JP6087738B2 - Fluorene compound having phenolic hydroxyl group and epoxy compound thereof - Google Patents

Description

  The present invention relates to a novel fluorene compound having four or more phenolic hydroxyl groups and a fluorene skeleton, a method for producing the fluorene compound, and a compound obtained by epoxidizing the fluorene compound.

  The epoxy resin is cured with various curing agents to form a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. Therefore, epoxy resins are used in a wide range of fields such as adhesives, paints, laminates, molding materials and casting materials. Conventionally, bisphenol A-type epoxy resins and the like are known as the most commonly used epoxy resins in the industry, but such epoxy resins sometimes have insufficient heat resistance depending on applications.

  On the other hand, compounds having a 9,9-bisphenylfluorene skeleton such as bisphenolfluorene (BPF) and bisphenoxyethanol fluorene (BPEF) are known to have an excellent function in heat resistance. It is also known to be used as a resin raw material.

  For example, JP 2005-162785 A (Patent Document 1) discloses a resin composition composed of a compound having a fluorene skeleton and a thermoplastic resin. , 9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene, 9,9- It describes that glycidyl ethers such as bis (4-glycidyloxyethoxy-3-methylphenyl) fluorene can be used.

  Since such an epoxy resin has a 9,9-bisphenylfluorene skeleton, characteristics such as heat resistance can be improved to some extent as compared with a conventional epoxy resin such as a bisphenol A type epoxy resin. However, with rapid technological innovation in recent years, improvements in various high-functional properties such as high heat resistance are being demanded more rapidly. For example, in printed circuit board applications and the like, there is a demand for epoxy resins having excellent mechanical strength, good handling properties, solvent solubility, etc. in addition to high heat resistance.

  Under such circumstances, JP-A-2008-285544 (Patent Document 2) discloses an epoxy compound represented by the following general formula (1).

  In this document, the epoxy compound having the above structure is described as having high heat resistance and low hygroscopicity.

  However, in such an epoxy compound, since the epoxy groups are close to each other, the curability (reactivity with the curing agent) is not sufficient, and therefore there is a possibility that desired physical properties (such as mechanical properties) may not be obtained. In some cases, epoxidation of all phenolic hydroxyl groups may not be performed efficiently even in the production process.

  JP-A-2008-273844 (Patent Document 3) discloses 9,9-bis (monomethylol-hydroxy) by reacting a fluorene having a phenolic hydroxyl group with an aldehyde in the presence of a base catalyst. It is disclosed that phenyl) fluorenes and the like can be obtained.

  In this document, the fluorene compound having a methylol group as described above is described as being useful as various resin raw materials (particularly, resin raw materials such as phenol resins, epoxy resins, acrylic resins, and polyester resins). Yes.

  Japanese Patent Application Laid-Open No. 2008-273999 (Patent Document 4) discloses a condensate obtained by condensing 9,9-bis (monomethylol-hydroxyphenyl) fluorene and the like in the presence of an acid catalyst. A phenol resin having a weight average molecular weight of 2000 or more is disclosed.

Japanese Patent Laying-Open No. 2005-162785 (Claim 1, paragraph numbers [0043] and [0044]) JP 2008-285544 A (claims, paragraph number [0009]) JP 2008-273844 A (claims, paragraph number [0008]) JP 2008-273999 A (claims, paragraph numbers [0013] and [0023])

  Accordingly, an object of the present invention is to provide a novel fluorene compound having a phenolic hydroxyl group and a method for producing the same.

  Another object of the present invention is to provide a novel epoxy compound having a good balance of properties such as heat resistance, mechanical properties, handling properties, and solvent solubility.

  As described above, Patent Document 3 discloses the applicability of 9,9-bis (monomethylol-hydroxyphenyl) fluorenes [dimethylol bodies of 9,9-bis (hydroxyphenyl) fluorenes] as resin materials. Although described, there is no disclosure about how to use it specifically as an epoxy resin.

  Under such circumstances, the present inventors have conducted extensive studies to solve the above problems, and as a result, 9,9-bis (monomethylol-hydroxyphenyl) fluorenes and the like, phenols (particularly 2, 4 and When specific phenols in which any two of the 6-positions are substituted with substituents) are reacted under predetermined conditions, they are not polymerized as in Patent Document 4, but methylol groups react and specific phenols A novel fluorene compound in which is bonded, and such a fluorene compound has a plurality (at least four) of phenolic hydroxyl groups and can be used as various resin materials. Glycidyl etherified epoxy compounds using various properties (heat resistance, mechanical properties (bending elasticity, bending strength, etc.), hand It found that ring resistance, solvent solubility, etc.) is a good balance with the material, and completed the present invention.

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

(In the formula, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ¹ and R ² are substituents, R ³ is a hydrogen atom or a hydrocarbon group, R ⁴ is a substituent that is not a hydroxyl group, and k is 0 to 0) (4), m and p are each an integer of 0 or more, and n, q and r are each an integer of 1 or more and may be the same or different.
In the above formula (1), the ring Z ¹ may be a benzene ring or a naphthalene ring, and the ring Z ² is directly bonded or connected to at least one selected from a benzene ring, a naphthalene ring, or a benzene ring and a naphthalene ring. It may be a ring bonded through a group, m may be 0 to 2, n may be 1 or 2, p may be 0 to 4, and q is 1 or 2, r may be 1 or 2, and R ² and R ⁴ may be a hydrocarbon group.

In particular, in the formula (1), rings Z ¹ and Z ² are benzene rings, m is 0 or 1, n is 1, p is 0 to 2, q is 1, r is 1, R ² is an alkyl group, R ³ may be a hydrogen atom, and R ⁴ may be an alkyl group or an aryl group.

  The compound represented by the formula (1) may typically be a compound represented by the following formula (1A).

(In the formula, X ¹ , X ² and X ³ represent a hydrogen atom or a substituent, and Z ¹ , R ¹ , R ² , R ³ , R ⁴ , k, m, n and r are the same as above, provided that (At least one of X ¹ , X ² and X ³ is a hydroxyl group.)
In the above formula (1A), X ¹ , X ² and X ³ may be a hydrogen atom or a hydroxyl group. In the formula (1A), any one of X ¹ , X ² and X ³ (for example, X ¹ ) may be a hydroxyl group.

  In particular, the compound represented by the formula (1) (or (1A)) may be a compound represented by the following formula (1B).

