TW202108730A - Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a sealant for a liquid crystal display element, the sealant having excellent storage stability and being capable of suppressing penetration of liquid crystal into the sealant and suppressing contamination of the liquid crystal by the sealant. The purpose of the present invention is also to provide a vertical conduction material and a liquid crystal display element manufactured using the sealant for a liquid crystal display element. The present invention is a sealant for a liquid crystal display element, containing a curable resin, a thermal radical polymerization initiator, and a thermosetting agent, the thermosetting agent containing an amine adduct curing agent which is particulate at 25 DEG C.

Description

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

The present invention relates to a sealing compound for a liquid crystal display element which is excellent in storage stability and can suppress insertion of liquid crystal into a sealing compound or liquid crystal contamination caused by the sealing compound. Moreover, this invention relates to the use of this sealing compound for liquid crystal display elements to manufacture an upper and lower conduction material and a liquid crystal display element.

In recent years, as a method of manufacturing liquid crystal display elements such as liquid crystal display cells, the methods disclosed in Patent Document 1 and Patent Document 2 have been used from the viewpoints of shortening the takt time and optimizing the amount of liquid crystal used. The liquid crystal dropping method called the dropping method uses a light-heat combined curing type sealant containing a curable resin, a photopolymerization initiator, and a thermosetting agent. In the dropping method, first, a rectangular sealing pattern is formed by dispensing one of the two substrates with electrodes. Then, the liquid crystal droplets are dropped into the sealing frame of the substrate in a state where the sealant is not hardened, and another substrate is superimposed under vacuum, and the sealing part is irradiated with light such as ultraviolet rays for pre-curing. After that, heating is performed to perform main curing, and a liquid crystal display element is produced. At present, this dropping method has become the mainstream of the manufacturing method of liquid crystal display elements.

In addition, various mobile devices with LCD panels, such as mobile phones and portable game consoles, are becoming popular in modern times, and miniaturization of the devices is the most pressing issue. As a method of miniaturization of the machine, the narrow edge of the liquid crystal display part can be cited, for example, a move to arrange the position of the sealing part under the black matrix (hereinafter, also referred to as narrow edge design).

However, in the narrow-edge design, since the sealant is arranged directly under the black matrix, if the dripping method is performed, the light irradiated when the sealant is hardened by light will be blocked, and the light will hardly reach the inside of the sealant. The conventional sealant does not harden sufficiently. If the curing of the sealant is not sufficient, the uncured sealant component will be eluted into the liquid crystal and the liquid crystal will be easily contaminated.

Therefore, it has been studied in the industry to harden the sealant only by heat, but if there is no pre-hardening by photopolymerization, there is a problem that the liquid crystal flows during heating and is inserted into the sealant part in the middle of curing to produce a sealing pattern. The damage, etc., or the liquid crystal is contaminated by the sealant whose viscosity is reduced by heating. Especially in recent years, with the narrowing of the edge of the panel, the width of the glued sealant has also become smaller, and the cross-sectional area of the sealant part after bonding has become smaller. Therefore, it is easy to cause damage to the sealing pattern.

In addition, in recent years, from the viewpoint of energy saving and liquid crystal stability, it has been desired to heat the sealant by heating at a low temperature in a short time to thermally harden the sealant. As a method to harden the sealant by heating at a low temperature and for a short time, consider using a thermal hardener or hardening accelerator with a low melting point. However, if a thermal hardener or hardening accelerator with a low melting point is used, there is a sealant The problem of poor storage stability.

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

[The problem to be solved by the invention]

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

The present invention is a sealing compound for liquid crystal display elements, which contains a curable resin, a thermal radical polymerization initiator, and a thermosetting agent. The thermosetting agent contains an amine adduct-based curing agent that is particulate at 25°C. The present invention will be described in detail below.

The present inventors found that by using a thermal radical polymerization initiator in combination with a particulate amine adduct curing agent at 25°C as a thermal curing agent, it is possible to obtain an excellent storage stability that can inhibit the insertion of liquid crystals. To the sealant or the sealant for liquid crystal display elements that cause liquid crystal contamination due to the sealant, the present invention has been completed. In the sealing compound for liquid crystal display elements of the present invention, the effect of suppressing insertion of liquid crystal into the sealing compound or liquid crystal contamination caused by the sealing compound is particularly remarkable when the sealing compound is hardened by only heat. In addition, the sealing compound for liquid crystal display elements of the present invention using a combination of a thermal radical polymerization initiator and an amine adduct-based curing agent in particulate form at 25°C as a thermal curing agent is even under low-temperature and short-time conditions It can also be fully hardened by heating it down.

The sealing compound for liquid crystal display elements of this invention contains a curable resin. The curable resin preferably contains a (meth)acrylic compound and an epoxy compound.

As the above-mentioned (meth)acrylic compound, for example, a (meth)acrylate compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid; and a (meth)acrylic acid compound obtained by reacting (meth)acrylic acid with epoxy Epoxy (meth)acrylate obtained by reacting a compound; urethane (meth)acrylate obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound )Wait. Among them, epoxy (meth)acrylate is preferred. In addition, in terms of high reactivity, the (meth)acrylic compound is preferably one having two or more (meth)acrylic groups in the molecule. Furthermore, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylic acid compound" means having an acrylic acid group or a methacrylic acid group (hereinafter also referred to as It is a compound of "(meth)acryloyl"). In addition, the above-mentioned "(meth)acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" means that all epoxy groups in the epoxy compound are combined with (meth)acrylic acid. The compound obtained by the reaction.

