TW201819523A - Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element - Google Patents

Abstract

One purpose of the present invention is to provide a sealing agent for liquid crystal display elements, which has excellent drawing properties, bondability, water vapor permeation preventing properties and low possibility of contamination of liquid crystals. Another purpose of the present invention is to provide: a vertically conducting material which is obtained using this sealing agent for liquid crystal display elements; and a liquid crystal display element. The present invention is a sealing agent for liquid crystal display elements, which contains a curable resin and a polymerization initiator and/or a thermal curing agent, and wherein 5 to 50 parts by weight of a compound represented by formula (1) is contained in 100 parts by weight of the curable resin. In formula (1), R1 represents a hydrogen atom or a methyl group; X represents a structure represented by one of formulae (2-1) to (2-3); and n represents a number of 2 to 6. In formulae (2-1) to (2-3), each of R2 and R3 independently represents a hydrogen atom or a methyl group; and in formula (2-1), R4 represents a hydrogen atom or a methyl group.

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 which is excellent in drawability, adhesion, moisture permeability prevention, and low liquid crystal contamination. 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, from the viewpoints of shortening the production time (Tact Time) and optimizing the amount of liquid crystal used, the methods described in Patent Documents 1 and 2 are used. The liquid crystal dropping method, which is called a dropping method, is a method in which a photo-thermal curing agent containing a curable resin, a photopolymerization initiator, and a thermosetting agent is used.

In the liquid crystal dropping method, first, a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing. Next, in the state where the sealant is not hardened, tiny liquid crystal droplets are dropped into the sealing frame of the substrate, overlapped with another substrate under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to temporarily harden. Thereafter, the liquid crystal display element is produced by heating and hardening it. Currently, the dripping method has become the mainstream of the manufacturing method of liquid crystal display elements.

In addition, nowadays, various mobile devices with a liquid crystal panel, such as a mobile phone and a portable game machine, have become widespread, and miniaturization of the device is the most required issue. 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 shorter, and it becomes easy to cause display unevenness due to the liquid crystal being contaminated with the sealant.

In addition, with the popularization of tablet terminals or mobile terminals, liquid crystal display elements are increasingly required to have reliability in humidity resistance when driven under high temperature and high humidity environments, and sealants are increasingly required to prevent water from penetrating from the outside. In order to improve the humidity resistance reliability of the liquid crystal display element, it is necessary to improve the adhesion of the sealant to the substrate and the like in order to prevent water from penetrating the interface between the sealant and the substrate, and to improve the moisture permeability of the sealant. However, it is difficult for the conventional sealants to be excellent in all of the drawability, adhesion, moisture permeability prevention, and low liquid crystal contamination.

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 which is excellent in drawability, adhesion, moisture permeability prevention, and low liquid crystal contamination. 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 contains 5 to 50 parts by weight of the following formula (1) in 100 parts by weight of the curable resin. ).

In the formula (1), R ¹ represents hydrogen or a methyl group, X represents a structure represented by the following formulae (2-1) to (2-3), and n is 2 to 6.

In formulae (2-1) to (2-3), R ² and R ³ each independently represent hydrogen or a methyl group, and in formula (2-1), R ⁴ represents hydrogen or a methyl group.

The present invention is explained in detail below.

The inventors have found that by using a compound having a specific structure as a curable resin in such a manner that the content becomes a specific ratio, a liquid crystal display element having excellent drawability, adhesion, moisture permeability resistance, and low liquid crystal contamination can be obtained. With a sealant, the present invention is completed.

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

The said curable resin contains the compound represented by the said Formula (1) (henceforth a "polymerizable compound of this invention"). By containing the polymerizable compound of the present invention, the sealant for a liquid crystal display element of the present invention is excellent in drawability, adhesion, moisture permeability prevention, and low liquid crystal contamination.

The curable resin is preferably a compound containing X in the formula (1) as a structure represented by the formula (2-1) or a structure represented by the formula (2-2) as the formula (1). Of compounds.

