JP6936544B2 - Epoxy resin composition having a bisphenol fluorene skeleton - Google Patents

Description

The present invention relates to an epoxy resin composition that gives a cured product having a dielectric loss tangent and a small coefficient of linear thermal expansion, and a cured product obtained by curing the epoxy resin composition.

Epoxy resins are generally cured with a curing agent to obtain a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc. Therefore, adhesives, paints, and laminates can be obtained. It is used in a wide range of fields such as plates, molding materials, and casting materials. Conventionally, as the most industrially used epoxy resin, there is a liquid or solid bisphenol A type epoxy resin. The epoxy resin is used, for example, as a printed wiring board material in the field of electrical and electronic components (for example, Patent Document 1).

However, in the field of printed wiring board materials, in recent years, the speed and frequency of signals in various electronic devices have been increasing, so that the materials have excellent electrical characteristics (low dielectric constant, low dielectric loss tangent). It is required to have. In particular, the dielectric loss tangent (tan δ) has a great influence on the reliability of electric signals (Patent Document 2), and therefore further reduction is required. However, the bisphenol A type epoxy resin particularly exceeds 1 GHz. There is a problem that the dielectric loss tangent in the high frequency region becomes large.

Further, in the field of semiconductor devices, CSP (chip size package: Chip Size Package) has been widely adopted in recent years. Since the printed wiring board used for the CSP is required to have a small coefficient of thermal expansion, the material of the printed wiring board is also required to have a small coefficient of thermal expansion. When the type epoxy resin was used, the coefficient of thermal expansion was large, and the package may be warped or cracked.

Japanese Unexamined Patent Publication No. 7-307576 Japanese Unexamined Patent Publication No. 2004-087639

An object of the present invention is to provide an epoxy resin composition that provides a cured product having a dielectric loss tangent and a small coefficient of thermal expansion.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an epoxy resin composition containing an epoxy resin having a fluorene skeleton represented by the following general formula (1) exhibits the above-mentioned characteristics. I found it. Specifically, the present invention includes the following.

[1] The following general formula (1):

（式中、Ｒ_１〜Ｒ_４はそれぞれ同一又は異なってアルキル基、アリール基又はハロゲン原子を表し、ｎ_１及びｎ_２はそれぞれ同一又は異なって１〜４の整数を表し、ｋ_１〜ｋ_４はそれぞれ同一又は異なって０〜４の整数を表す。ｋ_１〜ｋ_４が２以上である場合、それぞれ対応するＲ_１〜Ｒ_４は同一であっても異なってもよい。ｍは０以上の整数を表す。）
で表されるエポキシ樹脂と硬化剤とを含むエポキシ樹脂組成物。

(In the formula, R _{1 to} R ₄ represent the same or different alkyl group, aryl group or halogen atom, respectively, and n _{1 and n 2} represent the same or different integers 1 to 4, respectively, and k _{1 to k 4} Represent the same or different integers from 0 to _{4. When k 1} to k 4 are 2 or more, the corresponding R _{1 to} R ₄ may be the same or different. M is 0 or more. Represents an integer.)
An epoxy resin composition containing an epoxy resin represented by (1) and a curing agent.

[2] A cured product obtained by curing the epoxy resin composition according to [1].

According to the present invention, it is possible to provide an epoxy resin composition that provides a cured product having a dielectric loss tangent and a small coefficient of thermal expansion.

Further, since the epoxy resin composition of the present invention contains an epoxy resin having a fluorene skeleton, it also has features such as high heat resistance and high refractive index.

^{6 is a 1} H-NMR (CDCl ₃ ) chart of bisphenol represented by the formula (4) obtained in Production Example 1. ^{6 is a 13} C-NMR (CDCl ₃ ) chart of bisphenol represented by the formula (4) obtained in Production Example 1. ^{6 is a 1} H-NMR (CDCl ₃ ) chart of an epoxy resin represented by the formula (5) obtained in Example 1. ^{6 is a 13} C-NMR (CDCl ₃ ) chart of an epoxy resin represented by the formula (5) obtained in Example 1. It is a mass spectrometric chart of the epoxy resin represented by the formula (5) obtained in Example 1.

<Epoxy resin composition of the present invention>
The epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin represented by the above general formula (1) and a curing agent. Hereinafter, the epoxy resin composition of the present invention will be described in detail.

_{Examples of the substituents R 1 to} R ₄ of the epoxy resin represented by the above general formula (1) contained in the epoxy resin composition of the present invention include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group and the like). An alkyl group which may have a branch of, a cyclopentyl group, a cyclic alkyl group such as a cyclohexyl group), an aryl group (for example, an aromatic group which may have a substituent such as a phenyl group or a tolyl group), Alternatively, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) is exemplified. Among these substituents, an alkyl group having 1 to 4 carbon atoms which may have a branch is preferable from the viewpoint of availability of bisphenols represented by the general formula (2) described later.

