TW201736564A - Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

A purpose of the present invention is to provide a sealant for a liquid crystal display element, said sealant demonstrating superior adhesion as well as being able to minimize liquid crystal contamination. Another purpose of the present invention is to provide a vertical conduction material and a liquid crystal display element that are obtained using said sealant for a liquid crystal display element. The sealant for a liquid crystal display element includes a thermal curing agent and a curable resin, said curable resin including a compound expressed in formula (1). In formula (1), l, m, and n are each 0-6, and Y is 1-20.

Description

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

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

In recent years, as a method of manufacturing a liquid crystal display device, in view of shortening the tact time and optimizing the amount of liquid crystal used, as disclosed in Patent Document 1 and Patent Document 2, the use of the industry includes hardening. A photo-resisting method of a resin, a photopolymerization initiator, and a thermosetting agent for a photothermal heat-curing type sealant is called a dripping method.

Regarding the dropping method, first, a rectangular sealing pattern is formed by dispensing on one of two sheets of a transparent substrate with electrodes attached thereto. Then, in a state where the sealant is not cured, a small droplet of the liquid crystal is dropped on the entire surface of the transparent substrate, and immediately overlaps with the other transparent substrate, and the sealed portion is temporarily hardened by irradiating light such as ultraviolet rays. Then, it is heated and subjected to main hardening to produce a liquid crystal display element. By bonding the substrates under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency, and this dropping method is currently the mainstream of the liquid crystal display element manufacturing method.

In addition, in the contemporary era of mobile devices including mobile phones and mobile game boards, such as mobile phones and portable game machines, the miniaturization of devices is the most important issue. Miniaturized as a device The method includes a narrow edge of the liquid crystal display unit. For example, the position of the sealing portion is placed under a black matrix (hereinafter also referred to as a narrow edge design).

However, in the narrow edge design, since the sealant is disposed directly under the black matrix, if the dropping method is performed, the light irradiated when the sealant is light-cured is shielded, and the light does not reach the inside of the sealant and hardens. The problem of becoming inadequate. When the curing of the sealant is insufficient, the sealant component which is not cured is eluted in the liquid crystal, and the hardening reaction by the eluted sealant component is performed in the liquid crystal, so that liquid crystal contamination occurs.

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

Patent Document 2: International Publication No. 02/092718

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

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

In the formula (1), l, m and n are 0 to 6, respectively, and Y is 1 to 20.

The invention is described in detail below.

The inventors of the present invention have studied the use of a bisphenol S diglycidyl ether which is excellent in the adhesiveness and has low liquid crystal contamination as a curable resin which is blended in a sealing agent for liquid crystal display elements. However, even in the case of using bisphenol S diglycidyl ether, the effect of adhesion or suppression of liquid crystal contamination is insufficient.

Therefore, the inventors of the present invention have conducted further efforts and found that by using a bisphenol S-type epoxy resin having a specific structure, it is possible to obtain a sealant for a liquid crystal display element which is excellent in adhesion and can suppress liquid crystal contamination. The invention has been made.

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

The curable resin contains the compound represented by the above formula (1). By containing the compound represented by the above formula (1), the sealing agent for a liquid crystal display device of the present invention is excellent in adhesion and suppression of liquid crystal contamination.

In the above formula (1), l, m and n are each 0 to 6. The above l, m and n are preferably from 1 to 6, respectively, more preferably from 1 to 3.

Further, in the above formula (1), Y is 1 to 20. The above Y is preferably from 1 to 10, more preferably from 1 to 4.

Further, the values of l, m, n and Y in the above formula (1) are average values. Further, the case where l or m or n is 0 means that the ethylene oxide structural moiety to which l or m or n is attached becomes a bonding bond.

As a method of producing the compound represented by the above formula (1), for example, a method of polycondensation reaction of bisphenol S or ethylene oxide-modified bisphenol S with epichlorohydrin can be mentioned.

