TW201728662A - 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 curability 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 curable resin contains a curable resin having an epoxy group; the thermal curing agent contains an amine adduct compound that has a structure derived from an epoxy resin and a structure derived from an amine compound; and an amine compound, from which the amine adduct compound is derived, is an alkyl imidazole having an alkyl group with 1-20 carbon atoms.

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 low-temperature curability and storage stability. 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 method of using a curable resin, a photopolymerization initiator, and a thermosetting agent to form a photocurable heat-curing sealant is called a drip method. In the drip method, a rectangular seal 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.

From the viewpoint of energy saving or stability of liquid crystal, the above-mentioned sealant is desirably thermally cured 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, a heat hardener or a hardening accelerator having a lower melting point has been previously used. however, When a heat hardener or a hardening accelerator having a low melting point is used, there is a problem in that a reaction tends to occur near room temperature, and the storage stability of the sealant is lowered.

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 low-temperature curability and storage stability. 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, which comprises a curable resin and a thermosetting agent, wherein the curable resin contains a curable resin having an epoxy group, and the thermosetting agent contains a resin derived from an epoxy resin. The structure and the amine addition compound derived from the structure of the amine compound, the amine compound which is the source of the above amine addition compound is an alkylimidazole having an alkyl group having 1 to 20 carbon atoms.

Hereinafter, the present invention will be described in detail.

The present inventors have found that by using an addition object of an alkylimidazole having an alkyl chain of a specific length and an epoxy resin as a thermosetting agent, a sealing for a liquid crystal display element which can achieve both low-temperature hardenability and storage stability can be obtained. Agent to complete the present invention.

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

The above-mentioned thermosetting agent contains an amine-addition compound having a structure derived from an epoxy resin and a structure derived from an amine compound, and the amine compound is an alkylimidazole described below. By using such an amine addition compound as the above-mentioned thermosetting agent, it is possible to improve the hardenability at a low temperature while maintaining excellent storage stability.

As the epoxy resin which is a source of the above-mentioned amine addition compound, for example, the same as the curable resin having an epoxy group described below can be used. Among them, an epoxy resin having an aromatic ring is preferred. The epoxy resin which is a source of the above amine addition compound has an aromatic ring, and the storage stability of the obtained sealing compound for liquid crystal display elements can be further improved. The epoxy resin which is a source of the above amine addition compound is more preferably at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol E type epoxy resin. .

The amine compound which is a source of the above amine addition compound is an alkylimidazole having an alkyl group having 1 to 20 carbon atoms.

The alkylimidazole having 1 to 20 carbon atoms of the alkyl group is preferably one or two carbon atoms of the alkyl group, more preferably 2-methylimidazole.

As the above-mentioned amine addition compound, a compound represented by the following formula (1-1) and/or a compound represented by the following formula (1-2) can be preferably used.

Further, the following sealing agent for a liquid crystal display element is one of the inventions, which comprises a curable resin and a thermosetting agent, and the curable resin contains a curable resin having an epoxy group, and the thermosetting agent contains the following A compound represented by the formula (1-1) and/or a compound represented by the following formula (1-2).

In the formula (1-1) and the formula (1-2), R ¹ is an alkyl group having 1 to 20 carbon atoms, and in the formula (1-1), R ² and R ³ are each hydrogen or methyl, and they may be the same. It can also be different.

In addition, the thermosetting agent preferably contains a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), a compound represented by the following formula (2-3), and At least one of the group consisting of the compounds represented by the formula (2-4) is a compound represented by the above formula (1-1) and/or a compound represented by the above formula (1-2).

A preferred upper limit of the average particle diameter of the above amine addition compound is 3 μm. When the average particle diameter of the above amine addition compound is 3 μm or less, the gap defect of the obtained liquid crystal display element can be suppressed. The average particle diameter of the above amine addition compound is not particularly preferably a lower limit, but the substantial lower limit is 0.1 μm.

In the case of using an amine-addition compound having a commercially available average particle diameter of more than 3 μm, the average particle diameter can be made 3 μm or less by performing treatment such as pulverization or classification.

