JP6461721B2 - Epoxy compound and partially esterified epoxy compound thereof, production method thereof, and curable composition containing the same - Google Patents

Description

  The present invention relates to an epoxy compound and a partially esterified epoxy compound thereof, a production method thereof, and a curable resin composition containing the same.

  In the manufacturing method of a liquid crystal display element, the dropping method is a method in which a panel can be formed by directly dropping and bonding liquid crystal in a closed loop of a sealing agent under vacuum and releasing the vacuum. This dripping method has many merits such as a reduction in the amount of liquid crystal used and a time required for injecting the liquid crystal into the panel, and has become the mainstream method for manufacturing a liquid crystal panel using a large substrate. In a method including a dripping method, a seal / liquid crystal is applied and bonded together, then a gap is formed, alignment is performed, and the seal is cured mainly by ultraviolet curing.

Patent Document 1 discloses Compound 1 represented by the following formula as a raw material for a sealing agent as a compound having excellent liquid crystal elution properties. Here, “excellent in liquid crystal elution” means “solubility in liquid crystal is suppressed and contamination of liquid crystal is reduced”.

JP 2012-0777202 A

  The epoxy compound described in Patent Document 1 is excellent in liquid crystal elution, but has a problem of high viscosity. Moreover, when the epoxy compound of Patent Document 1 is partially (meth) acrylated, the viscosity is further increased. Therefore, there is a problem that the use of the partially (meth) acrylated epoxy compound obtained by partially (meth) acrylated the epoxy compound of Patent Document 1 becomes more difficult. Furthermore, a sealing agent composition obtained by adding a solid component such as an inorganic filler, an organic filler or a solid curing agent to an oligomer component which is a high viscosity epoxy compound and / or a partially (meth) acrylated epoxy compound, There was a problem that the viscosity became high and it was difficult to produce and apply the sealant.

  On the other hand, there is a method of reducing the viscosity by using an epoxy compound having a low molecular weight and a partially (meth) acrylated epoxy compound, but there is a problem that liquid stability and liquid crystal elution are deteriorated and display characteristics of liquid crystal are poor. It was.

  An object of the present invention is to obtain an epoxy compound and a partially esterified epoxy compound that have low viscosity and excellent liquid crystal elution.

〔式中、
Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、互いに独立に、水素、グリシジル又はメチルグリシジルであり、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４の少なくとも２つは、グリシジル又はメチルグリシジルであり、
Ｒ^５及びＲ^６は、互いに独立に、水素又はメチルであり、
Ｘ^１及びＸ^２は、互いに独立に、炭素原子数１〜４のアルキレン−炭素原子数６〜２０のアリーレン−炭素原子数１〜４のアルキレン、炭素原子数１〜４のアルキレン−炭素原子数６〜２０のアリーレン、又は基：−Ｙ^１−（Ｏ−Ｙ^１）_ｎ１−（式中、Ｙ^１は、炭素原子数１〜６のアルキレンであり、ｎ１は、０又は１〜６の整数である）である〕
［２］下記式（２）で示される部分エステル化エポキシ化合物。

〔式中、
Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は、互いに独立に、水素、グリシジル、メチルグリシジル又は基：−ＣＨ_２−ＣＲ^１７（ＯＲ^１８）−ＣＨ_２−Ｏ−Ｒ^１９（式中、Ｒ^１７は、水素又はメチルであり、Ｒ^１８は、水素又は（メタ）アクリロイルであり、Ｒ^１９は、（メタ）アクリロイルである）であり、
Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４の少なくとも２つは、グリシジル、メチルグリシジル又は基：−ＣＨ_２−ＣＲ^１７（ＯＲ^１８）−ＣＨ_２−Ｏ−Ｒ^１９であり、
Ｒ^１５及びＲ^１６は、互いに独立に、水素又はメチルであり、
Ｘ^１１及びＸ^１２は、互いに独立に、炭素原子数１〜４のアルキレン−炭素原子数６〜２０のアリーレン−炭素原子数１〜４のアルキレン、炭素原子数１〜４のアルキレン−炭素原子数６〜２０のアリーレン、又は基：−Ｙ^２−（Ｏ−Ｙ^２）_ｎ２−（式中、Ｙ^２は、炭素原子数１〜６のアルキレンであり、ｎ２は、０又は１〜６の整数である）であり、
グリシジル及びメチルグリシジルと基：−ＣＨ_２−ＣＲ^１７（ＯＲ^１８）−ＣＨ_２−Ｏ−Ｒ^１９との割合は、１０：９０〜９０：１０である〕
［３］エポキシ化合物であって、工程（１Ａ）〜（１Ｂ）：
（１Ａ）ジヒドロキシベンゼンのジグリシジルエーテル、ジヒドロキシベンゼンのジメチルグリシジルエーテル及びジヒドロキシベンゼンのグリシジルメチルグリシジルエーテルからなる群より選択される１以上の２官能エポキシ化合物と、ジヒドロキシ化合物とを反応させて、２官能エポキシ化合物の開環体を得る工程と、
（１Ｂ）工程（１Ａ）で得られた２官能エポキシ化合物の開環体のヒドロキシ基の少なくとも２つをエポキシ化する工程と
を含む方法により得られる、エポキシ化合物。
［４］部分エステル化エポキシ化合物であって、工程（１Ｃ）：
（１Ｃ）請求項３に記載のエポキシ化合物と、（メタ）アクリル酸又は（メタ）アクリル酸無水物とを反応させる工程
を含む方法により得られる、部分エステル化エポキシ化合物。
［５］（ａ）[１］の式（１）で示されるエポキシ化合物、（ｂ）[２］の式（２）で示される部分エステル化エポキシ化合物、（ｃ）[３］のエポキシ化合物、及び、（ｄ）[４］の部分エステル化エポキシ化合物からなる群より選択される１種以上の化合物を含む、硬化性組成物。
［６］液晶滴下工法用シール剤である、［５］の硬化性組成物。
［７］［５］又は［６］の硬化性組成物を硬化して得られる、硬化物。
［８］［５］又は［６］の硬化性組成物を硬化して得られる硬化物でシールされた、液晶表示体。 The present invention has the following configuration.
[1] An epoxy compound represented by the following formula (1).

[Where,
R ¹ , R ² , R ³ and R ⁴ are independently of each other hydrogen, glycidyl or methyl glycidyl, at least two of R ¹ , R ² , R ³ and R ⁴ are glycidyl or methyl glycidyl;
R ⁵ and R ⁶ are, independently of one another, hydrogen or methyl;
X ¹ and X ² are each independently an alkylene having 1 to 4 carbon atoms, an arylene having 6 to 20 carbon atoms, an alkylene having 1 to 4 carbon atoms, or an alkylene-carbon atom having 1 to 4 carbon atoms. 6-20 arylene or group: —Y ¹ — (O—Y ¹ ) _n1 — (wherein Y ¹ is alkylene having 1 to 6 carbon atoms, and n1 is 0 or an integer of 1 to 6 It is)
[2] A partially esterified epoxy compound represented by the following formula (2).

