WO2013058324A1 - Sealant for liquid crystal dropping process, vertical-conduction material, and liquid crystal display element - Google Patents

Abstract

Provided is a sealant for a liquid crystal dropping process, having excellent adhesion and line drawing properties. Also provided are a vertical-conduction material and liquid crystal display element manufactured using the sealant for a liquid crystal dropping process. A sealant for a liquid crystal dropping process, comprising: a curable resin containing resorcinol-type epoxy (meth)acrylate and a resin having an epoxy group; and surface-treated inorganic particles containing inorganic particles surface-treated with hexamethyldisilazane, and/or inorganic particles surface-treated with 3‑glycidoxypropyltrimethoxysilane; the surface-treated inorganic particles having an average particle diameter of at least 0.1 µm.

Description

Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element

The present invention relates to a sealant for a liquid crystal dropping method which is excellent in adhesiveness and straight line drawing properties. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.

In recent years, a method for manufacturing a liquid crystal display element such as a liquid crystal display cell has been disclosed in, for example, Patent Document 1 and Patent Document 2 from the conventional vacuum injection method from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. Such a photocurable resin, a photopolymerization initiator, a thermosetting resin, and a liquid crystal dropping method called a dropping method using a light and heat combined curing type sealant containing a thermosetting agent are being replaced.

In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame with the sealant being uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays to perform temporary curing. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.

In a liquid crystal display element, the sealant is required to have excellent straight line drawing properties, and at the time of manufacturing, it is required to increase the dispensing speed in order to improve the process efficiency. However, when the conventional sealant is drawn at high speed, the sealant cannot be drawn in a straight line stably, resulting in a problem of disconnection failure or waviness in the sealant line after drawing. there were. Normally, a filler is blended in the sealant, and in order to improve the straight line drawing property, it is conceivable to reduce the amount of the filler to be blended in the sealant, but if the amount of the filler is reduced, the sealant There is a problem that the agent is inferior in adhesion to the substrate and the alignment film.

JP 2001-133794 A International Publication No. 02/092718 Pamphlet

An object of this invention is to provide the sealing compound for liquid crystal dropping methods which is excellent in adhesiveness and linear drawing property. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.

The present invention relates to a curable resin containing a resorcinol-type epoxy (meth) acrylate and a resin having an epoxy group, inorganic fine particles whose surface is treated with hexamethyldisilazane, and / or a surface having 3-glycol. It contains surface-treated inorganic fine particles containing inorganic fine particles treated with cidoxypropyltrimethoxysilane, and the surface-treated inorganic fine particles are a sealing agent for liquid crystal dropping method having an average particle diameter of 0.1 μm or more.
The present invention is described in detail below.

This inventor obtains the sealing agent for liquid crystal dropping methods which is excellent in adhesiveness and linear drawing property by using combining the curable resin containing a resorcinol type epoxy (meth) acrylate, and specific surface treatment inorganic fine particles. As a result, the present invention has been completed.
The reason why the straight line drawing property of the sealant is improved by using a combination of resorcinol type epoxy (meth) acrylate and surface-treated inorganic fine particles is considered as follows. That is, resorcinol-type epoxy (meth) acrylate has a higher polarity than a resin usually used in a sealing agent for a liquid crystal dropping method, and therefore, when used in combination with a surface treatment inorganic fine particle having a low polarity, repulsion between the particle and the resin is caused. It is presumed that this was due to an increase in the apparent viscosity.

The sealing agent for 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 “(meth) acrylate” means acrylate or methacrylate. In the present specification, the “epoxy (meth) acrylate” represents a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid.

Examples of the resorcinol-type epoxy (meth) acrylate include those obtained by reacting (meth) acrylic acid and resorcinol-type epoxy resin in the presence of a basic catalyst according to a conventional method. In the present specification, the “(meth) acryl” means acryl or methacryl.

Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).

The minimum with preferable content of the resorcinol type | mold epoxy (meth) acrylate in the said curable resin is 20 weight%. If the content of the resorcinol-type epoxy (meth) acrylate is less than 20% by weight, the obtained liquid crystal dropping method sealant is inferior in straight line drawing property, and breaks during drawing or waviness after drawing. There are things to do. The more preferable lower limit of the content of the resorcinol type epoxy (meth) acrylate is 50% by weight, and the more preferable lower limit is 70% by weight.
Moreover, the upper limit with preferable content of a resorcinol type | mold epoxy (meth) acrylate in the said curable resin is 90 weight%. When the content of the resorcinol-type epoxy (meth) acrylate is 90% by weight or less, the obtained sealing agent for liquid crystal dropping method has improved adhesion and moisture resistance. The upper limit with more preferable content of the said resorcinol type | mold epoxy (meth) acrylate is 85 weight%.

The curable resin preferably contains bisphenol A type epoxy (meth) acrylate. By containing resorcinol-type epoxy (meth) acrylate and bisphenol A-type epoxy (meth) acrylate, the resulting sealant for liquid crystal dropping method has better straight line drawing properties at the time of dispensing, and liquid crystal contamination And the adhesion is also good.

