TWI858115B - Sealant for liquid crystal display element, upper and lower conductive material, and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a sealant for liquid crystal display elements that is excellent in storage stability, adhesion, and low liquid crystal contamination. In addition, the purpose of the present invention is to provide an upper and lower conductive material and a liquid crystal display element formed using the sealant for liquid crystal display elements. The present invention is a sealant for liquid crystal display elements, which contains a curable resin and a thermosetting agent, and the above-mentioned thermosetting agent contains a hydrazide compound, and the above-mentioned hydrazide compound has a structure shown in the following formula (1-1) and a structure shown in the following formula (1-2). In formula (1-1), Ar is an aromatic ring, and in formula (1-2), ^R1 is a hydrogen atom or a methyl group.

Description

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

The present invention relates to a sealant for a liquid crystal display element having excellent storage stability, adhesion, and low liquid crystal contamination properties. The present invention also relates to an upper and lower conductive material and a liquid crystal display element formed by using the sealant for a liquid crystal display element.

In recent years, as a manufacturing method for liquid crystal display elements such as liquid crystal display units, from the perspective of reducing the tact time and optimizing the amount of liquid crystal used, the method of dripping liquid crystal using a sealant as disclosed in Patent Documents 1 and 2 is called a dripping method. In the dripping method, first, a frame-shaped sealing pattern is formed on one of two substrates with electrodes by dispensing glue. Then, tiny liquid crystal drops are dripped into the frame of the sealing pattern in a state where the sealant is not cured, and after overlapping the other substrate under vacuum, the sealant is cured to produce a liquid crystal display element. This dripping method has become the mainstream manufacturing method of liquid crystal display elements.

In the current era when various mobile devices equipped with liquid crystal panels such as mobile phones and portable game consoles are becoming popular, the most demanded topic is the miniaturization of the devices. As a method of miniaturizing the devices, there is a narrow frame of the liquid crystal display part, for example, the position of the sealing part is arranged under the black matrix (hereinafter also referred to as narrow frame design).

However, in the narrow frame design, the sealant is placed directly below the black matrix. Therefore, if the dripping process is performed, the light irradiated when the sealant is photocured will be blocked, making it difficult for the light to reach the inside of the sealant. If it is a conventional sealant, the curing will be insufficient. In this way, if the sealant is not sufficiently cured, there is a problem that the uncured sealant components are dissolved into the liquid crystal, which makes it easy to cause liquid crystal contamination. In particular, in recent years, with the high polarization of liquid crystals, sealants are required to have further low liquid crystal contamination properties.

When it becomes difficult to cure the sealant by light, curing by heating is considered, and as a method for curing the sealant by heating, a thermosetting agent is mixed into the sealant. However, when a highly reactive thermosetting agent is used to improve the curability or adhesion of the sealant, the storage stability of the obtained sealant may deteriorate. Prior Art Literature Patent Literature

Patent document 1: Japanese Patent Publication No. 2001-133794 Patent document 2: International Publication No. 02/092718

[The problem that the invention wants to solve]

The purpose of the present invention is to provide a sealant for liquid crystal display elements that is excellent in storage stability, adhesion, and low liquid crystal contamination. In addition, the purpose of the present invention is to provide an upper and lower conductive material and a liquid crystal display element formed by using the sealant for liquid crystal display elements. [Technical means to solve the problem]

The present invention is a sealant for a liquid crystal display element, which contains a curable resin and a thermosetting agent, wherein the thermosetting agent contains a hydrazide compound, and the hydrazide compound has a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2).

In formula (1-1), Ar is an aromatic ring, and in formula (1-2), ^R1 is a hydrogen atom or a methyl group. The present invention is described in detail below.

After in-depth research, the inventors found that by using a thermosetting agent with a specific structure, a sealant for liquid crystal display elements with excellent storage stability, adhesion, and low liquid crystal contamination can be obtained, thereby completing the present invention.

The sealant for liquid crystal display elements of the present invention contains a thermosetting agent. The thermosetting agent contains a hydrazide compound. The hydrazide compound has the structure shown in the above formula (1-1) and the structure shown in the above formula (1-2). Hereinafter, the hydrazide compound having the structure shown in the above formula (1-1) and the structure shown in the above formula (1-2) is also referred to as the "hydrazide compound of the present invention". By containing the hydrazide compound of the present invention, the sealant for liquid crystal display elements of the present invention can be made excellent in storage stability, adhesion, and low liquid crystal contamination.

The reasons why the storage stability, adhesion, and low liquid crystal contamination of the obtained sealant for liquid crystal display elements can be improved by using the hydrazide compound of the present invention can be considered as follows. That is, it is believed that by having the structure represented by the above formula (1-1), the softening point of the hydrazide compound can be controlled, thereby improving the storage stability. In addition, it is believed that by having the structure represented by the above formula (1-2) containing a primary amine group, the adhesion of the obtained sealant can be improved. Furthermore, it is believed that by having such structures, the molecular weight of the hydrazide compound becomes higher, thereby suppressing elution into the liquid crystal.

In the hydrazide compound of the present invention, the preferred lower limit of the ratio of the structure represented by the above formula (1-1) is 5 mol%, and the preferred upper limit is 95 mol%. By making the ratio of the structure represented by the above formula (1-1) more than 5 mol%, the storage stability of the obtained sealant for liquid crystal display elements is further improved. By making the ratio of the structure represented by the above formula (1-1) less than 95 mol%, the adhesion of the obtained sealant for liquid crystal display elements is further improved. The preferred lower limit of the ratio of the structure represented by the above formula (1-1) is 10 mol%, the preferred upper limit is 90 mol%, and the further preferred upper limit is 50 mol%.

In the hydrazide compound of the present invention, the preferred lower limit of the ratio of the structure represented by the above formula (1-2) is 5 mol%, and the preferred upper limit is 95 mol%. By making the ratio of the structure represented by the above formula (1-2) more than 5 mol%, the adhesion of the obtained sealant for liquid crystal display elements is further improved. By making the ratio of the structure represented by the above formula (1-2) less than 95 mol%, the storage stability of the obtained sealant for liquid crystal display elements is further improved. The preferred lower limit of the ratio of the structure represented by the above formula (1-2) is 10 mol%, the preferred upper limit is 90 mol%, and the further preferred lower limit is 50 mol%.

