JP2013193958A - Epoxyfluorene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound giving a material excellent in optical properties such as (long-term) light resistance, transparency and refractive index, electrical properties such as dielectric constant, mechanical properties such as heat-resistance and compatibility with other resins in electronic and optical fields.SOLUTION: There are provided a new epoxyfluorene derivative obtained by epoxidizing a bisfluorene derivative or fluorene derivative having a specific structure, and a method for producing the epoxyfluorene derivative.

Description

  The present invention relates to a novel epoxy fluorene derivative.

  In recent years, in the field of electronic and optical materials, flat panel displays using liquid crystals, organic EL, etc. have higher definition, higher viewing angle, higher image quality, and higher light sources using light semiconductors such as light emitting diodes (LEDs). Improvements in the performance and improvement of optical and electronic components are being promoted, such as brightness, shorter wavelength, whitening, and higher frequency of electronic circuits and circuits and communications using light.

  In recent years, a solder reflow process has been devised as a manufacturing method for reducing the cost of electronic devices, and there is a demand for an electronic / optical material that does not deform, yellow or deteriorate even at a temperature higher than the reflow process (260 ° C.). . For applications such as optical lenses, a material having high refraction but having reflow resistance is desired.

  In addition, with the advancement of the information society, electronic circuits integrated with semiconductors, etc., have increased information volumes and communication speeds, and miniaturized devices, requiring circuit miniaturization, integration, and higher frequencies. It has become. Furthermore, an optical circuit using an optical waveguide or the like that enables higher-speed processing has been studied. Conventionally, a bisphenol A type epoxy resin or the like has been used as a sealing resin, an adhesive resin, a film, or a lens resin. However, these resins have problems such as a high dielectric constant in electronic circuits, insufficient heat resistance, and a decrease in transparency and yellowing due to deterioration of the resin in optical waveguide and LED sealing.

  A compound having an adamantane skeleton has high heat resistance, while its refractive index is not so high as 1.57, which is insufficient. (For example, see Patent Document 1)

  Moreover, although the epoxy compound which has a fluorene skeleton is also disclosed, the solubility to a general purpose solvent and the compatibility to another epoxy resin are inadequate. (For example, see Patent Document 2)

  Therefore, in the above-mentioned electronic / optical field, (long-term) light resistance, transparency, optical properties such as refractive index, electrical properties such as dielectric constant, mechanical properties such as heat resistance, and compatibility with other resins are excellent. Materials are needed.

JP 2011-57616 A JP 2004-182783 A

  Accordingly, an object of the present invention is to provide a novel fluorene derivative, which is useful in various fields of application such as optical applications, optical device applications, display device applications, mechanical component materials, electrical / electronic component materials, and the like. It is to provide a fluorene derivative that gives a product.

As a result of intensive studies, the present inventors have found a novel epoxy fluorene derivative that solves the above problems.
That is, the present invention provides (1) the following general formula (I)

(Wherein R ¹ is an alkylene group having 2 to 10 carbon atoms or an alkylene group having 2 to 10 carbon atoms substituted with a phenyl group, R ² is a methyl group or a hydrogen atom, and R ^{3 to} R ⁶ are each a carbon number. 1 to 5 alkyl groups, acetyl groups, phenyl groups or halogen atoms, m, n, o and p each represents an integer of 0 to 4))
(2) The epoxyfluorene derivative of (1), wherein m, n, o and p are all 0,
(3) The epoxyfluorene derivative of (1) or (2), wherein R ¹ is a pentylene group or a hexylene group, and R ² is a hydrogen atom,
(4) The following general formula (II)

