JP5172321B2 - Liquid crystal sealant - Google Patents

Description

The present invention relates to a liquid crystal sealant .

  Epoxy resins and (meth) acrylate resins have high electrical insulation and are excellent in various properties such as adhesion, transparency, weather resistance, moldability, and workability. Therefore, it has been actively used as a component of polymerizable compositions for various industrial uses such as electronic insulating materials, sealing materials, paints, sizing agents, and adhesives (see Patent Documents 1 and 2). With the recent remarkable development of electronic and electrical equipment, the polymerizable composition is strongly required to improve various properties such as shortening the curing time, lowering the viscosity, or increasing the purity. Therefore, development of compounds capable of improving various characteristics of the polymerizable composition has been actively conducted.

  At present, a compound having both a (meth) acryloyl group and a glycidyl group, which is further added to a polymerizable composition mainly composed of an epoxy resin or a (meth) acrylic resin, has attracted attention. Since the compound has a (meth) acryloyl group and a glycidyl group introduced in the same molecule, it is highly compatible with any of the above resins. In addition, since the compound has two kinds of organic groups having different polymerizability in the molecule, the polymerization reaction proceeds in a stepwise manner. When the compound is added to the polymerizable composition, it is homogeneous and hardened. A polymerizable composition with less unevenness is obtained.

  Recently, with the remarkable development of liquid crystal display panels, the demand for liquid crystal sealants, which are polymerizable compositions mainly composed of epoxy resins and (meth) acrylic resins, has increased remarkably. The liquid crystal sealant is a main constituent member of a liquid crystal display panel mounted on a small electronic device such as a mobile phone or a large liquid crystal television, and has a structure in which liquid crystal is sealed between two glass substrates. Are used as an adhesive for encapsulating liquid crystals or for bonding glass substrates together.

  In the field of manufacturing liquid crystal display panels, a technique capable of manufacturing a high-quality liquid crystal display panel with high productivity is desired. As a method of manufacturing a liquid crystal display panel, there are a liquid crystal injection method and a liquid crystal dropping method, which are different in the liquid crystal sealing method. The liquid crystal injection method is a method for manufacturing a liquid crystal display panel by injecting liquid crystal into an empty liquid crystal cell sandwiched between two glass substrates and having a liquid crystal sealant arranged in a frame shape. 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 (for example, see Patent Document 3). ).

  However, the liquid crystal injection method is productive because of the long injection time of the liquid crystal and the necessity of high-temperature heat treatment at a temperature of 120 to 150 ° C. for several hours in order to cure the liquid crystal sealant. Lowness is regarded as a problem. Therefore, recently, a liquid crystal dropping method, which is expected to significantly improve the productivity compared with the liquid crystal injection method, has been attracting attention for the reason that the liquid crystal injection time can be shortened. The liquid crystal dropping method drops the liquid crystal display panel by bonding two glass substrates after dropping the liquid crystal in a frame formed of a liquid crystal sealant so as to surround the display area on the substrate or on the other substrate. It is a manufacturing method.

  By the way, in a liquid crystal display panel, the uncured component of the liquid crystal sealant may be eluted into the liquid crystal and the liquid crystal may be contaminated. When the liquid crystal is contaminated, the display property of the liquid crystal display panel is deteriorated, which causes a problem. The possibility that the liquid crystal is contaminated increases when the liquid crystal sealant contains a compound having high solubility in the liquid crystal or when the liquid crystal sealant has low curability and the uncured state continues for a long time. Further, if an uncured portion remains in the cured product of the liquid crystal sealant, not only the liquid crystal can be contaminated, but also the adhesive strength between the cured product and the substrate constituting the liquid crystal display panel is likely to decrease. . Therefore, in the liquid crystal dropping method, in order to cure the liquid crystal sealant in a short time without leaving an uncured portion, a method of irradiating light in addition to heat to the liquid crystal sealant has attracted attention. As a liquid crystal sealant used in such a liquid crystal dropping method, a light and thermosetting liquid crystal sealant has been proposed (see, for example, Patent Documents 4 and 5).

  However, as the liquid crystal display panel becomes higher definition and narrower and the wiring of the liquid crystal display panel becomes more complicated, uncured portions remain in the cured liquid crystal sealant. This is because if the wiring becomes complicated, the wiring and the seal pattern of the liquid crystal sealing agent overlap with each other and light is not sufficiently irradiated. Therefore, at present, there is a demand for a liquid crystal sealant that is cured in a short time and has a low possibility of contaminating the liquid crystal, and a compound that is a raw material for the liquid crystal sealant.

As a liquid crystal sealant suitable for a liquid crystal dropping method, a liquid crystal sealant containing a partially acrylated or methacrylated epoxy resin obtained by reacting a bisphenol A type epoxy resin with acrylic acid or methacrylic acid (for example, Patent Document 6) and a liquid crystal sealing agent that includes an acrylated epoxy resin having a (meth) acryl group and a hydroxyl group, and the number of the (meth) acryl groups is larger than the number of the hydroxyl groups (for example, (See 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, has high solubility in liquid crystal, and easily contaminates the liquid crystal. Moreover, since it was confirmed that the liquid crystal sealing agent containing the partially acrylated epoxy resin of Patent Document 6 and the acrylated epoxy resin of Patent Document 7 has low curability, both of these resins are liquid crystal sealants. It was revealed that it is not appropriate as a raw material for

  Further, in the liquid crystal sealant, high viscosity stability at room temperature is regarded as important. Usually, the operation of applying the liquid crystal sealant on the substrate is performed at room temperature. A liquid crystal sealant having a high viscosity stability at room temperature can easily form a seal pattern having a desired line width on a substrate, and the frequency of supply to a coating apparatus such as a dispenser is reduced. This is because it is possible to improve the yield at the time of manufacturing. However, the partially methacrylated epoxy resin is not suitable as a raw material for the liquid crystal sealant because the proper viscosity at room temperature is not maintained and the viscosity stability is low.

  Therefore, the present invention is homogeneous and has both high curability and viscosity stability when it is contained in a polymerizable composition mainly composed of an epoxy resin such as a liquid crystal sealant or a (meth) acrylic resin. It is an object of the present invention to provide a compound that can be prepared and a resin composition containing the compound.

  As described above, the present inventors paid attention to the high frequency with which an epoxy resin and a (meth) acrylic resin are used together in an industrial material such as a liquid crystal sealant. As a result of extensive studies, the inventors have found that the above problems can be solved by providing a compound having high reactivity and high compatibility with an epoxy resin and the like, and has completed the present invention.

前記一般式（１−ａ）中の、
Ｒ_１１は水素原子または炭素数１〜１０のアルキル基を表し、
ｎは１または２の整数を表す。

前記一般式（１−ｃ）中の、
Ｒ_１２は水素原子またはメチル基を表し、
Ｒ_１３は水素原子または炭素数１〜１０のアルキル基を表す。

［５］ 前記（メタ）アクリル酸誘導体（２）が、アクリル酸、メタクリル酸、下記の一般式（２−ａ）、または一般式（２−ｂ）で表される化合物である［１］から［４］いずれかに記載の化合物。

前記一般式（２−ａ）中の、
Ｒ_２１は水素原子またはメチル基を表し、
Ｘ_２１は炭素数１〜１０のアルキレン基または下記の一般式（３）で表される基を表し、
Ｘ_２２は炭素数１〜２０のアルキレン基または炭素数２〜６のアルケニレン基を表す。

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_３１は前記一般式（２−ａ）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（２−ｂ）中の、
Ｒ_４１およびＲ_４２はそれぞれ独立して水素原子またはメチル基を表し、
Ｘ_４１およびＸ_４２の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（４）で表される基を表し、
Ｘ_４３は炭素数１〜２０のアルキレン基または炭素数２〜６のアルケニレン基を表し、
ｉおよびｊはそれぞれ独立して０または１の整数を表す。

前記一般式（４）中の、
Ｙ_５１およびＹ_５２はそれぞれ独立して炭素数１〜１０のアルキレン基を表し、
ＣＯ基は前記一般式（２−ｂ）中のアクリロイル基のＯと結合する。 That is, the said subject is solved by the compound which has the (meth) acryloyl group and glycidyl group of this invention.
[1] (1) Ring opening of a part of the glycidyl group of the epoxy compound having 3 or 4 glycidyl groups in the molecule and (2) a part of the carboxyl group of the (meth) acrylic acid derivative having a carboxyl group A compound having a (meth) acryloyl group and a glycidyl group obtained by addition reaction.
[2] The compound according to [1], wherein the epoxy compound (1) has a number average molecular weight of 400 to 800.
[3] The compound according to [1] or [2], wherein the compound having a (meth) acryloyl group and a glycidyl group has a number average molecular weight of 800 to 1800.
[4] The epoxy compound (1) is a compound represented by the following general formula (1-a), (1-b), (1-c), (1-d) or (1-e). The compound according to any one of [1] to [3].

In the general formula (1-a),
R ₁₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
n represents an integer of 1 or 2.

In the general formula (1-c),
R ₁₂ represents a hydrogen atom or a methyl group,
R ₁₃ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[5] From [1], wherein the (meth) acrylic acid derivative (2) is a compound represented by acrylic acid, methacrylic acid, the following general formula (2-a), or general formula (2-b): [4] The compound according to any one of the above.

In the general formula (2-a),
R ₂₁ represents a hydrogen atom or a methyl group,
X ₂₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by the following general formula (3),
X ₂₂ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms.

In the general formula (3),
Y ₃₁ and Y ₃₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
Y ₃₁ is bonded to O of the acryloyl group in the general formula (2-a),
n represents an integer of 1 to 10.

In the general formula (2-b),
R ₄₁ and R ₄₂ each independently represents a hydrogen atom or a methyl group;
One of X ₄₁ and X ₄₂ represents an alkylene group having 1 to 10 carbon atoms, and the other represents a group represented by the following general formula (4);
X ₄₃ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms,
i and j each independently represents an integer of 0 or 1.

In the general formula (4),
Y ₅₁ and Y ₅₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
The CO group is bonded to O of the acryloyl group in the general formula (2-b).

Moreover, the said subject is solved by the polymeric composition containing the compound of this invention.
[6] A polymerizable composition comprising the compound having a (meth) acryloyl group and a glycidyl group according to any one of [1] to [5].

  According to the present invention, a compound having a (meth) acryloyl group and a glycidyl group in the molecule and having both high reactivity and high viscosity stability can be obtained. The compound is highly compatible with both the epoxy resin and the (meth) acrylic resin, and is cured in a short time while proceeding with different polymerization reactions stepwise. Therefore, a resin composition containing an epoxy resin or (meth) acrylic resin and the compound can achieve both high viscosity stability and high curability.

