JP6426050B2 - Liquid crystal sealing agent and liquid crystal display cell using the same - Google Patents

Description

  The present invention relates to a liquid crystal sealing agent which is cured by light and / or heat, and relates to a liquid crystal sealing agent used in a liquid crystal dropping method. More specifically, the present invention relates to a liquid crystal sealing agent for liquid crystal dropping method, which is excellent in handling property, excellent in moisture resistance reliability, low in liquid crystal contamination, and high in adhesive strength.

  With the recent enlargement of liquid crystal display cells, a so-called liquid crystal dropping method with higher mass productivity has been proposed as a method of manufacturing liquid crystal display cells (see Patent Document 1 and Patent Document 2). Specifically, the liquid crystal is dropped inside the edge of the liquid crystal sealant formed on one of the substrates, and then the other substrate is bonded to seal the liquid crystal.

  However, in the liquid crystal dropping method, since the liquid crystal sealing agent in an uncured state comes in contact with the liquid crystal, at that time, the components of the liquid crystal sealing agent dissolve (elute) in the liquid crystal and reduce the resistance of the liquid crystal. There is a problem in that display defects occur.

  In order to solve this problem, at present, a combination of light and heat as a liquid crystal sealing agent for liquid crystal dropping method is used and put into practical use (Patent Documents 3 and 4). The liquid crystal dropping method using this liquid crystal sealant is characterized in that the liquid crystal sealant sandwiched between the substrates is irradiated with light for primary curing, and then heated for secondary curing. According to this method, the uncured liquid crystal sealing agent can be rapidly cured by light, and the dissolution (elution) of the liquid crystal sealing agent component in the liquid crystal can be suppressed. Furthermore, photocuring alone causes the problem of insufficient adhesive strength due to curing shrinkage at the time of photocuring, etc. However, in the case of a light and heat combined type, the stress relaxation effect is obtained by secondary curing by heating, and such a problem can be eliminated. Have.

  However, in recent years, along with the miniaturization of liquid crystal display elements, a light shielding portion in which light does not hit the liquid crystal sealing agent is generated by the metal wiring portion of the array substrate of the liquid crystal display element or the black matrix portion of the color filter substrate. The problem of defects is more serious than before. That is, due to the presence of the light shielding portion, the primary curing by the light becomes insufficient, and a large amount of uncured components remain in the liquid crystal sealing agent. In this state, if the process proceeds to a secondary curing process by heat, the dissolution of the uncured component into the liquid crystal has the result of being accelerated by heat and causes a display failure near the seal.

  In order to solve this problem, a method of improving the reactivity of the curable compound and advancing the curing before dissolving in the liquid crystal is very useful. For this reason, various studies have been made to improve the thermal reactivity. In the light shielding portion, a liquid crystal sealing agent which has not been sufficiently cured by light is made to react promptly from a low temperature, thereby suppressing liquid crystal contamination. For example, Patent Documents 5 and 6 disclose methods using thermal radical polymerization initiators. Patent Document 7 discloses a method of using a polyvalent carboxylic acid as a curing accelerator.

  However, the addition of a curing accelerator such as a thermal radical polymerization initiator or a polyvalent carboxylic acid can not be said to be sufficient to realize low liquid crystal contamination since there is elution to the liquid crystal itself. In addition, these components have the disadvantage of worsening the storage stability rather than the effect of increasing the reaction rate.

  As described above, although the development of the liquid crystal sealing agent for the liquid crystal dropping method is very energetically carried out, the liquid crystal sealing agent also has good storage stability while realizing low liquid crystal contamination. Has not been realized yet.

Japanese Patent Application Laid-Open No. 63-179323 Japanese Patent Application Laid-Open No. 10-239694 Patent No. 3583326 JP, 2004-61925, A Unexamined-Japanese-Patent No. 2004-126211 JP, 2009-8754, A International Publication 2008/004455

  The present invention relates to a liquid crystal sealing agent which is cured by heat and is extremely excellent in low liquid crystal contamination, thereby enabling high definition, high speed response, low voltage drive, and long life of a liquid crystal display device. Since it is excellent also in storage stability, it proposes the liquid crystal sealing agent for liquid crystal dropping methods whose workability is very good.

