JP6157001B2 - Epoxy resin having bisphenolfluorene skeleton - Google Patents

Description

  The present invention relates to a novel epoxy resin having a bisphenolfluorene skeleton. In addition, the present invention relates to an epoxy resin that has a high refractive index and is excellent in workability due to its softening point being 50 to 80 ° C. and can be suitably used for optical applications such as optical semiconductor encapsulating materials. .

Epoxy resins generally become cured products having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like by curing with various curing agents. Therefore, epoxy resins are used in a wide range of fields such as adhesives, paints, laminates, molding materials and casting materials.
Among them, an epoxy resin having a bisphenolfluorene skeleton has been actively researched and developed for use in the field of optical semiconductor sealing materials as an epoxy resin excellent in high refraction and heat resistance.

  As an epoxy resin having a bisphenol fluorene skeleton, an epoxy resin containing a conventionally known 9,9-bis (4-hydroxyphenyl) fluorene (BPF) as a diol component, for example, trade name “manufactured by Osaka Gas Chemical Co., Ltd.” PG-100 ". The softening point of this epoxy resin is 92 ° C. In addition, since the melting point is as high as 150 ° C., it is difficult to uniformly knead with other components as a composition. Further, although a resin having a softening point of 80 ° C. or higher can be formed by supercooling, there is a problem that the conditions for forming the resin are very difficult because of high crystallinity. In order to solve this problem, an epoxidized product obtained by adding ethylene oxide to the hydroxyl group of bisphenolfluorene is also known (Patent Document 1). However, in this case, the softening point is usually as low as 50 ° C. or less, and it is easy to stick. There is a problem with sex.

Japanese Patent Laid-Open No. 10-045871

  An object of the present invention is an epoxy resin having a bisphenolfluorene skeleton excellent in high refraction and heat resistance, and a novel bisphenolfluorene skeleton-containing epoxy resin excellent in workability due to a softening point of 50 to 80 ° C. It is to provide.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have a workability and fluidity at a softening point of a bisphenolfluorene skeleton-containing epoxy resin having a structure represented by the following formula (1) at 50 to 80 ° C. It was found to be excellent. Specifically, the present invention includes the following:

  [1] The following general formula (1):

（式中ｎは０または１以上の整数である。また、式中、Ｒ_１は炭素数が２以上のアルキル基、シクロアルキル基又はアリール基を示す。）
で表わされるビスフェノールフルオレン骨格を有するエポキシ樹脂。

(In the formula, n is 0 or an integer of 1 or more. In the formula, R ₁ represents an alkyl group, cycloalkyl group or aryl group having 2 or more carbon atoms.)
An epoxy resin having a bisphenolfluorene skeleton represented by:

[2]
An epoxy resin having a bisphenolfluorene skeleton represented by the general formula (1) according to [1], wherein the epoxy resin has a bisphenolfluorene skeleton in which R ₁ is an ethyl group.

[3]
In the presence of an alkali metal hydroxide, the following general formula (2):

（式中、Ｒ_１は炭素数が２以上のアルキル基、シクロアルキル基又はアリール基を示す。）
で表わされるフルオレン系ジオール化合物にエピハロヒドリンを反応させる工程を含む［１］または［２］記載のビスフェノールフルオレン骨格を有するエポキシ樹脂の製造方法。
［４］
［３］に記載の一般式（２）で表わされるフルオレン系ジオール化合物であって、Ｒ_１がエチル基であるフルオレン系ジオール化合物にエピハロヒドリンを反応させる工程を含む［１］または［２］記載のビスフェノールフルオレン骨格を有するエポキシ樹脂の製造方法。

(In the formula, R ₁ represents an alkyl group, cycloalkyl group or aryl group having 2 or more carbon atoms.)
A process for producing an epoxy resin having a bisphenolfluorene skeleton according to [1] or [2], comprising a step of reacting an epihalohydrin with a fluorene-based diol compound represented by the formula:
[4]
The fluorene-based diol compound represented by the general formula (2) according to [3], which comprises a step of reacting a fluorene-based diol compound in which R ₁ is an ethyl group with an epihalohydrin [1] or [2] A method for producing an epoxy resin having a bisphenolfluorene skeleton.

  According to the present invention, the above formula (1) is a novel bisphenolfluorene skeleton-containing epoxy resin that has high refraction, high heat resistance, low crystallinity, and excellent workability because it has a softening point of 50 to 80 ° C. It is possible to provide an epoxy resin having a bisphenolfluorene skeleton represented by formula (II) and a method for producing the same.

¹³ C-NMR of diepoxy bisphenol fluorene resin R ₁ is an ethyl group (1a) (CDCl ₃₎ is a chart. R ₁ is a mass spectrometry chart of diepoxy bisphenol fluorene resin is an ethyl group (1)-diepoxybicyclohexyl naphthalene resin (1).

