TW201819524A - 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 is capable of suppressing penetration of liquid crystals into the sealing agent and contamination of liquid crystals by the sealing agent. 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 the curable resin contains a compound that has a polymerizable functional group and a structure represented by formula (1).

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 device capable of suppressing penetration of a sealant by a liquid crystal or contamination of a liquid crystal by a sealant. 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 dropping method, first, a rectangular seal pattern is formed on one of the two transparent substrates with electrodes by dispensing. Next, in the state where the sealant is not hardened, minute liquid droplets of the liquid crystal are dropped on the entire surface inside the frame of the transparent substrate, and immediately overlap with another transparent substrate, and the sealing portion is irradiated with light such as ultraviolet rays to be temporarily hardened. Thereafter, the liquid crystal display element is produced by heating and performing main curing during the annealing of the liquid crystal. If the substrates are bonded under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency. At present, the dripping method has become the mainstream of the manufacturing method of the liquid crystal display element.

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 for miniaturization, narrow edge of the liquid crystal display portion can be cited, for example, the position of the sealing portion is arranged under a black matrix (hereinafter, also referred to as "narrow edge design").

However, if a liquid crystal display device with a narrow-edge design is manufactured by the dripping method, there are cases where a black matrix has a part that is not exposed to light at the sealing portion, and thus a portion where light hardening does not sufficiently occur, and an unhardened sealant is produced. Contact with liquid crystal. In this case, there are the following problems: the liquid crystal penetrates into the sealant, a seal break occurs and the liquid crystal leaks out; or the uncured sealant dissolves into the liquid crystal and contaminates the liquid crystal.

Prior art literature

Patent literature

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

Patent Document 2: International Publication No. 02/092718

The present invention relates to a sealant for a liquid crystal display device capable of suppressing penetration of a sealant by a liquid crystal or contamination of a liquid crystal by a sealant. 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 heat curing agent, and the curable resin contains a polymerizable functional group and a structure represented by the following formula (1) Compound.

The present invention will be described in detail below.

The present inventors have found that by using a compound having a specific structure as a curable resin, a sealant for a liquid crystal display element that can suppress penetration of a sealant by liquid crystal or liquid crystal contamination by a sealant can be obtained, and completed the present invention.

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

The said curable resin contains the compound which has a polymerizable functional group and the structure 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 becomes a person capable of suppressing penetration of the sealant by liquid crystal or liquid crystal contamination by the sealant.

Among these, the polymerizable compound of the present invention is preferably a compound having a polymerizable functional group and a structure represented by the following formula (2).

In formula (2), R ¹ and R ² each independently represent hydrogen or methyl.

The polymerizable functional group of the polymerizable compound of the present invention is preferably a (meth) acrylfluorenyl group or an epoxy group, and more preferably a (meth) acrylfluorenyl group.

In addition, in this specification, the "(meth) acrylfluorenyl" means acrylfluorenyl or methacrylfluorenyl.

The preferable lower limit of the molecular weight of the polymerizable compound of the present invention is 300, and the preferable upper limit is 4,000. When the molecular weight of the polymerizable compound of the present invention is within this range without deteriorating coating properties, the obtained sealant for a liquid crystal display element becomes a liquid crystal display device that suppresses penetration of the sealant by liquid crystal or liquid crystal contamination by the sealant. The effect is more excellent. In addition, in the present specification, as for a compound having a specific molecular structure, the above-mentioned "molecular weight" is a molecular weight obtained from a structural formula, but a compound having a wide distribution of polymerization degree and a compound having an unspecific modification site are used. When weight average molecular weight is shown. In the present specification, the "weight average molecular weight" is a value measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene. Examples of the column used when measuring the weight-average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).

It is preferable that the said curable resin contains the polymerizable compound of this invention, and also contains another polymerizable compound from a viewpoint of adhesiveness or moisture permeability prevention.

