TW201736562A - Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element - Google Patents

Abstract

One purpose of the present invention is to provide a sealing agent for liquid crystal display elements, which is capable of achieving a good balance between fast curing properties at low temperatures and storage stability. Another purpose of the present invention is to provide: a vertically conducting material which is obtained using this sealing agent for liquid crystal display elements; and a liquid crystal display element. The present invention is a sealing agent for liquid crystal display elements, which contains a curable resin and a thermal curing agent, and wherein the thermal curing agent contains a compound that has a structure represented by formula (1). In formula (1), X represents a structure having an aromatic ring; n represents an integer of 1 or more; and * represents a bonding position.

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 can achieve both storage stability and rapid hardenability at a low temperature. Moreover, the present invention relates to an upper and lower conductive material and a liquid crystal display element using the sealing agent for a liquid crystal display element.

In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display unit, as disclosed in Patent Document 1 and Patent Document 2, from the viewpoints of shortening the Tact Time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dripping method using a photocurable heat-curing sealant containing a curable resin, a photopolymerization initiator, and a thermosetting agent.

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

In addition, in the modernization of various mobile devices including liquid crystal panels such as mobile phones and portable game machines, the miniaturization of machines is the most important issue. As a method of downsizing the machine, a narrow edge of the liquid crystal display unit can be cited, for example, the position of the sealing portion is arranged in black. The operation under the matrix (hereinafter, also referred to as narrow edge design).

However, in the narrow edge design, since the sealant is disposed directly under the black matrix, when the drip method is performed, the light irradiated when the sealant is photohardened is shielded, and it is difficult for the light to reach the inside of the sealant. However, hardening has become insufficient in the conventional sealant. If the hardening of the sealant is insufficient as described above, there is a problem in that liquid crystal contamination is likely to occur due to elution of the unhardened sealant component into the liquid crystal.

Therefore, it is considered that the sealant is cured by heating the sealant, and from the viewpoint of energy saving or stability of the liquid crystal, it is desirable to thermally harden the sealant by heating at a low temperature for a short period of time.

As a method for hardening a sealant by heating at a low temperature for a short period of time, it is considered to use a hot hardener having a lower melting point, however, when a hot hardener having a lower melting point is used, a seal is obtained. The condition in which the storage stability is deteriorated.

Prior technical literature

Patent literature

Patent Document 1: Japanese Laid-Open Patent 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 can achieve both storage stability and rapid hardenability at a low temperature. 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 thermosetting agent contains a compound having a structure represented by the following formula (1).

In the formula (1), X is a structure having an aromatic ring, n is an integer of 1 or more, and * is a bonding position.

The invention is described in detail below.

The present inventors have found that a sealing agent for a liquid crystal display element which can achieve both storage stability and rapid hardening property at a low temperature can be obtained by using a compound having a specific structure as a thermosetting agent.

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

The above thermosetting agent contains a compound having a structure represented by the above formula (1). By using the compound having the structure represented by the above formula (1) as the above-mentioned thermosetting agent, the sealing agent for liquid crystal display elements of the present invention can achieve both storage stability and rapid hardenability at low temperatures.

In the above formula (1), n is preferably an integer of from 1 to 10, more preferably an integer of from 1 to 5.

Further, in the above formula (1), X is preferably a structure represented by the following formula (2-1), (2-2), (2-3), (2-4), or (2-5). More preferably, it is a structure represented by the following formula (2-1), and more preferably a structure in which R ¹ and R ² in the following formula (2-1) are a methyl group.

In the formula (2-1), R ¹ and R ² are each independently hydrogen or a methyl group, and in the formulae (2-1) to (2-5), * is a bonding position.

The compound having the structure represented by the above formula (1) preferably has a structure derived from a first-order diamine compound having a divalent aliphatic hydrocarbon group, and more preferably has a divalent alicyclic hydrocarbon group. Further, the structure of the first-stage diamine compound further preferably has a structure derived from a first-order diamine compound having a cyclohexyl group, and particularly preferably a compound having a structure represented by the following formula (3) or having the following formula; (4) A compound of the structure shown.