The hydrazide compound of the present invention may have other structures in addition to the structure represented by the above formula (1-1) and the structure represented by the above formula (1-2). The hydrazide compound of the present invention preferably has the structure represented by the following formula (2) as the other structure. By having the structure represented by the following formula (2), the adhesion of the obtained sealant for liquid crystal display elements is further improved.

In formula (2), ^R2 is a hydrogen atom or a methyl group, and ^R3 is a -C(=O) ^OR4 group ( ^R4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), a -CN group, ^{a -OR5} group ( ^R5 is an alkyl group having 1 to 10 carbon atoms), or a hydrogen atom.

In the hydrazide compound of the present invention, the preferred lower limit of the weight average molecular weight is 2000, and the preferred upper limit is 200,000. By making the above weight average molecular weight above 2000, the low liquid crystal contamination property of the obtained sealant for liquid crystal display elements is further improved. By making the above weight average molecular weight below 200,000, the handling property of the obtained sealant for liquid crystal display elements is further improved. The preferred lower limit of the above weight average molecular weight is 4000, and the preferred upper limit is 100,000. Furthermore, in this specification, the above weight average molecular weight is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and the value is obtained by polystyrene conversion. Examples of columns used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).

The preferred lower limit of the softening point of the hydrazide compound of the present invention is 65°C, and the preferred upper limit is 200°C. By making the softening point of the hydrazide compound of the present invention above 65°C, the storage stability of the obtained sealant for liquid crystal display elements is further improved. By making the softening point of the hydrazide compound of the present invention below 200°C, the adhesion of the obtained sealant for liquid crystal display elements is further improved. The preferred lower limit of the softening point of the hydrazide compound of the present invention is 90°C, and the preferred upper limit is 160°C. Furthermore, the above-mentioned softening point can be obtained by the global method according to JIS K 2207.

As a method for producing the hydrazide compound of the present invention, for example, the following method can be cited. That is, first, the compound represented by the following formula (3-1) and the compound represented by the following formula (3-2) are dissolved in a solvent such as tetrahydrofuran, and in the presence of a polymerization initiator such as azobisisobutyronitrile, the mixture is heated and stirred while nitrogen replacement is performed to react. After the obtained reaction product is concentrated, it is reprecipitated in an ethanol solution to obtain an intermediate polymer compound. The obtained intermediate polymer compound and hydrazine hydrate are dissolved in a solvent such as tetrahydrofuran, and reacted under reflux. After the reaction is completed, the solid matter is separated by concentration, thereby obtaining the hydrazide compound of the present invention. Furthermore, in addition to the compound represented by the following formula (3-1) and the compound represented by the following formula (3-2), a compound represented by the following formula (4) can also be used.

In formula (3-1), Ar is an aromatic ring, in formula (3-2), ^R1 is a hydrogen atom or a methyl group, and ^R6 is an alkyl group having 1 to 10 carbon atoms.

In formula (4), ^R2 is a hydrogen atom or a methyl group, and ^R3 is a -C(=O) ^OR4 group ( ^R4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), a -CN group, ^{a -OR5} group ( ^R5 is an alkyl group having 1 to 10 carbon atoms), or a hydrogen atom.

The content of the hydrazide compound of the present invention is preferably 1 part by weight relative to 100 parts by weight of the curable resin, and the preferred upper limit is 20 parts by weight. By making the content of the hydrazide compound of the present invention more than 1 part by weight, the curability or adhesion of the obtained sealant for liquid crystal display elements is more excellent. By making the content of the hydrazide compound of the present invention less than 20 parts by weight, the storage stability and low liquid crystal contamination of the obtained sealant for liquid crystal display elements are more excellent. The preferred lower limit of the content of the hydrazide compound of the present invention is 2 parts by weight, and the preferred upper limit is 15 parts by weight.

The sealant for liquid crystal display elements of the present invention may contain other thermosetting agents in addition to the hydrazide compound of the present invention within the scope that does not impair the purpose of the present invention. Examples of the above-mentioned thermosetting agents include: organic acid hydrazide, imidazole derivatives, amine compounds, polyphenol compounds, acid anhydrides, etc.

The sealant for liquid crystal display element of the present invention contains a curable resin. The curable resin preferably contains an epoxy compound. Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallylbisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, Resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compound, etc.

Examples of commercially available bisphenol A epoxy resins include jER828EL, jER1004 (both manufactured by Mitsubishi Chemical), and EPICLON850 (manufactured by DIC). Examples of commercially available bisphenol F epoxy resins include jER806, jER4004 (both manufactured by Mitsubishi Chemical), and EPICLON EXA-830CRP (manufactured by DIC). Examples of commercially available bisphenol E epoxy resins include EPOMIK R710 (manufactured by Mitsui Chemicals). Examples of commercially available bisphenol S epoxy resins include EPICLON EXA-1514 (manufactured by DIC Corporation). Examples of commercially available 2,2'-diallylbisphenol A epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available hydrogenated bisphenol epoxy resins include EPICLON EXA-7015 (manufactured by DIC Corporation). Examples of commercially available propylene oxide-added bisphenol A epoxy resins include EP-4000S (manufactured by ADEKA Corporation). Examples of commercially available resorcinol epoxy resins include EX-201 (manufactured by Nagase Chemicals Co., Ltd.). Examples of commercially available biphenyl epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Co., Ltd.). Examples of commercially available sulfide epoxy resins include YSLV-50TE (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.). Examples of commercially available diphenyl ether epoxy resins include YSLV-80DE (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.). Examples of commercially available dicyclopentadiene epoxy resins include EP-4088S (manufactured by ADEKA). Examples of commercially available naphthalene epoxy resins include EPICLON HP-4032 and EPICLON EXA-4700 (manufactured by DIC). Examples of commercially available phenol novolac epoxy resins include EPICLON N-770 (manufactured by DIC). Examples of commercially available o-cresol novolac epoxy resins include EPICLON N-670-EXP-S (manufactured by DIC). Examples of commercially available dicyclopentadiene novolac epoxy resins include EPICLON HP-7200 (manufactured by DIC Corporation). Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available naphthol novolac epoxy resins include ESN-165S (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.). Examples of commercially available glycidylamine epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.). Examples of commercially available alkyl polyol epoxy resins include ZX-1542 (manufactured by NIPPON STEEL Chemical & Material), EPICLON726 (manufactured by DIC), Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and DENACOL EX-611 (manufactured by Nagase Chemicals Co., Ltd.). Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (manufactured by NIPPON STEEL Chemical & Material), and Epolead PB (manufactured by DAICEL). Examples of commercially available glycidyl ester compounds include DENACOL EX-147 (manufactured by Nagase Chemicals Co., Ltd.). Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, and YSLV-90CR (all manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031 and jER1032 (both manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), and TEPIC (manufactured by Nissan Chemical Co., Ltd.).