As what is marketed among the said bisphenol A type epoxy (meth) acrylate, EBECRYL 3700 (made by Daicel-Cytec) etc. are mentioned, for example.

The minimum with preferable content of the bisphenol A type epoxy (meth) acrylate in the said curable resin is 10 weight%. When the content of the bisphenol A-type epoxy (meth) acrylate is less than 10% by weight, the obtained liquid crystal dropping method sealing agent has high thixotropic properties, and has a cleaning property such as a syringe or a nozzle used for coating. May get worse. The minimum with more preferable content of the said bisphenol A type epoxy (meth) acrylate is 20 weight%.
Moreover, the upper limit with preferable content of the bisphenol A type epoxy (meth) acrylate in the said curable resin is 60 weight%. When the content of the bisphenol A type epoxy (meth) acrylate is 60% by weight or less, the viscosity becomes a suitable range, and the coating property of the obtained liquid crystal dropping method sealing agent is improved. The upper limit with more preferable content of the said bisphenol A type epoxy (meth) acrylate is 50 weight%.

The curable resin contains a resin having an epoxy group.
Examples of the resin having an epoxy group include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2,2′-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, and propylene oxide. Addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy Resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphthalenephenol novolac epoxy resin, glycy Examples thereof include a zilamine type epoxy resin, an alkyl polyol type epoxy resin, a rubber-modified epoxy resin, and a glycidyl ester compound.

Examples of commercially available bisphenol A type epoxy resins include Epicoat 828EL, Epicoat 1004 (all manufactured by Mitsubishi Chemical Corporation), Epicron 850-S (manufactured by DIC Corporation), and the like.
As what is marketed among the said bisphenol F type epoxy resins, Epicoat 806, Epicoat 4004 (all are Mitsubishi Chemical Corporation make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include Epicoat YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Tohto Kasei Co., Ltd.).
Examples of commercially available glycidylamine epoxy resins include Epicoat 630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), Epicron 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611 ( Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Tohto Kasei Co., Ltd.), Epolide PB (manufactured by Daicel Chemical Industries, Ltd.), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031 and Epicoat 1032 ( These include Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation), and the like.

Moreover, you may contain resin which has an epoxy group and a (meth) acryloyloxy group in 1 molecule as resin which has the said epoxy group. Examples of such a compound include a partial (meth) acryl-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. Especially, it is preferable to contain the bisphenol A type partial (meth) acryl modified epoxy resin (partial (meth) acryl modified bisphenol A type epoxy resin).

Examples of the commercially available partial (meth) acryl-modified epoxy resin include UVACURE 1561 (manufactured by Daicel Cytec).

The minimum with preferable content of resin which has an epoxy group in the said curable resin is 5 weight%, and a preferable upper limit is 50 weight%. When the content of the resin having an epoxy group is 5% by weight or more, the adhesiveness and moisture resistance of the obtained liquid crystal dropping method sealing agent are improved. When the content of the resin having an epoxy group is 50% by weight or less, the sealing agent is hardly eluted into the liquid crystal, and it is possible to suppress the occurrence of display unevenness and the like in the obtained liquid crystal display element. A more preferable lower limit of the content of the resin having an epoxy group is 10% by weight, a more preferable upper limit is 42% by weight, and a still more preferable lower limit is 20% by weight.

Moreover, the said curable resin may contain other (meth) acrylic resins other than the said resorcinol type | mold epoxy (meth) acrylate and the said bisphenol A type | mold epoxy (meth) acrylate.
As the other (meth) acrylic resin, any resin having an acryloyloxy group or a methacryloyloxy group can be used without particular limitation. For example, the resorcinol-type epoxy (meth) acrylate and the bisphenol A-type epoxy can be used. Examples include other epoxy (meth) acrylates other than (meth) acrylate, (meth) acrylic acid esters, and the like.

As said other epoxy (meth) acrylate, for example, (meth) acrylic acid and epoxy resins other than the resorcinol type epoxy resin and the bisphenol A type epoxy resin among the resins having the above-mentioned epoxy group, according to a conventional method What is obtained by making it react in presence of a basic catalyst is mentioned.

Examples of the (meth) acrylic acid ester include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and a (meth) acrylic acid derivative having a hydroxyl group with isocyanate. Examples include urethane (meth) acrylate.

Examples of the monofunctional compounds of the ester compounds include 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, Methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2, 2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl ( (Meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) Chryrate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) ) Acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxy Examples thereof include propyl phthalate, glycidyl (meth) acrylate, and 2- (meth) acryloyloxyethyl phosphate.

Examples of the bifunctional ester compound 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-decandiol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (me ) Acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene rudi (meth) acrylate, 1,3-butylene Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) Acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate Polybutadiene di (meth) acrylate.

Examples of the ester compound having three or more functional groups include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri. (Meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide De additional glycerin tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, and the like.