In the formula (3), the X system has the same structure as the X in the formula (1), n is the same number as n in the formula (1), and the * is a bonding position.

In the formula (4), the X system has the same structure as X in the formula (1), n is the same number as n in the formula (1), and * is a bonding position.

The compound having a structure represented by the above formula (1) preferably has an epoxy group or a primary amino group at the terminal of the main chain, more preferably has a primary amino group at the terminal of the main chain, and more preferably is in the main chain. Both ends have a grade 1 amine group.

A preferred lower limit of the melting point of the compound having the structure represented by the above formula (1) is 60 ° C, and a preferred upper limit is 100 ° C. When the melting point of the compound having the structure represented by the above formula (1) is in this range, the obtained sealing agent for a liquid crystal display element is more excellent in both storage stability and rapid hardening property at a low temperature. A more preferred lower limit of the melting point of the compound having the structure represented by the above formula (1) is 65 ° C, and a preferred upper limit is 95 ° C.

Specific examples of the method for producing a compound having a structure represented by the above formula (1) include the following methods, that is, an aliphatic group such as 1,4-bis(aminomethyl)cyclohexane Grade 1 diamine, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol S diglycidyl ether, bis(4-glycidoxy Reaction with phenyl)ether, resorcinol diglycidyl ether, biphenyl-4,4'-diylbis(glycidyl ether).

The content of the compound having the structure represented by the above formula (1) is preferably 5 parts by weight, and preferably 120 parts by weight, based on 100 parts by weight of the curable resin. When the content of the compound having the structure represented by the above formula (1) is in this range, the obtained sealing agent for a liquid crystal display element is more excellent in both storage stability and rapid hardening property at a low temperature. A more preferred lower limit of the content of the compound having a structure represented by the above formula (1) is 10 parts by weight, a more preferred upper limit is 100 parts by weight, a still lower limit is 20 parts by weight, and a still more preferred upper limit is 60 parts by weight.

The above-mentioned thermosetting agent may contain other thermosetting agents in addition to the compound having the structure represented by the above formula (1) without departing from the object of the present invention.

Examples of the other heat curing agent include an oxime-based curing agent, an imidazole-based curing agent, a polyhydric phenol-based curing agent, and an acid anhydride-based curing agent. Among them, an lanthanide hardener can be preferably used.

Examples of the oxime-based curing agent include 1,3-bis(decylcarbonylethyl-5-isopropylhydantoin), diterpene sebacate, and diammonium isophthalate. As a commercially available product, for example, Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), SDH, IDH, and ADH (all of them are Otsuka Chemicals). Manufactured by the company, MDH (manufactured by Japan Finechem Co., Ltd.), etc.

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

The curable resin preferably contains an epoxy compound.

Examples of the epoxy compound 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. Bisphenol A Epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, thioether 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 novolac type epoxy Resin, biphenyl aldehyde varnish type epoxy resin, naphthol novolac type epoxy resin, epoxidized epoxide type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compound Wait.

For example, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 850 (made by DIC Corporation), 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 item of the bisphenol F-type epoxy resin.

As a commercial item in the above-mentioned bisphenol E type epoxy resin, EPOMIK R710 (made by Mitsui Chemicals Co., Ltd.), etc. are mentioned, for example.

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

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

As a commercial item in the said hydrogenated bisphenol type epoxy resin, EPICLON EXA7015 (made by the DIC company) etc. are mentioned, for example.

The commercially available product of the propylene oxide addition bisphenol A type epoxy resin is, for example, EP-4000S (manufactured by Adeka Co., Ltd.).

As a commercial item in the said resorcinol type epoxy resin, the EX-201 is mentioned, for example. (manufactured by Nagase ChemteX), etc.

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

For example, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like can be mentioned as a commercial product of the above-mentioned thioether type epoxy resin.

As a commercial item in the above-mentioned diphenyl ether type epoxy resin, YSLV-80DE (made by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc. are mentioned, for example.

The commercially available product of the above-mentioned dicyclopentadiene type epoxy resin is, for example, EP-4088S (manufactured by Adeka Co., Ltd.).

