TW201835213A - 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 has excellent bonding properties and low possibility of contaminating liquid crystals, and which enables the achievement of a liquid crystal display element that has excellent impact resistance. 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, a maleimide compound and a polymerization initiator, and wherein the curable resin contains a compound that has a polymerizable functional group, an alkylene oxide skeleton and a hydroxyl group.

Description

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

The present invention relates to a sealing agent for a liquid crystal display element which is excellent in adhesion and low liquid crystal contamination and which is excellent in impact resistance. 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, a liquid crystal display element is used, and a liquid crystal amount is shortened, and the liquid crystal amount is optimized. In the method of dropping, the method uses a photocurable heat-curing sealant containing a curable resin, a photopolymerization initiator, and a thermosetting agent.

In the liquid crystal dropping method, first, a sealing pattern of a rectangular shape is formed by dispensing on one of two substrates with electrodes. Then, the liquid crystal droplets 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 pre-cured by irradiating light such as ultraviolet rays. Then, it is heated and subjected to main hardening to produce a liquid crystal display element. At present, this dropping method is the mainstream of the manufacturing method of liquid crystal display elements.

In addition, various mobile devices including mobile phones, such as mobile phones and portable game machines, are becoming more and more popular, and miniaturization of devices is the most urgent issue. As a method of downsizing, a narrow frame of the liquid crystal display unit is exemplified, and for example, a step of arranging the position of the sealing portion below the black matrix (hereinafter also referred to as "narrow frame design") is performed.

With such a narrow bezel design, in the liquid crystal display element, the distance from the pixel region to the sealant becomes close, and display unevenness due to contamination of the liquid crystal by the sealant is likely to occur.

In addition, with the spread of the mobile terminal, the liquid crystal display element is required to have an impact resistance, and the sealant is required to be peeled off from the outside even when the liquid crystal display element is dropped from the outside. The higher the continuity. However, in the conventional sealant, it is difficult to achieve such high adhesion and low liquid crystal contamination at the same time.

[Previous Technical Literature]

[Patent Literature]

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

Patent Document 2: International Publication No. 02/092718

An object of the present invention is to provide a sealing agent for a liquid crystal display element which is excellent in adhesion and low liquid crystal contamination, and which is excellent in impact resistance. 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 element comprising a curable resin, a maleimide compound, and a polymerization initiator, and the curable resin contains a polymerizable functional group or an alkylene oxide. a compound of a skeleton and a hydroxyl group.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have studied to improve the adhesion of a sealing agent for a liquid crystal display element and the flexibility of a cured product by introducing an alkylene oxide skeleton into a curable resin having a polymerizable functional group, thereby improving the impact resistance of the liquid crystal display element. However, there is a problem that the obtained sealant has a situation in which liquid crystal contamination occurs due to the design of the liquid crystal display element. Therefore, the inventors of the present invention have conducted intensive studies and found that a resin having a hydroxyl group other than the alkylene oxide skeleton is used as a curable resin, and further, a maleimide compound is blended, whereby the adhesion and the lowness can be obtained. The present invention has been completed by a sealing agent for a liquid crystal display element of a liquid crystal display element which is excellent in liquid crystal contamination and excellent in impact resistance.

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

The curable resin contains a compound having a polymerizable functional group, an alkylene oxide skeleton, and a hydroxyl group (hereinafter also referred to as "the polymerizable compound of the present invention"). By using the polymerizable compound of the present invention in combination with the following maleimide compound, the sealing agent for a liquid crystal display device of the present invention is excellent in adhesion, softness of a cured product, and low liquid crystal contamination. .

From the viewpoint of the reactivity, the polymerizable compound of the present invention preferably has two or more polymerizable functional groups in one molecule.

Further, the polymerizable functional group of the polymerizable compound of the present invention is preferably a (meth) acrylonitrile group and/or an epoxy group.

In the present specification, the above "(meth)acryloyl group" means an acryloyl group or a methacryl group.

The polymerizable compound of the present invention preferably has one or more and ten or less of the above alkylene oxide skeletons in one molecule. When the amount of the above-mentioned alkylene oxide skeleton is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in the effect of simultaneously achieving adhesion and low liquid crystal contamination. The polymerizable compound of the present invention preferably has two or more and five or less of the above alkylene oxide skeletons in one molecule.

Examples of the alkylene group constituting the above alkylene oxide skeleton include an exoethyl group, a propyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. In particular, a hexamethylene group is preferred in that the effect of improving the adhesion between the sealant for a liquid crystal display element obtained and the flexibility of the cured product is improved.

The polymerizable compound of the present invention preferably has one or more and 30 or less of the above hydroxyl groups in one molecule. When the amount of the above-mentioned hydroxyl group is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in the effect of simultaneously achieving adhesion and low liquid crystal contamination. The polymerizable compound of the present invention preferably has two or more and 12 or less of the above hydroxyl groups in one molecule.

A preferred lower limit of the molecular weight of the polymerizable compound of the present invention is 600, and a preferred upper limit is 3,000. When the molecular weight of the polymerizable compound of the present invention is within this range, the obtained sealing agent for a liquid crystal display device is more excellent in the effect of improving adhesion, moisture permeability, or low liquid crystal contamination without causing deterioration in coatability and the like. . The lower limit of the molecular weight of the polymerizable compound of the present invention is preferably 700, and the upper limit is more preferably 1,500.

