TWI662077B - Sealant for liquid crystal display element, vertical conductive material, and liquid crystal display element - Google Patents

Abstract

An object of the present invention is to provide a sealant for a liquid crystal display element which is excellent in adhesiveness and moisture permeability prevention. Another object of the present invention is to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
The present invention is a sealant for a liquid crystal display device, which contains a curable resin, a polymerization initiator and / or a thermosetting agent, and the storage elastic modulus of the cured product at 25 ° C. is 0.8 to 3.0 GPa.

Description

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

The present invention relates to a sealant for a liquid crystal display element having excellent adhesiveness and moisture permeability prevention. The present invention also relates to a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

In recent years, as a method of manufacturing a liquid crystal display device, from the viewpoints of shortening the production time and optimizing the amount of liquid crystal used, the use of a hardening resin, light, etc. as disclosed in Patent Documents 1 and 2 has been used. A liquid crystal dropping method called a dropping method in which a photoinitiator of a polymerization initiator and a thermosetting agent is used together with a curing type sealant.

In the dropping method, first, a rectangular sealing pattern is formed by dispensing on one of two transparent substrates with electrodes. Then, in the state where the sealant is not hardened, minute droplets of liquid crystal are added to the entire frame of the transparent substrate, another transparent substrate is immediately overlapped, and the sealing portion is irradiated with light such as ultraviolet rays to perform pre-hardening. Thereafter, the liquid crystal display element is produced by heating and hardening it. The substrates are bonded under reduced pressure, so that the liquid crystal display element can be manufactured with extremely high efficiency. At present, the drop adding method has become the mainstream of the manufacturing method of the liquid crystal display element.

With the popularization of tablet terminals or mobile terminals, durability of impact tests, drop tests, etc. is gradually required for liquid crystal display elements, and adhesion to substrates is gradually required. In addition, with the narrow edge of the panel, the humidity resistance reliability in driving under high temperature and high humidity environment is required, and the sealant is further required to prevent water from penetrating from the outside. In order to improve the impact resistance and moisture resistance reliability of the liquid crystal display element, it is necessary to improve the adhesion between the sealant and the substrate, and the moisture permeability of the hardened material of the sealant is low. However, it is difficult to produce a sealant excellent in both adhesiveness and moisture permeability prevention.
[Prior technical literature]
[Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-133794 Patent Document 2: Japanese Patent Application Laid-Open No. 5-295087

[Problems to be Solved by the Invention]

The present invention relates to a sealant for a liquid crystal display element having excellent adhesiveness and moisture permeability prevention. Another object of the present invention is to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
[Technical means to solve the problem]

The present invention is a sealant for a liquid crystal display device, which contains a curable resin, a polymerization initiator and / or a thermosetting agent, and the storage elastic modulus of the cured product at 25 ° C. is 0.8 to 3.0 GPa.
The present invention is described in detail below.

The present inventors have found that by setting the storage elastic modulus of the cured product at 25 ° C to a specific range, a sealant for a liquid crystal display element having excellent adhesion and moisture permeability prevention can be obtained, and the present invention has been completed. .

Regarding the sealant for liquid crystal display elements of the present invention, the lower limit of the storage elastic modulus of the cured product at 25 ° C is 0.8 GPa, and the upper limit is 3.0 GPa. When the storage elastic modulus of the hardened | cured material at 25 degreeC is this range, the sealing compound for liquid crystal display elements of this invention becomes excellent in both adhesiveness and moisture permeability prevention. The lower limit of the storage elastic modulus of the hardened material at 25 ° C is 1.0 GPa, the upper limit is preferably 2.8 GPa, the lower limit is 1.2 GPa, and the upper limit is 2.6 GPa.
In addition, as a hardened product for measuring the storage elastic modulus at 25 ° C and the storage elastic modulus at 60 ° C described below, a 100 mW / cm ² ultraviolet ray (wavelength 365) was used for the sealant using a metal halide lamp. nm) After 30 seconds, it was heated at 120 ° C for 1 hour to harden it.
In addition, a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by IT Measurement Control Co., Ltd.) can be used for the storage elastic modulus, and the test piece has a width of 5 mm, a thickness of 0.35 mm, and a grip width at each measurement temperature. The measurement was performed under conditions of 25 mm, a heating rate of 10 ° C / min, and a frequency of 10 Hz.

Regarding the sealant for liquid crystal display elements of the present invention, the lower limit of the storage elastic modulus of the cured product at 60 ° C is preferably 0.04 GPa. When the storage elastic modulus of the hardened material at 60 ° C. is 0.04 GPa or more, the sealant for a liquid crystal display element of the present invention becomes more excellent in moisture permeability resistance. The lower limit of the storage elastic modulus of the hardened material at 60 ° C is more preferably 0.1 GPa.
Moreover, from a viewpoint of adhesiveness, the preferable upper limit of the storage elastic modulus of the said hardened | cured material at 60 degreeC is 2.5 GPa.

The sealing agent for liquid crystal display elements of this invention contains a curable resin, a polymerization initiator, and / or a thermosetting agent.
In the sealant for a liquid crystal display element of the present invention, as a method for setting the storage elastic modulus of the cured product at 25 ° C. to 0.8 to 3.0 GPa, it is preferable to use the compound contained in 1 molecule as the curable resin. A polymerizable compound having one or more polymerizable functional groups and one or more lactone ring-opening structures and / or one or more acrylonitrile-butadiene structures (hereinafter, also referred to as "polymerizable compounds (a ) "), In addition to the polymerizable compound (a), a ring-opening structure containing 1 polymerizable functional group in one molecule and no lactone and acrylonitrile-butadiene are more preferably used. A method of a monofunctional polymerizable compound having a structure (hereinafter, also referred to as "polymerizable compound (b)").

As a polymerizable functional group which the said polymerizable compound (a) has, a (meth) acryl fluorenyl group, an epoxy group, etc. are mentioned, for example. Among these, (meth) acrylfluorenyl is preferred.
In addition, in this specification, the "(meth) acrylfluorenyl" means acrylfluorenyl or methacrylfluorenyl.
The polymerizable compound (a) is preferably a polyfunctional polymerizable compound having two or more of the polymerizable functional groups in one molecule.

When the polymerizable compound (a) has a ring-opening structure of a lactone, examples of the lactone include γ-undecanolactone, ε-caprolactone, γ-decanolactone, and σ- Dodecanolactone, γ-nonalactone, γ-nonanolactone, γ-valerolactone, σ-valerolactone, β-butyrolactone, γ-butyrolactone Esters, β-propiolactone, σ-caprolactone, 7-butyl-2-oxetanone, and the like. Among them, the number of carbon atoms in the linear portion of the main skeleton at the time of ring opening is preferably 5 to 7, and more preferably ε-caprolactone. The polymerizable compound (a) may have a ring-opening structure of one type of lactone, or may have a ring-opening structure of two or more types of lactone.

