KR102048610B1 - Epoxy resin having binaphthalene skeleton - Google Patents

Abstract

(식 중, n은 0 또는 1 이상의 정수이다.)
로 나타내어지는 구조를 가지는 바이나프탈렌 골격 함유 에폭시 수지를 포함한다. 또한, 본 발명은, 알칼리 금속 수산화물 존재하에서, 2, 2＇-비스(2-히드록시에톡시)-1, 1＇-바이나프탈렌에 에피할로히드린을 반응시키는 것을 포함하는, 상기 식 (1)로 나타내어지는 신규한 바이나프탈렌 골격 함유 에폭시 수지의 제조 방법을 포함한다.This invention is following formula (1):
[Formula 1]

(Wherein n is an integer of 0 or 1 or more.)
The binaphthalene frame | skeleton containing epoxy resin which has a structure represented by this is included. In addition, the present invention includes reacting epihalohydrin with 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene in the presence of an alkali metal hydroxide. The manufacturing method of the novel binaphthalene frame | skeleton containing epoxy resin shown by 1) is included.

Description

Epoxy resin having binaphthalene skeleton {EPOXY RESIN HAVING BINAPHTHALENE SKELETON}

The present invention relates to a novel epoxy resin having a binaphthalene skeleton.

Generally, an epoxy resin is hardened | cured by various hardening | curing agents, and turns into hardened | cured material excellent in mechanical property, water resistance, chemical resistance, heat resistance, electrical property, etc. For this reason, epoxy resins are used in a wide range of fields, such as adhesives, coatings, laminates, molding materials, and casting materials.

Among them, the epoxy resin having a binaphthalene skeleton is an epoxy resin having a low water absorption and a low elastic modulus in a high temperature region, and research and development on the use in the field of semiconductor sealing materials and the like are actively performed. In addition, in the field of semiconductor sealing materials, it is required to fill the filler with high fillers in order to improve the solder crack resistance at the time of surface mounting, and in order to achieve the purpose of filling the filler, an epoxy resin having low melt viscosity and excellent flowability is required. (See Patent Document 1, for example)

On the other hand, as an epoxy resin which has a binaphthalene frame | skeleton, it is the following structural formula (2) in patent document 1 and patent document 2, for example:

[Formula 1]

The diglycidyl ether of binaphthol which is represented by is disclosed. However, Patent Document 1 describes that the softening point of the epoxy resin of the above formula (2) described in Examples 1 to 3 is 61 ° C to 79 ° C, and similarly, Patent Document 2 describes the formula (2) described in Examples. It is described that the softening point of the epoxy resin of 59 ° C to 60 ° C is difficult to handle, such as low softening point and blocking due to storage conditions even when treated as a solid. There is a problem in that the use is limited.

Japanese Unexamined Patent Publication "Japanese Patent Publication No. Hei 6-184131" Japanese Unexamined Patent Publication "Japanese Patent Publication No. 2009-292996"

An object of the present invention is to provide a novel binaphthalene skeleton-containing epoxy resin having a binaphthalene skeleton and having a low melt viscosity and a liquid at room temperature, which is excellent in workability and fluidity.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the binaphthalene frame | skeleton containing epoxy resin which has a structure represented by following formula (1) has a low melt viscosity, is a liquid at room temperature, and is excellent in workability and fluidity. I found out. It has also been found that the binaphthalene skeleton-containing epoxy resin has a high refractive index and an Abbe number. Specifically, the present invention includes the following.

[1] The following formula (1):

[Formula 2]

(Wherein n is 0 or an integer of 1 or more)

Diepoxy binaphthalene resin represented by.

[2]

Diepoxy binaphthalene according to [1], comprising the step of reacting epihalohydrin with 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene in the presence of an alkali metal hydroxide. Method for producing a resin.

According to the present invention, it is possible to provide a novel binaphthalene skeleton-containing epoxy resin having a binaphthalene skeleton and excellent in workability and fluidity, which is liquid even at room temperature. Moreover, since the binaphthalene frame | skeleton containing epoxy resin of this invention shows high refractive index and a high Abbe's number, use as a novel optical system material can also be expected.

1 is a ¹³ C-NMR (CDCl ₃ ) chart of diepoxy binaphthalene resin represented by Formula (1).
It is the mass spectrometry chart of diepoxy binaphthalene resin represented by Formula (1).