As a commercial item in the above-mentioned naphthalene type epoxy resin, EPICLON HP4032, EPICLON EXA-4700 (all manufactured by DIC Corporation), etc. are mentioned, for example.

As a commercial item in the above-mentioned phenol novolak-type epoxy resin, EPICLON N-770 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item in the above-mentioned o-cresol novolac type epoxy resin, EPICLON N-670-EXP-S (made by DIC company) etc. are mentioned, for example.

The commercially available product of the above-mentioned dicyclopentadiene novolac type epoxy resin is, for example, EPICLON HP7200 (manufactured by DIC Corporation).

For example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned as a commercial product of the above-mentioned biphenol novolak type epoxy resin.

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.

As a commercial item among the above-mentioned epoxy propylamine type epoxy resins, for example, jER630 (Mitsubishi) Manufactured by a chemical company, EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.

For example, ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) are mentioned as a commercial product of the above-mentioned alkyl polyol type epoxy resin. ), DENACOL EX-611 (manufactured by Nagase ChemteX), etc.

For example, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (made by Daicel Co., Ltd.), etc. are mentioned as a commercial item in the said rubber-modified epoxy resin.

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

Other commercially available products of the epoxy compound include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, and jER1032 ( All are manufactured by Mitsubishi Chemical Corporation, EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

As the above epoxy compound, a partially (meth)acrylic modified epoxy resin is also suitable.

In addition, 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, for example, It is obtained by reacting an epoxy group which is a part of an epoxy compound having two or more epoxy groups with (meth)acrylic acid.

As a commercial item in the said (meth)acrylic-modified epoxy resin, UVCURE1561 (made by Daicel-Allnex company) etc. are mentioned, for example.

Further, the curable resin preferably contains a (meth)acrylic compound.

Examples of the (meth)acrylic compound include a (meth) acrylate compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, and (meth)acrylic acid and an epoxy compound. An epoxy (meth) acrylate obtained by the reaction, an amine (meth) acrylate obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound, or the like. Among them, epoxy (meth) acrylate is preferred. Further, the (meth)acrylic compound is preferably one having two or more (meth)acrylonium groups in the molecule in terms of high reactivity.

In the present specification, the above "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above "(meth)acrylic compound" means having an acrylonitrile group or a methacrylic acid group (hereinafter, also A compound which is also referred to as "(meth)acryloyl group"). Further, the above "(meth) acrylate" means acrylate or methacrylate, and the above "epoxy (meth) acrylate" means that all epoxy groups in the epoxy compound are reacted with (meth)acrylic acid. The compound formed by the reaction.

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, (A) Dialkylpentene acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-(meth) acrylate Butoxyethyl ester, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy Ethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate, (methyl) 2,2,2-trifluoroethyl acrylate, 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) propylene methoxyethyl succinate, hexahydro phthalate 2-(methyl)propenyloxyethyl formate, 2-(methyl)propenyloxyethyl 2-hydroxypropyl phthalate, 2-(methyl) propylene methoxyethyl phosphate, Glycidyl (meth)acrylate and the like.

In addition, examples of the bifunctional one of the (meth) acrylate compounds 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, ethylene oxide modified di(meth) acrylate, (methyl) Acrylic acid 2-hydroxy-3 -(Meth)propylene methoxypropyl ester, carbonate diol di(meth) acrylate, polyether diol di(meth) acrylate, polyester diol di(meth) acrylate, poly Lactone diol di(meth) acrylate, polybutadiene diol di(meth) acrylate, and the like.

In addition, 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, caprolactone modified trimethylolpropane tri(meth) acrylate, ethylene oxide addition iso-cyanide Acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(methyl) phosphate Propylene methoxyethyl ester, di-trimethylolpropane tetra(meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dioxane Tetraol hexa(meth) acrylate or the like.

Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound with (meth)acrylic acid in the presence of a basic catalyst as usual.

As the epoxy compound which is a raw material for the synthesis of the epoxy (meth) acrylate, the same epoxy compound as the curable resin contained in the sealing agent for liquid crystal display elements of the present invention can be used.