Examples of monofunctional ones in the above-mentioned (meth)acrylate compounds include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate Ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , Isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Isobornyl methacrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyglycol (meth)acrylate, methoxypolyethylene glycol ( Meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol ( Meth)acrylate, (meth)acrylate 2,2,2-trifluoroethyl, (meth)acrylate 2,2,3,3-tetrafluoropropyl, (meth)acrylate 1H,1H,5H -Octafluoropentyl ester, imine (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)propylene succinate Glyoxyethyl, hexahydrophthalic acid 2-(meth)acryloyloxyethyl, phthalic acid 2-(meth)acryloyloxyethyl 2-hydroxypropyl, phosphoric acid 2- (Meth) acrylate oxyethyl, (meth) glycidyl acrylate, etc.

In addition, examples of the bifunctional ones in the above-mentioned (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol two (Meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neoprene Alcohol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentadiene di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylic acid 2-hydroxy-3-(meth)acryloxy propyl ester, carbonate glycol di(meth)acrylate, polyether glycol di(meth)acrylate, polyester glycol di(meth) Acrylate, polycaprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate, etc.

In addition, examples of the above-mentioned (meth)acrylate compounds having three or more functions include trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(methyl) ) Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid Acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, phosphoric acid tri[(methyl) ) Allyloxyethyl] ester, di-trimethylolpropane tetra (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, Dineopentaerythritol hexa(meth)acrylate and so on.

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

As the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2 , 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type epoxy resin Resin, dicyclopentadiene novolac type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, epoxy propyl amine type epoxy resin, alkyl polyol type epoxy resin , Rubber modified epoxy resin, glycidyl ester compound, etc.

Examples of commercially available bisphenol A epoxy resins include jER 828EL, jER 1004 (all manufactured by Mitsubishi Chemical Corporation); Epiclon 850 (manufactured by DIC), and the like. Examples of commercially available bisphenol F epoxy resins include jER 806 and jER 4004 (all manufactured by Mitsubishi Chemical Corporation). As a commercially available one among the above-mentioned bisphenol S-type epoxy resins, for example, Epiclon EXA1514 (manufactured by Dyson Co., Ltd.) and the like can be cited. As a commercially available one among the above-mentioned 2,2'-diallyl bisphenol A epoxy resins, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) and the like can be cited. As a commercially available one among the above-mentioned hydrogenated bisphenol epoxy resins, for example, Epiclon EXA7015 (manufactured by Dyson Co., Ltd.) and the like can be cited. As a commercially available one among the aforementioned propylene oxide-added bisphenol A epoxy resins, for example, EP-4000S (manufactured by ADEKA) and the like can be cited. As a commercially available one among the above-mentioned resorcinol-type epoxy resins, EX-201 (manufactured by Nagase Kasei Co., Ltd.) etc. are mentioned, for example. As a commercially available one among the above-mentioned biphenyl-type epoxy resins, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) etc. are mentioned, for example. Examples of commercially available sulfide epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). As a commercially available one among the above-mentioned diphenyl ether type epoxy resins, for example, YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be cited. As a commercially available one among the above-mentioned dicyclopentadiene-type epoxy resins, EP-4088S (manufactured by Adic Co., Ltd.) etc. are mentioned, for example. As a commercially available one among the above-mentioned naphthalene type epoxy resins, for example, Epiclon HP4032, Epiclon EXA-4700 (both manufactured by D&E Corporation), etc. can be cited. As a commercially available one among the said phenol novolak type epoxy resins, Epiclon N-770 (manufactured by Dyson Co., Ltd.) etc. are mentioned, for example. As a commercially available one among the o-cresol novolak type epoxy resins mentioned above, for example, Epiclon N-670-EXP-S (manufactured by Di Aisheng) etc. can be mentioned. As a commercially available one among the above-mentioned dicyclopentadiene novolak-type epoxy resins, for example, Epiclon HP7200 (manufactured by Di Aison Co., Ltd.) and the like can be cited. As a commercially available one among the above-mentioned biphenol novolac type epoxy resins, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like can be cited. As a commercially available one among the above-mentioned naphthol novolak type epoxy resins, for example, ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be cited. Examples of commercially available glycidyl amine epoxy resins include: jER 630 (manufactured by Mitsubishi Chemical Corporation); Epiclon 430 (manufactured by Di Aisheng); TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), etc. . As commercially available among the above-mentioned alkyl polyol type epoxy resins, for example, ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Epiclon 726 (manufactured by Di Aisheng Co., Ltd.); Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) Manufacturing); Denacol EX-611 (manufactured by Nagase Chemical Co., Ltd.), etc. Examples of commercially available rubber-modified epoxy resins include: YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); Epolead PB (manufactured by Daicel), etc. . As a commercial item among the said glycidyl ester compounds, Denacol EX-147 (manufactured by Nagase Kasei Co., Ltd.) etc. are mentioned, for example. Examples of other commercially available epoxy compounds include: YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); XAC4151 (manufactured by Asahi Kasei Co., Ltd.); jER 1031, jER 1032 (all manufactured by Mitsubishi Chemical Corporation); EXA-7120 (manufactured by Di Aisheng); TEPIC (manufactured by Nissan Chemical Corporation), etc.

Examples of commercially available epoxy (meth)acrylates include: EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX63182 (all manufactured by Daicel-Allnex); EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all are Shinnakamura Chemical Industrial company manufacturing); 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 200 , Epoxy Ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.); Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all manufactured by Nagase Chemical Co.), etc.

