TWI463225B - Liquid crystal drop method sealant, upper and lower conductive material and liquid crystal display element - Google Patents

Description

Sealant for liquid crystal dropping method, upper and lower conductive materials, and liquid crystal display element

The present invention relates to a sealing agent for a liquid crystal dropping method, which can prevent liquid crystal contamination even when a sealant component is eluted to a liquid crystal during production of a liquid crystal display element for dropping, thereby producing display quality and reliability. Liquid crystal display element. Further, the present invention relates to a vertical conduction material and a liquid crystal display element.

In the manufacturing method of the liquid crystal display element of the prior art, first, a seal pattern (which is provided with a liquid crystal injection port using a thermosetting sealant) is formed on either of the two transparent substrates with electrodes by screen printing. ), prebaking at 60 to 100 ° C to dry the solvent in the sealant. Then, holding the spacers to make the two substrates face each other, and then laminating them after bonding, and performing hot pressing at 110 to 220 ° C for 10 to 90 minutes, adjusting the gap near the sealant, and then 110 to 220 ° C in the oven. Heat for 10 to 120 minutes to allow the sealant to formally harden. Finally, liquid crystal is injected from the liquid crystal injection port, and finally, the liquid crystal injection port is sealed with a sealing agent, thereby manufacturing a liquid crystal display element.

However, in this manufacturing method, there are problems in that positional displacement due to deformation due to heating, unevenness in gap, and deterioration in adhesion between the sealant and the substrate occur, and the residual solvent is thermally expanded. Air bubbles, resulting in uneven gaps or seal paths; sealing hardening takes a long time; pre-baking process is complicated; the usable time of the sealant is shortened due to evaporation of the solvent; . especially Further, in a large-sized liquid crystal display device in recent years, the injection of liquid crystal takes a lot of time and becomes a big problem.

In view of this, a method of manufacturing a liquid crystal display element called a dropping method (using a sealant composed of a cured resin composition) has been studied. In the dropping method, first, a rectangular sealing pattern is formed on one of two transparent substrates with electrodes by screen printing or the like. Then, in a state where the sealant is not cured, fine droplets of the liquid crystal are dropped on the entire surface of the frame of the transparent substrate, and then another transparent substrate is immediately superposed, and the sealant is irradiated with ultraviolet rays to be pre-cured. Thereafter, it is heated as needed during the liquid crystal annealing, and further cured to form a liquid crystal display element. When the substrate is bonded under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency. In the future, it is expected that the dropping method will become the mainstream of the manufacturing method of the liquid crystal display device.

As a sealant for a liquid crystal dropping method used in a dropping method, since high adhesion is obtained, an epoxy resin is usually used as a thermosetting component. However, in the liquid crystal display element produced by the dropping method, there is a problem that display defects such as stains caused by alignment disorder of the liquid crystal are likely to occur. It is generally considered that the reason is that, in the step of the dropping method, the sealing agent for the liquid crystal dropping method in the unhardened state directly contacts the liquid crystal, and the sealant component is eluted to the liquid crystal before the sealing agent is completely cured.

In order to solve the above problem, for example, Patent Document 1 and Patent Document 2 disclose a sealing compound for a liquid crystal dropping method using a component having low solubility in liquid crystal. Since the above-mentioned sealant does not elute into the liquid crystal, it is considered that it does not cause liquid crystal contamination.

However, even when the liquid crystal display element is manufactured by the dropping method using the above-described sealing agent, liquid crystal contamination may be caused in some cases, and a liquid crystal display element having a small color unevenness and high quality image cannot be produced.

[Patent Document 1] Japanese Patent No. 3 583 326 [Patent Document 2] Japanese Patent Laid-Open No. 2001-133794

An object of the present invention is to provide a sealing compound for a liquid crystal dropping method which can prevent liquid crystal contamination even when a sealant component is eluted to a liquid crystal during production of a liquid crystal display element for dropping, thereby producing display quality and reliability. Excellent liquid crystal display element.

The present invention relates to a liquid crystal dropping method sealing agent comprising a curable resin and a photoradical initiator, wherein the photoradical initiator is completely dissolved at a concentration of 4% by weight relative to the liquid crystal at 120° C., After leaving at 20 ° C for 144 hours, it was not precipitated from the above liquid crystal; the above photoradical initiator, which has a light absorption coefficient of 50 mL/g at 405 nm measured in a solvent. More than cm.

The invention is described in detail below.

The inventors of the present invention have intensively studied and found that by using a photoradical initiator which is highly soluble in liquid crystals as a photoradical initiator for a liquid crystal dropping method, liquid crystal contamination can be prevented, and thus achievable A liquid crystal dropping method sealing agent for a liquid crystal display element excellent in quality and reliability, Thus, the present invention has been completed.

The sealing agent for liquid crystal dropping method of the present invention contains a photoradical initiator which is completely dissolved at a concentration of 4% by weight relative to the liquid crystal at 120 ° C, and then left at -20 ° C for 144 hours. Not precipitated from the above liquid crystal.

Conventionally, in the sealing compound for liquid crystal dropping methods, a photoradical initiator which has low solubility in liquid crystal is used in order to prevent liquid crystal contamination. However, there is a problem that liquid crystal contamination cannot be sufficiently prevented even if the above photoradical initiator is used.

The present inventors have found that liquid crystal contamination can be prevented by using a photoradical initiator which has high solubility to liquid crystals.

The photoradical initiator is a lower limit of 50 mL/g of the absorbance coefficient measured at 405 nm in a solvent. Cm. If the absorption coefficient is less than 50 mL/g. In the case of cm, the sealant using visible light is hardened and becomes insufficient. The preferred lower limit of the above absorption coefficient is 70 mL/g. Cm.

Since the above-mentioned light absorption coefficient tends to be higher as it is higher, there is no particular upper limit.

Further, the solvent is not particularly limited as long as it dissolves the photoradical initiator and does not absorb light at the measured absorption wavelength. Specifically, for example, acetonitrile, methanol or the like is used.

The above photoradical initiator is preferably light which does not absorb a wavelength of 500 nm or more. If the above-mentioned photoradical initiator absorbs light having a wavelength of 500 nm or more, a reaction may occur under a yellow light, and the sealant may become less rational.

