KR20130030275A - Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element - Google Patents

Abstract

An object of this invention is to provide the light shielding sealing compound for liquid crystal display elements which is excellent in adhesive strength with respect to a board | substrate even after exposure to the environment of high temperature, high humidity. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which are manufactured using this light-shielding sealing compound for liquid crystal display elements.
The present invention provides a light-shielding sealing agent for a liquid crystal dropping method containing a curable resin containing a curable compound having an unsaturated double bond, a radical polymerization initiator, and a light shielding agent, wherein the curable resin has a hydrogen bondable functional group of 0.5 × 10 ⁻³ to It is 3.0 * 10 <^-3> mol / g, and it is a light shielding sealing compound for liquid crystal display elements containing titanium black as said light-shielding agent.

Description

LIGHT-SHIELDING SEALING AGENT FOR LIQUID CRYSTAL DISPLAY ELEMENT, TOP-TO-BOTTOM CONDUCTIVE MATERIAL, AND LIQUID CRYSTAL DISPLAY ELEMENT}

An object of this invention is to provide the light shielding sealing compound for liquid crystal display elements which is excellent in adhesive strength with respect to a board | substrate even after exposure to the environment of high temperature, high humidity. Moreover, this invention relates to the vertical conduction material and the liquid crystal display element which are manufactured using this light-shielding sealing compound for liquid crystal display elements.

Conventionally, liquid crystal display elements, such as a liquid crystal display cell, oppose the transparent substrate in which the two electrodes were formed at predetermined intervals, seal the circumference with the sealing compound, and form a cell, and liquid crystal into a cell from the liquid crystal injection hole formed in the one part. And the liquid crystal injection hole was sealed by the sealing agent or the sealing agent, and it produced by the method called the vacuum injection system.

In the vacuum injection method, the sealing pattern which formed the liquid crystal injection hole which used the thermosetting sealing compound by screen printing on any one of the transparent substrates with two electrodes formed first is prebaked at 60-100 degreeC, and is a sealing compound. The solvent in it is dried. Subsequently, the spacers are sandwiched and the two substrates are opposed to each other to be aligned and bonded together. Then, a heat press is performed at 110 to 220 ° C. for 10 to 90 minutes to adjust the gap near the seal. It heats at 110-220 degreeC for 10 to 120 minutes in the inside, and hardens a sealing compound. Next, liquid crystal was injected from the liquid crystal injection hole, and finally, the liquid crystal injection hole was sealed using the sealing agent, and the liquid crystal display element was produced.

However, in recent years, the manufacturing method of liquid crystal display devices, such as a liquid crystal display cell, from the viewpoint of shortening a tact time and optimizing the amount of liquid crystal used, photocurable resin, such as an acrylic resin, photoradical polymerization initiator, and epoxy in the said vacuum injection system. It is changing by the liquid crystal dropping method called the dropping method using the sealing compound which consists of a curable resin composition for light and heat combinations containing thermosetting resins, such as resin, and a thermosetting agent.

In the liquid crystal dropping method, a seal pattern is first formed on one side of the board | substrate with which two electrodes were formed. Subsequently, in the state where the sealing agent is uncured, a microdroplet of the liquid crystal is added dropwise to the entire inner surface of the substrate, the other substrate is superimposed under vacuum, returned to normal pressure, and the seal is irradiated with ultraviolet rays to cure the photocurable resin. (A) curing step). Then, it heats and hardens thermosetting resin and a liquid crystal display element is produced.

By the way, in the modern age in which mobile devices with various liquid crystal panels, such as a mobile telephone and a portable game machine, are spreading, miniaturization of the device is the most demanded problem. As a method of downsizing, narrow frame formation of a liquid crystal display part is mentioned, For example, arrange | positioning the position of a seal part under a black matrix is performed.

However, since the conventional sealing compound was transparent or milky white, even in the black matrix which should originally suppress light leakage, the light passing through the sealing compound could not be shielded, resulting in a problem of low contrast.

Therefore, the method of making it light-shielding by adding a light-shielding agent etc. to a sealing compound is considered. For example, Patent Literatures 1-3 disclose a sealing agent containing a titanium black-based material, a carbon black-based material, or other light-shielding fine particles as the light-shielding component. Especially among these light-shielding agents, the titanium black type material with high insulation is considered to be preferable as a light-shielding agent contained in a sealing compound.

However, the sealing compound containing titanium black had the problem that the adhesive strength after that falls remarkably when it exposed to the environment of high temperature, high humidity.

Japanese Laid-Open Patent Publication 2006-099027 Japanese Laid-Open Patent Publication 2005-292801 International Publication No. 09/128470

An object of this invention is to provide the light shielding sealing compound for liquid crystal display elements which is excellent in adhesive strength with respect to a board | substrate even after exposure to the environment of high temperature, high humidity. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which are manufactured using this light-shielding sealing compound for liquid crystal display elements.

The present invention provides a light-shielding sealing compound for a liquid crystal dropping method containing a curable resin containing a curable compound having an unsaturated double bond, a radical polymerization initiator, and a light shielding agent, wherein the curable resin has a hydrogen bondable functional group of 0.5 ×. It is 10 <^-3> -3.0 * 10 <^-3> mol / g, It is the light-shielding sealing compound for liquid crystal display elements containing titanium black as said light-shielding agent.

Hereinafter, the present invention will be described in detail.

MEANS TO SOLVE THE PROBLEM In this light-shielding sealing compound for liquid crystal display elements containing titanium black, the hydrogen bondable functional group of curable resin containing the curable compound which has an unsaturated double bond is 0.5 * 10 <^-3> -3.0 * 10 <^-3> mol In the case of / g, it was found that the decrease in the adhesive strength after the high temperature and high humidity treatment could be suppressed, and the present invention was completed.

The light shielding sealing agent for liquid crystal display elements of this invention contains titanium black as a light shielding agent (henceforth the light shielding sealing compound of this invention).

