TWI746654B - Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

The object of the present invention is to provide a sealing compound for a liquid crystal display element that can suppress the penetration of the sealant due to the liquid crystal or the contamination of the liquid crystal caused by the sealant. 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.

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 polymerizable functional group represented by the following formula (1) The structure of the compound.

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 that can suppress penetration of a sealant caused by liquid crystals or contamination of liquid crystals caused by the sealant. In addition, the present invention relates to an upper and lower conduction material and a liquid crystal display element using this sealant for liquid crystal display elements.

In recent years, as a method of manufacturing liquid crystal display elements such as liquid crystal display units, from the viewpoints of shortening the tact time (Tact Time) and optimizing the amount of liquid crystal used, the methods disclosed in Patent Document 1 and Patent Document 2 have been used. The liquid crystal dropping method called the dropping method uses light and heat combined with a hardening type sealant containing a curable resin, a photopolymerization initiator, and a thermosetting agent.

In the dropping method, first, a rectangular sealing pattern is formed on one of the two transparent substrates with electrodes by dispensing. Next, the liquid crystal droplets are dropped onto the entire surface of the transparent substrate frame while the sealant is not hardened, and immediately overlap with another transparent substrate, and the sealing portion is irradiated with light such as ultraviolet rays to temporarily harden. After that, heating is performed during the annealing of the liquid crystal to perform main curing, thereby producing a liquid crystal display element. If the substrates are bonded under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency. At present, the dropping method has become the mainstream of the manufacturing method of the liquid crystal display element.

In addition, as various mobile devices with LCD panels, such as mobile phones and portable game consoles, have become popular nowadays, miniaturization of the devices is the most demanded issue. As a method of miniaturization, the narrow edge of the liquid crystal display portion can be cited, for example, the position of the sealing portion is arranged under the black matrix (hereinafter, also referred to as "narrow edge design").

However, if a liquid crystal display element with a narrow edge design is manufactured by the dropping method, there are situations where there is a part of the sealing part that is not exposed to light due to the black matrix, and therefore a part where the photocuring is not fully progressed, resulting in an uncured sealant. Contact with liquid crystal. In this case, there are the following problems: the liquid crystal penetrates into the sealant, resulting in a seal break and the liquid crystal leaks; or the uncured sealant elutes into the liquid crystal and contaminates the liquid crystal.

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2001-133794

Patent Document 2: International Publication No. 02/092718

The present invention relates to a sealant for liquid crystal display elements that can suppress penetration of a sealant caused by liquid crystals or contamination of liquid crystals caused by the sealant. 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.

The present invention is a sealing compound for liquid crystal display elements, which contains a curable resin, a polymerization initiator and/or a thermal curing agent, and the curable resin contains a polymer having a polymerizable functional group and a structure represented by the following formula (1) Compound.

The present invention will be described in detail below.

The present inventors discovered that by using a compound having a specific structure as a curable resin, a sealing compound for liquid crystal display elements that can suppress penetration of the sealant due to liquid crystal or contamination of liquid crystal caused by the sealant can be obtained, thereby completing the present invention.

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

The curable resin contains a compound having a polymerizable functional group and a structure represented by the formula (1) (hereinafter, also 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 becomes a thing which can suppress the penetration of a sealing compound by a liquid crystal, or the contamination of liquid crystal by a sealing compound.

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

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

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

In addition, in this specification, the above-mentioned "(meth)acryloyl group" means an acryloyl group or a methacryloyl group.

The preferred lower limit of the molecular weight of the polymerizable compound of the present invention is 300, and the preferred upper limit is 4000. When the molecular weight of the polymerizable compound of the present invention is in this range, the coating properties and the like are not deteriorated, and the obtained sealant for liquid crystal display elements can suppress the penetration of the sealant caused by the liquid crystal or the contamination of the liquid crystal caused by the sealant The effect is better. Furthermore, in this specification, for compounds with a specific molecular structure, the above-mentioned "molecular weight" is the molecular weight obtained from the structural formula, but for compounds with a wide distribution of degree of polymerization and compounds with unspecified modified sites, it is used The case where the weight average molecular weight is expressed. In this specification, the above-mentioned "weight average molecular weight" is a value determined by gel permeation chromatography (GPC) and calculated in terms of polystyrene. As the column used when measuring the weight average molecular weight converted from polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) can be cited.