In the above general formula (1), _{k 1 to k 4} representing the number of _{substituents (R 1 to} R ₄ ) are the same or different integers of 0 to 4, and are represented by the general formula (2) described later. From the viewpoint of availability of the bisphenols to be produced, it is preferably an integer of 0 to 2, and more preferably 0 or 1. When it is 2 or more, the corresponding substituents may be the same or different.

_{In the above general formula (1), n 1} and n ₂ representing the number of methylene groups connecting a phenyl group having a hydroxyl group and one phenyl group represent integers of 1 to 4 which are the same or different, respectively, and are described later in the general formula. From the viewpoint of availability of the bisphenols represented by (2), 1 or 2 is preferable, and 1 is more preferable.

In the above general formula (1), m representing the number of polymerizations is an integer of 0 or more, preferably an integer of m = 0 to 10, more preferably an integer of m = 0 to 2, and most preferably m = 0 or 1. Is. Although it is possible to obtain a compound having a single polymerization number m by purification, usually a mixture of compounds having a plurality of polymerization numbers m is used as the epoxy resin represented by the above general formula (1). ..

Examples of the curing agent contained in the epoxy resin composition of the present invention include bisphenols, phenol resins, acid anhydrides, amines, amides, imidazoles, thermal / photocationic polymerization initiators, organic phosphorus compounds, and guanidine derivatives. , Organic acid dihydrazide, boron halide amine complex, polypeptide-based curing agent, isocyanate-based curing agent, blocked isocyanate-based curing agent, and other commonly used curing agents for epoxy resins can be used. Specific examples of these curing agents include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, and 1,3-bis ( 4-Hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylketone, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, Phenolnovolak and its modifications, 1,12-diaminododecane, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, anhydrous Phthalic acid, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 2-phenylimidazole, 2-Ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-Phenylimidazole, 1-cyanoethyl-2-undecyl imidazole trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl ] -1,3,5-triazine, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, BF ₃ -amine complex And so on. These may be used alone or in combination of two or more. Among these curing agents, acid anhydrides (4-methylcyclohexane-1,2-dicarboxylic acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydro Phthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.) are preferable, and 4-methylcyclohexane-1,2-dicarboxylic acid anhydride is more preferable. By using acid anhydrides, a cured product having excellent transparency, tracking resistance and weather resistance can be obtained.

The amount of the curing agent used is preferably 0.5 to 1.5 mol, more preferably 0.7 to 1.2 mol, based on 1 mol of the total epoxy groups in the epoxy resin composition of the present invention. Curing can be completed by using 0.5 mol or more and 1.5 mol or less of the curing agent, and as a result, a cured product having good cured physical properties can be obtained.

In the epoxy resin composition of the present invention, in addition to the epoxy resin and the curing agent represented by the above general formula (1), a reaction diluent, a curing accelerator, a solvent, and if necessary, conventional additives and the like ( For example, glass fiber, an inorganic filler, a flame retardant, a sizing agent, a coupling agent, a coloring material, a stabilizer, an antistatic material, etc.) may be contained. Further, another epoxy resin may be used in combination.

In the epoxy resin composition of the present invention, as other epoxy resins that can be used in combination with the epoxy resin represented by the above general formula (1), bisphenol A type epoxy resin, bisphenol F type epoxy resin and other bisphenol type epoxy resins are used. Polyfunctional phenolic epoxy resin such as biphenyl type epoxy resin, phenol resin, novolak type epoxy resin, naphthalene type epoxy resin (epoxy resin made from naphthalene type epoxy resin or dihydroxynaphthalene), represented by the above general formula (1) Examples thereof include fluorene-based epoxy resins other than the epoxy resins (epoxy resins made from bisphenol fluorenes other than bisphenols represented by the general formula (2) described later). These other epoxy resins may be used alone or in combination of two or more. When another epoxy resin is used in combination, the amount used is usually 70 to 10 parts by weight, preferably 50 to 30 parts by weight, based on 100 parts by weight of the total epoxy resin contained in the epoxy resin composition of the present invention. be. By using 70 to 10 parts by weight of another epoxy resin, the viscosity of the epoxy resin composition is reduced and the handleability is further improved.

Examples of the curing accelerator that may be contained in the epoxy resin composition of the present invention include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2- (dimethyl). Examples thereof include tertiary amines such as aminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) undecene-7, and phosphines such as triphenylphosphine. These curing accelerators may be used alone or in combination of two or more. When the curing accelerator is used, the amount used is usually 0.2 to 5.0 parts by weight with respect to 100 parts by weight of the total epoxy resin in the epoxy resin composition of the present invention.

