JP2015157936A - Epoxy compound having fluorene skeleton and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorene skeleton-containing epoxy compound capable of achieving both flexibility and water resistance, and a method of producing the same.SOLUTION: The fluorene skeleton-containing epoxy compound is represented by the following formula. (In the formula, ring Z is an arene ring; Rrepresents a linear alkylene group; Rrepresents a branched chain alkylene group; Rrepresents a hydrogen atom or a methyl group; Rand Reach represent a substituent such as a hydrocarbon group; k is an integer of 0-4; m1 and m2 are each an integer of 1-5; the average value of m1+m2 is 2-10; n1 and n2 are each an integer of 1-10; the average value of n1+n2 is 2-20; p is 0 or an integer of 1 or more; and q is an integer of 1 or more.)

Description

  The present invention relates to a novel epoxy compound having a 9,9-bis (aryl) fluorene skeleton and having both flexibility and water resistance in addition to characteristics such as high heat resistance derived from the fluorene skeleton and a method for producing the same. .

  Epoxy resins react with various curing agents to form cured products with excellent impact resistance, chemical resistance, water resistance, heat resistance, electrical properties, etc., so adhesives, paints, casting materials, moldings It is used in a wide range of fields such as materials, laminates, and electronic materials.

  As the epoxy resin, a bisphenol A type epoxy resin is known and is most utilized industrially. However, the viscosity is extremely high and the handling property is inferior.

  Furthermore, a resin using a compound having a 9,9-bisphenylfluorene skeleton such as bisphenoxyethanol fluorene (BPEF) having high heat resistance as compared with a bisphenol A type resin as an epoxy resin raw material is also used. For example, Japanese Patent No. 3659532 (Patent Document 1) discloses an epoxy resin represented by the following formula.

(In the formula, n is an average value and represents a positive number greater than 0 and 20 or less, R independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and G represents a glycidyl group. .)

  In the examples of this document, an epoxy resin in which R is a hydrogen atom and the average value of n is 2.6 or 4.8 in the above formula is described. However, since it has a plurality of oxyethylene groups, the water resistance of the epoxy resin is low.

  JP-A-2009-155256 (Patent Document 2) discloses an epoxy resin represented by the following formula.

(In the formula, ring Z represents a condensed polycyclic aromatic hydrocarbon ring, R ¹ represents a cyano group, R ² represents an alkylene group, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrocarbon. And k is an integer of 0 to 4, m is an integer of 1 or more, n is 0 or an integer of 1 or more, and p is an integer of 1 or more.)

  In the examples of this document, 9,9-bis [6- (2-glycidyloxypropoxy) -2-naphthyl] fluorene (A) and 9,9-bis [6- (2-glycidyloxyethoxy) -2- Naphthyl] fluorene (B) is described. Since the former fluorene skeleton-containing compound (A) has an oxyethylene group, the water resistance is low, and the latter fluorene skeleton-containing compound (B) has an oxypropylene group and therefore has low flexibility.

  Thus, the epoxy resin cannot achieve both flexibility and water resistance. However, in order to use an epoxy resin as an electronic material such as a semiconductor encapsulant or a printed circuit board material encapsulant or a conductive adhesive such as a conductive paste, both flexibility and water absorption resistance are compatible. Desired.

  Japanese Unexamined Patent Publication No. 2013-203660 (Patent Document 3) discloses a fluorene skeleton-containing compound represented by the following formula.

(Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ⁴ are non-reactive substituents, R ² and R ³ are different alkylene groups, and m 1 and m 2 are the same or different and are 0 or An integer of 1 or more, n1 and n2 are the same or different and an integer of 1 or more, p is an integer of 0 to 4, q1 and q2 are the same or different of an integer of 1 or more, and r is 0 or an integer of 1 or more, When m1 and m2 are 0, R ³ represents an alkylene group having 4 or more carbon atoms, and when m1 and m2 are integers of 1 or more, R ³ has 4 or more carbon atoms having more carbon atoms than R ² . Represents an alkylene group.)
This document, oxyalkylene group (e.g., oxy- (C _2-3) alkylene group) and, the oxyalkylene oxyalkylene group of more 4 or more carbon atoms in the number of carbon atoms than the group (e.g., oxy-C _4-16 alkylene group) It is described that flexibility and water resistance can be imparted by combining with. In the examples, 9,9-bis [4- [2- (6-hydroxyhexyloxy) ethoxy] phenyl] fluorene is described. However, the properties of the compound are not specifically described. Moreover, it is difficult to adjust flexibility, and flexibility and water resistance cannot be greatly improved.
Japanese Patent No. 3659532 (Claims and Examples) JP 2009-155256 A (Claims, Examples) JP2013-203660A (Claims, [0019] [0022] [0023], Examples)

  Accordingly, an object of the present invention is to provide a novel fluorene skeleton-containing epoxy compound having both flexibility and water resistance in addition to excellent properties such as high heat resistance and a method for producing the same.

  Another object of the present invention is to provide a novel fluorene skeleton-containing epoxy compound having a low viscosity and excellent handling properties, a curable composition containing this epoxy compound, and a cured product thereof.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that an epoxy compound having a 9,9-bis (aryl) fluorene skeleton (for example, 9,9-bis (phenyl) fluorene skeleton, etc.) An epoxy compound that can achieve both flexibility and water resistance by combining an oxy linear alkylene group (eg, oxyethylene group) and an oxy branched alkylene group (eg, oxypropylene group) as a group Was found and the present invention was completed.

  That is, the epoxy compound of the present invention is represented by the following formula (1).

(In the formula, ring Z is an arene ring, R ¹ represents a linear alkylene group, R ² represents a branched alkylene group, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a halogen atom, Hydrogen group, hydroxyl group, alkoxy group, cycloalkyloxy group, aryloxy group, aralkyloxy group, mercapto group, alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, acyl group, carboxyl group, alkoxycarbonyl group, nitro A group, a cyano group or a substituted amino group, R ⁵ represents a hydrocarbon group, a cyano group or a halogen atom, k is an integer of 0 to 4, m1 and m2 are each an integer of 1 to 5, and an average value of m1 + m2 is 2 to 10, n1 and n2 are each an integer of 1 to 10, n1 + n2 is an average value of 2 to 20, p is an integer of 0 or 1 or more, q is 1 or less Of an integer.)

Ring Z may be a benzene ring, naphthalene ring or biphenyl ring, R ¹ is a linear C _2-6 alkylene group (eg, a linear C _2-3 alkylene group), and R ² is a branched C ² _3-6 alkylene group (for example, branched _C3-4 alkyl group) may be sufficient, and q may be an integer of 1-3 (for example, 1). Moreover, 2-4 may be sufficient as the average value of m1 + m2, and 8-15 may be sufficient as the average value of n1 + n2.