A preferred upper limit of the melting point of the above photoradical initiator is 85 °C. When the melting point of the photoradical initiator is more than 85 ° C, it may be completely dissolved at a concentration of 4% by weight relative to the liquid crystal at 120 ° C, and then left at -20 ° C for 144 hours, the photoradical initiator will It precipitates from the liquid crystal and causes liquid crystal contamination. A more preferable upper limit of the melting point of the above photoradical initiator is 80 °C. The lower limit of the melting point of the photoradical initiator is not particularly limited. However, in the liquid crystal dropping method, the step of connecting the uncured sealant and the liquid crystal at a normal temperature is employed, and in order to suppress the dissolution of the photoradical initiator as much as possible. To the liquid crystal, the lower limit is preferably 30 °C.

As the photoradical initiator, for example, an oxime ester compound can be mentioned. Specifically, for example, 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzylidenehydrazine)] represented by the following formula (1) can be mentioned. The commercial item of the oxime ester compound represented by the following formula (1) is, for example, IRGACURE OXE01 (manufactured by Ciba Specialty Chemicals Co., Ltd.).

The content of the photoradical initiator in the sealing compound for liquid crystal dropping methods of the present invention is not particularly limited, and a preferred lower limit is 0.2% by weight, and a preferred upper limit is 10% by weight. If the content of the above photoradical initiator is less than 0.2 When the weight is %, the curing may be insufficient. If it exceeds 10% by weight, liquid crystal contamination may occur and the adhesion to the substrate may be lowered. A more preferred lower limit of the content of the above photoradical initiator is 1.0% by weight, and a more preferred upper limit is 5.0% by weight.

The sealing compound for liquid crystal dropping methods of this invention contains a hardening resin.

The curable resin is not particularly limited, and preferably has a (meth)acryl group and an epoxy group. By having the above functional group, the sealing agent for the liquid crystal dropping method of the prior art can be hardened by two stages of photohardening and thermal hardening.

Further, in the above curable resin, in the case of having a (meth)acryl group and an epoxy group, a preferred upper limit of the ratio of the epoxy group to the total amount of the (meth)acryl group and the epoxy group is 40% by mole. If it exceeds 40% by mole, the solubility in the liquid crystal becomes high, causing contamination of the stain on the panel. A better upper limit is 30% by mole.

The curable resin is not particularly limited, and examples thereof include an ester compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, and an epoxy group obtained by reacting (meth)acrylic acid with an epoxy compound (methyl group). An acrylate and a (meth)acrylic acid urethane obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate.

The ester compound obtained by reacting the compound having a hydroxyl group with (meth)acrylic acid is not particularly limited, and examples of the monofunctional one include 2-hydroxyethyl (meth)acrylate and (meth)acrylic acid 2. -Hydroxypropyl ester, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (methyl) Isooctyl acrylate, lauryl (meth)acrylate, stearyl (meth) acrylate, isobutyl (meth) acrylate Tablet ester, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth)acrylate , (tetra) methacrylate (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol ( Methyl) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl ester, quinone imine (meth) acrylate, (meth) acrylate Ester, ethyl (meth)acrylate, n-butyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid 2-ethylhexyl ester, n-octyl (meth)acrylate, isodecyl (meth)acrylate, isotetradecyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, Phenyloxyethyl 2-(meth)acrylate, dicyclopentenyl (meth)acrylate, (methyl) Isodecyl enoate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, 2-(methyl) propylene methoxyethyl succinic acid, 2-(methyl) propylene oxime Ethyl hexahydrophthalic acid, 2-(methyl) propylene methoxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2-(methyl) propylene Oxyloxyethyl phosphate and the like.

Further, the ester compound obtained by reacting the compound having a hydroxyl group with (meth)acrylic acid is not particularly limited as a difunctional one, and examples thereof include 1,4-butanediol di(meth)acrylate. , 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10- Decanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)propene Acid ester, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol Di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol A di(methyl) Acrylate, ethylene oxide addition bisphenol F di(meth) acrylate, dimethylol dicyclopentadienyl di(meth) acrylate, 1,3-butylene glycol di(meth) acrylate Ester, neopentyl glycol di(meth) acrylate, ethylene oxide modified di(meth) acrylate, 2-hydroxy-3-propenyloxy propyl di(methyl) Acrylate, carbonate diol di(meth) acrylate, polyether diol di(meth) acrylate, polyester diol di(meth) acrylate, polycaprolactone diol di(methyl) Acrylate, polybutadiene diol di(meth) acrylate, and the like.

In addition, the ester compound obtained by reacting the compound having a hydroxyl group with (meth)acrylic acid is not particularly limited as the trifunctional or higher one, and examples thereof include pentaerythritol tri(meth)acrylate and trimethylol group. Propane tri(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modification Trimethylolpropane tri(meth)acrylate, ethylene oxide addition tris (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(methyl) Acrylate, bis(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerin Acrylate, tris(meth)acryloxyethyl phosphate, and the like.

As the ring obtained by reacting (meth)acrylic acid with an epoxy compound The oxygen (meth) acrylate is not particularly limited, and can be obtained, for example, by reacting (meth)acrylic acid with an epoxy resin in the presence of a basic catalyst according to a usual method.