The above-mentioned curable resin preferably contains the polymerizable compound of the present invention as well as other polymerizable compounds from the viewpoints of adhesiveness, moisture permeability resistance, and the like.

When the above-mentioned other polymerizable compound is contained, the lower limit of the content of the polymerizable compound of the present invention in 100 parts by weight of the curable resin is preferably 1 part by weight, and the upper limit is preferably 50 parts by weight. When the content of the polymerizable compound of the present invention is in this range, the adhesiveness, moisture permeability, and the like are not deteriorated, and the obtained sealing compound for liquid crystal display elements can suppress the penetration of the liquid crystal caused by the sealing compound or the sealing compound The liquid crystal pollution caused by the effect is more excellent. The lower limit of the content of the polymerizable compound of the present invention is more preferably 2 parts by weight, the upper limit is more preferably 45 parts by weight, and the lower limit is more preferably 20 parts by weight.

As the above-mentioned other polymerizable compound, other epoxy compounds or other (meth)acrylic compounds other than those included in the polymerizable compound of the present invention can be cited. Among them, it is preferable to use another epoxy compound in combination with an imidazole-based thermosetting agent in terms of the effect of suppressing the penetration of the sealant due to the liquid crystal or the contamination of the liquid crystal due to the sealant more excellent.

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 Vinyl novolac type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin , Glycidyl ester compounds, etc.

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

Examples of commercially available bisphenol F epoxy resins include jER806, jER4004 (all manufactured by Mitsubishi Chemical Corporation) and the like.

Examples of commercially available bisphenol E epoxy resins include R710 (manufactured by Printec) and the like.

As a commercially available one among the said bisphenol S type epoxy resin, EPICLON EXA1514 (made by DIC Corporation) etc. are mentioned, for example.

As a commercially available one among the above-mentioned 2,2'-diallyl bisphenol A epoxy resins, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) and the like can be cited.

As a commercially available one among the said hydrogenated bisphenol-type epoxy resin, EPICLON EXA7015 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial one among the said propylene oxide addition bisphenol A type epoxy resin, EP-4000S (made by ADEKA company) etc. are mentioned, for example.

As a commercially available one among the above-mentioned resorcinol-type epoxy resins, EX-201 (manufactured by Nagase ChemteX) etc. are mentioned, for example.

As a commercial item among the said biphenyl type epoxy resin, jER YX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

Examples of commercially available sulfide epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.

As a commercially available one among the above-mentioned diphenyl ether type epoxy resins, for example, YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be cited.

As a commercially available one among the above-mentioned dicyclopentadiene-type epoxy resins, EP-4088S (manufactured by ADEKA Corporation) etc. are mentioned, for example.

As commercially available 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 cited.

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

As a commercial item among the said ortho-cresol novolak type epoxy resin, EPICLON N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.

As a commercially available one among the said dicyclopentadiene novolak type epoxy resins, EPICLON HP7200 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item among the said biphenol novolak type epoxy resin, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

As a commercially available one among the above-mentioned naphthol novolak type epoxy resins, for example, ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be cited.

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

Examples of commercially available alkyl polyol type epoxy resins include: ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EPICLON726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) , DENACOL EX-611 (manufactured by Nagase ChemteX), etc.

As commercially available ones among the above-mentioned rubber-modified epoxy resins, for example, YR-450, YR-207 (both are manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Epolead PB (manufactured by Daicel), and the like.

As a commercial item among the said glycidyl ester compounds, DENACOL EX-147 (manufactured by Nagase ChemteX) etc. are mentioned, for example.

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

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

As said other (meth)acrylic compound, epoxy (meth)acrylate, (meth)acrylate compound, (meth)acrylate amine ester, etc. are mentioned, for example. Among them, epoxy (meth)acrylate is preferred. Moreover, in terms of the level of reactivity, the other (meth)acrylic compound described above is preferably one having two or more (meth)acrylic groups in the molecule.

Furthermore, in this specification, the above-mentioned "(meth)acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" means using one of the epoxy compounds A compound formed by the reaction of all epoxy groups with (meth)acrylic acid.

As said epoxy (meth)acrylate, the thing obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of a basic catalyst according to a conventional method, etc. are mentioned, for example.

The epoxy compound used as a raw material for synthesizing the epoxy (meth)acrylate may be the same as "the other epoxy compound that may be contained as the other polymerizable compound".