<Epoxy resin having a novel bisphenolfluorene skeleton>
The epoxy resin having a bisphenol fluorene skeleton of the present invention (hereinafter also simply referred to as “diepoxy bisphenol fluorene resin”) is an epoxy resin having a bisphenol fluorene skeleton represented by the general formula (1). In the general formula (1), R ₁ is an alkyl group having 2 or more carbon atoms, a cycloalkyl group, or an aryl group.

  Examples of the alkyl group include a straight chain having 2 to 20 carbon atoms such as an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, a pentyl group, and a hexyl group. A branched alkyl group can be mentioned. The alkyl group is preferably a linear or branched alkyl group having 2 to 8 carbon atoms, more preferably a linear or branched alkyl group having 2 to 6 carbon atoms, and still more preferably an ethyl group. .

  Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, an alkyl (eg, alkyl having 1 to 4 carbons) substituted cyclopentyl group, an alkyl (eg, an alkyl having 1 to 4 carbons) substituted cyclohexyl group, and the like Examples thereof include a cycloalkyl group having ˜16 (preferably having 5 to 8 carbon atoms) or an alkyl-substituted cycloalkyl group. The cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group.

  As an aryl group, a phenyl group, an alkyl (for example, C1-C4 alkyl) substituted phenyl group, and a naphthyl group can be mentioned, for example. The aryl group is preferably a phenyl group or an alkyl-substituted phenyl group (for example, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, etc.), and more preferably a phenyl group.

  The alkyl group, cycloalkyl group, and aryl group may have a substituent other than the alkyl group (for example, an alkoxyl group, an acyl group, a halogen atom, etc.).

In addition, in the substituent represented by R ₁ in the general formula (1), when R ₁ is a methyl group, the softening point tends to be significantly higher than the other groups.

The number of n in the diepoxybisphenol fluorene resin represented by the general formula (1) may be any number, and it is possible to obtain a single n number by purification. It is used as diepoxy bisphenol fluorene resin in a state in which it has. At this time, in order to obtain a diepoxybisphenol fluorene resin having a softening point of 50 to 80 ° C. excellent in workability, the ratio of the resin where n = 0 is usually 65% or more, preferably 85% or more. As for the n number, if the ratio of n = 0 is high as described above, a diepoxy bisphenol fluorene resin having a softening point of 50 to 80 ° C. can be obtained, preferably 0 or an integer of 1 to 10, more preferably 0 or An integer of 1 to 2, most preferably 0 or 1. If the ratio of the number of n exceeding 3 is increased, the softening point becomes too high, the handling property at the time of production and composition may be deteriorated, and the compatibility is deteriorated. In doing so, there is a possibility that inconveniences such as restrictions on the amount of addition occur. In addition, impurities such as monoglycidyl intermediate, a small amount of hydrolyzable chlorine, α-glycol, etc. are included, but as long as they do not harm the properties as an epoxy resin, there is no need to purify them. It may be a mixture of

  Although it is also a diepoxy bisphenol fluorene resin system, the epoxy resin which uses the conventionally well-known 9,9-bis (4-hydroxyphenyl) fluorene (BPF) as a diol component, for example, the brand name by Osaka Gas Chemical Co., Ltd. There is “PG-100”. The softening point of this epoxy resin is 92 ° C. Therefore, the diepoxy bisphenol fluorene resin represented by the above general formula (1) of the present invention has a softening point excellent in workability as compared with the conventionally known diepoxy bisphenol fluorene resin. Such a decrease in the softening point is presumed to be due to the difference in the position of the glycidyloxy group on the two phenyl groups and the presence of an alkyl group other than the methyl group.

  The diepoxy bisphenol fluorene resin represented by the general formula (1) has characteristics specific to the fluorene skeleton such as high heat resistance and high refractive index by having the fluorene skeleton. For example, the refractive index includes the presence or absence of impurities such as the kind of diepoxybisphenol fluorene resin represented by the above general formula (1) and its intermediate monoglycidyl body, a small amount of hydrolyzable chlorine, α-glycol, etc. Although it may vary depending on the rate, it is typically 1.6 or more. Furthermore, it may exhibit a refractive index of 1.62 or higher, and even more 1.65 or higher.

In addition, the 5% weight loss temperature is also determined by the kind of diepoxy bisphenol fluorene resin represented by the above general formula (1) and its intermediate monoglycidyl compound, a small amount of hydrolyzable chlorine, α-glycol and other impurities. Although it may vary depending on the presence / absence and content, it is typically 300 ° C. or higher. It may further exhibit a 5% weight loss temperature of 320 ° C. or higher, and even 350 ° C. or higher.

