TW201831593A - Sealant for liquid crystal display element, vertically conductive material, and liquid crystal display element - Google Patents

Abstract

The present invention addresses the problem of providing a sealant which is for a liquid crystal display element and enables even a liquid crystal display element with a thin-frame design to have excellent humidity-resistant reliability. In addition, the present invention addresses the problem of providing a vertically conductive material formed by using the sealant for a liquid crystal display element, and a liquid crystal display element. The present invention provides a sealant for a liquid crystal display element, the sealant containing a curable resin, a polymerization initiator and/or a thermosetting agent, and a water-absorbing filler.

Description

   Sealant for liquid crystal display element, vertical conductive material, and liquid crystal display element   

The present invention relates to a sealant for a liquid crystal display element that can be made into a liquid crystal display element with a narrow edge design, which is excellent in moisture resistance and reliability. The present invention also relates to a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display unit, the industry uses a hardening resin as disclosed in Patent Documents 1 and 2 based on viewpoints such as reduction of station time and optimization of the amount of liquid crystal used. A liquid crystal dropping method called a dropping method in which the light and heat of a photopolymerization initiator and a thermosetting agent are combined with a hardening type sealant.

In the dropping method, a rectangular sealing pattern is first formed by dispensing on one of two substrates with electrodes. Then, in the state where the sealant is not hardened, minute droplets of liquid crystal are dropped into the sealing frame of the substrate, another substrate is overlapped under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to temporarily harden. After that, it is heated and hardened to produce a liquid crystal display element. At present, the drop addition method has become a mainstream manufacturing method for liquid crystal display elements.

However, with the popularity of mobile devices with liquid crystal panels, such as mobile phones and portable game consoles, the miniaturization of devices is the most sought after issue in the industry. As a method of miniaturization, narrow edge of a liquid crystal display part can be mentioned, for example, the position of a sealing part is arrange | positioned under a black matrix (henceforth a narrow edge design).

With such a narrow-edge design, in a liquid crystal display element, the distance from the pixel region to the sealant becomes short, and display unevenness easily occurs due to contamination of the liquid crystal by the sealant.

In addition, with the popularization of tablet terminals or portable terminals, the liquid crystal display elements are increasingly required to have reliability in humidity resistance such as driving under high-temperature and high-humidity environments, and the sealant is further required to prevent the ingress of water from the outside. In order to improve the humidity resistance reliability of the liquid crystal display element, it is necessary to improve the adhesiveness of the sealant to the substrate and the like to prevent the ingress of water from the interface between the sealant and the substrate and to improve the moisture permeability of the sealant. As a method for improving the moisture permeability of the sealant, for example, a method in which a filler such as talc is blended is considered. However, even if fillers such as talc are blended in this manner, when a severe humidity resistance reliability test is performed, there is a problem that display unevenness occurs in the liquid crystal display element.

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2001-133794

Patent Document 2: International Publication No. 02/092718

An object of the present invention is to provide a sealant for a liquid crystal display element that can be made into a liquid crystal display element with a narrow edge design, which is excellent in moisture resistance reliability. Another object of the present invention is to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

The present invention is a sealant for a liquid crystal display element, which contains a curable resin, a polymerization initiator and / or a thermosetting agent, and a water-absorbing filler.

Hereinafter, the present invention will be described in detail.

The present inventors have found that even when a sealant exhibiting particularly excellent moisture permeability resistance is used in a conventional liquid crystal display element having a non-narrow edge design, for example, if the width of the frame portion around the liquid crystal display portion becomes as narrow as 2 mm or less The edge-designed liquid crystal display device also has the following cases: In the humidity resistance reliability test, moisture is infiltrated into the liquid crystal, and display unevenness occurs. The inventor believes that even when a sealant excellent in moisture permeability is used, the reason why it is poor in moisture resistance reliability when it is designed with a narrow edge is the alignment of polyimide and the like in the liquid crystal display element. The film becomes a water infiltration path. Therefore, the present inventors have found that the moisture immersed in the alignment film is retained in the sealant by incorporating a water-absorbent filler in the sealant. As a result, even a liquid crystal display element with a narrow edge design can be made with excellent moisture resistance reliability. This completes the present invention.

The sealing agent for liquid crystal display elements of this invention contains a water-absorptive filler. By blending the water-absorbing filler described above, the sealant for liquid crystal display elements of the present invention can be made into a liquid crystal display element with a narrow edge design and excellent in moisture resistance and reliability.

By using the sealant for liquid crystal display elements of the present invention, even a liquid crystal display element with a narrow edge design can be manufactured with excellent moisture resistance reliability. The reason is generally considered as follows, and it will be described using FIG. 1. FIG. 1 is a schematic diagram showing a method for preventing moisture from penetrating into a liquid crystal by using the sealant for a liquid crystal display element of the present invention.

As shown in FIGS. 1 (a) to (c), in the liquid crystal display element 1, the liquid crystal 4 is usually sealed with a sealant 3 for a liquid crystal display element arranged between the substrates 2 having the alignment film 5. In a conventional liquid crystal display device with a non-narrow edge design, as shown in FIG. 1 (a), the alignment film 5 is located more inward than the sealant 3, and the sealant 3 is used to prevent water 6 from entering the liquid crystal 4. However, in the case of a narrow-edge design, as shown in FIG. 1 (b), the alignment film 5 may be located further outside than the sealant 3. As a result, it is considered that the water 6 easily penetrates the liquid crystal 4 through the alignment film 5. On the other hand, in the case of using the above-mentioned sealing agent for a liquid crystal display element of the present invention containing a water-absorbing filler, as shown in FIG. 1 (c), the water 6 immersed in the alignment film 5 does not enter the liquid crystal 4 and Will be introduced into the sealant 3 by the water-absorbent filler. As a result, it is thought that moisture can be prevented from penetrating into the liquid crystal, and even a liquid crystal display element with a narrow edge design can be made excellent in humidity resistance.

