Hydrazide compound, curable resin composition, sealant for liquid crystal display element, and liquid crystal display element

Abstract

An object of the present application is to provide a novel hydrazide compound. In addition, an object of the present application is to provide a curable resin composition containing the hydrazide compound and excellent in storage stability and adhesiveness, a sealant for a liquid crystal display element formed using the curable resin composition and excellent in low liquid crystal contamination, and a liquid crystal display element. The present application is a hydrazide compound having one or more structures represented by the following formula (1) and two or more hydrazide groups in one molecule. In formula (1), * is a bonding position.

Description

TECHNICAL FIELD

[0001] The present application relates to a novel hydrazide compound. In addition, the present application relates to a curable resin composition containing the hydrazide compound and excellent in storage stability and adhesiveness, a sealant for a liquid crystal display element using the curable resin composition and excellent in low liquid crystal contamination, and a liquid crystal display element. BACKGROUND

[0002] In recent years, as a manufacturing method of a liquid crystal display element such as a liquid crystal display cell, from the viewpoint of shortening of production cycle time, optimization of the amount of liquid crystal used, and the like, a liquid crystal dropping method called a dropping process using a sealant disclosed in Patent Literature 1, Patent Literature 2 is used.

[0003] In the dropping process, first, a frame-shaped seal pattern is formed on one of two substrates with electrodes by dispensing. Next, a minute drop of liquid crystal is added in the frame of the seal pattern in a state where the sealant is not cured, and after the other substrate is overlapped under vacuum, the sealant is cured, and a liquid crystal display element is produced. At present, this dropping process is mainstream as a manufacturing method of a liquid crystal display element.

[0004] However, in the present age where various mobile devices with liquid crystal panels such as portable telephones, portable game machines are popular, miniaturization of the devices is the most required problem. As a method of miniaturization of the devices, a narrow edge of a liquid crystal display portion can be cited, for example, a position of a seal portion is disposed under a black matrix (hereinafter, also referred to as a narrow edge design).

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: Japanese Patent Application Laid-Open No. 2001-133794

[0008] Patent Literature 2: International Publication No. 02 / 092718 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] In the narrow edge design, since the sealant is disposed directly under the black matrix, if the dropping process is performed, light irradiated at the time of photocuring of the sealant is blocked, and the light is difficult to reach the inside of the sealant, and if the conventional sealant is used, sometimes the curing becomes insufficient. If the curing of the sealant becomes insufficient like this, uncured sealant components are eluted into the liquid crystal and precipitated, and thereby there is a problem that the liquid crystal display element is likely to cause display failure. In particular, in recent years, along with high polarization of the liquid crystal, even in the case where the conventional sealant which has not been a problem is used, there is a problem that display failure is likely to occur.

[0011] In cases where it is difficult to light-cure the sealant, or where light curing alone is insufficient, heating to cure it is considered. As a method for curing the sealant by heating, a thermosetting agent is incorporated into the sealant. However, when a highly reactive thermosetting agent is used to improve the sealant's curability and adhesion, the resulting sealant sometimes exhibits poor storage stability or liquid crystal contamination.

[0012] The object of this invention is to provide a novel acylhydrazine compound. Furthermore, the object of this invention is to provide a curable resin composition containing the acylhydrazine compound and exhibiting excellent storage stability and adhesion; a sealant for liquid crystal display elements prepared using the curable resin composition and exhibiting excellent low liquid crystal contamination; and a liquid crystal display element.

[0013] Methods for solving problems

[0014] The present invention 1 is an acylhydrazine compound, characterized in that it has one or more structures shown in the following formula (1) and two or more acylhydrazine groups in one molecule.

[0015] The present invention 2 is an acylhydrazine compound of the present invention 1, which has two or more of the structures shown in the above formula (1) in one molecule.

[0016] The present invention 3 is an acylhydrazine compound of the present invention 1 or 2, which has the structure shown in the following formula (2) as a structure containing the above-mentioned acylhydrazine group.

[0017] The present invention 4 is an acylhydrazine compound of the present invention 1, 2 or 3, which is represented by the following formula (3).

[0018] The present invention 5 is an acylhydrazine compound of the present invention 1, 2, 3 or 4, which is represented by the following formula (4).

[0019] This invention 6 is a curable resin composition containing a curable resin and a thermosetting agent, wherein the thermosetting agent comprises an acylhydrazine compound of this invention 1, 2, 3, 4 or 5.

[0020] The present invention 7 is a curable resin composition of the present invention 6, which further contains a photoradical polymerization initiator.

[0021] This invention 8 is a sealant for liquid crystal display elements, which is made using the curable resin composition of this invention 6 or 7.

[0022] The present invention 9 is a liquid crystal display element having a cured product of the sealant for liquid crystal display elements of the present invention 8.

[0023] [Chemical Formula 1]

[0024]

[0025] In equation (1), * represents the bonding position.

[0026] [Chemical Formula 2]

[0027]

[0028] In equation (2), Ar is an optional substituted aromatic ring, m is 1 or 2, and * is the bonding position.

[0029] [Chemical Formula 3]

[0030]

[0031] In formula (3), Y is an organic group, Ar is an optional substituted aromatic ring, m is 1 or 2, and n is 2 or 3.

[0032] [Chemical Formula 4]

[0033]

[0034] In formula (4), X is a polyfunctional glycidyl oxy compound residue, Ar is an optional substituted aromatic ring, m is 1 or 2, and n is 2 or 3.

[0035] The present invention will now be described in detail.

[0036] The inventors have discovered that by using an acylhydrazine compound with a specific structure as a thermosetting agent, a curable resin composition with excellent preservation stability and adhesion can be obtained. Furthermore, the sealant for liquid crystal display elements made using this curable resin composition exhibits excellent low liquid crystal contamination, thus completing the present invention.

