TW200949393A - Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element - Google Patents

Abstract

Disclosed is a sealing agent for use in a liquid crystal dropping process, which enable the production of a liquid crystal display element having reduced unevenness in color and high image quality even when the liquid crystal display element is produced by a dropping process. The sealing agent comprises a resin having a (meth)acryl group and a polymeric azo initiator.

Description

[Technical Field] The present invention relates to a liquid crystal dropping method sealing method for a liquid crystal display element which can produce a high-quality image having a small color unevenness even when a liquid crystal display element is manufactured by a dropping method. Agent. Further, the present invention relates to a liquid crystal panel sealing agent which is capable of producing a liquid crystal display element of high quality image having a small color unevenness when a liquid crystal display device is manufactured by a vacuum injection method. [Prior Art] ❹

Conventionally, a liquid crystal display element such as a liquid crystal display unit is produced by a method called a vacuum injection method in which two transparent substrates with electrodes are separated by a predetermined (four) partition (four), and a periphery thereof is sealed with a sealant. The unit injects liquid crystal into the unit from a liquid crystal injection port provided in a part of the unit, and seals the liquid crystal injection port with a sealant or a sealing agent. In the vacuum injection method, first, a seal pattern provided with a liquid crystal injection port using a thermosetting sealant is formed by screen printing on any of the two transparent substrates with electrodes, at 6 〇 丨〇〇 丨〇〇 丨〇〇 Prebaking is carried out to dry the solvent in the sealant. Next, the two substrates are opposed to each other with the spacer 胄 interposed therebetween, and they are aligned and bonded together. The hot pressing is performed for 1 to 9 minutes at 110 to 22 Torr, and the gap near the sealing member is adjusted, and then in the oven. The liquid crystal display element is produced by heating (10 to 120 minutes under the ι〇~22 generation to form a hardening of the sealant, then injecting liquid crystal from the liquid crystal injection port, and finally sealing the liquid crystal injection port with a sealing agent.) In view of shortening the takt time and optimizing the amount of liquid crystal, the liquid crystal display device such as a liquid crystal display device 3 200949393 is being manufactured by the above-described vacuum injection method into, for example, Patent Document 2 The liquid crystal dropping method disclosed in the method of dripping, 1 聃 渴 渴 渴 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' a sealing agent composed of a light-curing resin composition of a polymerization initiator, and a liquid crystal dropping method, first in one of two substrates with electrodes Then, in a state in which the sealant is not hardened, droplets of liquid crystal are dropped onto the entire surface of the substrate, and another substrate is superposed under vacuum, and after returning to normal pressure, ultraviolet rays are irradiated to the sealing portion. The curing of the acrylic resin (pre-hardening step). Thereafter, the epoxy resin is cured by heating to form a liquid crystal display element. However, various mobile devices including liquid crystal panels such as mobile phones and handheld game machines are popular today. The miniaturization of the device is a problem that is most demanded. The miniaturization technique is to narrow the edge of the liquid crystal display portion, and for example, the position of the sealing portion is placed under a black matrix (hereinafter also referred to as a narrow edge design). However, if the dropping method is carried out with a narrow edge design, there is a problem in that a portion of the acrylic resin which is not hardened by insufficient light irradiation due to the presence of light in the sealed portion due to the black matrix is present. After the pre-hardening step, the uncured acrylic resin is eluted to contaminate the liquid crystal, thereby causing liquid crystal display unevenness. In order to accurately illuminate the sealing portion under the black matrix, it is also considered to use a method of irradiating light from the back side of the substrate, that is, the array side. However, metal wiring, a transistor, etc. are also present on the & p train substrate, and are sealed. For the problem, in order to reliably harden the uncured acrylic resin even after light irradiation, it is considered to use a peroxide or an azo compound compounded with a low molecular weight as a component. A method of sealing a component which thermally cures an acrylic resin. When such a sealant is used, the acrylic resin which is not cured in the pre-hardening step can be cured by heating during liquid crystal annealing. However, there are the following problems: A low molecular weight peroxide or an azo compound is eluted into the liquid crystal to cause color unevenness around the sealing portion, resulting in a liquid crystal display element in which high quality image cannot be obtained. On the other hand, when a liquid crystal display device is manufactured by a vacuum injection method which is a conventional method, there is a problem similar to the case of the liquid crystal dropping method described above. In other words, when the liquid crystal display device is manufactured by the vacuum injection method, the sealing agent for the liquid crystal panel for liquid crystal sealing is in contact with the liquid crystal in an uncured state. Here, when the liquid crystal panel sealing agent is not irradiated with sufficient light, color unevenness is generated around the sealing portion, and a liquid crystal display element of high quality image cannot be obtained. In view of the above-mentioned status quo, it is an object of the present invention to provide a liquid crystal display by using a dropping method, in addition to the above-mentioned state of the art. In the case of a device, it is also possible to manufacture a sealing compound for a liquid crystal dropping method of a liquid crystal display element of a quality image having a small color unevenness. Further, an object of the present invention is to provide a liquid crystal panel sealing agent which is capable of producing a high-quality image having a low color unevenness when a liquid crystal display device is manufactured by a vacuum injection method. The present invention is a sealant for a liquid crystal dropping method comprising a resin having a (meth)acryl group and a high molecular azo initiator. The present invention is a sealing agent for a liquid crystal panel containing a resin having a (meth)acryl group and a high molecular odor initiator. The invention is described in detail below. The inventors of the present invention have conducted intensive studies and found that a sealant for a liquid crystal dropping method containing a resin having a (meth)acryl group and a polymer azo initiator, the azo initiator itself is liquid crystal when thermally hardened. The present invention has been completed without any adverse effect, and by curing an uncured (fluorenyl) acrylate-based resin, a liquid crystal display element having a low-quality, low-quality image can be produced. The sealing agent for a liquid crystal dropping method of the present invention contains a polymer azo initiator. In the sealant for a liquid crystal dropping method of the present invention, the use of such an initiator "even a sealing portion which is not irradiated to a portion of light due to a black matrix or the like" can be surely hardened by heat, and thus occurs. There are very few cases of liquid crystal contamination. In the present specification, the term "polymer azo initiator" means a compound having an even gas group and having a molecular weight of 300 or more which can be formed by radicals which harden a (meth)acrylic group by heat. Further, the above-mentioned polymer azo initiator generally generates a radical by decomposition by light irradiation, and therefore functions as a photoradical initiator. 200949393 The preferred lower limit of the number average molecular weight of the above polymer azo initiator is 1000 Å. The upper limit is 300,000. If the amount of the above-mentioned polymer azo initiator is less than 1GG0', the polymer azo initiator may adversely affect the liquid crystal. If it exceeds 3 Å, it becomes difficult to mix into (meth) The base of the acrylic tree. The lower limit of the number average molecular weight of the above polymer azo initiator is 5,000, and the upper limit is preferably 10,000 and the lower limit is 10,000 Å and the upper limit is 90,000.

