TW202204310A - Dihydrazide compound, curable resin composition, sealing agent for liquid crystal display elements, vertically conductive material, and liquid crystal display element - Google Patents

Abstract

One purpose of the present invention is to provide a novel dihydrazide compound. Another purpose of the present invention is to provide: a curable resin composition which contains the above-described dihydrazide compound and exhibits excellent storage stability, curability and adhesiveness; a sealing agent for liquid crystal display elements, said sealing agent using this curable resin composition and having excellently low possibility of contaminating liquid crystals; a vertically conductive material; and a liquid crystal display element. The present invention is a dihydrazide compound which has a divalent aliphatic hydrocarbon group wherein one or more hydrogen atoms are substituted by a group that contains an aromatic ring.

Description

Dihydrazide compound, curable resin composition, sealing compound for liquid crystal display element, vertical conduction material, and liquid crystal display element

The present invention relates to a novel dihydrazide compound. In addition, the present invention relates to a curable resin composition containing the dihydrazide compound and having excellent storage stability, curability and adhesiveness, and a liquid crystal display using the curable resin composition having excellent low liquid crystal contamination properties Sealant for element, vertical conduction material, and liquid crystal display element.

In recent years, as a method of manufacturing liquid crystal display elements such as liquid crystal display cells, methods such as those disclosed in Patent Document 1 and Patent Document 2 have been used from the viewpoints of shortening takt time and optimizing the amount of liquid crystal used. The liquid crystal dropping method called the dropping method of the sealant. In the dropping method, first, a frame-shaped sealing pattern is formed on one of the two substrates with electrodes by dispensing. Next, in the state where the sealant is not hardened, droplets of liquid crystal are dropped into the frame of the seal pattern, and the sealant is hardened after being overlapped with another substrate under vacuum, thereby producing a liquid crystal display element. At present, this dropping method is the mainstream of the manufacturing method of liquid crystal display elements.

Furthermore, in the modern age when various mobile devices with liquid crystal panels, such as mobile phones and portable game consoles, are widely used, the miniaturization of the devices is the subject of the highest demand. As a method for miniaturization of the machine, the narrow edge of the liquid crystal display portion can be mentioned. For example, the industry has carried out the operation of arranging the position of the sealing portion under the black matrix (hereinafter also referred to as the narrow edge design). prior art literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2001-133794 Patent Document 2: International Publication No. 02/092718

[The problem to be solved by the invention]

In the narrow-edge design, the sealant is placed directly under the black matrix. Therefore, when the dripping method is performed, the light irradiated when the sealant is light-hardened will be blocked, and it is difficult for the light to reach the interior of the sealant. The hardening will become insufficient. When the hardening of the sealing compound becomes insufficient as described above, there is a problem that the unhardened sealing compound component is eluted in the liquid crystal, and liquid crystal contamination is likely to occur. Especially in recent years, along with the high polarity of liquid crystal, even when using the sealant which had no problem before, liquid crystal contamination sometimes occurs, and the sealant is required to have further low liquid crystal contamination properties.

When it is difficult to photoharden the sealant, it is considered to be hardened by heating, and as a method for hardening the sealant by heating, an operation of mixing a thermosetting agent into the sealant is performed. However, when a thermosetting agent with high reactivity is used in order to improve the curability and adhesiveness of the sealant, the storage stability of the obtained sealant may become poor, or liquid crystal contamination may occur.

The object of the present invention is to provide a novel dihydrazide compound. Another object of the present invention is to provide a curable resin composition containing the dihydrazide compound and having excellent storage stability, curability and adhesiveness, and a curable resin composition using the curable resin composition and having excellent low liquid crystal contamination properties. A sealing compound for liquid crystal display elements, a vertical conduction material, and a liquid crystal display element. [Technical means to solve the problem]

The present invention relates to a dihydrazine compound having a divalent aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a group containing an aromatic ring. Hereinafter, the present invention will be described in detail.

The present inventors found that a curable resin composition excellent in storage stability, curability, and adhesiveness can be obtained by using a dihydrazide compound having a specific structure as a thermosetting agent, and further, using the curable resin composition The obtained sealing compound for liquid crystal display elements was excellent also in low liquid crystal contamination property, and completed this invention.

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 thermosetting agent, a curable resin composition excellent in storage stability, curability, and adhesiveness can be obtained. Moreover, since the solubility of the dihydrazide compound of this invention in highly polar liquid crystals is low, the low liquid crystal contamination property of the sealing compound for liquid crystal display elements using this curable resin composition is further excellent.

Examples of the above-mentioned group containing an aromatic ring include a phenyl group, a tolyl group, a benzyl group, a chlorophenyl group, a bromophenyl group, an aminophenyl group, a nitrophenyl group, a pyridyl group, a biphenyl group, and a methyl biphenyl group. Phenyl, naphthyl, anthracenyl, etc.

As said aliphatic hydrocarbon group, a methylene group, an ethylidene group, a propylidene group, a butylene group, a hexylene group, etc. are mentioned, for example.

The dihydrazine compound of the present invention is preferably represented by the following formula (1) in terms of both good reactivity and storage stability. As a compound represented by the following formula (1), for example, phenylsuccinic acid dihydrazide (a compound represented by the following formula (2)), benzylmalonate dihydrazide, phenylpropyl Diacid dihydrazine, etc. Among them, the dihydrazide compound of the present invention is more preferably represented by the following formula (2) in terms of bringing about steric hindrance capable of reducing contamination of liquid crystals.

