TW202313920A - Liquid crystal display element sealant and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a liquid crystal display element sealant that is excellent in terms of storage stability, adhesive properties, and low liquid crystal contamination properties. The purpose of the present invention is also to provide a liquid crystal display element obtained using the liquid crystal display element sealant. The present invention is a liquid crystal display element sealant containing a curable resin and a thermosetting agent, wherein the thermosetting agent includes an adduct between an epoxy compound and an amine compound having an amino group equivalent of at most 30.

Description

Sealant for liquid crystal display element and liquid crystal display element

The present invention relates to a sealant for liquid crystal display elements excellent in storage stability, adhesiveness, and low liquid crystal contamination. Moreover, this invention relates to the liquid crystal display element which used this 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 perspectives of shortening the production lead time and optimizing the amount of liquid crystal usage, the industry uses a sealing method as disclosed in Patent Document 1 and Patent Document 2. Liquid crystal drop method called drop processing method. In the drop processing method, first, a frame-shaped seal pattern is formed by dispensing on one of the two substrates with electrodes. Then, in the uncured state of the sealant, droplets of liquid crystal are dropped into the frame of the seal pattern, and another substrate is stacked under vacuum, and the sealant is cured to produce a liquid crystal display element. At present, the manufacturing method of liquid crystal display elements is mainly the drop processing method.

Furthermore, in the modern age when various mobile devices with liquid crystal panels, such as mobile phones and portable game consoles, are becoming popular, miniaturization of the devices is the most requested issue. As a method of miniaturization of the machine, the edge narrowing of the liquid crystal display part can be mentioned, for example, the position of the sealing part is arranged under the black matrix (hereinafter also referred to as narrow edge design). [Prior Art Literature] [Patent Document]

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

[Problem to be Solved by the Invention]

In the narrow edge design, the sealant is arranged directly under the black matrix, so if the drop processing method is used, the light irradiated when the sealant is photohardened will be blocked, and the light will not easily reach the inside of the sealant. Insufficient hardening for the agent. Insufficient hardening of the sealant in this way has a problem that uncured sealant components are eluted in the liquid crystal, and contamination of the liquid crystal is likely to occur. Especially in recent years, along with the high polarity of liquid crystals, liquid crystal contamination may sometimes occur when using a sealant that had no problems before, and further low liquid crystal contamination is required for the sealant.

When it is difficult to light-cure the sealant, it is considered to harden the sealant by heating, and as a method for hardening the sealant by heating, the industry has performed operations of mixing a thermosetting agent into the sealant. In addition, in the narrow edge design, the sealant is also arranged on the alignment film, so the sealant for liquid crystal display elements is required to have excellent adhesion not only to the substrate but also to the alignment film. However, when a highly reactive thermosetting agent is used to improve the curability or adhesiveness of the sealant, the storage stability of the obtained sealant may deteriorate, or liquid crystal contamination may occur.

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 property. Moreover, the object of this invention is to provide the liquid crystal display element which used this sealing compound for liquid crystal display elements. [Technical means to solve the problem]

The present invention 1 is a sealant for liquid crystal display elements, which contains a curable resin and a thermosetting agent, and the thermosetting agent includes: an adduct of an amine compound and an epoxy compound having an amine group equivalent weight of 30 or less. This invention 2 is the sealing compound for liquid crystal display elements like this invention 1 whose said amine group equivalent weight is 30 or less of amine compounds which are at least any one of hydrazine and carhydrazine. This invention 3 is the sealant for liquid crystal display elements according to this invention 1 or 2, wherein the adduct of an amine compound having an amine group equivalent weight of 30 or less and an epoxy compound is solid at 25°C. This invention 4 is the sealing compound for liquid crystal display elements like this invention 1, 2, or 3 whose said epoxy compound is an epoxy compound which has a structure derived from the compound which has a phenolic hydroxyl group. This invention 5 is a liquid crystal display element which has the hardened|cured material of the sealing compound for liquid crystal display elements of this invention 1, 2, 3, or 4. The present invention will be described in detail below.

The inventors of the present invention conducted research on improving storage stability and low liquid crystal contamination of a sealant for liquid crystal display elements by using an amine adduct of an epoxy compound as a thermosetting agent. However, the adhesiveness (especially the adhesiveness to an alignment film) of the obtained sealing compound for liquid crystal display elements may worsen. Therefore, the present inventors conducted diligent research and found that by using an adduct of an amine compound having an amine group equivalent weight of 30 or less and an epoxy compound as a thermosetting agent, storage stability, adhesiveness, and low The sealing compound for liquid crystal display elements which is excellent in both liquid crystal staining property has completed this invention.

The sealing compound for liquid crystal display elements of this invention contains a thermosetting agent. The above-mentioned thermosetting agent includes: an adduct of an amine compound having an amine group equivalent weight of 30 or less and an epoxy compound (hereinafter also referred to as "the adduct of the present invention"). By containing the adduct of the present invention, the sealing compound for liquid crystal display elements of the present invention is excellent in storage stability, adhesiveness, and low liquid crystal contamination. In addition, in this specification, the said "amine compound" means the compound which has an amino group, such as an amine compound, a hydrazine compound, and a hydrazine compound. Also, the above-mentioned "amino group equivalent" means a value calculated by (molecular weight of amine compound)/(number of amine groups in one molecule of amine compound), and the above-mentioned "number of amine groups" means the number of nitrogen atoms constituting amine groups. For example, regarding one hydrazine group (-NHNH ₂ group), the number of amine groups is assumed to be two for calculation.

The adduct of the present invention has a structure derived from an amine compound having an amine group equivalent weight of 30 or less, and a structure derived from an epoxy compound.

With regard to the amine-based compound having an amine group equivalent weight of 30 or less as the source of the adduct of the present invention, the lower limit of the amine equivalent weight is preferably 15, and the upper limit is 25. When the amine equivalent weight of the above-mentioned amine compound having an amine equivalent weight of 30 or less falls within this range, the obtained sealant for liquid crystal display elements is excellent in storage stability, adhesiveness, and low liquid crystal contamination become better. The more preferable lower limit of the amine equivalent weight of the above-mentioned amine compound having an amine equivalent weight of 30 or less is 16, and a more preferable upper limit is 23.

