KR101269792B1 - Liquid crystal sealing agent, liquid crystal display panel using same, method for producing the liquid crystal display panel, and liquid crystal display device - Google Patents

Abstract

An object of the present invention is to provide a liquid crystal sealing agent which is excellent in curability because the display reliability of the liquid crystal display panel is improved and the crosslinking density of the cured product is high. The liquid-crystal sealing agent of this invention contains the aliphatic epoxy resin (alpha) which has one or more hydroxyl groups and 3 or more epoxy groups and (meth) acryl group in total in one molecule, and the mass mean molecular weight of the said aliphatic epoxy resin (alpha) is 0.3 X10 ³ to 1.0 x 10 ³ .

Description

Liquid crystal sealing agent, the liquid crystal display panel using the same, its manufacturing method, and a liquid crystal display device TECHNICAL FIELD [LIQUID CRYSTAL SEALING AGENT, LIQUID CRYSTAL DISPLAY PANEL USING SAME, METHOD FOR PRODUCING THE LIQUID CRYSTAL DISPLAY PANEL, AND LIQUID CRYSTAL DISPLAY DEVICE}

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

Background Art In recent years, liquid crystal display panels have been widely used as image display panels of various electronic devices such as mobile phones and personal computers because of their advantages such as light weight and high precision. The liquid crystal display panel has a liquid crystal material (hereinafter, simply referred to as "liquid crystal") sandwiched between two transparent substrates provided with electrodes on the surface and the two transparent substrates, and the periphery of which is sealed with a liquid crystal sealing agent. .

Although the amount of the liquid crystal sealing agent is slightly used, the liquid crystal sealing agent is in direct contact with the liquid crystal, which greatly affects the reliability of the liquid crystal display panel. Therefore, in order to realize the high quality of a liquid crystal display panel, a high and various characteristic is currently requested | required of a liquid crystal sealing agent.

Conventionally, the liquid crystal display panel is mainly manufactured by the liquid crystal injection method. In general, the liquid crystal injection method comprises: 1) applying a liquid crystal sealing agent on one transparent substrate to form a mold for filling a liquid crystal, and 2) precuring the substrate to dry the liquid crystal sealing agent, Bonding the other transparent substrate, 3) bonding the two bonded substrates by heat and pressure fastening to obtain a cell for liquid crystal injection, and 4) injecting an appropriate amount of liquid crystal into the liquid crystal injection cell. It is a method including the process of sealing an injection hole and obtaining a liquid crystal display panel.

On the other hand, in recent years, the liquid crystal dropping method is examined as a manufacturing method of the liquid crystal display panel which can improve productivity. In the liquid crystal dropping method, 1) a step of applying a liquid crystal sealing agent on one transparent substrate to form a mold for filling a liquid crystal, and 2) a small amount of liquid crystal is dropped into the mold while the liquid crystal sealing agent is in an uncured state. And a step of overlapping the one transparent substrate and the other transparent substrate under high vacuum, and the step of curing the liquid crystal sealing agent to obtain a liquid crystal display panel. Usually, in the process of 3) and 4) of the liquid crystal dropping method, the liquid crystal sealing agent which has photocurability and thermosetting property is irradiated with light, such as an ultraviolet-ray, to temporarily harden a liquid crystal sealing agent, and is heat-hardened by heating.

By the way, in recent years, the liquid crystal display panel is required to have a high display reliability, specifically, the display does not change even under high temperature and high humidity conditions. As a liquid crystal sealing agent for obtaining high display reliability, a thermosetting resin mainly composed of an epoxy resin has been proposed.

Liquid epoxy resin is proposed as a liquid crystal sealing agent for liquid crystal injection methods or a liquid crystal sealing agent for liquid crystal dropping methods (for example, patent document 1 and 2). In these documents, bisphenol A type liquid epoxy resins and bisphenol F type liquid epoxy resins are preferred as liquid epoxy resins. However, since such liquid epoxy resin has solubility in liquid crystal even at normal temperature, it becomes a factor which lowers the display characteristic of a liquid crystal display panel.

As a liquid-crystal sealing agent with low solubility to a liquid crystal, the (meth) acrylic-acid modified epoxy resin obtained by making a crystalline epoxy resin and acrylic acid whose melting | fusing point 140 degrees C or less react is proposed (for example, patent document 3). Since this (meth) acrylic acid modified epoxy resin has high crystallinity, it is said that it is difficult to melt | dissolve with respect to a liquid crystal. Moreover, the liquid crystal sealing agent for liquid crystal dropping methods containing the (meth) acrylic acid modified epoxy resin and the liquid epoxy resin which has a hydroxyl group is also proposed (for example, patent document 5).

In addition, in recent years, since the production amount of a liquid crystal display panel increases, the hardening time shortening of the liquid crystal sealing agent is also calculated | required. In order to shorten the hardening time of a liquid crystal sealing agent, various proposals which optimize a hardening catalyst are made | formed. The liquid crystal sealing agent for liquid crystal injection methods containing a trisphenol-type epoxy resin and the imidazole system hardening accelerator which has a phenyl group in a 2nd position, and whose melting | fusing point is 170 degreeC or more is proposed (for example, patent document 4).

Japanese Patent Laid-Open No. 1998-273644 Japanese Patent No. 3955038 Japanese Patent Publication No. 2005-018022 Japanese Patent Laid-Open No. 2004-123909 Japanese Patent Publication No. 2005-232370

Although the (meth) acrylic acid modified epoxy resin of patent document 3 was hard to melt | dissolve with respect to a liquid crystal near room temperature, it was easy to melt | dissolve with respect to a liquid crystal under high temperature, high humidity conditions. For this reason, the liquid crystal sealing agent of patent document 3 may reduce the display characteristic of a liquid crystal display panel. Although the liquid crystal sealing agent of patent document 4 has a hardening rate higher than the conventional liquid crystal sealing agent, it was not yet a sufficient level. The hardened | cured material of the liquid crystal sealing agent of patent document 5 was low in crosslinking density, and was low in heat resistance.

That is, when used for a liquid crystal display panel, the liquid crystal injection method or liquid crystal dropping method that can be cured in a short time without changing the display characteristics (hereinafter also referred to as "excellent display reliability") even under high temperature and high humidity conditions Liquid crystal sealing agent for water is calculated | required. This invention is made | formed in view of the said situation, and an object of this invention is to provide the liquid crystal sealing agent which is excellent in sclerosis | hardenability, since the display reliability of a liquid crystal display panel is high, and the crosslinking density of hardened | cured material is high.

1st invention of this invention relates to the following liquid crystal sealing agents and its hardened | cured material.

[1] An aliphatic epoxy resin α having one or more hydroxyl groups and a total of three or more epoxy groups and (meth) acryl groups in one molecule, wherein the mass average molecular weight of the aliphatic epoxy resin α is 0.3 × 10 ³ to 1.0 Liquid crystal sealing agent of * 10 <^3> .

[2] The liquid crystal sealing agent according to [1], wherein the aromatic ring equivalent of the aliphatic epoxy resin α is 400 g / eq or more.

[3] The liquid crystal sealing agent according to [1] or [2], wherein the hydroxyl group equivalent of the aliphatic epoxy resin α is 100 to 300 g / eq, and the epoxy equivalent is 50 to 150 g / eq.

[4] An aliphatic epoxy resin α1 obtained by reacting an epoxidized compound of 3 moles or more (n-1) moles or less with a polyhydric alcohol compound having 1 mole of n-valent (n represents an integer of 4 or more), and the aliphatic Aliphatic epoxy resin (alpha) which consists of either or both of the aliphatic epoxy resin (alpha) 2 which contains both an epoxy group and a (meth) acryl group obtained by making epoxy resin (alpha) 1 and (meth) acrylic acid react, The mass mean of the said aliphatic epoxy resin (alpha) The liquid crystal sealing agent whose molecular weight is 0.3 * 10 <^3> -1.0 * 10 <^3> .

[5] The liquid crystal sealing agent according to [4], wherein the aromatic ring equivalent of the aliphatic epoxy resin α is 400 g / eq or more.

[6] The liquid crystal sealing agent according to any one of [1] to [5], further comprising a latent curing agent and a filler.

[7] The liquid crystal sealing agent according to any one of [1] to [6], wherein the aliphatic epoxy resin α is an aliphatic epoxy resin α2 containing both an epoxy group and a (meth) acryl group.

[8] The liquid crystal sealing agent according to any one of [1] to [7], further comprising an acrylic resin and an optical radical polymerization initiator.

[9] The liquid crystal sealing agent according to any one of [1] to [8], wherein the total amount of the aliphatic epoxy resin α is 5 to 65 mass% with respect to the liquid crystal sealing agent.

[10] The liquid crystal sealing agent according to any one of [1] to [9], further comprising an aromatic epoxy resin β.

[11] The liquid crystal sealing agent according to [10], wherein the softening point of the aromatic epoxy resin β is 50 ° C or higher.

[12] The liquid crystal sealing agent according to [10] or [11], wherein the content of the aromatic epoxy resin β is 5 to 40 mass% with respect to the total amount of the aliphatic epoxy resin α.

[13] A cured product obtained by curing the liquid crystal sealing agent according to any one of [1] to [12].

2nd invention of this invention relates to the manufacturing method of the following liquid crystal display panels.

[14] A first step of forming a sealing pattern of the liquid crystal sealing agent according to any one of [1] to [12] on the first substrate, and in the state where the sealing pattern is uncured, the sealing pattern of the first substrate. A second step of dropping liquid crystal into an enclosed area or an area of a second substrate opposite to the area enclosed by the sealing pattern, a third step of overlapping the first substrate and the second substrate through the sealing pattern, And a fourth step of thermally curing, or thermally curing and photocuring the sealing pattern.

