JP2014208804A - Epoxy resin having fluorene skeleton - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel epoxy resin that has an excellent handling property and the like due to its low viscosity in spite of having a fluorene skeleton and gives a cured product having high strength after being cured at room temperature or at near room temperature.SOLUTION: There is provided an epoxy resin including a monomer and/or a multimer of an ester type epoxy compound having a fluorene skeleton represented by following formulae (1d) or (1e). In the formulae, Rand Reach are the same or different substituent; k is an integer of 0 to 4; Ris the same or different divalent or trivalent hydrocarbon group such as a linear or branched Calkylene group or Calkane triyl group that may have a substituent; Ris a divalent hydrocarbon group such as a linear or branched Calkylene group; Ris the same or different substituent; p is an integer of 0 to 4.

Description

  The present invention relates to a novel epoxy resin having a fluorene skeleton, a curable composition containing the epoxy resin (epoxy resin composition), and a cured product of the epoxy resin or the curable composition.

  The epoxy resin forms a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. Therefore, epoxy resins are used in a wide range of fields such as adhesives, paints, laminates, molding materials and casting materials.

  On the other hand, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, etc. A compound having a 9,9-bisarylfluorene skeleton is known to have an excellent function in optical properties and the like, and it is also known to use such a compound as an epoxy resin raw material.

  For example, JP 2012-102228 A (Patent Document 1) discloses a curable composition containing 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene and a curing agent. In this document, when 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene is used, 9,9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis [4- ( It is described that the bending elastic modulus at high temperature can be reduced as compared with 2-glycidyloxyethoxy) phenyl] fluorene, 9,9-bis (4-glycidyloxy-3-phenylphenyl) fluorene, and the like.

  However, the glycidyl ether type epoxy resin having the 9,9-bisarylfluorene skeleton as described above is semi-solid or solid at room temperature, has high melting temperature and high melt viscosity, poor solvent solubility, etc. There was a problem in terms of.

JP 2012-102228 A (Claims, Examples)

  Accordingly, an object of the present invention is to provide an epoxy resin having a novel fluorene skeleton, a curable composition containing the epoxy resin, and a cured product thereof.

  Another object of the present invention is an epoxy resin that has a fluorene skeleton or a multimer such as a dimer and has low viscosity and excellent handling properties, and a curable composition containing the epoxy resin And providing a cured product thereof.

  Still another object of the present invention is to provide a high-strength fluorene skeleton-containing epoxy resin at ambient temperature (such as room temperature or near room temperature), a curable composition containing this epoxy resin, and a cured product thereof.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a novel glycidyl ester type epoxy resin having a fluorene skeleton by reacting a specific polycarboxylic acid having a fluorene skeleton with epihalohydrin or the like. In addition, such an epoxy resin has a fluorene skeleton, has excellent solvent solubility and low viscosity, and has excellent handling properties. Surprisingly, the present inventors have found that the elastic modulus at the environmental temperature is high and the strength at the environmental temperature can be improved or improved as compared with the glycidyl ether type epoxy resin having the fluorene skeleton.

  That is, the epoxy resin of the present invention includes a monomer of an ester type epoxy compound having a fluorene skeleton and / or a multimer thereof, and the monomer is represented by the following formula (1a) or (1b). .

Wherein R ¹ is the same or different substituent, k is an integer of 0 to 4, R ^2a is the same or different divalent or trivalent hydrocarbon group, and R ^2b is the same or different divalent carbon. Hydrogen group, R ³ is the same or different substituent, m is an integer of 0-3, n is 1 or 2, and p is an integer of 0-4.)
In the above formula (1a) or (1b), R ^2a is an aliphatic hydrocarbon group (for example, a linear or branched alkylene group or alkanetriyl group which may have a substituent), R ^2b. May be an aliphatic hydrocarbon group (for example, a linear or branched alkylene group which may have a substituent). In the formula (1a), n is 1, and R ^2a may have a substituent, a linear or branched C _1-10 alkylene group (for example, a C _1-6 alkylene group, In particular, it may be a C _1-4 alkylene group) or a C _1-10 alkanetriyl group (eg, a C _1-6 alkanetriyl group, especially a C _1-4 alkanetriyl group), and R ^2b is It may be a linear or branched C _1-10 alkylene group (for example, a C _1-6 alkylene group, particularly a C _1-4 alkylene group) which may have a substituent. In the formula (1a) or (1b), m may be 0. The epoxy resin may be composed of the monomer represented by the formula (1a) or (1b), and may contain a multimer (for example, a multimer such as a dimer or a trimer). Good.

  More specifically, the present invention also includes an epoxy resin represented by the following formula (1c).

[Wherein A is the following (1d) or (1e)

(R ^2a and R ^2b are the same or different and each represents a linear or branched C _1-4 alkylene group which may have a substituent, and R ¹ , k and p are the same as above), q represents 0 or an integer of 1 to 10]
The epoxy resin is an area ratio of gel permeation chromatogram of monomer and dimer or higher multimer, the former / the latter = 100/0 to 40/60 (for example, 90/10 to 50/50). It may be included in a proportion. The epoxy resin of the present invention has a feature that it has a low viscosity even when it contains a multimer.

  The present invention includes a curable composition containing the epoxy resin. Such a curable composition may be, for example, a curable composition containing an epoxy resin and a curing agent (particularly a phenolic curing agent). Moreover, the hardened | cured material which the said curable composition hardened | cured is also contained in this invention.

  The epoxy resin having a novel fluorene skeleton of the present invention is excellent in handling properties such as excellent solvent solubility and low viscosity despite having a fluorene skeleton. Surprisingly, despite having a similar fluorene skeleton, the elastic modulus at ambient temperature is higher than that of diglycidyl ether type epoxy resins of 9,9-bis (hydroxyaryl) fluorenes, A cured product having high strength can be obtained at ambient temperature.

[Epoxy resin]
In the epoxy resin of the present invention, the monomer of the epoxy compound is represented by the following formula (1a) or (1b).