[Wherein R ^2A represents a hydrogen atom, R ² or the following formula:

(Wherein R ³ , R ⁴ , X ¹ , X ² and X ³ are the same as above)
Wherein R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² , X ³ , k are the same as above. ]
In particular, in the above formula (1B), R ^2A may be a group R ² (eg, an alkyl group), and any one of X ^{1 to} X ³ (eg, X ¹ ) is a hydroxyl group. May be.

  In the present invention, the compound represented by the following formula (2) and the compound represented by the following formula (3) are reacted to produce the fluorene compound (the compound represented by the formula (1)). A method is also included.

(In the formula, Z ¹ , Z ² , R ¹ , R ² , R ³ , R ⁴ , k, m, n, p, q, and r are the same as above.)
In particular, the compound represented by the above formula (3) may be a compound represented by the following formula (3A).

(In the formula, R ⁴ , X ¹ , X ² and X ³ are the same as above.)
Moreover, in the said reaction, the usage-ratio of the compound represented by the said Formula (3) may be 2 mol or more with respect to 1 mol of compounds represented by the said Formula (2).

  The fluorene compound is useful as a resin material, particularly an epoxy resin material. Therefore, in the present invention, an epoxy compound using the fluorene compound, for example, an epoxy compound obtained by epoxidizing the fluorene compound (compound represented by the formula (1)) or an alkylene oxide adduct thereof, for example, the following formula The epoxy compound represented by (4) is also included.

[Wherein E represents the following formula (5)

(In the formula, R ⁵ represents an alkylene group, R ⁶ represents a hydrogen atom or a methyl group, and s represents an integer of 0 or more.)
Z ¹ , Z ² , R ¹ , R ² , R ³ , R ⁴ , k, m, n, p, q, r are the same as described above. ]
The compound represented by the formula (4) may typically be a compound represented by the following formula (4A).

Wherein Y ¹ , Y ² and Y ³ are a hydrogen atom, E or a substituent, and at least one of Y ¹ , Y ² and Y ³ is E, and E, Z ¹ , R ¹ , R ² , R ³ , R ⁴ , k, m, n, and r are the same as above.)
In particular, the compound represented by the formula (4) or (4A) may be a compound represented by the following formula (4B).

[Wherein R ^2B represents a hydrogen atom, R ² or the following formula:

(In the formula, R ³ , R ⁴ , Y ¹ , Y ² , Y ³ are the same as above.)
E, R ¹ , R ² , R ³ , R ⁴ , Y ¹ , Y ² , Y ³ , k are the same as above. ]
In the formula (5), s may be 0.

  Furthermore, in the present invention, curing comprising the epoxy compound (an epoxy compound obtained by epoxidizing a compound represented by the formula (1) or an alkylene oxide adduct thereof, or an epoxy compound represented by the formula (4)). And a cured product obtained by curing the curable composition.

  In the present invention, a novel fluorene compound having a phenolic hydroxyl group can be obtained. Such a fluorene compound can be used as various resin materials, and is particularly useful as a raw material for epoxy compounds (epoxy resins). Such an epoxy compound is obtained by epoxidizing (glycidyl etherification) the phenolic hydroxyl group of a fluorene compound, and has a good balance of properties such as heat resistance, mechanical properties, handling properties, and solvent solubility. .

[Fluorene compound]
The fluorene compound (phenol compound) of the present invention is represented by the following formula (1).

(In the formula, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ¹ and R ² are substituents, R ³ is a hydrogen atom or a hydrocarbon group, R ⁴ is a substituent that is not a hydroxyl group, and k is 0 to 0. (4), m and p are each an integer of 0 or more, and n, q and r are each an integer of 1 or more and may be the same or different.
In the formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z ¹ include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon (for example, indene, naphthalene, etc. C _8-20 condensed bicyclic hydrocarbons, preferably C _10-16 condensed bicyclic hydrocarbons), condensed tricyclic hydrocarbons (eg, anthracene, phenanthrene, etc.), etc. ]. The two rings Z ¹ may be the same or different rings, and may usually be the same ring. Preferred ring Z ¹ includes a benzene ring and a naphthalene ring, and may be a benzene ring in particular.

In the formula (1), the group R ¹ is usually a non-reactive group, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [for example, an alkyl group, Aryl group (C _6-10 aryl group such as phenyl group) and the like] and the like, in particular, an alkyl group and the like in many cases. 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), plural groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on different benzene rings 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.

The number of substitutions n of the hydroxyl group (—OH) substituted on ring Z ¹ is not particularly limited as long as it is 1 or more. For example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1 There may be. In particular, when ring Z ¹ is a benzene ring, n may be 1 to 2, in particular 1, respectively. In addition, the number of substitutions n of the hydroxyl group may be the same or different in different rings Z ¹ and is usually the same in many cases.

Incidentally, the substitution position of the hydroxyl group is not particularly limited, as long as the replaced with appropriate substitution positions according to the type of ring Z ^1. In particular, when ring Z ¹ is a benzene ring, the hydroxyl group is 3-position (or meta-position) or 4-position (or para-position), particularly 4-position (para-position) relative to the position where the benzene ring is bonded to fluorene. In many cases. At least a substituted hydroxyl group in a condensation polycyclic hydrocarbon ring Z ^1, to another hydrocarbon ring and a hydrocarbon ring attached to the 9-position of fluorene (e.g., 5-position of the naphthalene ring, 6-position, etc.) There are many cases.

The substituent R ² substituted on the ring Z ¹ is usually a non-reactive group [in particular, a group that is not a hydroxyl group and a group —CHR ³ OH (wherein R ³ is the same as described above)], for example, an alkyl group ( For example, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, preferably a C _1-8 alkyl group, etc., or a cycloalkyl group (C _5-8 such as a cyclohexyl group). Cycloalkyl group etc.), aryl group (eg C _6-10 aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group etc.), aralkyl group (C _6-10 aryl-C such as benzyl group, phenethyl group etc.) _1-4 such as an alkyl group) carbon atoms and the like; alkoxy group (methoxy group, a C _1-8 alkoxy group such as ethoxy group), cycloalkoxy (cyclohex key Aryloxy such as _{C 5-10} cycloalkyl group such group), _{C 6-10} aryloxy groups such as an aryloxy group (phenoxy group), _{C 6-10} aryl _-C such aralkyloxy group (a benzyloxy group _{1- 4-} alkyloxy group) -OR [wherein R represents a hydrocarbon group (such as the hydrocarbon group exemplified above). 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 group R ² includes a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _6-10 Aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group and the like), alkoxy group (C _1-4 alkoxy group and the like) and the like. More preferable group R ² is an alkyl group [C _1-4 alkyl group (especially methyl group) and the like], an aryl group [eg C _6-10 aryl group (especially phenyl group) and the like], particularly an alkyl group. Is preferred.