[0037] The hydrazide compound of the present invention has one or more of the structures shown in formula (1) above in one molecule. By using the hydrazide compound of the present invention having such a structure as a thermosetting agent, a curable resin composition with excellent storage stability and adhesion can be obtained. In addition, the hydrazide compound of the present invention does not readily dissolve into liquid crystals; therefore, a liquid crystal display element sealant made using this curable resin composition can produce a liquid crystal display element with excellent display performance. Furthermore, the curability of the curable resin composition containing the hydrazide compound of the present invention as a thermosetting agent is also excellent.

[0038] The acylhydrazine compound of the present invention preferably has two or more of the structures shown in the above formula (1) in one molecule.

[0039] The acylhydrazide compound of the present invention has two or more acylhydrazide groups in one molecule. More preferably, the acylhydrazide compound of the present invention has three or more of the above-mentioned acylhydrazide groups in one molecule, and even more preferably has four or more.

[0040] The acylhydrazine compound of the present invention preferably has the structure shown in the above formula (2) as a structure containing the above acylhydrazine group.

[0041] The optional substituted aromatic ring represented by Ar in formulas (2), (3), (4) and (11) described below can be, for example, a benzene ring, a pyridine ring, a naphthalene ring, etc. Among them, a benzene ring is preferred.

[0042] In addition, when the aromatic ring represented by Ar in the above formula (2), above formula (3), above formula (4) and below formula (11) is replaced, examples of substituents include methylene, aryl, alkynyl, amino, nitro, hydroxyl, carboxyl and the like.

[0043] The acylhydrazine compound of the present invention is preferably represented by the above formula (3), and more preferably by the above formula (4).

[0044] Examples of polyfunctional glycidyl oxy compounds that serve as sources of the polyfunctional glycidyl oxy compound residues in formula (4) include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol S diglycidyl ether, bis(4-glycidyloxyphenyl) ether, methylene bis(1,2-naphthyl)bis(glycidyl ether), 4'-biphenyl dimethyl bis(glycidyl ether), 3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl, 1,6-bis(2,3-epoxypropane-1-yloxy)naphthalene, 1,3,5-glycidyl ether-1,3,5-triazine-2,4,6-trione, and linear phenolic epoxy resins. Among these, bis(4-glycidyloxyphenyl) ether is preferred.

[0045] It should be noted that, in this specification, the term "polyfunctional glycidyl oxy compound" refers to a compound having two or more diglycidyl oxy groups in one molecule, and the term "polyfunctional glycidyl oxy compound residue" refers to the structure of the portion of the polyfunctional glycidyl oxy compound other than the glycidyl oxy group.

[0046] Specifically, examples of the hydrazide compounds of the present invention include compounds represented by the following formulas (5) to (10).

[0047] [Chemical Formula 5]

[0048]

[0049] In equation (5), R 1 ~R 8 Each can be independently a hydrogen atom, methylene, aryl, alkynyl, amino, nitro, hydroxyl, or carboxyl group.

[0050] [Chemical Formula 6]

[0051]

[0052] In equation (6), R 9 ~R 16 Each can be independently methylene, aryl, alkynyl, amino, nitro, hydroxyl, or carboxyl.

[0053] [Chemical Formula 7]

[0054]

[0055] In equation (7), R 17 ~R 28 Each can be independently methylene, aryl, alkynyl, amino, nitro, hydroxyl, or carboxyl.

[0056] [Chemical Formula 8]

[0057]

[0058] In equation (8), R 29 ~R 36 Each can be independently methylene, aryl, alkynyl, amino, nitro, hydroxyl, or carboxyl.

[0059] [Chemical Formula 9]

[0060]

[0061] In equation (9), R 37 ~R 42 Each can be independently methylene, aryl, alkynyl, amino, nitro, hydroxyl, or carboxyl.

[0062] [Chemical Formula 10]

[0063]

[0064] In equation (10), R 43 ~R 50 Each can be independently methylene, aryl, alkynyl, amino, nitro, hydroxyl, or carboxyl.

[0065] Examples of methods for manufacturing the hydrazide compounds of the present invention include the following.

[0066] That is, firstly, the above-mentioned polyfunctional glycidyloxy compound is reacted with the compound shown in formula (11) in toluene in the presence of a catalyst by heating. Next, the acylhydrazine compound of the present invention can be obtained by reacting the obtained reactants in methanol with the addition of hydrazine.

[0067] [Chemical Formula 11]

[0068]

[0069] In formula (11), R is an alkyl group with 1 to 4 carbon atoms, and Ar is an optional substituted aromatic ring.

[0070] Examples of compounds represented by formula (11) above include methyl paraben, methyl 3-hydroxybenzoate, methyl 4-(hydroxymethyl)benzoate, methyl 4-hydroxyphenylacetate, methyl (R)-(+)-2-(4-hydroxyphenoxy)propionate, methyl 6-hydroxy-2-naphthoate, methyl 2-hydroxy-1-naphthoate, methyl 3-hydroxy-2-naphthoate, methyl 5-hydroxynicotinic acid, methyl salicylate, dimethyl 5-hydroxyisophthalate, and dimethyl 4-hydroxyisophthalate. Methyl paraben and dimethyl 5-hydroxyisophthalate are preferred.

[0071] The hydrazide compounds of the present invention are suitable for use as thermosetting agents in curable resin compositions.

[0072] In addition, a curable resin composition containing a curable resin and a thermosetting agent, wherein the thermosetting agent contains the acylhydrazine compound of the present invention, is also one of the present inventions.

[0073] The preferred lower limit for the content of the hydrazide 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 hydrazide compound of the present invention is 3 parts by weight or more, the curable resin composition obtained exhibits superior curability and adhesion. When the content of the hydrazide compound of the present invention is 20 parts by weight or less, the curable resin composition obtained exhibits superior storage stability, and when used as a sealant for liquid crystal display elements, it exhibits superior low liquid crystal contamination. A more preferred lower limit for the content of the hydrazide compound of the present invention is 5 parts by weight, and a more preferred upper limit is 15 parts by weight.