The compound represented by the formula (1) may be a mixture of a plurality of compounds having different structures represented by X or values of n. In particular, the curable resin is preferably a compound containing X in the formula (1) as a structure represented by the formula (2-1), and X in the formula (1) is the formula (2-2) Both represented compounds of the structure.

Examples of the method for producing the polymerizable compound of the present invention include the following methods.

Examples of a method for producing a compound in which X in the formula (1) is a structure represented by the formula (2-1) or a structure represented by the formula (2-2) include the following resins, (A Base) acrylic acid, catalyst, and antioxidant are mixed and heated and stirred to make them react. The resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a bisphenol E type ring. Oxygen resin.

In addition, as a method for producing a compound in which X in the above formula (1) is a structure represented by the above formula (2-3), a resin such as the following, (meth) acrylic acid, and diethylene glycol monoethyl ether can be exemplified. A method in which a solvent such as acetate, a catalyst, and an antioxidant are mixed, and the mixture is heated and agitated to react them. The resin is bisphenol A, bisphenol F, or bisphenol E.

Examples of the catalyst used in each of the methods include triphenylphosphine, and examples of the antioxidant include dibutylhydroxytoluene, hydroquinone methyl ether, and the like.

Here, the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, or the bisphenol E type epoxy resin may contain bisphenol A, bisphenol F, or bisphenol E. In this case, a method for producing a compound in which X in the above-mentioned formula (1) is a structure represented by the above formula (2-1) or a structure represented by the above formula (2-2) can be performed, and A compound in which X in the above formula (1) is a structure represented by the above formula (2-1) or a structure represented by the above formula (2-2), and X in the above formula (1) is the above formula (2) -3) A mixture of compounds of the structure indicated.

In addition, in this specification, the "(meth) acrylic acid" means acrylic acid or methacrylic acid.

The lower limit of the content of the polymerizable compound of the present invention in 100 parts by weight of the curable resin is 5 parts by weight, and the upper limit is 50 parts by weight. When the content of the polymerizable compound of the present invention is within this range, the obtained sealant for a liquid crystal display element becomes excellent in drawability, adhesion, moisture permeability prevention, and low liquid crystal contamination. A preferred lower limit of the content of the polymerizable compound of the present invention is 10 parts by weight, a preferred upper limit is 45 parts by weight, a more preferred lower limit is 15 parts by weight, and a more preferred upper limit is 40 parts by weight.

The curable resin contains a polymerizable compound other than the polymerizable compound of the present invention.

Examples of the other polymerizable compound include epoxy compounds and other (meth) acrylic compounds other than those included in the polymerizable compound of the present invention.

In addition, in the present specification, the "(meth) acrylic compound" means a compound having a (meth) acryl group, and the "(meth) acryl group" means an acryl group or a methacryl group base.

Examples of the other epoxy compounds include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, and 2,2'-diene. Propyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, sulfide type Epoxy resin, diphenyl ether epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, dicyclopentadiene Ene novolac epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol epoxy resin, rubber modified epoxy resin , Glycidyl ester compounds, etc.

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

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

Examples of a commercially available bisphenol E-type epoxy resin include R710 (manufactured by Printec).

Examples of a commercially available bisphenol S-type epoxy resin include EPICLON EXA-1514 (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 commercially available one among the said hydrogenated bisphenol-type epoxy resin, Epiclon EXA-7015 (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).

Examples of a commercially available resorcinol-type epoxy resin include EX-201 (manufactured by Nagase Chemical Co., Ltd.) and the like.

Examples of the 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.) and the like.

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

As a commercially available one of the aforementioned naphthalene-type epoxy resins, for example, EPICLON HP4032, EPICLON EXA-4700 (both manufactured by DIC Corporation), and the like can be cited.

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

Examples of the commercially available o-cresol novolac-type epoxy resin include EPICLON N-670-EXP-S (manufactured by DIC Corporation) and the like.

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

As a marketer of the said biphenol novolak-type epoxy resin, NC-3000P (made by Nippon Kayakusho), etc. are mentioned, for example.

As a marketer of the said naphthol novolak-type epoxy resin, ESN-165S (made by Nippon Steel & Sumikin Chemical Co., Ltd.) etc. are mentioned, for example.