In the same ring Z ¹ , when m is plural (two or more), the groups R ² may be different from each other or the same. In the two rings Z ¹ , the groups R ² may be the same or different. The preferred substitution number m may be 0 to 8, preferably 0 to 4 (for example, 0 to 3), more preferably 0 to 2, particularly 0 to 1 (for example, 1). In the different rings Z ¹ , the substitution numbers m may be the same or different from each other, and may be usually the same.

The substitution position of the substituent R ² is not particularly limited, and may be substituted at an appropriate substitution position depending on the substitution position of the hydroxyl group. Usually, the ortho position and the para position are relative to the hydroxyl group. Of the carbon atoms located at, at least one is unsubstituted (that is, the substituent is a hydrogen atom). For example, when ring Z ¹ is a benzene ring and the hydroxyl group is substituted at the 4-position of the benzene ring, at least one substitution position at the 3-position or 5-position is often unsubstituted. Further, when ring Z ¹ is a naphthalene ring and the hydroxyl group is substituted at the 6-position of the naphthalene ring, at least one substitution position at the 5-position or the 7-position may be unsubstituted.

The substitution number r of the ring ^{Z 2} to be added to the ring ^{Z 1} is not particularly limited as long as it is 1 or more, e.g., 1-4, preferably 1-3, more preferably 1-2, even especially 1 Good. In particular, when ring Z ¹ is a benzene ring, r may be 1 to 2, in particular 1. In addition, the substitution number r of the ring Z ² may be the same or different in different rings Z ¹ , and is usually the same in many cases.

In the formula (1), the aromatic hydrocarbon ring represented by the ring Z ² is the same aromatic hydrocarbon ring as the ring Z ¹ (for example, a condensed polycyclic aromatic such as a benzene ring or a naphthalene ring). A ring (ring assembly ring) in which a plurality of aromatic hydrocarbon rings (arene rings such as a benzene ring and a naphthalene ring) are bonded directly or via a linking group, etc. Also good. Examples of the linking group include a hydrocarbon group [for example, an alkylene group (or an alkylidene group such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a 2,2-propanediyl group, a 2-propylidene group, a tetra C _1-20 alkylene group such as methylene group, pentamethylene group, 2,2-dimethylpropane-1,3-diyl group, butane-2,2-diyl group, hexafluoropropane-2,2-diyl group, Preferably a C _2-10 alkylene group, more preferably a C _2-6 alkylene group), an aryl alkylene group (for example, a C _6-10 aryl C _1— such as a phenylethane-1,1-diyl group, a diphenylmethylene group). ₄ alkylene group), an arylene group (e.g., _{C 6-10} aryl group such as phenylene group), arylene alkylene Down group (e.g., phenylene - _{C 6-10} arylene, such as di-2-propylidene group - di _{C 1-4} alkylene group), a cycloalkylene group (e.g., a cyclohexylidene group, 3,3,5-trimethyl-cyclohexylidene A group containing a hetero atom {eg, a group containing an oxygen atom [eg, an ether group (—O—), a carbonyl group (—CO—), an oxycarbonyl group (—OCO—), etc.]), A group containing a sulfur atom [for example, a thio group (—S—), a sulfinyl group, a sulfonyl group, etc.] and the like}. In addition, the hydrocarbon group as the linking group is further substituted with a substituent described below such as a substituent [eg, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.) (eg, a substituent exemplified in the group R ^2). )].

Incidentally, two rings Z ² may be the same or different rings, may be generally the same ring. Exemplary ring Z ² includes a ring in which at least one selected from a benzene ring, a naphthalene ring, a benzene ring and a naphthalene ring is bonded directly or via a linking group [for example, a biphenyl ring, a diphenylalkane ring (for example, And diphenyl C _1-10 alkane rings such as a diphenylmethane ring and a 2,2-diphenylpropane ring). Preferred ring Z ² includes a benzene ring and a naphthalene ring, and may be a benzene ring in particular.

In the group R ³ of the formula (1), the hydrocarbon group may be the hydrocarbon group exemplified in the section of the group R ² [eg, alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group] Group, C _1-6 alkyl group such as s-butyl group and t-butyl group, preferably C _1-4 alkyl group). The group R ³ may usually be a hydrogen atom or an alkyl group (such as a methyl group), in particular a hydrogen atom.

The number of substitutions q of the hydroxyl group (—OH) substituted on the ring Z ² is not particularly limited as long as it is 1 or more. For example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1 There may be. In particular, when the ring ^{Z 2} is a benzene ring, q is 1-2, may be particularly 1. Incidentally, the substitution number q of the hydroxyl groups are in different rings Z ^2, which may be identical or different, usually often identical.

Incidentally, the substitution position of the hydroxyl group is not particularly limited, as long as the replaced with appropriate substitution positions according to the type of the ring Z ^2. In particular, when ring Z ² is a benzene ring, the hydroxyl group is 2-position (or ortho-position) or 4-position (or para-position) relative to the position at which the benzene ring is bonded to the group —CH (R ³ ) —, In particular, it is often substituted at least at the 4-position (para-position). Further, the hydroxyl group is a hydrocarbon ring different from the hydrocarbon ring bonded to the group —CH (R ³ ) — in the condensed polycyclic hydrocarbon ring Z ² (for example, the 5-position, 6-position, etc. of the naphthalene ring). ) Is often substituted at least.

Further, the substituent represented by the group R ⁴ may be any group that is not a hydroxyl group [and group —CHR ³ OH (wherein R ³ is the same as above)], and the substituents exemplified for the R ² And the same substituents. Representative groups R ⁴ include hydrocarbon groups, alkoxy groups, and the like, and may preferably be hydrocarbon groups such as alkyl groups or aryl groups (particularly alkyl groups). The substitution position of R ⁴ is not particularly limited, and can be selected according to the position of the hydroxyl group and the group —CH (R ³ ) —, but is efficiently represented by the formula (1) without increasing the molecular weight. In order to obtain a compound, it may be preferable that the group R ⁴ is substituted in a specific positional relationship as described later.

In the same ring Z ² , when p is plural (two or more), the groups R ⁴ may be different from each other or the same. In the two rings Z ² , the groups R ⁴ may be the same or different. The number of substitution p can be selected according to the type of ring Z ² , and is, for example, 0 to 8, preferably 0 to 6 (for example, 0 to 4), more preferably 0 to 3 (for example, 0 to 2). ). Note that in a different ring Z ^2, substitution number p may be the same or different, may be a conventional same.