Examples of the material constituting the water-absorbing filler include oxides of alkaline earth metals, magnesium oxide, and molecular sieves.

Examples of the oxide of the alkaline earth metal include calcium oxide, strontium oxide, and barium oxide.

Among them, the water-absorbing filler is preferably calcium oxide and / or magnesium oxide from the viewpoint of water absorption, and the hydroxide after water absorption is also insoluble in water, so calcium oxide is more preferable.

A preferable lower limit of the average primary particle diameter of the water-absorbing filler is 0.5 μm, and a preferable upper limit is 5 μm. When the average primary particle diameter of the water-absorbing filler is 0.5 μm or more, the obtained liquid crystal display element becomes more excellent in moisture resistance reliability. When the average primary particle diameter of the water-absorbing filler is 5 μm or less, the obtained liquid crystal display element can be used to further suppress panel peeling and the like. A more preferable lower limit of the average primary particle diameter of the water-absorbing filler is 0.8 μm, and a more preferable upper limit is 3 μm.

The "average primary particle size" can be measured by a dynamic light scattering particle size measuring device ("ELSZ-1000S" manufactured by Otsuka Electronics Co., Ltd.) and the like.

A preferable lower limit of the specific gravity of the water-absorbing filler is 1.5 g / cm ³ , and a preferable upper limit is 3.3 g / cm ³ . When the specific gravity of the water-absorbent filler is in this range, the obtained liquid crystal display element becomes more excellent in moisture resistance reliability. A more preferable lower limit of the specific gravity of the water-absorbing filler is 2.0 g / cm ³ , and a more preferable upper limit is 3.0 g / cm ³ .

In addition, the above-mentioned "specific gravity" means the value measured by the method based on JIS Z8807.

Regarding the total surface area of the water-absorbent filler, a preferable lower limit per 100 g of the curable resin is 10 m ² , and a preferable upper limit is 100 m ² . By setting the total surface area of the water-absorbing filler to 10 m ² or more per 100 g of the curable resin, the obtained liquid crystal display element becomes more excellent in moisture resistance reliability. By setting the total surface area of the water-absorptive filler to 100 m ² or less, the obtained liquid crystal display element can further suppress panel peeling and the like. A more preferable lower limit of the total surface area of the water-absorbent filler is 20 m ² , and a more preferable upper limit is 80 m ² .

The "total surface area of the water-absorbing filler" can be calculated from the content of the water-absorbing filler and the BET specific surface area. The above-mentioned "BET specific surface area" can be measured by a BET method using nitrogen gas using a specific surface area measuring device (for example, "ASAP-2000" manufactured by Shimadzu Corporation).

A preferable lower limit of the average specific surface area of the water-absorbing filler is 5 m ² / g, and a preferable upper limit is 20 m ² / g. When the average specific surface area of the water-absorptive filler is within this range, the obtained liquid crystal display element becomes more excellent in moisture resistance reliability. A more preferable lower limit of the average specific surface area of the water-absorbing filler is 10 m ² / g, and a more preferable upper limit is 18 m ² / g.

The "average specific surface area" can be measured by a specific surface area measuring device (for example, "ASAP-2000" manufactured by Shimadzu Corporation, etc.) using a nitrogen gas BET method.

A preferable lower limit of the water absorption of the water-absorbing filler is 10% by weight. When the water absorption rate of the water-absorbent filler is 10% by weight or more, the obtained liquid crystal display element becomes more excellent in moisture resistance reliability. A more preferable lower limit of the water absorption of the water-absorbing filler is 20% by weight.

In addition, the preferable upper limit of the water absorption of the water-absorbing filler is not particularly limited, and the practical upper limit is 50% by weight.

In addition, the above-mentioned "water absorption rate" means a rate of change in weight when a high-temperature and high-humidity test is performed under an environment of a temperature of 80 ° C and a humidity of 90% RH for 1,000 hours. Specifically, when the weight before the high temperature and high humidity test (80 ° C, 90% RH, 1000 hours) is W ₁ and the weight after the high temperature and high humidity test is W ₂ , the following formula ( I).

Water absorption (% by weight) = ((W ₂ -W ₁ ) / W ₁ ) × 100 (I)

With respect to the content of the water-absorbing filler, a preferable lower limit is 0.5 part by weight and a preferable upper limit is 20 parts by weight based on 100 parts by weight of the curable resin. When the content of the water-absorbent filler is within this range, the obtained liquid crystal display element becomes more excellent in moisture resistance reliability. A more preferable lower limit of the content of the water-absorbing filler is 1.5 parts by weight, and a more preferable upper limit is 10 parts by weight.

Regarding the sealing agent for a liquid crystal display element of the present invention, when the above-mentioned water-absorbent filler is blended in a large amount, there is a concern that the water-absorbent filler swells due to absorption of moisture, which causes problems such as panel peeling. Therefore, it is preferable that the sealing agent for liquid crystal display elements of this invention contains the said water-absorptive filler and a silicon dioxide.