  Hereinafter, the present invention will be described in detail. In the present invention, the range of numerical values is indicated by “to”, and in this case, both end numbers are included. For example, “10 to 100” means “10 to 100”.

[Compound having (meth) acryloyl group and glycidyl group]
A compound having a (meth) acryloyl group and a glycidyl group (also referred to as “the compound of the present invention”) is (1) an epoxy compound having 3 or 4 glycidyl groups in the molecule (also simply referred to as an “epoxy compound”). (2) A compound obtained by ring-opening addition reaction of a part of carboxyl groups of a (meth) acrylic acid derivative having a carboxyl group.

(1) Epoxy compound having 3 or 4 glycidyl groups in the molecule “Epoxy compound having 3 or 4 glycidyl groups in the molecule” may be any compound having a predetermined number of glycidyl groups, It is not limited.

  It is preferable that the epoxy compound (1) has a number average molecular weight adjusted within a range of 400 to 800. When the said epoxy compound is used as a raw material of the compound of this invention, the solubility with respect to a liquid crystal is low, and a viscosity stability and a favorable compound are obtained. The number average molecular weight can be measured by gel permeation chromatography (GPC) using polystyrene as a standard, and can also be measured by electrolytic ionization mass spectrometry (FD-MS method).

  Preferred examples of the epoxy compound (1) include compounds represented by the following general formula (1-a), (1-b), (1-c), (1-d) or (1-e). included. One or more of these compounds may be used as the raw material for the compound of the present invention.

一般式（１−ａ）中の、
Ｒ_１１は水素原子または炭素数１〜１０のアルキル基を表し、
ｎは１または２の整数を表す。

In general formula (1-a),
R ₁₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
n represents an integer of 1 or 2.

一般式（１−ｃ）中の、
Ｒ_１２は水素原子またはメチル基を表し、
Ｒ_１３は水素原子または炭素数１〜１０のアルキル基を表す。

In general formula (1-c),
R ₁₂ represents a hydrogen atom or a methyl group,
R ₁₃ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ₁₁ in the general formula (1-a) and R ₁₃ in the general formula (1-c) represent an alkyl group having 1 to 10 carbon atoms. Preferred examples of the alkyl group include a methyl group, ethyl Group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, t-pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl Group and decyl group are included. Among _these, as _{R 11} and _{R 13,} a hydrogen atom, a methyl group, an ethyl group are preferable, more preferably a hydrogen atom.

  The epoxy compound represented by the general formula (1-a) may be a commercially available product or a newly synthesized product (synthetic product). Examples of the method for synthesizing the epoxy compound include a method in which an epihalohydrin is reacted with a trinuclear or tetranuclear compound of a novolak-type compound obtained by a condensation reaction of a phenol derivative and formalin according to a known epoxidation reaction. There is no particular limitation. Examples of the known epoxidation reaction include known methods for industrially producing existing epoxy compounds available as industrial raw materials. The compounds represented by the general formulas (1-b), (1-c), (1-d), and (1-e) may also be commercially available products or synthetic products.

(2) A (meth) acrylic acid derivative having a carboxyl group A (meth) acrylic acid derivative having a carboxyl group (sometimes simply referred to as a (meth) acrylic acid derivative) is a compound derived from (meth) acrylic acid. It is not particularly limited as long as it is a compound having a carboxyl group and a (meth) acryloyl group and capable of becoming (meth) acrylic acid. The (meth) acrylic acid derivative (2) may be acrylic acid or methacrylic acid. Among them, the (meth) acrylic acid derivative (2) is preferably a compound represented by acrylic acid, methacrylic acid, general formula (2-a) or general formula (2-b). The compounds of the present invention synthesized using these as raw materials are useful as raw materials for polymerizable compositions such as liquid crystal sealants because they have an appropriate viscosity and low solubility in liquid crystals.

前記一般式（２−ａ）中の、
Ｒ_２１は水素原子またはメチル基を表し、
Ｘ_２１は炭素数１〜１０のアルキレン基または下記の一般式（３）で表される基を表し、
Ｘ_２２は炭素数１〜２０のアルキレン基または炭素数２〜６のアルケニレン基を表す。

In the general formula (2-a),
R ₂₁ represents a hydrogen atom or a methyl group,
X ₂₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by the following general formula (3),
X ₂₂ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms.

Examples of the alkylene group having 1 to 10 carbon atoms preferable as X ₂₁ in the general formula (2-a) include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a cyclopentyl group. A len group, a hexamethylene group, a cyclohexylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group are included. Among these, X ₂₁ is preferably a C 2-6 alkylene group or a group represented by the formula (3).

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_３１は前記一般式（２−ａ）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 (3),
Y ₃₁ and Y ₃₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
Y ₃₁ is bonded to O of the acryloyl group in the general formula (2-a),
n represents an integer of 1 to 10.

Examples of preferable alkylene groups having 1 to 10 carbon atoms as Y ₃₁ and Y ₃₂ in the general formula (3) include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a cyclohexane group, A pentylene group, a hexamethylene group, a cyclohexylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group are included. Among these, an alkylene group having 2 to 6 carbon atoms is preferable. Moreover, although n in the said General formula (3) represents the integer of 1-10, the integer of 1-6 is preferable especially.

Examples of the alkylene group having 1 to 20 carbon atoms preferable as X ₂₂ in the general formula (2-a) include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a cyclopentyl group. Included are len group, hexamethylene group, cyclohexylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, nonamethylene group, dodecamethylene group, pentadecamethylene group, hexadecamethylene group, and octadecamethylene group. .

Examples of the alkenylene group having 2 to 6 carbon atoms that are preferable as X ₂₂ in the general formula (2-a) include —CH═CH— group, —CH═CH—CH ₂ — group, —CH═CH—CH. ₂ -CH ₂ - _{group, -CH 2 -CH = CH-CH} 2 - includes groups. Among them, as X ₂₂ , an alkylene group having 1 to 6 carbon atoms and a —CH═CH— group are preferable, and an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group, and A —CH═CH— group is more preferred.

前記一般式（２−ｂ）中の、
Ｒ_４１およびＲ_４２はそれぞれ独立して水素原子またはメチル基を表し、
Ｘ_４１およびＸ_４２の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（４）で表される基を表し、
Ｘ_４３は炭素数１〜２０のアルキレン基または炭素数２〜６のアルケニレン基を表し、
ｉおよびｊはそれぞれ独立して０または１の整数を表す。

In the general formula (2-b),
R ₄₁ and R ₄₂ each independently represents a hydrogen atom or a methyl group;
One of X ₄₁ and X ₄₂ represents an alkylene group having 1 to 10 carbon atoms, and the other represents a group represented by the following general formula (4);
X ₄₃ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms,
i and j each independently represents an integer of 0 or 1.

前記一般式（４）中の、
Ｙ_５１およびＹ_５２はそれぞれ独立して炭素数１〜１０のアルキレン基を表し、
ＣＯ基は前記一般式（２−ｂ）中のアクリロイル基のＯと結合する。

In the general formula (4),
Y ₅₁ and Y ₅₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
The CO group is bonded to O of the acryloyl group in the general formula (2-b).

Examples of preferable alkylene groups having 1 to 10 carbon atoms as Y ₅₁ and Y ₅₂ in the general formula (4) include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a cyclohexane group. A pentylene group, a hexamethylene group, a cyclohexylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group are included. In _particular, it is preferable _{Y 51} and _{Y 52} represents an alkylene group having 2 to 6 carbon atoms.

Examples of preferable alkylene groups having 1 to 10 carbon atoms as X ₄₁ and X ₄₂ in the general formula (2-b) include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group. , Cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, dodecamethylene group, pentadecamethylene group, hexadecamethylene group, octadecamethylene group. Among these, X ₄₁ and X ₄₂ are preferably an alkylene group having 2 to 6 carbon atoms or a group represented by the general formula (4).

Examples of the alkenylene group having 2 to 6 carbon atoms which are preferable as X ₄₃ in the general formula (2-b) include —CH═CH— group, —CH═CH—CH ₂ — group, —CH═CH—CH. ₂ -CH ₂ - _{group, -CH 2 -CH = CH-CH} 2 - includes groups. Among these, X ₄₃ is preferably an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group, or —CH═CH— group. It is more preferable that they are C1-C4 alkylene groups, such as a group, ethylene group, trimethylene group, tetramethylene group, and -CH = CH- group.

  Although the compound represented by the general formula (2-a) is industrially available, it can be easily produced by an esterification reaction as shown in the following schemes 1 to 3. Schemes 1 to 3 are esterification reactions of “a (meth) acrylic acid derivative having a hydroxy group” and “a compound having two carboxyl groups”. Examples of the carboxyl group also include groups that are precursors of carboxyl groups, such as acid halide groups and acid anhydride groups.

[Scheme 1]
As described below, the reaction of Scheme 1 is represented by a compound represented by the general formula (6) having two carboxyl groups (referred to as compound (6)) and a general formula (7) having a hydroxy group. This is a partial esterification reaction with a compound (referred to as compound (7)). The partial esterification reaction is a reaction in which only a part of a carboxyl group of a compound having a plurality of carboxyl groups in the molecule is esterified with a compound having a hydroxy group.

スキーム１中のＸ_２１、Ｘ_２２、Ｒ_２１は、前記一般式（２−ａ）と同様に定義される。

X ₂₁ , X ₂₂ and R _{21 in} Scheme 1 are defined in the same manner as in the general formula (2-a).

  In the reaction of Scheme 1, the compounding ratio of the compound (6) and the compound (7) is not particularly limited, but in order to finally obtain a compound having a carboxyl group as represented by the general formula (2-a) Is preferably less than the amount of compound (6) charged. Specifically, when the number of moles of the compound (6) is M1, and the number of moles of the compound (7) is M2, it is preferable that M1 / M2 ≧ 1. The compound represented by the general formula (2-a) may be simply referred to as the compound (2-a).

  Here, when the amount of compound (7) charged is larger than the total amount of compound (6), the esterification reaction proceeds excessively, and all carboxyl groups in compound (6) may be esterified. Becomes higher. In order to finally obtain the compound (2-a) leaving one carboxyl group, it is necessary to stop the esterification reaction at an appropriate stage, but it is not easy to stop the reaction accurately. . Therefore, in Scheme 1, it is preferable to appropriately adjust the charged amount of each compound.

  The reaction rate in Scheme 1 can be confirmed by known analytical means. When the esterification reaction proceeds while measuring the reaction rate, the final target product can be produced in an appropriate and high purification yield. Preferred examples of the analysis means include, but are not limited to, liquid chromatography, thin layer chromatography, and IR analyzer.

