TW201530234A - Liquid crystal sealing agent and liquid crystal display cell using the same - Google Patents

Abstract

An objective of this invention is to provide a liquid crystal sealing agent having improved dispersion of filling agent dispersed within the liquid crystal sealing agent, thereby decreasing blocking of nozzle during dispensing and gap defect during laminating. Provided is a liquid crystal sealing agent for liquid crystal dropping method, which comprises: a filler (a) with an average particle size A[[mu]m], a filler (b) with an average particle size B[[mu]m], and a curable compound (c), wherein, A[[mu]m] and B[[mu]m] satisfy with the conditions represented by the following functions (I) and (II). 3[mu]m ≤ A ≤ 20[mu]m...(I) 0.0005*A ≤ B ≤ 0.02*A...(II).

Description

Liquid crystal sealing agent and liquid crystal display unit using the same

The present invention relates to a liquid crystal sealing agent used in a liquid crystal dropping method. More specifically, it relates to a liquid crystal sealing agent for liquid crystal dropping method in which the agglomerate of the filler is removed and the filler is highly dispersed. Since the liquid crystal sealing agent for liquid crystal dropping method is a non-filler agglomerate, it is excellent in coating workability such as Dispense or Screen Printing, and does not cause cell gap of the liquid crystal display unit (Cell Gap) A poor liquid crystal sealant.

With the increase in the size of the liquid crystal display unit in recent years, a manufacturing method of a liquid crystal display unit has been proposed, that is, a liquid crystal dropping method (Patent Document 1 and Patent Document 2). Specifically, a method of manufacturing a liquid crystal display unit in which the liquid crystal sealing agent is cured by laminating a liquid crystal on the inner side of the liquid crystal sealing agent formed on one of the substrates and then bonding the other to the substrate.

However, in the liquid crystal dropping method, before the liquid crystal sealing agent is hardened, since the liquid crystal sealing agent is in contact with the liquid crystal, the phenomenon of embedding the liquid crystal sealing agent is caused by the pressure caused by the liquid crystal, and even collapse occurs. And it is considered a problem. This problem is a problem in the production of a liquid crystal display unit in which a portion which is shaded by wiring or the like and which is not sufficiently irradiated with ultraviolet rays is used in a liquid crystal dropping method in which light and heat are used in combination. Further, in the liquid crystal dropping method in which the ultraviolet ray is not irradiated and the liquid crystal sealing agent is only hardened by heat, it is a major problem.

In order to solve the above problems, a liquid crystal sealing agent used in the liquid crystal dropping method has been proposed (Patent Document 3 and Patent Document 4).

However, in general, the filler particles are likely to aggregate with each other and are difficult to use in the state of the original particles. That is, agglomerates (coarse particles) are present in the liquid crystal sealing agent, causing clogging of the nozzle (Nozzle) at the time of dispensing, meshing of the screen of the screen during screen printing, and the like, resulting in defects in the coating step.

Further, in the manufacturing process of the liquid crystal display unit, when the upper and lower substrates are bonded together, the aggregate in the liquid crystal sealing agent causes a defect in the cell gap (the liquid crystal sealing agent does not collapse until the desired cell gap).

The present invention relates to a liquid crystal sealing agent for a liquid crystal dropping method containing a filler, and solves the above problems.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-63-179323

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-239694

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-23419

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-141576

The present invention relates to a liquid crystal sealing agent used in a liquid crystal dropping method, and more particularly to a liquid crystal sealing agent for liquid crystal dropping method in which agglomerates are removed and a filler is highly dispersed. Since the liquid crystal sealing agent for liquid crystal dropping method is a non-filler agglomerate, it is excellent in coating workability, such as dispensing or screen printing, and does not generate the liquid-crystal sealing agent of the liquid-crystal display unit.

Further, by removing the aggregation of the filler, the characteristics of the filler can be maximized. This effect can be achieved to a greater extent, for example, when the filler body has an embedding resistance to liquid crystals.

As a result of intensive investigation, the present inventors have found that the effect of agglomerating the decomposed filler can be exhibited by using two kinds of fillers having substantially different average particle diameters, and the present invention has been completed.

Further, in the present specification, "(meth)acrylic" means "acrylic acid and/or methacrylic acid", and "(meth)acrylic acid radical means "acrylic fluorenyl group and/or methacryl fluorenyl group". Moreover, the "liquid crystal sealing agent for liquid crystal dropping method" may be described as "liquid crystal sealing agent".

That is, the present invention relates to the following:

1)

A liquid crystal sealing agent for liquid crystal dropping method, which comprises: filling agent (a) having an average particle diameter A [μm] and filling of an average particle diameter B [μm] The filler (b) and the curable compound (c); wherein A [μm] and B [μm] satisfy the conditions shown by the following formulas (I) and (II).

3μm≦A≦20μm. . . (I)

0.0005×A≦B≦0.02×A. . . (II)

2)

The liquid crystal sealing agent for a liquid crystal dropping method according to the above 1), wherein the above (a) is an organic filler.

3)

The liquid crystal sealing agent for a liquid crystal dropping method according to the above 1), wherein the above (b) is cerium oxide and/or aluminum oxide.

4)

The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above-mentioned, wherein the (a) is a hydrophobic filler, and the (b) is a hydrophilic filler.

5)

The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above-mentioned, wherein the above (a) is selected from the group consisting of urethane rubber, acrylic rubber, styrene rubber, and styrene olefin. One or two or more kinds of rubber fine particles of a group consisting of rubber and polyoxyethylene rubber.