[15] A first step of forming a sealing pattern of the liquid crystal sealing agent according to any one of [1] to [12] on a first substrate, and an agent which overlaps the first substrate and the second substrate through the sealing pattern. 2nd process, the 3rd process of thermosetting said sealing pattern and obtaining the liquid crystal injection cell which has the injection hole for injecting a liquid crystal, the 4th process of injecting a liquid crystal into the said liquid crystal injection cell through the injection hole, and the said injection hole The manufacturing method of the liquid crystal display panel containing the 5th process of sealing.

The third invention of the present invention relates to the following liquid crystal display panels and liquid crystal display devices.

[16] A display substrate, an opposing substrate mating with the display substrate, a frame-shaped sealing member interposed between the display substrate and the opposing substrate, and the sealing member between the display substrate and the opposing substrate. A liquid crystal display panel comprising a liquid crystal layer filled in an enclosed space, wherein the sealing member is a cured product according to [13].

[17] A liquid crystal display device comprising the liquid crystal display panel according to [16].

This invention can provide the liquid crystal sealing agent which is excellent in sclerosis | hardenability, since the display reliability of a liquid crystal display panel is raised, and the crosslinking density of hardened | cured material is high.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows an example of the manufacturing method of the liquid crystal display panel of this invention by the liquid crystal dropping method.
It is a figure which shows an example of the manufacturing method of the liquid crystal display panel of this invention by the liquid crystal injection method.

1. Liquid Crystal Sealing Agent

The liquid crystal sealing agent of this invention contains (A-1) epoxy resin (alpha) (aliphatic epoxy resin (alpha)), and if needed, (A-4) latent hardening | curing agent, (B) filler, (C) acrylic resin, (D) optical radical polymerization initiator, and the like.

(A) epoxy resin

(A-1) Epoxy Resin α

Epoxy resin (alpha) is an aliphatic epoxy resin, and has 1 or more hydroxyl groups in 1 molecule, and 3 or more epoxy groups and a (meth) acryl group in total.

The aliphatic epoxy resin in this invention is an epoxy resin which does not contain an aromatic ring in a molecule | numerator, or contains an aromatic ring substantially in a molecule | numerator. In general, the main chain structure of the aliphatic epoxy resin has flexibility because it does not have the same rigid structure as the aromatic epoxy resin. The liquid crystal sealing agent having flexibility tends to absorb internal stresses and the like, and has good adhesion and sealing properties even in an environment with a temperature change. For this reason, although it is preferable that epoxy resin (alpha) does not contain an aromatic ring in a molecule | numerator, you may have an aromatic ring in a molecule | numerator in the range in which the flexibility of an epoxy resin is maintained. What may have an aromatic ring in a molecule in the range in which the flexibility of an epoxy resin is maintained is also called "it does not contain an aromatic ring substantially in a molecule."

It is preferable that it is 400 g / eq or more, and, as for the aromatic ring equivalent of epoxy resin (alpha), it is more preferable that it is infinite. When the aromatic ring equivalent of epoxy resin (alpha) is less than 400 g / eq, flexibility cannot be provided to the hardened | cured material of a liquid crystal sealing agent, and adhesive strength falls. The aromatic ring equivalent of an epoxy resin can be calculated | required by dividing the molecular weight of an epoxy resin by the number of aromatic rings contained in one molecule of epoxy resin (alpha). When epoxy resin (alpha) contains a condensed ring, the number of the aromatic rings contained in a condensed ring is counted. For example, when a condensed ring is a structure derived from naphthalene, the number of the aromatic rings of the structure derived from naphthalene is two. When a condensed ring is a structure derived from anthracene, the number of the aromatic rings of the structure derived from anthracene is three.

The elasticity modulus of the hardened | cured material of such epoxy resin (alpha) is lower than the elasticity modulus of the hardened | cured material of aromatic epoxy resin (beta) mentioned later. For this reason, the hardened | cured material of the liquid crystal sealing agent of this invention containing epoxy resin (alpha) has flexibility, and reduces the internal stress which arises in a liquid crystal display panel. As a result, the hardened | cured material of the liquid crystal sealing agent of this invention has stable adhesiveness and sealing property also in the environment with a temperature change.

It is preferable that the viscosity measured at 25 degreeC and 2.5 rpm using an E-type viscosity meter of epoxy resin (alpha) is 2-300 Pa.s. It is because it is easy to apply | coat a liquid crystal sealing agent uniformly. The viscosity of the epoxy resin α can be controlled by the mass average molecular weight and the like of the epoxy resin α. In this invention, "-" contains the numerical value of both ends.

It is preferable that the mass mean molecular weight of epoxy resin (alpha) is 0.3 * 10 <^3> -1.0 * 10 <^3> . It is because it is easy to control the viscosity of a liquid crystal sealing agent to the said range. The mass average molecular weight of epoxy resin (alpha) can be measured by mass spectrometry, such as FD-MS.

When a liquid crystal sealing agent melt | dissolves in a liquid crystal, the display characteristic of a liquid crystal display panel may fall. Moreover, the hardened | cured material of an aliphatic epoxy resin tends to be low in heat resistance compared with the hardened | cured material of an aromatic epoxy resin. Therefore, in this invention, polar groups, such as a hydroxyl group, are introduce | transduced into epoxy resin (alpha), and the solubility with respect to a liquid crystal is made low. Moreover, many epoxy groups and (meth) acryl groups are introduce | transduced into epoxy resin (alpha), and the hardening rate and the crosslinking density of hardened | cured material are raised.

As described above, the epoxy resin α has a polar group selected from the group consisting of a hydroxyl group, a thiol group and a carboxyl group. This is to increase the molecular polarity of the epoxy resin α and to lower the solubility in the liquid crystal. It is preferable that epoxy resin (alpha) has a hydroxyl group in a molecule | numerator from the point of the high crosslinking density of hardened | cured material, and easy handling.

The hydroxyl group raises the polarity of the epoxy resin α and lowers the solubility in the liquid crystal. Moreover, since a hydroxyl group makes a hydrogen bond, it makes it easy to make the molecule | numerator of epoxy resin (alpha) adjoin and react. For this reason, it is thought that a hydroxyl group can also raise the crosslinking density of the hardened | cured material of epoxy resin (alpha).

It is preferable that the hydroxyl group equivalent of epoxy resin (alpha) is 100-300 g / eq. It is because an epoxy resin (alpha) can be hydrophilized without molecular weight becoming large too much. The hydroxyl group equivalent of epoxy resin (alpha) is measured by dissolving epoxy resin (alpha) in the pyridine containing acetic anhydride, reacting the hydroxyl group and acetic anhydride of epoxy resin (alpha), and then titrating the resulting acetic acid with KOH. Can be.

Conventionally, when introducing a hydroxyl group into aromatic epoxy resins, such as a bisphenol-type epoxy resin, hydroxyl group was produced by superposing | polymerizing and ring-opening an epoxy group. However, since the molecular weight of the aromatic epoxy resin itself was large, the molecular weight of the epoxy resin obtained was also large. The liquid crystal sealing agent containing the epoxy resin with a large molecular weight has high viscosity, and workability | operativity falls.

In comparison, the molecular weight of aliphatic epoxy resin is small compared with the molecular weight of aromatic epoxy resin. For this reason, a hydrophilized epoxy resin with a small molecular weight can be obtained by introducing a hydroxyl group into the main skeleton of the aliphatic epoxy resin. In general, aliphatic epoxy resins having a low molecular weight are easily dissolved in liquid crystals. However, since the aliphatic epoxy resin having a hydroxyl group introduced into the main skeleton is hydrophilic, its solubility in liquid crystals is low. That is, the liquid crystal sealing agent containing the epoxy resin (alpha) into which the hydroxyl group was introduce | transduced into the main skeleton is excellent in the balance of display reliability and workability of a liquid crystal display panel.

As described above, the epoxy resin α has three or more epoxy groups and (meth) acryl groups in total. For this reason, the crosslinking density of the hardened | cured material of the liquid crystal sealing agent containing epoxy resin (alpha) is high, and it is excellent in sclerosis | hardenability. Moreover, since the hardened | cured material of the liquid crystal sealing agent of this invention has a high crosslinking density, although it is a hardened | cured material of an aliphatic epoxy resin substantially, it is excellent in heat resistance.

It is preferable that the total number of the epoxy group and (meth) acryl group contained in 1 molecule of epoxy resin (alpha) is 3-6. Since epoxy resin (alpha) whose total number of epoxy groups and (meth) acryl groups contained in 1 molecule is less than 3 has low crosslinking density of hardened | cured material, the heat resistance of hardened | cured material becomes low. On the other hand, when the total number of the epoxy groups and (meth) acryl groups contained in one molecule of epoxy resin (alpha) is too large, the storage stability of epoxy resin (alpha) may fall.

The number of (meth) acryl groups contained in the epoxy resin α may be determined depending on the use. For example, the epoxy resin (alpha) 1 which does not contain a (meth) acryl group in a molecule | numerator is used for the liquid crystal sealing agent for liquid crystal injection systems in which thermosetting is calculated | required. Epoxy resin (alpha) 2 containing 1 or more (meth) acryl groups in a molecule | numerator is used for the liquid crystal sealing agent for liquid crystal dropping methods for which thermosetting and photocurability are calculated | required.

It is preferable that the epoxy group contained in epoxy resin (alpha) 1 is 3-6. As mentioned above, when the number of epoxy groups is too small, the crosslinking density of the hardened | cured material of epoxy resin (alpha) 1 will be low, and when too many, the storage stability of epoxy resin (alpha) 1 may fall.

The number of epoxy groups contained in one molecule of epoxy resin α1 can be determined by the molecular weight and epoxy equivalent of epoxy resin α1. For example, when the molecular weight of epoxy resin (alpha) 1 is 300 and epoxy equivalent is 100 g / eq, the number of epoxy groups contained in 1 molecule of epoxy resin (alpha) 1 is calculated | required as 300/100 = 3. When the number of obtained epoxy groups is a decimal number, the decimal point is rounded off. For example, when the molecular weight of the epoxy resin α1 is 320 and the epoxy equivalent is 109 g / eq, the number of epoxy groups contained in one molecule of the epoxy resin α1 may be 320/109 = 2.9 = 3.