Examples of the commercially available glycidylamine type epoxy resin include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like.

Examples of a commercially available one of the above-mentioned alkyl polyol-type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPICLON726 (manufactured by DIC Corporation), Epolight80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), DENACOL EX-611 (manufactured by Nagase Kasei Corporation), etc.

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

Examples of a commercially available glycidyl ester compound include DENACOL EX-147 (manufactured by Nagase Chemical Co., Ltd.) and the like.

Examples of other marketers among the above-mentioned other 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.

The curable resin may contain a compound having an epoxy group and a (meth) acrylfluorenyl group in one molecule as the other epoxy compound. Examples of such a compound include a part of (meth) acrylic acid obtained by reacting a part of epoxy groups with (meth) acrylic acid in an epoxy compound having two or more epoxy groups in one molecule. Quality epoxy resin.

Examples of commercially available ones of the above-mentioned (meth) acrylic modified epoxy resins include UVACURE1561 (manufactured by DAICEL-ALLNEX), BEEM-50 (manufactured by KSM), and the like.

Examples of the other (meth) acrylic compound include epoxy (meth) acrylate, (meth) acrylate compound, and (meth) acrylate. Among these, epoxy (meth) acrylate is preferable. In terms of the level of reactivity, the other (meth) acrylic compound is preferably one having two or more (meth) acrylfluorenyl groups in the molecule.

In addition, in the present specification, the "(meth) acrylate" means an acrylate or a methacrylate, and the "epoxy (meth) acrylate" means that an epoxy compound A compound obtained by reacting all epoxy groups with (meth) acrylic acid.

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.

As an epoxy compound used as a raw material for synthesizing the said epoxy (meth) acrylate, the same thing as "the said other epoxy compound which may be contained as said other polymerizable compound" is mentioned.

Examples of the epoxy (meth) acrylate of any commercially available, for example, include: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 (both DAICEL- (Made by ALLNEX); EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.); Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.); DENACOL Acrylate DA-141, DENACOL Acrylate DA-314, DENACOL Acrylate DA-911 (all manufactured by Nagase Kasei Corporation), and the like.

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, 2-methoxyethyl (meth) acrylate, 2-ethoxy (meth) acrylate Ethyl ester, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol ( (Meth) acrylates, phenoxy diethylene glycol (Meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate, (meth) acrylate 2, 2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, fluorenimine (meth) Acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (hexahydrophthalate) (Meth) acrylic acid ethoxyethyl ester, 2- (hydroxy) acrylic acid ethoxyethyl 2-hydroxypropyl phthalate, 2- (meth) acrylic acid oxyethyl phosphate, (methyl) Glycidyl acrylate and the like.

Examples of the bifunctional compound in the (meth) acrylate compound include 1,3-butanediol di (meth) acrylate and 1,4-butanediol di (meth) acrylate. , 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol 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 Alcohol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene di (meth) acrylate, ethylene oxide modified isotricyanate di (meth) acrylate, (meth) acrylic acid 2-Hydroxy-3- (meth) propylene ethoxypropyl ester, carbonate diol di (meth) propylene Ester, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) ) Acrylate, etc.

In addition, examples of the tri- or more functional group in the (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, and ethylene oxide-added 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 (meth) acrylate Acrylic ethoxyethyl, di-trimethylolpropane tetra (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dineopentyl Tetraol hexa (meth) acrylate and the like.

The (meth) acrylic acid amine ester can be reacted, for example, by making 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group and 1 equivalent of an isocyanate compound having 2 isocyanate groups in the presence of a tin-based compound having a catalytic amount. And get.

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diisocyanate. Benzyl-4,4'-diisocyanate (MDI), hydrogenated MDI, polymer MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzylamine diisocyanate, xylylene diisocyanate (XDI) , Hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) phosphorothioate, tetramethylxylylene diisocyanate, 1,6,11-undecane triisocyanate, etc. .

As the isocyanate compound, for example, 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 (Meth) 4-hydroxybutyl 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 epoxy acrylate and the like.