The preferred lower limit of the 10-hour half-life temperature of the above polymer azo initiator is 5 generations, and the preferred upper limit is 9n. The half-life temperature of the polymer azo compound is less than 5 〇. (:, the storage liquidity of the obtained liquid crystal dropping method with the sealant is deteriorated. 1 The half-life temperature of the above-mentioned polymer azo hydrazine exceeds the thief'. The liquid crystal dropping method of the present invention uses a seal: the hardening requires high temperature and long time. Will affect the productivity of the panel

The above polymer azo starting group is bonded to a plurality of polydioxides. The agent may have a structure in which a plurality of units such as polyoxynitride are bonded via a knot of a unit such as azo oxyhydrogen or (tetra) oxygen, and preferably an oxyethylene structure. Examples of such a polymer odor initiator include a polycondensate of 4,4.-cyanovaleric acid and a polyalkylene glycol, or 4,4, azo acid, and a terminal amine group. Polydimethyl silane (tetra) compound or the like; specifically, 'for example, νΡΕ·_, νΡΕ.〇4()1, νρΕ〇6〇ι VPS-0501, VPS·vine (all are pure chemical industry) In the above-mentioned polymer azo compound, the polymer azo compound represented by the following general formula (I), which is described in JP-A-2008-50572, and JP-A-200342784, can be used.

In the formula (I), R12, R13, R22 and r23 each independently represent an alkyl group or a cyano group having 1 to 10 carbon atoms, each independently being a number of 〇~4, and An and A12 are a polymer chain, γ" ΐ ΐ 2 is independently _c 〇〇 ·, -O-CO-, -NH-CO-, -CO-NH-, 〇· or -S-. In the above formula (I), the alkyl group having 1 to 10 carbon atoms represented by R 丨 2, Rl 3 , 尺 22 and R 23 may, for example, be a methyl group, an ethyl 'propyl group or an isopropyl group. , butyl, t-butyl, tert-butyl, isobutyl, pentyl, isopentyl 'tripentyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isethylene Base, third heptyl, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, n-decyl, n-decyl, and the like. In the above formula (I), the polymer chain represented by AH and A 2 is not particularly limited, and examples thereof include a polyoxyethylene (10) (four) ruthenium chain, a polymethylene chain, a poly-chain, and a poly-chain. Polyacetal chain, polyoxyalkylene chain, poly(meth)acrylic acid vinegar chain, polystyrene-ethylene acetate chain, polyamine chain, polyamidene chain 'polyurethane chain', poly Glandular bonds, polymorphic bonds, etc. Among them, a compound in which Y11 is ·〇·ε〇-, and Υ, 2 is -C0-0-, and a polymer bond represented by Au and 200949393 A12 is a polycondensation chain and a polyester chain, and is particularly inexpensive. It is easier to manufacture and therefore better. In the above formula (I), the compound represented by the following formula (II) in the polymer azo compound in which A" and Ai2 are a polyfluorene chain can provide a good solubility and easily control the molecular weight of the polymerization initiator. It is more preferable because it has a highly disperse grafted pigment. ❹ R21

(The ID is the same, R"* 0 independently indicates that the number of carbon atoms is 斗11, Ζ12, 22丨 and Ζ22 respectively represent carbon " 卞1, 卞, η, 8 and t They are independent of 〇~1〇〇〇, and the sum of ^'m+n and s + t are independently 2 or more. In the above formula (II), Z11, Z12, 721 η 22 shoulders early Zhao ii /i and 2 represent an alkylene group having a broken atomic number of 1 to 4, which may be exemplified by: A, gu yup ® subunit, ethyl, trisyl, propylene, isopropylidene Base, tomb, dying, butyl, butyl, ethyl, ethyl, ethyl, dimethyl, ethyl, etc.; rU and the number of carbon atoms of the table are alkyl propyl, isopropyl, Butyl, second butyl, first methyl, ethyl, yl, isopentyl, decyl-butyl, isobutyl, pentyl hexyl, hexyl, cyclohexylmethyl, ring ^-isoheptyl, third heptyl, n-octyl, isooctyl, 9 200949393 first octyl, 2-ethylhexyl, n-decyl, n-decyl, dodecyl, octadecyl, Tetodecyl and the like. The carbon atom represented by R" The number of carbon atoms of 1 to 4 in the fluorenyl group of ^24 is due to the provision of a highly dispersible grafting pigment, and the ester of a compound having a hydroxyl group at one end of the chain polymer and the azodicarboxylic acid compound In the case where the Au and A12 of the polymer azo compound represented by the above formula (I) are (four) bonds, the compound represented by the following formula (m) is It is preferable because it has good solubility and excellent water resistance.

In the formula (m), r12, r13, r22, r23, ub are the same as the above formula (I), and zm independently indicates that the number of carbon atoms is a ruthenium group, and R3丨 and r4i 八ai want to Α Α The number of atoms or carbon atoms is summer ~ 24 alkyl,? And u are independent of each other (10). The number.