Specific examples of the amine compound having an amine group equivalent weight of 30 or less include hydrazine, carbodihydrazide, and oxalyl dihydrazide. Among these, hydrazine and carbohydrazide are preferred from the viewpoint of making the obtained sealant for liquid crystal display elements more excellent in storage stability, adhesiveness, and low liquid crystal contamination. at least either.

Examples of the epoxy compound used as the source of the adduct of the present invention include bisphenol A epoxy compound, bisphenol F epoxy compound, bisphenol E epoxy compound, and bisphenol S epoxy compound. compound, 2,2'-diallyl bisphenol A epoxy compound, hydrogenated bisphenol epoxy compound, propylene oxide addition bisphenol A epoxy compound, resorcinol epoxy compound, Benzene type epoxy compound, thioether type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound, o-cresol novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound, biphenyl novolak type epoxy compound, naphthol novolak type epoxy compound, glycidylamine type epoxy compound, alkyl polyol type epoxy compound Compounds, rubber-modified epoxy compounds, glycidyl ester compounds, etc. Among them, "an epoxy compound having a structure derived from a compound having a phenolic hydroxyl group" is preferable. As the above-mentioned epoxy compound having a structure derived from a compound having a phenolic hydroxyl group, bisphenol A type epoxy compound, bisphenol F type epoxy compound, diphenyl ether type epoxy compound are more preferable, and diphenyl ether type epoxy compound is more preferable. Ether type epoxy compound. As said bisphenol A type epoxy compound, bisphenol A diglycidyl ether etc. are mentioned, for example. As said bisphenol F type epoxy compound, bisphenol F diglycidyl ether, a bisphenol F type epoxy polymer, etc. are mentioned, for example. As said diphenyl ether type epoxy compound, bis(4-glycidoxy phenyl) ether etc. are mentioned, for example.

The preferred lower limit of the mass average molecular weight of the adduct of the present invention is 200, and the preferred upper limit is 3000. By making the mass average molecular weight of the adduct of this invention 200 or more, the low liquid-crystal contamination property of the sealing compound for liquid crystal display elements obtained becomes more excellent. By making the mass average molecular weight of the adduct of this invention 3000 or less, the handling property of the sealing compound for liquid crystal display elements obtained becomes more excellent. A more preferable lower limit of the mass average molecular weight of the adduct of the present invention is 300, and a more preferable upper limit is 1500. In addition, in this specification, the said mass average molecular weight is the value calculated|required by polystyrene conversion by measuring using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). As a column for measuring the mass average molecular weight in terms of polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) and the like may be mentioned.

From the viewpoint of storage stability, the adduct of the present invention is preferably solid at 25°C. The preferable lower limit of the melting point of the adduct of the present invention is 60°C, and the more preferable lower limit is 90°C. Moreover, the upper limit of the melting point of the adduct of the present invention is preferably 180°C, more preferably 150°C, from the viewpoint of the curability of the sealing compound for liquid crystal display elements to be obtained. In addition, the said melting point can be calculated|required by differential scanning calorimetry or a commercially available melting point measuring apparatus.

The preferable lower limit of content of the adduct of this invention is 3 mass parts with respect to 100 mass parts of curable resins mentioned below, and a preferable upper limit is 70 mass parts. When content of the adduct of this invention is 3 mass parts or more with respect to 100 mass parts of curable resins, the adhesiveness of the sealing compound for liquid crystal display elements obtained becomes more excellent. When content of the adduct of this invention is 70 mass parts or less with respect to 100 mass parts of curable resins, the low liquid crystal contamination property and storage stability of the obtained sealing compound for liquid crystal display elements become more excellent. The more preferable minimum of content of the adduct of this invention is 6 mass parts with respect to 100 mass parts of curable resins, and a more preferable upper limit is 35 mass parts. Also, when the following epoxy compound is contained as the curable resin, the preferred lower limit of the content of the adduct of the present invention is 0.5 equivalents, and the preferred upper limit is 2.0 equivalents based on 1 equivalent of the epoxy compound. When content of the adduct of this invention is 0.5 equivalent or more with respect to 1 equivalent of the said epoxy compound, the curability or adhesiveness of the sealing compound for liquid crystal display elements obtained becomes more excellent. When content of the adduct of this invention is 2.0 equivalents or less with respect to 1 equivalent of the said epoxy compound, the storage stability and low liquid crystal contamination property of the obtained sealing compound for liquid crystal display elements become more excellent. The lower limit of the more preferable content of the adduct of this invention is 0.8 equivalent with respect to 1 equivalent of the said epoxy compound, and a more preferable upper limit is 1.2 equivalent.

The sealing compound for liquid crystal display elements of this invention contains curable resin. The curable resin described above preferably contains an epoxy compound. Examples of the epoxy compound include: bisphenol A epoxy compound, bisphenol F epoxy compound, bisphenol E epoxy compound, bisphenol S epoxy compound, 2,2'-diene Propyl bisphenol A type epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type Epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound, o-cresol novolak type epoxy compound, dicyclopentadiene Enzyme novolak type epoxy compound, biphenyl novolak type epoxy compound, naphthol novolak type epoxy compound, glycidylamine type epoxy compound, alkyl polyol type epoxy compound, rubber modified epoxy compound , glycidyl ester compounds, etc.