  The present inventors have found that the combination of a radical polymerization initiator and two or more types of polymerization inhibitors solves the above-mentioned problems, and the present invention has been achieved. That is, the present invention relates to the following 1) to 15). In the present specification, when "(meth) acrylic" is described, it means "acrylic" and / or "methacrylic".

1)
The liquid-crystal sealing compound for liquid crystal dropping methods which contains (A) 2 or more types of radical polymerization inhibitors, (B) radical polymerization initiator, and (C) (meth) acrylated epoxy compound.
2)
(A) One of two or more types of radical polymerization inhibitors is a polymerization inhibitor having a phenolic hydroxy group, and the other is a polymerization inhibitor having a free radical. Sealant.
3)
(B) The liquid-crystal sealing compound for liquid crystal dropping methods as described in said 1) or 2) whose radical polymerization initiator is a (B-1) thermal radical polymerization initiator.
4)
(B-1) The liquid crystal dropping method according to the above 3), wherein the thermal radical polymerization initiator does not contain an oxygen-oxygen bond (-O-O-) and a nitrogen-nitrogen bond (-N = N-) in the molecule. Sealant.
5)
The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1) to 4), further comprising (D) a urethane (meth) acrylate.
6)
Furthermore, the liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said 1) thru | or 5) which contains the (E) organic filler.
7)
6. Liquid crystal sealing compound for liquid crystal dropping method as described in said 6) whose said component (E) is a rubber | gum fine particle.
8)
7. The liquid crystal sealing agent for liquid crystal dropping method according to 7), wherein the component (E) is one or more rubber fine particles selected from the group consisting of acrylic rubber, styrene rubber, styrene olefin rubber and silicone rubber.
9)
(B) The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above 1), 2) and 5) to 8), wherein the radical polymerization initiator is (B-2) a photo radical polymerization initiator.
10)
Furthermore, the liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said 1) thru | or 9 containing the curable compound which has (F) epoxy group, and the (G) thermosetting agent.
11)
11. Liquid crystal sealing compound for liquid crystal dropping methods as described in said 10 whose said component (G) is organic acid hydrazide.
12)
Furthermore, the liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said 1) thru | or 11 which contains a (H) silane coupling agent.
13)
The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1) to 12), further comprising (I) an inorganic filler.
14)
In a liquid crystal display cell composed of two substrates, liquid crystal was dropped inside the edge of the liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1) to 13) formed on one of the substrates Thereafter, the other substrate is bonded, and then cured by light and / or heat.
15)
The liquid crystal display cell sealed by the hardened | cured material obtained by hardening | curing the liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said 1) thru | or 13).

  The liquid crystal sealing material of the present invention has extremely small influence on the liquid crystal display characteristics, and thus enables high definition, high speed response, low voltage drive, and long life of the liquid crystal display element. Furthermore, since the storage stability is also excellent, a highly reliable liquid crystal display element can be efficiently manufactured.

  The liquid crystal sealing agent of the present invention contains (A) two or more types of radical polymerization inhibitors, (B) a radical polymerization initiator, and (C) a (meth) acrylated epoxy compound.

In recent years, liquid crystal sealing agents mainly use a method of adding a thermal radical polymerization initiator that generates radicals by heat or a photo radical polymerization initiator that generates radicals by low energy long wavelength light to improve the curability of the light shielding portion It has become. In the case of a thermal radical polymerization initiator, the lower the reaction initiation temperature, the faster the curing of the sealing agent and the less the elution of the component of the sealing agent in the liquid crystal. Moreover, in the case of a radical photopolymerization initiator, the curability will be better if it shows a large absorption coefficient at a long wavelength. However, such liquid crystal sealants have poor storage stability and may gel during use.
In order to counter this gelation, it is known to add a polymerization inhibitor, suppress the reaction of the radical polymerization initiator, and enhance the storage stability. However, there is also a problem that the liquid crystal contamination is aggravated by suppressing the reaction of the radical polymerization initiator, and the solution is considered to be difficult as a contradictory problem.
The present inventors focused on the function or structure of the polymerization inhibitor as a result of sharp studies, and by using two types of polymerization inhibitors in combination, they have sufficient polymerization inhibiting ability, and further for the reaction suppression of the radical polymerization initiator It has been discovered that a liquid crystal sealing agent that can reduce the accompanying liquid crystal contamination can be realized.

