TW201708491A - 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 curability by visible light and is capable of suppressing 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 radical photopolymerization initiator, and wherein the radical photopolymerization initiator contains a compound represented by formula (1). In formula (1), each of two X moieties independently represents a phenyl group wherein a hydrogen atom may be substituted by an -OR1 group; each X moiety may have two or more -OR1 groups; in cases where two X moieties have two or more -OR1 groups in total, the -OR1 groups may be the same as or different from each other; R1 represents a hydrogen atom or an alkyl group having 1-3 carbon atoms; and n represents an integer of 1-10.

Description

Sealant for liquid crystal display element, upper and lower conductive materials, and liquid crystal display element

The present invention relates to a sealing agent for a liquid crystal display element which is excellent in visible light curability and can suppress liquid crystal contamination. Moreover, the present invention relates to an upper and lower conductive material and a liquid crystal display element using the sealing agent for a liquid crystal display element.

In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display unit, the use of the curable property as disclosed in Patent Document 1 and Patent Document 2 has been used in view of shortening the production time and optimizing the amount of liquid crystal used. The photothermal heat-curing sealant of a resin, a photopolymerization initiator, and a thermosetting agent is called a liquid crystal dropping method of a dropping method.

Regarding the dropping method, first, a rectangular sealing pattern is formed by dispensing on one of the two substrates with electrodes. Then, in a state where the sealant is not cured, fine droplets of the liquid crystal are dropped into the sealing frame of the substrate, and are superposed on the other substrate under vacuum, and the sealing portion is temporarily hardened by irradiating light such as ultraviolet rays. Thereafter, the film was heated and subjected to main hardening to produce a liquid crystal display element. Currently, this dropping method is becoming the mainstream of the manufacturing method of liquid crystal display elements.

However, mobile devices such as mobile phones and portable game consoles, which are equipped with liquid crystal panels, are becoming more and more popular, and the miniaturization of devices is the most important issue. As a method of miniaturizing the device, a narrow edge of the liquid crystal display portion can be cited, for example, the position of the sealing portion is performed. Configured under the black matrix (hereinafter, also known as narrow edge design).

However, in the case of a narrow-edge design, since the sealant is disposed directly under the black matrix, there is a problem that if the dripping method is performed, when the sealant is light-hardened, the irradiated light is blocked, and the light is hard to reach. The inside of the sealant and hardening become insufficient. As described above, when the curing of the sealant is insufficient, there is a problem in that the unhardened sealant component is eluted into the liquid crystal, and liquid crystal contamination is likely to occur.

Patent Document 3 discloses that a high sensitivity photopolymerization initiator is blended with a sealant. However, it is not possible to sufficiently photoharden the sealant by merely blending a high-sensitivity photopolymerization initiator. Further, Patent Document 4 discloses that a high-sensitivity photopolymerization initiator and a sensitizer are combined and blended in a sealant. However, there is a problem that liquid crystal contamination is likely to occur due to the use of a sensitizer.

Further, in the conventional dropping method, a sealing agent containing a curable resin having a radical polymerizable property and a photoradical polymerization initiator is often used, and the radical polymerizable compound is photocured to be irradiated with ultraviolet rays, but There is a problem that the liquid crystal is deteriorated by irradiation of ultraviolet rays. Therefore, it is considered that the sealant is photocured by using a cutoff filter of 400 nm or less and light having a wavelength in the visible light region. However, in this case, there is a problem that the sensitivity of the photoradical polymerization initiator cannot be sufficiently obtained.

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

Patent Document 2: International Publication No. 02/092718

Patent Document 3: International Publication No. 2011/002028

Patent Document 4: Japanese Laid-Open Patent Publication No. 2010-286640

An object of the present invention is to provide a sealing agent for a liquid crystal display element which is excellent in visible light curability and can suppress liquid crystal contamination. Moreover, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element using the sealing agent for a liquid crystal display element.

The present invention relates to a sealant for a liquid crystal display device comprising a curable resin and a photoradical polymerization initiator, and the photoradical polymerization initiator contains a compound represented by the following formula (1).

Formula (1), X 2 each independently represents a hydrogen atom may be substituted with a phenyl group of -OR ^1, each X may have more than two of the groups -OR ^1, X 2 in total have 2 or more of -OR ^In the case of ¹ base, each -OR ¹ group may be the same or different. R ¹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms. n represents an integer from 1 to 10.

The present inventors have surprisingly found that a compound having a specific structure has low contamination to liquid crystals and generates radicals with high sensitivity under visible light. Therefore, the inventors of the present invention have found that a compound for a liquid crystal display element which is excellent in visible light curability and can suppress liquid crystal contamination can be obtained by blending the compound as a photoradical polymerization initiator.

The sealing agent for liquid crystal display elements of this invention contains a photoradical polymerization initiator.

The photoradical polymerization initiator contains the compound represented by the above formula (1). By containing the compound represented by the above formula (1), the sealing agent for a liquid crystal display device of the present invention is excellent in visible light curability and can suppress liquid crystal contamination.

