JP2008088167A - Compound having (meth)acryloyl group and glycidyl group, polymerizable composition containing the compound and method for producing the compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having high compatibility with both of epoxy resins and acrylic resins having radical polymerizability and useful as a raw material for industrial materials owing to the effect to prevent the contamination of a liquid crystal in the case of using as a raw material for a liquid crystal sealing agent. <P>SOLUTION: The invention relates to a method for producing a compound having a (meth)acryloyl group and an epoxy group and expressed by general formula (1). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a compound containing a (meth) acryloyl group and a glycidyl group, a polymerizable composition containing the compound, and a method for producing the compound.

  Epoxy resins and (meth) acrylate resins have good electrical insulation and are excellent, and have excellent properties such as adhesiveness, transparency, weather resistance, moldability, and workability. It is used in a wide range of fields as a raw material for a polymerizable composition including a stopping material, a paint, a sizing agent, and an adhesive (see Patent Documents 1 and 2).

  With recent remarkable development of electronic and electrical devices, various properties such as rapid curing, low viscosity, and high purity are required for polymerizable compositions for various industrial uses. Therefore, studies for improving various properties of epoxy resins and acrylic resins, or development of compounds that act in combination with these resins to improve various properties of various polymerizable compositions have been actively conducted.

  Among them, compounds having both a (meth) acryloyl group and a glycidyl group are known as raw materials useful for improving various properties of a polymerizable composition mainly composed of an epoxy resin or a (meth) acrylate resin. The compound has an organic group having different polymerizability such as a (meth) acryloyl group and a glycidyl group in the same molecule. Therefore, it has the characteristics that it is highly compatible with both the epoxy resin and the acrylic resin exhibiting radical polymerizability, and can be cured by advancing the polymerization reaction stepwise.

  Recently, with the development of small electronic devices such as mobile phones and large liquid crystal televisions, the demand for liquid crystal sealants, which are the main constituent members of liquid crystal display panels, has increased remarkably. The liquid crystal sealing agent is used as an adhesive for encapsulating liquid crystal and bonding the two glass substrates together in a liquid crystal display panel having a structure in which liquid crystal is encapsulated between two glass substrates. It is a polymerizable composition.

  As a method for manufacturing a liquid crystal display panel, a liquid crystal injection method for manufacturing a liquid crystal display panel by injecting liquid crystal into an empty liquid crystal cell formed by a liquid crystal sealant between two substrates has been used for a long time. It has been. As a liquid crystal sealant used in the liquid crystal injection method, a thermosetting liquid crystal sealant mainly composed of an epoxy resin (hereinafter simply referred to as a thermosetting sealant) has been proposed (see, for example, Patent Document 3). . However, in the liquid crystal injection method, it takes time to inject liquid crystal, and high temperature heat treatment for several hours at 120 to 150 ° C. is required to cure the liquid crystal sealant. Lowness is regarded as a problem, and improving productivity is an urgent need. Therefore, recently, a liquid crystal dropping method has attracted attention as a method for manufacturing a liquid crystal display panel.

  The liquid crystal dropping method is a method for manufacturing a liquid crystal display panel by dropping liquid crystal onto a frame formed so as to surround a display region with a liquid crystal sealing agent, and then bonding two glass substrates together. As a liquid crystal sealant used in the liquid crystal dropping method, a light and thermosetting liquid crystal sealant has been proposed (see, for example, Patent Documents 4 and 5). In the liquid crystal dropping method, productivity is expected to be improved as compared with the liquid crystal injection method by shortening the liquid crystal injection time.

  By the way, at the time of manufacturing and using a liquid crystal display panel, liquid crystal contamination caused by elution of an uncured component of the liquid crystal sealant into the liquid crystal is a big problem. Liquid crystal contamination is more likely to occur as the time during which the liquid crystal sealant is present in an uncured state at the time of manufacturing the liquid crystal display panel becomes longer, and as the uncured portion remains in the cured liquid crystal sealant. Furthermore, if an uncured portion remains in the cured product, in addition to liquid crystal contamination, the adhesive strength between the cured product and the substrate constituting the liquid crystal display panel may be reduced. Due to the complexity of the wiring accompanying the high definition and narrow frame of the liquid crystal display panel, the wiring and the seal pattern of the liquid crystal sealant often overlap, resulting in insufficient light irradiation and uncured parts in the cured product. It is easy to remain. Therefore, in order to prevent the liquid crystal from being contaminated in the liquid crystal display panel, at present, development of a compound having low solubility in liquid crystal as a raw material for the liquid crystal sealant is being actively performed.

So far, from the viewpoint of obtaining a high-quality liquid crystal display panel, a liquid crystal containing, as a component, a partially acrylated or methacrylated epoxy resin obtained by reacting a bisphenol A type epoxy resin with acrylic acid or methacrylic acid. A liquid crystal sealant that includes a sealant (see, for example, Patent Document 6) and an acrylated epoxy resin having a (meth) acryl group and a hydroxyl group, wherein the number of the (meth) acryl groups is larger than the number of the hydroxyl groups has been proposed. (For example, refer to Patent Document 7).
JP 2000-355884 A Japanese Patent Laid-Open No. 01-234417 International Publication No. 2004/039885 Pamphlet JP 2001-133794 A JP 2002-214626 A Japanese Patent No. 3162179 JP 2005-195978 A

  However, the partially acrylated epoxy resin described in Patent Document 6 is a low molecular weight substance, so that it has high solubility in liquid crystal and easily contaminates the liquid crystal. Moreover, when the liquid crystal sealing agent was actually prepared using the partially acrylated epoxy resin of Patent Document 6 and the acrylated epoxy resin of Patent Document 7, it was confirmed that the liquid crystal sealing agent had low curability. Therefore, it was revealed that none of the resins is sufficient as a raw material for the liquid crystal sealant.

  Further, the liquid crystal sealant is required to be stable without changing the viscosity at room temperature (high viscosity stability). A liquid crystal sealant with high viscosity stability near room temperature makes it easy to form a seal pattern with a desired line width on a substrate, and the number of times of changing to a dispenser can be reduced. It is because it can improve. However, the partially methacrylated epoxy resin has a problem that the proper viscosity at room temperature is not maintained and the viscosity stability is low.

  Therefore, the present invention provides (meth) acryloyl groups and glycidyl groups useful as raw materials for various industrial materials including liquid crystal sealants, sealing materials, adhesives, and the like containing epoxy resins and (meth) acrylate resins as components. The object is to provide a compound containing. Another object of the present invention is to provide a compound capable of realizing high curability, high viscosity stability and the like when used in industrial materials such as liquid crystal sealants.

  As described above, the inventors of the present invention have made extensive studies in view of the fact that an epoxy resin and a (meth) acrylate resin are often used together in an industrial material such as a liquid crystal sealant. The present inventors have found that the above-mentioned problems can be solved by a compound having an excellent balance between the high compatibility with epoxy resins and the like, and have completed the present invention.

前記一般式（１）中の、
Ｒ_１１〜Ｒ_１６はそれぞれ独立して水素原子またはメチル基を表し、ただし、Ｒ_１３とＲ_１４の両方がメチル基であることはなく、かつＲ_１５とＲ_１６の両方がメチル基になることはなく；
Ｘ_１１およびＸ_１２はそれぞれ独立して炭素数１〜１０のアルキレン基または下記の一般式式（２）で表される基を表し；
Ｘ_１３およびＸ_１４はいずれか一方が炭素数１〜１０のアルキレン基、他方が下記の一般式（３）で表される基を表し；
Ａは下記の一般式（４）、（５）または（６）で表される基を表し；
Ｐはそれぞれ独立して水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、またはニトロ基を表し；
ａ、ｂおよびｃは０〜３の整数、ｄは１〜３の整数を表し、ここで、ａ＋ｂ＋ｃ＋ｄ＋ｍ＝６であり、かつａ、ｂおよびｃが同時に０になることはなく；
ｍは０〜４の整数、ｉおよびｊはそれぞれ独立して０または１の整数、ｋおよびｌは０〜１０の整数を表す。

前記一般式（２）中の、
Ｙ_２１およびＹ_２２はそれぞれ独立して炭素数１〜１０のアルキレン基を表し、
Ｙ_２１は前記一般式（１）中のアクリロイル基のＯと結合し、
ｎは１〜１０の整数を表す。

前記一般式（３）中の、
Ｙ_３１およびＹ_３２はそれぞれ独立して炭素数１〜１０のアルキレン基を表し、
Ｙ_３２は前記一般式（１）中のアクリロイル基のＯと結合する。

前記一般式（４）中の、
Ｒ_４１およびＲ_４２はそれぞれ独立して炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基またはニトロ基を表し、
Ｚは単結合、−Ｃ−（Ｒ_４３）（Ｒ_４４）−基、−Ｏ−基、−Ｓ−基、−ＳＯ_２−基、または下記の一般式（４ａ）で表される基を表し、ここで、Ｒ_４３およびＲ_４４はそれぞれ独立して水素原子、炭素数１〜４のアルキル基またはフェニル基を表し、
ｒおよびｓはそれぞれ独立して０〜４の整数を表す。

前記一般式（５）中の、
Ｒ_５１、Ｒ_５２、Ｒ_５３およびＲ_５４はそれぞれ独立して水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基またはニトロ基を表す。

前記一般式（６）中の、
Ｒ_６１およびＲ_６２はそれぞれ独立して水素原子または炭素数１〜４のアルキル基を表す。
［２］ 前記一般式（１）で表される化合物が、下記の一般式（７）〜（９）のいずれかで表される化合物である［１］記載の化合物。

［前記一般式（７）中の、
Ｒ_１１〜Ｒ_１６、Ｘ_１１〜Ｘ_１４、Ａ、Ｐ、ａ、ｂ、ｃ、ｄ、ｍ、ｉ、ｊ、ｋ、およびｌは、前記一般式（１）と同様に定義される］

［前記一般式（８）中の、
Ｒ_１１〜Ｒ_１６、Ｘ_１１〜Ｘ_１４、Ａ、Ｐ、ａ、ｂ、ｃ、ｄ、ｍ、ｉ、ｊ、ｋ、およびｌは、前記一般式（１）と同様に定義される］

［前記一般式（９）中の、
Ｒ_１１〜Ｒ_１６、Ｘ_１１〜Ｘ_１４、Ａ、Ｐ、ａ、ｂ、ｃ、ｄ、ｍ、ｉ、ｊ、ｋ、およびｌは、前記一般式（１）と同様に定義される］
［３］ 前記一般式（１）中のａとｂと０でない［１］または［２］記載の化合物。
［４］ 前記一般式（１）中のｃが０でなく、かつＲ_１１とＲ_１２のいずれか一方が水素原子であり、もう一方がメチル基である［１］〜［３］記載の化合物。 That is, the above problem is solved by the compound of the present invention.
[1] A compound having a (meth) acryloyl group and a glycidyl group in the molecule and represented by the following general formula (1).

In the general formula (1),
R _{11 to} R ₁₆ each independently represent a hydrogen atom or a methyl group, provided that both R ₁₃ and R ₁₄ are not methyl groups, and both R ₁₅ and R ₁₆ are methyl groups. Not;
X ₁₁ and X ₁₂ each independently represent an alkylene group having 1 to 10 carbon atoms or a group represented by the following general formula (2);
X ₁₃ and X ₁₄ each represents an alkylene group having 1 to 10 carbon atoms, and the other represents a group represented by the following general formula (3);
A represents a group represented by the following general formula (4), (5) or (6);
Each P independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a nitro group;
a, b and c are integers of 0 to 3, d is an integer of 1 to 3, wherein a + b + c + d + m = 6, and a, b and c are not 0 at the same time;
m is an integer of 0 to 4, i and j are each independently an integer of 0 or 1, and k and l are integers of 0 to 10.