  A known esterification catalyst may be added to the reaction mixture of Scheme 1 from the viewpoint of promoting the reaction. An esterification catalyst refers to a catalyst that activates an esterification reaction between a carboxylic acid and an alcohol. Preferred examples of the esterification catalyst include mineral acids such as hydrochloric acid and sulfuric acid; organic acids such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; Lewis acids such as boron trifluoride and aluminum trichloride. .

  The amount of the esterification catalyst added to the reaction mixture is preferably 0.001 to 50% by mass and more preferably 0.01 to 30% by mass with respect to the total mass of the reaction mixture. However, the amount of the esterification catalyst is not particularly limited as long as it is sufficient to promote the partial esterification reaction.

  In the partial esterification reaction, water is generated during the reaction. In order to promote the partial esterification reaction, it is preferable to remove water as a by-product from the reaction mixture. The method for removing water is not particularly limited. For example, a solvent having a boiling point similar to that of water, such as benzene or toluene, is added to the reaction mixture and water is azeotroped with the solvent, or molecular sieves or the like. A method of adding a dehydrating agent into the reaction mixture is included.

  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 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; Ether solvents such as tetrahydrofuran or dioxane; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or perchlene are included. One or more of these solvents may be included in the reaction mixture of Scheme 1.

  The reaction temperature of Scheme 1 is not particularly limited as long as it is a temperature at which the partial esterification reaction can proceed efficiently and sufficiently within a short time. Among them, the reaction temperature is preferably 50 to 150 ° C, more preferably 70 to 120 ° C.

  The reaction time in Scheme 1 may be appropriately set according to the reaction temperature, the charged amounts of compounds (6) and (7), and is not particularly limited. In consideration of the progress of the partial esterification reaction, the reaction time is preferably in the range of several minutes to 100 hours, more preferably 0.5 to 50 hours, and more preferably 1 to 20 hours. It is particularly preferred.

[Scheme 2]
As shown below, the reaction of Scheme 2 has two acid halide groups and is represented by the general formula (8) (referred to as compound (8)), a compound having a hydroxy group (7), And a two-stage reaction in which the compound (2-a) is finally produced by hydrolyzing the acid halide group in the compound represented by the general formula (9) remaining in the reaction mixture. is there.

スキーム２中の、
Ｘ_２１、Ｒ_２１、Ｘ_２２は、前記一般式（２−ａ）と同様に定義され、
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）を表す。

In Scheme 2,
X ₂₁ , R ₂₁ and X ₂₂ are defined in the same manner as in the general formula (2-a),
COL represents an acid halide group, in which L represents halogen (Cl or Br).

  In the reaction of Scheme 2, the compounding ratio of the compound (7) and the compound (8) is not particularly limited, but in order to finally obtain a compound having a carboxyl group as represented by the compound (2-a) In the partial esterification reaction of Scheme 2, the amount of compound (7) charged is preferably less than or equal to the total amount of compound (8) charged. Specifically, when the number of moles of the compound (8) is M3 and the number of moles of the compound (7) is M4, it is preferable that M3 / M4 ≧ 1.

  Here, when the amount of the compound (7) charged is larger than the total amount of the compound (8), the partial esterification reaction proceeds excessively, and finally a compound having a carboxyl group can be obtained. It becomes difficult. In this case, it is necessary to stop the partial esterification reaction at a desired reaction rate, but it is not easy to stop the reaction accurately. Therefore, in Scheme 2, it is preferable to appropriately adjust the charged amount of each compound.

  The reaction rate of Scheme 2 can be confirmed by a known analytical means. When the partial esterification reaction or the like proceeds while measuring the reaction rate, the final target product can be produced in a suitable and high purification yield. Examples of the analysis means include, but are not limited to, liquid chromatography, thin layer chromatography, or IR analysis apparatus.

  The partial esterification reaction may be performed in the absence of a solvent or in a solvent inert to such a reaction. Examples of 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 Ether solvents such as tetrahydrofuran or dioxane; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or perchlene. One or more of these solvents may be used in the reaction mixture of Scheme 2.

  In the partial esterification reaction, a hydrogen halide (for example, hydrogen chloride) is generated as a by-product by a reaction between an acid halogen group and a hydroxy group. Such hydrogen halide is preferably removed from the reaction mixture as much as possible because it may 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. Among them, it is useful to add a dehydrohalogenating agent in the reaction of Scheme 2 as a method for removing hydrogen halide because of its features such as high workability and easy handling.

  Preferable examples of the dehydrohalogenating agent include organic base compounds or inorganic base compounds. Examples of the organic base compound include triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo [2.2.2] octane (DABCO), and 1,8-diazabicyclo [5.4.0]. ] Undec-7-ene (DBU) is included. Examples of inorganic base compounds include sodium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium oxide. One or two or more of these compounds may be added to the reaction mixture of Scheme 2.

  The amount of the dehydrohalogenating agent added is not particularly limited as long as it is sufficient to remove the hydrogen halide formed in the reaction mixture. Especially, it is preferable that the addition amount of a dehydrohalogenating agent is 0.1-10 mol with respect to 1 mol of hydroxy groups, It is more preferable that it is 0.5-5 mol, It is 1-3 mol. It is particularly preferred.

  In Scheme 2, the second stage hydrolysis reaction is performed by adding water to the reaction mixture after the partial esterification reaction is completed. The procedure for adding water to the reaction mixture after completion of the partial esterification reaction is not particularly limited, and water may be added all at once or may be added dropwise. From the viewpoint of gradually progressing the reaction, the latter method by dropping is preferred. The amount of water added to the reaction mixture to cause hydrolysis is preferably 1 to 100 mol, preferably 5 to 50 mol, per 1 mol of acid halide groups remaining in the reaction mixture. More preferred.

  In the hydrolysis reaction, when the water is dropped, the reaction rate in the reaction mixture is confirmed by a known analysis means, and the hydrolysis can be stopped when the desired reaction rate is reached. Examples of analytical means include liquid chromatography, thin layer chromatography, and IR analyzers.

  Although the reaction temperature of Scheme 2 is not particularly limited, from the viewpoint of promoting a reaction such as a partial esterification reaction, the reaction temperature is preferably −78 to 150 ° C., more preferably −20 to 100 ° C. 0 to 80 ° C. is particularly preferable.

  The reaction time in Scheme 2 may be appropriately set according to the reaction temperature, the charged amounts of compounds (7) and (8), and is not particularly limited. From the viewpoint of promoting the reaction, the reaction time is preferably from several minutes to 100 hours, more preferably from 0.5 hours to 50 hours, and particularly preferably from 1 to 20 hours. When the reaction time is 1 to 20 hours, the reaction can be promoted without reducing productivity.

[Scheme 3]
As shown below, the reaction of Scheme 3 is a ring-opening esterification of a compound represented by general formula (10) having an acid anhydride group (referred to as compound (10)) and a compound having a hydroxy group (7). It is a reaction. Since the reaction of Scheme 3 is a ring-opening esterification reaction, the compound (2-a) in which the carboxyl group remains is easily obtained. Therefore, as a manufacturing method of a compound (2-a), it is the most preferable in the schemes 1-3.

スキーム３中の、
Ｘ_２１、Ｒ_２１、Ｘ_２２は、前記一般式（２−ａ）と同様に定義される。

In Scheme 3,
X ₂₁ , R ₂₁ and X ₂₂ are defined in the same manner as in the general formula (2-a).

  In the ring-opening esterification reaction, the compounding ratio of the acid anhydride group and the hydroxy group is not particularly limited, but from the viewpoint of promoting the ring-opening esterification reaction, the amount of the compound (7) having a hydroxy group is charged, It is preferable to set it as 0.1-10 mol with respect to 1 mol of compounds (10) which have an acid anhydride group, It is more preferable to set it as 0.5-5 mol, It is set as 0.8-3 mol. Is particularly preferred.

  The ring-opening esterification reaction may be performed in the absence of a solvent or in a solvent inert to the reaction. Examples of the solvent include a hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, a halogen solvent, and a polar solvent, but are not particularly limited.

  Examples of the hydrocarbon solvent include n-hexane, benzene, toluene or xylene. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester solvent include ethyl acetate or butyl acetate. Examples of the ether solvent include diethyl ether, tetrahydrofuran or dioxane. Examples of the halogen-based solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or perchlene. Examples of the polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. One or more of these solvents may be used in the reaction mixture of Scheme 3.

  A catalyst for activating the reaction may be added to the reaction mixture of Scheme 3 as necessary. Examples of the catalyst include organic phosphine compounds, tertiary amines, quaternary ammonium salts, organic phosphorus salts, imidazoles, and organometallic compounds.

  Examples of the organic phosphine compound include triphenylphosphine. Examples of compounds corresponding to the tertiary amines include triethylamine and triethanolamine. Examples of the compounds corresponding to the quaternary ammonium salts include trimethylammonium chloride and triethylbenzylammonium chloride. Examples of the compound corresponding to the organic phosphorus salt include tetrabutylphosphonium bromide and tetraphenylphosphonium bromide. Examples of the compound corresponding to the imidazoles include 2-methylimidazole. Examples of the organometallic compound include cobalt octenoate. One or more of these compounds may be added to the reaction mixture of Scheme 3.

  The amount of the catalyst added to the reaction mixture is preferably in the range of 0.01 to 10.0% by mass with respect to the mass of the reaction mixture from the viewpoint of obtaining a sufficient reaction rate, It is more preferable to set it as 5.0 mass%.

  The reaction temperature of Scheme 3 is not particularly limited as long as it is a temperature at which the ring-opening esterification reaction can proceed efficiently and sufficiently within a short time. Especially, it is preferable to set the said reaction temperature to 0-200 degreeC, and it is more preferable to set it as 0-150 degreeC.

  The reaction time in Scheme 3 may be appropriately set according to the reaction temperature, the charged amounts of compounds (7) and (10), and is not particularly limited. From the viewpoint of allowing the ring-opening esterification reaction to proceed efficiently and effectively, the reaction time is preferably several minutes to several tens of hours.

  In Scheme 3, the reaction may be stopped by advancing the reaction to a desired reaction rate while confirming the reaction rate by a known analysis means. Examples of the analysis means include, but are not limited to, liquid chromatography, thin layer chromatography, and IR analysis apparatus.

[Compound represented by formula (2-b)]
On the other hand, the compound represented by the general formula (2-b) (referred to as the compound (2-b)) is obtained by converting the compound (7) used as a raw material in the reactions of the above-mentioned schemes 1 to 3 to the following general formula (11). And a (meth) acryloyl derivative having a hydroxy group represented by (referred to as compound (11)).