  The refractive index of a general bisphenol A type epoxy resin that is widely used is about 1.57, and the 5% weight loss temperature is 267 ° C. Therefore, compared with these general bisphenol A type epoxy resins, the diepoxy bisphenol fluorene resin of the present invention is extremely excellent in terms of refractive index and heat resistance.

  The diepoxy bisphenol fluorene resin of the present invention is a material suitable as an optical resin even in terms of a low Abbe number. The fluorene-based polymer can exhibit a low Abbe number of 30 or less, further 27 or less, and even 25 or less at 20 ° C.

Thus, the diepoxy bisphenol fluorene resin of the present invention also has sufficient transparency and heat resistance required for optical resins.
And although it has such a fluorene skeleton, since the softening point is 50-80 degreeC, it is excellent also in handling property, and it can utilize also for a thermosetting resin raw material, a hardening | curing agent, etc. For example, the diepoxy bisphenol fluorene resin of the present invention may be used as it is as an epoxy resin or as a thermosetting resin raw material such as epoxy (meth) acrylate.

The diepoxy bisphenol fluorene resin of the present invention usually contains a curing agent, a diluent, a curing agent, a curing accelerator, if necessary, and a conventional additive (for example, a coloring material, a stabilizer, a filling agent). An epoxy resin composition containing an agent, an antistatic material, a flame retardant, etc.) may be constituted. You may comprise only the diepoxy bisphenol fluorene resin of this invention, and may use together with another epoxy resin.

Examples of other epoxy resins that can be used in combination with the diepoxy bisphenol fluorene resin of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins. These other epoxy resins may be used alone or in combination of two or more.

The epoxy resin composition containing the diepoxy bisphenol fluorene resin of the present invention has a property excellent in heat resistance because it has a fluorene skeleton, and has low viscosity before curing and good workability. It can be used in a wide range of fields requiring low viscosity. Specifically, it is useful as all electrical / electronic materials such as sealing materials, laminates, insulating materials, solder resists for printed boards, resist materials such as coverlays, color filters, and coating agents. In addition, it is useful as a raw material for optical materials because of its high refractive properties. In addition, it can be used in fields such as molding materials, adhesives, composite materials, paints, printing inks, photocurable resin materials, and photosensitive resin materials.

<Method for producing novel diepoxy binaphthalene resin>
Formula (1) below

（式中ｎは０または１以上の整数である。また、式中、Ｒ_１は炭素数が２以上のアルキル基、シクロアルキル基又はアリール基を示す。）
で表わされるジエポキシビスフェノールフルオレン樹脂の製造方法は特に制限されないが、アルカリ金属水酸化物存在下、下記一般式（２）：

(In the formula, n is 0 or an integer of 1 or more. In the formula, R ₁ represents an alkyl group, cycloalkyl group or aryl group having 2 or more carbon atoms.)
Although the manufacturing method of diepoxy bisphenol fluorene resin represented by this is not particularly limited, in the presence of an alkali metal hydroxide, the following general formula (2):

（式中、Ｒ_１は炭素数２以上のアルキル基、シクロアルキル基又はアリール基を示す。）
で表わされるフルオレン系ジオール化合物にエピハロヒドリンを反応させることにより得られる。

(In the formula, R ₁ represents an alkyl group having 2 or more carbon atoms, a cycloalkyl group, or an aryl group.)
It can be obtained by reacting an epihalohydrin with a fluorene diol compound represented by the formula:

The method for producing the fluorene-based diol compound of the above general formula (2) used as a raw material is not particularly limited, but preferably 9-fluorenone and the following general formula (3) under acidic conditions.

（式中、Ｒ_１は炭素数２以上のアルキル基、シクロアルキル基又はアリール基を示す。）
で表わされるｍ−アルキルフェノールと縮合反応させる方法が用いられる。なかでも、酸性化合物（有機酸及び／又は無機酸）とチオール化合物との存在下に上記縮合反応を行う方法は、高い反応選択性で目的のフルオレン系ジオール化合物を形成し得、高純度の当該フルオレン系ジオール化合物が高収率で得られ得ることから好ましく採用することができる。また、市販品（上記一般式（２）のＲ_１がエチル基の場合、商品名：ＴＢＩＳ−ＥＰ／田岡化学工業（株）製）を用いてもよい。

(In the formula, R ₁ represents an alkyl group having 2 or more carbon atoms, a cycloalkyl group, or an aryl group.)
A method of performing a condensation reaction with an m-alkylphenol represented by the formula: Among them, the method of performing the above condensation reaction in the presence of an acidic compound (organic acid and / or inorganic acid) and a thiol compound can form a desired fluorene-based diol compound with high reaction selectivity, and the high-purity Since a fluorene diol compound can be obtained in a high yield, it can be preferably employed. Also, (when _{R 1} in formula (2) ethyl group, trade name: TBIS-EP / Taoka Chemical Ltd. Co.) commercially may be used.