Particularly, in the formula (1), ring Z is a benzene ring or a naphthalene ring, ^{R 1} is an ethylene group, ^{R 2} is a propylene group, average of m1 + m2 is 2, n1 + average value of n2 is 9 to 12, ^{R 3} is hydrogen Atoms, k and p may be 0 and q may be 1.

  The epoxy compound may be a monomer or a multimer.

  The epoxy compound of the formula (1) can be prepared by reacting a compound represented by the following formula (2) with a compound represented by the following formula (3).

(In the formula, X represents a halogen atom, and rings Z, R ¹ , R ² , R ⁴ , R ⁵ , m1, m2, n1, n2, k, p, and q are the same as above.)

  The present invention includes a curable composition containing the epoxy compound of formula (1) and a curing agent, and a cured product obtained by curing the curable composition.

  In this specification, an epoxy compound is used synonymously with an epoxy resin.

  The fluorene skeleton-containing epoxy compound of the present invention is constituted by combining an oxy linear alkylene group (for example, oxyethylene group) and an oxy branched chain alkylene group (for example, oxypropylene group) as the oxyalkylene group. Because of this, it is excellent in flexibility and water resistance. That is, the epoxy compound of the present invention can achieve both flexibility and water resistance in addition to high heat resistance derived from a fluorene skeleton. Furthermore, even if the molecular weight (epoxy equivalent) is large, the viscosity is low and the handling property is excellent.

  Such an epoxy compound of the present invention is compatible with high heat resistance, flexibility and water resistance, and therefore can be used for various applications such as a sealant and an adhesive.

  The fluorene skeleton-containing epoxy compound of the present invention is represented by the following formula (1).

(In the formula, ring Z is an arene ring, R ¹ represents a linear alkylene group, R ² represents a branched alkylene group, R ³ represents a hydrogen atom or a methyl group, and R ⁴ and R ⁵ are substituted. K represents an integer of 0 to 4, m1 and m2 each represent an integer of 1 to 5, m1 + m2 has an average value of 2 to 10, n1 and n2 each have an integer of 1 to 10, and n1 + n2 has an average value of 2 to 2. 20, p is 0 or an integer of 1 or more, and q is an integer of 1 or more.)

In the above formula (1), the arene ring represented by the ring Z includes monocyclic hydrocarbon rings such as benzene rings and condensed polycyclic aromatic hydrocarbon rings [condensed bicyclic hydrocarbon rings (for example, naphthalene C _8-20 condensed bicyclic hydrocarbons such as rings and indene rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic hydrocarbon rings (eg, anthracene ring, phenanthrene ring, etc.), etc. Condensed bi- to tetracyclic hydrocarbon rings, etc.], ring-assembled arene rings [biarene rings (for example, bi-C _6-12 arene rings such as biphenyl rings and binaphthyl rings, preferably bi-C _6-10 arene rings, particularly biphenyl) Ring, etc.), tellarene ring (eg, Ter C _6-12 arene ring such as terphenyl ring) and the like]. In particular, a C _6-10 arene ring (such as a benzene ring and a naphthalene ring) and a bi C _6-10 arene ring (such as a biphenyl ring) are preferable. In addition, the two rings Z substituted at the 9-position of fluorene may be the same or different rings, and usually the same ring is preferable.

  In addition, the substitution position of the ring Z substituted at the 9th position of fluorene is not particularly limited. When the ring Z is a naphthalene ring, for example, a 1-naphthyl group, a 2-naphthyl group, etc. with respect to the 9th position of fluorene. It may be substituted because of the relationship. Moreover, when the ring Z is a ring assembly arene ring, for example, a biphenyl ring, the 3-position or 4-position of the biphenyl ring may be bonded to the 9-position of fluorene.

In the formula (1), the linear alkylene group R ¹ constituting the oxy linear alkylene group (OR ¹ ) is, for example, a straight chain such as an ethylene group, a trimethylene group, a tetramethylene group, or a pentamethylene group. such as linear _{C 2-6} alkylene group. examples of preferably linear _{C 2-4} alkylene group, more preferably a linear _{C 2-3} alkylene groups, particularly an ethylene group. In addition, when m1 and m2 are 2 or more, R ¹ may be composed of the same or different types of alkylene groups, and is usually often the same.

In the formula (1), the numbers (number of added moles) m1 and m2 of the oxy linear alkylene group (OR ¹ ) are the same or different and can each be selected from an integer of 1 to 5, for example, an integer of 1 to 4 , Preferably an integer of 1 to 3, more preferably an integer of 1 or 2 (particularly 1). Moreover, the average value of m1 + m2 can be selected from the range of about 2-10, for example, 2-8, Preferably it is 2-6, More preferably, it is 2-4 (for example, 2-3), 2 may be sufficient especially. .

In the formula (1), examples of the branched alkylene group R ² constituting the oxy branched alkylene group (OR ² ) include a propylene group, 1,2-butanediyl group, 1,3-butanediyl group, 2-methyl Examples include a branched C _3-6 alkylene group such as a -1,2-propanediyl group and a 2-methyl-1,3-propanediyl group, preferably a branched C _3-4 alkylene group, particularly a propylene group. . Note that when n1 and n2 is 2 or more, R ² may be composed of the same or different types of alkylene groups, typically, it is often the same. R ² may be a branched alkylene group having more carbon atoms than R ¹ .

In the formula (1), the number of oxy-branched alkylene groups (OR ² ) (number of added moles) n1 and n2 are the same or different and can each be selected from an integer of 1 to 10, for example, an integer of 1 to 9 , Preferably an integer of 2 to 8, more preferably an integer of 3 to 7, particularly an integer of 4 to 6. Moreover, the average value of n1 + n2 can be selected from the range of about 2 to 20, for example, 4 to 18 (for example, 6 to 18), preferably 7 to 16 (for example, 7.5 to 16), and more preferably 8 to It may be about 15 (for example, 8.5 to 14), particularly about 9 to 12 (for example, 10 to 12).

  The ratio of the average value of n1 + n2 and the average value of m1 + m2 is the former / the latter = 1 / 1-20 / 1, preferably 2 / 1-15 / 1 (eg 3 / 1-10 / 1), more preferably It may be about 3.5 / 1 to 8/1 (for example, 4/1 to 7/1), particularly about 4.5 / 1 to 6/1 (for example, 5/1 to 6/1).

