TWI422640B - Liquid crystal dripping process with sealant, upper and lower conductive material and liquid crystal display components - Google Patents

Description

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

The present invention relates to a sealing agent for a liquid crystal dropping method which is excellent in adhesion and straightness. Further, the present invention relates to an upper conductive material and a liquid crystal display element which are produced by using the sealing compound for a liquid crystal dropping method.

In recent years, a method of manufacturing a liquid crystal display element such as a liquid crystal display unit is being used in a vacuum injection method as disclosed in, for example, Patent Document 1 and Patent Document 2, from the viewpoint of shortening the tact time and optimizing the liquid crystal amount. A liquid crystal dropping method called a dropping method comprising a photocurable resin, a photopolymerization initiator, a thermosetting resin, and a thermosetting agent, which is a combination of a light curing agent and a heat curing type sealing agent.

In the dropping method, first, a sheet of a transparent substrate with electrodes attached thereto is formed into a rectangular sealing pattern by dispensing. Then, after the liquid crystal droplets are dropped onto the entire surface of the transparent substrate in a state where the sealant is not cured, the other transparent substrate is immediately superposed, and the sealing portion is temporarily hardened by irradiating light such as ultraviolet rays. Thereafter, it is heated and solidified at the time of liquid crystal annealing to produce 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, and the dropping method is currently the mainstream of the method for producing a liquid crystal display element.

In the liquid crystal display device, it is required that the sealant is excellent in linear drawability, and in order to achieve efficiency in the production process, it is required to increase the speed of distribution. However, in the case where the previous sealant is drawn at a high speed, there is a possibility that the sealant cannot be stably drawn in a straight line, and the disconnection is poor, or the outline is drawn. The line of sealant creates a problem of bending. A filler is usually blended in the sealant. In order to improve the linearity, it is conceivable to reduce the amount of the filler blended in the sealant. However, if the amount of the filler is reduced, there is adhesion of the sealant to the substrate or the alignment film. The problem of deterioration.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-133794

Patent Document 2: International Publication No. 02/092718

An object of the present invention is to provide a sealing compound for a liquid crystal dropping method which is excellent in adhesion and straightness. Further, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element which are produced by using the sealing compound for a liquid crystal dropping method.

The present invention relates to a sealing agent for a liquid crystal dropping method comprising a curable resin and a surface-treated inorganic fine particle, wherein the curable resin contains a resorcinol type epoxy (meth) acrylate and an epoxy group-containing resin, the surface The inorganic fine particles are treated with inorganic fine particles whose surface is treated with hexamethyldiazane, and/or inorganic fine particles whose surface is treated with 3-glycidoxypropyltrimethoxysilane; The average particle diameter of the fine particles is 0.1 μm or more.

Hereinafter, the present invention will be described in detail.

The present inventors have found that a combination of a curable resin containing a resorcinol type epoxy (meth) acrylate and a specific surface-treated inorganic fine particle can provide a sealant for a liquid crystal dropping method excellent in adhesion and straightness. Thus, the present invention has been completed.

By using resorcinol type epoxy (meth) acrylate and surface in combination The reason why the inorganic fine particles are treated and the linearity of the sealant can be improved is considered as follows. That is, it is presumed that the resorcinol type epoxy (meth) acrylate is higher in polarity than the resin generally used in the liquid crystal dropping method sealant, and therefore the surface is treated with a lower polarity. When the microparticles are used in combination, the repulsion between the particles and the resin becomes large, and the apparent viscosity is lowered.

The sealing compound for a liquid crystal dropping method of the present invention contains a curable resin.

The curable resin contains resorcinol type epoxy (meth) acrylate.

In the present specification, the above "(meth) acrylate" means acrylate or methacrylate. In the present specification, the above-mentioned "epoxy (meth) acrylate" means a compound obtained by reacting all of the epoxy groups in the epoxy resin with (meth)acrylic acid.

The resorcinol type epoxy (meth) acrylate is, for example, obtained by reacting (meth)acrylic acid with a resorcinol type epoxy resin in the presence of a basic catalyst according to a usual method. By. In the present specification, the above "(meth)acrylic acid" means acrylic acid or methacrylic acid.

The commercially available one of the resorcinol-type epoxy resins is, for example, EX-201 (manufactured by Nagase ChemteX Co., Ltd.).

A preferred lower limit of the content of the resorcinol type epoxy (meth) acrylate in the curable resin is 20% by weight. When the content of the above-mentioned resorcinol type epoxy (meth) acrylate is less than 20% by weight, the obtained liquid crystal dropping method sealing agent is inferior in linear drawing property, and is broken during drawing or curved after drawing. The situation. A more preferred lower limit of the content of the above resorcinol type epoxy (meth) acrylate is 50% by weight, and a still lower limit is preferably 70% by weight.

Further, a resorcinol type epoxy (meth)acrylic acid in the above curable resin A preferred upper limit of the content of the ester is 90% by weight. When the content of the resorcinol-type epoxy (meth) acrylate is 90% by weight or less, the adhesion and moisture resistance of the sealing compound for liquid crystal dropping methods obtained are improved. A more preferable upper limit of the content of the above resorcinol type epoxy (meth) acrylate is 85% by weight.

The curable resin preferably contains a bisphenol A type epoxy (meth) acrylate. By the resorcinol-type epoxy (meth) acrylate and the bisphenol A type epoxy (meth) acrylate, the liquid crystal dripping process sealant obtained by the method of dispensing is more excellent in linear straightness, and further Liquid crystal contamination and adhesion also became good.

The commercially available one of the bisphenol A type epoxy (meth) acrylates is, for example, EBECRYL 3700 (manufactured by Daicel-Cytec Co., Ltd.).

A preferred lower limit of the content of the bisphenol A type epoxy (meth) acrylate in the curable resin is 10% by weight. When the content of the bisphenol A type epoxy (meth) acrylate is less than 10% by weight, the obtained silicone resin dropping method sealant has high shakeability, and the syringe or nozzle used for coating is cleaned. Sexual deterioration. A more preferred lower limit of the content of the above bisphenol A type epoxy (meth) acrylate is 20% by weight.