<The manufacturing method of new diepoxy binaphthalene resin>

Equation (1) below

[Formula 3]

(Wherein n is 0 or an integer of 1 or more.)

The diepoxy binaphthalene resin represented by this is, for example, by reacting 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene and epihalohydrin in the presence of an alkali metal hydroxide. Obtained.

2, 2'-bis (2-hydroxyethoxy) -1 and 1'-binaphthalene which are used as a raw material can use a commercial item, and it is a common method, for example, 1, 1- bi- 2-naphthol, A predetermined amount of ethylene carbonate or ethylene oxide is reacted in the presence of an inert solvent and an alkali catalyst to make 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene as it is. You may use what refine | purified from the reaction product after completion | finish of reaction using the usual purification method (extraction, crystallization etc.). In the present invention, the purity of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene used as a raw material is usually 90% by weight or more, preferably 95% by weight or more, particularly Preferably it is 99 weight% or more.

As an alkali metal hydroxide in this invention, sodium hydroxide, potassium hydroxide, etc. are illustrated, for example, The usage-amount is 1 mol of hydroxyl groups of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene. The amount is usually 0.8 to 4.0 moles, preferably 2.0 to 3.0 moles per equivalent. The alkali metal hydroxide may be a solid or an aqueous solution.

Specific examples of the epihalohydrin used in the present invention include epichlorohydrin, epibromhydrin, and the like, and the amount thereof used is 2,2'-bis (2-hydroxyethoxy) -1,1. The molar ratio is usually from 2 to 30 moles, preferably from 3 to 20 moles, relative to 1 molar equivalent of the hydroxyl group of X-binaphthalene. In addition, the value (n number) of n which is the repeating unit number of diepoxy binaphthalene resin represented by said Formula (1) can be adjusted with usage-amount of epihalohydrin. Namely, when a large amount of epihalohydrin is used in excess of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene, a compound having n is obtained as a main component, and 2 When the usage-amount of epihalohydrin is reduced with respect to, 2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene, the ratio of the compound whose n is larger than 0 can be made high.

As a reaction method at the time of making 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene and epihalohydrin react, for example, 2,2'-bis (2- Hydroxyethoxy) -1,1'-binaphthalene and epihalohydrin were added to the reaction vessel for dissolution and mixing, and then alkali metal hydroxide was added at 20 ° C to 120 ° C, preferably 40 ° C to 90 ° C. Then, the diepoxy binaphthalene resin of the present invention can be obtained by reacting at 20 ° C to 120 ° C, preferably at 40 ° C to 90 ° C for 1 to 24 hours. In addition, although alkali metal hydroxide may be added collectively, in order to maintain predetermined | prescribed reaction temperature, it adds continuously by the method of dripping over a predetermined time, for example, 1 to 10 hours, or it divides and adds required amount It is desirable to.

When carrying out the above reaction, in the case of using an aqueous solution of an alkali metal hydroxide, an aqueous solution of the alkali metal hydroxide is continuously added into the reaction system, while the reaction system is refluxed under reduced pressure or under atmospheric pressure to avoid water and unreacted reaction. After dilution of hydrhydrin, the effluent is separated and water is removed out of the system, and epihalohydrin is preferably returned to the reaction system.

When carrying out the above reaction, it is preferable to use quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride and the like from the viewpoint of improving the reactivity. The use amount of a quaternary ammonium salt is usually 0.01 to 0.50 mol, preferably 0.02 to 0.20 mol, per 1 mol of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene. to be. In addition, when using a quaternary ammonium salt, the alkali metal hydroxide is usually added to a dissolution mixture of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene and epihalohydrin. Add before.

After the reaction, the diepoxy binaphthalene resin represented by the above formula (1) may be used as it is, but the post-treatment steps shown in the following <1> to <3> are appropriately performed to obtain the desired diepoxy binaphthalene resin. It is preferable.

<1> removal process and concentration process, such as inorganic powder

The reaction product obtained in the said reaction is filtered and / or washed with water, and liquid separation is performed as needed, and insoluble matter, an inorganic salt, and an alkali metal hydroxide are removed. Then, when epihalohydrin is excessively used in the said reaction, it is preferable to remove epihalohydrin in internal temperature 100 degreeC-150 degreeC, internal pressure 30mmHg or less, Preferably it is 10mmHg or less.

