TW201619285A - Liquid crystal sealing agent and liquid crystal display cell using the same and manufacturing method for liquid crystal display cell - Google Patents

Abstract

The present invention relates to a liquid crystal sealing agent which is cured by light and/or heat and, more particularly, to a liquid crystal sealing agent for a liquid crystal dropping method. The liquid crystal sealing agent of the present invention has low degree of liquid crystal contamination and enables to minimize the sizes of liquid crystal display devices while making the devices have high-speed responses, low operating voltages and long lifespan. Also, the liquid crystal sealing agent has excellent adhesion strength, thereby enabling to make a liquid crystal panel with excellent durability, vibration-proof properties, shockproof properties, impact resistant properties, etc. The liquid crystal sealing agent for a liquid crystal dropping method comprises: an epoxy compound; and an organic filler, wherein the amount of the organic filler is greater than or equal to six times and less than or equal to 20 times of the weight of the epoxy compound.

Description

Liquid crystal sealing agent and liquid crystal display unit using same

The present invention relates to a liquid crystal sealing agent which is cured by light and/or heat, and is a liquid crystal sealing agent which is used in a liquid crystal dropping method. Specifically, the liquid crystal sealing agent which is low in liquid crystal contamination, and which has high strength and which is not detached from the upper and lower substrates at the time of light and/or heat curing at the time of panel manufacture, is liquid-filled into the liquid crystal sealing agent.

In recent years, with the increase in the size of the liquid crystal display unit and the production method of the liquid crystal display unit, a so-called liquid crystal dropping method having higher mass productivity has been proposed (refer to Patent Document 1 and Patent Document 2). Specifically, a method of manufacturing a liquid crystal display cell in which liquid crystal is sealed by bonding the liquid crystal to the inside of the liquid crystal sealing agent formed on one of the substrates and then bonding the other substrate.

However, in the liquid crystal dropping method, since the liquid crystal sealing agent in an uncured state is in contact with the liquid crystal, the components of the liquid crystal sealing agent are dissolved (dissolved) in the liquid crystal at this time, and the resistance value of the liquid crystal is lowered, and the display defect near the sealing portion is generated. Problems.

In order to solve this problem, it is currently used as a liquid crystal using a combination of light and heat. The liquid crystal sealing agent for the method is dropped and put into practical use (Patent Documents 3 and 4). In the liquid crystal dropping method using the liquid crystal sealing agent, it is characterized in that the liquid crystal sealing agent held by the substrate is irradiated with light to be hardened once, and then heated and secondarily hardened. According to this method, the uncured liquid crystal sealing agent can be rapidly hardened by light, and the component of the liquid crystal sealing agent can be prevented from being dissolved (dissolved) in the liquid crystal. In addition, the problem of insufficient adhesion strength due to hardening and contraction at the time of photohardening is also caused by light hardening. However, if it is a combination of light and heat, stress relaxation effect can be obtained by secondary hardening by heating. And has the advantage of eliminating this problem.

However, in recent years, with the miniaturization of the liquid crystal display element, the metal wiring portion of the array substrate of the liquid crystal display element or the black matrix portion of the color filter substrate generates light that is not irradiated to the light shielding portion of the liquid crystal sealing agent, thereby sealing Poor display problems near the location have become more serious than before. That is, due to the presence of the light shielding portion, the primary hardening by the light is insufficient, and a large amount of the unhardened portion remains in the liquid crystal sealing agent. When the secondary hardening step according to heat is performed in this state, the dissolution of the unhardened portion to the liquid crystal is promoted by heat, which causes display failure in the vicinity of the liquid crystal sealing agent.

In addition, in order to solve the problem of the shortening of the manufacturing process or the problem of the light-shielding portion, a method of curing the liquid crystal sealing agent by heat has been proposed (Patent Document 5). However, in this method, since the heating step is entered in a state where the liquid crystal is in contact with the uncured liquid crystal sealing agent, further lower liquid crystal contamination of the liquid crystal sealing agent is required.

In order to solve these problems, to improve the inverse of the curable resin For the purpose of curing in the presence of the liquid crystal, it has been investigated for the improvement of the thermal reactivity. For example, in Patent Documents 5 to 7, a method of using a thermal radical initiator is disclosed. Further, Patent Document 8 discloses a method of using a polyvalent carboxylic acid as a curing accelerator.

However, the addition of such a thermal radical initiator or a polycarboxylic acid-like hardening accelerator has an effect of increasing the reaction rate, but includes the disadvantage of improving the curing shrinkage ratio, lowering the bonding strength, and deteriorating the storage stability. .

As described above, even if it is extremely laborious to develop a liquid crystal sealing agent for a liquid crystal dropping method, a liquid crystal sealing agent which can achieve low liquid crystal contamination while having good adhesion strength and storage stability has not been developed. .

[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 No. 3583326

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-61925

[Patent Document 5] Japan International Publication No. 2011/061910

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2004-126211

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2009-8754

[Patent Document 8] Japan International Publication No. 2008/004455

The present invention provides a liquid crystal sealing agent for a liquid crystal dropping method, which relates to a liquid crystal sealing agent which is cured by light and/or heat, and has high liquid crystal display unit due to low liquid crystal contamination and excellent strength. Fineness, high-speed reaction, low-voltage drive, and long life are also excellent in storage stability, and it is not peeled off during transportation during panel production, so workability is extremely good.

The invention of the present application has been intensively studied in order to solve the above problems, and as a result, it has been found that when the amount of the organic filler is excessive with respect to the epoxy compound, the epoxy compound is absorbed by the organic filler. As a result, the solubility in the liquid crystal can be lowered, and then the strength becomes excellent, and the film is not peeled off during transportation during the manufacture of the panel. That is, the present invention relates to the following 1) to 12).