Further, a preferred upper limit of the content of the bisphenol A type epoxy (meth) acrylate in the curable resin is 60% by weight. When the content of the bisphenol A type epoxy (meth) acrylate is 60% by weight or less, the viscosity is in a preferable range, and the coating property of the obtained sealing compound for liquid crystal dropping method is improved. A more preferable upper limit of the content of the above bisphenol A type epoxy (meth) acrylate is 50% by weight.

The curable resin contains a resin having an epoxy group.

Examples of the epoxy group-containing resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2'-diallyl bisphenol A type ring. Oxygen resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, thioether epoxy resin, diphenyl ether Type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin , phenol novolak type epoxy resin, naphthol novolac type epoxy resin, epoxy propyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, epoxy propyl group Ester compound and the like.

Among the bisphenol A type epoxy resins, for example, Epikote 828EL, Epikote 1004 (all manufactured by Mitsubishi Chemical Corporation), Epiclon 850-S (manufactured by DIC Corporation), and the like are mentioned.

The commercially available ones of the bisphenol F-type epoxy resins include, for example, Epikote 806 and Epikote 4004 (all manufactured by Mitsubishi Chemical Corporation).

The commercially available one of the bisphenol S-type epoxy resins is, for example, Epiclon EXA1514 (manufactured by DIC Corporation).

The commercially available one of the 2,2'-diallyl bisphenol A type epoxy resins is, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

The commercially available one of the hydrogenated bisphenol type epoxy resins is Epiclon EXA 7015 (manufactured by DIC Corporation).

Among the above-mentioned propylene oxide-added bisphenol A-type epoxy resins, for example, EP-4000S (manufactured by Adeka Co., Ltd.) or the like can be mentioned.

Among the above-mentioned resorcinol type epoxy resins, for example, EX can be cited. -201 (manufactured by Nagase ChemteX Co., Ltd.).

The commercially available one of the above-mentioned biphenyl type epoxy resins is, for example, Epikote YX-4000H (manufactured by Mitsubishi Chemical Corporation).

The commercially available one of the above-mentioned thioether type epoxy resins is, for example, YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.).

The commercially available one of the above-mentioned diphenyl ether type epoxy resins is, for example, YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.).

The commercially available one of the above-mentioned dicyclopentadiene type epoxy resins is, for example, EP-4088S (manufactured by Adeka Co., Ltd.).

The commercially available ones of the above naphthalene type epoxy resins include Epiclon HP 4032 and Epiclon EXA-4700 (all manufactured by DIC Corporation).

The commercially available one of the phenol novolac type epoxy resins is Epiclon N-770 (manufactured by DIC Corporation).

The commercially available one of the above o-cresol novolac type epoxy resins is Epiclon N-670-EXP-S (manufactured by DIC Corporation).

The commercially available one of the above-mentioned dicyclopentadiene novolac type epoxy resins is Epiclon HP7200 (manufactured by DIC Corporation).

The commercially available one of the above-mentioned biphenol novolak type epoxy resins is, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).

The commercially available one of the naphthol novolac type epoxy resins is, for example, ESN-165S (manufactured by Tohto Kasei Co., Ltd.).

The commercially available ones of the above-mentioned epoxy propylamine type epoxy resins include Epikote 630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.

Among the above-mentioned alkyl polyol-type epoxy resins, for example, ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), Epiclon 726 (manufactured by DIC Corporation), Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX- 611 (manufactured by Nagase ChemteX Co., Ltd.) and the like.

The commercially available ones of the rubber-modified epoxy resins include, for example, YR-450, YR-207 (all manufactured by Tohto Kasei Co., Ltd.), Epolead PB (manufactured by Daicel Chemical Industries, Ltd.), and the like.

The commercially available one of the above-mentioned glycidyl ester compounds may, for example, be Denacol EX-147 (manufactured by Nagase ChemteX Co., Ltd.).

Other commercially available ones of the above-mentioned epoxy resins include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (made by Asahi Kasei Corporation), Epikote 1031, and Epikote 1032 (both Mitsubishi). Manufactured by a chemical company, EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

In addition, the resin having an epoxy group may further contain a resin having an epoxy group and a (meth)acryloxy group in one molecule. As such a compound, for example, a partial (meth)acrylic modified epoxy resin obtained by reacting a part of an epoxy group of a compound having two or more epoxy groups with (meth)acrylic acid can be used. Among them, a (meth)acrylic acid modified epoxy resin (partial (meth)acrylic acid modified bisphenol A type epoxy resin) containing a bisphenol A type is preferable.

The commercially available one of the above-mentioned partial (meth)acrylic acid-modified epoxy resins is, for example, UVACURE 1561 (manufactured by Daicel-Cytec Co., Ltd.).

The content of the epoxy group-containing resin in the above curable resin is preferably The lower limit is 5% by weight, and the upper limit is preferably 50% by weight. When the content of the epoxy group-containing resin is 5% by weight or more, the adhesion and moisture resistance of the obtained sealing compound for liquid crystal dropping methods are improved. When the content of the epoxy group-containing resin is 50% by weight or less, the sealant is less likely to be eluted into the liquid crystal, and display unevenness in the obtained liquid crystal display element can be suppressed. A more preferred lower limit of the content of the above epoxy group-containing resin is 10% by weight, a more preferred upper limit is 42% by weight, and a still more preferred lower limit is 20% by weight.

Further, the curable resin may contain the resorcinol type epoxy (meth) acrylate or the other (meth) acryl type resin other than the bisphenol A type epoxy (meth) acrylate.

The other (meth)acrylic resin is not particularly limited as long as it is a resin having an acryloxy group or a methacryloxy group, and examples thereof include the above-mentioned resorcinol type epoxy (methyl group). An acrylate or a (meth) acrylate or a (meth) acrylate other than the above bisphenol A type epoxy (meth) acrylate.

Examples of the other epoxy (meth) acrylate include a benzenediol-type ring between (meth)acrylic acid and the above epoxy group-containing resin by the presence of a basic catalyst according to a usual method. It is obtained by reacting an epoxy resin other than an oxy resin or a bisphenol A type epoxy resin.

The (meth) acrylate may, for example, be an ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group, and reacting an isocyanate with a (meth)acrylic acid derivative having a hydroxyl group. The obtained (meth)acrylic acid amine ester and the like.