It is preferable that the epoxy equivalent of epoxy resin (alpha) 1 is 50-150 g / eq. The epoxy equivalent of epoxy resin (alpha) 1 can be measured by dissolving epoxy resin (alpha) 1 in the dioxane hydrochloric acid solution, and then titrating the amount of hydrochloric acid consumed by an epoxy group.

Epoxy resin α1 is obtained by any method. Epoxy resin (alpha) 1 is obtained by making 3 mol or more (n-1) mol or less epoxidized compound react with alkali with respect to 1 mol of n-valent aliphatic polyhydric alcohol compound. n is an integer of 4 or more.

Examples of the n-valent (n is an integer of 4 or more) aliphatic polyhydric alcohol compounds include xylitol, sorbitol, pentaerythritol, mannitol, diglycerin, polyglycerine, and the like. Epichlorohydrin etc. are contained in the example of an epoxidation compound.

Epoxy resin (alpha) 1 is also obtained by epoxidizing the aliphatic polyhydric alcohol compound which has an unsaturated double bond with peracid. In addition, epoxy resin (alpha) 1 is obtained also by making hydrogenated bisphenol, such as hydrogenated bisphenol-A epoxy resin, and epichlorohydrin react in presence of alkali.

Epoxy resin (alpha) 2 ((meth) acrylic acid modified epoxy resin) has an epoxy group and a (meth) acryl group in 1 molecule. For this reason, epoxy resin (alpha) 2 can improve the compatibility of an epoxy resin and an acrylic resin. As a result, a cured product having a high glass transition temperature (Tg) and excellent adhesion can be obtained.

The number of (meth) acryl groups contained in epoxy resin (alpha) 2 should just be one or more. Epoxy resin (alpha) 2 containing many (meth) acryl groups has high photocurability and high affinity with acrylic resin etc. Epoxy resin (alpha) 2 containing many epoxy groups has high thermosetting property, and its affinity with epoxy resin (alpha) 1 etc. is high.

Epoxy resin (alpha) 2 is obtained by making the above-mentioned epoxy resin (alpha) 1 and (meth) acrylic acid react. It is preferable to adjust reaction conditions so that (meth) acrylic acid may react preferentially rather than the hydroxyl group contained in epoxy resin (alpha) 1. For example, it is preferable to make epoxy resin (alpha) 1 and (meth) acrylic acid react at comparatively low temperature (30-100 degreeC) in presence of a tertiary amine. It is because reaction of the epoxy group contained in epoxy resin (alpha) 1, and the carboxyl group contained in (meth) acrylic acid takes precedence. It is preferable that epoxy resin (alpha) 1 is highly purified by molecular distillation, a washing method, etc.

(A-2) Aromatic Epoxy Resin β

The liquid crystal sealing agent of this invention may contain aromatic epoxy resin (beta).

Examples of the aromatic epoxy resin β include aromatic polyhydric glycidyl ether compounds obtained by reaction of aromatic diols or aromatic diols modified with ethylene glycol, propylene glycol, alkylene glycol, and epichlorohydrin; Novolak-type polyvalent glycidyl ether compounds obtained by reaction of polyphenols and epichlorohydrin; The glycidyl ether compound etc. which are obtained by reaction of a xylene phenol resin and epichlorohydrin are included.

Examples of aromatic diols include bisphenol A, bisphenol S, bisphenol F, bisphenol AD and the like. For example, the aromatic polyvalent glycidyl ether compound obtained by the reaction of bisphenol A and epichlorohydrin is a bisphenol A epoxy resin.

Examples of polyphenols include novolac resins derived from phenol and formaldehyde, novolac resins derived from cresol and formaldehyde, polyalkenylphenols and copolymers thereof.

Aromatic epoxy resin (beta) is a cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a triphenol methane type epoxy resin, a triphenol ethane type epoxy resin, a trisphenol, among others Type epoxy resins, dicyclopentadiene type epoxy resins, diphenyl ether type epoxy resins, biphenyl type epoxy resins, and the like are preferable. These may be used by one type or may be used in combination of 2 or more types.

The softening point by the round ball method of aromatic epoxy resin (beta) is 40 degreeC or more, Preferably it is 50 degreeC or more. When the softening point of aromatic epoxy resin (beta) exists in the said range, the solubility and diffusivity with respect to the liquid crystal of aromatic epoxy resin (beta) is low, and the display characteristic of the liquid crystal display panel obtained becomes favorable. Examples of the aromatic epoxy resin β having a softening point of 50 ° C. or more include a cresol novolac epoxy resin, a phenol novolac epoxy resin, and the like.

It is preferable that the mass mean molecular weight of aromatic epoxy resin (beta) is 0.1 * 10 <^4> -1.0 * 10 <^4> . When the mass average molecular weight of aromatic epoxy resin (beta) exists in the said range, a viscosity will not become high too much, compatibility with epoxy resin (alpha), the acrylic resin mentioned later, etc. are favorable, and the adhesive reliability of a liquid-crystal sealing agent improves. It is more preferable that the softening point by the round ball method of aromatic epoxy resin (beta) is 40 degreeC or more, and the mass mean molecular weight is 0.1 * 10 <^4> -1.0 * 10 <^4> .

The mass average molecular weight of the aromatic epoxy resin β can be measured based on polystyrene, for example, by gel permeation chromatography (GPC). It is preferable that aromatic epoxy resin (beta) is highly purified by the molecular distillation method.

(A-3) Other Epoxy Resin

The liquid crystal sealing agent of this invention may also contain other epoxy resin as needed. Other epoxy resins include (meth) acrylic acid modified aromatic epoxy resins. The (meth) acrylic acid modified aromatic epoxy resin is an aromatic epoxy resin having an epoxy group and a (meth) acryl group in one molecule.

Examples of the (meth) acryl-modified aromatic epoxy resin include resins obtained by reacting an aromatic epoxy resin with (meth) acrylic acid or phenyl methacrylate under a basic catalyst, for example. The aromatic epoxy resin which becomes a raw material may be well-known aromatic epoxy resins, such as a bisphenol-type epoxy resin and a novolak-type epoxy resin.

When using a bifunctional epoxy resin having two epoxy groups in a molecule such as bisphenol A type epoxy resin and bisphenol F type epoxy resin as a raw material, the ratio of the number of epoxy groups and the number of (meth) acryl groups is almost 1: 1. It is preferred to react the bifunctional epoxy resin with (meth) acrylic acid.

(A-4) latent curing agent

The liquid crystal sealing agent of this invention may contain a latent hardening | curing agent. The latent curing agent refers to a curing agent that does not cure the epoxy resin in a normal storage state (room temperature, visible light, etc.) even when mixed with an epoxy resin, but when heat or light is given. The liquid crystal sealing agent containing a latent hardener is excellent in storage stability, and also excellent in thermosetting. Although a latent hardener can use a well-known thing, It is preferable that the softening point temperature by melting | fusing point or ring-ball method (JACT test method: RS-2) is 100 degreeC or more. It is because the viscosity stability of a liquid crystal sealing agent can be improved.

Preferred examples of the latent curing agent include organic acid dihydrazide compounds, imidazoles, derivatives of imidazoles, dicyandiamides, aromatic amines, and the like. These may be used independently and may be used in combination of multiple.

It is preferable to add a latent hardener so that the ratio of the active hydrogen equivalent of the latent hardener to the epoxy equivalent of the whole epoxy resin may be 0.8 to 1.2. This is to increase the crosslinking density of the cured epoxy resin.

As such, the liquid crystal sealing agent containing the latent curing agent may be a one-liquid curable resin composition. Since a one-liquid curable resin composition does not need to mix a hardening | curing agent further at the time of its use, it is excellent in workability.

(B) filler

The liquid crystal sealing agent of this invention may contain the filler further. A filler means the filler added for the purpose of viscosity control of a liquid crystal sealing agent, the strength improvement of hardened | cured material, control of a linear expansion rate, etc. The hardened | cured material of the liquid crystal sealing agent containing a filler is easy to maintain adhesiveness even in the environment where temperature and humidity change are large (adhesion reliability improves).

The filler is not limited as long as it is usually used in the field of electronic materials. The filler may be an inorganic filler or may be an organic filler.

Examples of the inorganic filler include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, glass Inorganic fillers such as beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride and the like.

The organic filler may be polymer particles having a softening point temperature of more than 120 ° C. by a ball mouth method (JACT test method: RS-2). Examples of such an organic filler include polystyrene and a copolymer obtained by copolymerizing styrene with a monomer copolymerizable therewith, polyester fine particles, polyurethane fine particles, rubber fine particles and the like. Especially, an inorganic filler is preferable at the point which can reduce the linear expansion rate of a liquid crystal sealing agent, and can maintain the shape of a liquid crystal sealing agent favorably, and silicon dioxide, talc, etc. are especially preferable.

The shape of the filler is not particularly limited, and may be a spherical shape, a plate shape, a needle shape or the like, or an amorphous shape. It is preferable that the average primary particle diameter of a filler is 1.5 micrometers or less, and the specific surface area is 1m <^2> / g-500m <^2> / g.

The average primary particle diameter of a filler can be measured by the laser diffraction method described in JIS Z8825-1. The measurement of the specific surface area of a filler can be measured by the BET method as described in JIS Z8830.

The content of the filler is the total of (A-1) epoxy resin α, (A-2) aromatic epoxy resin β, (A-4) latent curing agent and (C) acrylic resin (hereinafter also referred to as "resin unit") It is preferable that it is 1-50 mass parts with respect to 100 mass parts, and it is more preferable that it is 10-30 mass parts.