Typical compounds represented by the formula (1) include compounds in which the ring Z ² is a benzene ring, for example, compounds represented by the following formula (1A).

(In the formula, X ¹ , X ² and X ³ represent a hydrogen atom or a substituent, and Z ¹ , R ¹ , R ² , R ³ , R ⁴ , k, m, n and r are the same as above, provided that (At least one of X ¹ , X ² and X ³ is a hydroxyl group.)
In X ¹ , X ² and X ³ of the formula (1A), examples of the substituent include a hydroxyl group in addition to the same group as the group R ⁴ (or group R ² ). The groups X ¹ , X ² and X ³ may be at least one (ie one, two or three) hydroxyl groups, preferably one is a hydroxyl group (eg X ¹ is a hydroxyl group) There may be. When one or two of the groups X ^{1 to} X ³ are hydroxyl groups, the remaining groups X ¹ , X ² or X ³ may preferably be hydrogen atoms (that is, the groups X ^{1 to} X ³ May preferably be a hydrogen atom or a hydroxyl group). Incidentally, groups X ¹ to X ^3, if not a hydroxyl group, in the same or different benzene rings, may be the same or different.

Incidentally, group -CH ^{(R 3)} to replace the ring ^{Z 1} - substituted position of may be selected depending on the number of substituents and the substitution positions of the hydroxyl group and the substituent ^{R 2} in the ring ^{Z 1,} usually, the ring ^{Z 1} In many cases, it is located in the ortho position or the para position with respect to the hydroxyl group. In particular, an example [(1B)] of a typical compound in the case where the ring Z ¹ is a benzene ring is shown.

[Wherein R ^2A represents a hydrogen atom, R ² or the following formula:

(Wherein R ³ , R ⁴ , X ¹ , X ² and X ³ are the same as above)
Wherein R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² , X ³ , k are the same as above. ]
In the above formula (1B), the two groups R ^2A may be the same or different. In particular, the group R ^2A may be the substituent R ² (eg, an alkyl group, an aryl group, etc.).

(Method for producing fluorene compound)
The fluorene compound of the present invention (compound represented by the above formula (1)) is not particularly limited. For example, the compound represented by the following formula (2) and the compound represented by the following formula (3) (phenol) And the like) can be efficiently produced. In this method, fluorene phenols [9,9-bis (hydroxyaryl) fluorenes] corresponding to the compound represented by the following formula (2) and a methylol body of the compound represented by the following formula (3) And may be reacted.

(In the formula, Z ¹ , Z ² , R ¹ , R ² , R ³ , R ⁴ , k, m, n, p, q, and r are the same as above.)
The compound represented by the above formula (2) is obtained by the method described in JP-A-2008-273844 {that is, 9,9-bis (hydroxyaryl) fluorenes [for example, 9,9, in the presence of a base catalyst]. -Bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, etc.] and an aldehyde [HCOR ³ (wherein R ³ is the same as above)] is produced by the method} it can. As disclosed in JP 2008-285544 A, fluorenephenols [9,9-bis (hydroxyaryl) fluorenes] corresponding to the compound represented by the following formula (2) and the following formula (3): When the phenols represented and aldehydes (formaldehyde etc.) are made to react at once, condensation of methylol bodies proceeds, making it difficult to obtain a desired compound (compound represented by the formula (1)).

Representative compounds represented by formula (2) include, for example, 9,9-bis (3-methylol-4-hydroxyphenyl) fluorene, 9,9-bis (3-methylol-5-substituted-4- Hydroxyphenyl) fluorene {eg, 9,9-bis (3-methylol-5-alkyl-4-hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxy-5-methyl-3-methylolphenyl) fluorene 9,9-bis (3-methylol-5-C _1-4 alkyl-4-hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-5-ethyl-3-methylolphenyl) fluorene], 9 , 9-bis (3-methylol-5-aryl-4-hydroxyphenyl) fluorene [for example, 9,9-bis (4-hydroxy-5-phenyl- 9,9-bis (monomethylol-hydroxyphenyl) such as 9,9-bis (3-methylol-5-C _6-8aryl -4-hydroxyphenyl) fluorene etc.] such as 3-methylolphenyl) fluorene Fluorenes: 9,9-bis (dimethylol-hydroxyphenyl) fluorenes such as 9,9-bis (3,5-dimethylol-4-hydroxyphenyl) fluorene.

In the formula (3), Z ² , R ⁴ , p and q are the same as those in the formula (1) including a preferable range. Typical compounds represented by the formula (3) include monophenols {for example, phenol, alkylphenol [cresol (o-cresol, m-cresol, p-cresol), ethylphenol (2-ethylphenol, etc.)]. Mono C _1-20 alkylphenols such as butylphenol, octylphenol, nonylphenol (eg mono C _1-10 alkylphenols etc.); di-C _1-10 alkylphenols such as xylenol], cycloalkylphenols (eg 2-cyclohexylphenol), arylphenols (Such as o-phenylphenol), alkoxyphenol (such as anisole such as o-methoxyphenol), phenol having a substituent such as aminophenol; Tall (alpha-naphthol, etc. β- naphthol), alkyl naphthol (methyl naphthol, ethyl naphthol, dimethyl naphthol, etc. C _1-4 alkyl naphthol such as propyl naphthol), etc.], etc.}, phenols having a plurality of phenolic hydroxyl groups [For example, dihydroxybenzene (catechol, resorcinol, hydroquinone), alkyl-dihydroxybenzene (mono- or di-C _1-6 alkyl-dihydroxybenzene such as dihydroxytoluene and dihydroxyxylene), aryl-dihydroxybenzene (2,3-dihydroxybiphenyl) , _{3,4-C 6-8} aryl such as dihydroxybiphenyl - dihydroxybenzene etc.), alkoxy - mono- or such dihydroxybenzene (3-methoxy catechol C _1-6 alkoxy - such as dihydroxybenzene), trihydroxy benzenes (pyrogallol, hydroxyhydroquinone, polyhydric phenols such as phloroglucinol, etc.); biphenol, bisphenols (bisphenol A, bisphenol F, and bisphenol S), etc.] Etc.

  In particular, the compound represented by the formula (3) may be a compound represented by the following formula (3A) (phenol corresponding to the formula (1A)). When such compounds are used as phenols, side reactions are unlikely to occur, and it is easy to obtain a compound represented by the formula (1) (or (1A)) efficiently.