The monofunctional one of the above ester compounds may, for example, be 2-hydroxy acrylate. Ethyl ethyl ester, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, isobutyl (meth)acrylate, (methyl) Third butyl acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate , 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy poly Glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2, 2, 3, (meth) acrylate, 3-tetrafluoropropyl ester, (meth)acrylic acid 1H, 1H, 5H-octafluoropentyl ester, quinone imine (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, ( N-butyl acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, (methyl) propyl Cyclohexyl acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, isomyristyl (meth) acrylate, (meth) acrylate 2-butoxyethyl ester, 2-phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, diethylamine (meth)acrylate Ethyl ester, dimethylaminoethyl (meth) acrylate, 2-(methyl) propylene methoxyethyl succinate, 2-(methyl) propylene methoxyethyl hexahydrophthalate, adjacent 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2-(meth) propylene methoxyethyl phosphate, and the like.

Examples of the bifunctional ones of the above ester compounds include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, and 1,6-. Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, 2-n-butyl-2-ethyl 1,3-1,3-propanediol di(meth) acrylate, dipropylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, ethylene glycol bis ( Methyl) 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(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentane Alkenyl di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified iso-cyanuric acid Methyl) acrylate, 2-hydroxy-3-(meth) propylene methoxypropyl (meth) acrylate, carbonate diol di(meth) acrylate, polyether diol di(meth) acrylate Ester, polyester diol di(meth) acrylate, polycaprolactone diol di(meth) acrylate , polybutadiene diol di(meth) acrylate, and the like.

Examples of the trifunctional or higher of the above ester compounds include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and propylene oxide addition trimethylolpropane III ( Methyl) acrylate, ethylene oxide addition trimethylolpropane tri(meth) acrylate, caprolactone modified trimethylolpropane tri(meth) acrylate, ethylene oxide addition Tris(meth)acrylate cyanurate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, di-trimethylolpropane tetra(methyl) Acrylate, pentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, tris(methyl)propenyloxyethyl phosphate Wait.

Examples of the isocyanate which is a raw material of the above (meth)acrylic acid amide ester 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, benzodiazepine Methyl diisocyanate (XDI), hydrogenated XDI, quaternary acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, 1,6,10-ten Monoalkyl triisocyanate and the like.

Further, as the isocyanate which is a raw material of the above (meth)acrylic acid urethane, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, or the like may be used. A chain extended isocyanate compound obtained by reacting a polyhydric alcohol such as a polyether diol, a polyester diol or a polycaprolactone diol with an excess of isocyanate.

Examples of the (meth)acrylic acid derivative having a hydroxyl group which is a raw material of the above (meth)acrylic acid amide include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth)acrylate or 2-hydroxybutyl (meth)acrylate; ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butyl a mono (meth) acrylate of a glycol such as an alcohol, 1,4-butanediol or polyethylene glycol; a mono-(methyl) monohydric alcohol such as trimethylolethane, trimethylolpropane or glycerol Acrylate or di(meth) acrylate; epoxy (meth) acrylate such as bisphenol A epoxy (meth) acrylate.

Specific examples of the (meth)acrylic acid amine ester include a borrowing Obtained by adding 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization inhibitor, 0.01 part by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate. 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 while stirring, the mixture was refluxed at 90 ° C and allowed to react for 2 hours.

The commercially available ones of the above (meth)acrylic acid amides include, for example, M-1100, M-1200, M-1210, 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 manufactured 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.), 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 (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

A preferred upper limit of the ratio of the epoxy group to the total amount of the (meth)acryloxy group and the epoxy group in the entire curable resin is 50 mol%. When the ratio of the epoxy group is 50% by mole or less, the solubility of the sealing agent to the liquid crystal is lowered to suppress liquid crystal contamination, and the display performance of the obtained liquid crystal display element is improved. A more preferable upper limit of the ratio of the above epoxy groups is 20 mol%.

The sealing agent for liquid crystal dropping method of the present invention contains surface-treated inorganic fine particles containing inorganic fine particles having a surface treated with hexamethyldiazane, and/or a surface of 3-glycidoxypropyltrimethyl Alkoxysilane treated inorganic microparticles. The surface-treated inorganic fine particles have an effect of improving adhesion by stress dispersion effect, improving linear expansion ratio, and the like. In the sealing compound for liquid crystal dropping method of the present invention, surface-treated inorganic fine particles and resorcinol-type epoxy (meth) acrylate are used in combination to obtain excellent adhesion and straightness.

The inorganic fine particles are preferably hydrophilic inorganics in consideration of the dispersibility in the hydrophilic curable resin which is a main component of the sealant of the present invention, the paintability of the sealant for a liquid crystal dropping method of the present invention, and the like. Microparticles. Examples of such inorganic fine particles include cerium oxide, diatomaceous earth, aluminum oxide, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, and gypsum. Calcium citrate, talc, glass beads, sericite active clay, bentonite, aluminum nitride, tantalum nitride, and the like. Among them, talc and cerium oxide are preferred, and cerium oxide is more preferable from the viewpoint of adhesion.

The lower limit of the average particle diameter of the surface-treated inorganic fine particles is 0.1 μm. When the average particle diameter of the surface-treated inorganic fine particles is less than 0.1 μm, the obtained sealing compound for liquid crystal dropping method is inferior in adhesion to the substrate or the alignment film. A preferred lower limit of the average particle diameter of the surface-treated inorganic fine particles is 0.3 μm, and a more preferred lower limit is 0.4 μm.

Further, a preferred upper limit of the average particle diameter of the surface-treated inorganic fine particles is 1.0 μm. When the average particle diameter of the surface-treated inorganic fine particles exceeds 1.0 μm, the obtained liquid crystal dropping method sealant may have poor linearity. A more preferable upper limit of the average particle diameter of the surface-treated inorganic fine particles is 0.8 μm, and a further preferred upper limit is 0.7 μm.

In the present specification, the average particle diameter means an average value of particle diameters of 10 particles obtained by observation using a scanning electron microscope at a magnification of 10,000 times. As the scanning electron microscope, S-4300 (manufactured by Hitachi High-Technologies Corporation) or the like can be used.