As what is marketed among the said bisphenol A type epoxy compounds, jER828EL, jER1004 (all are the Mitsubishi Chemical Corporation make), Epiclon850 (the DIC company make), etc. are mentioned, for example. As what is marketed among the said bisphenol F type epoxy compounds, jER806, jER4004 (all are the Mitsubishi Chemical Corporation make), Epiclon EXA-830CRP (the DIC Corporation make), etc. are mentioned, for example. As what is marketed among the said bisphenol E type epoxy compounds, Epomik R710 (made by Mitsui Chemicals Corporation) etc. are mentioned, for example. As what is marketed among the said bisphenol S type epoxy compounds, Epiclon EXA-1514 (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said 2,2'- diallyl bisphenol A type epoxy compounds, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said hydrogenated bisphenol type epoxy compounds, Epiclon EXA-7015 (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said propylene oxide addition bisphenol A type epoxy compounds, EP-4000S (made by ADEKA company) etc. are mentioned, for example. As what is marketed among the said resorcinol type epoxy compounds, EX-201 (made by a Nagase Chemtex company) etc. are mentioned, for example. As what is marketed among the said biphenyl type epoxy compounds, jER YX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example. As what is marketed among the said thioether type epoxy compounds, YSLV-50TE (made by Nippon Steel Chemical & Materials Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said diphenyl ether type epoxy compounds, YSLV-80DE (made by Nippon Steel Chemical & Materials Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said dicyclopentadiene type epoxy compounds, EP-4088S (made by ADEKA company) etc. are mentioned, for example. As what is marketed among the said naphthalene type epoxy compounds, Epiclon HP-4032, Epiclon EXA-4700 (all are the DIC company make), etc. are mentioned, for example. As what is marketed among the said phenol novolac type epoxy compounds, Epiclon N-770 (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said o-cresol novolak type epoxy compounds, Epiclon N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said dicyclopentadiene novolac type epoxy compounds, Epiclon HP-7200 (made by DIC Corporation) etc. are mentioned, for example. As what is marketed among the said biphenyl novolac type epoxy compounds, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said naphthol novolac type epoxy compounds, ESN-165S (made by Nippon Steel Chemical & Materials Co., Ltd.) etc. are mentioned, for example. As what is marketed among the said glycidylamine type epoxy compounds, jER630 (made by Mitsubishi Chemical Corporation), Epiclon430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemical Corporation), etc. are mentioned, for example. As what is marketed among the said alkyl polyol type epoxy compounds, ZX-1542 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), Epiclon726 (manufactured by DIC Corporation), Epolight80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) are mentioned, for example. , DENACOL EX-611 (manufactured by Nagase Chemtex), etc. As what is marketed among the said rubber modified epoxy compounds, YR-450, YR-207 (both are manufactured by Nippon Steel Chemical & Materials Co., Ltd.), Epolead P B (made by Daicel Corporation), etc. are mentioned, for example. As what is marketed among the said glycidyl ester compounds, DENACOL EX-147 (made by a Nagase Chemtex company) etc. are mentioned, for example. Examples of other commercially available epoxy compounds include: YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical & Materials Co., Ltd.), XAC4151 (manufactured by Asahi Kasei), jER1031, jER1032 (all 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 acid-modified epoxy compound can also be used suitably. Furthermore, in this specification, the above-mentioned partial (meth)acrylic acid modified epoxy compound means the following compound, which can be modified by making one part of the epoxy group of the epoxy compound having more than two epoxy groups and (methyl) ) obtained by the reaction of acrylic acid, and each molecule has more than one epoxy group and (meth)acryl group. In addition, in this specification, said "(meth)acryl" means acryl or methacryl, and said "(meth)acryl" means acryl or methacryl.

As what is marketed among the said partial (meth)acryl-modified epoxy compounds, UVACURE1561, KRM8030, KRM8287 (all are the DAICEL-ALLNEX company make) etc. are mentioned, for example.

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

Examples of the monofunctional ones among the above-mentioned (meth)acrylate compounds include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-(meth)acrylate Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate ester, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate ) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, Isocamphoryl (meth)acrylate, Dicyclopentenyl (meth)acrylate, Benzyl (meth)acrylate, 2-Methoxyethyl (meth)acrylate, 2-Ethoxy (meth)acrylate 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (Meth)acrylate, Phenoxydiethylene glycol (meth)acrylate, Phenoxypolyethylene glycol (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, Ethyl carbitol (Meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H (meth)acrylate, 5H-octafluoropentyl ester, imido(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 2-(meth)propylene Acyloxyethylsuccinic acid, 2-(meth)acryloxyethylhexahydrophthalate, 2-(meth)acryloxyethyl 2-hydroxypropylphthalate, phosphoric acid 2-(meth)acryloxyethyl ester, glycidyl (meth)acrylate, etc.

In addition, examples of bifunctional ones among the above-mentioned (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylic acid ester, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol Di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl- 2-Ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl Diol di(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, propylene oxide added bisphenol A di(meth)acrylate, ethylene oxide added bisphenol A Phenol F di(meth)acrylate, dimethylol dicyclopentadiene di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth) 2-Hydroxy-3-(meth)acryloxypropyl acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate ) acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.

In addition, examples of trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(methylolpropane) trimethylolpropane tri(methylolpropane) trimethylolpropane tri(methylolpropane tri(meth)acrylate) among the above-mentioned (meth)acrylate compounds are, for example, trimethylolpropane tri(meth)acrylate. base) acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition heterotrimerization Cyanate tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide added glycerol tri(meth)acrylate, neopentylthritol tri(meth)acrylate, phosphate ginseng(meth)acrylate ) acryloxyethyl ester, di-trimethylolpropane tetra(meth)acrylate, neopentylthritol tetra(meth)acrylate, dipenteoerythritol penta(meth)acrylate, dinew Pentaerythritol hexa(meth)acrylate, etc.

As said epoxy (meth)acrylate, the thing obtained by making an epoxy compound and (meth)acrylic acid react, etc. are mentioned, for example in the presence of an alkaline catalyst according to a normal method.

As an epoxy compound used as a raw material for synthesizing the said epoxy (meth)acrylate, the thing similar to the said epoxy compound which is the curable resin contained in the sealing compound for liquid crystal display elements of this invention can be used.

As what is marketed among the said epoxy (meth)acrylates, the epoxy (meth)acrylate by DAICEL-ALLNEX company, the epoxy (meth)acryl by Shin-Nakamura Chemical Industry Co., Ltd. are mentioned, for example ester, epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase Chemtex Corporation, and the like. EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL370 are mentioned as an epoxy (meth)acrylate by the said DAICEL-ALLNEX company. 8. EBECRYL3800, EBECRYL6040, EBECRYL RDX63182, etc. As epoxy (meth)acrylate by the said Shin-Nakamura Chemical Industry Co., Ltd., EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 etc. are mentioned, for example. Examples of epoxy (meth)acrylates manufactured by Kyoeisha Chemical Co., Ltd. include EPOXYESTER M-600A, EPOXYESTER 40EM, EPOXYESTER 70PA, EPOXYESTER 200PA, EPOXYESTER 80MFA, EPOXYESTER 3002M, EPOXYESTER 3002A, EPOXYESTER 1600A, EPOX YESTER 3000M, EPOXYESTER 3000A, EPOXYESTER 200EA, EPOXYESTER 400EA, etc. As epoxy (meth)acrylate by the Nagase Chemtex company mentioned above, Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 etc. are mentioned, for example.