When the other polymerizable compound is contained, a preferable lower limit of the content of the polymerizable compound of the present invention in 100 parts by weight of the curable resin is 1 part by weight, and a preferable upper limit is 50 parts by weight. When the content of the polymerizable compound of the present invention is within this range, the adhesiveness or moisture permeability prevention is not deteriorated, and the obtained sealant for a liquid crystal display element becomes a sealant that suppresses penetration of liquid crystal or a sealant. The effect of the liquid crystal contamination caused is more excellent. The more preferable lower limit of the content of the polymerizable compound of the present invention is 2 parts by weight, the more preferable upper limit is 45 parts by weight, and the more preferable lower limit is 20 parts by weight.

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. Among them, it is preferable to use another epoxy compound in combination with an imidazole-based thermosetting agent in terms of being more effective in suppressing penetration of the sealant by liquid crystal or liquid crystal contamination by the sealant.

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 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 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 marketer 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 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.

As a commercially available one among the above-mentioned ortho-cresol novolac-type epoxy resins, EPICLON N-670-EXP-S (made by DIC Corporation) etc. can be mentioned, for example.

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

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.

As a marketer of the above-mentioned alkyl polyol type epoxy resin, for example, ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPICLON726 (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 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 ChemteX).

Examples of other commercially available epoxy compounds include: YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); XAC4151 (manufactured by Asahi Kasei Corporation); jER1031, jER1032 ( All are 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 partially (meth) acrylic modified epoxy resin obtained by reacting a part of epoxy groups with (meth) acrylic acid in an epoxy compound having two or more epoxy groups. Wait.

As a marketer among the said (meth) acrylic modified epoxy resins, UVACURE 1561 (made by DAICEL-ALLNEX company) etc. are mentioned, for example.

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.

As the marketers of the aforementioned epoxy (meth) acrylates, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYLICE6063, EBECRYLDADX-63, 182 (182) (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 ChemteX), 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 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 epoxy acrylate and the like.

Examples of commercially available amine (meth) acrylates include: M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toa Kosei Corporation); EBECRYL 210, EBECRYL 220, EBECRYL 230, EBECRYL 270, EBECRYL 1290, EBECRYL 2220, EBECRYL 4827, EBECRYL 4842, EBECRYL 4858, EBECRYL 5129, EBECRYL 6700, EBECRYL 8402, EBECRYL 8803, EBECRYL 8804, EBECRYL 8807, EBECRYL 9260N (all manufactured by EXICE); Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H (all manufactured by Genji 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 Xinzhongcun Chemical Industry Company); AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all (Kyoeisha Chemical Co., Ltd.)

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, and Lucirin TPO (all are (Manufactured by BASF); NCI-930 (manufactured by ADEKA); SPEEDCURE EMK (manufactured by Nihon SiberHegner); benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.

Examples of the thermal radical polymerization initiator include azo compounds, organic peroxides, and the like. Among them, a starter composed of a polymer azo compound (hereinafter, also referred to as a “polymer azo starter”) 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, diacyl peroxide, Peroxydicarbonate and the like.

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.

As described above, the sealant for a liquid crystal display element of the present invention is preferably a combination of the other epoxy compounds and an imidazole-based thermosetting agent.

The imidazole-based thermosetting agent is more preferably a melting point of 80 ° C or lower.

Examples of the imidazole-based thermosetting agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-benzene Imidazolium trimellitate, 2,4-diamino-6- (2'-methylimidazolyl- (1 '))-ethyl-symmetric tris , 2,4-diamino-6- (2'-methylimidazolyl- (1 '))-ethyl-symmetric tris Isocyanuric acid adducts and the like.

In addition, as the imidazole-based thermosetting agent, an adduct type curing agent may also be used. By using the above-mentioned hardener of the adduct type, excessive thickening of the sealant can be suppressed.

Examples of the adduct-type curing agent include an adduct obtained by a reaction between an imidazole compound and an epoxy compound.

Examples of commercially available adduct-based hardeners include Amicure PN-23, Amicure PN-23J, Amicure PN-H, Amicure PN-31, Amicure PN-31J, Amicure PN-40, Amicure PN-40J, Amicure PN-50, Amicure PN-F, Amicure MY-24, Amicure MY-H (all manufactured by Ajinomoto Fine-Techno); P-0505 (manufactured by Shikoku Chemical Industry Co., Ltd.); P-200 ( Manufactured by Mitsubishi Chemical Corporation).

