HK1132335B

HK1132335B - Liquid crystal sealing agent, method for manufacturing liquid crystal display panel using the liquid crystal sealing agent, and liquid crystal display panel

Info

Publication number: HK1132335B
Application number: HK09110181.9A
Authority: HK
Inventors: 宫脇孝久; 种市大树; 成濑洋; 市川真一郎; 川崎登; 高木正利
Original assignee: 三井化学株式会社
Priority date: 2006-09-07
Filing date: 2007-09-06
Publication date: 2011-11-04

Description

Liquid crystal sealing agent, method for manufacturing liquid crystal display panel using same, and liquid crystal display panel

Technical Field

The present invention relates to a liquid crystal sealing agent, a method for manufacturing a liquid crystal display panel using the same, and a liquid crystal display panel.

Background

In recent years, with the progress of wider bandwidths and the development of small electronic devices such as digital cameras and cellular phones, the demand for liquid crystal display panels as flat panel displays has expanded abnormally in terms of thinness, light weight, and low power consumption. A liquid crystal display panel has a structure in which liquid crystal is sealed between 2 transparent substrates bonded with a liquid crystal sealant, and is a device for displaying an image by controlling the orientation of the liquid crystal by applying a voltage to the liquid crystal and adjusting the modulation of light transmitted through the substrates.

Conventionally, a liquid crystal display panel is manufactured mainly by a liquid crystal injection method in which liquid crystal is injected into a liquid crystal cell having an injection port disposed between 2 substrates, and then the injection port is closed (for example, see patent document 1). However, with the increasing demand for liquid crystal display panels, there is a strong demand for improvement in productivity in the field of liquid crystal display panel production, and in this case, the liquid crystal injection method has a serious problem of low productivity due to the time required for injecting the liquid crystal and the need for heat treatment at a temperature of 120 to 150 ℃ for several hours when curing the liquid crystal sealant.

Therefore, recently, a liquid crystal dropping method has attracted attention as a method for manufacturing a liquid crystal display panel in place of the liquid crystal injection method. The liquid crystal dropping method is a method in which a frame-shaped seal pattern is formed on one of 2 substrates with a liquid crystal sealant by using a dispenser (dispenser) or screen printing; dropping a trace amount of liquid crystal in the frame or on another substrate; in a high vacuum, 2 substrates were superposed in a state where the liquid crystal sealant was not cured; a method for manufacturing a liquid crystal display panel, comprising irradiating a liquid crystal sealing agent between 2 substrates with ultraviolet rays to pre-cure the liquid crystal sealing agent, and then post-curing the liquid crystal sealing agent by heating.

This liquid crystal dropping method shortens the time for filling the liquid crystal into the liquid crystal cell, and also shortens the curing time of the liquid crystal sealing agent by curing the liquid crystal sealing agent by the combination of light and heat, thereby improving the productivity as compared with the liquid crystal filling method. As a liquid crystal sealing agent using such a liquid crystal dropping method, a photo-and thermosetting liquid crystal sealing agent has been proposed (for example, see patent documents 2 and 3).

However, in the liquid crystal dropping method, since the liquid crystal is directly in contact with the liquid crystal sealing agent in an uncured state, components of the liquid crystal sealing agent are eluted into the liquid crystal, and the liquid crystal is easily contaminated. If the liquid crystal is contaminated, the display performance of the liquid crystal display panel is significantly reduced, which is a great problem. In addition, if uncured portions remain in the cured product of the liquid crystal sealing agent, contamination of the liquid crystal is also caused. This is because the liquid crystal sealant component in an uncured state is eluted from the uncured portion into the liquid crystal. If the uncured portion remains in the cured product of the liquid crystal sealing agent, not only the liquid crystal is contaminated, but also the adhesive strength between the substrate constituting the liquid crystal display panel and the cured product of the liquid crystal sealing agent is reduced, which may result in a reduction in the quality of the liquid crystal display panel. Therefore, from the viewpoint of preventing contamination of liquid crystal and improving the adhesive strength, it is desired to propose a liquid crystal sealing agent: the curing proceeds to every corner in a short time, and the curing property is high and good to the extent that the uncured part in the cured product is suppressed to be extremely small, and the solubility to the liquid crystal is low.

As a liquid crystal sealing agent for improving the adhesive strength, the following liquid crystal sealing agents have been proposed: the component (c) is a partially acrylated (アクリル -modified) or methacrylated epoxy resin obtained by reacting a bisphenol a type epoxy resin with acrylic acid or methacrylic acid (see, for example, patent document 4). In addition, as a liquid crystal sealing agent capable of preventing contamination of liquid crystal, the following liquid crystal sealing agents have been proposed: an acrylated epoxy resin containing a (meth) acrylic group ((メタ) アクリル group) and a hydroxyl group, the number of the (meth) acrylic group being greater than the number of the hydroxyl group (see, for example, patent document 5).

Patent document 1: international publication No. 2004/039885 pamphlet

Patent document 2: japanese patent laid-open publication No. 2001-133794

Patent document 3: japanese laid-open patent publication No. 2002-

Patent document 4: japanese patent No. 3162179

Patent document 5: japanese patent laid-open publication No. 2005-195978

Disclosure of Invention

Problems to be solved by the invention

However, the partially acrylated epoxy resin as described in patent document 4 has low curability and is a low molecular weight substance, and therefore has high solubility in liquid crystal and easily contaminates the liquid crystal. In addition, the liquid crystal sealing agent is preferably high in viscosity stability, which is regarded as important as the viscosity stability at around room temperature. The reason for this is that if the viscosity of the liquid crystal sealing agent is stable at around room temperature, a seal pattern having a desired line width can be easily formed on the substrate, and the yield in manufacturing the liquid crystal display panel can be improved. On the other hand, the partially methacrylated epoxy resin is not suitable as a raw material for a liquid crystal sealing agent because of its low viscosity stability at around room temperature.

Further, the acrylated epoxy resin as described in patent document 5 has very high viscosity stability, but on the other hand, the cured product of the liquid crystal sealing agent is likely to have uncured portions remaining because of its low curability. Therefore, it has been found that there is a problem that liquid crystal is contaminated and the adhesion strength between a cured product of the liquid crystal sealing agent and a substrate constituting the liquid crystal display panel is low.

Accordingly, a first object of the present invention is to provide a liquid crystal sealing agent which has high curability, has low solubility in liquid crystal, and can maintain high viscosity stability. A second object of the present invention is to provide a liquid crystal display panel in which liquid crystal contamination is prevented and the adhesion strength between a cured product of the liquid crystal sealant and a substrate constituting the liquid crystal display panel is high, while maintaining high productivity, by using the liquid crystal sealant of the present invention.

Means for solving the problems

The present inventors have made extensive studies and as a result, have found that the above problems can be solved by using a compound having a high molecular weight in a predetermined range by focusing attention on the molecular weight of a compound used as a raw material of a liquid crystal sealing agent, and have completed the present invention.

That is, the above problems can be solved by the liquid crystal sealing agent of the present invention.

(1) A liquid crystal encapsulant comprising: (a) a compound having a (meth) acryloyl group and a glycidyl group in the molecule and having a number average molecular weight of 500 to 2000, (b) a heat-latent curing agent, (c) a radical polymerization initiator, and (d) a filler.

(2) The liquid crystal sealing agent according to (1), wherein the component (a) is a compound represented by the following general formula (I):

in the general formula (I), the compound (I),

R₁₁～R₁₆each independently represents a hydrogen atom or a methyl group, wherein R₁₃And R₁₄Both not being methyl, R₁₅And R₁₆Both of which are not both methyl groups,

X₁₁and X₁₂Each independently represents an alkylene group having 1 to 10 carbon atoms or a group represented by the general formula (I-1),

X₁₃and X₁₄One of them represents an alkylene group having 1 to 10 carbon atoms, the other represents a group represented by the general formula (I-2),

a represents a group represented by the general formula (I-3a), (I-3b) or (I-3c),

p independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a nitro group,

a. b and c each independently represent an integer of 0 to 3, d represents an integer of 1 to 3, and m represents an integer of 0 to 4, where a + b + c + d + m is 6, and a, b and c are not 0 at the same time,

j represents an integer of 0 or 1, and k and l each represent an integer of 0 to 10;

in the general formula (I-1),

Y₂₁and Y₂₂Each independently represents an alkylene group having 1 to 10 carbon atoms,

Y₂₁and O of the acryloyl group in the general formula (I),

n represents an integer of 1 to 10;

in the general formula (I-2),

Y₃₁and Y₃₂Each independently represents an alkylene group having 1 to 10 carbon atoms,

Y₃₂and O of the acryloyl group in the general formula (I);

in the general formula (I-3a),

R₄₁and R₄₂Each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group,

z represents a single bond, -O-group, -S-group, -SO₂-radical, -C (R)₄₃)(R₄₄) A group or a group represented by the following general formula (t1) wherein R₄₃And R₄₄Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group;

r and s each independently represent an integer of 0 to 4;

in the general formula (I-3b),

R₅₁、R₅₂、R₅₃and R₅₄Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group;

in the general formula (I-3c),

R₆₁and R₆₂Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

(3) The liquid crystal sealing agent according to (2), wherein the compound represented by the general formula (I) is 1 or more compounds having 1 or more acryloyl groups, methacryloyl groups and epoxy groups in a molecule.

(4) The liquid crystal sealing agent according to any one of (1) to (3), wherein the component (a) is a compound having a (meth) acryloyl group and a glycidyl group obtained by reacting (i) an epoxy compound having 3 or 4 glycidyl groups in the molecule with (ii) a (meth) acrylic acid derivative having a carboxyl group.

(5) The liquid crystal sealing agent according to (4), wherein the component (i) is a compound represented by the general formula (i-1), (i-2), (i-3) or (i-4),

r in the general formula (i-1)₇₁Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

r in the general formula (i-2)₇₁Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

in the general formula (i-4),

R₈₁represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R₈₂represents a hydrogen atom or a methyl group.

(6) The liquid crystal sealing agent according to (4), wherein the component (B) is acrylic acid, methacrylic acid, a compound represented by the general formula (ii-1) or (ii-2),

in the general formula (ii-1),

R₉₁represents a hydrogen atom or a methyl group,

X₄₁an alkylene group having 1 to 10 carbon atoms or a group represented by the following general formula (t2),

X₄₂an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms;

in the general formula (t2), in the formula,

Y₅₁and Y₅₂Each independently represents an alkylene group having 1 to 10 carbon atoms,

Y₅₁represents an acryloyl group in the general formula (ii-1),

n represents an integer of 1 to 10;

in the general formula (ii-2),

R₉₂and R₉₃Each independently represents a hydrogen atom or a methyl group,

X₆₁represents a group represented by the following general formula (t3),

X₆₂an alkylene group having 1 to 10 carbon atoms,

X₆₃represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms,

i and j each independently represent an integer of 0 or 1;

in the general formula (t3), in the formula,

Y₇₁and Y₇₂Each independently represents an alkylene group having 1 to 10 carbon atoms,

the CO group is bonded to O of the acryloyl group in the general formula (ii-2).

(7) The liquid crystal sealing agent according to any one of (1) to (6), further comprising either one of (e) an epoxy resin and (f) an acrylic compound.

(8) A liquid crystal sealing agent according to any one of (1) to (7), wherein the component (c) is a photo radical polymerization initiator.

(9) A liquid crystal sealing agent according to any one of (1) to (7), wherein the component (c) is a thermal radical polymerization initiator.

(10) The liquid crystal sealing agent according to any one of (1) to (9), wherein the amount of the component (a) is 5 to 90 parts by mass per 100 parts by mass of the liquid crystal sealing agent.

The above problems are solved by a method for manufacturing a liquid crystal display panel and a liquid crystal display panel obtained by the method of the present invention.

(11) A method for manufacturing a liquid crystal display panel in which 2 substrates are bonded to each other with a liquid crystal sealant, the method comprising:

preparing 1 or more substrates having a frame-shaped display region formed so as to surround the pixel arrangement region with the liquid crystal sealing agent loaded in any one of (1) to (10);

dropping a liquid crystal into the uncured display region or onto another substrate;

a step of superposing the substrate on which the liquid crystal is dropped and another substrate;

and applying light and heat, or either light or heat, to the liquid crystal sealant sandwiched between the 2 substrates.

(12) A liquid crystal display panel obtained by the method for manufacturing a liquid crystal display panel according to the above (11).

Effects of the invention

According to the present invention, it is possible to provide a liquid crystal sealing agent which has high viscosity stability and curability, has high adhesion strength between a cured product of the liquid crystal sealing agent and a substrate constituting a liquid crystal display panel, and can prevent contamination of liquid crystal. Further, a method for manufacturing a liquid crystal display panel is provided, by using the liquid crystal sealing agent of the present invention, a high-quality liquid crystal display panel can be obtained while maintaining high productivity.

Detailed Description

Next, the present invention will be described in detail. The liquid crystal sealing agent of the present invention is characterized by comprising: (a) a compound having a number average molecular weight of 500 to 2000 and containing a (meth) acryloyl group and a glycidyl group in the molecule, (b) a heat-latent curing agent, (c) a radical polymerization initiator, and (d) a filler. Hereinafter, each component used in the liquid crystal sealing agent of the present invention will be described.

The compound (a) of the present invention having a (meth) acryloyl group and a glycidyl group in the molecule and having a number average molecular weight of 500 to 2000 (also referred to as the "component (a)") is a compound having an acryloyl group or a methacryloyl group and a glycidyl group in the molecule and having an optimized number average molecular weight of 500 to 2000. The number average molecular weight can be determined by Gel Permeation Chromatography (GPC) with polystyrene as a standard.

Since the component (a) of the present invention contains a (meth) acryloyl group exhibiting latent curability as described above, the viscosity stability is high even in a low temperature region such as near room temperature. On the other hand, since a glycidyl group having high reactivity is contained in the molecule, when the component (a) is used as a raw material of a liquid crystal sealing agent, a good liquid crystal sealing agent having high curability can be obtained. Such a liquid crystal sealing agent has high storage stability and high applicability to a substrate, and can be cured in a short time to every corner even in a light-shielding region. As a result, contamination of the liquid crystal can be prevented, the adhesion strength between the cured product of the liquid crystal sealing agent and the substrate is high, and a liquid crystal display panel having good display properties can be manufactured while maintaining high productivity.

The number average molecular weight of the component (a) of the present invention is adjusted to be in the range of 500 to 2000. Therefore, the solubility of the liquid crystal is suppressed to be low. Generally, a high molecular weight compound tends to have a high viscosity, but if the number average molecular weight is adjusted to fall within the above range, a liquid crystal sealing agent having a low viscosity can be obtained while suppressing the liquid crystal contamination. Further, the number average molecular weight of the component (a) is preferably 800 to 1800, from the viewpoint of reducing the solubility in liquid crystal and having low viscosity.

From the viewpoint of achieving both the improvement in curability of the liquid crystal sealing agent and the reduction in liquid crystal contamination, the first component (a) is preferably a compound containing 1 or more kinds of both of at least 1 acryloyl group, methacryloyl group, and epoxy group in the molecule. The higher the content of the highly reactive epoxy group or the like, the higher the curability of the compound. Further, the higher the molecular weight of the compound which can be the component (a), the more the liquid crystal contamination can be prevented.