Wherein R ¹ is the same or different substituent, k is an integer of 0 to 4, R ^2a is the same or different divalent or trivalent hydrocarbon group, and R ^2b is the same or different divalent carbon. A hydrogen group, R ³ is the same or different substituent, m is an integer of 0 to 3, n is 1 or 2, and p is an integer of 0 to 4.)
In the above formula (1a) or (1b), the group R ¹ is not particularly limited. For example, a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a carboxyl group, a hydrocarbon group [for example, An alkyl group, an aryl group (C _6-10 aryl group such as a phenyl group), etc.], and the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, such as _{C 1-12} alkyl group _{(e.g., C 1-8} alkyl groups, especially methyl groups, such as t- butyl group _{C 1- 4} alkyl group) and the like. In addition, when k is plural (2 to 4), the types of the plural groups R ¹ may be the same or different. Moreover, the kind of group R < ¹ > substituted by the different benzene ring may be the same or different. Further, the bonding position (substitution position) of the group R ¹ is not particularly limited, and examples thereof include the 2nd, 7th, 2nd and 7th positions of the fluorene ring. The preferred substitution number k is 0 to 1, in particular 0. The two substitution numbers k may be the same or different.

  In the formula (1a), n is 1 or 2 (particularly 1), and two n may be the same (that is, either 1 or 2) or different (that is, one n May be 1 and the other n may be 2), and may usually be the same.

In the formula (1a) or (1b), the group R ^2a is a divalent or trivalent hydrocarbon group, and R ^2b is a divalent hydrocarbon group. That is, in the formula (1a), when n = 1, the group R ^2a is a divalent hydrocarbon group, and when n = 2, the group R ^2a is a trivalent hydrocarbon group. Examples of the hydrocarbon corresponding to the hydrocarbon group include acyclic aliphatic hydrocarbons [for example, C ₁ -1 such as alkane (for example, methane, ethane, propane, butane, isobutane, pentane, isopentane, hexane, heptane, and octane). ₁₂ alkanes, preferably C _1-8 alkanes, more preferably C _1-4 alkanes, especially C _1-2 alkanes), alkenes (eg C _2-10 alkenes such as ethylene, propene, butene, pentene, etc.)], Alicyclic hydrocarbons [eg, cycloalkanes (eg, C _5-10 cycloalkanes such as cyclopentane, cyclohexane, preferably C _5-8 cycloalkanes), alkylcycloalkanes (eg, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane) _{C 1-4} alkyl C, such as _-10 cycloalkane, preferably _{C 1-2} alkyl _{C 5-8} cycloalkane), crosslinked cyclic hydrocarbon (e.g., norbornane, aliphatic hydrocarbons such as adamantane, etc.), etc.]; monocyclic arenes {benzene, alkylbenzenes [For example, C _1-4 alkylbenzene such as toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, etc.], alkenylbenzene (eg, C _2-10 alkenylbenzene such as styrene)}, and the like}, for example, naphthalene Aromatic hydrocarbons such as condensed polycyclic arenes such as anthracene, methylnaphthalene and dimethylnaphthalene).

The hydrocarbon (or hydrocarbon group) may have a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group (for example, a C _1-10 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group), a cycloalkyl group (a cyclohexyl group). C _5-8 cycloalkyl group, etc.), aryl groups (eg, C _6-10 aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, etc.), aralkyl groups (C, such as benzyl group, phenethyl group, etc.) Hydrocarbon groups such as _6-10 aryl-C _1-4 alkyl group); alkoxy groups (such as C _1-8 alkoxy groups such as methoxy group, ethoxy group), cycloalkoxy groups (C ₅ such as cyclohexyloxy group). _-10, etc. the cycloalkyl group), _{C 6-10} aryloxy groups such as an aryloxy group (phenoxy group), aralkyl Group -OR [where such alkoxy groups _{(C 6-10} aryl _{-C 1-4} alkyl group such as a benzyl group), R represents a hydrocarbon group (such as the above-exemplified hydrocarbon group). A group such as an alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group) —SR (wherein R is as defined above); an acyl group (such as a C _1-6 acyl group such as an acetyl group); Alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group; substituted amino group (for example, dimethyl) And a dialkylamino group such as an amino group). Preferred substituents are a hydrocarbon group (e.g., methyl group, ethyl group, propyl group, C _1-6 alkyl groups such as isopropyl group, butyl group, a phenyl group, a tolyl group, a xylyl group, C _6- such naphthyl groups ₁₀ aryl group). These substituents may be substituted with hydrocarbons alone or in combination of two or more.

Specific examples of the divalent hydrocarbon group which may have a substituent include, for example, a divalent aliphatic hydrocarbon group {for example, an alkylene group (for example, a methylene group, an ethylene group, an ethylidene group, a trimethylene group). , Propylene group, propylidene group, isopropylidene group, tetramethylene group, 2-methylpropane-1,3-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-2-ylidene Group, butane-2,3-diyl group, pentamethylene group, pentane-2,3-diyl group, hexamethylene group, etc., C _1-12 alkylene group, preferably C _1-8 alkylene group, more preferably C _{1 -4} alkylene, especially _{C 1-2} alkylene group), an aryl alkylene group [e.g., _{C 6-10} aryl _{C 1-4} alkylene, such as phenylethylene group , Preferably C _6-8 aryl C _1-2 alkylene group) alkylene group which may have a substituent such as, etc.]; cycloalkylene group (e.g., a cyclopentylene group, a cyclohexylene group (1, 4 A C _5-10 cycloalkylene group, such as a _{-cyclohexylene} group, preferably a C _5-8 cycloalkylene group), an alkyl cycloalkylene group (for example, a C _1-4 alkyl C _5-10 such as a methylcyclohexylene group). A cycloalkylene group which may have a substituent such as a cycloalkylene group; an alkylene-cycloalkylene group {for example, a methylene-cyclohexylene group [—CH ₂ —C ₆ H ₁₀ —] (methylene-1,4 - such as a cyclohexylene group), an ethylene - cyclohexylene group _{[-CH 2 CH 2 -C 6 H} 10 -] ( ethylene -1 C _1-4 alkylene-C ₅ such as ethylidene-cyclohexylene group [—CHCH ₃ —C ₆ H ₁₀ —] (ethylidene-1,4-cyclohexylene group, etc.). _An alkylene-cycloalkylene group which may have a substituent such as a _-10 cycloalkylene group, preferably a C _1-2 alkylene-C _5-8 cycloalkylene group, etc .; an alkylene-arylene group (eg, a methylene-phenylene group) An alkylene-arylene group _optionally having a substituent such as a C _1-4 alkylene-C _6-10 arylene group such as an ethylene-phenylene group; an alkylene-arylene-alkylene group (eg, methylene-phenylene-methylene (xylylene) _{C 1-4} alkylene _{-C 6-10} arylene _{-C 1-4} alkylene such groups Group), divalent aromatic hydrocarbon group [eg, arylene group (eg, phenylene group, naphthylene group, etc.), alkylarylene group (eg, methylphenylene group, dimethylphenylene group, etc.) An arylene group which may have a substituent such as a C _1-4 alkyl C _6-10 arylene group.