Examples of other thermosetting agents 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 coatability 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 soft particles from the viewpoint of improving the flexibility, adhesion, and the like of the cured product, or improving the effect of suppressing the penetration of the liquid crystal into the sealant or the elution of the sealant to the liquid crystal. .

Examples of the soft particles include polysiloxane particles, vinyl particles, amine ester particles, fluorine particles, and nitrile particles. Among these, polysiloxane particles and vinyl particles are preferred.

As said silicone particle | grains, a silicone rubber particle is preferable from a viewpoint of the dispersibility in resin.

As the vinyl-based particles, (meth) acrylic particles can be preferably used.

The (meth) acrylic particles can be obtained by polymerizing a monomer serving as a raw material by a known method. Specifically, for example, a method of suspension polymerization of a monomer in the presence of a radical polymerization initiator; a method in which non-crosslinked seed particles absorb the monomer in the presence of a radical polymerization initiator; A method in which seed particles are swollen to perform seed polymerization and the like.

Examples of the monomer used as a raw material for forming the (meth) acrylic particles include alkyl (meth) acrylates, (meth) acrylates containing oxygen atoms, nitrile-containing monomers, and fluorine-containing monomers. Monofunctional monomers such as (meth) acrylates.

Examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate. (Hexyl) hexyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearin (meth) acrylate Esters, cyclohexyl (meth) acrylate, isofluorenyl (meth) acrylate, and the like.

Examples of the (meth) acrylates containing oxygen atoms include 2-hydroxyethyl (meth) acrylate, glyceryl (meth) acrylate, polyoxyethylene (meth) acrylate, and (meth) ) Glycidyl acrylate and the like.

Examples of the nitrile-containing monomer include (meth) acrylonitrile.

Examples of the fluorine-containing (meth) acrylates include trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate.

Among them, alkyl (meth) acrylates are preferred because the homopolymer has a low Tg and can increase the amount of deformation when a load of 1 g is applied.

In order to have a crosslinked structure, tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dinepentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (Meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene di (meth) acrylate, 1, Multifunctional monomers such as 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and isotricyanic acid skeleton tri (meth) acrylate. Among them, (poly) ethylene glycol di (meth) acrylate and (poly) propylene glycol di (methyl) are preferred because the molecular weight between the crosslinking points is large and the amount of deformation can be increased when a load of 1 g is applied. Acrylate), (poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.

As for the usage-amount of the said crosslinkable monomer, in the whole monomer which becomes a raw material for forming the said (meth) acrylic particle, a preferable minimum is 1 weight%, and a preferable upper limit is 90 weight%. When the amount of the crosslinkable monomer used is 1% by weight or more, the solvent resistance is improved, and problems such as swelling and the like are not caused when kneaded with various sealant raw materials, and it is easy to uniformly disperse. When the use amount of the crosslinkable monomer is 90% by weight or less, the recovery rate can be reduced. A more preferable lower limit of the amount of the crosslinkable monomer used is 3% by weight, and a more preferable upper limit is 80% by weight.

Furthermore, in addition to these acrylic monomers, styrene-based monomers, vinyl ethers, vinyl carboxylates, unsaturated hydrocarbons, halogen-containing monomers, triallyl cyanurate, isotris Triallyl polycyanate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl allylamine, diallyl ether, γ- (meth) propylene Monomethoxypropyltrimethoxysilane, vinyltrimethoxysilane and other monomers.

Examples of the styrene-based monomer include styrene, α-methylstyrene, and trimethoxysilylstyrene.

Examples of the vinyl ethers include methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether.

Examples of the vinyl carboxylic acid esters include vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, and the like.

Examples of the unsaturated hydrocarbon include ethylene, propylene, isoprene, and butadiene.

Examples of the halogen-containing monomer include vinyl chloride, vinyl fluoride, and chlorostyrene.

As the (meth) acrylic particles, fine particles of core-shell (meth) acrylate copolymers can also be preferably used.

As a commercially available one of the core-shell (meth) acrylate copolymer fine particles, for example, F351 (manufactured by Ruiwon Chemical Co., Ltd.) and the like are mentioned.