The reactive diluent that may be contained in the epoxy resin composition of the present invention is a compound having a low viscosity epoxy group added for adjusting the viscosity, and in particular, a bifunctional or higher low viscosity epoxy compound is used. preferable. Examples of the reactive diluent include diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, alkylene diglycidyl ether, polyglycol diglycidyl ether, and polypropylene glycol diglycidyl. Ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, 4-vinylcyclohexene monooxide, vinylcyclohexendioxide, methylated vinylcyclohexendioxide, phenylglycidyl ether, 4-tert-butylphenyl glycidyl ether, o-phenylphenyl Examples include glycidyl ether. These reactive diluents may be used alone or in combination of two or more. The above-mentioned reactive diluent can be used within a range that does not impair the object of the present invention, and can be used, for example, within a range of 0 to 50% by weight contained in the total epoxy resin composition.

Examples of the solvent that may be contained in the epoxy resin composition of the present invention include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene. Glycol ethers such as glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, 3-methoxybutyl- Alkylene glycol monoalkyl ether acetates such as 1-acetate, aromatic hydrocarbons such as toluene and xylene, and ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone. , And ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, Examples thereof include esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.

<Curing product of the present invention>
Subsequently, the cured product of the present invention and a method for producing the same will be described in detail.

The cured product of the present invention is, for example, an epoxy resin and a curing agent represented by the above general formula (1), and other epoxy resins, reaction diluents, curing accelerators, solvents, inorganic fillers and flame retardants that can be used in combination if necessary. The epoxy resin composition of the present invention is obtained by sufficiently mixing the additives and the like to be blended as necessary until uniform, and the obtained epoxy resin composition is poured into a mold and cast. Obtained by curing with light and / or heat. For example, when curing by heat, the curing temperature varies depending on the curing agent used and other epoxy resins used in combination, but is usually in the range of 25 to 250 ° C, preferably in the range of 80 to 240 ° C, and preferably in the range of 100 to 230 ° C. The range of is more preferable. As a curing method, it is possible to cure at a high temperature at once, but it is preferable to raise the temperature stepwise to proceed with the curing reaction. Specifically, initial curing is performed at 80 to 150 ° C., and then post-curing is performed at 100 ° C. to 230 ° C.

The term "curing" as used in the present invention usually means that the epoxy resin composition is intentionally cured by heat and / or light or the like after mixing an epoxy resin, a curing agent, and other components to be blended if necessary. It means that the degree of curing may be controlled according to desired physical properties and applications. The degree of progress may be completely cured or semi-cured. The reaction rate between the epoxy group and the curing agent is usually 5 to 95%.

The cured product of the present invention is characterized by having a dielectric loss tangent and a small coefficient of thermal expansion. In the present invention, the coefficient of thermal expansion is small means that the coefficient of linear thermal expansion is small.

Specifically, the value of dielectric loss tangent is usually 0.0080 or less, preferably 0.0075 or less, and the coefficient of linear thermal expansion is usually 65 ppm or less, preferably 60 ppm or less.

Further, the cured product of the present invention is also characterized by high heat resistance because it is obtained by curing an epoxy resin composition containing an epoxy resin represented by the above general formula (1) having a fluorene skeleton. Specifically, the glass transition temperature, which is an index of physical heat resistance, is usually 130 ° C. or higher, preferably 140 ° C. or higher, and the 5% weight loss temperature, which is an index of chemical heat resistance, is usually 260 ° C. or higher. It is preferably 280 ° C. or higher.

The dielectric loss tangent, the coefficient of linear thermal expansion, the glass transition temperature, and the 5% weight loss temperature in the present invention are values measured by the measuring methods described later.

<Manufacturing method of epoxy resin represented by the above general formula (1)>
The epoxy resin represented by the above general formula (1) contained in the epoxy resin composition of the present invention is produced by, for example, a production method described later, and the following general formula (2):

（式中、Ｒ_１〜Ｒ_４、ｎ_１及びｎ_２、ｋ_１〜ｋ_４は前述の通りである。）
で表されるビスフェノール類とエピハロヒドリンとを反応させる方法により製造可能である。以下、上記一般式（１）で表されるエポキシ樹脂の製造方法について詳述する。

(In the formula, R _{1 to} R ₄ , n ₁ and n ₂ , and k _{1 to k 4} are as described above.)
It can be produced by a method of reacting bisphenols represented by (1) with epihalohydrin. Hereinafter, the method for producing the epoxy resin represented by the general formula (1) will be described in detail.