The above-mentioned amine ester (meth)acrylate can be obtained by, for example, reacting 2 equivalents of a (meth)acrylic acid derivative having a hydroxyl group with 1 equivalent of an isocyanate compound having 2 isocyanate groups in the presence of a catalytic amount of a tin-based compound obtain.

Examples of the isocyanate compound used as the raw material of the above-mentioned amine ester (meth)acrylate include: isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate. Methylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate Isocyanate, toluidine diisocyanate, XDI, hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, thiophosphate tris(isocyanatophenyl) ester, tetramethyl stubble Diisocyanate, 1,6,11-undecane triisocyanate, etc.

In addition, as the above-mentioned isocyanate compound, for example, ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone two The chain-extended isocyanate compound is obtained by the reaction of polyol such as alcohol and excess isocyanate compound.

Examples of (meth)acrylic acid derivatives having hydroxyl groups used as raw materials for the above amine ester (meth)acrylates include: 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate , 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl mono(meth)acrylates; or ethylene glycol, 1,2-propanediol, 1,3-propanediol , 1,3-butanediol, 1,4-butanediol, polyethylene glycol and other glycol mono(meth)acrylates; or trimethylolethane, trimethylolpropane, glycerin, etc. Mono(meth)acrylate or di(meth)acrylate of triol; or epoxy (meth)acrylate such as bisphenol A epoxy acrylate, etc.

Examples of commercially available amine ester (meth)acrylates include: M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.); EEBECRYL 210, EEBECRYL 220, EBECRYL 230, EBECRYL 270, EBECRYL 1290, EBECRYL 2220, EBECRYL 4827, EBECRYL 4842, EBECRYL 4858, EBECRYL 5129, EBECRYL 6700, EBECRYL 8402, EBECRYL 8803, EBECRYL 8804, EBECRYL 8260 (all manufactured by Daicel ); Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H ( All are manufactured by Neshang Industrial Co., Ltd.); U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U- 108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-201BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A (all manufactured by Shinnakamura Chemical Industry Co., Ltd.); AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.), etc.

As said epoxy compound, the epoxy compound used as a raw material for synthesizing the said epoxy (meth)acrylate, or a partially (meth)acrylic modified epoxy resin etc. are mentioned, for example. Furthermore, in this specification, the above-mentioned partial (meth)acrylic modified epoxy resin means a compound having at least one epoxy group and (meth)acrylic acid group in one molecule, for example, Part of the epoxy group of an epoxy compound having two or more epoxy groups in one molecule is obtained by reacting (meth)acrylic acid.

As a commercially available one of the above-mentioned partially (meth)acrylic modified epoxy resins, for example, UVACURE 1561 (manufactured by Daicel Zhanxin Co., Ltd.) and the like can be cited.

When the sealing compound for liquid crystal display elements of the present invention contains the (meth)acrylic compound and the epoxy compound, it is preferable that the ratio of the (meth)acryloyl group to the epoxy group is 30:70~95 : Method 5 blends the above-mentioned (meth)acrylic compound and the above-mentioned epoxy compound. When the ratio of the (meth)acryloyl group is 30% or more, the obtained sealing compound for liquid crystal display elements is more excellent in low liquid crystal contamination. When the ratio of the (meth)acryloyl group is 95% or less, the adhesiveness of the obtained sealing compound for liquid crystal display elements is more excellent.

In terms of suppressing liquid crystal contamination, the curable resin is preferably one having hydrogen bonding units such _{as -OH group, -NH— group, and -NH 2 group.}

The sealing compound for liquid crystal display elements of this invention contains a thermal radical polymerization initiator. Examples of the thermal radical polymerization initiator include those composed of an azo compound, an organic peroxide, or the like. Among them, from the viewpoint of suppressing liquid crystal contamination, a starter composed of an azo compound (hereinafter, also referred to as an "azo starter") is preferred, and a polymer azo compound is more preferred. The initiator (hereinafter, also referred to as "polymer azo initiator"). In addition, in this specification, the above-mentioned "polymer azo compound" means having an azo group and generating radicals which can harden the (meth)acryloyl group by heat. The number average molecular weight of the radical is 300 or more. Compound.

The preferred lower limit of the number average molecular weight of the polymer azo initiator is 1,000, and the preferred upper limit is 300,000. When the number average molecular weight of the above-mentioned polymer azo initiator is in this range, it is possible to prevent adverse effects on the liquid crystal, and it is easier to mix into the curable resin. The lower limit of the number average molecular weight of the polymer azo initiator is more preferably 5,000, the upper limit is more preferably 100,000, the lower limit is more preferably 10,000, and the upper limit is more preferably 90,000. In addition, in this specification, the above-mentioned number average molecular weight is the value calculated|required by the polystyrene conversion measured by gel permeation chromatography (GPC). As a column for measuring the number average molecular weight calculated by polystyrene conversion by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) can be cited.

Examples of the above-mentioned polymer azo initiator include those having a structure in which multiple units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group. The polymer azo initiator having a structure in which multiple units such as polyalkylene oxide are bonded via an azo group is preferably one having a polyethylene oxide structure. As such a polymer azo initiator, for example, a condensation polymer of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4 '-Azobis(4-cyanovaleric acid) and polydimethylsiloxane having a terminal amine group, etc., specifically, for example: VPE-0201, VPE-0401, VPE-0601 , VPS-0501, VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.), etc. In addition, examples of azo initiators other than the polymer azo initiator include V-65, V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

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

The content of the thermal radical polymerization initiator relative to 100 parts by weight of the curable resin has a preferred lower limit of 0.05 parts by weight and a preferred upper limit of 10 parts by weight. When the content of the thermal radical polymerization initiator is in this range, the liquid crystal contamination caused by the unreacted thermal radical polymerization initiator is suppressed, and the obtained sealing compound for liquid crystal display elements is more excellent in thermal curability . The lower limit of the content of the thermal radical polymerization initiator is more preferably 0.1 parts by weight, and the upper limit is more preferably 5 parts by weight.

