TW202116838A - Sealing agent for liquid crystal display elements, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

The object of this invention is to provide the sealing compound for liquid crystal display elements excellent in storage stability, adhesiveness, and low liquid crystal contamination. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using this sealant for liquid crystal display elements. The present invention is a sealing compound for liquid crystal display elements, which contains a curable resin and a thermosetting agent, and the thermosetting agent contains a hydrazine compound, and the hydrazine compound has a structure represented by the following formula (1-1) And the structure shown in the following formula (1-2). In the formula (1-1), Ar is an aromatic ring, and in the formula (1-2), R ¹ is a hydrogen atom or a methyl group.

Description

Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element

The present invention relates to a sealing compound for liquid crystal display elements which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. In addition, the present invention relates to an upper and lower conduction material and a liquid crystal display element using the sealing compound for liquid crystal display elements.

In recent years, as a method of manufacturing liquid crystal display elements such as liquid crystal display units, from the viewpoints of reduction of tact time (Tact Time) and optimization of liquid crystal usage, the methods described in Patent Document 1 and Patent Document 2 have been used. The disclosed liquid crystal dropping method using the sealant is called the dropping process method. In the dropping process, first, a frame-shaped seal pattern is formed by dispensing on one of the two substrates with electrodes. Then, in a state where the sealant is not hardened, minute liquid crystal drops are dropped into the frame of the seal pattern, and another substrate is overlapped under vacuum, and then the sealant is hardened to produce a liquid crystal display element. This dropping processing method has become the mainstream of the current manufacturing method of liquid crystal display elements.

In addition, with the popularization of various mobile devices with LCD panels, such as mobile phones and portable game consoles, the most demanding issue is the miniaturization of the devices. As a method of miniaturization of the machine, the narrow frame of the liquid crystal display part can be cited, 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 light to reach the inside of the sealant. If it is a conventional sealant, hardening becomes insufficient. In this way, if the curing of the sealant becomes insufficient, the uncured sealant component is eluted into the liquid crystal, which causes the problem of easy liquid crystal contamination. Particularly in recent years, as the polarities of liquid crystals have increased, sealants have been required to have lower liquid crystal contamination.

When it becomes more difficult to light-harden the sealant, it is considered to harden the sealant by heating. As a method for hardening the sealant by heating, a thermosetting agent is blended into the sealant. However, when a highly reactive thermosetting agent is used in order to improve the hardenability or adhesiveness of the sealant, the storage stability of the obtained sealant may deteriorate. Prior art literature Patent literature

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

[The problem to be solved by the invention]

The object of this invention is to provide the sealing compound for liquid crystal display elements excellent in storage stability, adhesiveness, and low liquid crystal contamination. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using this sealant for liquid crystal display elements. [Technical means to solve the problem]

The present invention is a sealing compound for liquid crystal display elements, which contains a curable resin and a thermosetting agent, and the thermosetting agent contains a hydrazine compound, and the hydrazine compound has a structure represented by the following formula (1-1) And the structure shown in the following formula (1-2).

In the formula (1-1), Ar is an aromatic ring, and in the formula (1-2), R ¹ is a hydrogen atom or a methyl group. Hereinafter, the present invention will be described in detail.

As a result of intensive research, the inventors found that by using a thermosetting agent having a specific structure, a sealing compound for a liquid crystal display element with excellent storage stability, adhesiveness, and low liquid crystal contamination can be obtained, thereby completing the present invention.

The sealing compound for liquid crystal display elements of this invention contains a thermosetting agent. The above-mentioned thermosetting agent contains a hydrazine compound. The above hydrazine compound has a structure represented by the above formula (1-1) and a structure represented by the above formula (1-2). Hereinafter, the hydrazine compound having the structure represented by the above formula (1-1) and the structure represented by the above formula (1-2) is also referred to as "the hydrazine compound of the present invention". By containing the hydrazine compound of the present invention, the sealing compound for liquid crystal display elements of the present invention can be excellent in storage stability, adhesiveness, and low liquid crystal contamination.

As the reason why the sealing compound for liquid crystal display elements obtained can be excellent in storage stability, adhesiveness, and low liquid crystal contamination by using the hydrazine compound of the present invention, it can be considered as follows. That is, it is considered that by having the structure represented by the above formula (1-1), the softening point of the hydrazine compound can be controlled, and thus the storage stability can be improved. Furthermore, it is thought that the adhesiveness of the obtained sealant can be improved by having the structure represented by the above formula (1-2) containing a primary amine group. Furthermore, it is thought that by having these structures, the molecular weight of the hydrazine compound becomes high, so that elution into the liquid crystal can be suppressed.

In the hydrazine 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 said formula (1-1) 5 mol% or more, the storage stability of the sealing compound for liquid crystal display elements obtained becomes more excellent. By making the ratio of the structure represented by the said formula (1-1) 95 mol% or less, the adhesiveness of the sealing compound for liquid crystal display elements obtained is more excellent. A more preferable lower limit of the ratio of the structure represented by the above formula (1-1) is 10 mol%, a more preferable upper limit is 90 mol%, and a more preferable upper limit is 50 mol%.

In the hydrazine 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 said formula (1-2) 5 mol% or more, the adhesiveness of the sealing compound for liquid crystal display elements obtained is more excellent. By making the ratio of the structure represented by the said formula (1-2) 95 mol% or less, the storage stability of the sealing compound for liquid crystal display elements obtained is more excellent. A more preferable lower limit of the ratio of the structure shown in the above formula (1-2) is 10 mol%, a more preferable upper limit is 90 mol%, and a more preferable lower limit is 50 mol%.

The hydrazine 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 hydrazine compound of the present invention preferably further has a structure represented by the following formula (2) as the other structure. By having the structure shown by following formula (2), the adhesiveness of the sealing compound for liquid crystal display elements obtained is more excellent.