In the general formula (2),
Y ₂₁ and Y ₂₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
Y ₂₁ is bonded to O of the acryloyl group in the general formula (1),
n represents an integer of 1 to 10.

In the general formula (3),
Y ₃₁ and Y ₃₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
Y ₃₂ is bonded to O of the acryloyl group in the general formula (1).

In the general formula (4),
R ₄₁ and R ₄₂ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group,
Z represents a single bond, —C— (R ₄₃ ) (R ₄₄ ) — group, —O— group, —S— group, —SO ₂ — group, or a group represented by the following general formula (4a). Here, R ₄₃ and R ₄₄ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group,
r and s each independently represent an integer of 0 to 4.

In the general formula (5),
R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group.

In the general formula (6),
R ₆₁ and R ₆₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
[2] The compound according to [1], wherein the compound represented by the general formula (1) is a compound represented by any one of the following general formulas (7) to (9).

[In the general formula (7),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1)]

[In the general formula (8),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1)]

[In the general formula (9),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1)]
[3] The compound according to [1] or [2], wherein a, b and not 0 in the general formula (1).
[4] The compound according to [1] to [3], wherein c in the general formula (1) is not 0, one of R ₁₁ and R ₁₂ is a hydrogen atom, and the other is a methyl group. .

［前記一般式（１０）中の、
Ｒ_１１〜Ｒ_１６、Ｘ_１１〜Ｘ_１４、Ａ、Ｐ、ａ、ｂ、ｃ、ｄ、ｍ、ｉ、ｊ、ｋ、およびｌは、前記一般式（１）と同様に定義される］

［前記一般式（１１）中の、
Ｒ_１３〜Ｒ_１６、Ａ、ｋおよびｌは前記一般式（１）と同様に定義される］ Moreover, the said subject is solved by the polymeric composition of this invention.
[5] A polymerizable composition comprising the compound according to any one of [1] to [4].
[6] The polymerizable composition according to [5], further comprising a compound represented by the following general formula (10) or general formula (11).

[In the general formula (10),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1)]

[In the general formula (11),
R _{13 to} R ₁₆ , A, k and l are defined in the same manner as in the general formula (1)]

［前記一般式（１２）中の、
Ｒ_１１〜Ｘ_１４、Ｐ、ａ、ｂ、ｃ、ｄ、ｍ、ｉ、ｊ、ｋおよびｌは、前記一般式（１）と同様に定義される］ Furthermore, the said subject is solved by the manufacturing method of the compound of this invention shown below.
[7] The process for producing a compound according to [1], comprising a step of reacting the compound represented by the general formula (11) with a compound represented by the following general formula (12).

[In the general formula (12),
R _{11 to} X ₁₄ , P, a, b, c, d, m, i, j, k and l are defined in the same manner as in the general formula (1)]

  According to the present invention, a compound having a glycidyl group and a (meth) acryloyl group having different polymerization properties, having high curability and high compatibility with both an epoxy resin and a (meth) acrylate resin exhibiting radical polymerizability. Can be provided. This compound is useful as a raw material for polymerizable compositions for various industrial uses including liquid crystal sealing agents, sealing materials, adhesives, and the like mainly composed of epoxy resins and acrylic resins. For example, when the compound is used as a raw material for a liquid crystal sealant, a liquid crystal sealant with low curability, high viscosity stability, and liquid crystal contamination can be provided.

Hereinafter, the present invention will be described in detail.
[Compound represented by the general formula (1)]
The compound represented by the following general formula (1) is a compound having a (meth) acryloyl group and a glycidyl group in the molecule.

前記一般式（１）中の、
Ｒ_１１〜Ｒ_１６はそれぞれ独立して水素原子またはメチル基を表し、ただし、Ｒ_１３とＲ_１４の両方がメチル基であることはなく、かつＲ_１５とＲ_１６の両方がメチル基になることはなく；
Ｘ_１１およびＸ_１２はそれぞれ独立して炭素数１〜１０のアルキレン基または下記の一般式（２）で表される基を表し；
Ｘ_１３およびＸ_１４はいずれか一方が炭素数１〜１０のアルキレン基、他方が下記の一般式（３）で表される基を表し；
Ａは下記の一般式（４）、（５）または（６）で表される基を表し；
Ｐはそれぞれ独立して水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、またはニトロ基を表し；
ａ、ｂおよびｃは０〜３の整数、ｄは１〜３の整数を表し、ここで、ａ＋ｂ＋ｃ＋ｄ＋ｍ＝６であり、かつａ、ｂおよびｃが同時に０になることはなく；
ｍは０〜４の整数、ｉおよびｊはそれぞれ独立して０または１の整数、ｋおよびｌは０〜１０の整数を表す。

In the general formula (1),
R _{11 to} R ₁₆ each independently represent a hydrogen atom or a methyl group, provided that both R ₁₃ and R ₁₄ are not methyl groups, and both R ₁₅ and R ₁₆ are methyl groups. Not;
X ₁₁ and X ₁₂ each independently represent an alkylene group having 1 to 10 carbon atoms or a group represented by the following general formula (2);
X ₁₃ and X ₁₄ each represents an alkylene group having 1 to 10 carbon atoms, and the other represents a group represented by the following general formula (3);
A represents a group represented by the following general formula (4), (5) or (6);
Each P independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a nitro group;
a, b and c are integers of 0 to 3, d is an integer of 1 to 3, wherein a + b + c + d + m = 6, and a, b and c are not 0 at the same time;
m is an integer of 0 to 4, i and j are each independently an integer of 0 or 1, and k and l are integers of 0 to 10.

X ₁₁ and X ₁₂ in the general formula (1) each independently represent an alkylene group having 1 to 10 carbon atoms. Preferred examples of the alkylene group include a methylene group, an ethylene group, a methylethylene group, and trimethylene. Group, tetramethylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group are included. Among these, an alkylene group having 2 to 6 carbon atoms is preferable. X ₁₁ and X ₁₂ are groups represented by the following general formula (2).

前記一般式（２）中の、
Ｙ_２１およびＹ_２２はそれぞれ独立して炭素数１〜１０のアルキレン基を表し、
Ｙ_２１は前記一般式（１）中のアクリロイル基のＯと結合し、
ｎは１〜１０の整数を表す。

In the general formula (2),
Y ₂₁ and Y ₂₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
Y ₂₁ is bonded to O of the acryloyl group in the general formula (1),
n represents an integer of 1 to 10.

Examples of the alkylene group having 1 to 10 carbon atoms that is preferable as Y ₂₁ and Y ₂₂ in the general formula (2) include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, A cyclopentylene group, a hexamethylene group, a cyclohexylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group are included. Among these, Y ₂₁ and Y ₂₂ are preferably an alkylene group having 2 to 6 carbon atoms. Moreover, although n in the said General formula (2) represents the integer of 1-10, it is more preferable that it is an integer of 1-6.

前記一般式（３）中のＹ_３２は、前記一般式（１）中のアクリロイル基のＯと結合する。 One of X ₁₃ and X ₁₄ in the general formula (1) represents a compound represented by the following general formula (3). Y ₃₁ and Y ₃₂ in the general formula (3) each independently represent an alkylene group having 1 to 10 carbon atoms. Examples of preferable alkylene groups include a methylene group, an ethylene group, a methylethylene group, A trimethylene group, a tetramethylene group, a pentamethylene group, a cyclopentylene group, a hexamethylene group, a cyclohexylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group are included. Among them, Y ₃₁ and Y ₃₂ are preferably an alkylene group having 2 to 6 carbon atoms.

Y ₃₂ in the general formula (3) is bonded to O of the acryloyl group in the general formula (1).

  Next, A in the compound represented by the general formula (1) will be described. Preferred examples of A include a group represented by the following general formula (4).

前記一般式（４）中の、
Ｒ_４１およびＲ_４２はそれぞれ独立して炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基またはニトロ基を表し、
Ｚは単結合、−Ｃ−（Ｒ_４３）（Ｒ_４４）−基、−Ｏ−基、−Ｓ−基、−ＳＯ_２−基、または下記の一般式（４ａ）で表される基を表し、ここで、Ｒ_４３およびＲ_４４はそれぞれ独立して水素原子、炭素数１〜４のアルキル基またはフェニル基を表し、
ｒおよびｓはそれぞれ独立して０〜４の整数を表す。

In the general formula (4),
R ₄₁ and R ₄₂ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group,
Z represents a single bond, —C— (R ₄₃ ) (R ₄₄ ) — group, —O— group, —S— group, —SO ₂ — group, or a group represented by the following general formula (4a). Here, R ₄₃ and R ₄₄ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group,
r and s each independently represent an integer of 0 to 4.

Examples of the alkyl group having 1 to 4 carbon atoms preferable as R ₄₁ and R ₄₂ in the general formula (4) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl. Group, t-butyl group is included. Preferred examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, and t-butoxy group. Among these, as R ₄₁ and R ₄₂ , a hydrogen atom, a methyl group or a methoxy group is preferable, and a hydrogen atom is more preferable.

Z in the compound represented by the general formula (4) is preferably a single bond, —C— (R ₄₃ ) (R ₄₄ ) — group, or —O— group, and —C— (R ₄₃ ) (R ₄₄ ) — group and —O— group are more preferable.

Examples of preferable alkyl group having 1 to 4 carbon atoms as R ₄₃ and R _{44 in the} —C— (R ₄₃ ) (R ₄₄ ) — group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and butyl. Group, isobutyl group, sec-butyl group, t-butyl group are included. Among _these, as _{R 43} and _{R 44,} a hydrogen atom, a methyl group, an ethyl group, a phenyl group, more preferably a hydrogen atom, more preferably a methyl group.

  In the compound represented by the general formula (1), when A is a group represented by the formula (4), the oxygen atom bonded to A and the bonding position of Z in two aromatic rings are each independently There are three embodiments in which the para-position, meta-position or ortho-position is in a positional relationship, preferably a para-position or an ortho-position, and more preferably a structure in a para-position positional relationship.

前記一般式（５）中の、
Ｒ_５１、Ｒ_５２、Ｒ_５３およびＲ_５４はそれぞれ独立して水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基またはニトロ基を表す。 Further, A in the general formula (1) may be a group represented by the following general formula (5).

In the general formula (5),
R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group.

Examples of preferred alkyl groups having 1 to 4 carbon atoms as R _{51 to} R ₅₄ in the general formula (5) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group. , T-butyl groups are included. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, and t-butoxy group. Among these organic groups, a hydrogen atom, a methyl group, or a methoxy group is more preferable, and a hydrogen atom is particularly preferable.

  When A in the compound represented by the general formula (1) is a group represented by the general formula (5), two oxygen atoms in the compound represented by the general formula (1) There are three modes in which the group is bonded to each other in a para, meta or ortho relationship, but the para or meta position is preferred, and the meta position is more preferred.

前記一般式（６）中の、
Ｒ_６１およびＲ_６２はそれぞれ独立して水素原子または炭素数１〜４のアルキル基を表す。 Further, A in the general formula (1) may be a group represented by the following general formula (6).

In the general formula (6),
R ₆₁ and R ₆₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Examples of preferable alkyl group having 1 to 4 carbon atoms as R ₆₁ and R ₆₂ in the general formula (6) include a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl as the alkyl group having 1 to 4 carbon atoms. Group, isobutyl group, sec-butyl group, t-butyl group are included. Preferably, they are a hydrogen atom or a methyl group, More preferably, it is a hydrogen atom.