(In the formula, R ⁴ , X ¹ , X ² and X ³ are the same as above.)
Representative examples of the compound represented by the formula (3A) include phenols substituted at the 2-position (or one ortho-position) and the 4-position (para-position) [for example, 2,4-dialkylphenol (for example, 2 2,4-C _1-4 alkylphenols such as, 4-xylenol)], etc., phenols substituted in the 2 and 6 positions (two ortho positions) [eg 2,6-dialkylphenols (eg 2,6 -2,6- _C1-4 alkylphenols such as xylenol)] resorcinol substituted at the 2- and 4-positions [eg 2,4-dialkylresorcinol (eg 2,4 such as 2,4-dimethylresorcinol) -C _1-4 alkyl resorcinol), etc.], 2-position and phloroglucinol the 4-position is substituted [for example, 2,4-dialkyl fluorosilicone Group Nord (e.g., 2,4-dimethyl-furo 2, _{4-C 1-4} alkyl phloroglucinol such phloroglucinol)], and others.

  In the reaction, the ratio of use with the compound represented by the formula (3) can be appropriately selected according to the number of ps in the formula (2), for example, the compound represented by the formula (2) 2 mol or more (for example, 2-20 mol) with respect to 1 mol, Preferably it is 2-15 mol, More preferably, 2-10 mol (for example, 2.1-8 mol) may be sufficient. In particular, in the formula (1) or (3), when p is 2, the use ratio of the compound represented by the formula (3) is 1 mol of the compound represented by the formula (2). 2-10 mol, Preferably it is 2-8 mol, More preferably, 2-6 mol (for example, 2-5 mol) may be sufficient.

  The reaction may be performed in the presence of an acid catalyst or a base catalyst, and typically may be performed in the presence of an acid catalyst. The acid catalyst is not particularly limited, and inorganic acids [for example, proton acids (sulfuric acid, hydrogen chloride (or hydrochloric acid), phosphoric acid, etc.), Lewis acids (boron trifluoride, aluminum chloride, zinc chloride, etc.), etc.], Organic acids {for example, sulfonic acids (alkane sulfonic acids such as methane sulfonic acid, arene sulfonic acids such as p-toluene sulfonic acid), aliphatic carboxylic acids [for example, alkane acids (for example, alkane mono-acids such as acetic acid and oxalic acid) Or a carboxylic acid such as a dicarboxylic acid). These acid catalysts may be used alone or in combination of two or more.

  The amount of the catalyst (particularly the acid catalyst) used is, for example, 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, more preferably 100 parts by weight of the compound represented by the formula (2). May be about 0.01 to 3 parts by weight. In the reaction system after synthesizing the compound represented by the formula (2), when the reaction with the compound represented by the formula (3) is carried out as it is, it is represented by the formula (2). An acid catalyst for neutralizing the base catalyst used in the synthesis of the compound may also be added.

  The reaction may be performed in a solvent. The solvent is not particularly limited. Alcohols (alkyl alcohols such as methanol, ethanol, isopropanol, and butanol, cyclohexanol, etc.), ketones (alkyl ketones such as acetone, diisopropyl ketone, and methyl isobutyl ketone, cyclohexanone, etc.), ethers (Dialkyl ethers such as diisopropyl ether, cyclic ethers such as tetrahydrofuran), glycol ethers (such as ethylene glycol monomethyl ether), alkylene glycol monoalkyl ether acetates (such as methyl cellosolve acetate and propylene glycol monomethyl ether acetate), esters (Such as ethyl acetate), nitriles, cellosolves, amides (such as dimethylformamide), sulfoxy Earth, hydrocarbons [aliphatic hydrocarbon (hexane, heptane etc.), (such as cyclohexane) alicyclic hydrocarbons, and aromatic hydrocarbons (toluene, xylene, etc.) and the like. These solvents may be used alone or in combination of two or more. In the reaction system after synthesizing the compound represented by the formula (2), when the reaction with the compound represented by the formula (3) is performed as it is, the solvent of the reaction system is used as it is. You may use, and you may add a solvent newly.

  In the reaction, the reaction temperature may be, for example, about 0 to 250 ° C., preferably 20 to 200 ° C., more preferably about 30 to 150 ° C. (for example, 50 to 100 ° C.). The reaction time may be, for example, 30 minutes to 48 hours, preferably 1 to 24 hours, more preferably about 1 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.

  In addition, the reaction mixture after completion | finish of reaction contains a solvent, a catalyst (a base catalyst, an acid catalyst, etc.), an unreacted component, etc. other than the compound represented by said Formula (1). For this reason, the compound represented by the formula (1) is separated from the reaction mixture after the reaction by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, and recrystallization, or a separation means combining these. It may be separated and purified.

[Uses of fluorene compounds and epoxy compounds]
Since the fluorene compound of the present invention (compound represented by the formula (1)) has plural (at least four) phenolic hydroxyl groups, various resin materials using such phenolic hydroxyl groups (for example, Phenol resin, epoxy resin, etc.). When used as a resin material, a phenolic hydroxyl group may be modified (for example, modified by addition of alkylene oxide) as necessary. In particular, the fluorene compound of the present invention is useful as an epoxy resin (epoxy compound) raw material. Hereinafter, the epoxy compound will be described in detail.

  The epoxy compound of the present invention is a compound obtained by epoxidizing (glycidyl etherification) the compound represented by the formula (1) or an alkylene oxide adduct thereof. An alkylene oxide adduct (specifically, an adduct in which an alkylene oxide is added to the phenolic hydroxyl group of the compound represented by the formula (1)) is represented by the formula (1) by a conventional method. It can be obtained by reacting a compound with an alkylene oxide. The number of moles of alkylene oxide added is, for example, about 1 to 10 moles, preferably 1 to 5 moles, and more preferably 1 to 4 moles (for example, 1 to 2 moles) per mole of phenolic hydroxyl group. May be. In addition, the epoxidation may be performed on a part or all of the phenolic hydroxyl group of the compound represented by the formula (1) or a group to which an alkylene oxide is added (that is, an alcoholic hydroxyl group). All the hydroxyl groups may be epoxidized.

  Representative epoxy compounds include compounds represented by the following formula (4).

[Wherein E represents the following formula (5)

(In the formula, R ⁵ represents an alkylene group, R ⁶ represents a hydrogen atom or a methyl group, and s represents an integer of 0 or more.)
Z ¹ , Z ² , R ¹ , R ² , R ³ , R ⁴ , k, m, n, p, q, r are the same as described above. ]
In the above formula (4), E corresponds to the hydroxyl group in the formula (1). In the formula (5), the group —OR ⁵ corresponds to the alkylene oxide adduct of the compound represented by the formula (1). The alkylene group R ⁵ is a C _2-6 alkylene group such as an ethylene group, a propylene group, a trimethylene group, a 1,2-butanediyl group or a tetramethylene group, preferably a C _2-4 alkylene group, more preferably a C _{2− 3} alkylene group is mentioned. When s is 2 or more, the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group.