Wherein R ⁷ is an alkyl group having 1 to 10 carbon atoms substituted with an alkyl group having 1 to 10 carbon atoms or a phenyl group, R ⁸ is a methyl group or a hydrogen atom, and R ^{9 to} R ¹⁰ are each independently An epoxy fluorene derivative represented by: an alkyl group having 1 to 5 carbon atoms, an acetyl group, a phenyl group or a halogen atom, and q and r each represents an integer of 0 to 4.
(5) The epoxy fluorene derivative of (4), wherein q and r are all 0.
(6) The epoxyfluorene derivative of (4) or (5), wherein R ⁷ is a phenylpropyl group, and R ⁸ is a hydrogen atom,
(7) A method for producing an epoxyfluorene derivative according to any one of (1) to (3), comprising reacting a compound represented by the following general formula (I ′) with an epihalohydrin in the presence of a base,

(Wherein R ¹ is an alkylene group having 2 to 10 carbon atoms or an alkylene group having 2 to 10 carbon atoms substituted with a phenyl group, and R ^{3 to} R ⁶ are each independently an alkyl group having 1 to 5 carbon atoms. , Acetyl group, phenyl group or halogen atom, m, n, o and p each represents an integer of 0 to 4.)
(8) Provided is a method for producing an epoxyfluorene derivative according to any one of (4) to (6), which comprises reacting a compound represented by the following general formula (II ′) with an epihalohydrin in the presence of a base. .

Wherein R ⁷ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 1 to 10 carbon atoms substituted with a phenyl group, and R ^{9 to} R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. , An acetyl group, a phenyl group or a halogen atom, q and r each represents an integer of 0 to 4.)

According to the present invention, a novel epoxy fluorene compound that provides a cured product excellent in heat resistance, optical characteristics, and compatibility is provided.
The epoxy fluorene compound of the present invention is used not only in fields where so-called conventional epoxy resins such as paints and adhesives have been used, but in particular, electrical and electronic materials such as cast products, sealing materials, laminates, and resist inks. It can be used suitably for an application. It is also useful as a raw material for precision molding materials and adhesives, and as a heat-resistant lens material.
Moreover, the epoxy fluorene compound of this invention can be hardened | cured by epoxy hardeners and hardening accelerators (catalysts), such as an amine, carboxylic acid, a carboxylic acid anhydride, and a phenol resin similarly to a conventionally well-known epoxy resin.

1 is a diagram illustrating a ¹ H-NMR spectrum of a compound obtained in Example 1. FIG. 2 is a diagram showing an IR spectrum of the compound obtained in Example 1. FIG. 3 is a diagram illustrating a ¹ H-NMR spectrum of a compound obtained in Example 2. FIG. 2 is a diagram showing an IR spectrum of the compound obtained in Example 2. FIG. 3 is a diagram illustrating a ¹ H-NMR spectrum of a compound obtained in Example 3. FIG. 2 is a diagram illustrating an IR spectrum of the compound obtained in Example 3. FIG.

  In the present invention, one novel epoxy fluorene derivative is represented by the following general formula (I):

(Wherein R ¹ is an alkylene group having 2 to 10 carbon atoms or an alkylene group having 2 to 10 carbon atoms (the number not including the carbon number of the phenyl group) substituted with a phenyl group, and R ² is a methyl group or a hydrogen atom. , R ^{3 to} R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms, an acetyl group, a phenyl group or a halogen atom, and m, n, o, and p each represents 0 or an integer of 1 to 4). It is an epoxy fluorene derivative shown by these.

R ¹ is an alkylene group having 2 to 10 carbon atoms. For example, R ¹ represents an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group or the like, a 1-methylethylene group, or a 1-methyl group. Examples include branched alkylene groups such as a propylene group and a 2-methylpropylene group. Examples of the C2-C10 alkylene group substituted with a phenyl group include a 1,4-benzenedimethylene group, a 1,4-benzenediethylene group, and a 1,4-benzenedipropylene group. .

R ¹ is preferably a butylene group, a pentylene group, a hexylene group or a 1,4-benzenediethylene group, more preferably a pentylene group or a hexylene group.

R ² represents a methyl group or a hydrogen atom.