The coefficient of variation of the particle diameter of the surface-treated inorganic fine particles (hereinafter also referred to as CV value) is preferably 15% or less. When the CV value of the particle diameter of the surface-treated inorganic fine particles exceeds 15%, the size of the surface-treated inorganic fine particles is largely deviated, and thus the obtained liquid crystal dropping method sealant may have poor linear drawability.

In addition, the CV value in this specification is a numerical value obtained by the following formula.

CV value (%) of particle size = (standard deviation of particle diameter / average particle diameter) × 100

The shape of the surface-treated inorganic fine particles is not particularly limited, but is preferably spherical.

Further, in the present specification, the above spherical shape means that the aspect ratio (long diameter/thickness) of the particles is less than 1.05. The above aspect ratio can be obtained by observation using the above scanning electron microscope.

The surface-treated inorganic fine particles contain inorganic fine particles (hereinafter also referred to as hexamethyldiazepine treated inorganic fine particles) treated with hexamethyldiazepine, and/or the surface is subjected to 3-glycidoxypropyl group. Trimethoxysilane-treated inorganic fine particles (hereinafter also referred to as 3-glycidoxypropyltrimethoxydecane treated inorganic fine particles).

By treating the inorganic fine particles with the above hexamethyldioxane, and/or the above-mentioned 3-glycidoxypropyltrimethoxydecane treated inorganic fine particles in combination with the above-mentioned resorcinol type epoxy resin, The sealant for a liquid crystal dropping method of the present invention is excellent in straightness and adhesion.

The hexamethyldioxane-treated inorganic fine particles can be produced, for example, by a method such as a sol-gel method, in which inorganic fine particles (hereinafter also referred to as raw inorganic fine particles) which are raw materials such as cerium oxide are used. Synthesizing and spraying hexamethyldioxane in a state in which the raw material inorganic fine particles are flowed; or adding raw material inorganic fine particles to an organic solvent such as ethanol or toluene, and further adding hexamethyldioxane and water, and then using The evaporator evaporates and dries water and organic solvent.

The 3-micropropoxypropyltrimethoxydecane-treated inorganic fine particles can be produced, for example, by synthesizing inorganic fine particles of a raw material by a method such as a sol-gel method, and flowing the raw inorganic fine particles. a mixture of sprayed water and 3-glycidoxypropyltrimethoxydecane in the state; or added raw inorganic particles in an organic solvent such as ethanol or toluene After further adding 3-glycidoxypropyltrimethoxydecane and water, the water and the organic solvent were evaporated to dryness using an evaporator.

The preferred lower limit of the content of the surface-treated inorganic fine particles in the sealing agent for liquid crystal dropping method of the present invention is 20 parts by weight based on 100 parts by weight of the curable resin, and the upper limit is preferably 160 parts by weight. When the content of the surface-treated cerium oxide is less than 20 parts by weight, the obtained sealing agent for a liquid crystal dropping method may have poor adhesion to a substrate or an alignment film. When the content of the surface-treated cerium oxide exceeds 160 parts by weight, the obtained liquid crystal dropping method sealant may have poor linearity.

In the case where the sealing agent for liquid crystal dropping method of the present invention contains the above-mentioned hexamethyldiazane to treat inorganic fine particles, the content of the above-mentioned hexamethyldiazepine-treated inorganic fine particles is preferably 100 parts by weight relative to the curable resin. The lower limit is 20 parts by weight, and the upper limit is preferably 150 parts by weight. When the content of the inorganic fine particles treated with the hexamethyldioxane is 20 parts by weight or more, the adhesion of the liquid crystal dropping method sealant to the substrate or the alignment film is improved. When the content of the inorganic fine particles treated with the hexamethyldiazepine is 150 parts by weight or less, the linearity of the sealant for liquid crystal dropping method is improved. A more preferred lower limit of the content of the above-mentioned hexamethyldioxane-treated inorganic fine particles is 40 parts by weight, more preferably 130 parts by weight, still more preferably 50 parts by weight, and still more preferably 100 parts by weight.

In the case where the sealing agent for liquid crystal dropping method of the present invention contains the above 3-glycidoxypropyltrimethoxydecane to treat inorganic fine particles, the above 3-glycidoxypropyltrimethoxydecane is treated with inorganic fine particles. A preferred lower limit of the content with respect to 100 parts by weight of the curable resin is 30 parts by weight, preferably The upper limit is 160 parts by weight. When the content of the inorganic fine particles treated by the 3-glycidoxypropyltrimethoxydecane is 30 parts by weight or more, the adhesion of the liquid crystal dropping method sealant to the substrate or the alignment film is improved. By treating the content of the inorganic fine particles with the above-mentioned 3-glycidoxypropyltrimethoxydecane to be 160 parts by weight or less, the linearity of the sealing agent for liquid crystal dropping method obtained is improved. A lower limit of the content of the above-mentioned 3-glycidoxypropyltrimethoxydecane-treated inorganic fine particles is 50 parts by weight, more preferably 140 parts by weight, and still more preferably 60 parts by weight, and further preferably a lower limit. 110 parts by weight.

The sealing agent for liquid crystal dropping method of the present invention preferably contains a thermal curing agent and/or a radical polymerization initiator.

Examples of the above-mentioned thermosetting agent include an organic acid hydrazine, an imidazole derivative, an amine compound, a polyphenol compound, an acid anhydride, and the like. Among them, solid organic acid hydrazine can be preferably used.

Examples of the above organic acid hydrazine include 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin, bismuth sebacate, diammonium isophthalate, and adipic acid. Diterpenes, diammonium malonate, etc. For example, Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), and the like are mentioned.

A preferred lower limit of the content of the above-mentioned thermosetting agent relative to 100 parts by weight of the epoxy group-containing resin is 1 part by weight, and a preferred upper limit is 50 parts by weight. When the content of the above-mentioned heat curing agent is 1 part by weight or more, the thermosetting property of the sealing compound for liquid crystal dropping method obtained is improved. By making the above thermal hardener When the content is 50 parts by weight or less, the viscosity is in a preferable range, and the coating property of the obtained sealing compound for liquid crystal dropping method is improved. A more preferable upper limit of the content of the above thermal curing agent is 30 parts by weight.