In the above formula (1), examples of X include a phenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 2-methoxyphenyl group, and a 3-methoxyphenyl group. , 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, and the like. Among them, a phenyl group and a 4-methoxyphenyl group are preferred, and a phenyl group is more preferred.

In the above formula (1), n represents an integer of 1 to 10. Wherein n is preferably an integer of 2 to 6, more preferably an integer of 3 to 5.

A preferred lower limit of the weight average molecular weight of the compound represented by the above formula (1) is 900. When the weight average molecular weight of the compound represented by the above formula (1) is 900 or more, the obtained sealing compound for liquid crystal display elements is more excellent in low liquid crystal contamination. The upper limit of the weight average molecular weight of the compound represented by the above formula (1) is not particularly limited, and is preferably less than 1300 from the viewpoints of easiness of synthesis, workability, compatibility with a curable resin, and the like. A more preferred lower limit of the weight average molecular weight of the compound represented by the above formula (1) is 950, and a more preferred upper limit is 1100.

In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and determined by polystyrene conversion. As a column for measuring the weight average molecular weight in terms of polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) or the like can be mentioned.

The content of the compound represented by the above formula (1) is preferably 0.3 parts by weight, and preferably 10 parts by weight, based on 100 parts by weight of the curable resin. By the above formula (1) When the content of the compound shown is 0.3 parts by weight or more, the obtained sealing agent for a liquid crystal display element is more excellent in photocurability. When the content of the compound represented by the above formula (1) is 10 parts by weight or less, the obtained sealing agent for a liquid crystal display element is more excellent in weather resistance, storage stability, and low liquid crystal contamination. A more preferred lower limit of the content of the compound represented by the above formula (1) is 0.5 part by weight, more preferably 5 parts by weight, and still more preferably 1 part by weight.

The sealing agent for liquid crystal display elements of the present invention may contain other photoradical polymerization initiators in addition to the compound represented by the above formula (1) within a range that does not cause adverse effects such as liquid crystal contamination.

Examples of the other photoradical polymerization initiators include a benzophenone compound, an acetophenone compound, a mercaptophosphine oxide compound, a titanocene compound, an oxime ester compound, and a benzoin ether system. Compound, diphenylethylenedione, 9-oxosulfur Wait.

Among the other photo-radical polymerization initiators mentioned above, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all are mentioned) BASF Corporation, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), Adeka Optomer N-1414, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka ARKLS NCI-839, Adeka ARKLS NCI-930, etc. (all manufactured by Adico).

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

The curable resin preferably contains a compound having a (meth) acrylonitrile group.

In the present specification, the above-mentioned "(meth)acryl fluorenyl group" means an acryl fluorenyl group or a methacryl fluorenyl group.

The compound having a (meth) acrylonitrile group may, for example, be a (meth) acrylate compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, by (meth) Epoxy (meth) acrylate obtained by reacting acrylic acid with an epoxy compound, urethane (meth) acrylate obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound Meth)acrylate) and so on.

In the present specification, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylate" means acrylate or methacrylate, the above-mentioned " Epoxy (meth) acrylate means a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid.

Among the above (meth) acrylate compounds, examples of the monofunctional ones include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylate. Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, isodecyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (methyl) Cyclohexyl acrylate, isodecyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylate 2-hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyl (meth)acrylate Ethyl ethyl ester, 2-butoxyethyl (meth)acrylate, methoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethyl carbitol ( Methyl) acrylate, (meth) acrylate Tetrahydrofurfuryl ester, 2-phenoxyethyl (meth)acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, (methyl) 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (A) Acrylic acid 1H,1H,5H-octafluoropentyl ester, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, quinone imine (meth) acrylate, succinic acid 2-(Meth)acryloyloxyethyl ester, 2-(methyl)propenyloxyethyl hexahydrophthalate, 2-(methyl)acryloxyl ethoxylate Ester 2-hydroxypropyl ester, (meth)acrylic acid propyl acrylate, 2-(meth) propylene methoxyethyl phosphate, and the like.

Further, among the above (meth) acrylate compounds, examples of the bifunctional ones include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylic acid. Ester, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, 2-positive Butyl-2-ethyl-1,3-propanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di( Methyl) acrylate, polyethylene glycol di(meth) acrylate, dipropylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, polypropylene glycol (meth) acrylate, epoxy B Alkane addition bisphenol A di(meth) acrylate, propylene oxide addition bisphenol A di(meth) acrylate, ethylene oxide addition bisphenol F di(meth) acrylate, dihydroxyl Dicyclopentadienyl di(meth) acrylate, neopentyl glycol di(meth) acrylate, ethylene oxide modified di(meth) acrylate, (methyl) 2-hydroxy-3-(methyl)propenyl propyl acrylate, carbonate diol di(methyl) propyl Acid ester, polyether diol di(meth) acrylate, polyester diol di(meth) acrylate, polycaprolactone diol di(meth) acrylate, polybutadiene diol di (a) Base) acrylate and the like.