In the present specification, the "molecular weight" is a molecular weight determined by a structural formula for a compound having a specific molecular structure, but is used for a compound having a broad distribution of polymerization degree and a compound having no modified portion. The case of weight average molecular weight. In the present specification, the above "weight average molecular weight" is determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and obtained by polystyrene conversion. For example, Shodex LF-804 (manufactured by Showa Denko KK) can be used as the column to be used for the measurement of the weight average molecular weight by the polystyrene conversion.

Specific examples of the polymerizable compound of the present invention include compounds represented by the following formula (1-1) or (1-2).

In the formula (1-1), A ¹ represents a structure represented by the following formulas (2-1) to (2-6), and X ¹ represents a methylene group, a methylmethylene group, a dimethylmethylene group, and an oxygen group. The atom, the sulfonyl group, the carbonyl group or the bonding bond, and Y ¹ each independently represent a group represented by the following formula (3-1) or (3-2), and n is 1 or more and 3 or less (average value).

In the formula (1-2), A ² represents a structure represented by the following formulas (4-1) to (4-7), and X ² represents a methylene group, a methylmethylene group, a dimethylmethylene group, and an oxygen group. An atom, a sulfonyl group, a carbonyl group or a bonding bond, Y ² represents a group represented by the following formula (5), and m is 1 or more and 3 or less (average value).

In the formulas (2-1) to (2-6), * indicates the bonding position.

In the formula (3-1), R ¹ represents a structure or a bond bond represented by the following formulas (6-1) to (6-6), and R ² represents a hydrogen atom or a methyl group, and in the formula (3-2), R ³ represents a structure or a bond bond represented by the following formulas (6-1) to (6-6), and in the formulae (3-1) and (3-2), * represents a bond position.

In the formulas (4-1) to (4-7), * indicates the bonding position.

In the formula (5), R ⁴ represents a hydrogen atom or a methyl group, and * represents a bonding position.

In the formulas (6-1) to (6-6), * indicates the bonding position.

Further, in the above formulae (6-1) to (6-6), the bonding position at the methylene side in the bonding position indicated by * becomes the above formula (3-1) or the above formula (3-2) The bonding position of the oxygen atom in the ).

A preferred lower limit of the content of the polymerizable compound of the present invention in 100 parts by weight of the curable resin is 10 parts by weight, and a preferred upper limit is 95 parts by weight. When the content of the polymerizable compound of the present invention is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in the effect of simultaneously achieving adhesion and moisture permeability resistance or low liquid crystal contamination. A lower limit of the content of the polymerizable compound of the present invention is preferably 15 parts by weight, more preferably 85 parts by weight, still more preferably 20 parts by weight, still more preferably 75 parts by weight, and even more preferably 40 parts by weight. Share.

The curable resin preferably contains a polymerizable compound other than the polymerizable compound of the present invention from the viewpoint of moisture permeability resistance and the like.

Examples of the other polymerizable compound include an epoxy compound other than those contained in the polymerizable compound of the present invention or another (meth)acrylic compound.

In the present specification, the above "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above "(meth)acrylic acid compound" means a compound having a (meth)acryl fluorenyl group.

Examples of the other 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'-dienes. Propyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy Resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol An aldehyde varnish type epoxy resin, a naphthol novolak type epoxy resin, a epoxidized acryl type epoxy resin, a rubber modified epoxy resin, a glycidyl ester compound, and the like.

For example, jER 828EL, jER 1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (manufactured by DIC Corporation), and the like are mentioned as a commercial product of the bisphenol A type epoxy resin.

The commercially available one of the bisphenol F-type epoxy resins may, for example, be jER 806 or jER 4004 (all manufactured by Mitsubishi Chemical Corporation).

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

As a commercial item of the said bisphenol S type epoxy resin, EPICLON EXA-1514 (made by the DIC company) etc. are mentioned, for example.

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

As a commercial item of the said hydrogenated bisphenol type epoxy resin, EPICLON EXA-7015 (made by the DIC company) etc. are mentioned, for example.

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

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

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

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

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

The commercially available ones of the above-mentioned naphthalene type epoxy resins include EPICLON HP4032 and EPICLON EXA-4700 (all manufactured by DIC Corporation).

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

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

The commercially available one of the above-mentioned dicyclopentadiene novolac type epoxy resins is exemplified by EPICLON HP7200 (manufactured by DIC Corporation).

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

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

For example, jER 630 (manufactured by Mitsubishi Chemical Corporation); EPICLON 430 (manufactured by DIC Corporation); TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc., may be mentioned as a commercially available one of the above-mentioned epoxy propylamine type epoxy resins.

For example, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (manufactured by Daicel Chemical Co., Ltd.), and the like are mentioned as a commercial product of the above-mentioned rubber-modified epoxy resin.

As a commercial one of the above-mentioned glycidyl ester compounds, for example, Denacol EX-147 (manufactured by Nagase Chemical Co., Ltd.) or the like can be mentioned.

Further, the curable resin may contain, as the above-mentioned other epoxy compound, a compound having an epoxy group and a (meth)acrylonium group in one molecule. As such a compound, for example, a partial (meth)acrylic acid modified by reacting a partial epoxy group of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid is exemplified. Epoxy resin, etc.