  In the condensation reaction, m-alkylphenol is usually used in an excess amount with respect to 9-fluorenone. The ratio of the amount of m-alkylphenol used relative to the amount of 9-fluorenone is usually 2.0 to 40 times (for example 2.1 to 40 times), preferably 3 to 30 times, more preferably, in molar ratio. 4 to 20 times. The condensation reaction can be performed in the presence or absence of a solvent, and an excess amount of m-alkylphenol is also preferably used as the solvent.

  As the organic acid, p-toluenesulfonic acid, methanesulfonic acid and the like can be used. As the inorganic acid, hydrohalic acid such as hydrochloric acid (hydrogen chloride aqueous solution), phosphoric acid, or the like can be used. The hydrogen chloride concentration of hydrochloric acid is preferably 10 to 37% by weight, more preferably 20 to 37% by weight, and still more preferably 25 to 37% by weight. Among them, it is preferable to use paratoluenesulfonic acid, hydrochloric acid (especially high-concentration hydrochloric acid) or the like because high reaction selectivity and thus high yield can be obtained. The acidic compound (organic acid and / or inorganic acid) can be used alone or in combination of two or more.

  When sulfuric acid (concentrated sulfuric acid) is used as the inorganic acid, the following general formula (4):

（式中、Ｒ_１は炭素数２以上のアルキル基、シクロアルキル基又はアリール基を示す。）
で表されるキサンテン系化合物が主要な反応生成物として生成することが本発明者らによって明らかになっており、この点で硫酸（濃硫酸）の使用は比較的不利である。パラトルエンスルホン酸、塩酸（とりわけ高濃度の塩酸）等の使用によれば、当該キサンテン系化合物の生成を効果的に抑制し、高い反応選択性で目的のフルオレン系ジオール化合物を得ることが可能である。

(In the formula, R ₁ represents an alkyl group having 2 or more carbon atoms, a cycloalkyl group, or an aryl group.)
It has been clarified by the present inventors that a xanthene compound represented by the formula (1) is produced as a main reaction product, and the use of sulfuric acid (concentrated sulfuric acid) is relatively disadvantageous in this respect. By using paratoluenesulfonic acid, hydrochloric acid (especially high-concentration hydrochloric acid), etc., it is possible to effectively suppress the formation of the xanthene compound and obtain the desired fluorene diol compound with high reaction selectivity. is there.

  The ratio of the amount of acidic compound (organic acid or inorganic acid) to be used relative to the amount of 9-fluorenone (in the case of a solution such as hydrochloric acid, the amount of acidic compound contained in the solution) is usually 0.05. -3 times, preferably 0.1-2 times, more preferably 0.2-1.5 times.

  Examples of the thiol compound include alkyl mercaptans [eg, alkyl mercaptans having 1 to 20 carbon atoms such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, n-lauryl mercaptan]; aralkyl mercaptans [eg, benzyl mercaptan Etc.]; mercaptocarboxylic acids (for example, thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid, etc.); and salts thereof (for example, Na Salt, K salt, etc.] can be used. A thiol compound can be used individually or in combination of 2 or more types.

  The ratio of the use amount of the thiol compound to the use amount of 9-fluorenone is usually 0.01 to 0.5 times, preferably 0.02 to 0.3 times, and more preferably 0.03 to 0.3 times in terms of molar ratio. 0.2 times.

  For example, if the condensation reaction is performed in the presence of an acidic compound (organic acid and / or inorganic acid) and a thiol compound, 9-fluorenone and m-alkylphenol as raw materials, an acidic compound, a thiol compound, Moreover, it can carry out by charging the solvent used as needed to reaction container, and stirring in air or inert gas atmosphere, such as nitrogen and helium. Liquid containing an acidic compound (for example, liquid acid itself (hydrochloric acid hydrochloric acid itself), solid acid dissolved in a solvent), or liquid containing an acidic compound and a thiol compound It is also effective to add the solution to a reaction vessel charged with another reagent while stirring.

  The reaction temperature is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 15 ° C. or higher from the viewpoint of the reaction rate. On the other hand, when the reaction temperature is excessively high, the by-product of the xanthene compound becomes prominent. Therefore, the reaction temperature is preferably 60 ° C or lower, more preferably 50 ° C or lower, and 40 ° C or lower. More preferably, it is particularly preferably 35 ° C. or lower. The progress of the reaction can be monitored by high performance liquid chromatography (HPLC) or the like.