前記一般式（１１）中の、
Ｒ_４１、Ｒ_４２、Ｘ_４１、Ｘ_４２、ｉおよびｊは、前記一般式（２−ｂ）と同様に定義される。

In the general formula (11),
R ₄₁ , R ₄₂ , X ₄₁ , X ₄₂ , i and j are defined in the same manner as in the general formula (2-b).

[Scheme 4]
A synthesis example of the compound (11) is described in Scheme 4. As shown below, the reaction of Scheme 4 has a glycidyl ether group and a compound represented by the general formula (12) (referred to as compound (12)), a hydroxy group and the general formula ( 13) a ring-opening esterification reaction with a compound represented by 13) (referred to as compound (13)).

スキーム４中の、
Ｘ_４１、Ｘ_４２、Ｒ_４１、Ｒ_４２、ｊ、ｉは、それぞれ前記一般式（２−ｂ）と同様に定義される。

In Scheme 4,
X ₄₁ , X ₄₂ , R ₄₁ , R ₄₂ , j, i are defined in the same manner as in the general formula (2-b).

  The ring-opening esterification reaction of Scheme 4 may be performed in the absence of a solvent or in a solvent inert to such reaction. Examples of 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; dichloromethane, chloroform Halogen solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane Is included. One or more of these solvents may be used in the reaction mixture of Scheme 4.

  In the ring-opening esterification reaction, a catalyst that activates the reaction may be added as necessary. Examples of such catalysts include organic phosphine compounds such as triphenylphosphine; tertiary amines such as triethylamine triethanolamine; quaternary ammonium salts such as trimethylammonium chloride and triethylbenzylammonium chloride; tetrabutylphosphonium bromide And organophosphorus salts such as tetraphenylphosphonium bromide; imidazoles such as 2-methylimidazole; and organometallic compounds such as cobalt octenoate. One or more of these solvents may be added to the reaction mixture of Scheme 4.

  The addition amount of the catalyst is preferably 0.01 to 10.0% by mass with respect to the total mass of the reaction mixture in Scheme 4, 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 activation catalysts are added, the total addition amount thereof is regarded as the addition amount of the catalyst.

  The reaction temperature in Scheme 4 is not particularly limited as long as it is a temperature at which the ring-opening esterification reaction can proceed efficiently and sufficiently within a short time. Especially, it is preferable to set the said reaction temperature to 0-200 degreeC, and it is more preferable to set it as 0-150 degreeC.

  The reaction time of Scheme 4 may be set as appropriate according to the reaction temperature, the charged amounts of the compounds (12) and (13), or the added amount or combination of a solvent or a catalyst, and is not particularly limited. From the viewpoint of sufficiently proceeding with this ring-opening esterification reaction, the reaction time is preferably several minutes to several tens of hours.

  In scheme 4, the reaction may be stopped at an arbitrary reaction rate while the reaction rate is confirmed by a known analysis means. Preferred examples of the analysis means include, but are not limited to, liquid chromatography, thin layer chromatography, and IR analyzer.

  Next, specific examples of the compound represented by the general formula (2-a) are shown in Tables 1 to 5, respectively.

  Specific examples of the compound represented by the general formula (2-b) are shown in Tables 6 to 14, respectively.

  Next, the manufacturing method of the compound of this invention is demonstrated. The method for producing the compound of the present invention is not particularly limited as long as it is a method capable of ring-opening addition reaction between the epoxy compound (1) and the (meth) acrylic acid derivative (2) as described above. A preferred synthesis example of the compounds of the present invention is illustrated in Scheme 5.

[Scheme 5]
The reaction of Scheme 5 includes a compound represented by the general formula (1-a) ′ in which n is 1 in the compound (1-a), and a compound (2-a) of a (meth) acrylic acid derivative having a carboxyl group. ) Are successively ring-opening esterified. Such a sequential ring-opening esterification reaction proceeds until a compound of the general formula (15) (referred to as compound (15)) as the final target product is produced. Compound (15) is one of the compounds of the present invention having both a glycidyl group and a (meth) acryloyl group in the molecule.

スキーム５中の、
Ｒ_１１は、前記一般式（１−ａ）と同様に定義され、
Ｒ_２１、Ｘ_２１、およびＸ_２２は、前記一般式（１−ａ）および一般式（２−ａ）と同様に定義される。

In Scheme 5,
R ₁₁ is defined in the same manner as in the general formula (1-a),
R ₂₁ , X ₂₁ , and X ₂₂ are defined in the same manner as in the general formula (1-a) and the general formula (2-a).

  The compound of the present invention has a (meth) acryloyl group showing latent curability and a highly reactive glycidyl group in the molecule like the compound (15). Therefore, the compound is highly compatible with (meth) acrylic resins and epoxy resins. Moreover, although the said compound has low reactivity at room temperature, its viscosity stability is kept high, but shows high reactivity by heating or irradiating light.

  Therefore, when a polymerizable composition is prepared by using the compound in combination with a (meth) acrylic resin or an epoxy resin, a homogeneous polymerizable composition having high viscosity stability at room temperature and high curability by heat or light. Is obtained. The liquid crystal sealant containing the compound easily forms a seal pattern having a desired line width on a substrate at room temperature. In addition, since the liquid crystal sealant has a stable viscosity for a long time in a coating apparatus such as a dispenser, the frequency of replacing the liquid crystal sealant in the coating apparatus is low. Further, since the liquid crystal sealing agent is cured in a short time, the manufacturing time of the liquid crystal display panel is shortened.

  The number average molecular weight of the compound of the present invention is preferably in the range of 800 to 1800. Such a compound has low solubility in liquid crystals while maintaining an appropriate viscosity. Therefore, the liquid crystal sealant containing the compound has high applicability and is good, and can be a high-quality liquid crystal sealant that hardly contaminates the liquid crystal.

  However, when the compound according to the present invention is a low molecular weight substance having a number average molecular weight of less than 800, the solubility in the liquid crystal is increased. Therefore, the liquid crystal sealing agent containing the compound tends to contaminate the liquid crystal. On the other hand, if the compound of the present invention is a high molecular weight product so that the number average molecular weight exceeds 1,800, the viscosity becomes high. Therefore, the liquid crystal sealant containing the compound has low applicability to the substrate, and only a liquid crystal sealant that is difficult to form a seal pattern having a desired shape can be obtained.

  The number average molecular weight of the compound can be easily adjusted by using an epoxy compound (1) having an appropriate molecular weight as a raw material. The number average molecular weight can be measured by gel permeation chromatography (GPC) using polystyrene as a standard, and can also be measured by electrolytic ionization mass spectrometry (FD-MS method).

  Reaction conditions such as the amount of raw material charged, reaction time, or reaction temperature involved in the reaction of Scheme 5 will be described. The compounding ratio of the compound (1-a) ′ that is the epoxy compound (1) and the compound (2-a) that is the (meth) acrylic acid derivative (2) is not particularly limited. However, in Scheme 5, since it is necessary to generate compounds (14) and (15) having a glycidyl group in the molecule, the amount of compound (2-a) charged is less than that of compound (1-a) ′. It is preferable. Specifically, the amount of compound (1-a) ′ charged is preferably 1 to 2.8 mol, and preferably 1.3 to 2.5 mol, per 1 mol of compound (2-a). It is more preferable.

  Here, when the amount of compound (2-a) charged is larger than the total amount of compound (1-a) ′, all three glycidyl groups in compound (1-a) ′ react with carboxyl groups. The compound represented by the following general formula (16) (referred to as compound (16)) is likely to be produced. Although the compound (16) has low solubility in the liquid crystal, it does not have a highly reactive glycidyl group and there is a concern about low curability. Therefore, the compound (16) is polymerizable such as a liquid crystal sealant. It is not suitable as a component of the composition. However, even if the final product in the reaction of Scheme 5 contains the compound (16) as a by-product, the characteristics of the polymerizable composition are not significantly impaired, and this is not a problem.

前記一般式（１６）中の、
Ｘ_２１は、前記一般式（１−ａ）と同様に定義され、
Ｘ_２２、Ｒ_１１、Ｒ_２１は、前記一般式（２−ａ）と同様に定義される。

In the general formula (16),
X ₂₁ is defined in the same manner as in the general formula (1-a),
X ₂₂ , R ₁₁ and R ₂₁ are defined in the same manner as in the general formula (2-a).

  When the amount of compound (2-a) charged is larger than the total amount of compound (1-a) ′ as described above, not all glycidyl groups in compound (1-a) ′ are allowed to react. It is necessary to stop the ring-opening esterification reaction. However, it is not easy to accurately stop the ring-opening esterification reaction at a desired reaction rate. Therefore, in the reaction of Scheme 5, it is preferable to appropriately adjust the amount of each compound charged.

  The sequential ring-opening esterification reaction 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, 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- Polar solvents such as dimethyl imidazolidinone, dimethyl sulfoxide, sulfolane are included. One or more of these solvents may be used in the reaction mixture.

  In the sequential ring-opening esterification reaction, a catalyst for activating the reaction may be added to the reaction mixture as necessary. Examples of such 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 Organic phosphorus salts such as bromide and tetraphenylphosphonium bromide; imidazoles such as 2-methylimidazole; and organometallic compounds such as cobalt octenoate.

  The addition amount of the catalyst in the reaction of Scheme 5 is preferably 0.01 to 10.0% by mass with respect to the total mass in the reaction mixture from the viewpoint of obtaining a sufficient reaction rate, It is more preferable to set it as 5.0 mass%.

  In the reaction of Scheme 5, a polymerization inhibitor may be added to the reaction mixture from the viewpoint of suppressing the reaction from proceeding excessively. A polymerization inhibitor means a compound that acts to suppress or stop polymerization. Examples of preferable polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, phenothiazine, pt-butylcatechol, p-benzoquinone, and naphthoquinone, but are not particularly limited. Moreover, this polymerization inhibitor can be used similarly in the above-mentioned schemes 1 to 4.

  The reaction temperature in Scheme 5 is not particularly limited as long as it is a temperature at which the ring-opening esterification reaction can proceed efficiently and sufficiently within a short time. Especially, it is preferable to set reaction temperature to 0-200 degreeC, and it is more preferable to set it as 0-150 degreeC. Further, the reaction time of Scheme 5 may be appropriately determined according to the reaction temperature, the charged amount of the compounds (1-a) ′ and (2-a), or the conditions such as the type and combination of the solvent and catalyst, There is no particular limitation. Among these, from the viewpoint of promoting the reaction, the reaction time is preferably several minutes to several tens of hours.

