WO2008016122A1 - Liquid crystal sealing material, process for production of liquid crystal display panels with the same, and liquid crystal display panels - Google Patents

Abstract

The invention relates to a liquid crystal sealing material applicable to liquid crystal display panels. The sealing material comprises (1) an epoxy resin, (2) at least one amine-type thermally latent curing agent having a melting point of 150°C or below which is selected from the group consisting of dihydrazide type, modified imidazole type, amine adduct type and polyaminourea type thermally latent curing agents, and (3) at least one amine-type thermally latent curing agent having a melting point of 180°C or above which is selected from the group consisting of dihydrazide type, modified imidazole type, and diamide type thermally latent curing agents. The sealing material exhibits a high curing rate and high moisture resistance. Further, the sealing material can keep its viscosity stability at a high level by virtue of its exhibiting low reactivity in a low-temperature region including room temperature, thus having a log pot life. Consequently, the use of the material in producing liquid crystal display panels makes it possible to produce high-quality liquid crystal display panels with the productivity kept at a high level.

Description

 Specification

 Liquid crystal sealing agent, liquid crystal display panel manufacturing method using the same, and liquid crystal display non-technical field

 The present invention relates to a liquid crystal sealant, a method for manufacturing a liquid crystal display panel using the same, and a liquid crystal display panel. Background art

 In recent years, liquid crystal display panels have been widely used as display panels for various electronic devices such as cellular phones because of their advantages such as thin, light weight and low power consumption. A liquid crystal display panel has a structure in which liquid crystal is sealed between two substrates bonded together with a liquid crystal sealant. The liquid crystal display panel controls the orientation of the liquid crystal by applying a voltage to the liquid crystal and modulates the transmitted light. A device that displays an image by adjusting.

 [0003] Liquid crystal display panels are mainly manufactured by a liquid crystal injection method or a liquid crystal dropping method. In the liquid crystal injection method, first, a liquid crystal sealant is applied to either one of two substrates by a dispenser or screen printing, and then the liquid crystal sealant is dried by a pre-curing process (preliminary drying). At this time, a part to be a liquid crystal injection port is provided in a part of the frame. Next, the two substrates are overlapped so as to face each other, and then the substrates are bonded together by heat-pressing. Then, after injecting liquid crystal into the empty cell from the liquid crystal injection port in a vacuum, the liquid crystal injection port is sealed with a liquid crystal sealant or the like to manufacture a liquid crystal display panel in which liquid crystal is sealed between the substrates. Is done.

On the other hand, the liquid crystal dropping method includes the following steps. First, a liquid crystal sealant is applied to one of the two substrates constituting the liquid crystal display panel to form a frame-shaped display region filled with liquid crystal. Here, the method for applying the liquid crystal sealant is not particularly limited, and generally, the same method as the liquid crystal injection method is used. Next, an appropriate amount of liquid crystal is dropped in the formed frame or on the other substrate, and the two substrates are superposed in a high vacuum with the liquid crystal sealant uncured. Then, the substrates are bonded together by returning the two stacked substrates to atmospheric pressure, etc., and then the liquid crystal sealant is cured. As a result, a liquid crystal display panel in which liquid crystal is sealed between the substrates is manufactured. In such a liquid crystal dropping method, post-curing by heating is generally performed after the liquid crystal sealant is temporarily cured by irradiating the stacked substrates with ultraviolet rays or the like.

 [0005] In the liquid crystal injection method described above, it takes a long time to inject liquid crystal into the cell, and in order to cure the liquid crystal sealant, heat treatment is performed at a temperature range of 120 to 150 ° C for several hours. Low productivity is regarded as a problem because it is necessary. In this respect, the liquid crystal dropping method can improve the productivity because the liquid crystal can be sealed in a shorter time than the liquid crystal injection method. Therefore, recently, the liquid crystal dropping method is becoming the mainstream manufacturing method for liquid crystal display panels.

 [0006] By the way, as a liquid crystal sealant used in a liquid crystal display panel, a thermosetting liquid crystal sealant (hereinafter, simply referred to as a thermosetting sealant) having an epoxy resin as a main component has been proposed (hereinafter referred to as a thermosetting sealant). For example, see Patent Document 1). However, such thermosetting sealants, when used in the manufacture of liquid crystal display panels, have a problem in that the arrangement of the seal is easily shifted and the curing speed is slow due to the fact that the viscosity is lowered by heat. Be seen.

 [0007] Curing speed is slow! When a liquid crystal sealant is used in the liquid crystal dropping method, components such as monomers gradually dissolve or ooze out from the uncured liquid crystal sealant. There is. In such a liquid crystal display panel in which components such as monomers are dissolved into the liquid crystal, it is difficult to control the orientation of the liquid crystal even when a voltage is applied. It becomes a problem. Therefore, from the viewpoint of improving the productivity and quality of liquid crystal display panels, it is desired to propose a liquid crystal sealant having a high curing rate.

 [0008] Therefore, a liquid crystal sealant that combines a photocurable component that is cured by UV irradiation and a thermosetting component that is cured by heating has been proposed as a liquid crystal sealant that has a fast curing speed! For example, see Patent Documents 2 and 3). In addition, the liquid crystal sealing agents proposed in Patent Documents 1 to 3 include 1,3-bis (hydrazinocalpoethyl) 5-isopropylhydantoin (melting point 120 ° C) having a melting point of 120 ° C as a thermal latent curing agent. ) Is used. Such a heat latent curing agent is expected to improve the curing rate because it melts rapidly at a general curing temperature of 120-; 150 ° C and is highly reactive.

Patent Document 1: Japanese Unexamined Patent Application Publication No. 2004_123909 Patent Document 2: JP 2001-133794 A

 Patent Document 3: Japanese Patent Laid-Open No. 2002-214626

 Disclosure of the invention

 Problems to be solved by the invention

 However, since the low-melting-point heat-latent curing agent has a relatively high water solubility, a liquid crystal sealant using such a heat-latent curing agent has a problem of moisture resistance. When a liquid crystal sealant that is concerned about moisture resistance is used in a liquid crystal display panel, the adhesive strength of the liquid crystal sealant after curing is lowered, and the display properties of the liquid crystal display panel may be deteriorated.

 [0010] Also, in the field of manufacturing liquid crystal display panels, the length of the pot life of the liquid crystal sealant is regarded as important. The pot life refers to the time during which the liquid crystal sealant can be preferably used. The phrase “a liquid crystal sealant can be preferably used” means that the liquid crystal sealant can be easily applied onto a substrate, and can be applied. The pot life of the liquid crystal sealant becomes shorter as the viscosity of the liquid crystal sealant increases. The reason is that when the viscosity of the liquid crystal sealant increases, it becomes difficult to apply the liquid crystal sealant on the substrate, and it is necessary to replace the liquid crystal sealant used in an apparatus such as a dispenser. Therefore, in order to increase the pot life of the liquid crystal sealant, it is preferable that the viscosity remains stable for a long time without change, that is, the viscosity stability is increased.

 [0011] However, the liquid crystal sealant containing the highly reactive thermal latent curing agent as described above easily proceeds in a low temperature region such as around room temperature, so that the viscosity increases. Therefore, the viscosity stability of the liquid crystal sealant is lowered and the pot life may be shortened.

[0012] In view of the above problems, the present invention provides a liquid crystal sealing agent that has a high curing rate and good moisture resistance, and further maintains a high viscosity stability for a long time. Is the first purpose. In addition, by using a liquid crystal sealant that has such excellent characteristics and a long service life, the liquid crystal display panel can be manufactured while maintaining high productivity and high humidity resistance reliability. A second object is to provide a manufacturing method for the above. Means for solving the problem

[0013] As a result of intensive studies, the present inventors have used the above-described thermal latent curing agent having a melting point of 150 ° C or lower and a thermal latent curing agent having a melting point of 180 ° C or higher in combination. The problem is solved As a result, the present invention has been completed.

 That is, the said subject is solved by the liquid-crystal sealing compound of this invention.

 [1] (1) an epoxy resin, (2) a first thermal latent curing agent having a melting point of 150 ° C or lower, and (3) a second thermal latent curing agent having a melting point of 180 ° C or higher. And the component (2) is one or more thermal latent curing agents selected from the group consisting of dihydrazide, imidazole, amine adduct, polyamine, and polyaminourea thermal latent curing agents. A liquid crystal sealant in which the component (3) is one or more thermal latent curing agents selected from the group consisting of dihydrazide-based, imidazole-based, and diamide-based thermal latent curing agents.

 [2] The liquid crystal sealant according to [1], wherein the components (2) and (3) are dihydrazide-based thermal latent curing agents.

 [3] The liquid crystal sealant according to [1] or [2], wherein the solubility of the component (3) in 100 ml of water at 25 ° C. is 20 g or less.

 [4] The liquid crystal sealant according to any one of [1] to [3], wherein the component (3) is a compound represented by the following general formula (A).

ただし、一般式 (A)中の Rは、炭素数 8以上のアルキレン基を表す。

However, R in the general formula (A) represents an alkylene group having 8 or more carbon atoms.

 [5] The liquid crystal sealant is a one-component type in which the components (1) to (3) are uniformly mixed.

 [6] The total blending amount of the component (2) and the component (3) is in a range of 100 parts by mass of the liquid crystal sealant;! To 25 parts by mass. [1] to [5] V, Liquid crystal sealant.

[7] When the compounding mass of the component (2) is W1 and the compounding mass of the component (3) is W2, 0 · 2≤W2 / (W1 + W2) ≤0.8 [1] ~ [6] The liquid crystal sealant according to any one of the above. [8] The sum of active hydrogen equivalents of component (2) and component (3) is 0.3 to 3.0 with respect to the epoxy equivalent of component (1). [1] to [7] Liquid crystal sealing agent in any one.

[0015] Further, the above problems are solved by the method for producing a liquid crystal display panel of the present invention and the liquid crystal display panel obtained thereby.

 [9] In a method for producing a liquid crystal display panel produced by bonding two opposing substrates through a liquid crystal sealant, a pixel array is formed using the liquid crystal sealant described in [1] to [8] above. A step of preparing a substrate having a frame-shaped display region formed so as to surround the region and provided with a liquid crystal inlet; and after heating the two substrates over the liquid crystal sealant, heating By pressing and bonding the substrates together, the liquid crystal is formed by a step of forming a liquid crystal cell between the substrates, a step of injecting liquid crystal into the liquid crystal cell from the inlet, and a sealing agent for sealing. And a step of sealing the injection port of the injected liquid crystal cell.