(C) acrylic resin

The liquid crystal sealing agent of this invention may contain an acrylic resin. Acrylic resin refers to acrylic acid esters and / or methacrylic acid esters or oligomers thereof.

Examples of the acrylic resin include diacrylates and / or dimethacrylates such as polyethylene glycol, propylene glycol and polypropylene glycol;

Diacrylates and / or dimethacrylates of tris (2-hydroxyethyl) isocyanurate;

Diacrylate and / or dimethacrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol;

Diacrylate and / or dimethacrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A;

Di or triacrylate and / or di or trimethacrylate of triols obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole trimethylolpropane;

Diacrylate and / or dimethacrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A;

Tris (2-hydroxyethyl) isocyanurate triacrylate and / or trimethacrylate;

Trimethylolpropanetriacrylate and / or trimethacrylate, or oligomers thereof;

Pentaerythritol triacrylate and / or trimethacrylate, or oligomers thereof;

Polyacrylates and / or polymethacrylates of dipentaerythritol;

Tris (acryloxyethyl) isocyanurate;

Caprolactone modified tris (acryloxyethyl) isocyanurate;

Caprolactone modified tris (methacryloxyethyl) isocyanurate;

Polyacrylates and / or polymethacrylates of alkyl modified dipentaerythritol;

Polyacrylates and / or polymethacrylates of caprolactone modified dipentaerythritol;

Hydroxypivalic acid neopentylglycol diacrylate and / or dimethacrylate;

Caprolactone modified hydroxypivalic acid neopentylglycol diacrylate and / or dimethacrylate;

Ethylene oxide modified phosphoric acid acrylate and / or dimethacrylate;

Ethylene oxide modified alkylated phosphate acrylates and / or dimethacrylates;

Neopentylglucol, trimethylolpropane, oligoacrylates and / or oligomethacrylates of pentaerythritol, and the like.

Examples of the acrylic resin include resins obtained by reacting all epoxy groups contained in the epoxy resin with (meth) acrylic acid. Examples of the epoxy resin to be used as raw materials include cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, triphenol methane type epoxy resins, triphenol ether type epoxy resins, and tris Phenol type epoxy resins, diphenyl ether type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, and the like.

(D) radical photopolymerization initiator

The liquid crystal sealing agent of this invention may contain an optical radical polymerization initiator. If the liquid crystal sealing agent contains an optical radical polymerization initiator, it is excellent in workability because the liquid crystal sealing agent can be temporarily cured by photocuring when the liquid crystal panel is produced.

As an optical radical polymerization initiator, a well-known thing is used. Examples of the optical radical polymerization initiators include benzoin compounds, acetophenones, benzophenones, thioxanthones, α-acyl oxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, Acylphosphine oxide compounds, organic pigment compounds, iron-phthalocyanine compounds, benzoins, benzoin ethers, anthraquinones and the like.

(E) epoxy modified particles

The liquid crystal sealing agent of this invention may contain an epoxy modified particle. Epoxy modified particles are thermoplastic resin particles modified with epoxy resin. It is preferable that especially an epoxy modified particle is contained in the liquid crystal sealing agent for liquid crystal injection system. It is because an epoxy modified particle can relieve the shrinkage stress which arises in the hardened | cured material of a liquid crystal sealing agent by the heating at the time of thermosetting.

Epoxy-modified particles are obtained by suspension polymerization of a resin containing an epoxy group and a double bond group with a monomer capable of radical polymerization. Examples of the resin containing an epoxy group and a double bond group include a resin obtained by reacting a bisphenol F-type epoxy resin with (meth) acrylic acid in the presence of a tertiary amine. Examples of the monomer capable of radical polymerization include butyl acrylate, glycidyl methacrylate, divinylbenzene, and the like.

It is preferable that it is 0.05-5 micrometers normally, and, as for the average particle diameter of epoxy modified particle | grains, it is more preferable that it is the range of 0.07-3 micrometers. This is because the gap of the space where the liquid crystal is filled in the liquid crystal cell is 5 μm or less in many cases. It is preferable that the addition amount of an epoxy modified particle is 1-30 mass parts with respect to 100 mass parts of resin units.

(F) Other additives

The liquid crystal sealing agent of this invention may contain various additives as needed. Examples of the additive include a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchange agent, a leveling agent, a pigment, a dye, a plasticizer, an antifoaming agent, and the like. In order to adjust the gap of the space where the liquid crystal is filled in the liquid crystal cell, a spacer or the like may be blended.

It is preferable that the liquid crystal sealing agent which hardens only by heating contains a thermal radical polymerization initiator. It is because even if a liquid crystal sealing agent contains the epoxy resin (alpha) 2 which has a (meth) acryl group, it can harden | cure only by heating.

The liquid crystal sealing agent of this invention (A-1) epoxy resin (alpha) and (A-2) aromatic epoxy resin (beta), (A-3) other epoxy resin, and (A-4) latent property further depending on a use. It may optionally contain one or more compounds selected from the group consisting of a curing agent, (B) filler, (C) acrylic resin and (D) optical radical polymerization initiator.

It is preferable that it is 5-65 mass% in a liquid crystal sealing agent, and, as for the total amount of epoxy resin (alpha), it is more preferable that it is 5-30 mass%.

It is preferable that the liquid crystal sealing agent used for a liquid crystal injection method contains (A-1) epoxy resin (alpha) 1 and (A-4) latent hardening | curing agent. This is because in the liquid crystal injection method, the liquid crystal sealing agent is often hardened only by heating.

It is preferable that the liquid crystal sealing agent used for a liquid crystal dropping method contains (A-1) epoxy resin (alpha) 2, (A-4) latent hardening | curing agent, (C) acrylic resin, and (D) optical radical polymerization initiator, ( It is more preferable that A-1) epoxy resin (alpha) 1 is further included. This is because it enables not only the thermal curing of the liquid crystal sealing agent but also the optical curing (curing in a short time).

(A-1) It is preferable that content of epoxy resin (alpha) 2 is 60 mass% or less in the resin unit of the liquid crystal sealing agent for liquid crystal dropping methods, It is more preferable that it is 25 mass% or less, It is more preferable that it is 15 mass% or less. It is preferable that it is 20 mass% or less in a resin unit, and, as for content of (C) acrylic resin, it is more preferable that it is 15 mass% or less. When the liquid crystal sealing agent for liquid crystal dropping methods contains the (A-3) (meth) acrylic acid modified aromatic epoxy resin, it is preferable that content is also 15 mass% or less in a resin unit.

It is preferable that content of an optical radical polymerization initiator is 0.3-5.0 mass parts with respect to 100 mass parts of resin units. By making content of an optical radical polymerization initiator into 0.3 mass part or more, the crosslinking density of the hardened | cured liquid crystal sealing agent by light irradiation improves. By making content of an optical radical polymerization initiator into 5.0 mass part or less, the storage stability of the liquid crystal sealing agent at the time of apply | coating a liquid crystal sealing agent to a board | substrate becomes favorable.

It is preferable that the liquid crystal sealing agent of this invention further contains (A-2) aromatic epoxy resin (beta) irrespective of a liquid crystal injection method or a liquid crystal dropping method. It is because heat resistance of a liquid crystal sealing agent can be improved. It is preferable that content of aromatic epoxy resin (beta) is 15 mass% or less in a resin unit. Moreover, it is preferable that it is 5-40 mass% with respect to the total amount of epoxy resin (alpha), and, as for content of aromatic epoxy resin (beta), it is more preferable that it is 5-30 mass%.

It is preferable that the viscosity measured at 25 degreeC and 2.5 rpm using the E-type viscosity meter of the liquid crystal sealing agent of this invention is 30-350 Pa.s. This is because the liquid crystal sealing agent can be applied uniformly and workability is good. The viscosity of the liquid crystal sealing agent can be controlled by the mass average molecular weight, content and the like of the epoxy resin α and the aromatic epoxy resin β. For example, when the mass ratio of the aromatic epoxy resin β to the epoxy resin α is reduced, the viscosity of the liquid crystal sealing agent can be lowered.

The liquid crystal sealing agent of this invention can be arbitrarily manufactured in the range which does not impair the effect of this invention. The liquid crystal sealing agent of this invention mixes and prepares the required component among (A-1) epoxy resin (alpha) and each component (A-2)-(F) mentioned above.

Examples of the mixing method of each component include mixing methods using known kneaders such as a double arm type stirrer, roll kneader, twin screw extruder, ball mill kneader, planetary stirrer and the like. It is preferable that kneading temperature is 25-35 degreeC. This is for kneading uniformly without gelling the liquid crystal sealing agent. The obtained mixture is sealed and filled in a glass bottle or a poly container after the filtration treatment by a filter and the vacuum defoaming treatment are performed as needed.

2. Liquid crystal display panel and manufacturing method thereof

The liquid crystal display panel of the present invention is provided in a space surrounded by a display substrate, an opposing substrate paired with the display substrate, a frame-shaped sealing member interposed between the display substrate and the opposing substrate, and a sealing member between the display substrate and the opposing substrate. And a filled liquid crystal layer. The hardened | cured material of the liquid crystal sealing agent of this invention can be used as a sealing member.

Both the display substrate and the opposing substrate are transparent substrates. The material of the transparent substrate may be glass or plastic such as polycarbonate, polyethylene terephthalate, polyether sulfone and PMMA.

On the surface of the display substrate or the counter substrate, a TFT on a matrix, a color filter, a black matrix, or the like may be disposed. The alignment film is further formed on the surface of the display substrate or the counter substrate. A well-known organic aligning agent, an inorganic aligning agent, etc. are contained in an oriented film.

The liquid crystal display panel can be manufactured using the liquid crystal sealing agent of the present invention. The manufacturing method of a liquid crystal display panel has the liquid crystal dropping method and the liquid crystal injection method.