In the present specification, the term "(meth)acrylic acid" means "acrylic acid" and/or "methacrylic acid", and the same, "(meth)acrylic acid group" means "acrylic acid" and/or "Methyl propylene sulfhydryl". In addition, the "liquid crystal sealing agent for liquid crystal dropping method" may be described as "liquid crystal sealing agent".

1) A liquid crystal sealing agent for liquid crystal dropping method, which comprises (A) an epoxy compound and (B) an organic filler, and the content of the component (B) is 6 mass times or more and 20 mass times or less of the component (A). .

2) The liquid crystal sealing agent for liquid crystal dropping method according to the above 1), wherein the component (B) organic filler is an organic filler which forms a core-shell structure based on the two types of rubber.

3) The liquid crystal sealing agent for liquid crystal dropping method according to the above 1) or 2), wherein the component (B) organic filler is an organic filler which forms a core-shell structure based on two kinds of (meth)acrylic rubber.

(4) The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1) to 3, further comprising (C) an acrylic compound.

(5) The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1 to 4, wherein the component (A) is an epoxy compound having a resorcinol skeleton.

(6) The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1 to 5, wherein the component (C) is a (meth) acrylate compound of resorcinol diglycidyl ether.

(7) The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1), further comprising (D) a photoradical polymerization initiator and/or a thermal radical polymerization initiator.

(8) The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1) to (7), further comprising (E) a heat hardening agent.

9) The liquid crystal sealing agent for liquid crystal dropping method according to the above 8), wherein the component (E) is an organic acid cerium compound.

10) The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1) to 6) which further contains (F) a decane coupling agent.

11) A method of manufacturing a liquid crystal display unit, characterized in that: In the liquid crystal display unit comprising the two substrates, the liquid crystal is dropped on one of the substrates, and the inside of the liquid crystal sealing agent for liquid crystal dropping method of any one of the above 1) to 10) is formed. Thereafter, the other substrate is bonded and then cured by ultraviolet rays and/or heat.

12) A liquid crystal display unit which is sealed by a cured product obtained by hardening a liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1) to 10).

In the liquid crystal dropping method, the liquid crystal sealing agent is applied to one of the substrates, and the liquid crystal is dropped on the other substrate, and then the respective substrates are bonded. Although the liquid crystal sealing agent and the liquid crystal are in an uncured state, the liquid crystal sealing agent is in contact with the liquid crystal. The liquid crystal sealant and the liquid crystal components are difficult to mix at room temperature, and the influence on the liquid crystal is limited. However, in the subsequent stage of heat hardening, when the liquid crystal exceeds the N-I point, it is easy to mix with the liquid crystal sealant component to cause liquid crystal contamination to proceed.

In the liquid crystal sealing agent for liquid crystal dropping method of the present invention, since the amount of the organic filler is excessive with respect to the epoxy compound, and the organic filler absorbs the epoxy compound and swells upon heating, the epoxy resin can be suppressed as much as possible. The liquid crystal pollution caused. Thereby, it is possible to exhibit extremely excellent display characteristics without causing disorder in the alignment of the display portion. Further, the swollen core-shell acrylic copolymer contributes to the elastic modulus of the cured product and enhances the bonding strength due to the rubber-like property.

Liquid crystal sealing agent for liquid crystal dropping method of the present invention, due to low liquid crystal contamination Since the dyeing property is extremely excellent in strength, it is possible to achieve high definition, high-speed reaction, low voltage driving, and long life of the liquid crystal display unit, and also excellent in preservability, so that workability is extremely excellent.

The invention is described in detail below.

The liquid crystal sealing agent for liquid crystal dropping method of the present invention contains an epoxy compound as the component (A). The epoxy compound is not particularly limited, and is preferably a bifunctional or higher epoxy compound, and examples thereof include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, and a phenol compound. Phenolic epoxy resin, cresol novolac epoxy resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester Type epoxy resin, glycidylamine type epoxy resin, ethyl carbamide type epoxy resin, isomeric cyanate type epoxy resin, phenolic novolac type epoxy resin having trisphenol methane skeleton, other two A diglycidyl ether compound of a functional phenol, a diglycidyl ether compound of a difunctional alcohol, and a halide or a hydrogenated product thereof. Among these, an epoxy resin having a resorcinol skeleton such as resorcinol diglycidyl ether is particularly preferable from the viewpoint of liquid crystal contamination. The content of the epoxy compound (A) is preferably from 0.1 to 13% by mass, more preferably from 0.1 to 10% by mass, based on the total amount of the liquid crystal sealing agent of the present invention.

In the present application, the epoxy compound is a part (meth)acrylic compound which is produced without synthesizing the component (C) (meth)acrylic compound. This is due to the large molecular weight of some (meth)acrylic compounds, which is difficult It is absorbed into component (B).

The above resorcinol diglycidyl ether can be synthesized, for example, by the following method. 5,500 g of resorcin, 37,000 g of epichlorohydrin, and 500 g of tetramethylammonium chloride were added and dissolved under stirring, and the temperature was raised to 70 °C. Next, 4000 g of fragmented sodium hydroxide was added in sections over 100 minutes, and then the reaction was further carried out at 70 ° C for 1 hour. After completion of the reaction, 15000 g of water was added and washed with water, and then excess epichlorohydrin or the like was distilled off from the oil layer under reduced pressure at 130 °C. 22200 g of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 °C. Next, 1000 g of a 30% by mass aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water 5550 g three times, and methyl isobutyl ketone was distilled off under reduced pressure at 180 ° C to obtain isophthalic acid. 10550 g of phenol diglycidyl compound. The epoxy resin obtained had an epoxy equivalent of 129 g/eq.