The commercially available ones of the above-mentioned partial (meth)acrylic acid-modified epoxy resins include, for example, UVACURE 1561 (manufactured by Daicel Co., Ltd.), BEEM-50 (manufactured by KSM Corporation), and the like.

Examples of the other (meth)acrylic compound include an epoxy (meth) acrylate, a (meth) acrylate compound, and an urethane (meth) acrylate. Among them, epoxy (meth) acrylate is preferred. Further, in terms of high reactivity, the other (meth)acrylic compound is preferably one having two or more (meth)acrylonium groups in the molecule.

In the present specification, the above "(meth) acrylate" means acrylate or methacrylate, and the above "epoxy (meth) acrylate" means that all epoxy groups in the epoxy compound are A compound obtained by reacting (meth)acrylic acid.

The epoxy (meth) acrylate may, for example, be obtained by reacting an epoxy compound with (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.

The epoxy compound to be used as a raw material for synthesizing the above epoxy (meth) acrylate is the same as the other epoxy compound described above as the other polymerizable compound.

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, 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)propenyloxyethyl ester, 2-(methyl)propenyloxyethyl 2-hydroxypropyl phthalate, 2-(methyl)propenyloxyethyl phosphate, (A Base) propylene acrylate and the like.

Further, examples of the difunctionality in the (meth) acrylate compound include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylate. 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, ethylene glycol II (Meth) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, 2-n-butyl-2 -ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl Alcohol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth) acrylate, dimethylol dicyclopentadienyl di(meth) acrylate, ethylene oxide modified di(meth) acrylate, (meth) acrylate 2-hydroxy-3-(methyl)propenyl propyl propyl ester, 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, phosphoric acid tris[(methyl) ) propylene methoxyethyl] ester, di-trimethylolpropane tetra (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa(meth) acrylate or the like.

The above amine ester (meth) acrylate can, for example, be equivalent to 2 equivalents of a (meth)acrylic acid derivative having a hydroxyl group and 1 equivalent of an isocyanate compound having 2 isocyanate groups in the presence of a catalytic amount of a tin-based compound. Obtained by carrying out the reaction.

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and Phenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, lower Norbornane diisocyanate, tolidine diisocyanate, decyl diisocyanate (XDI), hydrogenated XDI, quaternary acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) thiophosphate , tetramethyl decyl diisocyanate, 1,6,11-undecane triisocyanate, and the like.

Further, as the isocyanate compound, a chain extended isocyanate compound obtained by a reaction of a polyhydric alcohol with an excess of an isocyanate compound can also be used.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

Examples of the (meth)acrylic acid derivative having a hydroxyl group include a hydroxyalkyl mono(meth)acrylate, a mono(meth)acrylate of a glycol, and a mono(meth)acrylic acid of a triol. Ester or di(meth) acrylate, epoxy (meth) acrylate, and the like.

Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. 4-hydroxybutyl (meth)acrylate or the like.

Examples of the above-mentioned glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, and polyethylene glycol.

Examples of the trivalent alcohol include trimethylolethane, trimethylolpropane, and glycerin.

Examples of the epoxy (meth) acrylate include bisphenol A epoxy acrylate and the like.

As a commercial one of the above-mentioned amine ester (meth) acrylate, for example, an amine ester (meth) acrylate manufactured by Toagosei Co., Ltd., an amine ester (meth) acrylate manufactured by Daicel Saskatchewan Co., Ltd., An amine ester (meth) acrylate manufactured by Kokusai Industrial Co., Ltd., an amine ester (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., an amine ester (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like.

Examples of the amine ester (meth) acrylate produced by the above-mentioned East Asia Synthetic Co., Ltd. include M-1100, M-1200, M-1210, and M-1600.

As the amine ester (meth) acrylate manufactured by the above-mentioned competition, the company includes EBECRYL 210, EBECRYL 220, EBECRYL 230, EBECRYL 270, EBECRYL 1290, EBECRYL 2220, EBECRYL 4827, EBECRYL 4842, EBECRYL 4858, EBECRYL. 5129, EBECRYL 6700, EBECRYL 8402, EBECRYL 8803, EBECRYL 8804, EBECRYL 8807, EBECRYL 9260, and the like.

Examples of the amine ester (meth) acrylate produced by the above-mentioned Kosei Industrial Co., Ltd. include Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H, etc.

Examples of the amine ester (meth) acrylate produced by the above-mentioned New Nakamura Chemical Industry Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, and 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, etc.

Examples of the amine ester (meth) acrylate produced by the above-mentioned Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, and UA-306I. UA-306T and so on.

In the sealing agent for a liquid crystal display device of the present invention, the content ratio of the (meth)acryl fluorenyl group in the total of the (meth)acryl fluorenyl group and the epoxy group in the curable resin is preferably 50% by mole or more. And 95% or less.

The sealant for a liquid crystal display element of the present invention contains a maleimide compound.

By using the above-mentioned maleimide compound and the polymerizable compound of the present invention in combination, the sealing agent for a liquid crystal display device of the present invention is excellent in adhesion, softness of a cured product, and low liquid crystal contamination.

Furthermore, in the present invention, the maleimide compound is not contained in the curable resin and the photopolymerization initiator described below.

From the viewpoint of reactivity, the above-mentioned maleimide compound preferably has two or more maleimide groups in one molecule.