The above-mentioned urethane (meth)acrylate can be obtained, 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 isocyanate compounds used as raw materials for the above-mentioned urethane (meth)acrylate include: isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate , trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzidine diisocyanate Isocyanates, Xylylene Diisocyanate (XDI), Hydrogenated XDI, Lysine Diisocyanate, Triphenylmethane Triisocyanate, Phosphorothioate (isocyanatophenyl) Ester, Tetramethylxylylene Diisocyanate , 1,6,11-undecane triisocyanate, etc.

Moreover, the chain-extended isocyanate compound obtained by reaction of polyhydric alcohol and the excess isocyanate compound can also be used as the isocyanate compound used as the raw material of the said urethane (meth)acrylate. Examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone Ester diols, etc.

Examples of (meth)acrylic acid derivatives having a hydroxyl group include: hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of diol, mono(meth)acrylate of triol Acrylate or di(meth)acrylate, epoxy(meth)acrylate, etc. Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. , 4-hydroxybutyl (meth)acrylate, etc. As said dihydric alcohol, ethylene glycol, 1, 2- propanediol, 1, 3-propanediol, 1, 3- butanediol, 1, 4- butanediol, polyethylene glycol etc. are mentioned, for example. As said trivalent alcohol, trimethylolethane, trimethylolpropane, glycerin, etc. are mentioned, for example. As said epoxy (meth)acrylate, a bisphenol A epoxy (meth)acrylate etc. are mentioned, for example.

As what is marketed among the said urethane (meth)acrylates, the urethane (meth)acrylate by Toagosei Co., Ltd., the urethane (meth)acrylate by DAICEL-ALLNEX, etc. are mentioned, for example. Urethane (meth)acrylate manufactured by Negami Industry Co., Ltd., urethane (meth)acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like. As the urethane (meth)acrylate manufactured by the said Toagosei Co., Ltd., M-1100, M-1200, M-1210, M-1600 etc. are mentioned, for example. Examples of the above-mentioned urethane (meth)acrylate manufactured by DAICEL-ALLNEX include: EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260, etc. Examples of the above-mentioned urethane (meth)acrylate manufactured by Negami Industry Co., Ltd. include: ART RESIN UN-330, ART RESIN SH-500B, ART RESIN UN-1200TPK, ART RESIN UN-1255, ART RESIN UN-3320HB , ART RESIN UN-7100, ART RESIN UN-9000A, ART RESIN UN-9000H, etc. U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA are mentioned as the above-mentioned urethane (meth)acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. , 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 above-mentioned urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I , UA-306T, etc.

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 partially (meth)acrylic modified epoxy compound is contained, it is preferable to use The ratio of the (meth)acryl group in the total of the epoxy group and the (meth)acryl group in the said curable resin is 30 mol% or more and 95 mol% or less. By making the ratio of the said (meth)acryloyl group into this range, generation|occurrence|production 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, it is preferable that the curable resin has hydrogen bonding units such as -OH group, -NH- group, and -NH ₂ group.

化合物等。 作為上述光自由基聚合起始劑，具體而言，例如可例舉：1-羥基環己基苯基酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-1-丁酮、2-(二甲基胺基)-2-((4-甲基苯基)甲基)-1-(4-(4-嗎啉基)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-甲基噻吩基)-2-嗎啉基丙烷-1-酮、1-(4-(2-羥基乙氧基)-苯基)-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-(苯硫基)苯基)-1,2-辛二酮-2-(O-苯甲醯基肟)、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使用，亦可組合兩種以上使用。 It is preferable that the sealing compound for liquid crystal display elements of this invention contains a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include: benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, 9-oxothiophene compounds, and

compounds etc. As the above photoradical polymerization initiator, specifically, for example, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl Base)-1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1 -butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl Base-1-(4-methylthienyl)-2-morpholinopropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxyl-2-methyl -1-propane-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione-2-(O-benzoyl oxime), 2,4,6-tri Toluyl diphenylphosphine oxide, etc. The above photoradical polymerization initiators may be used alone or in combination of two or more.

The preferable lower limit of content of the said photoradical polymerization initiator is 0.5 mass parts with respect to 100 mass parts of said curable resins, and a preferable upper limit is 10 mass parts. By making content of the said radical photopolymerization initiator into this range, the obtained sealing compound for liquid crystal display elements suppresses contamination of a liquid crystal, and becomes more excellent in storage stability or photocurability. The more preferable lower limit of content of the said photoradical polymerization initiator is 1 mass part, and the more preferable upper limit is 7 mass parts.

The sealing compound for liquid crystal display elements of this invention may contain a thermal radical polymerization initiator. As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. are mentioned, for example. Among them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter also referred to as "azo initiator") is preferable, and an initiator composed of a high molecular weight azo compound is more preferable. Initiator (hereinafter also referred to as "polymeric azo initiator"). The above thermal radical polymerization initiators may be used alone or in combination of two or more. In addition, in this specification, the above-mentioned "polymeric azo compound" means a compound having an azo group, generating free radicals capable of reacting (meth)acryl groups with heat, and having a number average molecular weight of 300 or more. compound.

The preferable lower limit of the number average molecular weight of the above-mentioned polymeric azo compound is 1,000, and the preferable upper limit is 300,000. By making the number average molecular weight of the said high molecular weight azo compound into this range, it can prevent the adverse influence on a liquid crystal, and can mix it with curable resin easily. The lower limit of the number average molecular weight of the above-mentioned polymer azo compound is preferably 5000, the upper limit is 100,000, the lower limit is 10,000, and the upper limit is 90,000. In addition, in this specification, the said number average molecular weight is the value calculated|required by polystyrene conversion measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. As a column for measuring the number average molecular weight in terms of polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) and the like may be mentioned.