The liquid crystal sealing agent of the present invention uses (A) two or more types of radical polymerization inhibitors. The radical polymerization inhibitor is not particularly limited as long as it is a compound that reacts with a radical generated from a photopolymerization initiator, a thermal radical polymerization initiator or the like to prevent polymerization, and quinones, piperidines, hindered and the like Phenolic, nitroso and free radical components can be used. Specifically, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 1,4 dihydroxynaphthalene, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6 6,6-Tetramethyl-4-hydroxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-methoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4 -Phenoxypiperidine-1-oxyl, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t -Butylcresol, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) ester Pyeonate, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis-3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6) -T-Butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8 10-tetraoxaspiro [5,5] undecane, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl propionate) methane, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, paramethoxyphenol, 4-methoxy-1-naphthol , Thio Diphenylamine, aluminum salt of N-nitrosophenylhydroxyamine, trade name Adekastab LA-81, trade name Adekastab LA-82 (made by Adeka Co., Ltd.), 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl Free radical, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 3-carboxy-2 2,2,5,5-Tetramethylpyrrolidine 1-oxyl free radical, 2- (14-carboxytetradecyl) -2-ethyl-4,4-dimethyl-3-oxazolidinyloxy free radical, 4-hydroxy- 2,2,6,6-Tetramethylpiperidine 1-oxylbenzoa Free radical, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo The use of two or more of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical and the like can be mentioned, and It is not limited. Among them, naphthoquinone type, hydroquinone type, nitroso type piperazine type and free radical type radical polymerization inhibitors are preferable, and naphthoquinone, 1,4 dihydroxy naphthalene, 2-hydroxy naphthoquinone, hydroquinone, 2,6-di-tert-butyl- P-cresol, polystop 7300P (manufactured by Shoto Co., Ltd.), 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical is more preferable, and hydroquinone, 1,4 dihydroxynaphthalene, polystop 7300P Most preferred is 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Satsuto Co., Ltd.).
The (B) two or more radical polymerization inhibitors preferably have different functions or structures, but in particular, the radical polymerization inhibitor having a phenolic hydroxy group and the radical polymerization having a free radical It is preferable to use an agent in combination.
The content of the radical polymerization inhibitor is preferably 0.0001 to 2% by mass, more preferably 0.1 to 1.5% by mass, based on the total amount of the liquid crystal sealing agent according to the present invention, combining the above two types. .3 to 1% by mass is particularly preferred.

  In the liquid crystal sealing agent of the present invention, a component (B) radical polymerization initiator is used. The radical polymerization initiator may be either (B-1) thermal radical polymerization initiator or (B-2) photo radical polymerization initiator, or both may be used in combination.

Among the radical polymerization initiators, (B-1) a thermal radical polymerization initiator is used to improve the thermal reactivity. The thermal radical polymerization initiator is not particularly limited as long as it generates a radical by heating to initiate chain polymerization reaction, but organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, benzopinacol, etc. Preferably, benzopinacol is used. For example, as organic peroxides, Kayamec ^RTM A, M, R, L, LH, SP-30 C, Percadox CH-50 L, BC-FF, Cadox B-40 ES, Percadox 14, Trigonox ^RTM 22-70 E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester ^RTM P-70, TMPO-70, CND-C70, OO-50 E, AN, Kayabutyl ^RTM B, Perka Dox 16 Kayacaron ^RTM BIC-75, AIC-75 (manufactured by Kayaku Akzo Co., Ltd.), Permec ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC, PATM H, C, V, 22, MC, Percure ^RTM AH, AL, HB, Perbutyl ^RTM H, C, ND, L, Perkmill ^{RT M} H, D, Peroyl ^RTM IB, IPP, Perocta ^RTM ND, is available as such is a commercially available product (manufactured by NOF Co., Ltd.).
In addition, as a thermal radical polymerization initiator, the case where 10 hour half life temperature is 60 degrees C or less is preferable, and the case where it is 50 degrees C or less is still more preferable. Even if it is a thermal radical polymerization initiator having good reactivity, the composition of the present invention does not impair the storage stability and becomes an excellent liquid crystal sealing agent. In addition, the preferable lower limit of the 10-hour half-life temperature is about 25 ° C.

  As an azo compound, VA-044, V-070, VPE-0201, VSP-1001 etc. (made by Wako Pure Chemical Industries Ltd.) etc. are available as a commercial item. In the present specification, superscript RTM means a registered trademark.