In the epoxy compound which is a raw material for the synthesis of the epoxy (meth) acrylate, for example, bisphenol A such as EPIKOTE 828EL or EPIKOTE 1004 (all manufactured by Japan Epoxy Resins Co., Ltd.) may be mentioned as a commercial product. Type epoxy resin; bisphenol F type epoxy resin such as EPIKOTE 806, EPIKOTE 4004 (all manufactured by Japan Epoxy Resins Co., Ltd.); bisphenol E type epoxy resin such as R-710; EPICLON EXA1514 (manufactured by Dainippon Ink Co., Ltd.) Bisphenol S-type epoxy resin; 2,2'-diallyl bisphenol A type epoxy resin such as RE-810NM (manufactured by Nippon Kayaku Co., Ltd.); EPICLON EXA7015 (manufactured by Dainippon Ink Co., Ltd.) Hydrogenated bisphenol type epoxy resin; propylene oxide addition bisphenol A type epoxy resin such as EP-4000S (made by Asahi Kasei Co., Ltd.); and benzenediol type such as EX-201 (manufactured by Changchun Chemical Co., Ltd.) Epoxy resin; biphenyl type epoxy resin such as EPIKOTE YX-4000H (manufactured by Japan Epoxy Resins Co., Ltd.); sulfide type epoxy resin such as YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.); YSLV-80DE (manufactured by Dongdu Chemical Co., Ltd.) ) such as a diphenyl ether type epoxy resin; EP-4088S (made by Asahi Chemical Co., Ltd.) Dicyclopentadiene type epoxy resin; naphthalene type epoxy resin such as EPICLON HP4032, EPICLON EXA-4700 (all manufactured by Dainippon Ink Co., Ltd.); phenol phenolic aldehyde such as EPICLON N-770 (manufactured by Dainippon Ink Co., Ltd.) Varnish type epoxy resin; o-cresol novolac type epoxy resin such as EPICLON N-670-EXP-S (manufactured by Dainippon Ink Co., Ltd.); dicyclopentadiene such as EPICLON HP7200 (manufactured by Dainippon Ink Co., Ltd.) A novolac type epoxy resin such as a novolak type epoxy resin; a non-phenol novolak type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); a naphthol novolak type epoxy resin such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.); EPIKOTE 630 (Golden Japan Epoxy Resins Co., Ltd.), EPICLON 430 (manufactured by Dainippon Ink Co., Ltd.), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc.; ZX-1542 (manufactured by Tosho Kasei Co., Ltd.), EPICLON 726 (Daily Ink Co., Ltd.), EPOLIGHT 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), DENACOL EX-611 (manufactured by Changchun Chemical Co., Ltd.), etc., alkyl polyol type epoxy resin; YR-450, YR-207 (both Rubber modified epoxy resin manufactured by Dongdu Chemical Co., Ltd., 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 (Japan Epoxy) Bisphenol A type episulfide resin, such as manufactured by Resins Co., Ltd., may be exemplified by YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), EPIKOTE 1031, EPIKOTE 1032 (both It is manufactured by Japan Epoxy Resins Co., Ltd., EXA-7120 (manufactured by Dainippon Ink Co., Ltd.), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

Further, examples of the commercially available epoxy (meth) acrylate include EBECRYL 3700, EBECRYL 3600, EBECRYL 3701, EBECRYL 3703, EBECRYL 3200, EBECRYL 3201, EBECRYL 3702, EBECRYL 3412, EBECRYL 860, EBECRYL RDX63182 , EBECRYL 6040, EBECRYL 3800 (both manufactured by Daicel UCB); 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 Kyoeisha Chemical Co., Ltd.); DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, DENACOL ACRYLATE DA-911 (both are long 濑Chemical company manufacturing) and so on.

The (meth)acrylic acid urethane obtained by reacting the (meth)acrylic acid derivative having a hydroxyl group with an isocyanate is not particularly limited, and for example, 2 equivalents of a (meth)acrylic acid having a hydroxyl group can be obtained. The derivative is obtained by reacting one equivalent of a compound having two isocyanate groups in the presence of a tin-based compound as a catalyst.

The isocyanate which is a raw material of the above (meth)acrylic acid urethane is not particularly limited, and examples thereof include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and Methylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane II Isocyanate, tolidine diisocyanate, benzene dimethylene diisocyanate (XDI), hydrogenated XDI, diazonic acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethyl bis Toluene diisocyanate, 1,6,10-undecane triisocyanate, and the like.

Further, as the above isocyanate, for example, ethylene glycol can be used. Reaction of polyhydric alcohols such as glycerol, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, etc. with excess isocyanate The chain is extended isocyanate compound.

The (meth)acrylic acid derivative having a hydroxyl group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 4. a commercial product such as hydroxybutyl ester or 2-hydroxybutyl (meth)acrylate; or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, a mono(meth)acrylate of a glycol such as polyethylene glycol; a mono(meth)acrylate of a trihydric alcohol such as trimethylolethane, trimethylolpropane or glycerin; or a Epoxy (meth) acrylate such as acrylate or bisphenol A modified epoxy (meth) acrylate.

In addition, examples of the commercially available (meth)acrylic acid urethane include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei 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 are Daicel UCB companies) Manufacturing); ART RESIN UN-9000H, ART RESIN UN-9000A, ART RESIN UN-7100, ART RESIN UN-1255, ART RESIN UN-330, ART RESIN UN-3320HB, ART RESIN UN-1200TPK, ART RESIN SH-500B (All manufactured by Gensei Industrial Co., Ltd.); U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U -6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U- 340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA- 306T, UA-306I, etc.

In addition, it is preferable that the curable resin has at least one hydrogen bond functional group in one molecule in order to further suppress elution of the component of the sealing compound for liquid crystal dropping methods of the present invention to the liquid crystal before curing.

The hydrogen bond functional group is not particularly limited, and examples thereof include an -OH group, a -SH group, and a -NHR group (R represents an aromatic or aliphatic hydrocarbon, and derivatives thereof), a -COOH group, and a functional group such as an NHOH group; and a residue of -NHCO-, -NH-, -CONHCO-, -NH-NH-, etc. present in the molecule, wherein -OH is preferred from the viewpoint of easiness of introduction. base.

The curable resin having at least one hydrogen bond functional group in one molecule and having a (meth) propylene group may, for example, be the above-mentioned (meth)acrylic acid urethane or epoxy (meth) acrylate. Wait.

In the sealing compound for liquid crystal dropping methods of the present invention, in order to reduce the uncured residue at the time of curing, the curable resin is preferably a compound having two or more reactive groups in one molecule.

Further, a compound having a different reactive functional group in one molecule may be used as the curable resin. Examples of the compound include those having at least one epoxy group and (meth) propylene group in one molecule.

Examples of the compound having at least one epoxy group and (meth)acryl group in the above-mentioned one molecule include, for example, two or more epoxy groups. A compound obtained by reacting a part of the epoxy group with (meth)acrylic acid, a compound obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group, and glycidol with a difunctional or higher isocyanate.

The compound obtained by reacting a part of the epoxy group of the compound having two or more epoxy groups with (meth)acrylic acid can be obtained, for example, by an epoxy resin according to a conventional method in the presence of a basic catalyst. Obtained by the reaction of methyl)acrylic acid.

