Dihydrazide compound, curable resin composition, sealant for liquid crystal display device, upper and lower conductive material, and, liquid crystal display device

Abstract

The present invention aims to provide a novel dihydrazide compound. Furthermore, the present invention aims to provide a curable resin composition containing the dihydrazide compound and having excellent storage stability, curability, and adhesion, and a sealant for a liquid crystal display device having excellent low liquid crystal contamination resistance, an upper and lower conductive material, and a liquid crystal display device made using the curable resin composition. The present invention is a dihydrazide compound having a divalent aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a group containing an aromatic ring.

Description

Technology Field

[0001] The present invention relates to a novel dihydrazide compound. Furthermore, the present invention relates to a curable resin composition containing the dihydrazide compound and having excellent storage stability, curability, and adhesion, and to a sealant for a liquid crystal display device having excellent low liquid crystal contamination resistance, an upper and lower conductive material, and a liquid crystal display device made using the curable resin composition. Background Technology

[0002] Recently, as a method for manufacturing liquid crystal display elements such as liquid crystal display cells, a liquid crystal dropping method called a dropping method using a sealant as disclosed in Patent Document 1 and Patent Document 2 is being used in terms of shortening the takt time and optimizing the amount of liquid crystal used.

[0003] In the drop-down method, first, a seal pattern on a frame is formed on one of two electrode-attached substrates by dispensing. Then, a micro-droplet of liquid crystal is dropped into the frame of the seal pattern while the sealing agent is in an uncured state, and after overlapping the other substrate under vacuum, the sealing agent is cured to produce a liquid crystal display device. Currently, this drop-down method has become the mainstream method for manufacturing liquid crystal display devices.

[0004] However, in the modern era where various mobile devices equipped with liquid crystal panels, such as mobile phones and portable game consoles, are widely available, miniaturization of devices is the most demanded task. One method for miniaturizing devices is to narrow the frame of the liquid crystal display, and for example, the position of the seal is placed under the black matrix (hereinafter also referred to as the narrow frame design). Prior art literature

[0005] Japanese Published Patent Application No. 2001-133794, International Publication No. 02 / 092718 The problem to be solved

[0006] In narrow frame designs, the sealant is placed directly beneath the black matrix. Therefore, when the drop-drying method is performed, the light irradiated during photo-curing of the sealant is blocked, making it difficult for light to reach the interior of the sealant, resulting in insufficient curing with conventional sealants. When the curing of the sealant is insufficient in this way, there was a problem in that uncured sealant components leached into the liquid crystal, making it prone to liquid crystal contamination. In particular, with the recent increase in the polarity of liquid crystals, liquid crystal contamination has occurred even when using sealants that previously did not have this problem, so additional low liquid crystal contamination properties were required for the sealant.

[0007] When it becomes difficult to photo-cur the sealant, curing by heating is considered, and as a method to cure the sealant by heating, a heat-curing agent is incorporated into the sealant. However, when a highly reactive heat-curing agent is used to improve the curability or adhesion of the sealant, there have been cases where the resulting sealant has inferior storage stability or causes liquid crystal contamination.

[0008] The present invention aims to provide a novel dihydrazide compound. Furthermore, the present invention aims to provide a curable resin composition containing the dihydrazide compound and having excellent storage stability, curability, and adhesion, and a sealant for a liquid crystal display device having excellent low liquid crystal contamination resistance, an upper and lower conductive material, and a liquid crystal display device made using the curable resin composition. means of solving the problem

[0009] The present invention is a dihydrazide compound having a divalent aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a group containing an aromatic ring.

[0010] The present invention is described in detail below.

[0011] The inventors have discovered that by using a dihydrazide compound having a specific structure as a thermal curing agent, a curable resin composition with excellent storage stability, curability, and adhesion can be obtained, and furthermore, a sealant for a liquid crystal display device made using the curable resin composition also has excellent low liquid crystal contamination resistance, thereby completing the present invention.

[0012] The dihydrazide compound of the present invention has a divalent aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a group containing an aromatic ring. By using the dihydrazide compound of the present invention having such a structure as a thermal curing agent, a curable resin composition with excellent storage stability, curability, and adhesion can be obtained. In addition, since the dihydrazide compound of the present invention has low solubility in highly polar liquid crystals, a sealant for a liquid crystal display device made using the curable resin composition also has excellent low liquid crystal contamination resistance.

[0013] Examples of groups including the above-mentioned aromatic ring include, for instance, phenyl group, tolyl group, benzyl group, chlorophenyl group, bromophenyl group, aminophenyl group, nitrophenyl group, pyridyl group, biphenyl group, methylbiphenyl group, naphthyl group, anthracenyl group, etc.

[0014] Examples of the above aliphatic hydrocarbon groups include, for instance, methylene groups, ethylene groups, propylene groups, butylene groups, hexene groups, etc.

[0015] The dihydrazide compound of the present invention is preferably represented by the following formula (1) in that it combines good reactivity and storage stability.

[0016] Examples of compounds represented by the following formula (1) include phenylsuccinate dihydrazide (compound represented by the following formula (2)), benzylmalonicate dihydrazide, phenylmalonicate dihydrazide, etc.