A preferable divalent hydrocarbon group R ^2a is an alkylene group (a linear or branched alkylene group), for example, a C _1-10 alkylene group, preferably a C _1-4 alkylene group. Further, the preferred divalent hydrocarbon group R ^2b includes an alkylene group (eg, a C _1-10 alkylene group, preferably a C _1-4 alkylene group).

Specific examples of the trivalent hydrocarbon group R ^2a that may have a substituent include a trivalent hydrocarbon group corresponding to the divalent hydrocarbon group, for example, a trivalent aliphatic hydrocarbon group. [For example, a C _1-12 alkanetriyl group such as an alkanetriyl group (eg, ethanetriyl group (1,1,2-ethanetriyl, 1,2,3-propanetriyl, etc.), preferably a C _1-8 alkane Triyl group, more preferably C _2-4 alkanetriyl group, etc.)] and the like.

A typical alkanetriyl group represented by the group R ^{2a can} be represented, for example, by the following formula (1f).

(Wherein R ^2b , R ³ , m and p are the same as above)
In the formula (1a) or (1b), the types of the two groups R ^2a and R ^2b may be the same or different, and may usually be the same.

Preferable R ^2a and R ^2b are alkylene groups which may have a substituent. The alkylene group represented by R ^2a and R ^2b is a linear or branched alkylene group such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a 2-ethylethylene group, 2-methylpropane-1, Examples thereof include a C _1-8 alkylene group such as a 3-diyl group. Preferred alkylene groups are linear or branched C _1-6 alkylene groups (eg, C _1-4 alkylene such as methylene group, ethylene group, trimethylene group, propylene group, 2-methylpropane-1,3-diyl group). Group).

  Examples of the substituent of the alkylene group include an aryl group (such as a phenyl group) and a cycloalkyl group (such as a cyclohexyl group).

R ^2a is often a linear or branched C _2-4 alkylene group (eg, ethylene group, propylene group), and R ^2b is a linear or branched C _1-3 alkylene group (eg, Methylene group, ethylene group) in many cases. The alkylene group R ^2a having a substituent may be, for example, a 1-phenylethylene group, a 1-phenylpropane-1,2-diyl group, or the like.

  The coefficient p can be selected from an integer of 0 to 4, and may be generally 0 to 2, preferably 0 or 1.

In the formula (1a) or (1b), examples of R ³ include non-reactive substituents such as a hydrocarbon group (the hydrocarbon group exemplified above). Representative R ³ includes an alkyl group [for example, a group exemplified in the above R ¹ term such as a methyl group (eg, a C _1-4 alkyl group)].

Further, the substitution number m of R ³ may be 0-3, but is preferably 0-1, particularly 0. When m is 2 or 3, the plurality of R ³ may be the same or different groups.

A typical epoxy compound (monomer) represented by the formula (1a) is an epoxy compound in which R ^2a is a divalent aliphatic hydrocarbon group in the formula (1a), for example, 9,9- Bis (glycidyloxycarbonylalkyl) fluorenes [for example, 9,9-bis (glycidyloxycarbonylmethyl) fluorene, 9,9-bis (2-glycidyloxycarbonylethyl) fluorene, 9,9-bis (1-glycidyloxy) Carbonylethyl) fluorene, 9,9-bis (1-glycidyloxycarbonylpropyl) fluorene, 9,9-bis (2-glycidyloxycarbonylpropyl) fluorene, 9,9-bis (2-glycidyloxycarbonyl-1-methyl) Ethyl) fluorene, 9,9-bis (2-glycidyloxycarbonyl-1-methyl) Propyl) fluorene, 9,9-bis (2-glycidyloxycarbonylbutyl) fluorene, 9,9-bis (2-glycidyloxycarbonyl-1-methylbutyl) fluorene, 9,9-bis (5-glycidyloxycarbonylpentyl) 9,9-bis (glycidyloxycarbonyl C _1-6 alkyl) fluorene such as fluorene, preferably 9,9-bis (glycidyloxycarbonyl C _1-4 alkyl) fluorene, more preferably 9,9-bis (glycidyloxy) Carbonyl C _1-2 alkyl) fluorene and the like], 9,9-bis (glycidyloxycarbonylcycloalkyl) fluorenes [for example, 9,9-bis (glycidyloxy such as 9,9-bis (glycidyloxycarbonylcyclohexyl) fluorene) Carbonyl _5-8 cycloalkyl) fluorene], and the like; the formula ^(1a), the epoxy compound ^{R 2a} is a trivalent aliphatic hydrocarbon group, for example, 9,9-bis (diglycidyl oxycarbonyl alkyl) fluorenes [9,9-bis [di (glycidyloxycarbonyl) C _1-6 alkyl] fluorene such as 9,9-bis [1,2-di (glycidyloxycarbonyl) ethyl] fluorene, preferably 9,9- bis [di (glycidyloxy _{carbonyl) C 2-4} alkyl] fluorene, more preferably 9,9-bis [di (glycidyloxy _{carbonyl) C 2-3} alkyl) fluorene], and others.

  A typical epoxy compound (monomer) represented by the formula (1a) can be represented by the following formulas (1a-1) (1a-2).

(Wherein R ¹ , R ^2a , R ^2b , R ³ , k, m and p are the same as above)
A preferred compound (monomer) represented by the formula (1a) is a compound in which R ^2a is a C _2-6 alkylene group, such as 9,9-bis (2-glycidyloxycarbonylethyl) fluorene, -9,9-bis (glycidyloxycarbonyl C _2-6 alkyl) fluorene such as bis (2-glycidyloxycarbonylpropyl) fluorene. A preferred compound (monomer) represented by the formula (1b) (1c) is a compound in which p = 0 and R ^2b is a C _1-6 alkylene group, for example, 9- (1-glycidyloxy Carbonyl-2-glycidyloxycarbonylethyl) fluorene, compounds wherein p = 1 and R ^2b is a C _1-6 alkylene group, for example 9- (2-glycidyloxycarbonyl-3-glycidyloxycarbonylpropyl) fluorene 9- (glycidyloxycarbonyl-glycidyloxycarbonyl C _2-6 alkyl) fluorene and the like. The epoxy compound (monomer) may be used alone or in combination of two or more.