Examples of the isocyanate used as a raw material for the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4 ′. Diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (Isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate Etc. The.

In addition, as an isocyanate that is a raw material of the urethane (meth) acrylate, polyols such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like Chain-extended isocyanate compounds obtained by reaction with excess isocyanate can also be used.

Examples of the (meth) acrylic acid derivative having a hydroxyl group, which is a raw material of the urethane (meth) acrylate, include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). Hydroxyalkyl (meth) acrylates such as acrylate and 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc. Mono (meth) acrylates of dihydric alcohols, mono (meth) acrylates or di (meth) acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type epoxy ) Epoxy (meth) acrylates such as acrylate.

Specific examples of the urethane (meth) acrylate include, for example, 134 parts by weight of trimethylolpropane, 0.2 part 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. In addition, a reaction is performed for 2 hours with reflux stirring at 60 ° C., and then 51 parts by weight of 2-hydroxyethyl acrylate is added, and the reaction is performed for 2 hours with stirring at 90 ° C. while feeding air. Can be mentioned.

Commercially available urethane (meth) acrylates 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 482 Resin UN-9000H, Art Resin UN-9000A, Art Res UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Kogyo Co., Ltd.), U-122P, U-108A U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA -7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (All made by Shin-Nakamura Chemical Co., Ltd.), AH-600, AT-600, UA-306H, AI-600, A-101T, UA-101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.).

The upper limit with the preferable ratio of the epoxy group with respect to the total amount of the (meth) acryloyloxy group and an epoxy group in the said whole curable resin is 50 mol%. When the ratio of the epoxy group is 50 mol% or less, the solubility of the sealing agent in the liquid crystal is lowered, liquid crystal contamination is suppressed, and the display performance of the obtained liquid crystal display element is improved. A more preferable upper limit of the ratio of the epoxy group is 20 mol%.

The sealing agent for liquid crystal dropping method of the present invention comprises a surface treatment containing inorganic fine particles whose surface is treated with hexamethyldisilazane and / or inorganic fine particles whose surface is treated with 3-glycidoxypropyltrimethoxysilane. Contains inorganic fine particles. The surface-treated inorganic fine particles have roles such as improvement of adhesion due to stress dispersion effect, improvement of linear expansion coefficient, and the like. The sealing agent for liquid crystal dropping method of the present invention is excellent in adhesiveness and linear drawing by using surface-treated inorganic fine particles in combination with resorcinol type epoxy (meth) acrylate.
As the inorganic fine particles, considering the dispersibility in the above-described hydrophilic curable resin, which is the main component of the sealing agent of the present invention, the drawing property of the sealing agent for the liquid crystal dropping method of the present invention, etc. Inorganic fine particles are preferable. Examples of such inorganic fine particles include silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, gypsum, calcium silicate, Examples include talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride. Of these, talc and silica are preferable, and silica is more preferable from the viewpoint of adhesiveness.

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 liquid crystal dropping method sealing agent is inferior in adhesion to the substrate and the alignment film. A preferable lower limit of the average particle diameter of the surface-treated inorganic fine particles is 0.3 μm, and a more preferable lower limit is 0.4 μm.
Moreover, the preferable 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 sealing agent for liquid crystal dropping method may be inferior in linear drawing performance. A more preferable upper limit of the average particle diameter of the surface-treated inorganic fine particles is 0.8 μm, and a more preferable upper limit is 0.7 μm.
In the present specification, the average particle diameter means an average value of particle diameters of 10 particles observed at a magnification of 10,000 using a scanning electron microscope. As the scanning electron microscope, S-4300 (manufactured by Hitachi High-Technologies Corporation) or the like can be used.

The variation coefficient (hereinafter also referred to as CV value) of the particle diameter of the surface-treated inorganic fine particles is preferably 15% or less. When the CV value of the particle diameter of the surface-treated inorganic fine particles exceeds 15%, the obtained liquid crystal dropping method sealant may be inferior in linear drawing due to large variation in the size of the surface-treated inorganic fine particles. .
In addition, in this specification, a CV value is a numerical value calculated | required by a following formula.
CV value of particle diameter (%) = (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.
In the present specification, the spherical shape means that the aspect ratio (major diameter / thickness) of the particles is less than 1.05. The aspect ratio can be obtained by observing with the above-described scanning electron microscope.

The surface-treated inorganic fine particles are treated with hexamethyldisilazane-treated inorganic fine particles (hereinafter also referred to as hexamethyldisilazane-treated inorganic fine particles) and / or with a surface treated with 3-glycidoxypropyltrimethoxysilane. Inorganic fine particles (hereinafter also referred to as 3-glycidoxypropyltrimethoxysilane-treated inorganic fine particles).
By using the hexamethyldisilazane-treated inorganic fine particles and / or the 3-glycidoxypropyltrimethoxysilane-treated inorganic fine particles in combination with the aforementioned resorcinol-type epoxy resin, the seal for the liquid crystal dropping method of the present invention is used. The agent is excellent in straight line drawing properties and adhesiveness.