In formula (1), Ar is a group including an aromatic ring, m is an integer of 0 or more and 5 or less, and n is an integer of 0 or more and 5 or less. In addition, the case where m is 0 and the case where n is 0 each means that the carbon atom bonded to Ar is directly bonded to the carbon atom of the carbonyl group in the hydrazine group.

As a method for producing the dihydrazide compound of the present invention, the following methods and the like may be mentioned, for example. That is, first, the 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. The dihydrazine compound of the present invention can be obtained by adding hydrazine to the obtained reactant in methanol to carry out the reaction.

As said dicarboxylic acid, phenylmalonic acid, tolylmalonic acid, phenylsuccinic acid, tolysuccinic acid, benzylmalonic acid, benzylsuccinic acid, 2-benzene are mentioned, for example. Glutaric acid, 3-phenylglutaric acid, 2-benzylglutaric acid, 3-benzylglutaric acid, 2-phenyladipic acid, 3-phenyladipic acid, 2-benzylhexanoic acid Diacid, 3-benzyladipic acid, etc.

The dihydrazide compound of the present invention is suitably used as a thermosetting agent blended into a curable resin composition. A curable resin composition is also one of the present invention, and the curable resin composition contains a curable resin and a thermosetting agent, and the thermosetting agent contains the dihydrazide compound of the present invention.

The preferred lower limit of the content of the dihydrazide compound of the present invention relative to 100 parts by weight of the curable resin is 3 parts by weight, and the preferred upper limit is 20 parts by weight. When the content of the dihydrazide compound of the present invention is 3 parts by weight or more, the curability or adhesiveness of the obtained curable resin composition becomes more excellent. When the content of the dihydrazide compound of the present invention is 20 parts by weight or less, the storage stability of the obtained curable resin composition becomes more excellent, and when it is used in a sealant for liquid crystal display elements, liquid crystal contamination is reduced Sex becomes better. The more preferable lower limit of the content of the dihydrazide compound of the present invention is 5 parts by weight, and the more preferable upper limit is 15 parts by weight.

The curable resin composition of the present invention may contain other thermosetting agents in addition to the dihydrazine compound of the present invention within the range that does not inhibit the purpose of the present invention. As said thermosetting agent, the organic acid hydrazine other than the dihydrazide compound of this invention, an imidazole derivative, an amine compound, a polyphenol type compound, an acid anhydride etc. are mentioned, for example.

The curable resin composition of the present invention contains a curable resin. It is preferable that the said curable resin contains an epoxy compound. As said epoxy compound, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'- diene are mentioned, for example Propyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, 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 Novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthol novolak type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, cyclic epoxy resin Oxypropyl ester compounds, etc.

As what is marketed among the said bisphenol A epoxy resins, jER828EL, jER1004 (all are made by Mitsubishi Chemical Corporation), EPICLON850 (made by DIC Corporation), etc. are mentioned, for example. As what is marketed among the said bisphenol F type epoxy resins, jER806, jER4004 (all are made by Mitsubishi Chemical Corporation), EPICLON EXA-830CRP (made by DIC Corporation), etc. are mentioned, for example. As what is marketed among the said bisphenol E-type epoxy resins, Epomic R710 (made by Mitsui Chemicals Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said bisphenol S type epoxy resins, EPICLON EXA-1514 (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said 2, 2'- diallyl bisphenol A epoxy resin, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said hydrogenated bisphenol-type epoxy resins, EPICLON EXA-7015 (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said propylene oxide addition bisphenol A epoxy resin, EP-4000S (made by ADEKA company) etc. are mentioned, for example. As what is marketed among the said resorcinol-type epoxy resins, EX-201 (made by Nagase Chemical Co., Ltd.) etc. is mentioned, for example. As what is marketed among the said biphenyl type epoxy resins, jER YX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example. As what is marketed among the said sulfide type epoxy resins, YSLV-50TE (made by Nippon Steel Chemical Materials Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said diphenyl ether type epoxy resins, YSLV-80DE (made by Nippon Steel Chemical Materials Co., Ltd.) etc. is mentioned, for example. As what is marketed among the said dicyclopentadiene-type epoxy resins, EP-4088S (made by ADEKA company) etc. are mentioned, for example. As what is marketed among the said naphthalene-type epoxy resins, EPICLON HP-4032, EPICLON EXA-4700 (all are made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said phenol novolak-type epoxy resins, EPICLON N-770 (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said o-cresol novolak-type epoxy resins, EPICLON N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, EPICLON HP-7200 (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said biphenyl novolak-type epoxy resins, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said naphthol novolak-type epoxy resins, ESN-165S (made by Nippon Steel Chemical Materials Co., Ltd.) etc. is mentioned, for example. As what is marketed among the said glycidylamine type epoxy resins, jER630 (made by Mitsubishi Chemical Corporation), EPICLON430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemical Corporation), etc. are mentioned, for example. Among the above-mentioned alkyl polyol type epoxy resins, for example, ZX-1542 (manufactured by Nippon Steel Chemical Co., Ltd.), EPICLON726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) may, for example, be mentioned. , DENACOL EX-611 (manufactured by Nagase Chemical Co., Ltd.), etc. Among the above-mentioned rubber-modified epoxy resins, for example, YR-450, YR-207 (all manufactured by Nippon Steel Chemical Materials Co., Ltd.), Epolead PB (manufactured by Daicel Corporation), etc. may be mentioned. As what is marketed among the said glycidyl ester compounds, DENACOL EX-147 (made by Nagase Chemical Co., Ltd.) etc. are mentioned, for example. Examples of other commercially available epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical Materials Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 ( All are manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), etc.