Among these, preferable epoxy compounds (monomers) include compounds represented by the formula (1a) such as 9,9-bis (glycidyloxycarbonylalkyl) fluorenes [for example, 9,9-bis (glycidyl). Oxycarbonyl C _1-4 alkyl) fluorene] and the like.

  A preferable epoxy resin can be represented by the following formula (1c).

[Wherein A is the following (1d) or (1e)

(R ^2a and R ^2b are the same or different and each represents a linear or branched C _1-4 alkylene group which may have a substituent, and R ¹ , R ^2b , k and p are as defined above. The same), q represents 0 or an integer of 1 to 10]
Such an epoxy resin may be a monomer alone or a mixture of a monomer and a multimer (such as a dimer or a trimer). The multimer may include, for example, a dimer to a decamer (for example, a dimer to a pentamer, in particular, a dimer and a trimer). The epoxy resin of the present invention is viscous at room temperature and has a low viscosity even if the proportion of multimers such as dimers and trimers is large. On the other hand, in an epoxy resin, it is known that the hydroxyl group which exists in a repeating unit in a multimer contributes to adhesiveness. Therefore, it is excellent not only in handleability but also in fluidity and adhesion.

  The ratio of the epoxy compound (monomer) represented by the formula (1a) or (1b) to the dimer or higher multimer is the area ratio of the gel permeation chromatogram, the former / the latter = 100/0. May be about -40/60, and is generally 95 / 5-50 / 50 (for example, 90 / 10-50 / 50), preferably 85 / 15-60 / 40 (for example, 80 / 20-60 / 50). 40), especially about 85/15 to 65/35.

  The epoxy resin of the present invention may be either solid or liquid, and may be particularly liquid (viscous liquid). The viscosity at 25 ° C. of the liquid epoxy resin may be, for example, 10,000 to 150,000 mPa · s, preferably 30,000 to 120,000 mPa · s, and more preferably about 50,000 to 100,000 mPa · s.

  In addition, the epoxy equivalent of an epoxy resin is 100-3000 (for example, 125-2000 g / equivalent), for example, Preferably it is 150-1000 g / equivalent (for example, 200-800 g / equivalent), More preferably, it is about 250-750 g / equivalent. It may be.

(Method for producing epoxy resin)
Although the epoxy resin of this invention is not specifically limited, For example, it manufactures by making the compound (carboxylic acid) represented by following formula (A1) (A2) react with the compound represented by following formula (B). it can.

(In the formula, X represents a halogen atom, and R ¹ , R ^2a and R ^2b , R ³ , k, m and n are the same as described above.)
As the compound represented by the above formulas (A1) and (A2), a compound corresponding to the compound represented by the formula (1a) or (1b) can be used. As such a compound, for example, 9, 9 -Bis (carboxyalkyl) fluorenes [for example, 9,9-bis (2-carboxyethyl) fluorene, 9,9-bis (1-carboxyethyl) fluorene, 9,9-bis (2-carboxypropyl) fluorene 9 9,9-bis (2-carboxybutyl) fluorene, 9,9-bis (5-carboxypentyl) fluorene, etc., preferably 9,9-bis (carboxy C _1-6 alkyl) fluorene, preferably 9,9-bis (carboxy C _2-4 alkyl) fluorene 9,9-bis (di-carboxyalkyl) fluorenes [e.g., 9,9-bis (1,2-Jikarubokishie Le) fluorene, 9,9-bis (2,3-carboxypropyl) fluorene such as 9,9-bis (dicarboxy _{C 1-6} alkyl) fluorene], and others.

The compound represented by formula (A1) (A2) may be a commercially available product, conventional methods {e.g., the presence of a base catalyst, and fluorene, the corresponding halocarboxylic acid [i.e., X-R ^2a -(COOH) n (wherein X and R ^2a are as defined above)] may be reacted with an ester or salt, and the resulting ester or salt may be hydrolyzed. Moreover, you may prepare the compound represented by Formula (A1) (A2) using the Michael addition reaction of a fluorene and unsaturated carboxylic acid.

  In the formula (3), examples of the halogen atom X include a chlorine atom, a bromine atom, and an iodine atom, and may be a chlorine atom, in particular. A typical compound represented by the formula (3) includes epihalohydrin (such as epichlorohydrin).

  The usage-amount of the compound represented by Formula (B) can be adjusted according to the kind of catalyst, for example with respect to 1 mol of carboxyl groups of the compound represented by said Formula (A), 1 mol or more (for example, 1 to 15 mol), preferably 1.2 to 12 mol (for example, 1.5 to 10 mol), more preferably about 2 to 8 mol.

  The reaction may be performed in the presence of a base. Examples of the base include hydroxides (for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide) and hydrides (sodium hydride and hydrogenation). Inorganic such as potassium), carbonates (for example, alkali metal carbonates such as sodium carbonate, potassium carbonate, cesium carbonate), hydrogen carbonates (for example, alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate), etc. Bases; amines [eg, aliphatic amines (eg, triethylamine, tri-n-propylamine, tri-n-butylamine, triisopropylamine, diisopropylethylamine, dicyclohexylethylamine, diethylcyclohexylamine, tribenzylamine, N, N, N ', N'-tetramethylethyl Diamine, N, N, N ′, N′-tetramethylpropanediamine, 1-methylpiperidine, 1-ethylpiperidine, 1,2,2 ′, 6,6′-pentamethylpiperidine, 1-methylpyrrolidine, 1- Aliphatic tertiary amines such as ethylpyrrolidine, 4-methylmorpholine, 4-ethylmorpholine, 2,6-dimethylpiperazine), aromatic amines (for example, N, N-dimethylaniline, N, N-diethylaniline, etc.) Aromatic tertiary amines), heterocyclic amines (pyridine, lutidine, collidine, 4- (dimethylamino) pyridine, 4-pyrrolidinopyridine, imidazole, 1,5-diazabicyclo [4.3.0] nonene, 1,8-diazabicyclo [5.4.0] undecene etc.)], metal alkoxides (eg sodium methoxy , Sodium ethoxide, sodium-tert-butoxide, potassium-tert-butoxide, etc.), organometallic compounds (butyllithium, phenyllithium, isopropylmagnesium chloride, cyclohexylmagnesium bromide, phenylmagnesiumbromide, sodiumamide, lithiumdiisopropylamide, etc.), Examples include organic bases such as organic acid salts (for example, organic acid metal salts such as sodium acetate and potassium acetate).

