soluble resins (Ca) or (Cb) having different structures are 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 alkali-soluble resin may be prepared by changing the condensed ring structure-containing epoxy ester resin (B), polyhydric alcohol, polybasic carboxylic acid or anhydride thereof to the above-described method (order). ), For example, it is dissolved (suspended) in a cellosolve solvent such as ethyl cellosolve acetate or butyl cellosolve acetate and heated to react. 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 alkali-soluble resin, the condensed ring structure-containing epoxy ester resin (B) and the polyhydric alcohol include the hydroxyl group of the condensed ring structure-containing epoxy ester resin (B) and the hydroxyl group of the polyhydric alcohol. Is preferably adjusted so that the molar ratio (the hydroxyl group of the condensed ring structure-containing epoxy ester resin (B) / the hydroxyl group of the polyhydric alcohol) is from 99/1 to 50/50, and from 95/5 to 60/40. More preferably. 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 its anhydride is preferably 0.3 to 0.3 mol in terms of acid anhydride group with respect to a total of 1 equivalent (mol) of the condensed ring structure-containing epoxy ester resin (B) and the hydroxyl group of the polyhydric alcohol. It is used for the reaction at a ratio of 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 alkali-soluble resins (C), two or more kinds of 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 epoxy ester resin (B), the polyhydric alcohol, and the polybasic carboxylic acid or anhydride thereof, the reaction temperature is preferably 50 to 130 ° C., more preferably 70 to 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 fused ring structure-containing alkali-soluble resin (C) of the present invention thus obtained 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 alkali-soluble resin containing the condensed ring structure.
Usually, the radiation-sensitive alkali-soluble resin composition contains the condensed ring-containing 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 100 weights of the condensed ring-containing alkali-soluble resin (C). The radiation-reactive compound is preferably contained in an amount of 0.5 to 50 parts by weight with respect to parts. In the case of a negative radiation-sensitive alkali-soluble resin composition, for example, a photopolymerization initiator or an acrylate is used as the radiation-reactive compound, and usually 100 wt. For example, the photopolymerization initiator is preferably contained in an amount of 0.1 to 30 parts by weight, more preferably in the range of 0.4 to 10 parts by weight with respect to parts. In the case of acrylate, it is preferably contained in an amount of usually 0.1 to 50 parts by weight per 100 parts by weight of the condensed ring structure-containing alkali-soluble resin.
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 alkali-soluble resin having radiation polymerization properties, for example, an alkali-soluble resin (C1) is preferable. The ring-condensed structure-containing alkali-soluble resin having no radiation polymerizability contained in (2) can 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 alkali-soluble resin (C) of the present invention comprises the condensed ring-structure-containing alkali-soluble resin (C) and, if necessary, (a ) Photopolymerization initiator, (b) polymerizable monomer or oligomer other than the condensed ring-containing alkali-soluble resin (C), (c) a compound having an epoxy group, (d) an additive, (e) a solvent (F) contains 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 alkali-soluble resin ( C), which has radiation curability, and photocurable or thermosetting acrylate compounds other than the 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 alkali-soluble resin (C) of (b) above is a monomer or oligomer that can be polymerized by radiation, and has physical properties according to the intended use of the composition. It can be contained according to. 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 monomers and oligomers is contained in the composition in an amount of 50 parts by weight or less based on 100 parts by weight of the 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 an amount of 50 parts by weight or less per 100 parts by weight of the condensed ring structure-containing 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 Chemical Co., Ltd.), 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.
Moreover, these solid fine particles may be contained in an amount within a range that does not impair the original properties of the resin composition of the present invention.

The condensed ring structure-containing 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 a 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 alkali-soluble resin composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, Ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8 -Diazabicyclo (5.4.0) -7-undecene, 1,5-diazabicyclo (4.3.0) -5-nonane, preferably sodium carbonate, tetramethylammonium hydride Such as Kishido 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.

The cured film obtained by curing the composition of the present invention is excellent in heat resistance, transparency, adhesion to a substrate, acid resistance, alkali resistance, chemical resistance, solvent resistance, surface hardness, and the like. 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.

In addition, since the alkali-soluble resin having a condensed ring structure 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.

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

Example 1
(Synthesis of epoxy resin containing condensed ring structure)
A polyfunctional hydroxyl group-containing fused ring structure compound represented by the following formula (4.a) (in the above general formula (4), Z is a divalent group containing formula (7), and R ₁₅ , R ₁₆ = methyl group F ₁ = 2; f ₂ = 2; m ₉ = 0; m ₁₀ = 0; r ₁ = 1; r ₂ = 1) 250 g is dissolved in epichlorohydrin 800 g, and benzyltriethylammonium chloride 1.8 g And stirred at 100 ° C. for 5 hours. Next, 165 g of 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 (1), Z is a bivalent group containing Formula (7), A condensed ring structure-containing epoxy resin (1.a) in which s ₁ = 0, R ₁ , R ₂ = methyl group, q ₁ , q ₂ = 2, p ₁ , p ₂ = 0, m ₁ , m ₄ = 0 250 g was obtained. The epoxy equivalent of this resin was 270 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. A chart of ¹ H-NMR is shown in FIG.

[1] Melting point: 179.8 ° C. (by DSC, DSC210 type: manufactured by Seiko Electronics Co., Ltd.)

[2] ¹ H-NMR (solvent: CDCl ₃ , internal standard: TMS)
Peak δ, ppm
a 2.7-2.9 4H
b 3.3 2H
c 3.7-4.0 4H
d 2.2 12H
e 6.5 4H
f, g, h, i 6.9-7.3 8H

[3] MS m / n = 534 M ⁺ (apparatus: alliance ZQ4000 manufactured by Waters)

Example 2
(Synthesis of epoxy resin containing condensed ring structure)
100 g of the polyfunctional hydroxyl group-containing condensed ring structure compound represented by the formula (4.a) described in Example 1 is dissolved in 66 g of epichlorohydrin and 30 g of 1,4-dioxane, and 1.7 g of benzyltriethylammonium chloride is added. , And stirred at 100 ° C. for 5 hours. Next, 20 g of flaky sodium hydroxide was added at 70 ° C., and the reaction was stirred for 2 hours. Then, the salt produced | generated by filtration is removed, xylene is added, it wash | cleans with water, It concentrates, In said general formula (1), Z is a bivalent group containing Formula (7), _R1-4 = methyl group _{, q 1~4 = 2, p 1~4} = 0, m 1~4 = 0, s 1 is mainly composed of 0-3 to give a condensed ring structure-containing epoxy resin (1.b) 120 g. The epoxy equivalent of this resin was 319 g / eq.