As a method of reacting the bisphenol represented by the general formula (2) with epihalohydrin, for example, the bisphenol represented by the general formula (2) and epihalohydrin are mixed, and then the mixture is usually mixed at 20 to 120 ° C. An example is a method in which an alkali metal hydroxide is preferably added at 40 to 80 ° C. and then reacted at 20 to 120 ° C., preferably 40 to 100 ° C. (hereinafter, the reaction is referred to as an epoxidation reaction). There is). The alkali metal hydroxide may be added all at once, but in order to maintain the above-mentioned temperature, it is preferable to add the alkali metal hydroxide continuously over a certain period of time or in a required amount in divided portions.

Examples of the alkali metal hydroxide used in the epoxidation reaction include sodium hydroxide, potassium hydroxide and the like, and the amount used is usually 0.8 to 0.8 to 1 mol of the bisphenol represented by the above general formula (2). It is 10.0 mol, preferably 2.0 to 5.0 mol. The aqueous solution of the alkali metal hydroxide may be used. When an aqueous solution of alkali metal hydroxide is used, the aqueous solution is continuously added into the reaction system, and water and epihalohydrin are continuously distilled under reduced pressure or under normal pressure to separate the distillate. By doing so, water may be removed from the reaction system and epihalohydrin may be returned to the reaction system.

Specific examples of epichlorohydrin used in the epoxidation reaction include epichlorohydrin and epibrom hydrin, and the amount used is usually 2 to 40 mol, preferably 2 to 40 mol, based on 1 mol of the bisphenol represented by the above general formula (2). Use 4 to 30 mol. The m representing the number of polymerizations of the epoxy resin represented by the general formula (1) can be adjusted by the molar ratio of the bisphenols represented by the general formula (2) and epihalohydrin. That is, when epihalohydrin is used in a large excess with respect to the bisphenols represented by the above general formula (2), a compound having m of 0 is obtained as a main component, and by reducing the amount of epihalohydrin used, m is greater than 0. It is possible to increase the proportion of compounds.

When carrying out the epoxidation reaction, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, amyltriphenylphosphonium bromide, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium. The reaction rate can be improved by further adding a quaternary ammonium salt such as chloride or allyltriphenylphosphonium chloride and a quaternary phosphonium salt. The amount of these salts added is usually 0.01 to 0.50 mol, preferably 0.02 to 0.20 mol, based on 1 mol of the bisphenols represented by the general formula (2). When these salts are used, these salts are usually added before adding the alkali metal hydroxide to the mixture of the bisphenols represented by the general formula (2) and epihalohydrin.

After the epoxidation reaction, the reaction solution containing the epoxy resin represented by the general formula (1) is used as it is as a curing agent, if necessary, a reaction diluent, a curing accelerator, a solvent, and if necessary, the above-mentioned addition. An epoxy resin composition may be obtained by adding an agent or the like.

If necessary, the obtained reaction solution is filtered or washed with water to remove insoluble matter, inorganic salts, alkali metal hydroxides, or when an excessive amount of epihalohydrin is used, under heating and reduced pressure, for example, 100. It is also possible to improve the purity of the epoxy resin represented by the above general formula (1) by removing epihalohydrin at ~ 180 ° C. and an internal pressure of 30 mmHg or less, preferably 10 mmHg or less.

Further, in order to obtain an epoxy resin having a small amount of hydrolyzable halogen, a reaction solution containing the epoxy resin represented by the above general formula (1) or the epoxy resin represented by the above general formula (1) is used as benzene. It is also possible to dissolve in aromatic hydrocarbons such as toluene and xylene, add an aqueous solution of an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, and further carry out a ring closing reaction to ensure ring closing. .. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 15.0 mol, preferably 0, based on 1 mol equivalent of the hydroxyl group of the bisphenol represented by the above general formula (2) used in the epoxidation reaction. It is .20 to 7.5 mol and the reaction temperature is usually 20 to 120 ° C.

After completion of the ring-closing reaction, the by-produced tar and salt are removed by filtration or washed with water, and then the pH of the solution containing the epoxy resin represented by the above general formula (1) is 8.0 to 4. Neutralize by adding phosphoric acid, sodium phosphate, oxalic acid, acetic acid, carbonic acid, etc. so as to be 0.0, repeat washing with water, filter, and further under heating and reducing pressure, the reaction described above By distilling off the solvent used in the extraction or the like, an epoxy resin represented by the above general formula (1) having a small amount of hydrolyzable halogen can be obtained.