In the above formula (III), the group of carbon atoms having a number of carbon atoms represented by ζ丨3, 723, which is represented by Ζ3, 723, may be exemplified by a methylene group, an ethyl group, and a trimethylene group. , propylene, isopropylidene, tetramethylene, butylethyl ethyl, methyl ketone 7 and * methyl monomethyl ethyl, pentamethylene, hexamethylene Soil, octamethylene, 1,4,pentylene, decamethylene (deeamethyi, methyl, 1,4-undecanediyl, dodecamethylene, i, "heptadecane Examples of the dialkyl group, the octadecyl group, and the like; and the alkyl group represented by ～41 is an alkyl group of 200949393 24, and is exemplified as Rn and rZ1 in the above formula (π). R31 and R41 are used. In the alkyl group having 1 to 24 carbon atoms, the number of carbon atoms is 1 to 4, since a highly dispersible grafting pigment is provided, and a compound having a hydroxyl group at one end of the chain polymer and azodi It is preferred that the esterification reaction of the carboxylic acid compound has high reactivity. In the above formula (ΙΠ), P and oxime are from 20 to 100, and one of the chain polymers is provided by providing a grafting pigment of dispersible oxime. Terminal with hydroxyl The content of the above-mentioned polymer azo initiator in the sealing agent for liquid crystal dropping method of the present invention is not particularly limited as long as it has high reactivity with the esterification reaction of the azodicarboxylic acid compound. 100 parts by weight of the above (meth)acrylic group-containing resin, preferably lower limit is 01 parts by weight, and preferably has an upper limit of 30 parts by weight. If the content of the above hydrazine molecular azo initiator is less than parts by weight, the above has The polymerization of the (meth)acrylic resin may not be sufficiently carried out. When the content of the above polymer azo initiator is more than 3 parts by weight, the viscosity of the sealant for the liquid crystal dropping method becomes high, and the coating is high. The lower limit of the content of the above-mentioned polymer azo initiator is 〇. 5 parts by weight, and more preferably, the upper limit is 1 part by weight. The sealing agent for liquid crystal dropping method of the present invention contains ( The resin having a (meth)acrylic group is not particularly limited, and examples thereof include reacting a compound having a hydroxyl group with (meth)acrylic acid. 2 vinegar compound, # epoxy acrylate (meth) acrylate obtained by reacting (meth) acrylic acid with an epoxy compound, by using a (meth) propyl 11 200949393 enoic acid derivative having a hydroxyl group A urethane (meth) acrylate obtained by reacting with an isocyanate, etc. The ester compound obtained by reacting a compound having a hydroxyl group with the above (mercapto)acrylic acid is not particularly limited, and a monofunctional ester compound is not particularly limited. For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( Mercapto) isobutyl acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, ( Isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxyethylene (mercapto) acrylate, (mercapto)acrylic acid 2 -ethoxyethyl ester, (indenyl) tetrahydrofurfuryl acrylate (Methyl) benzyl acrylate, ethyl carbitol (mercapto) acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethyl acrylate Glycol (mercapto) propylene oxime ester, decyloxy polyethylene glycol (mercapto) acrylate, (meth)acrylic acid 2,2,2-trifluoroethyl ester, (meth)acrylic acid iso-2,2, 3,3-tetrafluoropropyl ester, (meth)acrylic acid 1H, 1H, 5H-octafluoropentyl ester, quinone imine (mercapto) 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 methacrylate, isodecyl (meth) acrylate, isotetradecyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- benzene (meth) acrylate Oxyethyl ester, dicyclopentenyl (meth)acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (mercapto) acrylate Methylaminoethyl ester, 2-(indolyl)propenyloxyethyl succinate, 2-(methyl)propenyloxyl hexahydroindoledicarboxylic acid 12 200949393 Ethylene, 2 hydroxypropyl phthalic acid 2-(indenyl) propylene methoxy acetate, glycidyl (meth) acrylate, 2-(indenyl) propylene methoxyethyl phosphate, and the like. Further, examples of the bifunctional ester compound include hydrazine, 4-butanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, hydrazine, and 6-hexanediol. Di(meth)acrylate, 1,9-nonanediol bis(indenyl)acrylate, 11〇-nonanediol di(meth)acrylate, 2-n-butyl-2-I-1,3-propanediol Di(meth) acrylate, dipropylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, polypropylene glycol (mercapto) acrylate, ethylene glycol di(meth) acrylate, two Ethylene glycol bis(indenyl) acrylate, tetraethylene glycol di(meth)acrylate vinegar, polyethylene glycol bis(indenyl)propionate, propylene oxide addition bismuth di(meth)acrylic acid Ester, ethylene oxide addition bisphenol A di(meth)acrylic acid lysine, ethylene oxide addition bisphenol F di(meth) acrylate, dimethylol biscyclopentadienyl di(meth) acrylate , 1,3-butanediol di(meth)acrylate, neopentyl alcohol-(meth)acrylic acid vinegar, ethylene oxide modified diisocyanate di(meth)propyl Acid ester, 2-hydroxy-3-(meth) propylene methoxypropyl (meth) acrylate, carbonate diol di(meth) acrylate, polyether diol di(methyl) propylene vinegar , polyglycol diol di(meth) acrylate vinegar, polycaprolactone di(meth) acrylate, polybutadiene diol di (meth) acrylate, and the like. Further, examples of the trifunctional or higher ester compound include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and propylene oxide addition trihydroxymercaptopropane tris(fluorenyl). Acrylate, ethylene oxide addition trimethylolpropane tris(methyl) acrylate, caprolactone modified trimethyl propyl trimethyl (meth) propionate, ethylene oxide addition Tris(mercapto)propyl acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(methyl) propyl 13 200949393 oleic acid vinegar, bis(trimethylolpropane) tetra(曱) Acrylate, pentaerythritol tetrakis(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, tris(meth)acryloxyl phosphate Ethyl ester and the like. The epoxy group (mercapto) acrylate obtained by reacting (meth)acrylic acid with an epoxy compound is not particularly limited, and examples thereof include epoxide and (meth) propylene. The acid is obtained by a reaction in the presence of an organic catalyst according to a general method. The epoxy compound which is a raw material for synthesizing the above epoxy (meth) acrylate is not particularly limited, and examples of the commercially available product include Epik〇te 828EL and Epikote 1004 (all of which are bismuth epoxy resins). Manufacture of bisphenol A type epoxy resin; Epikote 806, Epikote 4004 (all manufactured by Sakamoto Epoxy Co., Ltd.) and other bisphenol F type epoxy resin; Epici〇n EXa1514 (manufactured by Dainippon Ink Co., Ltd.) S-type epoxy resin; re-8 10ΝΜ (manufactured by Sakamoto Chemical Co., Ltd.) 2,2,-diallyl bisphenol A type epoxy resin; Epiclon EXA7〇15 (manufactured by Otsuka Ink Co., Ltd.) Bisphenol type epoxy resin; EP-4000S (manufactured by Asahi Kasei Co., Ltd.) and other propylene oxide addition double-presence A type epoxy resin; ex_2〇1 (manufactured by Changchun Chemical Co., Ltd.) and other isophthalic epoxy resin; Epikote YX-4000H (manufactured by Japan Epoxy Resin Co., Ltd.) such as biphenyl type epoxy resin; YSLV-50TE (made by Dongdu Chemical Co., Ltd.) and other sulfide type epoxy resin; YSLV-80DE (made by Dongdu Chemical Co., Ltd.) Resin; or EP-4088S (made by Asahi Kasei Co., Ltd.) Oxygen resin; Epiclon HP4032, Epiclon EXA-4700 (all manufactured by Otsuka Ink Co., Ltd.) and other naphthalene type epoxy resin; Epiclon N-770 (made by Dainippon Ink Co., Ltd.) and other phenol novolac type ring 200949393 Oxygen Resin; orthocresol novolac type epoxy resin such as Epiclon N-670-EXP-S (manufactured by Otsuka Ink Co., Ltd.); dicyclopentadiene novolac varnish such as Epiclon HP7200 (manufactured by Dainippon Ink Co., Ltd.) Type epoxy resin; biphenyl novolac type cyclic resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); naphthalene phenol novolac such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.) ) epoxy resin 'Epkote 630 (manufactured by Sakamoto Epoxy Co., Ltd.), Epiclon 430 (manufactured by Otsuka Ink Co., Ltd.), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and other glycidylamine type epoxy resin; ZX- 1 542 (manufactured by Tohto Kasei Co., Ltd.), Epiclon 726 (manufactured by Otsuka Ink Co., Ltd.), Ep〇Hght 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denac〇1 Εχ61 i (manufactured by Nagase Chemical Co., Ltd.) Burning polyol type epoxy resin; YR_45〇, yr_2〇7 (all manufactured by Dongdu Chemical Co., Ltd.), Epolead PB (made by Daicel Chemical Co., Ltd.), and other rubber-modified epoxy resins; Denac〇i ΕΧ_147 (Changfu Chemical Company) Manufactured), such as a glycidyl ester compound; bisphenol A type episulfide resin such as Epik〇te YL 7〇〇〇 (manufactured by Sakamoto Epoxy Co., Ltd.); YDC-1312 'YSLV-80XY > YSLV- 90CR (all are Dongdu Chemical Company)

