JP5198788B2 - Epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention relates to an epoxy resin composition containing a fluorene having a phenolic hydroxyl group, and a cured product obtained by curing the epoxy resin composition. The present invention also relates to a curing agent for epoxy resin and a method for improving solder crack resistance of a cured product obtained by curing an epoxy resin.

  Epoxy resins are generally cured with various curing agents to form a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. Therefore, it is used in a wide range of fields such as adhesives, paints, laminates, molding materials and casting materials. Conventionally, as an epoxy resin most used industrially, there is a liquid or solid bisphenol A type epoxy resin. Such a resin is used in the field of, for example, a semiconductor sealing material (Non-Patent Document 1), but has insufficient heat resistance and electrical properties, and requires high levels of heat resistance and electrical properties. It is difficult to apply in certain fields.

Further, due to the increase in environmental problems, it has become a challenge to cope with lead-free in the process of forming a semiconductor encapsulant. For this reason, switching from conventional Sn-Pb solder to lead-free solder (such as Sn-Ag solder) is progressing, but lead-free solder has a melting point of 20 ° C. or higher than conventional solder, Epoxy resins have insufficient solder crack resistance. In order to solve such a problem, it has been proposed to use a biphenyl type epoxy resin, an ortho cresol novolak epoxy resin or the like instead of the bisphenol A type epoxy resin generally used as a raw material of the epoxy resin ( Non-Patent Document 2) is a situation where even such an epoxy resin does not satisfy the current required specifications.
Hiroshi Horiuchi et al., “Performance of Epoxy Resin and Compounding Technology and Evaluation of Curing Agent, Application”, published by Technical Information Association, December 1997, first edition, pages 364-377 Masaaki Enomoto, Akira Esaka, "Heat-resistant polymer electronic materials", CMC Publishing, first published in May 2003, pages 157-160

  Accordingly, an object of the present invention is to provide an epoxy resin composition excellent in heat resistance and electrical characteristics and a cured product obtained by curing the epoxy resin composition.

  Another object of the present invention is to provide an epoxy resin composition excellent in solder crack resistance (solder heat resistance, heat resistance against solder) and a cured product obtained by curing the epoxy resin.

  Still another object of the present invention is to provide an epoxy resin composition having a wide application range and excellent practicality, and a cured product obtained by curing the epoxy resin.

  Another object of the present invention is to provide a curing agent for epoxy resins that can improve or improve properties such as heat resistance and electrical properties of epoxy resins.

  Still another object of the present invention is to provide a method for improving the solder crack resistance of an epoxy resin.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have been able to improve the heat resistance and electrical characteristics of the epoxy resin by combining the epoxy resin and fluorenes having a phenolic hydroxyl group. It has been found that the solder cracking property can be improved, and the present invention has been completed.

  That is, the epoxy resin composition of the present invention is composed of an epoxy resin and fluorenes having a phenolic hydroxyl group. In the resin composition, the epoxy resin may be, for example, a phenol type epoxy resin such as a novolac type epoxy resin.

  In the resin composition, the fluorene having a phenolic hydroxyl group may be, for example, a compound represented by the following formula (1) or a derivative thereof.

(In the formula, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a , R ^1b , R ^2a and R ^2b are the same or different and represent substituents. K1 and k2 are the same or different and represent 0-4. M1 and m2 are each an integer of 0 or 1 and n1 and n2 are each an integer of 1 or more When m1, m2, k1 or k2 is 2 or more, a plurality of R ^1a , R 2 ^1b , R ^2a and R ^2b may be the same or different.
In the formula (1), the ring Z ¹ and the ring Z ² may be a benzene ring or a naphthalene ring, and n1 and n2 may be 1 to 3, respectively. Typically, the fluorene having a phenolic hydroxyl group is at least one selected from 9,9-bis (monohydroxyphenyl) fluorenes and 9,9-bis (dihydroxyphenyl) fluorenes. In particular, 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene, 9,9-bis (dihydroxyphenyl) It may be at least one selected from fluorene and 9,9-bis (hydroxynaphthyl) fluorene.

  In the resin composition, the proportion of fluorenes having a phenolic hydroxyl group may be, for example, about 20 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin.

  The resin composition may further contain a curing accelerator (for example, amines).

  The present invention includes a cured product obtained by curing the resin composition. Such a cured product (or the resin composition) can be particularly suitably used as a sealing agent (semiconductor sealing agent) for electrical materials or electronic materials.

  The fluorenes having a phenolic hydroxyl group act as a curing agent for the epoxy resin and improve the heat resistance and various characteristics (insulating properties) of the epoxy resin. Therefore, the present invention also includes an epoxy resin curing agent composed of the fluorenes having a phenolic hydroxyl group.

  The present invention also includes a method for improving the solder crack resistance of a cured product obtained by curing an epoxy resin by using fluorenes having a phenolic hydroxyl group as a curing agent for an epoxy resin.

  In the present specification, the term “class” for a compound includes the case of “having no substituent” and the case of “having a substituent”, and “may have a substituent”. May mean.

  Since the epoxy resin composition (or its cured product) of the present invention contains phenols having a fluorene skeleton as a curing agent, it is excellent in heat resistance and electrical characteristics. In particular, since it has high heat resistance, it is excellent in solder crack resistance. Moreover, since the epoxy resin composition (or its cured product) of the present invention is excellent in various properties such as heat resistance as described above, it has a wide range of applications and is excellent in practicality. Such an epoxy resin of the present invention (or its cured product or cured molded product) is particularly excellent in solder crack resistance. Accordingly, the resin composition of the present invention or a cured product thereof is suitable as an electrical or electronic material sealing material (semiconductor sealing material, etc.), an electrical or electronic material such as a printed board, a capacitor, or a resistor, a paint, an adhesive, or the like. Used for. Furthermore, in this invention, the hardening | curing agent for epoxy resins which can improve or improve the characteristics, such as the heat resistance of an epoxy resin and an electrical property, can be provided.