  Surprisingly, the fluorene skeleton-containing epoxy compound of the present invention has a configuration that resembles a block structure as the average value of n1 + n2 increases with respect to the average value of m1 + m2, or the flexibility is unexpectedly improved. In addition, the higher the average value of n1 + n2, the higher the hydrophobicity due to the oxy-branched alkylene group, which may improve the water resistance. For example, the branched alkylene group may reduce water penetration space or improve water resistance. In addition, the water resistance can be improved even if the epoxy equivalent is large and the number of crosslinking points in the cured product is small. That is, as the composition ratio of the oxy branched alkylene group to the oxy linear alkylene group increases, both the flexibility and water resistance characteristics can be improved, and an epoxy compound (or epoxy resin) excellent in both characteristics is obtained. It is done. In particular, when the average value of n1 + n2 is greater than or equal to a predetermined value with respect to the average value of m1 + m2, the flexibility can be remarkably improved (or markedly), and even if the average value of n1 + n2 increases, a branched alkylene group Thus, hydrophobicity (or water resistance) can be increased. That is, when the number of oxy branched alkylene groups is adjusted to a predetermined number (predetermined value) or more with respect to the number of oxy linear alkylene groups, both water resistance and flexibility can be achieved at a higher level. Furthermore, even if the molecular weight is large, the viscosity is low and handling properties can be improved. In such an epoxy compound, in the formula (1), for example, the average value of m1 + m2 is 2 to 4 (particularly 2), and the average value of n1 + n2 is 7 (for example, 7.5) or more, for example, 7 to 20 ( For example, 7.5 to 20), preferably 8 to 18 (for example, 8.5 to 16), more preferably 9 to 15 (for example, 9.5 to 14), particularly 9 to 12 (for example, 9 to 11). ) In many cases. In addition, m1 and m2 are the same or different, 1 or 2 (especially 1), respectively, n1 and n2 are the same or different, respectively, for example, an integer of 3 to 10 (for example, an integer of 3 to 9), Preferably, it may be an integer of 4 to 8 (for example, an integer of 4 to 7), more preferably an integer of 4 to 6 (for example, 5 or 6).

  In the formula (1), the substitution number q may be the same or different and may be an integer of 1 or more, and may be, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1. . The number of substitutions q may be the same or different in each ring Z, and is usually the same in many cases. In addition, the substituent having an oxyalkylene group can be substituted at an appropriate position of the ring Z. For example, when the ring Z is a benzene ring, the 2-, 3-, 4-position of the phenyl group (particularly, 3 -Position and / or 4-position) in many cases, and when the ring Z is a naphthalene ring, it is substituted at the 5- to 8-position (for example, 5-position, 6-position, etc.) of the naphthyl group. May be. For example, when the group corresponding to the ring Z is a 2-naphthyl group (β-naphthyl group), the position of the substituent having the oxyalkylene group is often the 6-position of the naphthyl group, and the 1-naphthyl group ( α-naphthyl group), the position of the substituent having the oxyalkylene group is often the 5-position or 8-position (particularly the 5-position) of the naphthyl group. Further, when the ring Z is a biphenyl ring, when the 4-position of the biphenyl ring Z is bonded to the 9-position of fluorene, the substitution position of the substituent having an oxyalkylene group is the 2-position, 2′- In many cases, it is substituted at the 3'-position, 4'-position (particularly the 2-position).

In the formula (1), the group R ⁴ includes a halogen atom, a hydrocarbon group, a hydroxyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, a mercapto group, an alkylthio group, a cycloalkylthio group, an arylthio group. Group, aralkylthio group, acyl group, carboxyl group, alkoxycarbonyl group, nitro group, cyano group or substituted amino group.

Examples of the halogen atom represented by the group R ⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the hydrocarbon group, an alkyl group (a linear or branched C _1-10 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, or a t-butyl group) Cycloalkyl group (C _5-10 cycloalkyl group such as cyclopentyl group and cyclohexyl group), aryl group [phenyl group, alkylphenyl group (methylphenyl (tolyl) group, dimethylphenyl (xylyl) group, etc.), C _6-12 aryl groups such as naphthyl group and biphenyl group] and aralkyl groups (C _6-10 aryl-C _1-4 alkyl group such as benzyl group and phenethyl group) can be exemplified. The hydrocarbon group is an alkyl group (a linear or branched C _1-6 alkyl group such as a methyl group, preferably a linear or branched C _1-4 alkyl group), an aryl group (such as a phenyl group). In many cases, it is a C _6-10 aryl group. Incidentally, when the group R ⁴ is an aryl group, a group R ⁴ are each, together with the ring Z, it may form the ring assembly arene ring.

Examples of the alkoxy group represented by the group R ⁴ include a linear or branched C _1-10 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. Examples of the cycloalkyloxy group include a C _5-10 cycloalkyloxy group such as a cyclohexyloxy group, and examples of the aryloxy group (C _6-10 aryloxy group such as a phenoxy group) include aralkyloxy. Examples thereof include a group (for example, a C _6-10 aryl-C _1-4 alkyloxy group such as a benzyloxy group).

Examples of the alkylthio group represented by the group R ⁴ include a C _1-10 alkylthio group such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, a t-butylthio group, and the like. to be C _5-10 illustrate and cycloalkylthio groups such as cyclohexylthio group, arylthio group, can be exemplified the C _6-10 arylthio group such as thiophenoxy group, the aralkyl thio group, such as benzylthio group C _6- Examples thereof include ₁₀ aryl-C _1-4 alkylthio.

Examples of the acyl group represented by the group R ⁴ include a C _1-6 acyl group (alkylcarbonyl group) such as an acetyl group, and the alkoxycarbonyl group includes a C _1-4 alkoxy-carbonyl such as a methoxycarbonyl group. Examples include groups.

The substituted amino group, a dialkylamino group (e.g., di-C _1-4 alkylamino group such as dimethylamino group), dialkyl carbonyl amino group (e.g., di-C _1-4 alkyl, such as di-acetylamino group - carbonylamino group Etc.).

Among these groups R ⁴ , halogen atom, hydrocarbon group, alkoxy group, cycloalkyloxy group, aryloxy group, aralkyloxy group, acyl group, carboxyl group, alkoxycarbonyl group, nitro group, cyano group, substituted amino group Is preferred. In particular, a halogen atom, an alkyl group (a linear or branched C _1-6 alkyl group such as a methyl group), an aryl group (C _6-10 aryl group such as a phenyl group), an alkoxy group (such as a methoxy group) In particular, an alkyl group (particularly a methyl group) is preferable, such as a linear or branched C _1-4 alkoxy group.

The substitution number p is 0 or an integer of 1 or more. The preferred substitution number p may be 0 to 8, preferably 0 to 6 (for example, 0 to 5), more preferably 0 to 4, particularly 0 to 2 (for example, 0 to 1), particularly 0. In the same ring Z, when p is plural (two or more), the types of the groups R ⁴ may be the same or different from each other, and in two rings Z, the number of substitution p is the same or different from each other. May be. For example, when p is 1, the ring Z may be a benzene ring, a naphthalene ring or a biphenyl ring, and R ⁴ may be a methyl group.

In the formula (1), examples of the group R ⁵ include a hydrocarbon group, a cyano group, and a halogen atom. Examples of the hydrocarbon group represented by the group R ⁵ include an alkyl group (C _1-10 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, and t-butyl group). And an aryl group (C _6-10 aryl group such as phenyl group).