  In the general formula (1), each P independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a nitro group. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, t-pentyl, hexyl, heptyl Group, octyl group, nonyl group, decyl group are included. Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, t-butoxy group, pentyloxy group, hexyloxy group, heptyloxy Group, octyloxy group, nonyloxy group, decyloxy group are included. Among these, P is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, or a methoxy group, and particularly preferably a hydrogen atom.

  As a combination of a, b, c, d and m in the general formula (1), (a, b, c, d, m) = (1, 0, 0, 1, 4), (0, 1, 0, 1, 4), (0, 0, 1, 1, 4), (1, 1, 0, 1, 3), (2, 0, 0, 1, 3), (0, 2, 0, 1, 3) is preferred, (a, b, c, d, m) = (1, 0, 0, 1, 4), (0, 1, 0, 1, 4), (0, 0, 1, 1, 4) and (1, 1, 0, 1, 3) are more preferable.

  In the case where A in the compound represented by the general formula (1) is a group represented by the general formula (6), the bonding positions of two oxygen atoms bonded to the naphthalene ring are as follows: There are modes of 1, 5 position, 1, 8 position, 2, 6 position or 2, 7 position, preferably 1, 5 position, 2, 6 position or 2, 7 position, 2, 6 position Or the 2nd and 7th positions are more preferable.

  K and l in the compound represented by the general formula (1) represent an integer of 0 to 10, but are preferably 0 or an integer of 1 to 3, and more preferably 0.

  Moreover, when using the compound represented by the said General formula (1) as a raw material of polymeric composition represented by a liquid-crystal sealing compound, in addition to the high curability of polymeric composition, a viewpoint which makes water resistance high. Therefore, A in the compound is preferably a compound represented by the general formula (4) or (5), and more preferably a compound represented by the general formula (4). The polymerizable composition means a mixture containing at least one compound exhibiting polymerizability. The polymerizable compound constituting the mixture can be used alone or in combination of a plurality of types of compounds.

  In the general formula (1), an organic group having a (meth) acryloyl group, the number of the organic groups being an organic group c represented by c, and an organic group having a glycidyl group, The organic group d whose number is represented by d may be introduced at any position of the benzene ring. Among these, it is preferable that the substituent c and the substituent d described above are adjacent (vicinal). As the compound in which the substituent having a (meth) acryloyl group and the glycidyl group are adjacent to each other, compounds represented by the following general formulas (7) to (9) are preferable.

前記一般式（７）中の、
Ｒ_１１〜Ｒ_１６、Ｘ_１１〜Ｘ_１４、Ａ、Ｐ、ａ、ｂ、ｃ、ｄ、ｍ、ｉ、ｊ、ｋ、およびｌは、前記一般式（１）と同様に定義される。

In the general formula (7),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1).

前記一般式（８）中の、
Ｒ_１１〜Ｒ_１６、Ｘ_１１〜Ｘ_１４、Ａ、Ｐ、ａ、ｂ、ｃ、ｄ、ｍ、ｉ、ｊ、ｋ、およびｌは、前記一般式（１）と同様に定義される。

In the general formula (8),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1).

前記一般式（９）中の、
Ｒ_１１〜Ｒ_１６、Ｘ_１１〜Ｘ_１４、Ａ、Ｐ、ａ、ｂ、ｃ、ｄ、ｍ、ｉ、ｊ、ｋ、およびｌは、前記一般式（１）と同様に定義される。

In the general formula (9),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1).

[Method for producing compound represented by general formula (1)]
The compound containing a (meth) acryloyl group and a glycidyl group in the molecule represented by the general formula (1) of the present invention (sometimes referred to as “compound 1”) can be produced by the following method. it can.

[Scheme 1]
A typical synthesis method of the compound 1 includes a synthesis reaction shown in the following scheme 1. Scheme 1 is a ring-opening esterification reaction between the compound represented by the general formula (12) and the compound represented by the general formula (11).

  In the reaction of Scheme 1, the raw materials used for the production of Compound 1 will be described.

  The diglycidyl compound represented by the general formula (11) (sometimes referred to as “compound 11”) is easily available as a commercial product. The diglycidyl compound that is commercially available is generally produced by using a dihydroxy compound or dithiol compound and an epihalohydrin as raw materials and synthesizing these raw materials according to a known epoxidation reaction. The epoxidation reaction is not particularly limited as long as it is a method used when industrially producing an existing epoxy compound available as an industrial raw material.

  Although some of the carboxyl group-containing compounds represented by the general formula (12) (sometimes referred to as “compound 12”) are available as commercial products, each synthesis of Scheme 2 to Scheme 4 described below. It can also be produced by using a plurality of reactions.

  In the reaction of Scheme 1, the amount of the diglycidyl compound 11 used is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, relative to 1 mol of the carboxyl group in the compound 12. The amount is preferably 0.8 to 3 mol.

  When manufacturing the said compound 1 by the scheme 1, it is preferable to adjust the usage-amount of the said compound 11 and the compound 12 within the said range from a viewpoint which needs to leave a glycidyl group in the said compound 1. According to the stoichiometry, the compound 12 and the compound 11 may be reacted in an equal amount.

  However, since the two glycidyl groups of the compound 11 have the same reactivity, in the reaction of Scheme 1, when the amount of the compound 11 is less than the amount of the compound 12, the two glycidyl groups The group is opened, and a compound represented by the following general formula (10) (sometimes referred to as “compound 10”) is easily generated as a by-product. The compound 10 is obtained by adding two molecules of the compound 12 to the compound 11.

  In Scheme 1, when the above-mentioned by-product is produced, only the composition in which by-product and unreacted compound 11 are mixed in addition to compound 1 can be finally obtained, so the yield of compound 1 decreases. There is a high possibility of doing. On the other hand, when the amount of each raw material used in Scheme 1 is appropriately adjusted as described above, only Compound 1 can be produced at a high purification rate. However, since the by-product has no possibility of deteriorating the properties of the compound 1, there is no problem even if the by-product is contained in a polymerizable composition such as a liquid crystal sealant containing the compound 1 as a main component.

前記一般式（１０）中の、
Ｒ_１１〜Ｒ_１６、Ｘ_１１〜Ｘ_１４、Ａ、Ｐ、ａ、ｂ、ｃ、ｄ、ｍ、ｉ、ｊ、ｋ、およびｌは、前記一般式（１）と同様に定義される。

In the general formula (10),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1).

  The reaction of Scheme 1 may be performed in the absence of a solvent or in a solvent inert to such a reaction. Examples of solvents preferably used in Scheme 1 include hydrocarbon solvents such as n-hexane, benzene, toluene or xylene; ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone; ester systems such as ethyl acetate or butyl acetate. Solvents; ether solvents such as diethyl ether, tetrahydrofuran or dioxane; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene; N, N-dimethylformamide, N, N-dimethylacetamide, N , N-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane and other polar solvents. These solvents may be used alone or in combination of two or more.

  In Scheme 1, if necessary, a catalyst that acts to activate the reaction can also be used. Examples of catalysts include organic phosphine compounds such as triphenylphosphine; tertiary amines such as triethylamine and triethanolamine; quaternary ammonium salts such as trimethylammonium chloride and triethylbenzylammonium chloride; tetrabutylphosphonium bromide, tetra Organic phosphorus salts such as phenylphosphonium bromide; imidazoles such as 2-methylimidazole; and organometallic compounds such as cobalt octenoate. These catalysts may be used alone or in combination of two or more.

  The amount of the catalyst used is not particularly limited as long as it is sufficient to act on the activation of the reaction, but is preferably 0.01 to 10.0% by mass with respect to the total mass of the reaction mixture. More preferably, the content is 0.01 to 5.0% by mass. When the amount of the catalyst used is within the above range, it is preferable because a sufficient reaction rate can be obtained in the reaction of Scheme 1.

  Regarding the reaction conditions of Scheme 1, first, the reaction temperature is not particularly limited, but from the viewpoint of promoting the ring-opening esterification reaction, it is preferably in the range of 0 ° C to 200 ° C, more preferably 0 to 150 ° C. Also, the reaction time is not particularly limited, and may be set as appropriate according to the reaction temperature, the type of solvent used, a combination thereof, the amount of raw material used, and the like. From the viewpoint of promoting such a reaction, it is usually preferable to set it for several minutes to several tens of hours.

  Further, in the reaction of Scheme 1, it is possible to stop the reaction at an arbitrary reaction rate while confirming the reaction rate by a known analysis means (for example, liquid chromatography, thin layer chromatography, IR, etc.). In addition, after completion of the reaction of Scheme 1, the compound 1 may be post-treated with a known operation and treatment method (for example, neutralization, solvent extraction, water washing, liquid separation, solvent distillation, etc.). Good.

  As described above, the reaction solution containing the compound 1 finally obtained in the scheme 1 is often a mixture in which the compound 10 and the compound 11 are mixed in addition to the compound 1. Compound 1 can be used as a composition containing Compound 11 used as a raw material for Compound 1 and Compound 10 as a by-product depending on its use. However, Compound 1 can be used as a raw material for electronic materials such as liquid crystal sealants. When utilizing, it is preferable to isolate | separate and refine | purify compounds other than the compound 1 as needed. The means for separation and purification is not particularly limited, and a known method (for example, chromatography, treatment with activated carbon or various adsorbents, etc.) may be used. Thereby, the high purity compound 1 useful as a raw material for electronic materials can be isolated from the composition and manufactured.

  Next, schemes 2 to 4 which are methods for producing the compound represented by the general formula (12) will be described in detail. In the following reaction of Scheme 2, m = 0 in the general formula (1), that is, a case where the substituent P does not exist will be described as an example.

[Scheme 2]
As shown below, the reaction of Scheme 2 is carried out by reacting a compound represented by the following general formula (20) having two or more carboxyl groups (sometimes referred to as “compound 20”) and the following general formula having a hydroxy group ( 22) Dehydration partial esterification reaction with the compound represented by 22) (compound represented by “Compound 22”). Here, the compound 22 is a (meth) acrylic acid derivative having a hydroxy group.

前記スキーム２中の、ｅは２〜６の整数を表し、
ｆは１〜５の整数を表し、
前記一般式（２２）で表される化合物中のＡｃｒはそれぞれ独立して下記の一般式（１３）、（１４）、または（１５）で表される基を表す。

In Scheme 2, e represents an integer of 2 to 6,
f represents an integer of 1 to 5,
Acr in the compound represented by the general formula (22) independently represents a group represented by the following general formula (13), (14), or (15).

前記一般式（１３）で表される基中のＸ_１１は、前記一般式（１）と同様に定義される。

X ₁₁ in the group represented by the general formula (13) is defined in the same manner as in the general formula (1).

前記一般式（１４）で表される基中のＸ_１２は、前記一般式（１）と同様に定義される。

X ₁₂ in the group represented by the general formula (14) is defined similarly to the general formula (1).

前記一般式（１５）で表される基中の、
Ｒ_１１、Ｒ_１２、Ｘ_１３、Ｘ_１４、ｉおよびｊは、前記一般式（１）と同様に定義される。

In the group represented by the general formula (15),
R ₁₁ , R ₁₂ , X ₁₃ , X ₁₄ , i and j are defined in the same manner as in the general formula (1).

  In the reaction of Scheme 2, the quantitative ratio of the carboxyl group-containing compound represented by the general formula (20) and the hydroxy group-containing compound represented by the general formula (22) is not particularly limited. However, since it is necessary to leave a carboxyl group in the compound represented by the general formula (21), which is the final target product (sometimes referred to as “compound 21”), the amount of the hydroxy group is usually the carboxyl group. It is preferable to make it less than the total amount. If the amount of hydroxy groups is larger than the total amount of carboxyl groups, it is necessary to stop the reaction in Scheme 2 at the desired reaction rate stage in order to obtain compound 21 as the final target product.

