TW202112840A - Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a sealant for a liquid crystal display element, the sealant having excellent adhesion and moisture permeation prevention and being capable of suppressing liquid crystal contamination. The purpose of the present invention is also to provide a vertical conduction material and a liquid crystal display element obtained using the sealant for a liquid crystal display element. The present invention is a sealant for a liquid crystal display element, containing a curable resin, and a polymerization initiator and/or a thermosetting agent, the curable resin containing a compound having three or more polymerizable functional groups and one or more [epsilon]-caprolactone open-ring structures in each molecule thereof and not having a cyclic structure.

Description

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

The present invention relates to a sealant for liquid crystal display elements which is excellent in adhesiveness and moisture permeability and can suppress liquid crystal contamination. In addition, the present invention relates to an upper and lower conduction material and a liquid crystal display element using this sealing compound for liquid crystal display elements.

In recent years, regarding the manufacturing method of liquid crystal display elements such as liquid crystal display units, from the viewpoints of shortening the pitch time and optimizing the amount of liquid crystal used, conventionally known vacuum injection methods, such as those described in Patent Document 1 and Patent Document 2 The liquid crystal dropping method known as the dropping method, which uses light and heat combined with a hardening type sealant, is becoming the mainstream.

The dripping method first forms a rectangular seal pattern by drip coating on one of the two transparent substrates with electrodes. Next, when the sealant is not cured, droplets of liquid crystal are dropped on the entire surface of the frame of the transparent substrate, and the other transparent substrate is immediately superimposed, and the sealing part is irradiated with light such as ultraviolet rays for temporary curing. After that, heating is performed during the annealing of the liquid crystal for main curing, and a liquid crystal display element is produced. If the substrates are bonded under reduced pressure, liquid crystal display elements can be manufactured with extremely high efficiency.

With the popularization of tablet terminals or mobile terminals, liquid crystal display elements are increasingly required to have humidity resistance reliability in driving under high-temperature and high-humidity environments, and sealants are further required to prevent the penetration of water from the outside. In order to improve the moisture resistance reliability of the liquid crystal display element, it is necessary to improve the adhesion between the sealant and the substrate, etc., and to make the cured product of the sealant excellent in moisture permeability. However, it is difficult to balance adhesion and moisture permeability in sealants. Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2001-133794 Patent Document 2: Japanese Patent Laid-Open No. 5-295087

[The problem to be solved by the invention]

The object of the present invention is to provide a sealant for liquid crystal display elements which is excellent in adhesiveness and moisture permeability and can suppress liquid crystal contamination. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using this sealant for liquid crystal display elements. [Technical means to solve the problem]

The present invention is a sealing compound for liquid crystal display elements, which contains a curable resin, a polymerization initiator and/or a thermosetting agent, and the curable resin contains a compound having three or more polymerizable functions in one molecule A compound with a ring-opening structure of ε-caprolactone and one or more ε-caprolactone groups and no cyclic structure. Hereinafter, the present invention will be described in detail.

The inventors of the present invention found that by using a compound having 3 or more polymerizable functional groups and 1 or more ε-caprolactone ring-opening structure in one molecule, and not having a cyclic structure, as a curable resin, A sealant for a liquid crystal display element which is excellent in adhesiveness and moisture permeability and can suppress liquid crystal contamination can be obtained, thereby completing the present invention.

The sealing compound for liquid crystal display elements of this invention contains a curable resin. The above-mentioned curable resin contains a compound that has 3 or more polymerizable functional groups and 1 or more ε-caprolactone ring-opening structure in one molecule, and does not have a ring structure (hereinafter, also It is referred to as "the polymerizable compound of the present invention"). By containing the polymerizable compound of this invention, the sealing compound for liquid crystal display elements of this invention is excellent in adhesiveness and moisture permeability, and can suppress liquid crystal contamination.

The polymerizable compound of the present invention has 3 or more polymerizable functional groups in one molecule. As a polymerizable functional group which the polymerizable compound of this invention has, a (meth)acryl group, an epoxy group, an epithio group, etc. are mentioned, for example. Among them, the polymerizable compound of the present invention preferably has a (meth)acryloyl group as the polymerizable functional group, and more preferably all the polymerizable functional groups it has are (meth)acryloyl groups. Furthermore, in this specification, the above-mentioned "(meth)acryloyl group" means an acryloyl group or a methacryloyl group.

The polymerizable compound of the present invention preferably has 4 to 8 polymerizable functional groups in one molecule, and most preferably has 6 polymerizable functional groups in one molecule, from the viewpoint of compatibility of curability and moisture permeability prevention. Functional group.

The polymerizable compound of the present invention has one or more ring-opening structures of ε-caprolactone in one molecule. By having the ring-opening structure of the above-mentioned ε-caprolactone, the polymerizable compound of the present invention is excellent in adhesiveness.

The polymerizable compound of the present invention preferably has two or more ε-caprolactone ring-opening structures in one molecule, and more preferably has four or more ε-caprolactone ring-opening structures in one molecule, Furthermore, it is preferable to have 4-8 ε-caprolactone ring-opening structures in one molecule, and it is most preferable to have 6 ε-caprolactone ring-opening structures in one molecule.

Since the polymerizable compound of the present invention does not have a cyclic structure, the viscosity increase after blending can be suppressed, and the obtained sealing compound for liquid crystal display elements has excellent workability.