In addition to the above-mentioned thermal radical polymerization initiator, the sealing compound for liquid crystal display elements of the present invention may also contain a photoradical polymerization initiator. However, as described above, the sealing compound for liquid crystal display elements of the present invention inhibits liquid crystal insertion The effect of the sealant or the liquid crystal contamination caused by the sealant is particularly obvious when the sealant is hardened only by heat.

（thioxanthone）等。Examples of the aforementioned photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, phosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, Diphenyl ethylenedione, 9-oxysulfur

(Thioxanthone) and so on.

Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE 01, Lucirin TPO (all BASF (Manufactured by BASF); benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

The content of the photo radical polymerization initiator relative to 100 parts by weight of the curable resin has a preferred lower limit of 0.1 parts by weight and a preferred upper limit of 10 parts by weight. When the content of the photoradical polymerization initiator is 0.1 parts by weight or more, the obtained sealing compound for liquid crystal display elements is more excellent in photocurability. When the content of the above-mentioned radical photopolymerization initiator is 10 parts by weight or less, a lot of unreacted radical photopolymerization initiator does not remain, and the obtained sealing compound for liquid crystal display elements has more excellent weather resistance. The lower limit of the content of the photo radical polymerization initiator is more preferably 0.2 parts by weight, and the upper limit is more preferably 8 parts by weight.

The sealing compound for liquid crystal display elements of this invention contains a thermosetting agent. The said thermosetting agent contains the amine adduct type hardening agent which is particulate form at 25 degreeC. By containing the above-mentioned amine adduct hardener, when the sealing agent is heated, the sealing agent can be hardened at the temperature before the reaction of the thermal radical polymerization initiator starts, and the sealing agent caused by heating can be suppressed The viscosity is reduced.

As the above-mentioned amine adduct curing agent, for example, an adduct obtained by reacting an amine compound such as imidazole or a tertiary amine with a compound having an unsaturated double bond such as acrylonitrile or an epoxy compound, etc. Wait.

The preferred lower limit of the melting point of the above-mentioned amine adduct hardener is 70°C, and the preferred upper limit is 140°C. When the melting point of the above-mentioned amine adduct curing agent is in this range, the obtained sealing compound for liquid crystal display elements maintains excellent storage stability and has more excellent low-temperature curability. The lower limit of the melting point of the above-mentioned amine adduct hardener is more preferably 80°C, and the more preferable upper limit is 130°C.

Examples of commercially available amine adduct hardeners include: Amicure PN-23, Amicure PN-23J, Amicure PN-H, Amicure PN-31, Amicure PN-31J, Amicure PN-40, Amicure PN-40J, Amicure PN-50, Amicure PN-F, Amicure MY-24, Amicure MY-H (all manufactured by Ajinomoto Fine-Techno); P-055 (manufactured by Shikoku Kasei); P-200 (Mitsubishi) Manufactured by chemical companies) and so on.

The preferred upper limit of the average particle size of the above-mentioned amine adduct hardener is 3 μm. When the average particle diameter of the above-mentioned amine adduct hardener is 3 μm or less, the effect of preventing gap defects in the obtained liquid crystal display element is more excellent. The preferable lower limit of the average particle diameter of the above-mentioned amine adduct hardener does not particularly exist, and the actual lower limit is 0.1 μm. Furthermore, in the case of using a commercially available amine adduct-based hardener with an average particle size exceeding 3 μm, the average particle size can be made 3 μm or less by performing treatments such as pulverization or classification. In addition, in this specification, the average particle diameter of the above-mentioned amine adduct hardener and the following maximum particle diameter mean that by using laser diffraction on the amine adduct hardener before being blended into the sealant The value obtained by measuring with a type particle size distribution measuring device. As the above-mentioned laser diffraction particle size distribution measuring device, Mastersizer 2000 (manufactured by Malvern Corporation) or the like can be used.

The preferred upper limit of the maximum particle size of the above-mentioned amine adduct hardener is 5.0 μm. When the maximum particle size of the above-mentioned amine adduct curing agent is 5.0 μm or less, the effect of preventing gap defects in the obtained liquid crystal display element is more excellent. The upper limit of the maximum particle size of the above-mentioned amine adduct hardener is more preferably 4.5 μm. The preferred lower limit of the maximum particle size of the above-mentioned amine adduct hardener does not particularly exist, and the actual lower limit is 0.1 μm.

The amine adduct hardener is preferably contained in the particle size distribution of the amine adduct hardener measured by the laser diffraction particle size distribution measuring device. The ratio is 99% or more in terms of volume frequency. Since the content ratio of particles with a particle diameter of 3.0 μm or less is 99% or more in terms of volume frequency, the effect of preventing gap defects in the obtained liquid crystal display element is more excellent. The content of particles with a particle size of 3.0 μm or less is preferably 100%.

The content of the amine adduct-based curing agent is preferably 0.05 parts by weight, and the upper limit is preferably 40 parts by weight relative to 100 parts by weight of the curable resin. When the content of the above-mentioned amine adduct curing agent is 0.05 parts by weight or more, the low-temperature curability of the sealant for liquid crystal display elements obtained is improved, and the effect of inhibiting the insertion of the liquid crystal into the sealant or the contamination of the liquid crystal due to the sealant is improved. Excellent. When the content of the amine adduct-based curing agent is 40 parts by weight or less, the obtained sealing compound for liquid crystal display elements is more excellent in low liquid crystal contamination. The lower limit of the content of the above-mentioned amine adduct hardener is more preferably 0.1 parts by weight, and the upper limit is more preferably 30 parts by weight.