As commercially available among the above-mentioned epoxy (meth)acrylates, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, and EBECDALICELDX63 ALLNEX Corporation); EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shinnakamura Chemical Industry Co., Ltd.); Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.); DENACOL Acrylate DA-141, DENACOL Acrylate DA-314, DENACOL Acrylate DA-911 (all manufactured by Nagase ChemteX) and the like.

Examples of monofunctional ones in the above-mentioned (meth)acrylate compounds include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , Isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol ( Meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylate 1H, 1H, 5H -Otafluoropentyl ester, imine (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acrylic acid succinate Oxyethyl, hexahydrophthalic acid 2-(meth)acryloyloxyethyl, 2-hydroxypropyl phthalate 2-(meth)acryloyloxyethyl, phosphoric acid 2-(meth) Yl)acryloxyethyl, glycidyl (meth)acrylate and the like.

In addition, examples of the bifunctional one of the (meth)acrylate compounds described above 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-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl diacrylate 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 diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth) Acrylate, polycaprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate, etc.

In addition, examples of the above-mentioned (meth)acrylate compounds having three or more functions include trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(methyl) )Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modification trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid Acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, phosphoric acid tri(meth) Acrylic oxyethyl, di-trimethylolpropane tetra(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopentyl pentaerythritol penta(meth)acrylate, dineopentyl Tetraol hexa(meth)acrylate and the like.

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

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

In addition, as the above-mentioned isocyanate compound, for example, a chain-extended isocyanate compound obtained by the reaction of a polyol and an excess isocyanate compound can also be used.

Examples of the above-mentioned polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.

Examples of the (meth)acrylic acid derivative having a hydroxyl group include: hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of dihydric alcohol, and mono(meth)acrylic acid of trihydric alcohol Ester or di(meth)acrylate, epoxy (meth)acrylate, etc.

As the above-mentioned hydroxyalkyl mono(meth)acrylate, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (Meth) 4-hydroxybutyl acrylate and the like.

As said diol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc. are mentioned, for example.

As said triol, trimethylolethane, trimethylolpropane, glycerol, etc. are mentioned, for example.

As said epoxy (meth)acrylate, bisphenol A type epoxy acrylate etc. are mentioned, for example.

Examples of commercially available amine (meth)acrylates include: M-1100, M-1200, M-1210, and 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, EBECRYL 9260 (all manufactured by NEXDAICEL); 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 Nekami 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-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA- 7200, UA-W2A (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.); AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all Kyoeisha Chemical Co., Ltd.), etc.

It is preferable that the sealing compound for liquid crystal display elements of this invention sets the content ratio of the (meth)acryl group and epoxy group in a curable resin to 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.

(thioxanthone)系化合物等。 Examples of the aforementioned photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, acetoxyphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, 9-oxysulfur

(thioxanthone) series compounds, etc.

Commercially available photo-radical polymerization initiators include, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, IRGACURE OXE02, Lucirin TPO (all are BASF Corporation); NCI-930 (ADEKA Corporation); SPEEDCURE EMK (Nihon SiberHegner Corporation); 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.

In addition, the term "polymer azo compound" in the present specification means 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 above-mentioned polymer azo compound is 1,000, and the preferred upper limit is 300,000. By setting the number average molecular weight of the polymer azo compound 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 above-mentioned polymer azo compound is more preferably 5,000, the upper limit is more preferably 100,000, the lower limit is still 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 converted from polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) can be cited.

Examples of the above-mentioned polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group.

As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group, one having a polyethylene oxide structure is preferred. As such a polymer azo compound, for example, a condensation polymer of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'-azobis( 4-cyanovaleric acid) and polydimethylsiloxane with terminal amine group, etc.

Examples of commercially available ones among the above-mentioned polymer azo compounds include: VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

In addition, examples of azo compounds that are not polymers include V-65, V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

Examples of the above-mentioned organic peroxide include: ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, Peroxydicarbonate and so on.

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

Examples of the aforementioned photocationic polymerization initiator include onium salts such as aromatic diazonium, aromatic haloonium salt, and aromatic sulfonium salt; iron-arene complexes, titanocene complexes, and aryl groups. Organometallic complexes such as silanol-aluminum complexes, etc.