The preferable lower limit of the average primary particle diameter of the silicon dioxide is 0.1 μm, and the preferable upper limit is 2 μm. When the average primary particle diameter of the above-mentioned silicon dioxide is 0.1 μm or more, the obtained sealant for a liquid crystal display element becomes more excellent in coatability. By setting the average primary particle diameter of the silicon dioxide to be 2 μm or less, the effect of suppressing defects such as panel peeling of the obtained liquid crystal display element is more excellent. A more preferable lower limit of the average primary particle diameter of the silicon dioxide is 0.2 μm, and a more preferable upper limit is 1 μm.

Regarding the total surface area of the above-mentioned silicon dioxide, a preferable lower limit per 100 g of the curable resin is 20 m ² , and a preferable upper limit is 200 m ² . When the total surface area of the silicon dioxide is within this range, it is more excellent in suppressing defects such as panel peeling of the obtained liquid crystal display element. A more preferable lower limit of the total surface area of the above-mentioned silicon dioxide is 30 m ² , and a more preferable upper limit is 180 m ² .

The "total surface area of the silicon dioxide" can be calculated in the same manner as the "total surface area of the water-absorbing filler".

With regard to the content of the silicon dioxide, the preferred lower limit is 10 parts by weight, and the preferred upper limit is 400 parts by weight based on 10 parts by weight of the water-absorbing filler. When the content of the above-mentioned silicon dioxide is 10 parts by weight or more, the effect of suppressing defects such as panel peeling of the obtained liquid crystal display element is more excellent. When the content of the silicon dioxide is 400 parts by weight or less, the obtained sealant for a liquid crystal display element becomes more excellent in coating properties. A more preferable lower limit of the content of the silicon dioxide is 20 parts by weight, and a more preferable upper limit is 380 parts by weight.

The sealing agent for liquid crystal display elements of this invention may contain other fillers other than the said water-absorptive filler and the said silica within the range which does not inhibit the objective of this invention.

Examples of the other fillers include inorganic fillers such as talc and alumina, or organic fillers such as polyester particles, polyurethane particles, vinyl polymer particles, and acrylic polymer particles.

The sealing agent for liquid crystal display elements of this invention contains a curable resin.

The curable resin preferably contains a (meth) acrylic compound and / or an epoxy compound.

In addition, in the present specification, the above-mentioned "(meth) acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth) acrylic compound" means a compound having a (meth) acrylfluorenyl group, and the above-mentioned " "(Meth) acrylfluorenyl" means acrylfluorenyl or methacrylfluorenyl.

Examples of the (meth) acrylic compound include (meth) acrylate compounds, epoxy (meth) acrylates, and (meth) acrylates. Among these, epoxy (meth) acrylate is preferable. The (meth) acrylic compound is preferably one having two (meth) acrylfluorenyl groups in one molecule from the viewpoint of reactivity.

In addition, in this specification, the above-mentioned "(meth) acrylate" means an acrylate or a methacrylate, and the above-mentioned "epoxy (meth) acrylate" means that all epoxy in an epoxy compound is made A compound obtained by reacting a group with (meth) acrylic acid.

Examples of the monofunctional compound in the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate. Ester, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate , Isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Isoamyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl 2- (meth) acrylate, 2-ethyl (meth) acrylate Ethoxyethyl ester, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol Alcohol (meth) acrylate, phenoxydiethyl Glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate, (meth) acrylic acid 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, fluorenimine (methyl (Meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloxyethyl succinate, hexahydrophthalate 2- (meth) acryloxyethyl formate, 2- (meth) acryloxyethyl phthalate 2-hydroxypropyl, 2- (meth) acryloxyethyl phosphate, ( Glycidyl meth) acrylate and the like.

Moreover, as a bifunctional among the said (meth) acrylate compounds, 1, 3- butanediol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate can be mentioned, for example. , 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene diene Alcohol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl 2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide Addition of bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene di (meth) acrylate, ethylene oxide modified isotricyanic acid di (meth) acrylate, ( (Meth) acrylic acid 2-hydroxy-3- (meth) acrylic acid oxypropyl ester, carbonate diol bis (methyl) Base) acrylate, polyether glycol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (Meth) acrylates and the like.

In addition, examples of the tri- or more functional group in the (meth) acrylate compound include trimethylolpropane tri (meth) acrylate and ethylene oxide-trimethylolpropane tri (methyl) ) Acrylate, propylene oxide addition trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, ethylene oxide addition isocyanuric acid Acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, neopentyl tetraol tri (meth) acrylate, phosphate tri ((methyl) ) Acrylic ethoxyethyl) ester, bis (trimethylolpropane) tetra (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate and the like.

Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst in accordance with a conventional method.

Examples of the epoxy compound used as a raw material for synthesizing the aforementioned epoxy (meth) acrylate include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, 2 , 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin Resin, dicyclopentadiene novolac epoxy resin, biphenyl- novolac epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol epoxy resin, Rubber modified epoxy resin, glycidyl ester compound, etc.

Examples of commercially available bisphenol A epoxy resins include jER828EL, jER1004 (both manufactured by Mitsubishi Chemical Corporation), EPICLON 850CRP (manufactured by DIC Corporation), and the like.

Examples of a commercially available bisphenol F-type epoxy resin include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).

Examples of a commercially available bisphenol S-type epoxy resin include EPICLON EXA1514 (manufactured by DIC Corporation).