In addition to the above-mentioned amine adduct-based hardener, the above-mentioned thermosetting agent may contain other thermosetting agents. Examples of the above-mentioned other thermosetting agents include hydrazine-based curing agents, imidazole-based curing agents, polyphenol-based curing agents, and acid anhydride-based curing agents. Among them, hydrazine-based hardeners are suitably used.

Examples of the above-mentioned hydrazine-based hardener include: 1,3-bis(hydrazinocarbonylethyl)-5-isopropylhydantoin, dihydrazine sebacate, dihydrazide isophthalate, Commercially available dihydrazine adipate, dihydrazine malonate, etc. include, for example, Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine-Techno); SDH, IDH, ADH (all Otsuka Chemical Manufactured by the company); MDH (manufactured by Japan Finechem), etc.

The preferred lower limit of the melting point of the above-mentioned other thermal hardening agents is 140°C, and the preferred upper limit is 200°C. When the melting point of the above-mentioned other thermosetting agent is in this range, the obtained sealing compound for liquid crystal display elements is more excellent in thermosetting properties and low liquid crystal contamination. The lower limit of the melting point of the above-mentioned other thermal hardening agents is more preferably 150°C, and the more preferable upper limit is 190°C.

When the above-mentioned other thermosetting agent is contained, the lower limit of the content of the above-mentioned amine adduct based hardening agent relative to 100 parts by weight of the above-mentioned other thermosetting agent is preferably 0.3 parts by weight, and the upper limit is preferably 200 parts by weight. When the content of the amine adduct curing agent relative to 100 parts by weight of the other thermosetting agent is in this range, the obtained sealing compound for liquid crystal display elements maintains excellent storage stability and low liquid crystal contamination, and is cured at low temperature The sex is more excellent. The lower limit of the content of the amine adduct hardener relative to 100 parts by weight of the other thermal hardeners is more preferably 0.5 parts by weight, and the upper limit is more preferably 150 parts by weight.

When the other thermosetting agent is contained, the content of the thermosetting agent as a whole is relative to 100 parts by weight of the curable resin, the lower limit is preferably 1 part by weight, and the upper limit is preferably 50 parts by weight. When the content of the entire thermosetting agent is 1 part by weight or more, the obtained sealing compound for liquid crystal display elements has more excellent thermosetting properties. When the total content of the thermosetting agent is 50 parts by weight or less, the viscosity of the obtained sealant does not become too high, and the coatability is more excellent. The more preferable upper limit of the total content of the thermal hardening agent is 30 parts by weight.

The sealing compound for liquid crystal display elements of the present invention can also contain fillers for the purposes of improving viscosity, improving adhesion based on the stress dispersion effect, improving linear expansion, and further improving the moisture resistance of the cured product.

Examples of the aforementioned filler include: 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, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride and other inorganic fillers ; Or organic fillers such as polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, core-shell acrylate copolymer microparticles, etc. These fillers may be used alone or in combination of two or more kinds.

The lower limit of the content of the filler in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is preferably 10 parts by weight, and the upper limit is preferably 70 parts by weight. When the content of the filler is in this range, the deterioration of coatability and the like is suppressed, and the effects such as improvement of adhesiveness are more excellent. The lower limit of the filler content is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.

The sealing compound for liquid crystal display elements of this invention may contain a silane coupling agent. The above-mentioned silane coupling agent mainly functions as an adhesive auxiliary agent for bonding the sealant to the substrate and the like well. As the above-mentioned silane coupling agent, it is excellent in the effect of improving the adhesion with the substrate, etc., by chemically bonding with the curable resin to prevent the curable resin from flowing out into the liquid crystal, for example, N-phenyl is suitably used －3-Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanate Group propyl trimethoxysilane and so on. These silane coupling agents may be used alone or in combination of two or more kinds.

The lower limit of the content of the silane coupling agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is preferably 0.1 parts by weight, and the upper limit is preferably 20 parts by weight. When the content of the silane coupling agent is in this range, the generation of liquid crystal contamination is suppressed, and the effect of improving adhesion is more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.5 parts by weight, and the upper limit is more preferably 10 parts by weight.

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

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

The above-mentioned titanium black is a substance that has a higher transmittance in the vicinity of the ultraviolet region, especially light with a wavelength of 370 to 450 nm, compared to the average transmittance of light with a wavelength of 300 to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent having the following properties: it imparts light-shielding properties to the sealing compound for liquid crystal display elements of the present invention by sufficiently shielding light of a wavelength in the visible light region, and on the other hand, makes light of a wavelength near the ultraviolet region transmission. Therefore, as the above-mentioned photoradical polymerization initiator, the light of the wavelength (370~450 nm) whose transmittance of the above-mentioned titanium black becomes higher can be used to start the reaction, thereby further increasing the liquid crystal display of the present invention. Light-curing properties of sealant for components. On the other hand, as the light-shielding agent contained in the sealing compound for liquid crystal display elements of the present invention, a substance with high insulation is preferred, and as a light-shielding agent with high insulation, titanium black is also suitable. The optical density (OD value) per 1 μm of the titanium black is preferably 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better, and the OD value of the titanium black does not particularly have a preferable upper limit, and it is usually 5 or less.