In the case where the polymerizable compound (a) has a ring-opening structure of a lactone, the ring-opening structure of the lactone may be only one kind in one molecule, or may have a repeating structure. When the ring-opening structure of the lactone becomes a repeating structure, a preferable upper limit of the repeating number is 5.

The preferable lower limit of the molecular weight of the polymerizable compound (a) is 800, and the preferable upper limit is 4,000. When the molecular weight of the polymerizable compound (a) is within this range, the obtained sealant for a liquid crystal display element becomes more excellent in flexibility and moisture permeability prevention. A more preferable upper limit of the molecular weight of the polymerizable compound (a) is 2,000.
In addition, in the present specification, the "molecular weight" is a molecular weight determined from a structural formula for a compound having a specific molecular structure, but for a compound having a wide distribution of polymerization degree and a compound having a non-specific modification site. In some cases, the weight average molecular weight is used. The "weight-average molecular weight" is a value measured by gel permeation chromatography (GPC) and calculated by polystyrene conversion. Examples of the column used when measuring the weight-average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).

Among the polymerizable compounds (a), those having a ring-opening structure of a lactone are preferably those obtained by introducing a ring-opening structure of a lactone into the skeleton of the epoxy (meth) acrylate described below. Examples of the ring-opening structure of a lactone introduced into the skeleton of the epoxy (meth) acrylate include a compound represented by the following formula (1).

In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a group represented by the following formula (2-1) or (2-2), R ³ represents a structure derived from an acid anhydride, and R ⁴ represents a source From the structure of the epoxy compound, X represents a ring-opening structure of lactone, n represents an integer of 1 to 5, and a represents an integer of 1 to 4.

In formula (2-2), b represents an integer from 0 to 8, c represents an integer from 0 to 3, d represents an integer from 0 to 8, e represents an integer from 0 to 8, and any of b, c, and d It is 1 or more.

Specific examples of the polymerizable compound (a) include caprolactone modified bisphenol A type epoxy (meth) acrylate, and terminal carboxyl group-containing polybutadiene-acrylonitrile (CTBN) modified. Epoxy (meth) acrylate, ethylene glycol modified A-type epoxy (meth) acrylate, etc. The polymerizable compound (a) may be used alone or in combination of two or more kinds.

A preferable lower limit of the content of the polymerizable compound (a) in 100 parts by weight of the entire curable resin is 5 parts by weight, and a preferable upper limit is 80 parts by weight. When the content of the polymerizable compound (a) is within this range, it is easy to set the storage elastic modulus of the cured product at 25 ° C to the above range. A more preferable lower limit of the content of the polymerizable compound (a) is 10 parts by weight, and a more preferable upper limit is 60 parts by weight.

Examples of the polymerizable functional group included in the polymerizable compound (b) include the same as the polymerizable compound (a), and a (meth) acrylfluorenyl group is preferred.

From the viewpoint of suppressing liquid crystal contamination, the polymerizable compound (b) preferably has a hydrogen-bonding functional group.
Examples of the hydrogen-bonding functional group include -OH group, -NH ₂ group, -NHR group (R represents aromatic or aliphatic hydrocarbon and derivatives thereof), -COOH group, -CONH ₂ group Functional groups such as, -NHOH groups; or -NHCO-bonds, -NH-bonds, -CONHCO-bonds, -NH-NH-bonds, etc. present in the molecule. Among these, an -OH group is preferred.

The preferable lower limit of the molecular weight of the polymerizable compound (b) is 100, and the preferable upper limit is 2,000. When the molecular weight of the polymerizable compound (b) is 100 or more, it is difficult to elute into the liquid crystal. When the molecular weight of the said polymerizable compound (b) is 2000 or less, the sealing compound for liquid crystal display elements obtained will become more excellent in coating property. A more preferable lower limit of the molecular weight of the polymerizable compound (b) is 150, and a more preferable upper limit is 1,000.

Specific examples of the polymerizable compound (b) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like. 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloxyethyl succinate, hexahydrophthalic acid 2- (meth) acryloxyethyl ester, 2-(((butylamino) carbonyl) oxy) ethyl (meth) acrylate, aliphatic epoxy (meth) acrylate (eg, EBECRYL112 ( Daicel-Allnex company)), caprolactone (meth) acrylate (for example, SR495 (manufactured by Sadobo)), polypropylene glycol mono (meth) acrylate (for example, SR604 (manufactured by Sadoman)), Caprolactone modified (meth) acrylate (eg KUA-C2I (manufactured by KSM)), Polycarbonate modified (meth) acrylate (eg KUA-PC2I (made by KSM)), polyether Modified (meth) acrylic acid amine esters (such as KUA-PEA2I, KUA-PEB2I, KUA-PEC2I (all manufactured by KSM)), β-carboxyethyl (meth) acrylate (such as β-CEA (Daicel-Allnex (Manufactured by the company)), carboxy (meth) acrylate (eg, EBECRYL770 (manufactured by Daicel-Allnex)), methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (formaldehyde) N-butyl acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, (methyl) ) Isooctyl acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, and stearyl (meth) acrylate , Cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate , 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (methyl) Acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, (meth) acrylic acid Tetrahydrofurfuryl ester, ethyl carbitol ( (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H- (meth) acrylate Octafluoropentyl ester, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like. Among these, a monofunctional epoxy (meth) acrylate is preferable, and 2-hydroxy-3-phenoxypropyl (meth) acrylate is more preferable. The polymerizable compound (b) may be used alone or in combination of two or more kinds.
In addition, in the present specification, the "(meth) acrylate" means acrylate or methacrylate, and the "epoxy (meth) acrylate" means that all epoxy groups in the epoxy compound and (Meth) acrylic acid is a compound obtained by reaction.

The monofunctional epoxy (meth) acrylate is obtained by reacting a monofunctional epoxy compound with (meth) acrylic acid or the like, and has a structure derived from the monofunctional epoxy compound, and Structure of the (meth) acrylic acid.
Examples of the monofunctional epoxy compound include butyl glycidyl ether (eg, DY-BP (manufactured by Yokkaichi Kasei Co., Ltd.)) and 2-ethylhexyl glycidyl ether (eg, Epogsey 2EH (manufactured by Yokkaichi Kasei Co., Ltd.). )), Allyl glycidyl ether (eg EX-101 (manufactured by Nagase Chemical Co., Ltd.)), 2-ethylhexyl glycidyl ether (eg, EX-121 (Made by Nagase Chemical Co., Ltd.)), EO modification Phenyl glycidyl ether (such as EX-145 (manufactured by Nagase Kasei Co., Ltd.)), EO modified lauryl glycidyl ether (such as EX-171 (manufactured by Nagase Kasei Co., Ltd.)), phenyl glycidyl ether (such as EX-141 (manufactured by Nagase Chemical Co., Ltd.), p-third butyl phenyl glycidyl ether (eg, EX-146 (manufactured by Nagase Chemical Co., Ltd.)), dibromophenylglycidyl ether (eg, EX-147 (Manufactured by Nagase Kasei Corporation)) and so on.
Moreover, as a marketer among the said monofunctional epoxy (meth) acrylate, Epoxy Ester M-600A (made by Kyoeisha Chemical Co., Ltd.) etc. are mentioned, for example.