[0017] Among them, the dihydrazide compound of the present invention is more preferably represented by the following formula (2) in that it has steric hindrance that can reduce liquid crystal contamination.

[0018] [Chemical Formula 1]

[0019]

[0020] In equation (1), Ar is a group containing a directional ring, m is an integer between 0 and 5, and n is an integer between 0 and 5.

[0021] In addition, when m is 0 and n is 0, it means that the carbon atom bonded to Ar and the carbon atom of the carbonyl group in the hydrazide group are directly bonded, respectively.

[0022] [Chemical Formula 2]

[0023]

[0024] Methods for preparing the dihydrazide compound of the present invention include, for example, the following methods.

[0025] That is, first, a dicarboxylic acid having a divalent aliphatic hydrocarbon group is heated in methanol under an acidic catalyst, and then neutralized to obtain a methyl ester derivative. By adding hydrazine in methanol to the obtained reaction product and reacting it, the dihydrazide compound of the present invention can be obtained.

[0026] Examples of the above dicarboxylic acids include, for instance, phenylmalonic acid, tolylmalonic acid, phenylsuccinic acid, tolylmalonic acid, benzylmalonic acid, benzylsuccinic acid, 2-phenylglutaric acid, 3-phenylglutaric acid, 2-benzylglutaric acid, 3-benzylglutaric acid, 2-phenyladipoic acid, 3-phenyladipoic acid, 2-benzyladipoic acid, 3-benzyladipoic acid, etc.

[0027] The dihydrazide compound of the present invention is preferably used as a heat-curing agent incorporated into a curable resin composition.

[0028] A curable resin composition comprising a curable resin and a thermosetting agent, wherein the thermosetting agent comprises a dihydrazide compound of the present invention, is also one of the curable resin compositions of the present invention.

[0029] The preferred lower limit of the content of the dihydrazide compound of the present invention per 100 parts by weight of the curable resin is 3 parts by weight, and the preferred upper limit is 20 parts by weight. By having a content of 3 parts by weight or more of the dihydrazide compound of the present invention, the curable resin composition obtained has superior curability and adhesion. By having a content of 20 parts by weight or less of the dihydrazide compound of the present invention, the curable resin composition obtained has superior storage stability, and also, when used as a sealant for a liquid crystal display device, has superior low liquid crystal contamination resistance. A more preferred lower limit of the content of the dihydrazide compound of the present invention is 5 parts by weight, and a more preferred upper limit is 15 parts by weight.

[0030] The curable resin composition of the present invention may contain other thermosetting agents in addition to the dihydrazide compound of the present invention, to the extent that it does not impede the purpose of the present invention.

[0031] Examples of the above-mentioned heat-curing agents include organic acid hydrazides other than the dihydrazide compound of the present invention, imidazole derivatives, amine compounds, polyhydric phenolic compounds, acid anhydrides, etc.

[0032] The curable resin composition of the present invention contains a curable resin.

[0033] It is preferable that the above-mentioned curable resin includes an epoxy compound.

[0034] Examples of the above epoxy compounds include, for instance, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallylbisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A 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, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol novolak type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resin, glycidyl ester compounds, etc.

[0035] Among the above bisphenol A type epoxy resins that are commercially available, examples include jER828EL, jER1004 (both manufactured by Mitsubishi Chemical Corporation), EPICLON850 (manufactured by DIC Corporation), etc.

[0036] Among the above bisphenol F type epoxy resins that are commercially available, examples include jER806, jER4004 (both manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-830CRP (manufactured by DIC Corporation), etc.

[0037] Among the above bisphenol E type epoxy resins that are commercially available, examples include Epomic R710 (manufactured by Mitsui Chemical Co., Ltd.).

[0038] Among the above bisphenol S type epoxy resins that are commercially available, examples include EPICLON EXA-1514 (manufactured by DIC Corporation).

[0039] Among the above 2,2'-diallylbisphenol A type epoxy resins that are commercially available, examples include RE-810NM (manufactured by Nippon Hwayaku Co., Ltd.).

[0040] Among the above hydrogenated bisphenol-type epoxy resins that are commercially available, examples include EPICLON EXA-7015 (manufactured by DIC Corporation).

[0041] Among the above-mentioned propylene oxide-added bisphenol A type epoxy resins that are commercially available, examples include EP-4000S (manufactured by ADEKA).

[0042] Among the above resorcinol-type epoxy resins that are commercially available, examples include EX-201 (manufactured by Nagase Chemtex Co., Ltd.).

[0043] Among the above-mentioned biphenyl-type epoxy resins that are commercially available, examples include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).

[0044] Among the above-mentioned sulfide-type epoxy resins that are commercially available, examples include YSLV-50TE (manufactured by Nittetsu Chemical & Material Co., Ltd.).

[0045] Among the above-mentioned diphenyl ether-type epoxy resins that are commercially available, examples include YSLV-80DE (manufactured by Nittetsu Chemical & Material Co., Ltd.).

[0046] Among the above dicyclopentadiene-type epoxy resins that are commercially available, examples include EP-4088S (manufactured by ADEKA).

[0047] Among the above-mentioned naphthalene-type epoxy resins that are commercially available, examples include EPICLON HP-4032 and EPICLON EXA-4700 (both manufactured by DIC).