The manufacturing method of the liquid crystal display panel by a liquid crystal dropping method,

1) 1st process which forms the sealing pattern of the liquid crystal sealing agent of this invention in one board | substrate,

2) a second step of dropping liquid crystal into a region surrounded by a sealing pattern of the substrate or a region of the other substrate facing the region surrounded by the sealing pattern while the sealing pattern is uncured;

3) a third process of overlapping one substrate with the other substrate through a sealing pattern, and

4) 4th process of hardening a sealing pattern.

In the process of 2), the state in which a sealing pattern is uncured means the state which hardening reaction of a liquid crystal sealing agent does not advance to a gelation point. For this reason, in the process of 2), a sealing pattern can also be semi-hardened by light irradiation or heating. This is because the semi-cured liquid crystal sealing agent is difficult to dissolve in the liquid crystal. One substrate and the other substrate are respectively a display substrate or an opposing substrate.

Although the hardening by heating can also be performed at the process of 4), after hardening (temporary hardening) by light irradiation, it is preferable to harden | cure by hardening (main hardening).

Although photocuring time is based also on the composition of a liquid crystal sealing agent, it is about 10 minutes, for example. Light irradiation energy should just be energy of the grade which hardens reaction of epoxy resin (alpha) 2, an acrylic resin, etc. The light is preferably ultraviolet light. Although the thermosetting temperature is based also on the composition of a liquid crystal sealing agent, it is 120 degreeC, for example, and a thermosetting time is about 2 hours.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows an example of the manufacturing method of the liquid crystal display panel by a liquid crystal dropping method. As shown in FIG. 1A, the sealing pattern 14 of the liquid crystal sealing agent of this invention is formed in the board | substrate 12 [process of 1]. 1B, the liquid crystal 16 is dripped in the area | region enclosed with the sealing pattern 14 of the board | substrate 12 in the state in which the sealing pattern 14 is uncured (process of 2). Subsequently, as shown in FIG. 1C, the substrate 12 and the substrate 18 are overlapped through the sealing pattern 14 to obtain a laminate 20. The laminate 20 is irradiated with light to photocure the sealing pattern 14 [3] and 4). Thereafter, as shown in FIG. 1D, the laminate 20 is heated to further heat-cur the sealing pattern 14 (step 4).

In the liquid crystal dropping method, the contact time of an uncured liquid crystal sealing agent and a liquid crystal is comparatively long, and liquid crystal contamination is easy to produce. On the other hand, since the solubility to a liquid crystal is low in the liquid crystal sealing agent of this invention, a liquid crystal is hard to be contaminated. Therefore, the liquid crystal display panel obtained by the liquid crystal dropping method using the liquid crystal sealing agent of this invention is excellent in display reliability.

The manufacturing method of the liquid crystal display panel by a liquid crystal injection method,

1) 1st process which forms the sealing pattern of the liquid crystal sealing agent of this invention in one board | substrate,

2) a second process of overlapping one substrate and the other substrate through a sealing pattern;

3) a third step of thermally curing the sealing pattern to obtain a liquid crystal injection cell having an injection hole for injecting liquid crystal;

4) a fourth step of injecting the liquid crystal into the liquid crystal injection cell through the injection hole, and

5) The fifth process of sealing an injection hole is included.

In the process of 1) -3), the cell for liquid crystal injection is prepared. First, two transparent substrates (for example, glass plates) are prepared. And a sealing pattern is formed in one board | substrate with a liquid crystal sealing agent. What is necessary is just to harden a sealing pattern after the other board | substrate is laminated | stacked on the surface in which the sealing pattern of the board | substrate was formed. At this time, it is necessary to provide an injection hole for injecting liquid crystal into a part of the liquid crystal injection cell. The method of forming an injection hole includes the method of providing an opening part in drawing a sealing pattern; After forming a frame-shaped sealing pattern, the method of installing an opening by removing the sealing pattern of a desired part, etc. are included.

Although the thermosetting conditions in the process of 3) are based also on the composition of a liquid crystal sealing agent, they are about 2 to 5 hours at 150 degreeC, for example.

What is necessary is just to perform the process of 4) according to the well-known method of making the inside of the liquid crystal injection cell obtained by the process of 1)-3) into a vacuum state, and sucking a liquid crystal from the injection port of the liquid crystal injection cell. In the process of 5), after sealing a liquid crystal sealing agent in the injection port of the cell for liquid crystal injection, it can also harden.

2 is a diagram illustrating an example of a method of manufacturing a liquid crystal display panel by a liquid crystal injection method. In the same figure, members having the same functions as those in FIG. 1 have the same reference numerals. As shown in FIG. 2A, the sealing pattern 14 of the liquid crystal sealing agent of this invention is formed in the board | substrate 12 [process of 1]. As shown in FIG. 2B, the substrate 12 and the substrate 18 are superimposed through the sealing pattern 14, and then the sealing pattern 14 is thermally cured. Thereby, the cell 22 for liquid crystal injection which has the injection port 22A is obtained [process of 2 and 3]. As shown in FIG. 2C, the liquid crystal 16 is injected into the liquid crystal injection cell 22 through the injection port 22A. As shown in Fig. 2D, a liquid crystal sealing agent or the like is sealed in the injection port 22A and sealed (step 5).

Thus, in the liquid crystal injection method, when preparing the cell for liquid crystal injection, a liquid crystal sealing agent is thermosetted. For this reason, the time which an uncured liquid crystal sealing agent and a liquid crystal contact is comparatively short. However, even if curing of the liquid crystal sealing agent is insufficient, the liquid crystal may be injected into the cell for liquid crystal injection. Even in such a case, the liquid crystal sealing agent of this invention has low solubility to a liquid crystal, and it is hard to pollute a liquid crystal. As a result, the liquid crystal display panel obtained by the liquid crystal injection method using the liquid crystal sealing agent of this invention is also excellent in display reliability.

Moreover, since the hardened | cured material of the liquid crystal sealing agent of this invention has flexibility, the internal stress which arises in a liquid crystal display panel is reduced, and it has high sealing property. For this reason, the liquid crystal display panel which contains the hardened | cured material of the liquid crystal sealing agent of this invention as a sealing member is also excellent in the display reliability under high temperature, high humidity conditions.

[Example]

Synthesis Example 1

Synthesis of Liquid Epoxy Resin A (Epoxy Resin α1)

0.1 mole of xylitol was dissolved in 100 ml of dimethylsulfoxide. 0.4 mol of pellet-shaped potassium hydroxide was added to this solution, and 0.3 mol of epichlorohydrin was added dropwise at 25 ° C while stirring. After completion of the dropwise addition, the reaction was further stirred for 12 hours. 300 mL of pure water was added to the obtained reaction liquid after completion | finish of reaction, it extracted five times with hexane, and the extract liquid was collect | recovered. Hexane was distilled off from the extract and purified by silica gel chromatography to obtain 16.8 g of transparent liquid epoxy resin A.

The molecular weight of the liquid epoxy resin A was measured by electrolytic dissociation mass spectrometry (FD-MS method), and the molecular weight was 320. Furthermore, the hydroxyl group equivalent of liquid epoxy resin A was dissolved in the pyridine solution containing acetic anhydride, and hydrolyzed by water. After hydrolysis, the resulting acetic acid was measured by titration with KOH. The hydroxyl group equivalent of liquid epoxy resin A was 160 g / eq. In addition, the epoxy equivalent of liquid epoxy resin A was measured by the dioxane hydrochloride method. Epoxy equivalent was 109 g / eq. From the epoxy equivalent and molecular weight of liquid epoxy resin A, the epoxy group number of liquid epoxy resin A was computed as 320/109 = about 3.

[Synthesis Example 2]

Synthesis of Liquid Epoxy Resin B (Epoxy Resin α1)

0.1 mole of sorbitol was dissolved in 100 ml of dimethylsulfoxide. 0.4 mol of pellet-shaped potassium hydroxide was added to this solution, and 0.4 mol of epichlorohydrin was added dropwise at 25 ° C while stirring. After completion of the dropwise addition, the reaction was further stirred for 12 hours. 300 mL of pure water was added to the obtained reaction liquid after completion | finish of reaction, it extracted five times with hexane, and the extract liquid was collect | recovered. Hexane was distilled off from the extract and purified by silica gel chromatography to obtain 19.2 g of a transparent liquid epoxy resin B.

The molecular weight, hydroxyl group equivalent, and epoxy equivalent of the obtained liquid epoxy resin B were measured in the same manner as in Synthesis example 1. The molecular weight of liquid epoxy resin B was 406. The hydroxyl group equivalent of liquid epoxy resin B was 203g / eq, and the epoxy equivalent was 102g / eq. From the epoxy equivalent and molecular weight of liquid epoxy resin B, the number of epoxy groups of liquid epoxy resin B was computed as 406/203 = about 4.

[Synthesis Example 3]

Synthesis of Liquid Epoxy Resin C

0.1 mol of pentaerythritol was dissolved in 100 ml of dimethyl sulfoxide. 0.4 mol of pellet-shaped potassium hydroxide was added to this solution, and 0.2 mol of epichlorohydrin was added dropwise at 25 ° C while stirring. After completion of the dropwise addition, the reaction was further stirred for 12 hours. 300 mL of pure water was added to the obtained reaction liquid after completion | finish of reaction, it extracted five times with hexane, and the extract liquid was collect | recovered. Hexane was distilled off from the extract and purified by silica gel chromatography to obtain 24.8 g of a transparent liquid epoxy resin C.

The molecular weight, hydroxyl group equivalent, and epoxy equivalent of the obtained liquid epoxy resin C were measured in the same manner as in Synthesis example 1. The molecular weight of liquid epoxy resin C was 248. The hydroxyl group equivalent of the liquid epoxy resin C was 124 g / eq, and the epoxy equivalent was 124 g / eq. From the epoxy equivalent and molecular weight of liquid epoxy resin C, the number of epoxy groups of liquid epoxy resin C was computed as 248/124 = 2.