  The epoxy resin composition of the present invention is composed of an epoxy resin and fluorenes having a phenolic hydroxyl group. In such a resin composition, fluorenes having a phenolic hydroxyl group seem to act as a curing agent for the epoxy resin.

(Epoxy resin)
Examples of the epoxy resin (or epoxy compound) include glycidyl ether type epoxy resins [for example, epi-bis type epoxy resins; phenol type epoxy resins; brominated epoxy resins; glycol type epoxy resins (for example, bisphenols (such as bisphenol A)) or A reaction product of an alkylene oxide adduct of the hydrogenated product and epichlorohydrin); a diglycidyl ether of an alicyclic diol (eg, 1,4-cyclohexanedimethanol diglycidyl ether), a dicyclopentadiene type epoxy Epoxy resin having an alicyclic skeleton such as resin; poly (glycidyloxyphenyl) alkane (for example, 1,1,2,2-tetrakis (4-glycidyloxyphenyl) ethane, 1,1,1-tris (glycidyloxy) Phenyl) methane etc. Or tetra _{(glycidyloxyphenyl) C 1-4} alkane), epoxy resins (e.g., 1,5-di (glycidyloxy) having a naphthalene skeleton naphthalene, 1,6-di (glycidyloxy) naphthalene, 2,6-di Di (glycidyloxy) naphthalene, 2,7-di (glycidyloxy) naphthalene, 2,7-di (2-methyl-2,3-epoxypropyloxy) naphthalene, 2,2′-diglycidyloxybinaphthalene, etc. Diglycidyloxynaphthalenes such as bis (glycidyloxynaphthyl) C _1-6 alkanes such as (glycidyloxy) naphthalene and bis (2-glycidyloxynaphthyl) methane, and these di (glycidyloxy) naphthalenes are directly bonded or A linking group (for example, an alkylene group such as methylene group or ethylene group, or Tetraglycidyl ether (for example, bis [2,7-di (glycidyloxy) naphthyl] methane) linked via an alkylidene group), an epoxy resin having a xanthene skeleton (for example, 9-phenyl-2,7- Glycidyl ether having a condensed ring skeleton such as diglycidyloxy-1,3,4,5,6,8-hexamethylxanthene, etc.], glycidylamine type epoxy resins (for example, tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol) ), Glycidyl ester type epoxy resin (for example, reaction product of aromatic dicarboxylic acid (phthalic acid etc.) or its hydrogenated product (tetrahydrophthalic acid, hexahydrophthalic acid etc.) and epichlorohydrin, dimer acid glycidyl ester Etc.), including fluorene type Epoxy compounds (fluorene-based epoxy resins) [eg, fluorenes having the above-described phenolic hydroxyl groups such as bisphenoxyethanol fluorenediglycidyl ether, bisphenol fluorenediglycidyl ether, or polyglycidyl ethers of alkylene oxide adducts thereof], nitrogen-containing Type epoxy compounds (for example, triglycidyl isocyanurate, epoxy resin having a hydantoin skeleton, N, N-diglycidyl-4-glycidyloxyaniline, etc.), peracetic acid oxidation type epoxy compounds, silicon-containing type epoxy compounds, and the like.

  Examples of the epi-bis type epoxy resin (or epi-bis type glycidyl ether) include a compound represented by the following formula (2).

(In the formula, A ¹ and A ² are the same or different and are a direct bond or linking group, R ^a , R ^b , R ^c and R ^d are the same or different and the substituents a, b, c and d are the same. Or, differently, an integer of 0 to 4, n represents an integer of 0 or more.)
In the above formula (2), examples of the linking group represented by A ¹ and A ² include an alkylene group (for example, a C _2-10 alkylene group such as an ethylene group, a trimethylene group, and a propylene group, preferably C _{2− 6} alkylene group), alkylidene group (for example, C _1-10 alkylidene group such as methylene group, ethylidene group, isopropylidene group or 2,2-propanediyl group, preferably C _1-6 alkylidene group), sulfonyl group, carbonyl Group, oxycarbonyl group (—COO—), ether group, thioether group (—S—) and the like. In addition, examples of the substituent represented by R ^{a to} R ^d include a hydrocarbon group such as an alkyl group (such as a C _1-4 alkyl group such as a methyl group) and an alkoxy group (such as C ₁ such as a methoxy group). _-4 alkoxy group), carboxyl group, acyl group such as alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), etc. Is mentioned. In addition, the number of substituents a to d is preferably 0 to 2, and more preferably 0 to 1, respectively. In the formula (2), n may be, for example, 0 to 100, preferably 0 to 50, and more preferably about 0 to 30.

As a typical epi-bis type epoxy resin, a bisphenol A type epoxy resin (such as an epoxy resin in which the linking groups A ¹ and A ² are isopropylidene groups or 2,2-propanediyl groups in the formula (2)). A bisphenol AD type epoxy resin represented by the following formula (1b) (such as an epoxy resin in which the linking groups A ¹ and A ² are ethylidene groups in the above formula (2)), a bisphenol S type epoxy resin (the above formula (2) ) In which the linking groups A ¹ and A ² are sulfonyl groups), a bisphenol F-type epoxy resin (in the formula (2), such as an epoxy resin in which the linking groups A ¹ and A ² are methylene groups), Brominated bisphenol A type epoxy resin (in the formula (2), the linking groups A ¹ and A ² are isopropylidene groups or An epoxy resin that is a 2,2-propanediyl group, at least part or all of R ^a , R ^b , R ^c , and R ^d is a bromine atom, and a, b, c, and d are 1) Bisphenol-type epoxy resins such as bisphenol-type epoxy resins and biphenyl-type epoxy resins (such as an epoxy resin in which the linking groups A ¹ and A ² are direct bonds in the formula (2)).