Structural analysis was performed on the obtained epoxy resin. The results are shown below.

[1] GPC s ₁ 0 body = 72%, s ₁ 1 body = 19%, s ₁ 2 body = 4%, s ₁ 3 body ≧ 5% (apparatus: Alliance manufactured by Waters)

Example 3
(Synthesis of epoxy resin containing condensed ring structure)
A polyfunctional hydroxyl group-containing condensed ring structure compound represented by the following formula (4.c) (in the above general formula (4), Z is a divalent group containing formula (7), and f ₁ = 0, f ₂ = 0, m ₉ = 0, m ₁₀ = 0, r ₁ = 1, r ₂ = 1) 200 g is dissolved in epichlorohydrin 800 g, 1.7 g of benzyltriethylammonium chloride is added, and the mixture is added at 100 ° C. for 5 hours. Stir. Next, under reduced pressure (150 mmHg), 150 g of 40% aqueous sodium hydroxide solution was added dropwise at 70 ° C. 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 (1), Z is a bivalent group containing Formula (7), 210 g of a condensed ring structure-containing epoxy resin (1.c) in which s ₁ = 0, q ₁ , q ₂ = 0, p ₁ , p ₂ = 0, m ₁ , m ₄ = 0 was obtained. The epoxy equivalent of this resin was 260 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. ^{A 1} H-NMR chart is shown in FIG.

[1] Melting point: 141 ° C. (by DSC, DSC210 type: manufactured by Seiko Denshi Kogyo Co., Ltd.)

[2] ¹ H-NMR (solvent: CDCl ₃ , internal standard: TMS)
Peak δ, ppm
a 2.7-2.9 4H
b 3.3 2H
c 3.9-4.2 4H
d, e 6.7-6.9 8H
f, g, h, i 6.9-7.3 8H

[3] MS m / n = 496 (M + NH ₄ ) ⁺ (Device: alliance ZQ4000 manufactured by Waters)

Example 4
(Synthesis of epoxy resin containing condensed ring structure)
The polyfunctional hydroxyl group-containing condensed ring structure compound represented by the following formula (4.d) (in the above general formula (4), Z is a divalent group containing formula (7), and f ₁ = 0, f ₂ = 0, m ₉ = 1, m ₁₀ = 1, r ₁ = 1, r ₂ = 1, R _17-18 are hydrogen atoms) 200 g is dissolved in epichlorohydrin 800 g, and benzyltriethylammonium chloride 1 .4 g was added and stirred at 100 ° C. for 5 hours. Next, 120 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, remove the salt formed by filtration and, after washing with water, distilling off the epichlorohydrin, in the above formula (1), Z is a divalent radical comprising formula (7), s 1 ₌ 0 , Q ₁ , q ₂ = 0, p ₁ , p ₂ = 0, m ₁ , m ₄ = 1, R ₇ , R ₁₀ = hydrogen atom-containing epoxy resin (1.d) 215 g was obtained. . The epoxy equivalent of this resin was 350 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
a 2.6-2.8 4H
b 3.2 2H
c, d, e 3.4-4.1 12H
f, g 6.7-6.9 8H
h, i, j, k 6.9-7.3 8H

[2] MS m / n = 584 (M + NH ₄ ) ⁺ (apparatus: alliance ZQ4000 manufactured by Waters)

Example 5
(Synthesis of epoxy resin containing condensed ring structure)
A polyfunctional hydroxyl group-containing condensed ring structure compound represented by the following formula (4.e) (in the above general formula (4), Z is a divalent group including formula (11), and f ₁ = 0, f ₂ = 0, m ₉ = 0, m ₁₀ = 0, r ₁ = 1, r ₂ = 1) 160 g was dissolved in epichlorohydrin 800 g, 1.7 g of benzyltriethylammonium chloride was added, and the mixture was heated at 100 ° C. for 5 hours. Stir. Next, 160 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, remove the salt formed by filtration and, after washing with water, distilling off the epichlorohydrin, in the above formula (1), Z is a divalent radical comprising formula (11), s 1 ₌ 0 , Q ₁ , q ₂ = 0, p ₁ , p ₂ = 0, m ₁ , m ₄ = 0, 180 g of a condensed ring structure-containing epoxy resin (1.e) was obtained. The epoxy equivalent of this resin was 235 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
a, j, k 2.7-2.9 8H
b 3.3 2H
c 3.9-4.2 4H
d, e 6.7-7.1 8H
f, g, h, i 6.9-7.3 4H

[2] MS m / n = 432 (M + NH ₄ ) ⁺ (apparatus: Alliance ZQ4000 manufactured by Waters)

Example 6
(Preparation and Evaluation of Molded Body Using Thermosetting Resin Composition Containing Fused Ring Structure-Containing Epoxy Resin)
100 parts by weight of the condensed ring structure-containing epoxy resin (1.a) obtained in Example 1 and 60 parts by weight of methylhexahydrophthalic anhydride type curing agent (Rikacid MH-700 manufactured by Shin Nippon Rika Co., Ltd.) To the mixture, 1 part by weight of 2-ethyl-4-methylimidazole (2E4MZ) as a catalyst was mixed, and the obtained mixture was put into a stainless steel mold having a size of 100 mm × 100 mm and a thickness of 1 mm, and then in an oven at 100 ° C. for 1 hour. Subsequently, it heated at 180 degreeC for 4 hours, and was hardened. Using the obtained molded body (test piece), the following items were evaluated.

[1] Heat resistance:
Tg is measured by DSC (DSC210 type: manufactured by Seiko Denshi Kogyo Co., Ltd.).

[2] Dielectric constant and dielectric loss tangent:
Measured with a TR1,2100 type dielectric loss automatic measuring device (manufactured by Ando Electric Co., Ltd.).

[3] Elastic modulus:
Using a dynamic viscoelasticity measuring device DMS6100 (manufactured by Seiko Denshi Kogyo Co., Ltd.), in a temperature range of −50 to 250 ° C., a response when a sine wave of 1 Hz is given in a double-end bending mode is measured, and storage elastic modulus Find E '.

Table 1 shows the composition of the composition used in this example, and Table 2 shows the evaluation result of the obtained test piece. Tables 1 and 2 also show Examples 7 to 15 and Comparative Example 1 described later.