The content of the compound represented by the above formula (1) in the sealant for liquid crystal display elements of the present invention is preferably 1% by weight or more and less than 30% by weight. Expressed by the above formula (1) The content of the compound is in this range, and the obtained sealing agent for a liquid crystal display element is excellent in the coating property or the moisture-proof property, and the effect of adhesion and suppression of liquid crystal contamination is further excellent. The lower limit of the compound represented by the above formula (1) is preferably 5% by weight, more preferably 25% by weight, still more preferably 10% by weight, and still more preferably 20% by weight.

The curable resin preferably contains another curable resin in addition to the compound represented by the above formula (1).

Examples of the other curable resin include a (meth)acrylic compound or an epoxy compound other than the compound represented by the above formula (1).

The (meth)acrylic compound may, for example, be an epoxy (meth) acrylate obtained by reacting (meth)acrylic acid with an epoxy compound, and having (meth)acrylic acid and having a hydroxyl group. The (meth) acrylate compound obtained by the reaction of the compound, and the (meth)acrylic acid urethane obtained by reacting the isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group. Among them, epoxy (meth) acrylate is preferred. Further, in the case where the (meth)acrylic compound has high reactivity, it is preferably one having two or more (meth) acrylonitrile groups in the molecule.

In the present specification, the term "(meth)acrylate" means acrylate or methacrylate, and "epoxy (meth) acrylate" means all epoxy groups in the epoxy compound. A compound formed by reacting with (meth)acrylic acid.

The epoxy (meth) acrylate is, for example, obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of a basic catalyst according to a usual method.

Examples of the epoxy compound to be used as a raw material for synthesizing the above epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol E type. Epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl 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, phenolic phenolic Varnish type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type Epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compound, and the like.

For example, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), Epiclon 850CRP (made by Di Aisheng Co., Ltd.), etc. are mentioned as a commercial item of the said bisphenol A type epoxy resin.

For example, jER806 and jER4004 (all manufactured by Mitsubishi Chemical Corporation) and the like are mentioned as a commercial product of the bisphenol F-type epoxy resin.

For example, R710 (manufactured by Printec Co., Ltd.) or the like can be mentioned as a commercially available product of the bisphenol E type epoxy resin.

As a commercial item of the said bisphenol S type epoxy resin, Epiclon EXA1514 (made by the Dickson company) etc. are mentioned, for example.

The commercially available one of the 2,2'-diallyl bisphenol A type epoxy resins is, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

The commercially available one of the hydrogenated bisphenol type epoxy resins is, for example, Epiclon EXA7015 (manufactured by Di Ai Sheng Co., Ltd.).

The commercially available one of the propylene oxide addition bisphenol A type epoxy resins is, for example, EP-4000S (manufactured by Adhes Corporation).

The commercially available one of the resorcinol-type epoxy resins is, for example, EX-201 (manufactured by Nagase Chemical Co., Ltd.).

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

For example, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) or the like can be mentioned as a commercially available one of the above-mentioned thioether type epoxy resins.

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

The commercially available one of the above-mentioned dicyclopentadiene type epoxy resins is, for example, EP-4088S (manufactured by Adhes Corporation).

As a commercial item of the above-mentioned naphthalene type epoxy resin, Epiclon HP4032, Epiclon EXA-4700 (all manufactured by Di Aisheng Co., Ltd.), etc. are mentioned, for example.

As a commercial item of the above-mentioned phenolic novolak type epoxy resin, Epiclon N-770 (made by Di Aisheng Co., Ltd.) etc. are mentioned, for example.

As a commercial item of the above-mentioned o-cresol novolac type epoxy resin, Epiclon N-670-EXP-S (made by Di Ai Sheng Co., Ltd.), etc. are mentioned, for example.

As a commercial item of the above-mentioned dicyclopentadiene novolac type epoxy resin, Epiclon HP7200 (made by Di Aisheng Co., Ltd.), etc. are mentioned, for example.