[0074] The curable resin composition of the present invention may contain other thermosetting agents in addition to the hydrazide compound of the present invention, without prejudice to the purpose of the present invention.

[0075] Other thermosetting agents mentioned above include, for example, acylhydrazine compounds other than the acylhydrazine compounds of the present invention, imidazole derivatives, amine compounds, polyphenolic compounds, acid anhydrides, etc.

[0076] The curable resin composition of the present invention contains a curable resin.

[0077] The aforementioned curable resin preferably contains an epoxy compound.

[0078] Examples of the aforementioned epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthyl type epoxy resin, phenol linear phenolic type epoxy resin, o-cresol linear phenolic type epoxy resin, dicyclopentadiene linear phenolic type epoxy resin, biphenyl linear phenolic type epoxy resin, naphthol linear phenolic type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, and glycidyl ester compounds.

[0079] Commercially available examples of the aforementioned bisphenol A type epoxy resins include jER828EL, jER1004 (both manufactured by Mitsubishi Chemical Corporation), and EPICLON850 (manufactured by DIC Corporation).

[0080] Commercially available examples of the aforementioned bisphenol F type epoxy resins include jER806, jER4004 (both manufactured by Mitsubishi Chemical Corporation), and EPICLON EXA-830CRP (manufactured by DIC Corporation).

[0081] Commercially available examples of the aforementioned bisphenol E type epoxy resins include EPOMIC R710 (manufactured by Mitsui Chemicals).

[0082] Commercially available examples of the aforementioned bisphenol S-type epoxy resins include EPICLON EXA-1514 (manufactured by DIC).

[0083] Commercially available examples of the aforementioned 2,2'-diallyl bisphenol A type epoxy resins include, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

[0084] Commercially available examples of the aforementioned hydrogenated bisphenol type epoxy resins include EPICLON EXA-7015 (manufactured by DIC Corporation).

[0085] Commercially available examples of the aforementioned propylene oxide addition bisphenol A type epoxy resins include, for example, EP-4000S (manufactured by ADEKA).

[0086] Commercially available examples of the aforementioned resorcinol-type epoxy resins include, for example, EX-201 (manufactured by Nagase ChemteX).

[0087] Commercially available examples of the aforementioned biphenyl-type epoxy resins include JER YX-4000H (manufactured by Mitsubishi Chemical Corporation).

[0088] Commercially available products among the aforementioned thioether-type epoxy resins include, for example, YSLV-50TE (manufactured by NIPPON STEELC Chemical & Material Co., Ltd.).

[0089] Commercially available examples of the aforementioned diphenyl ether type epoxy resins include YSLV-80DE (manufactured by NIPPON STEELC Chemical & Material Co., Ltd.).

[0090] Commercially available examples of the aforementioned dicyclopentadiene-type epoxy resins include EP-4088S (manufactured by ADEKA).

[0091] Commercially available examples of the aforementioned naphthalene-type epoxy resins include EPICLON HP-4032 and EPICLON EXA-4700 (both manufactured by DIC).

[0092] Commercially available examples of the aforementioned phenolic linear epoxy resins include EPICLON N-770 (manufactured by DIC Corporation).

[0093] Commercially available products among the aforementioned o-cresol linear phenolic epoxy resins include, for example, EPICLON N-670-EXP-S (manufactured by DIC Corporation).

[0094] Commercially available examples of the aforementioned dicyclopentadiene linear phenolic epoxy resins include, for example, EPICLON HP-7200 (manufactured by DIC).

[0095] Commercially available examples of the aforementioned biphenyl linear phenolic epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).

[0096] Commercially available examples of the aforementioned naphthol linear phenolic epoxy resins include ESN-165S (manufactured by NIPPONSTEEL Chemical & Material Co., Ltd.).

[0097] Commercially available products among the aforementioned glycidylamine type epoxy resins include, for example, jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation).

[0098] Commercially available examples of the aforementioned alkyl polyol type epoxy resins include ZX-1542 (manufactured by NIPPON STEELC Chemical & Material), EPICLON726 (manufactured by DIC), EPOLIGHT 80MFA (manufactured by Kyoei Chemical Co., Ltd.), and DENACOL EX-611 (manufactured by Nagase ChemteX).

[0099] Commercially available examples of the aforementioned rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by NIPPON STEEL Chemical & Material), and EPOLEAD PB (manufactured by DAICEL).

[0100] Commercially available examples of the aforementioned glycidyl ester compounds include, for example, DENACOL EX-147 (manufactured by NagaseChemteX).

[0101] Other commercially available epoxy compounds mentioned above include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NIPPON STEEL Chemical & Material), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (both manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), and TEPIC (manufactured by Nissan Chemical Corporation).

[0102] As an example of the aforementioned epoxy compound, partially (meth)acrylic acid modified epoxy resin is also suitable.

[0103] It should be noted that, in this specification, the aforementioned (meth)acrylic acid modified epoxy resin means: a compound having one or more epoxy groups and one or more (meth)acryloyl groups in one molecule, which can be obtained by reacting a portion of the epoxy groups of an epoxy compound having two or more epoxy groups with (meth)acrylic acid.

[0104] It should be noted that in this specification, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, and "(meth)acryloyl" refers to acryloyl or methacryloyl.

[0105] Commercially available examples of the aforementioned (meth)acrylic acid modified epoxy resins include UVACURE1561 and KRM8287 (both manufactured by DAICL-ALLNEX).

[0106] In addition, the aforementioned curable resin may also contain (meth)acrylic compounds.