The number (addition mole number) s of oxyalkylene groups (OR ⁵ ) may be 0 or more, for example, 0 to 10 (for example, 0 to 6), preferably 0 to 4 (for example, 0 to 2), More preferably, it may be 0 to 1, particularly 0.

  The compound represented by the formula (4) may be a compound represented by the following formula (4A) (that is, an epoxy compound corresponding to the compound represented by the formula (1A)).

Wherein Y ¹ , Y ² and Y ³ are a hydrogen atom, E or a substituent (substituent which is not a hydroxyl group), at least one of Y ¹ , Y ² and Y ³ is E, and E, Z ¹ , R ¹ , R ² , R ³ , R ⁴ , k, m, n, and r are the same as above.)
Y ¹ , Y ² , and Y ³ correspond to X ¹ , X ² , and X ³ in the formula (1A), respectively. Therefore, in the formula ^(1A), when X 1 to X ³ is a hydroxyl group, the corresponding ^Y 1 to Y ³ becomes the E (or a group represented by the formula (5)).

  The compound represented by the formula (4) (or (4A)) is an epoxy compound represented by the following formula (4B) (that is, a compound represented by the formula (1B) or an alkylene oxide addition thereof. Epoxy compounds corresponding to the body).

[Wherein R ^2B represents a hydrogen atom, R ² or the following formula:

(In the formula, R ³ , R ⁴ , Y ¹ , Y ² , Y ³ are the same as above.)
E, R ¹ , R ² , R ³ , R ⁴ , Y ¹ , Y ² , Y ³ , k are the same as above. ]
Such an epoxy compound is multifunctional having a plurality (4 or more) of epoxy groups derived from the compound represented by the formula (1), and has many aromatic skeletons. They are characterized by being easy to mold, such as excellent solvent solubility and relatively low melting temperature. Therefore, the epoxy compound of the present invention is a well-balanced epoxy compound having excellent heat moldability, moldability while having properties such as high heat resistance, high refractive index, and high strength.

(Method for producing epoxy compound)
The epoxy compound is obtained by a conventional method, for example, by reacting the compound represented by the formula (1) or an alkylene oxide adduct thereof with the compound represented by the following formula (6) (epihalohydrin). be able to.

(In the formula, X represents a halogen atom, and R ⁶ is the same as described above.)
In the compound represented by the above formula (6), examples of the halogen atom represented by the group X include a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom and a bromine atom (particularly a chlorine atom) are preferable. . Specific compounds represented by the formula (6) include epihalohydrins [or halomethyloxiranes such as epichlorohydrin (chloromethyloxirane), epibromohydrin (bromomethyloxirane), etc.], 1-halomethyl- 2-methyloxirane (1-chloromethyl-2-methyloxirane etc.) etc. are mentioned.

  In the reaction with the compound represented by the formula (1) or its adduct of alkylene oxide, the use ratio of the compound represented by the formula (6) is the compound represented by the formula (1) or its alkylene oxide. For example, 1 to 30 mol (for example, 1.2 to 25 mol), preferably 1.3 to 20 mol, and more preferably 1.5 to 15 mol (for example, 2 mol) with respect to 1 mol of the hydroxyl group of the adduct. About 10 mol).

  In the epoxidation reaction (reaction of the compound represented by the above formula (1) or an adduct thereof with an alkylene oxide and the compound represented by the formula (6)), a catalyst may be appropriately used. Examples of the catalyst include a base (base catalyst), for example, a metal carbonate (an alkali metal such as sodium carbonate or an alkaline earth metal carbonate, an alkali metal such as sodium hydrogencarbonate or an alkaline earth metal bicarbonate), a carboxylic acid, and the like. Metal salt (such as alkali metal acetate or alkaline earth metal salt such as sodium acetate and calcium acetate), metal hydroxide (alkaline metal hydroxide such as sodium hydroxide and potassium hydroxide, alkaline earth such as calcium hydroxide) Examples thereof include inorganic bases such as metal hydroxides) and ammonia; organic bases such as amines and basic ion exchange resins (for example, strongly basic anion exchange resins having a quaternary ammonium base). The bases may be used alone or in combination of two or more.

  The amount of the catalyst (for example, base catalyst) used depends on the type of the catalyst, but for example, for example, 0.1 to 0.1 mol of the compound represented by the formula (1) or 1 mol of its alkylene oxide adduct. It may be about 20 mol, preferably about 0.2 to 10 mol, and more preferably about 1 to 5 mol.

  The reaction may be performed in the absence of a solvent or in a solvent.

  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 or may be performed while removing by-products. The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (such as nitrogen or a rare gas), and may be performed under normal pressure, increased pressure, or reduced pressure.

  In addition, the produced | generated compound (compound represented by said Formula (4)) was combined with separation methods, 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.

[Curable composition and cured product thereof]
The present invention includes a curable composition (epoxy resin composition) containing the epoxy compound. In addition, the epoxy component which comprises a curable composition is only the compound (or the epoxy compound represented by the said Formula (4)) which epoxidized the compound represented by the said Formula (1) or its alkylene oxide adduct. It may be configured and may contain other epoxy compounds (epoxy resins) as long as the effects of the present invention are not impaired. 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 ring-containing epoxy resins such as naphthalene) alkanes), glycidyl ester type epoxy resins, other epoxy resins having a fluorene skeleton. These other epoxy resins may be used alone or in combination of two or more.

  When other epoxy resin is used, the ratio of the compound represented by the above formula (1) or the epoxidized alkylene oxide adduct thereof to the entire epoxy resin component is, for example, 50 to 99.5% by weight, preferably May be 70 to 99% by weight (for example, 80 to 98.5% by weight), more preferably about 90 to 98% by weight.

The curable composition usually may further contain a curing agent. 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, phenol resins (novolak resins such as phenol novolak resins, cresol novolak resins, aralkyl novolak resins, etc.); phenols having a fluorene skeleton [eg, 9,9- Bis (hydroxyphenyl Fluorene (eg, 9,9-bis (4-hydroxyphenyl) fluorene), 9,9-bis (alkyl-hydroxyphenyl) fluorene (eg, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene 9,9-bis (mono- or di-C _1-4 alkyl-hydroxyphenyl) fluorene) such as 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (aryl- 9,9 such as hydroxyphenyl) fluorene (eg, 9,9-bis (mono or di C _6-10 aryl-hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene) -Bis (hydroxyphenyl) fluorenes; 9,9-bis (hydroxynaphthyl) fluorenes and the like] What phenolic compounds} like. These curing agents may be used alone or in combination of two or more.