Furthermore, in the present specification, the average particle diameter of the above amine addition compound and the maximum particle diameter described below mean an amine addition before blending with a sealant by using a laser diffraction type particle size distribution analyzer. The value obtained by the measurement of the compound. As the above-described laser diffraction type particle size distribution measuring apparatus, Mastersizer 2000 (manufactured by Malvern Co., Ltd.) or the like can be used.

A preferred upper limit of the maximum particle diameter of the above amine addition compound is 5.0 μm. When the maximum particle diameter of the above amine addition compound is 5.0 μm or less, the obtained liquid crystal display element is more excellent in gap retention. A more preferable upper limit of the maximum particle diameter of the above amine addition compound is 4.5 μm. The maximum particle diameter of the above amine addition compound is not particularly preferably a lower limit, but the substantial lower limit is 0.1 μm.

In the above-mentioned amine addition compound, among the particle size distributions of the amine addition compounds measured by the above-described laser diffraction type particle size distribution measuring apparatus, the content ratio of the particles having a particle diameter of preferably 3.0 μm or less is in volume frequency. Calculated as 99% or more. When the content ratio of the particles having a particle diameter of 3.0 μm or less is 99% or more in terms of volume frequency, the obtained liquid crystal display element is more excellent in gap retention. The content ratio of the particles having a particle diameter of 3.0 μm or less is preferably 100%.

The content of the above amine addition compound is preferably 0.3 parts by weight, more preferably 15 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned amine addition compound is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in low-temperature hardenability and more excellent in suppressing liquid crystal contamination. A more preferred lower limit of the content of the above amine addition compound is 0.4 parts by weight, more preferably 12 parts by weight, still more preferably 0.5 parts by weight, and still more preferably 10 parts by weight.

The above-mentioned thermosetting agent may contain other thermosetting agents in addition to the above amine addition compound.

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.

In the case where the other heat curing agent is contained, the content of the entire heat curing 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 entire heat curing agent is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in thermosetting property and coating property. A more preferable upper limit of the content of the above thermal curing agent is 30 parts by weight.

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

The curable resin contains a curable resin having an epoxy group.

Examples of the curable resin having an epoxy group include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol E epoxy resin, and a bisphenol S 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, phenol novolak type epoxy resin, o-cresol novolac type epoxy resin, Dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, epoxy propylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modification Type epoxy resin, glycidyl ester compound, and the like.

As a commercial item among the above-mentioned bisphenol A type epoxy resins, for example, jER828, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), and EPICLON 850 (DIC) are mentioned. Company manufacturing) and so on.

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.

Examples of the commercially available product of the bisphenol E-type epoxy resin include EPOX-MK R710 and EPOX-MK R1710 (all manufactured by Printec).

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 above-mentioned resorcinol type epoxy resin, EX-201 (made by Nagase ChemteX company) etc. are mentioned, for example.

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.

As a commercial item in the above-mentioned dicyclopentadiene type epoxy resin, for example, EP-4088S is mentioned. (made by ADEKA), etc.

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.

For example, jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like are mentioned as a commercial product of the above-mentioned epoxy propylamine type epoxy resin.

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.

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

Other commercially available products of the epoxy compound include, for example, YH-300, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

The above-mentioned epoxy group-containing curable resin may be a partial (meth)acrylic modified epoxy resin. 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, by having 2 molecules in one molecule. The epoxy group which is one part or more of the epoxy compound of the epoxy group is obtained by reacting with (meth)acrylic acid.

In the present specification, the above "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above "(meth)acrylylene group" means an acryl group or a methacryl group.

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

A preferred lower limit of the content of the above epoxy group-containing curable resin in 100 parts by weight of the curable resin is 1 part by weight, and preferably the upper limit is 100 parts by weight. When the content of the above-mentioned epoxy group-containing curable resin is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in adhesion. A more preferred lower limit of the content of the above epoxy group-containing curable resin is 2 parts by weight.

The curable resin may contain other curable resin in addition to the above-mentioned curable resin having an epoxy group. As the other curable resin, a (meth)acrylic compound is preferred.

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 more preferred. Further, the (meth)acrylic compound is preferably one having two or more (meth)acrylonium groups in the molecule in terms of high reactivity.