Examples of the halogen atom represented by the group R ⁵ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of these groups R ⁵ , a C _1-4 alkyl group such as a methyl group is preferable. In addition, when k is plural (2 or more), the groups R ⁵ may be different from each other or the same. Further, the groups R ⁵ substituted on the two benzene rings constituting the fluorene skeleton may be the same or different. The substitution position of the group R ⁵ for a benzene ring constituting the fluorene is not particularly limited, for example, be a 2-position or 7-position of the fluorene ring. The substitution number k is 0 to 4, preferably 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

  Since the epoxy compound (or epoxy resin) of the present invention combines an oxy linear alkylene group (for example, oxyethylene group) and an oxy branched chain alkylene group (for example, oxypropylene group), it is flexible. And excellent water resistance. The epoxy equivalent of the epoxy compound may be, for example, about 300 to 1500 g / eq, preferably 350 to 1200 g / eq, more preferably about 400 to 1000 g / eq (for example, 400 to 800 g / eq).

  Moreover, the viscosity (25 degreeC) of the said epoxy compound may be 1000-35000 mPa * s, for example, Preferably it is 1500-20000 mPa * s, More preferably, about 2000-10000 Pa * s may be sufficient. Particularly, an epoxy compound having a large average value of n1 + n2 often has a low viscosity even if the epoxy equivalent is large, and the viscosity (25 ° C.) of the epoxy compound is, for example, 500 to 5000 mPa · s, preferably 800 to It can also be set to 4000 mPa · s, more preferably about 1200 to 3000 mPa · s. The viscosity can be measured with a TV-22 viscometer according to JIS K7117-2.

  The epoxy compound may be a monomer of the compound represented by the formula (1) or a multimer (such as a dimer or a trimer). For example, in the formula (1), an epoxy compound in which q is 1 can be represented by the following formula (1A).

(In the formula, A is the following formula:

Wherein r represents 0 or an integer of 1 or more, and the rings Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , m1, m2, n1, n2, k, p are the same as above. )

  The epoxy compound may be a mixture of a monomer of the compound represented by formula (1) and the multimer. The ratio of such multimers is, for example, 0 to 20 parts by weight, preferably 0 to 10 parts by weight with respect to 100 parts by weight of the total amount of the monomer and multimer of the compound represented by the formula (1). (For example, 0.1 to 8 parts by weight), and more preferably about 0 to 5 parts by weight (for example, 0.2 to 3 parts by weight).

A representative compound in the formula (1) is 9,9-bis (glycidyl- (mono or poly) oxy branched alkoxy- (mono or poly) linear oxyalkoxyaryl) fluorene, such as 9,9. - bis (glycidyl - (mono or poly) oxy branched chain _{C 3-6} alkoxy - (mono or poly) linear _{C 2-6} alkyloxy alkoxy _{C 6-12} aryl) fluorene, and more preferably 9,9-bis (Glycidyl- (mono or poly) oxy branched C _3-4 alkoxy- (mono or poly) linear C _2-4 oxyalkoxy C _6-12 aryl) fluorene and the like.

When the ring Z is a benzene ring, the substituent having an oxyalkylene group is often substituted at the 3-position and / or 4-position of the phenyl group, and when the ring Z is a naphthalene ring. Is often substituted at the 5-position and / or the 6-position. Specific examples of the compound include compounds shown in Table 1 and Table 2 below. The compounds shown in Table 1 are compounds in which R ³ is a hydrogen atom or a methyl group, k = 0, p = 0, q = 1, m1, m2 = 1 or 2, n1, n2 = 4-10. In the compounds shown in Table 2, R ³ is a hydrogen atom or a methyl group, R ⁴ is a methyl group, k = 0, p = 1, q = 1, m1, m2 = 1 or 2, n1, n2 = 4 to 8 It is a compound which is an integer. In Tables 1 and 2, the substitution position of the group X indicates the substitution position of the substituent having an oxyalkylene group (referred to as group X) with respect to the ring Z, and m1 + m2 and n1 + n2 each represent an average value. In Table 2, the substitution position of R ^{4 represents} the substitution position of R ⁴ with respect to ring Z.

The fluorene skeleton-containing compound of the present invention can be produced by reacting a compound represented by the following formula (2) with a compound represented by the following formula (3) (such as epichlorohydrin). In addition, the compound represented by the formula (2) includes a compound represented by the following formula (4), a compound represented by the following formula (5) (such as alkylene oxide substituted by R ^2a ) and / or the following: It can be obtained by reacting a compound represented by the formula (6) (halo-branched alkanol).

(Wherein R ^2a represents an alkyl group substituted on the carbon atom of ring E, and ring E and R ^2a form a branched alkylene group represented by R ² in formula (1). R ¹ , R ² , R ³ , R ⁴ , R ⁵ , m1, m2, n1, n2, k, p, q are the same as above.)

  Examples of the compound represented by the formula (2) include a compound corresponding to the formula (1). Examples of the compound represented by the formula (3) include epihalohydrins (for example, epichlorohydrin, epibromohydrin, etc.), particularly epichlorohydrin.

  In the reaction of the compound represented by the formula (2) and the compound represented by the formula (3), the ratio of the latter is 1.5 to 30 mol, preferably 2 to 1 mol of the former hydroxyl group. The amount may be about 25 mol, more preferably 2.5 to 20 mol, particularly about 3 to 15 mol (for example, 3.5 to 10 mol).

In the reaction of the compound represented by the formula (2) and the compound represented by the formula (3), a catalyst may be used. Examples of the catalyst include quaternary ammonium salts (tetra C _1-20 alkyl ammonium halides such as tetramethyl ammonium chloride and tetramethyl ammonium bromide, benzyl tri C _1-4 alkyl ammonium halides such as benzyl trimethyl ammonium chloride), trimethylamine borane and the like. Examples include tri- _C1-4 alkylamine borane, crown ether, phosphonium salt, pyridinium salt and the like. The catalysts may be used alone or in combination of two or more.

  The ratio of the catalyst is not particularly limited, but is, for example, 0.001 to 1 mol (for example, 0.005 to 0.5 mol), preferably 0 with respect to 1 mol of the compound represented by the formula (2). It may be about 0.01 to 0.2 mol, more preferably about 0.05 to 0.1 mol.

  The reaction may be performed in the presence of a base in order to trap hydrogen halide generated by the reaction. Examples of the base include metal hydroxides (alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide) and metal carbonates (sodium carbonate and hydrogen carbonate). Inorganic bases such as alkali metal carbonates or alkaline earth metal salts such as sodium), amines (trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, heterocyclic tertiary such as pyridine) And organic bases such as amine). The bases may be used alone or in combination of two or more.

  Although the ratio of a base is not specifically limited, For example, 0.01-20 mol (for example, 0.05-10 mol) with respect to 1 mol of hydroxyl groups of the compound represented by the said Formula (2), Preferably it may be about 1 to 5 mol, more preferably about 1.5 to 3 mol.