Example 7
100 parts by weight of epoxy resin (1.a) was changed to a mixture of 50 parts by weight of epoxy resin (1.a) and 50 parts by weight of cresol novolac type epoxy resin (EOCN-102S manufactured by Nippon Kayaku Co., Ltd.) A test piece was prepared and evaluated in the same manner as in Example 6 except that the hydrophthalic anhydride type curing agent was changed to 68 parts by weight.

Example 8
Except that the epoxy resin (1.a) was changed to the condensed ring structure-containing epoxy resin (1.b) obtained in Example 2 and the methylhexahydrophthalic anhydride type curing agent was changed to 51 parts by weight. A test piece was prepared and evaluated under the same conditions as in Example 6.

Example 9
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 cresol novolac type epoxy resin (EOCN-102S manufactured by Nippon Kayaku Co., Ltd.), and methylhexa A test piece was prepared and evaluated under the same conditions as in Example 8 except that the hydrophthalic anhydride type curing agent was changed to 63 parts by weight.

Example 10
Except that the epoxy resin (1.a) was changed to the condensed ring structure-containing epoxy resin (1.c) obtained in Example 3 and the methylhexahydrophthalic anhydride type curing agent was changed to 63 parts by weight. A test piece was prepared and evaluated under the same conditions as in Example 6.

Example 11
100 parts by weight of epoxy resin (1.c) was changed to a mixture of 50 parts by weight of epoxy resin (1.c) and 50 parts by weight of cresol novolac type epoxy resin (EOCN-102S manufactured by Nippon Kayaku Co., Ltd.), and methylhexa A test piece was prepared and evaluated under the same conditions as in Example 10 except that the hydrophthalic anhydride type curing agent was changed to 69 parts by weight.

Example 12
Except that the epoxy resin (1.a) was changed to the condensed ring structure-containing epoxy resin (1.d) obtained in Example 4 and the methylhexahydrophthalic anhydride type curing agent was changed to 47 parts by weight. A test piece was prepared and evaluated under the same conditions as in Example 6.

Example 13
100 parts by weight of the epoxy resin (1.d) was changed to a mixture of 50 parts by weight of the epoxy resin (1.d) and 50 parts by weight of a cresol novolac type epoxy resin (EOCN-102S manufactured by Nippon Kayaku Co., Ltd.). A test piece was prepared and evaluated under the same conditions as in Example 12 except that the hydrophthalic anhydride type curing agent was changed to 61 parts by weight.

Example 14
Except that the epoxy resin (1.a) was changed to the condensed ring structure-containing epoxy resin (1.e) obtained in Example 5 and the methylhexahydrophthalic anhydride type curing agent was changed to 70 parts by weight. A test piece was prepared and evaluated under the same conditions as in Example 6.

Example 15
100 parts by weight of epoxy resin (1.e) was changed to a mixture of 50 parts by weight of epoxy resin (1.e) and 50 parts by weight of cresol novolac type epoxy resin (EOCN-102S manufactured by Nippon Kayaku Co., Ltd.), and methyl hexa A test piece was prepared and evaluated under the same conditions as in Example 14 except that the hydrophthalic anhydride type curing agent was changed to 73 parts by weight.

Comparative Example 1
Epoxy resin (1.a) was changed to bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.), and methylhexahydrophthalic anhydride type curing agent (Rikacide MH-700 manufactured by Shin Nippon Rika Co., Ltd.) was changed to 86. Except having changed into the weight part, the test piece was prepared similarly to Example 6 and evaluated.

As is clear from the results of Tables 1 and 2, it can be seen that when the condensed ring structure-containing epoxy resin of the present invention is used, a molded body having high heat resistance and electrical characteristics at a high level can be obtained.

Example 16
(Preparation and Evaluation of Thin Film Using Thermosetting Resin Composition Containing Epoxy Resin Containing Fused Ring Structure)
100 parts by weight of the condensed ring structure-containing epoxy resin (1.a) obtained in Example 1 and 1 part by weight of an aromatic sulfonium salt (Sun Aid SI-60 manufactured by Sanshin Chemical Industry Co., Ltd.) as a solvent are used as a solvent. Dissolved in cyclohexanone to give a 30% strength by weight solution. 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 3 shows the composition of the composition used in this example, and Table 4 shows the evaluation result of the obtained cured film. Tables 3 and 4 also show Examples 17 to 25 and Comparative Example 2 described later.

(1) 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.

(2) 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.

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

Example 17
Example 16 except that 100 parts by weight of the epoxy resin (1.a) was changed to a mixture of 50 parts by weight of the epoxy resin (1.a) and 50 parts by weight of a bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Corporation). A cured film was prepared and evaluated under the same conditions as those described above.

Example 18
A cured film was prepared and evaluated under the same conditions as in Example 16 except that the epoxy resin (1.a) was changed to the fused ring structure-containing epoxy resin (1.b) obtained in Example 2. It was.

Example 19
Example 18 except that 100 parts by weight of the epoxy resin (1.b) was changed to a mixture of 50 parts by weight of the 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.

Example 20
A cured film was prepared and evaluated under the same conditions as in Example 16 except that the epoxy resin (1.a) was changed to the fused ring structure-containing epoxy resin (1.c) obtained in Example 3. It was.

Example 21
Example 20 except that 100 parts by weight of epoxy resin (1.c) was changed to a mixture of 50 parts by weight of epoxy resin (1.c) 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.

Example 22
A cured film was prepared and evaluated under the same conditions as in Example 16 except that the epoxy resin (1.a) was changed to the condensed ring structure-containing epoxy resin (1.d) obtained in Example 4. It was.

Example 23
Example 22 except that 100 parts by weight of the epoxy resin (1.d) was changed to a mixture of 50 parts by weight of the epoxy resin (1.d) and 50 parts by weight of a bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Corporation). A cured film was prepared and evaluated under the same conditions as those described above.

Example 24
A cured film was prepared and evaluated under the same conditions as in Example 16 except that the epoxy resin (1.a) was changed to the fused ring structure-containing epoxy resin (1.e) obtained in Example 5. It was.

Example 25
Example 24 except that 100 parts by weight of the epoxy resin (1.e) was changed to a mixture of 50 parts by weight of the epoxy resin (1.e) 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 2
A cured film was prepared and evaluated under the same conditions as in Example 16 except that the epoxy resin (1.a) was changed to a bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.).