[Where,
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently of each other hydrogen, glycidyl, methyl glycidyl or a group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ (wherein R ¹⁷ Is hydrogen or methyl, R ¹⁸ is hydrogen or (meth) acryloyl, R ¹⁹ is (meth) acryloyl),
At least two of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are glycidyl, methyl glycidyl or a group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ ;
R ¹⁵ and R ¹⁶ are, independently of one another, hydrogen or methyl;
X ¹¹ and X ¹² are independently of each other an alkylene having 1 to 4 carbon atoms, an arylene having 6 to 20 carbon atoms, an alkylene having 1 to 4 carbon atoms, and an alkylene-carbon atom having 1 to 4 carbon atoms. 6-20 arylene or group: —Y ² — (O—Y ² ) _n2 — (wherein Y ² is alkylene having 1 to 6 carbon atoms, and n2 is 0 or an integer of 1 to 6 Is)
The ratio of glycidyl and methylglycidyl to the group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ is 10:90 to 90:10]
[3] An epoxy compound comprising steps (1A) to (1B):
(1A) One or more bifunctional epoxy compounds selected from the group consisting of diglycidyl ether of dihydroxybenzene, dimethyl glycidyl ether of dihydroxybenzene and glycidylmethyl glycidyl ether of dihydroxybenzene are reacted with a dihydroxy compound to produce a bifunctional compound. Obtaining a ring-opened product of the epoxy compound;
(1B) An epoxy compound obtained by a method comprising the step of epoxidizing at least two of the hydroxy groups of the ring-opened product of the bifunctional epoxy compound obtained in step (1A).
[4] Partially esterified epoxy compound, step (1C):
(1C) A partially esterified epoxy compound obtained by a method comprising a step of reacting the epoxy compound according to claim 3 with (meth) acrylic acid or (meth) acrylic anhydride.
[5] An epoxy compound represented by formula (1) of (a) [1], (b) a partially esterified epoxy compound represented by formula (2) of [2], (c) an epoxy compound of [3], And (d) a curable composition comprising one or more compounds selected from the group consisting of partially esterified epoxy compounds of [4].
[6] The curable composition according to [5], which is a sealant for a liquid crystal dropping method.
[7] A cured product obtained by curing the curable composition of [5] or [6].
[8] A liquid crystal display sealed with a cured product obtained by curing the curable composition of [5] or [6].

  According to the present invention, an epoxy compound and a partially esterified epoxy compound having low viscosity and excellent liquid crystal elution are obtained.

  Hereinafter, preferred embodiments of the present invention will be described.

[Epoxy compound]
(First epoxy compound)
The first epoxy compound is represented by the above formula (1). Formula (1) is an epoxy compound having a dihydric phenol as a mother nucleus.

In formula (1), R ¹ , R ² , R ³ and R ⁴ are independently of each other hydrogen, glycidyl or methyl glycidyl, and at least two of R ¹ , R ² , R ³ and R ⁴ are glycidyl. Or methyl glycidyl. It is preferable that at least three of R ¹ , R ² , R ³ and R ⁴ are glycidyl or methyl glycidyl, and more preferably that ^four of R ¹ , R ² , R ³ and R ⁴ are glycidyl or methyl glycidyl. preferable. Here, “glycidyl” is 2,3-epoxypropyl. “Methyl glycidyl” is 2,3-epoxy-2-methylpropyl.

  The number of glycidyl and methyl glycidyl can be calculated by high performance liquid chromatography (HPLC). Specifically, a peak corresponding to the number of glycidyl and methyl glycidyl is obtained by HPLC, and the abundance ratio of the number of glycidyl and methyl glycidyl can be calculated from the respective peak areas. Thereby, the number of glycidyl and methyl glycidyl contained in the compound can be calculated. Moreover, when the epoxy compound shown by Formula (1) is a mixture, the number of glycidyl and methyl glycidyl is computed as an average value of a mixture. That is, the number of epoxy groups can be determined by performing mass spectrometry (LC-MS) at each peak of HPLC, and the average number of epoxy groups in the mixture can be calculated from the abundance ratio of each component in the mixture. For example, the mixture of epoxy compounds represented by formula (1) may contain compounds having 1, 2, 3, or 4 epoxy groups, as well as multimers thereof. The “epoxy group” includes at least one of a glycidyl group and a methyl glycidyl group.

In formula (1), R ⁵ and R ⁶ are independently of each other hydrogen or methyl. R ⁵ and R ⁶ are the same and are preferably hydrogen.

In formula (1), X ¹ and X ² are independently of each other an alkylene having 1 to 4 carbon atoms, an arylene having 6 to 20 carbon atoms, an alkylene having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. An alkylene having 6 to 20 carbon atoms or a group: —Y ¹ — (O—Y ¹ ) _n1 — (wherein Y ¹ is an alkylene having 1 to 6 carbon atoms, and n1 is 0 Or an integer of 1 to 6.

  Examples of the alkylene having 1 to 4 carbon atoms include methylene, ethylene, trimethylene, and tetramethylene, and preferably methylene and ethylene. Further, the alkylene having 1 to 6 carbon atoms includes alkylene having 5 and 6 carbon atoms such as pentamethylene and hexamethylene in addition to the above alkylene having 1 to 4 carbon atoms. Arylene having 6 to 20 carbon atoms is a monocyclic or polycyclic aromatic group, and examples thereof include phenylene, naphthylene, and anthracenylene, and preferably phenylene.

Examples of the alkylene having 1 to 4 carbon atoms and the arylene having 6 to 20 carbon atoms and the arylene having 6 to 20 carbon atoms in the arylene having 6 to 20 carbon atoms are as described above. Alkylene having 1 to 4 carbon atoms-arylene having 6 to 20 carbon atoms such as -methylene-1,3-phenylene group, -methylene-1,4-phenylene group, -ethylene-1,3-phenylene group and- An ethylene-1,4-phenylene group is preferred. The order of bonding to each group in the alkylene having 1 to 4 carbon atoms and the arylene having 6 to 20 carbon atoms may be any, but the oxygen atom bonded to R ³ and R ⁴ includes It is preferable that the alkylene of 1 to 4 carbon atoms in the arylene having 6 to 20 carbon atoms is bonded.

  Examples of alkylene having 1 to 4 carbon atoms-arylene having 6 to 20 carbon atoms-alkylene having 1 to 4 carbon atoms and alkylene having 1 to 4 carbon atoms and arylene having 6 to 20 carbon atoms have been described above. It is as follows. Alkylene having 1 to 4 carbon atoms, arylene having 6 to 20 carbon atoms, alkylene having 1 to 4 carbon atoms, 1,3-phenylene bismethylene (m-xylylene) and 1,4-phenylene bismethylene (p -Xylylene) is preferred.

  n1 is 0 or an integer of 1 to 6, and n1 is preferably 0 or an integer of 1 to 4.

  In formula (1), the bonding position of oxygen to the benzene ring is not particularly limited, and the 1,2-position (catechol skeleton), 1,3-position (resorcinol skeleton), 1,4-position (hydroquinone skeleton) Is mentioned. Preferred are 1,3-position and 1,4-position, that is, those having resorcinol skeleton and hydroquinone skeleton. When the epoxy compound represented by the formula (1) has a resorcinol skeleton and a hydroquinone skeleton, the viscosity is lower, the liquid crystal elution is excellent, and the low-temperature curability is good.

From the above, the epoxy compound represented by the formula (1) is preferably the compound 2 represented by the following formula (1a) and the compound 4 represented by the following formula (1b).