The commercially available one of the above-mentioned biphenyl novolak type epoxy resins is, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).

As a commercial item of the above-mentioned naphthol novolac type epoxy resin, ESN-165S (made by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc. are mentioned, for example.

For example, jER630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by Dietsson Co., Ltd.), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like are mentioned as a commercially available product of the glycidylamine type epoxy resin.

As a commercially available one of the above-mentioned alkyl polyol type epoxy resins, for example, ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epiclon 726 (manufactured by Di Aisheng Co., Ltd.), and Epolight 80MFA (Kyoeisha Chemical Co., Ltd.) Manufactured), DENACOL EX-611 (manufactured by Nagase Chemical Co., Ltd.).

For example, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (manufactured by Daicel Corporation), and the like are exemplified as the commercially available ones of the rubber-modified epoxy resins.

The commercially available one of the above-mentioned glycidyl ester compounds is, for example, DENACOL EX-147 (manufactured by Nagase Chemical Co., Ltd.).

Other examples of the above-mentioned epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), and jER1031 and jER1032 ( All are manufactured by Mitsubishi Chemical Corporation, EXA-7120 (manufactured by Di Ai Sheng Co., Ltd.), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

Examples of the epoxy (meth) acrylate commercially available include 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 RDX63182 (all manufactured by Daisei Zhanxin Co., Ltd.), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all Xinzhongcun 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 400EA (both manufactured by Kyoei Chemical Co., Ltd.), DENACOL Acrylate DA-141, DENACOL Acrylate DA- 314, DENACOL Acrylate DA-911 (all manufactured by Changchun Chemical Company).

Examples of the monofunctional one in the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate. Ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , isodecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, (methyl) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Isodecyl methacrylate, biscyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxy B (meth) acrylate Ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (A) Acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, (meth) methacrylate, ethyl carbitol (meth) acrylate, (meth) acrylate 2, 2,2-trifluoroethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, quinone imine (methyl) Acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(methyl)propenyloxyethyl succinate, hexahydrofurfuric acid 2- (Meth) propylene methoxyethyl ester, 2-(methyl) propylene methoxyethyl ester 2-hydroxypropyl phthalate, 2-(methyl) propylene methoxyethyl phosphate, glycidol (Meth) acrylate, etc.

Further, examples of the difunctionality of the (meth) acrylate compound include 1,3-butanediol di(meth) acrylate and 1,4-butanediol di(meth) acrylate. 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, ethylene glycol II (Meth) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, 2-n-butyl-2 -ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl Alcohol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, di(meth)acrylate modified by isoamyl cyanide, (meth)acrylic acid 2-hydroxy-3-(methyl)propenyl propyl propyl ester, carbonate diol di(meth) propylene Acid ester, polyether diol di(meth) acrylate, polyester diol di(meth) acrylate, polycaprolactone diol di(meth) acrylate, polybutadiene diol di (a) Base) acrylate and the like.

Further, examples of the trifunctional or higher functional group of the (meth) acrylate compound include trimethylolpropane tri(meth)acrylate and ethylene oxide addition trimethylolpropane tris(methyl). Acrylate, propylene oxide addition trimethylolpropane tri(meth) acrylate, ethylene oxide addition tris (meth) acrylate, tri(meth) acrylate, Propylene oxide addition of tris(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(meth)propenyloxyethyl phosphate, di-trimethylolpropane tetra(methyl) Acrylate, neopentyltetrakis(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

As the above (meth)acrylic acid urethane, for example, (meth)acrylic acid having a hydroxyl group can be derived by using 1 equivalent of an isocyanate compound having 2 isocyanate groups. It is obtained by reacting 2 equivalents of a tin-based compound in the presence of a catalyst amount.

Examples of the isocyanate compound which is a raw material of the above (meth)acrylic acid urethane include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene group. Diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, Toluidine diisocyanate, benzodimethyl diisocyanate (XDI), hydrogenated XDI, quaternary acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate 1,6,11-undecane triisocyanate, and the like.