  The reaction may be performed in a solvent inert to the reaction. As the solvent, an aprotic solvent can be used. For example, hydrocarbons (aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene), halogenated hydrocarbons (chlorinated) Methylene, chloroform, carbon tetrachloride, etc.), esters (ethyl acetate, etc.), ethers (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran), ketones (acetone, methyl ethyl ketone, etc.), amides (dimethyl) Formamide, dimethylacetamide, etc.) and sulfoxides (dimethylsulfoxide, etc.). The solvents may be used alone or in combination of two or more.

  The reaction temperature and reaction time can be appropriately selected according to the type of raw material used. The reaction temperature may be, for example, 30 to 120 ° C, preferably 35 to 100 ° C, more preferably about 40 to 70 ° C. The reaction time may be, for example, 30 minutes to 48 hours, usually 1 to 36 hours, preferably about 2 to 24 hours.

  The reaction may be performed while refluxing. The reaction can be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.) with stirring, and may be performed under normal pressure, increased pressure, or reduced pressure.

  In addition, the produced | generated compound (compound represented by said Formula (1)) combined separation means, such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, etc., and these by the usual method. Separation and purification may be performed by separation means.

  The compound obtained by the reaction may be a single compound of the compound represented by the formula (1), or may be a compound containing a plurality of compounds in which m1 and m2 and / or n1 and n2 are different. Good.

  Examples of the compound represented by the formula (4) include compounds corresponding to the formulas (1) and (2).

In the compound represented by the formula (5), R ^2a represents an alkyl group substituted on a carbon atom of the ring E, and the rings E and R ^2a represent a branched alkylene represented by R ² in the formula (1). Form a group. Examples of the ring E include alkylene oxides having 2 to 5 carbon atoms such as ethylene oxide, trimethylene oxide, tetramethylene oxide (tetrahydrofuran), pentamethylene oxide (tetrahydropyran), and 2 to 2 carbon atoms such as ethylene oxide and trimethylene oxide. 3 alkylene oxides are preferred, especially ethylene oxide. Examples of R ^2a include C _1-6 alkyl groups such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, and s-butyl group, preferably a C _1-4 alkyl group, and more preferably Is preferably a _C1-2 alkyl group, particularly a methyl group. Specific examples of the compound represented by the formula (5) include C _3-8 alkylene oxides such as 1,2-epoxypropane, 1,2-epoxybutane, and 2-methyl-1,3-trimethylene oxide. Can be illustrated. Preferred compounds (5) are C _3-6 alkylene oxide, preferably C _3-4 alkylene oxide, in particular 1,2-epoxypropane.

In the compound represented by the formula (6), examples of the halogen atom X include a chlorine atom, a bromine atom and an iodine atom, which are often a chlorine atom and a bromine atom. The compound represented by the formula (6), the above-exemplified can be exemplified halo branched alkanols corresponding to R ^2, specifically, 1-halo-2-propanol, 2-halo-propanol, 1 -Halo-2-butanol, 2-halobutanol, 3-halo-2-methylpropanol, 3-halopropanol, 4-halo-2-propanol, 3-halo-2-methyl-2-propanol, 2-halo- Examples include halo-branched C _3-8 alkanols such as 2-methylpropanol and 3-halo-2,2-dimethylpropanol. Preferred haloalkanols are halo branched C _3-6 alkanols, preferably halo branched C _3-4 alkanols, especially compounds having 3 carbon atoms (3-halo-2-propanol, 2-halopropanol). is there.

  In the reaction of the compound represented by the formula (4) and the compound represented by the formula (5), the usage ratio of the latter is, for example, 1 to 25 mol (for example, 1 mol) with respect to 1 mol of the former hydroxyl group. .2 to 20 mol), preferably 1.5 to 10 mol, more preferably about 2 to 5 mol.

  The reaction between the compound represented by the formula (4) and the compound represented by the formula (5) may be performed in the presence of a base. As the base, the base exemplified in the reaction of the compound represented by the formula (2) and the compound represented by the formula (3) (for example, alkali metal hydroxide such as sodium hydroxide) can be used.

  Although the ratio of a base is not specifically limited, For example, 0.001-1 mol (for example, 0.005-0.5 mol) with respect to 1 mol of compounds represented by Formula (4), Preferably it is 0.00. It may be about 01 to 0.2 mol, more preferably about 0.05 to 0.1 mol.

  The reaction temperature and reaction time can be appropriately selected according to the type of raw material used. The reaction temperature may be, for example, about 0 to 170 ° C., preferably 10 to 150 ° C., more preferably about 20 to 130 ° C. (for example, 30 to 120 ° C.). The reaction time may be, for example, 30 minutes to 48 hours, usually 1 to 36 hours, preferably about 2 to 24 hours.

  In the reaction of the compound represented by the formula (4) and the compound represented by the formula (6), the ratio of the latter is, for example, 0.8 to 25 mol, preferably 1 mol with respect to 1 mol of the former hydroxyl group. It may be about 1 to 15 mol, more preferably about 1.2 to 10 mol (for example, 1.5 to 5 mol).

  The reaction may use a catalyst, or may be performed in the presence of a base in order to trap hydrogen halide generated by the reaction. As this catalyst and base, those exemplified in the reaction of the compound represented by the formula (2) and the compound represented by the formula (3) can be used.

  The ratio of the catalyst is not particularly limited, but is, for example, 0.001 to 1 mol (for example, 0.005 to 0.5 mol), preferably 1 mol with respect to 1 mol of the compound represented by the formula (4). About 0.01-0.2 mol, More preferably, about 0.05-0.1 mol may be sufficient.

  Although the ratio of a base is not specifically limited, For example, 0.01-30 mol (for example, 0.05-20 mol) with respect to 1 mol of hydroxyl groups of the compound represented by the said Formula (4), Preferably it may be about 1-10 mol, more preferably about 1.5-5 mol.

  The reaction temperature and reaction time can be appropriately selected according to the type of raw material used. The reaction temperature may be, for example, about 0 to 120 ° C, preferably about 30 to 100 ° C, and more preferably about 50 to 80 ° C. The reaction time may be, for example, 30 minutes to 48 hours, usually 1 to 36 hours, preferably about 2 to 24 hours.

  The reaction of the compound (4) with the compound (5) and / or the compound (6) may be carried out in the air or in an inert atmosphere (nitrogen, noble gas, etc.) with stirring. You may carry out under reduced pressure. The reaction may be performed while refluxing. Furthermore, the reaction may be performed in a solvent inert to the reaction. As the solvent, those exemplified in the reaction of compound (2) with compound (3) can be used. The produced compound (compound represented by the formula (2)) may be purified by a conventional method such as filtration, extraction, or crystallization.

The compound represented by the formula (4) may be produced by a known method, for example, by adding alkylene oxide (such as ethylene oxide) to the hydroxyl group of the ring Z, or alkylene carbonate (such as ethylene carbonate). ) May be added. Moreover, it can produce | generate by reaction with a fluorene and the hydroxy containing arene which has the ring Z, or the hydroxy containing arene which substituted the group [-O- (R < ¹ > O) _m2- H] _q to the ring Z.