 [10] In a method for producing a liquid crystal display panel produced by bonding two opposing substrates through a liquid crystal sealant, the pixel alignment is performed by the liquid crystal sealant described in [1] to [8] above. A step of preparing a substrate having a frame-shaped display region formed so as to surround the region, a step of dropping liquid crystal in the uncured display region or on the other substrate, A step of superimposing the substrate onto which the liquid crystal has been dropped and the other substrate under reduced pressure, and a step of curing the liquid crystal sealant between the two superimposed substrates by heating. Manufacturing method of display panel.

 [11] A liquid crystal display panel obtained by the method for producing a liquid crystal display panel according to [9] or [10] above.

 The invention's effect

 [0016] According to the present invention, it is possible to provide a liquid crystal sealant that has a high curing rate and good moisture resistance, and further maintains a high viscosity stability for a long time. In addition, by using a liquid crystal sealant that has such excellent characteristics and a long service life, a liquid crystal display panel that can be manufactured while maintaining high productivity with a high moisture resistance reliability. Can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION [0017] Next, the present invention will be described in detail. In the following description, “˜” is used to define a numerical range. “˜” in the present invention includes a boundary value. For example, “10 to 100” means 10 or more and 100 or less.

 [0018] The liquid crystal sealant of the present invention includes (1) an epoxy resin, (2) a thermal latent curing agent having a melting point of 150 ° C or lower, and (3) a thermal latent curing having a melting point of 180 ° C or higher. Agent.

 [0019] (1) Epoxy resin

 The epoxy resin of the present invention refers to a compound having one or more epoxy groups in the molecule. Preferred examples of the epoxy resin used in the liquid crystal sealant of the present invention include aromatic diols represented by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, and the like, and ethylene glycol. , Propylene glycol, alkylene glycol-modified diols, and aromatic polyvalent glycidyl ether compounds obtained by the reaction of epichlorohydrin; nopolac resins derived from phenol or talesol and formaldehyde, polyalkylolphenol And nopolac-type polyvalent glycidyl ether compounds obtained by the reaction of polyphenols typified by copolymers thereof and epichlorohydrin; glycidyl ether compounds of xylylene phenol resins.

 [0020] Especially preferred! /, Examples of epoxy resins include cresol nopolac type epoxy resin, phenol nopolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, triphenol methane type epoxy. Resin, triphenol type epoxy resin, trisphenol type epoxy resin, dicyclopentagen type epoxy resin and biphenyl type epoxy resin. Examples of particularly preferred epoxy resins include these acrylic rubber-modified epoxy resins.

 In the liquid crystal sealant of the present invention, these epoxy resins can be used alone or in combination of two or more.

[0022] Further, the epoxy resin used in the present invention preferably has a softening point temperature force of 0 ° C or higher measured by a ring and ball method and has a mass average molecular weight in the range of 1000 to 10,000. It is more preferable. Such an epoxy resin has low solubility and dispersibility in liquid crystals. Therefore, it is manufactured with a liquid crystal sealant that uses force and curable epoxy resin. The manufactured liquid crystal display panel 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, a resin purified by a molecular distillation method and the like from which impurities are removed is preferably used.

 [0023] The compounding amount of the epoxy resin is 5 to 50 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. S is preferable, and more preferably 10 to 30 parts by mass. Such a liquid crystal sealant has good heat resistance. However, if the force and the blending amount are less than 5 parts by mass, the mechanical strength of the cured product after curing the liquid crystal sealant will be low. On the other hand, if the blending amount exceeds 50 parts by mass, the heat resistance of the liquid crystal sealant may decrease.

 [0024] Latent curing agent]

 The heat latent curing agent is mixed with an epoxy resin while maintaining the reaction rate at the curing temperature of a normal liquid crystal sealant! / Even though it can extremely reduce the reaction rate in the low temperature region near room temperature. V, a curing agent that reacts with epoxy groups by heat or light. The liquid crystal sealant containing such a heat latent curing agent has high viscosity stability because of low reactivity during storage and storage.

 [0025] The liquid crystal sealant that is effective in the present invention has two types of thermal latent curing agents having different melting points, that is, (2) a first thermal latent curing agent having a melting point of 150 ° C or lower. And (3) a second thermal latent curing agent having a melting point of 180 ° C or higher is used in combination. In general, it is known that when a thermal latent curing agent is included in the liquid crystal sealant, the viscosity stability of the liquid crystal sealant during storage is high during storage. By the way, when the first heat latent curing agent having a low melting point and the second heat latent curing agent having a low melting point and low reactivity near room temperature are used in combination as in the present invention, the reaction near the room temperature is performed. The viscosity stability is extremely high because the properties are kept lower.

[0026] The thermal latent curing agent reacts with the epoxy group and cures the epoxy resin by accelerating the polymerization of the epoxy groups. However, not all thermal latent curing agents react with epoxy groups, and a part of them remains dispersed in the cured product. Here, if the thermal latent curing agent that constitutes this region is an easily water-absorbing substance in the region containing the thermal latent curing agent remaining in the cured product, the cured product itself also absorbs water. It tends to be certain that the force ^s moisture resistance is lowered. [0027] On the other hand, the liquid crystal sealant of the present invention has a low melting point when the liquid crystal sealant is heated at a curing temperature (120 to approximately 150 ° C) used in a normal liquid crystal dropping method. While the thermal latent curing agent is subjected to the reaction, a high melting point thermal latent curing agent remains in the cured product and is dispersed in the base material. Such a high-melting-point heat-latent curing agent has a rigid molecular skeleton and high crystallinity. Therefore, in the cured product obtained by curing the liquid crystal sealant of the present invention, a highly hydrophobic region composed of a high-melting-point thermal latent curing agent is dispersed and remains, so that the cured product Moisture resistance is extremely high.

 [0028] The liquid crystal sealant of the present invention is useful as a one-pack type and has high storage stability. A one-component type liquid crystal sealant is a liquid crystal sealant that contains a main component such as an epoxy resin and a curing promoting component such as a thermal latent curing agent that are uniformly mixed before use. . High storage stability means that the curing reaction hardly proceeds even when the liquid crystal sealant is stored near room temperature. Specifically, the rate of increase in viscosity when the liquid crystal sealant is stored at 25 ° C. for 5 days is preferably less than twice the viscosity of the liquid crystal sealant before storage.

 [0029] (2) Thermal latent curing agent having a melting point of 150 ° C or lower

 In the present invention, the “thermal latent curing agent having a melting point of 150 ° C. or lower” used as the first thermal latent curing agent is a thermal latent curing agent having a melting point of 150 ° C. or lower. A compound having

 [0030] Preferable examples of such component (2) include dihydrazide-based, imidazole-based, amine-duct-based, polyamine-based, and polyaminourea-based thermal latent curing agents. These may be used alone or in combination. In addition, the melting point of the thermal latent curing agent can be measured by a known melting point measuring device.

 [0031] The dihydrazide-based thermal latent curing agent refers to a compound having two hydrazide groups in one molecule and having thermal latent curability. Preferred examples of such a heat latent curing agent include organic acid dihydrazide.

[0032] The organic acid dihydrazide means an organic acid having two hydrazide groups in one molecule. Examples of the organic acid dihydrazide that is preferably used as the component (2) of the present invention include 1,3 bis (hydrazinocarboxyl) -5 isopropylhydantoin (melting point 120 ° C.), phosphorus Dihydrazide (mp ^{1 2 3~; 1 2 5 °} C) is included.

[0033] Examples of commercially available organic acid dihydrazide having a melting point of 150 ° C or lower include Amicure VDH (melting point 120 ° C, manufactured by Ajinomoto Fine Techno Co., Ltd.), 7, 11-octagen 1, 18 Amicure UDH (manufactured by Ajinomoto Fine Techno Co., Ltd., melting point 150 ° C.), which is dicarbohydrazide, is included.

 [0034] The imidazole-based thermal latent curing agent refers to (i) an imidazole derivative in which a substituent or the like is introduced into imidazole, or (ii) imidazole and a compound capable of forming a salt with this imidazole. Refers to a modified imidazole obtained.

 [0035] Examples of the component (i) include 2-phenol imidazole 2PZ (manufactured by Shikoku Kasei Co., Ltd., melting point 137 to 147 ° C), 2-methylimidazole azole 2MZ-P. (Shikoku Chemical Industries, Ltd., melting point 137-; 147 ° C), 1-cyanoethyl-2-phenylimidazole (Shikoku Chemicals, Ltd., melting point 105-111 ° C). These are readily available as commercial products.

 [0036] Examples of the compound as the component (ii) include a resin into which imidazole is introduced. Examples of such modified imidazole products include C11Z—CNS (melting point manufactured by Shikoku Kasei Kogyo Co., Ltd .; L43 to 149 ° C), 2PZ—OK (melting point 135 ° C manufactured by Shikoku Kasei Kogyo Co., Ltd.), Includes force hardener EH4346S (melting point 125 ° C), Ade force hardener EH4347S (melting point 105 ° C), and Adeka hardener EH4356S (melting point 110 ° C) (above, manufactured by ADEKA). These are easily available as commercial products.

 [0037] The amine adduct type heat latent curing agent is an addition compound obtained by reacting an amine compound having thermal latent curability and catalytic activity with any compound! /, Yeah. Such an amine adduct type heat latent curing agent is activated by the dissociation of the amine by heat. Examples of the amine compound include compounds having a 1,2, tertiary amino group.

[0038] Examples of the amine-adduct type thermal latent curing agent preferably used as the component (2) of the present invention include Amicure PN-40 (melting point 110 ° C), Amicure PN-23 (melting point 100 ° C), and Amicure PN. — 31 (melting point 115 ° C), Amicure PN—H (melting point 115 ° C), Amicure MY—24 (melting point 120 ° C), Amicure MY—H (melting point 130 ° C) (Ajinomoto Fine Techno Co., Ltd.) Manufactured). [0039] The polyamine thermal latent curing agent has a polymer structure that is a reaction product of an amine and an epoxy, and the amine having catalytic activity forms a stabilizing structure with an arbitrary compound. A compound showing latent curing is used. Examples of the polyamine thermal latent curing agent preferably used as the component (2) of the present invention include Adecano, one donor EH4357S (manufactured by ADEKA Corporation, melting point 73 to 83 ° C.).