As marketers of the aforementioned (meth) acrylic acid amine esters, for example: M-1100, M-1200, M-1210, M-1600 (all manufactured by Toa Kosei); EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270 , EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL 4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 (all manufactured by DAICEL-ALLNEXin-Arts-500, UNIP-Arts-500) Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H (all manufactured by Gensang Industrial Corporation); 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 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.) AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.), etc.

The sealing agent for liquid crystal display elements of this invention WHEREIN: It is preferable that the content ratio of the (meth) acryl fluorenyl group and an epoxy group in a curable resin is made into a molar ratio of 50: 50-95: 5.

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 photo radical polymerization initiator that generates radicals by light irradiation, or a thermal radical polymerization initiator that generates radicals by heating.

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

Examples of commercially available photoradical polymerization initiators include: IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, IRGACURE OXE02, Lucirin TPO (all (Manufactured by BASF); NCI-930 (manufactured by ADEKA); SPEEDCURE EMK (manufactured by Nihon SiberHegner); benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.).

Examples of the thermal radical polymerization initiator include an azo compound, an organic peroxide, and the like. Among these, an initiator composed of a polymer azo compound (hereinafter, also referred to as a "polymer azo initiator") is preferred.

The term "polymer azo compound" as used herein means a compound having an azo group and having a number-average molecular weight of 300 or more that generates radicals that can harden the (meth) acrylfluorenyl group by heat.

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, liquid crystal contamination can be suppressed and easily mixed with the curable resin. A more preferable lower limit of the number average molecular weight of the above polymer azo compound is 5000, a more preferable upper limit is 100,000, a more 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 measured by gel permeation chromatography (GPC), and calculated | required by polystyrene conversion. Examples of the column used when measuring the number average molecular weight obtained by polystyrene conversion by GPC include Shodex LF-804 (manufactured by Showa Denko Corporation).

Examples of the polymer azo compound include a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are 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 an azo group, it is preferable to have a polyethylene oxide structure. Examples of such polymer azo compounds include polycondensates of 4,4'-azobis (4-cyanovaleric acid) and polyalkylene glycol, or 4,4'-azobis ( 4-cyanovaleric acid) and polydimethylsiloxane having a terminal amine group.

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.).

Examples of the azo compound that is not a polymer include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).

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

As the above-mentioned cationic polymerization initiator, a photocationic polymerization initiator can be preferably 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, aromatic halide salts, and aromatic sulfonium salts; iron-arene complexes, titanocene complexes, and aryl groups Organometallic complexes such as silanol-aluminum complexes.

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

Regarding the content of the polymerization initiator, a preferred lower limit is 0.01 parts by weight, and a preferred upper limit is 10 parts by weight based on 100 parts by weight of the curable resin. When the content of the polymerization initiator is within this range, the obtained sealing agent for a liquid crystal display element is one which suppresses liquid crystal contamination and is more excellent in storage stability or hardenability. The more preferable lower limit of the content of the polymerization initiator is 0.1 part by weight, and the more preferable upper limit is 5 parts by weight.

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

Examples of the organic acid hydrazine include dihydrazine sebacate, dihydrazine isophthalate, dihydrazine adipate, and dihydrazine malonate.

Examples of the commercially available organic acid hydrazine include SDH and ADH (both manufactured by Otsuka Chemical Co., Ltd.); Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J (both Ajinomoto Fine-Techno Company)).

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 obtain a more excellent thermosetting property without deteriorating the drawability 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.

The sealing agent for a liquid crystal display element of the present invention preferably contains a filler for the purpose of viscosity adjustment, further improvement in adhesiveness by utilizing a stress dispersion effect, improvement in linear expansion rate, and further improvement in moisture permeability of a cured product. .

Examples of the filler include an inorganic filler and an organic filler.

Examples of the inorganic filler include silicon dioxide, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, and oxide. Iron, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, and the like.

Examples of the organic filler include polyester fine particles, polyurethane fine particles, ethylene polymer fine particles, and acrylic polymer fine particles.