When the component (a) is used as a raw material of the liquid crystal sealing agent, the amount of the component (a) used is preferably 5 to 90 parts by mass, more preferably 20 to 60 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. Therefore, not only the characteristics of the component (a) as described above are reflected as the characteristics of a preferable liquid crystal sealing agent, but also the adhesive strength between the cured product of the liquid crystal sealing agent and the substrate constituting the liquid crystal display panel is increased, and a liquid crystal display panel having excellent display properties can be obtained.

The component (a) in the present invention is preferably a compound represented by the following general formula (I) (also referred to as "first component (a)").

In the general formula (I), the compound (I),

R₁₁～R₁₆each independently represents a hydrogen atom or a methyl group,

wherein R is₁₃And R₁₄Both are not both methyl, and R₁₅And R₁₆Both of which are not both methyl groups,

a represents a group represented by the following general formula (I-3a), (I-3b) or (I-3c),

in the general formula (I-1),

Y₂₁and O of the acryloyl group in the general formula (I),

n represents an integer of 1 to 10;

in the general formula (I-2),

Y₃₂and O of the acryloyl group in the general formula (I);

in the general formula (I-3a),

z represents a single bond, -O-group, -S-group, -SO₂-radical, -C (R)₄₃)(R₄₄) A group or a group represented by the following general formula (t1) wherein R₄₃And R₄₄Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group,

r and s each independently represent an integer of 0 to 4;

in the general formula (I-3b),

in the general formula (I-3c), R₆₁And R₆₂Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

The compound represented by formula (I) can be synthesized as follows: reacting (i) a benzenedicarboxylic anhydride or a benzenetetracarboxylic anhydride with (ii) a hydroxyl group-containing (meth) acrylate to form a carboxylate group and a carboxyl group, and bonding a polyglycidyl ether to the carboxyl group formed by the reaction of (iii).

Examples of the (i) benzenedicarboxylic anhydride, benzenetetracarboxylic dianhydride, or benzenetricarboxylic anhydride include: phthalic anhydride, dodecenylphthalic anhydride, octenylphthalic anhydride, 1, 2, 4, 5-benzenetetracarboxylic dianhydride. These compounds may be used alone or in combination of a plurality of them.

Examples of the (ii) hydroxyl group-containing (meth) acrylate include: hydroxyalkyl (C2-C6) (meth) acrylate, polyalkylene (C2-C6) glycol mono (meth) acrylate, glycerin diacrylate, glycerin acrylate methacrylate, pentaerythritol tri (meth) acrylate, cyclohexane dimethanol mono (meth) acrylate, or lactone (C4-C8) modified or alkylene oxide (C2-C6) modified compounds thereof. These compounds may be used alone or in combination of a plurality of them.

Examples of the (iii) polyglycidyl ether include: phenol novolac type glycidyl ether, biphenol novolac type glycidyl ether, cresol novolac type glycidyl ether, bisphenol a type glycidyl ether, bisphenol AD type glycidyl ether, bisphenol F type glycidyl ether, diphenyl ether type glycidyl ether, thioether type glycidyl ether, oxysulfide type glycidyl ether, fluorene type glycidyl ether, adamantyl type glycidyl ether, resorcinol type glycidyl ether, catechol type glycidyl ether, hydroquinone type glycidyl ether. These compounds may be used alone or in combination of a plurality of them.

The compound represented by the general formula (I) must contain an acryloyl group or a methacryloyl group and a glycidyl group in the molecule.

In the reaction of binding the polyhydric glycidyl ether to the reaction product of the benzenedicarboxylic anhydride or benzenetetracarboxylic anhydride and the hydroxyl group-containing (meth) acrylate, the reaction temperature is preferably kept substantially constant within a range of 40 to 180 ℃, and more preferably 50 to 130 ℃ from the viewpoint of promoting the reaction. The reaction temperature is a temperature in a reaction mixture obtained by mixing various raw materials of the first component (a). The temperature in the reaction mixture can be easily measured by using a thermometer or the like.

In the reaction of binding the polyglycidyl ether, a catalyst is preferably used from the viewpoint of promoting the reaction. Preferred examples of the catalyst used herein include: organic phosphine compounds, tertiary amine compounds, quaternary ammonium salt compounds, organic phosphorus salt compounds, imidazole compounds and organic metal compounds.

Examples of the organic phosphine compound include triphenylphosphine. Examples of the tertiary amine compound include triethylamine, triethanolamine. Examples of the quaternary ammonium salt compound include trimethyl ammonium chloride, triethyl benzyl ammonium chloride. Examples of the organic phosphorus salt-based compound include tetrabutylphosphonium bromide, tetraphenylphosphonium bromide. Examples of the imidazole compounds include 2-methylimidazole. In addition, examples of the organometallic compound include cobalt octenoate.

The catalyst is preferably used in an amount sufficient to promote the reaction. Specifically, the amount of the catalyst used is preferably 0.01 to 5.0% by mass based on the total mass of the reaction mixture.

To the reaction mixture, a polymerization inhibitor may be added as needed. The polymerization inhibitor is a compound which inhibits the progress of the polymerization reaction in the reaction mixture or stops the reaction. The polymerization inhibitor is not particularly limited, and a known compound may be appropriately selected. Preferred examples of the polymerization inhibitor include: hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, phenothiazine, p-tert-butylcatechol, p-benzoquinone and naphthoquinone. These compounds may be used alone, or a plurality of them may be used in combination.

In addition, an organic solvent may be added to the reaction mixture. Examples of preferred organic solvents include: aromatic solvents such as toluene and xylene, ketone solvents such as cyclohexane, and glycol solvents such as propylene glycol monomethyl ether, but are not particularly limited. These organic solvents may be used alone or in combination of a plurality of them.

Preferred examples of the component (a) of the present invention include, in addition to the first component (a): a compound having a (meth) acryloyl group and a glycidyl group (also referred to as "component (a)") obtained by reacting (i) an epoxy compound having 3 or 4 glycidyl groups in the molecule with (ii) a (meth) acrylic acid derivative having a carboxyl group.

The method for producing the second component (a) of the present invention is not particularly limited, and for example, a method of reacting 1 or 2 glycidyl groups in the glycidyl group in the component (i) with the carboxyl group in the component (ii) can be mentioned.

The component (i) used as a raw material of the second component (a) is not particularly limited as long as it is a compound having 3 or 4 glycidyl groups in the molecule, but in order to obtain a preferable component (a) as a raw material of a liquid crystal sealing agent, a compound having a molecular weight of 400 to 800 is preferable as the component (i). Preferable examples of the component (i) having such a molecular weight include compounds represented by the following general formula (i-1), (i-2), (i-3) or (i-4).

R in the general formula (i-1)₇₁Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R in the general formula (i-2)₇₁Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

In the general formula (i-4),

R₈₂represents a hydrogen atom or a methyl group.

The R is₇₁And said R₈₁Examples of the alkyl group having 1 to 10 carbon atoms include: hydrogen atom, methyl, ethyl, propyl, isopropylAlkyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl. Among them, a hydrogen atom, a methyl group and an ethyl group are preferable, and a hydrogen atom is more preferable.

The 3-functional epoxy compound represented by the general formula (i-1) and the 4-functional epoxy compound represented by the general formula (i-2) may be any of commercially available products and synthetic products. When the epoxy compound is synthesized, the method for synthesizing the epoxy compound is not particularly limited. When these compounds are synthesized, for example, they can be synthesized as follows: epihalohydrin is reacted with 3 nuclei or 4 nuclei of a novolak-type compound obtained by a condensation reaction of a phenol derivative and formaldehyde according to a known epoxidation reaction. Examples of the known epoxidation reaction include known industrial production methods of existing epoxy compounds that can be obtained as industrial raw materials.

Further, the compounds represented by the general formulae (i-3) and (i-4) are not particularly limited, and may be any of commercially available products and synthetic products.

The component (ii) of the present invention is preferably acrylic acid, methacrylic acid, or a compound represented by the following general formula (ii-1) or (ii-2), from the viewpoint of increasing the molecular weight of the component (a) and achieving both high reactivity and high viscosity stability of a liquid crystal sealing agent when the component (a) is used as a raw material of the liquid crystal sealing agent.

In the general formula (ii-1),

R₉₁represents a hydrogen atom or a methyl group,

X₄₂represents a carbon number of 120 alkylene group or C2-6 alkenylene group.

As X in the general formula (ii-1)₄₁Examples of the preferable alkylene group having 1 to 10 carbon atoms include: methylene, ethylene, methylethylene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexamethylene, cyclohexylene, heptamethylene, octamethylene, nonamethylene and decamethylene. Wherein, X₄₁Preferably an alkylene group having 2 to 6 carbon atoms or a group represented by the general formula (t 2).

As X in the general formula (ii-1)₄₂Examples of the preferable alkylene group having 1 to 20 carbon atoms include: methylene, ethylene, methylethylene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexamethylene, cyclohexylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene, pentadecylene, hexadecamethylene, and octadecamethylene.

As X in the general formula (ii-1)₄₂Examples of the preferable alkenylene group having 2 to 6 carbon atoms include: -CH ═ CH-yl, -CH ═ CH-CH₂-radical, -CH ═ CH-CH₂-CH₂-radical, -CH₂-CH＝CH-CH₂-a radical. Wherein, as X₄₂The group 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 a group-CH ═ CH-, and more preferably an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group, or a group-CH ═ CH-.

In the general formula (t2), in the formula,

Y₅₁and stationO of the acryloyl group in the general formula (ii-1) is bonded,

n represents an integer of 1 to 10.

As Y in the general formula (t2)₅₁And Y₅₂Examples of the preferable alkylene group having 1 to 10 carbon atoms include: methylene, ethylene, methylethylene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexamethylene, cyclohexylene, heptamethylene, octamethylene, nonamethylene and decamethylene. Among them, an alkylene group having 2 to 6 carbon atoms is preferable. In the general formula (t2), n represents an integer of 1 to 10, and more preferably an integer of 1 to 6.

In the general formula (ii-2),

X₆₁represents a group represented by the following general formula (t3),

X₆₂an alkylene group having 1 to 10 carbon atoms,

i and j each independently represent an integer of 0 or 1.

In the general formula (t3), Y₇₁And Y₇₂Each independently represents an alkylene group having 1 to 10 carbon atoms, a CO group, and O in the acryloyl group of the general formula (ii-2).

As X in the general formula (ii-2)₆₂Examples of the preferable alkylene group having 1 to 10 carbon atoms include: methylene, ethylene, methylethylene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexamethylene, cyclohexylene, heptamethylene, octamethylene, nonamethylene and decamethylene.

As X in the general formula (ii-2)₆₃Examples of the preferable alkylene group having 1 to 20 carbon atoms include: methylene, ethylene, methylethylene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexamethylene, cyclohexylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene, pentadecylene, hexadecamethylene, and octadecamethylene.

As X in the general formula (ii-2)₆₃Examples of the preferable alkenylene group having 2 to 6 carbon atoms include: -CH ═ CH-yl, -CH ═ CH-CH₂-radical, -CH ═ CH-CH₂-CH₂-radical, -CH₂-CH＝CH-CH₂-a radical. In addition, X₅₃Preferably a C1-6 alkylene group such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, or the like, or a C1-6 alkylene group, or a C1-4 alkylene group, or a C-CH-group, such as methylene, ethylene, trimethylene, or tetramethylene.

Y in the general formula (t3)₇₁And Y₇₂Corresponding to the above X₆₁. As Y₇₁And Y₇₂Examples of preferred alkylene groups of (a) include: methylene, ethylene, methylethylene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexamethylene, cyclohexylene, heptamethylene, octamethylene, nonamethylene and decamethylene. Among them, the alkylene group is more preferably an alkylene group having 2 to 6 carbon atoms.

[ Process for producing Compound represented by the general formula (ii-1) ]

The compound represented by the above general formula (ii-1) may be industrially produced, and can be easily produced by an esterification reaction of a "hydroxyl group-containing (meth) acrylic acid derivative" and a "compound having 2 carboxyl groups" represented by reaction formulas 1 to 3 described later. Examples of the carboxyl group include precursors that can be carboxyl groups, such as acid halide groups and acid anhydride groups.

[ reaction formula 1]

The reaction of the following reaction formula 1 is a partial esterification reaction of a compound represented by the general formula (ii-1a) having 2 carboxyl groups and a compound represented by the general formula (ii-1b) having a hydroxyl group. The partial esterification reaction is a reaction in which only a part of carboxyl groups of a compound having a plurality of carboxyl groups in the molecule are esterified with a compound having a hydroxyl group.

Reaction scheme 1

In the reaction scheme 1, the reaction is carried out,

X₄₂represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms,

X₄₁an alkylene group having 1 to 10 carbon atoms or a group represented by the general formula (t2),

R₉₁represents a hydrogen atom or a methyl group.

In the reaction of the reaction formula 1, the amount ratio of the compound represented by the general formula (ii-1a) to the compound represented by the general formula (ii-1b) is not particularly limited, but since it is necessary to leave carboxyl groups in the compound represented by the general formula (ii-1) which is the final objective product, the amount of hydroxyl groups is preferably less than the total amount of carboxyl groups. Specifically, when the amount of the substance of the compound represented by the general formula (ii-1a) is M1 and the amount of the substance of the compound represented by the general formula (ii-1b) is M2, M1/M2 is preferably 1.

In the reaction of reaction formula 1, if the amount of hydroxyl groups used is more than the total amount of carboxyl groups, the esterification reaction proceeds excessively in the reaction mixture of reaction formula 1, and thus it is difficult for the carboxyl groups to partially remain in the final objective product. In this case, it is necessary to stop the esterification reaction in the middle of the reaction so as to leave 1 carboxyl group in the final objective product, but it is not easy to stop the reaction at a stage of a desired conversion, and therefore it is preferable to appropriately adjust the amount of each organic group to be used.

The conversion can be grasped by a known analytical means. Preferred examples of analytical means for determining the conversion include: liquid chromatography, thin layer chromatography and IR analysis devices. In addition, in reaction formula 1, in order to produce the compound represented by general formula (ii-1) which is the final target product more accurately and with improved purification yield, it is preferable to perform the esterification reaction while measuring an appropriate conversion rate.

In the partial esterification reaction of reaction formula 1, an esterification catalyst is preferably used from the viewpoint of promoting the reaction. The esterification catalyst is a catalyst for activating the esterification reaction of a carboxylic acid and an alcohol. Preferred examples of such esterification catalysts include: the inorganic acid, organic acid and lewis acid are not particularly limited, and any known compound may be used as the esterification catalyst. Examples of the inorganic acid include hydrochloric acid, sulfuric acid. Examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid. In addition, examples of the Lewis acid include boron trifluoride and aluminum trichloride.

The above-mentioned esterification catalyst is preferably used in a sufficient amount in order to promote the partial esterification reaction. The amount of the esterification catalyst used is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass, based on the total mass of the reaction mixture, from the viewpoint of promoting the partial esterification reaction.

In the partial esterification reaction, water is produced during the reaction. In this case, it is preferable to remove by-product water from the reaction mixture in order to promote the reaction, and a method for removing water from the reaction mixture is not particularly limited, and examples thereof include a method of azeotroping water with a solvent having a boiling point close to that of water, such as benzene or toluene, and a method of using a dehydrating agent such as a molecular sieve.

The reaction of formula 1 may be carried out in the absence of a solvent, or may be carried out in a solvent inert to the reaction. Examples of the solvent suitably used in reaction formula 1 include hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, ether-based solvents, and halogen-based solvents, but are not particularly limited.