Obtaining (mercapto)acrylic acid by reacting with an epoxy compound

Manufactured as 360 parts by weight of a desired epoxy resin (Εχ·2〇1, manufactured by Changchun Chemical Co., Ltd.) as a polymerization inhibitor, 2 parts by weight of p-methoxybenzene, 15 200949393 as a reaction catalyst triethylamine 2 parts by weight and 210 parts by weight of acrylic acid are stirred under reflux at 90 ° C for 5 hours while being sent to the air. The commercially available product of the above epoxy (meth) acrylate is, for example, : Ebecryl 3700, Ebecryl 3600, Ebecryl 3701, Ebecryl 3703, Ebecryl 3200, Ebecryl 3201, Ebecryl 3600, Ebecryl 3702, Ebecryl 3412, Ebecryl 860, Ebecryl RDX63182 'Ebecryl 6040, Ebecryl 3800 (all manufactured by Daicel-Cytec); EA -1020, EA-1010, EA-5520, EA-5323, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Industry 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 Kyoei Chemical Co., Ltd.); Denacol Ac Rylate DA-141, Denacol Acrylate DA-3 14, Denacol Acrylate DA-911 (all manufactured by Nagase Chemical Co., Ltd.), etc. The above-mentioned amine group obtained by reacting a (fluorenyl)acrylic acid derivative having a hydroxyl group with an isocyanate The formate (meth) acrylate may be present in a catalyst amount of a tin-based compound, for example, by making 2 equivalents of a (meth)acrylic acid derivative having a hydroxyl group and 1 equivalent of a compound having 2 isononanoate groups. The isocyanate which is a raw material of the urethane (meth) acrylate obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate is not particularly limited, and examples thereof include, for example, :isophorone diisocyanate, 200949393 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dipyridyl methane _4,4 , diisocyanate (MDI), deuterated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, stupid dimethyl diisocyanate (XDI), hydrogenated XDI Isoic acid diisocyanate, = phenylmethane triisocyanate, thiophosphoric acid tris(isocyanate phenyl) lysine, tetramethyl phthalic acid diisocyanate, 1,6,1 non-undecane triisocyanate, etc. . Further, the isocyanate which is a raw material of the urethane (mercapto) acrylate obtained by reacting a (fluorenyl)acrylic acid derivative having a hydroxyl group with an isocyanate is not particularly limited, and for example, Use: make ethylene glycol, propane = alcohol, sorbitol 'trihydroxymethyl propyl hydrazine ·, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, etc. A chain extended isocyanate compound obtained by reacting an alcohol with an excess of an isogastric acid ester. a (meth)acrylic acid derivative having a hydroxyl group (which is a raw material of the above-described urethane (meth) propionate obtained by reacting a (meth)acrylic acid derivative having an M group with an isocyanate) There is no particular limitation, for example,

a commercially available product of 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; or Mono(meth)acrylate of diol such as diol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol; trimethylolethane a mono(meth)acrylate or di(meth)acrylate of a trihydric alcohol such as trimethylolpropane or glycerol; a cyclodecyl acrylate such as a bisphenol A modified epoxy acrylate Wait. The above-mentioned urethane (meth) acrylate obtained by reacting a mercapto (mercapto)acrylic acid derivative with an isocyanate 17 200949393 ester, for example, can be used, for example, by the following According to the method, 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization inhibitor, 0.01 parts by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate were obtained. The mixture was reacted under reflux at 60 ° C for 2 hours, and then 51 parts by weight of 2-hydroxyethyl acrylate was added thereto, and the mixture was refluxed at 90 ° C while being sent to the air, and the mixture was reacted for 2 hours. The commercially available ones of the above urethane (meth) acrylates include, for example, M-1100, M-1200, M-1210, and M-1600 (all manufactured by East Asia Synthetic Co., Ltd.); Ebecryl 230, Ebecryl 270, Ebecryl 4858, Ebecryl 8402, Ebecryl 8804, Ebecryl 8803, Ebecryl 8807, Ebecryl 9260, Ebecryl 1290, Ebecryl 5129, Ebecryl 4842, Ebecryl 210, Ebecryl 4827, Ebecryl 6700, Ebecryl 220, Ebecryl 2220 (all Made by Daicel-Cytec); Artresin UN-9000H,

Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Gensei Industrial Co., Ltd.); 〇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 (all manufactured by Xinzhongcun Chemical Industry Co., Ltd.); AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I, etc. 18 200949393 The above-mentioned resin having a (meth)acrylic group is preferable in that it suppresses the adverse effect on the liquid crystal, and preferably has hydrogen bonding properties such as a mercapto group, a side group, and a mom group. The unit is preferably an epoxy (meth) acrylate in terms of ease of synthesis and the like. Further, in the case where the resin having a (meth)acrylic acid group has high reactivity, it is preferably one having 2 to 3 (fluorenyl) acrylate groups in the molecule. In order to improve the adhesion, the sealing agent for liquid crystal dropping method of the present invention preferably further contains a resin having an epoxy group.

The epoxy group-containing resin is not particularly limited, and examples thereof include bisphenol A type epoxy resins such as Epikote 828EL and Epikote 4 (all manufactured by Sakamoto Epoxy Co., Ltd.); Epik〇 Te 8〇6, Epik〇te 4〇〇4 (all manufactured by Japan Epoxy Resin Co., Ltd.), etc. (4) F-type epoxy resin; piclon EXA1514 (manufactured by Otsuka Ink Co., Ltd.) and other double s-type epoxy resin; RE- 810NM (manufactured by Sakamoto Chemical Co., Ltd.) 2 2, diallyl bisphenol A type epoxy resin, Epiclon EXA7015 (manufactured by Dainippon Ink Co., Ltd.), hydrogenated bisphenol type epoxy resin; EP_4〇〇〇s (available from Asahi Kasei Co., Ltd.) propylene oxide addition bisphenol A type epoxy resin; Εχ_2〇1 (manufactured by Changchun Chemical Co., Ltd.) isophthalate-type epoxy resin; Epik〇te γχ 4〇〇〇Η (Japan Epoxy resin produced by Epoxy Resin Co., Ltd.; sulfide type epoxy resin such as YSLV_5〇TE (made by Dongdu Chemical Co., Ltd.); epoxide type epoxy resin such as YSLV_8〇DE (made by Dongdu Chemical Co., Ltd.); eP_4088s (旭Epoxy resin manufacturing) and other bicyclopentadienyl epoxy resin; Epicl〇n HP4〇32 , Epiclon EXA-4700 (all manufactured by Dainippon Ink Co., Ltd.) and other Tsai-type epoxy resins; Epiclon N-770 (made by Dainippon Ink Co., Ltd.) and other phenolic varnish type ring tree 19 200949393 grease; Epiclon N-670-EXP-S ( O-cresol novolak type epoxy resin such as Otsuka Ink Co., Ltd.; dicyclopentadiene novolac type epoxy resin such as Epiclon HP7200 (manufactured by Otsuka Ink Co., Ltd.); NC-3000P (manufactured by Sakamoto Chemical Co., Ltd.) ) a non-phenol novolak type epoxy resin; a naphthol novolak type epoxy resin such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.);

Epikote 630 (manufactured by Sakamoto Epoxy Co., Ltd.), Epiclon 430 (manufactured by Otsuka Ink Co., Ltd.), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and other glycidylamine type epoxy resins; ZX-1542 (manufactured by Dongdu Chemical Co., Ltd.) ),

Epiclon 726 (manufactured by Dainippon Ink Co., Ltd.), Epolight 80MFA (manufactured by Kyoei Chemical Co., Ltd.), Denacol EX-611 (manufactured by Changchun Chemical Co., Ltd.), etc., and the like, YR-450, YR-207 (all manufactured by Dongdu Chemical Co., Ltd.); rubber-modified epoxy resin such as Epolead PB (manufactured by Daicel Chemical Co., Ltd.); glycidyl ester compound such as Denacol EX-147 (manufactured by Changchun Chemical Co., Ltd.); Epikote YL-7000 (Japanese ring) Bisphenol A type episulfide resin such as oxy resin company; ydc_1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (made by Asahi Kasei Corporation), Epikote 1031, Epikote 1032 ◎ ( Both are manufactured by Japan Epoxy Resin Co., Ltd., Exa-7 120 (manufactured by Dainippon Ink Co., Ltd.), TEPIC (manufactured by Suga Chemical Co., Ltd.), and the like. Further, the epoxy group-containing resin may be, for example, a compound having a (meth)acryl group and an epoxy group in the oxime molecule. Examples of such a compound include a compound obtained by reacting a part of an epoxy group of a compound having two or more epoxy groups with (meth)acrylic acid. The above-mentioned compound obtained by reacting a part of the epoxy group 20 200949393 with (mercapto)acrylic acid of a compound having two or more epoxy groups, for example, by using an epoxy resin and (mercapto)acrylic acid in accordance with a general method. Obtained by the reaction in the presence of a sexual catalyst. Specifically, for example, 190 g of a novolac type epoxy resin N-770 (manufactured by Otsuka Ink Co., Ltd.) is dissolved in 500 mL of toluene, and diphenylphosphine 〇.lg is added to the solution to form a uniform solution. 35 g of acrylic acid was dropped into the solution under stirring for 2 hours, and further stirred under reflux for 6 hours, followed by removal of toluene, whereby 50 mol% of an epoxy group and (meth) were obtained.