 [0040] The polyaminourea thermolatent curing agent refers to a compound having a urea bond obtained by reacting amine, urea and an isocyanate compound. Examples of the polyaminourea type thermal latent curing agent preferably used as the component (2) of the present invention include Fujicure FXE-100 0 (Fuji Kasei Kogyo Co., Ltd., melting point 120 ° C) and Fujicure FXE-1030 ( Fuji Chemical Industry Co., Ltd. melting point 140 ° C), and Omiquia 94 (ICI Japan Co., Ltd. melting point 127-129 ° C) are included.

 [0041] The component (2) used in the present invention preferably has a melting point of 100 ° C or higher. Such a heat-latent curing agent has a very good thermosetting property, and thus improves the curing rate of the liquid crystal scenery agent. If the melting point temperature is less than 100 ° C, there is a concern that the reactivity in the low temperature region will be higher than necessary and the viscosity stability will be extremely high.

 [0042] (3) Thermal latent curing agent having a melting point of 180 ° C or higher

 In the present invention, the “thermal latent curing agent having a melting point of 180 ° C. or higher” used as the second thermal latent curing agent is a thermal latent curing agent having a melting point of 180 ° C. or higher. A compound having Preferred examples of the second heat latent curing agent include dihydrazide-based, imidazole-based, and diamide-based heat latent curing agents. Since the liquid crystal sealant using such a heat latent curing agent has very good viscosity stability at room temperature, it is possible to produce a liquid crystal display panel while maintaining a long usable time. it can. The above-mentioned heat latent curing agents may be used alone or in combination of two or more.

 [0043] Among them, as the component (3), a dihydrazide thermal latent curing agent is preferable! Examples of such dihydrazide thermal latent curing agents include isophthalic acid dihydrazide (manufactured by IDH Nippon Finechem Co., Ltd., melting point 220 ° C), 1, 3, 5-tris (2-hydrazinocarbonylethyl) ) Monoisocyanurate (HCIC Nippon Finechem Co., Ltd., melting point 197 ° C).

Among the dihydrazide-based thermal latent curing agents, the component (3) includes an organic acid dihydrazide. Doca S, preferably a compound represented by the following general formula (A). The organic acid dihydrazide of the present invention refers to a compound having an alkylene group having 8 or more carbon atoms obtained by hydrazide conversion of an aliphatic dicarboxylic acid.

 Here, examples of the aliphatic dicarboxylic acid include adipic acid dihydrazide (manufactured by ADH Nippon Finechem Co., Ltd., solubility of 10 g in 100 ml of water having a melting point of 181 ° C. and 25 ° C.). A liquid crystal sealant using an organic acid dihydrazide represented by the general formula (A) has good water resistance. For this reason, since the cured liquid crystal sealant has high water resistance, when applied to a liquid crystal display panel, the adhesive strength between the liquid crystal sealant cured at high humidity and the substrate is high and has excellent moisture resistance. A liquid crystal display panel exhibiting reliability can be obtained.

[0046] [Chemical 2]

上記の一般式 (A)中の Rは、炭素数 8以上のアルキレン基を表す。

R in the general formula (A) represents an alkylene group having 8 or more carbon atoms.

[0047] Examples of the organic acid dihydrazide preferably used as the component (3) of the present invention include sebacic acid dihydrazide (manufactured by SDH Nippon Finechem Co., Ltd., insoluble in 100 ml of water having a melting point of 190 ° C and 25 ° C). ) And dodecanoic acid dihydrazide (N-12, manufactured by Nippon Finechem Co., Ltd., melting point 189 ° C, insoluble in 100 ml of water at 25 ° C).

[0048] The imidazole-based heat latent curing agent is the same as the definition described in the component (2),

 (i) An imidazole derivative in which a substituent or the like is introduced into imidazole, or (ii) an imidazole modified product obtained by reacting imidazole with a resin or a compound capable of forming a salt with imidazole. Among these, as the component (3), an imidazole compound having a melting point of 180 ° C. or higher by increasing the molecular weight or strengthening the bonding of the molecules constituting the resin skeleton is applicable.

[0049] Among the imidazole-based heat latent curing agents as described above, the component (3) is preferably an imidazole derivative as the component (i). Examples of such imidazole derivatives include 2,4-Diamino-6- [2, -ethyl-4, -methylimidazolinole (1,)]-ethyl-s-triazine is included. Such a compound is available as a commercial product such as Curesol 2E4MZ-A (manufactured by Shikoku Chemicals Co., Ltd., melting point 215 to 225 ° C.).

 [0050] The diamide heat latent curing agent of the present invention refers to a compound having two amide groups in one molecule and having heat latent curability. Examples of the diamide type heat latent curing agent preferably used as the component (3) of the present invention include dicyandiamide (melting point 209 ° C. and the like). Specific examples include AH-154 (melting point 200 ° C) and AH-162 (melting point 200 ° C) (manufactured by Ajinomoto Fine Tetano Co., Ltd.), which are readily available as commercial products. is there.

 [0051] The compounds preferably used as the component (3) may be used singly or in combination of two or more. In addition to the above component (3), hydrazides such as p-hydroxybenzoic acid hydrazide (PHBH Nippon Finechem Co., Ltd., melting point 264 ° C.) may be used. Furthermore, the heat latent curing agent used as component (3) is highly purified by the water washing method, recrystallization method, etc.

 [0052] The component (3) preferably has a solubility in 100 ml of water at 25 ° C of 20 g or less. Particularly preferably, the solubility is 5 g or less. Since the liquid crystal sealant using such component (3) has good moisture resistance, as a result, the moisture resistance reliability of the liquid crystal display panel is improved. Here, the closer the solubility of the component (3) is to Og, the better the moisture resistance of the liquid crystal sealant prepared. However, when the strength or solubility exceeds 20 g, the moisture resistance of the liquid crystal sheet agent is low and inferior, and therefore, when applied to a liquid crystal display panel, the moisture resistance reliability may be lowered.

[0053] In order to improve the moisture resistance and curing rate of the liquid crystal sealant, it is more preferable to use a dihydrazide-based thermal latent curing agent in combination as the component (2) and (3). To date, monohydrazide-based thermal latent curing agents for liquid crystal sealants are known. In this way, monohydrazide thermal latent curing agents having one hydrazide group as a functional group have a lower melting point and higher compatibility with other resins than polyfunctional types such as dihydrazide. The latent curability is good. On the other hand, however, a cured product of a liquid crystal sealant using such a heat-latent curing agent has a problem of low crosslinking density and low moisture resistance. Rolling force S, dihydrazide-based thermal latent curing agent has two hydrazide groups as functional groups Therefore, in addition to high latent curability, the reactivity is good. Therefore, when such a heat-latent curing agent is applied to a liquid crystal sealant, a cured product having a high crosslinking density and a good mechanical strength and water resistance can be obtained.

 [0054] The total amount of component (2) and component (3) is preferably from! To 25 parts by mass, more preferably from 3 to 20 parts by mass in 100 parts by mass of the liquid crystal sealant. Such a liquid crystal sealant has a long working life since it has good moisture resistance and viscosity stability. Further, since the moisture resistance is good, when applied to a liquid crystal display panel, a liquid crystal display panel having excellent display properties with high adhesive strength between the cured liquid crystal sealant and the substrate can be obtained. On the other hand, if the total amount exceeds 25 parts by mass, the viscosity stability is poor. If it is less than 1 part by mass, curing may be insufficient.

 [0055] Further, when the blending mass of component (2) is W1 and the blending mass of component (3) is W2, it is preferable that 0.2≤W2 / (W1 + W2) ≤0.8. More preferably, 0.4 ≦ W2 / (W1 + W2) ≦ 0.6. At this time, when a plurality of types of compounds are used as the components (2) and (3) in the preparation of the liquid crystal sealant, the total amount of the compounds used in each component is regarded as W1 and W2. Since such a liquid crystal sealant has good viscosity stability, the pot life is prolonged, and when such a liquid crystal sealant is applied to a liquid crystal display panel, the cured liquid crystal sealant is bonded to the substrate. A liquid crystal display panel with high strength and excellent moisture resistance can be obtained.

 [0056] Further, in the liquid crystal sealant of the present invention, the total of the active hydrogen equivalents of the components (2) and (3) described above is 0.3 to 3.0 with respect to the epoxy equivalent of the component (1). Preferably there is. The active hydrogen equivalent is the equivalent of hydrogen that can react with the epoxy groups of the components (2) and (3). Such an active hydrogen equivalent can also be calculated from the power that can be measured by NMR or the like from the charged amount of the material having the hydroxyl group.

[0057] The liquid crystal sealant in which the active hydrogen equivalent is suitably adjusted has high reactivity between the epoxy resin and the curing agent. Therefore, when the liquid crystal sealant is cured, the curing proceeds in a short time, and the curing proceeds sufficiently, so that an uncured portion hardly remains. Here, if the amount of active hydrogen exceeds 3.0, a large amount of component (2) remains in the cured liquid crystal sealant, which may reduce the strength and water resistance of the cured product. On the other hand, the active hydrogen equivalent is less than 0.3 In some cases, curing does not proceed well and uncured parts remain, and sufficient mechanical strength may not be obtained.

 [0058] As described above, regardless of the melting point, the thermal latent curing agent used in the present invention is an amin-based thermal latent curing agent having an amino group. A liquid crystal sealing agent using such an amine-based thermal latent curing agent has a very good viscosity stability at room temperature, so it has a long pot life and is preferably used as a one-component liquid crystal sealing agent. Can be used. Here, the one-component type liquid crystal sealant is a mixture of a curing agent such as a heat-latent curing agent and a main component that is a cured component such as an epoxy resin, which is stable during storage. Liquid crystal sealant with good properties (storage stability)! / ヽ ぅ.

 [0059] In addition, the amine-based thermal latent curing agent can be used during heating! /, And the active hydrogen contained in the amine-based thermal latent curing agent is ((6) component and (7) component (to be described later)). High nucleophilic addition to meth) acrylic groups. As a result, the liquid crystal sealant in which the amine-based latent heat curing agent is used has a very high curing rate when heated because of high thermosetting property. If such a liquid crystal sealant is used for the production of a liquid crystal display panel, curing proceeds without excess or deficiency even when there is a light-shielding area. As a result, a liquid crystal display panel with good display properties can be obtained. The productivity is good because the curing time is shortened.