  The number average molecular weight of the epoxy compound represented by the formula (1) is preferably 200 to 5,000. If it is such a range, adhesiveness will be favorable and the contamination | pollution property to a liquid crystal will be suppressed further.

  The epoxy equivalent of the epoxy compound represented by the formula (1) is 100 to 3,000 g / eq. It is preferable that it is 150-1,000 g / eq. It is more preferable that If it is such a range, adhesiveness will be favorable and the contamination | pollution property to a liquid crystal will be suppressed further. An epoxy equivalent is calculated | required as an average value of a mixture, when an epoxy compound is a mixture. In this invention, an epoxy equivalent is calculated | required based on JISK7236: 2001 (corresponding to ISO3001: 1999).

  The viscosity at 25 ° C. of the epoxy compound represented by the formula (1) can be 500 to 600,000 mPa · s, preferably 1,000 to 500,000 mPa · s, and preferably 2,000 to 300, More preferably, it is 000 mPa · s. If it is such a range, since it can be filled with many solid components, such as a hardening | curing agent and powder, the freedom degree of the design of a sealing compound mix | blend improves. The viscosity is a value measured using an E-type viscometer.

(Second epoxy compound)
The second epoxy compound is an epoxy compound, and steps (1A) to (1B):
(1A) One or more bifunctional epoxy compounds selected from the group consisting of diglycidyl ether of dihydroxybenzene, dimethyl glycidyl ether of dihydroxybenzene and glycidylmethyl glycidyl ether of dihydroxybenzene are reacted with a dihydroxy compound to produce a bifunctional compound. Obtaining a ring-opened product of the epoxy compound;
(1B) and a step of epoxidizing at least two hydroxy groups of the ring-opened product of the bifunctional epoxy compound obtained in step (1A).
The manufacturing method of a 2nd epoxy compound is as mentioning later including a preferable thing.

[Partially esterified epoxy compound]
(First partially esterified epoxy compound)
The partially esterified epoxy compound is represented by the formula (2).

In formula (2), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently of each other hydrogen, glycidyl, methyl glycidyl or a group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ^19. Wherein R ¹⁷ is hydrogen or methyl, R ¹⁸ is hydrogen or (meth) acryloyl, and R ¹⁹ is (meth) acryloyl.
At least two of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are glycidyl, methyl glycidyl or a group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ ;
R ¹⁵ and R ¹⁶ are, independently of one another, hydrogen or methyl;
X ¹¹ and X ¹² are independently of each other an alkylene having 1 to 4 carbon atoms, an arylene having 6 to 20 carbon atoms, an alkylene having 1 to 4 carbon atoms, and an alkylene-carbon atom having 1 to 4 carbon atoms. 6-20 arylene or group: —Y ² — (O—Y ² ) _n2 — (wherein Y ² is alkylene having 1 to 6 carbon atoms, and n2 is 0 or an integer of 1 to 6 Is)
The ratio of glycidyl and methylglycidyl to the group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ is 10:90 to 90:10]

The group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ is formed by reacting an epoxy group with (meth) acrylic acid or (meth) acrylic anhydride. When the epoxy group is a glycidyl group, R ¹⁷ is hydrogen, and when the epoxy group is a methyl glycidyl group, R ¹⁷ is methyl. R ¹⁷ is preferably hydrogen. When R ¹⁷ is hydrogen, synthesis is easy. When (meth) acrylic acid or (meth) acrylic anhydride is (meth) acrylic acid, R ¹⁸ is hydrogen, and (meth) acrylic acid or (meth) acrylic anhydride is (meth) acrylic anhydride. When it is a product, R ¹⁸ is (meth) acryloyl.

Preferably at least three of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are glycidyl, methyl glycidyl, or a group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ , wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are more preferably glycidyl, methyl glycidyl, or a group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ .

In formula (2), the number of glycidyl and methyl glycidyl and the number of (meth) acryloyloxy groups can be calculated by HPLC. Specifically, the peak corresponding to the number of each epoxy group and the number of each (meth) acryloyl group is obtained by HPLC, and the existence ratio of each number can be calculated from each peak area. Thus, in the partially esterified epoxy compound represented by the formula (2), glycidyl, methyl glycidyl, _group: the number of _{^{-CH 2 -CR 17 (OR 18)}} -CH 2 -O-R 19 is obtained. Moreover, when the partially esterified epoxy compound shown by Formula (2) is a mixture, the number of glycidyl and methyl glycidyl and the number of (meth) acryloyloxy groups are calculated as an average value of a mixture. For example, the mixture of the partially esterified epoxy compound represented by the formula (2) includes a mixture of the epoxy compounds represented by the formula (1) and a compound in which a part of those epoxy groups is a (meth) acryloyl group. May be. The “(meth) acryloyl group” includes at least one of an acryloyl group and a methacryloyl group.

In the partially esterified epoxy compound of formula (2), the ratio of glycidyl and methyl glycidyl to the group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ is 10:90 to 90:10. . Here, the ratio of the epoxy group and the group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ can be determined from HPLC and epoxy equivalent. Specifically, since the epoxy equivalent of the raw material epoxy compound is reduced by the amount of partial esterification, the degree of esterification can be calculated by measuring the epoxy equivalent of the partially esterified epoxy compound. Moreover, the molecular weight and abundance ratio of each component are calculated | required by performing mass spectrometry (LC-MS) in each peak of HPLC, and the ratio of the epoxy group and (meth) acryloyl group for every component can be calculated | required.

In the formula (2), R ¹⁵ and R ¹⁶ are independently of each other hydrogen or methyl. R ¹⁵ and R ¹⁶ are as defined above for R ⁵ and R ⁶ , including preferred ones.

In formula (2), X ¹¹ and X ¹² are independently of each other an alkylene having 1 to 4 carbon atoms, an arylene having 6 to 20 carbon atoms, an alkylene having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. An alkylene having 6 to 20 carbon atoms or a group: —Y ² — (O—Y ² ) _n2 — (wherein Y ² is an alkylene having 1 to 6 carbon atoms, and n2 is 0. Or an integer of 1 to 6. X ¹¹ and X ¹² are as defined above for X ¹ and X ² , including preferred ones.

  In formula (2), the bonding position of oxygen to the benzene ring is as described above in formula (1), including preferred ones.

  The viscosity at 25 ° C. of the partially esterified epoxy compound represented by the formula (2) can be 1,000 to 2,000,000 mP · s, and is 5,000 to 1,500,000 mP · s. Is preferable, and is more preferably 10,000 to 1,000,000 mP · s. If it is such a range, when apply | coating to a liquid crystal, it will be hard to produce a flow and it can suppress the contamination to a liquid crystal.

(Second partially esterified epoxy compound)
The second partially esterified epoxy compound is (1C) reacting an epoxy compound obtained by the method including the steps (1A) to (1B) with (meth) acrylic acid or (meth) acrylic anhydride. Is obtained. Here, the manufacturing method of a 2nd partially esterified epoxy compound is as mentioning later including a preferable thing.