<2> ring closure process

In order to make diepoxy binaphthalene resin with less content of hydrolysable halogen, after adding the organic solvent to the diepoxy binaphthalene resin after the said reaction or the diepoxy binaphthalene resin which performed the post-processing process shown by <1>, alkali By adding a metal hydroxide and stirring at 20 to 120 degreeC normally, it can be made into the diepoxy binaphthalene resin with less content of a hydrolysable halogen.

Any organic solvent may be used as long as it does not react with diepoxy binaphthalene resin or alkali metal hydroxide, and toluene, methyl isobutyl ketone, methyl ethyl ketone and the like can be exemplified. As the alkali metal hydroxide used in the ring closure step, for example, sodium hydroxide and potassium hydroxide may be used and may be solid or an aqueous solution, but an aqueous solution is preferably used. The amount of alkali metal hydroxide used is usually 0.01 to 2.5 mol, preferably 1 mol equivalent to 1 mol equivalent of hydroxyl groups of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene used for epoxidation. 0.20 to 1.2 moles. This ring-closure process is normally performed for 0.5 to 6 hours.

<3> refining process

After completion of the ring closing step, the reactant obtained in the ring closing step is filtered and / or washed with water and liquid separation as necessary to remove by-product tar powder and salt. Thereafter, neutralization is performed with acids such as phosphoric acid, sodium phosphate, oxalic acid and acetic acid so that the pH is 8.0 to 4.0. After neutralization, water washing and liquid separation are repeated, and insoluble matter is removed by filtration as necessary, and then the organic solvent used in the ring closure step is removed under reduced pressure to obtain the diepoxy binaphthalene resin of the present invention. .

<New diepoxy binaphthalene resin>

Equation (1) below

[Formula 4]

(Wherein n is 0 or an integer of 1 or more)

The value (n number) of n which is the repeating unit number of the diepoxy binaphthalene resin (henceforth the diepoxy binaphthalene resin of this invention) represented by the is in addition to the use of the diepoxy binaphthalene resin of this invention. Although it can select arbitrarily and the thing of single n number can also be obtained by refine | purification, what mixed the diepoxy binaphthalene resin from which n number differs is used normally as the diepoxy binaphthalene resin of this invention. Further, epichlorohydrin is further added to the diepoxybinaphthalene resin of the present invention to impurities such as monoglycidyl as an intermediate, a small amount of hydrolysable chlorine, α-glycol, and hydroxyl groups of n = 1 diepoxybinaphthalene resin. At least one of the triglycidyl bodies and the like may be mixed.

N number of the diepoxy binaphthalene resin of this invention becomes like this. Preferably it is an integer of 0 or 1-10, More preferably, it is an integer of 0 or 1-2, Most preferably, it is 0 or 1. When the ratio of n-number exceeding 3 becomes high, compatibility will worsen and a problem may arise, such as a restriction | limiting in addition amount when making a composition. In order to make a lower viscosity diepoxy binaphthalene resin, the ratio of resin which is n = 0 is made into 65% or more normally, Preferably it is 85% or more.

Although the diepoxy binaphthalene resin of this invention has the binaphthalene frame | skeleton which shows the characteristics, such as low water absorption and low elasticity modulus in a high temperature area | region, shows the characteristic which is liquid at room temperature and low melt viscosity. For example, since the melt viscosity in 100 degreeC of the diepoxy binaphthalene resin of this invention is 50-200 mPa * s, and melt viscosity in 150 degreeC is 5-30 mPa * s, it is excellent in handleability.

Since the diepoxy binaphthalene resin of this invention has characteristics, such as high heat resistance, and is low viscosity, it is excellent in handleability, and can be used also as a thermosetting resin raw material, a hardening | curing agent, etc. For example, the diepoxy binaphthalene resin of this invention can be used as it is like a general epoxy resin, and can also be used as thermosetting resin raw materials, such as an epoxy (meth) acrylate.

The diepoxy binaphthalene resin of this invention usually contains a hardening | curing agent, a diluent, a hardening accelerator, and also usual additives (for example, a coloring agent, a stabilizer, a filler, an antistatic agent, a flame retardant, etc.) etc. as needed. It can also be made from an epoxy resin composition. When making the said epoxy resin composition, the epoxy resin component contained in the said epoxy resin composition may be comprised only by the diepoxy binaphthalene resin of this invention, and may be used together with another epoxy resin.