In addition, the maleimide compound is preferably an aliphatic hydrocarbon group having a carbon number of 5 or more and 36 or less, from the viewpoint of flexibility of the cured product of the sealing agent for a liquid crystal display element. It is an aliphatic hydrocarbon group having a carbon number of 15 or more and 25 or less.

The aliphatic hydrocarbon group may be linear or branched, and preferably branched. In the case where the above aliphatic hydrocarbon group is branched, the preferred lower limit of the carbon number of each side chain is 4, the upper limit is preferably 12, the lower limit is preferably 6, and the upper limit is 9.

Specific examples of the maleimide compound can be a compound represented by the following formula (7) and/or a compound represented by the following formula (8).

In the formula (7), R ⁵ represents an alkylene group having 2 or more and 3 or less carbon atoms, and 1 is an integer of 2 or more and 40 or less.

In the formula (8), R ⁶ represents a divalent aliphatic hydrocarbon group having 5 or more and 36 or less carbon atoms.

In the above formula (8), the carbon number of R ⁶ is preferably 12 or more and 36 or less. Further, R ⁶ preferably has an aliphatic ring.

Specific examples of the compound represented by the above formula (8) include 1,20-bis-synylimideimide-10,11-dioctyl-icosane (the following formula (9-1) )))), 1-heptyl-n-butenylimine-2-exenyl succinimide, 4-octyl-5-heptylcyclohexane (the following formula (9-2) (a compound represented by the formula), 1,2-diexyloctylimideimide-3-octyl-4-hexylcyclohexane (a compound represented by the following formula (9-3)), and the like.

The compounds represented by the above formula (8) may be used singly or in combination of two or more. Further, the compound represented by the above formula (8) can be synthesized by the method described in the specification of U.S. Patent No. 5,973,166.

The content of the maleimide compound is preferably 0.5 parts by weight, and preferably 20 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned maleimide compound is in this range, the effect of simultaneously achieving the adhesiveness of the obtained sealing compound for liquid crystal display elements and low liquid crystal contamination is further excellent. A more preferred lower limit of the content of the above maleimide compound is 2 parts by weight, and a still more preferred upper limit is 10 parts by weight.

The sealing agent for liquid crystal display elements of this invention contains a polymerization initiator.

Examples of the polymerization initiator include a radical polymerization initiator, a cationic polymerization initiator, and the like.

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 an oxime ester compound, a benzophenone compound, an acetophenone compound, a fluorenyl phosphine oxide compound, a titanocene compound, and a benzoin ether compound. 9-oxygen sulfur Wait. Among them, an oxime ester compound is preferred because it is excellent in the effect of high sensitivity and suppressing liquid crystal contamination.

Examples of the above oxime ester-based compound include 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzhydrylhydrazine), O-ethenyl- 1-(6-(2-Methylbenzylidene)-9-ethyl-9H-indazol-3-yl)ethanone oxime and the like. Among them, O-ethinyl-1-(6-(2-methylbenzylidenyl)-9-ethyl-9H-indazol-3-yl)ethanone oxime is preferred.

The commercially available ones of the photo-radical polymerization initiators include, for example, a photoradical polymerization initiator manufactured by BASF Corporation, and a photoradical polymerization initiator which is manufactured by Tokyo Chemical Industry Co., Ltd.

Examples of the photoradical polymerization initiator produced by the BASF Corporation include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucirin TPO.

Examples of the photoradical polymerization initiator which is produced by the above-mentioned Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

These photoradical polymerization initiators may be used singly or in combination of two or more.

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

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

A preferred lower limit of the number average molecular weight of the above polymer azo compound is 1,000, and a preferred upper limit is 300,000. When the number average molecular weight of the above polymer azo compound is within this range, liquid crystal contamination can be suppressed and easily mixed with the curable resin. A lower limit of the number average molecular weight of the above polymer azo compound 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 above-mentioned number average molecular weight is determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and obtained by polystyrene conversion. For example, Shodex LF-804 (manufactured by Showa Denko KK) can be used as the column for measuring the number average molecular weight calculated by the polystyrene conversion by GPC.

The polymer azo compound is, for example, a structure in which a unit such as a polyalkylene oxide or a polydimethyl siloxane is bonded to a plurality of azo groups.

The polymer azo compound having a structure in which a plurality of units such as a polyalkylene oxide are bonded to each other via an azo group is preferably a polyethylene oxide structure.

Specific examples of the polymer azo compound include a polycondensate of 4,4′-azobis(4-cyanovaleric acid) and a polyalkylene glycol or 4,4′-azo. a polycondensate of bis(4-cyanovaleric acid) and a polydimethyl methoxyalkane having a terminal amine group.

The commercially available ones of the polymer azo compounds include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.).

In addition, as a commercially available azo compound which is not a polymer, for example, V-65, V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like are mentioned.

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

As the above cationic polymerization initiator, a photocationic polymerization initiator can be applied.

The photocationic polymerization initiator is not particularly limited as long as it is a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generation type or a nonionic photoacid generation type.

Examples of the photocationic polymerization initiator include an onium salt such as an aromatic diazonium salt, an aromatic halosulfonium salt or an aromatic onium salt; an iron-aromatic hydrocarbon complex and a titanocene complex. An organic metal complex such as an aryl stanol-aluminum complex or the like.