The preferable lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight. When the content of the filler is within this range, the paintability and the like are not deteriorated, and the effect such as further improvement of adhesion is more excellent. The more preferable lower limit of the content of the filler is 20 parts by weight, and the more preferable upper limit is 60 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 has a "function as a bonding aid for further adhering a sealing agent to a substrate and the like".

As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanate can be preferably used. Acid propyltrimethoxysilane and the like. These improvements are excellent in the effect of improving the adhesion to a substrate and the like, and by chemically bonding with the curable resin, it is possible to suppress the curable resin from flowing into the liquid crystal.

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 in this range, the effect such as suppressing the occurrence of liquid crystal contamination and further improving the adhesiveness is more excellent. 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 light transmittance in the vicinity of the ultraviolet range, particularly light having a wavelength of 370 to 450 nm, which is higher than the average light transmittance of light having a wavelength of 300 to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent that sufficiently shields light of a wavelength in a visible light range to provide light-shielding properties to the sealant for a liquid crystal display element of the present invention, and on the other hand, makes light of a wavelength near an ultraviolet range Through. 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-mentioned titanium black has 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, aluminum oxide, zirconia, and magnesium oxide. Surface-treated titanium black, such as those coated with inorganic components. Among them, those treated with an organic component are more preferable in that the insulation properties can be further improved.

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, and therefore, it can realize no leakage of light and have a high contrast, and has an excellent figure Liquid crystal display elements with display quality.

Examples of the commercially available titanium black include 12S, 13M, 13M-C, 13R-N, and 14M-C (all manufactured by Mitsubishi Materials); Tilack D (manufactured by Akaho Kasei).

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 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. By setting the primary particle diameter of the light-shielding agent to be in this range, it is possible to produce a more excellent light-shielding property without deteriorating the drawability and the like of the obtained sealant for a liquid crystal display element. A more preferable lower limit of the 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 primary particle diameter of the light-shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS), dispersing the light-shielding agent in a solvent (water, organic solvent, etc.).

A 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 a preferable upper limit is 80 parts by weight. When the content of the light-shielding agent is within this range, it is possible to exhibit more excellent light-shielding properties without reducing the adhesiveness of the obtained sealant for a liquid crystal display element to a substrate or the strength or drawability after curing. 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 sealing agent 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, and a polymerization inhibitor, if necessary.

Examples of the method for producing the sealant for a liquid crystal display element of the present invention include, for example, using a homomixer, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, and the like to harden the resin, A method of mixing a polymerization initiator and / or a thermosetting agent, and a silane coupling agent, etc., if necessary.

The conductive fine particles can be blended in the sealant for a liquid crystal display element of the present invention to produce a vertical conductive material. In addition, such a sealant for a liquid crystal display element of the present invention and a conductive material for upper and lower conductive particles are also one aspect of the present invention.

Examples of the conductive fine particles include metal balls, and a conductive metal layer formed on the surface of the resin fine particles. Among them, it is preferable that a conductive metal layer is formed on the surface of the resin microparticles because of the excellent elasticity of the resin microparticles, and the conductive connection can be achieved without damaging the transparent substrate or the like.

In addition, a liquid crystal display element formed by using the sealant for liquid crystal display elements of the present invention or the upper-lower conductive material of the present invention is also one aspect of the present invention.

As a method for manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method can be preferably used. Specifically, for example, a method having the following steps and the like can be cited.

First, the following steps are performed: applying the sealant for a liquid crystal display element of the present invention to a glass substrate or a polyethylene terephthalate substrate with an electrode such as an ITO film by screen printing, coating by a dispenser, or the like. Wait for one of the two substrates to form a frame-shaped seal pattern. Next, the following steps are performed: in a state where the sealant for a liquid crystal display element of the present invention is not hardened, minute liquid droplets of liquid crystal are dropped into a frame of a sealing pattern of a substrate and coated, and overlapped with another substrate under vacuum. Thereafter, a step of irradiating the sealing pattern portion of the sealant for a liquid crystal display element of the present invention with light such as ultraviolet rays to temporarily harden the sealant, and a step of heating the temporarily hardened sealant to formally harden, is performed by this method. A liquid crystal display element can be obtained.