As another epoxy resin which can be used together with the diepoxy binaphthalene resin of this invention, a novolak-type epoxy resin, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a biphenyl-type epoxy resin, etc. are mentioned. These other epoxy resins can also be used individually or in combination of 2 or more types.

Example

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these.

In addition, each measured value in the Example and the comparative example was measured according to the following method and measurement conditions.

[1] HPLC purity

The area percentage value at the time of performing HPLC measurement on the following measurement conditions was made into HPLC purity.

Equipment: "LC-2010AHT" made by Shimadzu Corporation

Column: L-column ODS (5μm, 4.6mmφ × 250mm)

Column temperature: 40 ° C

Detection wavelength: UV 254 nm

Mobile phase: Liquid A = 30% methanol, Liquid B = methanol

Mobile phase flow rate: 1.0 ml / min

Mobile phase inclination: B liquid concentration: 30% (0 minutes) → 100% (25 minutes later) → 100% (35 minutes later)

[2] NMR measurement

¹³ C-NMR was measured under the following measurement conditions.

Internal standard: tetramethylsilane

Solvent: CDCl ₃

Device: JEOL-ESC400 spectrometer

[3] LC-MS measurement

The target object was identified by separation and mass spectrometry under the following measurement conditions.

Device: "Xevo G2 Q-Tof" made by Waters Co., Ltd.

Column: "ACQUITY® UPLC® BEH® C18" made by Waters Co., Ltd. (1.7μm, 2.1mmφ × 100mm)

Column temperature: 40 ° C

Detection wavelength: UV-230-800nm

Mobile phase: A liquid = ultrapure water, B liquid = methanol

Mobile phase flow rate: 0.3 ml / min

Mobile phase inclination: Liquid B concentration: 60% (0 minutes) → 70% (after 10 minutes) → 100% (after 12 minutes)

Detection method: Q-Tof

Ionization method: ESI (+) method

Ion Source: voltage (+) 2.0kV, temperature 120 ℃

Sampling Cone ： Voltage: 10V, gas flow 50L / h

Desolvation Cas ： temperature 500 ℃, gas flow 1000L / h

[4] epoxy equivalent

It measured by the method according to JISK7236 using the automatic titrator (AT-5100 by Kyoto Electronics).

[5] melt viscosity

It measured by heating at 100-100 degreeC and 150 degreeC at 20-100 rpm with rotor HH-1 using the Brookfield viscometer (made by TOKIMEC®INC, MODEL: BBH).

[6] refractive index and Abbe number

Refractive index (wavelength: 589 nm) at 20 ° C and Abbe number (wavelength: 486, 589, 656 nm) at 20 ° C were measured using an Abbe refractometer (manufactured by Atago Co., Ltd. "Multiwavelength Abbe Refractometer # DR-2M"). . In addition, calculation of the sample preparation and refractive index Abbe's number was performed with the following method.

The obtained diepoxy binaphthalene resin of the present invention was dissolved in N, N-dimethylformamide to prepare 10% by weight, 20% by weight and 30% by weight solution, and the refractive index and Abbe number were measured under the conditions described above for each solution. It was. Next, the approximation curve was derived from the measured value of three points obtained, and the value at the time of extrapolating this at 100 weight% was made into the refractive index and Abbe's number of the obtained resin.

EXAMPLE 1

In a 200 ml glass reaction vessel equipped with a stirrer, a cooler, and a thermometer, 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene (manufactured by Takaoka Chemical Co., Ltd.) under a nitrogen atmosphere, Trademark TBIS-BNE) 15.00g (0.040mol), epichlorohydrin 74.20g (0.800mol) was added, and after heating and dissolving at 50 degreeC, 1.37g (0.006mol) of benzyl triethylammonium chloride was added. It heated up at 80 degreeC after addition, and added 6.65 g (0.166 mol) of granular sodium hydroxide over 80 minutes at the same temperature, and after stirring for 4 hours at the same temperature, analyzed the reaction product by HPLC, and the raw material 2 , 2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene was 0.1% or less.