[Curable composition]
The epoxy compound (or epoxy resin) may constitute a curable composition (such as a thermosetting or photocurable composition) containing a curing agent or the like.

  In the curable composition, the epoxy resin component may be composed of the epoxy compound, or may be composed in combination with another epoxy resin. Other epoxy resins include bisphenol type epoxy resins (bisphenol A type epoxy resins, bisphenol F type epoxy resins, etc.), biphenyl type epoxy resins, novolac type epoxy resins (phenol novolac type epoxy resins, cresol novolac type epoxy resins, etc.), Triphenolalkane type epoxy resin, phenol aralkyl type epoxy resin, heterocyclic type epoxy resin (including epoxy resin containing xanthene unit), stilbene type epoxy resin, condensed ring aromatic hydrocarbon modified epoxy resin (1,6-bis ( Glycidyloxy) naphthalene), glycidyl ester type epoxy resins, other epoxy resins having a fluorene skeleton, and the like. As these other epoxy resins, bisphenol type epoxy resins (for example, bisphenol A type epoxy resins) and the like are preferable. These other epoxy resins may be used alone or in combination of two or more.

  When used in combination with other epoxy resins, the ratio of the epoxy compound to the entire epoxy resin component is, for example, about 50 to 99% by weight, preferably 60 to 98% by weight, and more preferably about 70 to 95% by weight. Good.

  Examples of the curing agent include amine-based curing agents [in particular, primary amines such as chain aliphatic amines (for example, chain aliphatic polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine). Cycloaliphatic amines (eg mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxa Monocyclic aliphatic polyamines such as spiro (5.5) undecane; bridged cyclic polyamines such as norbornane diamine), araliphatic polyamines such as xylylenediamine, aromatic amines such as metaphenylenediamine, Diaminodiphenylmethane etc.)], polyaminoamide type hard Agents, acid anhydride curing agents (for example, aliphatic acid anhydrides such as dodecenyl succinic anhydride and polyadipic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride Aliphatic acid anhydrides such as acid, methylhymic anhydride, methylcyclohexene dicarboxylic acid anhydride; aromatic acids such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride Anhydride), phenol resin-based curing agents (for example, novolak resins such as phenol novolac resin and cresol novolak resin) and the like. As these curing agents, acid anhydride curing agents (such as hexahydrophthalic anhydride) and phenol resin curing agents (such as phenol novolac resin) are preferable. In particular, an acid anhydride curing agent is preferable for imparting flexibility. These curing agents may be used alone or in combination of two or more.

  The proportion of the curing agent is 0.1 to 500 parts by weight, preferably 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin component (when other epoxy resin is used, the total amount with the epoxy compound, hereinafter the same). It may be about 300 parts by weight, more preferably about 10 to 150 parts by weight. Moreover, the ratio of the functional group of a hardening | curing agent is 0.1-4.0 equivalent with respect to 1 equivalent of epoxy groups of an epoxy resin component, Preferably it is 0.3-2.0 equivalent, More preferably, it is 0.5- It may be about 1.5 equivalents.

  Moreover, the curable composition may contain the hardening accelerator. Examples of the curing accelerator include amines [eg, tertiary amines (eg, triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5 4.0) undecene-1), imidazoles (eg, alkylimidazoles such as 2-methylimidazole; arylimidazoles such as 2-phenylimidazole) and derivatives thereof (eg, phenol salts, phenol novolak salts, carbonates) ), Alkali metal or alkaline earth metal alkoxides, phosphines, amide compounds (such as dimer acid polyamides), Lewis acid complex compounds (such as boron trifluoride / ethylamine complexes), sulfur compounds [Polysa Fido, mercaptan compound (thiol compound), etc.], boron compounds (phenyl dichloroborane, etc.), condensable organic metal compound (an organic titanium compound, an organoaluminum compound) and the like. The curing accelerators may be used alone or in combination of two or more.

  The ratio (addition amount) of the curing accelerator is, for example, 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin component. Part (for example, 0.1 to 5 parts by weight).

  The curable composition may contain a reactive diluent. 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 Aldidiol diglycidyl ethers such as lucidiglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane di to triglycidyl ether, glycerin di to triglycidyl ether, polyglycol diglycidyl ether , Polypropylene glycol diglycidyl ether, etc.), diglycidyl aniline, cyclohexane dimethanol diglycidyl ether, cycloalkene oxides (eg, vinyl cyclohexene dioxide, methylated vinyl cyclohexene dioxide, etc.), etc.] Is mentioned. These reactive diluents may be used alone or in combination of two or more.

  The proportion of the reactive diluent may be, for example, 1 to 1000 parts by weight, preferably 5 to 500 parts by weight, and more preferably about 10 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin component.

  The curable composition is not limited to the thermosetting composition but may be a photocurable composition. This photocurable composition may contain 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 solvent. Examples of the solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; methyl Alkylene glycol monoalkyl ether acetates such as cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane; aliphatic hydrocarbons such as hexane Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones; methyl acetate, ethyl acetate, esters such as butyl acetate. These solvents may be used alone or in combination of two or more.

  The amount of the solvent used (added amount) can be selected, for example, from 0 to 500 parts by weight, for example, 10 to 400 parts by weight, preferably 20 to 300 parts by weight, based on 100 parts by weight of the epoxy resin component. Preferably, it may be about 30 to 200 parts by weight.

  The curable composition contains conventional additives such as colorants, stabilizers (thermal stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents, flame retardants, flame retardant aids, and the like. You may go out. You may use an additive individually or in combination of 2 or more types.

[Hardened product obtained by curing curable composition]
The present invention includes a cured product obtained by curing the curable composition. Since this hardened | cured material contains the epoxy compound represented by Formula (1), it is excellent in both the softness | flexibility and water resistance characteristics.

  The epoxy cured product of the present invention is excellent in water resistance because of having an oxy-branched alkylene group. That is, in a water absorption test according to JIS-K7209 (when the cured product is immersed in ion-exchanged water at a temperature of 25 ° C. for 24 hours), the water absorption is, for example, 0.1 to 1% by weight, preferably 0.2. It may be about -0.9 wt%, more preferably about 0.3-0.8 wt%.

  In the epoxy cured product of the present invention, the indentation hardness (temperature 25 ° C.) depends on the kind of the curing agent, but when measured according to ASTM D2240, for example, 20 to 99, preferably 30 to 95 (for example, 40 ˜90). In particular, in the formula (1), a cured product formed of an epoxy compound having a large average value of n1 + n2 can remarkably improve flexibility, so that the indentation strength is, for example, 5-70, preferably 10-65. More preferably, it can be about 15 to 60 (for example, 20 to 55). Such an epoxy cured product may have a Tg of 50 ° C. or lower, but can have a glass transition temperature (Tg) of room temperature or lower. That is, the glass transition temperature of this epoxy cured product is, for example, 25 ° C. or less (eg, −45 ° C. to 25 ° C.), preferably 20 ° C. or less (eg, −20 ° C. to 20 ° C.), more preferably 10 ° C. or less (for example, −15 ° C. to 10 ° C.), particularly 0 ° C. or less (for example, −10 ° C. to 0 ° C.). When the glass transition temperature is too high, flexibility is lowered. The indentation strength can be measured using a type C durometer hardness meter, and the glass transition temperature can be measured using a differential scanning calorimeter.