As said high molecular weight azo compound, the thing which has the structure which unites, such as a polyalkylene oxide or polydimethylsiloxane, couple|bonded via an azo group, is mentioned, for example. As the polymeric 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 polymeric azo compound, specifically, for example, a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'- Polycondensate of azobis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amino group, etc. Examples of commercially available polymeric azo initiators include: VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) wait. Moreover, as a non-polymeric azo initiator, V-65, V-501 (both are manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) etc. are mentioned, for example.

As said organic peroxide, a ketone peroxide, a peroxyketal, hydrogen peroxide, a dialkyl peroxide, a peroxyester, a diacyl peroxide, a peroxydicarbonate etc. are mentioned, for example.

The preferable lower limit of content of the said thermal radical polymerization initiator is 0.1 mass parts with respect to 100 mass parts of said curable resins, and a preferable upper limit is 10 mass parts. By making content of the said thermal radical polymerization initiator into this range, the obtained sealing compound for liquid crystal display elements suppresses contamination of a liquid crystal, and becomes more excellent in storage stability or thermosetting property. The more preferable lower limit of the content of the said thermal radical polymerization initiator is 0.3 mass parts, and the more preferable upper limit is 5 mass parts.

The sealant for liquid crystal display elements of the present invention may also contain a filler in order to increase viscosity, improve adhesiveness by utilizing stress dispersion effect, improve linear expansion rate, and improve moisture resistance of cured product.

As said filler, an inorganic filler or an organic filler can be used. Examples of the above-mentioned inorganic filler include: silica (silica), talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, oxide Zinc, 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 (polyurethane) microparticles, vinyl polymer microparticles, acrylic polymer microparticles, etc. are mentioned, for example. These fillers may be used alone or in combination of two or more.

The preferable lower limit of content of the said filler in 100 mass parts of sealing compounds for liquid crystal display elements of this invention is 10 mass parts, and a preferable upper limit is 70 mass parts. By making content of the said filler into this range, the effects, such as improvement of adhesiveness, will become more excellent, without deteriorating applicability etc.. A more preferable lower limit of the content of the above filler is 20 parts by mass, and a more preferable upper limit is 60 parts by mass.

The sealing compound for liquid crystal display elements of this invention may contain a silane coupling agent. The above-mentioned silane coupling agent mainly functions as an adhesive auxiliary agent for good adhesion of the sealant for liquid crystal display elements to the substrate and the like.

As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isopropyltrimethoxysilane, Cyanatopropyltrimethoxysilane, etc. These are excellent in the effect of improving the adhesiveness with a board|substrate etc., and can restrain curable resin from flowing out into liquid crystal by chemically bonding with curable resin. Among them, 3-glycidoxypropyltrimethoxysilane is preferred. The above-mentioned silane coupling agents may be used alone or in combination of two or more.

The preferable lower limit of content of the said silane coupling agent in 100 mass parts of sealing compounds for liquid crystal display elements of this invention is 0.1 mass parts, and a preferable upper limit is 10 mass parts. By making content of the said silane coupling agent into this range, generation|occurrence|production of liquid crystal contamination is suppressed, and the effect of improving adhesiveness becomes more excellent. The more preferable lower limit of the content of the said silane coupling agent is 0.3 mass parts, and the more preferable upper limit is 5 mass parts.

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

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

The aforementioned titanium black is a substance that has a higher transmittance for light near the ultraviolet region, especially for light with a wavelength of 370 nm to 450 nm, than the average transmittance for light with a wavelength of 300 nm to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent having the property of imparting light-shielding properties to the sealant for liquid crystal display elements of the present invention by sufficiently shielding light of wavelengths in the visible light region, and on the other hand, making light of wavelengths near the ultraviolet region light penetrates. Therefore, by using as the above-mentioned radical photopolymerization initiator, the photocuring property of the sealant for liquid crystal display elements of the present invention can be further increased by using the light that can start the reaction due to the light of the wavelength that the transmittance of the above-mentioned titanium black increases. . On the other hand, as the light-shielding agent contained in the sealing compound for liquid crystal display elements of this invention, it is preferable that it is a substance with high insulating property, and titanium black is also suitable as a light-shielding agent with high insulating property. 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 above-mentioned titanium black, the better. There is no particularly preferable upper limit for the OD value of the above-mentioned titanium black, but it is usually 5 or less.

Even if the above-mentioned titanium black has no surface treatment, it can also exert sufficient effect, but it can also use the surface treated with organic components such as coupling agent, or the surface treated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, Surface-treated titanium black coated with inorganic components such as magnesium oxide. Among them, those treated with an organic component are preferable in terms of further improving insulation properties. Also, since the liquid crystal display element manufactured by the sealant for liquid crystal display element of the present invention blended with the above-mentioned titanium black as the light-shielding agent has sufficient light-shielding properties, it can realize "high contrast without light leakage, and has "Excellent image display quality" liquid crystal display element.

As what is marketed among the said titanium blacks, the titanium black by Mitsubishi Materials Corporation, the titanium black by Ako Kasei Corporation, etc. are mentioned, for example. Examples of titanium black manufactured by Mitsubishi Materials Corp. include 12S, 13M, 13M-C, 13R-N, and 14M-C. As titanium black manufactured by the said Ako Kasei Co., Ltd., Tilack D etc. are mentioned, for example.

The lower limit of the specific surface area of the titanium black is preferably 13 m ² /g, the upper limit is 30 m ² /g, the lower limit is 15 m ² /g, and the upper limit is 25 m ² /g. In addition, the lower limit of the volume resistance of the titanium black is preferably 0.5 Ω·cm, the upper limit is 3 Ω·cm, the lower limit is 1 Ω·cm, and the 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 not more than the distance between the substrates of the liquid crystal display element. The lower limit is preferably 1 nm, and the upper limit is preferably 5000 nm. By making the primary particle diameter of the said light-shielding agent into this range, it can make light-shielding property more excellent, without deteriorating the applicability, etc. of the sealing compound for liquid crystal display elements obtained. The more preferable lower limit of the primary particle size of the above-mentioned sunscreen agent is 5 nm, the more preferable upper limit is 200 nm, the more preferable lower limit is 10 nm, and the more preferable upper limit is 100 nm. In addition, the primary particle diameter of the said light-shielding agent can be measured by dispersing the said light-shielding agent in a solvent (water, an organic solvent, etc.) using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS).