Titanium black is a substance in which the transmittance | permeability with respect to the light of the wavelength region 370-450 nm becomes high compared with the average transmittance | permeability with respect to the light of wavelength 300-800 nm. That is, the said titanium black is a light shielding agent which has the property to provide the light shielding property to the light shielding sealing compound of this invention by fully shielding the light of the wavelength of a visible light region, and to transmit the light of the wavelength vicinity of an ultraviolet region. Therefore, the photocurable property of the light-shielding sealing compound of this invention can be improved further by using what can start reaction by the light of wavelength (370-450 nm) which the transmittance | permeability of the said titanium black becomes high as an optical radical polymerization initiator mentioned later. . On the other hand, as the light-shielding agent contained in the light-shielding sealing agent of the present invention, a material having high insulation is preferable, and titanium black is also preferable as the light-shielding agent having high insulation.

It is preferable that the optical density (OD value) per micrometer is 3 or more, and, as for the said titanium black, it is more preferable that it is 4 or more. The higher the light shielding property of the titanium black, the better. The upper limit is not particularly preferable for the OD value of the titanium black, but is usually 5 or less.

The titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, and silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, and the like. Surface-treated titanium black, such as what is coat | covered with an inorganic component, can also be used. Especially, what is processed by the organic component is preferable at the point which can improve insulation.

In addition, the liquid crystal display device manufactured by using the light shielding sealant of the present invention can realize a liquid crystal display device having high contrast and excellent image display quality without leaking light because the light shielding sealant has sufficient light shielding properties. .

Although the said titanium black is not specifically limited, As a specific commercial item, for example, "12S", "13M", "13M-C", "13R-N" (all are the Mitsubishi material company make), "Tilac D" (Made by Ako Chemical Co., Ltd.) etc. are mentioned.

The minimum with a preferable specific surface area of the said titanium black is 13 m <2> / g, a preferable upper limit is 30 m <2> / g, a more preferable minimum is 15 m <2> / g, and a more preferable upper limit is 25 m <2> / g.

The minimum with preferable volume resistance of the said titanium black is 0.5 ohm * cm, a preferable upper limit is 3 ohm * cm, a more preferable minimum is 1 ohm * cm, and a more preferable upper limit is 2.5 ohm * cm.

In the light-shielding sealing compound of the present invention, the primary particle diameter of the 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, but the preferred lower limit is 1 nm, and the preferred upper limit is 5 m. When the primary particle diameter of the said light-shielding agent is less than 1 nm, the viscosity and thixotropy of the light-shielding sealing compound obtained may increase large, and workability may worsen. When the primary particle diameter of the said light-shielding agent exceeds 5 micrometers, the applicability | paintability to the board | substrate of the light-shielding sealing compound obtained may worsen. The minimum with a more preferable primary particle diameter of the said light-shielding agent is 5 nm, a more preferable upper limit is 200 nm, a more preferable minimum is 10 nm, and a more preferable upper limit is 100 nm.

Although content of the said light-shielding agent in the light-shielding sealing compound of this invention is not specifically limited, A preferable minimum is 5 weight%, and a preferable upper limit is 80 weight%. If content of the said light-shielding agent is less than 5 weight%, sufficient light-shielding property may not be obtained. When content of the said light-shielding agent exceeds 80 weight%, the adhesiveness with respect to the board | substrate of the light-shielding sealing compound obtained, the strength after hardening may fall, or drawing property may fall. The minimum with more preferable content of the said light-shielding agent is 10 weight%, a more preferable upper limit is 70 weight%, More preferably, a minimum is 30 weight%, and a more preferable upper limit is 60 weight%.

The light-shielding sealing agent of this invention contains curable resin.

The curable resin contains a curable compound having an unsaturated double bond. That is, the light-shielding sealing agent of the present invention starts the reaction by light and / or heat by containing a curable compound having an unsaturated double bond and a radical polymerization initiator described later, and specifically, can be cured by ultraviolet irradiation and / or heating. have.

The hydrogen bondable functional group of the said curable resin is 0.5 * 10 <^-3> -3.0 * 10 <^-3> mol / g. When the hydrogen bondable functional group of the said curable resin is less than 0.5x10 <^-3> mol / g, a resin component will be easy to elute to a liquid crystal, and liquid crystal contamination will arise. When the hydrogen bondable functional group of the said curable resin exceeds 3.0 * 10 <^-3> mol / g, the adhesive strength after the high temperature, high humidity process in the light-shielding sealing compound obtained will fall remarkably. The minimum with preferable hydrogen bondable functional group of the said curable resin is 0.7 * 10 <^-3> mol / g, a preferable upper limit is 2.5 * 10 <^-3> mol / g, and a more preferable minimum is 2.0 * 10 <^-3> mol / g.

In addition, in this specification, the hydrogen bondable functional group of curable resin is a value computed by the following formula, when curable resin consists of one type of compound.

Hydrogen bond functional group of curable resin = (number of hydrogen bond functional groups in 1 molecule of constituent compound) / (molecular weight of constituent compound)

In addition, when the said curable resin is comprised from the mixture of some resin, the hydrogen bondable functional group of curable resin is computed as a hydrogen bondable functional group per unit weight. For example, the curable resin is a compound A (hydrogen bond functional group α mol / g) of ag, compound B (hydrogen bond functional group β mol / g) of bg, compound C (hydrogen bond functional group of cg) In the case of consisting of γ mol / g), the hydrogen bondable functional group of the curable resin is represented by the following formula.

Hydrogen bond functional group of curable resin = (ax (alpha) + b * (beta) + cx (gamma)) / (a + b + c)

The hydrogen bondable functional group is not particularly limited as long as it is a functional group or a residue having hydrogen bondability. For example, -OH group, -NH ₂ group, -NHR group (R represents an aromatic or aliphatic hydrocarbon and derivatives thereof). ), Having a functional group such as -COOH group, -CONH ₂ group, -NHOH group, etc., but has a residue such as -NHCO- bond, -NH- bond, -CONHCO- bond, -NH-NH- bond in the molecule And the like.

As a compound which has the said hydrogen bondable functional group, a hydrogen bondable functional group may be independently in the said range, and may be adjusted to the said range by mixing two or more types. That is, the average value of the hydrogen bondable functional group of the compound which has a hydrogen bondable functional group to be used should just be in the said range.

The curable compound which has the said unsaturated double bond is not limited, For example, resin which has a vinyl group, an allyl group, a cinnamoyl group, a cinnamylidene group, a maleimide group, a (meth) acryloyloxy group etc. can be mentioned. Especially, resin which has a (meth) acryloyloxy group is preferable at the reactive point, and it is more preferable to have 2-3 (meth) acryloyloxy groups in a molecule | numerator.