Examples of the commercially available 2,2'-diallyl bisphenol A type epoxy resin include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

As a commercial one among the said hydrogenated bisphenol-type epoxy resins, Epiclon EXA7015 (made by DIC Corporation) etc. are mentioned, for example.

Examples of a commercially available propylene oxide-added bisphenol A type epoxy resin include EP-4000S (manufactured by ADEKA).

As a marketer among the said resorcinol-type epoxy resins, EX-201 (made by Nagase chemteX company) etc. are mentioned, for example.

Examples of a commercially available biphenyl type epoxy resin include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).

Examples of a commercially available thioether-type epoxy resin include YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.).

Examples of a commercially available diphenyl ether type epoxy resin include YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.).

Examples of a commercially available dicyclopentadiene-type epoxy resin include EP-4088S (manufactured by ADEKA).

Examples of the commercially available naphthalene-type epoxy resin include EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).

As a commercially available one among the said phenol novolak-type epoxy resins, Epiclon N-770 (made by DIC Corporation) etc. are mentioned, for example.

As a commercially available one of the ortho-cresol novolac-type epoxy resins, for example, EPICLON N-670-EXP-S (manufactured by DIC Corporation) can be cited.

Examples of a commercially available dicyclopentadiene novolac epoxy resin include EPICLON HP7200 (manufactured by DIC Corporation).

As a commercially available one among the above-mentioned biphenol novolak-type epoxy resins, NC-3000P (made by Nippon Kayaku Co., Ltd.) is mentioned, for example.

As a commercially available one of the aforementioned naphthol novolac-type epoxy resins, for example, ESN-165S (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) can be cited.

Examples of a commercially available glycidylamine type epoxy resin include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like.

As a marketer of the above-mentioned alkyl polyol type epoxy resin, for example, ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) DENACOL EX-611 (manufactured by Nagase chemteX).

Examples of commercially available rubber modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and Epolead PB (made by Daicel).

Examples of a commercially available glycidyl ester compound include DENACOL EX-147 (manufactured by Nagase ChemteX).

Examples of other commercially available ones among the aforementioned epoxy compounds include: YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (made by Asahi Kasei Corporation), jER1031, jER1032 (All manufactured by Mitsubishi Chemical Corporation), EXA-7120 (made by DIC Corporation), TEPIC (made by Nissan Chemical Corporation), etc.

Examples of the commercially available epoxy (meth) acrylates include epoxy (meth) acrylates manufactured by DAICEL-ALLNEX, and epoxy (meth) acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd. , Epoxy (meth) acrylates manufactured by Kyoeisha Chemical Co., Ltd., epoxy (meth) acrylates manufactured by Nagase chemteX, etc.

Examples of the epoxy (meth) acrylate of the above-described manufacturing company DAICEL-ALLNEX include, for example: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182 like.

Examples of the epoxy (meth) acrylate manufactured by the aforementioned Shin Nakamura Chemical Industry Company include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020.

Examples of the epoxy (meth) acrylate manufactured by the aforementioned Kyoeisha Chemical Company include: Epoxyester M-600A, Epoxyester 40EM, Epoxyester 70PA, Epoxyester 200PA, Epoxyester 80MFA, Epoxyester 3002M, Epoxyester 3002A, Epoxyester 1600A, Epoxyester 3000M , Epoxyester 3000A, Epoxyester 200EA, Epoxyester 400EA, etc.

Examples of the epoxy (meth) acrylate manufactured by the Nagase chemteX company include Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911, and the like.

The (meth) acrylic acid amine ester can be obtained, for example, by making 1 equivalent of an isocyanate compound having two isocyanate groups, and making 2 equivalent of a (meth) acrylic acid derivative having a hydroxyl group to a tin-based compound having a catalyst amount. It reacts with this isocyanate compound in the presence.

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenyl Methane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzylamine diisocyanate, xylylene diisocyanate (XDI), hydrogenation XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanophenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecane triisocyanate Wait.

In addition, as the isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyol with an excessive amount of an isocyanate compound can also be used.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of a diol, and mono (meth) acrylic acid of a triol. Esters or di (meth) acrylates, epoxy (meth) acrylates, and the like.

Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like 4-hydroxybutyl (meth) acrylate and the like.

Examples of the glycol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.

Examples of the triol include trimethylolethane, trimethylolpropane, and glycerol.

Examples of the epoxy (meth) acrylate include a bisphenol A-type epoxy acrylate.

As a marketer among the above (meth) acrylic acid amine esters, for example, (meth) acrylic acid esters manufactured by Toa Kosei Co., Ltd., (meth) acrylic acid amine esters manufactured by DAICEL-ALLNEX Co., Ltd. (Meth) acrylates, amine (meth) acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd., and (meth) acrylates manufactured by Kyoeisha Chemical Co., Ltd.

Examples of the (meth) acrylic acid amine ester manufactured by the Toa Synthesis Corporation include M-1100, M-1200, M-1210, and M-1600.

Examples of (meth) acrylic acid amines manufactured by the above-mentioned DAICEL-ALLNEX company include, for example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL9260 and so on.

Examples of the (meth) acrylic acid amine esters manufactured by the above Koshigami Corporation include ARTON Resin UN-330, ARTON Resin SH-500B, ARTON Resin UN-1200TPK, ARTON Resin UN-1255, ARTON Resin UN-3320HB, ARTON Resin UN-7100, ARTON Resin UN-9000A, ARTON Resin UN-9000H, etc.