As is apparent from the results of Tables 3 to 4, it can be seen that when the condensed ring structure-containing epoxy resin of the present invention is used, a cured thin film having high transparency and a high level of refractive index can be obtained.

Example 26
(Preparation and Evaluation of Fine Particle Dispersion Composition Using Thermosetting Resin Composition Containing Epoxy Resin Containing Fused Structure)
100 parts by weight of the condensed ring structure-containing epoxy resin (1.a) obtained in Example 1 and 41 parts by weight of a phenol novolac resin type curing agent (Phenolite TD-2131 manufactured by Dainippon Ink & Chemicals, Inc.) were used as solvents. And dissolved in propylene glycol monomethyl ether acetate to give a solution having a concentration of 30% by weight. Next, 141 parts by weight of fine particle titanium oxide (TTO-51 (A) manufactured by Ishihara Sangyo Co., Ltd.) was added to the prepared resin solution, and 1 in a ball mill using 0.3 mm diameter zirconia beads with a filling rate of 80%. After time dispersion, a fine particle dispersion composition of titanium oxide was obtained. The obtained fine particle dispersion composition was evaluated for the following items. The composition of the fine particle dispersion composition used in this example is shown in Table 5, and the evaluation results obtained are shown in Table 6. Tables 5 and 6 also show Examples 27 to 30 and Comparative Example 3 described later.

(1) Particle size distribution:
The particle size distribution is measured with a particle size distribution analyzer Nano-ZS (Malvern) immediately after dispersion and after storage at 40 ° C. for 2 weeks.
The smaller median diameter is judged to be more excellent in dispersibility.
Further, change rate of median diameter [| median diameter after storage at | 40 ° C. for 2 weeks−median diameter immediately after dispersion | / (median diameter immediately after dispersion)] × 100 is obtained. In this evaluation, the smaller the value, the better the dispersion stability.

(2) Viscosity:
Using a rheometer RS75 (Haake) parallel plate, the viscosity is measured under the conditions of a sample temperature of 23 ° C. and a shear rate of 300 s ⁻¹ . Data are obtained immediately after dispersion and after storage at 40 ° C. for 2 weeks.
Further, the viscosity change rate [| viscosity after storage at 40 ° C. for 2 weeks−viscosity immediately after dispersion | / (viscosity immediately after dispersion)] × 100 is determined to evaluate dispersion stability.
In this evaluation, the smaller the value, the better the dispersion stability.

Example 27
The epoxy resin (1.a) was changed to the condensed ring structure-containing epoxy resin (1.b) obtained in Example 2, 34 parts by weight of phenol novolac resin type curing agent, and 134 parts by weight of fine particle titanium oxide. A fine particle dispersion composition was prepared and evaluated under the same conditions as in Example 26 except for changing to parts.

Example 28
The epoxy resin (1.a) was changed to the condensed ring structure-containing epoxy resin (1.c) obtained in Example 3, 42 parts by weight of a phenol novolac resin type curing agent, and 142 parts by weight of fine particle titanium oxide A fine particle dispersion composition was prepared and evaluated under the same conditions as in Example 26 except for changing to parts.

Example 29
The epoxy resin (1.a) was changed to the condensed ring structure-containing epoxy resin (1.d) obtained in Example 4, 31 parts by weight of a phenol novolac resin type curing agent, and 131 parts by weight of fine particle titanium oxide. A fine particle dispersion composition was prepared and evaluated under the same conditions as in Example 26 except for changing to parts.

Example 30
The epoxy resin (1.a) was changed to the condensed ring structure-containing epoxy resin (1.e) obtained in Example 5, 47 parts by weight of a phenol novolac resin type curing agent, and 147 parts by weight of fine particle titanium oxide. A fine particle dispersion composition was prepared and evaluated under the same conditions as in Example 26 except for changing to parts.

Comparative Example 3
Except for changing epoxy resin (1.a) to bisphenol A type epoxy resin (AER260 manufactured by Asahi Kasei Epoxy Co., Ltd.), and changing phenol novolac resin type curing agent to 58 parts by weight and fine particle titanium oxide to 158 parts by weight. Produced a fine particle dispersion composition under the same conditions as in Example 26 and evaluated.

As is apparent from the results of Tables 5 to 6, it can be seen that when the condensed ring structure-containing epoxy resin of the present invention is used, a fine particle dispersion composition having excellent dispersibility and storage stability of dispersion can be obtained.

Example 31
(Synthesis of epoxy ester resin containing condensed ring structure)
In a 300 ml four-necked flask, 230 g of epoxy resin (1.a) obtained in Example 1 (epoxy equivalent 270 g / eq), 600 mg of triethylbenzylammonium chloride as a catalyst, 56 mg of 2,6-diisobutylphenol as a polymerization inhibitor , And 71 g of acrylic acid, and heated and dissolved at 90-100 ° 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 15 hours for the acid value to reach the target. In the general formula (12), Z is a divalent group including the formula (7), s ₁ = 0, R ₁ , R ₂ = methyl group, q ₁ , q ₂ = 2, p ₁ , p ₂ = A light yellow transparent and solid condensed ring structure-containing epoxy ester resin (12.a) in which 0, m ₁ , m ₄ = 0 and R ₁₉ = ethenyl group was obtained.

Example 32
(Synthesis of epoxy ester resin containing condensed ring structure)
In a 300 ml four-necked flask, 100 g of epoxy resin (1.b) obtained in Example 2 (epoxy equivalent 319 g / eq), 260 mg of triethylbenzylammonium chloride as a catalyst, 24 mg of 2,6-diisobutylphenol as a polymerization inhibitor , And 26 g of acrylic acid, and heated and dissolved at 90-100 ° 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 13 hours for the acid value to reach the target. In the said General formula (12), Z is a bivalent group containing Formula (7), _R1-4 = methyl group, _q1-4 = 2, _p1-4 = 0, _m1-4 = 0 , R ₁₉ = ethenyl group, s ₁ was mainly composed of 0 to 3 to obtain a light yellow transparent and solid condensed ring structure-containing epoxy ester resin (12.b).