Examples of the hydrocarbon-based solvent include n-hexane, benzene, or toluene. Examples of the ketone-based solvent include acetone, methyl ethyl ketone, or methyl isobutyl ketone. Examples of the ester-based solvent include ethyl acetate or butyl acetate. Examples of the ether-based solvent include diethyl ether, tetrahydrofuran, or dioxane. In addition, examples of the halogen-based solvent include dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, or tetrachloroethylene. These solvents may be used alone or in combination of plural kinds.

The reaction temperature of the reaction formula 1 is not particularly limited, but is preferably substantially constant within a range of 50 to 150 ℃ from the viewpoint of efficiently and sufficiently performing the partial esterification reaction in a short time, and more preferably 70 to 120 ℃.

The reaction time of the reaction formula 1 may be appropriately set depending on the reaction temperature, the kind, combination, and amount of the compound represented by the general formula (ii-1a), the compound represented by the general formula (ii-1b), the reaction solvent, and the like, and is not particularly limited. Considering the progress of the partial esterification reaction, the time is preferably in the range of several minutes to 100 hours, more preferably 0.5 to 50 hours, and particularly preferably 1 to 20 hours.

The reaction of equation 2 is a two-stage reaction as follows: partial esterification reaction of a compound represented by the general formula (ii-1c) having 2 acid halide groups and a compound represented by the general formula (ii-1b) having a hydroxyl group; and hydrolyzing the residual acid halide group in the reaction mixture to produce the final objective product, i.e., the compound of the formula (ii-1).

Reaction formula 2

In the reaction scheme 2, the reaction conditions are shown in the following formula,

R₉₁represents a hydrogen atom or a methyl group,

COL represents an acid halide group, wherein L represents a halogen (Cl or Br).

In the reaction formula 2, it is necessary to leave carboxyl groups in the final objective product. Therefore, in the first-stage reaction of reaction formula 2, i.e., the partial esterification reaction, it is preferable that the amount of hydroxyl groups is less than the total amount of acid halide groups. Here, if the amount of the hydroxyl group is more than the total amount of the acid halide group, it is necessary to stop the reaction at a stage of a desired conversion rate. However, it is difficult to stop the reaction accurately at a desired conversion, and therefore it is not preferable.

The conversion can be determined by known analytical means. If the conversion is appropriately measured during the progress of the reaction formula 2, the reaction can be stopped or carried out at a stage of a desired conversion. Preferred examples of the analysis means include liquid chromatography, thin layer chromatography and IR analysis devices.

The partial esterification reaction can be carried out in the absence of a solvent or in a solvent which is inert to the reaction. Examples of such solvents include hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, and halogen solvents.

In the partial esterification reaction, hydrogen halide (for example, hydrogen chloride) is produced as a by-product by the reaction of an acid halide group and a hydroxyl group. Since such a hydrogen halide may deteriorate the characteristics of the reaction product, it is preferable to remove it from the reaction mixture. The method for removing the hydrogen halide is not particularly limited, and a known method may be used, and the dehydrohalogenation agent is useful in view of characteristics such as easy handling.

Preferred examples of the dehydrohalogenation agent include organic base compounds or inorganic base compounds. Examples of the organic base compound include triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1, 4-diazobicyclo [2.2.2] octane (DABCO) and 1, 8-diazobicyclo [5.4.0] undec-7-ene (DBU). In addition, examples of the inorganic basic compound include sodium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium oxide. These compounds may be used alone or in combination of a plurality of them.

The amount of the dehydrohalogenation agent to be used is not particularly limited, but is preferably a sufficient amount for removing the hydrogen halide formed in the reaction mixture. From such a viewpoint, the amount of the dehydrohalogenating agent to be used is preferably 0.1 to 10 mol, more preferably 0.5 to 5mol, and particularly preferably 1 to 3mol based on 1mol of the hydroxyl group.

In the reaction scheme 2, the hydrolysis reaction, which is the reaction in the second stage, is carried out by adding water to the reaction mixture obtained at the end of the partial esterification reaction in the first stage. The method of adding water to the reaction mixture after the completion of the partial esterification reaction is not particularly limited, and water may be added all at once or may be added dropwise. Among them, the latter method by dropwise addition is preferable from the viewpoint of allowing the reaction to proceed slowly.

The amount of water used in the hydrolysis reaction is preferably 1 to 100 moles, and more preferably 5 to 50 moles, based on 1 mole of the acid halide group remaining in the reaction mixture, from the viewpoint of promoting the hydrolysis reaction.

In the hydrolysis reaction, when water is added dropwise, the conversion in the reaction mixture is confirmed by a known analytical means, and the operation of adding water dropwise is continuously carried out or terminated at a desired conversion, thereby allowing the reaction to proceed or stop. Examples of the analysis means include liquid chromatography, thin layer chromatography and IR analysis devices.

In the hydrolysis reaction, hydrogen halide (for example, hydrogen chloride) is produced as a by-product by the reaction between the residual acid halide and the added water, and such hydrogen halide may deteriorate the characteristics of the reaction product. It is therefore preferable to remove the hydrogen halide formed in the reaction mixture as much as possible. The method for removing the hydrogen halide is not particularly limited, and a dehydrohalogenation agent is preferably used from the viewpoints of handling, availability, and the like.

Examples of the dehydrohalogenation agent include an organic base compound or an inorganic base compound. Specifically, examples of the organic base compound include triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1, 4-diazobicyclo [2.2.2] octane (DABCO), 1, 8-diazobicyclo [5.4.0] undec-7-ene (DBU). On the other hand, examples of the inorganic basic compound include sodium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium oxide. These compounds may be used alone or in combination of a plurality of them.

The amount of the dehydrohalogenation agent to be used is not particularly limited, but is preferably an amount sufficient to remove hydrogen halide present in the reaction mixture. From such a viewpoint, the amount of the dehydrohalogenating agent to be used is preferably 0.5 to 10 mol, and more preferably 1 to 5mol, based on 1mol of the residual acid halide group.

In the reaction formula 2, the reaction temperature in the partial esterification reaction and the hydrolysis reaction is not particularly limited, but is preferably substantially constant in the range of-78 to 150 ℃, more preferably-20 to 100 ℃, and particularly preferably 0 to 80 ℃ from the viewpoint of promoting the partial esterification reaction.

The reaction time in the partial esterification reaction may be appropriately set depending on the reaction temperature, the kind or combination of the solvent used, the amount of the compound represented by the general formula (ii-1b) or the compound represented by the general formula (ii-1c) used, and the like, and is not particularly limited. From the viewpoint of promoting the reaction, it is usually preferably from several minutes to 100 hours, more preferably from 30 minutes to 50 hours. In this case, if the reaction time is set to 1 to 20 hours, the reaction can be accelerated without lowering the productivity, and therefore, it is preferable.

As shown below, the reaction of reaction formula 3 is a ring-opening esterification reaction of a compound represented by general formula (ii-1e) having an acid anhydride group and a compound represented by general formula (ii-1b) having a hydroxyl group. In the reaction of the reaction formula 3, the compound represented by the above general formula (ii-1) having a carboxyl group remaining therein can be easily obtained by a ring-opening esterification reaction. Therefore, among the reaction formulae 1 to 3, the reaction formula 3 is most preferable as the method for producing the compound represented by the general formula (ii-1).

Reaction formula 3

In the reaction scheme 3, the reaction is carried out,

R₉₁represents a hydrogen atom or a methyl group.

The ratio of the acid anhydride group and the hydroxyl group in the ring-opening esterification reaction is not particularly limited, and the amount of the hydroxyl group to be used is preferably 0.1 to 10 mol, more preferably 0.5 to 5mol, and particularly preferably 0.8 to 3mol based on 1mol of the acid anhydride group, from the viewpoint of promoting the ring-opening esterification reaction.

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

Examples of the hydrocarbon-based solvent include n-hexane, benzene, toluene, or xylene. Examples of the ketone-based solvent include acetone, methyl ethyl ketone, or methyl isobutyl ketone. Examples of the ester-based solvent include ethyl acetate or butyl acetate. Examples of the ether-based solvent include diethyl ether, tetrahydrofuran, or dioxane. Examples of the halogen-based solvent include dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, or tetrachloroethylene. In addition, examples of the polar solvent include N, N-dimethylformamide, N-dimethylacetamide, N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. These solvents may be used alone or in combination of plural kinds.

In the ring-opening esterification reaction, a catalyst for activating the reaction may be used as necessary. Examples of such catalysts include organic phosphine compounds, tertiary amine compounds, quaternary ammonium salt compounds, organic phosphorus salt compounds, imidazole compounds, and organic metal compounds.

Examples of the organic phosphine compound include triphenylphosphine. Examples of the tertiary amine compound include triethylamine, triethanolamine. Examples of the quaternary ammonium salt compound include trimethyl ammonium chloride, triethyl benzyl ammonium chloride. Examples of the organic phosphorus salt-based compound include tetrabutylphosphonium bromide, tetraphenylphosphonium bromide. Examples of the imidazole compounds include 2-methylimidazole. In addition, examples of the organometallic compound include cobalt octenoate. These compounds may be used alone or in combination of a plurality of them.

The amount of the catalyst used is preferably in the range of 0.01 to 10.0% by mass, more preferably 0.01 to 5.0% by mass, based on the mass of the reaction mixture, from the viewpoint of obtaining a sufficient reaction rate during the reaction.

The reaction temperature of the ring-opening esterification reaction is not particularly limited, and is preferably substantially constant within a range of 0 to 200 ℃, and more preferably 0 to 150 ℃ from the viewpoint of efficiently and effectively performing the reaction.

The reaction time of the ring-opening esterification reaction is not particularly limited, and may be appropriately set depending on the reaction temperature, the amount of the compound represented by the general formula (ii-1b), the compound represented by the general formula (ii-1e), and the like, or the kind or combination of the solvents. From the viewpoint of efficiently and effectively carrying out the reaction, it is usually preferably from several minutes to 10 hours.

In reaction formula 3, the reaction may be carried out or stopped at an arbitrary conversion rate while confirming the conversion rate by a known analysis means. Examples of the analysis means include liquid chromatography, thin layer chromatography and IR analysis devices.

Next, the compound represented by the general formula (ii-2) will be described. The compound represented by the general formula (ii-2) can be produced by replacing the compound represented by the general formula (ii-1b) used in the above reaction formulae 1 to 3 with a (meth) acryloyl derivative having a hydroxyl group represented by the following general formula (ii-2 a).

In the general formula (ii-2a),

R₉₂and R₉₃Each is independentAnd represents a hydrogen atom or a methyl group,

X₆₁represents a group represented by the general formula (t3),

X₆₂an alkylene group having 1 to 10 carbon atoms,

i and j each independently represent an integer of 0 or 1.

The compound represented by the general formula (ii-2a) can be produced according to the following reaction scheme 4.

Reaction formula 4

In the reaction scheme 4, the reaction conditions are shown in the specification,

X₆₁represents a group represented by the general formula (t3),

X₆₂an alkylene group having 1 to 10 carbon atoms,

i and j each independently represent an integer of 0 or 1.

The reaction of the above reaction formula 4 is a reaction of synthesizing a (meth) acryloyl derivative represented by the above general formula (ii-2a) having a hydroxyl group by a ring-opening esterification reaction of a compound represented by the above general formula (ii-2b) having a glycidyl ether group and a compound represented by the above general formula (ii-2c) having an alcohol group.

The ring-opening esterification reaction of reaction formula 4 may be carried out in the absence of a solvent, or may be carried out in a solvent inert to the reaction. Examples of such solvents include: hydrocarbon solvents such as N-hexane, benzene, toluene, and xylene, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ether solvents such as diethyl ether, tetrahydrofuran, and dioxane, halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and tetrachloroethylene, and polar solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. These solvents may be used alone or in combination of plural kinds.

In the ring-opening esterification reaction, a catalyst for activating the reaction may be used 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, organic phosphorus salts such as tetrabutylphosphonium bromide and tetraphenylphosphonium bromide, imidazoles such as 2-methylimidazole, and organic metal compounds such as cobalt octenoate. These catalysts may be used alone or in combination of a plurality of them.

The amount of the catalyst used is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 5.0% by mass, based on the total mass of the reaction mixture of the reaction formula 4, from the viewpoint of obtaining a sufficient reaction rate during the reaction. In the present invention, when a plurality of kinds of activated catalysts are used, the total amount of the activated catalysts is used as the amount of the catalysts.

The reaction temperature of the ring-opening esterification reaction is not particularly limited, and may be a sufficient temperature for the reaction. The reaction temperature is preferably substantially constant within a range of 0 to 200 ℃, and more preferably 0 to 150 ℃.

The reaction time of the ring-opening esterification reaction is not particularly limited, and may be appropriately set depending on the reaction temperature, the amount of the compound represented by the general formula (ii-2b) or the compound represented by the general formula (ii-2c) used as a raw material, or the kind, combination, amount and the like of a solvent, a catalyst and the like. From the viewpoint of sufficiently proceeding the reaction, it is usually preferably several minutes to 10 hours.

In addition, in the reaction formula 4, the reaction may be carried out or stopped at an arbitrary conversion rate while confirming the conversion rate by a known analysis means. Examples of the analysis means include liquid chromatography, thin layer chromatography and IR analysis devices.

[ reaction formula 5]

The preferred second component (a) of the present invention can be obtained, for example, by a reaction represented by the following reaction formula 5.

Reaction formula 5

In the above-mentioned reaction formula 5,

R₇₁represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R₉₁represents a hydrogen atom or a methyl group.

The reaction of the reaction formula 5 is a reaction in which a compound represented by the general formula (i-1) having 3 glycidyl groups and a compound represented by the general formula (ii-1) having a carboxyl group are used as raw materials, and ring-opening esterification is successively performed to finally produce a compound represented by the general formula (iii-2) having a glycidyl group and a (meth) acryloyl group in the molecule (also referred to as "successive ring-opening esterification reaction").

In the sequential ring-opening esterification reaction, first, a compound represented by the general formula (i-1) is used as a starting material, and 1 glycidyl group of the compound is subjected to a ring-opening esterification reaction with a carboxyl group in the compound represented by the general formula (ii-1), thereby producing a compound represented by the general formula (iii-1) which is a 2-functional epoxy resin. Then, the compound represented by the general formula (iii-1) and the compound represented by the general formula (ii-1) are further subjected to a ring-opening esterification reaction to finally produce a compound represented by the general formula (iii-2).

The compound represented by the above general formula (iii-2) is preferably a high molecular weight compound in view of suppressing the solubility in a liquid crystal to a low level. Further, since the epoxy resin composition has a glycidyl group in the molecule and has high reactivity with an epoxy curing agent, it exhibits high curability even in a light-shielded region.

In the sequential ring-opening esterification reaction, the ratio of the glycidyl group to the carboxyl group is not particularly limited, but in the reaction formula 5, it is necessary to leave a glycidyl group in the compound of the general formula (iii-1) which is an intermediate product of the reaction and the compound of the general formula (iii-2) which is a final object product. Therefore, the amount of carboxyl groups used is preferably smaller than the amount of glycidyl groups used. Specifically, the compound represented by the general formula (ii-1) is used in an amount of preferably 1 to 2.8 mol, more preferably 1.3 to 2.5 mol, based on 1mol of the compound represented by the general formula (i-1).