The liquid crystal sealing agent for liquid crystal dropping method of the present invention contains an organic filler as the component (B). Specific examples of the organic filler include, for example, polyamide fine particles such as nylon 6, nylon 12, and nylon 66; fluorine-based fine particles such as tetrafluoroethylene and vinylidene fluoride; and olefins such as polyethylene and polypropylene. Microparticles; polyester microparticles such as polyethylene terephthalate or polyethylene naphthalate; rubber microparticles such as natural rubber, isoprene rubber, and acrylic rubber. In the present specification, fine particles having rubber properties are described as rubber fine particles. That is, the polymer fine particles obtained by the polymerization of the acrylic resin and the elastomer are used as the acrylic rubber.

Preferred of the component (B) is rubber microparticles. Rubber particles, for example Examples thereof include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), and nitrile rubber (NBR). Ethylene-propylene rubber (EPM, EP), chloroprene rubber (CR), (meth)acrylic rubber (ACM, ANM), chlorinated polyethylene rubber (CSM), urethane rubber (PUR) Polyoxyethylene rubber (Si, SR), fluororubber (FKM, FPM), polysulfide rubber (polysulfide rubber), etc., preferably (meth)acrylic rubber, styrene rubber, styrene olefin rubber, or polyfluorene Oxygen rubber, especially acrylic rubber.

The component (B) is preferably a core-shell structure formed of two types of rubber. Specifically, it is a core-shell structure in which a core portion of a particle and a shell portion have fine particles of a polymer having different properties, and a core of a rubber-like polymer and a shell of a glassy polymer. The core portion and the shell portion are produced by polymerizing a polymerizable monomer. Examples of the polymerizable monomer include n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, and the like. (meth)acrylate monomer; aromatic vinyl compound such as styrene, vinyl toluene or α-methylstyrene; cyanide vinyl compound such as acrylonitrile or methacrylonitrile; cyanide Ethylene, 2-hydroxyethyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 2-hydroxyethyl phthalate, hydroxybutyl vinyl ether, monobutyl maleate, A Butyl ethyl acrylate and the like. Further, examples thereof include ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, and trishydroxymethyltri(meth)acrylate. Propyl ester, hexanediol di(meth)acrylate, hexanediol tri(meth)acrylate, oligo-di(meth)acrylic acid ethyl ester, low a crosslinkable monomer having two or more reactive groups such as polytrimethylene (meth)acrylic acid ethyl ester; an aromatic divinyl monomer such as divinylbenzene; and triallyl trimellitate; One type of these may be used or two or more types selected from the group consisting of triallyl isocyanate and the like.

Further, it is particularly preferable to form a core-shell structure composed of two kinds of (meth)acrylic rubber. That is, both the core portion and the shell portion are formed of (meth)acrylic rubber. Further, the particularly preferred core portion is n-butyl acrylate and the shell portion is methyl methacrylate. This is sold by Aica Industries Ltd. as Zefiac ^RTM F-351. The content of the fine particles (B) swelled by the resin is preferably from 0.6 to 90% by mass, particularly preferably from 0.6 to 60% by mass, based on the total amount of the liquid crystal sealing agent of the present invention.

Further, in order to realize the constitution of the present invention, the organic filler (B) may be subjected to a classification operation to obtain a desired average particle diameter and used. The optimum average particle diameter is from 0.1 to 10 μm, more preferably from 0.1 to 5 μm.

The average particle diameter can be measured by a laser diffraction scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd.; LMS-30).

In the liquid crystal sealing agent for liquid crystal dropping method of the present invention, the content of the component (B) is 6 mass times or more and 20 mass times or less of the component (A), and the amount of the organic filler is excessive with respect to the epoxy compound. At this time, since the organic filler absorbs the epoxy compound and swells during heating, the liquid crystal contamination due to the epoxy resin can be suppressed as much as possible. The ratio of the component (A) to the component (B) is more preferably 6 mass times or more and 15 mass times or less.