Example 33
(Synthesis of epoxy ester resin containing condensed ring structure)
In a 300 ml four-necked flask, 200 g (epoxy equivalent 260 g / eq) of the epoxy resin (1.c) obtained in Example 3, 510 mg of triethylbenzylammonium chloride as a catalyst, 47 mg of 2,6-diisobutylphenol as a polymerization inhibitor , And 64 g of acrylic acid, and heated and dissolved at 90-100 ° 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 13 hours for the acid value to reach the target. In the general formula (12), Z is a divalent group including the formula (7), and s ₁ = 0, q ₁ , q ₂ = 0, p ₁ , p ₂ = 0, m ₁ , m ₄ = 0 A light yellow transparent and solid condensed ring structure-containing epoxy ester resin (12.c) in which R ₁₉ = ethenyl group was obtained.

Example 34
(Synthesis of epoxy ester resin containing condensed ring structure)
In a 300 ml four-necked flask, 150 g of epoxy resin (1.d) obtained in Example 4 (epoxy equivalent 350 g / eq), 300 mg of triethylbenzylammonium chloride as a catalyst, 35 mg of 2,6-diisobutylphenol as a polymerization inhibitor , And 40 g of acrylic acid, and heated and dissolved at 90-100 ° 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 12 hours for the acid value to reach the target. In the general formula (12), Z is a divalent group including the formula (7), and s ₁ = 0, q ₁ , q ₂ = 0, p ₁ , p ₂ = 0, m ₁ , m ₄ = 1 A light yellow transparent and solid condensed ring structure-containing epoxy ester resin (12.d) in which R ₇ , R ₁₀ = hydrogen atom and R ₁₉ = ethenyl group was obtained.

Example 35
(Synthesis of epoxy ester resin containing condensed ring structure)
In a 300 ml four-necked flask, 100 g of epoxy resin (1.e) obtained in Example 5 (epoxy equivalent 235 g / eq), 330 mg of triethylbenzylammonium chloride as a catalyst, 24 mg of 2,6-diisobutylphenol as a polymerization inhibitor , And 35 g of acrylic acid, and heated and dissolved at 90-100 ° 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 12 hours for the acid value to reach the target. In the general formula (12), Z is a divalent group including the formula (11), and s ₁ = 0, q ₁ , q ₂ = 0, p ₁ , p ₂ = 0, m ₁ , m ₄ = 0. A light yellow transparent and solid condensed ring structure-containing epoxy ester resin (12.e) in which R ₁₉ = ethenyl group was obtained.

Example 36
(Preparation and evaluation of a cured film using a photocurable resin composition containing a condensed ring structure-containing epoxy ester resin)
100 parts by weight of the epoxy ester resin (12.a) having a condensed ring structure obtained in Example 31 and 3 parts by weight of Irgacure 907 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) as a solvent to obtain a concentration of 30 A weight percent solution was obtained. The solution containing the epoxy acrylate resin 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. Next, 300 mJ / cm < ² > light was irradiated with the high pressure mercury lamp (400W), and the coating film was hardened. The obtained cured film was evaluated for the following items. Table 7 shows the composition of the composition used in this example, and Table 8 shows the evaluation results of the obtained cured film. Tables 7 and 8 also show Examples 37 to 45 and Comparative Example 4 described later.

(1) 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.

(2) 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.

(3) Abrasion resistance (abrasion resistance)
While the surface of the cured film on the substrate is lightly pressed with # 1000 steel wool, the steel wool is reciprocated 30 times and rubbed. The degree of scratches on the surface of the coating film is judged according to the following criteria to evaluate the wear resistance.
○: Not scratched △: Scratched but gloss maintained ×: Innumerable scratched and lost gloss

(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.

Example 37
Except that 100 parts by weight of the epoxy ester resin (12.a) in Example 36 was changed to a mixture of 60 parts by weight of the epoxy ester resin (12.a) and 40 parts by weight of dipentaerythritol hexaacrylate (DPHA), Example A thin film was prepared and evaluated under the same conditions as in No.36.

Example 38
A thin film was prepared and evaluated under the same conditions as in Example 36 except that the epoxy ester resin (12.a) in Example 36 was changed to the epoxy ester resin (12.b).

Example 39
Example except that 100 parts by weight of the epoxy ester resin (12.b) in Example 38 was changed to a mixture of 60 parts by weight of the epoxy ester resin (12.b) and 40 parts by weight of dipentaerythritol hexaacrylate (DPHA). A thin film was prepared under the same conditions as in No. 38 and evaluated.

Example 40
A thin film was prepared and evaluated under the same conditions as in Example 36 except that the epoxy ester resin (12.a) in Example 36 was changed to the epoxy ester resin (12.c).

Example 41
Example 100 except that 100 parts by weight of the epoxy ester resin (12.c) in Example 40 was changed to a mixture of 60 parts by weight of the epoxy ester resin (12.c) and 40 parts by weight of dipentaerythritol hexaacrylate (DPHA). A thin film was prepared under the same conditions as in No. 40 and evaluated.

Example 42
A thin film was prepared and evaluated under the same conditions as in Example 36 except that the epoxy ester resin (12.a) in Example 36 was changed to the epoxy ester resin (12.d).

Example 43
Example except that 100 parts by weight of the epoxy ester resin (12.d) in Example 42 was changed to a mixture of 60 parts by weight of the epoxy ester resin (12.d) and 40 parts by weight of dipentaerythritol hexaacrylate (DPHA). A thin film was prepared under the same conditions as in No. 42 and evaluated.

Example 44
A thin film was prepared and evaluated under the same conditions as in Example 36 except that the epoxy ester resin (12.a) in Example 36 was changed to the epoxy ester resin (12.e).

Example 45
Example except that 100 parts by weight of the epoxy ester resin (12.e) in Example 44 was changed to a mixture of 60 parts by weight of the epoxy ester resin (12.e) and 40 parts by weight of dipentaerythritol hexaacrylate (DPHA). A thin film was prepared under the same conditions as in No. 44 and evaluated.

Comparative Example 4
A thin film was prepared and evaluated under the same conditions as in Example 36 except that the epoxy ester resin (12.a) in Example 36 was changed to a bisphenol A type epoxy acrylate resin.

As is apparent from the results of Tables 7 to 8, when the condensed ring structure-containing epoxy ester resin of the present invention is used, the transparency is high, the refractive index and heat resistance are high, and the degree of curing shrinkage is small. It can be seen that a cured thin film is obtained.