  Examples of the phenol type epoxy resin (phenol type glycidyl ether) include an epoxy resin represented by the following formula (3).

(In the formula, R ^e , R ^f , and R ^g are the same or different and represent a substituent. N is the same as above.)
In the above formula (3), the substituents R ^{e to} R ^g are the same as the substituents exemplified in the above-mentioned substituents R ^{a to} R ^d [for example, alkyl groups (C _{1- 4} alkyl group etc.), halogen atom etc.], hydroxyl group etc. are mentioned. In addition, the number of substituents e to g is preferably 0 to 2, and more preferably 0 to 1, respectively. Moreover, in said Formula (3), n may be 0-100, for example, Preferably it is 0-50, More preferably, about 0-30 may be sufficient.

Typical phenol type epoxy resins include phenol novolak type epoxy resins (for example, epoxy resins having 0 to 0 substituents in the above formula (3)), cresol novolak type epoxy resins (for example, the above formula ( 3), R ^e , R ^f , and R ^g are methyl groups and the number of substituents ^{e to g} is 1), brominated novolac epoxy resins (for example, in the formula (3), R ^e , R ^f , and R ^g are bromine atoms, and epoxy resins having the number of substituents ^{e to g} of 1).

  Examples of the dicyclopentadiene type epoxy resin (dicyclopentadiene type glycidyl ether) include an epoxy resin represented by the following formula (4).

(In the formula, R ^h , R ⁱ and R ^j are the same or different and represent a substituent. N is the same as above.)
In the above formula (4), the substituents R ^{h to} R ^j are the same as the substituents exemplified in the above-mentioned substituents R ^{e to} R ^g [for example, an alkyl group (C _{1- 4} alkyl group, etc.), halogen atom, hydroxyl group, etc.]. The number of substituents h to j is preferably 0 to 2, and more preferably 0 to 1, respectively. In the formula (4), n may be, for example, 0 to 100, preferably 0 to 50, and more preferably about 0 to 30.

  These epoxy resins may be used alone or in combination of two or more.

  These epoxy resins can be appropriately selected depending on the application. For example, in applications such as semiconductor encapsulants, phenol novolac type epoxy resins, biphenyl type epoxy resins and the like can be suitably used.

  In addition, the epoxy resin used by this invention may be prepared by a well-known method, and a commercial item may be used for it.

(Fluorenes having a phenolic hydroxyl group)
The fluorene having a phenolic hydroxyl group (sometimes simply referred to as fluorenes) is not particularly limited as long as it has a phenolic hydroxyl group and a fluorene skeleton, but is usually a compound represented by the following formula (1) Alternatively, it may be a derivative thereof.

(In the formula, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a , R ^1b , R ^2a and R ^2b are the same or different and represent substituents. K1 and k2 are the same or different and represent 0-4. M1 and m2 are each an integer of 0 or 1 and n1 and n2 are each an integer of 1 or more When m1, m2, k1 or k2 is 2 or more, a plurality of R ^1a , R 2 ^1b , R ^2a and R ^2b may be the same or different.
In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z ¹ and the ring Z ² include a benzene ring and a condensed polycyclic hydrocarbon ring (specifically, a condensed polycyclic ring containing at least a benzene ring). Hydrocarbon ring). The condensed polycyclic hydrocarbon corresponding to the condensed polycyclic hydrocarbon ring includes a condensed bicyclic hydrocarbon (for example, C _8-20 condensed bicyclic hydrocarbon such as indene and naphthalene, preferably C _10-16. Condensed bicyclic hydrocarbons) and condensed tricyclic hydrocarbons (for example, anthracene, phenanthrene, etc.) and the like. Preferable condensed polycyclic hydrocarbons include condensed polycyclic aromatic hydrocarbons (naphthalene, anthracene, etc.), and naphthalene is particularly preferable. Rings Z ¹ and Z ² may be the same or different rings, and may usually be the same ring.

Preferred rings Z ¹ and Z ² include a benzene ring and a naphthalene ring, and a benzene ring is particularly preferred.

The substituents represented by the groups R ^1a and R ^1b are not particularly limited, and may be a cyano group, a hydrocarbon group (for example, an alkyl group or the like), and is usually an alkyl group in many cases. Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . The groups R ^1a and R ^1b may be different from each other or the same. When k1 (or k2) is 2 or more, the groups R ^1a (or R ^1b ) may be different or the same in the same ring.

Note that the bonding position (substitution position) of the group R ^1a (or R ^1b ) with respect to the benzene ring constituting the fluorene skeleton is not particularly limited. Preferred substitution numbers k1 and k2 are 0 or 1, in particular 0. The substitution numbers k1 and k2 may be different but are usually the same.

Ring ^{Z 1} and ring ^{Z 2} substituents which n1 and n2 of the hydroxyl groups substituted is not particularly limited as long as n1 and n2 are satisfied one or more, respectively, for example, 1-4, preferably 1-3, more preferably May be 1-2, especially 1. In particular, when ring Z ¹ and ring Z ² are benzene rings, n 1 and n 2 may each be 1-2, especially 1. In addition, the substitution numbers n1 and n2 of the hydroxyl group may be the same or different in each of the rings Z ¹ and Z ² and are 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 position of the ring Z ¹ and the ring Z ^2. In particular, when ring Z ¹ and ring Z ² are benzene rings, the hydroxyl group is substituted at the 3-position (or meta position) or 4-position (or para position) relative to the position at which the benzene ring is bonded to fluorene. In particular, it is often substituted at least at the 4-position (para-position).