The hexamethyldisilazane-treated inorganic fine particles may be prepared by synthesizing inorganic fine particles (hereinafter also referred to as raw material inorganic fine particles) such as silica by a method such as a sol-gel method, A method of spraying disilazane, a method of adding raw material inorganic fine particles in an organic solvent such as alcohol or toluene, and further adding hexamethyldisilazane and water, followed by evaporating and drying the water and organic solvent with an evaporator, etc. Can be produced.

The 3-glycidoxypropyltrimethoxysilane-treated inorganic fine particles are prepared by synthesizing raw inorganic fine particles by a method such as a sol-gel method, and water and 3-glycidoxypropyltrimethoxysilane in a state where the raw inorganic fine particles are fluidized. Spraying the mixture liquid, or adding raw inorganic fine particles to an organic solvent such as alcohol or toluene, adding 3-glycidoxypropyltrimethoxysilane and water, and then evaporating the water and organic solvent. It can be produced by evaporating and drying with, for example.

In the sealing agent for liquid crystal dropping method of the present invention, the content of the surface-treated inorganic fine particles is preferably 20 parts by weight and preferably 160 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the surface-treated silica is less than 20 parts by weight, the obtained sealing agent for liquid crystal dropping method may be inferior in adhesion to the substrate or the alignment film. When content of the said surface treatment silica exceeds 160 weight part, the sealing compound for liquid crystal dropping methods obtained may become inferior to linear drawing property.

When the sealing agent for liquid crystal dropping method of the present invention contains the hexamethyldisilazane-treated inorganic fine particles, the preferred lower limit of the content of the hexamethyldisilazane-treated inorganic fine particles is 20 with respect to 100 parts by weight of the curable resin. Part by weight, the preferred upper limit is 150 parts by weight. When the content of the hexamethyldisilazane-treated inorganic fine particles is 20 parts by weight or more, the adhesion of the obtained sealing agent for liquid crystal dropping method to the substrate or alignment film is improved. When the content of the hexamethyldisilazane-treated inorganic fine particles is 150 parts by weight or less, the linear drawing property of the obtained sealing agent for liquid crystal dropping method is improved. The more preferable lower limit of the content of the hexamethyldisilazane-treated inorganic fine particles is 40 parts by weight, the more preferable upper limit is 130 parts by weight, the still more preferable lower limit is 50 parts by weight, and the still more preferable upper limit is 100 parts by weight.

When the sealing agent for liquid crystal dropping method of the present invention contains the above-mentioned 3-glycidoxypropyltrimethoxysilane-treated inorganic fine particles, the content of the above-mentioned 3-glycidoxypropyltrimethoxysilane-treated inorganic fine particles is A preferable lower limit is 30 parts by weight and a preferable upper limit is 160 parts by weight with respect to parts by weight. When the content of the 3-glycidoxypropyltrimethoxysilane-treated inorganic fine particles is 30 parts by weight or more, the adhesiveness of the obtained liquid crystal dropping method sealing agent to the substrate and the alignment film is improved. When the content of the 3-glycidoxypropyltrimethoxysilane-treated inorganic fine particles is 160 parts by weight or less, the linear drawing property of the obtained liquid crystal dropping method sealing agent is improved. The more preferable lower limit of the content of the 3-glycidoxypropyltrimethoxysilane-treated inorganic fine particles is 50 parts by weight, the more preferable upper limit is 140 parts by weight, the still more preferable lower limit is 60 parts by weight, and the still more preferable upper limit is 110 parts by weight. .

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

Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among these, solid organic acid hydrazide is preferably used.

Examples of the organic acid hydrazide include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like. Examples of commercially available organic acid hydrazides include Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.) and the like. .

With respect to the content of the thermosetting agent, a preferable lower limit is 1 part by weight and a preferable upper limit is 50 parts by weight with respect to 100 parts by weight of the resin having an epoxy group. When the content of the thermosetting agent is 1 part by weight or more, the thermosetting property of the obtained liquid crystal dropping method sealing agent is improved. When the content of the thermosetting agent is 50 parts by weight or less, the viscosity becomes a suitable range, and the applicability of the obtained liquid crystal dropping method sealing agent is improved. The upper limit with more preferable content of the said thermosetting agent is 30 weight part.

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

Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthones, and the like.
Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACUREOXE01, Lucin TPO (all from BASF M Examples include ether, benzoin ethyl ether, and benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.). Among these, IRGACURE651, IRGACURE907, benzoin isopropyl ether, and lucillin TPO are preferable because of the wide absorption wavelength range. These radical photopolymerization initiators may be used alone or in combination of two or more.

As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among these, a polymer azo initiator composed of a polymer azo compound is preferable.
In the present specification, the polymer azo initiator means a compound having an azo group and generating a radical capable of curing a (meth) acryloyloxy group by heat and having a number average molecular weight of 300 or more. . In this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column used when measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
Moreover, since the said polymeric azo initiator normally decomposes | disassembles also by light irradiation and generate | occur | produces a radical, it can function also as a radical photopolymerization initiator.

The preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo initiator is 1000 or more, adverse effects on the liquid crystal due to the polymer azo initiator can be suppressed. When the polymer azo initiator has a number average molecular weight of 300,000 or less, it can be easily mixed into the curable resin. The more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.

Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable. Examples of such polymer azo initiators include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid). Examples include polycondensates of polydimethylsiloxane having a terminal amino group.
Examples of commercially available polymer azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.). It is done.

The organic peroxide is not particularly limited, and examples thereof include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, and peroxydicarbonate.

Although content of the said radical polymerization initiator is not specifically limited, A preferable minimum is 0.1 weight part and a preferable upper limit is 30 weight part with respect to 100 weight part of said curable resins. When the content of the radical polymerization initiator is 0.1 parts by weight or more, the polymerizability of the obtained sealing agent for liquid crystal dropping method is improved. When the content of the radical polymerization initiator is 30 parts by weight or less, residual unreacted radical polymerization initiator is suppressed, and the weather resistance of the obtained liquid crystal dropping method sealing agent is improved. The minimum with more preferable content of the said radical polymerization initiator is 1 weight part, A more preferable upper limit is 10 weight part, Furthermore, a preferable upper limit is 5 weight part.

The sealing agent for liquid crystal dropping method of the present invention may contain a silane coupling agent. The silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.

As said silane coupling agent, since it is excellent in the effect which improves adhesiveness with a board | substrate etc. and it can suppress the outflow of curable resin in a liquid crystal by chemically bonding with curable resin, it is 3 for example. -Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These silane coupling agents may be used alone or in combination of two or more.

The sealing agent for liquid crystal dropping method of the present invention further comprises a reactive diluent for adjusting the viscosity, a spacer such as polymer beads for adjusting the panel gap, 3-P-chlorophenyl-1,1- You may contain additives, such as hardening accelerators, such as a dimethyl urea, an antifoamer, a leveling agent, and a polymerization inhibitor.

The sealing agent for liquid crystal dropping method of the present invention has a preferable lower limit of viscosity of 200,000 mPa · s and a preferable upper limit of 600,000 mPa · s measured at 25 ° C. and 1.0 rpm using an E-type viscometer. . When the viscosity is 200,000 mPa · s or more, the seal pattern formed using the obtained sealing agent for liquid crystal dropping method can be sufficiently maintained until it is heated and cured. By the said viscosity being 600,000 mPa * s or less, the applicability | paintability of the sealing compound for liquid crystal dropping methods improves.
As the E-type viscometer, for example, 5XHBDV-III + CP (manufactured by Brookfield, rotor No. CP-51) can be used.

Moreover, the preferable lower limit of the thixotropic index (TI value) is 1.0 and the preferable upper limit of the sealing agent for liquid crystal dropping method of the present invention is 3.0. When the TI value is 1.0 or more, the viscosity of the sealing agent for liquid crystal dropping method is in a suitable range at the time of application, and the applicability of the obtained sealing agent for liquid crystal dropping method is improved. Defoaming is facilitated when the TI value is 3.0 or less.
In the present specification, the “thixotropic index (TI value)” refers to the viscosity measured at 25 ° C. and 0.5 rpm using an E-type viscometer under the conditions of 25 ° C. and 5.0 rpm. It is the value divided by the measured viscosity.

In the sealing agent for liquid crystal dropping method of the present invention, the volume resistance value of the cured product is preferably 1 × 10 ¹³ Ω · cm or more, and the dielectric constant at 100 kHz is preferably 3 or more. When the volume resistance value is 1 × 10 ¹³ Ω · cm or more, it means that the liquid crystal dropping method sealing agent contains almost no ionic impurities. Occurrence of display unevenness due to the elution of the ionic impurities into the liquid crystal can be prevented. The dielectric constant of the liquid crystal is usually about ε // (parallel) is about 10 and ε⊥ (vertical) is about 3.5. Therefore, the dielectric constant of the sealing agent for liquid crystal dropping method of the present invention is 3 or more. As a result, it is possible to prevent display unevenness due to the sealing agent eluting into the liquid crystal.

Examples of the method for producing the sealant for the liquid crystal dropping method of the present invention include a curable resin and a surface treatment using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, and a three roll. Examples thereof include a method of mixing inorganic fine particles with an additive such as a thermosetting agent and / or a radical polymerization initiator and a silane coupling agent added as necessary.

A vertical conduction material can be manufactured by mix | blending electroconductive fine particles with the sealing compound for liquid crystal dropping methods of this invention. The vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.

The conductive fine particles are not particularly limited, and metal balls, those obtained by forming a conductive metal layer on the surface of resin fine particles, and the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.