Example 46
(Preparation and Evaluation of Fine Particle Dispersion Composition Using Thermosetting Resin Composition Containing Fused Ring Structure-Containing Epoxy Ester Resin)
100 parts by weight of the condensed ring structure-containing epoxy ester resin (12.a) obtained in Example 31 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) as a solvent to obtain a solution having a concentration of 30% by weight. Next, 100 parts by weight of fine particle titanium oxide (TTO-51 (A) manufactured by Ishihara Sangyo Co., Ltd.) was added to the resin solution prepared above, and a ball mill using 0.3 mm diameter zirconia beads with a filling rate of 80% For 1 hour to obtain a fine particle dispersion composition of titanium oxide. The obtained fine particle dispersion composition was evaluated for the following items. The results are shown in Tables 9 and 10. The results of Examples 47 to 50 and Comparative Example 5 described later are also shown in Tables 9 and 10.

(1) Particle size distribution:
The particle size distribution is measured with a particle size distribution analyzer Nano-ZS (Malvern) immediately after dispersion and after storage at 40 ° C. for 2 weeks.
The smaller median diameter is judged to be more excellent in dispersibility.
Further, change rate of median diameter [| median diameter after storage at | 40 ° C. for 2 weeks−median diameter immediately after dispersion | / (median diameter immediately after dispersion)] × 100 is obtained. In this evaluation, the smaller the value, the better the dispersion stability.

(2) Viscosity:
Using a rheometer RS75 (Haake) parallel plate, the viscosity is measured under the conditions of a sample temperature of 23 ° C. and a shear rate of 300 s ⁻¹ . Data are obtained immediately after dispersion and after storage at 40 ° C. for 2 weeks.
Further, the viscosity change rate [| viscosity after storage at 40 ° C. for 2 weeks−viscosity immediately after dispersion | / (viscosity immediately after dispersion)] × 100 is determined to evaluate dispersion stability.
In this evaluation, the smaller the value, the better the dispersion stability.

Example 47
A fine particle dispersion composition was prepared and evaluated under the same conditions as in Example 46 except that the epoxy ester resin (12.a) in Example 46 was changed to the epoxy ester resin (12.b).

Example 48
A fine particle dispersion composition was prepared and evaluated under the same conditions as in Example 46 except that the epoxy ester resin (12.a) in Example 46 was changed to the epoxy ester resin (12.c).

Example 49
A fine particle dispersion composition was prepared and evaluated under the same conditions as in Example 46 except that the epoxy ester resin (12.a) in Example 46 was changed to the epoxy ester resin (12.d).

Example 50
A fine particle dispersion composition was prepared and evaluated under the same conditions as in Example 46 except that the epoxy ester resin (12.a) in Example 46 was changed to the epoxy ester resin (12.e).

Comparative Example 5
A fine particle dispersion composition was prepared and evaluated under the same conditions as in Example 10 except that the condensed ring structure-containing epoxy ester resin (12.a) was changed to a bisphenol A type epoxy acrylate resin.

As is apparent from the results of Tables 9 to 10, it is understood that a fine particle dispersion composition excellent in dispersibility and storage stability of the dispersion can be obtained by using the condensed ring structure-containing epoxy ester resin of the present invention.

Example 51
(Synthesis of alkali-soluble resin containing condensed ring structure)
After adding 74 g of propylene glycol monomethyl ether acetate (PGMEA) to 85 g of the condensed ester-containing epoxy ester resin (12.a) prepared in Example 31 and dissolving it, 21 g of pyromellitic dianhydride (PMDA) and an odor as a catalyst Tetraethylammonium bromide (0.1 g) was mixed, and this was gradually heated and reacted at 110 to 115 ° C. for 14 hours. Next, 9.8 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and the mixture was reacted at 90 to 95 ° C. for 4 hours.
In this way, a PGMEA solution of the condensed ring structure-containing alkali-soluble resin (23.a) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.
The condensed ring structure-containing alkali-soluble resin (23.a) can be classified as a condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin.

Here, the average t is 8.6.

Example 52
(Synthesis of an alkali-soluble resin containing a condensed ring structure)
After adding 56 g of propylene glycol monomethyl ether acetate (PGMEA) to 64 g of the condensed ester-containing epoxy ester resin (12.a) prepared in Example 31 and dissolving it, 14 g of biphenyltetracarboxylic acid (BPDA) and tetraethylammonium bromide 0 0.1 g was mixed, and the temperature was gradually raised and reacted at 110 to 115 ° C. for 14 hours. Next, 7.3 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours.
In this way, a PGMEA solution of the condensed ring structure-containing alkali-soluble resin (23.a ′) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.
The condensed ring structure-containing alkali-soluble resin (23.a ′) can be classified as a condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin.

Here, the average t is 2.7.

Example 53
(Synthesis of an alkali-soluble resin containing a condensed ring structure)
After adding 85 g of propylene glycol monomethyl ether acetate (PGMEA) to 100 g of the epoxy ester resin (12.b) prepared in Example 32 and dissolving it, 12 g of biphenyltetracarboxylic acid (BPDA) and tetraethylammonium bromide were added. 0.1 g was mixed, and the temperature was gradually raised and reacted at 110 to 115 ° C. for 14 hours. Next, 33 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours.
In this way, a PGMEA solution of a condensed ring structure-containing alkali-soluble resin (23.b) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.
The condensed ring structure-containing alkali-soluble resin (23.b) can be classified as a condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin.

Here, S ₁ and S ₂ are each independently mainly 0 to 3.
Here, the average t is 6.6.

Example 54
(Synthesis of an alkali-soluble resin containing a condensed ring structure)
After adding 65 g of propylene glycol monomethyl ether acetate (PGMEA) to 80 g of the fused ester structure-containing epoxy ester resin (12.c) prepared in Example 33 and dissolving it, 12 g of biphenyltetracarboxylic acid (BPDA) and tetraethylammonium bromide 0 0.1 g was mixed, and the temperature was gradually raised and reacted at 110 to 115 ° C. for 14 hours. Next, 9.1 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours.
Thus, a PGMEA solution of the condensed ring structure-containing alkali-soluble resin (23.c) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.
The condensed ring structure-containing alkali-soluble resin (23.c) can be classified as a condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin.

Here, the average t is 4.4.

Example 55
(Synthesis of an alkali-soluble resin containing a condensed ring structure)
After adding 65 g of propylene glycol monomethyl ether acetate (PGMEA) to 80 g of the fused ester structure-containing epoxy ester resin (12.d) prepared in Example 34 and dissolving it, 15 g of biphenyltetracarboxylic acid (BPDA) and tetraethylammonium bromide 0 0.1 g was mixed, and the temperature was gradually raised and reacted at 110 to 115 ° C. for 14 hours. Next, 7.6 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours.
In this manner, a PGMEA solution of the condensed ring structure-containing alkali-soluble resin (23.d) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.
The condensed ring structure-containing alkali-soluble resin (23.d) can be classified as a condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin.