6)

The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above-mentioned, wherein the content of (a) is 5 parts by mass or more when the total amount of the liquid crystal sealing agent is 100 parts by mass. Less than 50 parts by mass.

7)

The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above-mentioned, wherein the content of the (b) is 1 part by mass or more when the total amount of the liquid crystal sealing agent is 100 parts by mass. Less than 20 parts by mass.

8)

The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above-mentioned, wherein the curable compound (c) is a (meth) acrylated epoxy resin, and the liquid crystal sealing agent further contains heat. Hardener (d).

9)

The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above-mentioned, wherein the curable compound (c) is a (meth) acrylate of resorcinol diglycidyl ether.

10)

The liquid crystal sealing agent for a liquid crystal dropping method according to the above 8), wherein the thermal curing agent (d) is an organic acid cerium compound.

11)

The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above 1 to 10, further comprising a thermal radical polymerization initiator (e).

12)

The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above 1), further comprising a silane coupling agent (f).

13)

The liquid crystal dropping method according to any one of the above 1) to 12) A liquid crystal sealing agent further containing an epoxy resin (g).

14)

A method of manufacturing a liquid crystal display unit, characterized in that, in a liquid crystal display unit comprising two substrates, liquid crystal is dropped on any one of the above-mentioned 1) to 13) formed on one of the substrates After the inner side of the crucible of the liquid crystal sealing agent for liquid crystal dropping method described in the above, the other substrate is bonded, and then hardened by heat.

15)

A liquid crystal display unit which is sealed with a cured product obtained by curing a liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above 1) to 13).

Since the liquid crystal sealing agent of the present invention is a filler-free aggregate, it is excellent in coating workability such as dispensing or screen printing, and does not cause a liquid crystal sealing agent which is defective in cell gap of the liquid crystal display unit. Therefore, in order to solve various problems in the manufacturing steps of the liquid crystal display unit.

The liquid crystal sealing agent of the present invention is characterized by comprising: a filler (a) having an average particle diameter A [μm] and a filler (b) having an average particle diameter B [μm], wherein A [μm] and B [μm The conditions satisfying the following formulas (I) and (II) are satisfied.

3μm≦A≦20μm. . . (I)

0.0005×A≦B≦0.02×A. . . (II)

[about the formula (1)]

The formula (I) is an average particle diameter of the filler (a) having a large average particle diameter. That is, the average particle diameter of the filler (a) is 3 μm or more and 20 μm or less. When the average particle diameter of the filler is small, the cohesive force tends to be high. Therefore, when it is less than 3 μm, the effect of the present invention cannot be sufficiently obtained. Further, when the average particle diameter of the filler is too large, it is not suitable for the production of a liquid crystal display unit even if it is not aggregated. A more preferable range of the average particle diameter is 3 μm or more and 15 μm or less, and particularly preferably 4 μm or more and 10 μm or less.

[about equation (II)]

The formula (II) represents the relationship between the filler (a) and the average particle diameter of the filler (b). That is, the average particle diameter of the filler (b) is 1/2000 or more and 1000/1000 or less of the average particle diameter of the filler (a). When the average particle diameter of the filler (b) is within this range, it is efficiently entered between the particles of the filler (a) and the particles of the filler (a), and the dispersibility of the filler (a) is improved. effect. Further, when the filler (a) is an organic filler, the shape may be deformed by external stress. However, when the filler (b) is in the above range, the deformation can be followed without being peeled off by the filler (a). . The average particle diameter of the filler (b) is more preferably 2/1000 or more and 15/1000 or less, and particularly preferably 5 or more and 1000 or less and 1000 or less.

In the present specification, the average particle diameter and the particle diameter can be measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by SEISHIN Co., Ltd.; LMS-30). Moreover, if it is a commercial item, it is also described in the catalogue of each company.

The above filler (a) means an organic filler and/or an inorganic filler.

Examples of the organic filler include polyfluorene fine particles such as nylon (Nylon) 6, nylon 12, and nylon 66; fluorine-based fine particles such as tetrafluoroethylene and difluoroethylene; and olefins such as polyethylene and polypropylene. Fine particles; polyester-based fine particles such as polyethylene terephthalate or polyethylene naphthalate; rubber fine particles such as natural rubber, isoprene rubber, and acrylic rubber. Preferred among them are rubber particles, such as natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene ‧ butadiene rubber (SBR), butyl rubber (IIR), nitrile rubber (NBR), ethylene ‧ propylene rubber (EPM, EP), chloroprene rubber (CR), acrylic rubber (ACM, ANM), chlorosulfonated polyethylene rubber (CSM) , Urethane rubber (PUR), polyoxynized rubber (SI, SR), fluororubber (FKM, FPM), polysulfide rubber (Thiokol) and the like. These solid components (I) can be used in combination of two or more kinds. Among these, polyoxyethylene rubber, styrene rubber, styrene olefin rubber, and acrylic rubber are preferred.

In the above polyoxyxene rubber, KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), TORAYFIL ^RTM E-5500, 9701, and EP-2001 (manufactured by Dow Corning Toray Co., Ltd.) are preferred. For the urethane rubber, it is preferably JB-800T, HB-800BK (Kenwon Industrial Co., Ltd.), and in the case of styrene rubber, preferably RABALON ^RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C SJ6300C (manufactured by Mitsubishi Chemical Corporation), in the case of styrene olefin rubber, SEPTON ^RTM SEPS2004 and SEPS2063 are preferred. In addition, in this specification, the superscript "RTM" means a registered trademark.