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, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxy (meth) acrylate Ethyl ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol ( Methyl) 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, hexahydrophthalic acid 2- (Meth) propylene methoxyethyl ester, 2-hydroxypropyl phthalate 2-(methyl) propylene oxy group B Ester, 2-(meth)acryloyloxyethyl 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) 2-hydroxy-3-(methyl)propenyl propyl acrylate, carbonate diol di(methyl) propyl Acid ester, polyether diol di(meth) acrylate, polyester diol di(meth) acrylate, polycaprolactone diol di(meth) acrylate, polybutadiene diol di (a) Base) acrylate and the like.

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 synthesizing the above epoxy (meth) acrylate, the same as the epoxy compound exemplified as the above-mentioned curable resin having an epoxy group 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 (all manufactured by Daicel-Allnex), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all 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 (both 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 (meth)acrylic acid amide obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound can be, for example, a hydroxyl group (meth) by the presence of a catalyst amount of a tin compound. 2 equivalents of an acrylic acid derivative are obtained by reacting 1 equivalent of an isocyanate compound having 2 isocyanate groups.

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, and 2,6-toluene. Isocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, hail Alkyl diisocyanate, tolidine diisocyanate, benzodimethyl diisocyanate (XDI), hydrogenated XDI, quaternary acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) phosphorothioate, tetramethyl Benzyl 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.

Examples of the (meth)acrylic acid derivative having a hydroxyl group which is a raw material of the above (meth)acrylic acid amide include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. a hydroxyalkyl mono(meth)acrylate such as 2-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate; or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3- a mono (meth) acrylate of a glycol such as butanediol, 1,4-butanediol or polyethylene glycol; or a monohydric alcohol such as trimethylolethane, trimethylolpropane or glycerol (meth) acrylate or di(meth) acrylate; or epoxy (meth) acrylate such as bisphenol A 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.), EBECRYL 210, EBECRYL 220, and EBECRYL. 230, EBECRYL 270, EBECRYL 1290, EBECRYL 2220, EBECRYL 4827, EBECRYL 4842, EBECRYL 4858, EBECRYL 5129, EBECRYL 6700, EBECRYL 8402, EBECRYL 8803, EBECRYL 8804, EBECRYL 8807, EBECRYL 9260 (all manufactured by 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 Xinzhongcun Chemical Industry Co., Ltd.), AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Gongrongshe Chemical Co., Ltd.) )Wait.

In the case where the curable resin contains the above-mentioned partial (meth)acrylic modified epoxy resin or the above (meth)acrylic compound, the epoxy group and the (meth)acrylonitrile group in the curable resin are preferably used. The ratio becomes 30:70~95:5. When the ratio of the epoxy group to the (meth) acrylonitrile group is within this range, the adhesion of the obtained sealing agent for a liquid crystal display element or the liquid crystal display of the sealing agent for a liquid crystal display element obtained by using the same can be further improved. Display performance of components.

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

As the above radical polymerization initiator, a thermal radical polymerization initiator or a photoradical polymerization initiator can be used.

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. By making the number average molecular weight of the above polymer azo initiators 1000 or more, liquid crystal contamination can be suppressed. By setting the number average molecular weight of the above polymer azo initiator to be within this range, it is possible to prevent adverse effects on the liquid crystal and to more easily mix in the curable resin. The lower limit of the number average molecular weight of the above polymer azo initiator is 5,000, more preferably 100,000, and still more preferably 10,000, and further preferably 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.

In addition, examples of the azo initiators other than the polymer hydride initiator include V-65 and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.).

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

The content of the thermal radical polymerization initiator is preferably 0.05 parts by weight, and preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the thermal radical polymerization initiator is 0.05 parts by weight or more, the obtained sealing agent for a liquid crystal display element is more excellent in thermosetting property. When the content of the thermal radical polymerization initiator is 10 parts by weight or less, the obtained sealing agent for a liquid crystal display element is more excellent in suppressing liquid crystal contamination. A more preferred lower limit of the content of the above thermal radical polymerization initiator is 0.1 part by weight, and a more preferred upper limit is 5 parts by weight.