The polymerizable compound of the present invention is more excellent in the effect of suppressing liquid crystal contamination, and preferably has one or more hydrogen-bonding functional groups in one molecule. As the above-mentioned hydrogen-bonding functional group, for example, a hydroxyl group (-OH), a primary amino group (-NH ₂ ), a secondary amino group (-NHR (R represents an aromatic or aliphatic hydrocarbon, and derivatives of these) )), carboxyl group (-COOH), primary amide group (-CONH ₂ ), hydroxyl amine group (-NHOH), amide bond (-NHCO-), imine bond (-NH-), amide bond ( -CONHCO-), hydrogenated azo bond (-NH-NH-), etc. Among them, a hydroxyl group is preferred.

As a method of producing the polymerizable compound of the present invention, for example, a (meth)acrylate having 3 or more (meth)acrylic groups in one molecule and not having a cyclic structure can be subjected to ε-caprolactone. Methods of ester modification, etc. In addition, in this specification, the above-mentioned "(meth)acrylate" means acrylate or methacrylate, and the above-mentioned "modification of (meth)acrylate with ε-caprolactone" means ( The ring-opening body or ring-opening polymer of ε-caprolactone is introduced between the alcohol-derived part of meth)acrylate and the (meth)acrylic acid group.

As a method of modifying the above-mentioned (meth)acrylic acid ester with ε-caprolactone, specifically, for example, an alcohol is reacted with ε-caprolactone at a high temperature in the presence of a catalyst to synthesize ε-caprolactone. After the lactone-modified alcohol, the ε-caprolactone-modified alcohol is esterified with (meth)acrylic acid using a dehydrating solvent in the presence of an acidic catalyst; or (meth)acrylic acid and ε- After the caprolactone is reacted to synthesize ε-caprolactone-modified (meth)acrylic acid, the ε-caprolactone-modified (meth)acrylic acid is esterified with alcohol. Furthermore, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid.

The polymerizable compound of the present invention preferably has a dendritic polymer structure in which a plurality of molecular chains are regularly branched from the central atom or central molecule. Specifically, for example, neopentylerythritol tri(methyl) Acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, dineopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate Base) acrylate, di-trimethylolpropane tetra (meth) acrylate, dineopentyl erythritol tetra (meth) acrylate, dineopentyl erythritol penta (meth) acrylate, dineopentaerythritol Ε-caprolactone modified body such as alcohol hexa (meth)acrylate. Among them, ε-caprolactone-modified dineopentaerythritol hexaacrylate represented by the following formula (1) is preferred.

In formula (1), l, m, n, o, p, and q each independently represent an integer of 1-12. As far as the obtained sealing compound for liquid crystal display elements is more excellent in all aspects of adhesion, moisture permeability, and low liquid crystal contamination, in the above formula (1), l, m, n, o, p , And q are preferably 1 or 2 respectively, and most preferably are 1 respectively.

The above-mentioned curable resin may contain other polymerizable compounds in addition to the polymerizable compound of the present invention. When the above-mentioned other polymerizable compound is contained, the content of the polymerizable compound of the present invention is preferably 1 part by weight and the upper limit is 80 parts by weight with respect to 100 parts by weight of the entire curable resin. When the content of the polymerizable compound of the present invention is 1 part by weight or more, the obtained sealing compound for liquid crystal display elements is more excellent in adhesiveness. When the content of the polymerizable compound of the present invention is 80 parts by weight or less, the obtained sealing compound for liquid crystal display elements is more excellent in moisture permeability. The lower limit of the content of the polymerizable compound of the present invention is more preferably 10 parts by weight, the upper limit is more preferably 70 parts by weight, the lower limit is still more preferably 30 parts by weight, and the upper limit is more preferably 60 parts by weight.

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

Examples of the above-mentioned other epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, and 2,2'-diene Propyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy 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 novolak type epoxy resin, dicyclopentadiene type epoxy resin Diene novolac type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified ring Oxygen resins, glycidyl ester compounds, etc.