The liquid crystal sealing agent for liquid crystal dropping method of the present invention is contained There is a (meth)acrylic compound as the component (C). The (meth)acrylic compound is not particularly limited as long as it has low solubility to liquid crystal, and examples thereof include ethyl urethane amide, (meth) acrylate, and (meth) acrylate epoxy ester. a compound having a propylene fluorenyl group as a functional group, specifically benzyl methacrylate, cyclohexyl methacrylate, glyceryl dimethacrylate, glyceryl triacrylate, EO modified glyceryl triacrylate, acrylic pentane Tetraol ester, trimethylolpropane triacrylate, tris(propyleneoxyethyl) isocyanurate, dinekapentayl hexaacrylate, phloroglucinol triacrylate, and the like. Further, from the viewpoint of liquid crystal contamination, a (meth)acrylic epoxy ester is particularly preferred. The (meth)acrylic acid epoxy ester can be obtained by subjecting acrylic acid or methacrylic acid to an esterification reaction with an epoxy resin having at least two or more epoxy groups in the molecule. This synthesis reaction can be carried out by a generally known method. For example, a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylphosphonium hydride, etc.) and a polymerization preventive agent (for example, formazan, hydroquinone, methyl group) are added. Hydrogen hydrazine, phenothiazine, dibutylhydroxytoluene, etc., and, for example, at 80 to 110 ° C, a predetermined equivalent ratio of acrylic acid or methacrylic acid is esterified with an epoxy resin. Further, examples of the epoxy resin having at least two epoxy groups in the molecule include a bisphenol A type epoxy resin, an alkyl substituted bisphenol A type epoxy resin, and an alkylene oxide addition double. Phenol A type epoxy resin, bisphenol F type epoxy resin, alkyl substituted bisphenol F type epoxy resin, alkylene oxide addition bisphenol F type epoxy resin, bisphenol S type epoxy resin, Alkyl substituted bisphenol S type epoxy resin, alkylene oxide addition bisphenol S type epoxy resin, phenolic novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type ring Oxygen resin, glycidylamine epoxy resin, dicyclopentadiene epoxy resin, polyfluorene modified epoxy resin, urethane modified epoxy resin, rubber modified ring Oxygen resin or the like, preferably bisphenol A type epoxy resin, alkyl substituted bisphenol A type epoxy resin, alkylene oxide addition bisphenol A type epoxy resin, bisphenol F type epoxy resin, Alkyl substituted bisphenol F type epoxy resin, alkylene oxide addition bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkyl substituted bisphenol S type epoxy resin, alkylene oxide plus Bisphenol S type epoxy resin. It is especially preferred to obtain (meth)acrylated resorcinol diglycidyl ether by esterification of acrylic acid or methacrylic acid with resorcinol diglycidyl ether. In the present invention, the content of the (meth)acrylic compound (component (C)) in the liquid crystal sealing agent is preferably from about 5 to 80% by mass based on the total amount of the liquid crystal sealing agent of the present invention, particularly preferably 20% by mass to 70% by mass.

(Meth)acrylated resorcinol diglycidyl ether can be synthesized, for example, by Japanese WO2004/104683.

For example, it is synthesized by the following method.

181.2 g of resorcinol diglycidyl ether was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene as a polymerization inhibiting agent was added thereto, and the temperature was raised to 60 °C. Then, 117.5 g of acrylic acid having 100% by weight of an epoxy group was added, and the temperature was further raised to 80 ° C. Then, 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and stirred at 98 ° C for about 30 hours. The obtained reaction liquid was washed with water and toluene was distilled off to obtain 253 g of the desired (meth)acrylated resorcinol diglycidyl ether.

The liquid crystal sealing agent of the present invention preferably further contains light A radical polymerization initiator and/or a thermal radical polymerization initiator is used as the component (D).

The photo-radical polymerization initiator of the component (D) is not particularly limited as long as it generates a radical by irradiation with ultraviolet light or visible light, and starts a chain polymerization reaction, and examples thereof include a benzyl group. Dimethyl ketal, 1-hydroxycyclohexyl ketone, diethyl thioxanthone, diphenyl ketone, 2-ethyl hydrazine, 2-hydroxy-2-methyl ethyl phenyl ketone, 2-methyl -[4-(methylthio)phenyl]-2-morpholinyl-1-propane, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, camphorquinone, 9-fluorenone , diphenyl disulfide, and the like. Specific examples include IRGACURE ^RTM 651, 184, 2959, 127, 907, 369, 379 EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE ^RTM 1173, LUCIRIN ^RTM TPO (both manufactured by BASF Corporation), SEIKUOL ^RTM Z , BZ, BEE, BIP, BBI (both manufactured by Seiko Chemical Co., Ltd.). In this specification, the superscript RTM means a registered trademark.

Further, from the viewpoint of liquid crystal contamination, it is preferred to use a (meth)acrylic group in the molecule, and for example, 2-methylpropenyloxyethyl isocyanate and 1-[4] are preferably used. A reaction product of -(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one. This compound can be obtained by the method described in Japanese Patent Laid-Open Publication No. 2006/027982.

The content of the total amount of the liquid crystal sealing agent when the photopolymerization initiator is used is usually 0.05 to 15% by mass, preferably 0.1 to 10% by mass.

The thermal radical polymerization initiator of the component (D) is not particularly limited as long as it is a compound which generates a radical by heating and starts a chain polymerization reaction, and examples thereof include an organic peroxide and an azo compound. As the benzoin compound, the benzoin ether compound, the acetophenone compound, the benzophenanol or the like, benzodinacol is preferably used. For example, organic peroxides include 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 (Kayaku Akzo Co., Ltd.), Permek ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC, Per TMH, C, V, 22, MC, Percure ^RTM AH, AL, HB, Perbutyl ^RTM H, C, ND, L, Percumyl ^RTM H, D, Perpyl ^RTM IB, IPP, Perocta ^RTM ND (manufactured by Nippon Oil Co., Ltd.), etc., are commercially available. In addition, an azo compound, VA-044, V-070, VPE-0201, VSP-1001 (made by Wako Pure Chemical Industries, Ltd.), etc. can be obtained as a commercial item.

The above thermal radical polymerization initiator is preferably a thermal radical polymerization initiator which does not have an oxygen-oxygen bond (-O-O-) or a 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 the molecule, which generates a large amount of oxygen or nitrogen when the radical is generated, and is sealed in the liquid crystal. The agent is hardened in the state in which the bubbles remain, and there is a fear that the properties such as the strength of the adhesive are lowered. Particularly preferred is a benzophenanol-based thermal radical polymerization initiator (including a chemically modified benzophenanol). Specific examples thereof include benzodinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-di Ethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy- 1,1,2,2-tetrakis(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetrakis(4-methylphenyl)ethane, 1 ,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(triethyldecyloxy)-1,1,2,2-tetra Phenylethane, 1,2-bis(tributylphosphinyloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethyldecyloxy- 1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethyldecyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tridecyl Methyl methoxy oxy-1,1,2,2-tetraphenylethane, etc., preferably 1-hydroxy-2-trimethyl decyloxy-1,1,2,2-tetraphenyl Ethane, 1-hydroxy-2-triethyl decyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tributylbutyloxycarbonyl-1,1 , 2,2-tetraphenylethane, 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethyl Alkyloxy-1,1,2,2-tetraphenylethane, 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, particularly preferred 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane.