Further, when the above acrylic rubber is used, an acrylic rubber having a core-shell structure composed of two types of acrylic rubber is preferable, and particularly preferably, the inner layer is n-butyl acrylate and the outer layer is methacrylic acid. Methyl ester. This is ZEFIAKKU ^RTM F-351 sold by AICA Industries, Inc.

Examples of the inorganic filler include molten cerium oxide, crystalline cerium oxide, cerium carbide, cerium nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, and talc. , clay, alumina, magnesia, zirconia, aluminum hydroxide, magnesium hydroxide, calcium citrate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, Asbestos, etc., preferably molten cerium oxide, crystalline cerium oxide, cerium nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, cerium Calcium acid, aluminum citrate, more preferably molten cerium oxide, crystalline cerium oxide, aluminum oxide, talc. These inorganic fillers can be used in combination of two or more kinds.

In the case of the filler (a), an organic filler is preferred. The reason is that the organic filler is deformed in response to the cell gap, and exhibits resistance to embedding of the liquid crystal.

Among the organic fillers, one or more rubber particles selected from the group consisting of urethane rubber, acrylic rubber, styrene rubber, styrene olefin rubber, and polyoxymethylene rubber are preferred, and more preferably It is an acrylic rubber and/or a polyoxyethylene rubber.

For organic fillers, KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), AFX-8, AFX-15 (manufactured by Sekisui Chemicals Co., Ltd.), JB-800T, and HB-800BK (manufactured by Kokusai Industrial Co., Ltd.).

The above filler (b) means an organic filler and/or an inorganic filler.

Examples of the organic filler include ZEFIAKKU ^RTM F-325, F-340, F-351 (manufactured by AICA Industrial Co., Ltd.), PARALOID EXL-2655 (manufactured by Wu Yu Chemical Industry Co., Ltd.), and the like.

Examples of the inorganic filler described above are the same as those enumerated above for the filler (a). However, the average particle diameter is limited to those satisfying the above formula (II) or satisfying the above formula (II) by the decomposition step. Further, the inorganic filler may be a surface treatment by various methods, but is preferably an untreated one.

The filler (b) is preferably cerium oxide or aluminum oxide, and particularly preferably fumed silica or fumed silica.

Regarding the surface polarities of the filler (a) and the filler (b), when the filler (a) is hydrophobic and the filler (b) is hydrophilic, it is one of preferred aspects of the invention. Since the curable resin (c) is relatively highly polar, higher dispersibility can be obtained by protecting the surface of the hydrophobic filler (a) with a hydrophilic filler (b).

Here, the hydrophilicity means that the surface is composed of a functional group having a hydrogen atom-bonding property such as a hydroxyl group or an amine group, or a hydrogen bond accepting component such as a metal oxide. Further, the hydrophobicity means a dimethyl dichlorosilane, a hexamethyldisilazane, an octyl decane, a polyoxygenated oil or a coupling agent having a nonpolar functional group at the terminal. Make the hydrophilic surface chemically bonded.

With respect to the content of the filler (a) in the liquid crystal sealing agent, when the total amount of the liquid crystal sealing agent of the present invention is 100 parts by mass, it is preferably 5 to 50 parts by mass, more preferably 7 to 40 parts by mass. More preferably, it is 10 to 30 parts by mass.

Further, in terms of the content of the filler (b) in the liquid crystal sealing agent, when the total amount of the liquid crystal sealing agent of the present invention is 100 parts by mass, it is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass. More preferably, it is 3 to 10 parts by mass.

The liquid crystal sealing agent for a liquid crystal dropping method of the present invention contains a curable compound (c).

The curable compound (c) is not particularly limited as long as it is polymerized by light or heat, but is preferably a curable compound having a (meth)acryl fluorenyl group.

Examples of the curable compound having a (meth) acrylonitrile group include (meth) acrylate and epoxy (meth) acrylate. Examples of the (meth) acrylate include benzyl methacrylate, cyclohexyl methacrylate, glyceryl dimethacrylate, glyceryl trimethacrylate, and EO-modified glyceryl trimethacrylate. , Pentaerythritol acrylate, Trimethylolpropane triacrylate, Tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa Acrylate Ester, Phloroglucinol Triacrylate, and the like. The epoxy (meth) acrylate is obtained by a known method from the reaction of an epoxy resin with (meth)acrylic acid. The epoxy resin to be used in the original class is not particularly limited, but is preferably a bifunctional or higher epoxy tree. The grease may, for example, be a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a Phenol novolac type epoxy resin, or a cresol novolac (Cresol novolac) Type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type ring Oxygen resin, glycidylamine type epoxy resin, Hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolak type epoxy resin having trisphenol methane skeleton, other ortho-benzene A diglycidyl ether compound of a bifunctional phenol such as diphenol or resorcin, a diglycidyl ether compound of a bifunctional alcohol, and a halide or a hydride thereof. Among these, from the viewpoint of liquid crystal contamination, an epoxy resin having a resorcinol skeleton such as resorcinol diglycidyl ether or the like is preferable. Further, the ratio of the epoxy group to the (meth)acryl fluorenyl group is not limited, but is appropriately selected from the viewpoints of step suitability and liquid crystal contamination.

Therefore, a preferred curable compound having a (meth)acryl fluorenyl group is a (meth)acryl fluorenyl group, and further a curable compound having a resorcinol skeleton such as resorcinol diglycidyl ether. A methacrylate of acrylate or resorcinol diglycidyl ether.

In addition, the content of the curable compound (c) in the liquid crystal sealing agent for liquid crystal dropping method is preferably in the range of 30 to 90 parts by mass when the total amount of the liquid crystal sealing agent is 100 parts by mass. More preferably, it is about 40 to 80 parts by mass.