Examples of the radical polymerization initiator include a photoradical polymerization initiator and a thermal radical polymerization initiator.

Examples of the photoradical polymerization initiator include a benzophenone compound, an acetophenone compound, a fluorenyl phosphine oxide compound, a titanocene compound, an oxime ester compound, and a benzoin ether compound. Oxygen and sulfur Wait.

In addition, as a commercial product of the photoradical polymerization initiator, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all manufactured by BASF Japan), benzoin methyl ether , benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), and the like. Among them, in terms of a wide absorption wavelength region, IRGACURE 651, IRGACURE 907, benzoin isopropyl ether, and Lucirin TPO are preferred. These photoradical polymerization initiators may be used singly or in combination of two or more.

Examples of the thermal radical polymerization initiator include those composed of an azo compound, an organic peroxide, and the like. Among them, a polymer azo initiator comprising a polymer azo compound is preferred.

In addition, the term "polymer azo initiator" as used herein means a compound having an azo group and generating a radical capable of hardening a (meth) propylene oxime by heat and having a number average molecular weight of 300 or more. . In the present specification, the above number average molecular weight is measured by gel permeation chromatography (GPC). Determined and valued by polystyrene conversion. As a column used for measuring the number average molecular weight in terms of polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) or the like can be mentioned. Further, the above-mentioned polymer azo initiator can be decomposed by irradiation light to generate a radical, and therefore can also function as a photoradical polymerization initiator.

A preferred lower limit of the number average molecular weight of the above polymer azo initiator is 1000, and a preferred upper limit is 300,000. When the number average molecular weight of the above polymer azo initiator is 1000 or more, the adverse effect of the polymer azo initiator on the liquid crystal can be suppressed. When the number average molecular weight of the above polymer azo initiator is 300,000 or less, it becomes easy to mix into a curable resin. A lower limit of the number average molecular weight of the above polymer azo initiator is 5,000, a higher limit is 100,000, and a lower limit is preferably 10,000, and a preferred upper limit is 90,000.

The polymer azo initiator is, for example, a structure in which a plurality of units such as polyalkylene oxide or polydimethyl siloxane are bonded via an azo group.

The polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group is preferably a polyethylene oxide structure. Examples of such a polymer azo initiator include a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and a polyalkylene glycol, or 4,4'-azobis. (4-cyanovaleric acid) and a polycondensate of polydimethyl methoxy alkane having a terminal amine group.

The commercially available ones of the above polymer azo initiators include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001. (all manufactured by Wako Pure Chemical Industries, Ltd.) and so on.

The organic peroxide is not particularly limited, and examples thereof include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, dinonyl peroxide, and peroxydicarbonate.

The content of the radical polymerization initiator is not particularly limited, and a preferred lower limit of 100 parts by weight of the curable resin is 0.1 part by weight, and a preferred upper limit is 30 parts by weight. By setting the content of the above-mentioned radical polymerization initiator to 0.1 part by weight or more, the polymerizability of the sealing compound for liquid crystal dropping method obtained is improved. When the content of the radical polymerization initiator is 30 parts by weight or less, the residual of the unreacted radical polymerization initiator is suppressed, and the weather resistance of the obtained sealing compound for liquid crystal dropping method is improved. A more preferred lower limit of the content of the above radical polymerization initiator is 1 part by weight, more preferably 10 parts by weight, and still more preferably 5 parts by weight.

The sealant for liquid crystal dropping method of the present invention may further contain a decane coupling agent. The above-mentioned decane coupling agent mainly functions as a bonding aid for adhering a sealing agent to a substrate or the like well.

The decane coupling agent is excellent in the effect of improving the adhesion to the substrate or the like, and is chemically bonded to the curable resin to suppress the flow of the curable resin into the liquid crystal. For example, it is preferable to use 3- Aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, and the like. These decane coupling agents may be used singly or in combination of two or more.

The sealing agent for liquid crystal dropping method of the present invention may also contain as needed Reactive diluent for adjusting viscosity, spacer for polymer particles to adjust panel spacing, hardening accelerator such as 3-p-chlorophenyl-1,1-dimethylurea, antifoaming agent, leveling agent Additives such as polymerization inhibitors.

The preferred lower limit of the viscosity of the sealant for liquid crystal dropping method of the present invention measured by an E-type viscometer at 25 ° C and 1.0 rpm is 200,000 mPa·s, and the upper limit is preferably 600,000 mPa·s. By setting the viscosity to 200,000 mPa·s or more, the sealing pattern formed by using the obtained sealing compound for liquid crystal dropping method can be sufficiently maintained until heat curing is performed. By setting the viscosity to 600,000 mPa·s or less, the coating property of the sealing compound for liquid crystal dropping method is improved.

In addition, as the E-type viscometer, for example, 5XHBDV-III+CP (manufactured by Brookfield Co., Ltd., rotor No. CP-51) or the like can be used.

Further, the preferred lower limit of the thixotropic index of the sealant for liquid crystal dropping method of the present invention is 1.0, and the upper limit is preferably 3.0. When the TI value is 1.0 or more, the viscosity of the sealing compound for liquid crystal dropping method at the time of coating is in a preferable range, and the coating property of the sealing compound for liquid crystal dropping method obtained is improved. By setting the above TI value to 3.0 or less, defoaming becomes easy.

In addition, in the present specification, the above-mentioned "shake index (TI value)" is a viscosity measured by dividing an E-type viscometer at 25 ° C and 0.5 rpm by a viscosity measured at 25 ° C and 5.0 rpm. And get the value.

The sealing agent for liquid crystal dropping method of the present invention preferably has a volume resistivity of the cured product of 1 × 10 ¹³ Ω ̇ cm or more and a dielectric constant of 3 or more at 100 kHz. When the volume resistance value is 1 × 10 ¹³ Ω ̇ cm or more, it means that the sealing compound for liquid crystal dropping method contains almost no ionic impurities, and for example, when used as a vertical conductive material, the ionic property can be prevented from being energized. The impurity is eluted into the liquid crystal to cause uneven display. Further, since the dielectric constant of the liquid crystal is usually ε//(parallel) of 10 and ε⊥ (vertical) of about 3.5, the dielectric constant of the sealing compound for liquid crystal dropping method of the present invention is 3 or more, thereby preventing The sealant is dissolved in the liquid crystal to cause uneven display.