In addition, in this specification, said "(meth) acryloyloxy group" means "acryloyloxy group or methacryloyloxy group."

Resin which has the said (meth) acryloyloxy group is not specifically limited, For example, the completeness obtained by making the (meth) acrylic acid react the compound which has a hydroxyl group, and (meth) acrylic acid and an epoxy compound ( The urethane (meth) acrylate etc. which are obtained by making a (meth) acrylic acid derivative which has a hydroxyl group react with a meth) acryl modified epoxy resin and an isocyanate are mentioned.

In addition, in this specification, said "(meth) acryl" means "acryl or methacryl", and said "(meth) acrylate" means "acrylate or methacrylate." In addition, in this specification, said "complete (meth) acryl modified epoxy resin" refers to the compound which made all the epoxy groups in an epoxy resin react with (meth) acrylic acid.

The ester compound obtained by making the said (meth) acrylic acid react with the compound which has a hydroxyl group is not specifically limited, As monofunctional thing, For example, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) Acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth Acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxyethyl (meth) arc Latex, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2, 2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, methyl (meth) acrylate, ethyl (meth ) Acrylate, n-butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (Meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, bicyclopentenyl ( To meth) acrylate, isodecyl (meth) acrylate, diethylamino (Meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxy Ethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, etc. are mentioned.

Moreover, as bifunctional thing, it is 1, 4- butanediol di (meth) acrylate, 1, 3- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, 1, for example. , 9-nonanedioldi (meth) acrylate, 1,10-decanedioldi (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanedioldi (meth) acrylate, dipropylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethyleneglycol di (meth) acrylate, propylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate Dimethyloldicyclopentadier Di (meth) acrylate, 1,3-butylene glycoldi (meth) acrylate, neopentylglycoldi (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3 -(Meth) acryloyloxypropyl (meth) acrylate, carbonatediol di (meth) acrylate, polyetherdioldi (meth) acrylate, polyesterdioldi (meth) acrylate, polycaprolactonedioldi ( Meth) acrylate, polybutadiene diol di (meth) acrylate, tricyclodecane dimethanol acrylate, etc. are mentioned.

Moreover, as trifunctional or more than trifunctional, for example, pentaerythritol tri (meth) acrylate, trimethylol propane tri (meth) acrylate, a propylene oxide addition trimethylol propane tri (meth) acrylate, and ethylene oxide addition trimethylol propane Tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, ethylene oxide addition isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, ditrimethylol propane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide addition glycerin tri (meth) acrylate, tris (meth) Acryloyloxyethyl phosphate etc. are mentioned.

The fully (meth) acryl modified epoxy resin obtained by making the said (meth) acrylic acid and an epoxy compound react is not specifically limited, For example, by reacting an epoxy resin and (meth) acrylic acid in presence of a basic catalyst according to a conventional method. What is obtained, etc. are mentioned.

The epoxy compound which becomes a raw material for synthesize | combining the said fully (meth) acryl modified epoxy resin is not specifically limited, For example, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, 2,2 ' -Diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, Dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalene phenol novolak Epoxy resins, glycidylamine epoxy resins, alkylpolyol epoxy resins, rubber modified When there may be mentioned resins, glycidyl ester compounds.

As what is marketed among the said bisphenol-A epoxy resins, Epicoat 828EL, Epicoat 1004 (all are the Mitsubishi Chemical Corporation make), Epitron 850-S (made by DIC Corporation), etc. are mentioned, for example.

As what is marketed among the said bisphenol F-type epoxy resins, Epicoat 806, Epicoat 4004 (all are the Mitsubishi Chemical Corporation make), etc. are mentioned, for example.

As what is marketed among the said bisphenol S-type epoxy resins, Epiclon EXA1514 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said 2,2'- diallyl bisphenol-A epoxy resin, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. is mentioned, for example.

As what is marketed among the said hydrogenated bisphenol-type epoxy resins, Epiclon EXA7015 (made by DIC Corporation) etc. is mentioned, for example.

As what is marketed among the said propylene oxide addition bisphenol-A epoxy resins, EP-4000S (made by ADEKA Corporation) etc. is mentioned, for example.

As what is marketed among the said resorcinol type epoxy resins, EX-201 (made by Nagase Chemtex Co., Ltd.) etc. is mentioned, for example.

As what is marketed among the said biphenyl type epoxy resins, Epicoat YX-4000H (made by Mitsubishi Chemical Corporation) etc. is mentioned, for example.

As what is marketed among the said sulfide type epoxy resins, YSLV-50TE (made by Shin-Nitetsu Chemical Co., Ltd.) etc. is mentioned, for example.

As what is marketed among the said diphenyl ether type epoxy resins, YSLV-80DE (made by Shin-Nitetsu Chemical Co., Ltd.) etc. is mentioned, for example.

As what is marketed among the said dicyclopentadiene type epoxy resins, EP-4088S (made by ADEKA Corporation) etc. is mentioned, for example.

As what is marketed among the said naphthalene type epoxy resins, Epiclon HP4032, Epiclon EXA-4700 (all are the DIC Corporation make), etc. are mentioned, for example.

As what is marketed among the said phenol novolak-type epoxy resins, Epiclon N-770 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said orthocresol novolak-type epoxy resins, Epiclon N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, Epiclon HP7200 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said biphenyl novolak-type epoxy resins, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. is mentioned, for example.

As what is marketed among the said naphthalene phenol novolak-type epoxy resins, ESN-165S (made by Shin-Nitetsu Chemical Co., Ltd.) etc. is mentioned, for example.

As what is marketed among the said glycidyl amine epoxy resins, Epicoat 630 (made by Mitsubishi Chemical Corporation), Epikron 430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemical Corporation), etc. are mentioned, for example. have.

As what is marketed among the said alkyl polyol type | mold epoxy resins, ZX-1542 (made by Shin-Nitetsu Chemical Co., Ltd.), epicron 726 (made by DIC Corporation), Eporite 80MFA (made by Kyoeisha Chemical Co., Ltd.), Denacol EX -611 (made by Nagase Chemtex Co., Ltd.), etc. are mentioned.