_ Acrylic varnish-type solid-state modified epoxy resin (in this case, 5〇% is partially acrylated). In the above-mentioned compound obtained by reacting a part of the epoxy group of the compound having two or more epoxy groups with (mercapto)acrylic acid, for example, Ebecryl 1561 (manufactured by DaiCel-Cytee Co., Ltd.) can be mentioned. When the epoxy group-containing resin is contained in the sealing agent for a liquid crystal dropping method of the present invention, the ratio of the (meth)acrylic acid group to the epoxy group is preferably 5 〇 50 to 95. 'The resin having a (meth)acrylic acid group is blended with a resin having an epoxy group. When the ratio of the (meth)acrylic group is 5% by weight or less, even if the thermal polymerization using the azo initiator starts, the epoxy resin component which is largely cured is contaminated, so that the liquid crystal is contaminated. If the ratio of (meth) propyl ketone group is 95% or more, the sergeant will not be able to exhibit sufficient adhesion. When the above-mentioned epoxy resin is contained in the sealing agent, it is preferable to further contain an epoxy thermal hardener. The above-mentioned epoxy heat hardening agent is not particularly limited, and examples thereof include an organic acid brewing oxime, a azole derivative, an amine compound, a plurality of expectorant compounds, and an acid anhydride. Among them, solid organic acid strontium is suitably used. 21 200949393 The above solid organic acid hydrazine is not particularly limited, and examples thereof include hydrazine monohydrate, bismuth isophthalate, diammonium adipate, and bismuth malonate. Other than Amicure VDH and Amicure UDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.). The content of the epoxy thermosetting agent is not particularly limited, and is preferably 1 part by weight, and preferably 50 parts by weight, based on 100 parts by weight of the epoxy group-containing resin. If the content of the above epoxy thermosetting agent is less than 1 part by weight, the effect of containing a thermosetting agent is hardly obtained. When the content of the above-mentioned epoxy heat-hardening agent is more than 50 parts by weight, the viscosity of the sealing compound for a liquid crystal dropping method of the present invention may become high, and the coating property may be impaired. A more preferable upper limit of the content of the epoxy thermosetting agent is 30 parts by weight. As described above, the sealing agent for liquid crystal dropping method of the present invention can not only thermally cure the above-mentioned (meth)acrylic group-containing resin but also cause photohardening by using the above-mentioned polymer azo initiator. However, the photopolymerization initiator may be further contained as needed. The photopolymerization initiator is not particularly limited, and examples thereof include Irgacure 184 and Irgacure 2959.

Irgacure 907 ^ Irgacure 819 ^ Irgacure 651 ^ Irgacure 369 ^ 〇Irgacure 3 79, Irgacure OXE01 (all manufactured by Ciba Specialty Chemicals); benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Lucirin τρ〇 (manufactured by BASF Japan) )Wait. The content of the photopolymerization initiator is not particularly limited, and a preferred lower limit is 〇·1 part by weight, and a preferred upper limit is 10 parts by weight, based on 10 parts by weight of the resin having a (fluorenyl) acrylate group. When the content of the photopolymerization initiator is less than 0.1 part by weight, the liquid crystal dropping method 22 200949393 of the present invention cannot be sufficiently photocured. If the content of the above photopolymerization initiator exceeds the weight loss, the storage stability is lowered. Colorant The sealant for liquid crystal dropping method of the present invention may further contain a light-shielding method using the above-mentioned light-blocking coloring agent to make the sealant of the liquid crystal droplet of the present invention have a narrow width from the back color. : When the lower side is oozing out to the outside, it is also possible to prevent leakage of the first self-sealing agent from the backing and reduce the contrast. + If the above-mentioned light-shielding coloring agent is added to the sealing compound in the conventional liquid crystal dropping method, 'there is a hindrance light In the case of the liquid crystal dropping method for a liquid crystal dropping method of the present invention, by using the above-mentioned resin having a (meth) acryl group and a polymer odor initiator, it is possible to use heat to: In the present specification, the term "shielding property" means light having a wavelength of 370 to 8.0 nm above the 嶋. The light-shielding coloring agent is not particularly limited as long as it imparts light-shielding properties to the liquid-sealing agent of the liquid crystal dropping method of the present invention after curing and has less impurities entering the liquid crystal. The above-mentioned light-blocking coloring agent is preferably a plurality of pigments and/or dyes which have a complementary color relationship with black pigment or, if mixed, black. The black pigment is not particularly limited, and examples thereof include iron oxide, black, aniline black, cyanine black, fuUerene, carbon black, and resin-coated carbon black. These black pigments may be used singly or in combination of two or more. Among them, in terms of insulation and workability, titanium black and / 23 200949393 or carbon black are preferred. The carbon black is limited to a small amount of impurities which are eluted into the liquid crystal. For example, it can be used in a tank, a lure, a heat, a furnace, a black, and a hot carbon black guide. A knows the carbon black. Among them, the money group wants to be coated with a grafted carbon H1 Λ ^ ^ '' surface coated with an insulating inorganic substance or an insulating right mother material from the viewpoint of insulation. Earth. Machine slave, and/or 纟Φ, acid magnetic black oxidized by f. This carbon black has low conductivity compared with untreated carbon black, so if it is used in the liquid crystal dripping of the present invention When a sealing agent is used, a liquid crystal display element having less current leakage and high reliability can be obtained. The blackening is not particularly limited, and specific commercial products include, for example, m-cut, 13MC' 13R_N (all of which are Mitsubishi Materials Corporation). Manufactured; TilackD (manufactured by Ako Chemical Co., Ltd.), etc., may also be used: the surface of the above titanium black is treated by a coupling agent; or is cerium oxide, titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. In the case of the inorganic component, the organic pigment is not particularly limited, and examples thereof include an azo pigment such as an insoluble azo pigment or a soluble azo pigment; Copper phthalocyanine blue Material, toothed copper phthalocyanine pigment, sulfonated copper phthalocyanine pigment, metal-free phthalocyanine pigment, phthalocyanine pigment such as dissimilar metal phthalocyanine pigment; amine-based ruthenium pigment, indanthrone pigment, isoindole a condensed polycyclic pigment such as a porphyrin pigment, a quinacridone pigment, a dioxazine pigment, a purple ring ketone pigment or an anthraquinone pigment, etc. Among them, an organic pigment such as a copper phthalocyanine pigment or a condensed polycyclic pigment β is preferably used. It is also possible to use a plurality of kinds of dyes as the auxiliary coloring component of the above-mentioned black pigment. The above-mentioned dyes having a complementary color relationship in the case of black mixing are not particularly limited, and examples thereof include a cyanine dye and a merocyanine dye. , rhydacyanine dye, oxime (〇χ〇η〇ι) dye, styrene dye, alkali styrene dye, stupid and quinone dye, quinolizine dye , coumarin dyes, thiazole dyes, indanthrene dyes, pyranthrone dyes, carbazole dyes, enamel dyes, dragons, sulphur blue, (four) Dye, acid azo dyeing , Η_ acid azo dye, triaryl alkyl ❹ Yue