Preferred as the component (B-1) are thermal radical polymerization initiators having no oxygen-oxygen bond (-O-O-) or nitrogen-nitrogen bond (-N = N-) in the molecule. A thermal radical polymerization initiator having an oxygen-oxygen bond (-O-O-) or a nitrogen-nitrogen bond (-N = N-) in the molecule emits a large amount of oxygen or nitrogen when a radical is generated, so a liquid crystal sealing agent It hardens in a state where air bubbles are left inside, and there is a possibility that the characteristics such as adhesive strength may be reduced. Particularly preferred are benzopinacol-based thermal radical polymerization initiators (including chemically modified benzopinacol). Specifically, 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-tetra (4-Methoxyphenyl) ethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, 1,2-bis (triethylsiloxy) -1,1,2,2-tetraphenyl Ethane, 1,2-bis (t-butyldimethylsiloxy) -1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1- Hydroxy-2-trie Lucyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1,1,2,2-tetraphenylethane, etc. may be mentioned, preferably 1-hydroxy-2 -Trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1 1,2,2-tetraphenylethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylsiloxy-1,1 , 2,2-tetraphenylethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, particularly preferably 1,2-biphenyl. It is (trimethylsiloxy) 1,1,2,2-phenylethane.
The benzopinacol is commercially available from Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., and the like. In addition, etherification of the hydroxy group of benzopinacol can be easily synthesized by a known method. The silyletherification of the hydroxy group of benzopinacol can be obtained by synthesis by heating the corresponding benzopinacol and various silylating agents under a basic catalyst such as pyridine. As silylating agents, generally known trimethylsilylating agents such as trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) and triethylsilylating agents Triethylchlorosilane (TECS), t-butylmethylsilane (TBMS) as a t-butyldimethylsilylating agent, etc. may be mentioned. These reagents can be easily obtained from the market such as silicon derivative manufacturers. The reaction amount of the silylating agent is preferably 1.0 to 5.0 moles per 1 mole of the hydroxy group of the target compound. More preferably, it is 1.5 to 3.0 times mol. If the molar ratio is less than 1.0 times the molar ratio, the reaction efficiency will be poor, and the reaction time will be long, thereby promoting thermal decomposition. If the amount is more than 5.0 times by mole, separation may be deteriorated during the recovery or purification may be difficult.

  It is preferred that the component (B-1) be finely divided and uniformly dispersed. The average particle size is preferably 5 μm or less, more preferably 3 μm or less, because if it is too large, it may cause defects such as gap formation when bonding the upper and lower glass substrates together during production of narrow gap liquid crystal display cells. . Moreover, although it may be fine without limit, the lower limit is usually about 0.1 μm. The particle size can be measured by a laser diffraction / scattering type particle size distribution measuring apparatus (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).

  The content of the component (B-1) is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass in the total amount of the liquid crystal sealing agent, and 0.001 to 3%. % By weight is particularly preferred.

The liquid crystal sealing agent of the present invention contains a component (B-2) photoradical polymerization initiator in order to form a photocurable liquid crystal sealing agent. The photo radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by irradiation of UV or visible light and initiates chain polymerization reaction, and examples thereof include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, Benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphos Hin oxide, camphor quinone, 9-fluorenone, diphenyl disulfide etc. can be mentioned. Specifically, IRGACURE ^RTM 651, 184, 2959, 127, 907, 369, 379 EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE ^RTM 1173, LUCIRIN ^RTM TPO (all manufactured by BASF Corporation), Seikoll ^RTM Z, BZ, BEE, BIP, BBI (all manufactured by Seiko Instruments Inc.) and the like can be mentioned.
Further, from the viewpoint of liquid crystal staining, it is preferable to use one having a (meth) acryl group in the molecule, for example, 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl]- The reaction product with 2-hydroxy-2 methyl-1-propan-1-one is preferably used. This compound can be obtained by preparation according to the method described in WO 2006/027982.

  The content of the component (B-2) photopolymerization initiator usable in the liquid crystal sealant of the present invention in the liquid crystal sealant is usually 0.1 to 20% by mass, preferably the total amount of the liquid crystal sealant of the present invention Is 0.2 to 15% by mass.