[Method for producing epoxy compound]
The manufacturing method of an epoxy compound is steps (1A) to (1B):
(1A) One or more bifunctional epoxy compounds selected from the group consisting of diglycidyl ether of dihydroxybenzene, dimethyl glycidyl ether of dihydroxybenzene and glycidylmethyl glycidyl ether of dihydroxybenzene are reacted with a dihydroxy compound to produce a bifunctional compound. Obtaining a ring-opened product of the epoxy compound;
(1B) epoxidizing at least two of the hydroxy groups of the ring-opened product of the bifunctional epoxy compound obtained in step (1A).

  Epoxidation of a hydroxy group includes making the hydroxy group a glycidyloxy group or a methylglycidyloxy group.

(Process (1A))
In the step (1A), in the bifunctional epoxy compound as the raw material compound, a hydroxy group is formed by ring opening of the epoxy group, and a hydroxy group derived from the dihydroxy compound is formed. Here, the ring-opened product of the bifunctional epoxy compound refers to a compound in which all the epoxy groups of the bifunctional epoxy compound are opened.

<Bifunctional epoxy compound>
The bifunctional epoxy compounds are diglycidyl ether of dihydroxybenzene, dimethyl glycidyl ether of dihydroxybenzene, and glycidyl methyl glycidyl ether of dihydroxybenzene. The diglycidyl ether of dihydroxybenzene is a compound in which the two hydroxy groups of dihydroxybenzene are glycidyloxy groups. Dimethyl glycidyl ether of dihydroxybenzene is a compound in which two hydroxy groups of dihydroxybenzene are methyl glycidyloxy groups. The glycidyl methyl glycidyl ether of dihydroxybenzene is a compound in which one hydroxy group of dihydroxybenzene is a glycidyloxy group and the other hydroxy group is a methyl glycidyloxy group. As the bifunctional epoxy compound, resorcinol diglycidyl ether, resorcinol dimethyl glycidyl ether, hydroquinone diglycidyl ether and hydroquinone dimethyl glycidyl ether are preferable, and resorcinol diglycidyl ether and hydroquinone diglycidyl ether are more preferable.

〔式中、Ｒ^３１及びＲ^３２は、独立して、水素又はメチルである〕 The bifunctional epoxy compound is a compound represented by the following formula (3).

[Wherein R ³¹ and R ³² are independently hydrogen or methyl]

Here, the epoxy compound represented by the formula (1) in which R ⁵ and R ⁶ are different from each other is a glycidyl methyl glycidyl ether of dihydroxybenzene, that is, one of R ³¹ and R ³² is hydrogen and the other is methyl. It can manufacture using the compound shown by Formula (3).

<Dihydroxy compound>
The dihydroxy compound is not particularly limited as long as it is a compound containing two hydroxy groups in the molecule. Examples of dihydroxy compounds include monoalkylene glycols and polyalkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol; Aromatic dialcohols such as 1,4-dimethanol, benzene-1,3-dimethanol, benzene-1,4-diethanol; 4-hydroxymethylphenol, 3-hydroxymethylphenol, 4-hydroxyethylphenol, and 3 -Hydroxyalkylphenols such as hydroxyethylphenol.

The dihydroxy compound has the following formula (4):
^HO-X 21 -OH (4)
[Wherein, X ²¹ represents alkylene having 1 to 4 carbon atoms, arylene having 6 to 20 carbon atoms, alkylene having 1 to 4 carbon atoms, alkylene having 1 to 4 carbon atoms, and 6 to 20 carbon atoms. Arylene or group: —Y ³ — (O—Y ³ ) _n3 — (wherein Y ³ is alkylene having 1 to 6 carbon atoms, and n3 is 0 or an integer of 1 to 6) Is)
The dihydroxy compound represented by the formula is particularly preferred. Here, X ²¹ is as described in X ¹ and X ² including preferable ones.

  Examples of the dihydroxy compound represented by the formula (4) include monoalkylene glycols and polyalkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, and triethylene glycol; benzene-1,4-dimethanol, benzene- Aromatic alcohols such as 1,3-dimethanol and benzene-1,4-diethanol; hydroxyalkylenephenols such as (2-hydroxyphenyl) methanol and (2-hydroxyphenyl) -2-ethanol are preferred.

〔式中、
Ｒ^２５及びＲ^２６は、互いに独立に、水素又はメチルであり、
Ｘ^２２及びＸ^２３は、互いに独立に、Ｘ^２１の意味を有する〕 In the step (1A), when the compound of formula (4) is used as the dihydroxy compound, the ring-opened product of the bifunctional epoxy compound is represented by the following formula (5).

[Where,
R ²⁵ and R ²⁶ are, independently of one another, hydrogen or methyl;
X ²² and X ²³ have the meaning of X ²¹ independently of each other]

  The usage-amount of a dihydroxy compound is 0.5 equivalent-10 equivalent with respect to 1 equivalent of epoxy groups in a bifunctional epoxy compound, Preferably it is 1 equivalent-8 equivalent. The formation of an epoxy ring-opened product can be confirmed by the reaction of all the epoxy groups with the dihydroxy compound by disappearance of the peak of the bifunctional epoxy compound as a raw material and the one-end reactant by using high performance liquid chromatography (HPLC). . Here, the one-end reactant refers to a reactant in which one of the two epoxy groups of the bifunctional epoxy compound is unopened.

<Reaction conditions>
The reaction in the step (1A) can be performed in the presence or absence of a metal catalyst. Any metal catalyst can be used as long as it is a catalyst used for the ring-opening reaction of an epoxy group. For example, metals such as copper, zinc, iron, magnesium, silver, calcium, tin, BF ₄ ⁻ , SiF ₆ ^2- or _PF ⁶ _-, CF 3 ^SO metal catalyst consisting of an anion of ^2, and the like. Preferred is tin borofluoride (Sn (BF ₄ ) ₂ ). The metal catalyst is 10 to 1,000 ppm, preferably 20 to 200 ppm, based on the weight of the total reaction mixture.

  The reaction in step (1A) can be performed in the presence or absence of a quaternary ammonium salt. Examples of the quaternary ammonium salts include tetraalkylammonium chlorides such as methyltrioctylammonium chloride, methyltridecylammonium chloride and tetramethylammonium chloride, and aralkyltrialkylammonium chlorides such as benzyltrimethylammonium chloride. Benzyltrimethylammonium is preferred. The amount of the quaternary ammonium salt used is 0.1 to 5% by weight, more preferably 0.5 to 2.0% by weight, based on the total weight of the bifunctional epoxy compound and dihydroxy compound.

  The reaction in the step (1A) can be performed in the presence or absence of an organic solvent. Organic solvents that can be used include aromatic hydrocarbons such as benzene and toluene: cycloaliphatic ketones such as cyclohexanone; and starting dihydroxy compounds.

  The reaction temperature in the step (1A) is not particularly limited and can be 50 ° C to 130 ° C, preferably 70 ° C to 120 ° C.

(Process (1B))
By the step (1B), at least two of the hydroxy groups of the epoxy ring-opened product of the bifunctional epoxy compound obtained in the step (1A) are epoxidized. In the step (1B), part or all of the hydroxy groups in the epoxy ring-opened product of the bifunctional epoxy compound are epoxidized. When the epoxy compound is a mixture of compounds in which two, three or four of the ring opening hydroxy groups of the bifunctional epoxy compound are epoxidized, in the total hydroxy groups of the epoxy ring opening of the bifunctional epoxy compound, 50% to 100% is preferably epoxidized, more preferably 75% to 100% is epoxidized.