As the above-mentioned epoxy compound, a partially (meth)acrylic acid-modified epoxy resin can also be suitably used. Furthermore, in this specification, the above-mentioned partially (meth)acrylic acid-modified epoxy resin refers to a compound having one or more epoxy groups and (meth)acrylic acid groups in one molecule, respectively, and can be obtained by reacting a part of the epoxy groups of an epoxy compound having two or more epoxy groups with (meth)acrylic acid. Furthermore, in this specification, the above-mentioned "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylic acid group" refers to acrylyl group or methacrylic acid group.

Examples of the commercially available (meth)acrylic modified epoxy resins include UVACURE1561 and KRM8287 (both manufactured by DAICEL-ALLNEX).

Furthermore, the curable resin may also contain a (meth)acrylic compound. Examples of the (meth)acrylic compound include (meth)acrylate compounds, epoxy (meth)acrylates, urethane (meth)acrylates, etc. Among them, epoxy (meth)acrylates are preferred. Furthermore, from the viewpoint of reactivity, the (meth)acrylic compound is preferably one having two or more (meth)acrylic groups in one molecule. Furthermore, in this specification, the so-called "(meth)acrylic compound" refers to a compound having a (meth)acrylic group. Furthermore, the so-called "(meth)acrylate" refers to an acrylate or a methacrylate, and the so-called "epoxy (meth)acrylate" refers to a compound formed by the reaction of all epoxy groups in an epoxy compound with (meth)acrylic acid.

Examples of the monofunctional (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, isoborneol (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 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, tetrahydrofuranmethyl (meth)acrylate, ethyl carbitol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoroethyl (meth)acrylate Fluoropropyl ester, 1H,1H,5H-octafluoropentyl (meth)acrylate, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalate 2-hydroxypropyl, 2-(meth)acryloyloxyethyl phosphate, glycidyl (meth)acrylate, etc.

In addition, examples of the bifunctional (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, tripropylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, propylene oxide added bisphenol A di(meth)acrylate, ethylene oxide added bisphenol F di(meth)acrylate, dihydroxymethyl dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylate 2-hydroxy-3-(meth)acryloyloxypropyl, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.

In addition, examples of the trifunctional or higher-functional (meth)acrylate compounds include trihydroxymethylpropane tri(meth)acrylate, ethylene oxide-added trihydroxymethylpropane tri(meth)acrylate, propylene oxide-added trihydroxymethylpropane tri(meth)acrylate, caprolactone-modified trihydroxymethylpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide-added glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, di-trihydroxymethylpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

Examples of the epoxy (meth)acrylate include those obtained by conventionally reacting an epoxy compound with (meth)acrylic acid in the presence of an alkaline catalyst.

As the epoxy compound used as a raw material for synthesizing the epoxy (meth)acrylate, the same epoxy compound as that mentioned above as the curable resin contained in the sealant for liquid crystal display element of the present invention can be used.

Examples of commercially available epoxy (meth)acrylates include epoxy (meth)acrylate manufactured by DAICEL-ALLNEX, epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry, epoxy (meth)acrylate manufactured by Kyoeisha Chemical, and epoxy (meth)acrylate manufactured by Nagase Chemicals. Examples of epoxy (meth) acrylates manufactured by the above-mentioned DAICEL-ALLNEX include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, and EBECRYL RDX63182. Examples of epoxy (meth) acrylates manufactured by the above-mentioned Shin-Nakamura Chemical Industry include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020. Examples of epoxy (meth) acrylates manufactured by the aforementioned Kyoeisha 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, EPOXY ESTER 400EA, etc. Examples of the epoxy (meth)acrylate manufactured by Nagase Chemicals include DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, and DENACOL ACRYLATE DA-911.

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

Examples of the isocyanate compound used as a raw material of the amine (meth)acrylate 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, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, thiophosphoric acid tris(isocyanatophenyl ester), tetramethylxylylene diisocyanate, and 1,6,11-undecane triisocyanate.

Furthermore, as the isocyanate compound used as the raw material of the above-mentioned amine (meth)acrylate, an extended isocyanate compound obtained by reacting a polyol with an excess of the isocyanate compound can also be used. As the above-mentioned polyol, for example, ethylene glycol, propylene glycol, glycerin, sorbitol, trihydroxymethylpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, etc. can be listed.

Examples of the (meth)acrylic acid derivatives having a hydroxyl group include hydroxyl alkyl mono(meth)acrylates, mono(meth)acrylates of diols, mono(meth)acrylates or di(meth)acrylates of triols, and epoxy(meth)acrylates. Examples of the hydroxyl alkyl mono(meth)acrylates include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate. Examples of the diols include ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, and polyethylene glycol. Examples of the triols include trihydroxymethylethane, trihydroxymethylpropane, and glycerol. Examples of the epoxy (meth)acrylate include bisphenol A type epoxy acrylate and the like.

As commercially available amine (meth) acrylates, for example, amine (meth) acrylates manufactured by Toagosei Co., Ltd., amine (meth) acrylates manufactured by DAICEL-ALLNEX Co., Ltd., amine (meth) acrylates manufactured by Negami Kogyo Co., Ltd., amine (meth) acrylates manufactured by Shin-Nakamura Chemical Co., Ltd., and amine (meth) acrylates manufactured by Kyoeisha Chemical Co., Ltd., etc. As commercially available amine (meth) acrylates manufactured by Toagosei Co., Ltd., for example, M-1100, M-1200, M-1210, M-1600, etc. can be cited. Examples of amine (meth)acrylates manufactured by the above-mentioned DAICEL-ALLNEX company include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260, etc. Examples of amine (meth)acrylates manufactured by the aforementioned Negami Industries 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 amine (meth)acrylates manufactured by the aforementioned 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, UA-W2A, etc. Examples of the amine (meth)acrylates manufactured by the aforementioned Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, and UA-306T.