  The reaction of Scheme 2 is a dehydration partial esterification reaction. Therefore, from the viewpoint of promoting the dehydration partial esterification reaction, it is preferable to use a known esterification catalyst in Scheme 2. Examples of such esterification catalysts include mineral acids (eg, hydrochloric acid, sulfuric acid); organic acids (eg, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid); Lewis acids (eg, boron trifluoride) , Aluminum trichloride) and the like. The amount of the esterification catalyst used is not particularly limited. However, from the viewpoint of promoting the dehydration partial esterification reaction in Scheme 2, it is usually preferable that the amount of the esterification catalyst used is 0.001 to 50% by mass with respect to the raw material mixture before the reaction. It is more preferable to set it as 01-30 mass%.

  In the dehydration partial esterification reaction in Scheme 2, water is generated during the reaction. At this time, in order to promote the reaction, it is preferable to remove water as a by-product from the reaction mixture. The method for removing water from the reaction mixture is not particularly limited. For example, a method of azeotropically boiling water with this solvent using a solvent having a boiling point substantially equal to that of water such as benzene or toluene, or known molecular sieves, etc. And a method using a dehydrating agent.

  The reaction of Scheme 2 may be performed in the absence of a solvent or in a solvent inert to such a reaction. Examples of such solvents include hydrocarbon solvents such as n-hexane, benzene or toluene; ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone; ester solvents such as ethyl acetate or butyl acetate; diethyl ether, tetrahydrofuran or Ether solvents such as dioxane; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or perchlene are included. These solvents may be used alone or in combination of two or more.

  The reaction conditions of Scheme 2 will be described. Although the reaction temperature of Scheme 2 is not particularly limited, it is preferably in the range of 50 to 150 ° C, more preferably 70 to 120 ° C, from the viewpoint of efficiently and sufficiently promoting the dehydration partial esterification reaction in a short time. . In addition, the reaction time in Scheme 2 depends on the reaction temperature, but usually it is preferably several minutes to 100 hours, more preferably 0.5 to 50 hours, and particularly preferably 1 to 20 hours. . Further, in Scheme 2, the reaction may be stopped at an arbitrary reaction rate while confirming the reaction rate by a known analysis means (for example, liquid chromatography, thin layer chromatography, IR, etc.).

[Scheme 3]
As shown below, the reaction of Scheme 3 is performed between the compound represented by the following general formula (25) having two or more acid halide groups (sometimes referred to as “compound 25”) and the compound 22 having a hydroxy group. This is a partial esterification reaction and a two-stage reaction in which the acid halide group remaining in the reaction mixture is hydrolyzed to produce the final target compound 21.

スキーム３中の、
前記一般式（２５）および（２６）で表される化合物中の、Ｌは塩素原子もしくは臭素原子を表し、
ｅは２〜６の整数を表し、
ｆは１〜５の整数を表し、
ＣＯＬは酸ハライド基を表しており、この中でＬはハロゲン（ＣｌまたはＢｒ）を表し、
前記一般式（２２）で表される化合物中のＡｃｒはそれぞれ独立して上記の一般式（１３）、（１４）、または（１５）で表される基を表し、
ＣＯＬはハライド基を示す。

In Scheme 3,
In the compounds represented by the general formulas (25) and (26), L represents a chlorine atom or a bromine atom,
e represents an integer of 2 to 6;
f represents an integer of 1 to 5,
COL represents an acid halide group, in which L represents halogen (Cl or Br),
Acr in the compound represented by the general formula (22) independently represents a group represented by the general formula (13), (14), or (15),
COL represents a halide group.

  In Scheme 3, it is necessary to leave a carboxyl group in the compound 21 which is the final target product. Therefore, in the partial esterification reaction, which is the first stage reaction of Scheme 3, it is preferable that the amount of hydroxy groups in compound 22 is less than the total amount of acid halide groups. When the amount of hydroxy groups is larger than the total amount of acid halide groups, it is necessary to stop the reaction at the desired reaction rate stage. However, since it is difficult to accurately stop the reaction at a desired reaction rate, it is preferable to adjust the amount ratio of the hydroxy group and the carboxyl group in advance.

  The reaction of Scheme 3 may be performed in the absence of a solvent or in a solvent inert to such a reaction. Examples of such solvents include hydrocarbon solvents such as n-hexane, benzene or toluene; ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone; ester solvents such as ethyl acetate or butyl acetate; diethyl ether, tetrahydrofuran or Ether solvents such as dioxane; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or perchlene are included. These solvents may be used alone or in combination of two or more.

  The reaction conditions of Scheme 3 will be described. In Scheme 3, the reaction temperature is not particularly limited throughout the entire reaction, but from the viewpoint of promoting the reaction, it is preferably in the range of −78 to 150 ° C., more preferably −20 to 100 ° C., and particularly preferably 0 to 80 ° C. preferable. The reaction time depends on the reaction temperature and the like, but is usually several minutes to 100 hours, preferably 0.5 to 50 hours, and more preferably 1 to 20 hours. Further, in Scheme 3, the reaction can be stopped at an arbitrary reaction rate while the reaction rate is confirmed by a known analysis means (for example, liquid chromatography, thin layer chromatography, IR, etc.).

  In the reaction of Scheme 3, a hydrogen halide (for example, hydrogen chloride) is generated as a by-product by the reaction between an acid halogen group and a hydroxy group. However, it is necessary to remove such a hydrogen halide from the reaction mixture as much as possible because it is necessary to deteriorate the properties of the reaction product. The method for removing the hydrogen halide is not particularly limited, and a known method may be used, but a dehydrohalogenating agent is useful from the viewpoint of easy handling.

  Preferred examples of such dehydrohalogenating agents include triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5. 4.0] organic base compounds such as undec-7-ene (DBU); or sodium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, etc. Inorganic base compounds are included. The amount of the dehydrohalogenating agent to be used is not particularly limited, but is preferably an amount sufficient to remove the hydrogen halide formed in the reaction mixture. From such a viewpoint, the amount of the dehydrohalogenating agent used is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, and more preferably 1 to 3 mol relative to 1 mol of the hydroxy group. Particularly preferred.

  The hydrolysis reaction, which is the second stage reaction in Scheme 3, is carried out by adding water to the reaction mixture obtained at the end of the first stage partial esterification reaction. The method of adding the water is not particularly limited, and water may be added all at once or may be dropped. From the viewpoint of gradually progressing the reaction, the latter dropping method is preferred. The amount of water used in the hydrolysis reaction is preferably greater than the amount of acid halide groups remaining in the reaction mixture, but is not particularly limited. From the viewpoint of promoting the hydrolysis reaction of the reaction mixture, the amount is preferably 1 to 100 mol, more preferably 5 to 50 mol, per 1 mol of the acid halide group remaining in the reaction mixture.

  In Scheme 3, the reaction temperature is not particularly limited throughout the entire reaction, but from the viewpoint of promoting the reaction, it is usually preferably in the range of −78 to 150 ° C., more preferably −20 to 100 ° C., and more preferably 0 to 80 ° C. Is particularly preferred. On the other hand, although reaction time is dependent also on reaction temperature, it is usually preferable that it is several minutes-100 hours, 0.5-50 hours are more preferable, and 1-20 hours are especially preferable. It is also possible to confirm the reaction rate by known analysis means (for example, liquid chromatography, thin layer chromatography, IR, etc.).

  In the hydrolysis reaction, a hydrogen halide (for example, hydrogen chloride) is generated as a by-product due to a reaction between the acid halide remaining in the reaction mixture and water to be added. There is a risk of deteriorating properties. For this purpose, it is preferable to remove as much hydrogen halide as possible in the reaction mixture. The method for removing the hydrogen halide is not particularly limited, but a dehydrohalogenating agent is preferably used from the viewpoints of workability and easy availability.

  Preferred examples of the dehydrohalogenating agent include those described above. The amount of the dehydrohalogenating agent used is not particularly limited, but is preferably 0.5 to 10 mol, more preferably 1 to 5 mol, based on 1 mol of the acid halide group remaining in the reaction mixture. .

[Scheme 4]
As shown below, the reaction of Scheme 4 is a compound represented by the following general formula (30) having an acid anhydride group (sometimes referred to as “compound 30”) and a general formula (22) having a hydroxy group. It is a ring-opening esterification reaction with the represented compound. In the reaction of Scheme 4, since a carboxyl group is generated together with the esterification reaction in the compound 30, it is the most preferable reaction mode as a method for synthesizing the compound represented by the general formula (12).

スキーム４中の、
前記一般式（２２）で表される化合物中のＡｃｒはそれぞれ独立して上記の一般式（１３）、（１４）、または（１５）で表される基を表す。

In Scheme 4,
Acr in the compound represented by the general formula (22) independently represents a group represented by the general formula (13), (14), or (15).

  In the reaction of Scheme 4, it is necessary to leave a carboxyl group in the compound represented by the general formula (31), which is the final target product (sometimes referred to as “compound 31”). Therefore, the amount ratio of the acid anhydride group to the hydroxy group is not particularly limited, but the amount of the hydroxy group is preferably 0.1 to 10 mol with respect to 1 mol of the acid anhydride group, 0.5 to 5 mol is more preferable, and 0.8 to 3 mol is particularly preferable.

  The reaction of Scheme 4 may be performed in the absence of a solvent or in a solvent. Such a solvent is not particularly limited as long as it is an inert solvent for the reaction. Examples of such solvents include hydrocarbon solvents such as n-hexane, benzene, toluene or xylene; ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone; ester solvents such as ethyl acetate or butyl acetate; Ether solvents such as ether, tetrahydrofuran or dioxane; Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or parkrene; N, N-dimethylformamide, N, N-dimethylacetamide, N, N- Examples include polar solvents such as dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. These solvents may be used alone or in combination of two or more.

  In the reaction of Scheme 4, a catalyst that exhibits an action of promoting the reaction may be used as necessary. Examples of such catalysts include organic phosphine compounds such as triphenylphosphine; tertiary amine compounds such as triethylamine and triethanolamine; quaternary ammonium salt compounds such as trimethylammonium chloride and triethylbenzylammonium chloride; tetra Organic phosphorus salt compounds such as butylphosphonium bromide and tetraphenylphosphonium bromide; imidazole compounds such as 2-methylimidazole; and organometallic compounds such as cobalt octenoate. The amount of the catalyst used is usually preferably 0.01 to 10.0% by mass and more preferably 0.01 to 5.0% by mass with respect to the total mass of the reaction mixture. It is preferable that the amount of the catalyst used be within the above range because a sufficient reaction rate can be obtained during the reaction.

  The reaction conditions of Scheme 4 will be described. Although the reaction temperature of Scheme 4 is not particularly limited, it is usually preferably in the range of 0 to 200 ° C., more preferably 0 to 150 ° C. from the viewpoint of promoting the reaction. The reaction time in Scheme 4 depends on conditions such as the reaction temperature, but is usually from several minutes to several tens of hours. Further, in Scheme 4, the reaction can be stopped at an arbitrary reaction rate while the reaction rate is confirmed by a known analysis means (for example, liquid chromatography, thin layer chromatography, IR, etc.).

  In Schemes 2 to 4, many of the hydroxy group-containing (meth) acrylic acid derivatives used as raw materials and represented by the general formula (22) are industrially available. Among them, the compound represented by the general formula (15) useful as the compound 22, that is, an acryloyl group and / or a methacryloyl group-containing compound (sometimes referred to as “(meth) acryloyl derivative”) It can be easily produced by the synthesis reaction shown in Scheme 5.