After completion of the reaction, an appropriate post-treatment operation can be performed to isolate the fluorene diol compound as crystals. Specific examples include extraction of a fluorene-based diol compound into an organic layer (organic solvent), neutralization of an acidic compound with an alkali, washing of the organic layer, concentration of the organic layer, crystallization, filtration, and drying. However, one or more of these operations may be omitted, and other operations may be added. Moreover, you may refine | purify the isolated crystal | crystallization as needed. Examples of the purification method include recrystallization (recrystallization) and impurity removal treatment using an adsorbent such as activated carbon. You may use for the manufacturing process of the above-mentioned diepoxy bisphenol fluorene resin, without isolating the fluorene type diol compound produced | generated by the condensation reaction as a crystal | crystallization. The purity of the fluorene-based diol compound of the general formula (2) is not particularly limited, but may be usually 95% by weight or more, preferably 99% by weight or more.

The alkali metal hydroxide is usually added at 20 to 120 ° C., preferably 40 to 80 ° C., to the mixture of the fluorene diol compound represented by the above general formula (2) and the epihalohydrin thus obtained. The diepoxy bisphenol fluorene resin represented by the said General formula (1) of this invention can be obtained by making it react at -120 degreeC, Preferably it is 40 to 80 degreeC for 1 to 48 hours. Alkali metal hydroxides may be added all at once, but in order to maintain a predetermined reaction temperature, it is preferable to add them continuously for a certain period of time, for example, 1 to 10 hours, or in a necessary amount.

Specific examples of the alkali metal hydroxide in the present invention include sodium hydroxide and potassium hydroxide, and the amount used is usually 0 with respect to 1 equivalent of the hydroxyl group of the fluorene-based diol compound represented by the general formula (2). .8 to 4.0 mol, preferably 1.0 to 2.5 mol. An aqueous solution of the alkali metal hydroxide may be used. In this case, the alkali metal hydroxide aqueous solution is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure. May be a method of continuously returning to the reaction system.

Specific examples of the epihalohydrin used in the present invention include epichlorohydrin, epibromohydrin and the like, and the amount used is usually 2 to 30 with respect to 1 equivalent of the hydroxyl group of the fluorene diol compound represented by the general formula (2). Mole, preferably 3 to 20 mol is used. In addition, n in the said Formula (1) can be adjusted with the molar ratio of the fluorene type diol compound and epihalohydrin represented by the said General formula (2). That is, when epihalohydrin is used in a large excess with respect to the fluorene-based diol compound represented by the general formula (2), a compound having n of 0 is obtained as a main component, and if the amount of epihalohydrin used is reduced, n becomes It is possible to increase the proportion of compounds greater than zero.

In the present invention, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride is preferably used as a catalyst from the viewpoint of improving the reactivity. When the quaternary ammonium salt is used, the amount used is usually 0.01 to 0.50 mol, preferably 0.02 to 0.20 mol, relative to 1 mol of the fluorene diol compound represented by the general formula (2). It is. When a quaternary ammonium salt is used, it is generally added before adding the alkali metal hydroxide to the dissolved mixture of the fluorene diol compound represented by the general formula (2) and the epihalohydrin.

Addition of an aprotic polar solvent such as dimethyl sulfoxide or dimethyl sulfone is also preferable for promoting the reaction. When an aprotic polar solvent is added, the amount used is usually 10 to 150% by weight, preferably 15 to 120% by weight, based on the amount of epihalohydrin.

After these epoxidation reactions, the reaction mass is filtered or washed with water to remove insolubles, inorganic salts, and alkali metal hydroxides. Alternatively, it may be left as it is. Thereafter, when an excessive amount of epihalohydrin is used, the epihalohydrin may be removed under reduced pressure by heating at 100 to 150 ° C. and a pressure of 30 mmHg or less, preferably 10 mmHg or less. Alternatively, it may be left as it is.

Thereafter, in order to obtain a diepoxy binaphthalene resin with less hydrolyzable halogen, the diepoxy binaphthalene resin subjected to the above post-treatment is again dissolved in a solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and sodium hydroxide. Alternatively, an aqueous solution of an alkali metal hydroxide such as potassium hydroxide can be added to carry out a ring closing reaction to ensure the ring closing. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 2.5 moles, preferably 0.000, based on 1 equivalent of the hydroxyl group of the fluorene diol compound represented by the general formula (2) used for the epoxidation. 20-1.2 mol. The reaction temperature is usually 20 to 120 ° C., and the reaction time is usually 0.5 to 6 hours.