[0048] Among the above phenol novolak type epoxy resins that are commercially available, examples include EPICLON N-770 (manufactured by DIC Corporation).

[0049] Among the above orthocresol novolak type epoxy resins that are commercially available, examples include EPICLON N-670-EXP-S (manufactured by DIC Corporation).

[0050] Among the above-mentioned dicyclopentadiene novolak type epoxy resins that are commercially available, examples include EPICLON HP-7200 (manufactured by DIC Corporation).

[0051] Among the above-mentioned biphenylnovolak type epoxy resins that are commercially available, examples include NC-3000P (manufactured by Nippon Hwayaku Co., Ltd.).

[0052] Among the above-mentioned naphthalenephenol novolak type epoxy resins that are commercially available, examples include ESN-165S (manufactured by Nittetsu Chemical & Material Co., Ltd.).

[0053] Among the above glycidylamine-type epoxy resins that are commercially available, examples include jER630 (manufactured by Mitsubishi Chemical), EPICLON430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).

[0054] Examples of the above-mentioned alkyl polyol-type epoxy resins that are commercially available include ZX-1542 (manufactured by Nittetsu Chemical & Material Co.), EPICLON726 (manufactured by DIC Co.), Epolite 80MFA (manufactured by Kyoei Chemical Co.), and Denacol EX-611 (manufactured by Nagase Chemtex Co.).

[0055] Among the above rubber-modified epoxy resins that are commercially available, examples include YR-450, YR-207 (both manufactured by Nittetsu Chemical & Material Co.), Eporide PB (manufactured by Daicel Co.), etc.

[0056] Among the above glycidyl ester compounds that are commercially available, examples include Denacol EX-147 (manufactured by Nagase Chemtex Co., Ltd.).

[0057] Other commercially available epoxy compounds among the above include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nittetsu Chemical & Materials), XAC4151 (manufactured by Asahi Chemical), jER1031, jER1032 (both manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical), etc.

[0058] As the above epoxy compound, a partially (meth)acrylic modified epoxy resin is also preferably used.

[0059] In addition, in this specification, the term "partially (meth)acrylic modified epoxy resin" means a compound having at least one epoxy group and one (meth)acryloyl group in one molecule, which can be obtained by reacting a portion of an epoxy compound having two or more epoxy groups with (meth)acrylic acid.

[0060] Additionally, in this specification, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acryloyl" means acryloyl or methacryloyl.

[0061] Among the above-mentioned (meth)acrylic modified epoxy resins that are commercially available, examples include UVACURE1561 and KRM8287 (both manufactured by Daicel Allnex).

[0062] In addition, the above-mentioned curable resin may include a (meth)acrylic compound.

[0063] Examples of the above (meth)acrylic compounds include (meth)acrylic acid ester compounds, epoxy (meth)acrylates, urethane (meth)acrylates, etc. Among these, epoxy (meth)acrylates are preferred. In addition, from the perspective of reactivity, it is preferable that the above (meth)acrylic compound has two or more (meth)acryloyl groups per molecule.

[0064] Furthermore, in this specification, the term "(meth)acrylic compound" means a compound having a (meth)acryloyl group. Also, the term "(meth)acrylate" means acrylate or methacrylate, and the term "epoxy(meth)acrylate" refers to a compound in which all epoxy groups in an epoxy compound are reacted with (meth)acrylic acid.

[0065] Among the above (meth)acrylic acid ester compounds, those with monofunctional properties include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, bicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethylcarbitol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, Examples include 1H,1H,5H-octafluoropentyl (meth)acrylate, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl 2-hydroxypropylphthalate, 2-(meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl phosphate, glycidyl (meth)acrylate, etc.

[0066] In addition, among the above (meth)acrylic acid ester compounds, those having difunctionality include, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(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, Examples include neopentyl glycol di(meth)acrylate, ethylene oxide-added bisphenol A di(meth)acrylate, propylene oxide-added bisphenol A di(meth)acrylate, ethylene oxide-added bisphenol F di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, ethylene oxide-modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.

[0067] In addition, among the above (meth)acrylic acid ester compounds having three or more functions, examples include trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. there is.

[0068] Examples of the above epoxy (meth)acrylates include those obtained by reacting an epoxy compound with (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.

[0069] As the epoxy compound serving as a raw material for synthesizing the above epoxy (meth)acrylate, the same as the epoxy compound described above can be used as the curable resin contained in the curable resin composition of the present invention.

[0070] Among the above epoxy (meth)acrylates that are commercially available, examples include the epoxy (meth)acrylate manufactured by Daicel Allnex, the epoxy (meth)acrylate manufactured by Shinnakamura Chemical Industry, the epoxy (meth)acrylate manufactured by Kyoei Chemical, and the epoxy (meth)acrylate manufactured by Nagase Chemtex.

[0071] Examples of the epoxy (meth)acrylates manufactured by Daicel AllNex Co., Ltd. include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182, etc.

[0072] Examples of the epoxy (meth)acrylates manufactured by Shin-Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020, etc.

[0073] Examples of the epoxy (meth)acrylates manufactured by Kyoei Chemical Co., Ltd. include, for instance, 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, etc.