As the above-mentioned epoxy compound, a partially (meth)acrylic-modified epoxy resin is also suitably used. In addition, the above-mentioned partially (meth)acrylic-modified epoxy resin in the present specification means that a partial epoxy group of an epoxy compound having two or more epoxy groups can be reacted with (meth)acrylic acid. A compound having one or more epoxy groups and (meth)acryloyl groups in one molecule was obtained. In addition, in this specification, the said "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the said "(meth)acryloyl group" means an acryl group or a methacryloyl group.

As what is marketed among the said partially (meth)acrylic-modified epoxy resins, UVACURE1561, KRM8287 (all are manufactured by DAICEL-ALLNEX Corporation) etc. are mentioned, for example.

Moreover, the said curable resin may contain a (meth)acrylic compound. As said (meth)acrylic compound, a (meth)acrylate compound, epoxy (meth)acrylate, urethane (meth)acrylate, etc. are mentioned, for example. Among them, epoxy (meth)acrylate is preferred. Moreover, it is preferable that the said (meth)acrylic compound has two or more (meth)acryloyl groups in 1 molecule from a reactive viewpoint. In addition, in this specification, the said "(meth)acrylic acid compound" means the compound which has a (meth)acryloyl group. In addition, the above-mentioned "(meth)acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" means that all epoxy groups in the epoxy compound are reacted with (meth)acrylic acid The obtained compound.

As a monofunctional one among the above-mentioned (meth)acrylate compounds, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-(meth)acrylate can be mentioned. Butyl, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate ester, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate ) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl ethyl ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, ethyl carbitol ( Meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H (meth)acrylate -Octafluoropentyl ester, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)propylene succinate 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl phthalate, 2-hydroxypropyl phosphate (Meth)acryloyloxyethyl ester, (meth)acrylate glycidyl and the like.

Moreover, as a bifunctional thing in the said (meth)acrylate compound, 1, 3- butanediol di(meth)acrylate, 1, 4- butanediol di(meth)acrylic acid are mentioned, for example Esters, 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, neopentyl Diol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bis(meth)acrylate Phenol F di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylic acid 2-Hydroxy-3-(meth)acryloyloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate Acrylate, polycaprolactone glycol di(meth)acrylate, polybutadiene glycol di(meth)acrylate, etc.

Moreover, as a trifunctional or more than trifunctional among the said (meth)acrylate compounds, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, base) acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isotrimer Cyanate tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, neotaerythritol tri(meth)acrylate, phosphate tri(methyl) ) Acryloyloxyethyl ester, di-trimethylolpropane tetra (meth) acrylate, neotaerythritol tetra (meth) acrylate, dipival erythritol penta (meth) acrylate, two new Pentaerythritol hexa(meth)acrylate, etc.

As said epoxy (meth)acrylate, what is obtained by making an epoxy compound and (meth)acrylic acid react in the presence of a basic catalyst by a conventional method, etc. are mentioned, for example.

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

As what is marketed among the said epoxy (meth)acrylates, the epoxy (meth)acrylate by DAICEL-ALLNEX, the epoxy (meth)acrylic by Shin-Nakamura Chemical Industry Co., Ltd. is mentioned, for example Ester, epoxy (meth)acrylate manufactured by Kyōeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase Chemical Co., Ltd., etc. Examples of epoxy (meth)acrylates manufactured by DAICEL-ALLNEX include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6603, EBECRYL3708, EBECRYL3800, etc. As epoxy (meth)acrylate manufactured by the said Shin-Nakamura Chemical Industry Co., Ltd., EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 etc. are mentioned, for example. Examples of epoxy (meth)acrylates manufactured by Kyōeisha Chemical Co., Ltd. include EPOXYESTER M-600A, EPOXYESTER 40EM, EPOXYESTER 70PA, EPOXYESTER 200PA, EPOXYESTER 80MFA, EPOXYESTER 3002M, EPOXYESTER 3002A, EPOXYESTER 1600A, EPOXYESTER 3000M, EPOXYESTER 3000A, EPOXYESTER 200EA, EPOXYESTER 400EA, etc. As an epoxy (meth)acrylate manufactured by the said Nagase Chemical Co., Ltd., Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 etc. are mentioned, for example.

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

As an isocyanate compound used as a raw material of the said urethane (meth)acrylate, isophorone diisocyanate, 2, 4- toluene diisocyanate, 2, 6- toluene diisocyanate, hexamethylene diisocyanate can be mentioned, for example , trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, bitoluidine Diisocyanate, stubble diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethyl stubble diisocyanate , 1,6,11-undecane triisocyanate, etc.

Moreover, the chain-extended isocyanate compound obtained by the reaction of a polyhydric alcohol and an excess isocyanate compound can also be used for the isocyanate compound used as the raw material of the said urethane (meth)acrylate. As said polyol, ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylolpropane, carbonate glycol, polyether glycol, polyester glycol, polycaprolactone glycol, etc. are mentioned, for example .