As a commercially available one among the above-mentioned photocationic polymerization initiators, for example, Adeka Optomer SP-150, Adeka Optomer SP-170 (all manufactured by ADEKA), etc. can be cited.

Regarding the content of the polymerization initiator, the lower limit is preferably 0.01 parts by weight, and the upper limit is preferably 10 parts by weight relative 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 mentioned above, it is preferable to use the sealing compound for liquid crystal display elements of this invention in combination of the said other epoxy compound and an imidazole-type thermosetting agent.

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

、2,4-二胺基-6-(2'-甲基咪唑基-(1'))-乙基-對稱三

異三聚氰酸加成物等。 Examples of the imidazole-based thermosetting agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-benzene. Imidazolium trimellitate, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-symmetric three

, 2,4-Diamino-6-(2'-methylimidazolyl-(1'))-ethyl-symmetric three

Isocyanuric acid adducts, etc.

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

As the above-mentioned adduct type curing agent, for example, an adduct obtained by the reaction of an imidazole compound with an epoxy compound or the like can be cited.

As commercially available among the above-mentioned adduct type hardeners, for example, Amicure PN-23, Amicure PN-23J, Amicure PN-H, Amicure PN-31, Amicure PN-31J, Amicure PN-40, Amicure PN-40J, Amicure PN-50, Amicure PN-F, Amicure MY-24, Amicure MY-H (all manufactured by Ajinomoto Fine-Techno); P-0505 (manufactured by Shikoku Chemical Industry Co., Ltd.); P-200 ( Mitsubishi Chemical Corporation), etc.

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

As said organic acid hydrazine, dihydrazine sebacate, dihydrazine isophthalate, dihydrazine adipic acid, dihydrazine malonate, etc. are mentioned, for example.

Examples of commercially available organic acid hydrazine include: 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 manufacturing) and so on.

Regarding the content of the thermosetting agent, with respect to 100 parts by weight of the curable resin, the lower limit is preferably 1 part by weight, and the upper limit is preferably 50 parts by weight. By making the content of the said thermosetting agent into this range, the coating property etc. of the sealing compound for liquid crystal display elements obtained are not deteriorated, and it can be set as the thing with more excellent thermosetting property. The more preferable upper limit of the content of the thermal hardening agent is 30 parts by weight.

From the viewpoint of improving the flexibility or adhesiveness of the cured product, or making the effect of inhibiting the penetration of the liquid crystal into the sealing compound or the elution of the sealing compound into the liquid crystal more excellent, the sealing compound for liquid crystal display elements of the present invention preferably contains soft particles .

Examples of the above-mentioned flexible particles include silicone-based particles, ethylene-based particles, urethane-based particles, fluorine-based particles, and nitrile-based particles. Among them, polysiloxane-based particles and ethylene-based particles are preferred.

As the above-mentioned silicone-based particles, silicone rubber particles are preferred from the viewpoint of dispersibility in the resin.

As the above-mentioned ethylene-based particles, (meth)acrylic particles can be preferably used.

The above-mentioned (meth)acrylic particles can be obtained by polymerizing monomers used as raw materials by a known method. Specifically, for example, a method of suspension polymerization of monomers in the presence of a radical polymerization initiator; and a method of making non-crosslinked seed particles absorb the monomer in the presence of a radical polymerization initiator. Seed particles swell to carry out seed polymerization, etc.

Examples of the monomers used to form the raw materials for the (meth)acrylic particles include: alkyl (meth)acrylates, oxygen-containing (meth)acrylates, nitrile-containing monomers, and fluorine-containing Monofunctional monomers such as (meth)acrylates.

As the above-mentioned alkyl (meth)acrylates, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate Base) hexyl acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate Esters, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, etc.

Examples of (meth)acrylates containing oxygen atoms include: 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, (methyl) ) Glycidyl acrylate, etc.

As said nitrile-containing monomer, (meth)acrylonitrile etc. are mentioned, for example.

As said fluorine-containing (meth)acrylates, trifluoromethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, etc. are mentioned, for example.

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

Furthermore, in order to have a crosslinked structure, tetramethylolmethane tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, dineopentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, diglycerol (Meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)tetramethylene di(meth)acrylate, 1, Multifunctional monomers such as 4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and isocyanuric acid skeleton tri(meth)acrylate. Among them, (poly)ethylene glycol bis(meth)acrylate and (poly)propylene glycol bis(meth)acrylate are preferred in terms of having a large molecular weight between crosslinking points and increasing the amount of deformation when a load of 1g is applied. Base) acrylate, (poly)tetramethylene di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate.