According to the present invention, it is possible to provide a sealant for a liquid crystal display element that is excellent in drawability, adhesion, moisture permeability prevention, and low liquid crystal contamination. 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.

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

(Preparation of the polymerizable compound A of the present invention)

340 parts by weight of a bisphenol A epoxy resin, 150 parts by weight of acrylic acid, 2.0 parts by weight of triphenylphosphine, and 0.1 parts by weight of dibutylhydroxytoluene were mixed and stirred at 120 ° C. for 24 hours to obtain The polymerizable compound A of the present invention is a light yellow transparent viscous substance. As the bisphenol A type epoxy resin, EPICLON EXA-850CRP (manufactured by DIC Corporation) was used. As the acrylic acid, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used. As the triphenylphosphine, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used.

The obtained polymerizable compound A of the present invention was analyzed by ¹ H-NMR, ¹³ C-NMR, and FT-IR. As a result, it was confirmed that R ¹ in formula (1) is hydrogen, X is a structure represented by formula (2-1) (R ² and R ³ are methyl groups, R ⁴ is hydrogen), and n is 3 (average value). A mixture of the compound and the compound in which R ¹ in formula (1) is hydrogen, X is a structure represented by formula (2-2) (R ² and R ³ are methyl groups), and n is 3 (average value).

(Examples 1 to 5 and Comparative Examples 1 to 3)

According to the blending ratios described in Table 1, the materials were mixed using a planetary mixer ("Defoaming Stir Taro" manufactured by Thinky), and then mixed using a three-roll mill, thereby preparing Examples 1 to 5 and comparison. Sealants for liquid crystal display elements of Examples 1 to 3.

<Evaluation>

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

(Drawability)

With respect to 100 parts by weight of each of the sealing compounds for liquid crystal display elements obtained in the examples and comparative examples, spacer particles having an average particle diameter of 5 μm ("Micropearl SP-2050", manufactured by Sekisui Chemical Industry Co., Ltd.) were used with a planetary stirring device. 1 Parts by weight are uniformly dispersed. Next, the sealant in which the spacer particles were dispersed was filled in a syringe for dispensing ("Musashi Engineering Co., Ltd." PSY-10E "), and after performing a defoaming treatment, a dispenser (Musashi Engineering Co.," SHOTMASTER " 300 ″), apply a sealant on the transparent electrode substrate with an ITO film by drawing a rectangular frame. Then, using a vacuum bonding device, another transparent substrate was bonded under a reduced pressure of 5 Pa. Using a metal halide lamp, the obtained unit was irradiated with 100 mW / cm ² of ultraviolet rays for 30 seconds, and then heated at 120 ° C. for 1 hour to harden the sealant to obtain a test piece. Observe the sealant in the obtained test piece, and set the case where the sealant is drawn with neat lines without poor breakage or bending, and set it as "◎". It was set to "○", and the case where there was no disconnection failure but the sealant was largely bent was set to "△", and the case where the disconnection failure occurred was set to "x" to evaluate the drawability.

(Adherence)

With respect to 100 parts by weight of each of the sealing compounds for liquid crystal display elements obtained in the examples and comparative examples, spacer particles having an average particle diameter of 5 μm ("Micropearl SP-2050", manufactured by Sekisui Chemical Industry Co., Ltd.) were used with a planetary stirring device. 1 Parts by weight are uniformly dispersed. Then, a very small amount of the spacer particle-dispersed sealant was taken out to the central portion of Corning Glass 1737 (20 mm × 50 mm × thickness 0.7 mm), and the same type of glass was superimposed thereon to spread the sealant for liquid crystal display elements. Thereafter, a metal halide lamp was irradiated with 100 mW / cm ² of ultraviolet rays for 30 seconds, and then heated at 120 ° C. for 1 hour to harden the sealant to obtain a test piece.