  The reaction of Scheme 5 may be stopped by advancing the reaction at an arbitrary reaction rate while confirming the reaction rate by a known analytical means such as liquid chromatography, thin layer chromatography, or IR. In Scheme 5, the compounds represented by the above (1-b), (1-c), and (1-d) may be appropriately selected and used instead of the compound (1-a) ′. Good.

  Next, specific examples of the liquid crystal sealant containing the compound of the present invention will be described. The liquid crystal sealant comprises (i) a compound of the present invention, (ii) a thermal latent curing agent, (iii) an epoxy resin, (iv) an acrylic compound, (v) a photo radical polymerization initiator, (vi) a filler. Etc. may be included. Moreover, you may contain well-known (vii) other additives, such as a silane coupling agent, as needed.

(Ii) Thermal latent curing agent A thermal latent curing agent is a functional group (epoxy group, etc.) of an epoxy resin under normal storage conditions (room temperature, under visible light, etc.) even when mixed with a main agent such as an epoxy resin. Although it does not react with a compound, it is a compound that reacts with a functional group to cure an epoxy resin when irradiated with heat or light.

  By including a thermal latent curing agent in the liquid crystal sealant, the viscosity stability of the liquid crystal sealant at room temperature is improved. Therefore, in order to draw a seal pattern on the substrate, a liquid crystal sealant filled in a screen printing machine or the like can be stably used for a long time. Thus, when the pot life of the liquid crystal sealant is increased, the productivity for manufacturing the liquid crystal display panel can be improved.

  The thermal latent curing agent is preferably a thermal latent epoxy curing agent that acts as a curing accelerator for the compound of the present invention and the epoxy resin (iii) described later. The heat latent epoxy curing agent refers to a compound that contributes to curing by reacting with a functional group of the epoxy resin by applying heat, although the reactivity at room temperature is low. The heat latent epoxy curing agent is not particularly limited, and a compound known as a heat latent epoxy curing agent can be used.

  Among these, from the viewpoint of obtaining a high-density crosslinked structure, an amine-based thermal latent curing agent having an amino group in the molecule is preferable. Preferable examples of the amine heat latent curing agent include, but are not limited to, organic acid dihydrazide compounds, imidazole and derivatives thereof, dicyandiamide, aromatic amines, epoxy-modified polyamines and polyaminoureas. One or two or more of these compounds may be added to the liquid crystal sealant.

  Further, the heat latent epoxy curing agent is particularly preferably one having a melting point or a softening point temperature by the ring and ball method of 100 ° C. or higher. This is because the liquid crystal sealant containing the thermal latent epoxy curing agent has very high viscosity stability at room temperature, and the pot life in manufacturing a liquid crystal display panel is further increased.

  Examples of the amine thermal latent curing agent having a melting point or a softening point temperature by the ring and ball method of 100 ° C. or higher include dicyandiamides, organic acid dihydrazides, and imidazole derivatives. Examples of compounds corresponding to the dicyandiamides include dicyandiamide (melting point 209 ° C.). Examples of the organic acid dihydrazide include adipic acid dihydrazide (melting point 181 ° C.) and 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (melting point 120 ° C.). Examples of the imidazole derivatives include 2,4-diamino-6- [2′-ethylimidazolyl- (1 ′)]-ethyltriazine (melting point: 215 to 225 ° C.), 2-phenylimidazole (melting point: 137 to 147 ° C.) Is included. It is preferable that the heat latent curing agent is highly purified by a water washing method, a recrystallization method, or the like. One or two or more of these compounds may be added to the liquid crystal sealant.

  The blending amount of the thermal latent curing agent is preferably 1 to 25 parts by mass and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. When the blending amount of the thermal latent curing agent is within the above range, a liquid crystal sealant having both high viscosity stability and curability can be obtained. The liquid crystal sealant can provide a liquid crystal display panel having high adhesion strength between the cured product of the liquid crystal sealant and the substrate and good adhesion reliability.

  A liquid crystal sealant containing such a heat latent curing agent is useful as a one-pack type because of its high storage stability. High storage stability means that the curing reaction hardly proceeds even when the liquid crystal sealant is stored at room temperature or lower. Specifically, it means that the increase rate of the viscosity when the liquid crystal sealant is stored at 25 ° C. for 5 days is about twice or less the viscosity of the liquid crystal sealant before storage. One-pack type liquid crystal sealant is composed of main components such as epoxy resin and curing accelerator components such as thermal latent curing agent, which are mixed in the pre-use stage, eliminating the need for mixing during use. Good and good.

(Iii) Epoxy resin The epoxy resin of the present invention refers to a compound having at least one epoxy group in the molecule but not having a (meth) acryloyl group. Examples of the epoxy resin include aromatic polyvalent glycidyl ether compounds, novolac type polyvalent glycidyl ether compounds, and glycidyl ether compounds.

  Examples of the aromatic polyvalent glycidyl ether compound include compounds obtained by reaction of aromatic diols and diols obtained by modifying them with various glycols and epichlorohydrin. Specific examples of the aromatic polyvalent glycidyl ether 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.

  Examples of the novolac type polyvalent glycidyl ether compound include compounds obtained by the reaction of a compound corresponding to polyphenols typified by polyalkenylphenol and copolymers thereof with epichlorohydrin. Examples of the glycidyl ether compound include a xylylene phenol resin.

  Among them, as the epoxy resin (iii), cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, triphenolmethane type epoxy resin, triphenolethane type epoxy resin, trisphenol Type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, and acrylic rubber-modified epoxy resin are preferable, and acrylic rubber-modified epoxy resin is particularly preferable. These epoxy resins may be used alone or in combination of two or more. The epoxy resin is preferably a resin that has been purified by a molecular distillation method or the like and from which impurities have been removed.

  The epoxy resin (iii) preferably has a softening point temperature measured by the ring and ball method of 40 ° C. or higher, and more preferably has a weight average molecular weight of 1000 to 10,000. The epoxy resin has low solubility and diffusibility in liquid crystals. Therefore, the liquid crystal sealant containing the epoxy resin is optimal for manufacturing a liquid crystal display panel with good display properties. The weight average molecular weight of the epoxy resin can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard.

  It is preferable to set it as 5-50 mass parts with respect to 100 mass parts of liquid crystal sealing agents, and, as for the compounding quantity of an epoxy resin, it is more preferable to set it as 10-30 mass parts. The liquid crystal sealant containing such an amount of epoxy resin is excellent in heat resistance. On the other hand, when the blending amount is less than 5 parts by mass or exceeds 50 parts by mass, the heat resistance of the liquid crystal sealant may be lowered.

(Iv) Acrylic Compound An acrylic compound refers to a compound having one or more acrylic groups in the molecule (excluding the compound of the present invention). A liquid crystal sealant containing an acrylic compound has high water resistance. Therefore, when applied to the manufacture of 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 increased, and a high-quality liquid crystal display panel excellent in moisture resistance reliability can be obtained.

  Examples of acrylic compounds also include (meth) acrylic resins such as acrylate and / or methacrylate monomers, or oligomers thereof. Although the compound mentioned later is contained in the preferable example of an acryl compound, it is not specifically limited.

  Examples of acrylic compounds include diacrylates and / or dimethacrylates such as polyethylene glycol, propylene glycol, polypropylene glycol; tris (2-hydroxyethyl) isocyanurate diacrylate and / or dimethacrylate; 4 per mole of neopentyl glycol. Diacrylate and / or dimethacrylate of diol obtained by adding at least 1 mole of ethylene oxide or propylene oxide; Diacrylate and / or diacrylate of diol obtained by adding 2 mole of ethylene oxide or propylene oxide to 1 mole of bisphenol A Methacrylate: Diol of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane Triacrylate and / or di- or trimethacrylate; Diacrylate and / or dimethacrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A; Tris (2-hydroxyethyl) isocyanurate triacrylate And / or trimethacrylate; trimethylolpropane triacrylate and / or trimethacrylate, or oligomer thereof; pentaerythritol triacrylate and / or trimethacrylate, or oligomer thereof; polyacrylate and / or polymethacrylate of dipentaerythritol; Loxyethyl) isocyanurate; caprolactone-modified tris (acryloxyethyl) isocyanate Caprolactone-modified tris (methacryloxyethyl) isocyanurate; alkyl-modified dipentaerythritol polyacrylates and / or polymethacrylates; caprolactone-modified dipentaerythritol polyacrylates and / or polymethacrylates; hydroxypivalate neopentyl glycol diacrylate and Caprolactone modified hydroxypivalate neopentyl glycol diacrylate and / or dimethacrylate; ethylene oxide modified phosphate acrylate and / or dimethacrylate; ethylene oxide modified alkylated phosphate acrylate and / or dimethacrylate; neopentyl glue Cole, trimethylolpropane, pentaerythrito And oligoacrylates and / or oligomethacrylates. You may add 1 type, or 2 or more types among these acrylic compounds.

  Examples of the acrylic compound (iv) include a (meth) acryl-modified epoxy resin. The (meth) acryl-modified epoxy resin is an epoxy resin having one or two glycidyl groups in the molecule, and part or all of the epoxy group is (meth) acrylated, and one or more acrylic groups in the molecule Refers to a compound into which is introduced. Since the (meth) acryl-modified epoxy resin is highly compatible with the epoxy resin and the acrylic resin, the compatibility of the compound of the present invention with the epoxy resin and the acrylic resin is not lowered. Therefore, the liquid crystal sealant to which the (meth) acryl-modified epoxy resin is added becomes a homogeneous liquid crystal sealant.

The (meth) acryl-modified epoxy resin refers to a resin obtained by modifying a known epoxy resin with a (meth) acryl compound such as (meth) acrylate acid or phenyl methacrylate. The modification can be easily performed under a catalyst such as a basic catalyst. Examples of epoxy resins used as raw materials for (meth) acryl-modified epoxy resins include cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and triphenolmethane type epoxy resins. , Triphenolethane type epoxy resin, trisphenol type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin are included, but are not particularly limited.
From the viewpoint of obtaining a liquid crystal sealant with high purity, the acrylic compound is preferably highly purified by a molecular distillation method, a cleaning method, or the like.

  The acrylic compound (iv) is preferably contained in the liquid crystal sealant together with the epoxy resin (iii). At this time, it is preferable that the addition amount of epoxy resin (iii) is 20-200 mass parts with respect to 100 mass parts of acrylic compounds (iv). When such a liquid crystal sealant is irradiated with light or heat, the glass transition temperature (Tg) is high, and a stable cured product can be obtained even at high temperatures. The Tg of the cured product can be measured with a dynamic viscoelasticity measuring device (DMA).