The above-mentioned benzophenanol is commercially available from Tokyo Chemical Industry Co., Ltd. and Wako Pure Chemical Industries Co., Ltd. Further, the hydroxy esterification of benzopinacol can be easily synthesized by a generally known method. Further, the hydroxy decyl ester of benzopinacol can be synthesized by heating a corresponding benzophenanol with various decylating agents under an alkaline catalyst such as pyridine. Examples of the decylating agent include trimethylchlorodecane (TMCS), hexamethyldioxane (HMDS), and N,O-bis(trimethyldecyl) which are generally known as trimethylsulfonating agents. Trifluoroacetamide (BSTFA), or triethylchlorodecane (TECS) as a triethylsulfonating agent, tertiary butylmethyl decane (TBMS) as a tertiary dimethyl dimethyl sulfonating agent, etc. . Such reagents can be easily obtained from markets such as hydrazine derivative manufacturers. The reaction amount of the alkylating agent is preferably 1.0 to 5.0 moles per mole of the hydroxyl group of the target compound. More preferably 1.5 to 3.0 times Mo. When it is less than 1.0 times mole, the reaction efficiency is deteriorated, the reaction time is increased, and thus thermal decomposition is promoted. When it is more than 5.0 times Moule, the separation property is deteriorated at the time of recovery, or it is difficult to refine.

The thermal radical polymerization initiator is preferably a fine particle size and uniformly dispersed. When the average particle diameter is too large, when a liquid crystal display unit having a narrow pitch is produced, a pitch or the like cannot be formed smoothly when the upper and lower glass substrates are bonded, which is a disadvantage, and therefore it is preferably 5 μm or less, and more preferably 3 μm or less. Further, although it can be refining without limitation, the lower limit is usually about 0.1 μm. The particle diameter can be measured by a laser diffraction scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd.; LMS-30).

The content of the thermal radical polymerization initiator is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass, particularly preferably 0.001 to 3% by mass, based on the total amount of the liquid crystal sealing agent.

The liquid crystal sealing agent of the present invention preferably further contains a thermal curing agent as the component (E). This component (E) is different from the thermal radical polymerization initiator described in the above component (D), and means a thermosetting agent which does not generate a radical. Specifically, the nucleation reaction is carried out by an unshared electron pair or an anion in the molecule, and examples thereof include polyamines, polyhydric alcohols, and organic acid hydrazine compounds. However, it is not limited to this. Among these, Tetra-based organic acid bismuth compounds are used. For example, an aromatic cerium diterpene terephthalate, diammonium isophthalate, diammonium 2,6-naphthoic acid, 2,6-pyridine dioxime, 1,2,4- Benzoquinone, 1,4,5,8-naphthoic acid tetraquinone 肼, 焦蜜石酸四醯肼 and so on. Further, examples of the aliphatic hydrazine compound include formazan, ethyl hydrazine, cesium propionate, bismuth oxalate, diammonium malonate, diterpene succinate, and bismuth glutarate. Dioxane adipate, diammonium pimelate, diterpene sebacate, 1,4-cyclohexanedioxime, diterpenic tartrate, diterpene malate, diimine diacetate肼, N, N'-hexamethylene bis-carbazide, triterpene citrate, triammonium oxyacetate, triterpene Cyclohexane tricarboxylate, 1,3-bis(decylcarboethyl) -5-isopropylethyl carbazide or the like having an intramethylene uregar skeleton, preferably having a phthalic acid carbendazim skeleton (a skeleton in which a carbon atom of the uremic urea ring is substituted by an isopropyl group) Antimony compound, tris(1-mercaptocarbonylmethyl) isocyanurate, tris(2-mercaptocarbonylethyl) isocyanurate, tris(1-nonylcarbonyl) Ethyl) ester, tris(3-mercaptocarbonylpropyl) isocyanurate, bis(2-mercaptocarbonylethyl) isocyanurate, and the like. From the balance of hardening reactivity and potential, it is preferably diammonium isophthalate, diammonium malonate, diammonium adipate, diterpene sebacate, isomeric cyanuric acid (1-mercaptocarbonylmethyl) ester, tris(2-mercaptocarbonylethyl) isocyanurate, tris(3-mercaptocarbonylpropyl) isocyanurate, especially preferably isophthalic acid Diterpene diformate, diterpene sebacate and tris(2-mercaptocarbonylethyl) isocyanurate.

The content of the component (E) thermosetting agent is preferably from 0.01 to 5% by mass, more preferably from 0.1 to 5% by mass, based on the total amount of the liquid crystal sealing agent.

The liquid crystal sealing agent of the present invention preferably further contains a decane coupling agent as the component (F). The component (F) decane coupling agent may, for example, be 3-glycidoxypropyltrimethoxy decane, 3-glycidoxypropylmethyldimethoxy decane or 3-glycidoxypropyl group. Diethoxy oxane, 2-(3,4-epoxy Cyclohexyl)ethyltrimethoxy decane, N-phenyl-γ-aminopropyltrimethoxy decane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, N-(2-amine Ethyl) 3-aminopropylmethyltrimethoxy decane, 3-aminopropyltriethoxy decane, 3-mercaptopropyltrimethoxy decane, vinyltrimethoxy decane, N-(2-(vinylbenzylamino) Ethyl) 3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropoxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, etc. . These decane coupling agents are available in the KBM series and KBE series sold by Shin-Etsu Chemical Co., Ltd., etc., and are easily available from the market. The content of the decane coupling agent (F) in the liquid crystal sealing agent is preferably 0.05 to 3% by mass.