Further, as the isocyanate compound which is a raw material of the above (meth)acrylic acid urethane, for example, ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane or carbonate diol can be used. A chain extended isocyanate compound obtained by reacting a polyhydric alcohol such as a polyether diol, a polyester diol or a polycaprolactone diol with an excess of an isocyanate compound.

Examples of the (meth)acrylic acid derivative having a hydroxyl group which is a raw material of the above (meth)acrylic acid urethane are 2-hydroxyethyl (meth)acrylate and 2-hydroxyl (meth)acrylate. a hydroxyalkyl (meth)acrylate such as propyl ester, 2-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, or ethylene glycol, propylene glycol, 1,3-propanediol, 1, a mono (meth) acrylate of a glycol such as 3-butanediol, 1,4-butanediol or polyethylene glycol, or a triol of trimethylolethane, trimethylolpropane or glycerol Epoxy (meth) acrylate such as mono (meth) acrylate or di (meth) acrylate or bisphenol A epoxy acrylate.

Examples of the commercially available (meth)acrylic acid urethane 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 (both Manufactured by Zhanxin Company, 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 Roots Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA- 5201P, UA-7100, UA-7200, UA-W2A (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA- 306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.), etc.

The epoxy compound of the other curable resin, for example, an epoxy compound or a part (meth) which is a raw material for synthesizing the above epoxy (meth) acrylate other than the compound represented by the above formula (1) Acrylic modified epoxy resin and the like.

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

Among the above-mentioned partial (meth)acrylic acid-modified epoxy resins, for example, UVACURE 1561 (manufactured by Daicel Co., Ltd.) and the like can be cited.

In the case of containing the above-mentioned other curable resin, the lower limit of the compound represented by the above formula (1) in 100 parts by weight of the curable resin is preferably 5 parts by weight, and preferably the upper limit is 25 parts by weight. When the content of the compound represented by the above formula (1) is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in coating property, adhesion property, moisture permeability resistance, and liquid crystal contamination suppression effect. The lower limit of the compound represented by the above formula (1) is preferably 10 parts by weight, more preferably 20 parts by weight.

In the case where the curable resin contains the above (meth)acrylic compound or the above-mentioned partial (meth)acrylic modified epoxy resin, it is preferred to use a (meth)acryloyl group and an epoxy group in the curable resin. The content ratio is set to 50:50 to 95:5 in terms of molar ratio.

The sealing agent for liquid crystal display elements of this invention contains a heat hardening agent.

From the viewpoint of reactivity, the above-mentioned thermosetting agent preferably contains a trifunctional or higher thermal curing agent.

In addition, the above-mentioned "trifunctional or higher thermal curing agent" refers to a thermosetting agent composed of a compound having three or more functional groups which are activated by heating and hardened by a curing reaction of a curable resin. .

Examples of the trifunctional or higher thermal curing agent include triterpene citrate, trimethyl sulfonium tricarboxylate, and 1,3,5-tris(2-carboxyethyl) isocyanurate.

The other of the above-mentioned thermosetting agents may, for example, be an organic acid dioxime, an imidazole derivative, an amine compound, a polyphenol compound or an acid anhydride. Among them, an organic acid dioxime can be suitably used.

Examples of the above-mentioned organic acid dihydric acid include diterpene sebacate, diammonium isophthalate, diammonium adipate, and diammonium malonate.

As a commercial one of the above-mentioned organic acid diterpenes, for example, SDH and ADH (both are mentioned) Amadeure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), etc.

The content of the above-mentioned thermosetting agent is preferably 1 part by weight, and preferably 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned heat-hardening agent is in this range, it is possible to improve the coating property of the obtained sealing compound for liquid crystal display elements and the like, and to further improve the thermosetting property. The upper limit of the above content of the hot hardener is preferably 30 parts by weight.

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

Examples of the radical polymerization initiator include a photoradical polymerization initiator which generates a radical by light irradiation, a thermal radical polymerization initiator which generates a radical by heating, and the like.