When the curable resin contains the (meth)acrylic compound in addition to the epoxy compound, or contains the partially (meth)acrylic modified epoxy compound, the ratio of the (meth)acrylic group in the curable resin to the total of the epoxy group and the (meth)acrylic group is preferably set to 30 mol% or more and 95 mol% or less. By setting the ratio of the (meth)acrylic group to be within this range, liquid crystal contamination is suppressed, and the adhesion of the obtained sealant for liquid crystal display elements is further improved.

From the viewpoint of further suppressing liquid crystal contamination, the curable resin preferably contains a unit having a hydrogen bonding property such as an -OH group, a -NH- group, or a _-NH2 group.

Preferably, the sealant for liquid crystal display element of the present invention further contains a photo-radical polymerization initiator. Examples of the photo-radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, 9-oxysulfur Compounds, etc. As the above-mentioned photoradical polymerization initiator, specifically, for example, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-linophenyl)-1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4- 1-Butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2- The photo-radical polymerization initiators include 1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-(phenylthio)phenyl)-1,2-octadione2-(O-benzoyloxime), 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. The photo-radical polymerization initiators may be used alone or in combination of two or more.

The content of the photo-radical polymerization initiator is preferably 0.5 parts by weight and preferably 10 parts by weight relative to 100 parts by weight of the curable resin. By setting the content of the photo-radical polymerization initiator within this range, the obtained sealant for liquid crystal display elements suppresses liquid crystal contamination and has better storage stability or photocurability. The lower limit of the content of the photo-radical polymerization initiator is more preferably 1 part by weight and the upper limit is more preferably 7 parts by weight.

The sealant for liquid crystal display elements of the present invention may also contain a thermal radical polymerization initiator. As the above-mentioned thermal radical polymerization initiator, for example, those composed of azo compounds or organic peroxides can be listed. Among them, from the viewpoint of suppressing liquid crystal contamination, the initiator composed of azo compounds (hereinafter, also referred to as "azo initiator") is preferred, and the initiator composed of polymer azo compounds (hereinafter, also referred to as "polymer azo initiator") is more preferred. The above-mentioned thermal radical polymerization initiator can be used alone or in combination of two or more. Furthermore, in this specification, the so-called "polymer azo compound" refers to a compound having an azo group and a number average molecular weight of 300 or more of free radicals that can harden (meth)acrylic groups by heat generation.

The preferred lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 1000, and the preferred upper limit is 300,000. By making the number average molecular weight of the above-mentioned high molecular weight azo compound within this range, adverse effects on liquid crystals can be prevented, and it can be easily mixed with a curable resin. The preferred lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 5000, and the preferred upper limit is 100,000, and the further preferred lower limit is 10,000, and the further preferred upper limit is 90,000. Furthermore, in this specification, the above-mentioned number average molecular weight is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and the value is obtained by converting to polystyrene. Examples of columns used when measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).

As the above-mentioned high molecular weight azo compound, for example, there can be cited a structure in which units such as polyalkyleneoxide or polydimethylsiloxane are multiple bonded via an azo group. As the above-mentioned high molecular weight azo compound having a structure in which units such as polyalkyleneoxide are multiple bonded via an azo group, it is preferably a structure of polyethylene oxide. As the above-mentioned high molecular weight azo compound, specifically, for example, there can be cited: a condensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or a condensate of 4,4'-azobis(4-cyanovaleric acid) and polydimethylsiloxane having a terminal amino group, etc. Examples of the commercially available polymer azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm and Koshun Chemical). In addition, examples of non-polymer azo initiators include V-65 and V-501 (all manufactured by Fujifilm and Koshun Chemical).

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

The lower limit of the content of the thermal free radical polymerization initiator relative to 100 parts by weight of the curable resin is preferably 0.1 parts by weight, and the upper limit is preferably 10 parts by weight. By making the content of the thermal free radical polymerization initiator within this range, liquid crystal contamination of the sealant for liquid crystal display elements is suppressed, and the storage stability or thermal curing property is made more excellent. The lower limit of the content of the thermal free radical polymerization initiator is more preferably 0.3 parts by weight, and the upper limit is more preferably 5 parts by weight.

The sealant for liquid crystal display elements of the present invention may also contain fillers for the following purposes: increasing viscosity, improving adhesion by stress dispersion effect, improving linear expansion rate, improving moisture resistance of cured products, etc.

As the above-mentioned filler, an inorganic filler or an organic filler can be used. As the above-mentioned inorganic filler, for example, there can be listed: silicon dioxide, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, aluminum oxide, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc. As the above-mentioned organic filler, for example, there can be listed: polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, etc. The above-mentioned fillers can be used alone or in combination of two or more.

The content of the filler is preferably 10 parts by weight and 70 parts by weight relative to 100 parts by weight of the sealant for liquid crystal display elements of the present invention. By making the content of the filler within this range, the effect of improving adhesion is more excellent without deteriorating the coating property. The better lower limit of the content of the filler is 20 parts by weight and the better upper limit is 60 parts by weight.

The sealant for liquid crystal display element of the present invention may also contain a silane coupling agent. The silane coupling agent mainly serves as a bonding aid for making the sealant for liquid crystal display element and the substrate etc. bond well.

As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc. can be suitably used. These silane coupling agents are excellent in improving the adhesion with the substrate, etc., and can inhibit the curable resin from flowing out into the liquid crystal by chemically bonding with the curable resin. The above-mentioned silane coupling agents can 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 sealant for liquid crystal display elements of the present invention is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. By making the content of the silane coupling agent within this range, the occurrence of liquid crystal contamination is suppressed, and the effect of improving adhesion is more excellent. The preferred lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the preferred upper limit is 5 parts by weight.

The sealing agent for liquid crystal display element of the present invention may also contain a light-shielding agent. By containing the light-shielding agent, the sealing agent for liquid crystal display element of the present invention can be suitably used as a light-shielding sealing agent.