R ^{3 to} R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms, an acetyl group, a phenyl group, or a halogen atom. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an isopropyl group. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.
Among these, R ^{3 to} R ⁶ are preferably a chlorine atom or a bromine atom.

  In the general formula (I), m, n, o and p each represents an integer of 0 to 4, and 0 is preferable.

  Examples of the compound represented by the general formula (I) include 9,9-ethylenebis (9-glycidyl-9H-fluorene), 9,9-butylenebis (9-glycidyl-9H-fluorene), 9,9- Pentylenebis (9-glycidyl-9H-fluorene), 9,9-hexylenebis (9-glycidyl-9H-fluorene), 9,9-heptylenebis (9-glycidyl-9H-fluorene), 9,9-octylenebis (9-glycidyl) -9H-fluorene), 9,9-nonylene bis (9-glycidyl-9H-fluorene), 9,9-decylene bis (9-glycidyl-9H-fluorene), etc., and 9,9-pentylene bis (9-glycidyl) -9H-fluorene) and 9,9-hexylenebis (9-glycidyl-9H-fluorene) are preferred.

  The other epoxy fluorene derivative can be represented by the following general formula (II).

(Wherein R ⁷ is an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms (the number not including the carbon number of the phenyl group) substituted with a phenyl group, and R ⁸ is a methyl group or a hydrogen atom. And R ^{9 to} R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms, an acetyl group, a phenyl group or a halogen atom, and q and r each represents 0 or an integer of 1 to 4).

When R ⁷ is an alkyl group having 1 to 10 carbon atoms, R ⁷ is methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. And a branched alkyl group such as a linear alkyl group such as 1-methylethyl group, 1-methylpropyl group, and 2-methylpropyl group. Moreover, as a C1-C10 alkyl group substituted by the phenyl group, 3-phenyl-1-propyl group etc. are mentioned, for example. R ⁷ is preferably a 3-phenyl-1-propyl group.

R ⁸ represents a methyl group or a hydrogen atom.

R ⁹ and R ¹⁰ may include the same substituents as those defined for R ^{3 to} R ⁶ above. Among these, a chlorine atom and a bromine atom are preferable.
q and r each represents an integer of 0 to 4, and 0 is preferable.

  As the compound represented by the general formula (II), 9H-fluorene (9-glycidyl-9-phenylpropyl) is preferable.

Next, the manufacturing method of the epoxy fluorene derivative of this invention is demonstrated.
The epoxyfluorene derivative of the general formula (I) can be obtained by reacting a 9,9-bisfluorene derivative represented by the following general formula (I ′) with an epihalohydrin in the presence of a base.

(In the formula, R ¹ , R ^{3 to} R ⁶ , m, n, o, and p are as defined above.)

  The compound represented by the general formula (I ') can be obtained by condensing fluorene or substituted fluorene and a diol in the presence of a base. The obtained compound represented by the general formula (I ′) is preferably removed of impurities by a method such as washing with water, distillation, recrystallization, reprecipitation and the like.

  Examples of the substituted fluorene include 1-methylfluorene, 2,3-benzofluorene, 1,2-benzofluorene, 2,7-dibromofluorene, 2-acetylfluorene, 1-benzylfluorene, 1-phenylfluorene, and the like. . In addition, substituted fluorene here refers to the fluorene in which a substituent does not exist in the 9th-position carbon atom. These can be purchased from JFE Chemical Corporation and Sigma Aldrich.

  Examples of the diol used for producing the 9,9′-bisfluorene derivative represented by the general formula (I ′) include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, and octane. Diol, nonanediol, decanediol, 1,4-benzenediethylenediol and the like can be mentioned. Among these, butanediol, pentanediol, hexanediol, and 1,4-benzenediethylenediol are preferable, and pentanediol and hexanediol are more preferable.