  The usage-amount of a base can be adjusted according to the kind of catalyst, For example, 0.05 mol or more (for example, 0.1-5 mol) with respect to 1 mol of carboxyl groups of the compound represented by the said Formula (A). ), Preferably 0.2 to 3 mol (for example, 0.3 to 2 mol), more preferably about 0.4 to 1.5 mol (for example, 0.5 to 1 mol).

The reaction may be performed in the presence of a solvent (in a solvent). The solvent is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbons (for example, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane; aromatic hydrocarbons such as toluene and xylene) ), Ethers (eg, dialkyl ethers such as diethyl ether; (poly) alkylene glycol dialkyl ethers such as 1,3-dimethoxypropane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether; tetrahydrofuran, 1,4-dioxane Cyclic ethers, etc.), ketones (eg, alkanones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cycloalkanones such as cyclohexanone), esters (eg, methyl acetate, ethyl acetate, etc.), amides ( Example, if, N, N- N, such as dimethylformamide, N- di _{C 1-4} alkyl formamide; N, N- N, such as dimethylacetamide, N- di _{C 1-4} alkyl acetamide; N- methylpyrrolidone), nitriles Organic solvents (eg, acetonitrile, propionitrile, etc.), sulfoxides (eg, dimethyl sulfoxide), sulfones (eg, cyclic sulfones such as sulfolane); inorganic solvents such as water. The solvents may be used alone or in combination of two or more. The solvent may be a mixed solvent of an organic solvent and an inorganic solvent (such as water). Moreover, you may use the amine as said base as a solvent.

  The proportion of the solvent is, for example, 0.1 to 30 parts by weight (for example, 0.2 parts per 1 part by weight of the total amount of the compound represented by the formula (A) and the compound represented by the formula (B)). ˜20 parts by weight), preferably 0.3 to 15 parts by weight (eg, 0.4 to 10 parts by weight), more preferably about 0.5 to 8 parts by weight (eg, 0.7 to 5 parts by weight). There may be.

  In addition, you may perform reaction in presence of a phase transfer catalyst as needed, when using water etc. as a solvent.

Examples of the phase transfer catalyst include tetraalkylammonium salts (eg, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, and methyltridecylammonium chloride). such as _1-20 alkylammonium halide), an aralkyl trialkyl ammonium salt (e.g., such as benzyltri C _1-4 alkyl ammonium halides such as benzyl trimethylammonium chloride) include quaternary ammonium salts such as. The phase transfer catalysts may be used alone or in combination of two or more.

  The amount of the phase transfer catalyst used is, for example, 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the compound represented by the formula (A) and the compound represented by the formula (B). Preferably it may be about 0.05 to 10 parts by weight, more preferably about 0.1 to 5 parts by weight.

  The reaction may be performed at room temperature (or room temperature), under cooling, or under heating, and the reaction temperature is not particularly limited, but is, for example, 0 to 200 ° C. (for example, 20 to 180 ° C.), preferably 30. -150 degreeC (for example, 40-120 degreeC), More preferably, about 50-100 degreeC may be sufficient. The reaction time may be, for example, about 1 minute to 48 hours, preferably 3 minutes to 24 hours, and more preferably about 1 to 12 hours (for example, 3 to 10 hours). The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure.

  After completion of the reaction, the reaction mixture is separated by a conventional method such as filtration, concentration, extraction, crystallization, recrystallization and the like, or a combination of these, and a solvent, a base catalyst, an unreacted component, etc. And may be separated and purified from the reaction mixture to obtain a resin containing the epoxy compound (monomer) and / or multimer represented by the formula (1a) or (1b).

  In addition, the epoxy resin produced | generated by reaction is a compound which does not belong to the category of the compound represented by said Formula (1a) or (1b), if it is a range which does not injure the characteristic as a product [For example, said Formula ( In A1) and (A2), a compound in which some of the carboxyl groups remain (for example, n is 1 in the formula (A1), and only one carboxyl group has reacted with the compound represented by the formula (B). Compound etc.)] and the like.

[Use of epoxy resin]
The epoxy resin of the present invention (an epoxy compound represented by formula (1a) or (1b) and / or a resin containing a multimer thereof) can be used as a thermosetting resin raw material, an additive (such as a curing agent) and the like. For example, the epoxy resin of the present invention may be used as it is as an epoxy resin or as a thermosetting resin raw material such as epoxy (meth) acrylate.

(Curable composition)
The epoxy resin of the present invention may constitute an epoxy resin composition (curable composition) containing a curing agent and the like. In the epoxy resin composition, the epoxy resin (epoxy resin component) may be composed only of the epoxy resin represented by the formula (1a) or (1b), or may be combined with other epoxy resins. Other epoxy resins include glycidyl ether type epoxy resins, such as bisphenol type epoxy resins (bisphenol A type epoxy resins, bisphenol F type epoxy resins, etc.), phenol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene modified Phenol (or cresol) novolac type epoxy resin, biphenyl type epoxy resin, triphenolalkane type epoxy resin (such as triphenolmethane type epoxy resin), phenol aralkyl type epoxy resin, heterocyclic type epoxy resin (epoxy resin containing xanthene unit) ), Stilbene type epoxy resins, condensed ring aromatic hydrocarbon modified epoxy resins (1,6-bis (glycidyloxy) naphthalene, bis (2,7-bis (glycidyloxy)) ) Naphthalene) naphthalene ring-containing epoxy resins such as alkanes), glycidyl ester type epoxy resins, other epoxy resins having a fluorene skeleton {eg, 9,9-bis (glycidyloxyphenyl) fluorene, 9,9-bis (alkyl -Glycidyloxyphenyl) fluorene, 9,9-bis (aryl-glycidyloxyphenyl) fluorene, 9,9-bis (glycidyloxynaphthyl) fluorene, 9,9-bis (glycidyloxyalkoxyphenyl) fluorene, 9,9- Diglycidyl ethers of 9,9-bis (hydroxyaryl) fluorenes such as bis (glycidyloxyalkoxynaphthyl) fluorene] and the like. These other epoxy resins may be used alone or in combination of two or more.