In addition, as the vinyl-based particles, for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles, and the like can be used.

The preferable lower limit of the average particle diameter of the soft particles is 0.01 μm, and the preferable upper limit is 10 μm. By setting the average particle diameter of the soft particles to be in this range, it becomes "improving the softness or adhesiveness of the hardened material of the obtained sealant for liquid crystal display elements, or suppressing the penetration of liquid crystal into the sealant or the dissolution of the sealant into the liquid crystal." "The effect is even better. A more preferable lower limit of the average particle diameter of the soft particles is 0.1 μm, and a more preferable upper limit is 8 μm.

In addition, in this specification, the average particle diameter of the said soft particle means the value obtained by the measurement which measured the particle | grains before mixing with the sealing agent using the laser diffraction type particle size distribution measuring device. As the above-mentioned laser diffraction type particle size distribution measurement device, Mastersizer 2000 (manufactured by Malvern) can be used.

The preferable lower limit of the hardness of the soft particles is 10, and the preferable upper limit is 50. By setting the hardness of the above-mentioned soft particles within this range, the effect of "improving the softness or adhesiveness of the hardened material of the obtained sealing agent for liquid crystal display elements, or suppressing the penetration of liquid crystal into the sealing agent or the sealant from dissolving into the liquid crystal" is achieved. Better. A more preferable lower limit of the hardness of the soft particles is 20, and a more preferable upper limit is 40.

In addition, in this specification, the hardness of the said soft particle means the A-type hardness of the A-type hardness meter measured by the method based on JISK6253.

The preferable lower limit of the content of the soft particles 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 50 parts by weight. By setting the content of the above-mentioned soft particles within this range without deteriorating coating properties and the like, it becomes "improving the flexibility or adhesion of the hardened material of the obtained sealing agent for liquid crystal display elements, or suppressing the penetration of liquid crystal into the sealing agent. Or liquid crystal contamination caused by a sealant. " A more preferable lower limit of the content of the soft particles is 10 parts by weight, and a more preferable upper limit is 45 parts by weight.

The sealing agent for a liquid crystal display element of the present invention preferably contains a filler for the purpose of improving viscosity, improving adhesiveness by using a stress dispersion effect, and improving linear expansion ratio.

Examples of the filler include inorganic fillers and organic fillers other than those contained in the soft particles.

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.

A 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 a preferable upper limit is 70 parts by weight. When the content of the filler is in this range, the coating properties and the like are not deteriorated, and the effects such as improvement of adhesion are 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 adhering a sealant to a substrate and the like well".

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 effects are excellent in improving the adhesion to a substrate and the like, and by chemically bonding with a 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 of suppressing the occurrence of liquid crystal contamination and improving the adhesion 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 inorganic component coatings. 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 titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore can achieve high contrast without leakage of light and excellent image. Liquid crystal display element of 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 making the primary particle diameter of the said light-shielding agent into this range, it can be made into the thing which is more excellent in light-shielding property, without deteriorating the coating property of the obtained sealing compound for liquid crystal display elements. 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.).

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, it is possible to exhibit more excellent light-shielding properties without reducing the adhesiveness of the obtained sealing agent 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 mixed with 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.

As the conductive fine particles, metal balls, those having a conductive metal layer formed on the surface of the resin fine particles, and the like can be used. Among them, conductive fine particles having a conductive metal layer formed on the surface of the resin fine particles are preferable because the conductive fine particles of the resin fine particles can achieve conductive connection 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 the 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, the step of irradiating light such as ultraviolet rays to the sealing pattern portion of the sealant for a liquid crystal display element of the present invention to temporarily harden the sealant, and the step of heating the temporarily hardened sealant to formally harden it can be performed by this method. A liquid crystal display element was obtained.

According to the present invention, it is possible to provide a sealant for a liquid crystal display device that can suppress penetration of a sealant by a liquid crystal or contamination of a liquid crystal by a sealant. 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 by explaining examples, but the present invention is not limited to these examples.