A dye, an oxazine dye, or the like. These dyes can also be used as an auxiliary coloring component of the above black: pigment. The particle diameter of the light-shielding coloring agent is not particularly limited to a preferred lower limit of the primary particles (Pri_ypartiele) and 1 () nm, and a preferred upper limit is _fine. If the particle size of the above-mentioned light-shielding property (4) is in this case, the dispersibility in the sealant for the dripping method of the present invention will be deteriorated. The content of the above-mentioned light-blocking coloring agent is not particularly limited, and it is preferably (4) parts by weight based on the amount of (4) by weight of the dropping method of the present invention. The upper limit is preferably 50 parts by weight. When the content of the light-shielding coloring is less than 5 parts by weight, if the sufficient light-shielding property is not more than 50 parts by weight, the sealing agent for the substrate of the present invention is used for the substrate:: properties and hardening The intensity will decrease or the drawability will decrease. The content of the above light-shielding colorant is more preferably 40 parts by weight. The lower limit is preferably 1 part by weight, and the upper limit is more than the sealing agent for the dropping method of the present invention, and may also contain... the ancient: the light-shielding coloring agent is an auxiliary preparation A 八 / , , , , 机 枓) Or the color of the author such as dye. For example, in Shangchengli, when the above black pigment is reddish black 25 200949393 color, the above shading can be made by adding a red complementary color, which is the complementary color of blue. Sex colorants are better black. The liquid crystal dropping method of the present invention preferably comprises a decane coupling agent. The above-mentioned decane coupling agent is mainly used as a further auxiliary agent for the liquid crystal dropping method sealing agent and the liquid crystal display element base plate. It is limited by the effect of improving the adhesion to a glass substrate or the like, and can be prevented from flowing out to the liquid by forming a chemical bond with the curable resin. (4) If it is suitable for decylaminopropyl hydrazine, it is suitable for Propyl trimethoxy oxalate, r glycidoxypropyl trimethoxy decane, orthocyanate propyl trimethoxy decane, and the like. These decane coupling agents may be used singly or in combination of two or more. The sealing agent for a liquid crystal dropping method of the present invention may further contain a filler for the purpose of improving the adhesion by the stress dispersion effect and improving the linear expansion ratio. The above filler is not particularly limited, and examples thereof include talc, asbestos-oxidation dream, Shixi steamed soil, bentonite, bentonite, carbonic acid carbonated town, oxidized Ming, montmorillonite, chopped algae, zinc oxide. , iron oxide, magnesium oxide, tin antimony oxide, titanium oxide, magnesium oxynitride, oxyhydroxide, glass beads, nitriding stone, barium sulfate, gypsum, calcium citrate, talc, glass beads, sericite active white soil road An inorganic filler such as soil or nitriding; or an organic filler such as polyester fine particles, polyurethane fine particles, ethylene polymer fine particles, or acrylic polymer fine particles. The liquid crystal dropping method of the present invention may further comprise a sealing agent, if necessary, a reactive diluent for adjusting the viscosity, a shaking agent for adjusting the shaking property, and 26 3-pair gas phenyl-i, _ polymerization inhibitor,

The conductive fine particles are not particularly limited, and a metal ball or a conductive metal layer formed on the surface of the resin fine particles can be used. Among them, in the case where the conductive fine metal layer is formed on the surface of the resin fine particles, since the resin fine particles have excellent elasticity, it is preferable because the conductive connection can be performed without damaging the electrode or the like. Further, a liquid crystal display element using the sealing agent for a liquid crystal dropping method of the present invention and/or a conductive material for the upper and lower sides of the present invention is also one of the inventions. 200949393 A spacer such as polymer beads for adjusting the gap between panels, a hardening accelerator such as dimethylurea, an antifoaming agent, a leveling agent, and other additives. For the production of the liquid crystal display device of the present invention, for example, a method in which the (meth)acrylic group-based resin or the polymer azo is started is exemplified by the method of 1. A method of mixing an agent, an additive or the like as needed, and the like. The upper and lower conductive materials can be produced by using the fine particles in the sealant for the liquid crystal dropping method of the present invention.冤 方法 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤 冤a liquid crystal dropping method: a step of forming a seal pattern with a sealant or the like; a step of applying a droplet of liquid crystal to a frame of a seal pattern, and superposing another substrate under vacuum; and sealing the liquid crystal dropping method of the present invention a step of pre-curing a light such as ultraviolet rays or the like, and a step of hardening the sealing pattern formed by the sealing agent or the like of the liquid crystal dropping method of the present invention. 0 27 200949393 This is a sealing using the liquid crystal dropping method of the present invention. The liquid crystal display element formed by the agent and/or the material of the present invention is also the sealing agent for a liquid crystal panel containing the resin having a (fluorenyl) acetoacetate group and a gas initiator, and is also the invention of the invention. When a liquid crystal display device is manufactured by a conventional method, that is, a vacuum injection method, a liquid crystal display device is manufactured by the above liquid crystal dropping method. 'Liquid crystal panel during sealing with the sealing agent in an uncured state into contact with the two liquid crystal. At this time, when sufficient light is not applied to the sealing agent for the liquid crystal panel, color unevenness is generated around the sealing portion, and the liquid crystal display element of high quality image is obtained without the method. When the sealing agent for a liquid crystal panel of the present invention is used as a sealant for producing a liquid crystal display device by a vacuum injection method, a liquid crystal display element of high quality image having a small color unevenness can be produced. It is especially effective when it is designed without a panel that is sufficiently exposed to ultraviolet light. The sealing agent for a liquid crystal panel of the present invention may contain an epoxy group-containing resin, an epoxy thermosetting agent, a photopolymerization initiator, a light-blocking colorant, and decane, similarly to the sealing agent for a liquid crystal dropping method of the present invention. Coupling agents, filling materials, various additives, and the like. According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method of a liquid crystal display element which can produce a high-quality image having a small color unevenness when a liquid crystal display element is produced by a dropping method. Further, it is possible to provide a liquid crystal panel sealing agent for a liquid crystal display element which can produce a high-quality image having a small color unevenness when a liquid crystal display device is manufactured by a vacuum injection method. [Embodiment] 28 200949393 Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the embodiments. (Synthesis of Epoxy Acrylic Acid Brewing (EX-201 Modified Product)) 12-g of EX-201 (resorcinol type epoxy resin) was dissolved in 500 mL of toluene, and triphenyl group was added to the solution. The phosphine lg forms a homogeneous solution. To the solution, 7 μg of acrylic acid was added dropwise thereto under reflux for 2 hours, and then further stirred under reflux for 8 hours. Next, toluene was removed to thereby obtain an epoxy acrylate having the entire epoxy group modified to an acrylic group (EX-201 modified product). (Synthesis of partially acrylated epoxy acrylate (N_77〇 partially modified product)) N-770 (novolac type epoxy resin) 19〇g was dissolved in 5OOmL of toluene. 'Triphenyl group was added to this solution. Phosphonium hydride was formed, and a homogeneous solution was formed, and 3 5 g of acrylic acid was added dropwise to the solution over 2 hours while stirring under reflux, followed by further refluxing for 6 hours. Next, toluene was removed, whereby a partially acrylated epoxy acrylate (N-770 partially modified product) in which 50 m% of the epoxy group was reformed to an acrylic group was obtained. (Examples 1 to 1 and Comparative Examples 1 to 3) According to the mixing ratios shown in Table 1, the materials were mixed using a planetary mixer ("Defoaming Taro" manufactured by Thinky Co., Ltd.), and the three-parent machine was further used. The mixture was mixed, and the sealants for liquid crystal dropping methods of Examples 1 to 10 and Comparative Examples 1 to 3 were prepared. As shown in FIG. 1 , the liquid crystal dropping method is applied to the substrate on which the transparent electrode and the alignment film are formed by using a dispenser to draw a square frame. 29 200949393 The sealing agent is used to seal the obtained liquid crystal dropping method. Painted inside the square frame. Then, a small droplet of liquid crystal ("JC-5004LA" manufactured by Chisso Co., Ltd.) was applied onto the entire surface of the transparent substrate, and another substrate having a transparent electrode and an alignment film was superposed in a vacuum to release the vacuum. 'Using a high-pressure mercury lamp to irradiate ultraviolet rays to the outer seal portion at i〇〇mW/cm2 for 30 seconds. At this time, the liquid crystal dropping method of the spot coating was covered with a sealant so as not to be irradiated with uv. Thereafter, the liquid crystal was annealed for 1 hour in the 12th generation, and the liquid crystal display element was obtained by heat-hardening with a sealant at the same time.