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, IRGACURE OXE02, Lucirin TPO (both may be mentioned). Manufactured by BASF Corporation, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.).

The content of the photoradical 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. The liquid crystal display element obtained by setting the content of the photoradical polymerization initiator to 0.1 part by weight or more The sealant for a part is more excellent in photocurability. When the content of the photoradical polymerization initiator is 10 parts by weight or less, the obtained sealing agent for a liquid crystal display element is more excellent in weather resistance. A more preferred lower limit of the content of the above photoradical polymerization initiator is 0.2 parts by weight, and a 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 talc, asbestos, silica, diatomaceous earth, bentonite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, and magnesium oxide. , inorganic fillers such as tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, tantalum nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride, or polyester microparticles, Organic fillers such as polyurethane microparticles, ethylene polymer microparticles, acrylic polymer microparticles, and core-shell acrylate copolymer microparticles. These fillers may be used singly or in combination of two or more.

A preferred lower limit of the content of the above filler in 100 parts by weight of the sealant for a liquid crystal display device of the present invention is 10 parts by weight, preferably 70 parts by weight. When the content of the filler is 10 parts by weight or more, the effect of improving the adhesion can be further improved. When the content of the filler is 70 parts by weight or less, the obtained sealant for a liquid crystal display element is more excellent in coatability. A more preferred lower limit of the content of the above filler is 20 parts by weight, and a more preferred upper limit is 60 parts by weight.

The sealant for a liquid crystal display element of the present invention may further contain a decane coupling agent. The above decane coupling agent has a secondary auxiliary agent which is mainly used for the sealing agent and the substrate. Features.

The decane coupling agent is excellent in the effect of improving the adhesion to a substrate or the like, and can be used to inhibit the flow of the curable resin into the liquid crystal by chemical bonding with the curable resin. For example, N can be preferably used. -phenyl-3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, and the like. These decane coupling agents may be used singly or in combination of two or more.

A preferred lower limit of the content of the above decane coupling agent in 100 parts by weight of the sealant for a liquid crystal display device of the present invention is 0.1 part by weight, and preferably the upper limit is 20 parts by weight. By setting the content of the above decane coupling agent to 0.1 part by weight or more, the adhesion to the substrate or the like can be further improved. When the content of the decane coupling agent is 20 parts by weight or less, the obtained sealing agent for a liquid crystal display element is more excellent in suppressing liquid crystal contamination. A more preferred lower limit of the content of the above decane coupling agent is 0.5 parts by weight, and a more preferred upper limit is 10 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 or isomeric cyanuric acid, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other coupling agents.

The method for producing the sealant for a liquid crystal display device of the present invention includes, for example, a homogenizer, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, or the like, and a curable resin. , a method of mixing a thermosetting agent, and an additive such as a filler or a decane coupling agent to be added as needed.

By incorporating conductive particles into the sealant for liquid crystal display elements of the present invention The sub-conducting material can be manufactured. 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 a metal ball or a conductive metal layer formed on the surface of the resin fine particles can be used. Among them, it is preferable that the conductive metal layer is formed on the surface of the resin fine particles by the excellent elasticity of the resin fine particles, and the conductive connection can be performed without damaging the transparent substrate or the like.

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: applying a sealant for a liquid crystal display element of the present invention to two transparent substrates having electrodes such as an ITO thin film by screen printing or a dispenser application a step of forming a frame-like sealing pattern; applying a droplet of liquid crystal to the entire surface of the sealing pattern, overlapping another substrate under vacuum; and irradiating the sealing pattern with ultraviolet rays, etc. a step of temporarily hardening the sealant by light; and a step of heating the temporarily hardened sealant to form a hardening.

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

(Manufacture of amine addition compound A)

300 mL of a n-butanol/toluene mixed solution having a mixing ratio of 1:1 was placed in a three-necked flask, and further, 38.0 parts by weight of bisphenol A type epoxy resin ("JER828" manufactured by Mitsubishi Chemical Corporation) and 2-methylimidazole were charged. (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.1 parts by weight. After heating and stirring at 65 ° C for 4 hours, solvent removal and vacuum drying were carried out to obtain an amine addition compound A having a structure derived from a bisphenol A type epoxy resin and a structure derived from 2-methylimidazole.