Examples of the commercially available ones of the epoxy (meth)acrylates include EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX63182 (both manufactured by Daicel-Allnex); EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA -1020 (both manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.); DENACOL Acrylate DA-141, DENACOL Acrylate DA-314, DENACOL Acrylate DA-911 (all manufactured by Nagase Chemtech X), and the like.

The above-mentioned (meth)acrylic acid amine ester can be obtained, for example, by a method in which a (meth)acrylic acid derivative having a hydroxyl group is present in an amount of 2 equivalents in the presence of a catalyst amount of a tin-based compound. The isocyanate-based isocyanate compound is reacted in an equivalent amount.

Examples of the isocyanate compound which is a raw material of the above (meth)acrylic acid amide ester include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and the like. Methylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, Benzyl diisocyanate (XDI), hydrogenated XDI, quaternary acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethyl dimethyl 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 amide, for example, ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol or polyether can be used. A chain extended isocyanate compound obtained by reacting a polyol such as an alcohol, a polyester diol or a polycaprolactone diol with an excess of an isocyanate compound.

As a raw material of the above (meth)acrylic acid amide, having a hydroxyl group (A) Examples of the acrylic acid derivative include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and (meth)acrylic acid 4- a hydroxyalkyl mono(meth)acrylate such as hydroxybutyl ester; or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, polyethylene glycol, etc. Mono (meth) acrylate of a monohydric alcohol; or a mono (meth) acrylate or di(meth) acrylate of a trihydric alcohol such as trimethylolethane, trimethylolpropane or glycerin; or bisphenol Epoxy (meth) acrylate such as A-type epoxy acrylate.

Examples of commercially available products of the above (meth)acrylic acid amide include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei Co., Ltd.); EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270 , EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL482, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 (all manufactured by Daicel-Allnex); 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 Gensei 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.).

In the case where the sealing compound for a liquid crystal display device of the present invention contains the epoxy compound and the (meth)acrylic compound, the ratio of the epoxy group to the (meth)acrylonitrile group is preferably 5:95 to 70. The above epoxy compound and the above (meth)acrylic compound are blended in a manner of 30. By setting the ratio of the epoxy groups to such a range, the obtained sealing agent for liquid crystal display elements suppresses generation of liquid crystal contamination, and is more excellent in adhesion.

The curable resin is preferably a unit having hydrogen bonding properties such as an -OH group, a -NH- group, or a -NH ₂ group from the viewpoint of suppressing liquid crystal contamination.

The sealing agent for liquid crystal display elements of the present invention preferably contains a radical polymerization initiator.

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

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. Benzene oxime, 9-oxo sulphur Wait.

As a commercial item among the photoradical polymerization initiators, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all are BASF Corporation) Manufactured; benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.

The thermal radical polymerization initiator may be, for example, an azo compound or an organic peroxide. Among them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter also referred to as "azo starter") is preferred, and a polymer is more preferred. An initiator composed of an azo compound (hereinafter also referred to as "polymer azo initiator").

In the present specification, the term "polymer azo compound" means an azo group, and the number average molecular weight of the radical which hardens the (meth) propylene fluorenyl group by heat is 300 or more. Compound.

A preferred lower limit of the number average molecular weight of the above polymer azo initiator is 1000, and a preferred upper limit is 300,000. When the number average molecular weight of the above polymer azo initiator is 1000 or more, liquid crystal contamination can be suppressed, and it can be easily mixed with a curable resin. A lower limit of the number average molecular weight of the above polymer azo initiator is 5,000, a higher limit is 100,000, and a lower limit is preferably 10,000, and a preferred upper limit is 90,000.

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

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

Further, examples of the azo initiator other than the polymer azo initiator include, for example, V. -65, V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.), etc.

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

The content of the radical polymerization initiator is preferably 0.1 part 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 more excellent in storage stability or hardenability. A more preferred lower limit of the content of the above radical polymerization initiator is 0.2 parts by weight, and a still more preferred upper limit is 8 parts by weight.