<Epoxy ring-opened product>
An epoxy ring-opened product of a bifunctional epoxy compound (hereinafter, also simply referred to as “epoxy ring-opened product”) is a raw material compound in the step (1B), and is a compound in which all of the epoxy groups of the aforementioned bifunctional epoxy compound are opened. It is. In the step (1B), for the epoxidation, a known reaction for epoxidizing a hydroxy group can be used, and examples thereof include an epichlorohydrin method and an oxidation method, preferably an epichlorohydrin method.

<< Epichlorohydrin Method >>
The epichlorohydrin method is a method of epoxidizing the hydroxy group of the epoxy ring-opened product by reacting the epoxy ring-opened product with epichlorohydrin or methyl epichlorohydrin in the presence of a phase transfer catalyst. .

  In the epichlorohydrin method, epichlorohydrin or methyl epichlorohydrin can be reacted in the number of moles corresponding to the desired number of epoxy groups. The amount of epichlorohydrin or methyl epichlorohydrin is 1.0 to 20 mol, preferably 3.0 to 15 mol, based on 1 mol of the hydroxyl group of the epoxy ring-opened product. For example, the amount of epichlorohydrin or methyl epichlorohydrin is 4 to 80 mol, preferably 12 to 60, relative to 1 mol of the compound represented by the formula (4) having 4 hydroxy groups in the molecule. Is a mole.

  Phase transfer catalysts include quaternary ammonium salts such as methyltrioctylammonium chloride, tetraalkylammonium chloride such as methyltridecylammonium chloride and tetramethylammonium chloride, and aralkyltrialkylammonium chloride such as benzyltrimethylammonium chloride. And benzyltrimethylammonium chloride is preferred. The amount of phase transfer catalyst used is from 0.1 to 5% by weight, more preferably from 0.5 to 2.0% by weight, based on the total weight of the reactants.

  The reaction in the epichlorohydrin method is carried out in the presence of a solvent such as a hydrocarbon such as hexane and pentane; an ether such as diethyl ether, t-butyl methyl ether and diisopropyl ether; or a ketone such as acetone and methyl ethyl ketone. However, excess epichlorohydrin and methyl epichlorohydrin can also be used as solvents. The reaction temperature is 30 to 90 ° C, preferably 40 to 65 ° C, and most preferably about 50 to about 55 ° C.

<< Oxidation process >>
The oxidation method is a method comprising a step of allylating the hydroxy group of the epoxy ring-opened product to obtain a diallyl ether compound and a step of oxidizing the allyloxy group or 2-methyl-2-propenyloxy group of the diallyl ether compound. . In the present invention, allylation of a hydroxy group includes making the hydroxy group an allyloxy group or a 2-methyl-2-propenyloxy group.

  The step of obtaining a diallyl ether compound comprises reacting an epoxy ring-opened product with allyl halide or 2-methyl-2-propenyl halide, thereby converting the hydroxy group of the epoxy ring-opened product into an allyloxy group or 2-methyl-2- This is a step of converting to a propenyloxy group. Specifically, after dissolving the epoxy ring-opened compound and allyl halide in dimethyl sulfoxide, a quaternary ammonium salt is added, and an alkaline aqueous solution is dropped while maintaining the reaction temperature at 40 ° C. or lower. The reaction is carried out at about 6 hours for about 6 hours.

  Examples of halides in allyl halide and 2-methyl-2-propenyl halide include chlorine and bromine. The addition amount of allyl halide and 2-methyl-2-propenyl halide is preferably 3 to 30 mol with respect to 1 mol of the hydroxy group of the epoxy ring-opened product.

  Examples of the quaternary ammonium salt include tetraalkylammonium halides such as tetrabutylammonium bromide or tetraarylammonium halides such as tetraphenylammonium chloride. The addition amount of the quaternary ammonium salt is preferably 0.001 mol to 0.1 mol with respect to 1 mol of the epoxy ring-opened product.

  Examples of the alkaline aqueous solution include calcium hydroxide, potassium hydroxide, and sodium hydroxide. As for the usage-amount of the alkali metal used, 1-8 equivalent is preferable with respect to 1 equivalent of hydroxy groups of an epoxy ring-opening body.

  The step of oxidizing the allyloxy group or 2-methyl-2-propenyloxy group of the diallyl ether compound is a step of reacting the diallyl ether compound with hydrogen peroxide in the presence of potassium carbonate. Specifically, a diallyl ether compound obtained by allylating the hydroxy group of the epoxy ring-opened product is added with a solvent such as alcohol such as methanol or ethanol, or a nitrile such as acetonitrile or benzonitrile, and potassium carbonate, and stirred for 5 -40%, preferably 30-35% hydrogen peroxide solution is dropped, and after completion of the dropping, the oxidation reaction is carried out for 0.5-12 hours, preferably 1-8 hours.

  The amount of hydrogen peroxide added is preferably 5 to 15 moles per mole of diallyl ether compound obtained by allylating the hydroxy group of the epoxy ring-opened product. Reaction temperature is 45 degrees C or less, for example, Preferably it is 20-40 degreeC.

  The method for producing an epoxy compound is preferably a method for producing an epoxy compound represented by the formula (1).

[Method for producing partially esterified epoxy compound]
The production method of the partially esterified epoxy compound is the step (1C):
(1C) The process of making the epoxy compound obtained by the manufacturing method containing the said process (1A)-(1B) react with (meth) acrylic acid or (meth) acrylic anhydride.

Although the epoxy compound obtained by the manufacturing method containing process (1A)-(1B) is not specifically limited, The compound shown by Formula (1a)-(1b) is preferable.
(Meth) acrylic acid and (meth) acrylic anhydride are not particularly limited, and examples thereof include commercially available acrylic acid, methacrylic acid, and (meth) acrylic anhydride.

(Reaction conditions)
The reaction amount of (meth) acrylic acid or (meth) acrylic anhydride with respect to 1 equivalent of the epoxy group of the epoxy compound obtained by the production method including the steps (1A) to (1B) is preferably 10 to 90 equivalent%. More preferably, it is 20-80 equivalent%, More preferably, it is 30-70 equivalent%, Especially preferably, it is 40-60 equivalent%. In the method for producing a partially esterified epoxy compound, the reaction of the glycidyl group and methyl glycidyl group with (meth) acrylic acid or (meth) acrylic anhydride proceeds quantitatively. The conversion rate can also be estimated from the epoxy equivalent.

  Unsaturation occurs when (meth) acrylic acid or (meth) acrylic anhydride is reacted within the above range with respect to 1 equivalent of epoxy group of the epoxy compound obtained by the production method including steps (1A) to (1B). Partially esterified epoxy that provides good resin properties for temporary fixation during primary polymerization in which only groups are reacted, and can form a homogeneous polymer without causing phase separation during secondary polymerization A compound can be obtained.

  The reaction can be carried out in the presence or absence of a basic catalyst. As a basic catalyst, the well-known basic catalyst used by reaction with an epoxy compound and (meth) acrylic acid or (meth) acrylic anhydride can be used. A polymer-supported basic catalyst in which a basic catalyst is supported on a polymer can also be used. The basic catalyst is preferably a trivalent organic phosphorus compound and / or an amine compound. The basic atom of the basic catalyst is phosphorus and / or nitrogen.