Among the above-mentioned curable compounds having a (meth)acryl fluorenyl group, it is preferred to contain three or more (meth) acrylonitrile groups in one molecule. Compound. A compound having three or more (meth) acrylonitrile groups in one molecule can achieve excellent embedding resistance because the crosslinking rate (reaction rate) is fast. Further, when this method is used, it is excellent in workability unlike the method of increasing the amount of the thermal radical polymerization initiator to increase the reactivity.

As the compound having three or more (meth) acryloyl fluorenyl groups in one molecule, KAYARAD ^RTM PET-30, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA- may be mentioned. 12. GPO-303, TMPTA, THE-330, TPA-320, TPA-330, D-310, D-330, RP-1040, UX-5000, DPHA-40H (above, manufactured by Nippon Kayaku Co., Ltd.) , NK Ester ^RTM A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM- 35E, A-TMMT, A-9550, A-DPH (above, Shin-Nakamura Chemical Industry Co., Ltd.), SR295, SR350, SR355, SR399, SR494, CD501, SR502, CD9021, SR9035, SR9041 (above, Sartomer) )Wait. Among these, it is preferred that the molar average molecular weight is 800 or more, preferably such as KAYARAD ^RTM DPCA-20, DPCA-30, DPEA-12. Further, a curable compound containing an alkylene oxide (-ORO-) of C1 to C4 in a molecule is preferable, and KAYARAD ^RTM DPEA-12 is particularly preferable.

The liquid crystal sealing agent for liquid crystal dropping method of the present invention may further contain a thermosetting agent (d).

The heat curing agent is not particularly limited, and examples thereof include polyvalent amines, polyhydric phenols, and hydrazine compounds. However, solid organic acid hydrazines are particularly preferably used. There may be mentioned, for example, Salicylic acid hydrazide, benzamidine, 1-naphthoic acid Hydrazide), p-xylylene dioxime, m-xylylene dioxime, 2,6-naphthalene dihydrazide, 2,6-Pyridine dihydrazide, 1,2,4 - benzotriazole, 1,4,5,8-naphthalene tetrapurine, Pyromellitic tetrathydrazide. In addition, if it is an aliphatic hydrazine compound, such as formazan, acetamidine, acetonide, acetonide, propylene dioxime, butyl bismuth, pentane quinone, hexamethylene dipyridamole肼, 癸二醯肼, 1,4-cyclohexane dioxin, tartar diquinone, apple diterpenoid, iminodiacetic acid dihydrazide, N, N'-hexa N,N'-Hexamethylene bissemicarbazide, Citric acid trihydrazide, Nitrilotriacetic acid trihydrazide, cyclohexane tricarboxylate, 1, 3-Bis(decylcarbonylethyl)-5-isopropylhydantoin or the like having an intramethylene uretazole skeleton, preferably having a valeric acid carbendazim skeleton (the carbon atom of the carbendazim ring is An isopropyl group-substituted bismuth compound, ginseng (1-mercaptocarbonylmethyl)isocyanurate, ginseng (2-mercaptocarbonylethyl)isocyanurate, ginseng (2-oxime) Alkylcarbonylethyl isocyanurate, ginseng (3-mercaptocarbonylpropyl) isocyanurate, bis(2-mercaptocarbonylethyl) isocyanurate, and the like. These heat curing agents may be used singly or in combination of two or more. In terms of the balance between hardening reactivity and potential, it is preferably meta-xylene dioxime, propylene dioxime, hexamethylene dioxime, ruthenium dioxime, ginseng (1-mercaptocarbonylmethyl) isocyanide. Urea, ginseng (2-mercaptocarbonylethyl) isocyanurate, ginseng (3-mercaptocarbonylpropyl) isocyanurate, particularly preferably propylene dioxime or quinone dioxime. When the total amount of the liquid crystal sealing agent is 100 parts by mass, the content of the heat curing agent is about 1 to 30 parts by mass.

The liquid crystal sealing agent for a liquid crystal dropping method of the present invention may further contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is not limited as long as it is a compound which initiates a polymerization reaction by generating a radical by heating, and examples thereof include an organic peroxide, an azo compound, a benzoin compound, a benzoin ether compound, and a benzene. Ethyl ketone compounds, Benzopinacole, etc., are suitable for use with benzopinacol. For organic peroxides, Kayamek ^RTM A, M, R, L, LH, SP-30C, Perkadox CH-50L, BC-FF, Kadox B-40ES, Perkadox 14, Trigonox ^RTM 22-70E, 23- C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester ^RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl ^RTM B, Perkadox 16, Kayacarbon ^RTM BIC -75, AIC-75 (above, manufactured by AKZO Co., Ltd.), Permek ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC, TMH, C, V, 22, MC, Percure ^RTM AH, AL, HB, Perbutyl ^RTM H, C, ND, L, Percumyl ^RTM H, D, Peroyl ^RTM IB, IPP, Perocta ^RTM ND (above, Nippon Oil Co., Ltd.) and the like are commercially available. Further, in the azo compound, VA-044, V-070, VPE-0201, VSP-1001, etc. (above, Wako Pure Chemical Industries, Ltd.) and the like can be obtained from commercially available products. In addition, in this specification, the superscript RTM means a registered trademark.