Since the conditions for reacting fluorene or substituted fluorene with a diol vary depending on the compound used, it is difficult to define them uniformly. However, in general, the diol is reacted in an amount of 0.5 to 0.8 mol, preferably 0.5 to 0.6 mol, with respect to 1 mol of fluorene or substituted fluorene.
Moreover, reaction temperature is 100-220 degreeC normally, Preferably, it is 180-220 degreeC.
Furthermore, reaction time is 5 to 20 hours normally, Preferably it is 10 to 12 hours. These reactions are carried out at normal pressure.

The 9,9′-bisfluorene derivative represented by the general formula (I ′) obtained by the above reaction is reacted with epihalohydrin in the presence of a base to introduce an epoxy group.
Examples of the epihalohydrin used include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and β-methylepibromohydrin. In the present invention, epibromohydrin is more preferable.

When the 9,9′-bisfluorene derivative represented by the general formula (I ′) is reacted with epihalohydrin, the conditions vary depending on the compounds used, and thus it is difficult to define them in a general manner. However, in general, epihalohydrin is reacted with 2 to 4 mol, preferably 2 to 3 mol with respect to 1 mol of the 9,9′-bisfluorene derivative of the general formula (I ′). It is 0 ° C to 70 ° C, preferably 20 ° C to 30 ° C.
Furthermore, reaction time is 0.02-72 hours normally, Preferably it is 0.05-20 hours, More preferably, it is 0.3-6 hours. These reactions are carried out at normal pressure.

Examples of the base used include KOH, NaOH, tBuOK, NaOEt and NaOMe when fluorene or substituted fluorene is reacted with diol.
Moreover, tBuOK is mentioned when making the 9,9'-bisfluorene derivative and epihalohydrin represented by general formula (I ') react.

  Examples of the reaction solvent used in the above reaction include (halogenated) aromatic hydrocarbons such as benzene, xylene, toluene and chlorobenzene, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, dioxane, diphenyl ether, tetrahydrofuran and the like. Ethers, chlorinated hydrocarbons such as methylene chloride, chloroform, trichlene, etc., acetic acid, dimethyl sulfoxide, dimethylimidazolidinone and other solvents inert to the epoxidation reaction. Can be used as a mixture.

Next, the manufacturing method of the epoxy fluorene derivative of general formula (II) is demonstrated.
The epoxyfluorene derivative of the general formula (II) can be obtained by reacting an epihalohydrin with a fluorene derivative represented by the following general formula (II ′) in the presence of a base.

（式中、Ｒ^７、Ｒ^９、Ｒ^１０、ｑ、ｒの定義は上記と同じである。）

(In the formula, the definitions of R ⁷ , R ⁹ , R ¹⁰ , q and r are the same as above.)

The fluorene derivative of the general formula (II ′) can be obtained by condensing fluorene or substituted fluorene with an alcohol in the presence of a base. The compound represented by the general formula (II ′) thus obtained is preferably removed of impurities by a method such as washing with water, distillation, recrystallization, reprecipitation or the like.
In addition, the substituted fluorene used here can use the compound similar to what is used when obtaining the fluorene derivative represented by the said general formula (I ').

  Examples of the alcohol used for producing the fluorene derivative represented by the general formula (II ′) include ethanol, methanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, and 3-phenyl- Examples include 1-propanol. Among these, propanol and 3-phenyl-1-propanol are preferable, and 3-phenyl-1-propanol is more preferable.

Since the conditions for reacting fluorene or substituted fluorene with an alcohol vary depending on the compound used, it is difficult to uniformly define the conditions. In general, however, the alcohol is reacted in an amount of 1.0 to 1.6 mol, preferably 1.0 to 1.2 mol, per mol of fluorene or substituted fluorene.
Moreover, reaction temperature is 100-220 degreeC normally, Preferably, it is 180-220 degreeC.
Furthermore, reaction time is 5 to 20 hours normally, Preferably it is 10 to 12 hours. These reactions are carried out at normal pressure.
An epoxyfluorene derivative of the general formula (II) can be obtained by reacting the fluorene derivative represented by the general formula (II ′) thus obtained with an epihalohydrin in the presence of a base.
The epihalohydrin used at this time can be the same as the epihalohydrin used when obtaining the epoxyfluorene derivative of the general formula (I).