As what is marketed among the said rubber modified epoxy resins, YR-450, YR-207 (all are the Shin-Nitetsu Chemical company make), Eporide PB (made by Daicel Corporation), etc. are mentioned, for example.

As what is marketed among the said glycidyl ester compounds, Denacol EX-147 (made by Nagase Chemtex) etc. is mentioned, for example.

As what is marketed among the said epoxy resins, others are YDC-1312, YSLV-80XY, YSLV-90CR (all are the Shin-Nitetsu Chemical company make), XAC4151 (made by Asahi Kasei Corporation), Epicoat 1031, Epicoat 1032, for example. (All are manufactured by Mitsubishi Chemical Corporation), EXA-7120 (made by DIC Corporation), TEPIC (made by Nissan Chemical Corporation), etc. are mentioned.

Specifically, the fully (meth) acryl modified epoxy resin obtained by making the said (meth) acrylic acid and an epoxy compound react is 360 weight part of resorcinol type epoxy resins (made by Nagase Chemtex Co., Ltd., "EX-201"), for example. 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst and 210 parts by weight of acrylic acid were stirred at reflux at 90 ° C. while sending air to react for 5 hours. A lecinol type epoxy resin can be obtained.

As what is marketed among the said full (meth) acryl modified epoxy resins, For example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYL6040 ), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, epoxy ester 1600A, epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, epoxy ester 400EA (all manufactured by Kyoisha Chemical Co., Ltd.), denacol acrylate DA-141, Denacol acrylate DA-314, denacol acrylate DA-911 (both manufactured by Nagase Chemtex), and the like.

The urethane (meth) acrylate obtained by making the said isocyanate react with the (meth) acrylic acid derivative which has a hydroxyl group, for example, catalyzes 2 equivalents of the (meth) acrylic acid derivative which has a hydroxyl group with respect to 1 equivalent of the compound which has two isocyanate groups. It can obtain by making it react in presence of tin type compound.

The isocyanate which becomes a raw material of the urethane (meth) acrylate obtained by making the said isocyanate react with the (meth) acrylic acid derivative which has a hydroxyl group is not specifically limited, For example, isophorone diisocyanate, 2, 4- tolylene diisocyanate, 2 , 6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, nord Boran diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, tetramethyl xylene diisocyanate, 1,6,10- Undecane triisocyanate etc. are mentioned.

Moreover, as an isocyanate used as the raw material of the urethane (meth) acrylate obtained by making the said isocyanate react with the (meth) acrylic acid derivative which has a hydroxyl group, for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene It is also possible to use chain extended isocyanate compounds obtained by the reaction of polyols with excess isocyanate, such as glycols, carbonatediols, polyetherdiols, polyesterdiols, polycaprolactonediols and the like.

The (meth) acrylic acid derivative having a hydroxyl group, which is a raw material of the urethane (meth) acrylate obtained by reacting the isocyanate with a (meth) acrylic acid derivative having a hydroxyl group, is not particularly limited. For example, 2-hydroxyethyl ( Commercial items, such as meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate, and ethylene glycol, propylene glycol, 1, Mono (meth) acrylates of dihydric alcohols such as 3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol, such as mono (meth) acrylates, trimethylolethane, trimethylolpropane, and glycerin Epoxy (meth) acrylates, such as a) acrylate or di (meth) acrylate and a bisphenol-A epoxy (meth) acrylate, etc. are mentioned.

Specifically, the urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with the isocyanate is specifically 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization inhibitor, and a reaction catalyst. 0.01 part by weight of butyltin dilaurate and 666 parts by weight of isophorone diisocyanate were added and reacted under reflux at 60 ° C. for 2 hours. Next, 51 parts by weight of 2-hydroxyethyl acrylate was added thereto, followed by air feeding. It can obtain by making it react at reflux at 2 degreeC and making it react for 2 hours.

As what is marketed among the said urethane (meth) acrylates, For example, M-1100, M-1200, M-1210, M-1600 (all are the Toa synthesis company make), ebecryl 230, ebecryl 270, ebecryl 4858. , Evercryl 8402, Evercryl 8804, Evercryl 8803, Evercryl 8807, Evercryl 9260, Evercryl 1290, Evercryl 5129, Evercryl 4842, Evercryl 210, Evercryl 4827, Evercryl 6700, Evercryl 220, Everev Krill 2220 (all made by Daicel Cytec Co., Ltd.), art resin UN-9000H, art resin UN-9000A, art resin UN-7100, art resin UN-1255, art resin UN-330, art resin UN-3320HB, art resin UN -1200TPK, art resin SH-500B (all manufactured by Negami Kogyo Co., Ltd.), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA- W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (both manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AH-600 , AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I and the like.

The said curable resin may contain other resins, such as resin which has an epoxy group, in addition to the curable compound which has an unsaturated double bond.

Resin which has the said epoxy group is not specifically limited, For example, the epoxy compound used as a raw material for synthesize | combining the said fully (meth) acryl modified epoxy resin, a partial (meth) acryl modified epoxy resin, etc. are mentioned.

In addition, in this specification, the said partial (meth) acryl modification epoxy resin means resin which has 1 or more of epoxy groups and (meth) acryloyloxy groups in 1 molecule, respectively, For example, it has two or more epoxy groups It can be obtained by reacting an epoxy group of a part of the resin with (meth) acrylic acid.

The said partial (meth) acryl modified epoxy resin is obtained by reacting an epoxy resin and (meth) acrylic acid in presence of a basic catalyst according to a conventional method, for example. Specifically, 190 g of phenol novolac type epoxy resin N-770 (manufactured by DIC Corporation) is dissolved in 500 ml of toluene, and 0.1 g of triphenylphosphine is added to the solution to obtain a uniform solution. 35 g of acrylic acid was added dropwise to the solution under reflux stirring for 2 hours, and then reflux stirring was further performed for 6 hours, and then, toluene was removed, thereby partially acryl-modified phenol novolac in which 50 mol% of the epoxy group reacted with (meth) acrylic acid. A type epoxy resin can be obtained (in this case, 50% partial acrylation).

As what is marketed among the said partial (meth) acryl modified epoxy resins, UVACURE1561 (made by Daicel Cytec Co., Ltd.) is mentioned, for example.