After completion of the ring closure reaction, by-product tars and salts are removed by filtration, or removed by washing with water, and then the phosphoric acid, sodium phosphate, Neutralizing by adding oxalic acid, acetic acid, carbonic acid, etc., repeating washing with water, filtering, and further distilling off solvents such as toluene, methyl isobutyl ketone, methyl ethyl ketone under heating and reduced pressure. An epoxy bisphenol fluorene resin is obtained.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. In the examples, each measurement value was in accordance with the following method and measurement conditions.

[1] HPLC purity The area percentage value when HPLC measurement was performed under the following measurement conditions was defined as HPLC purity.

・ Device: “LC-2010AHT” manufactured by Shimadzu Corporation
・ Column: “L-column ODS” manufactured by the Chemical Substance Evaluation Research Organization
(5μm, 4.6mmφ × 250mm)
-Column temperature: 40 ° C
・ Detection wavelength: UV 254nm
-Mobile phase: Liquid A = 30% methanol, Liquid B = methanol-Mobile phase flow rate: 1.0 ml / min-Mobile phase gradient: Liquid B concentration: 30% (0 minutes)-> 100% (after 25 minutes)-> 100 % (After 35 minutes)
[2] Epoxy equivalent Using an automatic titrator (AT-5100, manufactured by Kyoto Electronics Co., Ltd.), the epoxy equivalent was measured by a method according to JIS K7236.

[3] Measured by a JIS K2207 method using a softening point ring and ball type automatic softening point tester (ASP-MG2 type manufactured by Meitec).

[4] Refractive index and Abbe number Using an Abbe refractometer ("Multi-wavelength Abbe refractometer DR-2M" manufactured by Atago Co., Ltd.), the refractive index at 20 ° C (wavelength: 589 nm) and the Abbe number at 20 ° C (wavelength) : 486, 589, 656 nm). The refractive index and Abbe number were measured as follows. First, the obtained diepoxybisphenolfluorene resin of the present invention is dissolved in N, N-dimethylformamide to prepare 10 wt%, 20 wt% and 30 wt% solutions, and the refractive index and Abbe number of each solution are measured. did. Next, an approximate curve was derived from the obtained three measured values, and values obtained by extrapolating the approximate curve to 100% by weight were used as the refractive index and Abbe number of the diepoxybisphenol fluorene resin of the present invention.

[5] 5% weight reduction temperature Using a thermogravimetric instrument (Shimadzu Corporation TGA-50), the temperature was increased from room temperature to 500 ° C. at a rate of 10 ° C./minute under a nitrogen stream.

[6] NMR measurement
¹³ C-NMR was recorded on a JEOL-ESC400 spectrometer using tetramethylsilane as internal standard and CDCl ₃ as solvent.

[7] LC-MS measurement LC-MS was separated and mass analyzed under the following measurement conditions to identify the target product.
・ Device: “Xevo G2 Q-Tof” manufactured by Waters Co., Ltd.
Column: “ACQUITY UPLC BEH C18” manufactured by Waters Co., Ltd.
(1.7μm, 2.1mmφ × 100mm)
-Column temperature: 40 ° C
・ Detection wavelength: UV 230-500nm
-Mobile phase: Liquid A = ultrapure water, Liquid B = methanol-Mobile phase flow rate: 0.3 ml / min-Mobile phase gradient: Liquid B concentration: 78% (0 minutes) → 78% (after 7 minutes) → 100 % (After 12 minutes)
・ Detection method: Q-Tof
-Ionization method: ESI (+) method-Ion Source: Voltage (+) 2.0 kV, temperature 150 ° C
Sampling Cone: voltage 50V, gas flow 50L / h
Desolvation Cas: temperature 500 ° C., gas flow 1000 L / h

<Example 1>
Production example of diepoxy bisphenol fluorene resin 1a [9,9-bis (2-hydroxy-4-ethylphenyl) fluorene glycidyl ether] in which R ₁ in the general formula (1) is an ethyl group Stirrer, cooler and temperature In a 200 ml glass reaction vessel equipped with a meter, 15.00 g of 9,9-bis (2-hydroxy-4-ethylphenyl) fluorene (manufactured by Taoka Chemical Co., Ltd., trade name TBIS-EP) under a nitrogen atmosphere. (0.037 mol) and epichlorohydrin 40.97 g (0.443 mol) were charged, and benzyltriethylammonium chloride 0.54 g (0.0024 mol) was added. The temperature was raised to 80 ° C., 3.25 g (0.081 mol) of granular sodium hydroxide was added in portions over 50 minutes, and when the mixture was stirred at the same temperature for 2 hours, the reaction mixture was analyzed by HPLC. The raw material 9,9-bis (2-hydroxy-4-ethylphenyl) fluorene was 0.1% or less. The resulting reaction mixture was heated to 130 ° C., excess epichlorohydrin and the like were distilled off under reduced pressure of 10 mmHg, cooled to 80 ° C., and toluene was added to the residue to dissolve. To this toluene solution was added 6.17 g (0.037 mol) of a 24% by weight aqueous sodium hydroxide solution at 80 ° C., and the mixture was stirred at the same temperature for 3 hours. . Then, after adding and neutralizing an acid, the water layer was liquid-separated and removed. Next, after washing the organic layer with water, the organic layer is filtered to remove insolubles, and then concentrated under reduced pressure to distill off the toluene to give a pale yellow viscous solid diepoxybisphenolfluorene resin. 17.90 g of 1a was obtained. The yield was 93.5%. When the obtained diepoxy bisphenol fluorene resin 1a was analyzed by HPLC, in the above formula (1), n = 0 was 87.5%, 9,9-bis (2-hydroxy-4-ethylphenyl) fluorene. The monoglycidyl compound added with one epichlorohydrin was 2.0%, the formula (1) where n = 1 was 2.1%, and the epoxy equivalent was 279 g / eq. And the softening point was 68 degreeC. The refractive index at 20 ° C. was 1.60, and the Abbe number was 24.9. The 5% weight loss temperature was 308 ° C.