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

The titanium black is a substance having a higher transmittance to light near the ultraviolet region, especially to light of wavelengths of 370 nm to 450 nm, than the average transmittance to light of wavelengths of 300 nm to 800 nm. That is, the titanium black is a light-shielding agent having the following properties: it imparts light-shielding properties to the sealant for liquid crystal display elements of the present invention by fully blocking light of wavelengths in the visible light region, while allowing light of wavelengths near the ultraviolet region to penetrate. Therefore, by using a substance that can start a reaction with light of a wavelength whose transmittance of the titanium black becomes high as the photo-radical polymerization initiator, the light curing property of the sealant for liquid crystal display elements of the present invention can be further enhanced. On the other hand, as the light-shielding agent contained in the sealant for the liquid crystal display element of the present invention, it is preferably a substance with high insulation, and titanium black can also be suitably used as a light-shielding agent with high insulation. The optical density (OD value) per 1 μm of the titanium black is preferably 3 or more, and more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The upper limit of the OD value of the titanium black is not particularly limited, and is usually 5 or less.

Although the titanium black mentioned above can fully exert its effect even without surface treatment, titanium black that has been surface treated can also be used, such as titanium black that has been surface treated with an organic component such as a coupling agent, or titanium black that has been coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide. Among them, in terms of further improving the insulation, it is preferred to be treated with an organic component. In addition, the liquid crystal display element manufactured using the sealant for liquid crystal display elements of the present invention mixed with the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, so it is possible to realize a liquid crystal display element that does not leak light, has a higher contrast, and has excellent image display quality.

Examples of the titanium blacks on the market include: titanium black manufactured by Mitsubishi Materials Corporation, titanium black manufactured by Ako Chemicals Co., Ltd., etc. Examples of the titanium blacks manufactured by Mitsubishi Materials Corporation include: 12S, 13M, 13M-C, 13R-N, 14M-C, etc. Examples of the titanium blacks manufactured by Ako Chemicals Co., Ltd. include: TILACK D, etc.

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 resistivity of the titanium black is 0.5 Ω·cm, the more 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 primary particle size of the above-mentioned light-shielding agent is not particularly limited as long as it is less than the distance between the substrates of the liquid crystal display element. The preferred lower limit is 1 nm and the preferred upper limit is 5000 nm. By making the primary particle size of the above-mentioned light-shielding agent within this range, the light-shielding property can be made more excellent without deteriorating the coating property of the sealant for liquid crystal display elements. The preferred lower limit of the primary particle size of the above-mentioned light-shielding agent is 5 nm, the preferred upper limit is 200 nm, the further preferred lower limit is 10 nm, and the further preferred upper limit is 100 nm. The primary particle size of the sunscreen can be measured by dispersing the sunscreen in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The lower limit of the content of the above-mentioned light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is preferably 5 parts by weight, and the upper limit is preferably 80 parts by weight. By making the content of the above-mentioned light-shielding agent within this range, it is possible to exert a more excellent light-shielding property without significantly reducing the adhesion, strength after curing, and drawing properties of the sealant for liquid crystal display elements. The lower limit of the content of the above-mentioned light-shielding agent is more preferably 10 parts by weight, and the upper limit is more preferably 70 parts by weight, and the lower limit is further preferably 30 parts by weight, and the upper limit is further preferably 60 parts by weight.

The sealant for liquid crystal display elements of the present invention may further contain additives such as stress relaxants, reactive diluents, thixotropic agents, spacers, curing accelerators, defoamers, levelers, polymerization inhibitors, etc. as needed.

As a method for manufacturing the sealant for liquid crystal display elements of the present invention, for example, the following method can be cited: using a mixer, a curable resin, a thermosetting agent, and a thermal free radical polymerization initiator added as needed are mixed. As the above-mentioned mixer, for example, a homogenizer, a homogenizer, a universal mixer, a planetary mixer, a kneader, a three-roll grinder, etc. can be cited.

By mixing conductive microparticles into the sealant for liquid crystal display elements of the present invention, a vertical conductive material can be manufactured. Such a vertical conductive material containing the sealant for liquid crystal display elements of the present invention and conductive microparticles is also one of the present invention.

As the conductive particles, for example, metal spheres, resin particles with a conductive metal layer formed on the surface, etc. are used. Among them, resin particles with a conductive metal layer formed on the surface are preferred because the resin particles have excellent elasticity and can be electrically connected without damaging a transparent substrate.

A liquid crystal display element made by using the sealant for liquid crystal display element of the present invention or the top-bottom conductive material of the present invention is also one of the present invention.

The liquid crystal display element of the present invention is preferably a liquid crystal display element with a narrow frame design. Specifically, the width of the frame portion around the liquid crystal display part is preferably less than 2 mm. In addition, when manufacturing the liquid crystal display element of the present invention, the coating width of the sealant for the liquid crystal display element of the present invention is preferably less than 1 mm.

The sealant for liquid crystal display elements of the present invention can be suitably used to manufacture liquid crystal display elements by liquid crystal dripping processing. As a method for manufacturing the liquid crystal display element of the present invention by liquid crystal dripping processing, for example, the following method can be listed. The liquid crystal display element can be obtained by a method comprising the following steps: First, a step of forming a frame-shaped sealing pattern by applying the sealant for liquid crystal display elements of the present invention on a substrate by screen printing, dispensing, etc. Then, in a state where the sealant for liquid crystal display elements of the present invention is not cured, a step of applying tiny liquid crystal drops on the entire surface of the frame of the sealing pattern, and then immediately overlapping another substrate. Thereafter, a step of heating the sealant to cure it is performed. Furthermore, before the step of heating the sealant to harden it, a step of temporarily hardening the sealant by irradiating the seal pattern portion with light such as ultraviolet rays may be performed. [Effect of the invention]

According to the present invention, a sealant for a liquid crystal display element having excellent storage stability, adhesion, and low liquid crystal contamination can be provided. In addition, according to the present invention, a top-bottom conductive material and a liquid crystal display element formed by using the sealant for a liquid crystal display element can be provided.

The present invention is described in more detail below with reference to the following embodiments, but the present invention is not limited to the embodiments.