[0060] Further, the liquid crystal sealing agent of the present invention further comprises (4) filler, (5) other additives.

V! As described above, the liquid crystal sealant containing the components (1) to (5) is preferably used as a thermosetting liquid crystal sheet.

[0061] (4) Fila

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

[0062] The filler that can be preferably used in the present invention is not particularly limited as long as a known one is used. Examples of fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, Talc, asbestos powder, quartz powder, mica, glass fiber, talc, glass beads, sericite activated clay, Inorganic fillers such as totonite, aluminum nitride, and silicon nitride are included.

 [0063] As the filler of the present invention, polymethyl methacrylate, polystyrene, monomers constituting them and other monomers are copolymerized as long as the properties of the liquid crystal sealant other than the above inorganic fillers are not impaired. Copolymers, polyester fine particles, polyurethane fine particles, rubber fine particles, and other known organic fillers obtained by the above process are used.

 Among these, an inorganic filler is preferable from the viewpoint of improving the linear expansion coefficient and the shape retention of the seal pattern. Among such inorganic fillers, silicon dioxide and talc are more preferred because of their high UV transparency. Regardless of whether it is inorganic or organic, the filler used in the liquid crystal sealant of the present invention may be one that is graphitized with an epoxy resin or a silane coupling agent.

 [0065] The shape of the filler is not particularly limited, and may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or an atypical shape. The maximum particle size of the filler is preferably 6 m or less, more preferably 2 m or less. The particle size of the filler can be measured by a laser diffraction method. If a liquid crystal sealant containing a filler having such a particle size is used in a method for producing a liquid crystal display panel, a liquid crystal cell having very good cell gap dimensional stability can be formed.

 [0066] The content of the filler is preferably 1 to 40 parts by mass, more preferably 10 to 30 parts by mass in 100 parts by mass of the liquid crystal sealant excluding the filler. Thus, the liquid crystal sealing agent in which the blending amount of the filler is adjusted has good applicability to the substrate. Further, the filler may be used in combination with a photocurable resin. Thus, the liquid crystal sealing agent in which the filler and the photocurable resin are used in combination has a good photocurability and is cured in a short time. Furthermore, since the width of the cell gap is kept substantially constant, the dimensional stability is improved.

 [0067] (5) Other additives

If necessary, the liquid crystal sealant of the present invention may contain an additive. Examples of additives preferably used in the present invention include coupling agents such as thermal radical polymerization initiators and silane coupling agents, ion trapping agents, ion exchange agents, leveling agents, pigments, dyes, plastics Agent, antifoaming agent. These additives may be used alone or in combination of two or more kinds depending on the application. In addition, a spacer or the like may be included in order to secure the gap of the liquid crystal cell. The spacer may be included in the liquid crystal sealant, It can be applied to the substrate that makes up the liquid crystal display panel.

 [0068] When preparing a thermosetting sealant, a solvent may be included in order to improve the dispensability and screen printability. Such a solvent has good compatibility with the epoxy resin (1), has a boiling point in the range of 140 to 220 ° C, and is inactive to the epoxy group. It is preferable. Examples of such solvents include keton-based, ether-based and acetate-based solvents. These can be used alone or in combination.

 [0069] Further, in addition to the above components (1) to (5), the liquid crystal sealant of the present invention further comprises (6) attalinoleic acid ester and / or methacrylic acid ester monomers, or oligomers thereof,

(7) A (meth) acryl-modified epoxy resin having at least one epoxy group and (meth) acryl group in each molecule, and (8) a photoradical polymerization initiator may be included. Such a liquid crystal sealant is preferably used as a liquid crystal sealant that is cured by light and heat.

 [0070] (6) Acrylic acid ester and / or methacrylic acid ester monomer, or oligomer thereof

 Examples of the acrylic acid ester monomer and / or methacrylic acid ester monomer used in the present invention, or oligomers thereof include, but are not limited to, the force S including the following.

[0071] Diarylate and / or dimetatalylate such as polyethylene glycol, propylene glycol, polypropylene glycol; ditalariate and / or dimetatalylate of tris (2-hydroxyethyl) isocyanurate; 4 moles per mole of neopentyl glycol Diatalylate and / or dimetatalylate of a diol obtained by adding the above ethylene oxide or propylene oxide; Diatalylate of a diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A and / or Dimetatalylate: Diol or tritalylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane and / or Jiaku of diol obtained by adding Bisufuenonore A1 mole to 4 moles or more ethylene oxide or propylene oxide; is di- or tri meth tributary rate Relate and / or dimetatalylate; tris (2-hydroxyethyl) isocyanurate triarialate and / or trimetatalylate; trimethylolpropane tritalylate and / or trimetatalylate, or oligomer thereof; pentaerythritol triatariate Rate and / or trimetatalylate, or oligomers thereof; Polyatalylate and / or polymetatalylate of dipentaerythritol; Tris (Atari mouth kichetil) isocyanurate; Force prolataton-modified tris (Atari mouth kichetil) isocyanurate; Force prolatatatone Denatured tris (methacryloxychetyl) isocyanurate; poly- and / or polymethacrylate of alkyl-modified dipentaerythritol; Polypentalylate and / or polymetatalylate of dipentaerythritol; neopentyldaricol diatalate and / or dimetatalylate of hydroxybivalate; force prolataton modified hydroxynepentyldaricol diatalate and / or dimethacrylate of hydroxybivalate Ethylene oxide-modified phosphoric acid acrylate and / or dimetatalylate; ethylene oxide-modified alkylated phosphoric acid acrylate and / or dimetatalylate; neopentinoleggnoreole, trimethylonorepropane, pentaerythritole Includes oligoacrylates and / or oligometatalates.

[0072] Examples of acrylic ester and / or methacrylic ester monomers or oligomers thereof include cresol nopolac type epoxy resins, phenol nopolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F. All epoxy groups such as epoxy resin, triphenol methane type epoxy resin, triphenolethan type epoxy resin, trisphenol type epoxy resin, dicyclopentagen type epoxy resin, biphenyl type epoxy resin, etc. Also included is a resin obtained by reacting with rate acid, which is a (meth) acrylate of epoxy resin.

 [0073] These acrylate ester monomers and / or methacrylic ester monomers, or oligomers thereof may be used singly or in combination.

[0074] When the component (6) is included in the liquid crystal sealant, the amount of the (1) epoxy resin is preferably 20 to 200 parts by mass with respect to 100 parts by mass of the component (6). If such a liquid crystal sealant is cured by light or heat, a glass transition temperature (Tg) is high and a cured product can be obtained. The Tg of cured liquid crystal sealant can be measured with a dynamic viscoelasticity measuring device (DMA). wear. For the purpose of obtaining a high-purity liquid crystal sealant, it is preferable to use a component (6) that has been highly purified by a water washing method or the like.

 [0075] (7) (Meth) acrylic modified epoxy resin

 The (meth) acryl-modified epoxy resin of the present invention refers to a compound obtained by reacting an epoxy resin and (meth) acrylate. Examples of such compounds include (a) a compound having both a (meth) acrylic group and an epoxy group in one molecule, and (b) a polymer of (meth) acrylate in a matrix such as an epoxy resin. Dispersed compounds are included.

 [0076] Examples of the compound (a) having both a (meth) acrylic group and an epoxy group in one molecule include an epoxy resin such as a bisphenol type epoxy resin and a nopolac type epoxy resin, (meth) acrylic acid, For example, a resin obtained by reacting with phenylmetatalate under a basic catalyst is included. Since such a modified epoxy resin has both an epoxy group and a (meth) acryl group in the resin skeleton, it has excellent compatibility with the component (1) of the liquid crystal sealant. Therefore, a cured product having a high glass transition temperature (Tg) and high adhesiveness is obtained.

 [0077] Examples of the epoxy resin used as a raw material for the modified epoxy resin include a cresol nopolac type epoxy resin, a phenol nopolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a triphenol methane type. Epoxy resin, triphenol type epoxy resin, trisphenol type epoxy resin, dicyclopentagen type epoxy resin, biphenyl type epoxy resin are included. In addition, modified epoxy resins are highly purified by molecular distillation methods and washing methods.

 [0078] Examples of the compound in which the polymer of (b) (meth) acrylate is dispersed in a base material such as an epoxy resin include an acrylic rubber-modified epoxy resin obtained by acrylic modification of an epoxy resin. . As such an acrylic rubber-modified epoxy resin, a known and commercially available one may be used! /, Or an arbitrarily synthesized resin may be used! /.

 [0079] (8) Photoradical polymerization initiator

The photo radical polymerization initiator of the present invention refers to a compound that generates radicals by light. Examples of radical photopolymerization initiators include benzoin compounds, acetophenones, benzophenones, thixatones, a-lacoxime esters, benzoins, benzoin ethers, phenyl daloxylates, benzyls. , Azo compounds, anthraquinones , Diphenylsulfide compounds, acyl phosphine oxide compounds, organic dye compounds, and iron phthalocyanine compounds, but are not particularly limited, and known photopolymerization initiators are used. be able to. These may be used alone or in combination.

 [0080] The liquid crystal sealant containing such a radical photopolymerization initiator can be temporarily cured by photocuring, and therefore, the work process for manufacturing a liquid crystal display panel is facilitated. The amount of component (8) is preferably 0.0;! To 5 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. When the amount of the radical photopolymerization initiator is 0.01 parts by mass or more, it can be cured in a short time by irradiating light. When the blending amount is 5 parts by mass or less, a hardened material having a good liquid crystal sealant coating property and uniformly cured by light irradiation can be obtained.

 [0081] [Preparation method of liquid crystal sealant]

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

 Next, a method for manufacturing the liquid crystal display panel of the present invention will be described. The liquid crystal sealant of the present invention described above can also be applied to the liquid crystal injection method and the liquid crystal dropping method. Below, the manufacturing method of the liquid crystal display panel of this invention regarding a liquid crystal injection system and a liquid crystal dropping system is demonstrated one by one.