The method for producing the sealing agent for a liquid crystal dropping method of the present invention includes, for example, a method using a mixer such as a homomixer, a homomixer, a universal agitator, a planetary mixer, a kneader or a three-roll mill to obtain curability. The resin, the surface-treated inorganic fine particles, and a thermosetting agent and/or a radical polymerization initiator or a decane coupling agent to be added as needed are mixed.

The upper and lower conductive materials can be produced by incorporating conductive fine particles into the sealing compound for liquid crystal dropping method of the present invention. The sealing agent for liquid crystal dropping method of the present invention and the conductive material for the upper and lower conductive particles are also one of the inventions.

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, it is preferable that the conductive metal is formed on the surface of the resin fine particles 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 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 inventions.

As a method of manufacturing the liquid crystal display element of the present invention, for example, A method having the following steps: applying one of a transparent substrate having an electrode such as an ITO film and an alignment film to a liquid crystal dropping method sealant of the present invention by screen printing, dispenser coating, or the like to form a rectangular seal a liquid crystal droplet is applied to the entire surface of the transparent substrate in a state where the sealing agent for the liquid crystal dropping method of the present invention is not cured, and immediately overlaps another transparent substrate; the sealing compound for the liquid crystal dropping method of the present invention is used. The seal pattern portion is irradiated with light such as ultraviolet rays to temporarily cure the sealant, and the temporarily hardened sealant is heated to be completely hardened.

According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method which is excellent in adhesion and straightness. Moreover, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element which are produced by using the sealing compound for a liquid crystal dropping method.

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

(Synthesis of resorcinol type epoxy acrylate (curable resin A))

1000 parts by weight of a resorcinol type epoxy resin ("Denacol EX-201" manufactured by Nagase ChemteX) and 2 parts by weight of p-methoxyphenol as a polymerization inhibitor were used as a polymerization inhibitor at 90 ° C. 2 parts by weight of triethylamine of the reaction catalyst and 649 parts by weight of acrylic acid were stirred under reflux for 5 hours to cause a reaction. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained resin was obtained by using a natural combination of quartz and kaolin ("Sillitin V85" manufactured by Hoffmann-mineral Co., Ltd.) 10 weight. The column was filtered to obtain resorcinol type epoxy acrylate (curable resin A).

(Synthesis of bisphenol A epoxy acrylate (curable resin B))

1000 parts by weight of bisphenol A type epoxy resin ("Epikote 828EL" by Mitsubishi Chemical Corporation) and 2 parts by weight of p-methoxyphenol as a polymerization inhibitor were used as reaction hands at 90 ° C while air was supplied. 2 parts by weight of a solvent of triethylamine and 424 parts by weight of acrylic acid were stirred under reflux for 5 hours to cause a reaction. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained resin was filtered using a column of 10 parts by weight of a natural combination of quartz and kaolin ("Sillitin V85" manufactured by Hoffmann-mineral Co., Ltd.) to obtain a double Phenol A type epoxy acrylate (curable resin B).

(Synthesis of bisphenol F type epoxy acrylate (curable resin C))

1000 parts by weight of bisphenol F-type epoxy resin ("Epikote 806" manufactured by Mitsubishi Chemical Corporation) and 2 parts by weight of p-methoxyphenol as a polymerization inhibitor were used as reaction hands at 90 ° C while introducing air. 2 parts by weight of the triethylamine of the medium and 462 parts by weight of acrylic acid were stirred under reflux for 5 hours to cause a reaction. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained resin was filtered using a column of 10 parts by weight of a natural combination of quartz and kaolin ("Sillitin V85" manufactured by Hoffmann-mineral Co., Ltd.) to obtain a double Phenol F type epoxy acrylate (curable resin C).

(Synthesis of partially acrylic modified bisphenol A epoxy resin (curable resin D))

1000 parts by weight of bisphenol A type epoxy resin ("Epikote 828EL" manufactured by Mitsubishi Chemical Corporation) at 90 ° C while being air-injected 2 parts by weight of the inhibitor p-methoxyphenol, 2 parts by weight of triethylamine as a reaction catalyst, and 212 parts by weight of acrylic acid were stirred under reflux for 5 hours to cause a reaction. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained resin was filtered using a column of 10 parts by weight of a natural combination of quartz and kaolin ("Sillitin V85" manufactured by Hoffmann-mineral Co., Ltd.) to obtain 50 parts. % partially acrylic modified bisphenol A epoxy resin (curable resin D).

(Synthesis of partially acrylic modified resorcinol type epoxy resin (curable resin E))

1000 parts by weight of a resorcinol type epoxy resin ("Denacol EX-201" manufactured by Nagase ChemteX) and 2 parts by weight of p-methoxyphenol as a polymerization inhibitor were used as a polymerization inhibitor at 90 ° C. 2 parts by weight of triethylamine of the reaction catalyst and 325 parts by weight of acrylic acid were stirred under reflux for 5 hours to cause a reaction. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained resin was filtered using a column of 10 parts by weight of a natural combination of quartz and kaolin ("Sillitin V85" manufactured by Hoffmann-mineral Co., Ltd.) to obtain 50 parts. % partially acrylic modified resorcinol type epoxy resin (curable resin E).

(Preparation of hexamethyldiazane treatment of cerium oxide)

100 parts by weight of cerium oxide particles having an average particle diameter of 0.7 μm synthesized by a sol-gel method were placed in a Henschel mixer, and 0.5 parts by weight and six parts of water were sprayed while stirring under a nitrogen atmosphere. 10 parts by weight of methyl diazane, and heated at 260 ° C for 80 minutes, then cooled, crushed by a ball mill to prepare hexamethyldioxane to treat dioxane Huayu (average particle size is 0.7 μm).

Further, cerium oxide particles having an average particle diameter of 0.05 μm, cerium oxide particles having an average particle diameter of 0.1 μm, cerium oxide particles having an average particle diameter of 0.4 μm, and an average were synthesized by the sol-gel method in the same manner. The cerium oxide particles having a particle diameter of 1.0 μm were also subjected to the same operation to prepare cerium oxide treated with hexamethyldiazepine having an average particle diameter of 0.05 μm, 0.1 μm, 0.4 μm, and 1.0 μm, respectively.