As substituents R ^2a and R ^2b for substituting ring Z ¹ and ring Z ² (hereinafter, collectively referred to as ring Z), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group) C _1-20 alkyl group such as butyl group, s-butyl group, t-butyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group, etc., cycloalkyl group (cyclopentyl group, A C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 cycloalkyl group), an aryl group [eg, a phenyl group, an alkylphenyl group (methyl Phenyl group (or tolyl group, 2-methylphenyl group, 3-methylphenyl group, etc.), dimethylphenyl group (xylyl group, etc.), naphth _{C 6-10} aryl group such group, preferably a _{C 6-8} aryl group, especially a phenyl group, an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group) Hydrocarbon groups such as; alkoxy groups (C _1-4 alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group and t-butoxy group); acyl groups (C ₁ such as acetyl group) _-6 an acyl group); an alkoxycarbonyl group (such as a C _1-4 alkoxycarbonyl group such as methoxycarbonyl group), a halogen atom (fluorine atom, such as chlorine atom); nitro group; cyano group; carboxyl group; amino group; substituted An amino group (dialkylamino group etc.) etc. are mentioned.

Preferred substituents R ^2a and R ^2b are an alkyl group (eg, a C _1-6 alkyl group), a cycloalkyl group (eg, a C _5-8 cycloalkyl group), an aryl group (eg, a C _6-10 aryl group). , A hydrocarbon group such as an aralkyl group (for example, a C _6-8 aryl-C _1-2 alkyl group), a C _1-4 alkoxy group, etc., in particular, a C _1-4 alkyl group (particularly a methyl group), C _{A 6-8} aryl group is preferred. When m1 or m2 is 2 or more, the substituents R ^2a and R ^2b may be substituted alone or in combination of two or more in the same ring (ring Z ¹ or ring Z ² ). Further, the substituents R ^2a and R ^2b substituted on different rings Z ¹ and Z ² may be the same or different from each other, and may be usually the same.

The substitution numbers m1 and m2 of the substituents R ^2a and R ^2b can be appropriately selected according to the kind of the ring Z ¹ and the ring Z ² , and are not particularly limited. For example, 0 to 8, preferably 0 to 6 (For example, 1-5), More preferably, about 0-4 may be sufficient. In particular, when ring Z ¹ and ring Z ² are benzene rings, the number of substitutions m1 and m2 depends on the number of substitutions n1 and n2 of the hydroxyl group, but 0 to 3, preferably 0 to 2, respectively. 1 in particular. Incidentally, substituents which m1 and m2, in each ring Z ¹ and Z ^2, which may be identical or different, typically, is often the same.

  Typical fluorenes having a phenolic hydroxyl group include, for example, (1) 9,9-bis (hydroxyphenyl) fluorenes, (2) 9,9-bis (hydroxynaphthyl) fluorenes, and the like.

(1) 9,9-bis (hydroxyphenyl) fluorenes 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (monohydroxyphenyl) fluorenes, 9,9-bis (dihydroxyphenyl) Fluorenes, 9,9-bis (trihydroxyphenyl) fluorenes [eg, 9,9-bis (trihydroxyphenyl) fluorene such as 9,9-bis (2,4,6-trihydroxyphenyl) fluorene] In general, 9,9-bis (monohydroxyphenyl) fluorenes or 9,9-bis (dihydroxyphenyl) fluorenes, particularly 9,9-bis (monohydroxyphenyl) fluorenes, can be preferably used.

As 9,9-bis (monohydroxyphenyl) fluorenes, for example, 9,9-bis (hydroxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene (bisphenolfluorene) and the like], substituents 9,9-bis (monohydroxyphenyl) fluorene {e.g., 9,9-bis (alkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene (biscresol fluorene), 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-butylphenyl) fluorene, 9,9-bis (3-hydroxy-2-methylphenyl) fluorene 9,9-bis such _{(C 1-4} alkyl - hydroxyphenyl) fluorene 9,9-bis (diC _1-4 alkyl-hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-2,6-dimethylphenyl) fluorene], 9,9-bis (cycloalkyl) -Hydroxyphenyl) fluorene [eg, 9,9-bis (C _5-8 cycloalkyl-monohydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene], 9,9 -Bis (aryl-hydroxyphenyl) fluorene [eg, 9,9-bis (C _6-8 aryl-hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene], 9 , 9-bis (aralkyl-hydroxyphenyl) fluorene [for example, 9,9-bis (4-hydro Shi-3-benzyl-phenyl) fluorene such as 9,9-bis _{(C 6-8} aryl _{C 1-2} alkyl - hydroxyphenyl) fluorene, etc.], 9,9-bis (alkoxy - hydroxyphenyl) fluorene [e.g., 9 , 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, etc., 9,9-bis (C _1-4 alkoxy-hydroxyphenyl) fluorene etc.] and the like}.

As 9,9-bis (dihydroxyphenyl) fluorenes, fluorenes corresponding to the 9,9-bis (monohydroxyphenyl) fluorenes, for example, 9,9-bis (dihydroxyphenyl) fluorene [9,9- Bis (2,3-dihydroxyphenyl) fluorene, 9,9-bis (2,4-dihydroxyphenyl) fluorene, 9,9-bis (3,4-dihydroxyphenyl) fluorene (biscatecholfluorene), 9,9- Bis (3,5-dihydroxyphenyl) fluorene, etc.], 9,9-bis (dihydroxyphenyl) fluorene having a substituent {for example, 9,9-bis (alkyl-dihydroxyphenyl) fluorene [9,9-bis (3 , 4-Dihydroxy-5-methylphenyl) fluorene, 9,9-bis (3,4) Dihydroxy-6-methylphenyl) fluorene such as 9,9-bis _{(C 1-4} alkyl - dihydroxyphenyl) fluorene, 9,9-bis (2,4-dihydroxy-3,6-dimethylphenyl) of fluorene 9 , 9-bis _{(di-C 1-4} alkyl - dihydroxyphenyl) fluorene, etc.], 9,9-bis (aryl - dihydroxyphenyl) fluorene [e.g., 9,9-bis (3,4-dihydroxy-5-phenylphenyl ) 9,9-bis (C _6-8 aryl-dihydroxyphenyl) fluorene such as fluorene], 9,9-bis (alkoxy-dihydroxyphenyl) fluorene [eg, 9,9-bis (3,4-dihydroxy-) 5-methoxyphenyl) fluorene such as 9,9-bis _{(C 1-4} alkoxy - Jihido Kishifeniru) fluorene], etc.}, and others. The 9,9-bis (trihydroxyphenyl) fluorenes include fluorenes corresponding to the 9,9-bis (dihydroxyphenyl) fluorenes such as 9,9-bis (2,3,4-trihydroxyphenyl). ) Fluorene, 9,9-bis (2,4,6-trihydroxyphenyl) fluorene, 9,9-bis (2,4,5-trihydroxyphenyl) fluorene, 9,9-bis (3,4,5) 9,9-bis (trihydroxyphenyl) fluorene such as -trihydroxyphenyl) fluorene.