  In addition, when using another epoxy resin, the ratio of the epoxy resin represented by the formula (1a) or (1b) with respect to the entire epoxy resin component is, for example, 50 to 99% by weight, preferably 60 to 98% by weight, More preferably, it may be about 70 to 95% by weight.

  The epoxy resin composition may contain a reactive diluent, a curing agent, a curing accelerator, and the like as necessary. Examples of the reactive diluent include monofunctional epoxy group-containing compounds (for example, alkyl glycidyl ethers such as 2-ethylhexyl glycidyl ether, alkenyl glycidyl ethers such as allyl glycidyl ether, phenyl glycidyl ether, p-t-butyl. Glycidyl ethers such as aryl glycidyl ethers such as phenyl glycidyl ether, glycidyl ethers of phenol alkylene oxide adducts, glycidyl ethers of alkylene oxide adducts corresponding to these compounds; octylene oxide, styrene oxide, 4-vinyl Alkene oxides such as cyclohexene monooxide), polyfunctional epoxy compounds [for example, diglycidyl ether, polyol polyglycidyl ether (butanedio Rudiglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether alkanediol diglycidyl ethers, trimethylolpropane di to triglycidyl ether, glycerin di to triglycidyl ether, polyglycol diglycidyl ether, polypropylene Glycol diglycidyl ether), diglycidyl aniline, cyclohexane dimethanol diglycidyl ether, alkylene diglycidyl ether, cycloalkene oxides (eg vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, etc.) Etc.]. These reactive diluents may be used alone or in combination of two or more.

  In the epoxy resin composition, the ratio of the reactive diluent is, for example, 1 to 1000 weights with respect to 100 parts by weight of the epoxy resin (when other epoxy resin is used, the total amount with the above compound, the same applies hereinafter). Part, preferably 5 to 500 parts by weight, more preferably about 10 to 200 parts by weight.

Examples of the curing agent (curing agent for epoxy resin) include amine-based curing agents [particularly, primary amines such as chain aliphatic amines (for example, chains such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine). Cycloaliphatic amines such as mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, 3,9-bis (3-aminopropyl) -2,4 , 8,10-tetraoxaspiro (5.5) undecane and other monocyclic aliphatic polyamines; bridged cyclic polyamines such as norbornanediamine), araliphatic polyamines (eg, xylylenediamine), aromatic amines (For example, metaphenylenediamine, diaminodiphenylmethane, etc.) , Polyaminoamide curing agents, acid anhydride curing agents (eg, aliphatic acid anhydrides such as dodecenyl succinic anhydride, polyadipic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, Aliphatic acid anhydrides such as methylhexahydrophthalic anhydride, methyl hymic anhydride, methylcyclohexene dicarboxylic acid anhydride; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, etc. Aromatic phenols), phenolic curing agents {eg, phenolic resins (eg, novolak resins such as phenolic novolak resins and cresol novolac resins); phenols having a fluorene skeleton [eg, 9,9-bis (hydroxyphenyl) Fluorene (eg, 9, -Bis (4-hydroxyphenyl) fluorene), 9,9-bis (alkyl-hydroxyphenyl) fluorene (eg, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis ( 9,9-bis (mono or diC _1-4 alkyl-hydroxyphenyl) fluorene) such as 4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene (eg, 9,9-bis (hydroxyphenyl) fluorene such as 9,9-bis (mono- or di-C _6-10 aryl-hydroxyphenyl) fluorene) such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene Class 9,9-bis (hydride) such as 9,9-bis (6-hydroxy-2-naphthyl) fluorene Kishinafuchiru) such fluorenes] phenol compounds such}, and the like. These curing agents may be used alone or in combination of two or more.

  In addition, the hydroxyl group equivalent of a phenol resin type hardening | curing agent may be about 80-400, for example, Preferably it is 90-350, More preferably, about 100-300 may be sufficient.

  In the curable composition, the ratio of the curing agent is such that the functional group of the curing agent is 0. 1 mole relative to 1 mol of the epoxy group of the epoxy resin (or epoxy resin component) represented by the formula (1a) or (1b). 1-5.0 mol, preferably 0.3-2.0 mol (for example, 0.5-1.5 mol), more preferably 0.7-1.2 mol (for example, 0.9-1. You may adjust the ratio of both components so that it may become 1 mol).

  The curable composition may further contain a curing accelerator. The curing accelerator can be selected according to the type of the curing agent, for example, amines [eg, tertiary amines (eg, triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylamino Methyl) phenol, 1,8-diazabicyclo (5.4.0) undecene-1), imidazoles (eg, alkylimidazoles such as 2-methylimidazole; arylimidazoles such as 2-phenylimidazole) and derivatives thereof ( For example, salts such as phenol salts, phenol novolak salts, carbonates, formates, etc.)], alkali metal or alkaline earth metal alkoxides, phosphines (such as triphenylphosphine), amide compounds (such as dimer acid polyamide), Lewis acids Complexation Products (boron trifluoride / ethylamine complex, etc.), sulfur compounds [polysulfide, mercaptan compounds (thiol compound), etc.], boron compounds (phenyldichloroborane, etc.), condensable organometallic compounds (organic titanium compounds, organoaluminum compounds, etc.) Etc. The curing accelerators may be used alone or in combination of two or more.

  The proportion (addition amount) of the curing accelerator is, for example, 0.01 to 30 parts by weight, preferably 100 parts by weight of the epoxy resin (or epoxy resin component) represented by the formula (1a) or (1b). May be about 0.05 to 20 parts by weight, more preferably about 0.1 to 10 parts by weight.

  The curable composition is not limited to thermosetting, and may be a photocurable composition containing a photopolymerization initiator (cationic polymerization initiator, photoacid generator). Examples of the photopolymerization initiator include Bronsted acid onium salts (aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, and the like). The ratio of these photopolymerization initiators may be about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin component.