(V) Photoradical polymerization initiator The photoradical polymerization initiator of the present invention means a compound that is activated by absorbing light energy to generate radicals. The radical photopolymerization initiator is not particularly limited, and a known compound can be used as the radical photopolymerization initiator.

  Examples of radical photopolymerization initiators include benzoins, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxides Compounds, organic dye compounds, iron-phthalocyanine compounds, benzoins, benzoin ethers and anthraquinones.

  When preparing a photocurable liquid crystal sealant, the content of the photo radical polymerization initiator in the liquid crystal sealant is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. When the content of the radical photopolymerization initiator is 0.01 parts by mass or more, the liquid crystal sealing agent can be cured by light irradiation for a short time. Moreover, the liquid crystal sealing agent in which the content of the radical photopolymerization initiator is 5 parts by mass or less has high applicability, and a cured product that is uniformly cured without unevenness can be obtained. On the other hand, when a photocurable liquid crystal sealant is not prepared, it is not necessary to contain a photoradical polymerization initiator.

(Vi) Filler Filler is added for the purpose of improving the adhesive 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 the linear expansion. Refers to the filler.

  The filler is not particularly limited as long as a known filler is used. 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 long as the filler is within the range that does not impair the properties of the liquid crystal sealant, polymethyl methacrylate, polystyrene, copolymers obtained by copolymerizing monomers and other monomers, polyester fine particles, polyurethane fine particles, It may be a known organic filler such as rubber fine particles.

  Among them, inorganic fillers are preferable from the viewpoint of improving the linear expansion coefficient and shape retention, and silicon dioxide and talc are particularly preferable because of high UV transmittance. The filler may be graft-modified with an epoxy resin or a silane coupling agent regardless of inorganic or organic. 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 amount of filler contained in the liquid crystal sealant 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. The liquid crystal sealant is excellent in application property to the substrate and the adhesive strength between the cured liquid crystal sealant and the substrate constituting the liquid crystal display panel.

(Vii) Other additives The liquid crystal sealant is optionally combined with the above-described components together with 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, It may contain additives such as dyes, plasticizers and antifoaming agents. Further, the liquid crystal display panel may include a spacer for ensuring a space between liquid crystal cells formed between two substrates.

  The liquid crystal sealant includes a photocuring type that is cured by light, a thermosetting type that is cured by heat, or a combined type that is cured by using both light and heat. The compound of the present invention may be contained in any type of liquid crystal sealant.

  The thermosetting liquid crystal sealing agent may contain a known organic solvent from the viewpoint of improving the applicability by a screen printer or the like. The thermosetting liquid crystal sealant is precured at a temperature of 50 to 100 ° C. after a seal pattern is formed on one of the two substrates constituting the liquid crystal display panel and before being bonded to the other substrate. A liquid crystal sealant. Examples of such organic solvents include ketone solvents such as cyclohexanone; ether solvents such as diethylene glycol dimethyl ether, methyl carbitol, ethyl carbitol, and butyl carbitol; acetates such as diethylene glycol diacetate and alkoxydiethylene glycol monoacetate. Solvent; Toluene and hexane are included. One or two or more of these organic solvents may be used for the liquid crystal sealant.

  The content of the organic solvent is preferably 20% or less, more preferably 10% or less, with respect to the total mass of the liquid crystal sealant. The liquid crystal sealant has high applicability, and since the organic solvent hardly remains in the cured product obtained from the liquid crystal sealant, a liquid crystal display panel having high display properties can be obtained.

[Method for preparing liquid crystal sealant]
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. The machine can be appropriately selected and used. The liquid crystal sealant suitably mixed by any method is filtered through a filter to remove impurities. The liquid crystal sealant from which impurities have been removed is subjected to vacuum defoaming treatment, and then sealed in glass bottles and plastic containers, and stored and transported as necessary.

[Method of manufacturing liquid crystal display panel]
The polymerizable composition containing the compound 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 to the liquid crystal sealing agent of a liquid crystal dropping construction 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 of manufacturing the liquid crystal display panel is not particularly limited.

  A liquid crystal injection method, which is a common method for manufacturing a liquid crystal display panel, first applies a liquid crystal sealant on a glass substrate constituting the liquid crystal display panel, and then pre-cures the liquid crystal sealant by precuring treatment; The other glass substrate is bonded so as to face the glass substrate, and then the glass substrates are heated and pressed together; a vacuum is formed in an empty liquid crystal cell having an inlet formed between the two glass substrates. A liquid crystal display panel is manufactured by injecting liquid crystal therein; and sealing the injection port with a sealing agent or the like.

  In addition, the liquid crystal dropping method first prepares one or more substrates having a frame-like display area formed so that the pixel array area is surrounded by a liquid crystal sealant; in the display area in an uncured state Or a liquid crystal is dropped on the other substrate; after the substrate on which the liquid crystal is dropped and the other substrate are overlapped; light and heat are applied to the liquid crystal sealant sandwiched between the two substrates. Or a method for producing a liquid crystal display panel by curing a liquid crystal sealant by applying either light or heat.

  Regardless of the method for producing the liquid crystal display panel, the liquid crystal sealant of the present invention containing the compound of the present invention has latent curability and maintains an appropriate viscosity at room temperature, and thus is 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.

[Example 1]
In Example 1, as the epoxy compound (1), a phenol novolac type trifunctional epoxy resin corresponding to the compound represented by the general formula (1-a), and methacrylic acid as the (meth) acrylic acid derivative (2) and Then, a (meth) acrylic acid derivative having a carboxyl group was reacted to synthesize a compound A4 having a (meth) acryloyl group and a glycidyl group. The (meth) acrylic acid derivative having the carboxyl group was Compound A1 synthesized in Synthesis Example 1 described later. Compound A1 corresponds to compound 2-3 described in Table 1 above.

A phenol novolak type trifunctional corresponding to the compound represented by the general formula (1-a) as an epoxy compound (1) in a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube. SR-HP3 which is an epoxy resin (number average molecular weight 474 by FD-MS analysis manufactured by Sakamoto Yakuhin Kogyo Co., Ltd .; a compound in which R ₁₁ in the general formula (1-a) is a hydrogen atom and n = 1) 142. 4 g (0.3 mol), 20.7 g (0.24 mol) of methacrylic acid as the (meth) acrylic acid derivative (2), 73.3 g (0.3 mol) of compound A1, and 1. 3 g of tributylammonium bromide as a catalyst. 45 g and 0.01 g of phenothiazine as a polymerization inhibitor were mixed, heated to 80 ° C. while blowing dry air into the reaction solution, and reacted for 15 hours. After confirming that the acid value of the reaction solution became 2 mgKOH / g or less, 232 g of the reaction solution was diluted with 900 g of toluene and 300 g of ethyl acetate, washed with water with 300 g of ultrapure water 10 times, and then concentrated. 222 g of reaction product was obtained. This concentration was performed until the electric conductivity of the aqueous phase of the reaction solution separated by washing with water became 1 μS / cm or less. As a result of FD-MS analysis of the obtained reaction product, the number average molecular weight was 804. The synthesized product in this example is referred to as A4.

[Synthesis Example 1: Synthesis of Compound 2-3]
In a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 480 g (4.8 mol) of succinic anhydride, 577 g (4 mol) of 4-hydroxybutyl acrylate, and 0.05 g of phenothiazine as a polymerization inhibitor And heated to 110 ° C. for 5 hours. This reaction product was diluted with 2000 g of toluene, washed with 1000 g of ultrapure water 5 times, and concentrated to obtain 920 g of compound A1. As a result of analyzing the obtained compound A1 by HPLC and NMR, it was confirmed that the compound A1 had the structure of the intended compound 2-3 in Table 1.

[Example 2]
In Example 2, as the epoxy compound (1), a phenol novolac type tetrafunctional epoxy resin corresponding to the compound represented by the general formula (1-a) and the (meth) acrylic acid derivative (2) as described above were synthesized. Using Compound A1 synthesized in Example 1 and Compound A2 synthesized in Synthesis Example 2 described later as materials, Compound A5 corresponding to the compound of the present invention was synthesized.

In a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, an epoxy compound (1), phenol novolac type tetrafunctional epoxy resin YL-7284 (Japan Epoxy Resin FD-MS analysis) 318 g (0.5 mol) of the compound having the number average molecular weight of 636; R ₁₁ in the general formula (1-a) is a hydrogen atom and n = 2), 110 g (0.45 mol) of the compound A1, A2 (104 g, 0.45 mol), tributylammonium bromide (2.1 g) as a catalyst, and phenothiazine (0.05 g) as a polymerization inhibitor were mixed and heated to 80 ° C. while blowing dry air into the reaction solution. Reacted for hours.

  Next, after confirming that the acid value of the reaction solution became 2 mgKOH / g or less, 530 g of the reaction solution was diluted with 1200 g of toluene and 600 g of ethyl acetate, and washed with 500 g of ultrapure water 10 times and then concentrated. As a result, 509 g of a reaction product was obtained. This concentration was performed until the electrical conductivity of the aqueous phase when the obtained reaction product was washed with water was 1 μS / cm or less. As a result of FD-MS analysis of the obtained reaction product, the number average molecular weight was 1111. The compound synthesized in this example is referred to as A5.

[Synthesis Example 2: Synthesis of Compound 2-100]
In a 2000 ml four-necked flask equipped with a stirrer, gas introduction tube, thermometer, and cooling tube, 420 g (4.2 mol) of succinic anhydride, 656 g (5.0 mol) of 2-hydroxyethyl methacrylate, and phenothiazine as a polymerization inhibitor 0.05 g was mixed, heated to 110 ° C. and reacted for 5 hours. This reaction product was diluted with 2500 g of toluene, washed with 800 g of ultrapure water six times, and then concentrated to obtain 850 g of compound A2. As a result of analyzing the obtained compound A2 by HPLC and NMR, it was confirmed that the compound A2 had the target structure of Compound 2-100 in Table 1.

[Example 3]
In Example 3, the epoxy compound (1) corresponds to the compound of the present invention using a phenol novolac type tetrafunctional epoxy resin, the (meth) acrylic acid derivative (2), and the compound A3 of Synthesis Example 3 described later as a raw material. Compound A6 was synthesized.