[0107] Examples of the aforementioned (meth)acrylate compounds include (meth)acrylate compounds, epoxy (meth)acrylates, and urethane (meth)acrylates. Among these, epoxy (meth)acrylates are preferred. Furthermore, from the viewpoint of reactivity, the aforementioned (meth)acrylate compounds preferably have two or more (meth)acryloyl groups in one molecule.

[0108] It should be noted that, in this specification, the term "(meth)acrylic acid compounds" refers to compounds having a (meth)acryloyl group. Furthermore, the term "(meth)acrylate" refers to acrylates or methacrylates, and "epoxy (meth)acrylate" indicates a compound obtained by reacting all the epoxy groups in an epoxy compound with (meth)acrylic acid.

[0109] Examples of monofunctional compounds among the aforementioned (meth)acrylate compounds include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isononyl methacrylate, isodecanyl methacrylate, lauryl methacrylate, isomyrmethyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, 2-methoxyethyl methacrylate, and 2-ethoxyethyl methacrylate. Esters, 2-butoxyethyl methacrylate, 2-phenoxyethyl methacrylate, methoxyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl methacrylate, ethyl carbitol (meth)acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H,1H,5H-octafluoropentyl methacrylate, imide (meth)acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl phosphate, glycidyl methacrylate, etc.

[0110] Furthermore, examples of difunctional compounds among the aforementioned (meth)acrylate compounds include 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, and tripropylene glycol di(meth)acrylate. Ester, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, di(meth)acrylate dihydroxymethyl dicyclopentadiene ester, ethylene oxide modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl ester, carbonate glycol di(meth)acrylate, polyether glycol di(meth)acrylate, polyester glycol di(meth)acrylate, polycaprolactone glycol di(meth)acrylate, polybutadiene glycol di(meth)acrylate, etc.

[0111] In addition, examples of compounds with three or more functions among the aforementioned (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0112] Examples of the aforementioned epoxy (meth)acrylates include substances obtained by reacting an epoxy compound with (meth)acrylic acid in the presence of a basic catalyst using conventional methods.

[0113] As the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, the same substance as the epoxy compound described above that is contained in the curable resin composition of the present invention can be used.

[0114] Commercially available examples of the aforementioned epoxy (meth)acrylates include those manufactured by DAICL-ALLNEX, Shin-Nakamura Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd., and Nagase ChemteX.

[0115] Examples of epoxy (meth)acrylates manufactured by DAICEL-ALLNEX include EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3708, EBECRYL 3800, EBECRYL 6040, and EBECRYL RDX63182.

[0116] Examples of epoxy (meth)acrylates manufactured by Shin-Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020.

[0117] Examples of epoxy (meth)acrylates manufactured by Kyoei Chemical Co., Ltd. include 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, and EPOXY ESTER 400EA.

[0118] Examples of epoxy (meth)acrylates manufactured by Nagase ChemteX include DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, and DENACOL ACRYLATE DA-911.

[0119] The aforementioned urethane (meth)acrylates can be obtained, for example, by reacting a hydroxyl-containing (meth)acrylate derivative with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.

[0120] Examples of isocyanate compounds that can serve as raw materials for the aforementioned urethane (meth)acrylates include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornene diisocyanate, dimethylbiphenyl diisocyanate, phenylmethylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tri(phenyl) thiophosphate, tetramethylphenylmethylene diisocyanate, and 1,6,11-undecane triisocyanate.

[0121] Alternatively, the isocyanate compound used as a raw material for the aforementioned urethane (meth)acrylate can be a chain-extended isocyanate compound obtained by reacting a polyol with an excess of the isocyanate compound.

[0122] Examples of such polyols include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate glycol, polyether glycol, polyester glycol, and polycaprolactone glycol.

[0123] Examples of the above-mentioned (meth)acrylic acid derivatives having hydroxyl groups include hydroxyalkyl mono(meth)acrylates, mono(meth)acrylates of diols, mono(meth)acrylates or di(meth)acrylates of triols, epoxy (meth)acrylates, etc.

[0124] Examples of the above-mentioned mono(meth)acrylate hydroxyalkyl esters include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate.

[0125] Examples of the aforementioned diols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.

[0126] Examples of the aforementioned triols include trimethylolethane, trimethylolpropane, and glycerol.

[0127] Examples of the aforementioned epoxy (meth)acrylates include, for example, bisphenol A type epoxy acrylates.

[0128] Commercially available products among the aforementioned urethane (meth)acrylates include, for example, urethane (meth)acrylates manufactured by Toa Synthetic Co., Ltd., urethane (meth)acrylates manufactured by DAICL-ALLNEX Co., Ltd., urethane (meth)acrylates manufactured by Negami Kogyo Co., Ltd., urethane (meth)acrylates manufactured by Shin-Nakamura Chemical Co., Ltd., and urethane (meth)acrylates manufactured by Kyoeisha Chemical Co., Ltd.

[0129] Examples of urethane (meth) acrylates manufactured by the aforementioned Dong-A Synthetic Co., Ltd. include M-1100, M-1200, M-1210, and M-1600.

[0130] Examples of urethane (meth)acrylates manufactured by DAICEL-ALLNEX include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, and EBECRYL9260.

[0131] Examples of urethane (meth)acrylates manufactured by the aforementioned Nekami Kogyo Co., Ltd. include ArtResin UN-330, ArtResin SH-500B, ArtResin UN-1200TPK, ArtResin UN-1255, ArtResin UN-3320HB, ArtResin UN-7100, ArtResin UN-9000A, and ArtResin UN-9000H.

[0132] 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, 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, and UA-W2A.

[0133] Examples of urethane (meth)acrylates manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, and UA-306T.