The commercially available ones of the photocationic polymerization initiators include, for example, Adeka Optomer SP-150 and Adeka Optomer SP-170 (all manufactured by Adico Co., Ltd.).

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

The sealant for a liquid crystal display element of the present invention may further contain a heat hardener.

Examples of the above-mentioned thermosetting agent include an organic acid hydrazine, an amine compound, a polyphenol compound, an acid anhydride, and the like. Among them, organic acid bismuth can be applied.

Examples of the organic acid hydrazine include diindole azelaic acid, diterpene isophthalate, diammonium adipate, and diammonium malonate.

For example, the organic acid hydrazine manufactured by Otsuka Chemical Co., Ltd., and the organic acid hydrazine manufactured by Ajinomoto Fine-Techno Co., Ltd., etc. are mentioned as a commercial item of the above-mentioned organic-acids.

Examples of the organic acid hydrazine produced by the Otsuka Chemical Co., Ltd. include SDH, ADH, and the like.

Examples of the organic acid hydrazine produced by the above-mentioned Ajinomoto Fine-Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J.

The content of the above-mentioned thermosetting agent is preferably 1 part by weight, and preferably 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned heat-hardening agent is in this range, the obtained sealing compound for liquid crystal display elements is excellent in thermosetting property in the state which maintains excellent drawing property. A more preferable upper limit of the content of the above thermal curing agent is 30 parts by weight.

The sealing agent for a liquid crystal display device of the present invention preferably contains a filler for the purpose of adjusting the viscosity, further improving the adhesion by the stress dispersion effect, improving the coefficient of linear expansion, and further improving the moisture permeability of the cured product.

As the above filler, an inorganic filler or an organic filler can be used.

Examples of the inorganic filler include cerium oxide, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, and iron oxide. , magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, tantalum nitride, barium sulfate, calcium citrate, and the like.

Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.

A preferred lower limit of the content of the 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 a preferred upper limit is 70 parts by weight. When the content of the above-mentioned filler is within this range, the effect of further improving the adhesion without deteriorating the drawing property or the like is 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 decane coupling agent mainly functions as a further auxiliary agent for adhering the sealant to the substrate or the like.

As the above decane coupling agent, for example, 3-aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-isocyanato group can be used. Propyltrimethoxydecane, and the like. These decane coupling agents are excellent in the effect of improving adhesion to a substrate or the like, and by chemical bonding with a curable resin, the curable resin can be prevented from flowing out into the liquid crystal.

A preferred lower limit of the content of the 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 a preferred upper limit is 10 parts by weight. When the content of the above-mentioned decane coupling agent is within this range, it is possible to suppress the occurrence of liquid crystal contamination, and the effect of further improving the adhesion is more excellent. A more preferred lower limit of the content of the above decane coupling agent is 0.3 parts by weight, and a more preferred upper limit is 5 parts by weight.

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

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

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

The titanium black may exhibit sufficient effects even if it is not subjected to surface treatment, but may be treated with an organic component such as a surface coupler or an inorganic substance such as cerium oxide, titanium oxide, cerium oxide, aluminum oxide, zirconium oxide or magnesium oxide. Surface treated titanium black, such as component coatings. Among them, it is preferable that the organic component is processed to further improve the insulation property.

Moreover, since the liquid crystal display element manufactured by the sealing agent for liquid crystal display elements of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding property, it can realize that there is no light leakage, has high contrast, and is excellent. The image displays the quality of the liquid crystal display element.

For example, titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Chemical Co., Ltd. may be mentioned as a commercially available product of the above-mentioned titanium black.

Examples of the titanium black manufactured by Mitsubishi Materials Co., Ltd. include 12S, 13M, 13M-C, 13R-N, and 14M-C.

As the titanium black manufactured by the Ako Chemical Co., Ltd., for example, Tilack D or the like can be mentioned.

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

The primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display device, and a preferred lower limit is 1 nm, and a preferred upper limit is 5000 nm. When the primary particle diameter of the above-mentioned light-shielding agent is in this range, it is possible to improve the light-shielding property even when the visibility of the obtained sealing agent for a liquid crystal display element is not deteriorated. A more preferred 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 a preferred upper limit is 80 parts by weight. When the content of the above-mentioned light-shielding agent is in this range, it is possible to exhibit more excellent light-shielding properties without lowering the strength or the drawability of the obtained sealing agent for a liquid crystal display element to the substrate after curing or curing. A more preferred lower limit of the content of the above-mentioned opacifier is 10 parts by weight, more preferably 70 parts by weight, still more preferably 30 parts by weight, and still more preferably 60 parts by weight.

The sealant for a liquid crystal display device of the present invention may further contain an additive such as a reactive diluent, a spacer, a hardening accelerator, an antifoaming agent, a leveling agent, or a polymerization inhibitor, as needed.

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

In the sealing agent for a liquid crystal display device of the present invention, a preferred lower limit of the storage modulus of the cured product at 25 ° C is 0.8 GPa, and a preferred upper limit is 3.0 GPa. When the storage modulus of the cured product at 25 ° C is within this range, the sealing agent for a liquid crystal display device of the present invention is more excellent in the effect of simultaneously achieving adhesion and moisture permeability resistance or low liquid crystal contamination. A preferred lower limit of the storage modulus of the cured product at 25 ° C is 1.0 GPa, a preferred upper limit is 2.8 GPa, a more preferred lower limit is 1.2 GPa, and a more preferred upper limit is 2.6 GPa.