A preferable lower limit of the content of the polymerizable compound (b) in 100 parts by weight of the entire curable resin is 1 part by weight, and a preferable upper limit is 30 parts by weight. When the content of the polymerizable compound (b) is within this range, the storage elastic modulus of the cured product at 25 ° C. is easily within the above range. A more preferable lower limit of the content of the polymerizable compound (b) is 5 parts by weight, and a more preferable upper limit is 25 parts by weight.

The sealant for a liquid crystal display element of the present invention is preferably the curable resin, and contains a (meth) acrylfluorenyl group and an epoxy group in addition to the polymerizable compound (a) and the polymerizable compound (b). Polymerizable compound (hereinafter, also referred to as "polymerizable compound (c)"). By containing the said polymerizable compound (c), the sealing compound for liquid crystal display elements of this invention becomes a thing with more excellent adhesiveness.

Examples of the polymerizable compound (c) include a partial (meth) acrylic acid obtained by reacting an epoxy group of a part of an epoxy compound having two or more epoxy groups with (meth) acrylic acid. Modified epoxy resin, etc. In addition, in this specification, the "(meth) acrylic acid" means acrylic acid or methacrylic acid.

Examples of the epoxy compound used as a raw material of the polymerizable compound (c) include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, and 2,2′-di Allyl bisphenol A type epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide addition bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl 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, dicyclopentyl Diene novolac type epoxy compound, biphenol novolac type epoxy compound, naphthol novolac type epoxy compound, epoxy amine type epoxy compound, alkyl polyol type epoxy compound, rubber modified epoxy Compounds, propylene oxide compounds, and the like.

As a commercially available one among the said polymerizable compound (c), KRM8287 (made by Daicel-Allnex company) is mentioned, for example.

The content of the polymerizable compound (c) is preferably 5 parts by weight with respect to 100 parts by weight of the entire curable resin, and the preferred upper limit is 50 parts by weight. When the content of the polymerizable compound (c) is within this range, the effect of suppressing the occurrence of liquid crystal contamination and improving the adhesion can be further exerted. A more preferable lower limit of the content of the polymerizable compound (c) is 10 parts by weight, and a more preferable upper limit is 40 parts by weight.

The sealant for liquid crystal display elements of this invention may contain another polymerizable compound as a polymerizable compound within the range which does not inhibit the objective of this invention.

The other polymerizable compound is a polymerizable compound other than the polymerizable compound (a), the polymerizable compound (b), and the polymerizable compound (c), and examples thereof include polyfunctional (meth) acrylic compounds or Polyfunctional epoxy compounds and the like.

Examples of the polyfunctional (meth) acrylic compound as the other polymerizable compound include a polyfunctional (meth) acrylate compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid; A polyfunctional epoxy (meth) acrylate obtained by reacting (meth) acrylic acid with an epoxy compound; a polyfunctional (formaldehyde) obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound Group) amine acrylate and the like.

Examples of the bifunctional ones in the above-mentioned polyfunctional (meth) acrylate compounds include those having no ring-opening structure and acrylonitrile-butadiene structure of lactone, and examples thereof include 1,3-butanediol di ( (Meth) acrylates, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate , 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide 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 Alkyl Modified Isocyanuric Acid Di (meth) acrylate, (Meth) propylene 2-hydroxy-3- (meth) acrylic acid oxypropyl ester, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (methyl) Acrylate, polybutadiene glycol di (meth) acrylate, and the like.

In addition, examples of the trifunctional or higher functional group in the polyfunctional (meth) acrylate compound include those having no lactone ring-opening structure and acrylonitrile-butadiene structure, and examples thereof include trimethylolpropanetri (Meth) acrylate, ethylene oxide addition trimethylolpropane tri (meth) acrylate, propylene oxide addition trimethylolpropane tri (meth) acrylate, ethylene oxide addition Tris (meth) acrylate isocyanurate, tris (meth) acrylate, glycerol tris (meth) acrylate, propylene oxide addition glycerin tris (meth) acrylate, neopentaerythritol tris (meth) acrylate, phosphate tris (Meth) acrylic acid ethyl ethoxylate, di-trimethylolpropane tetra (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate and the like.

Examples of the polyfunctional epoxy (meth) acrylate include a ring-opening structure or an acrylonitrile-butadiene structure having no lactone and having more than two functions. Those obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of a vehicle.

Examples of the epoxy compound used as a raw material for synthesizing the above-mentioned polyfunctional epoxy (meth) acrylate include the same epoxy compounds as raw materials for the polymerizable compound (c).

As the polyfunctional (meth) acrylic acid amine ester, for example, a (meth) acrylic acid derivative having a hydroxyl group can be made by 1 equivalent to an isocyanate compound having two isocyanate groups in the presence of a tin-based compound due to a catalyst amount. It is obtained by reacting 2 equivalents.

Examples of the isocyanate compound used as a raw material of the polyfunctional (meth) acrylic acid amine ester include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate. Isocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, methylene Aniline diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) phosphorothioate, tetramethylxylylene dimethionate Isocyanate, 1,6,11-undecane triisocyanate, etc.

Moreover, as an isocyanate compound which becomes a raw material of the said polyfunctional (meth) acrylic acid amine ester, for example, ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylolpropane, carbonate diol, and polyether can be used. A chain-extended isocyanate compound obtained by reacting a polyhydric alcohol such as a diol and a polyester diol with an excessive amount of an isocyanate compound.

Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material of the polyfunctional (meth) acrylic acid amine ester include, for example, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Ester, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc .; or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4- Mono (meth) acrylates of diols such as butanediol and polyethylene glycol; or mono (meth) acrylates or diols of triols such as trimethylolethane, trimethylolpropane, and glycerol (Meth) acrylate; or epoxy (meth) acrylate such as bisphenol A epoxy (meth) acrylate.

Examples of the polyfunctional epoxy compound as the other polymerizable compound include the same epoxy compounds as the raw material of the polymerizable compound (c).

The sealing agent for liquid crystal display elements of this invention contains a polymerization initiator and / or a thermosetting agent.
Examples of the polymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.

Examples of the radical polymerization initiator include a thermal radical polymerization initiator that generates radicals by heating; a photo radical polymerization initiator that generates radicals by light irradiation; and the like.