The preferable lower limit of content of the said light-shielding agent in 100 mass parts of sealing compounds for liquid crystal display elements of this invention is 5 mass parts, and a preferable upper limit is 80 mass parts. By making content of the said light-shielding agent into this range, the adhesiveness of the sealing compound for liquid crystal display elements obtained, the intensity|strength after hardening, and drawing property are not greatly reduced, and the light-shielding property more excellent can be exhibited. The more preferable lower limit of the content of the said sunscreen agent is 10 mass parts, the more preferable upper limit is 70 mass parts, the more preferable lower limit is 30 mass parts, and the more preferable upper limit is 60 mass parts.

The sealant for liquid crystal display elements of the present invention may further contain additives such as stress relieving agents, reactive diluents, thixotropic agents, spacers, hardening accelerators, defoamers, leveling agents, and polymerization inhibitors as necessary.

As a method of manufacturing the sealing compound for liquid crystal display elements of this invention, the method etc. which mix curable resin, a thermosetting agent, and the photoradical polymerization initiator etc. which were added as needed, etc. are mentioned, for example. As said mixer, a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, etc. are mentioned, for example.

By mixing conductive fine particles in the sealant for liquid crystal display elements of the present invention, a vertical conduction material can be produced.

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

The liquid crystal display element which has the hardened|cured material of the sealing compound for liquid crystal display elements of this invention is also one of this invention.

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

The sealing compound for liquid crystal display elements of this invention can be used suitably for manufacture of the liquid crystal display element by the liquid crystal drop processing method. As a method of manufacturing the liquid crystal display element of this invention by the liquid crystal drop processing method, the following methods etc. are mentioned, for example. First, the steps of forming a frame-shaped sealing pattern on the substrate with the sealant for liquid crystal display elements of the present invention are performed by screen printing, dispenser coating, and the like. Then, the following steps are carried out: in the uncured state of the sealant for liquid crystal display elements of the present invention, droplets of liquid crystal are applied dropwise to the entire surface of the frame of the seal pattern, and another substrate is immediately overlapped. Then, the process of heating and hardening a sealing agent is performed, and the liquid crystal display element can be obtained by the method of performing each said process. In addition, before the step of heating and curing the sealant, a step of temporarily curing the sealant by irradiating the seal pattern portion with light such as ultraviolet rays may be performed. [Effect of Invention]

According to this invention, the sealing compound for liquid crystal display elements excellent in storage stability, adhesiveness, and low liquid crystal contamination property can be provided. Moreover, according to this invention, the liquid crystal display element which used this sealing compound for liquid crystal display elements can be provided.

The following examples are given to illustrate the present invention in more detail, but the present invention is not limited to these examples.

(Synthesis of Adduct A) In a 100 mL round bottom flask equipped with a reflux condenser, add 50 mL of tetrahydrofuran, 50 mL of ethanol, 10 g (0.2 moles) of hydrazine monohydrate, and bisphenol F 6.24 g (0.02 mol) of glycidyl ether was cooled under reflux while stirring overnight at 60°C. Then, the obtained solution was transferred to a 1000 mL volume round bottom flask, and 500 mL of water was added and stirred. Thereafter, the obtained mixed solution was filtered, and the residue was vacuum-dried at 60°C in a vacuum oven to obtain adduct A which was solid at 25°C. The mass average molecular weight of the adduct A is 1200. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR that the adduct A was an adduct having a structure derived from hydrazine and a structure derived from bisphenol F diglycidyl ether.

(Synthesis of Adduct B) In addition to using 38.4 g (0.02 mol) of bisphenol F-type epoxy polymer instead of 6.24 g (0.02 mol) of bisphenol F diglycidyl ether, with the above "(addition Synthesis of product A)" in the same manner, obtained adduct B which was solid at 25°C. The mass average molecular weight of the adduct B is 1950. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR that the adduct B is an adduct having a structure derived from hydrazine and a structure derived from bisphenol F-type epoxy polymer.

(Synthesis of Adduct C) In addition to using 6.8 g (0.02 mol) of bisphenol A diglycidyl ether instead of 6.24 g (0.02 mol) of bisphenol F diglycidyl ether, the above "(addition Synthesis of product A)" in the same manner, obtained adduct C which was solid at 25°C. The mass average molecular weight of the adduct C is 1250. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR that the adduct C is an adduct having a structure derived from hydrazine and a structure derived from bisphenol A diglycidyl ether.

(Synthesis of Adduct D) In addition to using 6.28 g (0.02 mol) of bis(4-glycidoxyphenyl) ether instead of 6.24 g (0.02 mol) of bisphenol F diglycidyl ether, with In the same manner as above "(Synthesis of Adduct A)", Adduct D which was solid at 25°C was obtained. The mass average molecular weight of the adduct D is 1200. By ¹ H-NMR, ¹³ C-NMR, and FT-IR, it was confirmed that the adduct D is an adduct having a structure derived from hydrazine and a structure derived from bis(4-glycidoxyphenyl) ether .

(Synthesis of Adduct E) In addition to using 11.4 g (0.02 mol) of phenol novolac type epoxy compound instead of 6.24 g (0.02 mol) of bisphenol F diglycidyl ether, with the above "(adduct Synthesis of A)" In the same manner, the adduct E which was solid at 25°C was obtained. The mass average molecular weight of the adduct E is 2300. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR that the adduct E was an adduct having a structure derived from hydrazine and a structure derived from a phenol novolac-type epoxy compound.

(Synthesis of Adduct F) In a 200 mL round bottom flask equipped with a reflux condenser, add 50 mL of tetrahydrofuran, 50 mL of water, 18 g (0.2 mol) of carbohydrazine, and bisphenol F 6.24 g (0.02 mol) of glycidyl ether was cooled under reflux while stirring overnight at 60°C. Then, the obtained solution was transferred to a 1000 mL volume round bottom flask, and 500 mL of water was added and stirred. Thereafter, the obtained mixed solution was filtered, and the residue was vacuum-dried at 60°C in a vacuum oven to obtain adduct F which was solid at 25°C. The mass average molecular weight of the adduct F is 1350. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR that the adduct F was an adduct having a structure derived from carbohydrazide and a structure derived from bisphenol F diglycidyl ether.