Among the above-mentioned bisphenol A epoxy resins, commercially available ones include, for example, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 850CRP (manufactured by DIC Corporation), and the like. Among the above-mentioned bisphenol F epoxy resins, commercially available ones include jER806, jER4004 (all manufactured by Mitsubishi Chemical Corporation) and the like. Among the above-mentioned bisphenol E epoxy resins, as a commercially available one, for example, R710 (manufactured by Printec) and the like can be cited. Among the above-mentioned bisphenol S-type epoxy resins, as a commercially available one, for example, EPICLON EXA1514 (manufactured by DIC Corporation) and the like can be cited. Among the above-mentioned 2,2'-diallyl bisphenol A epoxy resins, as a commercially available one, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) and the like can be cited. Among the above-mentioned hydrogenated bisphenol-type epoxy resins, as a commercially available one, for example, EPICLON EXA7015 (manufactured by DIC Corporation) and the like can be cited. Among the above-mentioned propylene oxide-added bisphenol A epoxy resins, as a commercially available one, for example, EP-4000S (manufactured by ADEKA Corporation) and the like can be cited. Among the above-mentioned resorcinol-type epoxy resins, as a commercially available one, for example, EX-201 (manufactured by Nagase Kasei Co., Ltd.) can be cited. Among the above-mentioned biphenyl type epoxy resins, commercially available ones include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation). Among the above-mentioned sulfide-type epoxy resins, as a commercially available one, for example, YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be cited. Among the above-mentioned diphenyl ether type epoxy resins, as a commercially available one, for example, YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be cited. Among the above-mentioned dicyclopentadiene-type epoxy resins, as a commercially available one, for example, EP-4088S (manufactured by ADEKA Corporation) and the like can be cited. Among the above-mentioned naphthalene-type epoxy resins, commercially available ones include, for example, EPICLON HP4032, EPICLON EXA-4700 (all manufactured by DIC Corporation), and the like. Among the above-mentioned phenolic novolak type epoxy resins, as a commercially available one, for example, EPICLON N-770 (manufactured by DIC Corporation) and the like can be cited. Among the above-mentioned ortho-cresol novolak type epoxy resins, as a commercially available one, for example, EPICLON N-670-EXP-S (manufactured by DIC Corporation) and the like can be cited. Among the above-mentioned dicyclopentadiene novolak-type epoxy resins, as a commercially available one, for example, EPICLON HP7200 (manufactured by DIC Corporation) and the like can be cited. Among the above-mentioned biphenol novolac type epoxy resins, as a commercially available one, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like can be cited. Among the above-mentioned naphthol-based novolak-type epoxy resins, as a commercially available one, for example, ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be cited. Among the above-mentioned glycidylamine-type epoxy resins, commercially available ones include, for example, jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like. Among the above-mentioned alkyl polyol type epoxy resins, commercially available ones include, for example, ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) , DENACOL EX-611 (manufactured by Nagase Chemical Co., Ltd.), etc. Among the above-mentioned rubber-modified epoxy resins, commercially available ones include YR-450, YR-207 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolead PB (manufactured by DAICEL), and the like. Among the above-mentioned glycidyl ester compounds, commercially available ones include, for example, DENACOL EX-147 (manufactured by Nagase Kasei Co., Ltd.). Among the above-mentioned epoxy compounds, other commercially available ones include, 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, jER1032 (all It is manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), etc.

Moreover, the said curable resin may contain the compound which has an epoxy group and a (meth)acryl group in 1 molecule as the said other epoxy compound. As such a compound, for example, a partial (meth)acrylic-modified epoxy resin obtained by reacting a partial epoxy group of an epoxy compound having two or more epoxy groups with (meth)acrylic acid Wait.

Among the above-mentioned partial (meth)acrylic-modified epoxy resins, as a commercially available one, for example, UVACURE 1561 (manufactured by DAICEL-ALLNEX) and the like can be cited.

Examples of the above-mentioned other (meth)acrylic compounds include epoxy (meth)acrylates obtained by reacting (meth)acrylic acid and epoxy compounds, and those obtained by reacting (meth)acrylic acid with hydroxyl groups. The (meth)acrylate compound obtained by the reaction of the compound, the (meth)acrylate amine ester obtained by reacting the isocyanate compound with the (meth)acrylic acid derivative having a hydroxyl group, etc. Among them, epoxy (meth)acrylate is preferred. In addition, the above-mentioned other (meth)acrylic compounds are preferably those having two or more (meth)acrylic groups in the molecule in terms of high reactivity. In addition, in this specification, the above-mentioned "epoxy (meth)acrylate" refers to a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid.

As said epoxy (meth)acrylate, what is obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of a basic catalyst in accordance with conventional practice, etc. are mentioned, for example.

As an epoxy compound used as a raw material for synthesizing the said epoxy (meth)acrylate, the thing similar to the other polymerizable compound mentioned above as the thing which can be contained as another epoxy compound is mentioned.

Among the above-mentioned epoxy (meth)acrylates, commercially available ones include, for example, EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3708, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX 63182 (all manufactured by DAICEL-ALLNEX), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all are Shin Nakamura Chemical Industry Co., Ltd.) Manufacturing), 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 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 Chemical Co., Ltd.), etc.

Among the above-mentioned (meth)acrylate compounds, monofunctional ones include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. Esters, 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, ( Isobornyl methacrylate, dicyclopentenyl (meth)acrylate, isobenzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyglycol (meth)acrylate, methoxypolyethylene glycol (Meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbitol (Meth)acrylate, (meth)acrylate 2,2,2-trifluoroethyl, (meth)acrylate 2,2,3,3-tetrafluoropropyl, (meth)acrylate 1H,1H, 5H-octafluoropentyl ester, imine (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)propylene succinate Acrylic oxyethyl ester, hexahydrophthalic acid 2-(meth)acrylic acid oxyethyl ester, phthalic acid 2-(meth)acrylic acid oxyethyl 2-hydroxypropyl ester, phosphoric acid 2- (Meth)acryloyloxyethyl, glycidyl (meth)acrylate, etc.

In addition, among the above-mentioned (meth)acrylate compounds, examples of bifunctional ones 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 two (Meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neoprene 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 isocyanuric acid di(meth)acrylate, (meth)acrylic acid 2-hydroxy-3-(meth)acryloxy propyl ester, carbonate glycol di(meth)acrylate, polyether glycol di(meth)acrylate, polyester glycol di(meth) Acrylate, polycaprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate, etc.