The liquid crystal display element using the sealing compound for liquid crystal dropping method of the present invention and / or the vertical conduction material of the present invention is also one aspect of the present invention.
As a method for producing the liquid crystal display element of the present invention, for example, the liquid crystal dropping method sealing agent of the present invention is applied to one of the transparent substrates having an electrode such as an ITO thin film and an alignment film by screen printing, dispenser coating, or the like. Then, a step of forming a rectangular seal pattern, the liquid crystal dropping method sealing agent of the present invention is applied in an uncured state, and liquid crystal microdrops are dropped onto the entire surface of the transparent substrate, and the other transparent substrate is immediately applied. The step of superimposing, the step of irradiating the seal pattern portion of the sealant for the liquid crystal dropping method of the present invention with light such as ultraviolet rays to temporarily cure the sealant, and the temporary curing by heating the temporarily cured sealant And a method having a step of causing the reaction to occur.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods excellent in adhesiveness and linear drawing property can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Synthesis of resorcinol type epoxy acrylate (curable resin A))
1000 parts by weight of resorcinol type epoxy resin (manufactured by Nagase ChemteX, “Denacol EX-201”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 649 parts by weight of acrylic acid, The reaction was carried out by stirring at 90 ° C. for 5 hours while feeding air. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). Resorcinol type epoxy acrylate (curable resin A) was obtained.

(Synthesis of bisphenol A type epoxy acrylate (curable resin B))
1000 parts by weight of a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “Epicoat 828EL”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 424 parts by weight of acrylic acid, The mixture was reacted by stirring at 90 ° C. for 5 hours while feeding. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). A bisphenol A type epoxy acrylate (curable resin B) was obtained.

(Synthesis of bisphenol F type epoxy acrylate (curable resin C))
1000 parts by weight of a bisphenol F type epoxy resin (Mitsubishi Chemical Co., Ltd., “Epicoat 806”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 462 parts by weight of acrylic acid, The mixture was reacted by stirring at 90 ° C. for 5 hours while feeding. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). A bisphenol F type epoxy acrylate (curable resin C) was obtained.

(Synthesis of partially acrylic-modified bisphenol A type epoxy resin (curable resin D))
1000 parts by weight of a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “Epicoat 828EL”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 212 parts by weight of acrylic acid, The mixture was reacted by stirring at 90 ° C. for 5 hours while feeding. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). 50% partially acrylic modified bisphenol A type epoxy resin (curable resin D) was obtained.

(Synthesis of partially acrylic modified resorcinol type epoxy resin (curable resin E))
1000 parts by weight of resorcinol type epoxy resin (manufactured by Nagase ChemteX, “Denacol EX-201”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 325 parts by weight of acrylic acid, The reaction was carried out by stirring at 90 ° C. for 5 hours while feeding air. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). 50% partially acrylic modified resorcinol type epoxy resin (curable resin E) was obtained.

(Preparation of hexamethyldisilazane-treated silica)
100 parts by weight of silica particles having an average particle diameter of 0.7 μm synthesized by the sol-gel method are placed in a Henschel mixer, and 0.5 parts by weight of water and 10 parts by weight of hexamethyldisilazane are sprayed while stirring in a nitrogen atmosphere. The mixture was heated at 80 ° C. for 80 minutes, cooled, and crushed with a ball mill to prepare hexamethyldisilazane-treated silica (average particle size 0.7 μm).
Similarly, silica particles having an average particle size of 0.05 μm, silica particles having an average particle size of 0.1 μm, silica particles having an average particle size of 0.4 μm, and silica particles having an average particle size of 1.0 μm are synthesized by the sol-gel method. The same operation was performed to prepare hexamethyldisilazane-treated silica having average particle sizes of 0.05 μm, 0.1 μm, 0.4 μm, and 1.0 μm, respectively.

(Preparation of silica treated with 3-glycidoxypropyltrimethoxysilane)
100 parts by weight of silica particles having an average particle diameter of 0.7 μm synthesized by the sol-gel method are put in a mixer, and 10 parts by weight of water and 2 parts by weight of 3-glycidoxypropyltrimethoxysilane are sprayed while stirring in a nitrogen atmosphere. The mixture was heated at 150 ° C. for 80 minutes, cooled, and crushed with a ball mill to prepare 3-glycidoxypropyltrimethoxysilane-treated silica (average particle size 0.7 μm).
Similarly, silica particles having an average particle size of 0.05 μm, silica particles having an average particle size of 0.1 μm, silica particles having an average particle size of 0.4 μm, and silica particles having an average particle size of 1.0 μm are synthesized by the sol-gel method. The same operation was performed to prepare 3-glycidoxypropyltrimethoxysilane-treated silica having average particle sizes of 0.05 μm, 0.1 μm, 0.4 μm, and 1.0 μm, respectively.

(Preparation of silica treated with 3-aminopropyltrimethoxysilane)
Same as “Preparation of silica treated with 3-glycidoxypropyltrimethoxysilane” except that 2 parts by weight of 3-aminopropyltrimethoxysilane was used instead of 2 parts by weight of 3-glycidoxypropyltrimethoxysilane. Then, 3-aminopropyltrimethoxysilane-treated silica (average particle size 0.7 μm) was prepared.