Preparation of (3-glycidoxypropyltrimethoxydecane treated cerium oxide)

100 parts by weight of cerium oxide particles having an average particle diameter of 0.7 μm synthesized by a sol-gel method were placed in a stirrer, and 10 parts by weight of water and 3-glycidoxypropyl group were sprayed while stirring under a nitrogen atmosphere. 2 parts by weight of trimethoxydecane, and heated at 150 ° C for 80 minutes, cooled, and crushed by a ball mill to prepare 3-glycidoxypropyltrimethoxydecane to treat cerium oxide (average particle diameter of 0.7) Mm).

Further, cerium oxide particles having an average particle diameter of 0.05 μm, cerium oxide particles having an average particle diameter of 0.1 μm, cerium oxide particles having an average particle diameter of 0.4 μm, and an average were synthesized by the sol-gel method in the same manner. The cerium oxide particles having a particle diameter of 1.0 μm were also subjected to the same operation to prepare cerium oxide treated with 3-glycidoxypropyltrimethoxydecane having an average particle diameter of 0.05 μm, 0.1 μm, 0.4 μm, and 1.0 μm, respectively. .

(Preparation of cerium oxide treated with 3-aminopropyltrimethoxydecane)

2 parts by weight of 3-aminopropylpropyltrimethoxydecane was used instead of 2 parts by weight of 3-glycidoxypropyltrimethoxydecane, and Preparation of glycidoxypropyltrimethoxydecane treated cerium oxide. In the same manner, 3-aminopropyltrimethoxydecane was treated to treat cerium oxide (average particle diameter of 0.7 μm).

(Preparation of cerium oxide treated by methacryloxypropyltrimethoxydecane)

2 parts by weight of methacryloxypropyltrimethoxydecane was used instead of 2 parts by weight of 3-glycidoxypropyltrimethoxydecane, and in addition to "3-glycidoxypropyl" Preparation of trimethoxydecane treated cerium oxide. In the same manner, methacryloxypropyltrimethoxydecane was treated to treat cerium oxide (average particle diameter of 0.7 μm).

(Preparation of hexamethyldiazane to treat talc)

100 parts by weight of talc particles ("SG-2000" manufactured by Nippon Talc Co., Ltd.) was placed in a blender, and 0.5 parts by weight of water and 10 parts by weight of hexamethyldioxane were sprayed while stirring under a nitrogen atmosphere. After heating at ° C for 80 minutes, it was cooled, and crushed by a ball mill to prepare hexamethyldiazepine-treated talc (having an average particle diameter of 1.0 μm).

Preparation of (3-glycidoxypropyltrimethoxydecane treated talc)

100 parts by weight of talc particles ("SG-2000" manufactured by Nippon Talc Co., Ltd.) was placed in a blender, and 10 parts by weight of water and 3-glycidoxypropyltrimethoxydecane 2 were sprayed while stirring under a nitrogen atmosphere. The parts by weight were heated at 150 ° C for 80 minutes, cooled, and crushed by a ball mill to prepare 3-glycidoxypropyltrimethoxydecane-treated talc (having an average particle diameter of 1.0 μm).

(Example 1)

70 parts by weight of a succinol type epoxy acrylate (curable resin A) as a curable resin, 20 parts by weight of bisphenol A type epoxy acrylate (curable resin B), and 50% partial acrylic acid modification 10 parts by weight of a bisphenol A type epoxy resin (curable resin D) is blended into a specific container, and after mixing and stirring by a planetary stirring device, the 2,2-dimethyl group which is a photoradical polymerization initiator is blended. 1 part by weight of oxy-2-phenylacetophenone ("Irgacure 651" manufactured by BASF Japan Co., Ltd.) and mixed by heating, and then mixed and stirred as a decane coupling agent of γ-glycidoxypropyltrimethoxydecane ( 1 part by weight of "KBM-403" manufactured by Shin-Etsu Silicone Co., Ltd., and treated with hexamethyldioxane as a filler by a planetary mixer ("Defoaming Taro" manufactured by Thinky Corporation) 15 parts by weight of cerium (average particle diameter: 0.7 μm) and 0.8 parts by weight of diammonium malonate (manufactured by Japan Finechem Co., Ltd.) as a thermosetting agent, and then uniformly mixed by a ceramic three-roll mill to obtain a sealant .

(Examples 2 to 25, Comparative Examples 1 to 8)

The curable resin and the filler were used as the materials and blending ratios described in Tables 1 to 4, and each was used in the same manner as in Example 1 using a planetary mixer ("Defoaming Stirring" by Thinky Co., Ltd.). After the materials were mixed and stirred, they were uniformly mixed by a ceramic three-roll mill, whereby the sealing agents for liquid crystal dropping methods of Examples 2 to 25 and Comparative Examples 1 to 8 were prepared.

<Evaluation>

The following evaluations were performed on the sealing compound for liquid crystal dropping methods obtained in the examples and the comparative examples. The results are shown in Tables 1 to 4.

(adhesive)

In the sealing compound for liquid crystal dropping method obtained in each of the examples and the comparative examples, 1% by weight of a ceria spacer ("SI-H055" manufactured by Sekisui Chemical Co., Ltd.) was blended, and a TN alignment film was attached to 2 sheets. One of the alkali glass test pieces (30×40 mm) was dropped in a small amount, and another glass test piece was attached thereto in a cross shape, and the resultant was irradiated with 3000 mJ/cm ² by a metal halide lamp. Ultraviolet rays were then heated at 120 ° C for 60 minutes, whereby a test piece was obtained. The obtained test piece was subjected to a tensile test (5 mm/min) using a collet disposed on the upper and lower sides. The obtained measurement value (kgf) is divided by the seal coating cross-sectional area (cm ² ), and the obtained value is 30 kgf/cm ² or more, and is set to "◎", 15 kgf/cm ² or more and less than 30 kgf/cm ^{2 .} In the case of "○", the case of 10 kgf/cm ² or more and less than 15 kgf/cm ² was set to "Δ", and the case where it was less than 10 kgf/cm ² was set to "x".