Here, the average t is 2.7.

Example 56
(Synthesis of an alkali-soluble resin containing a condensed ring structure)
After adding 120 g of propylene glycol monomethyl ether acetate (PGMEA) to 80 g of the fused ester structure-containing epoxy ester resin (12.e) prepared in Example 35 and dissolving, pyromellitic dianhydride (PMDA) 9.6 g and odor Tetraethylammonium bromide (0.1 g) was mixed, and this was gradually heated and reacted at 110 to 115 ° C. for 14 hours. Next, 12 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours.
In this manner, a PGMEA solution of the condensed ring structure-containing alkali-soluble resin (23.e) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.
The condensed ring structure-containing alkali-soluble resin (23.e) can be classified as a condensed ring structure-containing alkali-soluble radiation-polymerizable unsaturated resin.

Here, the average t is 25.

Example 57
(Preparation and Evaluation of Thin Film Using Composition Containing Fused Ring Structure-Containing Alkali-Soluble Resin)
30 parts by weight of the alkali-soluble resin (23.a) obtained in Example 51 as a solid content, 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 obtained substrate having the 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> 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

<2> 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.

<3> 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).

<4> Adhesiveness with substrate The obtained heat-cured film is evaluated by a cross-cut peel test according to JIS-K-5400.

<5> 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.

<6> 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.

<7> 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.

Table 11 shows the above results. The results of Examples 58 to 64 described later and Comparative Example 6 are also shown in Table 11.

<8> 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 wt% 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: Change in film thickness (%) before and after immersion in N-methylpyrrolidone for 5 minutes at 80 ° C. ((film thickness before immersion— Film thickness after immersion) / (film thickness before immersion)) × 100 is obtained. Furthermore, the film thickness change rate of Comparative Example 6 is set to 100, and the film thickness change rate of Examples 57 to 64 (film thickness change rate of Example / film thickness change rate of Comparative Example × 100) based on that is obtained. It was. Chemical resistance is evaluated from the calculated ratio.
In this evaluation, when the value is 100, there is no significant difference from Comparative Example 6, and the smaller the value is, the higher the chemical resistance is recognized.

The results are shown in Table 12. The results of Examples 58 to 64 described later and Comparative Example 6 are also shown in Table 12.

Example 58
A thin film was prepared and evaluated under the same conditions as in Example 57 except that dipentaerythritol hexaacrylate was changed to trimethylolpropane triacrylate (TMPTA).

Example 59
Further, a thin film was prepared and evaluated under the same conditions as in Example 57 except that a composition containing 6 parts by weight of a tetramethylbiphenyl type epoxy resin (Epicoat Yx-4000 manufactured by Japan Epoxy Resin Co., Ltd.) was used. .

Example 60
A thin film was produced under the same conditions as in Example 57, except that the alkali-soluble resin (23.a) was changed to the alkali-soluble resin (23.a ′) obtained in Example 52. Evaluation was performed.

Example 61
A thin film was prepared and evaluated under the same conditions as in Example 57 except that the alkali-soluble resin (23.a) was changed to the alkali-soluble resin (23.b) obtained in Example 53. Went.

Example 62
A thin film was prepared and evaluated under the same conditions as in Example 57 except that the alkali-soluble resin (23.a) was changed to the alkali-soluble resin (23.c) obtained in Example 54. Went.

Example 63
A thin film was prepared and evaluated under the same conditions as in Example 57 except that the alkali-soluble resin (23.a) was changed to the alkali-soluble resin (23.d) obtained in Example 55. Went.

Example 64
A thin film was prepared and evaluated under the same conditions as in Example 57, except that the alkali-soluble resin (23.a) was changed to the alkali-soluble resin (23.e) obtained in Example 56. Went.

Comparative Example 6
In Example 57, the thin film was formed under the same conditions as in Example 57 except that the alkali-soluble resin (23.a) was changed to the bisphenol A-type photopolymerizable unsaturated resin (23.f) represented by the following formula. Was created and evaluated.

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

As is clear from the results of Tables 11 to 12, when the condensed ring structure-containing alkali-soluble resin of the present invention is used, the refractive index and transparency are high, and the coating film drying property, heat resistance and chemical resistance are excellent. It can be seen that a cured thin film 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.

Example 65
(Preparation and Evaluation of Fine Particle Dispersion Composition Using Thermosetting Resin Composition Containing Alkali-Soluble Resin Containing Fused Ring Structure)
The alkali-soluble resin (23.a) was dissolved in 100 parts by weight of PGMEA as a solid content to obtain a solution having a concentration of 30% by weight. Next, 100 parts by weight of fine particle titanium oxide (TTO-51 (A) manufactured by Ishihara Sangyo Co., Ltd.) was added to the resin solution prepared above, and a ball mill using 0.3 mm diameter zirconia beads with a filling rate of 80% For 1 hour to obtain a fine particle dispersion composition of titanium oxide. The obtained fine particle dispersion composition was evaluated for the following items. The results are shown in Tables 13 and 14. The results of Examples 66 to 69 and Comparative Example 7 described later are also shown in Tables 13 and 14.

Example 66
A thin film was prepared and evaluated under the same conditions as in Example 65 except that the alkali-soluble resin (23.a) was changed to the alkali-soluble resin (23.b) obtained in Example 53. Went.

Example 67
A thin film was prepared and evaluated under the same conditions as in Example 65 except that the alkali-soluble resin (23.a) was changed to the alkali-soluble resin (23.c) obtained in Example 54. Went.

Example 68
A thin film was prepared and evaluated under the same conditions as in Example 65 except that the alkali-soluble resin (23.a) was changed to the alkali-soluble resin (23.d) obtained in Example 55. Went.

Example 69
A thin film was prepared and evaluated under the same conditions as in Example 65 except that the alkali-soluble resin (23.a) was changed to the alkali-soluble resin (23.e) obtained in Example 56. Went.

(1) Particle size distribution:
The particle size distribution is measured with a particle size distribution analyzer Nano-ZS (Malvern) immediately after dispersion and after storage at 40 ° C. for 2 weeks.
The smaller median diameter is judged to be more excellent in dispersibility.
Further, change rate of median diameter [| median diameter after storage at | 40 ° C. for 2 weeks−median diameter immediately after dispersion | / (median diameter immediately after dispersion)] × 100 is obtained. In this evaluation, the smaller the value, the better the dispersion stability.