<Evaluation> The following evaluations were carried out on the liquid crystal dropping display elements obtained in Examples 1 to 100, and the liquid crystal dropping display elements obtained in Comparative Examples 1 to 3. The results are shown in (panel display unevenness evaluation). For the obtained liquid crystal display element, in the % energized state and the non-energized state, the liquid crystal electrode in the spot coating was observed visually... cup and the crucible around the sealant for the droplet method. , with the result of the color and the inconsistency (4) as "◎", the evaluation of almost no color unevenness, and the evaluation of a small amount of color unevenness as "△" The situation was evaluated as "a lot of Xje's color (following the strength evaluation). With respect to the obtained liquid crystal dropping method, a planetary stirring device was used to make an average particle, and 100 parts by weight of the 'chemical industry company's:" polymer beads (made of water) The Mlcropearlsm is dispersed in weight, shape 30 200949393 into a homogeneous solution, including 4·ττ, and a very small amount is placed in Corning glass 1737 (20mmx 50mmxMmmt). Blood is like a central part. p 'overlays the same type of glass on it. The filming liquid crystal dropping method was spread with a sealant, and ultraviolet rays were irradiated with lGGmW/em2 for 20 seconds, and then heated at i2 ° C for 1 hour to obtain a test piece for the test piece. The strength of the bond was measured using a tensiometer (comparative units were N/cm2).

31 200949393 1 Comparative Example 3 1 1 1 100 1 r* IIIII ee VI ee XX 9s 1 Comparative Example 2 s S 1 IIIIIV) 00 e S jn 〇X 263 1 1 Comparative Example 1 O 1 IIIIII ee ο tfi SV) < 3 X 1—< jq 1 〈 施 o III III III III III III III III III III III III III III III III III III III III III | 实施 III III III III III III III III III III III III III III III III III III III III III III III III 285 285 285 285 285 285 285 285 285 285 285 285 285 285 285 1 r« II ! II — 艺 e VJ in s 〇〇 327 | Example 7 Nest so 1 IIII Μ I θθ ο VI V) IQ ◎ 〇jq 1 Example 6 Pan o 1 IIIII 00 s *Λ氏jn ◎ 〇 265 | 1 Example S so 1 IIIII w 00 ο in in ◎ ◎ Example 4 se 1 I Μ IIII 00 ο VI V) in ◎ ◎ 273 | 1 Example 3 so 1 ΓΊ I t III 00 e V) V) Tq ◎ ◎ 268 | Example 2 s 1 1 IIIII 1 1 ο If) 〇 o ◎ ◎ Example 1 s 1 1 IIIII 1 e ΙΛ 〇o ◎ iso I | £X-201 modified product | Ebecryl 3700 (Daicel ^Manufactured by Cytec) Epikote 806 (manufactured by Sakamoto Epoxy #麻) N-770 Partially modified VPE~0201 (molecular weight is about 20,000) (Wako Pure Chemicals) VPE*0401 (molecular weight is about 30,000) (manufactured by Wako Pure Chemical Co., Ltd.) VPE*0601 (molecular weight: approximately 30,000) (made by Wako Pure Chemical Co., Ltd.) VPS>0501 (Molecular weight About 40,000) (made by Heguang Pure* Co., Ltd.) VPS «J001 (molecular weight is about 80,000) (Waguang Pharmaceutical Co., Ltd. has BL public SI manufacturing) V-30 (molecular weight is about 140) (Woguang Pure Pharmaceutical Co., Ltd. Manufactured by the company Irgacur^ 184 (manufactured by Ciba Specialty Chemicals) Amicure VDH-J (manufactured by Ajinomoto Fine-Techno) Admafine SO-C2 (manufactured by Admatechs) ΚΒΜ403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 Acrylic based 1 1 epoxy group 1 1 non-passing weight 1 1__1 N/cm2 | tree with two enoic acid groups 腯 氡 腯 寒 腯 腯 « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « Photosynthetic polymerization starting 煞 hardening steel ruthenium dioxide filler 矽疣 coupling agent acryl-based / epoxy 芈 panel evaluation I followed by money 200949393 (Examples 11 to 15 and Comparative Examples 4 to 5) According to Table 2 The ratio of the records is calculated using a planetary mixer (Thinky A Division) "Defoaming Taro" was prepared by mixing the materials, and the sealing agents for liquid crystal panels of Examples 11 to 15 and Comparative Examples 4 to 5 were prepared.