Among the resins having the above epoxy groups, resins having only epoxy groups (hereinafter also referred to as resins having only epoxy groups) that do not have a (meth) acryloyloxy group as reactive functional groups are preferable because they do not cause liquid crystal contamination. However, you may add in the range which does not affect liquid-crystal contamination for the purpose of improving adhesiveness.

The upper limit with preferable content of resin which has only the said epoxy group is 10 weight% with respect to 100 weight part of whole curable resin. When content of resin which has only the said epoxy group exceeds 10 weight%, the light-shielding sealing compound for liquid crystal display elements obtained may cause liquid-crystal contamination.

When mix | blending resin which has the said (meth) acryloyloxy group and resin which has the said epoxy group as said curable resin, the ratio of the (meth) acryloyloxy group and the epoxy group of the said curable resin is 50: 50-95: It is preferable to mix | blend resin which has a (meth) acryloyloxy group, and resin which has an epoxy group so that it may become 5. When the ratio of the said (meth) acryloyloxy group is less than 50%, even if the radical polymerization by the radical polymerization initiator mentioned later is completed, many uncured epoxy resin components may exist and may contaminate a liquid crystal. When the ratio of the said (meth) acryloyloxy group exceeds 95%, the effect of improving adhesive force may not be fully acquired.

The light-shielding sealing agent of this invention contains a radical polymerization initiator. The radical polymerization initiator generates radicals by external stimulation such as ultraviolet irradiation or heating, and the light-shielding sealing agent for liquid crystal display elements of the present invention is used for photo radical polymerization initiators that generate radicals by ultraviolet irradiation, and / or heating. It contains the thermal radical polymerization initiator which generate | occur | produces a radical.

It is preferable that the light-shielding sealing agent of this invention contains a thermal radical polymerization initiator. Since the light-shielding sealing agent of this invention contains the said thermal radical polymerization initiator, even if there is a sealing part in the point which light does not reach by a black matrix etc., since it can harden | cure by heat, liquid crystal contamination is prevented. It is extremely rare.

The minimum with preferable 10-hour half life temperature of the said thermal radical polymerization initiator is 50 degreeC, and a preferable upper limit is 90 degreeC. When the 10-hour half life temperature of the said thermal radical polymerization initiator is less than 50 degreeC, the storage stability of the light shielding sealing compound for liquid crystal display elements obtained may worsen. When the 10-hour half-life temperature of the said thermal radical polymerization initiator exceeds 90 degreeC, high temperature and a long time are required for hardening of the light shielding sealing compound for liquid crystal display elements of this invention, and it may affect the productivity of a panel.

In addition, in this specification, said 10-hour half life temperature is the temperature at which the density | concentration of a thermal radical polymerization initiator becomes half the concentration before reaction, when thermal decomposition reaction is performed for 10 hours at constant temperature in presence of an inert gas.

The said thermal radical polymerization initiator is not specifically limited, Azo compound, an organic peroxide, etc. are mentioned. Especially, it is preferable that it is a polymeric azo initiator consisting of a polymeric azo compound.

In addition, in this specification, a polymeric azo initiator means the compound which has an azo group and produces the radical which can harden | cure the said curable resin with heat, 300 or more molecular weight.

In addition, the polymer azo initiator can also function as an optical radical polymerization initiator in that it is usually decomposed by light irradiation to generate radicals.

The minimum with preferable number average molecular weight of the said polymeric azo initiator is 1000, and a preferable upper limit is 300,000. When the number average molecular weight of the said polymeric azo initiator is less than 1000, a polymeric azo initiator may adversely affect a liquid crystal. When the number average molecular weight of the said polymeric azo initiator exceeds 300,000, mixing to the said curable resin may become difficult. The minimum with more preferable number average molecular weight of the said polymeric azo initiator is 5000, and a more preferable upper limit is 100,000, A further preferable minimum is 10,000, and a more preferable upper limit is 90,000.

The said polymeric azo initiator has a structure which has two or more units, such as a polydimethylsiloxane and a polyalkylene oxide, couple | bonded through the azo group, for example.

As a structure which two or more units, such as a polyalkylene oxide, couple | bonded, it is preferable to have a polyethylene oxide structure.

As such a polymeric azo initiator, For example, the polycondensate of 4,4'- azobis (4-cyanopentanoic acid) and polyalkylene glycol, 4,4'- azobis (4-cyanopentanoic acid), and a terminal The polycondensate of polydimethylsiloxane which has an amino group, etc. are mentioned, Specifically, For example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all are the Wako Pure Chemical Industries Ltd. make), etc. Can be mentioned.

As said polymeric azo initiator, the polymeric azo compound represented by following General formula (I) of Unexamined-Japanese-Patent No. 2008-50572 and Unexamined-Japanese-Patent No. 2003-12784 can also be used preferably.

[Formula 1]

In formula (I), R <^12> , R <^13> , R <^22> and R <^23> represent a C1-C10 alkyl group or cyano group each independently, a and b are the numbers of 0-4 each independently, A is ¹¹ and A ¹² are polymer chains, and Y ¹¹ and Y ¹² are each independently —CO—O—, —O—CO—, —NH—CO—, —CO—NH—, —O—, or —S—. .

In said general formula (I), as an alkyl group of 1-10 carbon atoms represented by R <^12> , R <^13> , R <^22> and R <^23> , For example, methyl, ethyl, propyl, isopropyl, butyl, s-butyl , t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc. are mentioned.

In the general formula (I), the polymer chains represented by A ¹¹ and A ¹² are not particularly limited, and examples thereof include polyoxyylene chains, polymethylene chains, polyether chains, polyester chains, polysiloxane chains, and poly (meth) s. ) Acrylate chains, polystyrene-vinyl acetate chains, polyamide chains, polyimide chains, polyurethane chains, polyurea chains, polypeptide chains and the like. Especially, the compound whose Y <^11> is -O-CO- and Y <^12> is -CO-O- is preferable, It is especially inexpensive and manufactured that the polymer chain represented by A <^11> and A <^12> is a polyether chain and a polyester chain. It is more preferable because it is easy.