<Method for producing bisphenols represented by the above general formula (2)>
The bisphenols represented by the general formula (2), which are the raw materials for the epoxy resin represented by the general formula (1), are, for example, in the presence of an acid, the following general formula (3):

（式中、Ｒ_５及びＲ_６はそれぞれ同一又は異なってアルキル基、アリール基又はハロゲン原子を表し、ｎは１〜４の整数を表し、ｊ_１及びｊ_２はそれぞれ同一又は異なって０〜４の整数を表す。ｊ_１及びｊ_２が２以上である場合、対応するＲ_５及びＲ_６はそれぞれ同一であっても異なってもよい。）
で表されるフェノール化合物と９−フルオレノン（以下、フルオレノンと称することがある）とを反応させることによって製造することができる（以下、該反応をビスフェノール化反応と称することがある）。以下、ビスフェノール化反応について具体的に詳述する。

(In the formula, R ₅ and R ₆ represent the same or different alkyl group, aryl group or halogen atom, respectively, n represents an integer of 1 to 4, and j ₁ and j ₂ represent the same or different 0 to 4, respectively. When j ₁ and j ₂ are 2 or more, the corresponding R ₅ and R ₆ may be the same or different, respectively.)
It can be produced by reacting a phenol compound represented by (hereinafter, may be referred to as fluorenone) with 9-fluorenone (hereinafter, the reaction may be referred to as a bisphenolization reaction). Hereinafter, the bisphenolization reaction will be described in detail.

The phenolic compound represented by the above general formula (3) is a generally available compound, and a commercially available product may be used, and a known method such as Journal of Organic Chemistry 1970, 35 (1), 57-62. It is also possible to produce a product having a desired structure by the method described in 1. In the general formula (3), the substituent (R _{5, R 6),} alkyl group (for example, a methyl group, an ethyl group, a propyl group, an alkyl group which may have a branch, such as an isopropyl group, cyclopentyl A cyclic alkyl group such as a group or cyclohexyl group), an aryl group (for example, an aromatic group which may have a substituent such as a phenyl group or a tolyl group), or a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine). Atomic atoms, iodine atoms, etc.) are exemplified. Among these substituents, an alkyl group having 1 to 4 carbon atoms which may have a branch is preferable from the viewpoint of easiness of producing bisphenols represented by the above general formula (2).

_{J 1} and j ₂ representing the number of substituents (R ₅ and R ₆ ) are the same or different integers of 0 to 4, respectively, and are from the viewpoint of ease of production of the phenol compound represented by the above general formula (3). It is preferably an integer from 0 to 2, and more preferably 0 or 1. When it is 2 or more, the corresponding substituents may be the same or different.

N, which represents the number of methylene groups connecting a phenyl group having a hydroxyl group and one phenyl group, represents the same or different integers of 1 to 4, and is easy to produce a phenol compound represented by the above general formula (3). 1 or 2 is preferable, and 1 is more preferable.

The amount of the phenol compound represented by the general formula (3) is usually 2 to 5 mol with respect to 1 mol of fluorenone, and the viewpoint of more economically producing bisphenols represented by the general formula (2). Therefore, preferably 2 to 3 mol is used. If necessary, two or more kinds of bisphenols represented by the general formula (2) may be mixed and used. By mixing and using two or more kinds, asymmetric bisphenols represented by the general formula (2) can be produced.

As the acid used in the bisphenolization reaction, various acids such as inorganic acid and organic acid can be used. Specific examples of the inorganic acid include sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid, heteropolyacid, zeolite, clay mineral and the like, and examples of the organic acid include methanesulfonic acid, trifluoromethanesulfonic acid and paratoluenesulfonic acid. , Ion exchange resin and the like. Among these acids, hydrochloric acid or p-toluenesulfonic acid is preferably used from the viewpoint of availability and handleability. The amount of the acid used is usually 0.1 to 5.0 mol with respect to 1 mol of fluorenone, and is preferably 0.5 to 0.5 mol with respect to 1 mol of fluorenone from the viewpoint of obtaining a sufficient reaction rate and easiness of post-treatment. Use 1.0 mol. These acids may be used alone or in admixture of two or more, if necessary.

When carrying out the bisphenolization reaction, a sulfur-containing compound can coexist from the viewpoint of improving the reaction rate. Examples of sulfur-containing compounds that can be used include mercaptocarboxylic acids, alkyl mercaptans, aralkyl mercaptans, and salts thereof. _{Specifically, for example, C 1-16} alkyl mercaptans such as thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiosuccinic acid, mercaptosuccinic acid, mercaptobenzoic acid, n-butyl mercaptan, dodecyl mercaptan and the like. Can be mentioned. Among these sulfur-containing compounds, dodecyl mercaptan is preferably used because of its good industrial handling. When these sulfur-containing compounds are used, the amount used is usually 0.01 to 1.0 parts by weight with respect to 1 part by weight of fluorenone, preferably from the viewpoint of obtaining a sufficient reaction rate and easiness of post-treatment. It is 0.01 to 0.50 parts by weight with respect to 1 part by weight. These sulfur-containing compounds may be used alone or in admixture of two or more, if necessary.