In addition, among the above-mentioned (meth)acrylate compounds, examples of trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(methyl) ) Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, Addition of propylene oxide to glycerol tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, di-trimethylolpropane tetra(methyl) ) Acrylate, neopentylerythritol tetra(meth)acrylate, dineopentol pentaerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, etc.

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

As the isocyanate compound used as the raw material of the (meth)acrylate amine ester, for example, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, Trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, toluidine diisocyanate , Xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) phosphorothioate, tetramethyl xylylene diisocyanate, 1, 6,11-Undecane triisocyanate, etc.

In addition, as the isocyanate compound used as the raw material of the aforementioned (meth)acrylate amine ester, for example, ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, and polyether diol can also be used. , Polyester diol, polycaprolactone diol and other polyols and excess isocyanate compounds obtained by the reaction of chain-extended isocyanate compounds.

Examples of (meth)acrylic acid derivatives having hydroxyl groups used as raw materials for the above-mentioned (meth)acrylate amine esters include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butane Mono(meth)acrylates of dihydric alcohols such as alcohol, 1,4-butanediol, polyethylene glycol; mono(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin ) Acrylate or di(meth)acrylate; or epoxy (meth)acrylate such as bisphenol A epoxy acrylate, etc.

Among the above-mentioned (meth)acrylate amine esters, commercially available ones include, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), 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, all manufactured by EBECRYL, NEX 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 Negami Kogyo), 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-201BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA- 7200, UA-W2A (all manufactured by Shinnakamura Chemical Industry Co., Ltd.), AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all are Kyoeisha Chemical Co., Ltd.), etc.

It is preferable that the sealing compound for liquid crystal display elements of this invention makes the content ratio of the (meth)acryl group and epoxy group in a curable resin 50:50-95:5 in molar ratio.

The sealing compound for liquid crystal display elements of this invention contains a polymerization initiator and/or a thermosetting agent. As said polymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, etc. are mentioned, for example.

Examples of the radical polymerization initiator include photoradical polymerization initiators that generate radicals by light irradiation, thermal radical polymerization initiators that generate radicals by heating, and the like.

系化合物等。Examples of the aforementioned photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, phosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, 9-Oxygen sulfur 𠮿

Department of compounds and so on.

Among the above-mentioned photoradical polymerization initiators, commercially available ones include, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all from BASF Manufacturing), NCI-930 (manufactured by ADEKA), SPEEDCURE EMK (manufactured by SiberHegner, Japan), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

Examples of the thermal radical polymerization initiator include those composed of 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. Furthermore, in this specification, the term "polymer azo compound" refers to a compound having an azo group and generating a radical that can harden the (meth)acryloyl group by heat and having a number average molecular weight of 300 or more.

The preferred lower limit of the number average molecular weight of the polymer azo initiator is 1,000, and the preferred upper limit is 300,000. When the number average molecular weight of the polymer azo initiator is in this range, liquid crystal contamination can be suppressed and it can be easily mixed with the curable resin. The lower limit of the number average molecular weight of the polymer azo initiator is more preferably 5,000, the upper limit is more preferably 100,000, the lower limit is more preferably 10,000, and the upper limit is more preferably 90,000. In addition, in this specification, the said number average molecular weight is the value calculated|required by the polystyrene conversion measured by gel permeation chromatography (GPC). As a column for measuring the number average molecular weight obtained by conversion from polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko), etc. can be cited.

Examples of the above-mentioned polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane 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 one having a polyethylene oxide structure. As such a polymer azo initiator, for example, a condensation polymer of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'-azo The polycondensate of bis(4-cyanovaleric acid) and polydimethylsiloxane having a terminal amine group, etc. Specifically, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501 , VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.), etc. In addition, examples of non-polymer azo compounds 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, diacyl peroxide, and peroxydicarbonate.

As the above-mentioned cationic polymerization initiator, a photocationic polymerization initiator can be suitably used. The above-mentioned photocationic polymerization initiator is not particularly limited as long as it generates protic acid or Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. Examples of the aforementioned photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic haloonium salts, and aromatic sulfonium salts, iron-arene complexes, titanocene complexes, aromatic Organometallic complexes such as silanol-aluminum complexes.

Among the above-mentioned photocationic polymerization initiators, commercially available ones include, for example, Adeka Optomer SP-150, Adeka Optomer SP-170 (all manufactured by ADEKA), and the like.

The content of the polymerization initiator is preferably 0.01 parts by weight, and the upper limit is preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the polymerization initiator is in this range, the obtained sealing compound for liquid crystal display elements suppresses liquid crystal contamination and is more excellent in storage stability or curability. The lower limit of the content of the polymerization initiator is more preferably 0.1 parts by weight, and the upper limit is more preferably 5 parts by weight.

As said thermosetting agent, organic acid hydrazine, imidazole derivatives, amine compounds, polyhydric phenolic compounds, acid anhydrides, etc. are mentioned, for example. Among them, organic acid hydrazine can be suitably used.

As said organic acid hydrazine, dihydrazine sebacate, dihydrazine isophthalate, dihydrazine adipic acid, dihydrazine malonate, etc. are mentioned, for example. Among the above-mentioned organic acid hydrazine, as commercially available ones, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all are Ajinomoto Fine-Techno Company manufacturing) and so on.