In formula (2), R ² is a hydrogen atom or a methyl group, R ³ is a -C(=O)OR ⁴ group (R ⁴ is a hydrogen atom or an alkyl group with 1 to 10 carbon atoms), -CN group, -OR ⁵ group (R ⁵ is an alkyl group having 1 or more and 10 or less carbon atoms), or a hydrogen atom.

In the hydrazine 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 said weight average molecular weight into 2000 or more, the low liquid crystal contamination property of the sealing compound for liquid crystal display elements obtained becomes more excellent. By making the said weight average molecular weight 200,000 or less, the sealing compound for liquid crystal display elements obtained is more excellent in rationality. A more preferable lower limit of the above-mentioned weight average molecular weight is 4000, and a more preferable upper limit is 100,000. In addition, in this specification, the said weight average molecular weight is the value calculated|required by the polystyrene conversion measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. As the column used when measuring the weight average molecular weight in terms of polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) can be cited.

The preferred lower limit of the softening point of the hydrazine compound of the present invention is 65°C, and the preferred upper limit is 200°C. By making the softening point of the hydrazine compound of this invention 65 degreeC or more, the storage stability of the sealing compound for liquid crystal display elements obtained becomes more excellent. By making the softening point of the hydrazine compound of this invention 200 degrees C or less, the adhesiveness of the sealing compound for liquid crystal display elements obtained is more excellent. A more preferable lower limit of the softening point of the hydrazine compound of the present invention is 90°C, and a more preferable upper limit is 160°C. In addition, the above-mentioned softening point can be obtained by the ring and ball method in accordance with JIS K 2207.

As a method of manufacturing the hydrazine compound of this invention, the following methods etc. are mentioned, for example. 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 used in a polymerization initiator such as azobisisobutyronitrile. In the presence, the reaction is performed by heating and stirring while performing nitrogen substitution. After concentrating the obtained reactant, the intermediate polymer compound is obtained by reprecipitating it in an ethanol solution. The obtained intermediate polymer compound and hydrazine hydrate are dissolved in a solvent such as tetrahydrofuran and reacted under reflux. After the completion of the reaction, concentration is performed to separate the solids, whereby the hydrazine compound of the present invention can be obtained. Moreover, in addition to the compound represented by the following formula (3-1) and the compound represented by the following formula (3-2), the compound represented by the following formula (4) can also be used.

In the formula (3-1), Ar is an aromatic ring, in the formula (3-2), R ¹ is a hydrogen atom or a methyl group, and R ⁶ is an alkyl group having 1 to 10 carbon atoms.

In formula (4), R ² is a hydrogen atom or a methyl group, R ³ is a -C(=O)OR ⁴ group (R ⁴ is a hydrogen atom or an alkyl group with 1 to 10 carbon atoms), -CN group, -OR ⁵ group (R ⁵ is an alkyl group having 1 or more and 10 or less carbon atoms), or a hydrogen atom.

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

The sealing compound for liquid crystal display elements of this invention may contain other thermosetting agents in the range which does not impair the objective of this invention in addition to the hydrazine compound of this invention. As said thermosetting agent, organic acid hydrazine, imidazole derivatives, amine compounds, polyphenol compounds, acid anhydrides, etc. are mentioned, for example.

The sealing compound for liquid crystal display elements of this 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, and 2,2'-diallyl Based 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 ring Oxygen resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, dicyclopentadiene Novolak type epoxy resin, biphenol novolak type epoxy resin, naphthol novolak type epoxy resin, epoxy propyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resin Resins, glycidyl ester compounds, etc.

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

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

As commercially available among the above-mentioned partially (meth)acrylic modified epoxy resins, for example, UVACURE1561, KRM8287 (all manufactured by DAICEL-ALLNEX), etc. can be cited.

Moreover, the said curable resin may contain a (meth)acryl compound. As said (meth)acrylic compound, (meth)acrylate compound, epoxy (meth)acrylate, urethane (meth)acrylate (urethane (meth)acrylate) etc. are mentioned, for example. Among them, epoxy (meth)acrylate is preferred. In addition, from the viewpoint of reactivity, the (meth)acrylic compound is preferably one having two or more (meth)acrylic groups in one molecule. In addition, in this specification, the above-mentioned "(meth)acrylic compound" refers to a compound having a (meth)acryloyl group. In addition, the above-mentioned "(meth)acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" means all epoxy groups and (meth)acrylates in the epoxy compound. A compound formed by the reaction of acrylic acid.

Examples of the monofunctional among the above-mentioned (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , Isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methyl tetrahydrofuran (meth)acrylate, ethyl carbitol (meth)acrylate Base) acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylate 1H, 1H, 5H- Octafluoropentyl ester, imine (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl Succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-(meth)acrylic acid Oxyethyl acrylate, glycidyl (meth)acrylate and the like.

In addition, examples of the bifunctional one among the above-mentioned (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol two (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 diacrylate Alcohol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth) Acrylic acid 2-hydroxy-3-(meth)acryloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth) ) Acrylate, polycaprolactonediol di(meth)acrylic acid, polybutadienediol di(meth)acrylate, etc.

In addition, examples of the above-mentioned (meth)acrylate compounds having trifunctional or higher functions include trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(methyl) )Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modification trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid Acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, phosphoric acid tri(meth) Acrylic oxyethyl, di-trimethylolpropane tetra(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopentyl pentaerythritol penta(meth)acrylate, dineopentyl Tetraol hexa(meth)acrylate and the like.