Examples of the compound having two or more epoxy groups include bisphenol A type epoxy resins such as EPIKOTE 828EL and EPIKOTE 1004 (all manufactured by Japan Epoxy Resins Co., Ltd.); EPIKOTE 806 and EPIKOTE 4004 (both Japan Epoxy) Bisphenol F type epoxy resin such as Resins; bisphenol E type epoxy resin such as R-710; bisphenol S type epoxy resin such as EPICLON EXA1514 (manufactured by Dainippon Ink Co., Ltd.); RE-810NM ( 2,2'-diallyl bisphenol A type epoxy resin manufactured by Nippon Kayaku Co., Ltd.; hydrogenated bisphenol type epoxy resin such as EPICLON EXA7015 (manufactured by Dainippon Ink Co., Ltd.); EP-4000S (Asahi Kasei) Ethylene oxide addition bisphenol A type epoxy resin manufactured by the company); benzenediol type epoxy resin such as EX-201 (manufactured by Changchun Chemical Co., Ltd.); EPIKOTE YX-4000H (manufactured by Japan Epoxy Resins Co., Ltd.) Such as biphenyl type epoxy resin; sulphate type epoxy resin such as YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.); phenyl ether type epoxy resin such as YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.); EP-4088S ( Dicyclopentadiene type epoxy resin manufactured by Asahi Chemical Co., Ltd.; EPICLON HP4032, E PICLON EXA-4700 (all manufactured by Dainippon Ink Co., Ltd.), etc.; EPICLON N-770 (manufactured by Dainippon Ink Co., Ltd.) A phenol novolak type epoxy resin; an o-cresol novolac type epoxy resin such as EPICLON N-670-EXP-S (manufactured by Dainippon Ink Co., Ltd.); a second ring of EPICLON HP7200 (manufactured by Dainippon Ink Co., Ltd.) a pentadiene novolac type epoxy resin; a biphenol novolak type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); a naphthol novolak type epoxy resin such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.) ; EPIKOTE 630 (manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON 430 (manufactured by Dainippon Ink Co., Ltd.), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and other glycidylamine type epoxy resin; ZX-1542 (manufactured by Tohto Kasei Co., Ltd.) , EPICLON 726 (manufactured by Dainippon Ink Co., Ltd.), EPOLIGHT 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), DENACOL EX-611 (manufactured by Changchun Chemical Co., Ltd.), etc., alkyl polyol type epoxy resin; 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 (Japan Epo The bisphenol A type episulfide resin manufactured by xy Resins Co., Ltd., and the like: YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation); EPIKOTE 1031, EPIKOTE 1032 (all manufactured by Japan Epoxy Resins Co., Ltd.); EXA-7120 (manufactured by Dainippon Ink Co., Ltd.); TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

The commercially available product obtained by reacting a part of the epoxy group of the compound having two or more epoxy groups with (meth)acrylic acid is exemplified by EBECRYL 1561 (manufactured by Daicel UCB Co., Ltd.).

As the compound obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group and glycidol with a difunctional or higher isocyanate, for example, one equivalent of a (meth)acrylic acid derivative having a hydroxyl group and glycidol can be used. It is obtained by reacting one equivalent of a compound having two isocyanate groups in the presence of a tin-based compound as a catalyst.

The difunctional or higher isocyanate is not particularly limited, and examples thereof include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and trimethyl six. Methylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, benzene Methylene diisocyanate (XDI), hydrogenated XDI, quaternary acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, 1,6,10- Undecane triisocyanate and the like.

Further, as the above-mentioned difunctional or higher isocyanate, for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, polyether diol, polyester diol can also be used. A chain-extended isocyanate compound obtained by reacting a polyol such as an alcohol or a polycaprolactone diol with an excess of isocyanate.

The (meth)acrylic acid derivative having a hydroxyl group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 4. a commercial product such as hydroxybutyl ester or 2-hydroxybutyl (meth)acrylate; or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, Mono(meth) acrylate of glycol such as polyethylene glycol; trishydroxyl a mono (meth) acrylate or a di(meth) acrylate of a trihydric alcohol such as methyl ethane, trimethylolpropane or glycerin; a bisphenol A modified epoxy (meth) acrylate or the like Epoxy (meth) acrylate and the like.

Further, the sealant of the present invention may contain a compound having an epoxy group in addition to the above-mentioned curable resin having a (meth)acryl group.

The compound having an epoxy group is not particularly limited, and examples thereof include an epichlorohydrin derivative, a cyclic aliphatic epoxy resin, and a compound obtained by a reaction of an isocyanate with glycidol.

Examples of the epichlorohydrin derivative include bisphenol A type epoxy resins such as EPIKOTE 828EL and EPIKOTE 1004 (all manufactured by Japan Epoxy Resins Co., Ltd.); EPIKOTE 806 and EPIKOTE 4004 (all manufactured by Japan Epoxy Resins Co., Ltd.). Such as bisphenol F type epoxy resin; bisphenol S type epoxy resin such as EPICLON EXA1514 (manufactured by Dainippon Ink Co., Ltd.); 2,2'- diallyl group such as RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) Bisphenol A type epoxy resin; hydrogenated bisphenol type epoxy resin such as EPICLON EXA7015 (manufactured by Dainippon Ink Co., Ltd.); propylene oxide addition bisphenol A type epoxy resin such as EP-4000S (made by Asahi Kasei Co., Ltd.) ; EX-201 (manufactured by Changchun Chemical Co., Ltd.), such as a benzene-based epoxy resin; EPIKOTE YX-4000H (manufactured by Japan Epoxy Resins Co., Ltd.), etc.; YSLV-50TE (manufactured by Dongdu Chemical Co., Ltd.) a thioether type epoxy resin such as a thioether type epoxy resin; a bisphenylene type epoxy resin such as YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.); and a dicyclopentadiene type epoxy resin such as EP-4088S (manufactured by Asahi Kasei Co., Ltd.); EPICLON HP4032, EPICLON EXA-4700 (all manufactured by Dainippon Ink Co., Ltd.), etc. Naphthalene type epoxy resin; EPICLON N-770 A phenol novolac type epoxy resin such as (manufactured by Dainippon Ink Co., Ltd.); an o-cresol novolac type epoxy resin such as EPICLON N-670-EXP-S (manufactured by Dainippon Ink Co., Ltd.); EPICLON HP7200 (Daily Ink) Naphthyl phenol varnish type epoxy resin, etc. manufactured by the company; naphthaldehyde varnish type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); naphthalene such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.) Phenolic novolac type epoxy resin; EPIKOTE 630 (manufactured by Japan Epoxy Resins Co., Ltd.); EPICLON 430 (manufactured by Dainippon Ink Co., Ltd.); TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and other glycidylamine type epoxy resin; ZX- 1542 (manufactured by Dongdu Chemical Co., Ltd.); EPICLON polyol epoxy resin; YR-450, YR-207 (all manufactured by Dongdu Chemical Co., Ltd.); rubber modified ring 726 of EPOLEAD PB (manufactured by Daicel Chemical Co., Ltd.) Alkyloxy resin such as EPOLIGHT 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), DENACOL EX-611 (manufactured by Changchun Chemical Co., Ltd.), and glycidol such as DENACOL EX-147 (manufactured by Changchun Chemical Co., Ltd.) Ester compound; EP Bisphenol A type episulfide resin such as IKOTE YL-7000 (manufactured by Japan Epoxy Resins Co., Ltd.), and other examples include YDC-1312, YSLV-80XY, and YSLV-90CR (all manufactured by Dongdu Chemical Co., Ltd.); XAC4151 (manufactured by Asahi Kasei Co., Ltd.) EPIKOTE 1031, EPIKOTE 1032 (all manufactured by Japan Epoxy Resins Co., Ltd.); EXA-7120 (manufactured by Dainippon Ink Co., Ltd.); TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