Among the polymeric azo compounds in which A ¹¹ and A ¹² are polyether chains in the general formula (I), the compound represented by the following general formula (II) has good solubility and is more preferable because molecular weight control of the polymerization initiator is easy. Do.

[Formula 2]

In formula (II), R <^12> , R <^13> , R <^22> , R <^23> , a and b are the same as said general formula (I), and R <^11> and R <^21> is a C1-C24 alkyl group each independently, Z ¹¹ , Z ¹² , Z ²¹ and Z ²² each independently represent an alkylene group having 1 to 4 carbon atoms, m, n, s and t each independently represent a number of 0 to 1000, and m + n The sum of s + t is independently 2 or more)

In the general formula (II), examples of the alkylene group having 1 to 4 carbon atoms represented by Z ¹¹ , Z ¹² , Z ²¹ and Z ²² include, for example, methylene, ethylene, trimethylene, propylene, propylidene and iso Propylidene, tetramethylene, butylene, isobutylene, ethyl ethylene, dimethyl ethylene and the like.

Moreover, as a C1-C24 alkyl group represented by R <^11> and R <^21> , For example, methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl , t-amyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl , Lauryl, stearyl, behenyl and the like. The C1-C24 alkyl group represented by R <^11> and R <^21> is preferable because the C1-C4 thing is highly reactive.

Among the compounds A ¹¹ and A ¹² of the polymer azo compound represented by the general formula (I) are polyester chains, the compound represented by the following general formula (III) is preferable because of its solubility and excellent water resistance.

(3)

In formula (III), R <^12> , R <^13> , R <^22> , R <^23> , a and b are the same as the said General formula (I), Z <^13> and Z <^23> are respectively independently C1-C18 alkylene Group, R ³¹ and R ⁴¹ each independently represent a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, and p and u each independently represent a number of 1 to 1000.

In the general formula (III), examples of the alkylene group having 1 to 18 carbon atoms represented by Z ¹³ and Z ²³ include methylene, ethylene, trimethylene, propylene, propylidene, isopropylidene, tetramethylene, Butylene, isobutylene, ethylethylene, dimethylethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, 1,4-pentanediyl, decamethylene, undecamethylene, 1,4-undecandiyl, dodecamethylene , 1,11-heptadecanediyl, octadecamethylene and the like.

In addition, examples of the alkyl group having 1 to 24 carbon atoms represented by R ³¹ and R ⁴¹ include those exemplified as R ¹¹ and R ²¹ in General Formula (II). The alkyl group having 1 to 24 carbon atoms represented by R ³¹ and R ⁴¹ is preferable because the carbon atoms having 1 to 4 are highly reactive.

In general formula (III), since p and u are 20-100, since reactivity is high, it is preferable.

The organic peroxide is not particularly limited and includes, for example, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate and the like.

Although content of the said thermal radical polymerization initiator in the light-shielding sealing compound of this invention is not specifically limited, A preferable minimum is 0.1 weight part and a preferable upper limit is 30 weight part with respect to 100 weight part of said curable resins. When content of the said thermal radical polymerization initiator is less than 0.1 weight part, hardening of the said light-shielding sealing compound may not fully advance. When content of the said thermal radical polymerization initiator exceeds 30 weight part, the viscosity of the light shielding sealing compound for liquid crystal display elements obtained may become high, and may adversely affect coating workability | operativity etc .. The minimum with more preferable content of the said thermal radical polymerization initiator is 0.5 weight part, and a more preferable upper limit is 10 weight part.

It is preferable that the light-shielding sealing agent of this invention contains a radical photopolymerization initiator. Since the light-shielding sealing compound of this invention contains a titanium black type material, it has light blocking property and photocurability by containing the said radical photopolymerization initiator.

In addition, it is preferable that the said radical photopolymerization initiator is photosensitive by irradiating the light of the wavelength range of 370-450 nm as mentioned above, but can be photosensitive by the light of the wavelength below 370 nm or the light exceeding 450 nm. May be used.

Such radical photopolymerization initiator is not particularly limited, but for example, IRGACURE127, IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE1300, IRGACURE1700, IRGACURE1870, IRGACURE2960, IRGACURE1870, IRGACURE1870 TPO, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, (all manufactured by BASF Japan), ESACURE TPO (manufactured by Lamberti), Speedcure TPO, Speedcure TPO-L (all manufactured by LAMBSON), MICURE TPO (Manufactured by MIWON), N-1414 (manufactured by ADEKA), Solvatron BIPE, Solvatron BIBE, biimidazole (manufactured by Kurogane Chemical), KAYACURE BP, KAYACURE DETX-S (all manufactured by Nippon Gunpowder), ESACURE KIP 150 (manufactured by Lamberti), S-121 (manufactured by Shinko Institute of Technology), Seikol BEE (manufactured by Seiko Chemical Co., Ltd.), KR-02 (manufactured by Light Chemical Co., Ltd.), and the like.

Although content of the said radical photopolymerization initiator is not specifically limited, A minimum with preferable 100 weight part of said curable resin is 0.1 weight part, and a preferable upper limit is 10 weight part. When content of the said radical photopolymerization initiator is less than 0.1 weight part, photopolymerization may not fully advance or reaction may be delayed too much. When content of the said radical photopolymerization initiator exceeds 10 weight part, workability may fall or reaction may become nonuniform. The minimum with more preferable content of a radical photopolymerization initiator is 1 weight part, and a more preferable upper limit is 5 weight part.

When the said curable resin contains resin which has the said epoxy group, it is preferable that the light shielding sealing compound for liquid crystal display elements of this invention contains a thermosetting agent further.

The said thermosetting agent is not specifically limited, For example, an organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride, etc. are mentioned. Especially, the organic acid hydrazide of room temperature solid is used preferably.

The said room temperature solid organic acid hydrazide is not specifically limited, For example, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid hydrazide, etc. are marketed, As what exists, SDH (made by Nippon Finechem Co., Ltd.), Amcure VDH, Amcure VDH-J, Amcure UDH (both by Ajinomoto Fine Techno Co., Ltd.), ADH (made by Otsuka Chemical Co., Ltd.), etc. are mentioned. .