The above-mentioned titanium black exhibits a sufficient effect even if the surface treatment is not performed, but the surface has been treated with organic components such as coupling agent, or it is treated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, etc. Surface-treated titanium black coated with inorganic components such as magnesium oxide. Among them, those that have been processed with organic components are preferred in terms of further improving insulation. In addition, the liquid crystal display element manufactured using the sealant for liquid crystal display element of the present invention blended with the titanium black as a light-shielding agent has sufficient light-shielding properties, so that there is no light leakage, high contrast, and excellent The image display quality of the liquid crystal display element.

Examples of commercially available titanium blacks include: 12S, 13M, 13M-C, and 13R-N (all manufactured by Mitsubishi Materials); 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, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω·cm, the preferred upper limit is 3 Ω·cm, the more preferred lower limit is 1 Ω·cm, and the more preferred upper limit is 2.5 Ω·cm.

The primary particle size of the aforementioned light-shielding agent is not particularly limited as long as it is less than the distance between the substrates of the liquid crystal display element, and the preferred lower limit is 1 nm, and the preferred upper limit is 5 μm. When the primary particle diameter of the said light-shielding agent is this range, the light-shielding property can be made more excellent without worsening the coatability etc. of the sealing compound for liquid crystal display elements obtained. The lower limit of the primary particle size of the sunscreen is more preferably 5 nm, the upper limit is more preferably 200 nm, the lower limit is more preferably 10 nm, and the upper limit is more preferably 100 nm. Furthermore, the primary particle size of the above-mentioned sunscreen can be measured by dispersing the above-mentioned sunscreen in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The lower limit of the content of the light-shielding agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is preferably 5 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the light-shielding agent is 5 parts by weight or more, the obtained sealing compound for liquid crystal display elements is more excellent in light-shielding properties. When the content of the light-shielding agent is 80 parts by weight or less, the obtained sealing compound for liquid crystal display elements is more excellent in adhesion to the substrate, strength after curing, and drawing properties. The lower limit of the content of the sunscreen is more preferably 10 parts by weight, the upper limit is more preferably 70 parts by weight, the lower limit is more preferably 30 parts by weight, and the upper limit is more preferably 60 parts by weight.

The sealing compound for liquid crystal display elements of the present invention may further contain a reactive diluent for adjusting the viscosity, spacers such as polymer beads for adjusting the gap between the panels, and 3-P-chlorophenyl-1,1 as needed. －Dimethylurea, isocyanuric acid and other hardening accelerators, defoamers, leveling agents, polymerization inhibitors, other coupling agents and other additives.

As a method of manufacturing the sealing compound for liquid crystal display elements of the present invention, for example, the following methods can be cited: using mixers such as homogeneous dispersers, homomixers, universal mixers, planetary mixers, kneaders, and three-roll mills , Mixing additives such as curable resin, thermal radical polymerization initiator, thermosetting agent and optionally filler or silane coupling agent.

The sealant for liquid crystal display elements of the present invention is preferably a glass substrate with ITO. 0.1 g of the sealant is coated in dots, and the glass substrate is heated at 120°C for 5 minutes while tilting the glass substrate at 45 degrees with respect to the horizontal plane. After that, the maximum moving distance of the sealant from the coating position is less than 20 mm. Since the above-mentioned moving distance is 20 mm or less, the shape retention during heating is excellent, and the insertion of the liquid crystal into the sealant or the contamination of the liquid crystal due to the sealant can be sufficiently suppressed. In addition, 0.1 g of the sealant was applied into dots on a glass substrate with ITO, and after the glass substrate was heated at 120°C for 5 minutes while the glass substrate was tilted 45 degrees with respect to the horizontal plane, the sealant moved from the application position The sealing compound for liquid crystal display elements whose maximum distance is 20 mm or less is also one of this invention.

By blending conductive fine particles in the sealing compound for liquid crystal display elements of the present invention, a vertical conduction material can be produced. In addition, such a top and bottom conduction material containing the sealing compound for liquid crystal display elements of the present invention and conductive fine particles is also one of the present invention.

As the conductive fine particles, for example, metal balls, those having a conductive metal layer formed on the surface of resin fine particles, or the like can be used. Among them, those with a conductive metal layer formed on the surface of the resin particles are more suitable due to the excellent elasticity of the resin particles, which can achieve conductive connection without damaging the transparent substrate or the like.

Moreover, the liquid crystal display element which has the sealing compound for liquid crystal display elements of this invention or the top and bottom conduction material of this invention is also one of this invention. As the method of manufacturing the liquid crystal display element of the present invention, the liquid crystal dropping method is suitably used. Specifically, for example, a method having the following steps can be mentioned: on one of two transparent substrates having electrodes such as an ITO film, by Screen printing, dispenser coating, etc. form the sealant for liquid crystal display elements of the present invention into a frame-shaped seal pattern; drop liquid crystal droplets onto the entire frame of the seal pattern, and overlap another substrate under vacuum; And heat it to harden the sealant. In addition, before the step of heating and hardening the sealant, a step of pre-hardening the sealant by light irradiation may also be performed. [Effects of Invention]

According to the present invention, it is possible to provide a sealing compound for a liquid crystal display element which is excellent in storage stability and can suppress the insertion of liquid crystal into the sealing compound or the contamination of the liquid crystal due to the sealing compound. In addition, according to the present invention, it is possible to provide a top-bottom conduction material and a liquid crystal display element manufactured using the sealing compound for liquid crystal display elements.

Hereinafter, examples are provided to illustrate the present invention in more detail, but the present invention is not limited to these examples.