The content of the thermosetting agent relative to 100 parts by weight of the curable resin has a preferred lower limit of 1 part by weight, and a preferred upper limit of 50 parts by weight. When the content of the thermosetting agent is in this range, it is possible to make it more excellent in thermosetting without deteriorating the coatability and the like of the obtained sealing compound for liquid crystal display elements. The more preferable upper limit of the content of the thermal hardening agent is 30 parts by weight.

In order to increase the viscosity, improve the adhesiveness obtained by the stress dispersion effect, improve the linear expansion rate, and improve the moisture permeability of the cured product, the sealing compound for liquid crystal display elements of the present invention preferably contains a filler.

Examples of the above-mentioned fillers include: silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, Inorganic fillers such as magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc., or polyester microparticles, polyurethane microparticles, Organic fillers such as vinyl polymer particles and acrylic polymer particles.

The lower limit of the content of the filler in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is preferably 10 parts by weight, and the upper limit is preferably 70 parts by weight. When the content of the filler is in this range, the effect of improving adhesiveness and the like is more excellent without deterioration of coatability and the like. The lower limit of the filler content is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.

It is preferable that the sealing compound for liquid crystal display elements of this invention contains a silane coupling agent. The above-mentioned silane coupling agent mainly functions as an adhesion auxiliary agent for good adhesion between the sealant and the substrate.

As the above-mentioned silane coupling agent, it is excellent in the effect of improving the adhesion to the substrate, etc., and can inhibit the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin, for example, 3- Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc.

The lower limit of the content of the silane coupling agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is preferably 0.1 parts by weight, and the upper limit is preferably 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 adhesion is more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.3 parts by weight, and the upper limit is more preferably 5 parts by weight.

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

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 above-mentioned titanium black is a substance that has a higher transmittance in the vicinity of the ultraviolet region, especially light with a wavelength of 370 to 450 nm, compared to the average transmittance of light with a wavelength of 300 to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent that imparts light-shielding properties to the sealing compound for liquid crystal display elements of the present invention by sufficiently shielding light of wavelengths in the visible light region, and has a property of transmitting light of wavelengths in the vicinity of the ultraviolet region. As the light-shielding agent contained in the sealing compound for liquid crystal display elements of the present invention, a substance with high insulation is preferable, and as a light-shielding agent with high insulation, titanium black is also preferable.

Although the above-mentioned titanium black has full effect without surface treatment, it can also be used with the surface treated with organic components such as coupling agents, or inorganic materials such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide. Titanium black with surface-treated components such as coated ones. Among them, those treated with organic components are preferable in terms of further improving insulation. In addition, the liquid crystal display element manufactured using the sealant for liquid crystal display element of the present invention containing the titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore can achieve no light leakage, high contrast, and excellent The image display quality of the liquid crystal display element.

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

The preferred lower limit of the specific surface area of the titanium black is 13 m ² /g, the preferred upper limit is 30 m ² /g, the more preferred lower limit is 15 m ² /g, and the more preferred upper limit is 25 m ² /g. In addition, the lower limit of the volume resistance of the titanium black is preferably 0.5 Ω･cm, the upper limit is preferably 3 Ω･cm, the lower limit is more preferably 1 Ω･cm, and the upper limit is more preferably 2.5 Ω･cm.

The primary particle size of the aforementioned light-shielding agent is not particularly limited as long as it is less than the distance between the substrates of the liquid crystal display element, and the preferred lower limit is 1 nm, and the preferred upper limit is 5000 nm. When the primary particle diameter of the said light-shielding agent is this range, it can be set as the thing with more excellent light-shielding property without worsening the coatability etc. of the sealing compound for liquid crystal display elements obtained. The lower limit of the primary particle size of the sunscreen is more preferably 5 nm, the upper limit is more preferably 200 nm, the lower limit is still more preferably 10 nm, and the upper limit is more preferably 100 nm. In addition, the primary particle size of the sunscreen can be measured by dispersing the sunscreen in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The lower limit of the content of the light-shielding agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is preferably 5 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the above-mentioned light-shielding agent is in this range, it is possible to exhibit more excellent light-shielding properties without reducing the adhesion of the obtained liquid crystal display element sealant to the substrate, the strength after curing, or the drawing properties. The lower limit of the content of the sunscreen is more preferably 10 parts by weight, the upper limit is more preferably 70 parts by weight, the lower limit is still more preferably 30 parts by weight, and the upper limit is more preferably 60 parts by weight.

The sealing compound for liquid crystal display elements of the present invention may further contain a stress reliever, a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, a defoamer, a leveling agent, a polymerization inhibitor, other additives, etc., if necessary.

As a method of manufacturing the sealant for liquid crystal display elements of the present invention, for example, mixing machines such as homodispersers, homomixers, universal mixers, planetary mixers, kneaders, and three-roll mills can be used to combine the curable resin, A method of mixing polymerization initiators and/or thermal hardeners, and optionally silane coupling agents and other additives.

By blending conductive fine particles in the sealing compound for liquid crystal display elements of the present invention, a vertical conduction material can be manufactured. In addition, such an upper and lower conduction material containing the sealing compound for liquid crystal display elements of the present invention and conductive fine particles is also one type of the present invention.

As the above-mentioned conductive fine particles, metal balls and resin fine particles having a conductive metal layer formed on the surface can be used. Among them, those with a conductive metal layer formed on the surface of the resin microparticles are suitable because of the excellent elasticity of the resin microparticles, which can be electrically connected without damaging the transparent substrate or the like.