 [0083] [Method of manufacturing liquid crystal display panel by liquid crystal injection method]

The method for producing a liquid crystal display panel by the liquid crystal injection method of the present invention is a method for producing a liquid crystal display panel produced by bonding two opposing substrates together through a liquid crystal sealant. Prepare a substrate having a frame-shaped display area that is formed so that the pixel array area is surrounded by a liquid crystal sealant that has a strong liquid crystal, and is provided with a liquid crystal inlet. And (2) a process of forming a liquid crystal cell between the substrates by laminating the two substrates through the liquid crystal sealant and then bonding the substrates together by heating and pressing. (3) a step of injecting liquid crystal into the liquid crystal cell from the injection port; and (4) a step of sealing the injection port of the liquid crystal cell into which the liquid crystal has been injected by a sealing agent. Include

In the step (1), a liquid crystal sealant is applied to one of the two substrates, and a substrate on which a frame-shaped display area is arranged is prepared. Here, an injection port into which liquid crystal is injected is formed in the frame-shaped display region.

 [0085] Examples of the two substrates used in the liquid crystal display panel of the present invention include a glass substrate on which TFTs are formed in a matrix, a substrate on which color filters and a black matrix are formed. Examples of substrate materials include glass, plastics such as polycarbonate, polyethylene terephthalate, polyethersulfone and PMMA. On the surface of such a substrate, a transparent electrode typified by indium oxide, an alignment film typified by polyimide, and other inorganic ion shielding films are applied! /.

 [0086] As the liquid crystal sealant, those which are effective in the present invention are preferably used. The liquid crystal sealant also acts as an adhesive to bond two substrates together at regular intervals just by forming a frame such as a display area. In the case of manufacturing a liquid crystal display panel by a liquid crystal injection method, a thermosetting sealant is particularly preferable among the liquid crystal sealants which are excellent in the present invention.

 [0087] The method for applying the liquid crystal sealant on the substrate is not particularly limited. Examples of such coating methods include screen printing and dispensing with a dispenser. The liquid crystal sealing agent may be applied to the surfaces of the substrates.

 [0088] The substrate after the liquid crystal sealant is applied is subjected to a precure treatment as necessary. Precure treatment refers to preliminary drying for pre-curing the liquid crystal sealant. There are no particular limitations on the pre-curing treatment, heating temperature and treatment time.

[0089] However, in the case where the liquid crystal sealant contains a solvent! /, At least 95% by mass of the total amount of the solvent in the liquid crystal sealant is removed, and the thermal potential contained in the liquid crystal sealant. It is preferable to set the heating temperature so as to be equal to or lower than the thermal activation temperature of the hardener. Solvent removal and Means to remove the solvent from the liquid crystal sealant by evaporating it. From this point of view, preferable heating conditions for the precure treatment are a heating temperature of 60 to 110 ° C and a heating time of 5 to 60 minutes.

[0090] In the precure treatment, it is preferable to shorten the heating time as the heating temperature is increased so that the characteristics of the liquid crystal sealant are not impaired by heat. At this time, even when the heating temperature is set to 110 ° C or higher, the force capable of removing the liquid crystal sealant can be hardened more than necessary, and the cell gap width may change. Therefore, the heating conditions during the precure treatment are appropriately determined according to the type of each component constituting the liquid crystal sealant.

 [0091] In the step (2), the substrate on which the liquid crystal sealant has been preliminarily dried and the other substrate are overlapped and aligned, and then heated and pressed. Since the liquid crystal sealant is cured by heating and pressing, the two substrates are bonded together via the liquid crystal sealant. At this time, the thickness of the liquid crystal sealant after bonding the substrates to each other can be made uniform within a range of 1.5 to 7.0 m by appropriately adjusting the pressurizing conditions for heat-pressing. It is preferable to do.

 [0092] The heating conditions for heat-pressing the substrates together are not particularly limited. Generally, if the heating conditions are 100 to 160 ° C and 0.5 to 24 hours, the liquid sealing agent can be hardened suitably.

 [0093] In addition, when heat-pressing two substrates, a single-wafer heat press may be used! /. A single-wafer heat press is a heat press that bonds two substrates together. Examples of such single-wafer heat presses include vacuum single-wafer heat presses that can be heated under vacuum, and rigid single-wafer heat that is forcibly heated and pressed via a hot plate under atmospheric pressure. A press machine is included.

[0094] When two substrates are bonded by a single-wafer heat press, first, the two superimposed substrates are heated and pressed at 100 to 160 ° C for 2 to 10 minutes and temporarily Glue. Next, release the pressure of the press machine and take out the two substrates attached from the press machine. Subsequently, the liquid crystal sealant is completely cured in a heating oven maintained at a substantially constant temperature. Here, the step of heating the liquid crystal sealing agent may be performed in two or more stages. Further, instead of the sheet press, a liquid crystal display cell may be manufactured by a batch heating and pressure bonding method. In the step (3), liquid crystal is injected into the injection liquid crystal cell. The liquid crystal is not particularly limited as long as it is appropriately determined according to the cell volume.

 [0096] In the step (4), the inlet of the liquid crystal cell into which the liquid crystal has been injected is sealed with a sealing agent for sealing. Examples of the sealant for sealing include a two-component curable sealant and an ultraviolet curable sealant, but are not particularly limited.

 [Method of manufacturing liquid crystal display panel by liquid crystal dropping method]

 The method for producing a liquid crystal display panel according to the liquid crystal dropping method of the present invention is a method for producing a liquid crystal display panel produced by bonding two opposing substrates through a liquid crystal sealant. Preparing a substrate having a frame-shaped display region formed so that the pixel array region is surrounded by the liquid crystal sealant, and (11) in the display region in an uncured state or the other substrate A step of dropping a liquid crystal on the substrate; (12) a step of superimposing the substrate on which the liquid crystal has been dropped and the other substrate under reduced pressure; and (13) a step between the two superimposed substrates And hardening the liquid crystal sealant in heating.

 In the step (10), a substrate including a display region on a frame formed so that the pixel array region is surrounded by the liquid crystal sealant is prepared according to the present invention. The substrate and the method for applying the liquid crystal sealant to the substrate used here are not particularly limited as long as they are the same as the liquid crystal injection method. In the case of producing a liquid crystal display liquid crystal display panel by a liquid crystal dropping method, a light and thermosetting sealant is preferably used.

 In the step (11), an appropriate amount of liquid crystal is dropped in an uncured frame serving as a display area or on the other substrate. This liquid crystal dropping is usually performed under atmospheric pressure. At this time, it is preferable to adjust the dropping amount of the liquid crystal according to the size of the frame so that the liquid crystal fits in 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 bonding. Therefore, excessive pressure is not applied to the frame! /, So there is little risk of breaking the seal forming the frame.

[0100] In the step (11), the other substrate on which the liquid crystal is dropped means a substrate different from the substrate having the display region. When liquid crystal is dropped on a substrate on which such a seal is not disposed, the other display area can be formed when the substrates are overlapped with each other. The liquid crystal may be dropped at an arbitrary position on the substrate.

 [0101] In the step (12), the substrate force on which the liquid crystal is dropped is superposed on the other substrate under reduced pressure. Here, the stacking of the substrates may be performed using a vacuum bonding apparatus or the like, but is not particularly limited. Usually, in the liquid crystal dropping method, the substrates are superposed under reduced pressure. The reason for overlaying under reduced pressure in this way is to bond the substrates together using a pressure difference.

 [0102] In the step (13), the liquid crystal sealant between the two superposed substrates is cured. The curing treatment of the liquid crystal sealant is not particularly limited as long as it is appropriately determined according to the type of the curing agent. When a photocurable liquid crystal sealant is used, light irradiation such as ultraviolet rays is performed, and when a thermosetting liquid crystal sealant is used, heat treatment is appropriately performed.

 [0103] Curing conditions such as the type of light irradiated for curing the liquid crystal sealant in the curing process, the irradiation time, or the temperature and time during heating are appropriately selected according to the composition of the liquid crystal sealant used. do it. For example, when the liquid crystal sealant is cured by light, the curing condition may be irradiated with ultraviolet rays under pressure within a range of 1000 to 18000 mJ. In addition, when the liquid crystal sealant is cured by heating, the liquid crystal sealant is sufficiently hardened if the heating temperature is within a range of 110 to 140 ° C with no pressure applied and heating is performed for 1 hour. The force S

 [0104] Regardless of the liquid crystal injection method or the liquid crystal dropping method, the liquid crystal display panel manufactured by combining the liquid crystal sealing agent of the present invention and the manufacturing method has good moisture resistance reliability. The present invention includes these liquid crystal display panels.

 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples according to the present invention.

 However, the present invention is not limited to the embodiment shown here.

 [0106] First, each component used in the preparation of the liquid crystal sealant in the examples and comparative examples will be described. In the following Examples and Comparative Examples, the following two types of liquid crystal sealants (liquid crystal sealants a and b) were appropriately selected and used. Here, the liquid crystal sealant a acts as a thermosetting sealant, and the liquid crystal sealant b acts as a light and thermosetting sealant.

[0107] (1) Epoxy resin As the epoxy resin, o-cresol nopolak type solid epoxy resin (EOCN-10 20-75 Nippon Kayaku Co., Ltd., softening point by ring and ball method 75 ° C, epoxy equivalent 215 g / eq) was used.

 [0108] (2) First thermal latent curing agent having a melting point of 150 ° C or lower

 The first heat-latent curing agent includes: (a) 2-phenylimidazole (manufactured by Ade force Hardener E H4346S ADEKA, melting point 125 ° C), (b) polyaminourea (Fujicure FXE-1000 Fuji (Chemical Industry Co., Ltd., melting point 120 ° C), (c) Aminada external system (Ade force hardener EH4357S ADEKA Co., Ltd., melting point 78 ° C), (d) l, 3-bis (hydrazino carbon) 4) Thermal latent hardeners of 1-Isopropyl Hydantoin (Amicure VDH Ajinomoto Fine-Techno Co., Ltd., 120 ° C; solubility in 100 ml of water at 25 ° C) were appropriately used.

 [0109] (3) Second thermal latent curing agent having a melting point of 180 ° C or higher

 The second heat-latent curing agent includes (a) diamide (AH-154, Ajinomoto Fine Techno Co., Ltd., melting point 200 ° C), (b) imidazole (Cureazole 2E4MZ-A Shikoku Chemicals Co., Ltd.) (Melting point 220 ° C), (c) dodecandiohydrazide (N-12, manufactured by Nippon Finechem Co., Ltd., melting point 189 ° C; insoluble in 100 ml of water at 25 ° C), (d) sebacic acid dihydrazide ( SDH Otsuka Chemical Co., Ltd., melting point 190 ° C), (e) Fatty acid dicarboxylic acid (ADH Nippon Finechem Co., Ltd. melting point 181 ° C; Solubility 10g in 25 ° C water 100g) It was.