The sealant for a liquid crystal display device of the present invention may contain a filler in order to improve the viscosity, improve the adhesion based on the stress dispersion effect, improve the coefficient of linear expansion, and further improve the moisture resistance of the cured product.

Examples of the filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, and zinc oxide. Inorganic fillers such as iron oxide, 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, An organic filler such as polyurethane microparticles, vinyl polymer microparticles, or acrylic polymer microparticles.

A preferred lower limit of the content of the above filler in 100 parts by weight of the sealant for a liquid crystal display device of the present invention is 10 parts by weight, and preferably the upper limit is 70 parts by weight. When the content of the above-mentioned filler is in this range, the coating property and the like are not deteriorated, and the effects such as improvement in adhesion are more excellent. A more preferred lower limit of the content of the above filler is 20 parts by weight, and a still more preferred upper limit is 60 parts by weight.

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

The decane coupling agent is excellent in the effect of improving the adhesion to a substrate or the like, and is chemically bonded to the curable resin to suppress the flow of the curable resin into the liquid crystal. For example, N-phenyl-3 is mentioned. -Aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-isocyanatepropylpropane Trimethoxy decane and the like.

A preferred lower limit of the content of the above decane coupling agent in 100 parts by weight of the sealing agent for a liquid crystal display device of the present invention is 0.1 part by weight, and a preferred upper limit is 20 parts by weight. When the content of the above decane coupling agent is in this range, the occurrence of liquid crystal contamination is suppressed, and the effect of improving the adhesion is more excellent. A more preferred lower limit of the content of the above decane coupling agent is 0.5 part by weight, and a more preferred upper limit is 10 parts 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 which has an improved transmittance of light in the vicinity of the ultraviolet region, particularly at a wavelength of 370 to 450 nm, as compared with the average transmittance of light having a wavelength of 300 to 800 nm. In other words, the titanium black has a light-shielding agent having a light-shielding property to the sealing agent for a liquid crystal display element of the present invention by sufficiently shielding light of a wavelength in the visible light region, and light having a wavelength near the ultraviolet region. penetrate. Therefore, by using the above-mentioned peptide black The photo-radical polymerization initiator of the liquid crystal display element of the present invention can be further increased as the photoradical polymerization initiator of the present invention can be further increased by the light having a wavelength of (370 to 450 nm). On the other hand, 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 optical density (OD value) per 1 μm of the titanium black is preferably 3 or more, and more preferably 4 or more. The higher the light-shielding property of the titanium black, the better, and the OD value of the titanium black is not particularly preferable, and is usually 5 or less.

The titanium black described above exhibits sufficient effects even if it is not surface-treated, but it can also be treated with an organic component such as a surface coupler or cerium oxide, titanium oxide, cerium oxide, aluminum oxide, or zirconium oxide. The inorganic component such as magnesium oxide is subjected to surface treatment of titanium black such as a coating. Among them, from the viewpoint of further improving the insulating property, it is preferred to carry out treatment with an organic component.

Further, since the liquid crystal display element produced by using the above-described titanium black as a light-shielding agent for the liquid crystal display element sealing agent of the present invention has sufficient light-shielding property, it can realize light-free light, has high contrast, and has excellent pattern. A liquid crystal display element that displays quality.

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

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

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

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

Further, 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).

A preferred lower limit of the content of the above-mentioned sunscreen agent in 100 parts by weight of the sealant for a liquid crystal display device of the present invention is 5 parts by weight, and preferably the upper limit is 80 parts by weight. By the content of the above-mentioned light-shielding agent, it is possible to exhibit more excellent light-shielding properties without lowering the adhesion of the obtained liquid crystal display element sealing agent to the substrate or the strength or the drawability after curing. A more preferred lower limit of the content of the above-mentioned sunscreen agent is 10 parts by weight, a more preferred upper limit is 70 parts by weight, a still lower limit is 30 parts by weight, and a still more preferred upper limit is 60 parts by weight.

The sealing agent for a liquid crystal display device of the present invention may further optionally contain a reactive diluent for adjusting the viscosity, a spacer such as a polymer bead for adjusting the gap of the panel, and 3-p-chlorophenyl-1,1- Additives such as a hardening accelerator such as dimethylurea, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other coupling agents.