[Synthesis Example 4]

Synthesis of Liquid Epoxy Resin D

0.1 mole of acetic acid and 2 mmol of triethanolamine were added to 0.1 mole of tetrafunctional liquid epoxy resin (YH-434: manufactured by Tohto Chemical Co., Ltd.), and the mixture was heated and stirred at 130 ° C. for 6 hours to produce an aromatic epoxy resin D having a hydroxyl group. 48.2 g was obtained.

The molecular weight, hydroxyl group equivalent, and epoxy equivalent of the obtained aromatic epoxy resin D were measured in the same manner as in Synthesis example 1. The molecular weight of aromatic epoxy resin D was 482. The hydroxyl group equivalent of aromatic epoxy resin D was 482 g / eq, and the epoxy equivalent was 161 g / eq. From the epoxy equivalent and molecular weight of aromatic epoxy resin D, the epoxy group number of aromatic epoxy resin D was computed as 482/161 = about 3.

In addition to the compound, the following materials were prepared.

Epoxy resin E: aliphatic epoxy monomer, 1, 6- hexanediol diglycidyl ether (made by Nagase ChemteX: EX-212L, epoxy equivalent 135 g / eq)

Epoxy Resin F: A hydroxyl group-containing epoxy monomer (manufactured by D.I.C .: EXA-7120)

Epoxy Resin G: Aromatic epoxy monomer, O-cresol novolac type epoxy resin (manufactured by Nihon Chemical Co., Ltd .: EOCN-1020-75, epoxy equivalent 215 g / eq)

Synthesis Example 5

Synthesis of Methacrylic Acid Modified Epoxy Resin A (Epoxy Resin α2)

0.5 mole of liquid epoxy resin A and 0.5 mole of methacrylic acid obtained in Synthesis Example 1 were heated and stirred at 110 ° C. for 6 hours while bubbling in dry air in the presence of 2 mmol of triethanolamine, and methacrylic modified epoxy resin A 203 g was obtained.

The molecular weight, hydroxyl group equivalent, and epoxy equivalent of the obtained methacryl modified epoxy resin A were measured similarly to the synthesis example 1. The molecular weight of methacrylic acid modified epoxy resin A was 406, the hydroxyl group equivalent was 135 g / eq and the epoxy equivalent was 203 g / eq.

[Synthesis Example 6]

Synthesis of Methacrylic Acid Modified Epoxy Resin B (Epoxy Resin α2)

0.5 moles of bisphenol F-type epoxy resin (Epothode YDF-8170C manufactured by DOTO Chemical Co., Ltd.) and 0.5 mole of methacrylic acid were heated at 110 ° C. for 6 hours while bubbling in dry air in the presence of 2 mmol of triethanolamine. The reaction was stirred. The reaction solution was diluted with toluene, washed 12 times with pure water, and toluene was distilled off to obtain 146 g of methacryl-modified epoxy resin B.

The molecular weight, hydroxyl group equivalent, and epoxy equivalent of the obtained methacryl modified epoxy resin B were measured similarly to the synthesis example 1. The molecular weight of methacrylic acid modified epoxy resin B was 396, the hydroxyl group equivalent was 396 g / eq and the epoxy equivalent was 396 g / eq.

The properties of the liquid epoxy resins A to G and the (meth) acryl modified epoxy resins A to B are shown in Table 1.

[Synthesis Example 7]

Synthesis of Epoxy Modified Particles

0.625 moles of bisphenol F-type epoxy resin (Epothode YDF-8170C manufactured by Dohto Chemical Co., Ltd.) and 0.12 mole of methacrylic acid were bubbled under dry air in 50 ml of toluene in the presence of 8.2 mmol of triethanolamine. Was reacted at 110 ° C for 5 hours. 0.16 mol of butyl acrylate, 0.16 mol of glycidyl methacrylate, 7.7 mmol of divinylbenzene, 7 mmol of azobismethylvaleronitrile and 14 mmol of azobisisobutyronitrile were added to the reaction solution. . This reaction liquid was polymerized at 70 degreeC for 3 hours, and also 90 degreeC for 1 hour, and epoxy modified particle | grains were obtained.

In addition, the following materials were prepared.

Latent curing agent A (epoxy curing agent A): 1, 3-bis (hydrazino carboethyl) -5-isopropyl hydantoin (Amicure VDH by Ajinomoto Co., Ltd., melting | fusing point 120 degreeC)

Latent curing agent B (epoxy curing agent B): Xylylene phenol novolak resin (made by Mitsui Chemicals, Mirex XLC-LL, melting | fusing point 120 degreeC)

Latent curing agent C (epoxy curing agent C): 2-phenylimidazole isocyanuric acid adduct (made by Shikoku Chemical Co., Ltd., curazole 2PZ-OK)

Acrylic resin: Bisphenol A type epoxy resin modified diacrylate

Filling material: spherical silica (manufactured by Nippon Shokubai, C-poster S-30)

Optical radical generating agent: Irgacure 184 (product made in Chiba specialty chemical company)

Coupling Agent: γ-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)

Solvent: Propylene Glycol Diacetate

Example 1

75 mass parts liquid epoxy resin B, 15 mass parts epoxy resin G, 10 mass parts latent curing agent A, 2 mass parts latent curing agent C, 30 mass parts filler, 10 mass parts epoxy modified particle, 1 mass part coupling agent, and 8 The mass part solvent was mixed with a Dalton mixer, and then fully kneaded using three rolls to obtain a paste liquid crystal sealing agent.

1) viscosity, 2) viscosity stability, 3) leak resistance, 4) dispense coating property, 5) screen printing applicability, 6) display characteristics of liquid crystal display panel, 7) sealing observation and 8) adhesion of liquid crystal sealing agent The strength was evaluated by the following method. Moreover, 9) glass transition temperature (Tg) of the hardened | cured material of a liquid crystal sealing agent was measured. The results are shown in Table 2.

1) Viscosity measurement

The viscosity of the liquid-crystal sealing agent was measured using the E-type rotational viscometer (made by BROOKFIELD: digital rheometer type DV-III ULTRA). Specifically, after leaving the liquid-crystal sealing agent to stand at 25 degreeC for 5 minutes, it measured at the rotation speed 2.5rpm using the CP-52 cone plate type sensor of 12 mm of radius and an angle of 3 degree. The viscosity at 25 degrees C and 2.5 rpm by the E-type viscosity meter of the paste-like liquid crystal sealing agent of Example 1 was 50 Pa.s.

2) viscosity stability

The liquid crystal sealing agent was weighed so that the mass of the liquid crystal sealing agent in the syringe for dispensing might be 10 g, and the defoaming process was performed. Using 2 g of them, the initial viscosity a was measured by the method similar to 1). Next, the liquid crystal sealing agent viscosity b after storing for one week at 23 degreeC 50% RH was measured again. The rate of increase of the viscosity b after one week with respect to the initial viscosity a was set to (b-a) / a. Viscosity stability was evaluated based on the following criteria.

The rate of increase is 1.5 times or less: excellent (symbol ◎)

The rate of increase is more than 1.5 times and less than 2 times: slightly inferior (symbol △)

The rate of increase above 2 times: inferior (symbol x)

3) Leak resistance

After adding 1 mass part of 5 micrometers spherical spacers further to the paste liquid mentioned above, it carried out the defoaming process and obtained the liquid crystal sealing agent containing a spacer. The viscosity stability of this liquid crystal sealing agent was measured with the following method.

The liquid crystal sealing agent containing the above-mentioned spacer was filled in the syringe for dispensing. And 50 sealing patterns (cross-sectional area 3500 micrometers ² ) of the liquid crystal sealing agent were produced on the glass substrate for liquid crystal display panels (made by Nippon Denki Glass Co., Ltd.) of 360 mm x 470 mm using the dispense apparatus (made by Hitachi Plant Technology). . A part of the sealing pattern was provided with a liquid crystal injection hole of 35 mm x 40 mm corner. The drawing speed was 100 mm / s.

This glass substrate was left to stand in an oven at 80 ° C. for 10 minutes, then taken out, and the opposite glass substrates were stacked together. The bonded two glass substrates were hot-pressed at 150 degreeC for 10 minutes using the vacuum heat press apparatus by Shin-Etsu Engineering Co., Ltd .. Thereby, the cell gap between two glass substrates was adjusted. Then, these two glass substrates were heated at 150 degreeC for 60 minutes in oven, and the sealing pattern was hardened.

The linearity (linearity of a sealing line) of the obtained sealing pattern was evaluated by the following method. The linearity of the sealing line is an indicator of leakage resistance.

% Of maximum width and minimum width of sealing line = (minimum width of sealing line / maximum width of sealing line) × 100

The ratio is 95% or more: ◎ (excellent)

The ratio is 80% or more but less than 95%: ○ (slightly excellent)

The ratio is less than 80%: × (lag)

When bubbles were contained in the sealing pattern, since leak resistance was inferior, it was made into x.

4) Dispensing coating

The liquid crystal sealing agent prepared in 20 g of said 3) was filled in the syringe for dispensing under vacuum. Subsequently, after discharging 1 g of the liquid-crystal sealing agent from the needle tip of 0.35 mm diameter of the syringe for dispense, it was left to stand at 23 degreeC for 1 day. Next, the dispensing syringe was set in the dispensing apparatus (made by Hitachi Plant Technology Co., Ltd.), and 50 sealing patterns of 35 mm x 40 mm were drawn on the 360 mm x 470 mm glass substrate for liquid crystal display panels (made by Nippon Denki Glass Co., Ltd.). The discharge pressure of the syringe was 0.3 MPa. The cross-sectional area of the sealing pattern was 3000 µm ² , and the drawing speed was 100 mm / s. The obtained sealing pattern was observed and evaluated as follows.