 [0110] (4) Fila

The fillers include (a) amorphous silica (MU-120 manufactured by Shin-Etsu Chemical Co., Ltd.), (b) amorphous alumina (UA-5105 manufactured by Showa Denko KK), (c) inorganic spherical silica (Sea Foster) Three types (S—30, produced by Nippon Shokubai Co., Ltd., average primary particle size 0.3111, specific surface area l lm ² / g) were appropriately used.

[0111] (5) Other additives

 As another additive, a silane coupling agent (γ-glycidoxypropyltrimethoxysilane ΚΒΜ-403 manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

[0112] (6) Acrylic acid ester and / or methacrylic acid ester monomer, or oligomer thereof (6) As the component, bisphenol A type epoxy dimetatalylate (3000M manufactured by Kyoeisha Chemical Co., Ltd.) and bisphenol Nore type A epoxy acrylate (EB-3700 manufactured by Daicel Scientific) are used as appropriate. Les

[0113] (7) (Meth) acrylic modified epoxy resin

 As the (meth) acryl-modified epoxy resin, an acrylic rubber-modified epoxy resin obtained by acrylic-modifying the epoxy resin obtained in Synthesis Example 1 below was used.

[0114] [Synthesis Example 1]

 Bisphenol A type epoxy resin (Epomic R—140P, Mitsui Chemicals) 600 g, which is a liquid epoxy resin, in a 2000 ml four-necked flask equipped with a stirrer, gas inlet tube, thermometer, and cooling tube Then, 12 g of clinoleic acid, dimethylenoethanolamine lg, and 50 g of 卜 noren were charged, and the mixture was heated and stirred at 110 ° C. for 5 hours in a dry air stream. Next, 350 g of phenolic relay 卜, 20 g of glycidinoremethacrylate 卜, dihi, dinolebenzene lg, azobisdimethylvaleronitrile lg, and 2 g of azobisisobutyronitrile are added to this mixture. Then, the reaction system was reacted at 70 ° C for 3 hours while introducing nitrogen into the reaction system, and then further reacted at 90 ° C for 1 hour. Finally, the prepared mixture was degassed under a reduced pressure of 110 ° C. Tolueneization was performed to obtain an acrylic rubber-modified epoxy resin.

 [0115] (8) Photoradical polymerization initiator

 As a radical photopolymerization initiator, 1-hydroxy-cyclohexroyl diruketone (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) was used.

 [0116] Further, propylene glycol diacetate (manufactured by Dunnol PGD A Dow Chemical Co., Ltd.) was used as a solvent as required. In addition to the above, as thermolatent curing agent A, a monohydrazide thermal latent curing agent (manufactured by SMH Otsuka Chemical Co., Ltd., melting point 148 ° C; solubility in 10 Oml of water at 25 ° C 1 Og Less than).

[0117] Further, in each of the examples and comparative examples, (i) viscosity stability of the liquid crystal sealant, (ii) adhesive strength of the thermosetting sealant, (iii) adhesive strength of the light and thermosetting sealant, (Iv) Measurement and evaluation of the display properties of a liquid crystal display panel using a thermosetting sealant and (V) the display properties of a liquid crystal display panel using a light and thermosetting sealant, respectively. The characteristics of were evaluated. Details of each measurement are shown below. Here, the viscosity of the liquid crystal sealant (i) is low. As the qualitative evaluation method, the same method was used for the thermosetting sealant, light, and thermosetting seal.

 [0118] (i) Viscosity stability of liquid crystal sealant

 Using an E-type viscometer, the viscosity value of the liquid crystal sealant at 25 ° C was measured. The liquid crystal sealant used for viscosity measurement was sealed in a polyethylene container and stored at 25 ° C for 5 days. Then, after a predetermined period of time, the viscosity value at 25 ° C was measured with an E-type viscometer, and based on the measured value, the viscosity value before sealing was set to 100, after 25 ° C / 5 days had passed. The change rate of the viscosity value was calculated. At this time, when the force and the rate of change are less than 10%, the viscosity stability is extremely high (◎), and when it is 10% or more and less than 15%, the viscosity stability is high (◯). When there was a change exceeding%, the viscosity stability was bad! /, (X), and was evaluated in three stages.

 [0119] (ii) Adhesive strength of thermosetting sealant

First, the liquid crystal sealing agent 1 mass _^0/0 were added glass fibers 5 m, screen-printed in a circular form having a diameter of lmm on the alkali-free glass of 25mmX 45m m X thickness 5 mm, 90 ° C, 10 min pre-cure Processed. Next, a similar glass paired with this substrate was bonded to a cross, fixed with a jig, and heat-treated at 120 ° C. for 60 minutes using an oven.

 [0120] Using a tensile tester (Model 210, manufactured by Intesco), the finished test piece was pulled at a rate of 2 mm / min and pulled in a direction parallel to the bottom of the glass. Was measured. Here, the adhesive strength was evaluated in two steps according to the magnitude of the plane tensile strength. That is, when the tensile strength is 15 MPa or more, the adhesive strength is particularly high (◎), when the tensile strength is more than lOMPa and less than 15 MPa, the adhesive strength is high (◯), and the tensile strength is less than lOMPa. The adhesive strength was low! /, (X).

[0121] In addition, a test piece prepared by the same method as described above is subjected to a pressure tacker test under the conditions of 121 ° C, 2 atm, 100% humidity and 40 hours, and then the planar tensile strength is measured by the same method as described above. Thus, the planar tensile strength before and after the pressure tacker test was compared. When the tensile strength after pressure tacker test is lOMPa or higher, the moisture-resistant adhesive reliability is particularly high (◎), and when the tensile strength is 7 MPa or higher and less than lOMPa, the moisture-resistant adhesive reliability is high (◯). When the tensile strength is less than 7 MPa, the moisture-resistant adhesion reliability is low (X). [0122] (iii) Adhesive strength of light and thermosetting sealant

First, the liquid crystal sealing agent 1 mass _^0/0 were added glass fibers 5 m, 25mm X 45m m X thickness screen printed on the alkali-free glass of 5mm in a circle with a diameter of lmm, similar glass comprising a pair Were pasted into a cross. Next, using a UV irradiation device (manufactured by Usio Electric Co., Ltd.), an ultraviolet ray of 100 mW / cm ² was applied to the place where a load was applied by sandwiching the two bonded substrates with clips. The test piece which hardened the liquid-crystal sealing compound only was produced. At this time, the irradiation energy of ultraviolet rays was set to 2000 mJ.

 [0123] The completed test piece was heat-treated at 120 ° C for 60 minutes in a nitrogen atmosphere using an oven. The plane tensile strength of the completed specimen was measured using a tensile tester (Model 210 manufactured by Intesco Corporation). At this time, the measurement of the plane tensile strength, the evaluation of the measurement results, and the comparison of the plane tensile strength before and after the pressure-tucker test were performed by the same method as the thermosetting sealant described above.

 [Iv] (iv) Display properties of liquid crystal display panels using thermosetting sealants

 Using a thermosetting sealant containing 1% by mass of 5 m glass fiber on a 40 mm x 45 mm glass substrate (RT—DM88PIN E HC) with a transparent electrode and alignment film, 0.5 mm A frame of 35mm x 40mm was drawn with a spring width of 50m and a thickness of 50m. At this time, a liquid crystal inlet was provided in the frame. In addition, a dispenser (manufactured by Shotmaster Musashi Engineering) was used for drawing.

 [0125] The drawn thermosetting sealant was pre-cured, heated and dried for 10 minutes, and the other glass substrate in a pair was placed on top of each other. The heat treatment was performed at 120 ° C for 60 minutes.

 [0126] Next, a liquid crystal material (MLC-11900-000 Merck Co., Ltd.) corresponding to the capacity of the cell after shelling is placed in the liquid crystal cell formed between the two substrates. After injecting from the inlet, the liquid inlet panel was sealed with a sealing agent (Struct Bond ES-302, Mitsui Chemicals) to produce a liquid crystal display panel.

[0127] Of the surface of the manufactured liquid crystal display panel, a deflection plate was attached to the front side, and a deflection plate with a reflection plate was attached to the rear side. The liquid crystal display panel was driven by applying a voltage of 5 V to the liquid crystal display panel with a direct current power supply. This When the liquid crystal display function near the seal formed by the liquid crystal sealant functions normally from the beginning of driving, the display performance of the liquid crystal display panel is evaluated in two stages according to the following criteria: did.

[0128] The display performance of such a liquid crystal display panel is good (◯) when the liquid crystal display function is exhibited until the time of sealing, and from the vicinity of the sealing toward the inside of the frame. When the display function is demonstrated up to a distance of 3 mm! /, NA! /, The display performance is markedly bad, and (X) is marked.

 [0129] In addition, after performing the pressure-tucker test on the above-mentioned liquid crystal display panel under the conditions of 121 ° C, 2 atm, 100% humidity, and 40 hours, the display performance of the liquid crystal display panel was further evaluated in the same manner. As a result, we compared the display properties of the liquid crystal display panels before and after the pressure-tucker test.

 [0130] (V) Display properties of liquid crystal display panels using light and thermosetting sealants

 On a 40 mm x 45 mm glass substrate (RT—DM88PIN E HC Co., Ltd.) with a transparent electrode and an alignment film, using a light and thermosetting sheathing agent containing 1% by mass of 5 m glass fiber, 0 A frame of 35 mm x 40 mm was drawn with a spring width of 5 mm and a thickness of 50 m. Dispenser (Shotmaster Musashi Engineering Co., Ltd.) was used for drawing.

[0131] Next, a liquid crystal material (MLC-11900-00 manufactured by Merck & Co., Inc.) corresponding to the volume of the panel after shelling was precisely dropped with a dispenser. Subsequently, the two glass substrates were stacked so as to face each other under a reduced pressure of 90 Pa, fixed by applying a load, and further using an ultraviolet irradiation device (manufactured by Usio Electric Co., Ltd.), lOOmW / The liquid crystal sealant was cured by irradiating UV light of cm ² . At this time, the irradiation energy of ultraviolet rays was set to 2000 mJ. A metal halide lamp is used as the light source, an integrated light intensity meter (UVR — T35 Topcon Co., Ltd.) with a measurement wavelength range of 300 to 390 nm and a peak sensitivity wavelength of 365 nm is used to measure the integrated light quantity. ) Was used. Further, after the liquid crystal sealant was cured by light, the liquid crystal sealant was further cured by heating at 120 ° C. for 60 minutes.