Examples of the photoradical polymerization initiator include a benzophenone compound, an acetophenone compound, a fluorenyl phosphine oxide compound, a titanocene compound, an oxime ester compound, and a benzoin ether compound. 9-oxygen sulfur A compound or the like.

As a commercial one of the above-mentioned photoradical polymerization initiators, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (both of which are BASF) Manufactured, NCI-930 (manufactured by Adico Co., Ltd.), SPEEDCURE EMK (manufactured by Siber Hegner Co., Ltd.), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.

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

In the present specification, the term "polymer azo compound" means a compound having an azo group and generating a radical capable of hardening a (meth) acrylonitrile group by heat, and having a number average molecular weight of 300 or more. .

The lower limit of the number average molecular weight of the above polymer azo initiator is preferably 1,000, and preferably the upper limit is 300,000. When the number average molecular weight of the above polymer azo initiator is within this range, liquid crystal contamination can be suppressed and the curable resin can be easily mixed. The lower limit of the number average molecular weight of the above polymer azo initiator is preferably 5,000, more preferably 100,000, and further preferably a lower limit of 10,000, and further preferably an upper limit of 90,000.

Further, in the present specification, the above-mentioned number average molecular weight is measured by gel permeation chromatography (GPC) and is determined by polystyrene conversion. For example, Shodex LF-804 (manufactured by Showa Denko KK) can be used as the column for measuring the number average molecular weight obtained by the polystyrene conversion by GPC.

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

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

In addition, examples of the azo compound which is not a polymer include V-65 and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.).

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

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

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

Examples of the filler include cerium oxide, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, and the like. Inorganic fillers such as magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, tantalum nitride, barium sulfate, calcium citrate; or polyester microparticles, polyamines An organic filler such as a formate fine particle, a vinyl polymer fine particle, or an acrylic polymer fine particle.

The lower limit of the above filler content in the sealant for liquid crystal display elements of the present invention is preferably 10% by weight, and preferably the upper limit is 70% by weight. When the content of the filler is within this range, the coating property and the like are not deteriorated, and the effects such as improvement in adhesion are more excellent. The lower limit of the above filler content is preferably 20% by weight, and more preferably the upper limit is 60% by weight.

The sealing agent for liquid crystal display elements of the present invention preferably contains a decane coupling agent. The above decane coupling agent mainly has a good adhesion agent for the sealing agent and the substrate. effect.

The decane coupling agent is excellent in the effect of improving adhesion to a substrate or the like, and chemically bonded to the curable resin can suppress the flow of the curable resin into the liquid crystal. For example, 3-aminopropyl can be suitably used. Trimethoxy decane, 3-mercaptopropyltrimethoxy decane, 3-glycidoxypropyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, and the like.

The lower limit of the content of the above decane coupling agent in the sealing agent for liquid crystal display elements of the present invention is preferably 0.1% by weight, and preferably the upper limit is 10% by weight. When the content of the above decane coupling agent is within this range, the occurrence of liquid crystal contamination is suppressed, and the effect of improving the adhesion is more excellent. The lower limit of the content of the above decane coupling agent is preferably 0.3% by weight, and more preferably the upper limit is 5% by weight.

The sealing agent for liquid crystal display elements of this invention may also contain an opacifier. The sealant for a liquid crystal display element of the present invention can be suitably used as a light-shielding sealant by containing the above-mentioned light-shielding agent.

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

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

The above-mentioned titanium black has a sufficient effect even if it is not surface-treated, but it also It is possible to use a surface-treated titanium black such as a surface treated with an organic component such as a coupling agent or an inorganic component such as cerium oxide, titanium oxide, cerium oxide, aluminum oxide, zirconium oxide or magnesium oxide. Among them, from the viewpoint of further improving the insulating property, it is preferred to carry out treatment with an organic component.