[0134] When the curable resin contains the aforementioned (meth)acrylic acid compound in addition to the aforementioned epoxy compound, or when it contains a portion of the aforementioned (meth)acrylic acid-modified epoxy compound, it is preferable that the ratio of (meth)acryloyl groups in the total of epoxy groups and (meth)acryloyl groups in the curable resin is 30 mol% or more and 95 mol% or less. With the (meth)acryloyl group ratio within this range, the resulting curable resin composition exhibits superior adhesion, and when used as a sealant for liquid crystal display elements, it demonstrates superior low liquid crystal contamination.

[0135] From the viewpoint of further suppressing liquid crystal contamination, the aforementioned curable resin preferably has units with hydrogen bonding such as -OH group, -NH- group, and -NH2 group.

[0136] The curable resin composition of the present invention preferably further contains a photoradical polymerization initiator.

[0137] Examples of photoradical polymerization initiators include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanoceramsite compounds, oxime ester compounds, benzoin ether compounds, and thioxanone compounds.

[0138] Examples of photoradical polymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholino)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime), and 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

[0139] The above-mentioned photoradical polymerization initiators can be used alone or in combination of two or more.

[0140] Relative to 100 parts by weight of the aforementioned curable resin, the preferred lower limit of the content of the aforementioned photoradical polymerization initiator is 0.5 parts by weight, and the preferred upper limit is 10 parts by weight. With the content of the aforementioned photoradical polymerization initiator within this range, the resulting curable resin composition exhibits superior storage stability and photocurability, and demonstrates superior low liquid crystal contamination when used as a sealant for liquid crystal display elements. A more preferred lower limit of the content of the aforementioned photoradical polymerization initiator is 1 part by weight, and a more preferred upper limit is 7 parts by weight.

[0141] The curable resin composition of the present invention may contain a thermal free radical polymerization initiator.

[0142] Examples of thermal free radical polymerization initiators include those composed of azo compounds and organic peroxides. From the viewpoint of suppressing liquid crystal contamination when the obtained curable resin composition is used as a sealant for liquid crystal display elements, initiators composed of azo compounds (hereinafter also referred to as "azo initiators") are preferred, and initiators composed of polymeric azo compounds (hereinafter also referred to as "polymeric azo initiators") are more preferred.

[0143] The above-mentioned thermal free radical polymerization initiators can be used alone or in combination of two or more.

[0144] It should be noted that, in this specification, the term "high molecular weight azo compound" refers to a compound having an azo group and having a number-average molecular weight of 300 or more that generates free radicals capable of curing (meth)acryloyl groups through heating.

[0145] The preferred lower limit for the number-average molecular weight of the aforementioned azo polymer is 1000, and the preferred upper limit is 300,000. By ensuring the number-average molecular weight of the azo polymer is within this range, adverse effects on the liquid crystal can be prevented when the obtained curable resin composition is used as a sealant for liquid crystal display elements, and it can be easily mixed into the curable resin. A more preferred lower limit for the number-average molecular weight of the aforementioned azo polymer is 5000, a more preferred upper limit is 100,000, a further preferred lower limit is 10,000, and a further preferred upper limit is 90,000.

[0146] It should be noted that, in this specification, the number-average molecular weight mentioned above is a value obtained by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it to polystyrene. Examples of columns used for determining the number-average molecular weight based on polystyrene conversion using GPC include the Shodex LF-804 (manufactured by Showa Denko Corporation).

[0147] Examples of such polymeric azo compounds include polymeric azo compounds having a structure formed by bonding multiple polyepoxide, polydimethylsiloxane, or other units via an azo group.

[0148] As for the aforementioned polymeric azo compounds having a structure formed by bonding multiple polyoxyalkylene units via azo groups, polymeric azo compounds having a polyoxyethylene structure are preferred.

[0149] Specifically, examples of the aforementioned high molecular weight azo compounds include condensation polymers of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycols, and condensation polymers of 4,4'-azobis(4-cyanovaleric acid) and polydimethylsiloxanes having terminal amino groups.

[0150] Commercially available products among the aforementioned polymeric azo initiators include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.).

[0151] In addition, examples of non-high molecular weight azo initiators include V-65 and V-501 (both manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.).

[0152] Examples of the aforementioned organic peroxides include peroxide ketones, peroxide ketals, hydrogen peroxide, dialkyl peroxides, peroxide esters, diacyl peroxides, and peroxydicarbonates.

[0153] Relative to 100 parts by weight of the aforementioned curable resin, the preferred lower limit of the content of the aforementioned thermal free radical polymerization initiator is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. With the content of the aforementioned thermal free radical polymerization initiator within this range, the resulting curable resin composition exhibits superior storage stability and thermosetting properties, and demonstrates superior low liquid crystal contamination when used as a sealant for liquid crystal display elements. A more preferred lower limit of the content of the aforementioned thermal free radical polymerization initiator is 0.3 parts by weight, and a more preferred upper limit is 5 parts by weight.

[0154] The curable resin composition of the present invention may contain fillers for purposes such as increasing viscosity, improving adhesion based on stress dispersion effect, improving coefficient of linear expansion, and improving moisture resistance of cured products.

[0155] Inorganic fillers or organic fillers can be used as the fillers mentioned above.

[0156] Examples of inorganic fillers mentioned above include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, montmorillonite, 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, and calcium silicate.

[0157] Examples of organic fillers mentioned above include polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, and acrylic polymer microparticles.

[0158] The above fillers can be used alone or in combination of two or more.

[0159] The preferred lower limit for the content of the 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. By keeping the filler content within this range, the coating properties and other properties will not deteriorate, and the improvement in adhesion and other effects will be even more superior. A more preferred lower limit for the content of the filler is 20 parts by weight, and a more preferred upper limit is 60 parts by weight.

[0160] The curable resin composition of the present invention may contain a silane coupling agent. The aforementioned silane coupling agent primarily functions as an adhesive aid for effectively bonding the curable resin composition to a substrate or similar material.