Further, as a cured product obtained by measuring the storage modulus at 25 ° C and the storage modulus of 60 ° C described below, after the sealing agent was irradiated with ultraviolet rays (wavelength 365 nm) of 100 mW/cm ² for 30 seconds using a metal halide lamp, It is heated at 120 ° C for 1 hour to harden it.

Further, the storage modulus can be obtained by using a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by IT Meter. and Control Co., Ltd.) at a measurement temperature of 5 mm in the test piece and 0.35 mm in thickness. The measurement was carried out under the conditions of a width of 25 mm, a temperature increase rate of 10 ° C/min, and a frequency of 10 Hz.

In the sealing agent for liquid crystal display elements of the present invention, a preferred lower limit of the storage modulus of the cured product at 60 ° C is 0.04 GPa. When the storage modulus of the cured product at 60 ° C is 0.04 GPa or more, the sealing agent for a liquid crystal display element of the present invention is more excellent in moisture permeability resistance. A lower limit of the storage modulus of the cured product at 60 ° C is 0.1 GPa.

Further, from the viewpoint of adhesion, the upper limit of the storage modulus of the cured product at 60 ° C is 2.5 GPa.

With respect to the sealant for liquid crystal display elements of the present invention, the preferred upper limit of the glass transition temperature of the cured product is 100 °C. When the glass transition temperature is 100° C. or lower, the sealing agent for a liquid crystal display device of the present invention is more excellent in adhesion. A more preferable upper limit of the glass transition temperature is 80 ° C, and a further preferred upper limit is 60 ° C.

Further, from the viewpoint of moisture permeability prevention and the like, the preferred lower limit of the glass transition temperature of the cured product is 40 ° C, and the lower limit is preferably 46 ° C.

Further, in the present specification, the above "glass transition temperature" means a temperature at which the maximum value due to the micro-Brown motion in the maximum value of the loss tangent (tan δ) obtained by the dynamic viscoelasticity measurement occurs. The glass transition temperature can be measured by a conventionally known method using a viscoelasticity measuring device or the like.

Further, as the cured product for measuring the glass transition temperature, the sealant is cured in the same manner as the cured product having the above-mentioned storage modulus.

The conductive particles can be produced by blending conductive fine particles in the sealing agent for a liquid crystal display device of the present invention. Further, the sealing agent for a liquid crystal display element of the present invention and the conductive fine particle upper and lower conductive materials are also one of the inventions.

As the conductive fine particles, for example, 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 realized 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 the liquid crystal display element of the present invention, a liquid crystal display element having a narrow bezel design is preferable. Specifically, it is preferable that the width of the frame portion around the liquid crystal display portion is 2 mm or less.

Moreover, the coating width of the sealing agent for liquid crystal display elements of the present invention in producing the liquid crystal display element of the present invention is preferably 1 mm or less.

As a method of producing the liquid crystal display element of the present invention, a liquid crystal dropping method can be applied, and specific examples thereof include the following methods.

First, the present invention is carried out by coating one of two substrates, such as a glass substrate of an electrode such as an ITO film or a polyethylene terephthalate substrate, by screen printing, dispensing, or the like. The sealant for a liquid crystal display element forms a frame-shaped seal pattern. Then, the liquid crystal droplets are dripped and applied to the frame of the sealing pattern of the substrate in a state where the sealing agent for a liquid crystal display element of the present invention is not cured, and the other substrate is superposed under vacuum. Then, a liquid crystal display element can be obtained by irradiating a portion of the seal pattern of the sealant for a liquid crystal display element of the present invention with light such as ultraviolet rays to pre-harden the sealant, and heating the pre-cured sealant And it is officially hardened.

According to the present invention, it is possible to provide a sealing agent for a liquid crystal display element of a liquid crystal display element which is excellent in adhesion and low liquid crystal contamination and which is excellent in impact resistance. 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 more detail by way of examples, but the invention is not limited to the examples.

(Production of Polymerizable Compound A of the Present Invention)

A bisphenol A type epoxy resin ("Epiclon EXA-850CRP" manufactured by DIC Corporation) 340.1 g (1 mol) and 1,6- were added to a flask equipped with a stirring blade and a cooling tube. Hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) 59.1 g (0.5 mol) was stirred at 150 ° C to dissolve the same. Then, 1.0 g of tetramethylammonium chloride was added, and the mixture was stirred at 150 ° C for 6 hours, whereby a modified epoxy resin was obtained. 200 g of the modified epoxy resin obtained, 9.0 g (0.13 mol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.1 g of a polymer-supported triphenylphosphine ("PS-Triphenyl phosphine" manufactured by Biotage Co., Ltd.) were used. The mixture was mixed and reacted at 100 ° C for 6 hours. After the completion of the reaction, the obtained resin was washed three times with toluene and water, whereby the polymerizable compound A of the present invention was obtained.

In addition, the polymerizable compound A of the present invention was confirmed to be a compound represented by the following formula (10) by GPC, ¹ H-NMR, ¹³ C-NMR and FT-IR analysis (n is 1 or more and 3 or less (average value)).