Examples of the trivalent organic phosphorus compound include alkylphosphines such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine and salts thereof, triphenylphosphine, tri-m-tolylphosphine, tris- (2 Arylphosphines such as, 6-dimethoxyphenyl) phosphine and salts thereof, phosphorous acid triesters such as triphenyl phosphite, triethyl phosphite and tris (nonylphenyl) phosphite and salts thereof. Trivalent phosphine / ethyl bromide, triphenyl phosphine / butyl bromide, triphenyl phosphine / octyl bromide, triphenyl phosphine / decyl bromide, triphenyl phosphine / isobutyl bromide, triphenyl phosphine / Examples thereof include propyl chloride, triphenylphosphine / pentyl chloride, triphenylphosphine / hexyl bromide and the like. Of these, triphenylphosphine (PPh ₃ ) is preferable.

  Examples of the amine compound include secondary amines such as diethanolamine, tertiary amines such as triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, trisdiethylaminomethylphenol, 1,5,7-triazabicyclo [4. 4.0] dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene (Me-TBD), 1,8-diazabicyclo [ 5.4.0] Undec-7-ene (DBU), 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] Examples include strongly basic amines such as non-5-ene (DBN) and 1,1,3,3-tetramethylguanidine, and salts thereof. Among these, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) is preferable. Examples of the salt of the amine compound include benzyltrimethylammonium chloride and benzyltriethylammonium chloride.

  The polymer for supporting the basic catalyst is not particularly limited, and a polymer obtained by crosslinking polystyrene with divinylbenzene, a polymer obtained by crosslinking acrylic resin with divinylbenzene, or the like is used. These polymers are solvents (for example, methyl ethyl ketone, methyl isobutyl ketone) used in the reaction of the epoxy compound obtained by the production method including steps (1A) to (1B) with (meth) acrylic acid or (meth) acrylic anhydride. , Toluene, etc.) and raw materials and products.

As the polymer-supported basic catalyst, a commercially available one may be used. Examples of commercially available polymer-supported basic catalysts include PS-PPh ₃ (diphenylphosphinopolystyrene, manufactured by Biotage), PS-TBD (1,5,7-triazabicyclo [4.4.0] deca-5. -Enpolystyrene, manufactured by Biotage Corporation).

  The proportion of the polymer-supported basic catalyst used is 0.5 to 5.0 milliequivalents of the polymer-supported base catalyst with respect to 1 equivalent of epoxy of the epoxy compound obtained by the production method including steps (1A) to (1B). It is preferable that it is 1.0-3.0 milliequivalent. It is preferable from the viewpoint of reaction rate, reaction time, and catalyst cost that the ratio of the polymer-supported basic catalyst is within the above range.

  The temperature in the reaction step of the epoxy compound obtained by the production method including steps (1A) to (1B) and (meth) acrylic acid or (meth) acrylic anhydride is preferably 60 to 120 ° C., more preferably 80 to It is 120 degreeC, More preferably, it is 90-110 degreeC.

  When the epoxy compound obtained by the production method including steps (1A) to (1B) is reacted with (meth) acrylic acid or (meth) acrylic anhydride in the presence of a catalyst, the reaction is performed to prevent gelation. It is necessary to keep the oxygen concentration in the gas phase in the system and on the reaction system appropriate. For example, when air is actively blown into the reaction system, it is necessary to be careful because it may cause oxidation of the catalyst and cause a decrease in activity.

  The reaction between the epoxy compound obtained by the production method including the steps (1A) to (1B) and (meth) acrylic acid or (meth) acrylic anhydride is performed by using a partially esterified epoxy compound obtained by this reaction such as ultraviolet rays. Since it is cured by active energy rays, it is desirable to carry out the reaction in a container that shields ultraviolet rays. In addition, the reaction between the epoxy compound obtained by the production method including the steps (1A) to (1B) and (meth) acrylic acid or (meth) acrylic anhydride is performed on the epoxy compound in order to prevent gas phase polymerization. On the other hand, the reaction may be carried out in the presence of a refluxing solvent exhibiting good solvent properties. In this case, it is preferable to remove the solvent after completion of the reaction. Examples of the reflux solvent include acetone and methyl ethyl ketone.

  The method for producing a partially esterified epoxy compound is preferably a method for producing a partially esterified epoxy compound represented by the formula (2).

[Curable composition]
(A) an epoxy compound represented by formula (1), (b) a partially esterified epoxy compound represented by formula (2), and (c) an epoxy compound obtained by a production method comprising steps (1A) to (1B), (D) The curable composition containing 1 or more types of compounds selected from the group which consists of the partially esterified epoxy compound obtained by the manufacturing method containing process (1A)-(1C) is demonstrated. The compound used as the base oligomer component contained in the curable resin composition is at least one compound selected from the group consisting of epoxy compounds and partially esterified epoxy compounds. For example, the epoxy compound represented by the formula (1) or the partially esterified epoxy compound represented by the formula (2) may be used alone, or one or more of the epoxy compounds represented by the formula (1) and the formula (2 A mixture of two or more of the partially esterified epoxy compounds represented by

(Further ingredients)
The curable composition can further contain a curing agent, a polymerization initiator, a filler, and a coupling agent.

  The curing agent is not particularly limited, and examples thereof include amine-based curing agents such as organic acid dihydrazide compounds, amine adducts, imidazole and derivatives thereof, dicyandiamide, aromatic amines, epoxy-modified polyamines, and polyaminoureas, and particularly organic acid dihydrazides. VDH (1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadien-1,18-dicarbohydrazide) and LDH ( Octadecane-1,18-dicarboxylic acid dihydrazide); commercially available from ADEKA as Adeca Hardener EH5030S, Ajinomoto Fine Techno Co., as Amicure PN-23, Amicure PN-30, Amicure MY-24, Amicure MY-H That amine adduct is preferred. These curing agents may be used alone or in combination. It is preferable that the compounding quantity of a hardening | curing agent is 1-150 weight part with respect to a total of 100 weight part of an epoxy compound and a partially esterified epoxy compound, It is preferable that it is 5-100 weight part, 10-80 weight part More preferably, it is a part.

  The polymerization initiator means a compound that is activated by absorbing light energy and generates radicals. The polymerization initiator is not particularly limited, and benzoins, acetophenones, benzophenones, thioxatones, α-acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxides And polymerization initiators of series compounds, benzoins, benzoin ethers and anthraquinones. The polymerization initiator is preferably one having a low solubility in the liquid crystal and a reactive group that itself does not gasify the decomposition product upon irradiation with light. As such a preferable polymerization initiator, for example, EY Resin KR-2 (manufactured by KS Corporation) and the like can be mentioned. The amount of the polymerization initiator is preferably 0.1 to 5 parts by weight, and more preferably 1 to 5 parts by weight with respect to a total of 100 parts by weight of the epoxy compound and the partially esterified epoxy compound.

  Moreover, a thermal radical polymerization initiator can also be used as a polymerization initiator. The thermal radical polymerization initiator is a polymerization initiator that generates radicals by heating and initiates a polymerization reaction. The thermal radical polymerization initiator is not particularly limited, and examples thereof include organic peroxides and azo compounds.