Water was added to the obtained reaction product, stirred, and filtered to remove insoluble matter. Thereafter, the aqueous layer was separated and removed, followed by water washing and separation, and then the organic layer was heated to 130 ° C and concentrated to an internal pressure of 10 mmHg. Thereafter, the mixture was cooled to 80 DEG C, toluene was added to the residue to dissolve the residue, and then, 5.00 g (0.030 mol) of 80 DEG C and 24 wt% sodium hydroxide aqueous solution was added to the toluene solution, followed by stirring at the same temperature for 6 hours. . After stirring, the insoluble component was removed by filtration, and the aqueous layer was separated and removed. Thereafter, water and acid were added to neutralize and the aqueous layer was separated. Subsequently, the organic layer was washed with water and separated, the organic layer was filtered to remove insoluble matters, and then concentrated under reduced pressure to obtain 17.27 g of a yellowish viscous liquid (89.2% of an apparent yield).

As a result of analyzing the obtained yellowish viscous liquid by HPLC, 86.6% of n = 0 in said Formula (1) was carried out to 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene. 4.8% of the monoglycidyl body to which one epichlorohydrin was added, 1.9% to n = 1 in the formula (1), and triglycidyl body to which epichlorohydrin was further added to the hydroxyl group having n = 1 was 1.8. It was confirmed that the diepoxy binaphthalene resin represented by the target Formula (1) was produced because 0.1% or less of% and the formula (1) contained n = 2 or more were contained. The physical property of obtained diepoxy binaphthalene resin is shown below.

Epoxy equivalent: 256 g / eq

Melt viscosity: 100 ° C: 80 mPa · s, 150 ° C: 15 mPa · s

Refractive index: 1.60

Abbe number: 21.5

The ¹³ C-NMR (CDCl ₃ ) chart of the obtained diepoxy binaphthalene resin is shown in FIG. 1. Here, from 115.4 to 154.2 ppm are attributed to carbon of the naphtharene skeleton, 43.9, 50.6, and 69.8 ppm belong to the carbon of glycidyl group, and 71.4 and 71.7 ppm belong to the carbon of ethoxy group.

Moreover, the result which analyzed the peak corresponding to n = 0 in said Formula (1) among the obtained diepoxy binaphthalene resin by LC-MS is shown in FIG. The calculated value (TOF MS ESI ⁺ ; C ₃₀ H ₃₀ O ₆ + Na) of the diepoxy binaphthalene resin in this analysis was 509.1940, and the measured value was 509.1955.

EXAMPLE 2

In a 200 ml glass reaction vessel equipped with a stirrer, a cooler, and a thermometer, 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene (manufactured by Takaoka Chemical Co., Ltd.) under a nitrogen atmosphere; Trademark TBIS-BNE) 15.00g (0.040mol), epichlorohydrin 74.20g (0.800mol) was added, and heated and dissolved at 50 ℃, 1.37g (0.006mol) benzyltriethylammonium chloride was added. After the addition, the temperature was raised to 80 ° C., and 8.00 g (0.200 mol) of granular sodium hydroxide was added at a similar temperature over 90 minutes, and stirred at the same temperature for 3 hours, after which the reaction product was analyzed by HPLC. 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene was 0.1% or less.

Water was added to the obtained reaction product to perform filtration to remove the insoluble fraction, and then heated to 130 ° C. and concentrated to an internal pressure of 10 mmHg. Then, it cooled to 60 degreeC, and toluene was added and dissolved in the residue. To this toluene solution, 3.30 g (0.020 mol) of an aqueous solution of sodium hydroxide at 60 ° C and 24% by weight was added and stirred at the same temperature for 2 hours, followed by filtration to remove the insoluble fraction, followed by separating an aqueous layer. Thereafter, water and acid were added to neutralize and the aqueous layer was separated. The organic layer was washed with brine and water several times, and the organic layer was filtered to remove insoluble matters and then concentrated under reduced pressure to give 16.64 g of a yellowish viscous liquid (85.5% in apparent yield).

As a result of analyzing the obtained yellow viscous liquid by HPLC, it is 82.3% that n = 0 in the said Formula (1), and it is epi in 2,2'-bis (2-hydroxyethoxy) -1,1'- binaphthalene. 5.0% monoglycidyl added with one chlorohydrin, 2.0% n = 1 in formula (1), and 2.1% triglycidyl added with epichlorohydrin to a hydroxyl group having n = 1 Since 0.2% of thing of n = 2 or more is contained in the said Formula (1), it confirmed that the diepoxy binaphthalene resin represented by the target Formula (1) was produced. The physical property of obtained diepoxy binaphthalene resin is shown below.