[0161] As the aforementioned silane coupling agents, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, and 3-isocyanate propyltrimethoxysilane are suitable examples. They exhibit excellent adhesion to substrates and the like, and when the obtained curable resin composition is used as a sealant for liquid crystal display elements, it can suppress the outflow of the cured resin into the liquid crystal.

[0162] The above-mentioned silane coupling agents can be used alone or in combination of two or more.

[0163] 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 parts by weight, and the preferred upper limit is 10 parts by weight. By achieving this range of silane coupling agent content, the effect of improving adhesion is more excellent, and when the obtained curable resin composition is used as a sealant for liquid crystal display elements, the low liquid crystal contamination is even more pronounced. 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.

[0164] The curable resin composition of the present invention may contain a light-blocking agent. By containing the aforementioned light-blocking agent, the curable resin composition of the present invention is suitable for use as a light-blocking sealant.

[0165] Examples of opacifiers include iron oxide, titanium black, aniline black, anthocyanin black, fullerene, carbon black, and resin-coated carbon black. Among these, titanium black is preferred.

[0166] The aforementioned titanium black is a material whose transmittance is higher for light in the vicinity of the ultraviolet region, particularly light with wavelengths of 370 nm and 450 nm, compared to its average transmittance for light with wavelengths of 300 nm and 800 nm. That is, the aforementioned titanium black is a light-blocking agent with the properties that it imparts light-blocking properties to the curable resin composition of the present invention by sufficiently blocking light wavelengths in the visible light region, while allowing light with wavelengths near the ultraviolet region to pass through. Therefore, as the aforementioned photoradical polymerization initiator, by using a polymerization initiator that can utilize light with wavelengths of increased transmittance of the aforementioned titanium black to initiate the reaction, the photocurability of the curable resin composition of the present invention can be further increased. Furthermore, as a 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 suitable as a light-blocking agent with high insulating properties.

[0167] The optical density (OD value) of the titanium black per 1 μm is preferably 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. There is no particular upper limit to the preferred OD value of the titanium black, which is usually 5 or less.

[0168] The aforementioned titanium black achieves its full effect even without surface treatment, but titanium black that has undergone surface treatment with organic components such as coupling agents, or titanium black coated with inorganic components such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide, can also be used. Among these, titanium black treated with organic components is preferred for its ability to further improve insulation.

[0169] Furthermore, the display element manufactured using the curable resin composition of the present invention, which incorporates the aforementioned titanium black as a light-shielding agent, has sufficient light-shielding properties. Therefore, it is possible to achieve a display element with no light leakage, high contrast, and excellent image display quality.

[0170] Commercially available titanium black products, such as those manufactured by Mitsubishi Materials and Akaho Kasei Corporation, are examples of such products.

[0171] Examples of titanium black produced by Mitsubishi Materials include 12S, 13M, 13M-C, 13R-N, and 14M-C.

[0172] Examples of titanium black manufactured by Akaho Chemical Co., Ltd. include Tilack D.

[0173] The preferred lower limit for the specific surface area of ​​the aforementioned titanium black is 13m².2 / g, with a preferred upper limit of 30m 2 / g, with a more preferred lower limit of 15m 2 / g, with a more preferred upper limit of 25m 2 / g.

[0174] In addition, the preferred lower limit of the volume resistivity of the above-mentioned 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.

[0175] The preferred lower limit for the primary particle size of the aforementioned opacifier is 1 nm, and the preferred upper limit is 5000 nm. By limiting the primary particle size of the opacifier to this range, superior opacity can be achieved without compromising the coatability or other properties of the resulting curable resin composition. A more preferred lower limit for the primary particle size of the aforementioned opacifier is 5 nm, a more preferred upper limit is 200 nm, a further preferred lower limit is 10 nm, and a further preferred upper limit is 100 nm.

[0176] It should be noted that the primary particle size of the above-mentioned opacifier can be determined using NICOMP 380ZLS (manufactured by PARTICLESIZING SYSTEMS) and by dispersing the opacifier in a solvent (water, organic solvent, etc.).

[0177] The preferred lower limit for the content of the above-mentioned opaque 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 setting the content of the opaque agent within this range, superior opacity can be achieved without significantly reducing the adhesion, cured strength, and paintability of the obtained curable resin composition. A more preferred lower limit for the content of the above-mentioned opaque agent is 10 parts by weight, a more preferred upper limit is 70 parts by weight, a further preferred lower limit is 30 parts by weight, and a further preferred upper limit is 60 parts by weight.

[0178] The curable resin composition of the present invention may further contain, as needed, additives such as stress relievers, reactive diluents, thixotropic agents, spacers, curing accelerators, defoamers, leveling agents, and polymerization inhibitors.

[0179] As a method for manufacturing the curable resin composition of the present invention, examples include mixing a curable resin, a thermosetting agent, and a photoradical polymerization initiator, which may be added as needed, using a mixer.

[0180] Examples of such mixers include homogenizers, homogenizing mixers, universal mixers, planetary mixers, kneaders, and three-roll mills.

[0181] The curable resin composition of the present invention is suitable for use as a sealant for display elements, and particularly suitable for use as a sealant for liquid crystal display elements. A sealant for liquid crystal display elements made using the curable resin composition of the present invention is also part of the present invention.

[0182] By incorporating conductive microparticles into the sealant for liquid crystal display elements of the present invention, it is possible to manufacture a material with both vertical and horizontal conductivity.

[0183] As the aforementioned conductive particles, examples include metal spheres and conductive particles on which a conductive metal layer is formed on the surface of resin particles. Among these, conductive particles on which a conductive metal layer is formed on the surface of resin particles are suitable because the excellent elasticity of the resin particles allows for conductive connections without damaging the transparent substrate or the like.