In addition, since the liquid crystal display element manufactured by using the sealing agent for liquid crystal display elements of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding property, it can realize no light leakage, has high contrast, and has excellent image display. Quality liquid crystal display elements.

The commercially available ones of the titanium blacks include, for example, 12S, 13M, 13M-C, 13R-N, and 14M-C (all manufactured by Mitsubishi Materials Corporation) and Tilack D (manufactured by Ako Chemical Co., Ltd.).

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

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

The primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display device. A preferred lower limit is 1 nm, and a preferred upper limit is 5000 nm. When the primary particle diameter of the above-mentioned light-shielding agent is in this range, it is possible to improve the coating property of the obtained sealing agent for a liquid crystal display element and the like, and to improve the light-shielding property. The lower limit of the primary particle diameter of the above-mentioned opacifier is 5 nm, more preferably 200 nm, and still more preferably 10 nm, and further preferably 100 nm.

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

The lower limit of the content of the above-mentioned light-shielding agent in the sealing agent for liquid crystal display elements of the present invention is preferably 5% by weight, and preferably the upper limit is 80% 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 lowering the adhesion between the obtained liquid crystal display element sealing agent and the strength or the drawability after curing. The lower limit of the above content of the opacifier is preferably 10% by weight, more preferably 70% by weight, even more preferably 30% by weight, and even more preferably 60% by weight.

The sealant for liquid crystal display elements of the present invention may further contain a stress relieving agent, a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other additives, as needed.

As a method of producing the sealing agent for liquid crystal display elements of the present invention, for example, a method such as a homogeneous phase disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll mill can be used. An additive such as a curable resin, a polymerization initiator, and/or a thermosetting agent, and a decane coupling agent to be added as needed is mixed.

The sealing agent for liquid crystal display elements of the present invention has an E-type viscometer and preferably has a lower viscosity of 50,000 mPa·s at a temperature of 25 ° C and 1 rpm, and preferably has an upper limit of 700,000 mPa·s. When the viscosity is within this range, the obtained sealing agent for a liquid crystal display element is excellent in coatability. The lower limit of the above viscosity is preferably 100,000 mPa‧s, and the upper limit is more preferably 500,000 mPa·s.

In addition, as the E-type viscometer, for example, 5XHBDV-III+CP (manufactured by Brookfield Co., Ltd., rotor No. CP-51) or the like can be used.

The upper and lower conductive materials can be produced by blending the conductive fine particles with the sealing agent for a liquid crystal display element of the present invention. Such a sealant and a guide for a liquid crystal display element of the present invention The conductive material above and below the electrical microparticles is also one of the inventions.

As the conductive fine particles, a metal ball or a conductive metal layer formed on the surface of the resin fine particles can be used. Among them, those having a conductive metal layer formed on the surface of the resin fine particles are excellent in elasticity by the resin fine particles, and can be electrically connected without loss of a transparent substrate or the like.

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

As a method of producing the liquid crystal display element of the present invention, a liquid crystal dropping method can be suitably used. Specifically, for example, a method of the following steps may be employed: on a sheet of two substrates such as a glass substrate or an ethylene terephthalate substrate with an electrode such as an ITO film, which is screen-printed and dispensed. a step of forming a seal pattern in a frame shape by applying a sealant for a liquid crystal display element of the present invention; and applying a droplet of liquid crystal to a substrate in a state where the sealant for a liquid crystal display element of the present invention is not cured; a step of overlapping the other substrate with a vacuum in the frame of the sealing pattern; a step of irradiating the sealing pattern portion of the sealing agent for a liquid crystal display element of the present invention with light such as ultraviolet rays to temporarily harden the sealing agent; and temporarily hardening the sealing agent; The sealant is heated to perform a step of hardening.

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

The invention is described in more detail below by way of examples, but the invention is not limited to the examples.