(Synthesis of Adduct G) In addition to using 38.4 g (0.02 mol) of bisphenol F epoxy polymer instead of 6.24 g (0.02 mol) of bisphenol F diglycidyl ether, the above "(addition Synthesis of product F)" in the same manner, obtained adduct G which was solid at 25°C. The mass average molecular weight of the adduct G is 2100. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR that the adduct G is an adduct having a structure derived from carbohydrazide and a structure derived from bisphenol F-type epoxy polymer.

(Synthesis of Adduct H) In addition to using 6.8 g (0.02 mol) of bisphenol A diglycidyl ether instead of 6.24 g (0.02 mol) of bisphenol F diglycidyl ether, the above "(addition Synthesis of product F)" in the same manner, obtained adduct H which was solid at 25°C. The mass average molecular weight of the adduct H is 1400. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR that the adduct H is an adduct having a structure derived from carbohydrazide and a structure derived from bisphenol A diglycidyl ether.

(Synthesis of Adduct I) In addition to using 6.28 g (0.02 mol) of bis(4-glycidoxyphenyl) ether instead of 6.24 g (0.02 mol) of bisphenol F diglycidyl ether, with In the same manner as in the above "(synthesis of adduct F)", adduct I was obtained as a solid at 25°C. The mass average molecular weight of the adduct I is 1350. By ¹ H-NMR, ¹³ C-NMR, and FT-IR, it was confirmed that the adduct I has a structure derived from carbohydrazine and a structure derived from bis(4-glycidoxyphenyl) ether adducts.

(Synthesis of Adduct J) In addition to using 11.4 g (0.02 mol) of a phenol novolac type epoxy compound instead of 6.24 g (0.02 mol) of bisphenol F diglycidyl ether, the above "(adduct Synthesis of F)" In the same manner, the adduct J which was solid at 25°C was obtained. The mass average molecular weight of the adduct J is 2500. It was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR that the adduct J is an adduct having a structure derived from a carbohydrazide and a structure derived from a phenol novolac-type epoxy compound.

(Examples 1-10, Comparative Examples 1-4) According to the blending ratios described in Tables 1 and 2, each material was mixed using a planetary mixer (manufactured by Thinky Corporation, "Defoaming Rentaro"), and then mixed using a three-roll mill to prepare Examples 1-10. The sealing compound for each liquid crystal display element of Comparative Examples 1-4.

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

(storage stability) About each sealing compound for liquid crystal display elements obtained in the Example and the comparative example, the initial viscosity immediately after manufacture, and the viscosity after manufacture and storage at 25 degreeC for 1 week were measured. (Viscosity after storage)/(Initial viscosity) is defined as the viscosity increase rate. If the viscosity increase rate is less than 2.0, it will be rated as "◎", and if it is more than 2.0 and less than 3.0, it will be rated as "○", and it will be 3.0. Those above were evaluated as "x", and storage stability was evaluated. In addition, the viscosity of the sealing compound for liquid crystal display elements was measured using the E-type viscometer (BROOK FIELD company make, "DV-III") at 25 degreeC and the conditions of rotation speed 1.0 rpm.

(Adhesive property) 1 mass parts of spacer fine particles were dispersed in 100 mass parts of each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. Micropearl SI-H050 (manufactured by Sekisui Chemical Co., Ltd.) was used as the spacer microparticles. Next, the sealant for liquid crystal display elements in which the spacer particles were dispersed was minutely dropped on one of two glass substrates (length 4.5 mm, width 2.5 mm) with an ITO thin film. Attach another glass substrate with an ITO film on it in a cross shape, irradiate 3000 mJ/cm ² of ultraviolet rays with a metal halide lamp, and then heat at 120°C for 60 minutes to obtain an adhesive test piece. When using a metal cylinder with a radius of 5 mm to press the end of the substrate in the adhesive test piece at a speed of 5 mm/min, measure the strength when the panel peels off. Divide the obtained measured value (kgf) by the seal diameter (cm), and evaluate the case where the obtained value is 3.0 kgf/cm or more as "◎", and the case where it exceeds 2.0 kgf/cm and is less than 3.0 kgf/cm The evaluation was "○", and the case of 2.0 kgf/cm or less was evaluated as "X", and the adhesiveness was evaluated. Also, a glass substrate with a polyimide alignment film for TN (manufactured by Nissan Chemical Co., Ltd., "SE6414") was used instead of the glass substrate with an ITO thin film, and the adhesiveness was evaluated in the same manner.

(Low liquid crystal contamination) 1 part by mass of spacer microparticles with an average particle diameter of 7 μm (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") was dispersed in each of the seals for liquid crystal display elements obtained in Examples and Comparative Examples 100 parts by mass of the solution was filled into a syringe and defoamed using a centrifugal defoamer (AWATORON AW-1). Using a dispenser, under the conditions of a nozzle diameter of 0.4 mmϕ, a nozzle gap of 42 μm, a syringe ejection pressure of 100-400 kPa, and a coating speed of 60 mm/sec, the liquid crystal display element sealant after defoaming treatment was formed into a frame Coated on one of the two substrates with alignment film and ITO thin film. At this time, the discharge pressure was adjusted so that the line width of the sealing compound for liquid crystal display elements might become about 1.0 mm. Then, droplets of liquid crystal (manufactured by Tokyo Chemical Industry Co., Ltd., "4-pentyl-4-biphenylcarbonitrile") are applied dropwise to the liquid crystal display element on the substrate coated with the sealant for liquid crystal display element The entire surface inside the frame was covered with a sealant, and after leaving for 2 hours, another substrate was bonded under vacuum. For the bonded substrate, let it stand for 15 minutes after bonding, and then use a metal halide lamp to irradiate 100 mW/ ^cm2 of ultraviolet rays for 30 seconds on the liquid crystal display element sealant to make the liquid crystal display element sealant Temporarily hardens. Then, it heated at 120 degreeC for 1 hour, it hardened mainly, and the liquid crystal display element was produced. About the obtained liquid crystal display element, the alignment disorder (display unevenness) was confirmed using the polarizing microscope (The product made by Keynes Corporation, "VHX-5000"). Alignment disorder is judged from the color unevenness of the display part. The case where the display unevenness is not observed in the liquid crystal display element is evaluated as "○", and the case where the display unevenness is confirmed is evaluated as "X", and the evaluation is low. Liquid crystal contamination.