Moreover, the liquid crystal display element which has the sealing compound for liquid crystal display elements of this invention or the top and bottom conduction material of this invention is also 1 type of this invention.

As a method of manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method can be suitably used. Specifically, for example, a method having the following steps: on one of two substrates such as a glass substrate with electrodes, such as an ITO film, or a polyethylene terephthalate substrate, by screen printing and separation The step of applying the sealant for liquid crystal display elements of the present invention by means of injector coating to form a frame-shaped seal pattern; when the sealant for liquid crystal display elements of the present invention is in an uncured state, it is on the substrate of the sealing pattern The step of dropping and coating tiny droplets of liquid crystal in the frame and superimposing another substrate under vacuum; the step of irradiating the sealing pattern part of the sealant for liquid crystal display element of the present invention with light such as ultraviolet light to temporarily harden the sealant; and The temporarily hardened sealant is heated to formally harden. [Effects of Invention]

According to the present invention, it is possible to provide a sealing compound for liquid crystal display elements which is excellent in adhesiveness and moisture permeability and can suppress liquid crystal contamination. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealing compound for liquid crystal display elements.

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

(Production of ε-caprolactone modified dineopentaerythritol hexaacrylate A) Make 25.4 parts by weight (0.1 mol) of dineopentaerythritol and 68.4 parts by weight (0.6 mol) of ε-caprolactone, acrylic acid To react with 43.2 parts by weight (0.6 mol), 0.01 parts by weight of hydroquinone as a polymerization inhibitor, 0.1 parts by weight of p-toluenesulfonic acid as a catalyst, and propylene glycol methyl ether acetate as a solvent were added to the flask ( PGMEA) 200 parts by weight, heated while circulating nitrogen gas. After reacting in an oil bath at 120°C for 6 hours, it was left to cool to room temperature, thereby obtaining ε-caprolactone-modified dineopentaerythritol hexaacrylate A as the polymerizable compound of the present invention. According to ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained ε-caprolactone-modified dineopentaerythritol hexaacrylate A is the l, m, and n in the above formula (1) , O, p, and q are 1 compounds.

(Production of ε-caprolactone modified dineopentaerythritol hexaacrylate B) Make 25.4 parts by weight (0.1 mol) of dineopentaerythritol and 137 parts by weight (1.2 mol) of ε-caprolactone, acrylic acid To react with 43.2 parts by weight (0.6 mol), 0.01 parts by weight of hydroquinone as a polymerization inhibitor, 0.1 parts by weight of p-toluenesulfonic acid as a catalyst, and propylene glycol methyl ether acetate as a solvent were added to the flask ( PGMEA) 200 parts by weight, heated while circulating nitrogen gas. After reacting in an oil bath at 120°C for 6 hours, it was left to cool to room temperature, thereby obtaining ε-caprolactone-modified dineopentaerythritol hexaacrylate B as the polymerizable compound of the present invention. According to ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained ε-caprolactone-modified dineopentaerythritol hexaacrylate B is the l, m, and n in the above formula (1) , O, p, and q are 2 compounds.

(Production of carboxylic acid addition ε-caprolactone modified neopentyl erythritol triacrylate) Add ε-caprolactone modified neopentyl erythritol triacrylate into the flask (reacted by reacting 1 mol of neopentyl erythritol with 8 mol of ε-caprolactone, and then esterifying with 3 mol of acrylic acid. The compound) 20 parts by weight (16.8 mmol), 1.98 parts by weight (16.8 mmol) of succinic anhydride as an acid anhydride, 0.01 parts by weight of hydroquinone as a polymerization inhibitor, and propylene glycol methyl ether acetate (PGMEA) as a solvent 20 parts by weight, heated while flowing nitrogen gas. Next, when the succinic anhydride is completely dissolved, 0.02 parts by weight of triethylamine as a catalyst is added, and after reacting in an oil bath at 120°C for 6 hours in a nitrogen environment, it is left to cool to room temperature to obtain the product of the present invention. The carboxylic acid addition of polymerizable compound ε-caprolactone modified neopentyl erythritol triacrylate.

(Examples 1 to 10 and Comparative Examples 1 to 5) According to the mixing ratios described in Tables 1 and 2, the materials were mixed with a planetary mixer (manufactured by Thinky, "Defoaming Stir Taro"), and then mixed with a three-roll mill to prepare Example 1 ~10, and the sealing compound for liquid crystal display elements of Comparative Examples 1 to 5.

＜Evaluation＞ The following evaluation was performed about the sealing compound for liquid crystal display elements obtained in an Example and a comparative example. The results are shown in Tables 1 and 2.

(Storage stability) Regarding each liquid crystal display element sealing compound obtained in the Examples and Comparative Examples, the initial viscosity immediately after manufacture and the viscosity when stored at 25°C for 1 week were measured, and (25°C, the viscosity after storage for 1 week) / (Initial viscosity) is the rate of change of viscosity. If the rate of change of viscosity is less than 1.1, it will be rated as "○", if it is 1.1 or more and less than 2.0, it is rated as "△", and if it is 2.0 or more, it is rated as "×" , Thereby evaluating storage stability. Furthermore, the viscosity of the sealant was measured using an E-type viscometer (manufactured by BROOK FIELD, "DV-III") at 25°C and a rotation speed of 1.0 rpm.