Further, among the above (meth) acrylate compounds, examples of the trifunctional or higher compound include trimethylolpropane tri(meth)acrylate and ethylene oxide addition trimethylolpropane tris(A). Acrylate, propylene oxide addition trimethylolpropane tri(meth) acrylate, caprolactone modified trimethylolpropane tri(meth) acrylate, neopentyl alcohol tris(methyl) Acrylate, epoxy B Alkane addition of tris(meth)acrylate, glycerol tri(meth) acrylate, propylene oxide addition glycerol tri(meth) acrylate, tris(methyl) propylene methoxy ethoxylate Ester, di-trimethylolpropane tetra(meth)acrylate, neopentyltetrakis(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol six (a) Base) acrylate and the like.

The epoxy (meth) acrylate may, for example, be obtained by reacting an epoxy compound with (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.

Examples of the epoxy compound to be used as a raw material for synthesizing the above epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. , 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolac type epoxy Resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, epoxy propylamine type epoxy resin, alkyl polyol type epoxy resin, rubber A modified epoxy resin, a glycidyl ester compound, a bisphenol A type episulfide resin, or the like.

Among the above-mentioned bisphenol A type epoxy resins, for example, jER828EL, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 850CRP (manufactured by DIC Corporation), and the like are mentioned. Among the above-mentioned bisphenol F-type epoxy resins, for example, jER806 and jER4004 (all manufactured by Mitsubishi Chemical Corporation) and the like are mentioned.

Among the above-mentioned bisphenol S-type epoxy resins, for example, EPICLON EXA 1514 (manufactured by DIC Corporation) can be mentioned.

Among the above 2,2'-diallyl bisphenol A type epoxy resins, for example, commercially available ones can be mentioned. RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

Among the above-mentioned hydrogenated bisphenol type epoxy resins, for example, EPICLON EXA 7015 (manufactured by DIC Corporation) can be mentioned.

Among the above-mentioned propylene oxide-added bisphenol A-type epoxy resins, for example, EP-4000S (manufactured by Adeco Co., Ltd.) or the like can be mentioned.

Among the above-mentioned resorcinol-type epoxy resins, for example, EX-201 (manufactured by Nagase Chemical Co., Ltd.) or the like can be mentioned.

Among the above-mentioned biphenyl type epoxy resins, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) or the like can be mentioned.

Among the above-mentioned thioether type epoxy resins, for example, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) or the like can be mentioned.

Among the above-mentioned diphenyl ether type epoxy resins, for example, YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like can be mentioned.

Among the above-mentioned dicyclopentadiene type epoxy resins, for example, EP-4088S (made by Adidas Co., Ltd.), etc. are mentioned as a commercial.

Among the above-mentioned naphthalene type epoxy resins, for example, EPICLON HP4032, EPICLON EXA-4700 (all manufactured by DIC Corporation), and the like can be mentioned.

Among the above-mentioned phenol novolac type epoxy resins, for example, EPICLON N-770 (manufactured by DIC Corporation) or the like can be mentioned.

Among the above-mentioned o-cresol novolac type epoxy resins, for example, EPICLON N-670-EXP-S (manufactured by DIC Corporation) can be mentioned as a commercially available product.

Among the above-mentioned dicyclopentadiene novolac type epoxy resins, for example, those commercially available may be mentioned. EPICLON HP7200 (manufactured by DIC Corporation).

Among the above-mentioned biphenyl novolak type epoxy resins, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) can be mentioned as a commercially available product.

Among the above-mentioned naphthol novolac type epoxy resins, for example, ESN-165S (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) or the like can be mentioned.

Among the above-mentioned propylene glycol-based epoxy resins, for example, jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like are mentioned.

Among the above-mentioned alkyl polyol type epoxy resins, for example, ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) are mentioned. ), DENACOL EX-611 (manufactured by Changchun Chemical Co., Ltd.), etc.

Among the above-mentioned rubber-modified epoxy resins, for example, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (manufactured by Daicel Corporation), and the like are mentioned.

Among the above-mentioned glycidyl ester compounds, for example, DENACOL EX-147 (manufactured by Nagase Chemical Co., Ltd.) or the like can be mentioned.

Among the above-mentioned bisphenol A-type episulfide resins, for example, jER YL-7000 (manufactured by Mitsubishi Chemical Corporation) may be mentioned.

Among the above-mentioned epoxy compounds, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, and jER1032 (for example, may be mentioned). All are manufactured by Mitsubishi Chemical Corporation, EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

Among the above-mentioned epoxy (meth) acrylates, for example, EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3402, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX 63182 (both are Dai Sai Cham) New company manufacturing), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Epoxy EsterM-600A, Epoxy Ester40EM, Epoxy Ester70PA, Epoxy Ester200PA, Epoxy Ester80MFA, Epoxy Ester3002M, Epoxy Ester3002A, Epoxy Ester1600A, Epoxy Ester3000M, Epoxy Ester3000A, Epoxy Ester200EA, Epoxy Ester400EA (all manufactured by Kyoei Chemical Co., Ltd.), Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all manufactured by Changchun Chemical Company).