The above (e) thermal radical polymerization initiator is preferably a thermal radical polymerization initiator having no oxygen-oxygen bond (-OO-) or nitrogen-nitrogen bond (-N=N-) in the molecule. . A thermal radical polymerization initiator having an oxygen-oxygen bond (-OO-) or a nitrogen-nitrogen bond (-N=N-) in a molecule, which is sealed in a liquid crystal due to a large amount of oxygen or nitrogen generated during radical generation The agent is hardened in the state of residual bubbles, and has the property of lowering the strength and the like. Particularly suitable for the thermal freedom of benzopinacol Base polymerization initiator (including chemically modified benzopinol). Specific examples thereof include: benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2 -tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra (4 -methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetrakis(4-methoxyphenyl)ethane, 1,2-bis(trimethyloxime) -1,1,2,2-tetraphenylethane, 1,2-bis(triethyldecyloxy)-1,1,2,2-tetraphenylethane, 1,2-double (Third butyl dimethyl decyloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethyl decyloxy-1,1,2,2-tetraphenyl Ethylethane, 1-hydroxy-2-triethylphosphonium-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethyloxyl-1, 1,2,2-tetraphenylethane, etc., preferably 1-hydroxy-2-trimethylphosphonium-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tri Ethyloxyl-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethyloxy-1,1,2,2-tetraphenylethane 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylphosphonium-1,1, 2,2-tetraphenylethane, 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, Best 1,2-bis (trimethyl silicon oxy) 1,1,2,2-tetraphenyl ethane.

The above benzopinacol is sold by Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries Co., Ltd., and the like. Further, the etherification of the hydroxyl group of benzopinacol can be easily synthesized by a known method. Further, the sulfhydryl etherification of the hydroxyl group of benzopinacol can be carried out by a method in which a corresponding benzopinacol and various thiolation reagents are heated under a basic catalyst such as pyridine. Examples of the thiolation reagent include trimethyl chlorodecane (TMCS), hexamethyldioxane (HMDS), and N, O-bis (the generally known trimethyl thiolation reagent). Trimethyldecyl)trifluoroacetamide (BSTFA) or as three Triethylchloromethane (TECS) of an ethyl thiolation reagent, third butyl methyl decane (TBMS) as a third butyl dimethyl thiolation reagent, or the like. These reagents are readily available from markets such as oxime derivatives manufacturers. The reaction amount of the thiolation reagent is preferably 1.0 to 5.0 times the hydroxyl group of the target compound. More preferably, it is 1.5 to 3.0 times Mo. When the amount is less than 1.0 times, the reaction efficiency is poor, and the reaction time becomes long to promote thermal decomposition. When it is more than 5.0 times Mo, it becomes difficult to separate or deteriorate the separation at the time of recovery.

(e) The thermal radical polymerization initiator is preferably obtained by pulverizing the particle size and uniformly dispersing. When the average particle diameter is too large, the gap between the upper and lower glass substrates is not easily formed when the liquid crystal display unit having a narrow gap is formed. Therefore, it is preferably 5 μm or less, and more preferably 3 μm or less. Further, it may be smashed without end, but the general lower limit is about 0.1 μm. The particle size can be measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by SEISHIN Co., Ltd.; LMS-30).

When the total amount of the liquid crystal sealing agent used in the present invention is 100 parts by mass, the content of the (e) thermal radical polymerization initiator is preferably 0.0001 to 10 parts by mass, more preferably 0.0005 to 5 parts by mass, particularly preferably It is 0.001 to 3 parts by mass.

The liquid crystal sealing agent for liquid crystal dropping method of the present invention can use (f) a decane coupling agent in an attempt to improve the adhesion strength or moisture resistance reliability. Examples of the decane coupling agent include: 3-lycidoxy-propyltrimethoxy silane, 3-glycidoxypropylmethyldimethoxy decane, and 3- Glycidyloxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxyanthracene Alkane, N-phenyl-γ-aminopropyltrimethoxydecane, N-(2-aminoethyl)3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)3- Aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxysilane, Mercaptopropyltrimethoxysilane, vinyltrimethoxydecane, N-(2-(vinyl) Benzylamino)ethyl)3-aminopropyltrimethoxydecane hydrochloride, 3-Methacryloxypropyl trimethoxysilane, 3-chloropropylmethyl Dimethoxydecane, 3-chloropropyltrimethoxydecane, and the like. These decane coupling agents are sold from Shin-Etsu Chemical Co., Ltd. as KBM series, KBE series, etc., and are readily available on the market. When the entire liquid crystal sealing agent used in the present invention is 100 parts by mass, the content of the decane coupling agent in the liquid crystal sealing agent is suitably from 0.05 to 3 parts by mass.

In the liquid crystal sealing agent for liquid crystal dropping method of the present invention, (g) an epoxy resin may be added to attempt to further increase the bonding strength. The epoxy resin to be used is not particularly limited, but is preferably a bifunctional or higher epoxy resin, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and double Phenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin , an aliphatic chain epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, an ethyl uret urea type epoxy resin, an isocyanurate type epoxy resin, and a trisphenol methane skeleton A phenol novolac type epoxy resin, other diglycidyl ether compounds such as bifunctional phenols, diglycidyl ether compounds of bifunctional alcohols, and halides, hydrides, and the like. Liquid crystal pollution From the viewpoint of properties, a bisphenol epoxy resin or a phenolic paint epoxy resin is preferred. In addition, when the total amount of the liquid crystal sealing agent is 100 parts by mass, the content of the curable resin having an epoxy group in the liquid crystal sealing agent is about 1 to 30 parts by mass.

The liquid crystal sealing agent of the present invention may contain, in addition to the above components and components which are required to be contained, such as a photopolymerization initiator, a radical polymerization inhibitor, a hardening accelerator, a pigment, a leveling agent, Defoamer, solvent, etc.