As a method of producing the sealant for liquid crystal display elements of the present invention, for example, a homogeneous phase disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, A mixer such as a three-roll mill, a method of mixing a curable resin, a thermosetting agent, a radical polymerization initiator, a filler, or the like.

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

The conductive fine particles are not particularly limited, and for example, a metal ball or a conductive metal layer formed on the surface of the resin fine particles can be used. Among them, in the case where a conductive metal layer is formed on the surface of the resin fine particles, the excellent elasticity of the resin fine particles can be electrically connected without loss of a transparent substrate or the like, which is preferable.

Further, the liquid crystal display element using the sealing agent for a liquid crystal display element of the present invention or the upper 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 preferably used. Specifically, for example, a method having the following steps, such as screen printing, dispensing, etc., is used. The sealing agent for liquid crystal display elements of the invention is applied to one of two transparent substrates having electrodes such as ITO thin films to form a frame-like sealing pattern; and the fine droplets of liquid crystal are dripped and applied in the frame of the sealing pattern. a step of superposing another substrate under vacuum; and a step of heating to harden the sealant. Further, the step of temporarily curing the sealant by light irradiation may be performed before the step of heating to cure the sealant.

According to the present invention, it is possible to provide a sealant for a liquid crystal display element which can achieve both storage stability and rapid hardenability at a low temperature. 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.

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

(Production of Compound A having the structure represented by Formula (1))

Addition of propylene glycol monomethylether acetate 500 to 71 parts by weight of 1,4-bis(aminomethyl)cyclohexane and 190 parts by weight of bisphenol A diglycidyl ether Parts by weight and 500 parts by weight of n-butanol were mixed and dissolved, and heated and stirred at 100 ° C for 3 hours. The obtained reaction mixture was subjected to solvent removal and drying, and the obtained solid matter was pulverized by a jet mill to obtain a compound A (melting point: 83 ° C) having the structure represented by the above formula (1). It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis that the obtained compound A having the structure represented by the formula (1) had the structure represented by the above formula (3) (X is the above formula (2). -1) The group shown (R ¹ and R ² are methyl)).

(Production of Compound B having the structure represented by Formula (1))

The same method as the above "(Production of Compound A having the structure of the formula (1))" is used, except that 170 parts by weight of bisphenol F diglycidyl ether is used instead of 190 parts by weight of bisphenol A diglycidyl ether. The compound B (melting point 68 ° C) having the structure represented by the above formula (1) was obtained. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis that the obtained compound B having the structure represented by the formula (1) had the structure represented by the above formula (3) (X is the above formula (2). -1) The group shown (R ¹ and R ² are hydrogen)).

(Production of Compound C having the structure represented by Formula (1))

The same method as the above "(Production of Compound A having the structure of the formula (1))" is used, except that 180 parts by weight of bisphenol E diglycidyl ether is used instead of 190 parts by weight of bisphenol A diglycidyl ether. The compound C (melting point 78 ° C) having the structure represented by the above formula (1) was obtained. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis that the obtained compound C having the structure represented by the formula (1) had the structure represented by the above formula (3) (X is the above formula (2). -1) The group shown (one of R ¹ and R ² is a methyl group and the other is a hydrogen)).

(Production of Compound D having the structure represented by Formula (1))

The same as the above "(Production of Compound A having the structure of the formula (1))", except that 130 parts by weight of resorcinol diglycidyl ether is used instead of 190 parts by weight of bisphenol A diglycidyl ether. Thus, a compound D (melting point 94 ° C) having the structure represented by the above formula (1) was obtained. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis that the obtained compound D having the structure represented by the formula (1) had the structure represented by the above formula (3) (X is the above formula (2). -4) The base shown).