[Scheme 5]
As shown below, the reaction of Scheme 5 is a ring-opening esterification reaction between the compound represented by the general formula (40) having a glycidyl ether group and the compound represented by the general formula (41) having an alcohol group. To synthesize a (meth) acryloyl derivative represented by the above general formula (15a) having a hydroxy group.

スキーム５において、
Ｒ_１１、Ｒ_１２、Ｘ_１３、Ｘ_１４、ｉ、およびｊは、前記一般式（１）と同様に定義される。

In Scheme 5,
R ₁₁ , R ₁₂ , X ₁₃ , X ₁₄ , i, and j are defined in the same manner as in the general formula (1).

  The ring-opening esterification reaction of Scheme 5 may be performed in the absence of a solvent or in a solvent inert to such reaction. Examples of such solvents include hydrocarbon solvents such as n-hexane, benzene, toluene or xylene; ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone; ester solvents such as diethyl ether, tetrahydrofuran or dioxane; Halogen-based solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or perchlene; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane, etc. Of polar solvents. These solvents may be used alone or in combination of two or more.

  In the ring-opening esterification reaction, a catalyst that acts to activate the reaction may be used as necessary. Examples of such catalysts include organic phosphine compounds such as triphenylphosphine; tertiary amine compounds such as triethylamine triethanolamine; quaternary ammonium salt compounds such as trimethylammonium chloride and triethylbenzylammonium chloride; tetrabutyl Organic phosphorus salt compounds such as phosphonium bromide and tetraphenylphosphonium bromide; imidazole compounds such as 2-methylimidazole; and organometallic compounds such as cobalt octenoate. These catalysts may be used alone or in combination of two or more.

  The amount of the catalyst used is preferably 0.01 to 10.0% by mass with respect to the total mass of the reaction mixture in Scheme 5, from the viewpoint of obtaining a sufficient reaction rate during the reaction, and 0.01 to 5. It is more preferable to set it as 0 mass%. In the present invention, when a plurality of types of solvents are used, the total usage amount thereof is regarded as the usage amount of the catalyst.

  Regarding the reaction conditions in Scheme 5, the reaction temperature for the ring-opening esterification reaction is not particularly limited, and may be any temperature that is sufficient to cause the reaction to proceed. The reaction temperature is preferably substantially constant in the range of 0 to 200 ° C, and more preferably 0 to 150 ° C. In addition, the reaction time required for the ring-opening esterification reaction is appropriately set according to the reaction temperature, the amount of the compound 40 and the compound 41 used as raw materials, or the type or combination of the solvent or catalyst, the amount of use, etc. There is no particular limitation. From the viewpoint of sufficiently proceeding such a reaction, it is usually preferable to set it to several minutes to several tens hours.

  In scheme 5, the reaction may be allowed to proceed or stopped at any reaction rate while the reaction rate is confirmed by a known analysis means. Examples of such analytical means include liquid chromatography, thin layer chromatography, and IR analyzers.

  Next, when the compound represented by the general formula (12) is produced as a raw material, the compound represented by the general formula (50) has two or more (acid halide groups or In the case of a compound having a structure in which a carboxyl group (including a precursor such as an acid anhydride group) is bonded, a method for producing the compound is shown in Scheme 6 and described.

[Scheme 6]
Scheme 6 shown below as the production method includes the above general formula by esterifying the acid chloride group of trimellitic acid chloride represented by the following general formula (50) and then ring-opening the acid anhydride group. The compound represented by (12) is produced.

スキーム６中の、
前記一般式（２２）で表される化合物中のＡｃｒはそれぞれ独立して上記の一般式（１３）、（１４）、または（１５）で表される基を表す。

In Scheme 6,
Acr in the compound represented by the general formula (22) independently represents a group represented by the general formula (13), (14), or (15).

  When a compound that is asymmetric as shown in Scheme 6 is produced, an isomer may be generated depending on the position of esterification reaction with Compound 22. The isomers in Scheme 6 mean the compound represented by the general formula (52a) and the compound represented by the general formula (52b). However, it is not necessary to separate the isomer from the finally obtained reaction mixture, and the reaction mixture containing the isomer may be used for the reaction of Scheme 1 described above as a raw material of the compound 12. Of course, isomers may be separated from the reaction mixture.

  The reaction in Scheme 6 is a synthesis reaction of a (meth) acryloyl derivative having a hydroxy group by ring-opening esterification of the compound in Scheme 6 having a glycidyl ether group and the compound in Scheme 2 having a carboxyl group.

  The reaction of Scheme 6 may be performed in the absence of a solvent or in a solvent. Such a solvent is not particularly limited as long as it is inert to the reaction. Examples of the solvent include hydrocarbon solvents such as n-hexane, benzene, toluene or xylene; ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone; ester solvents such as ethyl acetate or butyl acetate; diethyl ether, tetrahydrofuran Or ether solvents such as dioxane; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolide Polar solvents such as non, dimethyl sulfoxide and sulfolane are included. These solvents may be used alone or in combination of two or more.

  In the reaction of Scheme 6, if necessary, a catalyst exhibiting an action of promoting such a reaction can be used. Examples of such catalysts include organic phosphine compounds such as triphenylphosphine; tertiary amine compounds such as triethylamine and triethanolamine; quaternary ammonium salt compounds such as trimethylammonium chloride and triethylbenzylammonium chloride; tetra Organic phosphorus salt compounds such as butylphosphonium bromide and tetraphenylphosphonium bromide; imidazole compounds such as 2-methylimidazole; and organometallic compounds such as cobalt octenoate. The amount of the catalyst used is usually preferably 0.01 to 10.0% by mass and more preferably 0.01 to 5.0% by mass with respect to the total amount of the reaction mixture before the reaction of Scheme 6. If the amount of the catalyst used is within the above range, it is preferable because a sufficient reaction rate can be obtained in this reaction.

  Although the reaction temperature in Scheme 6 is not particularly limited, it is usually preferably in the range of 0 to 200 ° C, more preferably 0 to 150 ° C, from the viewpoint of promoting the reaction. In addition, the reaction time depends on conditions such as the reaction temperature, but usually it may be several minutes to several tens of hours. Further, in Scheme 6, the reaction can be stopped at an arbitrary reaction rate while the reaction rate is confirmed by a known analysis means (for example, liquid chromatography, thin layer chromatography, IR, etc.).

  Moreover, in the schemes 1 to 6 described above, it is preferable to use a polymerization inhibitor in order to prevent the polymerization reaction of the (meth) acryloyl group from proceeding excessively. Examples of such polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, phenothiazine, pt-butylcatechol, p-benzoquinone, and naphthoquinone, but are not particularly limited.

  Next, specific examples of the compound represented by the general formula (1) of the present invention are shown. Here, k and l in each formula represent an integer of 0 to 10, and n represents an integer of 1 to 10.

[Polymerizable composition]
The compound represented by the general formula (1) of the present invention has high compatibility with epoxy resins used for a wide range of applications as high-performance and high-functional resins and acrylic resins exhibiting radical polymerizability. Therefore, the compound represented by the general formula (1) of the present invention is useful as a raw material for various industrial materials such as adhesives and electrical insulating materials. Examples of such polymerizable compositions used as industrial materials include liquid crystal sealants, sizing agents used for the purpose of imparting water resistance to paper, adhesives for automobiles and electrical / electronic equipment, and others A sealant is included.

  The compound represented by the general formula (1) is a single compound or a compound represented by the general formula (1), but two or more compounds having different compositions may be used in combination. Good. As described above, by appropriately selecting and using the compound, a polymerizable composition having various characteristics can be designed as necessary.

  When preparing a polymerizable composition using the compound represented by the general formula (1) as a raw material, the amount of the compound used is a new amount resulting from the compound while maintaining the original properties of the epoxy resin and the acrylic resin. From the viewpoint of expressing the characteristics in the resin composition, it is preferably 5 to 90 parts by mass and more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the resin composition. However, the usage-amount of the said compound is not specifically limited, What is necessary is just to determine suitably according to the epoxy equivalent etc. of the epoxy resin used together.

  Since the compound represented by the general formula (1) of the present invention has two kinds of polymerizable organic groups, a (meth) acryloyl group and a glycidyl group, different polymerization reactions can occur. Therefore, when a polymerizable composition is prepared by using the compound in combination with a composition containing an epoxy resin or an acrylic resin as a main component, the compound exhibits high compatibility with each of the resins. An agent can be obtained. When the liquid crystal sealant is applied to the production of a liquid crystal display panel, particularly a liquid crystal dropping method, a cured product having almost no uncured portion is obtained in a short time, so that contamination of the liquid crystal can be suppressed, The adhesive strength between the substrate constituting the liquid crystal display panel and the cured product is high and good. In addition, the liquid crystal sealant of the present invention has a high viscosity stability near room temperature and is good. For this reason, it is possible to eliminate the decrease in yield, which has been regarded as a problem in the past, such as the line width being narrowed at the time of application as the viscosity of the liquid crystal sealant is increased, and the number of times the liquid crystal sealant is replaced with a dispenser.

[Liquid crystal sealant]
As an example of the polymerizable composition, a liquid crystal sealing agent using the compound represented by the general formula (1) of the present invention as a raw material will be specifically described. Examples of components that can be used in combination with the compound represented by the general formula (1) of the present invention as a raw material of the liquid crystal sealant include (b) a thermal latent epoxy curing agent, (c) an epoxy resin, (D) Acrylic acid ester monomers and / or methacrylic acid ester monomers and oligomers thereof, (e) photoradical polymerization initiators, and (f) fillers are included. Moreover, you may include additives, such as a silane coupling agent, with these components as needed. Hereinafter, details of each component will be described.

(B) Thermal Latent Epoxy Curing Agent The thermal latent epoxy curing agent of the present invention is an epoxy in a state where such a resin is normally stored (room temperature, under visible light, etc.) even when mixed with a main agent such as an epoxy resin. It means a curing agent that does not react with a functional group such as a group but exhibits a reactive activity with respect to the functional group by heat or light.

  When such a heat-latent epoxy curing agent is used as a raw material for the liquid crystal sealant, the proper viscosity of the liquid crystal sealant at room temperature is maintained. For this reason, such a liquid crystal sealant has a high viscosity stability at room temperature and can be kept well. Therefore, when a liquid crystal sealant is filled in a screen printing machine or a dispenser and a seal pattern is formed on a substrate, it takes a long time. A liquid crystal sealant can be used stably. Thus, it is preferable to increase the pot life of the liquid crystal sealant because productivity at the time of manufacturing the liquid crystal display panel is improved.

  Moreover, the liquid crystal sealing agent of the present invention containing the heat latent curing agent as described above is useful as a one-pack type. A one-component type liquid crystal sealant is a liquid crystal with excellent storage stability, in which the main component such as an epoxy resin and a curing accelerating component such as a thermal latent curing agent are uniformly mixed before use. A sealant. Excellent storage stability means that the curing reaction hardly proceeds even when the liquid crystal sealant is stored at room temperature or lower. Specifically, it is preferable that the increase rate of the viscosity when the liquid crystal sealant is stored at 25 ° C. for 5 days is not more than twice the viscosity of the liquid crystal sealant before storage.

  In the present invention, a known compound can be used as a heat-latent epoxy curing agent. From the viewpoint of maintaining a proper viscosity of a liquid crystal sealant at room temperature and providing a one-component liquid crystal sealant, an amine-based heat latent An epoxy curing agent is preferably used. Examples of the amine-based heat latent epoxy curing agent include organic acid dihydrazide compounds, imidazole and its derivatives, dicyandiamide, and aromatic amines. You may use these individually or in combination of multiple types.