Epoxy equivalent: 258 g / eq

Melt viscosity: 100 ° C: 87 mPa · s, 150 ° C: 17 mPa · s

EXAMPLE 3

In a 200 ml glass reaction vessel equipped with a stirrer, a cooler, and a thermometer, 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene (manufactured by Takaoka Chemical Co., Ltd.) under a nitrogen atmosphere; Trademark TBIS-BNE) 15.00g (0.040mol), epichlorohydrin 37.10g (0.400mol) was added, and after heating and dissolving at 50 ℃, 1.37g (0.006mol) benzyltriethylammonium chloride was added. After the addition, the temperature was raised to 80 ° C., and 6.65 g (0.166 mol) of granular sodium hydroxide was divided at 50 ° C. over 50 minutes, added, stirred at the same temperature for 4 hours, and then analyzed by reaction with HPLC. , 2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene was 0.1% or less.

Water was added to the obtained reaction product, and filtration was carried out to remove insoluble matters, and then heated to 130 ° C. and concentrated to 10 mmHg. Then, it cooled to 80 degreeC, and toluene was added to the residue, and it melt | dissolved. To this toluene solution, 10.95 g (0.082 mol) of an aqueous 30% sodium hydroxide solution at 80 ° C was added and stirred at the same temperature for 3 hours, followed by washing with water to remove the aqueous layer. Thereafter, water and acid were added to neutralize and the aqueous layer was separated. Furthermore, after washing with water and separating liquids, the organic layer was filtered to remove insoluble matters, and then concentrated under reduced pressure, 16.28 g of a yellowish viscous liquid (84.2% of an apparent yield) was obtained.

As a result of analyzing the obtained yellow viscous liquid by HPLC, it is 73.0% that n = 0 in said Formula (1), and it is carried out to 2,2'-bis (2-hydroxyethoxy) -1,1'- binaphthalene. The monoglycidyl body to which one epichlorohydrin was added was 2.1%, and in the formula (1), the triglycidyl body to which epichlorohydrin was further added was 4.1% and n = 1 to the hydroxyl group having n = 1. It was confirmed that the diepoxy binaphthalene resin represented by the target Formula (1) was produced because 1.2% of% and the above formula (1) contained n = 2 or more. The physical property of obtained diepoxy binaphthalene resin is shown below.

Epoxy equivalent: 251 g / eq

Melt viscosity: 100 ° C: 68 mPa · s, 150 ° C: 15 mPa · s

EXAMPLE 4

In a 200 ml glass reaction vessel equipped with a stirrer, a cooler, and a thermometer, 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene (manufactured by Takaoka Chemical Co., Ltd.) under a nitrogen atmosphere; A brand name TBIS-BNE) 20.00 g (0.053 mol) and epichlorohydrin 29.70 g (0.321 mol) were added thereto, and the mixture was heated and dissolved at 80 ° C., followed by addition of 1.82 g (0.008 mol) of benzyltriethylammonium chloride. Thereafter, 8.87 g (0.222 mol) of granular sodium hydroxide was added at the same temperature in 90 minutes, and the mixture was stirred at the same temperature for 3 hours. Then, the reaction product was analyzed by HPLC. Bis (2-hydroxyethoxy) -1,1'-binaphthalene was 0.1% or less.

After 40 g of toluene was added to the reaction product, the insoluble fraction was removed by filtration, and then, to this toluene solution, 4.50 g (0.027 mol) of an aqueous sodium hydroxide solution of 30 ° C and 24% by weight was added and stirred at the same temperature for 3 hours. Thereafter, water was added thereto, followed by water washing to separate the aqueous layer. Thereafter, water and acid were added to neutralize and the aqueous layer was separated. Furthermore, after washing with water and separating liquids, the organic layer was filtered to remove insoluble matters, and then concentrated under reduced pressure to obtain 25.26 g of a yellowish viscous liquid (apparent yield 97.9%).

As a result of analyzing the obtained yellowish viscous liquid by HPLC, it is 77.9% that n = 0 in the said Formula (1), and to 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene. 0.6% of monoglycidyl body to which one epichlorohydrin was added, 3.6% to n = 1 in formula (1), and triglycidyl body to which epichlorohydrin was further added to the hydroxyl group having n = 1.4 It was confirmed that the diepoxy binaphthalene resin represented by the target Formula (1) was produced because 1.5% of% and the above formula (1) contained n = 2 or more. The physical property of obtained diepoxy binaphthalene resin is shown below.