On the other hand, in reaction formula 5, if the amount of carboxyl groups used is larger than the amount of glycidyl groups used, the reaction is accelerated, and therefore, the possibility that all of the 3 glycidyl groups of the compound represented by general formula (i-1) and carboxyl groups undergo a ring-opening esterification reaction to produce a compound represented by general formula (iv) below is extremely high. The compound represented by the general formula (iv) has a high molecular weight and thus has a low solubility in a liquid crystal, but does not have a glycidyl group having a high reactivity with an epoxy curing agent. Therefore, the compound may have low curability and thus is not suitable as a raw material for a liquid crystal sealing agent.

In order to partially leave glycidyl groups in the compounds represented by the general formula (iii-1) and the compounds represented by the general formula (iii-2), it is necessary to stop the reaction at a stage of a desired conversion, but it is difficult to stop the reaction at a desired conversion with precision. Therefore, in the case of the reaction formula 5, it is preferable to adjust the ratio of the glycidyl group to the carboxyl group as described above.

In the general formula (iv) described above,

R₉₁represents a hydrogen atom or a methyl group.

The conversion can be grasped by a known analytical means. Preferred examples of analytical means for determining the conversion include: liquid chromatography, thin layer chromatography and IR analysis devices.

The successive ring-opening esterification reaction may be carried out in the absence of a solvent, or may be carried out in a solvent inert to the reaction. Examples of such solvents include hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, halogen solvents, and polar solvents.

In the sequential ring-opening esterification reaction, a catalyst for activating the reaction may be used as necessary. Examples of such catalysts include organic phosphine compounds, tertiary amine compounds, quaternary ammonium salt compounds, organic phosphorus salt compounds, imidazole compounds, and organic metal compounds.

In the catalyst, examples of the organic phosphine compound include triphenylphosphine. Examples of the tertiary amine compound include triethylamine, triethanolamine. Examples of the quaternary ammonium salt compound include trimethyl ammonium chloride, triethyl benzyl ammonium chloride. Examples of the organic phosphorus salt-based compound include tetrabutylphosphonium bromide, tetraphenylphosphonium bromide. Examples of the imidazole compounds include 2-methylimidazole. Examples of the organometallic compound include cobalt octenoate. These compounds may be used alone or in combination of a plurality of them.

The amount of the catalyst used is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 5.0% by mass, based on the total mass of the reaction mixture in the reaction formula 5, from the viewpoint of obtaining a sufficient reaction rate during the reaction.

The reaction temperature of the successive ring-opening esterification reaction is not particularly limited as long as it is a sufficient temperature for carrying out the reaction, and the reaction temperature is preferably substantially constant within a range of 0 to 200 ℃, and more preferably 0 to 150 ℃.

The reaction time of the sequential ring-opening esterification reaction may be appropriately set depending on the reaction temperature, the amount of the compound used, the kind or combination of the solvent, the catalyst, and the like, the amount used, and the like, and is not particularly limited. From the viewpoint of promoting the reaction, it is preferably several minutes to 10 hours.

The mode for producing a compound having a glycidyl group and a (meth) acryloyl group in the molecule by the sequential ring-opening esterification reaction shown in reaction formula 5 is not limited to the above-described mode. That is, as the starting material, that is, the component (i), it is possible to use the compound represented by the general formula (i-2), (i-3) or (i-4) in addition to the general formula (i-1), or as the component (ii) represented by the general formula (ii-1), it is possible to use acrylic acid or methacrylic acid in addition to the compound represented by the general formula (ii-1). These compounds may be used in combination as appropriate.

The component (a) of the present invention preferably has a Fedors theoretical solubility parameter (SP value) of 10 to 13 (cal/cm)³)^1/2The range of (1). There are various techniques and calculation methods for the calculation method of the solubility parameter (SP value), and the theoretical solubility parameter used in the present invention is preferably a parameter obtained by the calculation method of the Fedors invention (refer to japanese Society of next Society , vol.22, No.10(1986) (53) (566) (Journal of addition Society of japan), etc.). In this calculation method, since a value of density is not necessary, the solubility parameter can be easily calculated. The theoretical solubility parameter (SP value) of Fedors is calculated by the following equation.

SP value (Sigma Delta el/SigmaDelta vl)^1/2

Where Σ Δ el ═ Δ H-RT, Σ Δ vl ═ the sum of molar capacities

Here, if the solubility parameter (SP value) is within the above range, the solubility of the compound represented by the general formula (i-1) of the component (a) in the liquid crystal becomes small, and the possibility of contaminating the liquid crystal is suppressed to be low, so that the display property of the liquid crystal display panel is improved and excellent.

When the component (a) of the present invention is synthesized using a plurality of compounds as raw materials, the theoretical solubility parameter (SP value) can be calculated based on the sum of the mole fractions of the respective raw materials to be mixed. The theoretical solubility parameter calculated here is preferably within the above range.

Hereinafter, a component which can be used together with the component (a) as a raw material of a liquid crystal sealing agent will be described.

(b) Heat latent curing agent

The heat-latent curing agent in the present invention is a curing agent which does not react with a functional group such as an epoxy group in a state in which the resin is normally stored (at room temperature, under visible light, etc.) even when mixed with a main agent such as an epoxy resin, but exhibits reactivity with a functional group by heat or light.

When the liquid crystal sealing agent contains such a heat latent curing agent, the viscosity stability of the liquid crystal sealing agent is improved. Accordingly, the viscosity stability of the liquid crystal sealing agent at room temperature is well maintained, and therefore, the liquid crystal sealing agent can be stably used for a long time when a screen printer or a dispenser is filled with the liquid crystal sealing agent to draw a seal pattern on a substrate. Thus, if the service life of the liquid crystal sealant is increased, productivity in manufacturing the liquid crystal display panel can be improved.

As the heat latent epoxy curing agent of the present invention, a heat latent epoxy curing agent which functions as a curing accelerator for the epoxy group in the component (a) and the epoxy resin (e) described later is preferably used. The thermally latent epoxy resin is a compound having an epoxy group as a functional group and having thermal latency.

As the heat latent curing agent of the present invention, known ones can be used. Among them, amine-based heat latent curing agents having an amino group in the molecule are preferable. The amine-based heat latent curing agent is a compound having an amino group in the molecule and exhibiting heat latent properties. This amine-based heat latent curing agent does not react with an epoxy group at around room temperature, but rapidly reacts with an epoxy group by heating. In addition, in general, a cured product obtained by reacting an amine-based heat latent curing agent with an epoxy resin is a crosslinked polymer, and thus has low solubility in liquid crystal. The curing speed affected by the amine varies depending on the kind and amount of the amine, the kind of the epoxy resin, and the like. However, the amine-based heat-latent curing agent preferably used in the present invention is not particularly limited, and may be appropriately selected from compounds known as amine-based heat-latent curing agents.

Preferable examples of the amine-based heat latent curing agent include organic acid dihydrazide compounds, imidazole and its derivatives, dicyandiamide, aromatic amines, epoxy-modified polyamines, and polyaminourea. These may be used alone or in combination of plural kinds.

Further, as the heat latent curing agent, those having a melting point or a softening point temperature by a ring and ball method of 75 ℃ or higher are particularly preferable. The liquid crystal sealing agent containing the heat latent curing agent has better viscosity stability at room temperature, so that the service life of the liquid crystal display panel is further prolonged.

Examples of the amine-based heat latent curing agent having a melting point or softening point temperature of 75 ℃ or higher obtained by the ring and ball method include dicyandiamide compounds, organic acid dihydrazides and imidazole derivatives.

Examples of the dicyandiamide compounds include dicyandiamide (melting point 209 ℃ C.). Examples of the organic acid dihydrazide include adipic acid dihydrazide (melting point 181 ℃ C.), 1, 3-bis (hydrazinocarbonylethyl) -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.). These compounds may be used alone or in combination of a plurality of them.

The amount of the heat-latent curing agent is preferably 1 to 25 parts by mass, and more preferably 5 to 15 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. When the amount of the heat-latent curing agent is within the above range, the viscosity stability of the liquid crystal sealing agent is good. In addition, when the liquid crystal sealing agent is applied to a liquid crystal display panel, the bonding strength between the cured liquid crystal sealing agent and the substrate is high, so that the bonding reliability of the liquid crystal display panel is improved. The heat-latent curing agent used in the present invention is preferably subjected to high-purity treatment by a water washing method, a recrystallization method or the like.

The liquid crystal sealing agent of the present invention containing such a heat latent curing agent can be effectively used as a one-pack type. The one-pack type liquid crystal sealing agent is a liquid crystal sealing agent having excellent storage stability in which a main component such as an epoxy resin and a curing acceleration component such as a heat latent curing agent are uniformly mixed in advance at a stage before use. The term "excellent storage stability" means that the liquid crystal sealing agent hardly undergoes a curing reaction even when stored at room temperature or lower. Specifically, the rate of increase in viscosity when the liquid crystal sealing agent is stored at 25 ℃ for 5 days is preferably 2 times or less the viscosity of the liquid crystal sealing agent before storage.

(c) Free radical polymerization initiator

The radical polymerization initiator in the present invention is a compound that absorbs energy from light or heat to generate radicals. Examples of the radical polymerization initiator include a photo radical polymerization initiator, a thermal radical polymerization initiator.

In the present invention, as the component (c), a photo radical polymerization initiator is preferably used. The photo radical polymerization initiator is a compound that generates radicals when irradiated with light, that is, a compound that absorbs light energy and decomposes to generate radical active species. Since the liquid crystal sealing agent containing such a photo radical polymerization initiator can be cured by light irradiation, when used in a liquid crystal dropping method, a curing treatment such as post-curing is not required, and the curing time of the liquid crystal sealing agent can be shortened, thereby improving the production rate.

The photo radical polymerization initiator is not particularly limited, and any known compound can be used. Examples thereof include benzoin-based compounds, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, α -acyloxime ester-based compounds, benzoin ether-based compounds, benzoyl formate-based compounds, benzil-based compounds, azo-based compounds, anthraquinone-based compounds, diphenyl sulfide-based compounds, acylphosphine oxide-based compounds, organic pigment-based compounds, iron-phthalocyanine-based compounds. These may be used alone or in combination of plural kinds.

In the present invention, as described above, a thermal radical polymerization initiator may be used as the component (c). The thermal radical polymerization initiator is a compound which generates radicals upon heating, that is, a compound which absorbs thermal energy and decomposes to generate radical active species.

When a liquid crystal sealing agent is produced using such a thermal radical polymerization initiator and a photo radical polymerization initiator together, the liquid crystal sealing agent can be sufficiently cured in a short time by pre-curing the substrates with light after the substrates are attached and then heating the substrates. In this case, if the liquid crystal sealing agent is cured only with light, the liquid crystal sealing agent remains as an uncured portion in a light-shielded region where light is not directly irradiated, but if heat is used during curing, the curing can be performed to each corner of the liquid crystal sealing agent regardless of whether the liquid crystal sealing agent is in the light-shielded region or not. Therefore, when the liquid crystal sealing agent is applied to a liquid crystal display panel, the liquid crystal display panel which has extremely low liquid crystal contamination and excellent adhesion strength between the cured liquid crystal sealing agent and the substrate can be obtained.

The thermal radical polymerization initiator is not particularly limited, and any known compound can be used. Examples thereof include organic peroxides, azo compounds, substituted ethane compounds, benzoin ether compounds, acetophenone compounds.

Examples of the organic peroxide include compounds classified into ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacylperoxides, peroxydicarbonates.

Examples of the organic peroxide are shown below. The number in parentheses is the 10-hour half-life temperature (see Wako pure chemical industries, catalogues of API Corporation, and the above-mentioned Polymer handbook). Further, examples of the ketone peroxide include methyl ethyl ketone peroxide (109 ℃ C.), cyclohexanone peroxide (100 ℃ C.).

Examples of the azo compound include a water-soluble azo thermal radical polymerization initiator, an oil-soluble azo thermal radical polymerization initiator, and a polymeric azo thermal radical polymerization initiator.

Examples of the water-soluble azo-based thermal radical polymerization initiator include 2, 2 ' -azobis (2- (2-imidazolin-2-yl) propane) disulfate dihydrate (46 ℃ C.), 2 ' -azobis (N- (2-carboxyethyl) -2-methylpropionamidine) hydrate (57 ℃ C.), 2 ' -azobis (2- (1- (2-hydroxyethyl) -2-imidazolin-2-yl) propane) dihydrochloride (60 ℃ C.), 2 ' -azobis (1-imino-1-pyrrolidinyl-2-ethylpropane) dihydrochloride (67 ℃ C.), 2 ' -azobis (2-methyl-N- (2-hydroxyethyl) propionamide) (87 ℃ C.), and mixtures thereof, 2, 2 '-azobis (2- (2-imidazolin-2-yl) propane) dihydrochloride (44 ℃ C.), 2' -azobis (2-methylpropionamidine) dihydrochloride (56 ℃ C.), 2 '-azobis (2- (2-imidazolin-2-yl) propane) (61 ℃ C.), and 2, 2' -azobis (2-methyl-N- (1, 1-bis (hydroxymethyl) -2-hydroxyethyl) propionamide) (80 ℃ C.).

Examples of the oil-soluble azo-based thermal radical polymerization initiator include 2, 2 '-azobis (4-methoxy-2, 4-dimethylvaleronitrile) (30 ℃), dimethyl-2, 2' -azobis (2-methylpropionate) (66 ℃), 1 '-azobis (cyclohexane-1-carbonitrile) (88 ℃), 1' - ((cyano-1-methylethyl) azo) formamide (104 ℃), 2 '-azobis (N-cyclohexyl-2-methylpropionamide) (111 ℃), 2' -azobis (2, 4-dimethylpentanenitrile) (51 ℃), 2 '-azobis (2-methylbutyronitrile) (67 ℃), 2' -azobis (N- (2-propenyl) -2-methylpropionamide) (96 ℃), and the like, 2, 2' -azobis (N-butyl-2-methylpropionamide) (110 ℃ C.).

Examples of the polymer azo-based thermal radical polymerization initiator include polydimethylsiloxane unit-containing polymer azo-based thermal radical polymerization initiators and polyethylene glycol unit-containing polymer azo-based thermal radical polymerization initiators. In addition, these thermal radical polymerization initiators may be used alone, or a plurality of them may be used in combination.

The amount of the component (c) to be incorporated is preferably 0.01 to 5 parts by mass per 100 parts by mass of the liquid crystal sealing agent, regardless of the type of energy for generating radicals, such as light or heat. When the amount of the radical polymerization initiator is 0.01 parts by mass or more, the liquid crystal sealing agent can be cured in a short time by irradiating the liquid crystal sealing agent with light or heat appropriately selected. Further, when the blending amount of the component (c) is 5 parts by mass or less, the liquid crystal sealing agent has good coatability and a cured product which is uniformly cured by light irradiation can be obtained.

(d) Filler material

The filler in the present invention is used for the purpose of improving the adhesion reliability of the liquid crystal sealing agent by controlling the viscosity of the liquid crystal sealing agent, improving the strength of a cured product obtained by curing the liquid crystal sealing agent, and suppressing the linear expansion.

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

As the filler of the present invention, a known organic filler such as polymethyl methacrylate, polystyrene, a copolymer obtained by copolymerizing a monomer constituting these monomers with another monomer, polyester fine particles, polyurethane fine particles, or rubber fine particles may be used as long as the characteristics of the liquid crystal sealing agent are not impaired.

Among them, inorganic fillers are preferable from the viewpoint of improving the linear expansion coefficient and the shape retention property. Among these inorganic fillers, silica and talc are more preferable for the reason of high UV transmittance. The filler used in the liquid crystal sealing agent of the present invention may be inorganic or organic, and may be a filler obtained by graft modification with an epoxy resin, a silane coupling agent, or the like.