  A non-volatile or relatively high boiling point curing agent may be suitably used. When the curing agent has a boiling point, the boiling point of the curing agent is, for example, 120 ° C. or higher (for example, 130 to 400 ° C.), preferably 150 ° C. or higher (for example, 160 to 350 ° C.), and more preferably 180 ° C. or higher (for example, , 190 to 330 ° C.), particularly about 200 ° C. or higher (for example, 220 to 300 ° C.)

  In the curable composition, the ratio of the curing agent is the curing agent with respect to 1 mol of the epoxy group of the compound (or epoxy resin component) obtained by epoxidizing the compound represented by the formula (1) or an alkylene oxide adduct thereof. Functional group of 0.1 to 5.0 mol, preferably 0.3 to 2.0 mol (for example, 0.5 to 1.5 mol), more preferably 0.7 to 1.2 mol (for example, You may adjust the ratio of both components so that it may become 0.9-1.1 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 with respect to 100 parts by weight of the compound (or epoxy resin component) obtained by epoxidizing the compound represented by the formula (1) or an alkylene oxide adduct thereof. ˜30 parts by weight, preferably 0.05 to 20 parts by weight, more preferably about 0.1 to 10 parts by weight.

  If necessary, the curable composition may be prepared by adding a diluent (a reactive diluent such as a monofunctional epoxy compound, a solvent, etc.) and a conventional additive such as a colorant, a stabilizer (a heat stabilizer, an oxidation agent). An inhibitor, an ultraviolet absorber, etc.), a filler, an antistatic agent, a flame retardant, a flame retardant aid, and the like. Diluents and additives may be used alone or in combination of two or more.

  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 dot-shaped 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 is melted by heating, poured into a predetermined mold and heated to be cured, and a molded body having a desired shape can be obtained. Moreover, a cured film can be formed on a base material by apply | coating the liquid said curable composition on a base material, drying, and then heating. The molding method and the curing conditions are not particularly limited. For example, when molding using a predetermined mold, a molding method by heating and pressurization or a low-temperature molding method called cold press is used.

  When the curable composition is heated and melted, the heating temperature is, for example, 80 ° C. or higher (for example, 90 to 400 ° C.), preferably 100 ° C. or higher (for example, 110 to 350 ° C.), and more preferably 120 ° C. or higher. (For example, 130 to 300 ° C.), particularly about 140 to 250 ° C. (for example, 145 to 220 ° C.), or about 100 to 200 ° C. (for example, 120 to 180 ° C.).

  The curing treatment can be performed by heating or the like, and may be performed in combination. 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 into 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 method, gravure coating method, spray coating method, dipping method, screen The printing method etc. can be mentioned.

  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 resin 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.

  As described above, the coating film applied to the substrate is usually subjected to a curing treatment after being dried as necessary. In the curing process, the heating temperature and the heating time can be selected from the same ranges as described above.

  The cured product thus obtained has properties such as high heat resistance, high mechanical properties, and a high refractive index.

  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 by the following methods.

(Glass transition temperature (Tg))
The glass transition temperature (Tg) was measured with a differential scanning calorimeter (DSC, manufactured by SII, “DSC6220”).

(5% weight loss temperature)
A 5 wt% weight reduction temperature was measured by a differential thermogravimetric simultaneous measurement apparatus (TG / DTA, manufactured by SII, “TG / DTA6200”).

(Melt viscosity)
Using an ICI viscometer (cone & plate type, viscometer CAP2000 + H manufactured by Brookfield), the temperature was measured at 150 ° C. with cone 3 at 900 rpm.

(Bending test (strength / elastic modulus))
The bending test was measured by a method based on JIS K 7197.

( Synthesis Example 1)
Into a reactor having an internal volume of 1 L equipped with a stirrer and a cooling tube, 9,9-bis (4-hydroxy-3-methylol-5-methylphenyl) fluorene (synthesized according to Example 1 of JP 2008-273844 A) 190 g, 330 g of methyl isobutyl ketone, 266 g of 2,6-xylenol (5 mol relative to 1 mol of fluorene) and 4.5 g of oxalic acid were added and reacted at 120 ° C. with stirring for 6 hours. . After the reaction, methyl isobutyl ketone and unreacted 2,6-xylenol were distilled off under vacuum to obtain a product. The product was analyzed and confirmed to be a compound having the following structure.

¹³ C-NMR (CD ₃ OCD ₃ , d): 16.8 ppm (6C), 36.1 ppm (2C), 65.2 ppm (1C), 120.9 ppm (2C), 124.5 ppm (6C), 127. 1 ppm (4C), 128.1 ppm (4C), 128.4 ppm (2C), 128.8 ppm (4C), 129.5 ppm (2C), 132.6 ppm (2C), 138.2 ppm (2C), 140.8 ppm (2C), 152.2 ppm (2C), 152.3 ppm (2C), 153.2 ppm (2C).

  FD-MS: m / z 646.

(Example 1 )
100 g (0.155 mol) of product and 228 g of epichlorohydrin (2.48 mol, 1 mol of 1 mol of phenolic hydroxyl group of the product) obtained in a 1 L container having a stirrer, a condenser and a burette. The reaction solution was stirred at 60 ° C. to dissolve the product. Sodium hydroxide 24.8 g (0.620 mol) was added in six portions every 15 minutes, and the mixture was stirred at 60 ° C. for 4 hours. Epichlorohydrin 57 g (0.62 g) and sodium hydroxide 6.2 g (0.16 g) were added, and the mixture was further stirred for 1 hour. After completion of the reaction, 300 ml of methyl isobutyl ketone was added to the reaction solution and stirred at room temperature. The reaction solution was filtered through Celite. The obtained filtrate was further washed with 100 ml of methyl isobutyl ketone and 200 ml of distilled water. After washing, 150 g of sodium sulfate was added to the obtained organic layer and filtered through Celite. The obtained filtrate was evaporated under reduced pressure with an evaporator and dried with a drier to obtain a solid with a yield of 84%. As a result of analyzing the obtained solid, it was confirmed that it was an epoxy compound represented by the following formula.