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

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

Examples of commercially available epoxy (meth)acrylates among the above-mentioned epoxy (meth)acrylates include: epoxy (meth)acrylate manufactured by DAICEL-ALLNEX, and epoxy (meth)acrylate manufactured by Shinnakamura Chemical Industry Co., Ltd. , Epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase Kasei Co., Ltd., etc. As the epoxy (meth)acrylate manufactured by DAICEL-ALLNEX, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYLR6040, EB182182, etc. may be mentioned. Examples of the epoxy (meth)acrylate manufactured by Shin Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020, and the like. Examples of epoxy (meth)acrylates manufactured by the above-mentioned Kyoeisha Chemical Company 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 Chemical Co., Ltd. include DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, and DENACOL ACRYLATE DA-911.

The amine ester (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.

The isocyanate compound used as the raw material of the amine ester (meth)acrylate includes, for example, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, tri Methylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate (norbornane diisocyanate), combined Toluidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, thiophosphoric acid tris(isocyanatophenyl ester), tetramethylbenzene diisocyanate Methyl diisocyanate, 1,6,11-undecane triisocyanate, etc.

In addition, as the isocyanate compound used as the raw material of the amine ester (meth)acrylate, a chain-extended isocyanate compound obtained by reacting a polyol with an excess isocyanate compound can also be used. Examples of the above-mentioned polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.

Examples of (meth)acrylic acid derivatives having a hydroxyl group include hydroxyalkyl mono(meth)acrylates, mono(meth)acrylates of dihydric alcohols, and mono(meth)acrylates of trihydric alcohols. Ester or di(meth)acrylate, epoxy (meth)acrylate, etc. Examples of the hydroxyalkyl mono(meth)acrylate include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (Meth) 4-hydroxybutyl acrylate and the like. As said diol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc. are mentioned, for example. As said triol, trimethylolethane, trimethylolpropane, glycerol, etc. are mentioned, for example. As said epoxy (meth)acrylate, bisphenol A type epoxy acrylate etc. are mentioned, for example.

Examples of commercially available amine ester (meth)acrylates among the above-mentioned amine ester (meth)acrylates include: amine ester (meth)acrylate manufactured by Toagosei Co., Ltd., amine ester (meth)acrylate manufactured by DAICEL-ALLNEX, and root Urethane (meth)acrylate manufactured by industrial companies, urethane (meth)acrylate manufactured by Shinnakamura Chemical Industry Co., Ltd., urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., etc. As the amine ester (meth)acrylate manufactured by the Toagosei Co., Ltd., for example, M-1100, M-1200, M-1210, M-1600, etc. can be cited. Examples of the amine ester (meth)acrylate manufactured by the DAICEL-ALLNEX company include: EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5840, ECECL880, ECECL880 , EBECRYL9260, etc. As the amine ester (meth)acrylate manufactured by the aforementioned Negami Kogyo Co., Ltd., for example, Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H, etc. Examples of the urethane (meth)acrylate manufactured by Shinnakamura 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. As the urethane (meth)acrylate manufactured by the above-mentioned Kyoeisha Chemical Company, for example, AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T and so on.

As the above-mentioned curable resin, when the above-mentioned (meth)acrylic compound is contained in addition to the above-mentioned epoxy compound, or when the above-mentioned partial (meth)acrylic modified epoxy compound is contained, it is preferable to cure the above-mentioned The ratio of the (meth)acryloyl group in the resin to the total of the epoxy group and the (meth)acryloyl group is set to 30 mol% or more and 95 mol% or less. By making the ratio of the said (meth)acryl group into this range, the occurrence of liquid crystal contamination is suppressed, and the adhesiveness of the sealing compound for liquid crystal display elements obtained becomes more excellent.

From the viewpoint of further suppressing liquid crystal contamination, the curable resin is preferably one containing hydrogen-bonding units such _{as -OH groups, -NH- groups, and -NH 2 groups.}

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

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

啉基丙烷-1-酮、1-(4-(2-羥基乙氧基)-苯基)-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-(苯硫基)苯基)-1,2-辛二酮2-(O-苯甲醯肟) (1-(4-(phenylthio)phenyl)-1,2-octadione2-(O-benzoyloxime))、2,4,6-三甲基苯甲醯基二苯基氧化膦等。 上述光自由基聚合起始劑可單獨地使用，亦可組合2種以上使用。It is preferable that the sealing compound for liquid crystal display elements of this invention further contains a photoradical polymerization initiator. Examples of the aforementioned photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, and benzoin ethers. Compound, 9-oxysulfur

Compound etc. As the photo radical polymerization initiator, specifically, for example, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-olinylphenyl)- 1-Butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-

(Alpinyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(2,4,6-trimethylbenzyl) Phenyl phosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-

Linylpropane-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-(benzene Sulfuryl)phenyl)-1,2-octanedione 2-(O-benzoyloxime) (1-(4-(phenylthio)phenyl)-1,2-octadione2-(O-benzoyloxime)), 2 , 4,6-Trimethylbenzyl diphenyl phosphine oxide, etc. The above-mentioned radical photopolymerization initiators may be used singly or in combination of two or more kinds.

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

The sealing compound for liquid crystal display elements of this invention may contain a thermal radical polymerization initiator. Examples of the thermal radical polymerization initiator include those composed of an azo compound, an organic peroxide, or the like. Among them, from the viewpoint of suppressing liquid crystal contamination, a starter composed of an azo compound (hereinafter, also referred to as an "azo starter") is preferred, and a polymer azo compound is more preferred. The initiator (hereinafter, also referred to as "polymer azo initiator"). The above-mentioned thermal radical polymerization initiators may be used singly or in combination of two or more kinds. Furthermore, in this specification, the above-mentioned "polymer azo compound" refers to a radical having an azo group, and the number average molecular weight of a radical that can harden the (meth)acryloyl group by heat generation is 300 or more Compound.