  The cured product of the present invention can be obtained by reacting (curing treatment) the curable composition. The curing treatment can be performed by using a curing catalyst, heating, light irradiation (active energy ray irradiation), or the like, or a combination of these.

  When performing a hardening process by heating, as heating temperature, it is about 50-250 degreeC, for example, Preferably it is 70-220 degreeC, More preferably, about 80-200 degreeC (for example, 90-170 degreeC) may be sufficient. The curing treatment may be performed stepwise, for example, after heat treatment at a relatively low temperature (for example, about 50 to 130 ° C., preferably about 70 to 120 ° C.), then a relatively high temperature (for example, 140 to 350 ° C.). , Preferably about 150 to 300 ° C.). Such a curing treatment may be performed while molding or molding (or preforming) the curable composition according to the shape of the cured product. For example, the curable composition can be heated and melted, if necessary, poured into a predetermined mold and heated to be cured, and a molded body having a desired shape can be obtained. 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, a low-temperature molding method called a cold press, or the like is used.

  Further, the curable composition may be applied to the adhesion site and cured, or the substrate may be coated with the curable composition and cured. Furthermore, you may make it harden | cure by applying a curable composition to a predetermined site | part, and irradiating light or radiation (ultraviolet irradiation etc.).

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

  In the examples, various measurements were performed as follows.

(Water absorption test)
The test was conducted according to JIS K7209. That is, the sample (30 mm × 30 mm × 3 mm) was dried at 50 ° C. for 24 hours to be in an absolutely dry state. The sample was immersed in ion-exchanged water at a temperature of 25 ° C. for 24 hours, and the change in weight before and after the immersion was measured. This measurement was performed three times, and the average value was defined as the water absorption rate.

(Flexibility test)
The test was conducted according to ASTM D2240. That is, the indentation hardness was measured using a type C durometer hardness meter (manufactured by Teclock Co.).

(Epoxy equivalent)
The epoxy equivalent was measured according to JIS K7236. The end point was confirmed using a potentiometric titrator by the perchloric acid acetic acid solution titration method.

(viscosity)
The viscosity was measured according to JIS K7117-2. Using a TV-22 viscometer (cone plate type, “TVE-22L” manufactured by Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was measured according to the measured viscosity (01: 1 ° 34 × R24, 07). : 3 ° × R7.7) at 1 to 20 rpm (selected according to viscosity).

(Measurement of glass transition temperature (Tg))
It measured in the temperature range of -30-150 degreeC based on JISK7121 using the differential scanning calorimeter (The Seiko Instruments Co., Ltd. product, "DSC6220").

  (Synthesis Example 1)

(In the formula, the average value of m1 + m2 is 2, and the average value of n1 + n2 is 10.)

  582.0 g (0.57 mol) of a compound represented by the above formula (7) (referred to as “BPEF-10PO”), 576.8 g (6.27 mol) of epichlorohydrin and trimethylammonium in a three-necked flask with a Dean Stark 4.0 g (0.026 mol) of bromide (TMAB) was added. The inside of the system was replaced with argon, and the temperature was raised to 50 ° C. to dissolve the above components, and then 320.0 g (8.0 mol) of sodium hydroxide was added over 1 hour. Thereafter, the atmosphere was replaced with argon again and reacted at 80 ° C. for 9 hours. After the reaction, the reaction solution was subjected to suction filtration, and the filtrate was concentrated, and then heated to 70 ° C., and 500 g of methyl isobutyl ketone and 200 g of magnesium sulfate were added and dissolved.

  The obtained solution was filtered again and rinsed with toluene, and then 268.0 g of a 30% aqueous sodium hydroxide solution was added dropwise to the filtrate, followed by stirring at 70 ° C. for 1 hour in an argon atmosphere. Thereafter, methyl isobutyl ketone was added to the resulting solution, extracted and washed four times with distilled water, dehydrated and filtered, concentrated and dried, and a compound represented by the following formula (8) (referred to as “BPEF-10POG”) Got.

(In the formula, the average value of m1 + m2 is 2, and the average value of n1 + n2 is 10.)

  Moreover, the solid content concentration of the obtained epoxy compound was 94.4% by weight, the viscosity at 25 ° C. was 2300 mPa · s, and the epoxy equivalent was 638.

(Synthesis Example 2)
In the same manner as in Synthesis Example 1, except that the compound “BPEF-8PO” in which the average value of m1 + m2 is 2 and the average value of n1 + n2 is 8 is used instead of BPEF-10PO, In the formula (8), a compound “BPEF-8POG” having an average value of m1 + m2 of 2 and an average value of n1 + n2 of 8 was obtained. The resulting epoxy compound had a solid content concentration of 99.3% by weight, a viscosity at 25 ° C. of 12230 mPa · s, and an epoxy equivalent of 598.

(Synthesis Example 3)
In the same manner as in Synthesis Example 1, except that the compound “BPEF-5PO” in which the average value of m1 + m2 is 2 and the average value of n1 + n2 is 5 is used instead of BPEF-10PO, In the formula (8), a compound “BPEF-5POG” having an average value of m1 + m2 of 2 and an average value of n1 + n2 of 5 was obtained. The obtained epoxy compound had a solid content concentration of 98.8% by weight, a viscosity at 25 ° C. of 29610 mPa · s, and an epoxy equivalent of 552.

  “BPEF-10PO”, “BPEF-8PO”, and “BPEF-5PO” were prepared in the same manner as in Example 1 of JP-A No. 2001-139651, and 9,9-bis [4- (2-hydroxy Ethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd.) 1 mol was obtained by reacting propylene oxide (PO) with 10 mol, 8 mol and 5 mol, respectively.

  (Comparative Synthesis Example 1)

(In the formula, the average value of m1 + m2 is 2, and the average value of n1 + n2 is 10.)

  Instead of the compound (BPEF-10PO) obtained in Synthesis Example 1, the compound represented by the above formula (referred to as “BPEF-10EO”) was used, and the synthesis was performed in the same manner as in Synthesis Example 1, and the following formula Was obtained (referred to as “BPEF-10EOG”).

(In the formula, the average value of m1 + m2 is 2, and the average value of n1 + n2 is 10.)

  Moreover, the solid content concentration of the obtained epoxy compound was 99.5% by weight, the viscosity at 25 ° C. was 6040 mPa · s, and the epoxy equivalent was 467.