(Synthesis of Compound A) In a three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer, 208.3 g (2.0 mol) of styrene (manufactured by Fuji Films Wako Pure Chemical Industries, Ltd.) and 172.1 g (2.0 mol) of methyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 300 mL of tetrahydrofuran. 16.4 g (0.1 mol) of azobisisobutyronitrile was added to the obtained solution as a polymerization initiator, and the mixture was stirred at 80°C for 1 hour while replacing the atmosphere with nitrogen to allow the reaction to proceed. The obtained reaction product was concentrated and then reprecipitated in an ethanol solution to obtain an intermediate polymer compound. The obtained intermediate polymer compound and 113 g (2.3 mol) of hydrazine hydrate were dissolved in 200 mL of tetrahydrofuran in a three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer, and the mixture was reacted under reflux for 3 hours. After the reaction was completed, the solid was separated by concentration to obtain compound A. According to ¹ H-NMR, MS, and FT-IR, it was determined that the obtained compound A was a compound having the structure represented by the above formula (1-1) (Ar is a phenyl group), the structure represented by the above formula (1-2) (R ¹ is a hydrogen atom), and the structure represented by the above formula (2) (R ² is a hydrogen atom, and R ³ is a -C(=O)OCH ₃ group). The obtained compound A had a structure represented by the above formula (1-1) in an amount of 50 mol%. The obtained compound A had a weight average molecular weight of 15,000 and a softening point of 130°C.

(Synthesis of Compound B) Compound B, which is the hydrazide compound of the present invention, was obtained in the same manner as in the above "(Synthesis of Compound A)" except that the stirring time during stirring at 80°C while replacing the atmosphere with nitrogen was changed to 4 hours. Furthermore, based on ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained compound B was a compound having the structure represented by the above formula (1-1) (Ar is a phenyl group), the structure represented by the above formula (1-2) (R ¹ is a hydrogen atom), and the structure represented by the above formula (2) (R ² is a hydrogen atom, and R ³ is a -C(=O)OCH ₃ group). Furthermore, the obtained compound B had 50 mol% of the structure represented by the above formula (1-1). Furthermore, the weight average molecular weight of the obtained compound B was 70,000, and the softening point was 147°C.

(Synthesis of Compound C) Compound C, which is the hydrazide compound of the present invention, was obtained in the same manner as in the above "(Synthesis of Compound A)" except that the stirring time during stirring at 80°C was changed to 0.5 hours while replacing the atmosphere with nitrogen. Furthermore, based on ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained compound C was a compound having the structure represented by the above formula (1-1) (Ar is a phenyl group), the structure represented by the above formula (1-2) (R ¹ is a hydrogen atom), and the structure represented by the above formula (2) (R ² is a hydrogen atom, and R ³ is a -C(=O)OCH ₃ group). Furthermore, the obtained compound C had 50 mol% of the structure represented by the above formula (1-1). Furthermore, the obtained compound C had a weight average molecular weight of 3000 and a softening point of 92°C.

(Synthesis of Compound D) The same procedure as in the above "(Synthesis of Compound A)" was followed except that the amount of styrene blended was changed to 416.6 g (4.0 mol), the amount of methyl acrylate blended was changed to 86.0 g (1.0 mol), and the amount of hydrazine hydrate blended was changed to 60 g (1.2 mol), thereby obtaining Compound D, which is the hydrazide compound of the present invention. Furthermore, based on ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained Compound D is a compound having the structure represented by the above formula (1-1) (Ar is a phenyl group), the structure represented by the above formula (1-2) (R ¹ is a hydrogen atom), and the structure represented by the above formula (2) (R ² is a hydrogen atom, and R ³ is a -C(=O)OCH ₃ group). The obtained compound D had a structure represented by the above formula (1-1) in an amount of 80 mol%. The obtained compound D had a weight average molecular weight of 25,000 and a softening point of 156°C.

(Synthesis of Compound E) The same procedure as in the above "(Synthesis of Compound A)" was followed except that the amount of styrene blended was changed to 494.7 g (4.75 mol), the amount of methyl acrylate blended was changed to 21.5 g (0.25 mol), and the amount of hydrazine hydrate blended was changed to 20 g (0.4 mol), thereby obtaining Compound E, which is the hydrazide compound of the present invention. Furthermore, based on ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained Compound E is a compound having the structure represented by the above formula (1-1) (Ar is a phenyl group), the structure represented by the above formula (1-2) (R ¹ is a hydrogen atom), and the structure represented by the above formula (2) (R ² is a hydrogen atom, and R ³ is a -C(=O)OCH ₃ group). The obtained compound E had a structure represented by the above formula (1-1) in an amount of 95 mol%. The obtained compound E had a weight average molecular weight of 24,000 and a softening point of 200°C.

(Synthesis of Compound F) The same procedure as in the above "(Synthesis of Compound A)" was followed except that the amount of styrene blended was changed to 26.0 g (0.25 mol), the amount of methyl acrylate blended was changed to 408.7 g (4.75 mol), and the amount of hydrazine hydrate blended was changed to 275 g (5.5 mol), thereby obtaining Compound F, which is the hydrazide compound of the present invention. Furthermore, based on ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained Compound F is a compound having the structure represented by the above formula (1-1) (Ar is a phenyl group), the structure represented by the above formula (1-2) (R ¹ is a hydrogen atom), and the structure represented by the above formula (2) (R ² is a hydrogen atom, and R ³ is a -C(=O)OCH ₃ group). The obtained compound F had a structure represented by the above formula (1-1) in an amount of 5 mol%. The obtained compound F had a weight average molecular weight of 16,000 and a softening point of 69°C.

(Synthesis of Compound G) In a three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer, 86.1 g (1.0 mol) of methyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 116.1 g (1.0 mol) of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 150 mL of tetrahydrofuran. 16.4 g (0.1 mol) of azobisisobutyronitrile was added to the obtained solution as a polymerization initiator, and the mixture was stirred at 80°C for 2 hours while replacing the atmosphere with nitrogen to allow the reaction to proceed. The obtained reactant was concentrated and then reprecipitated in an ethanol solution to obtain an intermediate polymer compound. In a three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer, the intermediate polymer compound obtained and 113 g (2.3 mol) of hydrazine hydrate were dissolved in 100 mL of methanol and 10 mL of water, and the mixture was reacted under reflux for 3 hours. After the reaction was completed, the solid was separated by concentration to obtain compound G. According to ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained compound G was a compound represented by the following formula (5). In addition, the weight average molecular weight of the obtained compound G was 12,000, and the softening point was 64°C.