The preferred lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 1,000, and the preferred upper limit is 300,000. By setting the number average molecular weight of the above-mentioned polymer azo compound within this range, adverse effects on the liquid crystal can be prevented, and it can be easily mixed with the curable resin. The lower limit of the number average molecular weight of the above-mentioned polymer azo compound is more preferably 5,000, the upper limit is more preferably 100,000, the lower limit is still more preferably 10,000, and the upper limit is more preferably 90,000. In addition, in this specification, the said number average molecular weight is the value calculated|required by the polystyrene conversion when measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. As a column for measuring the number-average molecular weight converted from polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) can be cited.

Examples of the above-mentioned polymer azo compound include those having a structure in which multiple units such as polyalkyleneoxide or polydimethylsiloxane are bonded via an azo group. As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group, one having a polyethylene oxide structure is preferable. As the above-mentioned polymer azo compound, specifically, for example, a condensation polymer of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'-co Condensation polymer of nitrobis(4-cyanovaleric acid) and polydimethylsiloxane with blocked amine group, etc. Examples of commercially available ones among the above-mentioned polymer azo initiators include: VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), etc. . In addition, as an azo initiator that is not a polymer, for example, V-65, V-501 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and the like can be cited.

Examples of the above-mentioned organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, etc. .

The lower limit of the content of the thermal radical polymerization initiator is preferably 0.1 parts by weight, and the upper limit is preferably 10 parts by weight relative to 100 parts by weight of the curable resin. By setting the content of the thermal radical polymerization initiator within this range, liquid crystal contamination of the sealing compound for liquid crystal display elements is suppressed, and storage stability or thermosetting properties are more excellent. The lower limit of the content of the thermal radical polymerization initiator is more preferably 0.3 parts by weight, and the upper limit is more preferably 5 parts by weight.

The sealing compound for liquid crystal display elements of the present invention may also contain fillers for the following purposes: increasing viscosity, improving adhesiveness by stress dispersion effect, improving linear expansion, and improving moisture resistance of hardened products.

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

The lower limit of the content of the filler is preferably 10 parts by weight, and the upper limit is preferably 70 parts by weight with respect to 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention. By setting the content of the filler in this range, the effect of improving adhesiveness, etc., is more excellent without deteriorating coating properties and the like. The lower limit of the filler content is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.

The sealing compound for liquid crystal display elements of this invention may contain a silane coupling agent. The said silane coupling agent mainly has a role as an adhesive auxiliary agent for bonding the sealing compound for liquid crystal display elements, and a board|substrate etc. well.

As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) can be suitably used. ), 3-isocyanatopropyltrimethoxysilane, etc. These silane coupling agents have an excellent effect of improving adhesion to substrates, 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 agent may be used alone or in combination of two or more kinds.

The lower limit of the content of the silane coupling agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is preferably 0.1 parts by weight, and the upper limit is preferably 10 parts by weight. By setting the content of the silane coupling agent in this range, the occurrence of liquid crystal contamination is suppressed, and the effect of improving adhesion is more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.3 parts by weight, and the upper limit is more preferably 5 parts by weight.

The sealing compound for liquid crystal display elements of this invention may contain a light-shielding agent. By containing the said light-shielding agent, the sealing compound for liquid crystal display elements of this invention can be used suitably as a light-shielding sealing compound.

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

The above-mentioned titanium black is a substance with a higher transmittance for light near the ultraviolet region, especially for light with a wavelength of 370 nm or more and 450 nm or less than the average transmittance for light with a wavelength of 300 nm or more and 800 nm or less. That is, the above-mentioned titanium black is a light-shielding agent having the following properties: it imparts light-shielding properties to the sealing compound for liquid crystal display elements of the present invention by sufficiently blocking light of a wavelength in the visible light region, and on the other hand, makes light of a wavelength near the ultraviolet region penetrate. Therefore, it is possible to further enhance the photocuring of the sealing compound for liquid crystal display elements of the present invention by using the one capable of starting the reaction by the light of the wavelength whose transmittance of the titanium black increases as the photoradical polymerization initiator. Sex. On the other hand, as the light-shielding agent contained in the sealing compound for liquid crystal display elements of the present invention, a material with high insulation is preferred, 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, 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 above-mentioned titanium black exhibits sufficient effects even without surface treatment, it is also possible to use surface-treated titanium black, such as those whose surface has been treated with organic components such as coupling agents, or those with silicon oxide, titanium oxide, or oxidation. Covered with inorganic components such as germanium, alumina, zirconia, magnesia, etc. Among them, in terms of improving insulation properties, it is preferable that the organic component has been treated. In addition, the liquid crystal display element manufactured using the sealant for liquid crystal display element of the present invention blended with the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, so that it can achieve high contrast without light leakage, and has Liquid crystal display element with excellent image display quality.

Examples of commercially available titanium blacks include: titanium black manufactured by Mitsubishi Materials Corporation, titanium black manufactured by Ako Kasei Co., Ltd., and the like. As the titanium black manufactured by the above-mentioned Mitsubishi Materials Corporation, for example, 12S, 13M, 13M-C, 13R-N, 14M-C, etc. can be cited. As the titanium black manufactured by the aforementioned Ako Kasei Co., Ltd., for example, TILACK D and the like can be cited.

The preferred lower limit of the specific surface area of the titanium black is 13 m ² /g, the preferred upper limit is 30 m ² /g, the more preferred lower limit is 15 m ² /g, and the more preferred upper limit is 25 m ² /g. In addition, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω·cm, the preferred upper limit is 3 Ω·cm, the more preferred lower limit is 1 Ω·cm, and the more preferred upper limit is 2.5 Ω·cm.