  Furthermore, the curable composition may contain a non-reactive diluent (solvent). Examples of the solvent (or solvent) include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. Ethers; alkylene glycol monoalkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and propylene glycol monomethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; acetic acid Methyl, ethyl acetate, butyl acetate, methyl lactate, lactate ester Le like esters such as. These solvents may be used alone or in combination of two or more.

  The use amount (addition amount) of the solvent can be selected from the range of 0 to 500 parts by weight, for example, with respect to 100 parts by weight of the epoxy resin, for example, 10 to 400 parts by weight, preferably 20 to 300 parts by weight, and more preferably. May be about 30 to 200 parts by weight.

  If necessary, the curable composition may further contain conventional additives such as colorants, stabilizers (thermal stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents, flame retardants, Flame retardant aids may be included. You may use an additive individually or in combination of 2 or more types.

(Cured product)
The present invention also includes a cured product (or molded product) obtained by curing (or crosslinking) the curable composition. Such a cured product can be obtained by reacting (curing) the curable composition. Such a curing treatment may be performed while molding or molding (or preforming) the curable composition according to the shape of the cured product. In addition, as a shape of hardened | cured material, one-dimensional or two-dimensional hardened | cured material, such as a three-dimensional hardened | cured material, a cured film, and a hardened pattern, a point or a dot-like hardened | cured material, etc. are mentioned. Specifically, the molded body is a product having a desired shape formed from a cured product of the curable composition, a cured film formed from a cured product of the curable composition formed on a substrate ( Coating film) or the like. For example, the curable composition can be cured by pouring into a predetermined mold and heating to obtain a molded body having a desired shape.

  The curing process can be performed by heating or the like. Usually, the curing treatment is often performed at least by heating.

  In the curing treatment, the heating temperature may be, for example, about 50 to 250 ° C., preferably 70 to 220 ° C., and more preferably about 80 to 200 ° C. (for example, 100 to 190 ° C.). The heating time may be, for example, about 10 minutes to 24 hours, preferably 30 minutes to 18 hours, and more preferably about 1 to 12 hours (for example, 2 to 8 hours). The curing treatment may be performed stepwise, for example, after heat treatment at a relatively low temperature, heat treatment may be performed at a relatively high temperature (for example, about 150 to 350 ° C., preferably about 160 to 300 ° C.). .

  Moreover, when forming hardened | cured material in a film form (film form, thin film form), you may form by apply | coating the said curable composition to a board | substrate (or base | substrate). The substrate is, for example, an insulating substrate such as resin, glass or ceramic, a semiconductor substrate such as crystalline silicon or amorphous silicon, a conductor substrate such as metal, a conductor layer formed on these substrates, or a composite of these. Things.

  The coating method for forming a coating film (thin film) on the substrate is not particularly limited. For example, spin coating method, roll coating method, bar coating method, slit coating, gravure coating method, spray coating method, dipping method, screen printing. Law.

  The thickness of the coating film may be, for example, 0.01 μm to 10 mm, preferably 0.05 μm to 1 mm, more preferably about 0.1 to 100 μm, depending on the use of the cured product.

  The curable composition applied to the substrate may be subjected to a drying treatment as necessary. A drying process can be performed using a well-known method. The drying treatment may be performed, for example, under normal pressure, under pressure or under reduced pressure, or may be performed by heating with a heating means (hot plate, oven, etc.). Although the temperature at the time of warming changes also with the solvent to be used and the drying method, it is 40-200 degreeC normally, Preferably it is 50-170 degreeC, More preferably, about 60-150 degreeC may be sufficient.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  Various characteristics were measured under the following conditions.

(viscosity)
Using “TVE-22L” manufactured by Toki Sangyo Co., Ltd., it was measured twice at 25 ° C. in accordance with JIS K 5600-2-3, and the average value was calculated.

(Elastic modulus)
An average value was calculated by measuring 5 times at 23 ° C. in accordance with JIS K 7171 using “5582 type universal material testing machine” manufactured by Instron.

(Glass transition temperature (Tg))
Using a test apparatus “TMA 8310” (manufactured by Rigaku Corporation), the measurement was performed in a nitrogen atmosphere at a heating rate of 5 ° C./min in accordance with JIS K7197.

Example 1
In a 1 L vessel equipped with a stirrer and a condenser, 9,9-di (2-carboxyethyl) fluorene 62 g (0.20 mol), epichlorohydrin 148 g (1.61 mol), ion-exchanged water 200 g, Then, 3.2 g (0.010 mol) of tetrabutylammonium bromide was charged and stirred at 60 ° C. for 3 hours. After stirring, 148 g of epichlorohydrin and 96 g (0.24 mol) of a 10% aqueous sodium hydroxide solution were further added, and the mixture was stirred at 60 ° C. for 6 hours. After completion of the reaction, the obtained reaction solution was distilled off under reduced pressure using an evaporator. After distilling off the solvent, 200 g of methyl isobutyl ketone and 200 g of distilled water were added and washed with water at 60 ° C. The obtained organic layer was evaporated under reduced pressure with an evaporator and dried with a drier to obtain a viscous liquid.

  And when the obtained liquid was analyzed, it confirmed that the epoxy compound [9,9-di (2-glycidyl oxycarbonylethyl) fluorene] represented by a following formula was included.

  In addition, when it analyzed by the gel permeation chromatography (GPC) using THF as a solvent using the measuring device (HLC-8320GPC (made by Tosoh Corporation)), the monomer represented by the said formula was 70 area%. The dimer was 18 area%, and the other multimer was 12 area%.

  The viscosity of the obtained liquid at 25 ° C. was 85200 mPa · s.

Nuclear magnetic resonance (NMR) spectrum: Measured in deuterated chloroform using AV-300 (manufactured by Bruker).
¹ H-NMR (CDCl ₃ , 300 MHz) δ (ppm): 1.59 (t, J = 8.2 Hz, 4H), 2.41 (t, J = 8.2 Hz, 4H), 2.49 (dd , J = 2.6, 4.7 Hz, 2H), 2.73 (t, J = 4.7 Hz, 2H), 3.01 (m, 2H), 3.68 (dd, J = 6.3) 12.3 Hz, 2H), 4.16 (dd, J = 3.1, 12.3 Hz, 2H), 7.30-7.38 (m, 6H, Ar), 7.68 (d, J = 7) .6Hz, 2H, Ar)
¹³ C-NMR (CDCl ₃ , 75 MHz) δ (ppm): 28.7, 34.4, 44.5, 49.1, 53.4, 64.7, 120.0, 122.9, 127.6 , 127.7, 141.2, 147.2, 173.0
The refractive index was 1.547 as measured by using DR-M2 / 1410 (manufactured by Atago Co., Ltd.) at a temperature of 25 ° C. and 589 nm.