Examples of the (meth) acrylic acid amine ester manufactured by the aforementioned Shin Nakamura Chemical Industry Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U -10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000 , UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, etc.

Examples of the (meth) acrylic acid amine manufactured by Kyoeisha Chemical Co., Ltd. include, for example, AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA -306T and so on.

As said epoxy compound, the epoxy compound used as a raw material for synthesizing the said epoxy (meth) acrylate, or a partial (meth) acrylic modified epoxy resin etc. are mentioned, for example.

In addition, in the present specification, the so-called partially (meth) acrylic modified epoxy resin means a compound having one epoxy group and (meth) acrylfluorene group in each molecule. For example, 1 One of the epoxy compounds having two or more epoxy groups in the molecule is obtained by reacting a part of epoxy groups with (meth) acrylic acid.

As a marketer of the said partial (meth) acrylic-modified epoxy resin, UVACURE1561 (made by DAICEL-ALLNEX company) etc. are mentioned, for example.

The said curable resin can be used individually or in combination of 2 or more types.

When the sealing compound for liquid crystal display elements of this invention contains the said (meth) acrylic compound and the said epoxy compound, it is preferable that it is (meth) in the total of a (meth) acryl fluorenyl group and an epoxy group. The said (meth) acrylic compound and the said epoxy compound are mix | blended so that the ratio of an acrylyl group may become 30 mol% or more and 95 mol% or less. When the ratio of the (meth) acrylfluorenyl group is within this range, the occurrence of liquid crystal contamination is suppressed, and the obtained sealant for a liquid crystal display element becomes more excellent in adhesiveness.

The curable resin is preferably a unit having a hydrogen bond such as an -OH group, an -NH- group, or an -NH ₂ group from the viewpoint of suppressing liquid crystal contamination.

The sealing agent for liquid crystal display elements of this invention contains a polymerization initiator and / or a thermosetting agent.

Examples of the polymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.

Examples of the radical polymerization initiator include a thermal radical polymerization initiator that generates radicals by heating, a photo radical polymerization initiator that generates radicals by light irradiation, and the like.

Examples of the photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, fluorenylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, and benzoin-ether-based compounds. 9-oxysulfur Wait.

Examples of a commercially available photoradical polymerization initiator include a photoradical polymerization initiator manufactured by BASF Corporation, a photoradical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd., and the like.

Examples of the photoradical polymerization initiator manufactured by the BASF company include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucirin TPO.

Examples of the photoradical polymerization initiator produced by the Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Examples of the thermal radical polymerization initiator include an azo compound, an organic peroxide, and the like. Among them, a polymer azo initiator composed of a polymer azo compound is preferable.

In addition, in this specification, the term "polymer azo compound" means a compound having an azo group and generating a number-average molecular weight of free radicals that can harden a (meth) acryloxy group by heat, which is 300 or more.

A preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 1,000, and a preferable upper limit is 300,000. When the number average molecular weight of the above-mentioned polymer azo compound is within this range, it is possible to prevent adverse effects on the liquid crystal, and it is easy to mix into the curable resin. A more preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 5000, a more preferable upper limit is 100,000, a further preferable lower limit is 10,000, and a more preferable upper limit is 90,000.

In addition, in this specification, the said number average molecular weight is a value calculated | required by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and calculated | required by polystyrene conversion. Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).

Examples of the polymer azo compound include a structure having a plurality of units such as polyalkylene oxide or polydimethylsiloxane bonded via an azo group.

As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, a polymer having a polyethylene oxide structure is preferred.

Specific examples of the polymer azo compound include a polycondensate of 4,4'-azobis (4-cyanovaleric acid) and a polyalkylene glycol, or 4,4'-couple A polycondensate of nitrogen bis (4-cyanovaleric acid) and polydimethylsiloxane having a terminal amine group, and the like.

Examples of the commercially available polymer azo compound include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.).

In addition, as for a commercially available azo compound that is not a polymer, for example, V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.) and the like can be cited.

Examples of the organic peroxide include ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, peroxyester, difluorenyl peroxide, and peroxydicarbonate.

As the cationic polymerization initiator, a photocationic polymerization initiator can be suitably used. The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halide salts, and aromatic sulfonium salts, iron-propadiene complexes, and titanocene complexes. , Organometallic complexes such as arylsilanol-aluminum complexes, etc.

Examples of the commercially available photocationic polymerization initiator include Adeka Optomer SP-150 and Adeka Optomer SP-170 (both manufactured by ADEKA).

These polymerization initiators may be used alone or in combination of two or more kinds.

With respect to the content of the polymerization initiator, a preferred lower limit is 0.1 part by weight, and a preferred upper limit is 30 parts by weight based on 100 parts by weight of the curable resin. When the content of the polymerization initiator is 0.1 parts by weight or more, the obtained sealing agent for a liquid crystal display element becomes more excellent in hardenability. By setting the content of the polymerization initiator to 30 parts by weight or less, the obtained sealing agent for a liquid crystal display element becomes more excellent in storage stability. The more preferable lower limit of the content of the polymerization initiator is 1 part by weight, the more preferable upper limit is 10 parts by weight, and the more preferable upper limit is 5 parts by weight.

Examples of the thermosetting agent include organic hydrazine, imidazole derivatives, amine compounds, polyphenol compounds, and acid anhydrides. Among them, organic hydrazine can be suitably used.