The shape of the filler is not particularly limited, and may be any of a spherical, plate-like, needle-like, or amorphous material. The maximum particle diameter of the filler is preferably 6 μm or less, and more preferably 2 μm or less. The particle size of the filler can be measured by a laser diffraction method. When a liquid crystal sealing agent containing a filler having such a particle diameter is used in a method for manufacturing a liquid crystal display panel, a liquid crystal cell having excellent dimensional stability of cell gap can be formed.

The amount of the filler is preferably 1 to 40 parts by mass, and more preferably 10 to 30 parts by mass, based on 100 parts by mass of the liquid crystal sealing agent excluding the filler. The liquid crystal sealing agent having the filler content adjusted in this manner has good coatability on a substrate. The filler may be used in combination with the photocurable resin. The liquid crystal sealing agent using the filler and the photocurable resin in combination has good photocurability and is cured in a short time. Further, since the width of the cell pitch is kept substantially constant, dimensional stability is good.

The liquid crystal sealing agent of the present invention may further contain (e) an epoxy resin and (f) an acrylic compound, or either (e) an epoxy resin or (f) an acrylic compound.

(e) Epoxy resin

The epoxy resin in the present invention is a compound having 1 or more epoxy groups in the molecule. Examples of preferred epoxy resins for use in the liquid crystal sealing agent of the present invention include aromatic polyglycidyl ether compounds, novolak resins, novolak type polyglycidyl ether compounds, and glycidyl ether compounds.

Examples of the aromatic polyglycidyl ether compound include aromatic diol compounds and compounds obtained by reacting various diol-modified diol compounds thereof with epichlorohydrin. Examples of the aromatic diol compound include bisphenol a type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin. In addition, examples of the glycol include ethylene glycol, propylene glycol, alkylene glycol.

Examples of such novolak resins include compounds derived from phenol or cresol and formaldehyde. Examples of the novolak type polyglycidyl ether compound include compounds obtained by reacting a polyphenol compound represented by polyalkenylphenol or a copolymer thereof with epichlorohydrin. In addition, examples of the glycidyl ether compound include a xylylene phenol resin.

Among them, preferable examples of the (e) epoxy resin include cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, triphenol methane type epoxy resin, triphenol ethane type epoxy resin, triphenol type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin. Examples of particularly preferred epoxy resins include acrylic rubber-modified epoxy resins of these. In the liquid crystal sealing agent of the present invention, these epoxy resins may be used alone or in combination of a plurality of types.

The epoxy resin used in the present invention preferably has a softening point temperature of 40 ℃ or higher as measured by the ring and ball method, and more preferably has a weight average molecular weight of 1000 to 10000. Such an epoxy resin has low solubility and diffusibility in liquid crystal. Therefore, a liquid crystal display panel manufactured by using the liquid crystal sealing agent of the epoxy resin has 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. Further, as the epoxy resin, it is preferable to use a resin which has been purified by a molecular distillation method or the like to remove impurities.

The amount of the epoxy resin is preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. Such a liquid crystal sealing agent has good heat resistance. However, if the amount is less than 5 parts by mass, the curing rate is lowered, and if it exceeds 50 parts by mass, the heat resistance of the liquid crystal sealing agent may be lowered.

(f) Acrylic acid compound

The acrylic compound (アクリル compound) in the present invention means a compound having 1 or more acrylic groups (アクリル groups) in the molecule. The acrylic compound of the present invention also includes (meth) acrylic resins such as methacrylic resins. Examples of the acrylic compound include acrylate and/or methacrylate monomers, or oligomers thereof, are not particularly limited, and include known compounds. Since the liquid crystal sealing agent containing the acrylic compound has excellent water resistance, when applied to a liquid crystal display panel, a high-quality liquid crystal display panel can be obtained in which the cured product of the liquid crystal sealing agent has extremely high adhesion strength to a substrate constituting the liquid crystal display panel and which has excellent moisture resistance reliability.

Preferable examples of the acrylic compound (f) component include the following.

Diacrylates and/or dimethacrylates of polyethylene glycol, propylene glycol, polypropylene glycol, and the like; diacrylate and/or dimethacrylate of tris (2-hydroxyethyl) isocyanurate; a diacrylate and/or dimethacrylate of a diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol; a diacrylate and/or dimethacrylate of a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A; di-or triacrylates and/or di-or trimethacrylates of triols obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane; a diacrylate and/or dimethacrylate of a diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A; tris (2-hydroxyethyl) isocyanurate triacrylate and/or trimethacrylate; trimethylolpropane triacrylate and/or trimethacrylate, or oligomers thereof; pentaerythritol triacrylate and/or trimethacrylate, or oligomers thereof; polyacrylates and/or polymethacrylates of dipentaerythritol; tris (acryloylethyl) isocyanurate; caprolactone-modified tris (acryloxyethyl) isocyanurate; caprolactone-modified tris (methacryloyloxyethyl) isocyanurate; polyacrylates and/or polymethacrylates of alkyl-modified dipentaerythritol; polyacrylates and/or polymethacrylates of caprolactone-modified dipentaerythritol; hydroxyl trimethyl acetic acid neopentyl glycol diacrylate ester and/or dimethyl acrylate ester; caprolactone-modified hydroxypivalyl glycolate diacrylate and/or dimethacrylate; ethylene oxide-modified phosphoric acid acrylate and/or dimethacrylate; ethylene oxide-modified phosphoric acid acrylate and/or dimethacrylate; ethylene oxide-modified alkylated phosphoric acid acrylates and/or dimethacrylates; oligomeric acrylates and/or oligomeric methacrylates of neopentyl glycol, trimethylolpropane, pentaerythritol.

Examples of the acrylic compound (F) component include resins in which all epoxy groups of cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, triphenol methane type epoxy resin, triphenol ethane type epoxy resin, triphenol type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, and the like are reacted with (meth) acrylic acid to obtain an epoxy resin which is completely (meth) acrylated. These compounds may be used alone or in combination of two or more.

When the acrylic compound (f) is contained in the liquid crystal sealing agent, it is preferably used in combination with the epoxy resin (e). In this case, the amount of the component (e) is preferably 20 to 200 parts by mass based on 100 parts by mass of the component (f). When such a liquid crystal sealing agent is cured by light or heat, a cured product having a high glass transition temperature (Tg) can be obtained. The Tg of the cured product of the liquid crystal sealing agent can be measured by a dynamic viscoelasticity measuring apparatus (DMA). For the purpose of obtaining a high-purity liquid crystal sealing agent, it is preferable to use a component (f) which has been purified by a water washing method or the like.

Examples of the (meth) acrylic acid-modified epoxy resin preferably used in the present invention include: a resin obtained by reacting an epoxy resin with (meth) acrylic acid or phenyl methacrylate in the presence of, for example, a basic catalyst. Examples of the epoxy resin include a bisphenol type epoxy resin or a novolac type epoxy resin.

The (meth) acrylic-modified epoxy resin having both an epoxy group and a (meth) acrylic group in the skeleton exhibits high compatibility with the component (e). Therefore, the liquid crystal sealing agent containing the (meth) acrylic acid-modified epoxy resin and the component (e) has a high glass transition temperature (Tg) and is excellent in durability and heat resistance. Further, the adhesive strength between the cured product of the liquid crystal sealing agent and the substrate constituting the liquid crystal display panel is increased.

Examples of the epoxy resin as a raw material of the (meth) acrylic acid-modified epoxy resin include cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, triphenol methane type epoxy resin, triphenol ethane type epoxy resin, triphenol type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin. The (meth) acrylic acid-modified epoxy resin is preferably highly purified by a molecular distillation method, a washing method, or the like.

(g) Other additives

The liquid crystal sealing agent of the present invention may contain an additive, if necessary. Examples of the additives preferably used in the present invention include a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion scavenger, an ion exchanger, a leveling agent, a pigment, a dye, a plasticizer, and an antifoaming agent. These additives may be used alone or in combination of a plurality of them, depending on the use.

In addition, in order to secure the pitch of the liquid crystal cell, a spacer may be further included. The spacer may be contained in the liquid crystal sealing agent or may be applied in advance to a substrate constituting the liquid crystal display panel.

In the preparation of the thermosetting sealing agent, an organic solvent may be contained for the purpose of improving the coating property of a dispenser or the screen printing property. The organic solvent is preferably highly compatible with the epoxy resin of the component (e), has a boiling point in the range of 140 to 220 ℃, and is inert to an epoxy group. Examples of such organic solvents include ketone-based solvents, ether-based solvents, and acetate-based solvents. These may be used alone or in combination of plural kinds.

(method for producing liquid Crystal sealing agent)

The method for producing the liquid crystal sealing agent of the present invention is not particularly limited, and a known technique can be used. Examples of means for mixing the components of the liquid crystal sealing agent include a double arm mixer, a roll mixer, a twin screw extruder, a ball mill mixer, and a planetary mixer, but are not particularly limited, and a known mixing machine may be used. The liquid crystal sealing agent mixed by any method is filtered by a filter to remove impurities. Then, the resulting mixture is subjected to vacuum defoaming treatment, sealed and filled in a glass bottle or a plastic container, and stored and transported as needed.

(method of manufacturing liquid Crystal display Panel)

Next, a method for manufacturing a liquid crystal display panel according to the present invention will be described. The liquid crystal sealing agent of the present invention can be applied to either a liquid crystal injection method or a liquid crystal dropping method. Hereinafter, a method for manufacturing a liquid crystal display panel according to the present invention relating to a liquid crystal injection method and a liquid crystal dropping method will be described in order.

A method for manufacturing a liquid crystal display panel according to the present invention is a method for manufacturing a liquid crystal display panel by attaching 2 substrates facing each other with a liquid crystal sealant, the method including: (1) preparing 1 or more substrates having a frame-shaped display region formed so as to surround a pixel arrangement region with the liquid crystal sealing agent of the present invention; (2) dropping a liquid crystal into the uncured display region or onto another substrate; (3) a step of superposing the substrate on which the liquid crystal is dropped and another substrate; (4) and applying light and heat, or either light or heat, to the liquid crystal sealant sandwiched between the 2 substrates.

(1) In the step (2), a substrate in which a frame-shaped display region is arranged by applying a liquid crystal sealing agent to one of 2 substrates is prepared. Here, the frame formed by the liquid crystal sealing agent is formed so as to surround the pixel arrangement region.

The liquid crystal sealing agent of the present invention is useful as the liquid crystal sealing agent. The liquid crystal sealing agent not only forms a frame of a display region or the like, but also functions as an adhesive for attaching 2 substrates at a constant interval. Examples of the method of applying the liquid crystal sealing agent to the substrate include dispensing with a dispenser and screen printing, and the method is not particularly limited and may be a known technique. In the case of manufacturing a small-sized liquid crystal display panel, it is preferable to coat the liquid crystal display panel by screen printing from the viewpoint of improving productivity.

Examples of the 2-piece substrate used for the liquid crystal display panel include a glass substrate in which TFTs are formed in a matrix shape, a color filter, and a substrate in which a black matrix is formed. Examples of the material of the substrate include plastics such as glass, polycarbonate, polyethylene terephthalate, polyether sulfone, and PMMA.

Alignment films may be formed on the opposing surfaces of the substrates. The alignment film is not particularly limited, and for example, a known alignment film containing an organic alignment agent or an inorganic alignment agent can be used. The spacer may be dispersed on the substrate in advance. The spacer is effective in uniformly maintaining the cell pitch by using spherical silica particles in general. In general, an in-plane spacer which is dispersed in advance on a substrate or a spacer which is contained in a liquid crystal sealing agent is used. The type and size of the spacer are not particularly limited, and any known spacer may be used depending on the desired cell pitch, etc.

(2) In the step (2), a proper amount of liquid crystal is dropped onto the inside of the frame or another substrate which is the display region in an uncured state. Here, the other substrate on which the liquid crystal is dropped is a different substrate from the substrate including the display region. When dropping the liquid crystal onto another substrate, the liquid crystal may be dropped into a region which can be a display region when the substrates are overlapped with each other.

In addition, it is preferable that the dropped liquid crystal is contained in the frame by adjusting the dropping amount of the liquid crystal according to the size of the frame. If the liquid crystal is dropped into the frame in this way, the capacity of the liquid crystal does not exceed the capacity of the empty cell surrounded by the frame and the substrate after the attachment. Therefore, excessive pressure is not applied to the frame, and the seal forming the frame is not broken.

(3) In the step (2), the substrate on which the liquid crystal is dropped is stacked on another substrate. Here, the overlapping operation is preferably performed under reduced pressure by a vacuum pasting device or the like. In the subsequent step, the 2 substrates stacked under reduced pressure were returned to atmospheric pressure, and the substrates were bonded to each other by the difference in atmospheric pressure.

(4) In the step (2), light and heat, or either light or heat, are applied to the liquid crystal sealing agent sandwiched between the 2 substrates. Accordingly, radicals are generated in the liquid crystal sealing agent by the action of the radical polymerization initiator, and the curing reaction of the main agent and the curing agent is accelerated, so that the liquid crystal sealing agent is cured.

In the step (4), the kind of light to be applied to the liquid crystal sealing agent, the irradiation time, the temperature and time during heating, and the like are not particularly limited, and may be appropriately selected depending on the composition of the liquid crystal sealing agent and the like. For example, when the liquid crystal sealing agent is cured by heat, the heating temperature is preferably 40 to 90 ℃ and the heating time is preferably 1 to 120 minutes from the viewpoint of accelerating the curing of the liquid crystal sealing agent. If necessary, the liquid crystal sealing agent may be heat-cured once and then post-cured at 110 to 150 ℃ for 30 to 90 minutes. Examples of the heating means for the liquid crystal sealing agent include known heating devices such as an oven, a hot plate, and a hot press, and are not particularly limited.

In the present invention, the step (3) may be followed by a step of returning the stacked 2 substrates from the reduced pressure to the atmospheric pressure. If the substrates thus superposed under reduced pressure are restored from reduced pressure to atmospheric pressure, a difference in air pressure is generated between the inside and outside of the frame, and thus 2 substrates are pressed from both the outside thereof, and thus the substrates are adhered to each other.

In addition, in recent liquid crystal dropping method, for the purpose of improving productivity, the following method is adopted: a plurality of frames were formed on the substrates with a liquid crystal sealant, and after 2 substrates were bonded to each other, the outer peripheries of the frames were cut to cut out the respective liquid crystal display panels. Such a method is also suitable for use in the present invention.

The liquid crystal sealing agent of the present invention has high viscosity stability, low solubility to liquid crystal, and contains a component (a) having high curability, a curing agent having thermal latency, a radical polymerization initiator, and a filler. When a liquid crystal display panel is manufactured by a liquid crystal dropping method using such a liquid crystal sealing agent, curing is sufficiently performed even in the presence of a light-shielding region, and work can be performed while maintaining storage stability and high coatability. Accordingly, the uncured part of the cured product of the liquid crystal sealing agent is extremely small, and as a result, a liquid crystal display panel in which contamination of the liquid crystal is prevented and the adhesive strength between the cured product of the liquid crystal sealing agent and the substrate is high can be obtained.