FIG. 1 shows a ¹³ C-NMR (CDCl ₃ ) chart of the obtained diepoxybisphenol fluorene resin. Here, 62.0 ppm is the carbon at the 9th position of fluorene, 111.8 to 156.7 ppm is the carbon of the fluorene skeleton, the carbon of the benzene ring derived from m-ethylphenol, 15.6 ppm, 28.5 ppm is the ethyl group Carbon, 44.3 to 44.7 ppm, 49.6 ppm, and 67.8 to 68.9 ppm are attributed to carbon of the glycidyl group. Moreover, among the obtained diepoxy bisphenol fluorene resins 1a, the results of mass spectrometry obtained using LC-MS for n = 0 in the above formula (1) are shown in FIG. Calculated-diepoxybicyclohexyl naphthalene resin in the present analysis _{^{(TOF MS ESI +; C 35}} H 34 O 4 + Na): is 541.2355, found was 541.2355.

<Example 2>
In a 200 ml glass reaction vessel equipped with a stirrer, a cooler and a thermometer, 9,9-bis (2-hydroxy-4-ethylphenyl) fluorene (Taoka Chemical Industries, Ltd. TBIS-EP) 10.00 g (0.025 mol), epichlorohydrin 27.30 g (0.295 mol) and dimethyl sulfoxide 10.00 g were charged, heated to 50 ° C., and granular sodium hydroxide 2.00 g (0.050 mol). Was added in portions over 60 minutes, and then the mixture was heated to 70 ° C. and stirred at the same temperature for 5 hours. When the reaction mixture was analyzed by HPLC, the raw material 9,9-bis (2-hydroxy -4-Ethylphenyl) fluorene was 0.1% or less. The resulting reaction mixture was heated to 130 ° C., excess epichlorohydrin and the like were distilled off under reduced pressure of 10 mmHg, cooled to 80 ° C., and methyl isobutyl ketone was added to the residue to dissolve it. To this methyl isobutyl ketone solution was added 4.11 g (0.025 mol) of a 24 wt% sodium hydroxide aqueous solution at 70 ° C., and the mixture was stirred for 4 hours at the same temperature. Removed. Then, after adding and neutralizing an acid, the water layer was liquid-separated and removed. Next, after washing the organic layer with water, the organic layer is filtered to remove insolubles, and then concentrated under reduced pressure to distill off methyl isobutyl ketone, thereby producing a light yellow viscous solid diepoxy bisphenol. 12.06 g of fluorene resin 1a was obtained. The yield was 94.5%. When the obtained diepoxy bisphenol fluorene resin 1a was analyzed by HPLC, in the above formula (1), n = 0 was 87.5%, 9,9-bis (2-hydroxy-4-ethylphenyl) fluorene. The monoglycidyl compound added with one epichlorohydrin was 1.5%, in the above formula (1), n = 1 was 3.7%, and the epoxy equivalent was 287 g / eq. And the softening point was 70 degreeC.