50 sealing patterns with no sealing cuts or scratches: ◎ (excellent)

Number of sealing patterns with no sealing cuts or scratches at all: 48 to 49: △ (slightly inferior)

Less than 48 sealing patterns with no sealing cuts or scratches: × (deteriorated)

5) Screen printing applicability

The liquid crystal sealing agent prepared in said 3) is apply | coated using a screen printing machine (made by Tokai Seiki Co., Ltd.), and the sealing pattern of 35 mm x 40 mm is carried out on the glass substrate (made by Nippon Denki Glass Co., Ltd.) of 360 mm x 470 mm by 50 Made by dog. The sealing pattern after 80 times of printing was observed and evaluated as follows.

Number of sealing patterns without any sealing cuts or scratches: 50 (excellent)

48 to 49 sealing patterns where no sealing cut or sealing scratch occurred: △ (slightly inferior)

Less than 48 sealing patterns without any sealing cuts or scratches: × (deteriorated)

6) Display characteristics of liquid crystal display panel

On the 40 mm x 45 mm glass substrate (RT-DM88-PIN made from EHC company) which arrange | positioned the transparent electrode and the orientation film, the liquid crystal sealing agent prepared by said 3) was discharged by the dispenser (Shortmaster: Musashi Engineering Co., Ltd.), and 35 mm x A 40 mm rectangular sealing pattern (cross section 3500 µm ² ) was drawn. A liquid crystal injection hole was provided in a part of the sealing pattern.

This glass substrate was left to stand in an oven at 80 ° C. for 10 minutes, then taken out, and the opposite glass substrates were stacked together. The two glass substrates which were bonded were heat-pressed at 150 degreeC for 10 minutes using the vacuum heat press apparatus (made by Shin-Etsu Engineering Co., Ltd.). Thereby, the cell gap between two glass substrates was adjusted. Then, these two glass substrates were heated at 150 degreeC for 60 minutes in oven, and the sealing pattern was hardened. This obtained the cell for liquid crystal injection.

A liquid crystal material (MLC-11900-000: manufactured by Merck Co., Ltd.) was injected into the liquid crystal injection cell through the liquid crystal injection port. Thereafter, the ultraviolet curable resin was sealed in the liquid crystal injection hole. This obtained the liquid crystal display panel.

This liquid crystal display panel was left to stand at 70 degreeC and 95% RH for 500 hours, and the color unevenness generate | occur | produced in the liquid crystal around the sealing part of a liquid crystal display panel before and after standing was visually observed. Next, this liquid crystal display panel was driven at an applied voltage of 5 V using a DC power supply device. At this time, the display characteristic of the liquid crystal display panel was evaluated whether the liquid crystal display function of the liquid-crystal sealing agent vicinity functions normally from the initial stage of driving. Evaluation criteria were as follows.

When the liquid crystal display function is exhibited until sealing: Good display characteristics (symbol ◎)

When an abnormality in the display function is found within 0.3 mm near the sealing: Display characteristics are inferior (symbol △)

When abnormality of the display function is found in excess of 0.3 mm near the sealing: Display characteristics are significantly inferior (symbol ×)

7) Observation of the sealing

The liquid crystal sealing agent prepared in said 3) was apply | coated on the alkali free glass substrate of 25 mm x 45 mm thickness 0.7mm with the screen board, and the circular sealing pattern of diameter 1mm was obtained.

This glass substrate was left to stand in an oven at 80 ° C. for 10 minutes, then taken out, and the opposite alkali free glass substrates were stacked together and fixed. The two alkali free glass substrates which were fixed were bonded by heat-pressing at 150 degreeC for 60 minutes using the vacuum heat press apparatus (made by Shin-Etsu Engineering Co., Ltd.). Two alkali free glass substrates (henceforth "test piece") which were bonded were stored for 24 hours in the thermostat of 25 degreeC and 50% of humidity. The sealing state after storage was observed with the naked eye and an optical microscope.

The state of the sealing was evaluated as follows.

Visually spilled and voided: × (delayed)

Visually with slight voids or spills: △ (slightly lagging)

Visually free from voids and spillage, but with light microscopy to separate sealing: ○ (Good)

No voids and spills with the naked eye, and no sealing separation by optical microscope observation: (excellent)

8) adhesive strength

The plane tensile strength (adhesive strength) of the test piece taken out from the thermostat of said 7) was measured using the tensile test apparatus (made by Intesco). The tensile speed was 2 mm / minute. The adhesive strength was evaluated as follows.

Adhesive strength of 15 MPa or more: ◎ (excellent)

Adhesive strength is 7 MPa or more and less than 15 MPa: △ (slightly inferior)

Adhesive strength less than 7 MPa: × (deteriorated)

9) Glass transition temperature of hardened liquid crystal sealant

After apply | coating a liquid crystal sealing agent on a support body, it heated (hardened) and produced the film of thickness 100micrometer. The glass transition temperature of this film was measured at the temperature increase rate of 5 degree-C / min by dynamic viscoelasticity measuring method (DMS). In the case where the glass transition temperature was not measured, "-" is indicated in Table 2.

[Examples 2 to 4]

The liquid crystal sealing agent was obtained like Example 1 except having set it as the composition shown in Table 2. In addition, the liquid crystal sealing agent was evaluated similarly to Example 1. The results are shown in Table 2.

[Example 5]

40 mass parts liquid epoxy resin B, 10 mass parts epoxy resin G, 5 mass parts latent hardener A, 20 mass parts acrylic resin, 25 mass parts methacrylic acid modified epoxy resin B, 1 mass part optical radical generator, 20 mass After mixing negative filler and a 1 mass part coupling agent with a Dalton mixer, it knead | mixed enough using three rolls and obtained the paste liquid crystal sealing agent. The viscosity of the liquid crystal sealing agent was measured by the method similar to the above-mentioned. The viscosity in 25 degreeC by the E-type viscosity meter (2.5 rpm) of the liquid crystal sealing agent was 300 Pa.s.

In addition, about 2) viscosity stability, 4) dispense coating property, and 5) screen printing coating property of a liquid crystal sealing agent were measured and evaluated similarly to the above-mentioned. Moreover, 3) leakage resistance of the liquid crystal sealing agent, 6) the display characteristic of a liquid crystal display panel, 7) sealing observation, and 8) adhesive strength were evaluated as follows. The results are shown in Table 2.

3) Liquid crystal leak resistance (leak resistance)

1 mass part of 5 micrometers spherical spacers were further added to the liquid crystal sealing agent, and the defoaming process was carried out, and the liquid crystal sealing agent containing a spacer was obtained. This liquid crystal sealing agent was filled into the syringe for dispensing under a yellow lamp. Furthermore, a rectangular sealing pattern (cross section 3500 µm ² ) of 35 mm × 40 mm corners was formed on a glass substrate for liquid crystal display panel (manufactured by Nihon Denki Glass Co., Ltd.) of 360 mm × 470 mm using a dispense device (manufactured by Hitachi Plant Technology, Inc.). Made by dog. The drawing speed was 100 mm / s. On the outer periphery of each of the 50 sealing patterns, a sealing pattern was further produced under the conditions described above to obtain a double-shaped sealing pattern.

A liquid crystal material (MLC-11900-000: manufactured by Merck Co., Ltd.) corresponding to the panel content after bonding was added dropwise to the inside of the sealing pattern of the glass substrate using a dispense apparatus (manufactured by Hitachi Plant Technology Co., Ltd.).

The glass substrate mentioned above and the opposing glass substrate were piled up under the pressure reduction of 5 Pa using the vacuum bonding apparatus (made by Shin-Etsu Engineering Co., Ltd.). After bonding two glass substrates hold | maintained for 3 minutes in the light-shielding box, it temporally hardened by irradiating an ultraviolet-ray of 2000mJ / cm <^2> , and then hardening by heating at 120 degreeC for 60 minutes.

The sealing method linearity (linearity of a sealing line) of the obtained liquid crystal display panel was evaluated with the following method. The linearity of the sealing line is an indicator of leakage resistance.

% Of maximum width and minimum width of sealing line = (minimum width of sealing line / maximum width of sealing line) × 100

The ratio is 95% or more: ◎ (excellent)

The ratio is 80% or more but less than 95%: ○ (slightly excellent)

The ratio is less than 80%: × (lag)

About liquid crystal entering in a sealing line, since leakage resistance was inferior, it was made into x.

6) Display characteristics of liquid crystal display panel

On a 40mm x 45mm glass substrate (RT-DM88-PIN, manufactured by EHC) with a transparent electrode and an alignment film, a 35 mm x 40 mm rectangular sealing pattern (cross-sectional area) of a liquid crystal sealing agent using a dispenser (short master: Musashi Engineering) 3500 µm ² ) (main sealing) was drawn. Moreover, the sealing pattern of the type similar to a main sealing was drawn in the outer periphery of this main sealing. Next, the liquid crystal material (MLC-11900-000: product made by Merck) which corresponded to the panel content after bonding was dripped precisely in the frame of the main sealing using a dispenser.

The glass substrates to be paired were bonded to this glass substrate under reduced pressure, and then air-opened and held for 3 minutes in a light shielding box. Then, the ultraviolet-ray of 2000mJ / cm <^2> was irradiated to the bonded glass substrate. Subsequently, the bonded glass substrate was heated at 120 degreeC for 1 hour, the sealing pattern was hardened and the liquid crystal display panel was obtained.

This liquid crystal display panel was left to stand at 70 degreeC and 95% RH for 500 hours, and the color unevenness generate | occur | produced in the liquid crystal around the sealing part before and after standing was visually observed. This liquid crystal display panel was driven at an applied voltage of 5 V using a DC power supply device. The display characteristic of the liquid crystal display panel was evaluated whether the liquid crystal display function near the liquid crystal sealing agent at this time functions normally from the beginning of a drive. Evaluation criteria were as follows.