Regarding the amount of the crosslinkable monomer used, in the entire monomer used as the raw material for forming the (meth)acrylic particles, the lower limit is preferably 1% by weight, and the upper limit is preferably 90% by weight. By setting the usage amount of the above-mentioned crosslinkable monomer to 1% by weight or more, the solvent resistance is improved, and it is easy to uniformly disperse without causing problems such as swelling when kneading with various sealant raw materials. By making the use amount of the above-mentioned crosslinkable monomer 90% by weight or less, the recovery rate can be reduced. A more preferable lower limit of the amount of the crosslinkable monomer used is 3% by weight, and a more preferable upper limit is 80% by weight.

Furthermore, in addition to these acrylic monomers, styrenic monomers, vinyl ethers, vinyl carboxylates, unsaturated hydrocarbons, halogen-containing monomers, triallyl cyanurate, isotriene monomers can also be used. Triallyl cyanate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ-(meth)propylene Monomers such as oxypropyl trimethoxysilane and vinyl trimethoxysilane.

As said styrene-type monomer, styrene, α-methylstyrene, trimethoxysilyl styrene, etc. are mentioned, for example.

As said vinyl ethers, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, etc. are mentioned, for example.

As said vinyl carboxylates, vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, etc. are mentioned, for example.

As said unsaturated hydrocarbon, ethylene, propylene, isoprene, butadiene etc. are mentioned, for example.

As said halogen-containing monomer, vinyl chloride, vinyl fluoride, chlorostyrene, etc. are mentioned, for example.

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

As a commercially available one among the said core-shell (meth)acrylate copolymer microparticles|fine-particles, F351 (made by Zeon Chemical Co., Ltd.) etc. are mentioned, for example.

In addition, as the above-mentioned ethylene-based particles, for example, polyvinylidene benzene particles, polychloroprene particles, butadiene rubber particles, and the like can also be used.

The preferred lower limit of the average particle diameter of the soft particles is 0.01 μm, and the preferred upper limit is 10 μm. By setting the average particle diameter of the soft particles in this range, it is possible to "improve the flexibility or adhesiveness of the cured product of the sealant for liquid crystal display elements obtained, or to suppress the penetration of the liquid crystal into the sealant or the elution of the sealant into the liquid crystal. "This effect is better." The lower limit of the average particle diameter of the soft particles is more preferably 0.1 μm, and the upper limit is more preferably 8 μm.

In addition, in this specification, the average particle size of the soft particles mentioned above means the value obtained by the following measurement: the particles before being blended into the sealant are measured using a laser diffraction particle size distribution measuring device. As the above-mentioned laser diffraction particle size distribution measuring device, Mastersizer 2000 (manufactured by Malvern Corporation) or the like can be used.

The preferred lower limit of the hardness of the soft particles is 10, and the preferred upper limit is 50. By setting the hardness of the soft particles in this range, it is an effect of "improving the flexibility or adhesiveness of the cured product of the sealant for liquid crystal display elements obtained, or suppressing the penetration of the liquid crystal into the sealant or the elution of the sealant into the liquid crystal" The better one. The lower limit of the hardness of the soft particles is more preferably 20, and the upper limit is more preferably 40.

Furthermore, in this specification, the hardness of the soft particles mentioned above means the type A hardness measured by a method based on JIS K6253.

The lower limit of the content of the soft particles 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 50 parts by weight. By setting the content of the above-mentioned soft particles within this range, the coating properties are not deteriorated, and the flexibility or adhesiveness of the cured product of the obtained sealing compound for liquid crystal display elements is improved, or the penetration of liquid crystal into the sealing compound is suppressed. Or liquid crystal contamination caused by the sealant" which has a better effect. The lower limit of the content of the soft particles is more preferably 10 parts by weight, and the upper limit is more preferably 45 parts by weight.

The sealing compound for liquid crystal display elements of the present invention preferably contains a filler for the purpose of improving viscosity, improving adhesiveness using a stress dispersion effect, and improving linear expansion coefficient.

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

Examples of the above-mentioned inorganic fillers include: silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, oxide Iron, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc.