When carrying out the bisphenolization reaction, the reaction may be carried out in the presence of a solvent, if necessary. Examples of the solvent that can be used include aliphatic hydrocarbons, aromatic hydrocarbons, ethers, and halogenated hydrocarbons. Examples of aliphatic hydrocarbons include alkanes such as hexane, heptane, octane and decane, examples of aromatic hydrocarbons include benzene, toluene, xylene and ethylbenzene, and examples of ethers are dialkyls such as diethyl ether. Cyclic ethers such as ethers, tetrahydrofuran and dioxane are exemplified, and as halogenated hydrocarbons, aliphatic halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, and aromatic halogens such as chlorobenzene and dichlorobenzene are exemplified. Hydrocarbons are exemplified. Among these solvents, aromatic hydrocarbons such as toluene and xylene are preferably used from the viewpoint of availability and handleability. When these solvents are used, the amount used is usually 0.1 to 10 parts by weight with respect to 1 part by weight of fluorenone, preferably 0. 10 parts by weight with respect to 1 part by weight of fluorenone from the viewpoint of obtaining a sufficient reaction rate and economically. Use 5 to 5.0 parts by weight. These solvents may be used alone or in admixture of two or more, if necessary.

In the bisphenolization reaction, for example, fluorenone, a phenol compound represented by the above general formula (3), an acid, and if necessary, a sulfur-containing compound and a solvent are placed in a reactor, and the internal temperature is usually 50 to 200 ° C., preferably 80 to 80 to. It is carried out by stirring at 140 ° C. Further, from the viewpoint of obtaining a sufficient reaction rate, the reaction may be carried out while dehydrating under normal pressure or reflux under reduced pressure, if necessary.

After the bisphenolization reaction, the bisphenols represented by the above general formula (2) can be taken out by a conventional method such as neutralization, washing with water, concentration, crystallization, filtration and the like, if necessary. The obtained bisphenols represented by the general formula (2) can also be purified by a conventional method such as recrystallization, distillation, adsorption, or column chromatography. Further, if necessary, the obtained reaction solution may be used as it is for the production of the above-mentioned epoxy resin.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited thereto. In addition, in Examples and the like, each measured value was in accordance with the following method and measurement conditions. The production rate (residual rate) and purity of each component described in Examples and the like below are area percentages obtained by performing HPLC analysis under the following conditions.

[1] HPLC analysis ・ Equipment: "LC-2010AHT" manufactured by Shimadzu Corporation
-Column: "SUMIPAX ODS A-212" manufactured by Sumika Chemical Analysis Service Co., Ltd. (5 μm, 6.0 mmφ x 150 mm)
-Column temperature: 40 ° C
-Detection wavelength: UV 254 nm
-Mobile phase: Liquid A = acetonitrile, liquid B = water-Mobile phase flow rate: 1.0 ml / min-Mobile phase gradient: Liquid A concentration: 50% (0 minutes) → 100% (40 minutes later) → 50% ( 60 minutes later)

[2] NMR measurement
^{1 1} H-NMR and ¹³ C-NMR were recorded by a JEOL-ESC400 spectrometer using chloroform-d1 as a solvent.

[3] LC-MS measurement LC-MS was separated and mass spectrometrically analyzed under the following measurement conditions to identify the target product.

-Device: "Xevo G2 Q-Tof" manufactured by Waters Corp.
-Column: "ACQUITY UPLC BEH C18" manufactured by Japan Waters Corp. (1.7 μm, 2.1 mmφ x 100 mm)
-Column temperature: 40 ° C
-Detection wavelength: UV 220-500 nm
-Mobile phase: Liquid A = 10 mM ammonium acetate water, Liquid B = acetonitrile-Mobile phase flow rate: 0.3 ml / min Mobile phase gradient: Liquid B Concentration: 80% (0 minutes) → 100% (10 minutes later) → 100 % (15 minutes later)
Detection method: Q-Tof
Ionization method: ESI (+) method Ion Source: Voltage (+) 2.0 kV, temperature 120 ° C
Sample Cone: Voltage 30V, Gas flow 50L / h
-Desolution Gas: Temperature 500 ° C, gas flow 1000 L / h

[4] Epoxy equivalent The measurement was carried out using an automatic titrator (AT-5100 manufactured by Kyoto Electronics Co., Ltd.) in accordance with JIS K7236.

[5] Dissipation Factor The cured products obtained in each Example and Comparative Example were adjusted for 24 hours or more in a room with a temperature of 23 ° C and a humidity of 50%, and then Agilent Technologies Co., Ltd. Agilent E4991A RF impedance / A material analyzer was used to measure the dielectric loss tangent at a frequency of 1 GHz.

[6] 5% Weight Loss Temperature Using a thermogravimetric analyzer (TG-DTA 8121 / S manufactured by Rigaku Co., Ltd.), the temperature was raised from room temperature to 500 ° C. at 10 ° C./min under a nitrogen stream for measurement.