  From the viewpoint of expressing the viscosity stability of the liquid crystal sealant and the high reactivity with respect to the functional group, the amount of the thermal latent epoxy curing agent used is 1 to 25 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. It is preferable that there is 5 to 15 parts by mass. Since such a liquid crystal sealant has high viscosity stability and reactivity, there are very few uncured portions in the cured product of the liquid crystal sealant. Therefore, the contamination of the liquid crystal is suppressed, and the adhesive strength between the substrate constituting the liquid crystal display panel and the cured product is increased, so that the display property of the liquid crystal display panel is high and good.

(C) Epoxy resin The epoxy resin of the present invention means a compound having one or more epoxy groups in the molecule. Preferable examples of the epoxy resin used in the present invention include aromatic polyvalent glycidyl ether compounds, novolac type polyvalent glycidyl ether compounds, and glycidyl ether compounds.

  Preferable examples of the aromatic polyvalent glycidyl ether compound include aromatic diol compounds and compounds obtained by reacting diol compounds modified with various glycols with epichlorohydrin. Examples of the aromatic diol compound include bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin. Examples of the glycol include ethylene glycol, propylene glycol, and alkylene glycol.

  Preferred examples of the novolak resin include compounds derived from phenol or cresol and formaldehyde. Examples of the novolac type polyvalent glycidyl ether compound include compounds obtained by the reaction of a polyphenol compound typified by polyalkenylphenol or a copolymer thereof and epichlorohydrin. Examples of the glycidyl ether compound include a xylylene phenol resin.

  The amount of the epoxy resin used is preferably 1 to 40 parts by mass and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. Such a liquid crystal sealant has good heat resistance. However, when the blending amount is less than 5 parts by mass, the curing rate is slow, and when it exceeds 50 parts by mass, the heat resistance of the liquid crystal sealant may be lowered.

(D) Acrylic Compound The acrylic compound of the present invention means a compound having one or more acrylic groups in the molecule, and includes (meth) acrylic resins such as methacrylic resins. Preferable examples of the component (d) that is such an acrylic compound include acrylic acid ester monomers and / or methacrylic acid ester monomers, or oligomers thereof, but are not particularly limited, and include known compounds. Since the liquid crystal sealant containing such an acrylic compound has extremely good water resistance, when applied to a liquid crystal display panel, the adhesive strength between the cured product of the liquid crystal sealant and the substrate constituting the liquid crystal display panel is high. A high-quality liquid crystal display panel that is extremely high and excellent in moisture resistance reliability can be obtained.

  Preferred examples of the acrylic compound as component (d) of the present invention include diacrylates and / or dimethacrylates such as polyethylene glycol; triacrylate (2-hydroxyethyl) isocyanurate diacrylates and / or dimethacrylates; Acrylates and / or dimethacrylates are included.

  Preferred examples of the acrylic compound (d) component include cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, triphenolmethane type epoxy resin, and triphenolethane type epoxy. (Meth) acrylate-modified epoxy resin in which the epoxy group contained in epoxy resin such as resin, trisphenol type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin is (meth) acrylylated included. Here, the (meth) acrylate-modified epoxy resin means a compound having both a (meth) acryl group and an epoxy group in the molecule.

(E) Photoradical polymerization initiator The photoradical polymerization initiator of the present invention means a compound that absorbs energy by light and generates radicals. Examples of radical photopolymerization initiators include benzoin compounds, acetophenones compounds, benzophenones compounds, thioxanthones compounds, α-acyloxime esters compounds, phenylglyoxylate compounds, benzyl compounds, azo compounds, diphenyl Examples thereof include sulfide compounds, acylphosphine oxide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoin ether compounds, and anthraquinone compounds, but are not particularly limited.

  Since the liquid crystal sealant prepared using such a radical photopolymerization initiator as a raw material can be cured by light irradiation, when used in a liquid crystal dropping method, a curing treatment such as after cure is unnecessary, and Since the curing time of the layer sealant is shortened, productivity can be improved.

  From the viewpoint of enhancing the photocurability of the liquid crystal sealant, the amount of the radical photopolymerization initiator used is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. When the liquid crystal sealant is not cured by light, the photoradical polymerization initiator may not be used.

(F) Filler The filler according to the present invention is to improve the adhesion reliability of the liquid crystal sealant by controlling the viscosity of the liquid crystal sealant, improving the strength of the cured product obtained by curing the liquid crystal sealant, or suppressing linear expansion. The filler used for the purpose of.

  The filler that can be preferably used in the present invention is not particularly limited, and includes known fillers that can be normally used in the field of electronic materials. Examples of fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, Inorganic fillers such as asbestos powder, quartz powder, mica, glass fiber, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride are included.

  As the filler of the present invention, polymethyl methacrylate, polystyrene, copolymers obtained by copolymerizing monomers constituting these and other monomers, polyester fine particles, as long as the properties of the liquid crystal sealant are not impaired Further, known organic fillers such as polyurethane fine particles and rubber fine particles may be used.

  Among these, inorganic fillers are preferable from the viewpoint of improving the linear expansion coefficient and shape retention. Among such inorganic fillers, silicon dioxide and talc are more preferable because of their high UV transmittance. Regardless of inorganic or organic, the filler used in the liquid crystal sealing agent of the present invention may be graft-modified with an epoxy resin or a silane coupling agent.

  The shape of the filler is not particularly limited, and may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or an atypical shape. The maximum particle size of the filler is preferably 6 μm or less, and more preferably 2 μm or less. The particle size of the filler can be measured by laser diffraction. If a liquid crystal sealant containing a filler having such a particle size is used in a method for producing a liquid crystal display panel, a liquid crystal cell with very good cell gap dimensional stability can be formed.

  The blending amount of the filler is preferably 2 to 40 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the liquid crystal sealant excluding the filler. Thus, the liquid crystal sealing agent in which the blending amount of the filler is adjusted has good applicability to the substrate.

(G) Other additives The liquid crystal sealant of the present invention may contain additives as necessary. Examples of the additive preferably used in the present invention include a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchange agent, a leveling agent, a pigment, a dye, a plasticizer, and an antifoaming agent. Is included. These additives may be used alone or in combination of two or more kinds depending on the application. Further, a spacer or the like may be included in order to secure a gap of the liquid crystal cell. The spacer may be included in the liquid crystal sealant, or may be used by previously applying to a substrate constituting the liquid crystal display panel.

  The method for preparing the liquid crystal sealant of the present invention is not particularly limited, and a known technique can be used. Examples of means for mixing each component of the liquid crystal sealant include a double-arm stirrer, a roll kneader, a twin screw extruder, a ball mill kneader, and a planetary stirrer, but are not particularly limited and are publicly known. Any kneading machine may be used. The liquid crystal sealant suitably mixed by any method is filtered through a filter to remove impurities. And after a vacuum defoaming process, a glass bottle or a plastic container is hermetically filled and stored and transported as necessary.

[Method of manufacturing liquid crystal display panel]
The liquid crystal sealing agent of the present invention can be applied to both a liquid crystal injection method and a liquid crystal dropping method. Especially, it is preferable to apply the liquid-crystal sealing compound of this invention to a liquid-crystal dripping method from a viewpoint which can implement | achieve the improvement in productivity at the time of manufacture of a liquid crystal display panel. Regardless of the liquid crystal injection method or the liquid crystal dropping method, the method for producing a liquid crystal display panel using the liquid crystal sealant of the present invention is not particularly limited.

  Among the above, the main liquid crystal injection method known as a method for manufacturing a liquid crystal display panel is that a liquid crystal sealant is first applied to a glass substrate constituting the liquid crystal display panel and then subjected to a precure treatment, thereby performing a liquid crystal sealant. The other glass substrate is bonded so as to face the glass substrate, and then the glass substrates are heated and pressed together; an empty space having an injection port formed between the two glass substrates. A liquid crystal display panel is manufactured by injecting liquid crystal into a liquid crystal cell in a vacuum; and sealing the injection port with a sealing sealant or the like.

  Moreover, the following method is mentioned as a liquid crystal dropping construction method. In the liquid crystal dropping method, first, one or more substrates having a frame-shaped display region formed so that the pixel array region is surrounded by a liquid crystal sealant are prepared; A liquid crystal is dropped on one substrate; after the substrate on which the liquid crystal is dropped and the other substrate are overlapped; light and heat or light on the liquid crystal sealant sandwiched between the two substrates Alternatively, it is a method for producing a liquid crystal display panel by curing the liquid crystal sealant by applying either one of heat.

  Regardless of the method for producing the liquid crystal display panel, the liquid crystal sealant of the present invention containing the compound represented by the general formula (1) has latent curability and maintains an appropriate viscosity at room temperature. Useful as a one-pack type. Further, even when the liquid crystal sealant is cured by applying light, the reactivity in the light shielding area is high, and the curing proceeds to every corner in a short time. Therefore, since there are very few uncured portions remaining in the cured product of the liquid crystal sealant, liquid crystal contamination is suppressed, and the adhesive strength between the substrate constituting the liquid crystal display panel and the cured product is kept high. A display panel can be obtained.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention. However, the present invention is not limited to the embodiment shown here. Further, “%” and “part” in each example and comparative example mean “% by mass” and “part by mass”, respectively.

  In each Example and Comparative Example, a liquid crystal sealant was prepared using the compound represented by the general formula (1) synthesized by the following method and other raw materials, the characteristics of the prepared liquid crystal sealant, and The adhesive strength and display properties of a liquid crystal display panel produced using a liquid crystal sealant were evaluated. Next, the raw materials used for the preparation of the liquid crystal sealant will be described.

(A) Compound represented by general formula (1) The compound represented by the general formula (1) was produced by the methods of Examples 1 to 18 below.

[Example 1: Compound represented by Formula (1-225)]
First, in a 1000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 74 g (0.5 mol) of phthalic anhydride, 107 g (0.5 mol) of glycerol acrylate methacrylate, and 0.5 g of triethylamine as a catalyst Then, 0.5 g of phenothiazine was mixed as a polymerization inhibitor, heated to 80 ° C. and reacted for 1 hour, further heated to 130 ° C. and reacted for 2 hours. After the reaction, the reaction solution was diluted with 1000 g of ethyl acetate, washed with ultrapure water five times and then concentrated to obtain 158 g of glycerol acrylate methacrylate-modified phthalic acid.

  Next, in a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 158 g of the obtained glycerol acrylate methacrylate-modified phthalic acid and 156 g of 4,4′-bisphenol F diglycidyl ether ( 0.5 mol), 5 g of triethanolamine as a catalyst, and 1 g of hydroquinone as a polymerization regulator for terminating the polymerization were mixed and then heated to 80 ° C. and reacted for 2 hours. After confirming that the acid value of the reaction solution was 2 mgKOH / g or less, the reaction solution was diluted with 1000 g of ethyl acetate, washed with ultrapure water 5 times and concentrated to obtain 320 g of a reaction product. It was. The obtained reaction product was column-separated with silica gel to obtain 150 g of compound A represented by the formula (1-225). As a result of analyzing the compound A1 by HPLC and NMR, it was confirmed that the compound A1 had a purity of 80% and had the target structure. The compound synthesized in this example is referred to as A1. A 1H-NMR chart of Compound A1 is shown in FIG.

  The purity of the compound by the above HPLC analysis is calculated from the peak area obtained when the compound subjected to purity measurement is analyzed by HPLC. That is, when the measurement target is subjected to HPLC analysis, the peak area of the target component is a1, the peak area of the by-product is a2, and the impurity peak other than the other solvent is a3, {a1 / (a1 + a2 + a3)} × A value calculated by 100. The greater the calculated value approaches 100%, the higher the purity of the compound can be considered.