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. By setting the content of the filler in this range, the coating properties and the like are not deteriorated, and the effects such as improvement of adhesiveness are more excellent. The lower limit of the content of the filler 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 has a "function as an adhesive agent for bonding a sealant to a substrate, etc.".

As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanide can be preferably used. Acid group propyl trimethoxysilane and so on. These have excellent effects of improving adhesion with substrates, etc., and by chemically bonding with the curable resin, the curable resin can be prevented from flowing into the liquid crystal.

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. By setting the content of the silane coupling agent 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 whose light transmittance in the vicinity of the ultraviolet range, especially light with a wavelength of 370-450nm, is higher than the average light transmittance of light with a wavelength of 300-800nm. That is, the above-mentioned titanium black is a light-shielding agent having the following properties: it imparts light-shielding properties to the sealing compound for liquid crystal display elements of the present invention by sufficiently shielding light of a wavelength in the visible light range, and on the other hand, makes light of a wavelength near the ultraviolet range Through. 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.

The above-mentioned titanium black exhibits sufficient effects even if it is not surface-treated, but it can also be used with the surface treated with organic components such as coupling agent, or with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide. Surface-treated titanium black that is coated with other inorganic components. Among them, those treated with organic components are better in that they can further improve the 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 high contrast without light leakage, and excellent images Display quality liquid crystal display element.

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

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

The primary particle size of the 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. By making the primary particle diameter of the said light-shielding agent into this range, the coating property etc. of the sealing compound for liquid crystal display elements obtained are not deteriorated, and it can be set as the thing with more excellent light-shielding property. 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. By setting the content of the light-shielding agent in this range, it is possible to exhibit more excellent light-shielding properties without reducing the adhesiveness of the obtained sealing compound for liquid crystal display elements to the substrate, or the strength or drawing properties after curing. 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 additives such as a reactive diluent, a spacer, a hardening accelerator, a defoamer, a leveling agent, and a polymerization inhibitor as necessary.

As a method of manufacturing the sealing compound for liquid crystal display elements of the present invention, for example, the curable resin, A method of mixing polymerization initiators and/or thermal hardeners, and optionally added silane coupling agents, etc.

The vertical conduction material can be manufactured by blending conductive fine particles in the sealing compound for liquid crystal display elements of the present invention. In addition, such a top and bottom conduction material containing the sealing compound for liquid crystal display elements of the present invention and conductive fine particles is also one of the present invention.

As the conductive fine particles, metal balls, those having a conductive metal layer formed on the surface of the resin fine particles, or the like can be used. Among them, the conductive fine particles with a conductive metal layer formed on the surface of the resin fine particles can achieve conductive connection without damaging the transparent substrate and the like due to the excellent elasticity of the resin fine particles, which is preferable.

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

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

First, perform the following steps: by screen printing, dispenser coating, etc., the sealant for liquid crystal display elements of the present invention is coated on a glass substrate with electrodes such as an ITO film or a polyethylene terephthalate substrate A frame-shaped seal pattern is formed on one of the two substrates. Next, the following steps are performed: in the uncured state of the sealant for liquid crystal display elements of the present invention, small liquid droplets of liquid crystal are dropped into the frame of the sealing pattern of the substrate and coated, and overlapped with another substrate under vacuum. After that, 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 rays to temporarily harden the sealant, and the step of heating the temporarily hardened sealant to perform full hardening, can be achieved by this method. A liquid crystal display element was obtained.

According to the present invention, it is possible to provide a sealant for a liquid crystal display element that can suppress the penetration of the sealant caused by the liquid crystal or the contamination of the liquid crystal caused by the sealant. Moreover, according to this invention, the upper and lower conduction material and the liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.

Hereinafter, examples are disclosed to describe the present invention in further detail, but the present invention is not limited to these examples.

(Production of polymerizable compound A of the present invention)

Add 228 g (1.0 mol) of bisphenol A and 92 g (1.0 mol) of epichlorohydrin to a reactor equipped with a stirring device, a thermometer, and a dropping funnel, heat to 100°C, and drop 5 g (0.1 mol) of sodium ethoxide to dissolve The solution in 30 g of ethanol was stirred for 5 hours after the dripping was completed. After that, the reactants are washed with 0.1 mol/L hydrochloric acid and ion exchange water to remove the generated salt and impurities. Then, the epichlorohydrin is distilled off and dried under reduced pressure to obtain a partially epoxidized resin of bisphenol A as an intermediate.