[0132] A deflection film was pasted on both surfaces of the two substrates bonded together to form a liquid crystal display panel. Apply a voltage of 5V to this liquid crystal display panel with a DC power supply. As a result, the liquid crystal display panel was driven. At this time, it is visually observed whether the liquid crystal display function in the vicinity of the seal formed by the liquid crystal sealant functions normally from the beginning of driving, and the display properties of the liquid crystal display panel are determined in two stages according to a predetermined standard. evaluated. Here, the criteria for evaluating the display properties of the liquid crystal display panel are the same as those of the above-described thermosetting sealant, and thus detailed description thereof is omitted.

[0133] Further, the above-mentioned liquid crystal display panel was subjected to a pressure-tucker test under the conditions of 121 ° C, 2 atm, 100% humidity, 40 hours, and the display properties of the liquid crystal display panel were evaluated in the same manner. We compared the display properties of the liquid crystal display panels before and after the pressure tacker test.

 [0134] Furthermore, the evaluation results of each liquid crystal sealant were tabulated, and the characteristics of the liquid crystal sealant were comprehensively evaluated according to the following criteria in three stages. Here, in each of the evaluation results, if the viscosity stability, adhesiveness, and / or all of the display properties of the liquid crystal display panel are particularly good (◎), the liquid crystal sealant When the properties are particularly good (◎) and the viscosity stability, adhesiveness, and display properties of the liquid crystal display panel are all good (◯) in the evaluation results, the properties of the liquid crystal sealant are good (○ In each evaluation result, if the viscosity stability, adhesiveness, or display property of the liquid crystal display panel is unfavorable, that is, if there is even one X, the liquid crystal sealant has poor properties! / , (X).

 [0135] [Example 1]

(1) 25 parts by mass of O-cresol nopolac epoxy resin (EOCN-1020-75 manufactured by Nippon Kayaku Co., Ltd.) as a component, propylene glycol diacetate (Daanol PGDA Dow Chemical Co., Ltd.) as a solvent ) Heat-dissolved in 15 parts by mass. Furthermore, 20 parts by mass of an acrylic rubber-modified epoxy resin of Synthesis Example 1 described later, and 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (Amicure VDH-J Ajinomoto Fine Techno Co., Ltd.) as component (2) 9 parts by mass, as component (3), dodecandiohydrazide (N-12, Nihon Finkechem) 4 parts by mass, 2, 4-diamino-6- [2, 1-ethyl-1,4-methylimidazolyl- (1 ')] -Ethyru s-triazine (Cureazole 2E4MZ—A Shikoku Kasei Kogyo Co., Ltd.) 2 parts by mass, (4) Amorphous silica (MU120 Shin-Etsu Chemical Co., Ltd.) 2 parts by mass, amorphous Alumina (UA-5105, Showa Denko) 13 parts by mass, (5) as component 5 parts by mass of doxypropyltrimethoxysilane (KBM403, Shin-Etsu Chemical Co., Ltd.) was added and premixed with a mixer. Subsequently, after kneading until the solid material becomes 5 m or less using three rolls, the kneaded product is vacuum defoamed to prepare a thermosetting sealant.

; ^^

 [Example 2]

 A liquid crystal sealant was prepared in the same manner as Example 1 except that (3) component was 4 parts by mass of sebacic acid dihydrazide (SDH).

[0137] [Example 3]

 The amount of component (2) is 2 parts by mass, and component (3) is 2, 4 diamino-6- [2'-ethyl-4, -methylimidazolinole (1,1)] ethyl s triazine (Cureazole 2E4MZ-A) A liquid crystal sealant was prepared in the same manner as in Example 1 except that was not used and that 13 parts by mass of dodecandiohydrazide (N-12) was used.

[Example 4]

 The amount of component (2) is 13 parts by weight, and component (3) is 2,4 diamino-6- [2 'ethyl 4, -methylimidazolinole (1,)] ethyl s triazine (Cureazole 2E4MZ-A) A liquid crystal sealant was prepared in the same manner as in Example 1 except that was not used and that 2 parts by mass of dodecandiohydrazide (N-12) was used.

[Example 5]

 The component (2) is 9 parts by mass of 2-phenylimidazole (Ade force hardener EH-4346S), and the component (3) is 2,4 diamino-6- [2'-ethyl-4'-methylimidazolyl (1 ' )] A liquid crystal sealant was prepared in the same manner as in Example 1 except that ethyl s triazine (Curazole 2E4MZ-A) was not used and dodecandiohydrazide (N-12) was changed to 6 parts by mass.

[0140] [Example 6]

(2) Component is 9 parts by mass of polyaminourea (Fujicure FXE-1000), and (3) component is 2,4-diamino-6- [2'-ethyl-4'-methylimidazolinole (1 ')]-ethyl s- A liquid crystal sealant was prepared in the same manner as in Example 1 except that triazine (Curazole 2E4MZ-A) was not used and dodecandiohydrazide (N-12) was 6 parts by mass. [0141] [Example 7]

 (2) Component is 9 parts by mass of amine amine system (Ade force hardener EH—4357S), and (3) component is 2,4 diamino-6— [2'-ethyl 4'-methylimidazolyl (1 ')]-ethyl s A liquid crystal sealant was prepared in the same manner as in Example 1 except that triazine (Curazole 2E4MZ-A) was not used and dodecandiohydrazide (N 12) was 6 parts by mass.

 [0142] [Example 8]

 A liquid crystal sealant was prepared in the same manner as in Example 1 except that the amount of the component (2) was 6 parts by mass and the component (3) was 9 parts by mass of fatty acid dicarboxylic acid (ADH).

 [Example 9]

 (1) As a component, 15 parts by mass of O cresol nopolac epoxy resin (EOCN-1020-75 manufactured by Nippon Kayaku Co., Ltd.) is added to bisphenol A type epoxy dimetatalylate (epoxy ester 3000M manufactured by Kyoeisha Chemical Co., Ltd.) ) Heated and dissolved in 30 parts by mass to obtain a uniform solution. Next, after cooling this mixed solution, 20 parts by mass of bisphenol A type epoxy acrylate (EB37 00 manufactured by Daicel Cytec Co., Ltd.), (8) 1-hydroxycyclohexyl phenyl-ketone as a photo radical polymerization initiator (Irgacure 184 manufactured by Ciba-Pesatique Mical Co., Ltd.) 2 parts by mass, as component (2), 1,3-bis (hydrazinocarboxyl) -5-isopropylhydantoin (Amicure VDH-J Ajinomoto Fine Techno Co. 6 parts by mass, 3 parts as imidazole (Cureazole 2E4MZ-A, Shikoku Kasei Kogyo Co., Ltd.) and 4 parts by mass of dodecandiohydrazide (N-12, Nihon Finechem Co., Ltd.) (4) 20 parts by mass of spherical silica (Sea Foster S-30 manufactured by Nippon Shokubai Co., Ltd.) as component, and (5) γ-glycidoxypropyltrimethoxy as component 1 part by mass of silane (KBM403, Shin-Etsu Chemical Co., Ltd.) was added and premixed with a mixer. Furthermore, knead with 3 rolls until the solid material is 5〃m or less, filter with a lO ^ m filter (MSP-10-E10S ADV ANTEC), and then vacuum defoaming A light and thermosetting liquid crystal sealant was prepared.

[Example 10]

(3) Sebasic acid dihydrazide (SDH) instead of dodecandiohydrazide (N-12) A liquid crystal sealant was prepared in the same manner as Example 9 except that the amount was 4 parts by mass.

[Example 11]

 (2) All components are the same as Example 9 except that the amount of component is 2 parts by mass, and that component (3) is 10 parts by mass of dodecanediohydrazide (N-12 Nihon Finechem Co., Ltd.). A liquid crystal scenery agent was prepared.

[Example 12]

 A liquid crystal sealant was prepared in the same manner as in Example 9 except that the amount of component (2) was 10 parts by mass, and that component (3) was dodecandiohydrazide (N-12) 2 parts by mass. .

[Example 13]

 (2) All components are the same as Example 9 except that 6 parts by mass of 2-phenylimidazole (Ade force hardener EH4346S) and 3 parts of dodecandiohydrazide (N-12) are 6 parts by mass. A liquid crystal sealant was prepared.

[Example 14]

 Except that the component (2) was 6 parts by mass of polyaminourea (Fujicure FXE-1000) and the component (3) was 6 parts by mass of dodecandiohydrazide (N-12), all were the same as in Example 9. A liquid crystal sealant was prepared.

 [Example 15]

 (2) All components were the same as in Example 9 except that the component was 6 parts by weight of amine amine system (Ade force hardener EH4357S) and 6 parts by weight of dodecanohydrazide (N-12 Nihon Finechem Co., Ltd.). An agent was prepared.

[Example 16]

 (2) Component is 1,3-bis (hydrazinocarboethyl) 5-isopropylhydantoin (Amicure VDH) 6 parts by mass, (3) Component is diamide (AH-154) 5 parts by mass, fatty acid dicarbon A liquid crystal sealant was prepared in the same manner as in Example 9 except that 6 parts by mass of acid (ADH) was used.

 [0151] [Comparative Example 1]

Except for using (3) component and (2) component being 1,3-bis (hydrazinocarboxyl) 5-isopropylhydantoin (amicure VDH) 15 parts by mass same A liquid crystal sealant was prepared.

[0152] [Comparative Example 2]

 A liquid crystal sealant was prepared in the same manner as in Example 1 except that the component (2) was not used and that the component (3) was (d) 15 parts by mass of sebacic acid dihydrazide (SDH).

[Comparative Example 3]

 (2) Component is 9 parts by mass of monohydrazide-based thermal latent curing agent (SMH), (3) Component is imidazole (Cureazole 2E4MZ-A), 2 parts by mass, and dodecandiohydrazide (N — 12) 4 A liquid crystal sealant was prepared in the same manner as in Example 1 except that the amount was changed to parts by mass.

 [Comparative Example 4]

 A liquid crystal sealant was prepared in the same manner as in Example 9 except that the component (3) was not used and the component (2) was changed to 12 parts by mass.