(Production of Polymerizable Compound B of the Present Invention)

In the face of a flask equipped with a stirring blade and a cooling tube, nitrogen gas was blown in, and bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with 228.3 g (1 mol) and 1,6-hexanediol diglycidyl ether ( 460 g (2 mol) manufactured by Kyoeisha Chemical Co., Ltd., "Epolight 1600", and stirred at 150 ° C to dissolve the same. Then, 1.0 g of tetramethylammonium chloride was added, and the mixture was stirred at 150 ° C for 6 hours, whereby a modified epoxy resin was obtained. 350 g of the modified epoxy resin obtained, 18.0 g (0.25 mol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.1 g of a polymer-supported triphenylphosphine ("PS-Triphenyl phosphine" manufactured by Biotage Co., Ltd.) were used. The mixture was mixed and reacted at 100 ° C for 6 hours. After the completion of the reaction, the obtained resin was washed three times with toluene and water, whereby the polymerizable compound B of the present invention was obtained.

In addition, the polymerizable compound B of the present invention was confirmed to be a compound represented by the following formula (11) by GPC, ¹ H-NMR, ¹³ C-NMR and FT-IR analysis (n is 1 or more and 3 or less (average value)).

(Production of Polymerizable Compound C of the Present Invention)

One of the bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.), 228.3 g (1 mol) and triethylene glycol divinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), was placed in a flask equipped with a stirring blade and a cooling tube. 175 g (0.86 mol), stirred at 120 ° C to dissolve the same. Then, the mixture was stirred for 6 hours, whereby a polyphenol resin was obtained. 400 g of the obtained polyphenol resin, 925 g (10 mol) of epichlorohydrin (manufactured by Tokyo Chemical Industry Co., Ltd.), and 200 g of n-butanol were added to dissolve the same. Then, the temperature was raised to 65 ° C, and the pressure was reduced to azeotropic pressure, and the reaction was carried out while removing the water layer. After unreacted epichlorohydrin was distilled off by distillation under reduced pressure, 1000 g of methyl isobutyl ketone and 100 g of n-butanol were added and stirred, and 20 g of a 10% aqueous sodium hydroxide solution was further added, and the reaction was carried out at 80 ° C for 2 hours. . After the completion of the reaction, the mixture was washed with water until the cleaning solution became neutral, and a modified epoxy resin was obtained. 350 g of the modified epoxy resin obtained, 72.06 g (1 mol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.1 g of a polymer-supported triphenylphosphine ("PS-Triphenyl phosphine" manufactured by Biotage Co., Ltd.) were used. The mixture was mixed and reacted at 100 ° C for 6 hours. After the completion of the reaction, the obtained resin was washed three times with toluene and water, whereby the polymerizable compound C of the present invention was obtained.

In addition, the polymerizable compound C of the present invention was confirmed to be a compound represented by the following formula (12) by GPC, ¹ H-NMR, ¹³ C-NMR and FT-IR analysis (m is 1 or more. 3 or less (average value)).

(Examples 1 to 7 and Comparative Examples 1 to 3)

According to the blending ratios shown in Table 1, each material was mixed using a planetary mixer (manufactured by Shinki Co., Ltd., "Debuxing Stirring Taro"), and then mixed using a three-roll mill to prepare Examples 1 to 7. And the sealing agent for liquid crystal display elements of the comparative examples 1-3.

<evaluation>

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

Further, a compound in which R ⁶ is a hexamethylene group in the above formula (8) is used as a maleimide compound instead of the compound represented by the above formula (9-3), and The sealant for liquid crystal display elements was prepared in the same manner, and the following evaluation was carried out. As a result, the same results as in Example 1 were obtained.

(hardenability)

Each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples was applied to a glass substrate to a thickness of about 5 μm, and then the glass substrates of the same size were stacked. Then, ultraviolet rays (wavelength 365 nm) of 100 mW/cm ^{2 were} irradiated for 30 seconds using a metal halide lamp. The amount of change (reduction rate) of the peak derived from the (meth) acrylonitrile group before and after the light irradiation was measured using an infrared spectroscopic device ("FTS3000" manufactured by BIORAD Co., Ltd.).

When the rate of decrease of the peak derived from the (meth) acrylonitrile group after light irradiation is 95% or more, it is set to "◎", and when it is 85% or more and less than 95%, it is set to "○", and 75 When the amount is less than or equal to 85%, it is set to "△", and when it is less than 75%, it is set to "X", and the hardenability is evaluated.

(adhesive)

1 part by weight of the spacer fine particles ("Micropearl SI-H050", manufactured by Sekisui Chemical Co., Ltd.) 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. Then, the sealing agent in which the spacer particles were dispersed was applied to the substrate of the two rubbed alignment films and the transparent electrodes by a dispenser at a line width of 1 mm so that the display portion was 45 mm × 55 mm. One of a length of 75 mm, a width of 75 mm, and a thickness of 0.7 mm. Then, droplets of liquid crystal (manufactured by Chisso Corporation, "JC-5004LA") were dropped and applied to the entire frame of the sealing agent of the substrate with the transparent electrode, and the other substrate with the transparent electrode was immediately bonded. Then, the sealant portion was irradiated with ultraviolet rays (wavelength 365 nm) of 100 mW/cm ² for 30 seconds using a metal halide lamp, and then heated at 120 ° C for 1 hour, thereby sealing each liquid crystal display element obtained in the examples and the comparative examples. For the agent, 10 (10 unit) liquid crystal display elements were produced.