Examples of the photo-radical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, fluorenylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin-ether-based compounds, and the like. 9-Oxanthkou Yamaguchi magnitude.

Examples of commercially available photoradical polymerization initiators include: IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucirin TPO (all BASF companies) Manufacturing); benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

Examples of the thermal radical polymerization initiator include an azo compound, an organic peroxide, and the like. Among them, a polymer azo initiator composed of a polymer azo compound is preferable.
In addition, in the present specification, the polymer azo initiator means a compound having an azo group and generating a number-average molecular weight of a radical capable of hardening (meth) acryloxy group by heat to 300 or more. .

A preferable lower limit of the number average molecular weight of the polymer azo initiator is 1,000, and a preferable upper limit is 300,000. When the number average molecular weight of the above-mentioned polymer azo initiator is within this range, it is possible to prevent adverse effects on the liquid crystal and to easily mix into the curable resin. A more preferable lower limit of the number average molecular weight of the above-mentioned polymer azo initiator is 5000, a more preferable upper limit is 100,000, a more preferable lower limit is 10,000, and a more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value measured by gel permeation chromatography (GPC), and calculated | required by polystyrene conversion. Examples of the column for measuring the number average molecular weight based on polystyrene conversion by GPC include Shodex LF-804 (manufactured by Showa Denko).

Examples of the polymer azo initiator include a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group.
As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group, those having a polyethylene oxide structure are preferred. Examples of such a polymer azo initiator include a polycondensate of 4,4'-azobis (4-cyanovaleric acid) and a polyalkylene glycol, or 4,4'-azo Polycondensates of bis (4-cyanovaleric acid) and polydimethylsiloxane having a terminal amine group, and specific examples thereof include VPE-0201, VPE-0401, VPE-0601, and VPS-0501. , VPS-1001 (both manufactured by Wako Pure Chemical Industries).
Examples of the azo compound that is not a polymer include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).

Examples of the organic peroxide include ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, peroxyester, difluorenyl peroxide, and peroxydicarbonate.

As the above-mentioned cationic polymerization initiator, a photocationic polymerization initiator can be preferably used. The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generation type or a nonionic photoacid generation type.
Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halide salts, and aromatic sulfonium salts; iron-propadiene complexes and titanocene complexes , Organometallic complexes such as arylsilanol-aluminum complexes, etc.

Examples of commercially available photocationic polymerization initiators include Adeka Optomer SP-150 and Adeka Optomer SP-170 (both manufactured by ADEKA).

Content of the said polymerization initiator is 100 weight part with respect to the whole curable resin, Preferably a minimum is 0.1 weight part, and a preferable upper limit is 30 weight part. When the content of the polymerization initiator is 0.1 part by weight or more, the obtained sealing agent for a liquid crystal display element becomes more excellent in hardenability. When the content of the above-mentioned polymerization initiator is 30 parts by weight or less, the obtained sealing agent for a liquid crystal display element becomes more excellent in storage stability. The more preferable lower limit of the content of the polymerization initiator is 1 part by weight, the more preferable upper limit is 10 parts by weight, and the more preferable upper limit is 5 parts by weight.

Examples of the thermosetting agent include organic acid hydrazine, imidazole derivatives, amine compounds, polyphenol compounds, and acid anhydrides. Among them, solid organic hydrazine is preferably used.

Examples of the solid organic acid hydrazine include 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin, dihydrazine sebacate, and dihydrazine isophthalate. , Dihydrazine adipate, dihydrazine malonate, etc., as the marketers, for example: SDH, MDH, ADH (manufactured by Otsuka Chemical Co., Ltd.); Amicure VDH, Amicure VDH-J, Amicure UDH (both are Ajinomoto Fine-Techno).

Content of the said thermosetting agent is 100 weight part with respect to the whole curable resin, Preferably a minimum is 1 weight part, and a preferable upper limit is 50 weight part. When the content of the above-mentioned thermosetting agent is 1 part by weight or more, the obtained sealing agent for a liquid crystal display element becomes one having more excellent thermosetting properties. When the content of the above-mentioned thermosetting agent is 50 parts by weight or less, the obtained sealant for a liquid crystal display element becomes more excellent in coatability. A more preferable upper limit of the content of the heat curing agent is 30 parts by weight.

The sealing agent for liquid crystal display elements of the present invention preferably contains soft particles. The soft particles are used as barriers between other sealant components and the liquid crystal when manufacturing a liquid crystal display element, and have the function of preventing liquid crystal from penetrating into the sealant and the sealant from eluting into the liquid crystal.

The soft particles preferably have a maximum particle diameter of 100% or more of the cell gap of the liquid crystal display element, and are 5 to 20 μm. The soft particles have a maximum particle size of 100% or more of the cell gap, which may cause rebound. However, by setting the maximum particle size of the soft particles to 20 μm or less, the gap caused by springback may not be caused. Defective, and a liquid crystal display element was produced.
In addition, the cell gap of a liquid crystal display element is not limited because it varies with display elements, but the cell gap of a general liquid crystal display element is 2 to 10 μm.

The lower limit of the maximum particle diameter of the soft particles is preferably 100% of the cell gap of the liquid crystal display element, and is 5 μm. That is, when the cell gap of the liquid crystal display element is 5 μm or less, the preferable lower limit of the maximum particle size of the soft particles is 5 μm. When the cell gap of the liquid crystal display element exceeds 5 μm, the The lower limit of the maximum particle diameter is preferably 100% of the cell gap of the liquid crystal display element. The maximum particle diameter of the soft particles is 5 μm and is equal to or higher than the above-mentioned preferable lower limit value of 100% of the cell gap of the liquid crystal display element, so that the effect of suppressing sealing interruption or liquid crystal contamination is more excellent.
In addition, from the viewpoint of suppressing a decrease in adhesiveness due to rebound or a defective gap in the liquid crystal display element, a preferable upper limit of the maximum particle diameter of the soft particles is 20 μm. A more preferable upper limit of the maximum particle diameter of the soft particles is 15 μm. Furthermore, from the viewpoint of suppressing a decrease in adhesiveness due to rebound or poor gaps in the liquid crystal display element, the maximum particle diameter of the soft particles is preferably 2.6 times or less the cell gap. The more preferable upper limit of the maximum particle diameter of the soft particles is 2.2 times the unit gap, and the more preferable upper limit is 1.7 times the unit gap.
In addition, in this specification, the maximum particle diameter and the following average particle diameter of the above-mentioned soft particles mean that the particles before being incorporated in the sealant are measured by using a laser diffraction particle size distribution measuring device. Value. As the above-mentioned laser diffraction type distribution measuring device, Mastersizer 2000 (manufactured by Malvern) can be used.