[7] Glass transition temperature and coefficient of linear thermal expansion A test piece (3.0 mm × 3.0 mm × 3.0 mm) was prepared from each of the cured products obtained in each Example and each Comparative Example, and a thermomechanical analyzer (thermomechanical analyzer (3.0 mm × 3.0 mm × 3.0 mm) was prepared. Using TMA-7100 manufactured by Hitachi High-Tech Science Co., Ltd.), the temperature was set to 30 ° C and the temperature was raised to 270 ° C at a heating rate of 5 ° C / min, and the temperature was determined as follows from the TMA curve of the second run. ..
-Glass transition temperature: Temperature at the inflection point of the TMA curve-Linear coefficient of thermal expansion: Average value between 40 ° C and temperatures below the glass transition

<Production example 1 Production example of bisphenol represented by the following formula (4)>

In a 500 ml glass reaction vessel equipped with a stirrer, cooler and thermometer, 40.03 g (0.222 mol) of 9-fluorenone, 173.20 g (0.666 mol) of 2-benzyl-6-phenylphenol, 1- Add 2.26 g (0.011 mol) of dodecanethiol, 26.20 g (0.138 mol) of paratoluenesulfonic acid / monohydrate and toluene, raise the temperature to 120 ° C, and stir for 4 hours while refluxing and dehydrating at the same temperature. bottom. The obtained reaction solution was cooled to 60 ° C., water was added, the mixture was neutralized with 24% sodium hydroxide, cooled to room temperature, and the precipitated crystals were filtered. Next, the obtained crystals were washed twice with toluene, washed three times with water, and dried under reduced pressure to obtain 104.70 g of white crystals of bisphenol represented by the above formula (4) (9). -Yield based on fluorenone: 69.1%). The HPLC purity of the white crystals was 98.6%.
^{Further, the 1} H-NMR and ¹³ C-NMR spectral values of the obtained bisphenol represented by the above formula (4) are shown below, and the NMR charts are shown in FIGS. 1 and 2.

^{1 1} H-NMR (CDCl ₃ )
δ (ppm): 3.93 ppm (4H, s), 5.12 (2H, s), 6.91 (2H, d), 7.06 (2H, d), 7.15-7.40 (26H) , M), 7.71 (2H, d)

¹³ C-NMR (CDCl ₃ )
δ (ppm): 36.83 ppm, 64.33 ppm, 120.20 ppm, 126.00 ppm, 127.19 ppm, 127.35 ppm, 127.68 ppm, 127.75 ppm, 127.78 ppm, 127.94 ppm, 128.38 ppm, 128 .75 ppm, 129.26 ppm, 130.72 ppm, 137.39 ppm, 137.97 ppm, 140.06 ppm, 140.59 ppm, 149.26 ppm, 151.78 ppm

<Manufacturing example 2 Production example of epoxy resin represented by the following formula (5)>

（式中、ｍ_１は０以上の整数を表す。）

(In the formula, m ₁ represents an integer greater than or equal to 0.)

In a 500 ml glass reaction vessel equipped with a stirrer, a cooler and a thermometer, 50.02 g (0.073 mol) of bisphenol represented by the above formula (4) obtained in Production Example 1 under a nitrogen atmosphere, 203.36 g (2.197 mol) of epichlorohydrin and 1.67 g (0.007 mol) of benzyltriethylammonium chloride were charged and heated to 70 ° C., and then stirred at the same temperature for 3.5 hours. After stirring, the reaction solution was analyzed by HPLC. As a result, the residual ratio of bisphenol represented by the above formula (4) as a raw material was 0.5% or less.
After completion of the reaction, the obtained reaction solution was heated to 120 ° C., and excess epichlorohydrin and the like were distilled off under a reduced pressure of 10 mmHg to obtain a concentrate. Then, the mixture was cooled to 110 ° C., toluene was added to the obtained concentrate to dissolve it, and the mixture was cooled to 60 ° C., and then 61.30 g (0.366 mol) of a 24 wt% sodium hydroxide aqueous solution was added at 60 ° C. The mixture was stirred at the same temperature for 3.5 hours. After stirring, the mixture was allowed to stand, and the lower layer was separated and removed.
Then, after neutralizing by adding an acid, the aqueous layer was separated and removed. Next, after washing the organic layer with water, activated carbon is added to the organic layer, the mixture is stirred at 60 ° C. for 2 hours, filtered to remove insoluble matter and activated carbon, and then concentrated under reduced pressure to distill off toluene. Obtained 56.18 g of an epoxy resin represented by the above formula (5), which is a pale yellow solid.
When the obtained epoxy resin represented by the above formula (5) was analyzed by HPLC, _{96.1% had m 1} = 0 in the above formula (5), and the epoxy equivalent was 402 g / eq. ..
^{Further, 1} H-NMR, ¹³ C-NMR and LC-MS spectral values of the obtained epoxy resin represented by the above formula (5) are shown below, and each NMR chart and mass spectrometry are shown in FIGS. 3 to 5. Show the chart.