<Example 3>
In a 200 ml glass reaction vessel equipped with a stirrer, a cooler and a thermometer, 9,9-bis (2-hydroxy-4-ethylphenyl) fluorene (Taoka Chemical Industries, Ltd. TBIS-EP) 20.00 g (0.049 mol), epichlorohydrin 91.04 g (0.984 mol) were charged, and tetrabutylammonium bromide 0.95 g (0.0030 mol) was added. Furthermore, when the temperature was raised to 85 ° C., 13.52 g (0.162 mol) of 48 wt% sodium hydroxide was added in portions over 110 minutes, and the mixture was stirred for 12 hours at the same temperature. The raw material 9,9-bis (2-hydroxy-4-ethylphenyl) fluorene was 0.1% or less. Water is added to the resulting reaction mixture to dissolve the generated salts, etc., the generated insoluble matter is removed by filtration, the lower layer is separated, heated to 130 ° C., and then excess epichlorohydrin, etc. is distilled under reduced pressure of 10 mmHg. After cooling to 80 ° C., toluene was added to the residue and dissolved. To this toluene solution was added 6.17 g (0.037 mol) of a 24% by weight aqueous sodium hydroxide solution at 80 ° C., and the mixture was stirred at the same temperature for 4 hours. The insoluble matter was filtered off, and the lower layer was separated and removed. . Then, after adding and neutralizing an acid, the water layer was liquid-separated and removed. Next, after washing the organic layer with water, the organic layer is filtered to remove insolubles, and then concentrated under reduced pressure to distill off the toluene to give a pale yellow viscous solid diepoxybisphenolfluorene resin. 23.60 g of 1a was obtained. The yield was 93.2%. When the obtained diepoxy bisphenol fluorene resin 1a was analyzed by HPLC, in the above formula (1), n = 0 was 87.5%, 9,9-bis (2-hydroxy-4-ethylphenyl) fluorene. The monoglycidyl compound added with one epichlorohydrin was 1.8%, n = 1 in the above formula (1) was 1.6%, and the epoxy equivalent was 276 g / eq. And the softening point was 69 degreeC.

<Comparative Example 1>
Production example raw material of diepoxy bisphenol fluorene resin 1b [9,9-bis (2-hydroxy-4-methylphenyl) fluorene glycidyl ether] in which R ₁ in the general formula (1) is a methyl group is 9,9-bis (2-Hydroxy-4-methylphenyl) fluorene (Taoka Chemical Industries, Ltd., trade name TBIS-MMP) Except for changing to 15.00 g (0.040 mol), epoxidation reaction and reaction in the same manner as in Example 1. Post-treatment was performed later to obtain 14.30 g of a light yellow solid diepoxy bisphenol fluorene resin 1b. The yield was 83.0%. The epoxy purity of the obtained epoxy resin 1b is 82.5% when n = 0 in the above formula (1), and one epichlorohydrin is present in 9,9-bis (2-hydroxy-4-methylphenyl) fluorene. The added monoglycidyl body was 0.5%, in the above formula (1), n = 1 was 2.8%, and the epoxy equivalent was 266 g / eq. And the softening point was 106 degreeC. The refractive index at 20 ° C. was 1.60, and the Abbe number was 22.6. The 5% weight loss temperature was 318 ° C.

  Table 1 shows the results of the softening point, refractive index, Abbe number, and 5% weight loss temperature of the diepoxy bisphenol fluorene resin 1a of the present invention obtained in Example 1 and the diepoxy bisphenol fluorene resin 1b obtained in Comparative Example 1. Shown in Table 1 shows the following formula (5) for comparison with a conventionally known epoxy bisphenol fluorene resin:

で表わされる９，９−ビス［４−（２−ヒドロキシエトキシ）フェニル］フルオレンエポキシ樹脂（大阪ガスケミカル（株）製の商品名「ＰＧ−１００」）の公表値を併せて記載する。

The published value of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene epoxy resin (trade name “PG-100” manufactured by Osaka Gas Chemical Co., Ltd.) represented by

Thus, the diepoxy bisphenol fluorene resin of this invention has sufficient transparency and heat resistance comparable to conventionally well-known diepoxy bisphenol resin.
And although it has such a fluorene skeleton, a softening point is 50-80 degreeC and is excellent in workability | operativity.

Claims (4)

The following general formula (1):

(In the formula, n is 0 or an integer of 1 or more. In the formula, R ₁ represents an alkyl group, cycloalkyl group or aryl group having 2 or more carbon atoms.)
An epoxy resin having a bisphenolfluorene skeleton represented by: An epoxy resin having a bisphenolfluorene skeleton represented by the general formula (1) according to claim 1, wherein the epoxy resin has a bisphenolfluorene skeleton in which R ₁ is an ethyl group. In the presence of an alkali metal hydroxide, the following general formula (2):

(In the formula, R ₁ represents an alkyl group, cycloalkyl group or aryl group having 2 or more carbon atoms.)
The method for producing an epoxy resin having a bisphenolfluorene skeleton according to claim 1 or 2, comprising a step of reacting an epihalohydrin with a fluorene-based diol compound represented by the formula: A fluorene-based diol compound represented by the general formula (2), of an epoxy resin having a bisphenol fluorene skeleton according to claim 3 Symbol mounting comprises the step of reacting the epihalohydrin fluorene-based diol compound R ₁ is an ethyl group Production method.

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