(Examples 1 to 14, Comparative Examples 1 to 6) According to the blending ratios described in Tables 1 and 2, the materials were mixed using a planetary mixer (manufactured by Thinky, "Defoaming Rintaro"), and then further mixed using a three-roll mill to prepare and implement The sealing compound for each liquid crystal display element of Examples 1 to 14 and Comparative Examples 1 to 6. In addition, the "PN-23J" and "PN-40J" in the table used as hardeners for amine adducts are used in the form of particles at 25°C. They are crushed and classified to make "PN-23J" The average particle size of "PN-40J" is 1.2 μm, and the average particle size of "PN-40J" is 1.1 μm.

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

(Storage stability) For each liquid crystal display element sealing compound obtained in the Examples and Comparative Examples, the initial viscosity immediately after manufacture and the viscosity when stored at 25°C for 3 days were measured, and the (viscosity after storage at 25°C for 3 days)/( The initial viscosity) was set as the rate of change in viscosity. If the rate of change in viscosity was less than 1.5, set to "○", and if the rate of change of viscosity was 1.5 or more, set to "×" to evaluate the storage stability. Furthermore, the viscosity of the sealant was measured using an E-type viscometer (manufactured by BROOK FIELD, "DV-III") at 25°C with a rotation speed of 1.0 rpm.

(Shape retention) 0.1 g of each liquid crystal display element sealant obtained in the examples and comparative examples was applied to a glass substrate with ITO in dots, and the glass substrate was placed at 120°C while the glass substrate was tilted 45 degrees with respect to the horizontal plane. In the oven, observe the glass substrate after heating for 5 minutes, and measure the movement distance of the sealant from the coating position. When the maximum moving distance of the sealant from the application position is 20 mm or less, set it as "○", and when it exceeds 20 mm, set it as "×" to evaluate the shape retention.

(Curing characteristics) With respect to 100 parts by weight of each liquid crystal display element sealant obtained in the examples and comparative examples, spacer particles with an average particle diameter of 5 μm (manufactured by Sekisui Chemical Industry Co., Ltd., Micropearl SP-2050") 1 part by weight is uniformly dispersed, the obtained sealant is coated on a glass substrate with ITO and bonded, and then the sealant is fully crushed and put into an oven at 120°C or 110°C . After that, the substrate was peeled off with a cutter, and the spectrum of the sealant was measured by the micro-IR method, and the conversion rate of acryl group and the conversion of epoxy group in the sealant were obtained by the following methods based on each spectrum rate. That is, 815~800 cm ^{- 1} peak area to the peak area of Bing Xixi group of the 920~910 cm ^{- 1} peak area to the peak area of epoxy groups, will 845~820 cm ^{- 1} peak area of Set as the reference peak area, calculate the conversion rate of acryl group and the conversion rate of epoxy group by the following formula, set the average value of 80% or more to "○", and set the value of less than 80% to "×" to evaluate the curability of the light-shielding part. Conversion rate of acrylic base = {1-(peak area of acrylic base after ultraviolet irradiation/reference peak area after ultraviolet irradiation)/(peak area of acrylic base before ultraviolet irradiation/reference peak area before ultraviolet irradiation )}×100 Epoxy group conversion rate = {1－(Epoxy group peak area after UV irradiation/reference peak area after UV irradiation)/(Epoxy group peak area before UV irradiation/Before UV irradiation The reference wave peak area)}×100

(Prevention of insertion) With respect to 100 parts by weight of each liquid crystal display element sealant obtained in the examples and comparative examples, spacer particles with an average particle diameter of 5 μm (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SP-2050") 1 part by weight is uniformly dispersed, and the obtained sealant is filled into a dispensing syringe (manufactured by Musashi Engineering, "PSY-10E"), and after defoaming treatment, Using a dispenser (manufactured by Musashi Kogyo Co., Ltd., "SHOTMASTER 300"), one of two glass substrates with rubbed alignment film and ITO is applied to form a frame with a line width of 1 mm Sealants. Then, a droplet of TN liquid crystal (manufactured by Chisso, "JC-5001LA") was applied to the entire frame of the sealant by a liquid crystal dropping device, and another glass substrate was immediately bonded to obtain a unit. The obtained cell was heated at 120° C. for 1 hour to thermally harden the sealant, thereby obtaining a liquid crystal display element (cell gap 5 μm). For the sealants for liquid crystal display elements obtained in Examples 8 to 14 and Comparative Examples 4 to 6, heating at 120°C for 1 hour to heat the sealant was irradiated with a metal halide lamp for 100 mW/ cm ² of ultraviolet light for 30 seconds to pre-harden the sealant. The shape of the sealing part was observed for each of the obtained liquid crystal display elements. As a result, the shape of the sealing part is not disturbed by the internal liquid crystal as "○", the shape of the sealing pattern is slightly disturbed as "Δ", and the shape of the sealing part is quite disturbed as "×" And evaluate the prevention of insertion.

(Display performance of liquid crystal display element) Drive the liquid crystal display element obtained in the above "(Insertion prevention)" with a voltage of AC3.5 V, and visually observe the presence or absence of display unevenness (color unevenness). Set the case where there is no display unevenness at the periphery of the liquid crystal display element to "◎", and set the case where the display unevenness is slightly lighter to "○", and there will be a clear and thicker display unevenness. Set it as "Δ", and set the case where the clear and thick display unevenness not only exists in the peripheral part, but also spread to the center part, as "×" to evaluate the display performance of the liquid crystal display element. Furthermore, the liquid crystal display elements evaluated as "◎" and "○" are at a level that there is no problem in practical use.