In a liquid crystal display panel, the degree of contamination of liquid crystal, that is, the liquid crystal contamination of the liquid crystal display panel, can be evaluated by the Δ NI point, which is the difference in NI points. The NI point is a temperature at which the liquid crystal undergoes phase transition from a nematic phase to an isotropic phase (isotropic phase). The phase transition temperature can be measured from the inflection point of the exothermic peak using a differential thermal analyzer. The Δ NI point is the difference between the "NI point of uncontaminated liquid crystal" and the "NI point of contaminated liquid crystal". If a raw material or a liquid crystal sealing agent having high liquid crystal contamination is mixed with the liquid crystal, the absolute value of the Δ NI point increases. On the other hand, when the liquid crystal contamination property of the raw material or the liquid crystal sealant is low, the absolute value of the Δ NI point decreases. Thus, the smaller the Δ NI point, the lower the liquid crystal contamination.

Examples

The present invention will be described in more detail below with reference to examples and comparative examples of the present invention. However, the present invention is not limited to the embodiment shown below.

(a) Compound containing (meth) acryloyl group and glycidyl group in molecule and having number average molecular weight of 500 to 2000

As the component (a), the compounds synthesized in the following synthetic examples 1 to 10 were used. Wherein the compounds synthesized in Synthesis examples 1 to 4 correspond to the first component (a), and the compounds synthesized in Synthesis examples 7 to 10 correspond to the second component (a). The compounds synthesized in synthesis examples 5 and 6 have a predetermined organic group in the molecule, but the number average molecular weight is out of the range of 500 to 2000.

In each synthesis example, the acid value of the reaction mixture sampled at an arbitrary stage during the synthesis was calculated by the following method, and the synthesis reaction was carried out while appropriately confirming the degree of progress of the reaction from the calculated acid value. The acid value was calculated as follows: a sample appropriately sampled from the reaction mixture was dissolved in a diethyl ether-ethanol solution, and a phenolphthalein ethanol solution was added, and an ethanol solution of KOH (0.1N) was added dropwise until the resulting solution became colorless, and the acid value was calculated from the amount of KOH consumed.

The number average molecular weight of the final target product obtained in each synthesis example was measured by the following method. The number average molecular weight was measured by (1) Gel Permeation Chromatography (GPC) using polystyrene as a standard and (2) field desorption mass spectrometry (FD-MS method).

Synthesis example 1

In synthesis example 1, (meth) acryloyl group and glycidyl group-containing compound a1 was synthesized by reacting a glycerol acrylate methacrylate-modified phthalic acid with bisphenol F diglycidyl ether.

First, 74g (0.5mol) of phthalic anhydride, 271g (0.5mol) of glycerin acrylate methacrylate, 0.7g of tributylammonium bromide as a catalyst, and 0.5g of phenothiazine as a polymerization inhibitor were mixed in a 500ml four-necked flask equipped with a stirrer, a gas inlet, a thermometer, and a condenser, and the mixture was heated to 80 ℃ for 1 hour and further heated to 130 ℃ for 2 hours.

276g (0.4mol) of the reaction product, 125g (0.4mol) of bisphenol F type epoxy resin (EPOTHTOYDF-8170C, manufactured by Tokyo chemical Co., Ltd.), 0.6g of tributylammonium bromide as a catalyst and 0.1g of hydroquinone monomethyl ether as a polymerization inhibitor were put into a 500ml four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer and a condenser, heated and mixed at 80 ℃ and reacted while blowing dry air until the acid value became 2mgKOH/g or less. Then, the reaction product was separated by silica gel column to obtain compound a 1. The obtained compound a1 was analyzed by HPLC and NMR, and it was confirmed to be a compound containing a (meth) acryloyl group and a glycidyl group.

When the number average molecular weight of compound a1 was measured by GPC, the number average molecular weight of compound a1 obtained as a single peak was 689. Further, when the number average molecular weight of compound a1 was measured by FD-MS method, it was a single peak and the same molecular weight was found (689).

Synthesis example 2

In Synthesis example 2, 2-hydroxyethyl acrylate-modified 4-methacryloyloxyethyl trimellitic acid and bisphenol F diglycidyl ether were reacted in the following manner to synthesize a compound A2 having a (meth) acryloyl group and a glycidyl group.

First, in a 1000ml four-necked flask equipped with a stirrer, a gas inlet, a thermometer, and a condenser, 152g (0.5mol) of 4-methacryloyloxyethyl trimellitic anhydride, 58g (0.5mol) of 2-hydroxyethyl acrylate, 0.7g of tributylammonium bromide as a catalyst, and 0.5g of phenothiazine as a polymerization inhibitor were mixed, heated to 80 ℃ and reacted for 1 hour, and further heated to 130 ℃ and reacted for 2 hours. Then, 168g (0.4mol) of the reaction product, 125g (0.4mol) of bisphenol F type epoxy resin (EPOTHTOYDF-8170C, manufactured by Tokyo chemical Co., Ltd.), 0.6g of tributylammonium bromide as a catalyst and 0.1g of hydroquinone monomethyl ether as a polymerization inhibitor were put into a 500ml four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer and a condenser tube. The resulting mixture was heated to 80 ℃ and then reacted while blowing dry air until the acid value became 2mgKOH/g or less.

The reaction mixture was diluted with 1000g of ethyl acetate, washed repeatedly with ultrapure water 5 times, and then concentrated. Then, the reaction product was separated by silica gel column to obtain compound a 2. The obtained compound a2 was analyzed by HPLC and NMR, and it was confirmed to be a compound containing a (meth) acryloyl group and a glycidyl group. When the number average molecular weight of compound a2 was measured by GPC, the number average molecular weight of compound a2 obtained as a single peak was 733. The number average molecular weight of compound A2 was also a single peak and the same molecular weight as determined by FD-MS.

Synthesis example 3

In synthesis example 3, compound a3 having a (meth) acryloyl group and a glycidyl group was synthesized by reacting 2-hydroxymethylacrylate-modified phthalic acid with bisphenol F diglycidyl ether in the following manner.

First, 74g (0.5mol) of phthalic anhydride, 65g (0.5mol) of 2-hydroxyethyl methacrylate, 0.7g of tributylammonium bromide as a catalyst, and 0.5g of phenothiazine as a polymerization inhibitor were mixed in a 500ml four-necked flask equipped with a stirrer, a gas inlet tube, a thermometer, and a condenser, and the mixture was heated to 80 ℃ to react for 1 hour, and further heated to 130 ℃ to react for 2 hours. After the reaction, the reaction mixture was diluted with 1000g of ethyl acetate, washed with ultrapure water repeatedly for 5 times, and then concentrated. 111g (0.4mol) of the reaction product, 125g (0.4mol) of bisphenol F type epoxy resin (EPOTHTOYDF-8170C, manufactured by Tokyo Kabushiki Kaisha), 0.6g of tributylammonium bromide as a catalyst, and 0.1g of hydroquinone monomethyl ether as a polymerization inhibitor were put into a 500ml four-neck flask equipped with a stirrer, a gas inlet tube, a thermometer, and a condenser tube. The resulting mixture was heated to 80 ℃ and then reacted while blowing dry air until the acid value became 2mgKOH/g or less.

The reaction mixture was diluted with 1000g of ethyl acetate, washed repeatedly with ultrapure water 5 times, and then concentrated. Then, the reaction product was separated by silica gel column to obtain compound a 3. The composition of the compound A3 thus obtained was analyzed by HPLC and NMR, and it was confirmed that the compound contained a methacryloyl group and a glycidyl group. Further, as a result of GPC analysis of compound A3, the number average molecular weight of compound A3 obtained as a single peak was 591. The number average molecular weight of compound A3 was also a single peak and the same molecular weight as determined by FD-MS.

Synthesis example 4

In synthesis example 4, a carboxylic acid derivative was reacted with bisphenoxyethanol fluorene diglycidyl ether to synthesize a compound a4 having a (meth) acryloyl group and a glycidyl group.

First, 6-caprolactone adduct of 2-hydroxyethyl acrylate (manufactured by Daiiol chemical Co., Ltd., trade name: Polsel (プラクセル) FA3) was purified by column chromatography using silica gel. In a 1000ml five-necked flask equipped with a stirrer, a gas inlet tube, a thermometer, a condenser and a funnel were charged 48g of sodium hydride and 200g of toluene, and the mixture was ice-cooled under a nitrogen stream. 229g (0.5mol) of purified 6-caprolactone adduct of 2-hydroxyethyl acrylate was dissolved in 200g of toluene, and the solution was added dropwise over 2 hours.

Then, after the reaction mixture after the completion of the dropwise addition was kept for 1 hour while cooling with ice, the reaction mixture was filtered to remove unreacted sodium hydride. Subsequently, 185g (2mol) of epichlorohydrin, 5g of tetramethylammonium chloride and 0.1g of hydroquinone monomethyl ether were added to the reaction mixture, and after mixing, the mixture was stirred at 70 ℃ for 3 hours while blowing dry air.

Thereafter, the reaction mixture after the completion of the reaction was washed 5 times with ultrapure water, and then heated at 120 ℃ under reduced pressure to distill off excess impurities such as epichlorohydrin, thereby obtaining a reaction product (A4a) of epichlorohydrin and a 6-caprolactone adduct of 2-hydroxyethyl acrylate. Subsequently, 206g (0.4mol) of the reaction product (A4a), 120g (0.4mol) of 6- ((6-acryloyloxy) hexanoyloxy) hexanoic acid (ARONIX M-5300, manufactured by Toyo Seisaku-sho Co., Ltd.) (molecular weight 300) purified by a chromatography column, 0.6g of tributylammonium bromide as a catalyst, and 0.1g of hydroquinone monomethyl ether as a polymerization inhibitor were mixed, heated to 80 ℃ and reacted while blowing dry air until the acid value became 2mgKOH/g or less to obtain a reaction product (A4 b).

Then, 163g (0.2mol) of the obtained reaction product (A4b), 61g (0.2mol) of 4-methacryloyloxyethyl trimellitic anhydride, and 0.5g of phenothiazine as a polymerization inhibitor were mixed and reacted at 80 ℃ for 1 hour, and then further at 130 ℃ for 2 hours to obtain a reaction product (A4 c). Then, 112G (0.1mol) of the reaction product (A4c), 55G (0.1mol) of bisphenoxyethanol fluorene diglycidyl ether (BPEF-G, manufactured by Osaka gas chemical Co., Ltd.), 0.2G of tributylammonium bromide as a catalyst and 0.1G of hydroquinone monomethyl ether as a polymerization inhibitor were charged into a 300ml four-neck flask equipped with a stirrer, a gas introduction tube, a thermometer and a condenser, mixed, heated to 80 ℃ and reacted while blowing dry air until the acid value became 2mgKOH/G or less. The obtained reaction product was separated by silica gel column to obtain compound a 4.

The obtained compound a4 was analyzed by HPLC and NMR, and it was confirmed to be a compound containing a (meth) acryloyl group and a glycidyl group. Further, the number average molecular weight of compound a4 obtained as a single peak was 1670 as a result of GPC analysis of compound a 4. Further, the number average molecular weight of compound A4 was also a single peak and the same molecular weight as determined by FD-MS method.

Synthesis example 5

In synthesis example 5, an epoxy resin obtained by methacryl-modifying a bisphenol a epoxy resin was synthesized.

First, 175g of bisphenol A type epoxy resin (Aipi clone (エピクロン)850CRP, manufactured by Dainippon ink chemical Co., Ltd.), 43g of methacrylic acid, 0.2g of triethanolamine as a catalyst and 0.2g of hydroquinone monomethyl ether as a polymerization inhibitor were mixed in a 500ml four-necked flask equipped with a stirrer, a gas inlet pipe, a thermometer and a condenser, and heated and stirred at 110 ℃ for 5 hours while blowing dry air, to obtain a methacrylic acid-modified bisphenol A type epoxy resin. The obtained resin was repeatedly washed with ultrapure water 12 times to obtain compound a 5. The obtained compound a5 was analyzed by HPLC and NMR, and it was confirmed that it was a bisphenol a type epoxy resin in which 50% of epoxy groups were methacryloyl-modified. Further, the number average molecular weight of the obtained compound a5 was 427 as a result of GPC analysis.

Synthesis example 6

In synthesis example 6, an epoxy resin obtained by modifying a bisphenol F epoxy resin with an acryloyl group was synthesized.

First, 175g of bisphenol F type epoxy resin (Aipi clone 850CRP, manufactured by Dainippon ink chemical Co., Ltd.), 37g of acrylic acid, 0.2g of triethanolamine as a catalyst and 0.2g of hydroquinone monomethyl ether as a polymerization inhibitor were mixed in a 500ml four-neck flask equipped with a stirrer, a gas inlet pipe, a thermometer and a condenser, and heated and stirred at 110 ℃ for 12 hours while blowing dry air, to obtain an acrylic-modified bisphenol A type epoxy resin. The obtained resin was repeatedly washed with ultrapure water 12 times. The resin was analyzed by HPLC and NMR, and it was confirmed that 50% of the epoxy groups were acryloyl-modified bisphenol A epoxy resin (Compound A6). Further, the number average molecular weight of the compound a6 obtained was 412 as a result of GPC analysis.

Synthesis example 7

In synthesis example 7, a compound a7 having a (meth) acryloyl group and a glycidyl group was synthesized by reacting a phenol novolac type 3-functional epoxy resin with a (meth) acrylic acid derivative.

First, a phenol novolac type 3-functional epoxy resin (SR-HP3, manufactured by Saka pharmaceutical industries, Ltd., number average molecular weight measured by FD-MS: 474)142.4g (0.3mol), 20.7g (0.3mol) of methacrylic acid, 73.3g (0.3mol) of the compound B1 described later, 1.45g of tributylammonium bromide as a catalyst, and 0.01g of phenothiazine as a polymerization inhibitor were charged into a 2000ml four-necked flask equipped with a stirrer, a gas inlet pipe, a thermometer, and a condenser, and heated and mixed at 80 ℃ and reacted for 15 hours while blowing dry air until the acid value became 2mgKOH/g or less. Compound B1 used herein is a reaction product of 2-hydroxyethyl methacrylate and succinic anhydride.

232g of the obtained reaction solution was diluted with 900g of toluene and 300g of ethyl acetate. The diluted reaction solution was washed with ultrapure water 300g/l for 10 times, and concentrated until the conductivity of the aqueous phase became 1. mu.S/cm or less, whereby 222g of Compound A7 was obtained. The FD-MS analysis of the obtained compound a7 showed that the number average molecular weight was 804.

Synthesis example 8

In synthesis example 8, an epoxy resin having a (meth) acryloyl group and a glycidyl group was synthesized by reacting a phenol novolac type 4-functional epoxy resin with a (meth) acrylic acid derivative.

A2000 ml four-necked flask equipped with a stirrer, a gas inlet, a thermometer, and a condenser was charged with 318g (0.5mol) of a phenol novolak type 4-functional epoxy resin (YL-7284, manufactured by Nippon epoxy resin Co., Ltd., number average molecular weight 636), 104g (0.45mol) of the compound B1 described later, 110g (0.45mol) of the compound B2, 2.1g of tributylammonium bromide as a catalyst, and 0.05g of phenothiazine as a polymerization inhibitor, as a compound represented by the general formula (i-2), heated and mixed at 80 ℃ and reacted for 15 hours while blowing dry air until the acid value became 2mgKOH/g or less. Compound B2 used herein is a reaction product of 4-hydroxybutylacrylate and succinic anhydride.