The primary particle size of the aforementioned 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, and the preferred lower limit is 1 nm, and the preferred upper limit is 5000 nm. By making the primary particle diameter of the said light-shielding agent into this range, the light-shielding property can be made more excellent without deteriorating the coatability etc. of the sealing compound for liquid crystal display elements. The lower limit of the primary particle size of the sunscreen is more preferably 5 nm, the upper limit is more preferably 200 nm, the lower limit is still more preferably 10 nm, and the upper limit is more preferably 100 nm. In addition, 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 light-shielding agent in 100 parts by weight of the sealing compound 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 setting the content of the above-mentioned light-shielding agent within this range, it is possible to exhibit more excellent light-shielding properties without greatly degrading the adhesiveness, strength after curing, and drawing properties of the sealant for liquid crystal display elements. . The lower limit of the content of the sunscreen is more preferably 10 parts by weight, the upper limit is more preferably 70 parts by weight, the lower limit is still more preferably 30 parts by weight, and the upper limit is more preferably 60 parts by weight.

The sealing compound for liquid crystal display elements of the present invention may further contain additives such as a stress reliever, a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, a defoamer, a leveling agent, and a polymerization inhibitor, if necessary.

As a method of manufacturing the sealing compound for liquid crystal display elements of this invention, the following method etc. are mentioned, for example, using a mixer, mixing a curable resin, a thermosetting agent, and a thermal radical polymerization initiator etc. which may be added as needed. Examples of the above-mentioned mixer include a homogeneous disperser, a homomixer, an all-purpose mixer, a planetary mixer, a kneader, and a three-roll mill.

By blending conductive fine particles in the sealing compound for liquid crystal display elements of the present invention, a vertical conduction material can be manufactured. Such top and bottom conduction materials containing the sealing compound for liquid crystal display elements of the present invention and conductive fine particles are also one of the present invention.

As the conductive fine particles, for example, metal balls, those having a conductive metal layer formed on the surface of resin fine particles, or the like can be used. Among them, a conductive metal layer formed on the surface of the resin fine particles is preferable because of the excellent elasticity of the resin fine particles and can be electrically connected without damaging the transparent substrate or the like.

The liquid crystal display element which uses the sealing compound for liquid crystal display elements of this invention or the top and bottom conduction material of this invention is also one of this invention.

As the liquid crystal display element of the present invention, a liquid crystal display element with a narrow frame design is preferred. Specifically, the width of the frame around the liquid crystal display portion is preferably 2 mm or less. Moreover, when manufacturing the liquid crystal display element of this invention, the coating width of the sealing compound for liquid crystal display elements of this invention is preferably 1 mm or less.

The sealing compound for liquid crystal display elements of this invention can be used suitably for manufacturing a liquid crystal display element by a liquid crystal dropping process method. As a method of manufacturing the liquid crystal display element of this invention by a liquid crystal dropping process method, the following methods etc. are mentioned, for example. The liquid crystal display element can be obtained by a method including the following steps: first, a step of forming a frame-shaped sealing pattern by screen printing and dispensing coating is equivalent to coating the sealant for liquid crystal display elements of the present invention on a substrate . Then, in a state where the sealant for liquid crystal display elements of the present invention is not hardened, a step of dripping and coating tiny liquid crystal droplets on the entire surface of the frame of the seal pattern, and then immediately superimposing another substrate. After that, a step of heating and hardening the sealant is performed. In addition, before the step of heating and hardening the sealant, a step of irradiating the seal pattern portion with light such as ultraviolet rays to temporarily harden the sealant may also be performed. [Effects of Invention]

According to the present invention, it is possible to provide a sealing compound for a liquid crystal display element which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealing compound for liquid crystal display elements.

Hereinafter, embodiments are disclosed to describe the present invention in more detail, but the present invention is not limited to these 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 Fujifilm Wako Pure Chemical Industries, Ltd.) and methyl acrylate (Tokyo Kasei Kogyo Co., Ltd.) Manufacturing) 172.1 g (2.0 mol) was 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 it was reacted by stirring at 80°C for 1 hour while performing nitrogen substitution. After concentrating the obtained reactant, it is re-precipitated in an ethanol solution, thereby obtaining an intermediate polymer compound. In a three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer, the obtained intermediate polymer compound and 113 g (2.3 mol) of hydrazine hydrate were dissolved in 200 mL of tetrahydrofuran, and reacted under reflux for 3 hours. After the completion of the reaction, concentration is performed to separate the solids, thereby obtaining Compound A. According to ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained compound A has the structure represented by the above formula (1-1) (Ar is a phenyl group), and the compound A represented by the above formula (1-2) The compound of the structure (R ¹ is a hydrogen atom) and the structure shown in the above formula (2) (R ² is a hydrogen atom, R ³ is a -C(=O)OCH ₃ group). In addition, the obtained compound A has a structure represented by the above formula (1-1) at 50 mol%. Furthermore, the weight average molecular weight of the obtained compound A was 15000, and the softening point was 130 degreeC.

(Synthesis of Compound B) Except that the stirring time when stirring at 80°C while replacing with nitrogen was changed to 4 hours, the hydrazine compound of the present invention was obtained in the same manner as in the above-mentioned "(Synthesis of compound A)"的 Compound B. Furthermore, according to ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained compound B has the structure represented by the above formula (1-1) (Ar is a phenyl group), and the above formula (1-2) The compound shown in the structure (R ¹ is a hydrogen atom) and the structure shown in the above formula (2) (R ² is a hydrogen atom, R ³ is a -C(=O)OCH ₃ group). In addition, the obtained compound B has a structure represented by the above formula (1-1) at 50 mol%. 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) The stirring time when stirring at 80°C while replacing nitrogen with nitrogen was changed to 0.5 hours, except that the same procedure as in the above-mentioned "(Synthesis of Compound A)" was carried out to obtain the 醯 of the present invention Compound C of hydrazine compound. Furthermore, according to ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained compound C has the structure represented by the above formula (1-1) (Ar is a phenyl group), and the above formula (1-2) The compound shown in the structure (R ¹ is a hydrogen atom) and the structure shown in the above formula (2) (R ² is a hydrogen atom, R ³ is a -C(=O)OCH ₃ group). In addition, the obtained compound C has a structure represented by the above formula (1-1) at 50 mol%. Furthermore, the weight average molecular weight of the obtained compound C was 3000, and the softening point was 92 degreeC.