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 Composition (parts by mass) hardening resin Resorcinol-type epoxy acrylate (manufactured by DAICEL-ALLNEX, "KRM8076") 42 42 42 42 42 42 42 42 42 42 Bisphenol A type epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL3700") 33 33 33 33 33 33 33 33 33 33 Partially acrylic-modified diphenyl ether-type epoxy compound (manufactured by DAICEL-ALLNEX, "KRM8030") 25 25 25 25 25 25 25 25 25 25 heat hardener Adducts of the present invention Adduct A Amine compounds Hydrazine (amine equivalent weight 16) 6.3 - - - - - - - - - epoxy compound Bisphenol F Diglycidyl Ether Adduct B Amine compounds Hydrazine (amine equivalent weight 16) - 32.7 - - - - - - - - epoxy compound Bisphenol F type epoxy polymer Adduct C Amine compounds Hydrazine (amine equivalent weight 16) - - 6.7 - - - - - - - epoxy compound Bisphenol A Diglycidyl Ether Adduct D Amine compounds Hydrazine (amine equivalent weight 16) - - - 6.3 - - - - - - epoxy compound bis(4-glycidoxy phenyl) ether Adduct E Amine compounds Hydrazine (amine equivalent weight 16) - - - - 7.7 - - - - - epoxy compound Phenol Novolak Type Epoxy Compounds Adduct F Amine compounds Carbohydrazine (amine equivalent weight 23) - - - - - 8.2 - - - - epoxy compound Bisphenol F Diglycidyl Ether Adduct G Amine compounds Carbohydrazine (amine equivalent weight 23) - - - - - - 34.7 - - - epoxy compound Bisphenol F type epoxy polymer Adduct H Amine compounds Carbohydrazine (amine equivalent weight 23) - - - - - - - 8.7 - - epoxy compound Bisphenol A Diglycidyl Ether Adduct I Amine compounds Carbohydrazine (amine equivalent weight 23) - - - - - - - - 8.2 - epoxy compound bis(4-glycidoxy phenyl) ether Adduct J Amine compounds Carbohydrazine (amine equivalent weight 23) - - - - - - - - - 9.7 epoxy compound Phenol Novolak Type Epoxy Compounds Photoradical polymerization initiator Oxime ester compound (manufactured by ADEKA Corporation, "ADEKA ARKLS NCI-930") 2 2 2 2 2 2 2 2 2 2 Inorganic filler Silicon dioxide (manufactured by Admatechs, "Admafine SO-C1") 33 33 33 33 33 33 33 33 33 33 organic filler Acrylic polymer microparticles (manufactured by Aica Kogyo, "Zefiac F351") 13 13 13 13 13 13 13 13 13 13 Silane coupling agent 3-Glycidoxypropyltrimethoxysilane (manufactured by Chisso, "Sila-Ace S-510") 1 1 1 1 1 1 1 1 1 1 evaluate storage stability ○ ○ ◎ ◎ ○ ○ ○ ○ ○ ○ Continuity Adhesion to glass substrate with ITO film ◎ ○ ◎ ◎ ○ ◎ ○ ◎ ○ ○ Adhesion to polyimide alignment film ◎ ○ ◎ ◎ ○ ◎ ○ ◎ ○ ○ Low liquid crystal contamination ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

[Table 2] comparative example 1 2 3 4 Composition (parts by mass) hardening resin Resorcinol-type epoxy acrylate (manufactured by DAICEL-ALLNEX, "KRM8076") 42 42 42 42 Bisphenol A type epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL3700") 33 33 33 33 Partially acrylic-modified diphenyl ether-type epoxy compound (manufactured by DAICEL-ALLNEX, "KRM8030") 25 25 25 25 heat hardener Malonylhydrazine (manufactured by Otsuka Chemical Co., Ltd., "MDH") 2.2 - - - Amine adduct (manufactured by ADEKA, "EH-5057PK") Amine compounds 1,4-bis(aminomethyl)cyclohexane (amino group equivalent weight 71) - 5.8 - - epoxy compound bisphenol A type epoxy compound Hydrazine - - 0.5 - carbohydrazine - - - 1.5 Photoradical polymerization initiator Oxime ester compound (manufactured by ADEKA Corporation, "ADEKA ARKLS NCI-930") 2 2 2 2 Inorganic filler Silicon dioxide (manufactured by Admatechs, "Admafine SO-C1") 33 33 33 33 organic filler Acrylic polymer microparticles (manufactured by Aica Kogyo, "Zefiac F351") 13 13 13 13 Silane coupling agent 3-Glycidoxypropyltrimethoxysilane (manufactured by Chisso, "Sila-Ace S-510") 1 1 1 1 evaluate storage stability ○ ◎ x x Continuity Adhesion to glass substrate with ITO film ◎ x ○ ○ Adhesion to polyimide alignment film ◎ x ○ ○ Low liquid crystal contamination x ○ ○ x [Industrial availability]

According to this invention, the sealing compound for liquid crystal display elements excellent in storage stability, adhesiveness, and low liquid crystal contamination property can be provided. Moreover, according to this invention, the liquid crystal display element which used this sealing compound for liquid crystal display elements can be provided.

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Claims (5)

A sealant for liquid crystal display elements, which contains curable resin and thermosetting agent, and is characterized in that: The above-mentioned thermosetting agent includes: an adduct of an amine compound having an amine group equivalent weight of 30 or less and an epoxy compound. The sealing compound for liquid crystal display elements according to claim 1, wherein the amine-based compound having an amino group equivalent weight of 30 or less is at least any one of hydrazine and hydrazide. The sealant for liquid crystal display elements according to claim 1 or 2, wherein the adduct of an amine compound having an amine group equivalent weight of 30 or less and an epoxy compound is solid at 25°C. The sealing compound for liquid crystal display elements of claim 1, 2, or 3 whose said epoxy compound is an epoxy compound which has a structure derived from the compound which has a phenolic hydroxyl group. A liquid crystal display element having a cured product of the sealant for liquid crystal display elements of claim 1, 2, 3 or 4.