In addition, the cyclic aliphatic epoxy resin is not particularly limited, and examples of the commercially available product include CELLOXIDE 2021, CELLOXIDE 2080, CELLOXIDE 3000, EPOLEAD GT300, and EHPE. Made by Daicel Chemical Co., Ltd.).

The compound obtained by reacting the isocyanate with glycidol is not particularly limited. For example, two equivalents of glycidol and a compound having two isocyanate groups can be reacted in the presence of a tin-based compound as a catalyst. And get.

The isocyanate is not particularly limited, and examples thereof include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. , diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, benzene dimethylene diisocyanate (XDI), hydrogenated XDI, diazonic acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, 1,6,10-undecane triisocyanate Wait.

Further, as the above isocyanate, for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, polyether diol, polyester diol, poly propylene can also be used. A chain-extended isocyanate compound obtained by reacting a polyol such as a lactone diol with an excess of isocyanate.

The sealing agent for liquid crystal dropping methods of the present invention preferably further contains a thermosetting agent.

The thermal curing agent is not particularly limited, and examples thereof include an amine compound, a polyphenol compound, and an acid anhydride.

The amine compound may, for example, be a compound having one or more mono- to tertiary amino groups in one molecule. Specifically, for example, isophthalic acid can be cited. An aromatic amine such as an amine or a diaminodiphenylmethane; an imidazole compound such as 2-methylimidazole, 1,2-dimethylimidazole or 1-cyanoethyl-2-methylimidazole; 2-methylimidazole An imidazoline compound such as a porphyrin; a diterpene compound such as diterpene sebacate or dioxonium isophthalate; AJICURE PN-23, AJICURE MY-24, AJICURE VDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) And other amine adducts; and dicyandiamide.

The polyphenol-based compound is not particularly limited, and examples thereof include a polyphenol compound such as EPICURE 170 and EPICURE YL6065 (all manufactured by Japan Epoxy Resins Co., Ltd.), and a novolak type such as EPICURE MP402FPI (manufactured by Japan Epoxy Resins Co., Ltd.). Phenol resin.

The acid anhydride is not particularly limited, and examples thereof include EPICURE YH-306 and YH-307 (all manufactured by Japan Epoxy Resins Co., Ltd.).

These thermosetting agents may be used singly or in combination of two or more. Among them, a diterpene compound is preferred from the viewpoint of excellent low-temperature curability and storage stability.

The amount of the thermosetting agent to be added is not particularly limited, and is preferably 1 part by weight, and preferably 100 parts by weight, per 100 parts by weight of the curable resin. When the amount of the thermosetting agent is less than 1 part by weight, the curing of the curable resin may be insufficient. When the amount is more than 100 parts by weight, the storage stability of the sealing compound for liquid crystal dropping method of the present invention may be There is a deterioration, and when it is made into a hardened material, there is a possibility that the moisture resistance is lowered. A more preferable upper limit of the amount of the above-mentioned thermosetting agent is 20 parts by weight.

The sealing agent for liquid crystal dropping methods of the present invention preferably further contains a decane coupling agent. The above decane coupling agent mainly has the function of a secondary auxiliary agent, which is followed by The auxiliary agent is used to satisfactorily adhere the liquid crystal display element substrate of the liquid crystal display method of the present invention.

The decane coupling agent is not particularly limited, and examples thereof include γ-aminopropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, and γ-isocyanate. Propyltrimethoxydecane, and the like. These decane coupling agents may be used singly or in combination of two or more. In addition, the γ-glycidoxypropyltrimethoxydecane-based compound having an epoxy group can be used in a range that does not deteriorate the display quality of the liquid crystal display device produced by the dropping method.

The amount of the decane coupling agent to be added is not particularly limited, and the lower limit is 0.1 part by weight, and the upper limit is preferably 10 parts by weight based on 100 parts by weight of the curable resin. When the amount of the above decane coupling agent is less than 0.1 part by weight, the performance may not be sufficiently exhibited. If it exceeds 10 parts by weight, the remaining decane coupling agent may be eluted to the liquid crystal to lower the display quality. A more preferred lower limit of the amount of the above decane coupling agent is 0.5 parts by weight, and a more preferred upper limit is 3 parts by weight.

In addition, the sealing agent for liquid crystal dropping methods of the present invention may contain a filler in order to improve the adhesion, the coefficient of linear expansion, and the like by the stress dispersion effect.

The filler is not particularly limited, and examples thereof include talc, asbestos, cerium oxide, diatomaceous earth, bentonite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, magnesium oxide, titanium oxide, and hydrogen. Inorganic fillers of magnesium oxide, aluminum hydroxide, glass beads, barium sulfate, gypsum, calcium silicate, sericite, activated clay, etc.; or polyester microparticles, polyurethane microparticles An organic filler such as an ethylene polymer microparticle or an acrylic polymer microparticle.