(Adhesion) For 100 parts by weight of each liquid crystal display element sealant obtained in the examples and comparative examples, spacer particles with an average particle diameter of 5 μm (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SP-2050”) 1 part by weight is evenly dispersed, and a very small amount is placed in the center of Corning Glass 1737 (20 mm×50 mm×thickness 0.7 mm), and the same type of glass is superimposed on it to unfold the liquid crystal display element. ^{The sealant was irradiated with ultraviolet light of 100 mW/cm 2 for} 30 seconds using a metal halide lamp, and then heated at 120° C. for 1 hour to harden the sealant to obtain an adhesive test piece. For the obtained adhesive test piece, the adhesive strength was measured using a tensiometer. The case where the bonding strength is 330 N/cm ² or more is rated as "◎", and the case where the ^{bonding strength is more than 300 N/cm 2} and less than 330 N/cm ² is rated as "〇", and the bonding strength is 270 N/cm ^{The case of 2} or more and less than 300 N/cm ² was rated as "△", and the case of bonding strength less than 270 N/cm ² was rated as "×" to evaluate the adhesion.

(Anti-moisture permeability) The sealants for liquid crystal display elements obtained in the examples and comparative examples were applied in a smooth release film with a thickness of 200 to 300 μm using a coater, and then irradiated with a metal halide lamp for 30 After 100 mW/cm ² of ultraviolet rays per second, it was heated at 120°C for 1 hour to obtain a cured film for measuring moisture permeability. Use the method based on JIS Z 0208 to test the moisture permeability of moisture-proof packaging materials (cup method) to make a moisture permeability test cup, install the obtained cured film for moisture permeability measurement, and put it at a temperature of 80°C and a humidity of 90% Measure the moisture permeability in a constant temperature and humidity oven of RH. The case where the obtained moisture permeability value is less than 50 g/m ² ･24 hr is rated as "〇", and the case ^{where the obtained value of moisture permeability is less than 50 g/m 2} ･24hr and less than 70 g/m ² ･24hr is rated as "△", the case of 70 g/m ² ･24hr or more was rated as "×" to evaluate the moisture permeability.

(Display performance of liquid crystal display element (low liquid crystal contamination)) For 100 parts by weight of each liquid crystal display element sealant obtained in the examples and comparative examples, a spacer with an average particle diameter of 5 μm was made by a planetary stirring device Particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SP-2050") are uniformly dispersed in 1 part by weight, and the obtained sealant is filled into a dispensing syringe (manufactured by Musashi High-Tech Co., Ltd., "PSY-10E"). After the defoaming treatment, a dispenser (manufactured by Wu Zou High-Tech Co., "SHOTMASTER 300") is used to apply the sealant in a frame shape on one of the two transparent electrode substrates with ITO film. Then, the tiny drops of TN liquid crystal (manufactured by Chisso, "JC-5001LA") were dropped using a liquid crystal dropping device and applied to the frame of the sealant, and another transparent was laminated using a vacuum laminating device under a vacuum of 5 Pa The electrode substrate, and the unit is obtained. ^{After irradiating the obtained cell with ultraviolet rays of 100 mW/cm 2 for} 30 seconds using a metal halide lamp, it was heated at 120° C. for 1 hour to harden the sealant, and a liquid crystal display element was obtained. Regarding the obtained liquid crystal display element, visually observe the display unevenness on the liquid crystal around the sealing part (especially the corner part). The case where the display unevenness is not confirmed is rated as "〇", and a slight display unevenness is confirmed The case was rated as "△", and the case where serious display unevenness was confirmed was rated as "×" to evaluate the display performance of the liquid crystal display element (low liquid crystal contamination).

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 Composition (parts by weight) Hardening resin The polymerizable compound of the present invention ε-Caprolactone modified dineopentaerythritol hexaacrylate A 1 10 30 50 - - - - 10 10 ε-Caprolactone modified dineopentaerythritol hexaacrylate B - - - - 10 50 60 - - - Carboxylic acid addition ε-caprolactone modified neopentyl erythritol triacrylate - - - - - - - 10 - - Other polymeric compounds Dineopentaerythritol hexaacrylate (manufactured by DAICEL-ALLNEX, "DPHA") - - - - - - - - - - Bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL 3700") 69 60 40 20 60 20 10 60 60 60 ε-Caprolactone modified bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL 3708") - - - - - - - - - - Partial acrylic modified bisphenol E epoxy resin (manufactured by DAICEL-ALLNEX, "KRM8287") 30 30 30 30 30 30 30 30 30 30 Light radical polymerization initiator 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzyloxime) (manufactured by BASF Corporation, "IRGACURE OXE01") 2 2 2 2 2 2 2 2 2 2 Thermal radical polymerization initiator Polymer azo initiator (manufactured by Wako Pure Chemical Industries, Ltd., "VPE-0201") 5 5 5 5 5 5 5 5 - 5 Thermal hardener Dihydrazine malonate (manufactured by Otsuka Chemical Co., "MDH", melting point 150°C) 10 10 10 10 10 10 10 10 10 10 Filler Silicon dioxide (manufactured by Admatechs, "Admafine SO-C2") 20 20 20 20 20 20 20 20 20 - Silane coupling agent 3-Glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403") 2 2 2 2 2 2 2 2 2 2 Stress reliever Core-shell acrylate copolymer particles (manufactured by ZEON Chemical Co., Ltd., "F351") 15 15 15 15 15 15 15 15 15 15 Sunscreen Titanium black (manufactured by Mitsubishi Materials Corporation, "14M-C") - - - - - - - - - 20 Evaluation Storage stability 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Continuity 〇 〇 ◎ ◎ 〇 ◎ ◎ 〇 〇 〇 Anti-moisture permeability 〇 〇 〇 〇 〇 △ △ 〇 〇 〇 Display performance of liquid crystal display element (low liquid crystal pollution) 〇 〇 〇 〇 〇 〇 △ 〇 〇 〇