About the obtained test piece, the adhesion strength was measured using the tensiometer. The case where the bonding strength is 3.5 kg / cm ² or more is "◎", the case where the bonding strength is 3.0 kg / cm ² or more and less than 3.5 kg / cm ² is "○", and the bonding strength is 2.5 kg. The case where the adhesion strength was not less than 3.0 kg / cm ² or more and less than 3.0 kg / cm ² was regarded as "Δ", and the case where the adhesion strength was less than 2.5 kg / cm ² was regarded as "X", and the adhesion was evaluated.

(Anti-moisture permeability)

Using a coater, each of the sealants for liquid crystal display elements obtained in the examples and comparative examples was applied in a shape of a smooth release film with a thickness of 200 to 300 μm. Next, the applied sealant was irradiated with ultraviolet rays of 100 mW / cm ² for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to harden the sealant to obtain a cured film for measuring moisture permeability. The moisture permeability test cup was prepared by the moisture permeability test method (cup projection method) according to JIS Z 0208, and the obtained hardened film for moisture permeability measurement was installed, and the temperature was measured at 80 ° C and 90% RH. The moisture permeability was measured in a constant temperature and humidity oven. The case where the moisture permeability is less than 40 g / m ² ‧24hr is "◎", and the case where the moisture permeability is 40g / m ² ‧24hr or more and less than 60g / m ² ‧24hr is "○", which is 60g / m ² ‧24hr or more but less than 80g / m ² ‧24hr is regarded as “△”, and 80g / m ² ‧24hr or more is regarded as “×” to evaluate the moisture permeability prevention property.

(Low liquid crystal pollution)

With respect to 100 parts by weight of each of the sealing compounds for liquid crystal display elements obtained in the examples and comparative examples, spacer particles having an average particle diameter of 5 μm ("Micropearl SP-2050", manufactured by Sekisui Chemical Industry Co., Ltd.) were used with a planetary stirring device. 1 Parts by weight are uniformly dispersed. Next, the sealant in which the spacer particles were dispersed was filled in a syringe for dispensing ("Musashi Engineering Co., Ltd." PSY-10E "), and after performing a defoaming treatment, a dispenser (Musashi Engineering Co.," SHOTMASTER " 300 ″), apply a sealant on the transparent electrode substrate with an ITO film by drawing a rectangular frame. Next, a small liquid droplet of TN liquid crystal ("JC-5001LA", manufactured by Chisso Corporation) was dropped using a liquid crystal dropping device and coated, and another transparent substrate was bonded under a vacuum of 5 Pa using a vacuum bonding device. The obtained cell was irradiated with ultraviolet rays of 100 mW / cm ² for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to thermally harden the sealant to obtain a liquid crystal display element (cell gap 5 μm).

Regarding the obtained liquid crystal display element, the display unevenness caused by the liquid crystal (especially the corner portion) around the sealing portion was visually observed. As a result, a case where no display unevenness (color unevenness) was found at all was set to "◎", and a case where a lighter display unevenness was found outside the pixel area of the peripheral portion was set to "○", and The case where there is a noticeable display unevenness outside the pixel region of the peripheral part is set to "△", and the case where the noticeable display unevenness diffuses into the pixel region is set to "x" to evaluate low liquid crystal contamination.

[Industrial availability]

According to the present invention, it is possible to provide a sealant for a liquid crystal display element that is excellent in drawability, adhesion, moisture permeability prevention, and low liquid crystal contamination. 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.

Claims (3)

A sealing agent for a liquid crystal display element, which contains a curable resin, a polymerization initiator, and / or a thermosetting agent, and contains 5 to 50 parts by weight of the following formula (1) in 100 parts by weight of the curable resin. ), In the formula (1), R ¹ represents hydrogen or methyl, X represents a structure represented by the following formulae (2-1) to (2-3), and n is 2 to 6, In formulae (2-1) to (2-3), R ² and R ³ each independently represent hydrogen or a methyl group, and in formula (2-1), R ⁴ represents hydrogen or a methyl group.     A vertical conduction material containing a sealant for liquid crystal display elements and conductive fine particles in the first patent application scope.         A liquid crystal display element is obtained by using a sealant for a liquid crystal display element in the scope of patent application No. 1 or an upper and lower conduction material in the scope of patent application.