  Note that bis (monohydroxyphenyl) fluorenes can be prepared by various synthesis methods, for example, (a) a method of reacting a fluorenone with a phenol in the presence of hydrogen chloride gas and mercaptocarboxylic acid (reference [J. Appl. Polym. Sci., 27 (9), 3289, 1982], JP-A-6-145087, JP-A-8-217713), (b) 9-fluorenone in the presence of an acid catalyst (and alkyl mercaptan) A method of reacting alkylphenols (JP 2000-26349 A), (c) a method of reacting fluorenones and phenols in the presence of hydrochloric acid and thiols (such as mercaptocarboxylic acid) (JP 2002-47227 A). (D), (d) in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acid), fluorenones and phenols are reacted to form hydrocarbons It can manufacture using the method (Japanese Unexamined Patent Publication No. 2003-221352) etc. which make it crystallize with the crystallization solvent comprised by the kind and the polar solvent.

  In addition, 9,9-bis (di- or trihydroxyphenyl) fluorenes can be obtained by using the corresponding polyhydric alcohols (dihydroxy) instead of phenols in the above-mentioned 9,9-bis (monohydroxyphenyl) fluorenes production method. Phenols and trihydroxyphenols). Among these methods, in particular, when the method (c) using hydrochloric acid or the method (d) using a specific crystallization solvent is applied, the product may be obtained with higher yield and higher purity. Many.

(2) 9,9-bis (hydroxynaphthyl) fluorenes, for example, 9,9-bis (hydroxynaphthyl) fluorenes {for example, 9,9-bis (hydroxynaphthyl) fluorene [for example, 9,9-bis [6 -(2-hydroxynaphthyl)] fluorene (or 6,6- (9-fluorenylidene) -di (2-naphthol)), 9,9-bis [1- (6-hydroxynaphthyl)] fluorene (or 5,5 -(9-fluorenylidene) -di (2-naphthol)), 9,9-bis [1- (5-hydroxynaphthyl)] fluorene (or 5,5- (9-fluorenylidene) -di (1-naphthol)) 9,9-bis [1- (6- (2-hydroxynaphthyl)] fluorene [or 5,5 ′-(9-fluorenylidene) -di (2-naphthol)] and the like] 9,9-bis (monohydroxynaphthyl) fluorene which may have a substituent}, 9,9-bis (polyhydroxynaphthyl) fluorene corresponding to these 9,9-bis (monohydroxynaphthyl) fluorenes (For example, 9,9-bis (di- or trihydroxynaphthyl) fluorenes) and the like.

  In addition, 9,9-bis (hydroxynaphthyl) fluorenes are produced by using hydroxynaphthalenes (for example, naphthol (1-naphthol) instead of phenols in the method for producing 9,9-bis (monohydroxyphenyl) fluorenes. Naphthols such as 2-naphthol) and polyhydroxynaphthalenes such as dihydroxynaphthalene).

  These fluorenes having a phenolic hydroxyl group may be used alone or in combination of two or more.

Preferred fluorenes having a phenolic hydroxyl group include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene (for example, 9,9-bis (mono or di C _1-4). 9,9-bis (hydroxyphenyl) fluorenes (especially 9,9-bis (monohydroxyphenyl) fluorenes and 9,9-bis (dihydroxyphenyl) fluorenes) such as alkyl-hydroxyphenyl) fluorene) At least one selected from the group consisting of 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-monohydroxyphenyl) fluorene [in particular, 9,9-bis (4-hydroxy-3) -Methylphenyl) fluorene (biscresol fluorene), 9,9-bis (4 9,9-bis (mono or diC _1-4 alkyl-hydroxyphenyl) fluorene] such as -hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene [in particular 9 9,9-bis (C _6-8 aryl-hydroxyphenyl) fluorene] such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene], 9,9-bis (dihydroxyphenyl) fluorene [for example, biscatechol Fluorene etc.], and at least one selected from 9,9-bis (hydroxynaphthyl) fluorene is preferred.

In particular, the fluorene having a hydrocarbon group in the ring Z ¹ and the ring Z ² such as 9,9-bis (alkyl-hydroxyphenyl) fluorene and 9,9-bis (aryl-hydroxyphenyl) fluorene includes the ring Z ¹ and the ring Compared with the case of using fluorene having an unsubstituted fluorene skeleton in Z ² [for example, 9,9-bis (4-hydroxyphenyl]) fluorene], it is advantageous in improving heat resistance. Further, fluorenes in which ring Z ¹ and ring Z ² such as 9,9-bis (hydroxynaphthyl) fluorene are condensed aromatic hydrocarbon rings such as naphthalene ring are not only improved in heat resistance and refractive index. Further, the thermal expansion can be reduced, which is advantageous in improving the dimensional accuracy.