As the (meth)acrylic acid derivative having the above-mentioned hydroxyl group, for example, hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of dihydric alcohol, and mono(meth)acrylate of trihydric alcohol may be mentioned. Acrylate or di(meth)acrylate, epoxy (meth)acrylate, etc. As said hydroxyalkyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, for example , 4-hydroxybutyl (meth)acrylate, etc. As said dihydric alcohol, ethylene glycol, propylene glycol, 1, 3- propylene glycol, 1, 3- butanediol, 1, 4- butanediol, polyethylene glycol, etc. are mentioned, for example. As said trihydric alcohol, trimethylolethane, trimethylolpropane, glycerol etc. are mentioned, for example. As said epoxy (meth)acrylate, bisphenol A type epoxy acrylate etc. are mentioned, for example.

As a marketed thing among the said urethane (meth)acrylate, the urethane (meth)acrylate manufactured by Toagosei Corporation, the urethane (meth)acrylate manufactured by DAICEL-ALLNEX Corporation, Urethane (meth)acrylate manufactured by Negami Kogyo Co., Ltd., urethane (meth)acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., urethane (meth)acrylate manufactured by Kyeisha Chemical Co., Ltd., etc. As an amine ester (meth)acrylate manufactured by the said Toagosei Co., Ltd., M-1100, M-1200, M-1210, M-1600 etc. are mentioned, for example. As the amine ester (meth)acrylate manufactured by DAICEL-ALLNEX, for example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECLEL84, EBECRYL8807, EBECRYL9260, etc. Examples of urethane (meth)acrylates manufactured by Negami Kogyo 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 urethane (meth)acrylates manufactured by Shin-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 urethane (meth)acrylates manufactured by Kyōeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I , UA-306T, etc.

In the case of containing the above-mentioned (meth)acrylic compound as the above-mentioned curable resin in addition to the above-mentioned epoxy compound, or the case of containing the above-mentioned partially (meth)acrylic-modified epoxy compound as the above-mentioned curable resin, it is preferable. The ratio of the (meth)acryloyl group in the total of the epoxy group and the (meth)acryloyl group in the curable resin is 30 mol % or more and 95 mol % or less. When the ratio of the above-mentioned (meth)acryloyl group is within this range, the adhesiveness of the obtained curable resin composition becomes more excellent, and when it is used for a sealing compound for liquid crystal display elements, its low liquid crystal Contamination will become more excellent.

It is preferable that the said curable resin has a hydrogen bondable unit, such as a -OH group, -NH- group, _-NH2 group, from a viewpoint of suppressing the contamination of a liquid crystal more.

化合物等。 作為上述光自由基聚合起始劑，具體而言，例如可例舉：1-羥基環己基苯基酮、2-苄基-2-二甲胺基-1-(4-

啉基苯基)-1-丁酮、2-(二甲胺基)-2-((4-甲基苯基)甲基)-1-(4-(4-

啉基)苯基)-1-丁酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮、雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物、2-甲基-1-(4-甲硫基苯基)-2-

啉基丙烷-1-酮、1-(4-(2-羥基乙氧基)-苯基)-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-(苯硫基)苯基)-1,2-辛二酮2-(O-苯甲醯基肟)（1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyloxime)）、2,4,6-三甲基苯甲醯基二苯基膦氧化物等。 上述光自由基聚合起始劑可單獨使用，亦可組合使用2種以上。The curable resin composition of the present invention preferably further contains a photoradical polymerization initiator. As the above-mentioned photoradical polymerization initiator, for example, benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and 9-oxosulfur compounds may be mentioned. 𠮿

compounds, etc. As said photoradical polymerization initiator, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-

Linophenyl)-1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-

Lino)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzyl) Phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-

Linopropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(benzene Thio)phenyl)-1,2-octanedione 2-(O-benzoyloxime) (1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyloxime)) , 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. The above-mentioned photoradical polymerization initiators may be used alone or in combination of two or more.

The content of the above-mentioned photoradical polymerization initiator is preferably 0.5 parts by weight and the upper limit is preferably 10 parts by weight relative to 100 parts by weight of the above-mentioned curable resin. When the content of the above-mentioned photoradical polymerization initiator is within this range, the storage stability or photocurability of the curable resin composition obtained becomes more excellent, and it is used in the case of a sealant for liquid crystal display elements At times, the low liquid crystal contamination property will become more excellent. A more preferable lower limit of the content of the above-mentioned photo-radical polymerization initiator is 1 part by weight, and a more preferable upper limit is 7 parts by weight.

The curable resin composition of the present invention may contain a thermal radical polymerization initiator. As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. are mentioned, for example. Among them, from the viewpoint of suppressing liquid crystal contamination when the obtained curable resin composition is used in a sealing compound for liquid crystal display elements, an initiator composed of an azo compound (hereinafter, also referred to as "Azo initiator"), more preferably an initiator composed of a polymer azo compound (hereinafter also referred to as a "polymer azo initiator"). The above thermal radical polymerization initiators may be used alone or in combination of two or more. In addition, the above-mentioned "polymer azo compound" in this specification means that it has an azo group, generates a radical capable of curing a (meth)acryloyl group by heat, and has a number average molecular weight of 300 or more. compound.

The preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 1,000, and the preferable upper limit is 300,000. When the number-average molecular weight of the above-mentioned polymer azo compound is within this range, the obtained curable resin composition can be prevented from adversely affecting the liquid crystal when the obtained curable resin composition is used as a sealant for liquid crystal display elements, and can be easily mixed to in hardening resin. A more preferable lower limit of the number-average molecular weight of the polymer azo compound is 5,000, a more preferable upper limit is 100,000, a further preferable lower limit is 10,000, and a further preferable upper limit is 90,000. Furthermore, in this specification, the above-mentioned number average molecular weight is measured by gel permeation chromatography (GPC) under the condition of a flow rate of 1 mL/min for a tetrahydrofuran solution with a sample concentration of 0.5% by weight. The value obtained in terms of polystyrene. For GPC, for example, HPLC-9210 2NEXT (manufactured by Nippon Analytical Industries, Ltd.) and the like can be used, and as a column used for GPC, JAIGEL2H (manufactured by Nippon Analytical Industries, Ltd.) etc. can be mentioned, for example.

As said high molecular azo compound, the thing which has the structure which several units, such as polyalkylene oxide and polydimethylsiloxane, couple|bond via an azo group is mentioned, for example. As the polymer azo compound having a structure in which units such as a plurality of polyalkylene oxides are bonded via an azo group, those having a polyethylene oxide structure are preferred. As said polymer azo compound, the polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'- Condensation polymer of nitrogen bis (4-cyanovaleric acid) and polydimethylsiloxane with terminal amine group, etc. Among the above-mentioned polymer azo initiators, commercial ones include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Wait. Moreover, as a non-polymer azo initiator, V-65, V-501 (both are manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) etc. are mentioned, for example.

As said organic peroxide, ketone peroxide, peroxy ketal (peroxy ketal), hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide (diacyl peroxide) can, for example be mentioned. peroxide), peroxide dicarbonate, etc.

The content of the thermal radical polymerization initiator is preferably 0.1 parts by weight and the upper limit is preferably 10 parts by weight relative to 100 parts by weight of the curable resin. When the content of the above-mentioned thermal radical polymerization initiator is in this range, the storage stability or thermosetting property of the obtained curable resin composition becomes more excellent, and it is used in the case of a sealant for liquid crystal display elements At times, the low liquid crystal contamination property will become more excellent. A more preferable lower limit of the content of the above thermal radical polymerization initiator is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.

The curable resin composition of the present invention may contain a filler for the purpose of increasing the viscosity, improving the adhesiveness under the stress dispersion effect, improving the coefficient of linear expansion, and improving the moisture resistance of the cured product.

As the above-mentioned filler, an inorganic filler or an organic filler can be used. As said inorganic filler, for example, silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, oxide Iron, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc. As said organic filler, polyester microparticles|fine-particles, urethane microparticles|fine-particles, vinyl polymer microparticles|fine-particles, acrylic polymer microparticles|fine-particles etc. are mentioned, for example. The above-mentioned fillers may be used alone or in combination of two or more.

The preferred lower limit of the content of the above-mentioned filler in 100 parts by weight of the curable resin composition of the present invention is 10 parts by weight, and the preferred upper limit is 70 parts by weight. When the content of the above-mentioned filler is within this range, the effects of improving the adhesiveness and the like can be made more excellent without deteriorating the applicability and the like. A more preferable lower limit of the content of the above filler is 20 parts by weight, and a more preferable upper limit is 60 parts by weight.

The curable resin composition of the present invention may contain a silane coupling agent. The above-mentioned silane coupling agent mainly functions as an adhering aid for favorable adhesion of the curable resin composition to a substrate and the like.

As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanato are suitably used. Propyltrimethoxysilane, etc. These are excellent in the effect of improving the adhesiveness with a board|substrate etc., when using the obtained curable resin composition as the sealing compound for liquid crystal display elements, it can suppress that curable resin flows out into a liquid crystal. The above-mentioned silane coupling agents may be used alone or in combination of two or more.

The preferred lower limit of the content of the silane coupling agent in 100 parts by weight of the curable resin composition of the present invention is 0.1 part by weight, and the preferred upper limit is 10 parts by weight. When the content of the above-mentioned silane coupling agent is in this range, the effect of improving adhesion becomes more excellent, and when the obtained curable resin composition is used for a sealing compound for liquid crystal display elements, the liquid crystal contamination property is low. become better. A more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.

The curable resin composition of this invention may contain a light-shielding agent. By containing the said light-shielding agent, the curable resin composition of this invention can be used suitably as a light-shielding sealing agent.

As said light-shielding agent, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, etc. are mentioned, for example. Among them, titanium black is preferred.

The above-mentioned titanium black is a substance that has a higher transmittance for light with a wavelength of 370 nm or more and 450 nm or less than the average transmittance for light with a wavelength of 300 nm or more and 800 nm or less. That is, the above-mentioned titanium black is a light-shielding agent which imparts light-shielding properties to the curable resin composition of the present invention by sufficiently blocking light of wavelengths in the visible light region, and has a property of transmitting light of wavelengths in the vicinity of the ultraviolet region. Therefore, the photocurability of the curable resin composition of the present invention can be improved by using a light of a wavelength having a high transmittance of the titanium black to initiate a reaction as the photoradical polymerization initiator. further increase. On the other hand, as the light-shielding agent contained in the curable resin composition of the present invention, a material with high insulating properties is preferable, and titanium black is also suitable as a light-shielding agent with high insulating properties. The optical density (OD value) per 1 μm of the titanium black is preferably 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black has no particular upper limit, and is usually 5 or less.