[0184] A liquid crystal display element having a cured form of the sealant for liquid crystal display elements of the present invention is also one of the present inventions.

[0185] The sealant for liquid crystal display elements of the present invention does not readily dissolve into liquid crystals containing polar groups. Therefore, when the liquid crystal display element of the present invention is made of liquid crystal containing liquid crystal molecules with polar groups, the effect of suppressing display defects is more significant compared to conventional sealants. That is, the liquid crystal display element of the present invention is preferably made of liquid crystal containing liquid crystal molecules with polar groups.

[0186] Examples of polar groups in the aforementioned liquid crystal molecules include fluorine groups, chlorine groups, and cyano groups.

[0187] As the liquid crystal display element of the present invention, a liquid crystal display element with a narrow bezel design is preferred. Specifically, the width of the frame portion surrounding the liquid crystal display section is preferably 2 mm or less.

[0188] Furthermore, the coating width of the sealant for the liquid crystal display element of the present invention is preferably 1 mm or less when manufacturing the liquid crystal display element of the present invention.

[0189] The sealant for liquid crystal display elements of the present invention is suitable for use in the manufacture of liquid crystal display elements using liquid crystal droplet technology.

[0190] As a method for manufacturing the liquid crystal display element of the present invention by liquid crystal droplet process, the following methods can be cited as examples.

[0191] First, the following steps are performed: a frame-shaped sealing pattern for the liquid crystal display element of the present invention is formed on a substrate using screen printing, a distributor coating, or the like. Next, the following steps are performed: while the liquid crystal display element sealant of the present invention is not cured, tiny droplets of liquid crystal are applied to the entire surface within the frame of the sealing pattern, and another substrate is immediately overlapped. Then, by performing a step of heating the sealant to cure it, a liquid crystal display element can be obtained. Alternatively, before the step of heating the sealant to cure it, a step of irradiating the sealing pattern portion with light such as ultraviolet light to temporarily cure the sealant can be performed.

[0192] Invention Effects

[0193] According to the present invention, novel acylhydrazine compounds can be provided. Furthermore, the present invention can provide curable resin compositions containing the acylhydrazine compound and exhibiting excellent storage stability and adhesion; sealants for liquid crystal display elements prepared using the curable resin compositions and exhibiting excellent low liquid crystal contamination; and liquid crystal display elements. Detailed Implementation

[0194] The present invention will be described in more detail below with examples, but the present invention is not limited to these examples.

[0195] (Synthesis example 1)

[0196] In a 300L flask, 31.6g of bisphenol F diglycidyl ether was dissolved in 100mL of toluene, followed by the addition of 31.95g of methylparaben and 3g of triphenylphosphine. The mixture was heated at 90°C for 12 hours to allow the reaction to proceed. The solvent in the resulting reaction solution was removed by distillation using an evaporator. 200mL of isopropanol was added and dissolved, followed by the addition of 20g of hydrazine monohydrate. The mixture was stirred at 40°C for 6 hours to allow the reaction to proceed. The resulting reaction solution was cooled, and the precipitate was recovered by filtration using a Kiriyama funnel. After washing with methanol, the precipitate was dried under vacuum to obtain the compound shown in formula (12).

[0197] It should be noted that the structure of the compound shown in formula (12) is obtained through... 1 Confirmed by H-NMR and FT-IR.

[0198] [Chemical Formula 12]

[0199]

[0200] (Synthesis example 2)

[0201] By replacing 31.6 g of bisphenol F diglycidyl ether with 34.6 g of bisphenol A diglycidyl ether, and otherwise operating in the same manner as in Synthesis Example 1, the compound shown in the following formula (13) was obtained.

[0202] It should be noted that the structure of the compound shown in formula (13) is obtained through... 1 Confirmed by H-NMR and FT-IR.

[0203] [Chemical Formula 13]

[0204]

[0205] (Synthesis example 3)

[0206] By replacing 31.6 g of bisphenol F diglycidyl ether with 29.9 g of 1,3,5-glycidyl ether-1,3,5-triazine-2,4,6-trione and 31.95 g of methylparaben with 47.9 g of methylparaben, the same procedure as in Synthesis Example 1 was performed to obtain the compound shown in Formula (14).

[0207] It should be noted that the structure of the compound shown in formula (14) is obtained through... 1 Confirmed by H-NMR and FT-IR.

[0208] [Chemical Formula 14]

[0209]

[0210] (Synthesis Example 4)

[0211] By replacing 31.6 g of bisphenol F diglycidyl ether with 31.7 g of bis(4-glycidyloxyphenyl) ether, the same procedure as in Synthesis Example 1 was followed to obtain the compound shown in formula (15) below.

[0212] It should be noted that the structure of the compound shown in formula (15) is obtained through... 1 Confirmed by H-NMR and FT-IR.

[0213] [Chemical Formula 15]

[0214]

[0215] (Synthesis Example 5)

[0216] By replacing 31.6 g of bisphenol F diglycidyl ether with 31.7 g of bis(4-glycidyloxyphenyl) ether and 31.95 g of methylparaben with 45.7 g of dimethyl 5-hydroxyisophthalate, the same procedure as in Synthesis Example 1 was followed to obtain the compound shown in formula (16).

[0217] It should be noted that the structure of the compound shown in formula (16) is obtained through... 1Confirmed by H-NMR and FT-IR.

[0218] [Chemical Formula 16]

[0219]

[0220] (Synthesis Example 6)

[0221] By changing 31.6 g of bisphenol F diglycidyl ether to 36.2 g of bisphenol S diglycidyl ether, and otherwise operating in the same manner as in Synthesis Example 1, the compound shown in the following formula (17) was obtained.

[0222] It should be noted that the structure of the compound shown in formula (17) is obtained through... 1 Confirmed by H-NMR and FT-IR.