The derivative of the compound represented by the formula (1) or a derivative thereof is a condensate of fluorenes having a phenolic hydroxyl group [for example, a phenol resin containing a fluorene having a phenolic hydroxyl group as a phenol component (for example, a novolak resin). )] And the like. Such a phenol resin may be a phenol resin having only a fluorene having a phenolic hydroxyl group as a phenol component, and a fluorene having a phenolic hydroxyl group and another phenol (or a phenol having no fluorene skeleton, For example, it may be a cocondensate having a phenol component such as hydroxy C _6-10 arene such as phenol, cresol and naphthol.

  The fluorene having a phenolic hydroxyl group may be usually composed of a compound represented by the formula (1).

  In the epoxy resin composition of the present invention, the ratio between the epoxy resin and the fluorene having a phenolic hydroxyl group is, for example, the former / the latter (molar ratio) = 1 / 0.01 to 1/1, preferably 1 / 0.0. It may be about 03 to 1 / 0.8, more preferably about 1 / 0.05 to 1 / 0.7. The proportion of fluorenes having a phenolic hydroxyl group is, for example, 1 to 200 parts by weight, preferably 5 to 150 parts by weight (for example, 10 to 120 parts by weight), more preferably 100 parts by weight of the epoxy resin. It may be about 20 to 100 parts by weight (for example, 20 to 80 parts by weight). In addition, the ratio between the fluorene having a phenolic hydroxyl group and the epoxy resin is usually such a ratio that the epoxy group becomes excessive with respect to the hydroxy group. For example, the epoxy group (EA) in the epoxy resin The equivalent ratio [(EA) / (HB)] of the hydroxy group (HB) in the fluorene phenol is 1 / 0.05 to 1 / 0.95, preferably 1 / 0.1 to 1 / 0.6. Further, the ratio of the fluorenes and the epoxy resin may be adjusted so that it is more preferably about 1 / 0.2 to 1 / 0.5. With such a ratio, the reaction (curing) can be performed while adjusting properties such as fluidity and strength of the epoxy resin.

  The epoxy resin composition of the present invention may further contain a curing agent, a curing accelerator (or reaction accelerator), a reactive diluent, an additive, a solvent, and the like, if necessary.

  Examples of the curing agent (or other curing agent or curing agent other than phenols having a fluorene skeleton) include phenol resin-based curing agents (phenol novolac resin, cresol novolac resin, etc.) and the like. These curing agents may be used alone or in combination of two or more. When using a curing agent (other curing agent), the ratio of the curing agent is 100 parts by weight or less (for example, 0.1 to 70 parts by weight), preferably 100 parts by weight of phenols having a phenolic hydroxyl group. May be 50 parts by weight or less (for example, 0.5 to 30 parts by weight), more preferably 20 parts by weight or less (for example, 1 to 10 parts by weight). Usually, the resin composition of the present invention may not substantially contain a curing agent.

  Examples of the curing accelerator include amines {for example, amines [particularly tertiary amines such as triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, diethylenetriamine, triethylenetetramine, metaxylylenediamine, diamino. Diphenylmethane, tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5.4.0) undecene-1, imidazoles (2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl- Alkyl imidazoles such as 4-methylimidazole; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-benzyl-2-phenyl Aryl imidazoles such as ruimidazole] and derivatives thereof (eg, phenol salts, phenol novolac salts, carbonates, formate salts, etc.), alkali metal or alkaline earth metal alkoxides (sodium alkoxides such as sodium ethoxide, etc.) )}, Phosphines [eg, organic phosphines (first, second, and third phosphines) such as ethylphosphine, propylenephosphine, phenylphosphine, triphenylphosphine, trialkylphosphine, etc.], amide compounds (dimers) Acid polyamides), acid anhydrides (phthalic anhydride, tetrahydromethyl phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, methyl nadic acid anhydride, etc.), Lewis acid complex compounds (boron trifluoride / ethylamine complex) Etc.), sulfur compounds [polysulfide, mercaptan compounds (thiol compounds), etc.], halides (haloalkanes such as chloroform, dichloromethane, trichloromethane, etc.), silicon compounds [1,2-disilylethane, alkyl silicates, polyalkoxysilanes, etc. ], Boron compounds (such as phenyldichloroborane), condensable organometallic compounds [organic titanium compounds (such as tetraalkoxytitanium), organoaluminum compounds (trialkoxyaluminum such as trismethoxyaluminum, triaryloxyaluminum such as trisphenoxyaluminum) ) Etc.].

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

  Preferred curing accelerators include amines (such as imidazoles) and derivatives thereof.

  The ratio (addition amount) of the curing accelerator is, for example, 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the epoxy resin. It may be a degree. Moreover, the ratio of a hardening accelerator is 0.1-50 weight part (for example, 0.2-30 weight part) with respect to 100 weight part of fluorenes which have a phenolic hydroxyl group, Preferably 0.3-20 weight Part (for example, 0.4 to 15 parts by weight), more preferably about 0.5 to 5 parts by weight.

  As the reactive diluent, for example, a low-viscosity epoxy compound to be added for viscosity adjustment, particularly a bifunctional or higher-functional epoxy compound can be suitably used. Such reactive diluents include, for example, polyglycidyl ethers [for example, diglycidyl ether, polyol polyglycidyl ether (butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglyceride). Glycidyl ether, polyglycol diglycidyl ether, polypropylene glycol diglycidyl ether, diglycidyl aniline, cyclohexane dimethanol diglycidyl ether, alkylene diglycidyl ether, etc.], monoglycidyl ethers (for example, phenyl glycidyl ether, 4-tert- Glycidyl ethers such as butylphenyl glycidyl ether and o-phenylphenyl glycidyl ether); Alkene oxides (for example, 4-vinylcyclohexene oxide, vinylcyclohexene dioxide, such as methylated vinylcyclohexene dioxide) and the like. These reactive diluents can be used alone or in combination of two or more.