The above-mentioned titanium black exhibits sufficient effects even if it is not surface-treated, but it is also possible to use those whose surface is treated with organic components such as coupling agents, or those made of silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. Surface-treated titanium black such as those covered with inorganic components. Among them, those treated with organic components are preferred in that the insulating properties can be further improved. In addition, the display element manufactured using the curable resin composition of the present invention in which the above-mentioned titanium black is blended as a light-shielding agent has sufficient light-shielding properties, thus preventing light leakage and having a high contrast ratio, and an excellent image display can be realized Quality display components.

As a commercially available thing among the said titanium black, the titanium black by Mitsubishi Materials Corporation, the titanium black by Ako Chemicals, etc. are mentioned, for example. As the titanium black manufactured by the above-mentioned Mitsubishi Materials Corporation, for example, 12S, 13M, 13M-C, 13R-N, 14M-C, etc. may be mentioned. As the above-mentioned titanium black manufactured by Ako Kasei Co., Ltd., Tilack D etc. are mentioned, for example.

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

The preferred lower limit of the primary particle size of the above-mentioned sunscreen agent is 1 nm, and the preferred upper limit is 5000 nm. When the primary particle size of the light-shielding agent is within this range, it is possible to make the obtained curable resin composition more excellent in light-shielding properties without deteriorating the coatability or the like of the obtained curable resin composition. The preferred lower limit of the primary particle size of the sunscreen agent is 5 nm, the more preferred upper limit is 200 nm, the further preferred lower limit is 10 nm, and the further preferred upper limit is 100 nm. In addition, the primary particle diameter of the said light-shielding agent can be measured by dispersing the said light-shielding agent in a solvent (water, an organic solvent, etc.) using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS).

The preferred lower limit of the content of the above-mentioned sunscreen 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. When the content of the above-mentioned light-shielding agent is within this range, more excellent light-shielding properties can be exhibited without greatly reducing the adhesiveness, strength and drawing properties after curing of the curable resin composition obtained. The more preferable lower limit of the content of the above-mentioned sunscreen agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, and the more preferable lower limit is 30 parts by weight, and the more preferable upper limit is 60 parts by weight.

The curable resin composition of the present invention may further contain additives such as stress moderators, reactive diluents, thixotropic agents, spacers, curing accelerators, antifoaming agents, leveling agents, and polymerization inhibitors as necessary.

As a method of producing the curable resin composition of the present invention, for example, a method of mixing a curable resin, a thermosetting agent, a photo-radical polymerization initiator added as needed, etc., using a mixer, etc. may be mentioned. As said mixer, a homodisperser, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill etc. are mentioned, for example.

The curable resin composition of the present invention is suitably used as a sealing agent for display elements, especially as a sealing agent for liquid crystal display elements. The sealing compound for liquid crystal display elements which uses the curable resin composition of this invention is also one of this invention.

A vertical conduction material can be produced by mixing electroconductive fine particles with the sealing compound for liquid crystal display elements of this invention. The sealing compound for liquid crystal display elements and the electroconductive fine particle containing such a sealing compound for liquid crystal display elements of the present invention are also one of the present invention.

As said electroconductive microparticles|fine-particles, the thing which formed the conductive metal layer etc. on the surface of metal balls, resin microparticles|fine-particles, etc., for example, can be used. Among them, those having a conductive metal layer formed on the surface of the resin fine particles are suitable because they can realize conductive connection without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.

The liquid crystal display element using the sealing compound for liquid crystal display elements of this invention or the up-down conduction material of this invention is also one of this invention. The sealing compound for liquid crystal display elements of the present invention has low compatibility with liquid crystal molecules having a polar group. Therefore, when the liquid crystal display element of the present invention uses a liquid crystal including liquid crystal molecules having a polar group, it is different from the conventional one. The effect of suppressing display failure becomes more conspicuous than the sealant. That is, it is preferable to use the liquid crystal containing the liquid crystal molecule which has a polar group as the liquid crystal display element of this invention. As a polar group of the said liquid crystal molecule, a fluorine group, a chlorine group, a cyano group etc. are mentioned, for example.

As the liquid crystal display element of the present invention, a liquid crystal display element with a narrow edge design is preferred. Specifically, the width of the frame portion around the liquid crystal display portion is preferably 2 mm or less. Moreover, it is preferable that the coating width of the curable resin composition of this invention at the time of manufacture of the liquid crystal display element of this invention is 1 mm or less.