It is preferable that the content ratio of the particles having a particle diameter of 5 μm or more in the particle size distribution of the soft particles measured by the laser diffraction type distribution measuring device is 60% or more by volume frequency. Since the content ratio of particles having a particle diameter of 5 μm or more is 60% or more in terms of volume frequency, the effect of suppressing sealing interruption or liquid crystal contamination is more excellent. The content ratio of particles having a particle diameter of 5 μm or more is more preferably 80% or more.

From the viewpoint of further exerting the effect of suppressing the interruption of the seal or the liquid crystal contamination, it is preferable that the above-mentioned soft particles contain particles having a particle size distribution of 70% or more in the entire soft particles and 100% or more of the cell gap of the liquid crystal display element. More preferably, it is composed only of particles having a cell gap of 100% or more of the liquid crystal display element.

A preferable lower limit of the average particle diameter of the soft particles is 2 μm. When the average particle diameter of the soft particles is 2 μm or more, the effect of suppressing sealing interruption or liquid crystal contamination is more excellent. A more preferable lower limit of the average particle diameter of the soft particles is 4 μm.
Moreover, from a viewpoint of suppressing the fall of the adhesiveness by a rebound, or a gap defect of a liquid crystal display element, the preferable upper limit of the average particle diameter of the said soft particle is 15 micrometers. A more preferable upper limit of the average particle diameter of the soft particles is 12 μm.

As the soft particles, two or more kinds of soft particles having different maximum particle diameters may be used in combination. That is, soft particles having a maximum particle diameter of less than 100% of the cell gap of the liquid crystal display element and soft particles having a maximum particle diameter of 100% or more of the cell gap of the liquid crystal display element can be mixed and used.

From the viewpoint of suppressing defective cell gaps, the coefficient of variation (hereinafter, also referred to as the CV value) of the particle diameter of the soft particles is preferably 30% or less. The CV value of the particle size of the soft particles is more preferably 28% or less.
In addition, in this specification, the CV value of a particle diameter is a value calculated | required from the following formula.
CV of particle size (%) = (standard deviation of particle size / average particle size) × 100

Regarding the soft particles, even if the maximum particle diameter, the average particle diameter, or the CV value is outside the above range, the maximum particle diameter, the average particle diameter, or the CV value can be brought into the above range by classification. In addition, soft particles having a particle diameter of less than 100% of the cell gap of the liquid crystal display element do not contribute to the suppression of the interruption of the seal or the generation of liquid crystal contamination. If blended in the sealant, the thixotropic value may increase, so It is preferably removed by classification.
Examples of a method for classifying the soft particles include methods such as wet classification and dry classification. Among them, wet classification is preferred, and wet sieve classification is more preferred.

Examples of the soft particles include polysiloxane-based particles, vinyl-based particles, urethane-based particles, fluorine-based particles, and nitrile-based particles. Among these, polysiloxane particles and vinyl particles are preferred.

From the viewpoint of dispersibility in a resin, the polysiloxane particles are preferably polysiloxane rubber particles.
As a marketer of the above-mentioned polysiloxane particles, for example, KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (made by Shin-Etsu Chemical Industry Co., Ltd.); Torayfil E -506S, EP-9215 (manufactured by Toray Dow Corning), etc., can be classified and used. These polysiloxane particles may be used alone or in combination of two or more.

As the vinyl-based particles, (meth) acrylic particles are preferably used. The (meth) acrylic particles can be obtained by polymerizing a monomer serving as a raw material by a known method. Specifically, for example, a method of suspension polymerization of a monomer in the presence of a radical polymerization initiator; a method of causing monomers to be absorbed by non-crosslinked particles in the presence of a radical polymerization initiator, thereby Method for seed swelling and polymerization of seeds.

Examples of the monomer used as a raw material for forming the (meth) acrylic particles include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) Butyl acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, ( (Meth) acrylic acid alkyl esters such as stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isoamyl (meth) acrylate; or 2-hydroxyethyl (meth) acrylate, glycerol ( (Meth) acrylates, polyoxyethylene (meth) acrylates, glycidyl (meth) acrylates and other oxygen-containing (meth) acrylates; or nitrile-containing monomers such as (meth) acrylonitrile; Or monofunctional monomers such as fluorine-containing (meth) acrylates such as trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate. Among them, alkyl (meth) acrylates are preferred because the homopolymer has a low Tg and a large amount of deformation when a load of 1 g is applied.

In order to have a crosslinked structure, tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, and tetramethylolmethane di (meth) acrylate can be used. , Trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dinepentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol Di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene di (meth) acrylate, 1 Multifunctional monomers such as 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and isotricyanic acid skeleton tri (meth) acrylate. Among these, (poly) ethylene glycol di (meth) acrylate and (poly) propylene glycol di are preferred in terms of a large molecular weight between crosslinking points and a large amount of deformation when a load of 1 g is applied. (Meth) acrylate, (poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylic acid ester.

The amount of the crosslinkable monomer used is preferably 1% by weight, and the preferable upper limit is 90% by weight in the entire monomer that becomes the raw material for forming the (meth) acrylic particles. When the amount of the crosslinkable monomer used is 1% by weight or more, the solvent resistance is improved, and problems such as swelling and the like are not caused when kneaded with various sealant raw materials, and it is easy to uniformly disperse. By using the above-mentioned crosslinkable monomer in an amount of 90% by weight or less, the recovery rate can be lowered, and problems such as springback are not easily caused. A more preferable lower limit of the amount of the crosslinkable monomer used is 3% by weight, and a more preferable upper limit is 80% by weight.

Furthermore, in addition to these acrylic monomers, styrene monomers such as styrene and α-methylstyrene; or vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether can also be used. ; Or vinyl acid esters such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate; or unsaturated hydrocarbons such as ethylene, propylene, isoprene, butadiene; or vinyl chloride, fluorine Halogen-containing monomers such as ethylene and chlorostyrene; or triallyl isocyanurate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl propylene Monomers such as amines, diallyl ethers, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, and vinyltrimethoxysilane.

As the vinyl-based particles, for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles, and the like can be used.

Examples of commercially available amine ester-based particles include, for example, Art-pearl (manufactured by Negami Industry Co., Ltd.), Daimicbeaz (manufactured by Daihichi Chemical Co., Ltd.), and the like can be classified and used.

From a viewpoint of suppressing the fall of the adhesiveness of the sealing compound for liquid crystal display elements obtained, or the gap of the obtained liquid crystal display element being poor, the preferable lower limit of the hardness of the said soft particle is 10, and a preferable upper limit is 50. The lower limit of the hardness of the soft particles is more preferably 20, and the upper limit of the hardness is 40.
In addition, in this specification, the hardness of the said soft particle means the hardness of the A-type durometer measured by the method based on JISK 6253.