[0074] Examples of the epoxy (meth)acrylates manufactured by Nagase Chemtex Co., Ltd. include, for instance, denacol acrylate DA-141, denacol acrylate DA-314, denacol acrylate DA-911, etc.

[0075] The above urethane (meth)acrylate can be obtained, for example, by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.

[0076] Examples of isocyanate compounds that serve as raw materials for the above urethane (meth)acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidin diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecane triisocyanate, etc.

[0077] In addition, as the isocyanate compound that serves as a raw material for the above urethane (meth)acrylate, a chain-extended isocyanate compound obtained by the reaction of a polyol with an excess isocyanate compound can also be used.

[0078] Examples of the above polyols include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, etc.

[0079] Examples of (meth)acrylic acid derivatives having the above hydroxyl group include hydroxyalkyl mono(meth)acrylates, mono(meth)acrylates of divalent alcohols, mono(meth)acrylates or di(meth)acrylates of trivalent alcohols, epoxy(meth)acrylates, etc.

[0080] Examples of the above hydroxyalkyl mono(meth)acrylates include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, etc.

[0081] Examples of the above divalent alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc.

[0082] Examples of the above trivalent alcohols include trimethylolethane, trimethylolpropane, glycerin, etc.

[0083] Examples of the above epoxy (meth)acrylates include, for instance, bisphenol A type epoxyacrylate.

[0084] Among the above urethane (meth)acrylates that are commercially available, examples include urethane (meth)acrylate manufactured by Toa Synthetic Co., Ltd., urethane (meth)acrylate manufactured by Daicel AllNex Co., Ltd., urethane (meth)acrylate manufactured by Negami Industrial Co., Ltd., urethane (meth)acrylate manufactured by Shinnakamura Chemical Co., Ltd., and urethane (meth)acrylate manufactured by Kyoei Chemical Co., Ltd.

[0085] Examples of urethane (meth)acrylates used in the manufacture of the above-mentioned Toa synthetic yarn include M-1100, M-1200, M-1210, M-1600, etc.

[0086] Examples of the urethane (meth)acrylates manufactured by Daicel AllNex Co., Ltd. include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260, etc.

[0087] Examples of the urethane (meth)acrylates manufactured by Negami Industrial Co., Ltd. include Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H, etc.

[0088] Examples of the urethane (meth)acrylates manufactured by Shin-Nakamura Chemical Industry Co., Ltd. include, for instance, 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, etc.

[0089] Examples of the urethane (meth)acrylates manufactured by Kyoei Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T, etc.

[0090] When the above curable resin contains the above (meth)acrylic compound in addition to the above epoxy compound, or contains the above partially (meth)acrylic modified epoxy compound, it is preferable that the ratio of (meth)acryloyl groups in the total sum of epoxy groups and (meth)acryloyl groups in the above curable resin be 30 mol% or more and 95 mol% or less. By having the ratio of (meth)acryloyl groups within this range, the resulting curable resin composition has superior adhesion, and when used as a sealant for liquid crystal display devices, it has superior low liquid crystal contamination resistance.

[0091] In order to further suppress liquid crystal contamination, it is preferable that the above-mentioned curable resin has hydrogen bonding units such as -OH groups, -NH- groups, and -NH2 groups.

[0092] The curable resin composition of the present invention preferably additionally contains a photoradical polymerization initiator.

[0093] Examples of the above-mentioned photoradical polymerization initiators include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, etc.

[0094] The above-mentioned photoradical polymerization initiator is, specifically, for example, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedion Examples include 2-(O-benzoyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.

[0095] The above photoradical polymerization initiator may be used alone or in combination of two or more types.

[0096] The content of the above photoradical polymerization initiator is preferably 0.5 parts by weight at the lower limit and 10 parts by weight at the upper limit, with respect to 100 parts by weight of the above curable resin. By having the content of the above photoradical polymerization initiator within this range, the curable resin composition obtained has superior storage stability and photocurability, and also has superior low liquid crystal contamination resistance when used as a sealant for liquid crystal display devices. A more preferred lower limit for the content of the above photoradical polymerization initiator is 1 part by weight, and a more preferred upper limit is 7 parts by weight.

[0097] The curable resin composition of the present invention may contain a thermal radical polymerization initiator.

[0098] Examples of the above thermal radical polymerization initiators include those composed of azo compounds or organic peroxides. Among these, in order to suppress liquid crystal contamination when the resulting curable resin composition is used as a sealant for a liquid crystal display device, an initiator composed of an azo compound (hereinafter also referred to as an "azo initiator") is preferred, and an initiator composed of a polymer azo compound (hereinafter also referred to as a "polymer azo initiator") is more preferred.

[0099] The above thermal radical polymerization initiator may be used alone or in combination of two or more types.

[0100] In addition, in this specification, the term “polymer azo compound” means a compound having an azo group and generating a radical capable of curing (meth)acryloyl groups by heat, having a number average molecular weight of 300 or more.