  The filler is added for the purpose of improving the adhesive reliability of the curable composition by controlling the viscosity of the curable composition, improving the strength of the cured product obtained by curing the curable composition, or suppressing the linear expansion. The A filler is not specifically limited, The well-known inorganic filler and organic filler used with respect to the composition containing an epoxy compound are mentioned. As inorganic fillers, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride Is mentioned. Examples of the organic filler include polymethyl methacrylate, polystyrene, a copolymer obtained by copolymerizing a monomer constituting these and another monomer, polyester fine particles, polyurethane fine particles, and rubber fine particles. In the present invention, inorganic fillers such as silicon dioxide and talc are particularly preferable. It is preferable that the compounding quantity of a filler is 2-40 weight part with respect to 100 weight part of an epoxy compound and a partially esterified epoxy compound, and it is more preferable that it is 5-30 weight part.

  The coupling agent is added for the purpose of further improving the adhesion to the liquid crystal display substrate. The coupling agent is not particularly limited, and examples include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. The amount of the silane coupling agent is preferably 0.1 to 10 parts by weight and more preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the total of the epoxy compound and the partially esterified epoxy compound. preferable.

  The curable composition is preferably a sealing agent for liquid crystal dropping method.

[Hardened product of curable composition]
The present invention is also directed to a cured product of the curable composition. The curable composition is cured by applying heat by irradiation of energy rays such as ultraviolet rays, or by applying heat before, after or simultaneously with irradiation of energy rays such as ultraviolet rays. The method for curing the curable composition containing the epoxy compound and the partially esterified epoxy compound is to irradiate the curable composition containing the epoxy compound and the partially esterified epoxy compound with energy rays such as ultraviolet rays, or to apply heat. Alternatively, it includes a step of applying heat after irradiation with energy rays such as ultraviolet rays.

  A cured product of the curable composition is used for sealing the liquid crystal display. Therefore, this invention also makes object the liquid crystal display body sealed with the hardened | cured material obtained by hardening | curing a curable composition.

  The epoxy compound and the partially esterified epoxy compound can be used as an oligomer component of a high-grade sealant that has a low viscosity, has low solubility in liquid crystal, and can prevent contamination of the liquid crystal.

  EXAMPLES Next, specific embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Comparative Example 1] Production of Compound 1

  Compound 1 was synthesized according to Synthesis Example 1 of JP2012-077720.

[Comparative Example 2]
A bisphenol A type epoxy resin (EXA850CRP, manufactured by DIC Corporation) was used as an epoxy compound of Compound 1-1 for comparison.

[Comparative Example 3]
Resorcinol type epoxy resin (EX-201, manufactured by Nagase ChemteX Corporation) was used as an epoxy compound of Compound 1-2 for comparison.

Example 1 Production of Compound 2

  117 g of resorcinol type epoxy resin (EX-201, manufactured by Nagase ChemteX), 152 g of 2- (4-hydroxyphenyl) ethanol (manufactured by Kanto Chemical Co., Ltd.), 1.8 g of benzyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), butanol ( 200 g) (manufactured by Kanto Chemical Co., Inc.) was placed in a flask equipped with a thermometer and a stirrer, and stirred at 110 ° C. for 20 hours. After completion of the reaction, the mixture was cooled to room temperature, 300 g of methyl isobutyl ketone was added, and the mixture was washed twice with 500 g of 1% aqueous sodium hydroxide solution and twice with 500 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 243 g of a ring-opened product of a yellow transparent viscous product. It was confirmed by high performance liquid chromatography (HPLC) that all of the epoxy groups were opened due to the disappearance of the peak of the raw material epoxy resin and the compound in which only one epoxy group was opened.

  EX-201-2- (4-hydroxyphenyl) ethanol ring-opened body 100g, epichlorohydrin (manufactured by Wako Pure Chemical Industries, Ltd.) 445g, benzyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 15g, thermometer, condenser, dean -Place in a 1 liter 3-neck round bottom flask equipped with a Stark trap, dropping funnel and stirrer. The mixture was then heated to about 50 ° C. with stirring under a reduced pressure of 50 torr, and 120 g of 48% aqueous sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added dropwise over 3 hours. Among the water / epichlorohydrin mixture distilled azeotropically, stirring was continued while returning epichlorohydrin to the reaction system. Stirring was continued for 3 hours after the addition. The reaction mixture was then cooled to room temperature, added with 500 mL of dichloromethane, and washed 4 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 126 g of a brown transparent viscous epoxy compound (Compound 2).

Example 2 Production of Compound 3 (In Formula (2), the bonding position of oxygen to the phenyl group is the 1,3-position, R ¹⁵ and R ¹⁶ are hydrogen, and X ¹¹ and X ¹² are -Ethylene-1,3-phenylene-, and four of R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ are glycidyl groups and groups: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O— R ¹⁹ , R ¹⁷ is hydrogen, R ¹⁸ is hydrogen, R ¹⁹ is methacryloyl, a glycidyl group and a group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ Of compounds having a 50:50 ratio)

80 g of Compound 2, 18 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), PS-PPh ₃ (diphenylphosphinopolystyrene, manufactured by Biotage Corp.) 2.0 g as a catalyst, 20 mg of BHT (dibutylhydroxytoluene), thermometer and stirrer Placed in attached flask and stirred at 100 ° C. for 10 hours. After completion of the reaction, the catalyst was removed by filtration to obtain 72 g of a partially methacrylated epoxy compound (Compound 3).

Example 3 Production of Compound 4

  Hydroquinone type epoxy resin (EX-203, manufactured by Nagase ChemteX Corporation) 80 g, 2- (4-hydroxyphenyl) ethanol (manufactured by Kanto Chemical Co.) 106 g, benzyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.0 g, methyl isobutyl 400 g of ketone (manufactured by Kanto Chemical Co., Inc.) was placed in a round bottom flask equipped with a thermometer and a stirrer and stirred at 110 ° C. for 20 hours. After completion of the reaction, the mixture was cooled to room temperature and washed twice with 500 g of a 1% aqueous sodium hydroxide solution and twice with 500 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 111 g of a ring-opened product of a yellow transparent viscous product. It was confirmed by high performance liquid chromatography (HPLC) that all of the epoxy groups were opened due to the disappearance of the peak of the raw material epoxy resin and the compound in which only one epoxy group was opened.

  EX-203-2- (4-hydroxyphenyl) ethanol ring-opened 80 g, epichlorohydrin (manufactured by Wako Pure Chemical Industries, Ltd.) 356 g, benzyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 12 g, thermometer, cooling tube, Dean -Place in a 1 liter 3-neck round bottom flask equipped with a Stark trap, dropping funnel and stirrer. The mixture was then heated to about 50 ° C. with stirring under a reduced pressure of 50 torr, and 120 g of 48% aqueous sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added dropwise over 3 hours. Among the water / epichlorohydrin mixture distilled azeotropically, stirring was continued while returning epichlorohydrin to the reaction system. Stirring was continued for 3 hours after the addition. The reaction mixture was then cooled to room temperature, added with 500 mL of dichloromethane, and washed 4 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 95 g of a yellow transparent viscous epoxy compound (Compound 4).