The photopolymerization initiator is not particularly limited as long as it is a compound which generates a radical or an acid by irradiation with ultraviolet light or visible light to initiate a chain polymerization reaction, and examples thereof include benzyldimethyl group. Ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, diphenyl ketone, 2-ethyl onion (2-Ethyl anthraquinone), 2-hydroxy-2-methyl 2-Hydroxyl-2-methylpropiophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholinyl-1-propane (2-Methyl-[4-(methylthio)phenyl) ]-2-morpholino-1-propane), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone (9-Fluorenone), diphenyldisulfide, and the like. Specifically, IRGACURE ^RTM 651, 184, 2959, 127, 907, 396, 379 EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE ^RTM 1173, LUCIRIN ^RTM TPO (all manufactured by BASF Corporation), SEIKUOL ^RTM Z, BZ, BEE, BIP, BBI (all manufactured by Seiko Chemical Co., Ltd.).

Further, from the viewpoint of liquid crystal contamination, it is preferred to use a (meth) acrylonitrile group in the molecule, and it is suitable to use, for example, 2-methacryloyloxyethyl isocyanate and 1- A reaction product of [4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one. This compound can be produced by the method described in International Publication No. 2006/027982.

The content of the photopolymerization initiator to be used in the total amount of the liquid crystal sealing agent is usually 0.001 to 3% by mass, preferably 0.002 to 2% by mass.

The radical polymerization inhibitor is not particularly limited as long as it reacts with a radical generated by a photopolymerization initiator or a thermal radical polymerization initiator to inhibit polymerization, and a Quinone system can be used. Piperidine, Hindered phenol, Nitroso, and the like. Specific examples thereof include naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6,-tetramethylpiperidine-1- Oxide, 2,2,6,6,-tetramethyl-4-hydroxypiperidine-1-oxide, 2,2,6,6,-tetramethyl-4-methoxypiperidine-1- Oxide, 2,2,6,6,-tetramethyl-4-phenoxypiperidine-1-oxide, hydroquinone, 2-methylhydroquinone, 2-methoxy-p-benzene Diphenol, para-benzoquinone, butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-t-butyl cresol, Β-(3,5-di-t-butyl)-4-hydroxyphenyl)propionate (Stearyl β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), 2, 2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'- Butylene bis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5) -Methylphenyl)propenyloxy]ethyl](3,9-Dis[1,1-dimethyl-2-[β-(3-t-butyl-4-hydroxyl-5-methylphenyl)propionyloxy]ethyl ]), 2,4,8,10-tetraoxaspiro[5,5]undecane, 肆-[methylene-3-(3', 5'-di-t-butyl-4'-hydroxyphenylpropionate) methane, 1,3,5-gin (3',5'-di-t-butyl third-4'-hydroxybenzene Methyl)-s-three -2,4,6-(1H,3H,5H)triketone, p-methoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N-nitrosophenylhydroxylamine aluminum salt The product name is ADK STAB LA-81, and the trade name is ADK STAB LA-82 (made by Adeka Co., Ltd.), but is not limited thereto. Among these, preferred are naphthoquinone, hydroquinone, nitroso, and piperazine. (piperazine) is a free radical polymerization inhibitor, more preferably naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-t-butyl-P-cresol, Polystop 7300P (Bodong Co., Ltd.) Company system), the best is Polystop 7300P (made by Bodong Co., Ltd.).

The radical polymerization inhibitor is a method of adding the component (c) or a method of dissolving the component (c) in the production of the liquid crystal sealing agent, but in order to obtain a more effective effect, it is preferably a liquid crystal sealing agent. It is dissolved in component (c) at the time of manufacture.

In the total amount of the liquid crystal sealing agent of the present invention, the content of the radical polymerization inhibitor is preferably from 0.0001 to 1% by mass, more preferably from 0.001 to 0.5% by mass, particularly preferably from 0.01 to 0.2% by mass.

The hardening accelerator may, for example, be an organic acid or an imidazole.

The organic acid may, for example, be an organic carboxylic acid or an organic phosphoric acid, but is preferably an organic carboxylic acid. Specific examples include: phthalic acid, isophthalic acid An aromatic carboxylic acid such as dicarboxylic acid, terephthalic acid, trimimellitic acid, benzophenone tetracarboxylic acid or furan dicarboxylic acid; succinic acid, adipic acid, Dodecanedioic acid, azelaic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, ginseng (2-carboxymethyl)isocyanurate, ginseng (2-carboxyethyl)isocyanurate An acid ester, ginseng (2-carboxypropyl) isocyanurate, bis(2-carboxyethyl) isocyanurate or the like.

Further, examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1 -benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl- 2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6(2'-methylimidazolium(1'))ethyl-s-three (2,4-Diamino-6(2'-methylimidazole(1'))ethyl-s-triazine), 2,4-diamino-6(2'-undecylimidazolium (1'))ethyl- S-three 2,4-Diamino-6(2'-ethyl-4-methylimidazolium (1'))ethyl-s-three 2,4-Diamino-6(2'-methylimidazolium(1'))ethyl-s-three ‧Isocyanuric acid adduct, 2:3 adduct of 2-methylimidazole-isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl- 3,5-Dimethylolimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethyl Imidazole and the like.

In the case of using a hardening accelerator, when the total amount of the liquid crystal sealing agent is 100 parts by mass, it is usually 0.1 to 10% by mass, preferably 1 to 5% by mass.