(Synthesis of Compound D) The blending amount of styrene was changed to 416.6 g (4.0 mol), the blending amount of methyl acrylate was changed to 86.0 g (1.0 mol), and the blending amount of hydrazine hydrate was changed to 60 g (1.2 mol), except for this, the same procedure as in the above "(synthesis of compound A)" was carried out to obtain compound D which is the hydrazine compound of the present invention. Furthermore, according to ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained compound D has the structure represented by the above formula (1-1) (Ar is a phenyl group), and the above formula (1-2) The compound shown in the structure (R ¹ is a hydrogen atom) and the structure shown in the above formula (2) (R ² is a hydrogen atom, R ³ is a -C(=O)OCH ₃ group). In addition, the obtained compound D has a structure represented by the above formula (1-1) at 80 mol%. Furthermore, the weight average molecular weight of the obtained compound D was 25,000, and the softening point was 156°C.

(Synthesis of Compound E) The blending amount of styrene was changed to 494.7 g (4.75 mol), the blending amount of methyl acrylate was changed to 21.5 g (0.25 mol), and the blending amount of hydrazine hydrate was changed to Except 20 g (0.4 mol), the same procedure as in the above "(synthesis of compound A)" was carried out to obtain compound E as the hydrazine compound of the present invention. Furthermore, according to ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained compound E has the structure represented by the above formula (1-1) (Ar is a phenyl group), and the above formula (1-2) The compound shown in the structure (R ¹ is a hydrogen atom) and the structure shown in the above formula (2) (R ² is a hydrogen atom, R ³ is a -C(=O)OCH ₃ group). In addition, the obtained compound E has 95 mol% of the structure represented by the above formula (1-1). Furthermore, the weight average molecular weight of the obtained compound E was 24000, and the softening point was 200 degreeC.

(Synthesis of compound F) The blending amount of styrene was changed to 26.0 g (0.25 mol), the blending amount of methyl acrylate was changed to 408.7 g (4.75 mol), and the blending amount of hydrazine hydrate was changed to Except for 275 g (5.5 mol), the same procedure as in the above-mentioned "(synthesis of compound A)" was carried out to obtain compound F which is the hydrazine compound of the present invention. Furthermore, according to ¹ H-NMR, MS, and FT-IR, it was confirmed that the obtained compound F has the structure represented by the above formula (1-1) (Ar is a phenyl group), and the above formula (1-2) The compound shown in the structure (R ¹ is a hydrogen atom) and the structure shown in the above formula (2) (R ² is a hydrogen atom, R ³ is a -C(=O)OCH ₃ group). In addition, the obtained compound F has a structure represented by the above formula (1-1) at 5 mol%. Furthermore, the weight average molecular weight of the obtained compound F was 16000, and the softening point was 69 degreeC.

(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 2-hydroxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.) Manufactured by Industrial Company) 116.1 g (1.0 mol) was 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 it was allowed to react with stirring at 80°C for 2 hours while replacing with nitrogen. After concentrating the obtained reactant, it is re-precipitated in an ethanol solution, thereby obtaining an intermediate polymer compound. In a three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer, the obtained intermediate polymer compound and 113 g (2.3 mol) of hydrazine hydrate were dissolved in 100 mL of methanol and 10 mL of water. It reacted for 3 hours. After the completion of the reaction, concentration is performed to separate the solids, thereby obtaining 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) According to the blending ratios described in Tables 1 and 2, using a planetary mixer (manufactured by Thinky, "Defoaming Stirring Taro"), the materials were mixed and then mixed using a three-roll mill to prepare and implement The sealing compound for each liquid crystal display element of Examples 1 to 10 and Comparative Examples 1 to 3.

＜Evaluation＞ The following evaluation was performed about each sealing compound for liquid crystal display elements obtained in an Example and a comparative example. The results are shown in Tables 1 and 2.

(Storage stability) With respect to each sealing compound for liquid crystal display elements obtained in the Examples and Comparative Examples, the initial viscosity immediately after the production and the viscosity after storage at 25° C. for 1 week after the production were measured. Use (viscosity after storage)/(initial viscosity) as the viscosity increase rate. If the viscosity increase rate is less than 1.1, it is marked as "◎", if the viscosity is greater than 1.1 and less than 1.5, it is marked as "○", and 1.5 or more and not Those with a score of 2.0 were recorded as "△", and those with a score of 2.0 or higher were recorded as "×", to evaluate the storage stability. In addition, the viscosity of the sealing compound for liquid crystal display elements was measured using an E-type viscometer (manufactured by BROOK FIELD Co., Ltd., "DV-III") at 25°C with a rotation speed of 1.0 rpm.