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Composition (parts by weight) Hardening resin Bisphenol A epoxy acrylate (manufactured by Daicel Zhanxin, "EBECRYL 3700") 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Bisphenol A type epoxy resin (manufactured by Di Aisheng, "Epiclon 850") 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Thermal radical polymerization initiator Polymer azo initiator (manufactured by Wako Pure Chemical Industries, Ltd., "VPE-0201") 5 5 5 5 - - 5 5 5 5 5 - - 5 Organic peroxide-based initiator (manufactured by NOF Corporation, "Peroyl L") - - - - 1 1 - - - - - 1 1 - Light radical polymerization initiator 1-Hydroxycyclohexyl phenyl ketone (manufactured by BASF, "IRGACURE 184") - - - - - - - 1 1 1 1 1 1 1 Thermal hardener Amine adduct series hardener PN-23J (manufactured by Ajinomoto Fine-Techno, melting point 90℃～110℃) 3 0.1 30 - 3 - 3 3 0.1 30 - 3 - 3 PN-40J (manufactured by Ajinomoto Fine-Techno, melting point 100℃～125℃) - - - 3 - 3 - - - - 3 - 3 - other Dihydrazine sebacate (manufactured by Otsuka Chemical Co., "SDH", melting point 186°C) 20 20 20 20 20 20 - 20 20 20 20 20 20 - Imidazole-based hardener (manufactured by Shikoku Chemical Co., Ltd., "2MA-OK") - - - - - - - - - - - - - - Filler Silicon dioxide (manufactured by Admatechs, "Admafine SO-C2") 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Evaluation Storage stability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Shape retention ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Hardening characteristics 120°C ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ 110°C ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Prevent penetration ○ △ ○ ○ ○ ○ ○ ○ △ ○ ○ ○ ○ ○ Display performance of liquid crystal display element ◎ ○ ○ ◎ ○ ○ ◎ ◎ ○ ○ ◎ ○ ○ ◎

[Table 2] Comparative example 1 2 3 4 5 6 Composition (parts by weight) Hardening resin Bisphenol A epoxy acrylate (manufactured by Daicel Zhanxin, "EBECRYL 3700") 50 50 50 50 50 50 Bisphenol A type epoxy resin (manufactured by Di Aisheng, "Epiclon 850") 50 50 50 50 50 50 Thermal radical polymerization initiator Polymer azo initiator (manufactured by Wako Pure Chemical Industries, Ltd., "VPE-0201") - 5 5 - 5 5 Organic peroxide-based initiator (manufactured by NOF Corporation, "Peroyl L") - - - - - - Light radical polymerization initiator 1-Hydroxycyclohexyl phenyl ketone (manufactured by BASF, "IRGACURE 184") - - - 1 1 1 Thermal hardener Amine adduct series hardener PN-23J (manufactured by Ajinomoto Fine-Techno, melting point 90℃～110℃) 3 - - 3 - - PN-40J (manufactured by Ajinomoto Fine-Techno, melting point 100℃～125℃) - - - - - - other Dihydrazine sebacate (manufactured by Otsuka Chemical Co., "SDH", melting point 186°C) 20 20 20 20 20 20 Imidazole-based hardener (manufactured by Shikoku Chemical Co., Ltd., "2MA-OK") - - 3 - - 3 Filler Silicon dioxide (manufactured by Admatechs, "Admafine SO-C2") 20 20 20 20 20 20 Evaluation Storage stability ○ ○ X ○ ○ X Shape retention X X ○ X X ○ Hardening characteristics 120°C X ○ ○ X ○ ○ 110°C X X ○ X X ○ Prevent penetration X X ○ X X ○ Display performance of liquid crystal display element X X ○ X X ○ [Industrial availability]

According to the present invention, it is possible to provide a sealing compound for a liquid crystal display element which is excellent in storage stability and can suppress the insertion of liquid crystal into the sealing compound or the contamination of the liquid crystal due to the sealing compound. In addition, according to the present invention, it is possible to provide a top-bottom conduction material and a liquid crystal display element manufactured using the sealing compound for liquid crystal display elements.

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Claims (8)

A sealant for liquid crystal display elements, which contains a curable resin, a thermal radical polymerization initiator and a thermal hardener, The thermosetting agent contains an amine adduct system curing agent in the form of particles at 25°C. For example, the sealing compound for liquid crystal display elements in the first item of the scope of patent application, wherein the average particle size of the amine adduct curing agent is 3 μm or less. For example, the sealing compound for liquid crystal display elements of the first or second patent application, wherein the amine adduct hardener has a melting point of 70°C to 140°C. For example, the sealing compound for liquid crystal display elements in the scope of patent application 1, 2 or 3, which further contains a hydrazine-based hardening agent as a thermal hardening agent. For example, the sealing compound for liquid crystal display elements of the first, second, third, or fourth patent application, wherein the thermal radical polymerization initiator is an azo initiator. A sealant for liquid crystal display elements, which is as follows: 0.1 g of the sealant is coated in dots on a glass substrate with ITO, and the glass substrate is heated at 120°C while the glass substrate is tilted 45 degrees with respect to the horizontal plane After 5 minutes, the maximum moving distance of the sealant from the coating position is less than 20 mm. An up-and-down conduction material containing the sealant for liquid crystal display elements of the 1, 2, 3, 4, 5, or 6 scope of the patent application and conductive microparticles. A liquid crystal display element with the first, second, third, fourth, fifth, or sixth patent application sealant for the liquid crystal display element or the seventh patent application upper and lower conductive material.