The liquid crystal sealing agent of the present invention contains a (meth) acrylated epoxy compound as the component (C).
The component (C) (meth) acrylated epoxy compound is preferably an epoxy acrylate which can be obtained by a well-known reaction of an epoxy compound and (meth) acrylic acid. Further, in this case, all of the epoxy groups may be (meth) acrylated or a part may be (meth) acrylated. For example, (meth) acrylic acid and a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibin etc.) having a predetermined equivalent ratio to an epoxy compound, and a polymerization inhibitor (eg, methoquinone, Hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene and the like are added to obtain an esterification reaction at, for example, 80 to 110 ° C. Although it does not specifically limit as an epoxy compound used as a raw material, The epoxy compound of 2 or more functions is preferable, For example, a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a phenol novolak epoxy compound Cresol novolac epoxy compound, bisphenol A novolac epoxy compound, bisphenol F novolac epoxy compound, alicyclic epoxy compound, aliphatic chain epoxy compound, glycidyl ester epoxy compound, hydantoin epoxy compound, isocyanurate epoxy compound , Phenol novolac type epoxy compounds having a triphenolmethane skeleton, other, diglycidyl ether of difunctional phenols, difunctional alcohols Glycidyl ethers, and their halides, and the like hydrogenated product. Among these, from the viewpoint of liquid crystal staining, bisphenol-type epoxy compounds and novolac-type epoxy compounds are more preferable. Further, the ratio of the epoxy group to the (meth) acryloyl group is not limited, and is appropriately selected from the viewpoint of process compatibility and liquid crystal contamination.

  From a viewpoint of content of a component (C), 20-90 mass% is preferable in a liquid-crystal sealing compound component, More preferably, it is 40-70 mass%.

The liquid-crystal sealing compound of this invention may contain a urethane (meth) acrylate compound as a component (D). The urethane (meth) acrylate compound can impart flexibility to the cured product, thereby contributing to the improvement of the adhesive strength.
The urethane (meth) acrylate is not particularly limited as long as it is a (meth) acrylic resin having a urethane bond, but polyether modified urethane (meth) acrylate, polyester modified (meth) acrylate, polycarbonate modified (meta) And the like. Specifically, as the polyether modified urethane (meth) acrylate, KAYARAD UX-4101, KAYARAD UX-2301, KAYARAD UX-2201 (all manufactured by Nippon Kayaku Co., Ltd.), and as the polyester modified (meth) acrylate, KAYARAD UX-3301 And KAYARAD UX-3204 (manufactured by Nippon Kayaku Co., Ltd.), and examples of polycarbonate-modified (meth) acrylates include KAYARAD UXT-6100 (manufactured by Nippon Kayaku Co., Ltd.), and the like. KAYARAD UX-3204 and KAYARAD UXT-6100 are preferable, and KAYARAD UXT-6100 is more preferable.

The liquid crystal sealing agent of the present invention may contain an organic filler as the component (E). Examples of the organic filler include urethane particles, acryl particles, styrene particles, styrene olefin particles, and silicone particles. In addition, as silicone microparticles, KMP-594, KMP-597, KMP-598 (made by Shin-Etsu Chemical Co., Ltd.), Trefil ^RTM E-5500, 9701, EP-2001 (made by Toray Dow Corning) are preferable, and as urethane microparticles, JB- 800T, HB-800BK (Kegami Kogyo Co., Ltd.), preferred as styrene fine particles are Lavalon ^RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (Mitsubishi Chemical), and as styrene olefin fine particles is Septon ^RTM SEPS 2004, SEPS 2063 is preferred.
These organic fillers may be used alone or in combination of two or more. Moreover, it is good also as core-shell structure using 2 or more types. Among these, acrylic fine particles and silicone fine particles are preferable.
When using the said acryl fine particle, the case where it is an acryl rubber of the core-shell structure which consists of 2 types of acryl rubber is preferable, Especially preferably, a thing whose core layer is n-butyl acrylate and whose shell layer is methyl methacrylate is preferable. This is marketed by Aika Industry Co., Ltd. as Zefiac ^RTM F-351.
Further, as the above-mentioned silicone fine particles, there can be mentioned organopolysiloxane crosslinked powder, linear dimethylpolysiloxane crosslinked powder and the like. Moreover, as composite silicone rubber, what coated silicone resin (for example, polyorgano silsesquioxane resin) on the surface of the said silicone rubber is mention | raise | lifted. Among these fine particles, particularly preferred are silicone rubber of linear dimethylpolysiloxane crosslinked powder or complex silicone rubber microparticles of silicone resin-coated linear dimethylpolysiloxane crosslinked powder. These may be used alone or in combination of two or more. Also, preferably, the shape of the rubber powder is spherical with less thickening of viscosity after addition. When the component (D) is used in the liquid crystal sealant of the present invention, it is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the liquid crystal sealant.