[Example 2: Mixture of compound represented by formula (1-393) and compound represented by formula (1-409)]
First, in a 1000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 152 g (0.5 mol) of 4- {2- (methacryloyloxy) ethoxycarbonyl} -phthalic anhydride and 2- 72 g (0.5 mol) of hydroxybutyl acrylate, 0.5 g of triethylamine as a catalyst, and 0.5 g of phenothiazine as a polymerization regulator for suppressing polymerization were mixed and heated to 80 ° C. for 1 hour. The mixture was further heated to 130 ° C. and reacted for 2 hours. After the reaction, the reaction solution was diluted with 1000 g of ethyl acetate, washed with water with ultrapure water five times, and concentrated to obtain 190 g of a reaction product.

  In a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 190 g of the obtained reaction product, 156 g (0.5 mol) of 4,4′-bisphenol F diglycidyl ether, After mixing 5 g of triethanolamine as a catalyst and 1 g of hydroquinone as a polymerization regulator for stopping the polymerization, the mixture was heated to 80 ° C. and reacted for 2 hours. After confirming that the acid value of the reaction solution became 2 mgKOH / g or less, the reaction solution was diluted with 1000 g of ethyl acetate, washed with ultrapure water 5 times and then concentrated to obtain 361 g of a reaction product. It was. The obtained reaction product was subjected to column separation with silica gel to obtain 118 g of composition A2 which is a mixture of the compound represented by the general formula (1-393) and the compound represented by the formula (1-409). It was. As a result of HPLC and NMR analysis of the obtained composition A2, it was confirmed that the composition was composed of a compound having a target structure and a purity of 95%. The compound synthesized in this example is referred to as A2. A 1H-NMR chart of Composition A2 is shown in FIG.

[Example 3: Compound represented by Formula (1-83)]
In Example 3, the same operation as in Example 1 was performed except that 2-hydroxyethyl methacrylate was used instead of glycerol acrylate methacrylate used as the raw material of compound A1, and the compound was represented by the formula (1-83). 75 g of the compound A3 was synthesized. As a result of HPLC and NMR analysis of the obtained compound A3, it was confirmed that the purity was 98% and the compound had the target structure. The compound synthesized in this example is referred to as A3. A 1H-NMR chart of Compound A3 is shown in FIG.

[Example 4: Compound represented by Formula (1-3)]
In Example 4, all operations were performed in the same manner as in Example 1 except that 4-hydroxybutyl acrylate was used instead of glycerol acrylate methacrylate used as a raw material for compound A1, and the formula (1-3) was used. 40 g of the compound A4 to be synthesized was synthesized. As a result of HPLC and NMR analysis of the obtained compound A4, it was confirmed that the compound had a purity of 93% and the target structure. The compound synthesized in this example is referred to as A4. A 1H-NMR chart of Compound A4 is shown in FIG.

[Example 5: Compound represented by Formula (1-87 (n = 1))]
In Example 5, the same operation as in Example 1 was carried out except that caprolactone-modified 2-hydroxyethyl methacrylate was used instead of glycerol acrylate methacrylate used as the starting material for compound A1, and the above formula (1-87) 327 g of composition A5 represented by (n = 1 (average)) was synthesized. The compound synthesized in this example is referred to as A5. As a result of HPLC and FD-MS analysis of the obtained compound A5, it was confirmed that the composition A5 was a mixture of a plurality of compounds having different caprolactone addition numbers. m / z = 590 (n = 0), 704 (n = 1), 818 (n = 2), 932 (n = 3), 1046 (n = 4)

[Example 6: Compound represented by Formula (1-46)]
In Example 6, except that 4-hydroxybutyl acrylate was used instead of glycerol acrylate methacrylate used as the raw material of compound A1, resorcin diglycidyl ether was used instead of 4,4′-bisphenol F diglycidyl ether. All in the same manner as in Example 1, 64 g of the compound A6 represented by the formula (1-46) was synthesized. As a result of HPLC and NMR analysis of the obtained compound A6, it was confirmed that the purity was 97% and the compound had the target structure. The compound synthesized in this example is referred to as A6. A 1H-NMR chart of Compound A6 is shown in FIG.

[Example 7: Compound represented by Formula (1-1)]
In Example 7, the same operation as in Example 1 was carried out except that 2-hydroxyethyl acrylate was used instead of glycerol acrylate methacrylate used as a raw material for compound A1, and the compound was represented by the formula (1-1). As a result, 74 g of Compound A7 was synthesized. As a result of analyzing the obtained compound A7 by HPLC and NMR, it was confirmed that the compound A7 had a purity of 99% and had the target structure. The compound synthesized in this example is referred to as A7. A 1H-NMR chart of Compound A7 is shown in FIG.

[Example 8: Compound represented by formula (1-126)]
In Example 8, except that 2-hydroxyethyl methacrylate was used instead of glycerol acrylate methacrylate used as a raw material of compound A1, and resorcin diglycidyl ether was used instead of 4,4′-bisphenol F diglycidyl ether. All in the same manner as in Example 1, 67 g of compound A8 represented by the formula (1-126) was synthesized. As a result of analyzing the compound A8 by HPLC and NMR, it was confirmed that the compound A8 had a purity of 95% and had the target structure. The compound synthesized in this example is referred to as A8. A 1H-NMR chart of Compound A8 is shown in FIG.

[Example 9: Mixture of compounds represented by formula (1-425) and formula (1-437)]
In Example 9, the same procedure as in Example 2 was carried out except that bisphenol A diglycidyl ether was used instead of 4,4′-bisphenol F diglycidyl ether used as the starting material for compound A2. 136 g of composition A9, in which the compound represented by (1-393) and the compound represented by formula (1-409) were mixed, was synthesized. As a result of HPLC and NMR analysis of the obtained composition A9, it was confirmed that the purity was 97% and the compound having the target structure was mixed. The compound synthesized in this example is referred to as A9. A 1H-NMR chart of Composition A9 is shown in FIG.

(B) Heat-latent epoxy curing agent As the heat-latent epoxy curing agent, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (Amicure VDH-J manufactured by Ajinomoto Co., Inc.) was used.

(C) Epoxy resin As the epoxy resin, a uniform solution in which o-cresol novolak epoxy resin (EOCN-1020-75 manufactured by Nippon Kayaku Co., Ltd.) was dissolved in heat in an epoxy ester 3000M subjected to high-purification treatment was used.

(E) Photoradical polymerization initiator As the photoradical polymerization initiator, 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals) was used.

(F) Filler As the filler, spherical silica (Admafine A-802, manufactured by Admatechs) was used.

[Example 10]
As a component (c), 5 parts of o-cresol novolac epoxy resin (EOCN-1020-75 manufactured by Nippon Kayaku Co., Ltd.) was heated and dissolved in 10 parts of highly purified epoxy ester 3000M to prepare a uniform solution. To this cooled solution, 52 parts of the compound A1 synthesized in Example 1 as component (a) and 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184) as a photoradical initiator as component (e) were added. 2 parts of Ciba Peshatti Chemical), 10 parts of 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (Amicure VDH-J Ajinomoto Co.) as component (b), spherical as component (f) 20 parts of silica (Admafine A-802, manufactured by Admatechs) and 1 part of γ-gridoxypropyltrimethoxysilane as an additive were added and premixed with a mixer. Furthermore, it knead | mixed until the solid raw material became 5 micrometers or less with 3 rolls, and filtered with the filter (made by ADVANTEC, MSP-10-E10S) with an opening of 10 micrometers. A liquid crystal sealing agent (P1) was prepared by subjecting the obtained filtrate to a vacuum defoaming treatment.

[Example 11]
As a component (a), a liquid crystal sealant (P2) was prepared in the same manner as in Example 1 except that 52 parts of the compound synthesized in Example 2 was used instead of Compound A1 synthesized in Example 1.

[Example 12]
As a component (a), a liquid crystal sealant (P3) was prepared in the same manner as in Example 1 except that 52 parts of the compound synthesized in Example 3 was used instead of Compound A1 synthesized in Example 1.

[Example 13]
As a component (a), a liquid crystal sealant (P4) was prepared in the same manner as in Example 1, except that 52 parts of the compound synthesized in Example 4 was used instead of Compound A1 synthesized in Example 1.

[Example 14]
As a component (a), a liquid crystal sealant (P5) was prepared in the same manner as in Example 1, except that 52 parts of the compound synthesized in Example 5 was used instead of Compound A1 synthesized in Example 1.

[Example 15]
As a component (a), a liquid crystal sealant (P6) was prepared in the same manner as in Example 1, except that 52 parts of the compound synthesized in Example 6 was used instead of Compound A1 synthesized in Example 1.

[Example 16]
As a component (a), a liquid crystal sealant (P7) was prepared in the same manner as in Example 1, except that 52 parts of the compound synthesized in Example 7 was used instead of Compound A1 synthesized in Example 1.

[Example 17]
As a component (a), a liquid crystal sealant (P8) was prepared in the same manner as in Example 1 except that 52 parts of the compound synthesized in Example 8 was used instead of Compound A1 synthesized in Example 1.

[Example 18]
As a component (a), a liquid crystal sealant (P9) was prepared in the same manner as in Example 1 except that 52 parts of the compound synthesized in Example 9 was used instead of Compound A1 synthesized in Example 1.

[Comparative Example 1]
Liquid crystal sealant (C1) in the same manner as in Example 1 except that 52 parts of Compound B1 synthesized in Synthesis Example 1 below was used as component (a) instead of Compound A1 synthesized in Example 1 above. Was prepared.

[Synthesis Example 1]
Synthesis of methacryl-modified epoxy resin 175 g of bisphenol F type epoxy resin: “Dainippon Ink Chemical Co., Ltd., trade name Epicron 850CRP” in a 1000 ml four-necked flask equipped with a stirrer, gas introduction tube, thermometer, and cooling tube Methacrylic acid: 43 g, triethanolamine: 0.2 g as a reaction accelerator, and hydroquinone: 0.2 g as a polymerization inhibitor are mixed and heated and stirred in a dry air stream at 110 ° C. for 5 hours to methacryl-modified bisphenol F type An epoxy resin (Compound B1) was obtained. The obtained compound B1 was highly purified by repeating the washing treatment with ultrapure water 12 times.

[Comparative Example 2]
Liquid crystal sealant (C2) in the same manner as in Example 1 except that 52 parts of Compound B2 synthesized in Synthesis Example 2 below was used as the component (a) instead of Compound A1 synthesized in Example 1 above. Was prepared.

[Synthesis Example 2]
Synthesis of acrylic modified epoxy resin 175 g of bisphenol F type epoxy resin: “Dainippon Ink Chemical Co., Ltd., trade name Epicron 850CRP” in a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, Acrylic acid: 37 g, Triethanolamine: 0.2 g as a reaction accelerator, Hydroquinone: 0.2 g as a polymerization inhibitor are mixed, heated and stirred in a dry air stream at 110 ° C. for 12 hours, and acrylic modified bisphenol F type epoxy A resin (Compound B2) was obtained. The obtained compound B2 was highly purified by repeating the washing treatment with ultrapure water 12 times.

[Comparative Example 3]
As component (a), instead of compound A1 synthesized in Example 1, 26 parts of Compound B1 obtained in Synthesis Example 1 and 26 parts of Compound B2 obtained in Synthesis Example 2 were mixed. A liquid crystal sealant (C3) was prepared in the same manner as in Example 1 except that the product B3 was used.

[Comparative Example 4]
As a component (a), a liquid crystal sealant (C4) was prepared in the same manner as in Example 1 except that 52 parts of the epoxy ester 3000M was used instead of the compound A1 synthesized in Example 1.