In the liquid crystal display unit of the present invention, one of the predetermined electrodes is formed on the substrate, and the substrates are arranged to face each other at a predetermined interval, and the liquid crystal sealing agent of the present invention is sealed around the liquid crystal sealing agent in the gap. The type of liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a light-transmissive composite substrate composed of at least one of glass, quartz, plastic, tantalum, and the like. In the production method, a spacer (Spacer) such as a glass fiber (gap control material) is added to the liquid crystal sealing agent, and then a dispenser or screen printing is used on one of the pair of substrates. After the liquid crystal sealing agent is applied to the device or the like, it is temporarily hardened at 80 to 120 ° C as needed. Thereafter, the liquid crystal was dropped on the inside of the crucible of the liquid crystal sealing agent, and another glass substrate was superposed in a vacuum to form a gap. After the gap is formed, irradiated with ultraviolet rays as required 1000mJ / cm ² to 6000mJ / cm ^2, followed by curing at 90 to 130 ℃ 1 to 2 hours, thereby to obtain a liquid crystal display unit according to the present invention. The liquid crystal display unit of the present invention obtained in this manner is not excellent in display failure due to liquid crystal contamination, and is excellent in adhesion and moisture resistance reliability. Examples of the spacer include, for example, glass fibers, Silica beads, and polymer beads. The diameter varies depending on the purpose, and is usually 2 to 8 μm, preferably 4 to 7 μm. The amount of use of the liquid crystal sealing agent of the present invention is generally from 0.1 to 4% by mass, preferably from 0.5 to 2% by mass, still more preferably from 0.9 to 1.5% by mass, based on 100% by mass of the liquid crystal sealing agent.

The liquid crystal sealing agent used in the method for producing a liquid crystal display unit of the present invention can be obtained by the following method. First, the mixed component (g) is dissolved in the component (c) as needed. Next, the mixture is dissolved in the component (f) as needed. Next, components (a) and (b) are added, and components (d) and (e), an antifoaming agent, a leveling agent, a solvent, and the like are added as needed, by a known mixing device. For example, a three-roller, a sand mill, a ball mill, etc. are uniformly mixed and filtered by a metal mesh (Mesh).

Since the liquid crystal sealing agent of the present invention is a filler-free agglomerate, it is excellent in coating workability such as dispensing or screen printing, and does not cause cell gap defects of the liquid crystal display unit. Moreover, the resistance to the embedding of the liquid crystal is also good, and in the bonding step and the heating step of the substrate in the liquid crystal dropping method, liquid crystal embedding or sealant collapse does not occur. Therefore, the production of a stable liquid crystal display unit can be realized. Moreover, the elution of the liquid crystal of the constituent components is extremely small, and the display failure of the liquid crystal display unit can be reduced. Moreover, since it is excellent in storage stability, it is suitable for manufacture of a liquid crystal display unit. Further, the cured product is excellent in various cured properties such as strength, heat resistance, and moisture resistance, and particularly, the moisture permeability is extremely low. Therefore, by using the liquid crystal sealing agent of the present invention, a liquid crystal display unit having excellent reliability can be produced. Further, the liquid crystal display unit produced by using the liquid crystal sealing agent of the present invention sufficiently satisfies the essential characteristics of the liquid crystal display unit such as high voltage holding ratio and low ion density.

In the method for producing a liquid crystal display unit of the present invention, since the liquid crystal is less likely to be embedded in the liquid crystal sealing agent, it can be suitably used only by a hot liquid crystal dropping method, and it is more preferable from the viewpoint of production cycle (Tact).

(Example)

Hereinafter, the present invention will be described in more detail based on Synthesis Examples and Examples, but the present invention is not limited by the examples. In addition, “parts” and “%” in this document are quality standards unless otherwise stated.

[Synthesis Example 1] [Synthesis of a full acrylate of resorcinol diglycidyl ether]

181.2 g (EX-201: manufactured by NAGASECHEMTEX Co., Ltd.) of resorcinol diglycidyl ether was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene was added thereto as a polymerization inhibitor, and the temperature was raised to 60 °C. Thereafter, 117.5 g of acrylic acid having 100% equivalent of an epoxy group was added, and the temperature was further raised to 80 ° C. 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C for about 30 hours to obtain a reaction liquid. The reaction liquid was washed with water, and toluene was distilled off to obtain 293 g of an epoxy acrylate of the intended resorcinol diglycidyl ether. The theoretical equivalent of the reactive epoxy equivalent of the obtained epoxy acrylate was 183.

[Synthesis Example 2] Synthesis of [1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane]

100 parts (0.28 mol) of commercially available benzopinacol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 350 parts of dimethylformaldehyde. To this was added 32 parts of pyridine (0.4 mol) as a base catalyst, and 150 parts (0.58 mol) of BSTFA (manufactured by Shin-Etsu Chemical Co., Ltd.) as a thiolation reagent, and the temperature was raised to 70 ° C, followed by stirring for 2 hours. The obtained reaction liquid was cooled, and 200 parts of water was added while stirring, and the product was precipitated while the unreacted thiolation reagent was deactivated. After the precipitated product was separated by filtration, it was sufficiently washed with water, and then the obtained product was dissolved in acetone, and water was added thereto to recrystallize and purify. 105.6 parts of the target 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane was obtained (yield 88.3%).

As a result of HPLC (High Performance Liquid Chromatography) analysis, the purity was 99.0% (area percentage).

[Examples 1 to 7, Comparative Examples 1 to 2]

Liquid crystal was carried out using the components shown in Table 1 below, (a), (b), and the like. Manufacture of sealants. The manufacturing method is as follows.

First, the component (g) is heated and dissolved and mixed with the component (c), and after cooling to room temperature, the component (f) is added and stirred. Then, components (a), (b), (d), (e) and a hardening accelerator were sequentially added, and uniformly mixed by a three-roller.