The said thermosetting agent can be used individually or in combination of 2 or more types.

Examples of the organic hydrazine include decanediozine, m-xylylenedihydrazine, hexamethylenedihydrazine, and malondihydrazine.

Examples of the commercially available organic hydrazine include organic hydrazine manufactured by Otsuka Chemical Co., Ltd., and organic hydrazine manufactured by Ajinomoto Fine-Techno.

Examples of the organic hydrazine produced by the Otsuka Chemical Company include SDH, ADH, and the like.

Examples of the organic hydrazine produced by the Ajinomoto Fine-Techno company include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J, and the like.

With respect to the content of the thermosetting agent, a preferred lower limit is 1 part by weight and a preferred upper limit is 50 parts by weight based on 100 parts by weight of the curable resin. By setting the content of the above-mentioned thermosetting agent to be in this range, it is possible to make the one having more excellent thermosetting properties without deteriorating the coating properties and the like of the obtained sealing agent for a liquid crystal display element. A more preferable upper limit of the content of the heat curing agent is 30 parts by weight.

It is preferable that the sealing agent for liquid crystal display elements of this invention contains a silane coupling agent. The above-mentioned silane coupling agent mainly functions as a bonding agent for adhering a sealant to a substrate or the like well.

As the silane coupling agent, for example, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane and the like. These silane coupling agents are excellent in the effect of improving the adhesion to a substrate and the like. By chemically bonding with the curable resin, the curable resin can be further suppressed from flowing into the liquid crystal.

These silane coupling agents may be used alone or in combination of two or more kinds.

A preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 0.1 part by weight, and a preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, the obtained sealing agent for a liquid crystal display element is one which suppresses the occurrence of liquid crystal contamination and is more excellent in adhesion. A more preferable lower limit of the content of the silane coupling agent is 0.3 part by weight, and a more preferable upper limit is 5 parts by weight.

The sealing agent for liquid crystal display elements of this invention may contain a light-shielding agent. By containing the said light-shielding agent, the sealing agent for liquid crystal display elements of this invention can be used suitably as a light-shielding sealing agent.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among these, titanium black is preferred.

The titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, and particularly in the vicinity of the wavelength of 370 nm to 450 nm, compared to the average transmittance of the light in the wavelength range of 300 nm to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent having properties such that light-shielding properties are provided to the sealant for a liquid crystal display element of the present invention by sufficiently shielding light of a wavelength in a visible light region, and light of a wavelength near an ultraviolet region is provided. penetrate. As the light-shielding agent contained in the sealing agent for a liquid crystal display element of the present invention, a substance having a high insulating property is preferable, and as a light-shielding agent having a high insulating property, titanium black is also preferable.

The above titanium black exhibits sufficient effects even if it is not surface-treated, but it can also be treated with organic components such as coupling agents on its surface, or silicon oxide, titanium oxide, germanium oxide, alumina, zirconia, and magnesium oxide. Surface-treated titanium black, such as those coated with inorganic components. Among these, from the viewpoint of further improving the insulation properties, those treated with an organic component are preferred.

In addition, the liquid crystal display element manufactured by using the sealant for liquid crystal display elements of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, so that it can realize no light leakage, have high contrast, and have excellent images. Liquid crystal display element of display quality.

Examples of the commercially available titanium black include titanium black manufactured by Mitsubishi Materials, titanium black manufactured by Ako Chemical Co., and the like.

Examples of the titanium black manufactured by the Mitsubishi Materials company include 12S, 13M, 13M-C, 13R-N, and 14M-C.

Examples of the titanium black manufactured by the Ako Chemical Co., Ltd. include Tilack D and the like.

The preferable lower limit of the specific surface area of the titanium black is 13 m ² / g, the preferable upper limit is 30 m ² / g, the more preferable lower limit is 15 m ² / g, and the more preferable upper limit is 25 m ² / g.

In addition, the preferred lower limit of the volume resistance of the titanium black is 0.5Ω‧cm, the preferred upper limit is 3Ω‧cm, the more preferred lower limit is 1Ω‧cm, and the more preferred upper limit is 2.5Ω‧cm.

The average primary particle diameter of the above-mentioned light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display element. The preferred lower limit is 1 nm, and the preferred upper limit is 5000 nm. If the average primary particle diameter of the light-shielding agent is less than 1 nm, there may be a case where the viscosity or shake-solubility of the obtained sealant for a liquid crystal display element is greatly increased, and workability is deteriorated. When the average primary particle diameter of the above-mentioned light-shielding agent exceeds 5000 nm, the obtained sealant for a liquid crystal display element may be inferior in coating properties on a substrate. A more preferable lower limit of the average primary particle diameter of the above-mentioned sunscreen is 5 nm, a more preferable upper limit is 200 nm, a more preferable lower limit is 10 nm, and a more preferable upper limit is 100 nm.

The average primary particle diameter of the light-shielding agent can be measured by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the light-shielding agent is within this range, the adhesiveness of the obtained sealant for a liquid crystal display element, the strength after curing, and the effect of suppressing deterioration in drawing properties and improving the light-shielding property become more excellent. A more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a more preferable lower limit is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.

The sealant for liquid crystal display elements of the present invention may further contain additives such as a reactive diluent, a spacer, a hardening accelerator, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other coupling agents, as necessary.