A drop test was performed in which each liquid crystal display element was dropped from a height of 2 m. After the drop test, the liquid crystal leakage caused by peeling or cracking in all the units is set to "◎", and the liquid crystal display element of one unit or more and less than four units has liquid crystal leakage. ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○.

(water permeability)

Each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples was applied to a thickness of 200 μm or more and 300 μm or less by a coater in a smooth release film form. Then, the applied sealant was irradiated with ultraviolet rays (wavelength 365 nm) of 100 mW/cm ² for 30 seconds using a metal halide lamp, and then heated at 120 ° C for 1 hour to cure the sealant to obtain a cured film for moisture permeability measurement. A moisture permeability test cup is prepared by a moisture permeability test method (cup method) of a moisture-proof packaging material according to JIS Z 0208, and the obtained cured film for moisture permeability measurement is installed, and the temperature is 60 ° C and the humidity is 90% RH. The moisture permeability was measured in a constant temperature and humidity oven. When the moisture permeability is less than 30 g/m ² ‧24 hr, it is set to "○", and when it is 30 g/m ² ‧24 hr or more and less than 70 g/m ² ‧24 hr, it is set to "△", and 70 g/m ² ‧ The case of 24 hr or more was set to "x" to evaluate the moisture permeability.

(low liquid crystal pollution)

With respect to the respective sealants for liquid crystal display elements obtained in the examples and the comparative examples, liquid crystal display elements were produced in the same manner as described above for "(continuity)".

After the liquid crystal display element obtained was subjected to a 100-hour operation test, it was visually confirmed that the liquid crystal alignment was disordered in the vicinity of the sealant after the temperature was applied at 80 ° C for 1,000 hours.

The alignment disorder is judged based on the color unevenness of the peripheral portion and the display portion, and the case where the color unevenness is completely absent is "○", and the case where the color unevenness is slightly confirmed in the peripheral portion is set to "△". The case where the color unevenness spread to the display portion was set to "x", and the low liquid crystal contamination was evaluated.

[Industrial availability]

According to the present invention, it is possible to provide a sealing agent for a liquid crystal display element of a liquid crystal display element which is excellent in adhesion and low liquid crystal contamination and which is excellent in impact resistance. 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 (9)

 A sealant for a liquid crystal display element, comprising a curable resin, a maleimide compound, and a polymerization initiator, the curable resin containing a compound having a polymerizable functional group, an alkylene oxide skeleton, and a hydroxyl group .    The sealing agent for liquid crystal display elements of the first aspect of the invention, wherein the compound having a polymerizable functional group, an alkylene oxide skeleton and a hydroxyl group has two or more polymerizable functional groups in one molecule.    The sealant for a liquid crystal display element according to claim 1 or 2, wherein the polymerizable functional group is a (meth) acrylonitrile group and/or an epoxy group.   The sealant for a liquid crystal display element according to claim 1 or 2, wherein the compound having a polymerizable functional group, an alkylene oxide skeleton and a hydroxyl group is a compound represented by the following formula (1-1) or (1-2) : In the formula (1-1), A ¹ represents a structure represented by the following formulas (2-1) to (2-6), and X ¹ represents a methylene group, a methylmethylene group, and a dimethyl group. a group, an oxygen atom, a sulfonyl group, a carbonyl group or a bonding bond, and Y ¹ each independently represents a group represented by the following formula (3-1) or (3-2), and n is 1 or more and 3 or less (average value). In the formula (1-2), A ² represents a structure represented by the following formulas (4-1) to (4-7), and X ² represents a methylene group, a methylmethylene group, a dimethylmethylene group, an oxygen atom, a sulfo acyl, carbonyl bond or bond, Y ² represents represented by the following formula (5) group, m is 1 or more and 3 or less (average); In the formulas (2-1) to (2-6), * indicates the bonding position; In the formula (3-1), R ¹ represents a structure or a bond bond represented by the following formulas (6-1) to (6-6), and R ² represents a hydrogen atom or a methyl group, and in the formula (3-2), R ³ represents a structure or a bond bond represented by the following formulas (6-1) to (6-6), and in the formulae (3-1) and (3-2), * represents a bond position; In the formulas (4-1) to (4-7), * indicates the bonding position; In the formula (5), R ⁴ represents a hydrogen atom or a methyl group, and * represents a bonding position; In the formulas (6-1) to (6-6), * indicates the bonding position.  The sealant for a liquid crystal display element of claim 1, wherein the maleimide compound has two or more maleimide groups in one molecule.    The sealant for a liquid crystal display element according to the first, second, third, fourth or fifth aspect of the invention, wherein the maleimide compound has an aliphatic hydrocarbon group having 5 or more and 36 or less carbon atoms.    A sealant for a liquid crystal display element according to the first, second, third, fourth, fifth or sixth aspect of the invention, wherein the polymerization initiator contains an oxime ester compound.    A top-bottom conductive material comprising a sealant for a liquid crystal display element and conductive fine particles of the first, second, third, fourth, fifth, sixth or seventh aspect of the patent application.    A liquid crystal display element is obtained by using a sealing agent for a liquid crystal display element of the first, second, third, fourth, fifth, or seventh aspect of the patent application or a lower conductive material of the eighth aspect of the patent application.