Although content of the said thermosetting agent is not specifically limited, A preferable minimum is 1 weight part and a preferable upper limit is 50 weight part with respect to 100 weight part of said curable resins. When content of the said thermosetting agent is less than 1 weight part, the effect which contains a thermosetting agent is hardly obtained. When content of the said thermosetting agent exceeds 50 weight part, the viscosity of the light-shielding sealing compound obtained may become high, and applicability etc. may be impaired. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.

It is preferable that the light-shielding sealing agent of this invention contains a filler for the purpose of the improvement of a viscosity, the improvement of adhesiveness by a stress dispersion effect, the improvement of a linear expansion rate, the further improvement of the moisture resistance of hardened | cured material, etc.

The filler is not particularly limited, for example, talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide Inorganic fillers such as aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, activated sericite clay, aluminum nitride, organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles. Can be mentioned.

It is preferable that the light-shielding sealing agent of this invention contains a silane coupling agent. The silane coupling agent serves mainly as an adhesion assisting agent for satisfactorily bonding a sealant and a substrate.

Although the said silane coupling agent is not specifically limited, For example, (gamma) -aminopropyl trimethoxysilane, (gamma)-mercaptopropyl trimethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, etc. are used preferably.

The light-shielding sealing agent of the present invention may further contain, if necessary, a reactive diluent for adjusting the viscosity, a thixotropic agent for adjusting thixotropy, a spacer such as polymer beads for adjusting the panel gap, and 3-P-chloro A curing accelerator such as phenyl-1,1-dimethylurea, an antifoaming agent, a leveling agent, a polymerization inhibitor, or other additives may be contained.

The method for producing the light-shielding sealing agent of the present invention is not particularly limited, and for example, the curable resin, the radical polymerization initiator, the light-shielding agent, and an additive to be blended as necessary may be mixed by a conventionally known method. And the like can be mentioned.

It is preferable that the optical density (OD value) of the hardened | cured body which hardened the light-shielding sealing agent of this invention is 2.0 or more, when the thickness of a hardened body is 2-7 micrometers. If the OD value of the said hardened | cured material is less than 2.0, light shielding property may become inadequate, light may leak to the liquid crystal display element manufactured by the dropping method, and high contrast may not be obtained. As for the OD value of the said hardened | cured material, it is more preferable that it is 2.5 or more, and it is still more preferable that it is 3.0 or more. The higher the OD value of the cured product, the better. However, when the light shielding agent is blended too much in order to increase the OD value of the cured product, the workability decreases or the drawability decreases due to the thickening of the sealing agent. In order to balance with the compounding quantity of, the upper limit with preferable OD value of the said hardened | cured material is five.

The light-shielding sealing agent of this invention produces the adhesion test piece which bonds two glass substrates crosswise via the light-shielding sealing compound for liquid crystal display elements of this invention, About the adhesion test piece A pressure cooker test (121 degreeC, It is preferable that adhesive strength at the time of performing 100% RH, 0.2 Mpa) for 24 hours will be 30 kgf / cm <2> or more. If the adhesive strength at the time of the pressure cooker test is less than 30 kgf / cm <2>, the liquid crystal display element obtained may become inferior in reliability in high temperature, high humidity environment.

A vertical conduction material can be manufactured by mix | blending electroconductive fine particles with the light shielding sealing compound for liquid crystal display elements of this invention. The vertical conduction material containing the light shielding sealing compound for liquid crystal display elements of this invention, and electroconductive fine particles is also one of this invention.

The said electroconductive fine particles are not specifically limited, A metal ball, the thing in which the conductive metal layer was formed in the surface of resin fine particles, etc. can be used. Among them, the conductive metal layer is preferably formed on the surface of the resin fine particles because of the excellent elasticity of the resin fine particles, which can be electrically connected without damaging the transparent substrate or the like.

The liquid crystal display element manufactured using the light-shielding sealing compound for liquid crystal display elements of this invention, and / or the vertical conduction material of this invention is also one of this invention.

As a method of manufacturing the liquid crystal display element of this invention, the light-shielding sealing compound for liquid crystal display elements of this invention is formed by screen printing, dispenser application, etc. to one side of the transparent substrate in which two electrodes, such as an ITO thin film, were formed, for example. The process of forming a rectangular seal pattern, the light-shielding sealing agent for liquid crystal display elements, etc. of this invention is apply | coated dropwise to the whole surface in the range of a transparent substrate, and apply | coats the other transparent substrate immediately by dropping the micro droplet of a liquid crystal. Process and the method which has the process of temporarily hardening a sealing compound by irradiating light, such as an ultraviolet-ray, to the sealing pattern parts, such as the light shielding sealing compound for liquid crystal display elements of this invention, and the process of heating and temporarily hardening the temporarily hardened sealing compound, etc. Can be mentioned.

According to this invention, the light-shielding sealing compound for liquid crystal display elements excellent in the adhesive strength with respect to a board | substrate can be provided even after exposure to the environment of high temperature, high humidity. Moreover, the vertical conduction material and liquid crystal display element which are manufactured using this light-shielding sealing compound for liquid crystal display elements can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows typically the procedure to produce a liquid crystal display element by a liquid crystal dropping system in an Example and a comparative example.

Although an Example is given to the following and the aspect of this invention is demonstrated in detail, this invention is not limited only to these Examples.

(Synthesis of Fully Acrylic Modified Epoxy Resin)

120 g of resorcinol-type epoxy resins (manufactured by Nagase Chemtex Co., Ltd., "EX-201") were dissolved in 500 ml of toluene, and 0.1 g of triphenylphosphine was added to the solution to obtain a uniform solution. 70 g of acrylic acid was added dropwise to the solution over 2 hours under reflux stirring, and then reflux stirring was further performed for 8 hours. Next, the complete acrylic modified resorcinol type epoxy resin (EX-201 modified product) which modified all the epoxy groups by the acryl group was obtained by removing toluene.

(Synthesis of partially acrylic modified epoxy resin)

190 g of phenol novolac-type epoxy resins ("N-770" manufactured by DIC Corporation) were dissolved in 500 ml of toluene, 0.1 g of triphenylphosphine was added to make a uniform solution, and 35 g of acrylic acid was added to the obtained solution. After dropping over 2 hours under reflux stirring, reflux stirring was further performed for 6 hours. Next, the partially acryl-modified phenol novolak-type epoxy resin (N-770 partial modified | denatured product) which modified | denatured 50 mol% of epoxy groups by the acryloyloxy group was obtained by removing toluene.