In addition to the above components, the liquid crystal sealing agent of the present invention may, for example, be a copolymerization inhibitor, an inorganic filler, a curing accelerator such as an organic acid or an imidazole compound, a pigment, a planarizing agent, an antifoaming agent, a solvent, or the like. additive.

The radical polymerization preventing agent is not particularly limited as long as it can be prevented from reacting with a radical generated by a photopolymerization initiator or a thermal radical polymerization initiator, and the like, and a lanthanoid 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-oxyl, 2,2 6,6-tetramethyl-4-hydroxypiperidin-1-yloxy, 2,2,6,6-tetramethyl-4-methoxypiperidin-1-yloxy, 2,2,6 ,6-tetramethyl-4-phenoxypiperidin-1-yloxy, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, p-benzoquinone, butylated hydroxymethoxybenzene, 2,6-di(tributyl)-4-ethylphenol, 2,6-di(tributyl)cresol, stearyl beta-(3,5-di(tributyl)- 4-hydroxyphenyl)propionic acid Ester, 2,2'-methylenebis(4-ethyl-6-tributylphenol), 4,4'-thiobis-3-methyl-6-tertiary butyl phenol, 4,4 '-Aden bis(3-methyl-6-tertiary butyl phenol), 3,9-bis[1,1-dimethyl-2-[β-(3-tri-butyl-4-hydroxy-) 5-methylphenyl)propoxycarbonyl]ethyl], 2,4,8,10-tetraoxose [5,5]undecane, tetra-[methylene-3-(3',5 '-Di(tertiary butyl)-4'-hydroxyphenylpropionate)methane, 1,3,5-tris(3',5'-di(tri-butyl)-4'-hydroxybenzyl )-Secondary-triazine-2,4,6-(1H,3H,5H)trione, p-methoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N-Asia The ammonium salt of nitrophenylhydroxylamine, trade name: Adeka Stab LA-81, trade name: Adeka Stab LA-82 (made by Adeka Co., Ltd.), etc., is not limited to this. Among these, a radical polymerization preventing agent of a naphthoquinone type, a hydroquinone type, or a nitroso piperidine type is preferable, and a naphthoquinone, a 2-hydroxynaphthoquinone, a hydroquinone, 2,6- Tertiary butyl) p-cresol, Polystop 7300P (manufactured by Berton Co., Ltd.), and most preferred is Polystop 7300P (manufactured by Bodson Co., Ltd.).

The content of the liquid crystal sealing agent to be added in the total amount of the liquid crystal sealing agent of the present invention is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.5% by mass, particularly preferably 0.001 to 0.5% by mass.

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, talc, clay, alumina, Magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium citrate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos fiber, etc., preferably For melting cerium oxide, crystalline cerium oxide, cerium nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, slippery Stone, clay, alumina, aluminum hydroxide, calcium citrate, 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. When the average particle diameter is too large, when a liquid crystal display unit having a narrow pitch is produced, a pitch or the like cannot be formed smoothly when the upper and lower glass substrates are bonded, which is a disadvantage, and therefore it is preferably 3 μm or less, preferably 2 μm or less. The particle diameter can be measured by a laser diffraction scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd.; LMS-30).

In the liquid crystal sealing agent of the present invention, when the inorganic filler is used, the total amount of the liquid crystal sealing agent is usually 5 to 50% by mass, preferably 5 to 40% by mass. When the content of the inorganic filler is less than 5% by mass, the adhesion strength to the glass substrate is lowered, and the moisture resistance reliability is deteriorated. Therefore, the strength may be greatly lowered after moisture absorption. Further, when the content of the inorganic filler is more than 50% by mass, the content of the filler is too large, and it is difficult to be crushed, and the gap of the liquid crystal cell may not be formed.

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, and is preferably an organic carboxylic acid. Specific examples thereof include aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, diphenyl ketone tetracarboxylic acid, and furan dicarboxylic acid, succinic acid, and adipic acid. Dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, tris(2-carboxymethyl) isocyanurate, tris(2-carboxyethyl) isocyanurate Ester, tris(2-carboxypropyl) isocyanurate, bis(2-carboxyethyl) isocyanurate, and the like.

Further, examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl group. -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-di-triazine, 2,4-diamino-6(2'-ten Monoalkylimidazolium (1')) ethyl-di-triazine, 2,4-diamino-6 (2'-ethyl-4-methylimidazolium (1')) ethyl-di- Triazine, 2,4-diamino-6(2'-methylimidazolium(1'))ethyl-di-triazine-isocyanuric acid adduct, 2-methylimidazole isotrimerization 2:3 adduct of cyanic acid, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-3,5-dimethylolimidazole, 2-phenyl-4-hydroxymethyl- 5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the like.

In the liquid crystal sealing agent of the present invention, when a curing accelerator is used, the total amount of the liquid crystal sealing agent is usually 0.1 to 10% by mass, preferably 1 to 5% by mass.