[0101] The preferred lower limit of the number average molecular weight of the polymer azo compound is 1,000, and the preferred upper limit is 300,000. Since the number average molecular weight of the polymer azo compound is within this range, the resulting curable resin composition can be easily mixed into the curable resin while preventing adverse effects on the liquid crystal when used as a sealant for a liquid crystal display device. A more preferred lower limit of the number average molecular weight of the polymer azo compound is 5,000, and a more preferred upper limit is 100,000; an even more preferred lower limit is 10,000, and an even more preferred upper limit is 90,000.

[0102] In addition, in this specification, the number average molecular weight is a value obtained by measuring a tetrahydrofuran solution with a sample concentration of 0.5 wt% using gel permeation chromatography (GPC) at a flow rate of 1 mL / min and converting it to polystyrene. For GPC, for example, HPLC-9210 2NEXT (manufactured by Nippon Analytical Industry Co., Ltd.) can be used, and for the column used in GPC, for example, JAIGEL2H (manufactured by Nippon Analytical Industry Co., Ltd.) can be used.

[0103] Examples of the above polymeric azo compounds include those having a structure in which multiple units, such as polyalkylene oxide or polydimethylsiloxane, are bonded together via an azo group.

[0104] As for the polymeric azo compound having a structure in which multiple units such as polyalkylene oxide are bonded via the above-mentioned azo group, it is preferable that it have a polyethylene oxide structure.

[0105] Specifically, the above polymer azo compounds include, for example, a polycondensation of 4,4'-azobis(4-cyanopenic acid) and polyalkylene glycol, or a polycondensation of 4,4'-azobis(4-cyanopenic acid) and polydimethylsiloxane having terminal amino groups.

[0106] Among the above polymer azo initiators that are commercially available, examples include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm Wako Junyaku Co., Ltd.).

[0107] In addition, non-polymer azo initiators include, for example, V-65 and V-501 (both manufactured by Fujifilm Wako Junyaku Co., Ltd.).

[0108] Examples of the above organic peroxides include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, etc.

[0109] The content of the thermal radical polymerization initiator is preferably 0.1 parts by weight and preferably 10 parts by weight per 100 parts by weight of the curable resin. By having the content of the thermal radical polymerization initiator within this range, the curable resin composition obtained has superior storage stability and thermal curability, and also has superior low liquid crystal contamination resistance when used as a sealant for liquid crystal display devices. A more preferred lower limit for the content of the thermal radical polymerization initiator is 0.3 parts by weight and a more preferred upper limit is 5 parts by weight.

[0110] The curable resin composition of the present invention may contain a filler for the purpose of improving viscosity, improving adhesion through stress dispersion effect, improving the coefficient of linear expansion, improving the moisture resistance of the cured product, etc.

[0111] As the above filler, inorganic fillers or organic fillers may be used.

[0112] Examples of the above-mentioned inorganic fillers include silica, talc, glass beads, asbestos, gypsum, diatomite, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc.

[0113] Examples of the above organic fillers include polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, etc.

[0114] The above filler may be used alone or in combination of two or more types.

[0115] In 100 parts by weight of the curable resin composition of the present invention, the preferred lower limit of the content of the filler is 10 parts by weight, and the preferred upper limit is 70 parts by weight. Since the content of the filler is within this range, the coating properties, etc., are not deteriorated, and the effects such as the improvement of adhesion are more superior. The more preferred lower limit of the content of the filler is 20 parts by weight, and the more preferred upper limit is 60 parts by weight.

[0116] The curable resin composition of the present invention may contain a silane coupling agent. The silane coupling agent primarily serves as an adhesion aid for good adhesion between the curable resin composition and a substrate, etc.

[0117] As the above silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, etc. are preferably used. These have an excellent effect of improving adhesion to a substrate, etc., and when the resulting curable resin composition is used as a sealant for a liquid crystal display device, it can suppress the leakage of the curable resin into the liquid crystal.

[0118] The above silane coupling agent may be used alone, or two or more types may be used in combination.

[0119] In 100 parts by weight of the curable resin composition of the present invention, the preferred lower limit of the content of the silane coupling agent is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. Since the content of the silane coupling agent is within this range, the effect of improving adhesion is more superior, and furthermore, when the obtained curable resin composition is used as a sealant for a liquid crystal display device, the low liquid crystal contamination resistance is more superior. A more preferred lower limit of the content of the silane coupling agent is 0.3 parts by weight, and a more preferred upper limit is 5 parts by weight.

[0120] The curable resin composition of the present invention may contain a light-blocking agent. By containing the light-blocking agent, the curable resin composition of the present invention can preferably be used as a light-blocking sealant.

[0121] Examples of the above-mentioned light-blocking agents include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, etc. Among these, titanium black is preferred.

[0122] The above titanium black is a material that exhibits a higher transmittance for light in the ultraviolet region, particularly for light with a wavelength of 370 nm to 450 nm, compared to the average transmittance for light with a wavelength of 300 nm to 800 nm. That is, the above titanium black is a light-blocking agent that imparts light-blocking properties to the curable resin composition of the present invention by sufficiently shielding light with wavelengths in the visible light region, while transmitting light with wavelengths near the ultraviolet region. Therefore, by using a photoradical polymerization initiator capable of initiating a reaction by light with a wavelength at which the transmittance of the titanium black increases, the photocurability of the curable resin composition of the present invention can be further enhanced. Furthermore, as the light-blocking agent contained in the curable resin composition of the present invention, a material with high insulating properties is preferred, and titanium black is also preferred as a light-blocking agent with high insulating properties.