The above (meth)acrylic acid amide can be obtained, for example, by reacting 2 equivalents of a (meth)acrylic acid derivative having a hydroxyl group with a tin compound having 1 isocyanate compound having 2 isocyanate groups in an amount of a catalyst. .

Examples of the isocyanate compound which is a raw material of the above (meth)acrylic acid amide ester include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate. Trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, lower Alkyl diisocyanate, tolidine diisocyanate, decyl diisocyanate (XDI), hydrogenated XDI, quaternary acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethyl extension Mercapto diisocyanate, 1,6,11-undecane triisocyanate, and the like.

Further, as the above isocyanate compound, for example, ethylene glycol can be used. Chains obtained by reacting polyols such as propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and excess isocyanate compound Extended isocyanate compound.

Examples of the (meth)acrylic acid derivative having a hydroxyl group which is a raw material of the above (meth)acrylic acid amide include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, and 1, a mono(meth)acrylate of a glycol such as 4-butanediol or polyethylene glycol, or a mono(meth)acrylate of a triol such as trimethylolethane, trimethylolpropane or glycerin Or an epoxy (meth) acrylate such as di(meth)acrylate or bisphenol A epoxy (meth) acrylate.

Among the above-mentioned (meth) acrylates, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (all manufactured by Daicel Co., Ltd.), Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100 , Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Gensei Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U-10H, U-15HA, U-122A, U-122P, U-108, U-108A, U-324A, U-340A, U-340P, U- 1084A, U-2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ), AI-600, AH-600, AT-600, UA-101I, UA -101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.).

The compound having a (meth) acrylonitrile group is preferably a hydrogen bond unit having a -OH group, a -NH- group or a -NH ₂ group in terms of suppressing adverse effects on the liquid crystal.

In addition, as for the compound having a (meth) acrylonitrile group, it is preferred that the compound has 2 to 3 (meth) acrylonitrile groups in the molecule in terms of high reactivity.

The curable resin may contain an epoxy compound in order to improve the adhesion of the obtained sealing compound for a liquid crystal display element.

Examples of the epoxy compound include an epoxy compound which is a raw material for synthesizing the above epoxy (meth)acrylate, or a partially (meth)acrylic modified epoxy resin.

In the present specification, the above-mentioned partial (meth)acrylic acid-modified epoxy resin means a compound having one or more of an epoxy group and a (meth)acryloyl group in one molecule, for example, It is obtained by reacting a partial epoxy group of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid.

When the curable resin contains the compound having a (meth)acryl fluorenyl group and the epoxy compound, the ratio of the (meth) acrylonitrile group to the epoxy group is preferably 30:70 to 95:5. The above compound having a (meth) acrylonitrile group and the above epoxy compound are blended in the same manner. When the ratio of the (meth)acrylonitrile group is 30% or more, the obtained sealing compound for liquid crystal display elements is more excellent in low liquid crystal contamination. When the ratio of the (meth)acrylonitrile group is 95% or less, the obtained sealant for a liquid crystal display element is more excellent in adhesion.

The sealant for a liquid crystal display element of the present invention may contain a sensitizer.

The sensitizer is excellent in the photosensitizing effect on the compound represented by the above formula (1). In terms of aspect, it is preferred to contain an amine-based sensitizer.

Examples of the amine-based sensitizer include a compound represented by the following formula (2), 4,4′-bis(diethylamino)benzophenone, and 2-(dimethylamino)benzoic acid. Ethyl ester, ethyl 4-(dimethylamino)benzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, isoamyl 4-(dimethylamino)benzoate, 4-( Butyloxyethyl dimethylamino)benzoate and the like. In particular, the sealing agent for a liquid crystal display element obtained is excellent in curability, and is preferably a compound represented by the following formula (2).

In the formula (2), z represents an integer of 1 or more, and P is (poly)ethylene glycol, (poly)propylene glycol, (poly)butanediol, glycerin, trimethylolpropane, di-trimethylolpropane, The residue of pentaerythritol, dipentaerythritol, or caprolactone polyol.

In the above formula (2), z represents an integer of 1 or more, and a preferred lower limit is 2, and a preferred upper limit is 6. When the above z is 2 or more, the obtained sealing agent for a liquid crystal display element is more excellent in low liquid crystal contamination. When the above z is 6 or less, the viscosity does not become too high, and the operability is more excellent.

In the above formula (2), P is (poly)ethylene glycol, (poly)propylene glycol, (poly)butanediol, glycerin, trimethylolpropane, di-trimethylolpropane, pentaerythritol, two The residue of pentaerythritol, or caprolactone polyol.

A preferred lower limit of the molecular weight of P in the above formula (2) is 100, and a preferred upper limit is 2000. When the molecular weight of P is 100 or more, the obtained sealing compound for liquid crystal display elements is more excellent in low liquid crystal contamination. When the molecular weight of P is 2,000 or less, the viscosity does not become too high, and the operability is more excellent.

The compound represented by the above formula (2) preferably has a z of 2 in the formula (2) and P is a residue of polyethylene glycol.