An example of a method of producing the liquid crystal sealing agent of the present invention is as follows. First, the component (C) and the component (D) are heated and mixed in the component (A) as necessary, and after cooling to room temperature, the component (B) and the component (E) are added, and the necessary component (F) and defoaming agent are added. The flattening agent, the solvent, and the like are uniformly mixed by a generally known mixing device such as a three-roll mill, a sand mill, a ball mill, etc., and are filtered by a metal sieve to obtain a liquid crystal sealing agent of the present invention.

In the liquid crystal display unit of the present invention, one of the predetermined electrodes is formed on the substrate, and the substrate is disposed at a predetermined interval, and the present invention is The liquid crystal sealing agent seals the periphery and seals the liquid crystal in the gap. The type of the liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a substrate having a combination of light transmittance of at least one of glass, quartz, plastic, germanium, and the like. In this method, a spacer (a gap control material) such as glass fiber is added to the liquid crystal sealing agent of the present invention, and the liquid crystal sealing agent is applied to the pair of substrates by using a dispenser or a screen printing device. After one side, it is necessary to pre-harden at 80 to 120 °C. Then, the liquid crystal was dropped on the inside of the crucible of the liquid crystal sealing agent, and the other glass substrate was bonded in a vacuum to form a gap. After the gap is formed, it is cured at 90 to 130 ° C for 1 to 2 hours, whereby the liquid crystal display unit of the present invention can be obtained. The liquid crystal display unit of the present invention thus obtained does not cause display failure due to liquid crystal contamination, and is excellent in adhesion and moisture resistance. Examples of the spacer include glass fibers, ceria beads, polymer beads, and the like. The diameter varies depending on the purpose, and is usually 2 to 8 μm, preferably 4 to 7 μm. The amount is usually 0.1 to 4% by mass, preferably 0.5 to 2% by mass, and more preferably 0.9 to 1.5% by mass based on 100% by mass of the liquid crystal sealing agent of the present invention.

In the liquid crystal sealing agent of the present invention, the liquid crystal is extremely low in pollution. Therefore, the liquid crystal display unit produced by using the liquid crystal sealing agent of the present invention can satisfy the necessary characteristics as a liquid crystal display unit having a high voltage holding ratio and a low ion density.

Further, since the cured product obtained by light and heat curing has rubber elasticity, it has extremely high bonding strength. Therefore, by using the liquid crystal sealing agent of the present invention, a liquid crystal display unit having excellent reliability can be produced.

[Examples]

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

[Synthesis Example 1] [Synthesis of resorcinol diglycidyl ether] [step 1]

5,500 g of resorcin, 37,000 g of epichlorohydrin, and 500 g of tetramethylammonium chloride were placed in a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, and dissolved under stirring, and the temperature was raised to 70 °C. Next, 4000 g of fragmented sodium hydroxide was added in sections over 100 minutes, and then the reaction was further carried out at 70 ° C for 1 hour. After completion of the reaction, 15000 g of water was added and washed with water, and then excess epichlorohydrin or the like was distilled off from the oil layer under reduced pressure at 130 °C. 22200 g of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 °C. Then, 1000 g of a 30% by mass aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water 5550 g three times, and methyl isobutyl ketone was distilled off under reduced pressure at 180 ° C to obtain m-phenylene diene. 10550 g of phenol diglycidyl compound. The epoxy resin obtained had an epoxy equivalent of 129 g/eq.

[Synthesis Example 2] [Synthesis of Acrylate of Resorcinol Diglycidyl Ether]

181.2 g of resorcinol diglycidyl ether obtained in the above Synthesis Example 1 was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene as a polymerization inhibiting agent was added thereto, and the temperature was raised to 60 °C. Then, 117.5 g of acrylic acid having 100% by weight of an epoxy group was added, and the temperature was further raised to 80 ° C. Then, 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and stirred at 98 ° C for about 30 hours. The obtained reaction liquid was washed with water and toluene was distilled off, whereby 253 g of an acrylate compound of the objective resorcinol diglycidyl ether was obtained.

[Reference Synthesis Example 1] [Synthesis of acrylates of bisphenol A epoxy resin]

282.5 g of bisphenol A type epoxy resin (product name: YD-8125, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene as a polymerization inhibitor was added. Thus, the temperature was raised to 60 °C. Then, 117.5 g of 100% equivalent of acrylic acid of epoxy group was added, and the temperature was further raised to 80 ° C. Then, 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and 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, whereby 395 g of an acrylate of the objective bisphenol A type epoxy resin was obtained.

[Example 1]

The photopolymerization initiator was added to the acrylate compound of the epoxy resin synthesized in Synthesis Example 1 and the benzenediol diglycidyl ether synthesized in Synthesis Example 2 at a ratio shown in the following Table 1. , dissolved at 90 ° C by heating. Cool to room temperature, add decane coupling agent, heat hardener, organic fill A liquid crystal sealing agent is prepared by filling a filler, an inorganic filler or the like.

[Comparative Example 1]

The bisphenol A type epoxy resin and the acrylate compound of the bisphenol A type epoxy resin synthesized in Reference Synthesis Example 1 and the one described in the table are used as the hardener resin, and other examples and examples The same is used to prepare a liquid crystal sealing agent.

Epoxy compound A: resorcinol diglycidyl ether (synthesized in Synthesis Example 1)

Epoxy Compound B: Bisphenol A type epoxy resin (Epikote 828: Japan Epoxy Resin Co., Ltd.)

Organic filler: core-shell acrylic copolymer (F-351S: Aica Industries, Inc.)