The preferable lower limit of the content of the soft particles is 15% by weight based on the entire sealant for a liquid crystal display element. When the content of the soft particles is 15% by weight or more, the effect of suppressing the interruption of sealing or the occurrence of liquid crystal contamination is more excellent. A more preferable lower limit of the content of the soft particles is 20% by weight. In addition, from the viewpoint of suppressing a decrease in adhesiveness due to rebound or poor gaps in the liquid crystal display element, the preferable upper limit of the content of the soft particles is 50% by weight based on the entire sealant for the liquid crystal display element. A more preferable upper limit of the content of the soft particles is 40% by weight.

The sealant for liquid crystal display elements of the present invention preferably contains a filler for the purpose of improving viscosity, further improving adhesion based on stress dispersion effect, improving linear expansion ratio, and improving moisture resistance of hardened materials. .

Examples of the filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated white clay, alumina, zinc oxide, Inorganic fillers such as iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate; or polyester fine particles, Organic fillers such as polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.

Content of the said filler is 100 weight part with respect to the whole curable resin, Preferably a minimum is 10 weight part, and a preferable upper limit is 70 weight part. When the content of the filler is within this range, effects such as suppressing deterioration in coatability and improving adhesion can be further exerted. A more preferable lower limit of the content of the filler is 20 parts by weight, and a more preferable upper limit is 60 parts by weight.

In order to further improve the adhesiveness, the sealing agent for a liquid crystal display element of the present invention preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly functions as a bonding aid for adhering a sealant to a substrate and the like well.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like are preferably used.

Content of the said silane coupling agent is 100 weight part with respect to the whole curable resin, Preferably a minimum is 0.1 weight part, and a preferable upper limit is 20 weight part. When the content of the silane coupling agent is within this range, the effect of suppressing the occurrence of liquid crystal contamination and improving the adhesiveness can be further exerted. A more preferable lower limit of the content of the silane coupling agent is 0.5 part by weight, and a more preferable upper limit is 10 parts by weight.

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

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

Compared with the average transmittance of the above-mentioned titanium black to light having a wavelength of 300 to 800 nm, the material having a higher transmittance to the vicinity of the ultraviolet region, particularly to light having a wavelength of 370 to 450 nm. That is, the above-mentioned titanium black is a light-shielding agent having properties such that light-shielding properties are provided to the sealant for a liquid crystal display element of the present invention by sufficiently shielding light of wavelengths in the visible light region, and light of wavelengths near the ultraviolet region penetrate. As the light-shielding agent contained in the sealant for a liquid crystal display element of the present invention, a substance having high insulation properties is preferred, and as a light-shielding agent having high insulation properties, titanium black is also preferred.

The above-mentioned titanium black exhibits sufficient effects even if it is not subjected to a surface treatment, but the surface can also be treated with organic components such as a coupling agent, or treated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconia, and oxide. Surface-treated titanium black, such as those coated with inorganic components such as magnesium. Among them, those treated with an organic component are preferred from the viewpoint of further improving insulation properties.
In addition, the liquid crystal display element manufactured by using the sealant for liquid crystal display elements of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, so that no leakage of light can be achieved, a high contrast ratio, and excellent Liquid crystal display element with image display quality.

As the marketer of the titanium black, for example, 12S, 13M, 13M-C, 13R-N, and 14M-C (all manufactured by Mitsubishi Materials Corporation); Tilack D (manufactured by Ako Chemical Co., Ltd.) and the like.

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, a preferable lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, a preferable upper limit is 3 Ω · cm, a more preferable lower limit is 1 Ω · cm, and a more preferable upper limit is 2.5 Ω · cm.

The primary particle diameter of the above-mentioned light-shielding agent is not particularly limited as long as it is equal to or less 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 5 μm. When the primary particle diameter of the light-shielding agent is within this range, the viscosity or thixotropy of the obtained sealant for a liquid crystal display element does not increase significantly, and the coatability is more excellent. The lower limit of the primary particle diameter of the above-mentioned sunscreen is more preferably 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.
The primary particle size of the light-shielding agent can be measured using a particle size distribution meter (for example, "NICOMP 380ZLS" manufactured by PARTICLE SIZING SYSTEMS).

A preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and a preferable upper limit is 80 parts by weight. When the content of the above-mentioned light-shielding agent is within this range, the effect of improving the adhesiveness and the strength after curing of the obtained sealant for a liquid crystal display element can be further exerted, and the effect of improving the light-shielding property without reducing the drawing properties is further exerted. A more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a more preferable lower limit is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.

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

Examples of the method for producing the sealant for a liquid crystal display element of the present invention include a method using a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill. Mix additives such as a curable resin, a polymerization initiator and / or a thermosetting agent, and a silane coupling agent, if necessary.

Regarding the sealant for liquid crystal display elements of the present invention, a preferable upper limit of the glass transition temperature of the cured product is 100 ° C. When the glass transition temperature is 100 ° C. or lower, the sealant for a liquid crystal display element of the present invention is more excellent in adhesiveness. The more preferable upper limit of the glass transition temperature is 80 ° C, and the more preferable upper limit is 60 ° C.
From the viewpoint of moisture permeability prevention, the lower limit of the glass transition temperature of the hardened material is preferably 40 ° C, and the more preferable lower limit is 46 ° C.
Furthermore, in the present specification, the above-mentioned "glass transition temperature" means a temperature at which a maximum value due to micro-Brownian motion occurs among the maximum values of the loss tangent (tan δ) obtained by dynamic viscoelasticity measurement. The glass transition temperature can be measured by a conventionally known method using a viscoelasticity measuring device or the like.
Moreover, as a hardened | cured material which measures the said glass transition temperature, the thing which hardened the sealant in the same way as the hardened | cured material which measured the said storage elastic modulus was used.

The fine conductive material can be manufactured by mixing conductive fine particles in the sealant for a liquid crystal display element of the present invention. In addition, such a sealant for a liquid crystal display element of the present invention and a conductive material for upper and lower conductive particles are also one aspect of the present invention.

As the conductive fine particles, metal balls, those having a conductive metal layer formed on the surface of the resin fine particles, and the like can be used. Among them, those having a conductive metal layer formed on the surface of the resin microparticles are preferred because of the excellent elasticity of the resin microparticles so as to realize conductive connection without damaging the transparent substrate or the like.

In addition, a liquid crystal display element formed by using the sealant for liquid crystal display elements of the present invention or the upper-lower conductive material of the present invention is also one aspect of the present invention.

The sealant for liquid crystal display elements of the present invention can be preferably used for manufacturing a liquid crystal display element by a liquid crystal dropping method.
As a method for manufacturing the liquid crystal display element of the present invention by a liquid crystal dropping method, specifically, for example, a method having the following steps may be mentioned: the substrate is subjected to screen printing by a screen printing method, a dispenser application, or the like. The sealant and the like for the display element are formed into a rectangular seal pattern. In the uncured state of the sealant and the like for the liquid crystal display element of the present invention, minute droplets of the liquid crystal are applied dropwise to the entire frame of the transparent substrate, and overlapped immediately. A substrate; irradiating light such as ultraviolet rays to a sealing pattern portion of the sealant for a liquid crystal display element of the present invention to pre-harden the sealant; and heating the pre-cured sealant to formally harden the sealant.