530g of the obtained reaction solution was diluted with 1200g of toluene and 600g of ethyl acetate. The diluted reaction solution was washed 10 times with ultrapure water at 500g/l, and concentrated until the conductivity of the aqueous phase became 1. mu.S/cm or less, whereby 509g of Compound A8 was obtained. The FD-MS analysis of the obtained compound A8 showed that the number average molecular weight was 1111.

Synthesis example 9

In synthesis example 9, an epoxy resin having a (meth) acryloyl group and a glycidyl group was synthesized by reacting a phenol novolac type 4-functional epoxy resin with a (meth) acrylic acid derivative in the following manner.

A2000 ml four-necked flask equipped with a stirrer, a gas inlet tube, a thermometer and a condenser was charged with 318g (0.5mol) of a phenol novolak type 4-functional epoxy resin (YL-7284, manufactured by epoxy resins, Japan, having a number average molecular weight of 636 measured by FD-MS method) as the compound represented by the general formula (i-2), 425g (0.9mol) of the compound B3 described later, 2.1g of tributylammonium bromide as a catalyst and 0.05g of phenothiazine as a polymerization inhibitor, and the mixture was heated and mixed at 80 ℃ and then reacted for 15 hours while blowing dry air until the acid value became 2mgKOH/g or less. Compound B3 used herein is a reaction product of caprolactone 3mol of modified methacrylate and succinic anhydride.

740g of the obtained reaction solution was diluted with 1200g of toluene and 600g of ethyl acetate. The diluted reaction solution was washed with 600g/l of ultrapure water 10 times, and concentrated until the conductivity of the aqueous phase became 1. mu.S/cm or less, whereby 730g of Compound A9 was obtained. The FD-MS analysis of the obtained compound a9 showed a number average molecular weight of 1770.

Synthesis example 10

In synthesis example 10, an epoxy resin having a (meth) acryloyl group and a glycidyl group was synthesized by reacting a 3-functional epoxy resin with a (meth) acrylic acid derivative.

A2000 ml four-necked flask equipped with a stirrer, a gas inlet, a thermometer, and a condenser was charged with 184g (0.4mol) of a 3-functional epoxy resin VG-3102 (number average molecular weight of 460 by FD-MS, manufactured by Mitsui chemical Co., Ltd.) as a compound represented by the general formula (i-4), 92g (0.40mol) of the compound B1 described later, 97.6g (0.40mol) of the compound B2, 2.0g of tributylammonium bromide as a catalyst, and 0.05g of phenothiazine as a polymerization inhibitor, heated and mixed at 80 ℃ and reacted for 8 hours while blowing dry air until the acid value became 2mgKOH/g or less.

370g of the obtained reaction solution was diluted with 900g of toluene and 300g of ethyl acetate. The diluted reaction solution was washed with ultrapure water 300g/l for 10 times, and concentrated until the conductivity of the aqueous phase became 3. mu.S/cm or less, whereby 361g of Compound A10 was obtained. The FD-MS analysis of the obtained compound a10 showed that the number average molecular weight was 934.

Next, a description will be given of synthetic examples of (meth) acrylic acid derivatives (B1 to B3) used in the above synthetic examples.

(Synthesis of Compound B1)

In a 2000ml four-necked flask equipped with a stirrer, a gas inlet, a thermometer and a condenser, 420g (4.2mol) of succinic anhydride, 656g (5.0mol) of 2-hydroxyethyl methacrylate and 0.05g of phenothiazine as a polymerization inhibitor were mixed and reacted at 110 ℃ for 5 hours. The reaction product was diluted with 2500g of toluene, washed with 800g of ultrapure water repeatedly for 6 times, and then concentrated to obtain 850g of compound B1. HPLC and NMR analyses of the obtained compound B1 revealed that the desired compound B1 was obtained as a reaction product of 2-hydroxyethyl methacrylate and succinic anhydride.

(Synthesis of Compound B2)

In a 2000ml four-necked flask equipped with a stirrer, a gas inlet tube, a thermometer and a condenser, 480g (4.8mol) of succinic anhydride, 577g (4mol) of 4-hydroxybutylacrylate and 0.05g of phenothiazine as a polymerization inhibitor were mixed and reacted at 110 ℃ for 5 hours. The reaction product was diluted with 2000g of toluene, washed repeatedly with 1000g of ultrapure water for 5 times, and then concentrated to obtain 920g of compound B2. HPLC and NMR analyses of the obtained compound B2 revealed that the desired compound B2 was obtained as a reaction product of 4-hydroxybutylacrylate and succinic anhydride.

(Synthesis of Compound B3)

In a 2000ml four-necked flask equipped with a stirrer, a gas inlet tube, a thermometer and a condenser, 120g (1.2mol) of succinic anhydride, 472g (1.0mol) of a purified 6-caprolactone 3mol adduct of 2-hydroxyethyl methacrylate and 0.05g of phenothiazine as a polymerization inhibitor were mixed and reacted at 110 ℃ for 5 hours. The purified 6-caprolactone 3mol adduct of 2-hydroxyethyl methacrylate was a purified product of a commercially available 6-caprolactone 3mol adduct of 2-hydroxyethyl methacrylate (Polsel FA3, manufactured by Daiiol chemical Co., Ltd.) by column chromatography.

The reaction product was diluted with 2000g of toluene, washed with 1000g of ultrapure water repeatedly for 10 times, and then concentrated to obtain 584g of compound B3. HPLC and NMR analyses of the obtained compound B3 revealed that the desired compound B3 was obtained as a reaction product of caprolactone 3mol of a modified methacrylate and succinic anhydride.

(b) Heat latent curing agent

As the heat latent curing agent, 2 kinds of (i)1, 3 bis (hydrazinocarbonylethyl) -5-isopropylhydantoin (AJICURE VDH-J, manufactured by Ajijinsu Kogyo Co., Ltd.) and (ii) adipic acid dihydrazide (ADH, manufactured by Nippon Fine chemical Co., Ltd.) were appropriately selected and used.

(c) Free radical polymerization initiator

As the radical polymerization initiator, 1-hydroxycyclohexyl phenyl ketone (Irgacure184, manufactured by Ciba specialty Chemicals) functioning as a photo radical polymerization initiator was used.

(d) Filler material

As the filler, spherical silica (1 st-order average particle diameter 0.7 μm) (admafine A-802, manufactured by ADMATECH Co., Ltd.) was used.

(e) Epoxy resin

As the epoxy resin, o-cresol novolac type solid epoxy resin (EOCN-1020-75, manufactured by Nippon chemical Co., Ltd.) was used.

(f) Acrylic acid compound

As the component (f), the following compounds are suitably selected for use: (i) a compound obtained by diluting dimethacrylate (epoxy ester 3000M, manufactured by Kyoeisha chemical Co., Ltd.) of bisphenol A type resin with toluene and ultrapure water, and repeating washing 12 times to thereby carry out high-purity treatment; (ii) a compound obtained by diluting diacrylate which is an adduct of bisphenol A, EO (BISCOAT #700, manufactured by Osaka organic Chemicals Co., Ltd.) with toluene and ultrapure water, and washing the diluted product 12 times to obtain a high-purity product.

(g) Other additives

As the additive, gamma-glycidoxypropyltrimethoxysilane (KBM403, manufactured by shin-Etsu chemical Co., Ltd.) sold as a silane coupling agent was used.

In each of the examples and comparative examples, the viscosity stability of the liquid crystal sealant, the adhesive strength of the liquid crystal sealant, and the display properties of the liquid crystal display panel were measured and evaluated, and the properties of the liquid crystal sealant were evaluated. The measurement is specifically as follows. The adhesive strength of the liquid crystal sealing agent was evaluated by measuring 2 of (1) the adhesive strength of a liquid crystal sealing agent cured with light or heat, and (2) the adhesive strength of a liquid crystal sealing agent cured with heat. The display of the liquid crystal display panel was evaluated by measuring samples in three modes: (1) liquid crystal display panels produced by a general method, (2) display properties of liquid crystal display panels with light-shielding regions, and (3) display properties of liquid crystal display panels produced by heat curing alone.

(viscosity stability of liquid Crystal sealing agent)

The viscosity value of the liquid crystal sealing agent at 25 ℃ was measured using an E-type viscometer. For the measurement of viscosity, 100 parts by mass of a liquid crystal sealing agent was put into a polyethylene container, sealed, and then stored at 25 ℃ for 5 days. Subsequently, after a predetermined period of time, the viscosity at 25 ℃ was measured with an E-type viscometer. Then, using the measured values, the rate of change in viscosity value after 25 ℃ C./5 days, assuming that the viscosity value before sealing was 100, was calculated. At this time, the viscosity stability of the liquid crystal sealant was evaluated in the following 2 grades: when the change rate was 20% or less, the viscosity stability was evaluated to be high, and the value was good (°); when the change of more than 20% was present, the viscosity stability was evaluated as low, and it was poor (x).

(adhesive Strength of liquid Crystal sealing agent)

1. Adhesive strength of photo-and thermosetting liquid crystal sealant

First, a liquid crystal sealing agent to which 1 mass% of 5 μm glass fiber was added was screen-printed in a circular shape with a diameter of 1mm on alkali-free glass of 25mm × 45mm × 5mm in thickness. Then, the same glass as the substrate in pair was pasted in a cross shape, fixed by a jig, and irradiated with 100mW/cm by an ultraviolet irradiation apparatus (manufactured by Youjingwangmi Co., Ltd.)²The liquid crystal sealing agent is cured by the ultraviolet ray of (2). In this case, the ultraviolet light was set to have an illuminance energy of 2000 mJ.

The test piece obtained by curing the liquid crystal sealing agent with light was subjected to heat treatment at 120 ℃ for 60 minutes in an oven to prepare a test piece. As for the plane tensile strength of the finished test piece, a tensile tester (type 210, manufactured by INTESCO Co., Ltd.) was used, and the plane tensile strength was measured by setting a tensile rate of 2 mm/min and carrying out a peeling and pulling in a direction parallel to the bottom surface of the glass. Here, the adhesive strength was evaluated in 2 grades according to the magnitude of the plane tensile strength. That is, the case where the tensile strength was 10MPa or more was evaluated as good adhesive strength (. largecircle.), and the case where the tensile strength was less than 10MPa was evaluated as poor adhesive strength (. largecircle.).

2. Adhesive strength of heat-cured liquid crystal sealant

First, a liquid crystal sealing agent containing 1 mass% of 5 μm glass fibers was screen-printed on alkali-free glass 25mm × 45mm × 5mm thick in a circular shape having a diameter of 1mm, and the same glass paired therewith was cross-pasted and fixed. Next, the 2 bonded substrates were heat-treated at 120 ℃ for 60 minutes using an oven, and the liquid crystal sealing agent was cured only by heat curing to prepare test pieces.

As for the plane tensile strength of the finished test piece, it was measured using a tensile tester (model 210, manufactured by INTESCO Co., Ltd.). In this case, the measurement of the in-plane tensile strength and the evaluation of the measurement results are the same as those described for the adhesive strength of the light-and heat-cured liquid crystal sealing agent (a).

(display of liquid Crystal display Panel)

1. Display property of liquid crystal display panel manufactured by performing light and heat curing

A liquid crystal sealing agent containing 5 μm glass fiber in an amount of 1% by mass was used to form a 35mm × 40mm frame shape having a line width of 0.5mm and a thickness of 50 μm on a 40mm × 45mm glass substrate (RT-DM88 PINEHC) having a transparent electrode and an alignment film. The drawing was performed by using a dispenser (ShotMaster, manufactured by Wucang engineering Co., Ltd.).

Next, a liquid crystal material (MLC-11900-00, manufactured by merck) corresponding to the amount of the panel content after the substrates were attached to each other was precisely dropped onto a glass substrate paired with the substrate on which the seal pattern was formed, using a dispenser. Next, 2 glass substrates were stacked under a reduced pressure of 90Pa to seal the liquid crystal, and then irradiated with 100mW/cm by an ultraviolet irradiation apparatus (manufactured by Youwang electric Co., Ltd.)²The liquid crystal sealing agent is cured by the ultraviolet ray of (2). In this case, the irradiation energy of ultraviolet rays was set to 2000 mJ. The light source is a metal halide lamp. In the measurement of the cumulative light amount, an ultraviolet cumulative light amount meter (UVR-T35, manufactured by Topukang) having a measurement wavelength range of 300 to 390nm and a peak sensitivity wavelength of 365nm was used. Further, after curing the liquid crystal sealing agent by light, the liquid crystal sealing agent was cured after further heat treatment at 120 ℃ for 60 minutes.

The two surfaces of the 2 substrates after the bonding were bonded with respective deflection films to produce a liquid crystal display panel. The liquid crystal display panel was driven by applying a voltage of 5V to the liquid crystal display panel by a dc power supply device. At this time, whether the liquid crystal display function in the vicinity of the seal formed by the liquid crystal sealant normally functions from the initial stage of driving was visually observed, and the display performance of the liquid crystal display panel was evaluated in 2 steps according to a predetermined standard. Here, the case where the liquid crystal display function was exhibited up to the edge of the seal was evaluated as good display property (°), and the case where the display function was not exhibited up to a distance of 0.3mm or more from the vicinity of the edge of the seal to the inside of the frame was evaluated as significantly poor display property (×).

2. Display performance of liquid crystal display panel with light-shielding region

A liquid crystal sealing agent with 1 mass% of 5 μm glass fiber was used to draw a 35mm × 40mm frame shape with a line width of 0.5mm and a thickness of 50 μm on a 40mm × 45mm glass substrate (manufactured by RT-DM88PIN EHC) with a transparent electrode and an alignment film. The drawing was performed by using a dispenser (ShotMaster, manufactured by Wucang engineering Co., Ltd.).

Next, a liquid crystal material (MLC-11900-00, manufactured by merck) in an amount corresponding to the internal volume of the panel after the attachment was precisely dropped using a dispenser. Next, 2 glass substrates were stacked under reduced pressure of 90Pa, and then fixed by applying a load, and further, the sealing portion as the front substrate was covered with an aluminum tape so that ultraviolet rays were not directly irradiated. Then, the liquid crystal sealing agent was cured by light and heat in the same manner as the measurement method of the liquid crystal display panel, thereby producing a liquid crystal display panel with a light-shielding region.

The display function of the completed liquid crystal display panel was measured and evaluated in the same manner as in the above "1. evaluation method of display property of liquid crystal display panel produced by performing light and heat curing". Here, the criteria for evaluating the display performance of the liquid crystal display panel are the same as those described above, and therefore, detailed description thereof is omitted.

3. Display property of liquid crystal display panel manufactured only by heat curing

Next, a liquid crystal material (MLC-11900-00, manufactured by merck) corresponding to the amount of the panel content after the substrates were attached to each other was precisely dropped using a dispenser. Subsequently, 2 glass substrates were stacked under a reduced pressure of 90Pa, and then heated in an oven at 120 ℃ for 60 minutes to cure the liquid crystal sealing agent.

Alignment films were attached to both surfaces of the 2 substrates after the attachment, respectively, to prepare a liquid crystal display panel. The liquid crystal display panel was driven by applying a voltage of 5V to the liquid crystal display panel by a dc power supply device. At this time, whether the liquid crystal display function in the vicinity of the seal formed by the liquid crystal sealant normally functions from the initial stage of driving was visually observed, and the display performance of the liquid crystal display panel was evaluated in 2 steps according to a predetermined standard. Here, the criteria for evaluating the display characteristics of the liquid crystal display panel are the same as those of the above-described method, and therefore, the description thereof is omitted.