(Examples 1-17, and Comparative Examples 1-9)

After mix | blending each curable resin according to the compounding ratio described in Tables 1-3, the thermal radical polymerization initiator and / or the radical photopolymerization initiator were mix | blended. Subsequently, after completely dissolving the thermal radical polymerization initiator and / or the radical photopolymerization initiator, the mixture is stirred using a planetary stirrer (Shinki Co., Ltd., Awatori Lantaro), followed by a light shielding agent, a thermal curing agent, a filler, and a silane. The coupling agent was blended and stirred again with a planetary stirrer. Then, the light-shielding sealing compound for liquid crystal display elements of an Example and a comparative example was prepared by disperse | distributing uniformly using three rolls.

FIG. 1: is a figure which shows typically the procedure to produce a liquid crystal display element by a liquid crystal dropping system in an Example and a comparative example. As shown in FIG. 1, the obtained light shielding sealing compound for liquid crystal display elements was apply | coated to the board | substrate with which the transparent electrode and the orientation film were formed with the dispenser so that the edge of a square might be drawn. Subsequently, the microdroplets of the liquid crystal ("JC-5004LA" manufactured by Jisso Corporation) were applied dropwise to the entire inner surface of the edge of the transparent substrate, and the substrate having the transparent electrode and the alignment film formed thereon in a vacuum was superimposed, and after the vacuum was released, The ultraviolet-ray of 100 mW / cm <2> was irradiated for 30 second to the edge seal part using the high pressure mercury lamp. Then, liquid crystal annealing was performed at 120 degreeC for 1 hour, the light-shielding sealing compound for liquid crystal display elements was thermosetted, and the liquid crystal display element was obtained.

<Evaluation>

The following evaluation was performed about the light shielding sealing compound for liquid crystal display elements and liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1-3.

(Adhesive strength)

Take the light-shielding sealing compound for liquid crystal display elements obtained by the trace amount in the center part of a glass substrate (20 mm x 50 mm x 1.1 mmt), and overlap the glass substrate of the same size so that it may become a cross shape, and press and spread the sealing compound for liquid crystal display elements by pressing it. It was. After irradiating an ultraviolet-ray of 100 mW / cm <2> in that state for 30 second, it heated at 120 degreeC for 1 hour, and obtained the initial stage adhesion test piece. Moreover, about the obtained initial adhesion test piece, the pressure cooker test (121 degreeC, 100% RH, 0.2 Mpa) was performed for 24 hours, and the adhesive test piece after high temperature, high humidity process was obtained. The adhesive strength (kgf / cm <2>) was measured about the obtained initial adhesion test piece and the adhesion test piece after high temperature, high humidity treatment using the tension gauge.

(Optical density (OD value))

1 g of silica spacers (Sekisui Chemical Co., Ltd. make, "Micropearl SI") of diameter 5 micrometers were added to 100 g of light-shielding sealing compounds for liquid crystal display elements obtained, and mixing and stirring were performed.

The light-shielding sealing compound for liquid crystal display elements containing the obtained spacer was apply | coated on the glass substrate of 20 mm x 20 mm, the glass substrate of the same size was superimposed on the board | substrate, and a load was applied, it pressed to the diameter of a spacer, and it crushed thickness. Was made uniform. Next, after irradiating 100 mW / cm <2> ultraviolet-rays for 30 second using the metal halide lamp, it heated at 120 degreeC for 1 hour, and obtained the optical test piece. About the obtained optical test piece, optical density (OD value) was measured using X-rite 360T ((nu)) (made by X-rite).

(Display performance (color nonuniformity) of liquid crystal display element)

About the obtained liquid crystal display element, the color nonuniformity generate | occur | produced in the liquid crystal around the light shielding sealing compound for liquid crystal display elements was visually observed. As a result, "(circle)" and the case where there was little color irregularity were "(circle)" and the case where there was little color nonuniformity was evaluated as "(circle)" and the case where there was quite a color nonuniformity as "x" when there was no color nonuniformity at all. .

As shown in Table 1, 2, the adhesive strength after the high temperature and high humidity test of the light-shielding sealing compound obtained by the Example was 30 kgf / cm <2> or more, and all were the level which is satisfactory practically at all. In addition, the optical density (OD value) was all very high at 3.0 or more, and had sufficient light-shielding property. As for the color nonuniformity, it was the level which has no problem at all in practical use to the extent there is no, little, or weakness at all.

Industrial availability

According to this invention, the light-shielding sealing compound for liquid crystal display elements excellent in the adhesive strength with respect to a board | substrate can be provided even after exposure to the environment of high temperature, high humidity. Moreover, the vertical conduction material and liquid crystal display element which are manufactured using this light-shielding sealing compound for liquid crystal display elements can be provided.

Claims (6)

As a light-shielding sealing compound for liquid crystal dropping methods containing curable resin containing the curable compound which has an unsaturated double bond, a radical polymerization initiator, and a light shielding agent,
The curable resin has a hydrogen bondable functional group of 0.5 × 10 ⁻³ to 3.0 × 10 ⁻³ mol / g,
Titanium black is contained as said light-shielding agent, The light-shielding sealing compound for liquid crystal display elements characterized by the above-mentioned. The method of claim 1,
The curable compound which has an unsaturated double bond has a (meth) acryloyloxy group, The light-shielding sealing compound for liquid crystal display elements characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The radical polymerization initiator contains a thermal radical polymerization initiator, The light-shielding sealing compound for liquid crystal display elements characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The radical polymerization initiator contains a polymeric azo initiator and / or the radical photopolymerization initiator which photosensitizes with light of the wavelength range of 370-450 nm, The light-shielding sealing compound for liquid crystal display elements characterized by the above-mentioned. The light-shielding sealing compound for liquid crystal display elements and electroconductive fine particles of Claim 1, 2, 3, or 4 are contained, The vertical conduction material characterized by the above-mentioned. It is manufactured using the light-shielding sealing compound for liquid crystal display elements of Claim 1, 2, 3, or 4, and / or the vertical conduction material of Claim 5, The liquid crystal display element characterized by the above-mentioned.

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