[0123] The above titanium black preferably has an optical density (OD value) of 3 or higher per 1 μm, and more preferably 4 or higher. The higher the light-blocking properties of the above titanium black, the better. Although there is no specific upper limit for the OD value of the above titanium black, it is usually 5 or lower.

[0124] Although the above titanium black exhibits sufficient effectiveness even without surface treatment, surface-treated titanium black may also be used, such as one whose surface is treated with organic components like coupling agents, or one coated with inorganic components such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, or magnesium oxide. Among these, one treated with organic components is preferred as it can further improve insulation properties.

[0125] In addition, a display element manufactured using the curable resin composition of the present invention, which incorporates the titanium black as a light-blocking agent, has sufficient light-blocking properties, so there is no light leakage and it has high contrast, thereby enabling the realization of a display element with excellent image display quality.

[0126] Among the above titanium blacks currently on the market, examples include titanium black manufactured by Mitsubishi Materials and titanium black manufactured by Ako Chemical Co., Ltd.

[0127] Examples of the titanium black manufactured by Mitsubishi Materials Co., Ltd. include 12S, 13M, 13M-C, 13R-N, 14M-C, etc.

[0128] Examples of titanium black manufactured by the above-mentioned Ako Chemical Company include Tirak D, etc.

[0129] The preferred lower limit of the specific surface area of ​​the above titanium black is 13 m² / g, the preferred upper limit is 30 m² / g, the more preferred lower limit is 15 m² / g, and the more preferred upper limit is 25 m² / g.

[0130] In addition, the preferred lower limit of the volume resistivity of the above titanium black is 0.5 Ω·cm, the preferred upper limit is 3 Ω·cm, the more preferred lower limit is 1 Ω·cm, and the more preferred upper limit is 2.5 Ω·cm.

[0131] The preferred lower limit of the primary particle size of the light-shielding agent is 1 nm, and the preferred upper limit is 5000 nm. Since the primary particle size of the light-shielding agent is within this range, the light-shielding properties can be made superior without worsening the coatability of the resulting curable resin composition. A more preferred lower limit of the primary particle size of the light-shielding agent is 5 nm, a more preferred upper limit is 200 nm, an even more preferred lower limit is 10 nm, and an even more preferred upper limit is 100 nm.

[0132] In addition, the primary particle size of the light-blocking agent can be measured by dispersing the light-blocking agent in a solvent (water, organic solvent, etc.) using a NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

[0133] The preferred lower limit of the content of the light-blocking agent in 100 parts by weight of the curable resin composition of the present invention is 5 parts by weight, and the preferred upper limit is 80 parts by weight. By having the content of the light-blocking agent within this range, superior light-blocking properties can be exhibited without significantly reducing the adhesion, strength after curing, and drawing properties of the obtained curable resin composition. A more preferred lower limit of the content of the light-blocking agent is 10 parts by weight, and a more preferred upper limit is 70 parts by weight; an even more preferred lower limit is 30 parts by weight, and an even more preferred upper limit is 60 parts by weight.

[0134] The curable resin composition of the present invention may additionally, if necessary, contain additives such as stress relievers, reactive diluents, thixotropic agents, spacers, curing accelerators, defoaming agents, leveling agents, and polymerization inhibitors.

[0135] Methods for preparing the curable resin composition of the present invention include, for example, a method of mixing a curable resin, a heat-curing agent, and a photoradical polymerization initiator, etc., using a mixer.

[0136] Examples of the above-mentioned mixers include, for instance, a homodisperser, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mixer, etc.

[0137] The curable resin composition of the present invention is preferably used as an encapsulant for display devices and is particularly preferably used as a sealant for liquid crystal display devices. A sealant for a liquid crystal display device made using the curable resin composition of the present invention is also one of the present invention.

[0138] By incorporating conductive fine particles into the sealant for a liquid crystal display element of the present invention, an up-and-down conductive material can be manufactured. An up-and-down conductive material containing such a sealant for a liquid crystal display element of the present invention and conductive fine particles is also one of the present invention.

[0139] As the above conductive microparticles, for example, metal balls or resin microparticles having a conductive metal layer formed on their surface can be used. Among these, resin microparticles having a conductive metal layer formed on their surface are preferred because conductive connection is possible without damaging a transparent substrate, etc., due to the excellent elasticity of the resin microparticles.

[0140] A liquid crystal display element formed using the sealant for the liquid crystal display element of the present invention or the upper and lower conductive material of the present invention is also one of the present invention.

[0141] Since the sealant for a liquid crystal display element of the present invention has low compatibility with liquid crystal molecules having polar groups, when the liquid crystal display element of the present invention is formed using a liquid crystal containing liquid crystal molecules having polar groups, the effect of suppressing display defects becomes more pronounced compared to conventional sealants. That is, it is preferable that the liquid crystal display element of the present invention be formed using a liquid crystal containing liquid crystal molecules having polar groups.

[0142] Examples of polar groups of the above liquid crystal molecules include fluoro groups, chloro groups, cyano groups, etc.