When the fluorene derivative represented by the general formula (II ′) is reacted with epihalohydrin, the conditions vary depending on the compounds used, and therefore it is difficult to define them in general. In general, however, epihalohydrin is reacted in an amount of 1 to 2 mol, preferably 1 mol to 1.4 mol, per mol of the fluorene derivative of the general formula (II ′).
The reaction temperature is 0 to 70 ° C, preferably 20 to 30 ° C.
Furthermore, reaction time is 0.02-72 hours normally, Preferably it is 0.05-20 hours, More preferably, it is 0.3-6 hours. These reactions are carried out at normal pressure.

Examples of the base used include KOH, NaOH, tBuOK, NaOEt and NaOMe when fluorene or substituted fluorene is reacted with alcohol.
Moreover, tBuOK is mentioned when making the fluorene derivative represented by general formula (II ') and epihalohydrin react.

  The fluorene derivative of the present invention thus obtained is excellent in compatibility, optical characteristics, heat resistance and transparency, and can be used as an optical material and an electronic material.

  Hereinafter, the present invention will be described in more detail with reference to synthesis examples, but the present invention is not limited to these examples. In addition, the identification method of the compound described in the synthesis example was based on the following method.

(1) ¹ H-NMR and ¹³ C-NMR: Measured with an AVANCE III nuclear magnetic resonance apparatus manufactured by Bruker, Inc. using tetramethylsilane (TMS) as an internal standard substance.
(2) IR spectrum: FTIR measuring apparatus manufactured by JEOL Ltd. JIR-RFX3002 FT-IR Spectrophotometer was used for measurement.

Example 1
Method for synthesizing 9,9-pentylenebis (9-glycidyl-9H-fluorene) 83 g (0.5 mol) of fluorene in a 2 L metal four-necked separable flask equipped with a temperature controller, stirrer, Dean-Stark and nitrogen inlet , 1,5-pentanediol (31 g, 0.3 mol), KOH (21 g, 0.375 mol), and xylene (200 mL) were charged, heated to 180-210 ° C. with stirring under a nitrogen stream, and then reacted for 8 hours. The product was neutralized with 25% aqueous phosphoric acid. 500 mL of toluene was added thereto, and then washed twice with 1.2 L of ion exchange water. Toluene and xylene were distilled off under reduced pressure, washed with methanol, and then filtered to obtain 9,9-pentylenebis (9H-fluorene) as a white solid. It was.
50 g (0.13 mol) of this white solid was placed in a 500 mL three-necked flask equipped with a nitrogen introducer, a magnetic stirrer, and a 200 mL dropping tube, and 35 g (0.31 mol) of t-BuOK and 200 mL of dimethyl sulfoxide were added and stirred. Thereafter, a solution prepared by dissolving 50 g (0.36 mol) of epibromohydrin in 100 mL of dimethyl sulfoxide was dropped from the dropping tube and stirred for 1 hour. Thereafter, 100 mL of water was added to stop the reaction, and washing with ion exchange water was performed three times with a small amount of hydrochloric acid, and this was separated by column chromatography to obtain a transparent viscous liquid.
Since the methine proton of fluorene disappeared from the ¹ H-NMR spectrum (FIG. 1) and IR-spectrum (FIG. 2) of the compound and a spectrum derived from an epoxy group and a pentylene group could be confirmed, 9,9-pentylenebis ( 9-glycidyl-9H-fluorene).