  Examples of additives include reinforcing agents or fillers, colorants, pigments, flame retardants, and curable compounds (curable monomers, oligomers, or resins).

  As the reinforcing agent or filler, a powdery or fibrous reinforcing agent or filler is used. Examples of powdery reinforcing agents or fillers include metal oxides (aluminum oxide, magnesium oxide, etc.), metal carbonates (calcium carbonate, magnesium carbonate, etc.), silicon compounds (diatomaceous earth powder, basic magnesium silicate, Examples thereof include calcined clay, finely divided silica, fused silica, and crystalline silica), metal hydroxide (such as aluminum hydroxide), kaolin, mica, quartz powder, graphite, and molybdenum disulfide. Examples of the fibrous reinforcing agent or filler include glass fiber, ceramic fiber, carbon fiber, alumina fiber, silicon carbide fiber, boron fiber, polyester fiber, and polyamide fiber.

  Examples of colorants (or pigments or flame retardants) include titanium dioxide, iron black, molybdenum red, bitumen, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, bromine compounds, triphenyl phosphate, and the like. Is mentioned. Furthermore, the curable compound is used for the purpose of improving the properties of the resin in the final coating film, adhesive layer, molded article, etc., for example, alkyd resin, melamine resin, fluororesin, vinyl chloride resin, acrylic resin, A silicone resin, a polyester resin, etc. are mentioned. You may add these additives (curable compound etc.) in the quantity of the range which does not impair the original property of the resin composition of this invention.

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

  Examples of the solvent (or solvent) include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Glycol ethers such as ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol monobutyl ether; Cole monoalkyl ether acetates; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; and 2-hydroxy Ethyl propionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate And esters such as ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate. These solvents may be used alone or in combination of two or more.

  The present invention also includes a cured product (or molded product) obtained by curing (or crosslinking) the epoxy resin composition. Such a cured product can be obtained by reacting (curing) the epoxy resin composition. Such a curing treatment may be performed while molding the epoxy resin composition or after molding (or preforming) depending on 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 epoxy resin composition, a cured film formed from a cured product of the epoxy resin composition formed on a substrate ( Coating film) or the like. For example, typically, the epoxy resin composition can be heated and melted, if necessary, poured into a predetermined mold, and cured by heating to obtain a molded body having a desired shape. Moreover, a cured film can be formed on a base material by apply | coating the liquid said epoxy composition which may contain the solvent 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. As a method by heating and pressing, for example, a method of filling the mold with the epoxy resin composition of the present invention at normal pressure by a method called hand lay-up or spray lay-up and then heat-curing; using a transfer press device Examples thereof include a method of heating and compressing by injection molding; and a continuous molding method such as a continuous lamination molding method, a continuous drawing method called pultrusion, and a filament winding molding method.

  In these molding methods, an intermediate molding material can be obtained by mixing the resin composition with a reinforcing agent or impregnating the reinforcing agent, and then molding and curing the intermediate molding material. Examples of the reinforcing agent include woven fabrics and nonwoven fabrics formed of resin, glass and the like. As an intermediate molding material using such a reinforcing agent, for example, a sheet-like intermediate molding material called SMC (sheet molding compound); a liquid or solid intermediate called BMC (berg molding compound) or premix Examples of the molding material include prepregs obtained by impregnating the epoxy resin composition of the present invention into glass cloth or mat.

  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. Usually, the curing treatment is often performed at least by heating. The curing process (or curing reaction) proceeds by the reaction (addition reaction) of the hydroxyl group of the fluorene and the epoxy group of the epoxy resin.

  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, 90 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 (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.).

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

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

  The thickness of the coating film may be, for example, about 0.01 μm to 10 mm, 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. The curing treatment can be performed by heat treatment in a gas containing water vapor or in air, usually in air. In curing, the heat treatment temperature can be selected from the same range as described above. In addition, you may perform a hardening process by light irradiation with a heating as needed.

  The epoxy resin composition of the present invention is easily cured by heat. Since such an epoxy resin composition of the present invention is excellent in molding processability, as described above, it is easy to mold into a predetermined shape by a mold or to form a thin film on a substrate. A cured product obtained by curing such an epoxy resin composition (or a molded body and a cured film) has excellent heat resistance and environmental resistance, high mechanical strength such as bending properties, high toughness, and thermal shock. And good moldability. For example, the glass transition temperature of the cured product is 155 ° C. or higher (for example, about 160 to 300 ° C.), preferably about 165 to 250 ° C.

  In addition to the properties such as heat resistance, the cured product (molded product) is excellent in insulation, has small curing shrinkage and excellent dimensional stability, so that the epoxy resin composition of the present invention (or The cured product) is useful for electrical and electronic materials such as an electrical material or an electronic material sealing agent (sealing material), a printed circuit board, a capacitor, and a resistor. In particular, the epoxy resin composition of the present invention (or a cured product thereof) has both excellent heat resistance and excellent various properties (insulating properties, mechanical properties), and therefore has excellent solder crack resistance, It can be suitably used as a sealing agent for electrical materials or electronic materials (or a sealing agent for semiconductors).

  Furthermore, since the resin composition of the present invention is excellent in heat resistance, adhesiveness, curability and the like, it is suitably used for potting materials and coating materials for various electronic parts such as capacitors. When used as a sealing material for an electronic insulating material or as a potting agent, it can be used in the same manner as a sealing resin using an epoxy resin that has been conventionally used. Furthermore, since cured | curing material is excellent in transparency, it is useful also as a thermosetting resin composition for optical devices.