To a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, a phenol novolac type tetrafunctional epoxy resin, YL-7284 (Japan Epoxy Resin, FD-MS method, number average molecular weight 636; 318 g (0.50 mol) of compound (3) in which R ₁₁ is a hydrogen atom and n = 2 in formula (1-a), 425 g (0.76 mol) of compound A3, 2.1 g of tributylammonium bromide as a catalyst, and a polymerization inhibitor 0.05 g of phenothiazine was added, heated and mixed at 80 ° C., and further reacted for 15 hours while blowing dry air until the acid value became 2 mgKOH / g or less. 740 g of the resulting reaction solution was diluted with 1200 g of toluene and 600 g of ethyl acetate, and washed with 600 g of ultrapure water and concentrated 10 times to obtain 730 g of a reaction product. This concentration was performed until the electric conductivity of the aqueous phase of the reaction solution became 1 μS / cm or less. As a result of FD-MS analysis of the obtained reaction product, the number average molecular weight was 1770. The synthesized product in this example is referred to as A6.

[Synthesis Example 3: Synthesis of Compound 2-44]
A 6-hexanolide 3-mole adduct of 2-hydroxyethyl methacrylate (Plaxel FM3 manufactured by Daicel Chemical Industries) was subjected to column purification to prepare a purified 6-hexanolide 3-mole adduct of 2-hydroxyethyl methacrylate.

  In a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 120 g (1.2 mol) of succinic anhydride and 472 g (1.0 mol) of a 6-hexanolide 3-mol adduct of 2-hydroxyethyl methacrylate were added. ), 0.05 g of phenothiazine as a polymerization inhibitor was mixed, heated to 110 ° C., and reacted for 5 hours. The obtained reaction solution was diluted with 2000 g of toluene, and washed with 1000 g of ultrapure water and concentrated 10 times to obtain 584 g of a reaction product. As a result of analyzing the obtained reaction product by HPLC and NMR, it was confirmed to be the compound 2-44 in Table 1. The synthesized product in this example is referred to as A3.

[Example 4]
In Example 4, as the epoxy compound (1), the trifunctional epoxy resin corresponding to the compound represented by the general formula (1-b), and the compounds A1 and A2 as the (meth) acrylic acid derivative (2). Compound A7 corresponding to the compound of the present invention was synthesized as a raw material.

To a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, a trifunctional epoxy resin VG-3102 (number average molecular weight 460 by Mitsui Chemicals, FD-MS method; general formula (1- c) Compound in which R ₁₂ and R ₁₃ are both hydrogen atoms) 184 g (0.40 mol), 97.6 g (0.40 mol) of the compound A1, 92 g (0.40 mol) of the compound A2, tributyl as a catalyst 2.0 g of ammonium bromide and 0.05 g of phenothiazine as a polymerization inhibitor were mixed, heated to 80 ° C. while blowing dry air into the reaction solution, and allowed to react for 8 hours. After confirming that the acid value of the reaction solution is 2 mgKOH / g or less, dilute the obtained 370 g of the reaction solution with 900 g of toluene and 300 g of ethyl acetate, and repeat washing with 300 g of ultrapure water repeatedly 10 times. Gave 361 g of reaction product. This concentration was performed until the electric conductivity of the aqueous phase of the reaction solution became 3 μS / cm or less. As a result of FD-MS analysis of the obtained reaction product, the number average molecular weight was 934. The synthesized product in this example is referred to as A7.

[Example 5]
In Example 5, the compound A8 corresponding to the compound of the present invention was synthesized using the trifunctional epoxy resin as the epoxy compound (1) and the compounds A1 and A2 as the (meth) acrylic acid derivative (2).

  GTR-1800, a trifunctional epoxy resin (number-average molecular weight 622 according to FD-MS method, manufactured by Nippon Kayaku Co., Ltd.), 249 g (0) was added to a 2000 ml four-necked flask equipped with a stirrer, gas introduction tube, thermometer, and cooling tube. 40 mol), 97.6 g (0.40 mol) of the compound A1, 92 g (0.40 mol) of the compound A2, 2.0 g of tributylammonium bromide as a catalyst, and 0.05 g of phenothiazine as a polymerization inhibitor. The reaction solution was heated to 80 ° C. while blowing dry air and allowed to react for 8 hours. After confirming that the acid value of the reaction solution became 2 mgKOH / g or less, 435 g of the resulting reaction solution was diluted with 1000 g of toluene and 350 g of ethyl acetate, and washed with 400 g of ultrapure water repeatedly and concentrated 10 times. 425 g of reaction product was obtained. As a result of FD-MS analysis of the obtained reaction product, the number average molecular weight was 1097. The compound synthesized in this example is referred to as A8.

  Liquid crystal sealants containing the compounds A4 to A8 obtained in the above Examples 1 to 5 were prepared. In addition, the liquid crystal display panel display properties were measured for the purpose of evaluating the viscosity stability of the obtained liquid crystal sealant, the adhesive strength with the substrate constituting the liquid crystal display panel, and the liquid crystal contamination of the liquid crystal sealant. It evaluated according to.

Components of the liquid crystal sealant other than (i) are shown below.
[Raw materials used]
(Ii) Thermal Latent Curing Agent Adipic acid dihydrazide (ADH manufactured by Nihon Finechem).

(Iii) Epoxy resin o-cresol novolac type solid epoxy resin (EOCN-1020-75 Nippon Kayaku Co., Ltd. product).

(Iv) Acrylic compound Bisphenol A, EO adduct diacrylate (Biscoat # 700, manufactured by Osaka Organic Chemical Industry Co., Ltd.). The compound was used after being purified with a purity by repeating the operation of diluting with toluene and ultrapure water and washing with ultrapure water 12 times.

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

(Vi) Filler Spherical silica (manufactured by Admafine A-802 Admatechs; primary average particle size 0.7 μm).

(Vii) Other additives γ-glycidoxytrimethoxysilane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) which is a silane coupling.

[Example 6]
As (iii), 5 parts by mass of o-cresol novolac epoxy resin was heated and dissolved in 10 parts by mass of bisphenol A and EO adduct diacrylate subjected to high purity treatment as (iv) to obtain a uniform solution. To this cooled solution, as (i), 52 parts by weight of compound A4, (v), 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone acting as a photo radical initiator, (ii), 10 parts by weight of adipic acid dihydrazide, 20 parts by weight of spherical silica as (vi), 1 part by weight of γ-glycidoxypropyltrimethoxysilane acting as a silane coupling agent as (vii) were added and premixed with a mixer . Subsequently, these mixtures were kneaded with three rolls until the solid raw material became 5 μm or less, and then the kneaded mixture was filtered with a filter having an aperture of 10 μm (MSP-10-E10S ADVANTEC). A liquid crystal sealant (P1) was prepared by vacuum degassing the obtained filtrate.

[Example 7]
As (i), a liquid crystal sealant (P2) was obtained in the same manner as in Example 6 except that 52 parts by mass of compound A5 was added instead of compound A4.

[Example 8]
As (i), a liquid crystal sealant (P3) was obtained in the same manner as in Example 6 except that 52 parts by mass of compound A6 was added instead of compound A4.

[Example 9]
As (i), a liquid crystal sealant (P4) was obtained in the same manner as in Example 6 except that 52 parts by mass of compound A7 was added instead of compound A4.

[Example 10]
As (iii), 15 parts by mass of o-cresol novolac epoxy resin was heated and dissolved in 22 parts by mass of bisphenol A and EO adduct diacrylate subjected to high purity to obtain a uniform solution. In this cooled solution, 20 parts by weight of compound A4 as (i), 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone acting as a photo radical initiator as (v), and (ii) as adipine 15 parts by weight of acid dihydrazide, 25 parts by weight of spherical silica as (vi), and 1 part by weight of γ-glycidoxypropyltrimethoxysilane acting as a silane coupling agent as (vii) were added and premixed with a mixer. . Subsequently, these mixtures were kneaded with three rolls until the solid raw material became 5 μm or less, and then filtered with a filter having an opening of 10 μm. A liquid crystal sealant (P5) was prepared by vacuum degassing the obtained filtrate.

[Comparative Example 1]
As (i), a liquid crystal sealant (C1) was prepared in the same manner as in Example 6 except that 52 parts by mass of Compound A9 of Synthesis Example 4 described later was added instead of Compound A4.

[Synthesis Example 4: Synthesis of methacryloyl-modified epoxy resin]
A 500 ml four-necked flask equipped with a stirrer, gas inlet tube, thermometer, and condenser tube is 175 g of bisphenol A type epoxy resin (Epicron 850CRP manufactured by Dainippon Ink & Chemicals, Inc.), 43 g of methacrylic acid, and triethanolamine as a catalyst. Was mixed with 0.2 g of hydroquinone monomethyl ether as a polymerization inhibitor. The reaction solution was heated to 110 ° C. while blowing dry air and stirred with heating for 5 hours. The obtained reaction product was repeatedly washed 12 times with ultrapure water. As a result of HPLC and NMR analysis of this reaction product, it was confirmed that 50% of the epoxy group was a bisphenol A type epoxy resin modified with methacryloyl. As a result of FD-MS analysis of the obtained reaction product, the number average molecular weight was 426. The synthesized product in this example is referred to as A9.

[Comparative Example 2]
As (i), a liquid crystal sealant (C2) was prepared in the same manner as in Example 6 except that 52 parts by mass of Compound A10 of Synthesis Example 5 described later was added instead of Compound A4.

[Synthesis Example 5: Synthesis of acryloyl-modified epoxy resin]
A 500 ml four-necked flask equipped with a stirrer, gas inlet tube, thermometer, and cooling tube is 175 g of bisphenol F type epoxy resin (Epicron 850CRP, manufactured by Dainippon Ink & Chemicals, Inc.), 37 g of acrylic acid, and triethanolamine as a catalyst. Was mixed with 0.2 g of hydroquinone monomethyl ether as a polymerization inhibitor. The reaction mixture was heated to 110 ° C. while blowing dry air and stirred for 12 hours. The obtained reaction product was washed with ultrapure water 12 times. As a result of HPLC and NMR analysis of this reaction product, it was confirmed that 50% of the epoxy group was a bisphenol A type epoxy resin modified with acryloyl. Further, as a result of FD-MS analysis of the reaction product, the number average molecular weight was 412. The synthesized product in this example is referred to as A10.

[Comparative Example 3]
As (i), a liquid crystal sealant (C3) was prepared in the same manner as in Example 6 except that 26 parts by mass of compound A9 and 26 parts by mass of compound A10 were added instead of compound A4.

[Comparative Example 4]
A liquid crystal sealant (i) was prepared in the same manner as in Example 1 except that 52 parts by mass of epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd.), which is a diacrylate of bisphenol A type epoxy resin, was added instead of compound A4. C4) was prepared.

[Comparative Example 5]
As (i), a liquid crystal sealant (C5) was prepared in the same manner as in Example 6 except that 52 parts by mass of Compound A6 of Synthesis Example 6 described later was added instead of Compound A4.