The amount of the filler to be added is not particularly limited, and the lower limit is 1 part by weight, and the upper limit is preferably 100 parts by weight based on 100 parts by weight of the curable resin. If the amount of the above filler is less than 1 part by weight, performance may not be sufficiently exhibited. When the amount is more than 100 parts by weight, the workability such as the drawability of the sealing compound for liquid crystal dropping methods of the present invention is lowered. A more preferred lower limit of the amount of the above filler is 10 parts by weight, and a more preferred upper limit is 50 parts by weight.

The upper limit of the viscosity of the sealing agent for liquid crystal dropping method of the present invention measured by using an E-type viscometer at 25 ° C is 600,000 mPa. s. If the above viscosity exceeds 600,000 mPa. s, the drawability is insufficient, and the liquid crystal display element cannot be manufactured by the dropping method. The preferred lower limit of the above viscosity is 100,000 mPa. s, the upper limit is 450,000 mPa. s.

The E-type viscometer for measuring the viscosity of the sealing agent for a liquid crystal dropping method of the present invention is not particularly limited, and examples thereof include "DV-III" manufactured by Brookfield Corporation.

The method for producing the sealing agent for a liquid crystal dropping method of the present invention is not particularly limited, and examples thereof include a method in which a predetermined amount of the curable resin, a photoradical initiator, and a visible amount are used by a conventionally known method. The above-mentioned heat hardener and decane coupling agent are blended as needed. At this time, in order to remove the ionic impurities contained, it may be brought into contact with the ion-adsorbing solid.

The sealing agent for liquid crystal dropping method of the invention has a viscosity of 600,000 mPa. s Hereinafter, it is also excellent in drawability. In addition, since the curable resin contains a photoradical initiator having high solubility in the liquid crystal, when a liquid crystal display element is produced by a dropping method, a liquid crystal display element of high quality image can be produced without causing liquid crystal contamination.

The upper and lower conductive materials can be produced by blending conductive fine particles in the sealing compound for liquid crystal dropping methods of the present invention. The above-mentioned sealing agent for liquid crystal dropping method of the present invention and conductive fine particles are also one of the present invention.

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 a conductive metal layer is formed on the surface of the resin fine particles, it is preferable because the resin fine particles have excellent elasticity and can be electrically connected without damaging the transparent substrate or the like.

The liquid crystal display element formed by using the sealing compound for liquid crystal dropping method of the present invention and/or the upper conductive material of the present invention is also one of the present inventions.

As a method of producing the liquid crystal display element of the present invention, for example, a method of the following steps: one of two transparent substrates of an ITO (Indium Tin Oxide) film and the like, a screen a step of forming a rectangular seal pattern by a dispenser or the like by a dispenser for the liquid crystal dropping method of the present invention, and a transparent substrate in a state where the sealant for a liquid crystal dropping method of the present invention is not cured. a step of dropping and applying a small droplet of liquid crystal on the entire surface of the frame, and immediately superposing another transparent substrate; and irradiating the portion of the sealing pattern of the sealing compound for liquid crystal dropping method of the present invention with ultraviolet light or the like to pre-harden Step; And a step of heating the pre-hardened seal pattern to form a seal pattern formed by the sealant for liquid crystal dropping method of the present invention.

The liquid crystal display element formed by using the sealing compound for liquid crystal dropping method of the present invention and/or the upper conductive material of the present invention is also one of the present inventions.

According to the present invention, it is possible to provide a sealing agent for a liquid crystal dropping method which can prevent liquid crystal contamination even when a sealant component is eluted to a liquid crystal during production of a liquid crystal display element for dropping, thereby producing display quality and A liquid crystal display element with excellent reliability.

The invention is further illustrated by the following examples, but the invention is not limited to the examples.

<Synthesis of Curable Resin>

(Synthesis of epoxy acrylate (1))

170 g of bisphenol A type epoxy resin 850 CRP (manufactured by Dainippon Ink Co., Ltd.) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added to the solution to prepare a homogeneous solution. After 72 g of acrylic acid was dropped into the solution under reflux for 2 hours, the mixture was further stirred under reflux for 8 hours.

Then, toluene was removed, whereby an epoxy acrylate (1) (850 CRP completely modified product) obtained by converting all of the epoxy groups into an acrylonitrile group was obtained.

(bisphenol E type epoxy acrylate resin obtained by reacting a part of an epoxy group with acrylic acid (synthesis of partially modified resin (2))

163 g of bisphenol E type epoxy resin R-710 (manufactured by Mitsui Chemicals, Inc.) The solution was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added to the solution to prepare a homogeneous solution. After 54 g of acrylic acid was added dropwise to the solution under reflux for 2 hours, the mixture was further stirred under reflux for 6 hours. Toluene was removed, whereby a bisphenol E type epoxy acrylate resin (partially modified resin (2)) obtained by reacting 75 mol% of an epoxy group with acrylic acid was obtained.

Further, the reforming rate was measured by dissolving the resin in a hydrochloric acid-dioxane solution (HCl-dioxane), and then using KOH to titrate the amount of hydrochloric acid consumed by the epoxy group.

(a bisphenol F type epoxy acrylate resin obtained by reacting a part of an epoxy group with acrylic acid (synthesis of a partially modified resin (3))

156 g of bisphenol F type epoxy resin 830CRP (manufactured by Dainippon Ink Co., Ltd.) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added to the solution to prepare a homogeneous solution. 54 g of acrylic acid was added dropwise to the solution under reflux for 2 hours, and the mixture was further stirred under reflux for 6 hours. Toluene was removed, whereby a bisphenol F type epoxy acrylate resin (partially modified resin (3)) obtained by reacting 75 mol% of an epoxy group with acrylic acid was obtained.

Further, the reforming rate was measured by dissolving the resin in a hydrochloric acid-dioxane solution, and then using KOH to titrate the amount of hydrochloric acid consumed by the epoxy group.