[0143] As for the liquid crystal display element of the present invention, a liquid crystal display element with a narrow frame design is preferred. Specifically, it is preferred that the width of the frame portion surrounding the liquid crystal display part is 2 mm or less.

[0144] In addition, when manufacturing the liquid crystal display element of the present invention, it is preferable that the coating width of the curable resin composition of the present invention be 1 mm or less.

[0145] The sealant for a liquid crystal display element according to the present invention can be preferably used in the manufacture of a liquid crystal display element by a liquid crystal dropping method.

[0146] Methods for manufacturing the liquid crystal display element of the present invention by the liquid crystal dropping method include, for example, the following methods.

[0147] First, a process is performed to form a seal pattern on a frame on a substrate by screen printing, dispenser application, etc., using the seal agent for a liquid crystal display device of the present invention. Subsequently, a process is performed in which a micro-droplet of liquid crystal is deposited and applied to the entire surface within the frame of the seal pattern while the seal agent for a liquid crystal display device of the present invention is in an uncured state, and another substrate is immediately superimposed. After that, a liquid crystal display device can be obtained by a method in which a process of heating and curing the seal agent is performed. Alternatively, a process of pre-curing the seal agent by irradiating light, such as ultraviolet light, onto the seal pattern portion may be performed prior to the process of heating and curing the seal agent. Effects of the invention

[0148] According to the present invention, a novel dihydrazide compound can be provided. Furthermore, the present invention can provide a curable resin composition containing the dihydrazide compound and having excellent storage stability, curability, and adhesion, and a sealant for a liquid crystal display device, an upper and lower conductive material, and a liquid crystal display device formed using the curable resin composition and having excellent low liquid crystal contamination. Specific details for implementing the invention

[0149] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0150] (Synthesization Example 1 (Synthesization of Phenylsuccinate Dihydrazide))

[0151] 19.4 g of phenylsuccinic acid and 0.49 g of sulfuric acid were added to 50 mL of methanol in a branched flask and reacted under reflux for 10 hours. After cooling the reaction solution to room temperature, 1.11 g of triethylamine was added to neutralize it, and 20.0 g of hydrazine monohydrate was additionally added and reacted at 25°C for 6 hours. The precipitate was recovered by filtration using a Kiriyama funnel, washed with methanol, and vacuum dried to obtain phenylsuccinic acid dihydrazide (a compound represented by Formula (2) above).

[0152] In addition, the structure of the obtained phenylsuccinate dihydrazide is, 1 It was confirmed by H-NMR, MS, and FT-IR.

[0153] (Synthesization Example 2 (Synthesization of Benzylmalonic Acid Dihydrazide))

[0154] Except for changing 19.4 g of phenylsuccinic acid to 19.4 g of benzylmalonic acid, benzylmalonic acid dihydrazide (a compound in which Ar in formula (1) is a benzyl group, m is 0, and n is 0) was obtained in the same manner as in Synthesis Example 1.

[0155] In addition, the structure of the obtained benzylmalonic acid dihydrazide is, 1 It was confirmed by H-NMR, MS, and FT-IR.

[0156] (Synthesization Example 3 (Synthesization of Phenylmalonic Acid Dihydrazide))

[0157] Except for changing 19.4 g of phenylsuccinic acid to 18.0 g of phenylmalonic acid, phenylmalonic acid dihydrazide (a compound in which Ar is a phenyl group, m is 0, and n is 0 in the above formula (1)) was obtained in the same manner as in Synthesis Example 1.

[0158] In addition, the structure of the obtained phenylmalonic acid dihydrazide is, 1 It was confirmed by H-NMR, MS, and FT-IR.

[0159] (Examples 1–5, Comparative Examples 1–3)

[0160] Each curable resin composition of Examples 1 to 5 and Comparative Examples 1 to 3 was prepared by mixing each material according to the mixing ratios listed in Table 1 using a planetary stirrer (manufactured by Shinki Co., "Awatori Rentaro") and then further mixing using three rollers.

[0161] <Evaluation>

[0162] The following evaluations were performed on each curable resin composition obtained in the examples and comparative examples. The results are shown in Table 1.

[0163] (Preservation stability)

[0164] For each curable resin composition obtained in the examples and comparative examples, the initial viscosity immediately after preparation and the viscosity after storage at 25°C for one week after preparation were measured. (Viscosity after storage) / (Initial viscosity) was defined as the thickening ratio, and storage stability was evaluated by marking a thickening ratio of less than 1.05 as “○”, 1.05 or more but less than 1.10 as “△”, and 1.10 or more as “×”.

[0165] In addition, the viscosity of the curable resin composition was measured using an E-type viscometer (manufactured by BROOK FIELD, “DV-III”) at 25°C under conditions of a rotation speed of 1.0 rpm.

[0166] (Hardening)

[0167] For each curable resin composition obtained in the examples and comparative examples, the reaction rate of the epoxy group (reduction rate of peaks derived from the epoxy group) was measured using an infrared spectrometer after curing by heating at 120°C for 1 hour following irradiation with 100 mW / cm² ultraviolet light using a metal halide lamp for 30 seconds. Curability was evaluated by assigning “○” when the reaction rate was 90% or more, “△” when it was 80% or more but less than 90%, and “×” when it was less than 80%.