[Synthesis Example 6: Synthesis of methacryloyl-modified epoxy resin]
In a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 175 g of bisphenol A type epoxy resin (Epicron 850CRP manufactured by Dainippon Ink & Chemicals, Inc.), 115 g of Compound A1 of Synthesis Example 1 0.2 g of triethanolamine as a catalyst and 0.2 g of hydroquinone monomethyl ether as a polymerization inhibitor were mixed. The reaction solution was heated to 110 ° C. while blowing dry air and stirred for 6 hours. The obtained reaction product was washed with ultrapure water 12 times. As a result of HPLC and NMR analysis of this reaction product, it was confirmed that 50% of the epoxy group was a bisphenol A type epoxy resin modified with 2-methacryloyloxyethyl succinic acid. As a result of FD-MS analysis of the obtained reaction product, the number average molecular weight was 581. The synthesized product in this example is referred to as A6.

[Test method]
In each Example and Comparative Example, the viscosity stability of the obtained 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 by the methods described later. The display properties of the above-mentioned liquid crystal display panel are as follows: (1) a liquid crystal display panel produced by light and thermosetting, and (2) a liquid crystal display panel with a light-shielding area. Targeted.

[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. Then, the 25 degreeC viscosity value of the liquid-crystal sealing compound after progress for a predetermined period was measured with the E-type viscosity meter. When the viscosity value of the liquid crystal sealant before sealing is η1 and the viscosity value of the liquid crystal sealant after a predetermined period is η2, the change in the viscosity value calculated by {(η2−η1) / η1} × 100 The rate was calculated and the rate of change was used as an index of η stability. At this time, when the rate of change is 20% or less, the viscosity stability is high and good (◯), and when the rate of 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]
1. Adhesive strength of liquid crystal sealant after light and heat curing First, liquid crystal sealant to which 1% by mass of 5 μm glass fiber is added is screen-printed in a circular shape with a diameter of 1 mm on an alkali-free glass of 25 mm × 45 mm × 5 mm thickness. did. Next, the obtained substrate and a pair of similar glass substrates were bonded together in a cross shape and fixed with a jig to form a laminate. The laminate was cured by irradiating with 100 mW / cm ² ultraviolet rays using an ultraviolet irradiation device (USHIO INC.). 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 placed in an oven and heat-treated at 120 ° C. for 60 minutes to prepare a test piece. Using the tensile tester (Model 210, manufactured by Intesco), the tensile strength of the finished test piece is set to 2 mm / min, and is pulled in the direction parallel to the glass bottom. The strength 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).

2. 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 × thickness 5 mm. Next, the obtained substrate and a pair of similar glass substrates were bonded together in a cross and fixed with a jig to form a laminate. This laminate was heated in an oven at 120 ° C. for 60 minutes to obtain a test piece.

  Using the tensile tester (Model 210, manufactured by Intesco), the tensile strength of the finished test piece is set to 2 mm / min, and is pulled in the direction parallel to the glass bottom. The strength was measured. The adhesive strength was evaluated by the same method as described above.

[Display properties of LCD panel]
1. Display properties of light and heat-cured liquid crystal display panel A liquid crystal seal in which 1% by mass of 5 μm glass fiber is added on a 40 mm × 45 mm glass substrate (RT-DM88PIN ECH) with a transparent electrode and an alignment film. Using the agent, a frame shape of 35 mm × 40 mm was drawn with a line width of 0.5 mm and a thickness of 50 μm. A dispenser (manufactured by Shotmaster Musashi Engineering Co., Ltd.) was used for drawing.

Next, a liquid crystal material (MLC-11900-000 manufactured by Merck & Co., Inc.) corresponding to the panel internal volume after pasting was precisely dropped into the drawing with a dispenser. Subsequently, the two glass substrates were stacked under a reduced pressure of 90 Pa, and then the liquid crystal sealant was cured by irradiating with 100 mW / cm ² of ultraviolet light using an ultraviolet irradiation device (USHIO INC.). I let you. 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 Topcon Co., Ltd.) 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 sealing agent was cured by light, the liquid crystal sealing agent 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. The liquid crystal display panel was driven by applying a voltage of 5 V to the liquid crystal display panel 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 three 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). Moreover, the display characteristic was inferior (Δ) when an abnormality in the display function was confirmed in the vicinity of 0.3 mm or less in the vicinity of sealing.

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 type of 35 mm × 40 mm with a line width of 0.5 mm and a thickness of 50 μm. A dispenser (manufactured by Shotmaster Musashi Engineering Co., Ltd.) was used for drawing.

  Next, a liquid crystal material (MLC-11900-000 manufactured by Merck & Co., Inc.) corresponding to the panel internal volume after pasting was precisely dropped into the drawing with a dispenser. Subsequently, the two glass substrates are overlapped under a reduced pressure of 90 Pa, fixed by applying a load, and further, the entire sealing portion of the front substrate is covered with aluminum tape so that ultraviolet rays are not directly irradiated. Was coated as follows. 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.

A deflection film was attached to both surfaces of the two substrates bonded together to form a liquid crystal display panel. Further, the display property of the liquid crystal display panel was evaluated in the same manner as the evaluation method of “1. Display property of light and heat-cured liquid crystal display panel” described above.

3. Display property of liquid crystal display panel produced only by thermosetting Liquid crystal seal containing 1% by mass of 5 μm glass fiber on a 40 mm × 45 mm glass substrate (RT-DM88PIN EHC Co., Ltd.) with a transparent electrode and an alignment film. Using the agent, a frame shape of 35 mm × 40 mm was drawn with a line width of 0.5 mm and a thickness of 50 μm. A dispenser (manufactured by Shotmaster Musashi Engineering Co., Ltd.) was used for drawing.

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 were overlapped so that the liquid crystal was sealed, and then the liquid crystal sealant was 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. Further, the display property of the liquid crystal display panel was evaluated in the same manner as the evaluation method of “1. Display property of light and heat-cured liquid crystal display panel” described above.

  Table 15 shows the results of measurement and evaluation of the viscosity stability of the liquid crystal sealants prepared in Examples 6 to 10 and Comparative Examples 1 to 5, and the adhesive strength and display properties of the liquid crystal display panels to which the liquid crystal sealants were applied. Show.

  As shown in Table 15, each liquid crystal sealant (P1 to P5) containing the compound of the present invention has high viscosity stability and is good, and the liquid crystal display panel to which the liquid crystal sealant is applied is It was confirmed that both the display properties of the liquid crystal display panel and the adhesive strength were both high and good regardless of the curing conditions and the presence or absence of the light shielding area.

  On the other hand, among Comparative Examples 1 to 5, as in Comparative Example 1, the compound of the present invention is a compound having both a (meth) acryloyl group and a glycidyl group having a structure different from that of the present invention. The liquid crystal sealant containing compounds having different structures has low viscosity stability, and each liquid crystal display panel to which the liquid crystal sealant is applied has liquid crystal display unevenness in the vicinity of the seal, resulting in a decrease in display performance. Comparative Example 3 is an example in which a liquid crystal sealant containing two types of compounds having both a (meth) acryloyl group and an epoxy group was prepared, but the viscosity stability of the liquid crystal sealant was low and the liquid crystal sealant was applied. In the liquid crystal display panel, display unevenness of the liquid crystal occurred in the vicinity of the seal, and the display performance deteriorated.

  Comparative Example 4 is an example in which a methacrylated epoxy resin having no epoxy group in the molecule is used, but the viscosity stability of the liquid crystal sealant and the adhesive strength of the liquid crystal display panel to which the liquid crystal sealant is applied are It was confirmed that it was extremely low. Comparative Example 5 is an example in which a compound having both a methacryloyl group and an epoxy group having a number average molecular weight of less than 800 is used. The liquid crystal display panel to which the viscosity stability of the liquid crystal sealant and the liquid crystal sealant are applied is used. It was confirmed that the display property of was low and inferior.

  Since the compound of the present invention is highly compatible with both the epoxy resin and the acrylic resin exhibiting radical polymerizability, while maintaining the original properties of each resin such as the high adhesiveness of the epoxy resin and the high reactivity of the acrylic resin, Furthermore, new characteristics such as high reactivity can be imparted. Therefore, the compound is useful for various industrial materials such as liquid crystal sealants, sizing agents such as carbon fibers, glass fibers, and aramid fibers, adhesives for automobiles and electric / electronic devices, and liquid crystal sealants.

Claims (6)

(1) have a three or four glycidyl groups in the molecule, and a part of the glycidyl groups of the epoxy compound a number average molecular weight of 400 to 800,
(2) a carboxyl group having a carboxyl group (meth) acrylic acid derivative thereof,
A liquid crystal sealant containing a compound having a (meth) acryloyl group and a glycidyl group, which is obtained by reacting. 2. The liquid crystal sealant according to claim 1, wherein the compound having a (meth) acryloyl group and a glycidyl group has a number average molecular weight of 800 to 1800. The epoxy compound as the component (1) is a compound represented by the following general formula (1-a), (1-b), (1-c), (1-d) or (1-e). The liquid crystal sealing agent according to claim 1 or 2 .

[In the general formula (1-a),
R ₁₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
n represents an integer of 1 or 2]

[In the general formula (1-c),
R ₁₂ represents a hydrogen atom or a methyl group,
R ₁₃ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]

The epoxy compound as the component (1) is a compound represented by the general formula (1-a), (1-b), (1-c) or (1-e). Liquid crystal sealant. Wherein (2) is a component (meth) acrylic acid derivatives, acrylic acid, methacrylic acid, the following formula (2-a), or formula (2-b) a compound represented by claim 1 The liquid crystal sealing agent according to any one of 4 .

[In the general formula (2-a),
R ₂₁ represents a hydrogen atom or a methyl group,
X ₂₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by the following general formula (3),
X ₂₂ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms]

[In the general formula (3),
Y ₃₁ and Y ₃₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
Y ₃₁ is bonded to O of the acryloyl group in the general formula (2-a),
n represents an integer of 1 to 10]

[In the general formula (2-b),
R ₄₁ and R ₄₂ each independently represents a hydrogen atom or a methyl group;
X ₄₁ and X ₄₂ each represents an alkylene group having 1 to 10 carbon atoms, and the other represents a group represented by the following general formula (4),
X ₄₃ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms,
i and j each independently represents an integer of 0 or 1]

[In the general formula (4),
Y ₅₁ and Y ₅₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
The CO group is bonded to O of the acryloyl group in the general formula (2-b)] The (meth) acrylic acid derivative as the component (2) is a compound represented by methacrylic acid, the general formula (2-a), or the general formula (2-b). Liquid crystal sealant.