  “BPEF-10EO” was prepared in the same manner as in Example 1 of JP-A-2001-139651, and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd.) (Made) It obtained by making it react using 10 mol of ethylene oxide (EO) with respect to 1 mol.

(Example 1)
6 parts by weight of bisphenol A type epoxy resin [manufactured by Mitsubishi Chemical Co., Ltd., JER828], 24 parts by weight of BPEF-10POG obtained in Synthesis Example 1, and phenol novolac resin [Gundei Co., Ltd.] 7.3 parts by weight of Chemical Industries, PSM-4261] was added, and the mixture was stirred at 100 ° C. for 1 hour and mixed. Thereafter, 0.16 part by weight of triphenylphosphine was added and heated at 150 ° C. for 5 hours to obtain an epoxy cured product 1.

(Example 2)
30 parts by weight of BPEF-10POG obtained in Synthesis Example 1 and 7.7 parts by weight of an acid anhydride curing agent [manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH-700] are added and stirred at 100 ° C. for 1 hour. , Mixed. Thereafter, 0.19 part by weight of triphenylphosphine was added and heated at 115 ° C. for 5 hours to obtain a cured epoxy product 2.

(Example 3)
An epoxy cured product 3 was obtained in the same manner as in Example 2 except that BPEF-8POG was used instead of BPEF-10POG and 8.2 parts by weight of an acid anhydride curing agent was added.

Example 4
Epoxy cured product 4 was obtained in the same manner as in Example 2 except that BPEF-5POG was used instead of BPEF-10POG, and 8.9 parts by weight of the acid anhydride curing agent was added.

(Comparative Example 1)
6 parts by weight of bisphenol A type epoxy resin [manufactured by Mitsubishi Chemical Co., Ltd., JER828], 24 parts by weight of BPEF-10EOG obtained in Comparative Synthesis Example 1, and phenol novolak resin [Co., Ltd.] 8.7 parts by weight of Gunei Chemical Industry PSM-4261] was added, and the mixture was stirred at 100 ° C. for 1 hour and mixed. Thereafter, 0.16 part by weight of triphenylphosphine was added and heated at 150 ° C. for 5 hours to obtain an epoxy cured product 3.

(Comparative Example 2)
30 parts by weight of BPEF-10EOG obtained in Comparative Synthesis Example 1 and 10.5 parts by weight of an acid anhydride curing agent [manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH-700] are added and stirred at 100 ° C. for 1 hour. And mixed. Thereafter, 0.20 part by weight of triphenylphosphine was added and heated at 115 ° C. for 5 hours to obtain an epoxy cured product 4.

  Table 3 shows the results of water absorption, indentation hardness, and glass transition temperature of the cured epoxy products obtained in Examples 1 and 2 and Comparative Examples 1 and 2.

  As Table 3 shows, the epoxy hardened | cured material of Examples 1-4 has a low water absorption rate and indentation intensity | strength, and can make water resistance and a softness | flexibility compatible. In particular, in Examples 1 and 2, compared with Comparative Examples 1 and 2, the water absorption rate and the indentation strength are very low, and both water resistance and flexibility are excellent. As shown in Examples 2 to 4, as the average value of n1 + n2 increases, the glass transition temperature decreases. In Example 2, the glass transition temperature is 0 ° C. or lower, and the indentation hardness is significantly low.

The fluorene skeleton-containing epoxy compound of the present invention (or a cured product thereof) is excellent in both flexibility and water resistance in addition to properties such as high heat resistance and high refractive index derived from the fluorene skeleton. In addition to being useful as an insulating material between layers of electronic components, solder resists for printed circuit boards, resist materials such as coverlays, etc., color filters, inks (printing inks, etc.), sealing Stopper (semiconductor sealing agent, etc.), paint, coating agent, adhesive, adhesive, underfill, antistatic agent, filler, conductive member or conductive material, laminated material, thermal material (thermal paper material, etc.), Carbon materials, insulating materials, foams, pressure sensitive materials, optical materials (transparent materials) [eg lenses (reflow lenses, pickup lenses, micro lenses, etc.), polarized Film, antireflection film, film for touch panels, flexible substrate film, a display film, a fuel cell membrane, fiber, optical waveguide, the hologram is a useful as any material, such as (electric and electronic materials, optical materials). In addition, the said epoxy compound can be utilized also as thermosetting or photocurable resin raw materials, such as an epoxy (meth) acrylate.

Claims (9)

An epoxy compound represented by the following formula (1).

(In the formula, ring Z is an arene ring, R ¹ represents a linear alkylene group, R ² represents a branched alkylene group, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a halogen atom, Hydrogen group, hydroxyl group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, mercapto group, alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, acyl group, carboxyl group, alkoxycarbonyl group, nitro group , A cyano group or a substituted amino group, R ⁵ represents a hydrocarbon group, a cyano group or a halogen atom, k is an integer of 0 to 4, m1 and m2 are each an integer of 1 to 5, and an average value of m1 + m2 is 2 -10, n1 and n2 are each an integer of 1 to 10, the average value of n1 + n2 is 2 to 20, p is 0 or an integer of 1 or more, and q is 1 or more Is a number.) In formula (1), ring Z is a benzene ring, naphthalene ring or biphenyl ring, R ¹ is a linear C _2-6 alkylene group, R ² is a branched C _3-6 alkyl group, and q is The epoxy compound according to claim 1, which is an integer of 1 to 3. In formula (1), ring Z is a benzene ring, naphthalene ring or biphenyl ring, R ¹ is a linear C _2-3 alkylene group, R ² is a branched C _3-4 alkyl group, and average value of m1 + m2 The epoxy compound according to claim 1 or 2, wherein n is 2 to 4, n1 + n2 has an average value of 8 to 15, and q is 1. In the formula (1), the ring Z is a benzene ring or a naphthalene ring, ^{R 1} is an ethylene group, ^{R 2} is a propylene group, average of m1 + m2 is 2, n1 + average value of n2 is 9 to 12, ^{R 3} is a hydrogen atom The epoxy compound according to claim 1, wherein k and p are 0 and q is 1. The epoxy compound according to any one of claims 1 to 4, which is represented by the following formula (1A).

(In the formula, A is the following formula:

Wherein r represents 0 or an integer of 1 or more, and the rings Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , m1, m2, n1, n2, k, p are the same as above. ) Following formula (2)

(In the formula, rings Z, R ¹ , R ² , R ⁴ , R ⁵ , k, m1, m2, n1, n2, p, and q are the same as above.)
And a compound represented by the following formula (3)

(In the formula, X represents a halogen atom, and R ³ is the same as above.)
The method of manufacturing the epoxy compound in any one of Claims 1-5 by making the compound represented by these react.   A curable composition comprising the epoxy compound according to claim 1 and a curing agent.   A cured product obtained by curing the curable composition according to claim 7. The hardened | cured material of Claim 8 whose glass transition temperature of hardened | cured material is 25 degrees C or less.