  In such an epoxy resin composition of the present invention (or a cured product thereof), since the fluorene having a phenolic hydroxyl group acts as a curing agent for the epoxy resin, a fluorene skeleton is introduced into the cured product and cured. Improve the properties of the product (heat resistance, etc.). Therefore, the present invention also includes an epoxy resin curing agent composed of the fluorenes having a phenolic hydroxyl group. In particular, in the present invention, solder crack resistance can be improved at a high level by introducing a fluorene skeleton as described above. Therefore, the present invention includes a method for improving the solder crack resistance of a cured product obtained by curing an epoxy resin by using fluorenes having a phenolic hydroxyl group as a curing agent for an epoxy resin.

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

Example 1
57 parts by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (Osaka Gas Chemical Co., Ltd.) was added to 174 parts by weight of a phenol novolac epoxy resin (Japan Epoxy Resin Co., Ltd., “Epicoat 152”). ) And dissolved by heating to 170 ° C. Then, it cooled to 70 degreeC, 2-ethyl-4-methylimidazole (made by Tokyo Chemical Industry Co., Ltd.) 1.7 weight part was added as a hardening accelerator, and it stirred until the hardening accelerator melt | dissolved. The obtained mixture was poured into a 2500 mm × 2000 mm × 3 mm thick stainless steel mold and heated at 100 ° C. for 1 hour in a constant temperature drier (manufactured by ASONE Co., Ltd., DO-600FA), and subsequently heated at 180 ° C. for 4 hours. Heat cured. Using the obtained molded body (test piece), the following items were evaluated.

(1) Glass transition temperature:
The glass transition temperature (Tg) was measured by DSC (DSC220 type, manufactured by Seiko Instruments Inc.).

(2) Dielectric constant and dielectric loss tangent:
Using a 4294A type impedance analyzer (manufactured by Agilent Technologies), the dielectric constant and dielectric loss tangent were measured at a frequency of 1 MHz.

(Comparative Example 1)
In Example 1, instead of 57 parts by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 34 parts by weight of bisphenol A (manufactured by Kishida Chemical) was used, and the same as in Example 1. Test specimens were prepared and evaluated.

(Example 2)
In Example 1, instead of 57 parts by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 6,6 ′-(9-fluorenylidene) -di (2-naphthol) (or 6,6 A test piece was prepared in the same manner as in Example 1 except that 83 parts by weight of '-(9-fluorenylidene) -bis (2-naphthol), manufactured by Osaka Gas Chemical Co., Ltd., “bisnaphtholfluorene”) was used. Evaluation was performed.

(Example 3)
In Example 1, instead of 57 parts by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene (Osaka Gas Chemical) A test piece was prepared and evaluated in the same manner as in Example 1 except that 61 parts by weight were used.

Example 4
In Example 1, instead of 57 parts by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 53 weights of 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd.) A test piece was prepared and evaluated in the same manner as in Example 1 except that the part was used.

(Example 5)
In Example 1, instead of 174 parts by weight of “Epicoat 152”, 166 parts by weight of cresol novolac type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “Epicoat 828”) was used in the same manner as in Example 1. Test specimens were prepared and evaluated.

  The evaluation results of Examples and Comparative Examples are shown in Table 1.

  As is apparent from Table 1, when a fluorene having a phenolic hydroxyl group is used as a curing agent, an epoxy resin molded article having a high Tg and excellent heat resistance can be obtained as compared with the case of using bisphenol A. I understood. In addition, it was found that the use of fluorenes having a phenolic hydroxyl group is lower in both dielectric constant and dielectric loss tangent, and the performance is higher.

Claims (11)

An epoxy resin composition composed of an epoxy resin and a fluorene having a phenolic hydroxyl group ,
A resin composition in which the epoxy resin is a novolac-type epoxy resin and the fluorene having a phenolic hydroxyl group is a compound represented by the following formula (1) .

(In the formula, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a , R ^1b , R ^2a and R ^2b are the same or different and represent substituents. K1 and k2 are the same or different and represent 0-4. M1 and m2 are each an integer of 0 or 1 and n1 and n2 are each an integer of 1 or more When m1, m2, k1 or k2 is 2 or more, a plurality of R ^1a , R 2 ^1b , R ^2a and R ^2b may be the same or different. In the formula (1), a ring ^{Z 1} and the ring ^{Z 2} is a benzene ring or a naphthalene ring, the resin composition of claim 1 wherein n1 and n2 are each 1 to 3.   The resin composition according to claim 1, wherein the fluorene having a phenolic hydroxyl group is at least one selected from 9,9-bis (monohydroxyphenyl) fluorenes and 9,9-bis (dihydroxyphenyl) fluorenes. object.   Fluorenes having a phenolic hydroxyl group are 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene, 9,9- The resin composition according to claim 1, which is at least one selected from bis (dihydroxyphenyl) fluorene and 9,9-bis (hydroxynaphthyl) fluorene. The resin composition according to claim 1, wherein the fluorene having a phenolic hydroxyl group is 9,9-bis (hydroxynaphthyl) fluorene.   The resin composition according to claim 1, wherein the proportion of the fluorenes having a phenolic hydroxyl group is 20 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin.   Furthermore, the resin composition of Claim 1 containing a hardening accelerator.   A cured product obtained by curing the resin composition according to claim 1. The hardened | cured material of Claim 8 used as a sealing agent of an electrical material or an electronic material. A curing agent for a novolac-type epoxy resin composed of fluorenes having a phenolic hydroxyl group, wherein the fluorene having a phenolic hydroxyl group is a compound represented by the formula (1) according to claim 1 Agent. As a curing agent for novolac type epoxy resin, a fluorene having a phenolic hydroxyl group is used to improve the solder crack resistance of a cured product obtained by curing the novolac type epoxy resin , and the fluorene having a phenolic hydroxyl group is The method which is a compound represented by Formula (1) of Claim 1.