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

228 g (1.0 mol) of bisphenol A and 92 g (1.0 mol) of epichlorohydrin were added to a reactor equipped with a stirring device, a thermometer, and a dropping funnel, heated to 100 ° C, and 5 g (0.1 mol) of sodium ethoxylate was dissolved by dropping. The solution prepared in 30 g of ethanol was stirred for 5 hours after the dropping was completed. Thereafter, the reactant was washed with 0.1 mol / L hydrochloric acid and ion-exchanged water, and the generated salt and impurities were removed. Then, the epichlorohydrin was distilled off and dried under reduced pressure to obtain a partially epoxidized resin of bisphenol A as an intermediate.

142 g of the obtained intermediate, 36 g (0.5 mol) of acrylic acid, 500 g of diethylene glycol monoethyl ether acetate, 1 g of triphenylphosphine, and 100 mg of hydroquinone methyl ether were added to a reactor equipped with a stirring device and a thermometer. Then, heat and stir at 120 ° C for 5 hours. The obtained reaction solution was reprecipitated with methanol and dried under reduced pressure to obtain a polymerizable compound A (weight average molecular weight 380) of the present invention as a reaction product.

Furthermore, by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained polymerizable compound A of the present invention has an acrylic fluorenyl group as a polymerizable functional group and has the above formula (2). A compound having the structure shown (R ¹ and R ² are methyl).

(Production of the polymerizable compound B of the present invention)

200 g (1.0 mol) of bisphenol F and 92 g (1.0 mol) of epichlorohydrin were added to a reactor equipped with a stirring device, a thermometer, and a dropping funnel, heated to 100 ° C, and 5 g (0.1 mol) of sodium ethoxylate was dissolved by dropping. The solution prepared in 30 g of ethanol was stirred for 5 hours after the dropping was completed. Thereafter, the reactant was washed with 0.1 mol / L hydrochloric acid and ion-exchanged water, and the generated salt and impurities were removed. Next, epichlorohydrin was distilled off and dried under reduced pressure to obtain a partially epoxidized resin of bisphenol F as an intermediate.

Add 128 g of the obtained intermediate, 36 g (0.5 mol) of acrylic acid, 500 g of diethylene glycol monoethyl ether acetate, 1 g of triphenylphosphine, and 100 mg of hydroquinone methyl ether into a reactor equipped with a stirring device and a thermometer. Then, heat and stir at 120 ° C for 5 hours. The obtained reaction solution was reprecipitated with methanol and dried under reduced pressure to obtain a polymerizable compound B (weight average molecular weight 350) of the present invention as a reaction product.

Furthermore, by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained polymerizable compound B of the present invention has an acrylic fluorenyl group as a polymerizable functional group and has the above formula (2). Compounds of the structure shown (R ¹ and R ² are hydrogen).

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

Add 150 g of novolac resin (weight average molecular weight 3300), 36 g (0.5 mol) of acrylic acid, 500 g of diethylene glycol monoethyl ether acetate, 1 g of triphenylphosphine, and 100 mg of hydroquinone methyl ether to the attached stirring device and thermometer The reactor was heated and stirred at 120 ° C for 5 hours. As the novolak resin, EP6050G (manufactured by Asahi Organic Materials Co., Ltd.) was used. The obtained reaction solution was reprecipitated with methanol, and dried under reduced pressure to obtain a polymerizable compound C (weight average molecular weight 3800) of the present invention.

Furthermore, by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained polymerizable compound C of the present invention has an acrylic fluorenyl group as a polymerizable functional group and has the above formula (1) Compounds of the indicated structure.

(Production of the polymerizable compound D of the present invention)

Add 150 g of novolac resin (weight 4800), 36 g (0.5 mol) of acrylic acid, 500 g of diethylene glycol monoethyl ether acetate, 1 g of triphenylphosphine, and 100 mg of hydroquinone methyl ether to the The reactor was heated and stirred at 120 ° C for 5 hours. As the novolak resin, EPR5030G (manufactured by Asahi Organic Materials Co., Ltd.) was used. The obtained reaction solution was reprecipitated with methanol, and dried under reduced pressure to obtain a polymerizable compound D (weight average molecular weight 5300) of the present invention.

Furthermore, by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained polymerizable compound D of the present invention has an acrylic fluorenyl group as a polymerizable functional group and has the above formula (1) Compounds of the indicated structure.