¹³ C-NMR (THF-d ₈ , δ): 15.6 ppm (4C), 15.7 ppm (2C), 35.1 ppm (2C), 43.3 ppm (2C), 43.4 ppm (2C), 49. 9ppm (2C), 50.0ppm (2C), 64.7ppm (1C), 73.5ppm (2C), 73.8ppm (2C), 119.9ppm (2C), 126.1ppm (2C), 127.1ppm (2C), 127.3 ppm (2C), 128.3 ppm (2C), 129.1 ppm (2C), 129.3 ppm (4C), 130.0 ppm (2C), 130.2 ppm (4C), 133.9 ppm ( 2C), 136.5 ppm (2C), 140.1 ppm (2C), 141.3 ppm (2C), 151.8 ppm (2C), 153.9 ppm (2C) 154.2ppm (2C)
FD-MS: m / z 870.

  The resulting epoxy compound had a glass transition temperature of 189 ° C., a melt viscosity at 150 ° C. of 1308 mPa · s, and a 5 wt% weight reduction temperature of 250 ° C.

  Further, the obtained epoxy compound was completely dissolved in a general-purpose solvent (methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, etc.) even at a high concentration of 20% by weight at room temperature (25 ° C.).

(Comparative Example 1)
9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd.) and epichlorohydrin Synthesized by reaction. Hereinafter, the glass transition temperature of BCFG] was measured and was as high as 189 ° C., but did not melt at 150 ° C. BCFG was not dissolved in general-purpose solvents (such as methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate) at 20% by weight at room temperature (25 ° C.).

(Example 2 )
The epoxy compound obtained in Example 1 and a phenol novolak resin (manufactured by Gunei Chemical Industry Co., Ltd., PSM-4261, hydroxyl group equivalent of 105, softening temperature of about 80 ° C.) as the curing agent were combined with the former / the latter (equivalent ratio). ) = 1/1, and melt-mixed at 160 ° C. for 5 minutes using a two roll (manufactured by Inoue Seisakusho, roll rotation speed: front 23.0 rpm, back 20.7 rpm). To the molten mixture, triphenylphosphine as a curing accelerator was added at a ratio of 1% by weight, and again mixed at 110 ° C. for 3 minutes using a two-roll. Thereafter, the obtained mixture was pulverized in a mortar.

The pulverized mixture was put into a mold and pressed and hardened with a cold pressure (about 100 kgf / cm ² ) to form a tablet. The tablet is put in a mold (150 mm × 150 mm × 0.5 mm) heated to 150 ° C., and this mold is set in a press machine (26 ton manual compression molding machine, manufactured by Toho Press) and pressed to 100 kgf / cm ^2. did. The pressure was maintained for 15 minutes (5 minutes at the initial temperature, 10 minutes at 150 ° C.), and then cooled at 100 kgf / cm ² with a cooling press (water cooling). The obtained cured product was post-cured with a dryer at 175 ° C. for 5 hours.

  The obtained cured product had a flexural modulus and a flexural strength at 25 ° C. of 3310 MPa and 74.1 MPa, respectively, and was found to be a high-strength cured product.

  Since the fluorene compound of the present invention has 4 or more phenolic hydroxyl groups and has many aromatic skeletons containing a fluorene skeleton, a resin having excellent characteristics can be obtained efficiently when used as a resin raw material. be able to. In particular, the epoxy compound of the present invention obtained using such a fluorene compound has excellent moldability (handling properties and solvent solubility) despite having many aromatic skeletons. It is useful for imparting heat resistance, high refractive index, excellent mechanical strength and the like to the resin.

  The use of such a resin can be selected according to the type of resin. For example, an epoxy compound (epoxy resin) is an insulating material (such as an insulating material between electronic component layers), a resist material (such as a solder resist for printed circuit boards) In addition to being useful as color filters, inks (printing inks, etc.), sealants (semiconductor sealants, etc.), paints, coating agents, adhesives, adhesives, antistatic agents, fillers, conductive members or Conductive materials, laminated materials, thermal materials (thermal paper materials, etc.), carbon materials, insulating materials, foams, pressure sensitive materials, optical materials (transparent materials) [eg lenses (reflow lenses, pickup lenses, micro lenses, etc.) , Polarizing film, antireflection film, touch panel film, display film, fuel cell film, optical fiber, optical waveguide, hologram, etc. It is useful as any material such as a resin material] constituting the (electric and electronic materials, optical materials).

Claims (8)

An epoxy compound represented by the following formula (4) .

[ Wherein , rings Z ¹ and Z ² are the same or different and each is an aromatic hydrocarbon ring, R ¹ and R ² are the same or different and each is a substituent, and R ³ is the same or different and each represents a hydrogen atom or a hydrocarbon group. , R ⁴ is the same or different and is not a hydroxyl group, k is the same or different and is an integer of 0 to 4, m and p are the same or different and are each an integer of 0 or more, n, q and r are the same Or, differently, it represents an integer of 1 or more, and E represents the following formula (5)

(In the formula, R ⁵ represents an alkylene group, R ⁶ represents a hydrogen atom or a methyl group, and s represents an integer of 0 or more.)
The group represented by these is shown. ] In formula (4), ring Z ¹ Is a benzene ring or naphthalene ring, ring Z ² Is a ring in which at least one selected from a benzene ring, a naphthalene ring, or a benzene ring and a naphthalene ring is bonded directly or via a linking group, m is 0 to 2, n is 1 or 2, and p is 0 to 4 , Q is 1 or 2, r is 1 or 2, R ² And R ⁴ The epoxy compound according to claim 1, wherein is a hydrocarbon group. In formula (4), ring Z ¹ And Z ² Is a benzene ring, m is 0 or 1, n is 1, p is 0 to 2, q is 1, r is 1, R ² Is an alkyl group, R ³ Is a hydrogen atom, R ⁴ The epoxy compound according to claim 1 or 2, wherein is an alkyl group or an aryl group. The epoxy compound in any one of Claims 1-3 represented by a following formula (4A).

Wherein Y ¹ , Y ² and Y ³ are a hydrogen atom, E or a substituent, and at least one of Y ¹ , Y ² and Y ³ is E, and E, Z ¹ , R ¹ , R ² , R ³ , R ⁴ , k, m, n, and r are the same as above.) The epoxy compound of Claim 4 represented by a following formula (4B).

[Wherein R ^2B represents a hydrogen atom, R ² or the following formula:

(In the formula, R ³ , R ⁴ , Y ¹ , Y ² , Y ³ are the same as above.)
E, R ¹ , R ² , R ³ , R ⁴ , Y ¹ , Y ² , Y ³ , k are the same as above. ] The epoxy compound according to any one of claims 1 to 5 , wherein s is 0. The curable composition containing the epoxy compound in any one of Claims 1-6 . A cured product obtained by curing the curable composition according to claim 7 .