Epoxy equivalent: 254 g / eq

Melt viscosity: 100 ° C: 77 mPa · s, 150 ° C: 16 mPa · s

EXAMPLE 5

2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene (product made from Takaoka Chemical Co., Ltd.) in a 200 ml glass reaction vessel equipped with a stirrer, a cooler and a thermometer under a nitrogen atmosphere. 20.00 g (0.053 mol) of TBIS-BNE) and 20.80 g (0.225 mol) of epichlorohydrin were added thereto, and the mixture was heated and dissolved at 80 ° C., followed by addition of 2.58 g (0.008 mol) of tetrabutylammonium bromide. Thereafter, 8.87 g (0.222 mol) of granular sodium hydroxide was added at a constant temperature over 80 minutes, and stirred at the same temperature for 2 hours. Then, the reaction product was analyzed by HPLC. Bis (2-hydroxyethoxy) -1,1'-binaphthalene was 0.1% or less.

40 g of toluene was added to the obtained reaction product, followed by filtration to remove the insoluble fraction, and then, to the toluene solution, 4.50 g (0.027 mol) of an aqueous sodium hydroxide solution of 40 ° C and 24% by weight was added and stirred at the same temperature for 2 hours. Thereafter, water was added, water washing was performed, and the aqueous layer was separated. Thereafter, water and acid were added to neutralize and the aqueous layer was separated. Subsequently, after performing a water washing and separating operation, the organic layer was filtered to remove insoluble matters, and then concentrated under reduced pressure to obtain 25.34 g of a yellowish viscous viscous liquid (apparent yield 98.3%).

As a result of analyzing the obtained yellow viscous liquid by HPLC, it is 68.3% that n = 0 in said Formula (1), and it is carried out to 2,2'-bis (2-hydroxyethoxy) -1,1'- binaphthalene. 0.4% of monoglycidyl bodies to which one epichlorohydrin was added, 3.9% to n = 1 in Formula (1) above, and triglycidyl body to which epichlorohydrin was further added to the hydroxyl group having n = 1 was 9.0 It was confirmed that the diepoxy binaphthalene resin represented by the target Formula (1) was produced from 3.2% containing% = n = 2 or more in Formula (1). The physical property of obtained diepoxy binaphthalene resin is shown below.

Epoxy equivalent: 280 g / eq

Melt viscosity: 100 ° C: 150 mPa · s, 150 ° C: 23 mPa · s

[Comparative Example 1]

Epoxidation reaction and post-treatment after reaction were carried out similarly to Example 1 except having changed the raw material into 11.45 g (0.040 mol) of 1,1'- bi-2- naphthols, and it is represented by said Formula (2) of a pale yellow solid. 14.30 g of an epoxy resin mainly composed of diglycidyl ether of binaphthol (apparent yield 91.9%, HPLC purity 90.4%) was obtained. The physical property of the obtained epoxy resin is shown below.

Epoxy equivalent: 218 g / eq

Melt viscosity: 100 ° C: 825 mPa · s, 150 ° C: 40 mPa · s

Since the diepoxy binaphthalene resin of this invention or the epoxy resin composition containing the said diepoxy binaphthalene resin has a binaphthalene frame | skeleton, it has the characteristics of low water absorption, low elasticity in high temperature range, etc., and low viscosity before hardening And because of its good workability, it can be used in a wide range of fields where heat resistance and low viscosity are required. Specifically, it is useful as all electrical and electronic materials, such as a sealing material, a laminated board, an insulating material, solder materials for printed circuit boards, a resist material, such as a coverlay, a color filter, and a coating agent. Moreover, since it has characteristics such as high refractive index and low Abbe's number, it is also useful as an optical material raw material. In addition, it can be used also in fields such as molding materials, adhesives, composite materials, paints, printing inks, photocurable resin raw materials, and photosensitive resin raw materials.

Claims (2)

Formula (1) below:
[Formula 1]

(Wherein n is an integer of 0 or 1 or more.)
Diepoxy binaphthalene resin represented by. Of the diepoxy binaphthalene resin of claim 1 comprising the step of reacting epihalohydrin with 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene in the presence of an alkali metal hydroxide. Manufacturing method.

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