(Adhesion) The sealants for liquid crystal display elements obtained in the examples and comparative examples were filled in a dispensing syringe (manufactured by Musashi Engineering, "PSY-10E"), and defoaming treatment was performed. Using a dispenser (manufactured by Musashi Engineering, "SHOTMASTER300"), the liquid crystal display device sealant after the defoaming treatment is dispensed in the inner square 30 mm from the end of the glass substrate (150 mm × 150 mm), And overlap another glass substrate (110 mm×110 mm) under vacuum. Using a high-pressure mercury lamp, 100 mW/cm ² of ultraviolet light was irradiated for 30 seconds to temporarily harden the sealant for liquid crystal display elements, and then heated at 120°C for 1 hour to thermally harden the sealant for liquid crystal display elements to obtain an adhesive test sheet. Use a metal rod with a radius of 5 mm to press into the end of the substrate of the obtained adhesive test piece at a speed of 5 mm/min, measure the strength (kgf) when the panel is peeled off at this time, and calculate the adhesive force (kg/cm) ). If the adhesive force is 3.5 kg/cm or more, it is recorded as "◎", if the adhesive force is 3.0 kg/cm or more and less than 3.5 kg/cm, it is recorded as "〇", and the adhesive force is 2.0 kg/cm or more. And the case of less than 3.0 kg/cm is recorded as "△", and the case of adhesion less than 2.0 kg/cm is recorded as "×" to evaluate the adhesion.

(Low liquid crystal contamination (NI point)) 0.1 g of the sealing compound for each liquid crystal display element obtained in the examples and comparative examples, and 1 g of liquid crystal (manufactured by Tokyo Chemical Industry Co., Ltd., "4-pentyl-4-bibenzonitrile") were added to the sample bottle. The sample bottle was placed in an oven at 120°C for 1 hour, and then allowed to stand to restore the temperature to 25°C, then the liquid crystal portion was taken out and filtered with a 0.2 μm filter to prepare a liquid crystal sample for evaluation . Seal 10 mg of the obtained liquid crystal sample for evaluation in an aluminum sample pan, use a differential scanning calorimeter (manufactured by TA Instrument, "DSC-Q100"), and measure the NI point at a temperature rise rate of 5°C/min. . Furthermore, the sealing compound for liquid crystal display elements and 10 mg of the above-mentioned liquid crystals that were not in contact were sealed in an aluminum sample pan, and the NI point was measured under the conditions of a temperature increase rate of 5°C/min, and the result was regarded as a blank group. The difference between the NI point measured by the liquid crystal sample for evaluation and the NI point of the blank group is -2°C or higher is marked as "◎", and the case where the temperature is higher than -3°C and less than -2°C is marked as "○" 、The case above -5°C and below -3°C is recorded as "△", and the case below -5°C is recorded as "×" to evaluate the low liquid crystal contamination.

、噴嘴間距42 μm、注射器之噴出壓100〜400 kPa、塗佈速度60 mm/sec之條件，於2片附有配向膜及ITO之基板之一基板上塗佈為框狀。此時，以液晶顯示元件用密封劑之線寬變為約1.5 mm之方式調整噴出壓。繼而，將微小之液晶（東京化成工業公司製造、「4-戊基-4-聯苯腈（4-pentyl-4-biphenylcarbonitrile）」）滴，滴下塗佈於塗佈有液晶顯示元件用密封劑之基板之液晶顯示元件用密封劑之框內整個面，並於真空下貼合另一基板。貼合後立即使用金屬鹵素燈，對液晶顯示元件用密封劑部分照射100 mW/cm² 之紫外線30秒鐘而使液晶顯示元件用密封劑暫時硬化。繼而，於120℃進行1小時加熱而使液晶顯示元件用密封劑正式硬化，以此製作液晶顯示元件。 關於實施例及比較例中所獲得之各液晶顯示元件用密封劑，製作3個液晶顯示元件，針對所獲得之各液晶顯示元件，藉由目視確認液晶顯示元件剛製作完後之液晶顯示元件用密封劑附近之液晶配向混亂。配向混亂係根據顯示部之色不均進行判斷，將於液晶顯示元件之周邊部完全未觀察到顯示不均之情形記為「◎」、將觀察到些許較淺之顯示不均之情形記為「〇」、將存在較清楚且較深之顯示不均之情形記為「△」、將較清楚且較深之顯示不均不僅存在於周邊部，而且亦擴張至中央部之情形記為「×」，以此評價液晶顯示元件之顯示性能。(Display performance of liquid crystal display element) Each liquid crystal display element obtained by dispersing 1 part by weight of spacer particles ("Micropearl SI-H050", manufactured by Sekisui Chemical Industry Co., Ltd.) with an average particle diameter of 5 μm in the examples and comparative examples Fill a syringe with 100 parts by weight of the sealant, and defoam with a centrifugal defoamer (Awatron AW-1). Use a dispenser to apply the liquid crystal display device sealant after defoaming treatment to the nozzle diameter of 0.4 mm

, The nozzle pitch is 42 μm, the ejection pressure of the syringe is 100~400 kPa, and the coating speed is 60 mm/sec. Coated into a frame shape on one of the two substrates with alignment film and ITO. At this time, the discharge pressure was adjusted so that the line width of the sealant for liquid crystal display elements became approximately 1.5 mm. Next, drop a minute liquid crystal (manufactured by Tokyo Chemical Industry Co., Ltd., "4-pentyl-4-biphenylcarbonitrile (4-pentyl-4-biphenylcarbonitrile)"), and apply it to the sealant coated with liquid crystal display elements. The entire surface of the substrate of the liquid crystal display element sealant frame is attached to another substrate under vacuum. Immediately after bonding, a metal halide lamp was used to irradiate the sealing compound for liquid crystal display elements with 100 mW/cm ² ultraviolet rays for 30 seconds to temporarily harden the sealing compound for liquid crystal display elements. Then, it heated at 120 degreeC for 1 hour, the sealing compound for liquid crystal display elements was fully hardened, and the liquid crystal display element was produced. Regarding the sealants for liquid crystal display elements obtained in the examples and comparative examples, three liquid crystal display elements were produced. For each liquid crystal display element obtained, the liquid crystal display element was visually confirmed for the liquid crystal display element immediately after the liquid crystal display element was produced. The alignment of the liquid crystal near the sealant is disordered. The alignment disorder is judged based on the color unevenness of the display. The case where no display unevenness is observed at the periphery of the liquid crystal display element is marked as "◎", and the case where a little lighter display unevenness is observed is recorded as "〇", the case where there is a clearer and deeper display unevenness is marked as "△", and the case where the clearer and deeper display unevenness not only exists in the peripheral part, but also expands to the center part is recorded as "×" to evaluate the display performance of the liquid crystal display element.