Among the above sensitizers, examples of the amine sensitizer include an anthracene derivative, an anthracene derivative, a coumarin derivative, and 9-oxosulfuric acid. Derivatives, anthraquinone derivatives, and the like.

Examples of the above anthracene derivative include 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, and 9,10-dipropoxyfluorene.

Examples of the above anthracene derivative include 2-ethylanthracene, 1-methylanthracene, 1,4-dihydroxyindole, and 2-(2-hydroxyethoxy)anthracene.

The coumarin derivative may, for example, be 7-diethylamino-4-methylcoumarin or the like.

As the above 9-oxygen sulfur Derivatives, for example, 2,4-diethyl 9-oxosulfur 2-chloro 9-oxosulfur 4-isopropyl 9-oxosulfur 1-chloro-4-propyl 9-oxosulfur Wait.

As the anthraquinone derivative, for example, anthraquinone or the like can be mentioned.

Further, a benzophenone-based compound which is exemplified as the above other photoradical polymerization initiator may be used as the sensitizer.

The content of the sensitizer is preferably 0.1 part by weight based on 100 parts by weight of the curable resin, and a preferred upper limit is 2 parts by weight. By the content of the above sensitizer In addition, it is possible to maintain the excellent low liquid crystal contamination of the obtained sealant for liquid crystal display elements, and to exhibit a higher sensitizing effect. A more preferred lower limit of the content of the above sensitizer is 0.2 parts by weight, and a more preferred upper limit is 1 part by weight.

The content ratio of the compound represented by the above formula (1) to the above sensitizer is preferably a compound represented by the formula (1) in a weight ratio: sensitizer = 1:0.1 to 1:0.7. When the content ratio of the compound represented by the above formula (1) to the sensitizer is within this range, the sealing agent for a liquid crystal display device of the present invention is particularly excellent in the effect of suppressing liquid crystal contamination and the visible light curability. The content of the compound represented by the above formula (1) and the above sensitizer is more preferably a compound represented by the formula (1): a sensitizer = 1:0.2 to 1:0.6.

The sealant for a liquid crystal display element of the present invention may further contain a thermal radical polymerization initiator.

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

In the present specification, the term "polymer azo initiator" means a radical having an azo group and which generates a radical capable of hardening a (meth) propylene oxime by heat, and has a number average molecular weight of 300 or more. Compound.

A preferred lower limit of the number average molecular weight of the above polymer azo initiator is 1000, and a preferred upper limit is 300,000. When the number average molecular weight of the above polymer azo initiator is within this range, it is possible to prevent adverse effects on the liquid crystal and to more easily mix in the curable resin. A lower limit of the number average molecular weight of the above polymer azo initiator is 5,000, a higher limit is 100,000, and a preferred lower limit is 10,000, and a preferred upper limit is 90,000.

In the present specification, the above-mentioned number average molecular weight is a value measured by gel permeation chromatography (GPC) and obtained by polystyrene conversion. As a column for measuring the number average molecular weight in terms of polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) or the like can be mentioned.

The polymer azo initiator is, for example, a structure in which a plurality of units such as polyalkylene oxide or polydimethyloxane are bonded via an azo group.

The polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group is preferably a polyethylene oxide structure. As such a polymer azo initiator, for example, a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and a polyalkylene glycol, or 4,4'-azo may be mentioned. a polycondensate of bis(4-cyanovaleric acid) and a polydimethyl methoxyalkane having a terminal amino group, and specific examples thereof include VPE-0201, VPE-0401, VPE-0601, and VPS-0501. , VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.) and so on.

In addition, examples of the non-polymer azo compound include V-65 and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.).

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

The content of the thermal radical polymerization initiator is preferably 0.05 parts by weight, and preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned thermal radical polymerization initiator is within this range, liquid crystal contamination due to the unreacted thermal radical polymerization initiator is suppressed, and the obtained sealant for a liquid crystal display element is more excellent in thermosetting property. By. A more preferred lower limit of the content of the above thermal radical polymerization initiator is 0.1 part by weight, and a more preferred upper limit is 5 parts by weight.

The sealant for a liquid crystal display element of the present invention may further contain a heat hardener.

Examples of the above-mentioned thermosetting agent include an organic acid hydrazine, an imidazole derivative, an amine compound, a polyphenol compound, and an acid anhydride. Among them, organic acid hydrazine can be preferably used.

Examples of the organic acid hydrazine include diindole azelaic acid, diterpene isophthalate, diammonium adipate, and diammonium malonate.

Among the above-mentioned organic acid bismuth, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J (all are Ajinomoto Fine- Techno company) and so on.

The content of the above-mentioned thermosetting agent is preferably 1 part by weight, and preferably 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned heat curing agent is 1 part by weight or more, the obtained sealing agent for a liquid crystal display element is more excellent in thermosetting property. When the content of the above-mentioned heat-hardening agent is 50 parts by weight or less, the viscosity of the obtained sealing agent for a liquid crystal display element does not become excessively high, and the coating property is further excellent. A more preferable upper limit of the content of the above thermal curing agent is 30 parts by weight.