The sealing compound for liquid crystal display elements of this invention can be used suitably for manufacture of the liquid crystal display element by the liquid crystal dropping method. As a method of manufacturing the liquid crystal display element of this invention by a liquid crystal dropping method, the following method etc. are mentioned, for example. First, the step of forming a frame-shaped seal pattern on a substrate is performed by performing screen printing, dispenser coating, or the like with the sealant for liquid crystal display elements of the present invention. Next, the following steps are performed, in the state where the sealant for liquid crystal display elements of the present invention is not cured, droplets of liquid crystal are dropped and coated on the entire surface of the frame of the seal pattern, and immediately overlapped with another substrate. Then, a liquid crystal display element can be obtained by the method of performing the process of heating and hardening a sealing compound. Moreover, you may perform the process of irradiating light, such as an ultraviolet-ray to a sealing pattern part, and hardening a sealing compound temporarily before the process of heating and hardening a sealing compound. [Effect of invention]

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 adhesiveness, and a liquid crystal display using the curable resin composition having excellent low liquid crystal contamination properties Sealant for element, vertical conduction material, and liquid crystal display element.

Hereinafter, the present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1 (synthesis of phenylsuccinic acid dihydrazide)) 50 mL of methanol, 19.4 g of phenylsuccinic acid and 0.49 g of sulfuric acid were added to an eggplant-shaped flask, and the reaction was carried out under reflux for 10 hours. After cooling the reaction solution to normal temperature, 1.11 g of triethylamine was added for neutralization, and 20.0 g of hydrazine monohydrate was further added, and the mixture was reacted at 25° C. for 6 hours. Using a Kiriyama funnel, the precipitate was collected by filtration, washed with methanol, and then vacuum-dried to obtain phenylsuccinic acid dihydrazide (the compound represented by the above formula (2)). In addition, the structure of the obtained phenylsuccinic acid dihydrazide was confirmed by ¹ H-NMR, MS and FT-IR.

(Synthesis Example 2 (Synthesis of Benzylmalonate Dihydrazide)) Benzylpropane was obtained in the same manner as in Synthesis Example 1, except that 19.4 g of phenylsuccinic acid was changed to 19.4 g of benzylmalonic acid. Dihydrazine diacid (a compound in which Ar in the above formula (1) is a benzyl group, m is 0, and n is 0). In addition, the structure of the obtained benzylmalonate dihydrazide was confirmed by ¹ H-NMR, MS and FT-IR.

(Synthesis Example 3 (Synthesis of Phenylmalonate Dihydrazide)) Phenylpropane was obtained in the same manner as in Synthesis Example 1, except that 19.4 g of phenylsuccinic acid was changed to 18.0 g of phenylmalonic acid. Dihydrazine diacid (a compound in which Ar in the above formula (1) is a phenyl group, m is 0, and n is 0). In addition, the structure of the obtained phenylmalonate dihydrazide was confirmed by ¹ H-NMR, MS and FT-IR.

(Examples 1 to 5, Comparative Examples 1 to 3) Examples 1 to 5 were prepared by mixing each material with a planetary mixer (manufactured by Thinky, "Defoaming and Stirring Taro") according to the blending ratio described in Table 1, and then using a three-roll mill. , Each of the curable resin compositions of Comparative Examples 1 to 3.

＜Evaluation＞ The following evaluations were performed on each curable resin composition obtained in Examples and Comparative Examples. The results are shown in Table 1.

(Storage stability) For each curable resin composition obtained in Examples and Comparative Examples, the initial viscosity immediately after production and the viscosity after storage at 25° C. for one week after production were measured. Let (viscosity after storage)/(initial viscosity) be the viscosity increase rate, the case where the viscosity increase rate is less than 1.05 is marked as "○", the case where the viscosity increase rate is not less than 1.05 and less than 1.10 is marked as "△", and 1.10 is marked as "△". The above cases were marked with "X", and the storage stability was evaluated. In addition, the viscosity of the curable resin composition was measured using an E-type viscometer (manufactured by BROOK FIELD, Inc., "DV-III") at 25°C under the condition of a rotational speed of 1.0 rpm.

(Curable) Each of the curable resin compositions obtained in Examples and Comparative Examples was cured by heating at 120°C for 1 hour after irradiating ultraviolet rays of 100 mW/cm ² with a metal halide lamp for 30 seconds, and then using an infrared spectrometer to measure The reaction rate of the epoxy group (the reduction rate of the peak derived from the epoxy group). The case where the reaction rate was 90% or more was marked with "○", the case where the reaction rate was more than 80% and less than 90% was marked with "△", and the case where the reaction rate was less than 80% was marked with "X", and the curability was evaluated. Note that UMA600 (manufactured by Agilent Technologies) was used as the infrared spectrometer.

(Adhesion) Each of the curable resin compositions obtained in Examples and Comparative Examples was filled in a syringe for dispensing (manufactured by Musashi High-Tech Co., Ltd., "PSY-10E"), and defoaming treatment was performed. The curable resin composition after defoaming treatment was dispensed by a dispenser (manufactured by Musashi High-Tech Co., Ltd., "SHOTMASTER300") to the inner circumference of the glass substrate (150 mm × 150 mm) 30 mm from the edge, and then placed in a vacuum. Next, another glass substrate (110 mm × 110 mm) was overlapped and attached. The curable resin composition was temporarily cured by irradiating ultraviolet rays of 100 mW/cm ² for 30 seconds using a metal halide lamp, and then the curable resin composition was thermally cured by heating at 120° C. for 1 hour to obtain an adhesive test piece. When a metal rod with a radius of 5 mm was used to press the end of the obtained substrate to which the test piece was attached at a speed of 5 mm/min, the strength (kgf) at the time of panel peeling was measured, and the adhesive force (kg/cm) was calculated. The case where the adhesive force was 150 kg/cm or more was marked as "○", the case where the adhesive force was 100 kg/cm or more and less than 150 kg/cm was marked as "△", and the adhesive force was less than 100 kg/cm The case of cm was marked as "X", and the adhesion was evaluated.