Examples of the method for producing the sealant for a liquid crystal display element of the present invention include, for example, a hardening resin using a homomixer, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill. A method of mixing additives such as a polymerization initiator and / or a thermosetting agent, a water-absorbent filler, and a silane coupling agent added as needed.

The lower limit of the viscosity measured by the E-type viscometer at 25 ° C and 1 rpm of the sealant for a liquid crystal display element of the present invention is 150,000 mPa · s, and the preferred upper limit is 500,000 mPa · s. By making the said viscosity into this range, the sealing compound for liquid crystal display elements obtained will become more excellent in coating property. The lower limit of the above viscosity is 200,000 mPa‧s, and the upper limit is 400,000 mPa‧s.

By blending conductive fine particles with the sealant for a liquid crystal display element of the present invention, a vertical conductive material can be manufactured. Such a sealant for a liquid crystal display element of the present invention and a conductive material for the upper and lower conductive particles are also one aspect of the present invention.

The conductive fine particles are not particularly limited, and those having a conductive metal layer formed on the surfaces of metal balls and resin fine particles can be used. Among them, it is preferable that a conductive metal layer is formed on the surface of the resin fine particles because the excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.

A liquid crystal display element formed by using the sealant for liquid crystal display elements of the present invention or the vertical conduction material of the present invention is also one of the present invention.

As the liquid crystal display element of the present invention, a liquid crystal display element with a narrow edge design is preferred. Specifically, the width of the frame portion around the liquid crystal display unit is preferably 2 mm or less.

In addition, the coating width of the sealant for a liquid crystal display element of the present invention when the liquid crystal display element of the present invention is manufactured is preferably 1 mm or less.

As a method for manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method can be suitably used. Specifically, for example, the following methods can be cited.

First, the following steps are performed: forming a frame-shaped seal on one of two transparent substrates having an electrode such as an alignment film and an ITO film by screen printing, dispensing coating, etc. pattern. Then, the following steps are performed: a droplet of a liquid crystal coating is dripped on the entire surface of the frame of the seal pattern, and another substrate is overlapped under vacuum. Thereafter, a liquid crystal display element can be obtained by a method that irradiates light such as ultraviolet rays to the seal pattern portion to temporarily harden the sealant, and heats the temporarily hardened sealant to formally harden it.

According to the present invention, it is possible to provide a sealant for a liquid crystal display element that can be made into a liquid crystal display element with a narrow edge design, which is excellent in moisture resistance reliability. Furthermore, according to the present invention, it is possible to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

1‧‧‧LCD display element

2‧‧‧ substrate

3‧‧‧Sealant for liquid crystal display element

4‧‧‧ LCD

5‧‧‧alignment film

6‧‧‧ Moisture

FIG. 1 is a schematic diagram showing a method of preventing moisture from penetrating into a liquid crystal by using the sealant for a liquid crystal display element of the present invention.

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples.

(Examples 1 to 5, Comparative Examples 1, 2)

According to the blending ratios described in Table 1, the materials were mixed using a planetary mixer ("Defoaming Rintaro" manufactured by Thinky), and then mixed using a three-roll mill to prepare Example 1. ~ 5. Sealants for liquid crystal display elements of Comparative Examples 1 and 2. In addition, each of the liquid crystal display element sealants obtained in the examples and comparative examples was used to produce a vertical conductive material and a liquid crystal display element.

<Evaluation>

The following evaluations were performed about each sealing agent for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Table 1.

(Viscosity)

About each sealant for liquid crystal display elements obtained by the Example and the comparative example, the viscosity at 25 degreeC and 1 rpm was measured using the E-type viscosity meter (made by Toki Sangyo company, "VISCOMETER TV-22").

(Coatability)

1% by weight of a silicon dioxide spacer (manufactured by Sekisui Chemical Industry Co., Ltd., "SI-H055") was added to each of the sealants for liquid crystal display elements obtained in Examples and Comparative Examples, and defoaming treatment was performed to remove the seal. The foam in the agent was filled with a syringe for dispensing ("Musashi Engineering Co., Ltd.""PSY-10E"), and the foam was defoamed again. Next, using a dispenser ("SHOTMASTER300", manufactured by Musashi Engineering, Inc.), one of the two glass substrates with an alignment film for VA was coated with a sealant in a frame shape, and the other glass substrate was superimposed and vacuum bonded. The device bonded two substrates under a reduced pressure of 5 Pa. The bonded cell was irradiated with 3000 mJ / cm ² of ultraviolet rays by a metal halide lamp, and then heated at 120 ° C. for 1 hour to harden the sealant to produce a test piece. Observe the sealant in the obtained test piece. Set the case where the sealant has no broken wires and no undulations at the ends and draws neat lines. Set it to "◎". The case where the undulation occurs slightly is set to "○", the case where there is no disconnection failure but the undulation is clearly generated at the end of the sealant is set to "△", and the case where the disconnection failure occurs is set to "×". The applicability was evaluated.

(Adherence)

To each of the sealants for liquid crystal display elements obtained in the examples and comparative examples, a silicon dioxide spacer ("SI-H055" manufactured by Sekisui Chemical Industry Co., Ltd.) was added in an amount of 1% by weight. One of the glass substrates (30 × 40mm) of the alignment film. Another glass substrate was bonded to this in a cross shape, and ultraviolet rays of 3000 mJ / cm ^{2 were} irradiated with a metal halide lamp, followed by heating at 120 ° C. for 1 hour to obtain a test piece. The obtained test piece was subjected to a tensile test (5 mm / sec) using suction cups arranged on the upper and lower sides. A case where the value obtained by dividing the obtained measured value by the seal coating cross-sectional area is 3.0 kgf / cm ² or more is set to "◎", and is 2.5 kgf / cm ² or more and less than 3.0 kgf / cm ² the situation is set to "○" will 2.0kgf / cm ² or more and less than the case of 2.5kgf / cm ² is set to the "△", the situation will be less than 2.0kgf / cm ² of the set to "×" for then Evaluation.