(Examples 1 to 8 and Comparative Example 1)

In accordance with 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 to prepare Examples 1 to 8 and The sealing agent for liquid crystal display elements of Comparative Example 1.

<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 unit after bonding was irradiated with 100 mW / cm ² of ultraviolet rays for 30 seconds, and then heated at 120 ° C. for 1 hour to thermally harden the sealant to produce a unit. Observe the sealant in the obtained unit. Set the case where the sealant is drawn with cleanliness without broken wires or bends to "○". Set the end of the sealant without broken wires with bends to cause bending. In other cases, it was set to "△", and in the case where a disconnection failure occurred, it 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 150 N / cm ² or more is "○", the case where the bonding strength is 50 N / cm ² or more and less than 150 N / cm ² is "△", and the bonding strength is less than 50 N / cm ² In the case of "x", the adhesivity was evaluated.

(Anti-moisture permeability)

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 by a liquid crystal dropping device and applied, and another transparent substrate was bonded under a vacuum of 5 Pa by a vacuum bonding device. Immediately after bonding, a 100 mW / cm ² ultraviolet ray was irradiated for 30 seconds using a metal halide lamp, and then the sealant was thermally cured by heating at 120 ° C. for 1 hour to obtain a liquid crystal display element (cell gap 5 μm). The obtained liquid crystal display element was exposed to PCT conditions (121 ° C, 100% RH, 2 atm) for 12 hours. The liquid crystal display element after being exposed to the PCT condition was observed with an optical microscope. As a result, a case where water was not mixed into the liquid crystal portion was set to "○", and a case where water was mixed slightly was set to "△". The case where a large amount of water was mixed so that it could be confirmed visually was set to "×" to evaluate the moisture permeability prevention.

(Infiltration prevention)

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 by a liquid crystal dropping device and applied, and another transparent substrate was bonded under a vacuum of 5 Pa by a vacuum bonding device. After bonding, it was left at room temperature for 10 minutes, and then irradiated with 100 mW / cm ² of ultraviolet light for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to heat harden the sealant to obtain a liquid crystal display element (cell gap 5 μm) . The obtained liquid crystal display element was observed for the shape of a sealing pattern. As a result, the shape of the seal pattern was not disturbed by the internal liquid crystal as "○", the shape of the seal pattern was disordered but the liquid crystal did not break through the seal pattern as "△", and the liquid crystal broke through the seal pattern On the other hand, leakage to the outside was evaluated as "x" and the infiltration prevention property was evaluated.

[Industrial availability]

According to the present invention, it is possible to provide a sealant for a liquid crystal display element that can suppress penetration of a sealant by a liquid crystal or contamination of a liquid crystal by a sealant. 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 (7)

A sealing agent for a liquid crystal display element, comprising a curable resin, a polymerization initiator, and / or a thermosetting agent, wherein the curable resin contains a polymerizable functional group and is represented by the following formula (1) Structural compounds, For example, the sealant for a liquid crystal display element according to the first patent application range, wherein the compound having a polymerizable functional group and a structure represented by formula (1) has a polymerizable functional group and a structure represented by the following formula (2) Of compounds, In formula (2), R ¹ and R ² each independently represent hydrogen or methyl.     For example, the sealant for a liquid crystal display element according to claim 1 or 2, wherein the polymerizable functional group is a (meth) acrylfluorenyl group or an epoxy group.         For example, the sealant for a liquid crystal display element in the scope of claims 1, 2 or 3, wherein the molecular weight of the compound having a polymerizable functional group and a structure represented by formula (1) is 300 to 4000.         For example, the sealant for a liquid crystal display element according to the scope of patent application No. 1, 2, 3 or 4, wherein the content of the compound having a polymerizable functional group and a structure represented by formula (1) in 100 parts by weight of the curable resin is 1 ~ 50 parts by weight.         A vertical conduction material comprising a sealant for a liquid crystal display element and conductive fine particles in the scope of claims 1, 2, 3, 4 or 5.         A liquid crystal display element is obtained by using a sealant for liquid crystal display elements in the scope of patent application No. 1, 2, 3, 4 or 5 or a conductive material in the scope of patent application No. 6.