As shown in FIG. 2, the sealing agent for the liquid crystal dropping method of Example 1 was applied to the substrate on which the transparent electrode and the alignment crucible were formed, and the dispenser was used to interrupt a part of the square frame, and then another layer was formed. The transparent electrode and the substrate of the alignment film are pressurized until the sealing agent reaches a predetermined gap, and heat treatment is performed at 120 ° C for 1 hour, thereby obtaining the empty cell H hollowing unit before the liquid crystal injection becomes a vacuum state, and the liquid crystal is made ( "JC_5〇〇4LA" manufactured by Chisso Co., Ltd. is in contact with a part of the square frame which is interrupted, and then returned to normal pressure for 2 hours, thereby obtaining a unit filled with liquid crystal inside. Next, using the sealing agents of Examples 丨丨 to 丨5 and Comparative Examples 4 to 5, a portion of the square frame was sealed with the obtained sealing agent for the liquid crystal panel, and then a high pressure mercury lamp was used to i 〇〇mW. /em2 irradiates the sealing agent with ultraviolet rays for 30 seconds. Thereafter, the liquid crystal was annealed at i2 〇〇 c for 1 hour, and the sealing agent was thermally cured to obtain a liquid crystal display element. Further, at this time, it was also obtained by irradiating the sealing agent with ultraviolet rays at i 2 〇. The liquid crystal display element under the condition of liquid crystal annealing for 1 h was carried out under the arm. <Evaluation> With respect to the liquid crystal display elements obtained in Examples 11 to 15 and Comparative Examples 4 to 5, panel display unevenness evaluation was performed by the following method. The results are shown in Table 2. 33 200949393 (Evaluation of Panel Display Unevenness) For the obtained LCD card, the name of the LCD card is not visible. In the energized state and the non-energized state, it is visually observed in the vicinity of the sealing part, ★ 甘 s 丨 丨 into the night crystal The resulting color is uneven. In the case of the result, the result is evaluated as "◎", and the evaluation of "uneven" and uneven color is evaluated as "Ρ" Λ / ^ ^ Τ price is 〇", and there will be a small amount of color unevenness. The situation was evaluated as "△", and the situation in which the right-handed wood was handed over to Syria was also evaluated as "Γχ". 34 200949393 [3 ΐ Comparative Example 5 1 〇 1 1 1 1 ΙΛ 〇 ◎ ◎ XX 丨 Comparative Example 4 1 〇 1 1 1 1 1 VJ 〇〇 < XX Example 15 Ο 1 1 1 <N fH ΙΛ d ◎ ◎ ◎ 例 Example 14 ο 1 1 < s 1 - tn ο ◎ ◎ ◎ 例 Example 13 ο 1 r < i 1 - VJ ◎ ◎ ◎ ◎ Example 12 ο Η η 1 1 i — ΙΛ d ◎ ◎ ◎ ◎ Example 11 ο μ 1 1 1 1 \η ο ◎ ◎ ◎ ◎ ΕΧ-201 modified product _ 灭 S IS tear s Meng il a treasure 0 /-N «2 «I ^ Gc Xt ^ m Dragon I* Ffj襄Ts il ^壕?? ti Χξ N,^/ flF g豸Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) ΚΒΜ403 (manufactured by Shin-Etsu Chemical Co., Ltd.) Non-energized power supply Non-energized power supply 1 Acrylic-based resin polymer couple Nitrogen starter photopolymerization initiator decane coupler panel evaluation (with UV irradiation) Panel evaluation (no UV irradiation) 200949393 C Reference example 1~5) According to the compounding ratio shown in Table 3, the company manufactures " Defoaming Taro] 'Lettering the machine (Thinky mixes the materials, Yi Yifeng uses a three-roller to mix it) to prepare a reference for you &qu Ott; $step using a sealant. Liquid crystal dropping method <Evaluation> For the liquid crystal dropping method for the susceptor in Reference Examples 1 to 5, the sealant was used, and the 〇D value 夂 hardenability was obtained by the following method. The evaluation is carried out in the same way as in the case of the same method. The results are shown in Table 3. (The measurement of optical density (OD value)) is obtained by the method of 妒酤 τ & In the liquid crystal dropping method, a niobium dioxide spacer (M1 Cropearl Sl) manufactured by Sekisui Chemical Co., Ltd., which is a spacer, is added as a spacer, and the mixture is stirred. The liquid crystal dropping method of the spacer is coated on a glass substrate of 5 mm×50 mm with a sealant, and the glass substrate of the same size is re-raised on the substrate, and a load is applied to the diameter of the spacer to make the thickness be hooked. The metal dentate lamp was irradiated with l〇〇mW/cm2 for 30 seconds. Then, 'the hourly hardening was carried out in a 12GC supply box' to obtain a measurement sample of the light-shielding sealant. For the obtained medium, the sample "Kou" was used by Konica Corporation. Manufacturing pDA·丨〇〇Measured optical density (〇D value). (Evaluation of hardenability) The thickness of the sealant was about 5 "m, and the liquid crystal dropping method was sandwiched between two pieces of poly(p-di-di-f-acid) A sample was prepared between the ethylene glycol films. J with a mercury lamp! The sample was irradiated with ultraviolet rays for 〇〇mW/cm2, 36 200949393 and then heat-treated at 120 ° C for 1 hour. After the heat treatment, when the polyethylene terephthalate film was peeled off, the case where no stickiness remained on both surfaces was evaluated as "〇", and the case where the tackiness remained on either side was evaluated as "X".

37 200949393 [ε ΐ ΙΛ sister 1 00 V) 〇1 〇jn V) XXXXX sister 1 00 in armpit 1 V) I/) η <s rn XXXXX 1 <s 1 1 νϊ d 1 s 100 ο V) ◎ ◎ ◎ ◎ ◎ fS 1 1 1 V) ο 衮 1 100 ο fS 〇 ◎ ◎ ◎ ◎ 4V 1 <s 1 1 ο 1 1 100 ο d 〇 ◎ ◎ ◎ ◎ EX-201 modified Ebecryl 3700 (Daicel - manufactured by Cytec) Epikote 806 (manufactured by Nippon Epoxy Resin Co., Ltd.) <s襄ιΜ入$1 g* 寻1 ύ Irgacure 184 (manufactured by Ciba Specialty Chemicals) Amicure VDH-J (manufactured by Ajinomoto Fine~Techno) Admafine SO-C2 (manufactured by Admatechs) ΚΒΜ403 (manufactured by Shin-Etsu Chemical Co., Ltd.) Titanium black (13Μ-Τ manufactured by Mitsubishi Materials Corporation, particle size 60nm) Carbon black (#2600 manufactured by Mitsubishi Chemical Corporation, particle size 13nm) 4 1 OD value 1 Hardenability ➢ Electrolytic resin with acrylic group Resin with epoxy group Polymer azo initiator Photopolymerization initiator Thermal curing agent Ceria filler decane coupling #1 Light-blocking coloring agent Acrylic group / Epoxy group ratio panel evaluation (with UV irradiation) Panel evaluation (no ultraviolet irradiation) 200949393 ^ [Industrial Applicability] According to the present invention, it is possible to provide a liquid crystal display element of a liquid crystal display element which can produce a high-quality image having a small color unevenness when a liquid crystal display element is manufactured by a dropping method. The dropping method is dense (four) 丨. Further, it is possible to provide a sealing agent for a liquid crystal panel of a liquid crystal display element which can produce a high-quality image having a small color unevenness when a liquid crystal display device is manufactured by a vacuum injection method. [FIG. 1' is not intended to be implemented. In the examples and comparative examples, a procedure for producing a liquid crystal display element by a liquid crystal dropping method was used. Fig. 2 is a view schematically showing a procedure for producing a liquid crystal display element by a vacuum injection method in the examples and the comparative examples. [Main component symbol description] None 鬌 39

Claims (1)

200949393 VII. Patent application scope: 1. A sealant for a liquid crystal dropping method, which comprises: a resin having a (meth)-propylglycolic acid group and a polymer azo initiator. 2. In the case of the liquid crystal dropping method for the μth range, the south molecular azo initiator contains a polydimethyl oxalate unit or a (4) oxy-oxide unit. 3. A liquid crystal according to the scope of the patent application, which further comprises an epoxy group-containing resin and an epoxy heat hardener. 4. A sealing agent for a liquid crystal dropping method according to Patent Application No. 2 or 3, which further contains a photopolymerization initiator. 5. The method of dropping according to the scope of Patent No. 2, 3 or 4 of the patent application is sealed by the fact that it further contains a light-blocking colorant. 6. A top-and-bottom conductive material, comprising: a liquid crystal droplet under/without sealant and conductive particles according to the scope of claims 2, 3, 4 or 5. A sealing agent for a liquid crystal panel, comprising: a resin having a (meth)acryl group and a polymer azo initiator. 8. A liquid crystal display element, which is characterized in that: the use of the towel, the scope of the patent scope, paragraph 2, 3'4, 5 or 6 of the liquid crystal roughing method for the sealant and / or towel, please apply the scope of the sixth item Made of conductive materials. A liquid crystal display element comprising: a liquid crystal panel (iv) mouthpiece according to item 7 of the patent application.