Example 1

5 parts by mass of an o-cresol novolak epoxy resin (EOCN-1020-75, manufactured by Nippon chemical Co., Ltd.) as the component (e) was dissolved in 10 parts by mass of a high-purity treated epoxy ester (3000M, manufactured by Kyoho chemical Co., Ltd.) by heating to prepare a uniform solution. To the cooled solution, 52 parts by mass of compound a1 as component (a), 2 parts by mass of 1-hydroxycyclohexylphenylketone (Irgacure184, manufactured by nubuck) functioning as a photo-radical initiator as component (c), 10 parts by mass of 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin (ajucurevdh-J, manufactured by ajmarmot technologies), 20 parts by mass of spherical silica (admafine a-802, manufactured by ADMATECH corporation) as component (d), and 1 part by mass of γ -glycidoxypropyltrimethoxysilane (KBM403, manufactured by shin-Etsu chemical industries, Ltd.) as component (g) were added, and premixed by a mixer. Further, the resulting mixture was kneaded by a three-roll mill until the solid material became 5 μm or less, and then filtered by a filter (MSP-10-E10S, manufactured by ADVANTEC) having a mesh opening of 10 μm. The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P1).

Example 2

A liquid crystal sealing agent (P2) was produced in the same manner as in example 1, except that 52 parts by mass of compound a2 was used instead of compound a1 as component (a).

Example 3

A liquid crystal sealing agent (P3) was produced in the same manner as in example 1, except that 52 parts by mass of compound A3 was used instead of compound a1 as component (a).

Example 4

A liquid crystal sealing agent (P4) was produced in the same manner as in example 1, except that 52 parts by mass of compound a4 was used instead of compound a1 as component (a).

Example 5

5 parts by mass of an o-cresol novolak epoxy resin (EOCN-1020-75, manufactured by Nippon chemical Co., Ltd.) as the component (e) was dissolved in 24 parts by mass of a high-purity treated epoxy ester (3000M, manufactured by Kyoho chemical Co., Ltd.) by heating to prepare a uniform solution. To the cooled solution, 20 parts by mass of compound a2 as component (a), 5 parts by mass of 1-hydroxycyclohexylphenylketone (Irgacure184, manufactured by nubuck) functioning as a photo-radical initiator as component (c), 15 parts by mass of 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin (ajocurevdh-J, manufactured by ajinomoto technologies), 30 parts by mass of spherical silica (admafine a-802, manufactured by ADMATECH co) as component (d), and 1 part by mass of γ -epoxypropoxysilane (KBM403, manufactured by shin-shikoku chemical industries co) as component (g) were added, and premixed by a mixer. Next, the mixture was kneaded by a three-roll mill until the solid material became 5 μm or less, and then filtered by a filter (MSP-10-E10S, manufactured by ADVANTEC) having a mesh opening of 10 μm. The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P5).

Example 6

6 parts by mass of an o-cresol novolak epoxy resin (EOCN-1020-75, manufactured by Nippon chemical Co., Ltd.) as the component (e) was dissolved in 6 parts by mass of a high-purity treated epoxy ester (3000M, manufactured by Kyoho chemical Co., Ltd.) under heating to prepare a uniform solution. To the cooled solution, 9 parts by mass of Compound A2, 26 parts by mass of Compound A5, and 26 parts by mass of Compound A-6 as component (a) were added, 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone (Irgacure184, manufactured by Ciba Seikagaku corporation) functioning as a photo radical polymerization initiator as the component (c), 10 parts by mass of 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin (AJICURE VDH-J, manufactured by AJIMUSU Kogyo Co., Ltd.) as the component (b), 14 parts by mass of spherical silica (admafine A-802, manufactured by ADMATECH Co., Ltd.) as the component (d), and 1 part by mass of γ -glycidoxypropyltrimethoxysilane (KBM403, manufactured by shin-Etsu chemical Co., Ltd.) as the component (g) were premixed by a mixer. Next, the mixture was kneaded by a three-roll mill until the solid material became 5 μm or less, and the kneaded mixture was filtered by a filter (MSP-10-E10S, manufactured by ADVANTEC) having a mesh opening of 10 μm. The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P6).

Example 7

81 parts by mass of compound A2 as component (a), 10 parts by mass of 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin (AJICURE VDH-J, manufactured by AJIOMINGYOUJIN Co., Ltd.) as component (b), 8 parts by mass of spherical silica (admafine A-802, manufactured by ADMATECH Co., Ltd.) as component (d), and 1 part by mass of gamma-glycidoxypropyltrimethoxysilane (KBM403, manufactured by shin-Etsu chemical Co., Ltd.) as component (g) were premixed by a mixer. Next, the mixture was kneaded by a three-roll mill until the solid material became 5 μm or less, and the kneaded mixture was filtered by a filter (MSP-10-E10S, manufactured by ADVANTEC) having a mesh opening of 10 μm. The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P7).

Example 8

5 parts by mass of an o-cresol novolak epoxy resin (EOCN-1020-75, manufactured by Nippon chemical Co., Ltd.) as the component (e) was dissolved in 10 parts by mass of a high-purity-treated diacrylate ester of bisphenol A, EO adduct (BISCOAT # V700, manufactured by Osaka organic chemical Co., Ltd.) as the component (f) under heating to prepare a uniform solution. To the cooled solution, 52 parts by mass of compound a7 as a component (a), 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone (Irgacure184, manufactured by Ciba specialty Chemicals) functioning as a photo radical polymerization initiator as a component (c), 10 parts by mass of adipic acid dihydrazide (ADH, manufactured by Nippon Fine chemical Co., Ltd.), 20 parts by mass of spherical silica (admafine a-802, manufactured by ADMATECH Co., Ltd.) as a component (d), and 1 part by mass of γ -glycidoxypropyltrimethoxysilane (KBM, manufactured by shin-Etsu chemical Co., Ltd.) as a component (g) were added, and premixed by a mixer. Next, the mixture was kneaded by a three-roll mill until the solid material became 5 μm or less, and then the kneaded mixture was filtered by a filter (MSP-10-E10S, manufactured by ADVANTEC) having a mesh opening of 10 μm. The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P8).

Example 9

A liquid crystal sealing agent (P9) was produced in the same manner as in example 1, except that 52 parts by mass of compound A8 was used instead of compound a1 as component (a).

Example 10

A liquid crystal sealing agent (P10) was produced in the same manner as in example 1, except that 52 parts by mass of compound a9 was used instead of compound a1 as component (a).

Example 11

A liquid crystal sealing agent (P11) was produced in the same manner as in example 1, except that 52 parts by mass of compound a10 was used instead of compound a1 as component (a).

Example 12

15 parts by mass of an o-cresol novolak epoxy resin (EOCN-1020-75, manufactured by Nippon chemical Co., Ltd.) as the component (e) was dissolved in 22 parts by mass of a high-purity-treated diacrylate ester of bisphenol A, EO adduct (BISCAAT # V700, manufactured by Osaka organic chemical Co., Ltd.) by heating to prepare a uniform solution, and the solution was cooled. To the cooled solution, 20 parts by mass of compound a7 as a component (a), 2 parts by mass of 1-hydroxycyclohexylphenylketone (Irgacure184, manufactured by nubuck corporation) functioning as a photo radical initiator as a component (c), 15 parts by mass of adipic acid dihydrazide (ADH, manufactured by japan fine chemical co., ltd.), 25 parts by mass of spherical silica (admafine a-802, manufactured by ADMATECH co., ltd.) as a component (d), and 1 part by mass of γ -glycidyloxytrimethoxysilane (KBM403, manufactured by shin-Etsu chemical industries, Ltd.) as a component (g) were added, and premixed by a mixer. Next, the mixture was kneaded by a three-roll mill until the solid material became 5 μm or less, and the kneaded mixture was filtered by a filter (MSP-10-E10S, manufactured by ADVANTEC) having a mesh opening of 10 μm. The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P12).

Comparative example 1

A liquid crystal sealing agent (Q1) was produced in the same manner as in example 1, except that 52 parts by mass of compound a5 was used instead of compound a1 as component (a).

Comparative example 2

A liquid crystal sealing agent (Q2) was produced in the same manner as in example 1, except that 52 parts by mass of compound a6 was used instead of compound a1 as component (a).

Comparative example 3

A liquid crystal sealing agent (Q3) was produced in the same manner as in example 1, except that 26 parts by mass of compound a5 and 26 parts by mass of compound a6 were used instead of compound a1 as the component (a).

Comparative example 4

A liquid crystal sealing agent (Q4) was produced in the same manner as in example 1, except that 62 parts by mass of epoxy ester 3000M was used as the component (a) instead of compound a1 and epoxy ester 3000M used in example 1.

Comparative example 5

A liquid crystal sealing agent (Q5) was produced in the same manner as in example 8 except that 52 parts by mass of compound C1 synthesized by the following synthesis method was used as component (a) instead of compound a 7.

(Synthesis of Compound C1)

175g of bisphenol A type epoxy resin (Aipi clone 850CRP, manufactured by Dainippon ink chemical Co., Ltd.), 43g of methacrylic acid, 0.2g of triethanolamine as a catalyst and 0.2g of hydroquinone monomethyl ether as a polymerization inhibitor were mixed in a 500ml four-necked flask equipped with a stirrer, a gas inlet tube, a thermometer and a condenser, and the mixture was heated and stirred at 110 ℃ for 5 hours while blowing dry air, whereby Compound C1 was obtained. The compound C1 thus obtained was repeatedly washed with ultrapure water 12 times. HPLC and NMR analyses of the compound C1 confirmed that the epoxy group was 50% methacryloyl-modified bisphenol A epoxy resin. The FD-MS analysis of the obtained compound C1 showed a number average molecular weight of 426.

Comparative example 6

A liquid crystal sealing agent (Q6) was produced in the same manner as in example 8 except that 52 parts by mass of compound C2 synthesized by the following synthesis method was used as component (a) instead of compound a 7.

(Synthesis of Compound C2)

175g of bisphenol A type epoxy resin (Aipi clone 850CRP, manufactured by Dainippon ink chemical Co., Ltd.), 37g of acrylic acid, 0.2g of triethanolamine as a catalyst and 0.2g of hydroquinone monomethyl ether as a polymerization inhibitor were mixed in a 500ml four-necked flask equipped with a stirrer, a gas inlet tube, a thermometer and a condenser, and the mixture was heated and stirred at 110 ℃ for 12 hours while blowing dry air, whereby Compound C2 was obtained. The compound C2 thus obtained was repeatedly washed with ultrapure water 12 times. As a result of HPLC and NMR analyses of the compound C2, it was confirmed that the epoxy group was 50% acryloyl-modified bisphenol A epoxy resin. The FD-MS analysis of the obtained compound C2 showed a number average molecular weight of 412.

Comparative example 7

A liquid crystal sealing agent (Q7) was produced in the same manner as in example 1, except that 26 parts by mass of the compound C1 and 26 parts by mass of the compound C2 were used instead of the compound a1 as the component (a).

Comparative example 8

A liquid crystal sealing agent (Q8) was produced in the same manner as in example 8, except that 52 parts by mass of an epoxy ester (3000A, manufactured by kyo chemical corporation) which is a diacrylate of a bisphenol a type epoxy resin was used in place of the compound a7 used in example 8.

The evaluation results of the liquid crystal sealing agents obtained in examples 1 to 12 and comparative examples 1 to 8 are summarized in tables 1 and 2.

As shown in tables 1 and 2, the liquid crystal sealants to which the liquid crystal sealants P1 to P12 according to the present invention were applied were confirmed to be good in terms of the viscosity stability, the adhesive strength, the display properties in the vicinity of the seal of the liquid crystal display panel using the same, and the display properties in the vicinity of the seal of the light-shielding region. Further, even when the liquid crystal sealing agent was cured by only heat curing, it was confirmed that the adhesive strength was high and the display property of the liquid crystal display panel was excellent.

On the other hand, as shown in comparative examples 1 to 6, all of the liquid crystal sealants using, as a raw material, a compound having both a (meth) acryloyl group and an epoxy group but a number average molecular weight of less than 500 were low in viscosity stability, and were inferior to those of the examples in display property because display unevenness of liquid crystal occurred in the vicinity of the seal. As shown in comparative examples 4 and 8, the liquid crystal sealing agent using a methacrylated epoxy resin having a structure different from that of the present invention as a raw material was found to have low viscosity stability and low adhesive strength, and was found to be significantly poor.

Industrial applicability of the invention

The liquid crystal sealing agent of the present invention has high viscosity stability and curability, and is excellent. Therefore, the possibility that the seal pattern line width becomes narrow or the number of times of replacing the liquid crystal sealant with a device such as a dispenser is increased can be suppressed to a low level, and therefore, the yield can be improved and the liquid crystal display panel can be manufactured under the condition that the curing time is shortened. Further, the liquid crystal sealing agent is also suitable for a liquid crystal dropping method because the solubility in liquid crystal can be suppressed to a low level.

The present application claims priority based on application numbers JP2006-243057, JP2006-243059 and JP2006-350198, JP2006-350317 applied on 9/7/2006 and application numbers JP2006-350198 and JP2006-350317 applied on 26/12/2006. The contents described in the specification of these applications are all incorporated in the present specification.

Claims

1. A liquid crystal encapsulant comprising: (a) a compound having a (meth) acryloyl group and a glycidyl group in a molecule and having a number average molecular weight of 500 to 2000, (b) a heat-latent curing agent, (c) a radical polymerization initiator, and (d) a filler,

the component (a) is a compound having a (meth) acryloyl group and a glycidyl group obtained by reacting (i) an epoxy compound having 3 or 4 glycidyl groups in the molecule with (ii) a (meth) acrylic acid derivative having a carboxyl group.

2. The liquid crystal sealing agent according to claim 1, wherein the component (i) is a compound represented by the following general formula (i-1), (i-2), (i-3) or (i-4),

in the general formula (i-4), R₈₁R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms₈₂Represents a hydrogen atom or a methyl group.

3. A liquid crystal sealing agent according to claim 1, wherein the component (ii) is acrylic acid, methacrylic acid, a compound represented by the following general formula (ii-1) or (ii-2),

in the general formula (ii-1),

R₉₁represents a hydrogen atom or a methyl group,

in the general formula (t2), in the formula,

Y₅₁and O of the acryloyl group in the general formula (ii-1),

n represents an integer of 1 to 10;

in the general formula (ii-2),

X₆₁represents a group represented by the following general formula (t3), X₆₂An alkylene group having 1 to 10 carbon atoms,

i and j each independently represent an integer of 0 or 1;

in the general formula (t3), in the formula,

4. The liquid crystal sealing agent according to claim 1, further comprising either (e) an epoxy resin or (f) an acrylic compound.

5. A liquid crystal sealing agent according to claim 1, wherein the component (c) is a photo radical polymerization initiator.

6. A liquid crystal sealing agent according to claim 1, wherein the component (c) is a thermal radical polymerization initiator.

7. The liquid crystal sealing agent according to claim 1, wherein the content of the component (a) is 5 to 90 parts by mass based on 100 parts by mass of the liquid crystal sealing agent.

8. A method for manufacturing a liquid crystal display panel in which 2 substrates are bonded to each other with a liquid crystal sealant, the method comprising:

preparing 1 or more substrates having a frame-shaped display region formed so as to surround a pixel arrangement region with the liquid crystal sealing agent according to claim 1;

9. A liquid crystal display panel obtained by the method for manufacturing a liquid crystal display panel according to claim 8.