The substrate is preferably a flexible substrate.
Examples of the flexible substrate include plastic substrates using polyethylene terephthalate, polyester, poly (meth) acrylate, polycarbonate, polyether, or the like. Moreover, the sealing compound for liquid crystal display elements of this invention can also be used when adhering a normal glass substrate.
On the above substrate, a transparent electrode made of indium oxide or the like, an alignment film made of polyimide or the like, an inorganic ion shielding film, etc. are usually formed.
[Effect of the invention]

According to the present invention, it is possible to provide a sealant for a liquid crystal display element having excellent adhesion and moisture permeability prevention. Furthermore, according to the present invention, it is possible to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

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

(Example 1)
A planetary mixer (manufactured by Thinky, "Defoaming Stir Taro") will be used as the polymerizable compound (a) to modify the bisphenol A epoxy acrylate (produced by Daicel-Allnex, "EBECRYL 3708") 75 10 parts by weight of 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., "Epoxy Ester M-600A") as a polymerizable compound (c) Part of acrylic modified bisphenol E-type epoxy resin (made by Daicel-Allnex, "KRM8287") 15 parts by weight, 1- (4- (phenylthio) phenyl)-as photoradical polymerization initiator 1,2-octanedione-2- (O-benzylidene oxime) (manufactured by BASF, "IRGACURE OXE01"), 1 part by weight of dihydrazine malonate (manufactured by Otsuka Chemical Co., Ltd., "MDH") 1 part by weight, 50 parts by weight of silicon dioxide (manufactured by Admatechs, "Admafine SO-C2") as a filler, 3-glycidoxypropyltrimethoxysilane as a silane coupling agent ( 1 part by weight of "KBM-403" manufactured by Shin-Etsu Chemical Industry Co., Ltd. and used as a stress relief agent Shell acrylate copolymer fine particles (Zeon Kasei Corporation, "F351") After mixing 10 parts by weight, further using a three-roll mill and mixed, thereby preparing a liquid crystal display element with a sealant.
The obtained sealant for a liquid crystal display element was a hardened product obtained by irradiating an ultraviolet ray (wavelength 365 nm) of 100 mW / cm ² with a metal halide lamp for 30 seconds, and then heating it at 120 ° C. for 1 hour. Using a dynamic viscoelasticity measuring device ("DVA-200" manufactured by IT Measurement Control Co., Ltd.) at 25 ° C, at a test strip width of 5 mm, a thickness of 0.35 mm, a grip width of 25 mm, a heating rate of 10 ° C / min, and a frequency of 10 The storage elastic modulus measured under the condition of Hz was 1.0 GPa, and the storage elastic modulus measured under the same condition at 60 ° C was 0.04 GPa.

(Examples 2 to 10 and Comparative Examples 1 and 2)
The materials for the blending ratios described in Table 1 were stirred and mixed in the same manner as in Example 1 to prepare the sealants for liquid crystal display elements of Examples 2 to 10 and Comparative Examples 1 and 2.
A cured product was prepared for each of the obtained sealants for liquid crystal display elements in the same manner as in Example 1. The obtained cured products were measured at 25 ° C and 60 ° C in the same manner as in Example 1. The storage elastic modulus is shown in Table 1.

＜ Evaluation ＞
The following evaluations were performed about each sealing agent for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Table 1.

(Glass transition temperature)
Each of the sealants for liquid crystal display elements obtained in the examples and comparative examples was irradiated with 100 mW / cm ² of ultraviolet rays (wavelength 365 nm) for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to produce a thickness of 300 μm. The film is used as a test piece. The obtained test piece was measured for dynamic viscoelasticity at a temperature of -80 ° C to 200 ° C and 10 Hz using a dynamic viscoelasticity measuring device ("DVA-200" manufactured by IT Measurement Control Co., Ltd.) to obtain a loss tangent ( The temperature of the maximum value of tan δ) is taken as the glass transition temperature.

(Adherence)
A small amount of each of the obtained sealants for liquid crystal display elements obtained in Examples and Comparative Examples was placed on a 20 mm x 50 mm polyethylene terephthalate (PET) film (manufactured by Lindec, " PET5011 ") is superposed on the central portion of PET5011, and the sealant for liquid crystal display elements is spread. In this state, a metal halide lamp was irradiated with 100 mW / cm ² of ultraviolet rays (wavelength 365 nm) for 30 seconds, and then heated at 120 ° C. for 1 hour to prepare a subsequent test piece. The adhesion strength of the obtained test piece was measured using EZgraph (manufactured by Shimadzu Corporation). Further, a glass substrate was used instead of PET5011, and a test piece was produced in the same manner, and the adhesion strength was measured.
Set the bonding strength to 1 N / cm or more as "○", set the bonding strength to 0.5 N / cm or more and less than 1 N / cm to "△", and set the bonding strength to less than 0.5 N / cm. The evaluation was “×”, and the adhesion to the PET film was evaluated.

(Anti-moisture permeability)
Each of the liquid crystal display element sealants obtained in the examples and comparative examples was applied in a smooth release film form with a coater to a thickness of 200 to 300 μm, and irradiated with a metal halide lamp at 100 mW / cm ² After 30 seconds of ultraviolet light (wavelength 365 nm), it was heated at 120 ° C for 1 hour, thereby obtaining a cured film for measuring moisture permeability. The moisture permeability test cup was produced by the method of moisture permeability test method (cup method) according to JIS Z 0208, and the obtained hardened film for moisture permeability measurement was installed, and the temperature was set to 60 ° C and humidity 90%. RH was measured in a constant temperature and humidity oven. The case where the obtained moisture permeability value is less than 70 g / m ² · 24 hr is set to "○", and the case where the value of the obtained moisture permeability is 70 g / m ² · 24 hr or more and less than 100 g / m ² · 24 hr is set. It was "△", and the case where it was 100 g / m ² · 24 hr or more was "×", and the moisture permeability prevention was evaluated.