In formula (5), m and n are repeated numbers.

(Examples 1 to 10, Comparative Examples 1 to 3) The materials were mixed according to the blending ratios listed in Tables 1 and 2 using a planetary mixer (manufactured by Thinky, "Defoaming Mixer Taro"), and then mixed using a three-roll grinder to prepare the sealants for liquid crystal display elements of Examples 1 to 10 and Comparative Examples 1 to 3.

<Evaluation> Each of the sealants for liquid crystal display elements obtained in the examples and comparative examples was evaluated as follows. The results are shown in Tables 1 and 2.

(Storage stability) For each of the sealants for liquid crystal display elements obtained in the embodiment and the comparative example, the initial viscosity immediately after production and the viscosity after storage at 25°C for 1 week after production were measured. The viscosity increase ratio was expressed as (viscosity after storage)/(initial viscosity), and the viscosity increase ratio was recorded as "◎" for less than 1.1, "○" for more than 1.1 and less than 1.5, "△" for more than 1.5 and less than 2.0, and "×" for more than 2.0, and the storage stability was evaluated by this method. In addition, the viscosity of the sealant for liquid crystal display elements was measured using an E-type viscometer (manufactured by Brookfield, "DV-III") at 25°C and a rotation speed of 1.0 rpm.

(Adhesion) Each of the liquid crystal display element sealants obtained in the embodiment and the comparative example was filled in a syringe for dispensing glue ("PSY-10E" manufactured by Musashi Engineering) and defoamed. The defoamed liquid crystal display element sealant was dispensed on the inner side of the edge of the glass substrate (150 mm × 150 mm) by using a glue dispenser ("SHOTMASTER300" manufactured by Musashi Engineering) within 30 mm, and then overlapped and bonded to another glass substrate (110 mm × 110 mm) under vacuum. Using a high-pressure mercury lamp, 100 mW/ ^cm2 ultraviolet rays were irradiated for 30 seconds to temporarily cure the sealant for liquid crystal display elements. Then, the sealant for liquid crystal display elements was thermally cured by heating at 120°C for 1 hour to obtain a bonding test piece. A metal rod with a radius of 5 mm was pressed into the end of the substrate of the obtained bonding test piece at a speed of 5 mm/min, and the strength (kgf) at which the panel peeled off was measured, and the bonding force (kg/cm) was calculated. Adhesion was evaluated by marking "◎" for a adhesion force of 3.5 kg/cm or more, "○" for a adhesion force of 3.0 kg/cm or more but less than 3.5 kg/cm, "△" for a adhesion force of 2.0 kg/cm or more but less than 3.0 kg/cm, and "×" for a adhesion force less than 2.0 kg/cm.

(Low liquid crystal contamination (NI point)) Add 0.1 g of each sealant for liquid crystal display elements obtained in the embodiment and comparative example and 1 g of liquid crystal (manufactured by Tokyo Chemical Industry Co., Ltd., "4-pentyl-4-biphenylnitrile") to the sample bottle. The sample bottle is placed in an oven at 120°C for 1 hour, then left to stand until the temperature returns to 25°C, the liquid crystal portion is taken out and filtered using a 0.2 μm filter to prepare a liquid crystal sample for evaluation. 10 mg of the obtained liquid crystal sample for evaluation is sealed in an aluminum sample plate, and the NI point is measured using a differential scanning calorimeter (manufactured by TA instrument, "DSC-Q100") at a heating rate of 5°C/min. Furthermore, the liquid crystal display element was sealed with a sealant and 10 mg of the above-mentioned liquid crystal that was not in contact was placed in an aluminum sample plate, and the NI point was measured at a temperature increase rate of 5°C/min, and the result was used as a blank group. The case where the difference between the NI point measured by the evaluation liquid crystal sample and the NI point of the blank group was -2°C or more was recorded as "◎", the case where it was -3°C or more and less than -2°C was recorded as "0", the case where it was -5°C or more and less than -3°C was recorded as "△", and the case where it was less than -5°C was recorded as "×", and the low liquid crystal contamination was evaluated.

(Display performance of liquid crystal display element) 1 part by weight of spacer microparticles with an average particle size of 5 μm (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each liquid crystal display element sealant obtained in the embodiment and the comparative example, and the mixture was filled into a syringe and defoamed using a centrifugal defoamer (Awatron AW-1). Using a glue dispenser, the defoamed liquid crystal display element sealant was sprayed onto a nozzle with a diameter of 0.4 mm. , nozzle distance 42 μm, syringe ejection pressure 100-400 kPa, coating speed 60 mm/sec, it is coated in a frame shape on one of the two substrates with alignment film and ITO. At this time, the ejection pressure is adjusted so that the line width of the sealant for liquid crystal display elements becomes about 1.5 mm. Then, tiny drops of liquid crystal ("4-pentyl-4-biphenylcarbonitrile" manufactured by Tokyo Chemical Industry Co., Ltd.) are dripped and coated on the entire surface of the frame of the liquid crystal display element sealant on the substrate coated with the liquid crystal display element sealant, and the other substrate is bonded under vacuum. Immediately after lamination, a metal halogen lamp was used to irradiate the liquid crystal display element sealant portion with ultraviolet light of 100 mW/ ^cm2 for 30 seconds to temporarily cure the liquid crystal display element sealant. Subsequently, the liquid crystal display element sealant was heated at 120°C for 1 hour to formally cure the liquid crystal display element sealant, thereby producing a liquid crystal display element. Three liquid crystal display elements were produced for each of the liquid crystal display element sealants obtained in the embodiment and the comparative example, and for each of the obtained liquid crystal display elements, the disorder of the liquid crystal alignment near the liquid crystal display element sealant immediately after the liquid crystal display element was produced was visually confirmed. The alignment disorder is judged based on the color unevenness of the display part. The situation where no display unevenness is observed at the periphery of the liquid crystal display element is recorded as "◎", the situation where some shallow display unevenness is observed is recorded as "0", the situation where clearer and deeper display unevenness exists is recorded as "△", and the situation where clearer and deeper display unevenness exists not only at the periphery but also extends to the central part is recorded as "×". The display performance of the liquid crystal display element is evaluated in this way.