(Production of the compound represented by the formula (1) (l=m=n=0, Y=2 (average value))

200 parts by weight of bis(4-hydroxyphenyl)fluorene, 370 parts by weight of epichlorohydrin, 185 parts by weight of dimethyl hydrazine, and 5 parts by weight of tetramethylammonium chloride, and dissolved under stirring, and then heated to 50 ° C . Then, after 60 parts by weight of sodium hydroxide was added in portions, the mixture was reacted at 50 ° C for 3 hours. After completion of the reaction, the mixture was washed with water, and an excess of epichlorohydrin or the like was distilled off from the oil layer at 130 ° C under reduced pressure using an evaporator. 450 parts by weight of methyl isobutyl ketone was added to the residue, dissolved, and the temperature was raised to 70 °C. 10 parts by weight of a 30% aqueous sodium hydroxide solution was added under stirring, and reacted for 1 hour, and then washed with water three times, and methyl isobutyl ketone was distilled off at 180 ° C under reduced pressure using a rotary evaporator. After reacting the obtained substance with ethyltriphenylphosphonium acetate as a catalyst, it is washed with water to synthesize the compound represented by the formula (1) (l=m=n=0, Y=2 (average value)). Further, the compound obtained was a compound represented by the formula (1) (l = m = n = 0, Y = 2 (average value)), which was confirmed by ¹ H-NMR, ¹³ C-NMR and IR.

(Production represented by formula (1) (production of l=m=n=1 (average value), Y=3 (average value))

170 parts by weight of bis[4-(2-hydroxyethoxy)phenyl]anthracene, 370 parts by weight of epichlorohydrin, 185 parts by weight of dimethyl hydrazine, and 5 parts by weight of tetramethylammonium chloride, and stirred under stirring Dissolved and warmed to 50 °C. Then, after 60 parts by weight of sodium hydroxide was added in portions, the mixture was reacted at 50 ° C for 3 hours. After completion of the reaction, the mixture was washed with water, and an excess of epichlorohydrin or the like was distilled off from the oil layer at 130 ° C under reduced pressure using an evaporator. 450 parts by weight of methyl isobutyl ketone was added to the residue, dissolved, and the temperature was raised to 70 °C. 10 parts by weight of a 30% aqueous sodium hydroxide solution was added under stirring, and reacted for 1 hour, and then washed with water three times, and methyl isobutyl ketone was distilled off at 180 ° C under reduced pressure using a rotary evaporator. Ethyltriphenylphosphonium acetate is used as a catalyst to react the obtained material, and then washed with water to synthesize the compound represented by the formula (1) (l=m=n=1 (average value), Y= 3 (average)). Further, the obtained compound is a compound represented by the formula (1) (l = m = n = 1 (average value), Y = 3 (average value)) by ¹ H-NMR, ¹³ C-NMR and IR. Undergo verification.

(Examples 1 to 8 and Comparative Examples 1, 2)

According to the blending ratios shown in Table 1, the materials were mixed using a planetary mixer (manufactured by Shinki Co., Ltd., "Defoaming Taro"), and then mixed using a three-roll mill to prepare Examples 1 to 8 and compare them. The sealing agent for liquid crystal display elements of Examples 1 and 2.

<evaluation>

The following evaluations were performed on the sealants for liquid crystal display elements obtained in the examples and the comparative examples. The results are shown in Table 1.

(coating property)

Each of the sealants for liquid crystal display elements obtained in the examples and the comparative examples was applied onto a glass substrate using a dispenser ("SHOTMASTER 300" manufactured by Musashi Kogyo Co., Ltd.). When the dispensing nozzle was fixed to 400 μm, the nozzle gap was fixed to 30 μm, and the discharge pressure was fixed at 300 kPa, the coating was evaluated as “◎” when the coating was successfully applied without blurring or dripping. The case where the blur or the liquid was slightly generated was evaluated as "○", and the case where the coating crack was not applied but the large blur or dripping was evaluated as "Δ" was evaluated, and the coating crack or the coating was completely unapplied. It was "x" to evaluate the coatability.