[Table 2] Comparative example 1 2 3 4 5 Composition (parts by weight) Hardening resin The polymerizable compound of the present invention ε-Caprolactone modified dineopentaerythritol hexaacrylate A - - - - - ε-Caprolactone modified dineopentaerythritol hexaacrylate B - - - - - Carboxylic acid addition ε-caprolactone modified neopentyl erythritol triacrylate - - - - - Other polymeric compounds Dineopentaerythritol hexaacrylate (manufactured by DAICEL-ALLNEX, "DPHA") - 1 10 50 - Bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL 3700") 70 69 60 20 60 ε-Caprolactone modified bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL 3708") - - - - 10 Partial acrylic modified bisphenol E epoxy resin (manufactured by DAICEL-ALLNEX, "KRM8287") 30 30 30 30 30 Light radical polymerization initiator 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzyloxime) (manufactured by BASF Corporation, "IRGACURE OXE01") 2 2 2 2 2 Thermal radical polymerization initiator Polymer azo initiator (manufactured by Wako Pure Chemical Industries, Ltd., "VPE-0201") 5 5 5 5 5 Thermal hardener Dihydrazine malonate (manufactured by Otsuka Chemical Co., "MDH", melting point 150°C) 10 10 10 10 10 Filler Silicon dioxide (manufactured by Admatechs, "Admafine SO-C2") 20 20 20 20 20 Silane coupling agent 3-Glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") 2 2 2 2 2 Stress reliever Core-shell acrylate copolymer particles (manufactured by ZEON Kasei Co., Ltd., "F351") 15 15 15 15 15 Sunscreen Titanium black (manufactured by Mitsubishi Materials Corporation, "14M-C") - - - - - Evaluation Storage stability 〇 〇 〇 〇 〇 Continuity X X X X X Anti-moisture permeability 〇 〇 〇 〇 X Display performance of liquid crystal display element (low liquid crystal pollution) 〇 〇 〇 〇 〇 [Industrial availability]

According to the present invention, it is possible to provide a sealing compound for liquid crystal display elements which is excellent in adhesiveness and moisture permeability and can suppress liquid crystal contamination. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealing compound for liquid crystal display elements.

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Claims (9)

A sealing compound for liquid crystal display elements, which contains a curable resin, a polymerization initiator and/or a thermosetting agent, and is characterized in that: The said curable resin contains a compound which has 3 or more polymerizable functional groups and 1 or more ε-caprolactone ring-opened structure in 1 molecule, and does not have a cyclic structure. For example, the sealing compound for liquid crystal display element of the first item of the scope of patent application, which has 3 or more polymerizable functional groups and 1 or more ε-caprolactone ring-opening structure in one molecule, and does not have a cyclic ring The polymerizable functional group possessed by the compound of the structure is a (meth)acryloyl group. For example, the sealing compound for liquid crystal display elements of the first or second patent application, which has 3 or more polymerizable functional groups and 1 or more ε-caprolactone ring-opening structure in one molecule, and does not have The cyclic structure compound has two or more ε-caprolactone ring-opening structures in one molecule. For example, the sealing compound for liquid crystal display elements of the third item of the scope of patent application, which has 3 or more polymerizable functional groups and 1 or more ε-caprolactone ring-opening structure in one molecule, and does not have a cyclic ring The structure of the compound has more than 4 ε-caprolactone ring-opening structures in one molecule. For example, the sealing compound for liquid crystal display elements of 1, 2, 3, or 4 in the scope of patent application, which has 3 or more polymerizable functional groups and 1 or more ε-caprolactone ring-opening structure in one molecule And a compound that does not have a cyclic structure has one or more hydrogen-bonding functional groups in one molecule. For example, the first, second, third, fourth, or fifth sealant for liquid crystal display elements in the scope of patent application, which has 3 or more polymerizable functional groups and 1 or more ε-caprolactone in one molecule. A compound having a ring structure and not having a ring structure has a dendrimer structure. For example, the first, second, third, fourth, fifth, or sixth sealant for liquid crystal display elements in the scope of the patent application, in which 100 parts by weight of the curable resin has 3 or more polymerizable functional groups in one molecule and 1 The content of the compound having more than one ε-caprolactone ring-opening structure and not having a cyclic structure is 1 to 80 parts by weight. An up-and-down conduction material containing the sealing compound for liquid crystal display elements of the 1, 2, 3, 4, 5, 6 or 7 patent application range and conductive fine particles. A liquid crystal display element, which has the sealant for liquid crystal display elements of the 1, 2, 3, 4, 5, 6 or 7 patent applications or the upper and lower conductive materials of the 8 patent applications.