[Example 4] Production of Compound 5 (In Formula (2), the bonding position of oxygen to the phenyl group is 1,4-position, R ¹⁵ and R ¹⁶ are hydrogen, and X ¹¹ and X ¹² are -Ethylene-1,4-phenylene- and four of R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ are glycidyl groups and groups: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O— R ¹⁹ , R ¹⁷ is hydrogen, R ¹⁸ is hydrogen, R ¹⁹ is methacryloyl, a glycidyl group and a group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ Compound with a ratio of 50:50)

80 g of Compound 4, 19 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), PS-PPh ₃ (diphenylphosphinopolystyrene, manufactured by Biotage Corp.) 2.1 g as a catalyst, 20 mg of BHT (dibutylhydroxytoluene), thermometer and stirrer Placed in attached flask and stirred at 100 ° C. for 6 hours. After completion of the reaction, the catalyst was removed by filtration to obtain 70 g of a partially methacrylated epoxy compound (Compound 5).

(Measurement of viscosity and epoxy equivalent)
About the compound of Examples 1-4 and Comparative Examples 1-2, the viscosity which measured the viscosity at the rotational speed of 2.5 rpm of the cone rotor using the E-type viscosity meter (TOKI Sangyo Co., Ltd. RE105U), and JISK7236: The epoxy equivalent measured by 2001 is shown in Table 1.

(NI point measurement)
About the compound of Examples 1-4 and Comparative Examples 1-2, NI point was measured with the following method. The elution property of the epoxy compound or the partially esterified epoxy compound into the liquid crystal can be evaluated by changing the NI point (nematic-isotropic point) which is the phase transition temperature of the liquid crystal. The NI point of the liquid crystal is determined by the mixed composition of each component of the liquid crystal and is a unique value for each formulation. In general, it is known that the NI point is lowered when some kind of impurities (other components) are mixed in the liquid crystal, and the degree of impurity mixing can be evaluated from the NI point. Here, a small NI point change indicates that contamination of the liquid crystal of the epoxy compound and the partially esterified epoxy compound is reduced, and such an epoxy compound and the partially esterified epoxy compound have excellent liquid crystal elution properties. .

(Preparation of measurement sample)
An ampule bottle was charged with 0.1 g of an epoxy compound and a partially (meth) acrylated epoxy compound, and 1 g of liquid crystal (MLC-11900-080, manufactured by Merck) was added. The bottle was placed in an oven at 120 ° C. for 1 hour, and then allowed to stand at room temperature. After returning to room temperature (25 ° C.), the liquid crystal portion was taken out and filtered through a 0.2 μm filter to obtain a liquid crystal sample for evaluation. The NI point was measured using a differential scanning calorimeter (DSC, manufactured by PerkinElmer, Pyris 6). A 10 mg liquid crystal sample for evaluation was sealed in an aluminum sample pan, and the measurement was performed under the condition of a temperature rising rate of 5 ° C./min.

(Curing test)
The DSC exothermic peak was measured for the compounds of Example 1 and Comparative Examples 1-2. An equivalent latent curing agent (amine adduct EH5030S (manufactured by ADEKA)) was mixed with the epoxy compound and the partially (meth) acrylated epoxy compound shown in Table 2 to obtain a mixture. Thereafter, 10 mg was taken out from the mixture and subjected to DSC measurement. The DSC measurement conditions are 25 ° C. to 200 ° C. and a temperature increase rate of 5 ° C./min in a nitrogen atmosphere. A lower exothermic peak temperature indicates curing at a lower temperature. The results are shown in Table 2.

  The results are shown in Tables 1 and 2.

  The epoxy compounds and partially esterified epoxy compounds of Examples have a low viscosity, a small NI point change, and excellent liquid crystal elution properties. On the other hand, the epoxy compound of the comparative example has a large NI point change and is inferior in liquid crystal elution. Moreover, by comparing Example 5 with Comparative Examples 4 and 5, the epoxy compound of Example 2 has a low DSC exothermic peak temperature and excellent low-temperature curability.

  The epoxy compound and the partially esterified epoxy compound of the present invention are useful as a raw material for a sealant capable of maintaining high reliability because of low viscosity and excellent liquid crystal elution.

Claims (8)

An epoxy compound represented by the following formula (1).

[Where,
R ¹ , R ² , R ³ and R ⁴ are independently of each other hydrogen, glycidyl or methyl glycidyl, at least two of R ¹ , R ² , R ³ and R ⁴ are glycidyl or methyl glycidyl;
R ⁵ and R ⁶ are, independently of one another, hydrogen or methyl;
X ¹ and X ² are each independently an alkylene having 1 to 4 carbon atoms, an arylene having 6 to 20 carbon atoms, an alkylene having 1 to 4 carbon atoms, or an alkylene-carbon atom having 1 to 4 carbon atoms. 6-20 arylene or group: —Y ¹ — (O—Y ¹ ) _n1 — (wherein Y ¹ is alkylene having 1 to 6 carbon atoms, and n1 is 0 or an integer of 1 to 6 It is) A partially esterified epoxy compound represented by the following formula (2).

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently of each other hydrogen, glycidyl, methyl glycidyl or a group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ (wherein R ¹⁷ Is hydrogen or methyl, R ¹⁸ is hydrogen or (meth) acryloyl, R ¹⁹ is (meth) acryloyl),
At least two of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are glycidyl, methyl glycidyl or a group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ ;
R ¹⁵ and R ¹⁶ are, independently of one another, hydrogen or methyl;
X ¹¹ and X ¹² are independently of each other an alkylene having 1 to 4 carbon atoms, an arylene having 6 to 20 carbon atoms, an alkylene having 1 to 4 carbon atoms, and an alkylene-carbon atom having 1 to 4 carbon atoms. 6-20 arylene or group: —Y ² — (O—Y ² ) _n2 — (wherein Y ² is alkylene having 1 to 6 carbon atoms, and n2 is 0 or an integer of 1 to 6 Is)
The
The ratio of glycidyl and methylglycidyl to the group: —CH ₂ —CR ¹⁷ (OR ¹⁸ ) —CH ₂ —O—R ¹⁹ is 10:90 to 90:10] A method for producing an epoxy compound, comprising steps (1A) to (1B):
(1A) One or more bifunctional epoxy compounds selected from the group consisting of diglycidyl ether of dihydroxybenzene, dimethyl glycidyl ether of dihydroxybenzene and glycidylmethyl glycidyl ether of dihydroxybenzene are reacted with a dihydroxy compound to produce a bifunctional compound. Obtaining a ring-opened product of the epoxy compound;
(1B) A method for producing an epoxy compound comprising a step of epoxidizing at least two of the hydroxy groups of the ring-opened product of the bifunctional epoxy compound obtained in step (1A) . A process for producing a partially esterified epoxy compound, the process (1C):
(1C) A step of reacting the epoxy compound according to claim 1 or 2 or the epoxy compound obtained by the production method according to claim 3 with (meth) acrylic acid or (meth) acrylic anhydride. A method for producing a partially esterified epoxy compound. (A) 1 which is selected from an epoxy compound and (b) partially esterified epoxy compound or Ranaru group represented by the formula (2) according to claim 2 represented by formula (1) according to claim 1 A curable composition comprising at least one compound.   The curable composition of Claim 5 which is a sealing compound for liquid crystal dropping methods.   Hardened | cured material obtained by hardening | curing the curable composition of Claim 5 or 6.   The liquid crystal display body sealed with the hardened | cured material obtained by hardening | curing the curable composition of Claim 5 or 6.