(Anti-moisture permeability)

Each sealing agent for liquid crystal display elements obtained by the Example and the comparative example was apply | coated on the smooth release film using the coater so that thickness might become 200 micrometers or more and 300 micrometers or less. Then, 3000 mJ / cm ² of ultraviolet rays were irradiated using a metal halide lamp, and then heated at 120 ° C. for 1 hour, thereby obtaining a film for measuring moisture permeability. A water vapor transmission test cup was prepared by the method of the water vapor transmission test method (cup method) of the moisture-proof packaging material according to JIS Z 0208, and the obtained film for water vapor transmission measurement was installed, and the temperature was 80 ° C and 90% RH. In a constant temperature and humidity oven, and measure the moisture permeability. When the value of the obtained moisture permeability is less than 50g / m ² ‧24hr, it is set to "◎", and when the value of 50g / m ² ‧24hr or more and less than 80g / m ² ‧24hr is set to "○", A case of 80 g / m ² ‧24hr or more and less than 110g / m ² ‧24hr was set to "△", and a case of 110g / m ² ‧24hr or more was set to "×" to evaluate the moisture permeability prevention property.

(Low liquid crystal pollution and humidity resistance)

1 part by weight of spacer particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each sealing agent for each liquid crystal display element obtained in the examples and comparative examples, and the line width of the sealing agent was 1mm, the outer edge of the alignment film becomes the outer side of the sealant, and it is coated on one of the two rubbed substrates with an alignment film and a transparent electrode by a dispenser. Then, a small droplet of liquid crystal (manufactured by Chisso, "JC-5004LA") was dripped onto the entire surface of the sealant frame of the substrate with a transparent electrode, and another substrate was immediately bonded, and a metal was used for the sealant portion. The halide lamp was irradiated with 100 mW / cm ² of ultraviolet light for 30 seconds, and then heated at 120 ° C. for 1 hour to harden the sealant to obtain a liquid crystal display element. With respect to each of the sealants for liquid crystal display elements obtained in the examples and comparative examples, a liquid crystal display element was prepared under each of the following evaluation conditions.

The obtained liquid crystal display element was set to a state where a voltage was applied for 240 hours under an environment of 60 ° C. and 80% RH, and then the degree of disordered liquid crystal alignment near the sealant was visually confirmed. In addition, the obtained liquid crystal display element was put into a state where a voltage was applied at 60 ° C. and 80% RH for 1,000 hours, and then the degree of disordered liquid crystal alignment near the sealant was visually confirmed.

The disorder of liquid crystal alignment is judged based on color unevenness. According to the degree of color unevenness, the situation of completely colorless unevenness is set to "◎", and the situation of slight color unevenness is set to "○". The case of color unevenness was set to "△", and the case of considerable color unevenness was set to "x" to evaluate low liquid crystal contamination and humidity resistance reliability.

In addition, the liquid crystal display elements evaluated as "◎" and "○" are levels that are practically without problems, the liquid crystal display elements of "△" are levels that may cause problems due to different designs, and the liquid crystal display elements of "x" are Unusable level.

[Industrial availability]

According to the present invention, it is possible to provide a sealant for a liquid crystal display element that can be made into a liquid crystal display element with a narrow edge design, which is excellent in moisture resistance reliability. In addition, according to the present invention, a top-to-bottom conductive material and a liquid crystal display element formed using the sealant for a liquid crystal display element can be provided.

Claims (10)

    A sealing agent for a liquid crystal display element, which contains a curable resin, a polymerization initiator and / or a thermosetting agent, and a water-absorbing filler.         The sealing agent for a liquid crystal display element according to claim 1, wherein the water-absorbing filler is calcium oxide and / or magnesium oxide.         The sealing agent for a liquid crystal display element according to claim 2, wherein the water-absorbing filler is calcium oxide.         The sealant for liquid crystal display elements according to claim 1, 2 or 3, wherein the average primary particle diameter of the water-absorbing filler is 0.5 μm or more and 5 μm or less.     The sealant for liquid crystal display elements according to claim 1, 2, 3, or 4, wherein the total surface area of the water-absorbing filler is 10 m ² or more and 100 m ² or less per 100 g of the curable resin.     The sealant for liquid crystal display elements according to claim 1, 2, 3, 4 or 5, wherein the content of the water-absorbing filler is 0.5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the curable resin.         The sealant for liquid crystal display elements according to claim 1, 2, 3, 4, 5, or 6, which contains silica.         The sealant for liquid crystal display elements according to claim 7, wherein the content of the silicon dioxide is 10 parts by weight or more and 400 parts by weight or less based on 10 parts by weight of the water-absorbing filler.         A vertical conduction material comprising the sealant for liquid crystal display elements and conductive fine particles according to claim 1, 2, 3, 4, 5, 6, 7, or 8.         A liquid crystal display element is formed by using the sealant for liquid crystal display elements according to claim 1, 2, 3, 4, 5, 6, 7, or 8 or the conductive material described above and below.