When liquid crystal display can be achieved until sealing: Good display characteristics (symbol ◎)

When an abnormality in the display function is found within 0.3 mm near the sealing: Display characteristics are inferior (symbol △)

When abnormality of the display function is found in excess of 0.3 mm near the sealing: Display characteristics are significantly inferior (symbol ×)

7) Observation of the sealing

Using the liquid crystal sealing agent (the liquid crystal sealing agent containing a spherical spacer) prepared in said 3), the sealing pattern of diameter 1mm circular shape was apply | coated on the alkali free glass plate of 25mm * 45mm thickness 0.7mm with the screen board. Next, the paired alkali free glass plates were piled up in a cross and fixed. After irradiating 2000mJ / cm <^2> ultraviolet-rays to the two glass plates which were piled up and fixed, it bonded by heating at 120 degreeC for 60 minutes. Two glass plates (henceforth "test piece") which were bonded were stored for 24 hours in the thermostat of 25 degreeC and 50% of humidity. The sealing state after storage was observed with the naked eye and an optical microscope.

The state of the sealing was evaluated as follows.

Visually spilled and voided: × (delayed)

Visually with slight voids or spills: △ (slightly lagging)

Visually free from voids and spillage, but with light microscopy to separate sealing: ○ (Good)

No voids and spills with the naked eye, and no sealing separation by optical microscope observation: (excellent)

8) adhesive strength

The plane tensile strength (adhesion strength) of the test piece taken out from the thermostat of 7) was measured using the tensile test apparatus (made by Intesco). The tensile speed was 2 mm / minute. Adhesive strength was evaluated as follows.

Adhesive strength of 15 MPa or more: ◎ (excellent)

Adhesive strength is 7 MPa or more and less than 15 MPa: △ (slightly inferior)

Adhesive strength less than 7 MPa: × (deteriorated)

[Examples 6 to 10]

Except having set it as the composition shown in Table 2, it carried out similarly to Example 5, and obtained the liquid crystal sealing agent. In addition, the liquid crystal sealing agent was evaluated similarly to Example 5. The results are shown in Table 2.

[Comparative Examples 1 to 6]

Liquid crystal sealing agent was obtained like Example 1 except having set it as the composition shown in Table 3. In addition, the liquid crystal sealing agent was evaluated similarly to Example 1. The results are shown in Table 3.

[Comparative Examples 7 to 12]

Except having set it as the composition shown in Table 3, it carried out similarly to Example 5, and obtained the liquid crystal sealing agent. In addition, the liquid crystal sealing agent was evaluated similarly to Example 5. The results are shown in Table 3.

In Examples 1-10, it turns out that all the display characteristics under the high temperature, high humidity conditions of a liquid crystal display panel are excellent.

Moreover, when the number of the epoxy groups contained in 1 molecule of the epoxy resin contained in a liquid crystal sealing agent is large from the comparison of Example 5 and 6 and Example 9 and 10, the adhesive strength of the hardened | cured material can be seen. It is considered that the epoxy group contained in the epoxy resin reacts with the functional group on the surface of the glass substrate to increase adhesiveness.

On the other hand, in Comparative Examples 1-12, there was nothing which showed the favorable display characteristic on the high temperature, high humidity conditions of a liquid crystal display panel. For example, in the comparative example 5 using the liquid crystal sealing agent containing epoxy resin C, it turns out that the display characteristic under the high temperature, high humidity conditions of a liquid crystal display panel is low. It is considered that the leak resistance of the cured liquid crystal sealing agent is low. In Comparative Examples 6 and 12, it can be seen that the display characteristics of the liquid crystal display panel are low. Since the liquid crystal sealing agent of Comparative Examples 6 and 12 contains many aromatic epoxy resins D, it is considered that the softness | flexibility of the hardened | cured material fell and sealing property fell. In Comparative Examples 1, 3, 7 and 8, it can be seen that the display characteristics and the leak resistance of the liquid crystal display panel are low. It is considered that the liquid crystal sealing agents of Comparative Examples 1, 3, 7 and 8 are easily dissolved in the liquid crystal, including the epoxy resin E not containing a hydroxyl group or the epoxy resin G.

This application claims the priority based on Japanese Patent Application No. 2008-253612 for which it applied on September 30, 2008. The contents described in the above specification and drawings are all incorporated herein by reference.

[Industry availability]

The liquid crystal sealing agent of this invention has high crosslinking density of hardened | cured material, and is excellent in sclerosis | hardenability. Moreover, when hardened | cured material of the liquid crystal sealing agent of this invention is applied as a sealing member (liquid crystal sealing part), there exists no deformation | transformation of a sealing member and leakage of the liquid crystal to the sealing member, and the liquid crystal panel excellent in display reliability can be provided. For this reason, the liquid crystal sealing agent of this invention is suitable for manufacture of a liquid crystal display panel.

12, 18: substrate
14: sealing pattern
16: liquid crystal
20: laminate
22: cell for liquid crystal injection
22A: inlet

Claims (19)

In one molecule, the aliphatic epoxy resin (alpha) which has one or more hydroxyl groups and 3 or more epoxy groups and a (meth) acryl group in total is included,
The hydroxyl group equivalent of the said aliphatic epoxy resin (alpha) is 300g / eq or less, the mass mean molecular weight is 0.3 * 10 <^3> -1.0 * 10 <^3> ,
The total amount of the said aliphatic epoxy resin (alpha) is 5-65 mass% with respect to the liquid crystal sealing agent. The method of claim 1,
The aromatic ring equivalent of the said aliphatic epoxy resin (alpha) is 400 g / eq or more. The method of claim 1,
The hydroxyl group equivalent of the said aliphatic epoxy resin (alpha) is 100-300 g / eq, and the epoxy equivalent is 50-150 g / eq liquid crystal sealing agent. Aliphatic epoxy resin (alpha) 1 obtained by making 3 mol or more (n-1) mol or less of epoxidized compounds react with 1 mol of n-valent (n represents an integer of 4 or more), and
Aliphatic epoxy resin (alpha) which consists of either or both of the aliphatic epoxy resin (alpha) 2 containing both an epoxy group and a (meth) acryl group obtained by making the said aliphatic epoxy resin (alpha) 1 and (meth) acrylic acid react,
The hydroxyl group equivalent of the said aliphatic epoxy resin (alpha) is 300 g / eq or less, and the mass mean molecular weight is 0.3 * 10 <^3> -1.0 * 10 <^3> liquid crystal sealing agent. The method of claim 4, wherein
The aromatic ring equivalent of the said aliphatic epoxy resin (alpha) is 400 g / eq or more. The method of claim 1,
A liquid crystal sealing agent further comprising a latent curing agent and a filler. The method of claim 1,
The said aliphatic epoxy resin (alpha) is aliphatic epoxy resin (alpha) 2 containing both an epoxy group and a (meth) acryl group, The liquid crystal sealing agent. The method of claim 7, wherein
Liquid crystal sealing agent further containing an acrylic resin and an optical radical polymerization initiator. delete The method of claim 1,
The liquid crystal sealing agent which further contains aromatic epoxy resin (beta). 11. The method of claim 10,
The softening point of the said aromatic epoxy resin (beta) is 50 degreeC or more liquid crystal sealing agent. 11. The method of claim 10,
Content of the said aromatic epoxy resin (beta) is 5-40 mass% with respect to the total amount of the said aliphatic epoxy resin (alpha). Hardened | cured material formed by hardening | curing the liquid crystal sealing agent of Claim 1. 1st process which forms the sealing pattern of the liquid crystal sealing agent of Claim 1 in a 1st board | substrate,
A second step of dropping a liquid crystal onto a region surrounded by the sealing pattern of the first substrate or a region of a second substrate facing the region surrounded by the sealing pattern while the sealing pattern is uncured;
A third process of overlapping the first substrate and the second substrate through the sealing pattern, and
A fourth step of thermally curing the sealing pattern
Method of manufacturing a liquid crystal display panel comprising a. A first step of forming a sealing pattern of the liquid crystal sealing agent according to claim 8 on the first substrate;
A second step of dropping a liquid crystal onto a region surrounded by the sealing pattern of the first substrate or a region of a second substrate facing the region surrounded by the sealing pattern while the sealing pattern is uncured;
A third process of overlapping the first substrate and the second substrate through the sealing pattern, and
A fourth step of photocuring and thermally curing the sealing pattern
Method of manufacturing a liquid crystal display panel comprising a. 1st process which forms the sealing pattern of the liquid crystal sealing agent of Claim 1 in a 1st board | substrate,
A second process of overlapping the first substrate and the second substrate through the sealing pattern;
A third step of thermally curing the sealing pattern to obtain a liquid crystal injection cell having an injection hole for injecting liquid crystal;
A fourth step of injecting a liquid crystal into the liquid crystal injection cell through the injection hole, and
A fifth process of sealing the injection hole
Method of manufacturing a liquid crystal display panel comprising a. The display substrate,
An opposite substrate paired with the display substrate,
A frame-shaped sealing member interposed between the display substrate and the opposing substrate, and
A liquid crystal layer filled in a space surrounded by the sealing member between the display substrate and the opposing substrate
A liquid crystal display panel comprising:
The said sealing member is a liquid crystal display panel of the hardened | cured material of Claim 13. A liquid crystal display device comprising the liquid crystal display panel according to claim 17. The method of claim 1,
Aliphatic epoxy resin (alpha) 1 obtained by making the said aliphatic epoxy resin (alpha) react with 3 mol or more (n-1) mol or less epoxidized compounds with respect to 1 mol of n-valent (n represents an integer greater than or equal to 4). ego,
The polyhydric alcohol compound is xylitol, sorbitol, pentaerythritol, mannitol, diglycerin or polyglycerol.

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