(Production of Compound E having the structure represented by Formula (1))

Except that 180 parts by weight of biphenyl-4,4'-diylbis(epoxypropyl ether) was used instead of 190 parts by weight of bisphenol A diglycidyl ether, as shown in the above formula (1) In the same manner as in the production of the compound A of the structure, a compound E (melting point: 98 ° C) having the structure represented by the above formula (1) was obtained. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis that the obtained compound E having the structure represented by the formula (1) had the structure represented by the above formula (3) (X is the above formula (2). -3) The base shown).

(Production of Compound F having the structure represented by Formula (1))

In the same manner as the above "(Production of Compound A having the structure represented by Formula (1))", except that 245 parts by weight of bisphenol A type epoxy resin is used instead of 190 parts by weight of bisphenol A diglycidyl ether, Compound F (melting point: 109 ° C) having the structure represented by the above formula (1) was obtained. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis that the obtained compound F having the structure represented by the formula (1) had the structure represented by the above formula (3) (X is the above formula (2). -1) The group shown (R ¹ and R ² are methyl)).

(Production of Compound G having the structure represented by Formula (1))

In addition to using 71 parts by weight of diaminophenylmethane to replace 71 parts by weight of 1,4-bis(aminomethyl)cyclohexane, the above "(Production of Compound A having the structure represented by Formula (1))" In the same manner, a compound G (melting point: 97 ° C) having the structure represented by the above formula (1) was obtained. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis that the obtained compound G having the structure represented by the formula (1) has the above formula (1) wherein X is the above formula (2-1). The structure of the group shown (R ¹ and R ² are methyl groups).

(Production of Compound H having the structure represented by Formula (1))

In addition to using 71 parts by weight of 1,3-bis(aminomethyl)cyclohexane to replace 71 parts by weight of 1,4-bis(aminomethyl)cyclohexane, with the above "(having formula (1) In the same manner as in the production of the compound A of the structure shown, the compound H (melting point 81 ° C) having the structure represented by the above formula (1) was obtained. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis that the obtained compound H having the structure represented by the formula (1) had the structure represented by the above formula (4) (X is the above formula (2). -1) The group shown (R ¹ and R ² are methyl)).

(Production of Compound I having the structure represented by Formula (1))

In addition to using 71 parts by weight of 1,3-bis(aminomethyl)cyclohexane to replace 71 parts by weight of 1,4-bis(aminomethyl)cyclohexane, with the above "(having formula (1) In the same manner as in the production of the compound B of the structure shown, a compound I (melting point: 67 ° C) having the structure represented by the above formula (1) was obtained. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis that the obtained compound I having the structure represented by the formula (1) has the structure represented by the above formula (4) (X is the above formula (2). -1) The group shown (R ¹ and R ² are hydrogen)).

(Production of epoxy-imidazole addition compound)

To 20 parts by weight of 2-methylimidazole and 190 parts by weight of bisphenol A diglycidyl ether, 500 parts by weight of toluene and 500 parts by weight of n-butanol were added, mixed and dissolved, and heated and stirred at 70 ° C for 2 hours. . The obtained reaction mixture was subjected to solvent removal and drying, and the obtained solid matter was pulverized by a jet mill to obtain an epoxy-imidazole addition compound.

(Examples 1 to 15, Comparative Examples 1, 2)

According to the blending ratios shown in Tables 1 and 2, each material was mixed using a planetary mixer ("Drying Stirring Taro" manufactured by Thinky Co., Ltd.), and then mixed using a three-roll mill, thereby preparing Example 1 ~15. Each of the sealing agents for liquid crystal display elements of Comparative Examples 1 and 2.

<evaluation>

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

(save stability)

For each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples, the initial viscosity immediately after the production and the viscosity at the time of storage at 25 ° C for 3 days were measured, and the viscosity was maintained after storage at 25 ° C for 3 days. / (initial viscosity) As the viscosity change rate, the viscosity change rate is less than 1.2, and it is set to "○", and if it is 1.2 or more, it is set to "△", and if it is 1.5 or more, it is set to "x". The storage stability was evaluated.

Further, the viscosity of the sealant was measured using an E-type viscometer ("DV-III" manufactured by BROOK FIELD) at 25 ° C and a rotation speed of 1.0 rpm.