(Example 2)
Method for synthesizing 9,9-hexylenebis (9-glycidyl-9H-fluorene) 83 g of fluorene (0.2 g) in a 2 L metal four-necked separable flask equipped with a temperature controller, stirrer, Dean Stark, and nitrogen introducer. 5 mol), 35 g (0.3 mol) of 1,6-hexanediol, 21 g (0.375 mol) of KOH, and 200 mL of xylene were heated to 180-210 ° C. with stirring under a nitrogen stream, and then reacted for 8 hours. The reaction product was neutralized with 25% aqueous phosphoric acid solution. 500 mL of toluene was added thereto, and then washed twice with 1.2 L of ion-exchanged water. Then, toluene and xylene were distilled off under reduced pressure, washed with methanol, and filtered to obtain 9,9-hexylenebis (9H-fluorene) as a white solid. It was.
50 g (0.13 mol) of this white solid is placed in a 500 mL three-necked flask equipped with a nitrogen introducer, a magnetic stirrer, and a 200 mL dropping tube, and 35 g (0.31 mol) of t-BuOK and 200 mL of dimethyl sulfoxide are added and stirred. Thereafter, a solution prepared by dissolving 50 g (0.36 mol) of epibromohydrin in 100 mL of dimethyl sulfoxide is dropped from a dropping tube and stirred for 1 hour. Thereafter, 100 mL of water was added to stop the reaction, and washing with ion exchange water was performed three times with a small amount of hydrochloric acid, and this was separated by column chromatography to obtain white crystals.
From the ¹ H-NMR spectrum (FIG. 3) and IR-spectrum (FIG. 4) of the compound, the methine proton of fluorene disappeared, and the spectrum derived from the epoxy group and hexylene group was confirmed. It was confirmed to be xylene bis (9-glycidyl-9H-fluorene).

(Example 3)
Method for synthesizing 9H-fluorene (9-glycidyl-9-phenylpropyl) 83 g (0.5 mol) of fluorene in a 2 L metal four-necked separable flask equipped with a temperature controller, stirrer, Dean Stark, and nitrogen introducer, Charged with 82 g (0.6 mol) of 3-phenyl-1-propanol, 21 g (0.375 mol) of KOH, and 200 mL of xylene, heated to 180-210 ° C. with stirring under a nitrogen stream, and then allowed to react for 8 hours before producing a reaction. The product was neutralized with 25% aqueous phosphoric acid solution. 500 mL of toluene was added and then washed twice with 1.2 L of ion exchange water, and then toluene and xylene were distilled off under reduced pressure, washed with methanol and filtered to obtain 9H-fluorene (9-phenylpropyl) as a white solid. .
50 g (0.18 mol) of this white solid is placed in a 500 mL three-necked flask equipped with a nitrogen introducer, a magnetic stirrer, and a 200 mL dropping tube, and 35 g (0.31 mol) of t-BuOK and 200 mL of dimethyl sulfoxide are added and stirred. Thereafter, a solution prepared by dissolving 26 g (0.25 mol) of epibromohydrin in 100 mL of dimethyl sulfoxide is dropped from a dropping tube and stirred for 1 hour. Thereafter, 100 mL of water was added to stop the reaction, and washing with ion exchange water was performed three times with a small amount of hydrochloric acid, and this was separated by column chromatography to obtain a transparent viscous liquid.
From the ¹ H-NMR spectrum (FIG. 5) and IR-spectrum (FIG. 6) of the compound, the methine proton of fluorene disappeared, and the spectrum derived from the epoxy group and 3-phenyl-1-propylene group could be confirmed. , 9H-fluorene (9-glycidyl-9-phenylpropyl).