The sealing agent for a liquid crystal display element of the present invention preferably contains a filler in order to improve the viscosity, improve the adhesion of the stress dispersion effect, improve the linear expansion ratio, and further improve the moisture resistance of the cured product.

Examples of the filler include talc, asbestos, cerium oxide, diatomaceous earth, bentonite, bentonite, calcium carbonate, magnesium carbonate, aluminum oxide, montmorillonite, zinc oxide, iron oxide, magnesium oxide, and tin oxide. , titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, tantalum nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride and other inorganic fillers, or polyester microparticles, polyurethane microparticles , ethylene polymer microparticles, acrylic polymer microparticles And other organic fillers. These fillers may be used singly or in combination of two or more.

A preferred lower limit of the content of the above filler in 100 parts by weight of the sealant for a liquid crystal display device of the present invention is 10 parts by weight, and a preferred upper limit is 70 parts by weight. When the content of the filler is 10 parts by weight or more, the effect of improving the adhesion is more excellent. When the content of the filler is 70 parts by weight or less, the viscosity of the obtained sealant for a liquid crystal display element does not become too high, and the coating property is further excellent. A more preferred lower limit of the content of the above filler is 20 parts by weight, and a still more preferred upper limit is 60 parts by weight.

The sealing agent for liquid crystal display elements of the present invention preferably contains a decane coupling agent. The above-mentioned decane coupling agent mainly functions as a bonding aid for adhering a sealing agent to a substrate or the like well.

The decane coupling agent is excellent in the effect of improving the adhesion to a substrate or the like, and is chemically bonded to the curable resin to suppress the flow of the curable resin into the liquid crystal. For example, it is preferably used: - aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, and the like. These decane coupling agents may be used singly or in combination of two or more.

A preferred lower limit of the content of the above decane coupling agent in 100 parts by weight of the sealant for a liquid crystal display device of the present invention is 0.1 part by weight, and a preferred upper limit is 10 parts by weight. When the content of the above decane coupling agent is within this range, the effect of suppressing the generation of liquid crystal contamination and improving the adhesion is more excellent. A more preferred lower limit of the content of the above decane coupling agent is 0.3 parts by weight, and a more preferred upper limit is 5 parts by weight.

The sealing agent for liquid crystal display elements of this invention may also contain a shielding agent. The sealing agent for a liquid crystal display element of the present invention can be preferably provided by containing the above-mentioned sunscreen agent Used as a light-shielding sealant.

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

The titanium black is a substance which improves the transmittance of light in the vicinity of the ultraviolet region, in particular, light having a wavelength of 370 to 450 nm, as compared with the average transmission transmittance of light having a wavelength of 300 to 800 nm. In other words, the titanium black has a light-shielding agent having a light-shielding property to the sealing agent for a liquid crystal display element of the present invention by sufficiently shielding light of a wavelength in the visible light region, and light having a wavelength near the ultraviolet region. transmission. The light-shielding agent contained in the sealing agent for liquid crystal display elements of the present invention is preferably a material having high insulating properties, and is preferably a titanium black as a light-shielding agent having high insulating properties.

The titanium black may exhibit sufficient effects even if it is not surface-treated, and may be treated with an organic component such as a surface coupler or cerium oxide, titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, magnesium oxide, or the like. Surface treated titanium black such as inorganic component coating. Among them, it is preferable that the organic component treatment can further improve the insulation property.

In addition, since the liquid crystal display element manufactured by the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has sufficient light-shielding property, it can realize light-free leakage and has high contrast and excellent image. Display quality liquid crystal display elements.

Among the above-mentioned titanium blacks, for example, 12S, 13M, 13M-C, 13R-N, and 14M-C (all manufactured by Mitsubishi Materials Corporation) and Tilack D (manufactured by Ako Chemical Co., Ltd.) may be mentioned. .

A preferred lower limit of the specific surface area of the above titanium black is 13 m ² /g, a preferred upper limit is 30 m ² /g, a more preferred lower limit is 15 m ² /g, and a more preferred upper limit is 25 m ² /g.

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

The primary particle diameter of the 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 device, and the lower limit is preferably 1 nm, and the upper limit is preferably 5 μm. When the primary particle diameter of the above-mentioned light-shielding agent is in this range, the coating property of the obtained sealing compound for liquid crystal display elements and the like are not deteriorated, and the light-shielding property can be further improved. A lower limit of the primary particle diameter of the above-mentioned opacifier is 5 nm, a more preferred upper limit is 200 nm, and a further preferred lower limit is 10 nm, and a further preferred upper limit is 100 nm.

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

A preferred lower limit of the content of the above-mentioned sunscreen agent in 100 parts by weight of the sealant for a liquid crystal display device of the present invention is 5 parts by weight, and a preferred upper limit is 80 parts by weight. When the content of the light-shielding agent is 5 parts by weight or more, the obtained sealing agent for a liquid crystal display element is more excellent in light-shielding property. When the content of the above-mentioned light-shielding agent is 80 parts by weight or less, the obtained sealing agent for a liquid crystal display element is excellent in adhesion to a substrate, strength after hardening, and portability. A more preferred lower limit of the content of the above-mentioned opacifier is 10 parts by weight, more preferably 70 parts by weight, still more preferably 30 parts by weight, and still more preferably 60 parts by weight.