[Test method]
In each example and comparative example, the viscosity stability of the liquid crystal sealant, the adhesive strength of the liquid crystal sealant, and the display properties of the liquid crystal display panel were measured and evaluated, and the characteristics of the liquid crystal sealant were evaluated. Details of each measurement are shown below. Here, the display properties of the liquid crystal display panel are two types of liquid crystal display panels: (1) a liquid crystal display panel produced by light and thermosetting, and (2) a liquid crystal display panel provided with a light shielding area. Subject to sex evaluation.

[Viscosity stability of liquid crystal sealant]
The viscosity value at 25 ° C. of the liquid crystal sealant was measured using an E-type viscometer. At the time of viscosity measurement, 100 parts by mass of the liquid crystal sealing agent was put in a polyethylene container and sealed, and then stored in an atmosphere at 25 ° C. for 5 days. Subsequently, after a predetermined period of time, a viscosity value at 25 ° C. was measured with an E-type viscometer. And the change rate of the viscosity value after 25 degreeC / 5 day progress when the viscosity value before sealing was set to 100 using the measured value was computed. At this time, when the rate of change is 20% or less, the viscosity stability is high and good (◯), and when the change exceeds 20%, the viscosity stability is low and poor (x). The viscosity stability of the liquid crystal sealant was evaluated in two stages.

[Adhesive strength of liquid crystal sealant]
First, a liquid crystal sealant to which 1% by mass of a 5 μm glass fiber was added was screen-printed in a circular shape having a diameter of 1 mm on an alkali-free glass of 25 mm × 45 mm × 5 mm in thickness. Next, the same glass paired with this substrate was bonded to a cross and then fixed with a jig, and then irradiated with 100 mW / cm ² of ultraviolet rays using an ultraviolet irradiation device (USHIO INC.). The liquid crystal sealant was cured. At this time, the illuminance energy of ultraviolet rays was set to 2000 mJ.

  The test piece in which the liquid crystal sealant was cured by light was heat-treated at 120 ° C. for 60 minutes using an oven to prepare a test piece. By using a tensile tester (Model 210, manufactured by Intesco Corporation), the tensile strength of the finished test piece is 2 mm / min, and the tensile strength is flattened by peeling in the direction parallel to the glass bottom. Was measured. Here, the adhesive strength was evaluated in two stages according to the magnitude of the plane tensile strength. That is, when the tensile strength was 10 MPa or more, the adhesive strength was good (◯), and when the tensile strength was less than 10 MPa, the adhesive strength was low and inferior (x).

[Display properties of LCD panel]
1. Display property of liquid crystal display panel produced by light and thermosetting 1% by mass of 5 μm glass fiber was added on a 40 mm × 45 mm glass substrate (RT-DM88PIN EHC) provided with a transparent electrode and an alignment film. Using a liquid crystal sealant, a frame type of 35 mm × 40 mm was drawn with a line width of 0.5 mm and a thickness of 50 μm. For drawing, a dispenser (manufactured by Shotmaster Musashi Engineering Co., Ltd.) was used.

Next, a liquid crystal material (MLC-11900-000 manufactured by Merck & Co., Inc.) corresponding to the panel internal capacity after bonding the substrates together is precisely dispensed on a glass substrate paired with the substrate on which the seal pattern is formed. It was dripped. Subsequently, under a reduced pressure of 90 Pa, the two glass substrates are overlapped so that the liquid crystal is sealed, and then an ultraviolet ray irradiation device (USHIO INC.) Is used to emit 100 mW / cm ² ultraviolet rays. Irradiated to cure the liquid crystal sealant. At this time, the irradiation energy of ultraviolet rays was 2000 mJ. A metal halide lamp was used as the light source. For measurement of the integrated light amount, an ultraviolet integrated light meter (UVR-T35 manufactured by Topcon Corporation) having a measurement wavelength range of 300 to 390 nm and a peak sensitivity wavelength of 365 nm was used. Further, after the liquid crystal sealant was cured by light, the liquid crystal sealant was further cured by heat treatment at 120 ° C. for 60 minutes.

  A deflection film was attached to both surfaces of the two substrates bonded together to form a liquid crystal display panel. This liquid crystal display panel was driven by driving a voltage of 5 V with a DC power supply device. At this time, whether or not the liquid crystal display function in the vicinity of the seal formed by the liquid crystal sealant functions normally from the beginning of driving was visually observed, and the display properties of the liquid crystal display panel were evaluated in two stages according to predetermined criteria. Here, when the liquid crystal display function is exhibited until the seal, the display property is good (◯), and the display function is from 0.3 mm or more away from the vicinity of the seal toward the inside of the frame. When it was not exhibited, the display property was markedly bad (x).

2. Display properties of a liquid crystal display panel with a light-shielding area Liquid crystal sealant containing 1% by mass of 5 μm glass fiber on a 40 mm × 45 mm glass substrate (RT-DM88PIN ECH Co., Ltd.) with a transparent electrode and an alignment film Was used to draw a frame of 35 mm × 40 mm with a line width of 0.5 mm and a thickness of 50 μm. For drawing, a dispenser (manufactured by Shotmaster Musashi Engineering Co., Ltd.) was used.

  Next, a liquid crystal material (MLC-11900-000 manufactured by Merck & Co., Inc.) corresponding to the panel internal volume after pasting was precisely dropped with a dispenser. Subsequently, the two glass substrates are overlapped under a reduced pressure of 90 Pa, and then fixed by applying a load. Further, the sealing portion of the substrate that is the front surface is not directly irradiated with aluminum tape using aluminum tape. Covered. And the liquid crystal display panel which attached | subjected the light-shielding area was produced by hardening the liquid-crystal sealing compound with light and a heat | fever by the same method as the measuring method of the said liquid crystal display panel.

  The display function of the completed liquid crystal display panel was measured and evaluated by the same method as “1. Evaluation method of display properties of liquid crystal display panel produced by light and thermosetting” described above. Here, since the criteria for evaluating the display properties of the liquid crystal display panel are the same as described above, detailed description thereof is omitted.

  Each evaluation result by the liquid crystal sealing agent obtained in Examples 10 to 18 and Comparative Examples 1 to 4 is summarized in Table 1.

  As shown in Table 1, each liquid crystal sealant using the compound represented by the general formula (1) of the present invention as a raw material has high viscosity stability and is excellent. It was confirmed that the liquid crystal display panel manufactured by using the liquid crystal display panel was excellent in both the display property and the adhesive strength of the liquid crystal display panel regardless of the presence or absence of the light shielding area.

  On the other hand, as in Comparative Examples 1 and 4 among Comparative Examples 1 to 4, a compound having a (meth) acryl group and an epoxy group having a structure different from that of the compound represented by the general formula (1). The liquid crystal sealant used as a raw material has low viscosity stability, and each liquid crystal display panel manufactured using the liquid crystal sealant has display unevenness due to liquid crystal display unevenness in the vicinity of the seal. Comparative Example 3 is an example in which a liquid crystal sealant was prepared by using two types of compounds having both a (meth) acryloyl group and an epoxy group. However, the viscosity stability of the liquid crystal sealant was low, and the liquid crystal sealant was The liquid crystal display panel manufactured using the liquid crystal display unevenness occurred in the vicinity of the seal, and the display performance was lowered. Comparative Example 4 is an example in which a methacrylated epoxy resin having no epoxy group in the molecule is used. The liquid crystal display panel manufactured using the viscosity stability of the liquid crystal sealant and the liquid crystal sealant. It was confirmed that the adhesive strength of was extremely low.

  Since the compound represented by the general formula (1) of the present invention has high compatibility with both the epoxy resin and the acrylic resin having radical polymerizability, the high adhesiveness of the epoxy resin, the high reactivity of the acrylic resin, etc. Further, while maintaining the original characteristics of each resin, new characteristics such as higher reactivity can be imparted. Therefore, the compound is useful as a raw material for various industrial materials such as liquid crystal sealing agents, sizing agents such as carbon fibers, glass fibers, and aramid fibers, or adhesives and sealing agents for automobiles and electric / electronic devices.

FIG. 1 is a diagram showing a 1H-NMR chart of Compound A1. FIG. 2 is a diagram showing a 1H-NMR chart of composition A2. FIG. 3 is a diagram showing a 1H-NMR chart of Compound A3. FIG. 4 is a diagram showing a 1H-NMR chart of Compound A4. FIG. 5 is a diagram showing a 1H-NMR chart of Compound A6. FIG. 6 is a diagram showing a 1H-NMR chart of Compound A7. FIG. 7 is a view showing a 1H-NMR chart of Compound A8. FIG. 8 is a diagram showing a 1H-NMR chart of composition A9.

Claims (7)

A compound having a (meth) acryloyl group and a glycidyl group in the molecule and represented by the following general formula (1).

[In the general formula (1),
R _{11 to} R ₁₆ each independently represent a hydrogen atom or a methyl group, provided that both R ₁₃ and R ₁₄ are not methyl groups, and both R ₁₅ and R ₁₆ are methyl groups. Not;
X ₁₁ and X ₁₂ each independently represent an alkylene group having 1 to 10 carbon atoms or a group represented by the following general formula (2);
X ₁₃ and X ₁₄ each represents an alkylene group having 1 to 10 carbon atoms, and the other represents a group represented by the following general formula (3);
A represents a group represented by the following general formula (4), (5) or (6);
Each P independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a nitro group;
a, b and c are integers of 0 to 3, d is an integer of 1 to 3, wherein a + b + c + d + m = 6, and a, b and c are not 0 at the same time;
m is an integer of 0 to 4, i and j are each independently an integer of 0 or 1, and k and l are integers of 0 to 10]

[In the general formula (2),
Y ₂₁ and Y ₂₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
Y ₂₁ is bonded to O of the acryloyl group in the general formula (1),
n represents an integer of 1 to 10]

[In the general formula (3),
Y ₃₁ and Y ₃₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
Y ₃₂ is bonded to O of the acryloyl group in the general formula (1)]

[In the general formula (4),
R ₄₁ and R ₄₂ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group,
Z represents a single bond, —C— (R ₄₃ ) (R ₄₄ ) — group, —O— group, —S— group, —SO ₂ — group, or a group represented by the following general formula (4a). Here, R ₄₃ and R ₄₄ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group,
r and s each independently represent an integer of 0 to 4]

[In the general formula (5),
R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group.

[In the general formula (6),
R ₆₁ and R ₆₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] The compound according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by any one of the following general formulas (7) to (9).

[In the general formula (7),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1)]

[In the general formula (8),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1)]

[In the general formula (9),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1)]   The compound according to claim 1, wherein a and b in the general formula (1) are not 0. The compound according to claim 1, wherein c in the general formula (1) is not 0, one of R ₁₁ and R ₁₂ is a hydrogen atom, and the other is a methyl group.   Polymeric composition containing the compound in any one of Claims 1-4. The polymerizable composition according to claim 5, further comprising a compound represented by the following general formula (10) or general formula (11).

[In the general formula (10),
R _{11 to} R ₁₆ , X _{11 to} X ₁₄ , A, P, a, b, c, d, m, i, j, k, and l are defined in the same manner as in the general formula (1)]

[In the general formula (11),
R _{13 to} R ₁₆ , A, k and l are defined in the same manner as in the general formula (1)] The method for producing a compound according to claim 1, comprising a step of reacting the compound represented by the general formula (11) with a compound represented by the following general formula (12).

[In the general formula (12),
R _{11 to} X ₁₄ , P, a, b, c, d, m, i, j, k and l are defined in the same manner as in the general formula (1)]

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