(adhesive)

100 parts by weight of each of the sealants for liquid crystal display elements obtained in the examples and the comparative examples, and a spacer particle having an average particle diameter of 5 μm (manufactured by Sekisui Chemical Co., Ltd., "Micropearl SP-2050") 1 by the planetary stirring device The parts by weight are uniformly dispersed, and placed in a very small amount in the central portion of Corning glass 1737 (20 mm × 50 mm × thickness 0.7 mm), and the same type of glass is superposed thereon to spread the liquid crystal display element with a sealant, using a metal halide lamp The ultraviolet rays of 100 mW/cm ^{2 were} irradiated for 30 seconds, and then heated at 120 ° C for 1 hour to harden the sealant, thereby obtaining a test piece.

The subsequent strength of the obtained test piece was measured using a tensiometer. The measured value obtained by the (kgf) divided by the cross sectional area of the seal-coated (cm & lt ^2), the case of ² or more is obtained from 35kgf / cm was evaluated as "◎" will be ² or more and less than 35kgf 30kgf / cm In the case of /cm ^{2 ,} it is evaluated as "○", and when it is 25 kgf/cm ² or more and less than 30 kgf/cm ^{2 ,} it is evaluated as "△", and when it is less than 25 kgf/cm ^{2 ,} it is evaluated as "X", and thus The evaluation was performed next.

(Display performance of liquid crystal display element (low liquid crystal contamination))

100 parts by weight of each of the sealants for liquid crystal display elements obtained in the examples and the comparative examples, and a spacer particle having an average particle diameter of 5 μm (manufactured by Sekisui Chemical Co., Ltd., "Micropearl SP-2050") 1 weight. The parts were uniformly dispersed, and the obtained sealant was filled in a syringe for injection ("PSY-10E" manufactured by Musashi Kogyo Co., Ltd.), and after defoaming treatment, a dispenser was used ("SHOTMASTER300" manufactured by Musashi Industrial Co., Ltd. The sealant was applied in a frame shape to one of two transparent electrode substrates with an ITO film attached thereto. Then, a tiny drop of TN liquid crystal (manufactured by Chisso Corporation, "JC-5001LA") was dropped into the frame of the sealant by a liquid crystal dropping device, and another transparent electrode substrate was vacuumed at 5 Pa by a vacuum bonding device. Under the fit, and get the unit. The obtained unit was irradiated with ultraviolet rays of 100 mW/cm ² for 30 seconds using a metal halide lamp, and then heated at 120 ° C for 1 hour to harden the sealant to obtain a liquid crystal display element.

With respect to the obtained liquid crystal display element, the display unevenness of the liquid crystal (especially the corner portion) around the sealing portion was visually observed, and the case where the display unevenness was not confirmed was evaluated as "◎", and it was confirmed that it was slightly When the display unevenness is evaluated as "○", it is confirmed that the display unevenness is evaluated as "△", and the case where the display unevenness is confirmed is evaluated as "X", thereby displaying the liquid crystal display element. Performance (low liquid crystal contamination) was evaluated.

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

[Industrial availability]

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

Claims (6)

A sealant for a liquid crystal display element, comprising a curable resin and a thermosetting agent, wherein the curable resin contains a compound represented by the following formula (1). In the formula (1), l, m and n are 0 to 6, respectively, and Y is 1 to 20. The sealant for a liquid crystal display element according to the first aspect of the invention, wherein Y in the formula (1) is 1 to 10. The sealant for a liquid crystal display element according to claim 1 or 2, wherein l, m and n in the formula (1) are each 1 to 6. The sealant for a liquid crystal display element of the first, second or third aspect of the invention, wherein the thermosetting agent contains a trifunctional or higher thermal hardener. A top-bottom conductive material comprising a sealant for a liquid crystal display element of the first, second, third or fourth aspect of the patent application and conductive fine particles. A liquid crystal display element is obtained by using a sealant for a liquid crystal display element of the first, second, third or fourth aspect of the patent application or a conductive material above the fifth item of the patent application.