Acrylic compound A: a reaction product of resorcinol diglycidyl ether and acrylic acid (synthesized in Synthesis Example 2)

Acrylic compound B: a reaction product of bisphenol A type epoxy resin (Epikote 828) and acrylic acid (synthesized in Reference Synthesis Example 1)

Photoradical polymerization initiator A: Irg 2959 (manufactured by BASF Corporation) and Karenz MOI (manufactured by Showa Denko Co., Ltd.) reaction product (refer to Japanese Patent No. 4468920)

Photoradical polymerization initiator B: Lucirin TPO (manufactured by BASF Corporation)

Thermal Hardener A: Diterpenoid azelaic acid (SDH: manufactured by Japan Finechem Co., Ltd.)

Thermal Hardener B: Diterpenic isophthalic acid (IDH: manufactured by Japan Finechem Co., Ltd.)

Decane coupling agent A: 3-glycidoxypropyltrimethoxy decane (Sila-Ace S-510: manufactured by Chisso Corporation)

Decane coupling agent B: N-2-(aminoethyl)-3-aminopropyltrimethoxy decane (KBM-603: manufactured by Shin-Etsu Chemical Co., Ltd.)

Inorganic filler A: cerium oxide (SE-1030SEZ: manufactured by Admatechs)

Inorganic filler B: Alumina (SP-C: C.I. Chemical Co., Ltd.)

Inorganic filler C: Zirconium phosphate (IXE-100: manufactured by Toagosei Co., Ltd.)

Rubber: Paraloid (EXL-2655: manufactured by Rphm and Haas)

The evaluation test was carried out in the following manner.

[Solubility test of epoxy compound into liquid crystal]

The liquid crystal sealing agent was sandwiched between two release films (manufactured by Lintec Co., Ltd.: PET-38 AL-5), and formed into a thickness of 100 μm using a laminator, and then a UV irradiator (UVX-manufactured by Ushio Inc.) was used. 02516S1AFL01), irradiated through a film at an illuminance of 100 mW/cm ² and an integrated light amount of 4000 mJ/cm ² , and then peeled off the release film to prepare a cured film. 0.1 g of the liquid crystal sealing agent after hardening was placed in a sample bottle, and 1 g of liquid crystal (manufactured by Merck Co., Ltd.: MLC-3007) was added, and the mixture was placed in an oven at 120 ° C for 1 hour. After standing at room temperature for 30 minutes, the liquid crystal was taken out, and pentadecane was used as an internal standard, and the amount of eluted epoxy resin was quantitatively determined by gas chromatography for the component dissolved in the liquid crystal. The results are summarized in Table 2.

[Next strength test]

The glass substrate was cut into two types of 12 mm × 24 mm and 18 mm × 30 mm, and a liquid crystal sealing agent (including a 1% 5.25 μm gap agent (manufactured by Nippon Electric Glass Co., Ltd.: PF-50S) was dispensed by a dispenser or a screen printing machine. The glass substrate of 12 mm × 24 mm was applied to the glass substrate of 18 mm × 30 mm, and a UV irradiation machine (UVX-02516S1AFL01, manufactured by Ushio Inc.) was used, and the illuminance was 100 mw/cm ² . A test piece was produced by irradiating an amount of light of 3000 mJ/cm ² to form a test piece. The obtained test piece was lifted up to the glass end using a bonding strength tester (manufactured by Seiko Co., Ltd.: SS-30WD) to measure the subsequent strength. The results are summarized in Table 2.

From the results of the second table, it was confirmed that the liquid crystal sealing agent for liquid crystal dropping method of the invention of the present application has low liquid crystal contamination (e.g., solubility of epoxy resin to liquid crystal) and high adhesion strength. As described above, the liquid crystal sealing agent for liquid crystal dropping method of the invention of the present application can easily produce an excellent liquid crystal display unit.

[Industrial Applicability]

The liquid crystal sealing agent for liquid crystal dropping method of the present invention has low liquid crystal contamination, so that high definition, high-speed reaction, low voltage driving, and long life of the liquid crystal display unit can be achieved, and the bonding strength is extremely high. Excellent, it provides a liquid crystal panel excellent in durability such as vibration, impact, and dust resistance.

Claims (12)

A liquid crystal sealing agent for liquid crystal dropping method, which comprises (A) an epoxy compound and (B) an organic filler, and the content of the component (B) is 6 mass times or more and 20 mass times or less of the component (A). The liquid crystal sealing agent for liquid crystal dropping method of claim 1, wherein the organic filler of the component (B) is an organic filler which forms a core-shell structure according to the two types of rubber. The liquid crystal sealing agent for liquid crystal dropping method of claim 1, wherein the component (B) organic filler is an organic filler which forms a core-shell structure based on two kinds of (meth)acrylic rubber. The liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 3, which further contains (C) an acrylic compound. The liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 4, wherein the component (A) is an epoxy compound having a resorcinol skeleton. The liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 5, wherein the component (C) is a (meth) acrylate compound of resorcinol diglycidyl ether. The liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 6, which further contains (D) a photoradical polymerization initiator and/or a thermal radical polymerization initiator. The liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 7, which further contains (E) a heat hardener. Liquid crystal sealing agent for liquid crystal dropping method of claim 8, wherein The aforementioned component (E) is an organic acid cerium compound. The liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 6, which further contains (F) a decane coupling agent. A method of manufacturing a liquid crystal display unit, characterized in that the liquid crystal according to any one of claims 1 to 10 is formed by dropping liquid crystal on one of the liquid crystal display units composed of two substrates. After the inside of the crucible of the liquid crystal sealing agent for the method is dropped, the other substrate is bonded, and then cured by ultraviolet rays and/or heat. A liquid crystal display unit which is sealed by a cured product obtained by hardening a liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 10.