By the ¹ H-NMR, ¹³ C-NMR, and IR measurement of the obtained amine addition compound A, it was confirmed that it was a compound represented by the above formula (2-1).

(Manufacture of amine addition compound B)

300 mL of a n-butanol/toluene mixed solution having a mixing ratio of 1:1 was placed in a three-necked flask, and further, an aliphatic epoxy resin ("YH-300" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) was added, and 30.0 parts by weight and 2 Methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was 4.1 parts by weight. After heating and stirring at 65 ° C for 4 hours, solvent removal and vacuum drying were carried out to obtain an amine addition compound B having a structure derived from an aliphatic epoxy resin and a structure derived from 2-methylimidazole.

By the ¹ H-NMR, ¹³ C-NMR, and IR measurement of the obtained amine addition compound B, it was confirmed that it was a compound represented by the above formula (2-2).

(Manufacture of amine addition compound C)

300 mL of a n-butanol/toluene mixed solution having a mixing ratio of 1:1 was placed in a three-necked flask, and In addition, 38.0 parts by weight of bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation) and 20.3 parts by weight of 2-heptadecylimidazole ("C17Z" manufactured by Shikoku Chemicals Co., Ltd.) were charged. After heating and stirring at 65 ° C for 4 hours, solvent removal and vacuum drying were carried out to obtain an amine addition compound C having a structure derived from a bisphenol A type epoxy resin and a structure derived from 2-heptadecylimidazole. .

By the ¹ H-NMR, ¹³ C-NMR, and IR measurement of the obtained amine addition compound C, it was confirmed that it was a compound represented by the above formula (2-3).

(Manufacture of amine addition compound D)

300 mL of a n-butanol/toluene mixed solution having a mixing ratio of 1:1 was placed in a three-necked flask, and further, an aliphatic epoxy resin ("YH-300" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) was added, and 30.0 parts by weight and 2 Heptadecyl imidazole ("C17Z" manufactured by Shikoku Chemicals Co., Ltd.) was 20.3 parts by weight. After heating and stirring at 65 ° C for 4 hours, solvent removal and vacuum drying were carried out to obtain an amine addition compound D having a structure derived from an aliphatic epoxy resin and a structure derived from 2-heptadecylimidazole.

By the ¹ H-NMR, ¹³ C-NMR, and IR measurement of the obtained amine addition compound D, it was confirmed that it was a compound represented by the above formula (2-4).

(Manufacture of amine addition compound E)

300 mL of a n-butanol/toluene mixed solution having a mixing ratio of 1:1 was placed in a three-necked flask, and further, 38.0 parts by weight of bisphenol A type epoxy resin ("JER828" manufactured by Mitsubishi Chemical Corporation) and 2-phenylimidazole were charged. (manufactured by Wako Pure Chemical Industries, Ltd.) 7.2 parts by weight. After heating and stirring at 65 ° C for 4 hours, solvent removal and vacuum drying were carried out to obtain an amine addition compound E having a structure derived from a bisphenol A type epoxy resin and a structure derived from 2-phenylimidazole.

By the ¹ H-NMR, ¹³ C-NMR, and IR measurement of the obtained amine addition compound E, it was confirmed that it was a compound represented by the following formula (3).

(Examples 1 to 7 and Comparative Examples 1 to 4)

According to the blending ratios shown in Table 1, each of the materials was mixed using a planetary mixer (manufactured by Thinky Co., Ltd., "defoaming and stirring"), and then mixed using a three-roll mill to prepare Examples 1 to 7, Each of the sealing agents for liquid crystal display elements of Examples 1 to 4 was used.

<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 Table 1.

(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 1.3, which is "◎", and it is 1.3 or more, and if it is less than 1.5, it is set to "○", and it is 1.5 or more, and it is less than 2.0. When it is set to "△", it is set to "X" for 2.0 or more, and the storage stability is evaluated.