^{1 1} H-NMR (CDCl ₃ )
δ (ppm): 2.21 (dd, J = 2.80, J = 2.0, 2H), 2.55 (t, J = 4.00, 2H), 2.80 (m, 2H), 3.17-3.27 (m, 4H), 3.98 (s, 4H), 6.97 (d, J = 2.40, 2H), 7.05 (d, J = 2.00, 2H) ), 7.10-7.40 (m, 26H), 7.72 (d, J = 7.60, 2H).

¹³ C-NMR (CDCl ₃ )
δ (ppm): 36.37, 44.75, 49.96, 64.55, 73.44, 120.19, 125.84, 125.99, 127.12, 127.46, 127.67, 128 .17, 128.23, 128.51, 128.71, 128.84, 129.16, 130.57, 134.04, 134.25, 138.60, 140.02, 140.99, 141.58 , 151.09, 153.09.

Mass analysis value: 812.3742 (Calculated molecular weight of epoxy resin represented by the above formula (5) (TOF MS ESI ⁺ ; C ₅₅ H ₄₂ O ₄ + NH ₄ ): 812.3740)

<Example 1>
In a plastic container, 3.00 g of the epoxy resin represented by the above formula (5) obtained in Production Example 2 and 7.00 g of a bisphenol A type epoxy resin (manufactured by AER 260 Asahi Kasei Chemicals Co., Ltd.) were charged, and at 160 ° C. It was melted. After melting, 7.49 g of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride and 0.50 g of triphenylphosphine were added, stirred with a disper, and defoamed under reduced pressure (0.6 to 1.0 kPa). A cured product was obtained by heating at 110 ° C. for 2 hours, 140 ° C. for 2 hours, and 170 ° C. for 2 hours using a high-temperature incubator (ETAC HT310, Kusumoto Kasei Co., Ltd.).

<Comparative example 1>
In a plastic container, 5.00 g of bisphenol A type epoxy resin (manufactured by AER 260 Asahi Kasei Chemicals Co., Ltd.), 4.44 g of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, and 0.25 g of triphenylphosphine are charged. , Stir with a disper, defoam under reduced pressure (0.6 to 1.0 kPa), and then use a high temperature incubator (ETAC HT310, Kusumoto Kasei Co., Ltd.) at 105 ° C for 2 hours and 135 ° C for 2 hours. A cured product was obtained by heating at 155 ° C. for 2 hours and curing.

<Reference example 1>
As an epoxy resin having a conventionally known bisphenol fluorene skeleton, the following formula (6):

（式中、ｍ_２は０または１以上の整数である。）
で表わされるエポキシ樹脂（東京化成（株）社製、白色結晶、ｍ_２＝０であるものの割合：９７．３％、エポキシ当量：２３４ｇ／ｅｑ）について同様に硬化物を作成し評価を行った。

(In the formula, m ₂ is an integer greater than or equal to 0 or 1.)
A cured product was similarly prepared and evaluated for the epoxy resin represented by (Tokyo Kasei Co., Ltd., white crystal, _{ratio of m 2} = 0: 97.3%, epoxy equivalent: 234 g / eq). ..

In a plastic container, 6.00 g of an epoxy resin represented by the above formula (6) and 14.00 g of a bisphenol A type epoxy resin (manufactured by AER 260 Asahi Kasei Chemicals Co., Ltd.) were charged and melted at 160 ° C. After melting, 16.75 g of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride and 1.00 g of triphenylphosphine were further charged, stirred with a disper, and defoamed under reduced pressure (0.6 to 1.0 kPa). Then, using a high-temperature incubator (ETAC HT310, Kusumoto Kasei Co., Ltd.), the mixture was heated at 110 ° C. for 2 hours, 135 ° C. for 2 hours, and 160 ° C. for 2 hours to cure to obtain a cured product.

Claims (2)

The following general formula (1):

(In the formula, R _{1 to} R ₄ represent the same or different alkyl group, aryl group or halogen atom, respectively, and n _{1 and n 2} represent the same or different integers 1 to 4, respectively, and k _{1 to k 4} Represent the same or different integers from 0 to _{4. When k 1} to k 4 are 2 or more, the corresponding R _{1 to} R ₄ may be the same or different. M is 0 or more. Represents an integer.)
An epoxy resin composition containing an epoxy resin represented by (1) and a curing agent (however, the epoxy resin represented by the above general formula (1) is excluded as a curing agent) . A cured product obtained by curing the epoxy resin composition according to claim 1.

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