(2) Viscosity:
Using a rheometer RS75 (Haake) parallel plate, the viscosity is measured under the conditions of a sample temperature of 23 ° C. and a shear rate of 300 s ⁻¹ . Data are obtained immediately after dispersion and after storage at 40 ° C. for 2 weeks.
Furthermore, the viscosity change rate [(viscosity after storage at 40 ° C. for 2 weeks−viscosity immediately after dispersion) / (viscosity immediately after dispersion)] × 100 is determined, and the dispersion stability is evaluated.
In this evaluation, the smaller the value, the better the dispersion stability.

Comparative Example 7
A fine particle dispersion composition was prepared under the same conditions as in Example 17 except that the alkali-soluble resin (23.a) was changed to the bisphenol A-type photopolymerizable unsaturated resin (23.f). went.

As is apparent from the results of Tables 13 to 14, it is understood that a fine particle dispersion composition excellent in dispersibility and storage stability of dispersion can be obtained by using the alkali-soluble resin of the present invention.

According to the present invention, a novel condensed ring structure-containing epoxy resin, a condensed ring structure-containing epoxy ester resin, a condensed ring structure-containing alkali-soluble resin, and a simple production method thereof are thus provided. 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 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;

Claims (14)

A condensed ring structure-containing epoxy ester resin which is an epoxy acrylate resin represented by the following general formula (17).

Y _1-4 is a group independently selected from the following general formula (18) or the following general formula (19), and p _1-4 are each independently an integer of 0-4.

Here, Y _5-6 are each independently a group represented by the following general formula (19), and p _5-6 are each independently an integer of 0-4.

Here, Z in the general formulas (17), (18), and (19) represents a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings. A condensed ring structure 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 _1-6 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, an optionally substituted phenyl group, or a halogen atom Q _1-6 are each independently an integer of 0 to 4, m _1-8 and s _1-2 are each independently an integer of 0 to 10, and R _7-14 and R ₂₀ are Each independently represents a hydrogen atom or a methyl group, and the structural formula may be bilaterally symmetric or asymmetric. Further, a plurality of _{R 1~14, R 20, Y 1~6} are may be the same or may be different. The condensed ester-containing epoxy ester resin according to claim 1, which is an epoxy acrylate resin represented by the following general formula (20).

Here, Z, R _1-4 , q _1-4 , R _7-10 , m _1-4 , R ₂₀ , s ₁ are the same as described above, and are asymmetric even if the structural formula is symmetrical. May be. Moreover, several R _{< 1 > -4} , R _{<7> -10} , R _{< 20 >} may be the same and may differ. The condensed ester-containing epoxy ester resin according to claim 1, which is an epoxy acrylate resin represented by the following general formula (21).

Here, Z, R _1-2 , q _1-2 , R ₇ , R ₁₀ , m ₁ , m ₄ , R ₂₀ are the same as described above, and h _1-2 are each independently from 1 to 5 It is an integer, and the structural formula may be symmetric or asymmetric. Moreover, several R _<1-2 >, R _{< 7 >} , R _{< 10 >} , R _{< 20} > may be the same and may differ. Z is a divalent group containing a condensed ring structure selected from the group consisting of the following formulas (7) to (9). The condensed ring structure-containing epoxy ester resin according to any one of claims 1 to 3.

The condensed ring-containing epoxy ester resin according to any one of claims 1 to 3, wherein Z is a divalent group including a condensed ring structure selected from the group consisting of the following formulas (10) to (11).

It is a manufacturing method of the condensed ring structure containing epoxy ester resin as described in any one of Claims 1-5, Comprising: The condensed ring structure containing epoxy resin shown by following General formula (1), and (meth) acrylic acid are included. A method comprising a step of reacting, or a step of reacting a polyfunctional hydroxyl group-containing condensed ring structure compound of the following general formula (4) with glycidyl (meth) acrylate.

Here, Y _1-4 are each independently a group selected from the following general formula (2) or the following general formula (3), and p _1-4 are each independently an integer of 0-4.

Here, Y _5-6 are each independently a group represented by the following general formula (3), and p _5-6 are each independently an integer of 0-4.

Here, Z in the general formulas (1) and (2) 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 _1-6 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, q _{1 to 6} are each independently an integer of 0 to 4. Further, R _{7 to 14 in the} general formulas (1), (2) and (3) are each independently a hydrogen atom or a methyl group, and m _{1 to 8} and s _{1 to 2} are each independently 0 to It is an integer of 10, and the structural formula may be symmetrical or asymmetrical. A plurality of R _1-14 and Y _1-6 may be the same or different.

Here, Z is the same as described above, and each of R _{15 to 16} is 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, A phenyl group which may have a substituent, or a halogen atom, f _1-2 are each independently an integer of 0 to 4, and R _17-18 are each independently a hydrogen atom or a methyl group. _{M 9 to 10} are each independently an integer from 0 to 10, and r _{1 to 2} are each independently an integer from 1 to 5, and even if the structural formula is symmetrical, it is asymmetric. There may be. Moreover, several _R15-18 may be the same and may differ. The condensed ring structure containing epoxy ester resin composition containing the condensed ring structure containing epoxy ester resin as described in any one of Claims 1-5. The condensed ring structure containing epoxy ester resin composition of Claim 7 containing an organic pigment and / or inorganic microparticles | fine-particles. The molded object obtained by hardening the condensed ring structure containing epoxy ester resin composition of Claim 7 or 8. A condensed ring structure-containing alkali-soluble resin obtained by reacting a condensed basic structure-containing epoxy ester resin according to any one of claims 1 to 5 with a polybasic carboxylic acid or an anhydride thereof. It is a manufacturing method of the condensed ring structure containing alkali-soluble resin of Claim 10, Comprising: The condensed ring structure containing epoxy ester resin as described in any one of Claims 1-5, and polybasic carboxylic acid, or its A method comprising the step of reacting with an anhydride. A radiation-sensitive alkali-soluble resin composition comprising the condensed ring-structure-containing alkali-soluble resin according to claim 10. The radiation-sensitive alkali-soluble resin composition according to claim 12, comprising an organic pigment and / or inorganic fine particles. The molded object obtained by hardening the radiation sensitive alkali-soluble resin composition of Claim 12 or 13.

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