[0168] In addition, the UMA600 (manufactured by Agilent Technologies) was used as the infrared spectrometer.

[0169] (Adhesion)

[0170] Each curable resin composition obtained in the examples and comparative examples was filled into a dispensing syringe (manufactured by Musashi Engineering Co., Ltd., “PSY-10E”) and subjected to degassing treatment. The curable resin composition after degassing treatment was dispensed using a dispenser (manufactured by Musashi Engineering Co., Ltd., “SHOTMASTER300”) to a four-sided area 30 mm inward from the end of a glass substrate (150 mm × 150 mm), and another glass substrate (110 mm × 110 mm) was laminated over it under vacuum. The curable resin composition was pre-cured by irradiating with ultraviolet light of 100 mW / cm² using a metal halide lamp for 30 seconds, and then the curable resin composition was heat-cured by heating at 120°C for 1 hour to obtain an adhesion test specimen. When the end of the substrate of the obtained adhesive test specimen was pressed in at a speed of 5 mm / min using a metal rod with a radius of 5 mm, the strength (kgf) at which panel delamination occurred was measured, and the adhesive strength (kg / cm) was calculated.

[0171] Adhesion was evaluated by marking “○” when the adhesive strength was 150 kg / cm or more, “△” when the adhesive strength was 100 kg / cm or more but less than 150 kg / cm, and “×” when the adhesive strength was less than 100 kg / cm.

[0172] (Low liquid crystal contamination)

[0173] 1 part by weight of spacer microparticles (manufactured by Sekisui Chemical Industry, “Micro Pearl SI-H050”) with an average particle size of 5 μm were dispersed in 100 parts by weight of each curable resin composition obtained in the examples and comparative examples, filled into a syringe, and degassed using a centrifugal degasser (Awatron AW-1). The curable resin composition after degassment treatment was applied in a frame shape to one side of two alignment films and an ITO-attached substrate using a dispenser under conditions of a nozzle diameter of 0.4 mmφ, a nozzle gap of 42 μm, a syringe discharge pressure of 100 to 400 kPa, and a coating speed of 60 mm / sec. At this time, the discharge pressure was adjusted so that the line width of the curable resin composition was approximately 1.5 mm. Next, a microdroplet of liquid crystal (manufactured by Tokyo Kasei Kogyo Co., Ltd., “4-pentyl-4-biphenylcarbonitrile”) was applied by dropping it onto the entire surface within the frame of the curable resin composition of a substrate coated with the curable resin composition, and the other substrate was laminated under vacuum. Immediately after lamination, the curable resin composition was partially cured by irradiating the portion of the curable resin composition with ultraviolet light of 100 mW / cm² using a metal halide lamp for 30 seconds. Subsequently, the curable resin composition was partially cured by heating at 120°C for 1 hour to perform full curing, thereby fabricating a liquid crystal display device.

[0174] For the obtained liquid crystal display element, liquid crystal alignment disorder (display non-uniformity) near the seal immediately after fabrication was visually inspected. Alignment disorder was judged based on color non-uniformity of the display area, and the liquid crystal contamination was evaluated by assigning “○” when no display non-uniformity was visible in the liquid crystal display element, “△” when there was display non-uniformity in the periphery (within 500 μm from the curable resin composition), and “×” when display non-uniformity spread not only to the periphery but also to the center of 500 μm or more.

[0175]

[0176] Industrial applicability

[0177] According to the present invention, a novel dihydrazide compound can be provided. Furthermore, the present invention can provide a curable resin composition containing the dihydrazide compound and having excellent storage stability, curability, and adhesion, and a sealant for a liquid crystal display device having excellent low liquid crystal contamination resistance, an upper and lower conductive material, and a liquid crystal display device made using the curable resin composition.

Claims

Claim 1 A sealing agent for a liquid crystal display device comprising a curable resin composition containing a curable resin and a thermal curing agent, wherein the thermal curing agent comprises a dihydrazide compound having a divalent aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted for a phenyl group or a benzyl group. Claim 2 In claim 1, the dihydrazide compound having a divalent aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a phenyl group or a benzyl group is a sealant for a liquid crystal display element, which is a dihydrazide compound represented by the following formula (1). In formula (1), Ar is a phenyl group or a benzyl group, m is an integer between 0 and 5, and n is an integer between 0 and 5. Claim 3 In claim 2, the dihydrazide compound represented by the above formula (1) is a sealant for a liquid crystal display element, which is a dihydrazide compound represented by the following formula (2). Claim 4 A sealant for a liquid crystal display device according to claim 1, 2, or 3, wherein the curable resin composition further comprises a photoradical polymerization initiator. Claim 5 An upper and lower conductive material containing a sealant for a liquid crystal display element as described in claim 1, 2, or 3 and conductive fine particles. Claim 6 A liquid crystal display element formed using a sealing agent for a liquid crystal display element described in claim 1, 2, or 3, or an upper and lower conductive material containing a sealing agent for a liquid crystal display element described in claim 1, 2, or 3 and conductive fine particles. Claim 7 delete Claim 8 delete

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