 [0155] [Comparative Example 5]

 (2) No component is used, and (3) component is sebacic acid dihydrazide (SDH) 12 parts by mass, (4) component filler is 2 parts by mass, (5) component is 5 parts by mass, (6) A liquid crystal sealant was prepared in the same manner as in Example 9 except that 20 parts by mass of epoxydimethalate and 15 parts by mass of epoxy acrylate were included.

[0156] [Comparative Example 6]

 (2) Component is 6 parts by mass of monohydrazide thermal latent curing agent (SMH), (3) Component is imidazole (Cureazole 2E4MZ—A) 2 parts by mass, Dodecandiohydrazide (N-12) 4 quality Example 9 except that the amount of the component was changed to 2 parts by weight, 5 parts of the component (5), 5 parts by weight of the component (5), and 20 parts by weight of the epoxy dimetatalate of the component (6). A liquid crystal sealant was prepared in the same manner as described above.

 [0157] Tables 1 to 3 collectively show the components, blending amounts, and evaluation results of the liquid crystal sealants used in the examples and comparative examples.

[0158] [Table 1] Actual Actual Actual Out M Out M Out Out Out Composition Ingredient Solubility

 Example Example Example Example Example Example Example Example

1 2 3 4 5 6 7 8

(1) Epoxy resin 25 25 25 25 25 25 25

 (a) Insoluble ―--9

 (b)

 First insoluble ― 9 ―

(2)

 Thermal latent curing agent (c) Insoluble 9

 (d)> 100 9 9 2 13-One ― 6

(a) Insoluble

 (b) Insoluble 2 2

 Second

 (3) (c) Insoluble 4 ― 13 2 6 6 6

 Thermal latent curing agent

 (d) Insoluble-4

 (e) 10 9

(a) 2 2 2 2 2 2 2 2

(4) Fila

 (b) 13 13 13 13 13 13 13 13

(5) Other supplements [1 agent 5 5 5 5 5 5 5 5

(7) Acryl rubber modified epoxy resin 20 20 20 20 20 20 20 20 Solvent 15 15 15 15 15 15 15 15

Ratio of (2) component to (3) component 0.6 0.6 0.9 0.1 0.4 0.4 0.4 0.6

(i) Viscosity stability 〇 ◎ ◎ 〇 © 〇 〇 © Initial ◎ 〇 〇 〇 ◎ 〇

(ii) Adhesive strength

Evaluation After moisture absorption ◎ ◎ 〇 〇 〇 〇 X value

 Initial ○ ○ ○ ○ ○ ○ ○ ○

(iv) Displayability

After moisture absorption ○ ○ Δ ○ ○ ○ ○ Δ Comprehensive evaluation ○ ○ ○]

Real real real real real real

 Application Application Application Application Application Application Component Composition Solubility

 Example Example Example Example Example Example Example Example

9 1 0 1 1 1 2 1 3 1 4 1 5 1 6

(1) Epoxy resin 15 15 15 15 15 15 15 15

 (a) Insoluble 6-No. (b)

 1 insoluble-―--― 6 ―-

(2)

 Thermal latent curing agent (c) Insoluble 6

 (d)> 1 00 6 6 2 10---6

(a) Insoluble

 (b) Insoluble 2 2

 Second

 (3) (c)

 Thermal latent curing agent Insoluble 4 10 2 6 6 6

 (d) Insoluble ― 4

 (e) 10 6

(4) Filler (c) 20 20 20 20 20 20 20 20

(5) Other additives 1 1 1 1 1 1 1 1 Epoxy dimethacrylate 30 30 30 30 30 30 30 30

(6)

 Epoxy acrylate 20 20 20 20 20 20 20 20

(8) Photoradical polymerization initiator 2 2 2 2 2 2 2 2

Mixing ratio of (2) component and (3) component 0.5 0.5 0.8 0.2 0.5 0.5 0.5 0.5

(i) Viscosity stability ○ ○ © ○ ◎ ○ ◎ ○ Initial ® ○ ○ ○ ○ ○ © ○

(iii) Adhesive strength

Evaluation After moisture absorption ◎ ◎ 〇 X 〇 X X value Initial 〇 〇 〇 〇 〇 〇 〇

(v) Displayability

After moisture absorption ○ ○ △ ○ ○ ○ ○ Δ Comprehensive evaluation ○ ○ ◎ ◎ ○

Ratio ratio ratio ratio comparison comparison comparison composition component solubility

 Example Example Example Example Example Example

1 2 3 4 5 6

(1) Epoxy resin ― 25 25 25 15 25 25

 (a) Insoluble

 (b)

 First insoluble

 (2)

 Thermal latent curing agent (c) Insoluble

 (d)> 1 00 15 ― 12 ― ―

(a) Insoluble

 (b) Insoluble--2-1 2 Second

 (3) (c) ― ― 4 ―-4 Thermal latent curing agent Insoluble

 (d) Insoluble ― 15 ― ― 12 ―

(e) 10

 Thermal latent moistening agent A 1 0 <― 9 ― ― 6

 (a) 2 2 2 ―-―

(4) Filler (b) 13 13 13 One ―-

(c) ― ― ― 20 2 2

(5) Other additives 5 5 5 1 5 5 Epoxy dimethacrylate ― ― ― 30 20 20

(6)

 Epoxy acrylate-One-20 15 15

(7) Acrylic rubber-modified epoxy resin 20 20 20 ― ― ―

(8) Photo radical polymerization initiator ― 1-2 2 2 Solvent 15 15 15 1 ― ―

Mixing ratio of (2) component and (3) component 0 0 0 0 0 0

(i) Viscosity stability X ◎ X X ◎ X Initial ○ X ○ ○ X ○

(ϋ) Adhesive strength

 Evaluation After moisture absorption X X X X X X value

 Initial ○ O ○ ○ ○ ○

(iv) Displayability

After moisture absorption XOXXOX Overall evaluation XXXXXX As is clear from Tables 1 and 2, the liquid crystal sealants of Examples 1 to 16 to which the present invention was applied were manufactured using the above-mentioned viscosity stability, adhesive strength, and the above. LCD display panel It was confirmed that the display is very excellent.

[0162] On the other hand, in the case of a liquid crystal sealant comprising one kind of thermal latent curing agent and an epoxy resin, as is clear from the results of the comparative examples shown in Table 3, Compared with each example, the viscosity stability, the adhesive strength, and the display property of the liquid crystal display panel are deteriorated. It was also confirmed that various properties such as viscosity stability deteriorated when a monohydrazide compound was used as the thermal latent curing agent. From the above results, it is clear that among the hydrazide compounds, dihydrazide-based thermal latent curing agents that are not monohydrazide-based compounds are suitable for liquid crystal sealants.

 Industrial applicability

 [0163] The liquid crystal sealant of the present invention uses two types of heat-latent curing agents having different melting points, so that the curing speed is high and the moisture resistance is high. Also, since the viscosity stability is kept high for a long time, the pot life is long. When such a liquid crystal sealant is applied to a liquid crystal display panel, the adhesive strength between the cured liquid crystal sealant and the substrate is increased, so that a liquid crystal display panel having high moisture resistance reliability and excellent display properties can be obtained. Therefore, the liquid crystal sheathing agent of the present invention is also useful as an adhesive for various optical devices including liquid crystal display panels.

 [0164] This application claims the priority based on the application number JP2006-213939ί filed on August 4, 2006. All the contents described in the application specification are incorporated herein by reference.

Claims

The scope of the claims  [1] (1) epoxy resin,  (2) a first thermal latent curing agent having a melting point of 150 ° C or lower;  (3) a second thermal latent curing agent having a melting point of 180 ° C or higher,  The component (2) is one or more thermal latent curing agents selected from the group consisting of dihydrazide, imidazole, amine adduct, polyamine, and polyaminourea thermal latent curing agents,  A liquid crystal sealant in which the component (3) is one or more thermal latent curing agents selected from the group consisting of dihydrazide, imidazole, and diamide thermal latent curing agents.  [2] The liquid crystal sealant according to claim 1, wherein the components (2) and (3) are dihydrazide-based thermal latent curing agents.  [3] The liquid crystal sealant according to claim 1, wherein the solubility of the component (3) in 100 ml of water at 25 ° C. is 20 g or less.  [4] The liquid crystal sealant according to claim 1, wherein the component (3) is a compound represented by the following general formula (A).  [Chemical 1]

However, R in the general formula (A) represents an alkylene group having 8 or more carbon atoms. 5. The liquid crystal sealant according to claim 1, wherein the liquid crystal sealant is a one-component type in which the components (1) to (3) are uniformly mixed. [6] The liquid crystal sealant according to claim 1, wherein the total blending amount of the component (2) and the component (3) is! To 25 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. [7] When the blending mass of the component (2) is W1, and the blending mass of the component (3) is W2,  2. The liquid crystal sealant according to claim 1, wherein 2≤W2 / (W1 + W2) ≤0.8. [8] The total of active hydrogen equivalents of the component (2) and the component (3) is the epoxy of the component (1). 2. The liquid crystal sealant according to claim 1, wherein the liquid crystal sealant is 0.3 to 3.0 with respect to the equivalent weight. [9] In a manufacturing method of a liquid crystal display panel manufactured by bonding two opposing substrates through a liquid crystal sealant! /,  A step of preparing a substrate having a frame-like display region formed so that a pixel array region is surrounded by the liquid crystal sealing agent according to claim 1 and provided with a liquid crystal injection port; and A step of forming a liquid crystal cell between the two substrates by superimposing the two substrates through bonding, followed by heat-pressing and bonding the same substrate; Injecting liquid crystal into  Sealing the inlet of the liquid crystal cell into which the liquid crystal has been injected with a sealing agent;  A method for manufacturing a liquid crystal display panel comprising [10] In a manufacturing method of a liquid crystal display panel manufactured by bonding two opposing substrates through a liquid crystal sealant!  Preparing a substrate having a frame-shaped display region formed so that the pixel array region is surrounded by the liquid crystal sealant according to claim 1;  Dropping the liquid crystal in the uncured display area or on the other substrate;  A step of superimposing the substrate onto which the liquid crystal has been dropped and the other substrate under reduced pressure, a step of curing the liquid crystal sealant between the two superposed substrates by heating,  A method for manufacturing a liquid crystal display panel comprising [11] A liquid crystal display panel obtained by the method for manufacturing a liquid crystal display panel according to claim 9 or 10.