As a method of producing the sealant for a liquid crystal display element of the present invention, for example, a mixer such as a homogeneous phase disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll mill can be used to impart curability. Resin, 9-oxosulfur A method of mixing an additive such as a polymerization initiator, an amine sensitizer, or a decane coupling agent to be added as needed.

The upper and lower conductive materials can be produced by incorporating conductive fine particles into the sealing agent for a liquid crystal display device of the present invention. Moreover, such a sealing agent for a liquid crystal display element of the present invention and a conductive upper and lower conductive material are also one of the inventions.

As the conductive fine particles, a conductive metal layer formed on the surface of the metal ball or the resin fine particles can be used. Among them, it is preferable that a conductive metal layer is formed on the surface of the resin fine particles because the excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.

Further, the liquid crystal display element having the sealant for a liquid crystal display element of the present invention or the underlying conductive material of the present invention is also one of the inventions.

As a method of producing the liquid crystal display device of the present invention, for example, a method of the following steps, such as a glass substrate with an electrode such as an ITO film or a polyethylene terephthalate substrate, is used. a step of forming a rectangular seal pattern by screen printing, dispenser application, or the like, such as a sealant for a liquid crystal display device of the present invention, and a liquid crystal display element sealing agent or the like in the uncured state. a step of applying a small droplet to the sealing frame of the substrate and superimposing it on the other substrate under vacuum; and irradiating the sealing pattern portion such as the sealing agent for a liquid crystal display element of the present invention with light such as ultraviolet rays to temporarily cure the sealing agent. a step of heating the temporarily hardened sealant to form a hardening process.

According to the present invention, it is possible to provide a sealing agent for a liquid crystal display element which is excellent in visible light curability and can suppress liquid crystal contamination. Moreover, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element using the sealing agent for a liquid crystal display element.

1‧‧‧Chromium-deposited substrate on one side of one side

11‧‧‧Chromium evaporation department

2‧‧‧The substrate on which the entire single side was subjected to chrome evaporation

21‧‧‧Chromium evaporation department

3‧‧‧Location A

4‧‧‧Location B

5‧‧‧Location C

Fig. 1 is a schematic view for explaining a method of evaluating the hardenability of a light-shielding portion.

Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited to the examples.

(Examples 1 to 9 and Comparative Examples 1 to 4)

According to the blending ratios shown in Tables 1 and 2, each material was mixed using a planetary mixer (manufactured by Shinki Co., Ltd., "Defoaming Taro"), and then mixed by a three-roll mill to prepare and carry out the preparation. Each of the sealing agents for liquid crystal display elements of Examples 1 to 9 and Comparative Examples 1 to 4.

In addition, "Omnipol 910" in the table is a compound of the formula (1) wherein X is a phenyl group, n is 3 to 5, and a weight average molecular weight is 1032, and "Omnipol ASA" is a formula (2) wherein z is 2 And P is a compound of a residue of polyethylene glycol.

<evaluation>

The following evaluations were performed for each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples. The results are shown in Tables 1 and 2.

(photohardenability)

1 part by weight of the spacer fine particles ("Micropearl SI-H050", manufactured by Sekisui Chemical Co., Ltd.) was dispersed in 100 parts by weight of each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples. On the substrate, a glass substrate of the same size was placed on the substrate, and then light of 100 mW/cm ^{2 was} irradiated with a metal halide lamp for 10 seconds to prepare a photocurable test piece. Regarding the light irradiation, two types of modes were performed in the case of a non-cut filter and a case where there is a cut filter of 400 nm or less, and three test pieces were produced for each mode. Using an infrared spectroscopic device ("FTS3000" manufactured by BIORAD), the peak area of 815 to 800 cm ^-1 was set as the peak area from the acrylonitrile group, and the amount of change from the peak area of the acryl fluorenyl group before and after the irradiation of light was measured. This was evaluated for photocurability. The peak area from the acrylonitrile group is derived from the peak area of 845 to 820 cm ^-1 as the reference peak area. The case where the peak area of the acrylonitrile group is reduced by 90% or more after the light irradiation is set to "◎", and the peak area from the acrylonitrile group is reduced by 80% or more and less than 90% after the light irradiation. ○", after the light irradiation, the peak area from the acrylonitrile group is reduced by 70% or more, and the case where the peak area is less than 80% is "△", and the peak area from the acrylonitrile group is less than 70% after the light irradiation. In the case of "X", the photocurability was evaluated.

Further, the amount of change from the peak area of the acrylonitrile group before and after the light irradiation was an average value obtained from three test pieces.