[Table 1] Embodiment 1 2 3 4 5 6 7 8 9 10 Composition (parts by weight) Hardening resin Bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL3700") 50 50 50 50 50 50 50 50 - - Caprolactone-modified bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL3708") 35 35 35 35 35 35 35 35 - - Bisphenol A epoxy resin (manufactured by DIC Corporation, "EPICLON EXA-850CRP") 15 15 15 15 15 15 15 15 - - Bisphenol A epoxy methacrylate (manufactured by DAICEL-ALLNEX, "KRM7985") - - - - - - - - 70 - Partially methacrylic acid modified bisphenol E type epoxy resin (manufactured by DAICEL-ALLNEX, "KRM8276") - - - - - - - - 30 - Resorcinol type epoxy acrylate (manufactured by DAICEL-ALLNEX, "KRM8076") - - - - - - - - - 70 Partially acrylic modified bisphenol E type epoxy resin (manufactured by DAICEL-ALLNEX, "KRM8287") - - - - - - - - - 30 Heat hardener The hydrazide compound of the present invention Compound A (weight average molecular weight 15000, formula (1-1) 50 mol%, softening point 130°C) 5 2 10 - - - - - 5 5 Compound B (weight average molecular weight 70,000, formula (1-1) 50 mol%, softening point 147°C) - - - 5 - - - - - - Compound C (weight average molecular weight 3000, formula (1-1) 50 mol%, softening point 92°C) - - - - 5 - - - - - Compound D (weight average molecular weight 25000, formula (1-1) 80 mol%, softening point 156°C) - - - - - 5 - - - - Compound E (weight average molecular weight 24000, formula (1-1) 95 mol%, softening point 200°C) - - - - - - 5 - - - Compound F (weight average molecular weight 16000, formula (1-1) 5 mol%, softening point 69°C) - - - - - - - 5 - - Photoradical polymerization initiator 2,2-Dimethoxy-1,2-diphenylethane-1-one (manufactured by IGM Resins, "Omnirad 651") 2 2 2 2 2 2 2 2 2 2 Thermal free radical polymerization initiator High molecular weight azo initiator (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., "VPE-0201") 2 2 2 2 2 2 2 2 2 2 Filler Silicon dioxide (Admafine SO-C2, manufactured by Admatechs) 20 20 20 20 20 20 20 20 20 20 Silane coupling agent 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") 1 1 1 1 1 1 1 1 1 1 Reviews Preserve stability ◎ ◎ ○ ◎ ○ ◎ ◎ △ ◎ ○ Adhesion ◎ ○ ◎ ◎ ◎ ○ △ ○ ○ ◎ Low liquid crystal contamination (NI point) ◎ ○ ◎ ○ ○ ○ △ ◎ ○ ◎ Display performance of liquid crystal display devices ◎ ○ ◎ ◎ ○ ◎ ○ ◎ ○ ○

[Table 2] Comparison Example 1 2 3 Composition (parts by weight) Hardening resin Bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL3700") 50 50 50 Caprolactone-modified bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL3708") 35 35 35 Bisphenol A epoxy resin (manufactured by DIC Corporation, "EPICLON EXA-850CRP") 15 15 15 Heat hardener other Malonic acid dihydrazide (manufactured by Japan Finechem, "MDH", molecular weight 132, softening point 152°C) 5 - - Adipic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd., "ADH", molecular weight 174, softening point 182°C) - 5 - Compound G (weight average molecular weight 12000, formula (1-1) 0 mol%, softening point 64°C) - - 5 Photoradical polymerization initiator 2,2-Dimethoxy-1,2-diphenylethane-1-one (manufactured by IGM Resins, "Omnirad 651") 2 2 2 Thermal free radical polymerization initiator High molecular weight azo initiator (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., "VPE-0201") 2 2 2 Filler Silicon dioxide (Admafine SO-C2, manufactured by Admatechs) 20 20 20 Silane coupling agent 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") 1 1 1 Reviews Preserve stability × △ × Adhesion ◎ ◎ ○ Low liquid crystal contamination (NI point) △ △ ○ Display performance of liquid crystal display devices × × ○ [Industrial Availability]

According to the present invention, a sealant for a liquid crystal display element having excellent storage stability, adhesion, and low liquid crystal contamination can be provided. In addition, according to the present invention, a top-bottom conductive material and a liquid crystal display element formed by using the sealant for a liquid crystal display element can be provided.

without

without

Claims (7)

A sealant for a liquid crystal display element, comprising a curable resin and a thermosetting agent, wherein the thermosetting agent comprises a hydrazide compound, and the hydrazide compound has a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2):

In formula (1-1), Ar is an aromatic ring, in formula (1-2), R ¹ is a hydrogen atom or a methyl group, and in the above hydrazide compound, the ratio of the structure represented by the above formula (1-1) is 5 mol% or more and 95 mol% or less. As for the sealant for liquid crystal display element of claim 1, wherein the above-mentioned hydrazide compound further has a structure represented by the following formula (2):

In formula (2), ^R2 is a hydrogen atom or a methyl group, and ^R3 is a -C(=O) ^OR4 group ( ^R4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), a -CN group, ^{a -OR5} group ( ^R5 is an alkyl group having 1 to 10 carbon atoms), or a hydrogen atom. As in claim 1 or 2, the sealant for liquid crystal display elements, wherein the weight average molecular weight of the above-mentioned hydrazide compound is greater than 2000 and less than 200,000. As in claim 1 or 2, the sealant for liquid crystal display elements, wherein the softening point of the above-mentioned hydrazide compound is above 65°C and below 200°C. The sealant for liquid crystal display elements as claimed in claim 1 or 2 further contains a photo-radical polymerization initiator. A vertical conductive material, which contains a sealant for a liquid crystal display element according to claim 1, 2, 3, 4 or 5 and conductive microparticles. A liquid crystal display element, which is made using the sealant for liquid crystal display elements of claim 1, 2, 3, 4 or 5 or the upper and lower conductive material of claim 6.