(Formulation example)
12.5 g of 9,9-pentylenebis (9-glycidyl-9H-fluorene) synthesized in Example 1 and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (trade name: Celoxide 2021P) 7.5 g of Daicel) and 5.0 g of biphenyl type oxetane (trade name: OX-BP, Ube Industries) were mixed to obtain a base resin. 0.1 g of aromatic sulfonium salt (trade name: Sun-Aid SI-80L, manufactured by Sanshin Chemical Co., Ltd.) was added as a curing agent. Further, 0.1 g of IRGANOX 1076 (manufactured by Ciba Japan), 0.1 g of AO-80 (manufactured by Adeka), 0.1 g of HCA (manufactured by Sanko), and 0 of IRGAFOS 38 (manufactured by Ciba Japan) as antioxidants. .19 g, 0.1 g of SUMIRIZER TP-D (Sumitomo Chemical Co., Ltd.) was added, and mixing was performed using 10 ml of chloroform as a solvent. This was stirred at 50 ° C. under reduced pressure to remove the solvent, thereby preparing a curable composition.

  A mold in which a 0.5 mm spacer is sandwiched between two glass plates of 2.5 cm × 8 cm, respectively, and a mold in which a 3 mm spacer is sandwiched are prepared, and the curable composition described above is poured into the glass. It was cured by performing three-stage heating at 6 ° C. and 6 hours at 180 ° C. Thereafter, the Abbe number of the 3 mm compound plate removed from the mold was measured using a refractometer (DR-M2 manufactured by ATAGO), and the result was 28.6. In addition, after reflow heating the 0.5 mm plate removed from the mold 5 times under the conditions of 150 ° C. × 60 seconds, 200 ° C. × 20 seconds, 260 ° C. × 10 seconds, the 400 nm transmittance was measured with a UV spectrum meter (SHIMADZU UV -1650PC), the result was 80.5%.

Claims (8)

The following general formula (I)

(In the formula, R ¹ is an alkylene group having 2 to 10 carbon atoms or an alkylene group having 2 to 10 carbon atoms substituted with a phenyl group, R ² is a methyl group or a hydrogen atom, and R ^{3 to} R ⁶ are each independently And an epoxy fluorene derivative represented by: an alkyl group having 1 to 5 carbon atoms, an acetyl group, a phenyl group or a halogen atom, and m, n, o and p each represents an integer of 0 to 4.   The epoxy fluorene derivative according to claim 1, wherein m, n, o and p are all 0. The epoxy fluorene derivative according to claim 1 or 2, wherein R ¹ is a pentylene group or a hexylene group, and R ² is a hydrogen atom. The following general formula (II)

Wherein R ⁷ is an alkyl group having 1 to 10 carbon atoms substituted with an alkyl group having 1 to 10 carbon atoms or a phenyl group, R ⁸ is a methyl group or a hydrogen atom, and R ^{9 to} R ¹⁰ are each independently And an epoxy fluorene derivative represented by: an alkyl group having 1 to 5 carbon atoms, an acetyl group, a phenyl group or a halogen atom, and q and r each represents an integer of 0 to 4.   The epoxy fluorene derivative according to claim 4, wherein q and r are all 0. The epoxy fluorene derivative according to claim 4 or 5, wherein R ⁷ is a phenylpropyl group, and R ⁸ is a hydrogen atom. The manufacturing method of the epoxy fluorene derivative in any one of Claims 1-3 including making the compound represented with the following general formula (I ') react with epihalohydrin in presence of a base.

(Wherein R ¹ is an alkylene group having 2 to 10 carbon atoms or an alkylene group having 2 to 10 carbon atoms substituted with a phenyl group, and R ^{3 to} R ⁶ are each independently an alkyl group having 1 to 5 carbon atoms. , Acetyl group, phenyl group or halogen atom, m, n, o and p each represents an integer of 0 to 4.) The manufacturing method of the epoxy fluorene derivative in any one of Claims 4-6 including making the compound represented with the following general formula (II ') react with epihalohydrin in presence of a base.

(In the formula, R ⁷ is an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted with a phenyl group, and R ^{9 to} R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. , An acetyl group, a phenyl group or a halogen atom, q and r each represents an integer of 0 to 4.)

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