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

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

(Production of polymerizable compound B of the present invention)

Add 200 g (1.0 mol) of bisphenol F and 92 g (1.0 mol) of epichlorohydrin to a reactor equipped with a stirring device, a thermometer, and a dropping funnel, heat to 100°C, and dropwise to dissolve 5 g (0.1 mol) of sodium ethoxide The solution in 30 g of ethanol was stirred for 5 hours after the dripping was completed. After that, the reactants are washed with 0.1 mol/L hydrochloric acid and ion-exchanged water, and the generated salt and impurities are removed. Then, the epichlorohydrin is distilled off and dried under reduced pressure to obtain a partially epoxidized resin of bisphenol F as an intermediate.

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

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

(Production of polymerizable compound C of the present invention)

Add 150 g of novolak resin (weight average molecular weight 3300), 36 g (0.5 mol) of acrylic acid, 500 g of diethylene glycol monoethyl ether acetate, 1 g of triphenyl phosphine, and 100 mg of hydroquinone methyl ether into the attached stirring device and thermometer In the reactor, heat and stir at 120°C for 5 hours. As the novolak resin, EP6050G (manufactured by Asahi Organic Materials Co., Ltd.) was used. The obtained reaction liquid was re-precipitated with methanol, and dried under reduced pressure, thereby obtaining the polymerizable compound C (weight average molecular weight 3800) of the present invention.

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

(Production of polymerizable compound D of the present invention)

Add 150g of novolac resin (weight molecular weight 4800), 36g (0.5mol) of acrylic acid, 500g of diethylene glycol monoethyl ether acetate, 1g of triphenylphosphine, and 100mg of hydroquinone methyl ether into the attached stirring device and thermometer. In the reactor, heating and stirring were performed at 120°C for 5 hours. As the novolak resin, EPR5030G (manufactured by Asahi Organic Materials Co., Ltd.) was used. The obtained reaction liquid was re-precipitated with methanol and dried under reduced pressure, thereby obtaining the polymerizable compound D (weight average molecular weight 5300) of the present invention.

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

(Examples 1 to 8 and Comparative Example 1)

According to the blending ratio described in Table 1, the materials were mixed using a planetary mixer (manufactured by Thinky, "Defoaming Taro"), and then mixed using a three-roll mill to prepare Examples 1 to 8 and The sealing compound for liquid crystal display elements of Comparative Example 1.

<evaluation>

About the sealing compound for liquid crystal display elements obtained in an Example and a comparative example, the following evaluation was performed. The results are shown in Table 1.

(Descriptive)

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") were made using a planetary stirring device. Parts by weight are evenly dispersed. Then, the sealant with the spacer particles dispersed therein was filled into a dispensing syringe (manufactured by Musashi Engineering, "PSY-10E"), and after defoaming treatment, a dispenser (manufactured by Musashi Engineering, "SHOTMASTER 300"), coat the sealant on the transparent electrode substrate with ITO film by drawing a rectangular frame. Then, using a vacuum bonding device, another transparent substrate was bonded under a reduced pressure of 5 Pa. Using a metal halide lamp, the unit after bonding was irradiated with 100mW/cm ² of ultraviolet rays for 30 seconds, and then heated at 120°C for 1 hour to thermally harden the sealant to produce a unit. Observe the sealant in the obtained unit, set the condition that the sealant has no broken wires or bends and draw neat lines as "○", and set the ends without broken wires but the sealant to bend Set the case of etc. as "△", and set the case of defective wire breakage as "×" to evaluate the paintability.

(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") were made using a planetary stirring device. Parts by weight are evenly dispersed. Then, a very small amount of the sealant dispersed with spacer particles was taken out to the center of Corning Glass 1737 (20mm×50mm×thickness 0.7mm), and the same type of glass was superimposed on it to spread the sealant for liquid crystal display elements. After that, a metal halide lamp was used to irradiate ^{ultraviolet rays of 100 mW/cm 2} for 30 seconds, and then heated at 120° C. for 1 hour to harden the sealant, thereby obtaining a test piece.

For the obtained test piece, the adhesive strength was measured using a tensiometer. If the adhesive strength is 150N/cm ² or more, set it as "○", if the adhesive strength is 50N/cm ² or more and less than 150N/cm ² is set as "△", and the adhesive strength is less than 50N/cm ² The situation is set as "×" and the adhesion is evaluated.