[0223] [Chemical Formula 17]

[0224]

[0225] (Examples 1-9, Comparative Examples 1-3)

[0226] According to the mixing ratios recorded in Table 1, the materials were mixed using a planetary mixer (THINKY Corporation, "Defoaming Rentarō"), and then further mixed using a three-roll mill, thereby preparing the curable resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3.

[0227] It should be noted that the "compound represented by formula (18)" in Table 1 refers to the compound represented by formula (18) below.

[0228] [Chemical Formula 18]

[0229]

[0230] <Evaluation>

[0231] The curable resin compositions obtained in the Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1.

[0232] (Maintain stability)

[0233] For each curable resin composition obtained in the Examples and Comparative Examples, the initial viscosity immediately after manufacturing and the viscosity after storage at 25°C for 1 week were measured. The viscosity increase rate was defined as (viscosity after storage) / (initial viscosity), with "○" indicating a viscosity increase rate less than 1.05, "△" indicating a viscosity increase rate greater than or equal to 1.05 but less than 1.10, and "×" indicating a viscosity increase rate greater than or equal to 1.10. The storage stability was evaluated.

[0234] It should be noted that the viscosity of the curing resin composition was measured using an E-type viscometer (manufactured by BROOK FIELD, "DV-III") at 25°C and 1.0 rpm.

[0235] (Adhesion)

[0236] The curable resin compositions obtained in the examples and comparative examples were filled into a dispensing syringe (manufactured by Musashi Engineering, "PSY-10E") and degassed. The degassed curable resin compositions were then dispensed using a dispenser (manufactured by Musashi Engineering, "SHOTMASTER300") to the inner perimeter of a glass substrate (150mm × 150mm) 30mm from the end. Another glass substrate (110mm × 110mm) was then overlapped and bonded under vacuum. The substrate was then irradiated with a metal halide lamp at 100mW / cm². 2 The curable resin composition was temporarily cured by exposing it to ultraviolet light for 30 seconds. Then, it was heat-cured at 120°C for 1 hour to obtain an adhesive test piece. Using a metal rod with a radius of 5 mm, the strength (kgf) at which panel peeling occurred was measured when the metal rod was pressed into the end of the substrate of the obtained adhesive test piece at a speed of 5 mm / min. The adhesive force (kg / cm) was then calculated.

[0237] The adhesion is evaluated by marking the adhesive strength as "◎" for a strength of 200 kg / cm or more, "○" for a strength of 150 kg / cm or more but less than 200 kg / cm, "△" for a strength of 100 kg / cm or more but less than 150 kg / cm, and "×" for a strength of less than 100 kg / cm.

[0238] (Display performance of liquid crystal display elements)

[0239] One part by weight of spacer microparticles (manufactured by Sekisui Chemicals Co., Ltd., "Micropearl SI-H050") with an average particle size of 5 μm was dispersed in 100 parts by weight of each curable resin composition obtained in the Examples and Comparative Examples and filled into a syringe. Degassing was performed using a centrifugal degassing machine (Awatron AW-1). Using a dispenser, under conditions of a nozzle diameter of 0.4 mmφ, a nozzle spacing of 42 μm, a syringe ejection pressure of 100–400 kPa, and a coating speed of 60 mm / s, the degassed curable resin composition was applied in a frame shape to one of two substrates with an alignment film and ITO. The ejection pressure was adjusted so that the linewidth of the curable resin composition was approximately 1.5 mm. Next, tiny droplets of liquid crystal (manufactured by Tokyo Chemical Industry Co., Ltd., "4-pentyl-4-biphenylnitrile") were applied to the entire surface of the frame of the curable resin composition on the substrate coated with the curable resin composition, and the other substrate was bonded under vacuum. Immediately after bonding, irradiate the curing resin composition with a metal halide lamp at 100 mW / cm². 2 The resin composition is temporarily cured by exposing it to ultraviolet light for 30 seconds. Next, it is fully cured by heating at 120°C for 1 hour to produce a liquid crystal display element.

[0240] For the obtained liquid crystal display elements, liquid crystal alignment disorder (display unevenness) near the sealant immediately after the liquid crystal display element was visually confirmed. Alignment disorder was judged based on the color unevenness of the display area. A case where no display unevenness was observed in the liquid crystal display element was marked as "○", a case where display unevenness existed in the peripheral area (within 500 μm of the curable resin composition) was marked as "△", and a case where display unevenness not only existed in the peripheral area but also extended to the central area of ​​more than 500 μm was marked as "×". Low liquid crystal contamination was evaluated.

[0241] [Table 1]

[0242]

[0243] Industrial availability

[0244] According to the present invention, novel acylhydrazine compounds can be provided. Furthermore, the present invention can provide curable resin compositions containing the acylhydrazine compound and exhibiting excellent storage stability and adhesion; sealants for liquid crystal display elements prepared using the curable resin compositions and exhibiting excellent low liquid crystal contamination; and liquid crystal display elements.

Claims

1. An acylhydrazine compound, characterized in that, Represented by the following formula (4) or the following formula (18), ， In formula (4), X represents the structure of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol S diglycidyl ether, bis(4-glycidyloxyphenyl) ether, 3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl, and 1,3,5-glycidyl ether-1,3,5-triazine-2,4,6-trione, excluding the glycidyloxy group; Ar represents a benzene ring; m is 1 or 2; and n is 2 or 3. 。 2. A curable resin composition comprising a curable resin and a thermosetting agent, The thermosetting agent comprises the acylhydrazine compound of claim 1.

3. The curable resin composition according to claim 2, further comprising a photoradical polymerization initiator.

4. A sealant for a liquid crystal display element, which is made using the curable resin composition according to claim 2 or 3.

5. A liquid crystal display element having a cured product of the sealant for liquid crystal display elements as described in claim 4.

Images