(low temperature hardenability)

Each of the liquid crystal display element sealing agents obtained in the examples and the comparative examples was irradiated with ultraviolet rays of 100 mW/cm ² for 30 seconds using a metal halide lamp, and then measured by an FT-IR measuring instrument ("UMA600" manufactured by Agilent Technologies Co., Ltd.). The reaction rate of the epoxy group at a temperature of 100 ° C for 40 minutes (reduced from the peak of the epoxy group). When the reaction rate of the epoxy group is 90% or more, it is set to "○", and when it is less than 90% and 70% or more, it is set to "△", and when it is less than 70%, it is set to "X", and low temperature hardening is evaluated. Sex.

(Display performance of liquid crystal display elements)

1 part by weight of the separator (manufactured by Sekisui Chemical Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples, and the two wirings were rubbed. One of the film and the substrate with the transparent electrode was coated with a syringe so that the line width of the sealant was 1 mm, thereby forming a seal for a liquid crystal display element.

Then, a small droplet of liquid crystal (manufactured by Chisso Co., Ltd., "JC-5004LA") was applied dropwise to the entire surface of the sealant frame, and then another color filter substrate with a transparent electrode was attached immediately, using a metal halide. The lamp was irradiated with ultraviolet rays (wavelength 365 nm) of 100 mW/cm ² for 30 seconds, and then heated at 100 ° C for 40 minutes to obtain a liquid crystal display element.

After the 100-hour operation test was performed on the liquid crystal display element obtained, the liquid crystal alignment in the vicinity of the sealant after the voltage of 1000 hours was applied at 80 ° C was visually confirmed.

The alignment disorder is judged according to the color unevenness of the display portion, depending on the degree of color unevenness, The case where the color unevenness was not confirmed at all was evaluated as "◎", and the case where a slight color unevenness was confirmed was evaluated as "○", and the case where the color unevenness was slightly confirmed was evaluated as "△", which will be clearly The case where the color unevenness was confirmed was evaluated as "X", and the low liquid crystal contamination was evaluated.

In addition, the liquid crystal display elements evaluated as "◎" and "○" are grades which are practically problem-free, and "△" is a level which may cause problems depending on the display design of the liquid crystal display element, and "×" is intolerant. At the level of practical application.

[Industrial availability]

According to the present invention, it is possible to provide a sealant for a liquid crystal display element which can achieve both storage stability and rapid hardenability at a low temperature. 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 (7)

A sealant for a liquid crystal display device, comprising a curable resin and a thermosetting agent, wherein the thermosetting agent contains a compound having a structure represented by the following formula (1) In the formula (1), X is a structure having an aromatic ring, n is an integer of 1 or more, and * is a bonding position. The sealant for liquid crystal display elements of the first aspect of the invention, wherein X in the formula (1) is the following formula (2-1), (2-2), (2-3), (2-4) ), or the structure shown in (2-5) In the formula (2-1), R ¹ and R ² are each independently hydrogen or a methyl group, and in the formulae (2-1) to (2-5), * is a bonding position. The sealant for a liquid crystal display element according to the first aspect of the invention, wherein the compound having the structure represented by the formula (1) contains a compound having a structure represented by the following formula (3). In the formula (3), the X system has the same structure as the X in the formula (1), n is the same number as n in the formula (1), and the * is a bonding position. The sealing agent for liquid crystal display elements of the first aspect or the second aspect of the invention, wherein the compound having the structure represented by the formula (1) contains a compound having a structure represented by the following formula (4). In the formula (4), the X system has the same structure as X in the formula (1), n is the same number as n in the formula (1), and * is a bonding position. The sealant for a liquid crystal display element according to the first, second, third or fourth aspect of the invention, wherein the compound having the structure represented by the formula (1) has a melting point of 60 ° C to 100 ° C. A top-bottom conductive material containing a sealant for a liquid crystal display element of the first, second, third, fourth or fifth aspect of the patent application and conductive fine particles. A liquid crystal display element which is obtained by using a sealing agent for a liquid crystal display element of the first, second, third, fourth or fifth aspect of the patent application or a conductive material for a lower surface of the sixth aspect of the patent application.