Further, the viscosity of the sealant was measured using an E-type viscometer ("DV-III" manufactured by BROOK Field Co., Ltd.) 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 filled in a syringe for dispensing ("PSY-10E" manufactured by Musashi Engineering Co., Ltd.), and subjected to defoaming treatment. Then, using a dispenser (manufactured by Musashi Engineering Co., Ltd., "SHOTMASTER 300"), a sheet of a transparent electrode substrate with two ITO films was applied, and a sealant was applied so as to draw a rectangular frame. Then, a liquid droplet dropping device is used to drip a small droplet of TN liquid crystal ("JC-5001LA" manufactured by Chisso Co., Ltd.) into a frame of the formed sealant, and the vacuum bonding device is used to reduce the amount of 5 Pa. Pressing and bonding another transparent substrate. After the bonded unit was irradiated with ultraviolet rays of 3,000 mJ/cm ² by a metal halide lamp, and then heated at 100 ° C for 60 minutes, the sealing agent was thermally cured to prepare a liquid crystal display element. The irradiation of ultraviolet rays is performed by cutting off light having a wavelength of 340 nm or less by a filter. The obtained liquid crystal display element was stored at a temperature of 80 ° C for 100 hours, and then driven at a voltage of 3.5 V AC, and visually observed. The case where the display unevenness (color unevenness) is not displayed at the peripheral portion of the liquid crystal display element is set to "◎", and the case where a slight display unevenness is seen is set to "○", and there will be clear and deep In the case where the display unevenness is set to "△", the display unevenness of the liquid crystal display element is evaluated not only in the peripheral portion but also in the case where the central portion is extended to the "X". .

(visible light hardening)

Each of the sealing materials for liquid crystal display elements obtained in Example 5 was applied onto a glass substrate at about 5 μm, and a glass substrate of the same size was stacked on the substrate, and then, light of 100 mW/cm ^{2 was} irradiated with a metal halide lamp. Seconds. The light irradiation is performed by cutting off light having a wavelength of 380 nm or less by a filter. The peak derived from the acrylonitrile group before and after the light irradiation was measured using an infrared spectroscopic device ("FTS3000" manufactured by BIORAD Co., Ltd.), and the decrease rate of the peak derived from the acrylonitrile group after light irradiation was derived. The case where the reduction rate of the peak derived from the acrylonitrile group after irradiation with light is 93% or more is "◎", and when it is 85% or more and less than 93%, it is set to "○", which is 75%. In the case where the above is less than 85%, it is set to "△", and when it is less than 75%, it is set to "X", and the visible light hardenability is evaluated.

[Industrial availability]

According to the present invention, it is possible to provide a sealant for a liquid crystal display element which can achieve both low-temperature curability and storage stability. Further, 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 element, comprising a curable resin and a thermosetting agent, wherein the curable resin contains a curable resin having an epoxy group, and the thermosetting agent contains a resin derived from an epoxy resin. The structure and the amine addition compound derived from the structure of the amine compound, the amine compound which is the source of the above amine addition compound is an alkylimidazole having an alkyl group having 1 to 20 carbon atoms. The sealing agent for liquid crystal display elements of the first aspect of the invention, wherein the alkylimidazole having an alkyl group having 1 to 20 carbon atoms is 2-methylimidazole. The sealant for a liquid crystal display element according to claim 1 or 2, wherein the epoxy resin which is a source of the amine addition compound has an aromatic ring. The sealing agent for liquid crystal display elements of claim 1, wherein the epoxy resin which is a source of the amine addition compound is selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin. And at least one of the group consisting of bisphenol E type epoxy resins. A sealant for a liquid crystal display device, comprising a curable resin and a thermosetting agent, wherein the curable resin contains a curable resin having an epoxy group, and the thermosetting agent contains the following formula (1-1) a compound represented by the formula (II) and/or a compound represented by the following formula (1-2), In the formula (1-1) and the formula (1-2), R ¹ is an alkyl group having 1 to 20 carbon atoms, and in the formula (1-1), R ² and R ³ are each hydrogen or methyl, and they may be the same. It can also be different. A top-bottom conductive material comprising a sealant for a liquid crystal display element and a conductive fine particle of the first, second, third, fourth or fifth aspect of the patent application. 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 above the sixth aspect of the patent application.