(Low Liquid Crystal Contamination) 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") with an average particle diameter of 5 μm was dispersed in each of the curable resin compositions obtained in Examples and Comparative Examples 100 parts by weight was filled into a syringe and defoamed by a centrifugal defoamer (AWATRON AW-1). Using a dispenser, under the conditions of a nozzle diameter of 0.4 mmϕ, a nozzle pitch of 42 μm, an injection pressure of a syringe of 100 to 400 kPa, and a coating speed of 60 mm/sec, the curable resin composition after defoaming treatment is formed into a frame shape Coated on one of the substrates with two alignment films and ITO. At this time, the discharge pressure was adjusted so that the line width of the curable resin composition was about 1.5 mm. Next, a fine droplet of liquid crystal (manufactured by Tokyo Chemical Industry Co., Ltd., "4-pentyl-4-biphenylcarbonitrile") was dropped and applied to the curable resin composition of the substrate coated with the curable resin composition. The whole surface of the frame of the object is attached to another substrate under vacuum. Immediately after bonding, the curable resin composition was irradiated with ultraviolet rays of 100 mW/cm ² for 30 seconds using a metal halide lamp to temporarily cure the curable resin composition. Next, it heated at 120 degreeC for 1 hour, and it hardened|cured the main, and produced the liquid crystal display element. About the obtained liquid crystal display element, it was confirmed by visual observation that the liquid crystal alignment in the vicinity of the sealant immediately after the liquid crystal display element was produced was disturbed (display unevenness). Alignment disorder was judged based on color unevenness in the display portion, and the case where no display unevenness was found in the liquid crystal display element was marked as "○", and the peripheral portion (within 500 μm from the curable resin composition) had display unevenness. It was marked with "△", and the case where the display unevenness existed not only in the peripheral part but also diffused 500 μm or more and even reached the central part was marked with "X", and the low liquid crystal contamination property was evaluated.

[Table 1] Example Comparative example 1 2 3 4 5 1 2 3 Composition (parts by weight) hardening resin Bisphenol A type epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL3700") 35 35 35 35 35 35 35 35 Caprolactone-modified bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL3708") 30 30 30 30 30 30 30 30 Partially acrylic modified bisphenol F type epoxy resin (manufactured by DAICEL-ALLNEX, "KRM8287") 25 25 25 25 25 25 25 25 Thermal hardener The dihydrazide compound of the present invention Phenylsuccinate dihydrazine 9 4.5 13.5 - - - - - benzylmalonate dihydrazine - - - 9 - - - - Phenylmalonate dihydrazine - - - - 9 - - - other Malonate dihydrazide (manufactured by Japan Finechem, "MDH") - - - - - 7 - - 1,3-Bis(hydrazinocarbonylethyl)-5-isopropylhydantoin (manufactured by Ajinomoto Fine-Techno, "Amicure VDH") - - - - - - 7 - Polyamine latent hardener (made by ADEKA, "ADEKA HARDENER EH-5057PK") - - - - - - - 7 Photoradical Polymerization Initiator 2,2-Dimethoxy-1,2-diphenylethan-1-one (manufactured by IGM Resins, "Omnirad 651") 2 2 2 2 2 2 2 2 filler Silicon dioxide (manufactured by Admatechs, "Admafine SO-C2") 25 25 25 25 25 25 25 25 stress reliever Core-shell acrylate copolymer microparticles (manufactured by Aica Kogyo, "F351") 17 17 17 17 17 17 17 17 Silane coupling agent 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") 2 2 2 2 2 2 2 2 Content of thermosetting agent relative to 100 parts by weight of curable resin (parts by weight) 10 5 15 10 10 7.8 7.8 7.8 evaluate storage stability ○ ○ △ ○ ○ ○ × ○ sclerosing ○ △ ○ ○ ○ ○ ○ ○ continuity ○ △ ○ ○ ○ ○ ○ × Low liquid crystal contamination ○ ○ ○ △ △ × ○ ○ [Industrial Availability]

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 adhesiveness, and a liquid crystal display using the curable resin composition having excellent low liquid crystal contamination properties Sealant for element, vertical conduction material, and liquid crystal display element.

without

without

Claims (8)

A dihydrazide compound having a divalent aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a group containing an aromatic ring. The dihydrazide compound of claim 1, which is represented by the following formula (1):

; In formula (1), Ar is a group including an aromatic ring, m is an integer of 0 or more and 5 or less, and n is an integer of 0 or more and 5 or less. The dihydrazide compound of claim 2, which is represented by the following formula (2):

. A curable resin composition containing a curable resin and a thermosetting agent, The above-mentioned thermosetting agent contains the bishydrazide compound of claim 1, 2 or 3. The curable resin composition according to claim 4, which further contains a photoradical polymerization initiator. A sealing compound for liquid crystal display elements using the curable resin composition of claim 4 or 5. A vertical conduction material comprising the sealing compound for liquid crystal display elements of claim 6 and conductive fine particles. A liquid crystal display element using the sealant for liquid crystal display element of claim 6 or the upper and lower conduction material of claim 7.