(Low liquid crystal pollution)
1 part by weight of spacer particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each of the sealants for liquid crystal display elements obtained in the examples and comparative examples, and two sheets were rubbed. One of the alignment film and the substrate of the transparent electrode (length 75 mm, width 75 mm, thickness 0.7 mm) is applied by a dispenser with a line width of 1 mm so that the display portion becomes 45 mm × 55 mm .
Then, a small drop of liquid crystal (manufactured by Chisso, "JC-5004LA") was added dropwise to the entire frame of the sealant coated on the substrate with a transparent electrode, and another color filter substrate with a transparent electrode was immediately bonded. Using a metal halide lamp, the sealant portion was irradiated with 100 mW / cm ² of ultraviolet light (wavelength 365 nm) for 30 seconds, and then heated at 120 ° C. for 1 hour to obtain a liquid crystal display element.
After the obtained liquid crystal display device was subjected to a 100-hour operation test, visual inspection confirmed that the alignment of the liquid crystal near the sealant was disordered after the voltage was applied at 80 ° C for 1000 hours.
The alignment disorder is judged by the color unevenness of the display part. According to the degree of color unevenness, the case where there is no color unevenness at all is set to "◎", and the case where there is a slight color unevenness is set to "○". A case where there is a slight color unevenness is set to "△", and a case where there is a considerable color unevenness is set to "X", and low liquid crystal contamination is evaluated.
In addition, the liquid crystal display elements evaluated as "◎" and "○" are levels at which there is no practical problem at all, and "△" is a level that may become a problem due to the display design of the liquid crystal display element, and "×" is not a level Withstand practical levels.

(Impact resistance of liquid crystal display elements)
For each of the sealants for liquid crystal display elements obtained in the examples and comparative examples, ten (10 cell) liquid crystal display elements were produced in the same manner as in the above-mentioned "(low liquid crystal pollution)", and each liquid crystal display was performed. Drop test for components dropped from a height of 2 m. The case where no liquid crystal leakage due to peeling or cracking occurred in all cells after the drop test was set to "○", and the case where liquid crystal leakage occurred in a liquid crystal display element having one cell or more and less than five cells was set to "△", the case where liquid crystal leakage of a liquid crystal display element having 5 or more cells was set to "×", and the impact resistance of the liquid crystal display element was evaluated.

[Table 1]
Examples Comparative example 1 2 3 4 5 6 7 8 9 10 1 2 Composition (parts by weight) Hardening resin Polymerizable compound (a) Caprolactone modified bisphenol A epoxy acrylate (manufactured by Daicel-Allnex, "EBECRYL3708", weight average molecular weight 1500) 75 45 70 75 - 80 - 75 75 75 40 - CTBN modified epoxy acrylate (manufactured by Daicel-Allnex, "KRM8342", weight average molecular weight 3500) - - - - 75 - 80 - - - - - Polymerizable compound (b) 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., "Epoxy Ester M-600A", molecular weight 222) 10 30 5 - 10 - - 10 10 10 35 - 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., "Light Ester HO-A", molecular weight 116) - - - 10 - - - - - - - - Polymerizable compound (c) Partial acrylic modified bisphenol E-type epoxy resin (manufactured by Daicel-Allnex, "KRM8287") 15 15 15 15 15 20 20 15 15 15 15 15 Other polymerizable compounds Bisphenol A epoxy acrylate (manufactured by Daicel-Allnex, "EBECRYL3700") - - 10 - - - - - - - - 75 Photo radical polymerization initiator 1- (4- (phenylthio) phenyl) -1,2-octanedione-2- (O-benzylideneoxime) (manufactured by BASF, "IRGACURE OXE01") 1 1 1 1 1 1 1 1 1 1 1 1 Thermal radical polymerization initiator Polymer azo radical initiator (manufactured by Wako Pure Chemical Industries, Ltd., "VPE-0201") - - - - - - - 5 - 5 - - Heat hardener Dihydrazine malonate (manufactured by Otsuka Chemical Co., Ltd., "MDH") 1 1 1 1 1 1 1 1 1 1 1 1 Filler Silicon dioxide (manufactured by Admatechs, "Admafine SO-C2") 50 50 50 50 50 50 50 50 50 - 40 40 Silane coupling agent 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM-403") 1 1 1 1 1 1 1 1 1 1 1 1 Stress relieving agent Core-shell acrylate copolymer particles (manufactured by Zeon Kasei, "F351") 10 10 10 10 10 10 10 10 10 10 10 10 Soft particles Silicone rubber particles (manufactured by Shin-Etsu Chemical Co., Ltd., "KMP-601") - - - - - - - - 30 - - - Sunscreen Titanium black (manufactured by Mitsubishi Materials Corporation, "14M-C") - - - - - - - - - 50 - - Storage modulus of hardened material at 25 ° C (GPa) 1.0 0.8 3.0 1.1 0.8 2.0 0.9 0.9 0.9 0.8 0.5 4.0 Storage modulus of hardened material at 60 ℃ (GPa) 0.04 0.04 0.6 0.05 0.04 0.1 0.04 0.04 0.04 0.04 0.02 2.5 Evaluation Glass transition temperature (℃) 45 40 75 46 42 80 41 43 41 40 30 120 Continuity ○ ○ △ ○ ○ △ △ ○ ○ ○ ○ X Moisture permeability ○ △ ○ ○ ○ ○ ○ ○ ○ △ X ○ Low liquid crystal pollution ◎ ○ ○ ◎ ◎ ○ ○ ◎ ◎ ◎ X X Impact resistance of liquid crystal display elements ○ ○ △ ○ ○ ○ ○ ○ ○ ○ ○ X

[Industrial availability]

According to the present invention, it is possible to provide a sealant for a liquid crystal display element having excellent adhesion and moisture permeability prevention. Furthermore, according to the present invention, it is possible to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

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Claims (8)

A sealant for a liquid crystal display element, which contains a curable resin, a polymerization initiator, and / or a thermosetting agent, and is characterized in that:
The storage elastic modulus of the cured product at 25 ° C is 0.8 to 3.0 GPa, and the glass transition temperature of the cured product is 46 ° C or more and less than 60 ° C. For example, the sealant for liquid crystal display elements in the scope of application for patent No. 1 has a storage elastic modulus of the cured product at 60 ° C. of 0.04 GPa or more. For example, the sealant for liquid crystal display elements in the scope of application for patents 1 or 2, wherein the curable resin contains: a ring-opening structure having one or more polymerizable functional groups and one or more lactones in one molecule and / Or a polymerizable compound having one or more acrylonitrile-butadiene structures. For example, the sealant for a liquid crystal display element according to item 3 of the patent application, wherein the curable resin contains a ring-opening structure and an acrylonitrile-butadiene structure having one polymerizable functional group in one molecule and no lactone. Of monofunctional polymerizable compounds. For example, the sealant for a liquid crystal display element in the fourth item of the patent application, wherein 100 parts by weight of the entire curable resin has a polymerizable functional group in one molecule and does not have a ring-opening structure of lactone and acrylonitrile- The content of the monofunctional polymerizable compound having a butadiene structure is 1 to 30 parts by weight. A vertical conduction material containing a sealant for liquid crystal display elements and conductive fine particles in the first or second scope of the patent application. A liquid crystal display element is formed by using a sealant for a liquid crystal display element in the scope of claims 1 or 2. The invention relates to a liquid crystal display element, which is formed by using upper and lower conducting materials in the sixth scope of the patent application.