(Anti-moisture permeability)

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") were made using a planetary stirring device. Parts by weight are evenly dispersed. Then, the sealant with the spacer particles dispersed therein was filled into a dispensing syringe (manufactured by Musashi Engineering, "PSY-10E"), and after defoaming treatment, a dispenser (manufactured by Musashi Engineering, "SHOTMASTER 300"), coat the sealant on the transparent electrode substrate with ITO film by drawing a rectangular frame. Then, a liquid crystal dropping device was used to drop tiny droplets of TN liquid crystal (manufactured by Chisso, "JC-5001LA") and applied, and another transparent substrate was bonded using a vacuum bonding device under a vacuum of 5 Pa. Immediately after bonding, a metal halide lamp was used to irradiate ^{ultraviolet rays of 100 mW/cm 2} for 30 seconds, and further heated at 120° C. for 1 hour to thermally cure the sealant, thereby obtaining a liquid crystal display element (cell gap 5 μm). The obtained liquid crystal display element was exposed to PCT conditions (121° C., 100% RH, 2 atm) for 12 hours. The liquid crystal display element after exposure to PCT conditions was observed with an optical microscope. As a result, the case where no water was mixed into the liquid crystal portion was set to "○", and the case where water was slightly mixed in was set to "△". The case where a large amount of water is mixed so that it can be confirmed visually is set to "×", and the moisture permeability is evaluated.

(Prevention of penetration)

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") were made using a planetary stirring device. Parts by weight are evenly dispersed. Then, the sealant with the spacer particles dispersed therein was filled into a dispensing syringe (manufactured by Musashi Engineering, "PSY-10E"), and after defoaming treatment, a dispenser (manufactured by Musashi Engineering, "SHOTMASTER 300"), coat the sealant on the transparent electrode substrate with ITO film by drawing a rectangular frame. Then, a liquid crystal dropping device was used to drop tiny droplets of TN liquid crystal (manufactured by Chisso, "JC-5001LA") and applied, and another transparent substrate was bonded using a vacuum bonding device under a vacuum of 5 Pa. After bonding, leave it at room temperature for 10 minutes, then use a metal halide lamp to irradiate 100mW/cm ² of ultraviolet rays for 30 seconds, and then heat at 120°C for 1 hour to thermally harden the sealant to obtain a liquid crystal display element (cell gap 5μm) . For the obtained liquid crystal display element, the shape of the seal pattern was observed. As a result, the shape of the seal pattern is set to "○" if the shape of the seal pattern is not disturbed by the internal liquid crystal, and the shape of the seal pattern is disordered but the liquid crystal does not penetrate the seal pattern as "△", and the liquid crystal penetrates the seal pattern The leakage to the outside is set as "×" and the penetration prevention property is evaluated.

[Industrial availability]

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

Claims (7)

A sealing compound for liquid crystal display elements, which contains a curable resin, and a polymerization initiator and/or a thermosetting agent, characterized in that the curable resin contains a polymerizable functional group and a compound represented by the following formula (1) Structure compound,

The sealing compound for liquid crystal display elements of the first item of the scope of patent application, wherein the compound having a polymerizable functional group and a structure represented by formula (1) has a polymerizable functional group and a structure represented by the following formula (2) The compound,

In formula (2), R ¹ and R ² each independently represent hydrogen or methyl. For example, the sealing compound for liquid crystal display elements of the first or second patent application, wherein the polymerizable functional group is a (meth)acryloyl group or an epoxy group. For example, the sealing compound for liquid crystal display elements of the first or second item of the scope of patent application, wherein the molecular weight of the compound having a polymerizable functional group and the structure represented by formula (1) is 300 to 4000. For example, the sealing compound for liquid crystal display element of the first or second item of the scope of patent application, wherein 100 parts by weight of the curable resin has a compound having a polymerizable functional group and a structure represented by formula (1) The content is 1-50 parts by weight. An up-and-down conduction material, which contains the sealing compound for liquid crystal display elements of item 1, 2, 3, 4, or 5 in the scope of patent application and conductive fine particles. A liquid crystal display element that uses the sealant for liquid crystal display elements of item 1, 2, 3, 4, or 5 in the scope of patent application or the upper and lower conductive material of item 6 in the scope of patent application.