The liquid crystal sealing agents prepared in Examples 1 to 7 and Comparative Examples 1 to 2 were subjected to the following evaluations. The results are summarized in Table 2.

[Filterability test]

As a method of evaluating the presence of aggregates, a filterability test was carried out.

This is a method of measuring the time and the amount of filtration by filtering 4 g of the liquid crystal sealing agent prepared in the above Examples 1 to 7 and Comparative Examples 1 to 2 in a gold mesh of 6 mm Φ 635 mesh. Since the liquid crystal sealing agent having a large amount of aggregates is gradually blocked due to the mesh openings, the filtration speed is slow, but the dispersed liquid crystal sealing agent can pass at a constant speed.

Filterability evaluation

○: Sealant 4g can be filtered at a certain speed

△: The speed of the sealant 4g gradually becomes slower, but it can still be filtered.

×: Sealant 4g cannot be filtered and blocked

[Next strength test]

If agglomerates are present, there is no uniformity in the liquid crystal sealing agent, so that the strength is lowered, but the liquid crystal sealing agent which is uniformly dispersed becomes no deviation, and the bonding strength is improved.

1 g of a glass fiber (PF-30S: manufactured by Nippon Electric Glass Co., Ltd.) having a diameter of 3 μm was added as a spacer to 100 g of the liquid crystal sealing agent. This liquid crystal sealing agent was applied onto a glass substrate of 50 mm × 50 mm, and a glass piece of 1.5 mm × 1.5 mm was bonded to the liquid crystal sealing agent, and the film was placed in an oven at 120 ° C for 1 hour to be cured. The shear strength of the glass piece was measured using a bond tester (SS-30WD: manufactured by Sejin Corporation). The results are shown in Table 2.

From the results of Table 2, according to the liquid crystal sealing agent for liquid crystal dropping method of the embodiment of the present invention, as a result, there was no agglomerate and the filtration speed was not lowered. On the other hand, it is understood that the liquid crystal sealing agent of the comparative example has agglomerates, and the filterability is gradually lowered.

Moreover, the liquid crystal sealing agent of the present invention can also be confirmed in terms of adhesion strength.

(industrial availability)

Since the liquid crystal sealing agent for a liquid crystal dropping method of the present invention is a flocculent without a filler, it is excellent in coating workability such as dispensing or screen printing, and does not cause a cell gap defect of the liquid crystal display unit. Moreover, the resistance to the embedding of the liquid crystal is also good, and in the step of bonding the substrates in the liquid crystal dropping method, the heating step does not cause liquid crystal embedding or collapse of the sealant. Therefore, the production of a stable liquid crystal display unit can be realized. Enter In the liquid crystal sealing agent, the liquid crystal sealing agent for liquid crystal dropping method, which is excellent in the strength of the liquid crystal sealing agent, can easily produce a liquid crystal display unit having excellent long-term reliability.

Claims (15)

A liquid crystal sealing agent for a liquid crystal dropping method, comprising: a filler (a) having an average particle diameter A [μm], a filler (b) having an average particle diameter B [μm], and a curable compound (c); A[μm] and B[μm] satisfy the conditions shown by the following formulas (I) and (II), 3 μm ≦A ≦ 20 μm. . . (I) 0.0005 × A ≦ B ≦ 0.02 × A. . . (II). The liquid crystal sealing agent for a liquid crystal dropping method according to the first aspect of the invention, wherein the (a) is an organic filler. The liquid crystal sealing agent for a liquid crystal dropping method according to the first or second aspect of the invention, wherein the (b) is cerium oxide and/or aluminum oxide. The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the items 1 to 3, wherein (a) is a hydrophobic filler, and (b) is a hydrophilic filler. The liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 4, wherein the (a) is selected from the group consisting of urethane rubber, acrylic rubber, styrene rubber, and styrene olefin. One or two or more kinds of rubber fine particles of a group consisting of rubber and polyoxyethylene rubber. The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the first to fifth aspects of the present invention, wherein the content of (a) is 5 when the total amount of the liquid crystal sealing agent is 100 parts by mass. Above the mass, not Up to 50 parts by mass. The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the first aspect of the present invention, wherein the content of the (b) is 1 when the total amount of the liquid crystal sealing agent is 100 parts by mass. More than the mass part, less than 20 parts by mass. The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the first aspect, wherein the curable compound (c) is a (meth) acrylated epoxy resin, and the liquid crystal is dropped. The liquid crystal sealing agent for the working method further contains a heat hardener (d). The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the preceding claims, wherein the curable compound (c) is (meth)acrylic acid of resorcinol diglycidyl ether. Esterified product. The liquid crystal sealing agent for a liquid crystal dropping method according to claim 8, wherein the thermal curing agent (d) is an organic acid cerium compound. The liquid crystal sealing agent for liquid crystal dropping methods of any one of Claims 1 to 10 further contains a thermal radical polymerization initiator (e). The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the items 1 to 11, further comprising a decane coupling agent (f). The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the items 1 to 12, further comprising an epoxy resin (g). A method of manufacturing a liquid crystal display unit, characterized in that, in a liquid crystal display unit composed of two substrates, liquid crystal is dropped on one of the substrates as in the first aspect of the patent application. In the inside of the crucible of the liquid crystal sealing agent for liquid crystal dropping method according to any one of the items 13, the other substrate is bonded, and then hardened by heat. A liquid crystal display unit which is a liquid crystal display unit which is sealed by a cured product obtained by curing a liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 13.