(bisphenol E type epoxy acrylate resin obtained by reacting one part of an epoxy group with acrylic acid (synthesis of partially modified resin (4))

163 g of bisphenol E type epoxy resin R-710 (manufactured by Mitsui Chemicals, Inc.) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added to the solution to prepare a homogeneous solution. 2 hours in the solution under reflux and stirring After 36 g of acrylic acid was dropped, the mixture was further stirred under reflux for 6 hours. Toluene was removed, whereby a bisphenol E type epoxy acrylate resin (partially modified resin (4)) obtained by reacting 50 mol% of an epoxy group with acrylic acid was obtained.

Further, the reforming rate was measured by dissolving the resin in a hydrochloric acid-dioxane solution, and then using KOH to titrate the amount of hydrochloric acid consumed by the epoxy group.

(a biphenyl ether type epoxy acrylate resin obtained by reacting a part of an epoxy group with acrylic acid (synthesis of a partially modified resin (5))

157 g of a diphenyl ether type epoxy resin YSLV-80DE (manufactured by Nippon Steel Chemical Co., Ltd.) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added to the solution to prepare a homogeneous solution. After 36 g of acrylic acid was added dropwise to the solution under reflux for 2 hours, the mixture was further stirred under reflux for 6 hours. Toluene was removed, whereby a bisphenol E type epoxy acrylate resin (partially modified resin (5)) obtained by reacting 50 mol% of an epoxy group with acrylic acid was obtained.

Further, the reforming rate was measured by dissolving the resin in a hydrochloric acid-dioxane solution, and then titrating the amount of hydrochloric acid consumed by the epoxy group with KOH.

(Example 1)

100 parts by weight of the partially modified resin (2), 2 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE OXE01), and 16 parts by weight of a heat hardener (Ajinomoto Fine-Techno) Manufactured by the company, AJICURE VDH), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), The mixture was stirred by a planetary stirring device (manufactured by Thinky Co., Ltd., de-soaked), and then uniformly mixed by a ceramic three-roll mill to obtain a sealant for liquid crystal dropping method.

(Example 2)

50 parts by weight of the synthesized epoxy acrylate (1), 50 parts by weight of the partially modified resin (4), and 2 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals, IRGACURE) OXE01), 16 parts by weight of a heat hardener (AJICURE VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of decane as a filler The coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) was blended, stirred with a planetary stirring device (manufactured by Thinky Co., Ltd., and de-soaked), and then uniformly mixed by a ceramic three-roll mill to obtain a liquid crystal dropping method. Sealants.

(Example 3)

100 parts by weight of the partially modified resin (2), 5 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE OXE01), and 16 parts by weight of a heat hardener (Ajinomoto Fine-Techno) Manufactured by the company, AJICURE VDH), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) The stirring device (manufactured by Thinky Co., Ltd., de-soaked) was stirred, and then uniformly mixed by a ceramic three-roll mill to obtain a sealing agent for a liquid crystal dropping method.

(Example 4)

50 parts by weight of the synthesized epoxy acrylate (1), 50 parts by weight of the partially modified resin (4), 0.5 part by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals, IRGACURE) OXE01), 16 parts by weight of a heat hardener (Ajicure VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of decane The coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) was blended, stirred with a planetary stirring device (manufactured by Thinky Co., Ltd., and de-soaked), and then uniformly mixed by a ceramic three-roll mill to obtain a liquid crystal dropping method. Sealants.

(Example 5)

50 parts by weight of the synthesized epoxy acrylate (1), 50 parts by weight of the partially modified resin (4), and 5 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals, IRGACURE) OXE01), 16 parts by weight of a heat hardener (AJICURE VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.), 22 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 8 parts by weight of talc, 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) was blended, and the mixture was stirred by a planetary stirring device (manufactured by Thinky Co., Ltd., de-soaked, and then uniformly mixed by a ceramic three-roll mill). Thus, a sealant for a liquid crystal dropping method is obtained.

(Example 6)

50 parts by weight of the synthesized epoxy acrylate (1), 50 parts by weight of the partially modified resin (4), and 2 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals, IRGACURE) OXE01), 5 parts by weight As a thermosetting agent, diammonium adipate, 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) The blending was carried out, and the mixture was stirred by a planetary stirring device (manufactured by Thinky Co., Ltd., and soaked in Taro), and then uniformly mixed by a ceramic three-roll mill to obtain a sealing agent for a liquid crystal dropping method.

(Example 7)

50 parts by weight of the synthesized epoxy acrylate (1), 25 parts by weight of the synthesized partial modified resin (4), 25 parts by weight of the synthesized partially modified resin (5), 2 parts by weight Photoradical initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE OXE01), 16 parts by weight of a heat hardener (AJICURE VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.), 30 parts by weight of spherical cerium oxide as a filler ( Manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), and stirred by a planetary stirring device (manufactured by Thinky Co., Ltd., de-soaked) The roll mill was uniformly mixed to obtain a sealant for liquid crystal dropping method.

(Example 8)

50 parts by weight of the synthesized epoxy acrylate (1), 25 parts by weight of the synthesized partial modified resin (4), 25 parts by weight of the synthesized partially modified resin (5), 2 parts by weight Photoradical initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE OXE01), 10 parts by weight of bismuth sebacate as a heat hardener, and 30 parts by weight of spherical cerium oxide as a filler (manufactured by Admatechs Co., Ltd.) , SO-C1), and 2 parts by weight of decane The mixture (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) was blended, stirred with a planetary stirring device (manufactured by Thinky Co., Ltd., and de-soaked), and then uniformly mixed by a ceramic three-roll mill to obtain a liquid crystal dropping method seal. Agent.

(Comparative Example 1)

100 parts by weight of the partially modified resin (2), 2 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals, DAROCURE TPO), and 16 parts by weight of a heat hardener (Ajinomoto Fine-Techno) Manufactured by the company, AJICURE VDH), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) The stirring device (manufactured by Thinky Co., Ltd., de-soaked) was stirred, and then uniformly mixed by a ceramic three-roll mill to obtain a sealing agent for a liquid crystal dropping method.

(Comparative Example 2)

50 parts by weight of the synthesized epoxy acrylate (1), 50 parts by weight of the partially modified resin (3), and 2 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals, DAROCURE) TPO), 16 parts by weight of a heat hardener (AJICURE VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of decane as a filler The coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) was blended, stirred with a planetary stirring device (manufactured by Thinky Co., Ltd., and de-soaked), and then uniformly mixed by a ceramic three-roll mill to obtain a liquid crystal dropping method. Sealants.