[Table 1] Example 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 type epoxy methacrylate (manufactured by DAICEL-ALLNEX, "KRM7985") - - - - - - - - 70 - Partially methacrylic modified bisphenol E epoxy resin (manufactured by DAICEL-ALLNEX, "KRM8276") - - - - - - - - 30 - Resorcinol type epoxy acrylate (manufactured by DAICEL-ALLNEX, "KRM8076") - - - - - - - - - 70 Partial acrylic modified bisphenol E epoxy resin (manufactured by DAICEL-ALLNEX, "KRM8287") - - - - - - - - - 30 Thermal hardener The hydrazine compound of the present invention Compound A (weight average molecular weight 15000, formula (1-1) 50 mole%, softening point 130°C) 5 2 10 - - - - - 5 5 Compound B (weight average molecular weight 70,000, formula (1-1) 50 mole%, softening point 147°C) - - - 5 - - - - - - Compound C (weight average molecular weight 3000, formula (1-1) 50 mole%, softening point 92°C) - - - - 5 - - - - - Compound D (weight average molecular weight 25000, formula (1-1) 80 mole%, softening point 156℃) - - - - - 5 - - - - Compound E (weight average molecular weight 24000, formula (1-1) 95 mole%, softening point 200℃) - - - - - - 5 - - - Compound F (weight average molecular weight 16000, formula (1-1) 5 mol%, softening point 69°C) - - - - - - - 5 - - Light radical 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 radical polymerization initiator Polymer azo initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "VPE-0201") 2 2 2 2 2 2 2 2 2 2 Filler Silicon dioxide (manufactured by Admatechs, "Admafine SO-C2") 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 Evaluation Storage stability ◎ ◎ 〇 ◎ 〇 ◎ ◎ △ ◎ 〇 Continuity ◎ 〇 ◎ ◎ ◎ 〇 △ 〇 〇 ◎ Low liquid crystal contamination (NI point) ◎ 〇 ◎ 〇 〇 〇 △ ◎ 〇 ◎ Display performance of liquid crystal display element ◎ 〇 ◎ ◎ 〇 ◎ 〇 ◎ 〇 〇

[Table 2] Comparative 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 Thermal hardener other Dihydrazine malonate (manufactured by JAPAN FINECHEM, "MDH", molecular weight 132, softening point 152°C) 5 - - Dihydrazine adipic acid (manufactured by Otsuka Chemical Co., "ADH", molecular weight 174, softening point 182°C) - 5 - Compound G (weight average molecular weight 12000, formula (1-1) 0 mole%, softening point 64°C) - - 5 Light radical polymerization initiator 2,2-Dimethoxy-1,2-diphenylethane-1-one (manufactured by IGM Resins, "Omnirad 651") 2 2 2 Thermal radical polymerization initiator Polymer azo initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "VPE-0201") 2 2 2 Filler Silicon dioxide (manufactured by Admatechs, "Admafine SO-C2") 20 20 20 Silane coupling agent 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") 1 1 1 Evaluation Storage stability X △ X Continuity ◎ ◎ 〇 Low liquid crystal contamination (NI point) △ △ 〇 Display performance of liquid crystal display element X X 〇 [Industrial availability]

According to the present invention, it is possible to provide a sealing compound for a liquid crystal display element which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealing compound for liquid crystal display elements.

no

no

Claims (8)

A sealing compound for liquid crystal display elements, which contains a curable resin and a thermosetting agent, characterized in that the thermosetting agent contains a hydrazine compound, and the hydrazine compound has a structure represented by the following formula (1-1) And the structure shown in the following formula (1-2):

In the formula (1-1), Ar is an aromatic ring, and in the formula (1-2), R ¹ is a hydrogen atom or a methyl group. The sealing compound for liquid crystal display elements of Claim 1 whose ratio of the structure represented by the said formula (1-1) in the said hydrazine compound is 5 mol% or more and 95 mol% or less. The sealing compound for liquid crystal display elements according to claim 1 or 2, wherein the hydrazine compound further has a structure represented by the following formula (2):

In formula (2), R ² is a hydrogen atom or a methyl group, R ³ is a -C(=O)OR ⁴ group (R ⁴ is a hydrogen atom or an alkyl group with 1 to 10 carbon atoms), -CN group, -OR ⁵ group (R ⁵ is an alkyl group having 1 or more and 10 or less carbon atoms), or a hydrogen atom. The sealing compound for liquid crystal display elements of 2 or 3, wherein the weight average molecular weight of the hydrazine compound is 2000 or more and 200,000 or less. The sealing compound for liquid crystal display elements of 2, 3, or 4, wherein the softening point of the above-mentioned hydrazine compound is 65°C or more and 200°C or less. The sealing compound for liquid crystal display elements of 2, 3, 4, or 5, which further contains a photoradical polymerization initiator. An up-and-down conduction material containing the sealant for liquid crystal display elements of claim 1, 2, 3, 4, 5, or 6 and conductive fine particles. A liquid crystal display element which is formed by using the sealant for liquid crystal display elements of claim 1, 2, 3, 4, 5, or 6, or a material that conducts the upper and lower parts of claim 7.