(Preparation of methacryloxypropyltrimethoxysilane-treated silica)
Except that 2 parts by weight of methacryloxypropyltrimethoxysilane was used in place of 2 parts by weight of 3-glycidoxypropyltrimethoxysilane, the same as “Preparation of silica treated with 3-glycidoxypropyltrimethoxysilane” was performed. Thus, methacryloxypropyltrimethoxysilane-treated silica (average particle size 0.7 μm) was prepared.

(Preparation of talc treated with hexamethyldisilazane)
100 parts by weight of talc particles (manufactured by Nippon Talc Co., Ltd., “SG-2000”) are placed in a mixer, and 0.5 parts by weight of water and 10 parts by weight of hexamethyldisilazane are sprayed while stirring in a nitrogen atmosphere at 150 ° C. After heating for 80 minutes, the mixture was cooled and crushed with a ball mill to prepare hexamethyldisilazane-treated talc (average particle size: 1.0 μm).

(Preparation of 3-glycidoxypropyltrimethoxysilane-treated talc)
100 parts by weight of talc particles (“SG-2000” manufactured by Nippon Talc Co., Ltd.) are placed in a mixer, and 10 parts by weight of water and 2 parts by weight of 3-glycidoxytrimethoxysilane are sprayed while stirring under a nitrogen atmosphere. After heating at 80 ° C. for 80 minutes, the mixture was cooled and crushed with a ball mill to prepare 3-glycidoxypropyltrimethoxysilane-treated talc (average particle size: 1.0 μm).

Example 1
As the curable resin, 70 parts by weight of resorcinol type epoxy acrylate (curable resin A), 20 parts by weight of bisphenol A type epoxy acrylate (curable resin B), and 50% partially acrylic modified bisphenol A type epoxy resin (curable resin) D) 10 parts by weight was mixed in a predetermined container, mixed and stirred with a planetary stirrer, and then 2,2-dimethoxy-2-phenylacetophenone (manufactured by BASF Japan, “Irgacure 651” as a photo radical polymerization initiator). ”) 1 part by weight was mixed and heated and mixed, and 1 part by weight of γ-glycidoxypropyltrimethoxysilane (“ KBM-403 ”manufactured by Shin-Etsu Silicone Co., Ltd.) as a silane coupling agent was mixed and stirred as a filler. 15 parts by weight of hexamethyldisilazane-treated silica (average particle size 0.7 μm) and thermosetting After mixing and stirring 0.8 parts by weight of malonic acid dihydrazide (manufactured by Nihon Finechem Co., Ltd.) using a planetary stirrer (manufactured by Shinky Co., Ltd., “Awatori Netaro”), uniformly with a ceramic three roll A sealant was obtained by mixing.

(Examples 2 to 25, Comparative Examples 1 to 8)
The curable resin and the filler were the materials and blending ratios described in Tables 1 to 4, and each material was treated with a planetary stirrer (Shinky Co., “Awatori Kentaro”) in the same manner as in Example 1. After mixing and stirring, the mixture was further mixed uniformly with a ceramic three roll to prepare the sealing agents for liquid crystal dropping methods of Examples 2 to 25 and Comparative Examples 1 to 8.

<Evaluation>
The following evaluation was performed about the sealing agent for liquid crystal dropping methods obtained by the Example and the comparative example. The results are shown in Tables 1 to 4.

(Adhesiveness)
1% by weight of a silica spacer (“SI-H055” manufactured by Sekisui Chemical Co., Ltd.) is added to the sealing agent for liquid crystal dropping method obtained in each example and each comparative example, and two sheets of alkali glass with a TN alignment film A test piece (30 × 40 mm) was finely dropped on one side and the other glass test piece was bonded in a cross shape to the sample, and irradiated with 3000 mJ / cm ² of ultraviolet rays with a metal halide lamp, and then 120 ° C. The adhesive test piece was obtained by heating for 60 minutes. A tensile test (5 mm / min) was performed on the obtained adhesive test piece with a chuck arranged vertically. The value obtained by dividing the obtained measured value (kgf) by the cross-sectional area (cm ² ) of seal application is 30 kgf / cm ² or more, “◎”, and 15 kgf / cm ² or more and less than 30 kgf / cm ² the "○", was to evaluate the case was less than 10kgf / cm ² or more 15kgf / cm ² as "△", "×" the case was less than 10kgf / cm ^2.