(Comparative Example 3)

50 parts by weight of the synthesized epoxy acrylate (1), 50 parts by weight of the partially modified resin (4), and 5 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals, DAROCURE) 1173), 16 parts by weight of a heat hardener (AJICURE VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of decane as a filler. The coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) was blended, stirred with a planetary stirring device (manufactured by Thinky Co., Ltd., and de-soaked), and then uniformly mixed by a ceramic three-roll mill to obtain a liquid crystal dropping method. Sealants.

(Comparative Example 4)

100 parts by weight of the partially modified resin (2), 2 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 819), and 16 parts by weight of a heat hardener (Ajinomoto Fine-Techno) Manufactured by the company, AJICURE VDH), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) A stirring device (manufactured by Thinky Co., Ltd., de-soaked) was stirred and uniformly mixed by a ceramic three-roll mill to obtain a sealing agent for a liquid crystal dropping method.

(Comparative Example 5)

100 parts by weight of the partially modified resin (2), 2 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 379), and 16 parts by weight of a heat hardener (Ajinomoto Fine-Techno) the company Manufactured, AJICURE VDH), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) were formulated in a planetary manner. After stirring, the stirring apparatus (manufactured by Thinky Co., Ltd.) was stirred and then uniformly mixed by a ceramic three-roll mill to obtain a sealing agent for liquid crystal dropping method.

<Evaluation of photoradical initiators>

The following evaluations were carried out on the photoradical initiators used in the examples and the comparative examples.

The results are shown in Tables 1 and 2.

(1) Evaluation of liquid crystal solubility of photoradical initiators

0.5 g of liquid crystal and a fixed amount of photoradical initiator were added to the glass vial so that the photoradical initiator became 4% by weight with respect to the liquid crystal. The lid of the vial was capped and placed in an oven at 120 ° C for 1 hour. After 1 hour, it was taken out from the oven and left at -20 ° C for 144 hours to visually observe the precipitation state of the photoradical initiator.

Further, in the liquid crystal system, MLC-6609 (VA, manufactured by Merck Co., Ltd.) and ZN-5001LA (TN, manufactured by Chisso Co., Ltd.) were used.

(2) Determination of the absorption coefficient of photoradical initiator

1 mol of DAROCURE TPO and IRGACURE OXE01 were dissolved in 1 L of acetonitrile, and the resulting solution was added to a 1 cm quartz cell, and the absorbance at 405 nm was measured using a spectrophotometer.

1 mole of DAROCURE 1173, IRGACURE 819 and IRGACURE 379 were dissolved in 1 L of methanol, and the resulting solution was added to In a 1 cm quartz cell, a spectrophotometer was used to measure the absorbance at 405 nm.

Furthermore, if the groove length is set to l [cm], the molar concentration is c [mol/L], and the molar absorption coefficient is set to ε [L/mol. Cm], according to the lambert-beer law, Mohr absorbance = ε cl.

<Evaluation of Sealant for Liquid Crystal Dropping Method>

Liquid crystal dropping method prepared in Examples 1 to 8 and Comparative Examples 1 to 5 The following evaluation was carried out with a sealant.

The results are shown in Table 3.

(1) Evaluation of hardenability

The liquid crystal display element is sandwiched in the glass with a sealant. In this state, light was irradiated so that the irradiation amount of light having a wavelength of 405 nm became 3000 mJ/cm ² . In addition, a 400 nm cut-off filter was used for the illumination. Thereafter, the reaction rate of the propylene group was measured using an analytical method of FT-IR (Fourier Transform Infrared). When the reaction rate of the propylene group was less than 50%, it was evaluated as "x", 50 to 70% was evaluated as "△", and when more than 70% was evaluated as "○".

(2) Evaluation of liquid crystal display panel (color spot evaluation)

On one of the alignment film and the transparent substrate on which the electrode is attached, a sealant for a liquid crystal display element is applied by using a dispenser to draw a rectangular frame. Then, liquid crystal ("ZN-5001LA" manufactured by Merck Co., Ltd.) was dropped, and another substrate was bonded, and then the high pressure mercury lamp was irradiated at 100 mW/cm ^{2 for} 30 seconds to be hardened. At this point, use a 400 nm cut-off filter. Then, it was thermally hardened at 120 ° C for 1 hour to prepare a liquid crystal display panel.

With respect to the obtained liquid crystal display panel (the number of samples was five), it was visually confirmed that the alignment of the liquid crystal in the vicinity of the sealant immediately after the liquid crystal display panel was formed was disordered. The alignment disorder is judged according to the stain of the display portion, and according to the degree of the stain, ◎ (completely no stain), ○ (with traces), △ (with a little stain), × (with a large number of stains) The evaluation was carried out in 4 stages. Furthermore, the liquid crystal display panel evaluated as ◎ and ○ is a level that is completely problem-free in practical use.

Industrial availability

According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method which can prevent liquid crystal contamination even when liquid crystal is eluted by a sealant component in the production of a liquid crystal display element for dropping, thereby enabling display quality and reliability. Excellent liquid crystal display element.

Claims (5)

A sealant for liquid crystal dropping method, which comprises a curable resin and a photoradical initiator, wherein the photoradical initiator is completely dissolved at a concentration of 4% by weight relative to the liquid crystal at 120 ° C. After that, it was not precipitated from the liquid crystal after being left at -20 ° C for 144 hours, and the photoradical initiator was determined to have an absorption coefficient of 50 mL/g at 405 nm in a solvent. More than cm. The sealing agent for liquid crystal dropping method of claim 1, wherein the photoradical initiator is 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzylidene)肟)]. The sealant for liquid crystal dropping method according to claim 1 or 2, wherein the curable resin has a (meth) propylene group and an epoxy group, and the ratio of the epoxy groups is relative to the (meth) propylene group and the ring. The total amount of the oxy group is 40 mol% or less. The upper and lower conductive material is a sealing agent for liquid crystal dropping method and conductive fine particles according to any one of claims 1 to 3. A liquid crystal display element is formed by using a sealing compound for liquid crystal dropping method according to any one of claims 1 to 3 and/or a conductive material for upper and lower parts of the fourth application.