(Example 2)
The liquid (epoxy resin) obtained in Example 1 and a phenol novolac resin (manufactured by Gunei Chemical Industry Co., Ltd., trade name “PSM-4261”) as a curing agent are weighed in a predetermined amount, and a 100 ° C. two roll mill. Kneaded. The kneaded product was transferred to a beaker and heated again to 100 ° C., and a predetermined amount of triphenylphosphine (TPP) was added to prepare a cast cured plate to obtain a cured product.

  It was 4030 MPa when the bending elastic modulus in 25 degreeC was measured about the obtained hardened | cured material. Moreover, the glass transition temperature of the obtained hardened | cured material was 89 degreeC.

(Comparative Example 1)
In Example 1, except that 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd.) was used instead of 9,9-di (2-carboxyethyl) fluorene. In the same manner as in Example 1, a white powder was obtained and confirmed to be an epoxy resin represented by the following formula.

  The obtained epoxy resin was solid as described above, and the viscosity (melt viscosity) at 150 ° C. was 282 mPa · s.

(Comparative Example 2)
In Example 2, instead of the epoxy resin obtained in Example 1, a cured product was obtained in the same manner as in Example 2 except that the epoxy resin obtained in Comparative Example 1 was used.

  The obtained cured product had a flexural modulus at 25 ° C. of 3245 MPa, which was found to be considerably lower than when the epoxy resin of Example 1 was used.

(Comparative Example 3)
In Example 1, instead of 9,9-di (2-carboxyethyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (produced by Osaka Gas Chemical Co., Ltd.) was used. Except for the above, a white powder was obtained in the same manner as in Example 1 and confirmed to be an epoxy resin represented by the following formula.

  The obtained epoxy resin was solid as described above, and the viscosity at 185 ° C. (melt viscosity) was 109 mPa · s.

(Comparative Example 4)
In Example 2, instead of the epoxy resin obtained in Example 1, a cured product was obtained in the same manner as in Example 2 except that the epoxy resin obtained in Comparative Example 3 was used.

  The obtained cured product had a flexural modulus at 25 ° C. of 3688 MPa, which was larger than that obtained when the epoxy resin of Comparative Example 1 was used, but still remained as compared with the case where the epoxy resin of Example 1 was used. I found it low.

(Comparative Example 5)
In Example 1, instead of 9,9-di (2-carboxyethyl) fluorene, 9,9-bis (6-hydroxy-2-naphthyl) fluorene (according to Example 1 of JP 2007-99741 A) The white powder was obtained in the same manner as in Example 1 except that it was used, and it was confirmed that it was an epoxy resin represented by the following formula.

  The obtained epoxy resin was solid as described above, and the viscosity at 180 ° C. (melt viscosity) was 3357 mPa · s, which was very high.

(Comparative Example 6)
In Example 2, instead of the epoxy resin obtained in Example 1, a cured product was obtained in the same manner as in Example 2 except that the epoxy resin obtained in Comparative Example 5 was used.

  The obtained cured product had a flexural modulus at 25 ° C. of 3660 MPa, which was larger than that in the case of using the epoxy resin of Comparative Example 1, but still in comparison with the case of using the epoxy resin of Example 1. I found it low.

  The epoxy resin (or curable composition or cured product) of the present invention is useful as, for example, an insulating material between electronic component layers, a solder resist for printed circuit boards, a resist material such as a coverlay, a color filter, Ink (printing ink, etc.), sealant (semiconductor sealant, etc.), paint, coating agent, adhesive, pressure-sensitive adhesive, underfill, antistatic agent, filler, conductive member or conductive material, laminated material, heat sensitive material (Such as thermal paper materials), carbon materials, insulating materials, foams, pressure sensitive materials, optical materials (transparent materials) [eg lenses (reflow lenses, pickup lenses, micro lenses, etc.), polarizing films, antireflection films, Film for touch panel, film for flexible substrate, film for display, film for fuel cell, optical fiber, optical waveguide, hologram ] It is useful as any material, such as (electric and electronic materials, optical materials). In particular, since it has low viscosity, high fluidity, and excellent adhesion, it is suitable for applications that cannot be heated excessively and that requires processing at low temperatures, such as a sealing agent for electronic components such as semiconductors.

Claims (8)

An epoxy resin containing a monomer of an ester type epoxy compound having a fluorene skeleton and / or a multimer thereof, wherein the monomer is represented by the following formula (1a) or (1b).

Wherein R ¹ is the same or different substituent, k is an integer of 0 to 4, R ^2a is the same or different divalent or trivalent hydrocarbon group, R ^2b is a divalent hydrocarbon group, R ³ represents the same or different substituent, m represents an integer of 0 to 3, n represents 1 or 2, and p represents an integer of 0 to 4. In formula (1a) or (1b), R ^2a may be a linear or branched alkylene group or alkanetriyl group which may have a substituent, and R ^2b may have a substituent. The epoxy resin according to claim 1, which is a good linear or branched alkylene group. In formula (1a) or (1b), n is 1, and R ^2a may have a substituent, a linear or branched C _1-6 alkylene group or a C _1-6 alkanetriyl group The epoxy resin according to claim 1, wherein R ^2b is a linear or branched C _1-6 alkylene group which may have a substituent, and m is 0. The following formula (1c)

[Wherein A is the following (1d) or (1e)

(R ^2a and R ^2b are the same or different and each represents a linear or branched C _1-4 alkylene group which may have a substituent, and R ¹ , R ^2b , k and p are as defined above. The same), q represents 0 or an integer of 1 to 10]
The epoxy resin in any one of Claims 1-3 represented by these.   The monomer and the dimer or higher multimer are contained in a ratio of the former / the latter = 100/0 to 40/60 in the area ratio of the gel permeation chromatogram. Epoxy resin.   A curable composition comprising the epoxy resin according to claim 1 and a curing agent.   The curable composition of Claim 6 in which a hardening | curing agent contains a phenol type hardening | curing agent.   Hardened | cured material which the curable composition of Claim 6 or 7 hardened | cured.