(drawability)

In the sealing compound for liquid crystal dropping method obtained in each of the examples and the comparative examples, 1% by weight of a ceria spacer ("SI-H055" manufactured by Sekisui Chemical Co., Ltd.) was blended, and defoaming treatment was performed to remove the sealant. Bubble in the middle. Then, it was filled in a dispensing syringe ("PSY-10E" manufactured by Musashi Engineering Co., Ltd.) manufactured by a precision nozzle ("NH-0.3" manufactured by Musashi Engineering Co., Ltd.) having an inner diameter of 300 μm, and defoaming treatment was performed again. Then, a sealant (coating speed: 100 mm/sec) was applied to a transparent electrode substrate with an ITO film by using a dispenser ("SHOTMASTER 300" manufactured by Musashi Engineering Co., Ltd.), and vacuum-applied. The bonding apparatus was bonded to another transparent substrate under a reduced pressure of 5.0 Pa at 23 °C. The bonded cells were irradiated with ultraviolet rays of 3,000 mJ/cm ² by a metal halide lamp, and then heated at 120 ° C for 60 minutes to thermally cure the sealant, and five liquid crystal cells were produced for each of the sealants. When the sealant in the liquid crystal cell was observed, the case where the sealant was not broken and the end portion was bent and a straight line was drawn was set to "◎", and no breakage was observed, but the end portion of the sealant was slightly In the case where the bending occurred, it was set to "○", and the case where the wire was not broken was set to "△" when the end portion of the sealant was significantly bent, and the case where the wire breakage occurred was "x".

(liquid crystal contamination (specific resistance retention rate))

1.0 g of liquid crystal ("JC-5001LA" manufactured by Chisso Co., Ltd.) was placed in the vial, and 0.02 g of the sealing compound for liquid crystal dropping method obtained in each of the examples and the comparative examples was added and shaken, followed by heating at 120 ° C. 1 hour. After returning to room temperature (25 ° C), a liquid crystal specific resistance measuring device ("6517A" manufactured by KEITHLEY Instruments Co., Ltd.) was used, and an electrode for liquid ("LE-21 type" manufactured by Ando Electric Co., Ltd.) was used for the electrode at a standard temperature and humidity. The liquid crystal specific resistance of the liquid crystal portion was measured in a state (20 ° C, 65% RH). The liquid crystal specific resistance retention ratio was determined by the following formula, and the liquid crystal specific resistance retention ratio was set to "○" when the specific resistance ratio of the liquid crystal was higher than 0.1, and the liquid crystal contamination property was evaluated by setting "Δ" when the liquid crystal specific resistance retention ratio was 0.1 or less.

Liquid crystal specific resistance retention ratio = (using liquid crystal specific resistance after adding a sealant / using liquid crystal specific resistance when no sealant is added) × 100

(Evaluation of color unevenness of liquid crystal display elements)

The sealing agent obtained in each of the examples and the comparative examples was filled in a dispensing syringe ("PSY-10E" manufactured by Musashi Engineering Co., Ltd.) and subjected to defoaming treatment. Then, a sealant was applied to the transparent electrode substrate with an ITO film by using a dispenser ("SHOTMASTER 300" manufactured by Musashi Engineering Co., Ltd.) to draw a rectangular frame. Then, droplets of TN liquid crystal ("JC-5001LA" manufactured by Chisso Co., Ltd.) were dropped by a liquid crystal dropping device, and another transparent substrate was bonded by a vacuum bonding apparatus under a reduced pressure of 5 Pa. The bonded cells were irradiated with ultraviolet rays of 3,000 mJ/cm ² by a metal halide lamp, and then heated at 120 ° C for 60 minutes to thermally cure the sealant, and five liquid crystal display elements were produced for each of the sealants. The obtained liquid crystal display element was subjected to AC (alternating current) voltage driving of 3.5 V, and the periphery of the sealant of the intermediate color was visually observed. The case where the color unevenness was not observed in the vicinity of the sealant portion was set to "○", and the case where the slight color unevenness was observed was set to "△", and the case where the color density of the clear and thick color was uneven was set to "×". And evaluate.

[Industrial availability]

According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method which is excellent in adhesion and straightness. Moreover, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element which are produced by using the sealing compound for a liquid crystal dropping method.

Claims (10)

A sealing agent for a liquid crystal dropping method comprising a curable resin containing resorcinol-type epoxy (meth) acrylate and a resin having an epoxy group, and surface-treated inorganic fine particles, wherein the surface-treated inorganic fine particles Inorganic microparticles having a surface treated with hexamethyldiazane and/or inorganic microparticles having a surface treated with 3-glycidoxypropyltrimethoxysilane; average of the surface treated inorganic microparticles The particle diameter is 0.1 μm or more. The sealant for liquid crystal dropping method according to claim 1, wherein the inorganic fine particles are cerium oxide. The sealant for a liquid crystal dropping method according to the first aspect of the invention, wherein the content of the surface-treated inorganic fine particles is 20 to 160 parts by weight based on 100 parts by weight of the curable resin. The sealant for a liquid crystal dropping method according to the first aspect of the invention, wherein the content of the benzenediol-type epoxy (meth) acrylate in the curable resin is 20% by weight or more. The sealant for a liquid crystal dropping method according to the first aspect of the invention, wherein the curable resin contains bisphenol A type epoxy (meth) acrylate. The sealant for a liquid crystal dropping method according to claim 5, wherein the content of the bisphenol A type epoxy (meth) acrylate in the curable resin is 10% by weight or more. The sealant for a liquid crystal dropping method according to the first aspect of the invention, wherein the surface-treated inorganic fine particles have an average particle diameter of 1.0 μm or less. A top-and-bottom conductive material containing patent claims 1, 2, 3, The sealing agent for the liquid crystal dropping method of 4, 5, 6 or 7 and the conductive fine particles. A liquid crystal display element produced by using a sealing agent for a liquid crystal dropping method of the first, second, third, fourth, fifth, sixth or seventh aspect of the patent application. A liquid crystal display element manufactured by using a conductive material on the upper side of the eighth application of the patent application.