(Drawability)
1% by weight of a silica spacer (“SI-H055” manufactured by Sekisui Chemical Co., Ltd.) is added to the liquid crystal dropping method sealing agent obtained in each Example and each Comparative Example, and defoaming treatment is performed in the sealing agent. The foam was removed. After that, it was filled into a dispensing syringe (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.) equipped with a precision nozzle (manufactured by Musashi Engineering Co., Ltd., “NH-0.3”), and defoamed again. Next, using a dispenser (Musashi Engineering Co., Ltd., “SHOTMASTER300”), a transparent electrode substrate with an ITO thin film was coated with a sealing agent so as to draw a rectangular frame (coating speed 100 mm / sec), and the other transparent substrate was applied. Then, bonding was performed at 23 ° C. under a reduced pressure of 5.0 Pa using a vacuum bonding apparatus, and the cells after bonding were irradiated with 3000 mJ / cm ² ultraviolet rays using a metal halide lamp, and then heated at 120 ° C. for 60 minutes. Thus, the sealant was thermally cured, and five liquid crystal cells were produced for each sealant. When the sealant was observed and a clean line was drawn on the sealant with no disconnection and no waviness at the end, “◎”, when there was no disconnection but there was a slight waviness at the end of the sealant Was evaluated as “◯”, a case where there was no disconnection failure but the end of the sealant was clearly wavy, and a case where a disconnection failure occurred was evaluated as “X”.

(Liquid crystal contamination (specific resistance retention))
In a sample bottle, 1.0 g of liquid crystal (manufactured by Chisso Corporation, “JC-5001LA”) was added, and 0.02 g of the liquid crystal dropping method sealing agent obtained in each Example and each Comparative Example was added and shaken. Heated at 0 ° C. for 1 hour. After returning to room temperature (25 ° C.), a liquid crystal specific resistance measuring device (manufactured by KEITHLEY Instruments, “6517A”) and a liquid electrode (manufactured by Ando Electric, “LE-21 type”) as the electrode are used, and the standard temperature and humidity The liquid crystal specific resistance of the liquid crystal part was measured in the state (20 ° C., 65% RH). The liquid crystal resistivity holding ratio is obtained by the following formula. When the liquid crystal resistivity holding ratio is higher than 0.1, “◯” is given, and when the liquid crystal resistivity holding ratio is 0.1 or less, “△” is given. Sex was evaluated.
Liquid crystal specific resistance retention ratio = (use liquid crystal specific resistance after addition of sealant / use liquid crystal specific resistance without addition of sealant) × 100

(Evaluation of color unevenness of liquid crystal display elements)
The sealing agent obtained in each Example and each Comparative Example was filled in a syringe for dispensing (manufactured by Musashi Engineering, “PSY-10E”) and subjected to defoaming treatment. Next, a sealant was applied to a transparent electrode substrate with an ITO thin film in a rectangular frame using a dispenser (manufactured by Musashi Engineering Co., Ltd., “SHOTMASTER 300”). Subsequently, fine droplets of TN liquid crystal (manufactured by Chisso Corporation, “JC-5001LA”) were dropped and applied with a liquid crystal dropping device, and the other transparent substrate was bonded with a vacuum bonding device under a reduced pressure of 5 Pa. The bonded cells were irradiated with 3000 mJ / cm ² ultraviolet rays with a metal halide lamp, and then heated at 120 ° C. for 60 minutes to thermally cure the sealing agent, thereby producing five liquid crystal display elements for each sealing agent. The obtained liquid crystal display element was driven with a voltage of AC 3.5 V, and the periphery of the halftone sealant was visually observed. The case where no color unevenness was observed at all around the sealant part was evaluated as “◯”, the case where slightly light color unevenness was observed as “Δ”, and the case where clear dark color unevenness was observed as “X”.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods which is excellent in adhesiveness and linear drawing property can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.

Claims (9)

1. A curable resin containing a resorcinol-type epoxy (meth) acrylate and a resin having an epoxy group, inorganic fine particles treated with hexamethyldisilazane on the surface, and / or 3-glycidoxypropyltrimethyl on the surface. Contains surface-treated inorganic fine particles containing inorganic fine particles treated with methoxysilane,
   The surface-treated inorganic fine particles have an average particle size of 0.1 μm or more.
2. The sealing agent for liquid crystal dropping method according to claim 1, wherein the inorganic fine particles are silica.
3. 3. The sealing agent for liquid crystal dropping method according to claim 1, wherein the content of the surface-treated inorganic fine particles is 20 to 160 parts by weight with respect to 100 parts by weight of the curable resin.
4. 4. The sealing agent for liquid crystal dropping method according to claim 1, wherein the content of resorcinol type epoxy (meth) acrylate in the curable resin is 20% by weight or more.
5. The sealing agent for liquid crystal dropping method according to claim 1, wherein the curable resin contains bisphenol A type epoxy (meth) acrylate.
6. 6. The sealing agent for liquid crystal dropping method according to claim 5, wherein the content of bisphenol A type epoxy (meth) acrylate in the curable resin is 10% by weight or more.
7. 7. The sealing agent for liquid crystal dropping method according to claim 1, wherein the surface-treated inorganic fine particles have an average particle size of 1.0 [mu] m or less.
8. A vertical conduction material comprising the sealing agent for a liquid crystal dropping method according to claim 1, 2, 3, 4, 5, 6 or 7, and conductive fine particles.
9. A liquid crystal display element manufactured using the sealing agent for liquid crystal dropping method according to claim 1, 2, 3, 4, 5, 6 or 7, and / or the vertical conduction material according to claim 8.