(liquid crystal contamination)

1 part by weight of the spacer fine particles ("Micropearl SI-H050", manufactured by Sekisui Chemical Co., Ltd.) was dispersed in 100 parts by weight of each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples to obtain a seal for a liquid crystal display element. The agent was applied to one of the two substrates with transparent electrodes by a dispenser using a line width of the sealant of 1 mm. Then, a small droplet of liquid crystal (manufactured by Chisso Corporation, "JC-5004LA") was applied dropwise to the entire surface of the sealant of the substrate with the transparent electrode, and immediately attached to another substrate with a transparent electrode, The sealant portion was irradiated with ultraviolet rays of 100 mW/cm ² for 30 seconds using a metal halide lamp, and further heated at 120 ° C for 1 hour to harden the sealant to obtain a liquid crystal display element. Regarding the light irradiation, two types of modes were performed in the case of a non-cut filter and a case where there is a cut filter of 400 nm or less, and three liquid crystal display elements were produced for each mode.

With respect to the obtained liquid crystal display element, liquid crystal contamination in the vicinity of the sealant after the voltage was applied at 60 ° C for 1,000 hours was visually confirmed.

The liquid crystal contamination is judged based on the color unevenness of the three liquid crystal display elements. According to the degree of color unevenness, it is set to "◎" in the case where all the liquid crystal display elements are completely colorless, and at least one liquid crystal display element is slightly In the case where the color unevenness is set to "○", it is set to "△" when there is a slight color unevenness in at least one liquid crystal display element, and it is assumed that at least one liquid crystal display element has a considerable color unevenness. "X" to evaluate the liquid crystal contamination.

In addition, the liquid crystal display elements evaluated as "?" and "○" are grades which are practically problem-free.

(shading portion hardenability)

The light-shielding portion hardenability of each of the liquid crystal display element sealing agents obtained in the examples and the comparative examples was measured and measured for the conversion ratio of the acrylonitrile group at each measurement point as follows. Fig. 1 is a schematic view for explaining a method of evaluating the hardenability of a light-shielding portion.

A substrate 1 on which one side of one of the glass (length 30 mm, width 30 mm, thickness 0.7 mm) manufactured by Corning Co., Ltd. was subjected to chrome evaporation, and a substrate 2 on which the entire one surface was subjected to chrome evaporation was prepared (Fig. 1 (a) )). A composition obtained by adding 1% by weight of polymer beads of 5 μm to each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples was applied to the central portion of the surface of the substrate 1 which was subjected to the chromic deposition. 20 mg, and the surface side of the substrate 1 to which each of the compositions was applied was superposed on the side of the chrome-deposited surface of the substrate 2, and then sufficiently pressed (Fig. 1 (b)).

Then, the superimposed substrate was irradiated with ultraviolet rays of 100 mW/cm ² for 30 seconds from the surface of the substrate 1 using a metal halide lamp through a cut filter of 400 nm or less. The substrate 1 and 2 were peeled off using a cutter, and the direct ultraviolet irradiation portion (position A), the point 15 μm from the side of the direct-illumination portion of the ultraviolet ray irradiation portion (position B), and the direct irradiation from the ultraviolet ray were irradiated by the micro-IR method. The sealant (Fig. 1 (c)) at a point (position C) of 30 μm from the side of the light-shielding portion was used to confirm the peak derived from the acrylonitrile group using an infrared spectroscopic device ("FTS3000" manufactured by BIORAD Co., Ltd.).

The peak area of 815 to 800 cm ^{-1 was taken as} the peak area from the acrylonitrile group, and the amount of change before and after the light irradiation from the peak area of the acryl fluorenyl group was measured, whereby the photocurability was evaluated. The peak area from the acrylonitrile group is derived from the peak area of 845 to 820 cm ^-1 as the reference peak area. The case where the peak area of the acrylonitrile group is reduced by 90% or more after the light irradiation is set to "◎", and the peak area from the acrylonitrile group is reduced by 80% or more and less than 90% after the light irradiation. ○", after the light irradiation, the peak area from the acrylonitrile group is reduced by 70% or more, and the case where the peak area is less than 80% is "△", and the peak area from the acrylonitrile group is less than 70% after the light irradiation. In the case of "X", the photocurability (shading portion hardenability) was evaluated.

[Industrial availability]

According to the present invention, it is possible to provide a sealing agent for a liquid crystal display element which is excellent in visible light curability and can suppress liquid crystal contamination. Moreover, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element using the sealing agent for a liquid crystal display element.

Claims (4)

A sealant for a liquid crystal display element, comprising a curable resin and a photoradical polymerization initiator, wherein the photoradical polymerization initiator contains a compound represented by the following formula (1); Formula (1), X 2 each independently represents a hydrogen atom may be substituted with a phenyl group of -OR ^1, each X may have more than two of the groups -OR ^1, X 2 in total have 2 or more of -OR ^In the case of ¹ group, each -OR ¹ group may be the same or different; R ¹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms; and n represents an integer of 1 to 10. A sealant for a liquid crystal display element according to claim 1, which contains a shielding agent. A top-bottom conductive material containing the sealant for a liquid crystal display element of the first or second aspect of the patent application and the conductive fine particles. A liquid crystal display element having the sealing agent for a liquid crystal display element of claim 1 or 2 or the upper conductive material of the third aspect of the patent application.