  The liquid crystal sealing agent of the present invention may further contain a curable resin having an epoxy group (F), if necessary. As the curable resin having such an epoxy group, for example, bisphenol A epoxy compound, bisphenol F epoxy compound, bisphenol S epoxy compound, phenol novolac epoxy compound, cresol novolac epoxy compound, bisphenol A novolac epoxy Compound, bisphenol F novolac epoxy compound, alicyclic epoxy compound, aliphatic chain epoxy compound, glycidyl ester type epoxy compound, hydantoin type epoxy compound, isocyanurate type epoxy compound, phenol novolac type epoxy compound having triphenolmethane skeleton And others, diglycidyl ethers of difunctional phenols, diglycidyl ethers of difunctional alcohols, and their halides And hydrogenated products thereof.

  The liquid crystal sealing agent of the present invention may contain component (G) a thermosetting agent. The heat curing agent is not particularly limited, and examples thereof include polyhydric amines, polyhydric phenols, hydrazide compounds and the like, and polyhydrazide compounds are particularly preferably used. For example, aromatic hydrazide terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridine dihydrazide, 1,2,4-benzenetrihydrazide, 1,4,5,8-naphthoic acid Tetrahydrazide, pyromellitic acid tetrahydrazide and the like can be mentioned. In the case of aliphatic hydrazide compounds, for example, form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, 1,4- Cyclohexane dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylene bissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexane tricarboxylic acid trihydrazide, 1,3-bis (hydrazino carbono Hydantoin skeleton such as ethyl) -5-isopropyl hydantoin, preferably valine hydantoin skeleton (where carbon atom of hydantoin ring is substituted by isopropyl group Compounds, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonyl). Examples include propyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate and the like. From the balance of curing reactivity and latency, preferably, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris ( 2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, particularly preferably malonic acid dihydrazide, tris (2-hydrazinocarbonylethyl) isocyanurate. The content of the thermosetting agent (B) is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on the total amount of the liquid crystal sealing agent, and two or more of them may be mixed. You may use it.

The liquid crystal sealing agent of the present invention can improve adhesion strength and moisture resistance by adding a silane coupling agent as the component (H).
As component (H), 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl tritrile Methoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropyl Chill dimethoxysilane, 3-chloropropyl trimethoxy silane, and the like. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. as KBM series, KBE series etc., they are easily available from the market. When using a component (H) in the liquid-crystal sealing compound of this invention, 0.05-3 mass% is suitable in the liquid-crystal sealing compound total amount.

  In the liquid crystal sealing agent of the present invention, the component (I) inorganic filler can be used to improve adhesion strength and humidity resistance. As this (I) inorganic filler, fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, Aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc. are mentioned, and preferably fused silica, crystalline silica, nitrided Silicon, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, more preferably fused silica, crystalline silica, agar Mina, is a talc. These inorganic fillers may be used as a mixture of two or more. The average particle size is 3 μm or less, preferably 2 μm or less, because it is a defect factor such that when the size is too large, the gap formation during bonding of the upper and lower glass substrates can not be made well. The particle size was measured by a laser diffraction / scattering type particle size distribution measuring apparatus (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).

  The content of the inorganic filler (I) in the liquid crystal sealing agent which can be used in the liquid crystal sealing agent of the present invention is usually 3 to 60% by mass, preferably 5 to 50% by mass based on the total amount of the liquid crystal sealing agent of the present invention is there. If the content of the inorganic filler is too small, the adhesive strength to the glass substrate may be reduced, and the moisture resistance may be deteriorated, so that the reduction in adhesive strength after moisture absorption may be increased. In addition, when the content of the inorganic filler is too large, the filler content is too large, so that it may be difficult to be crushed and the gap of the liquid crystal cell may not be formed.

  The inorganic filler (I) which can be used in the liquid crystal sealing agent of the present invention may be surface-treated with an epoxysilane compound or the like having a structure in which an epoxy skeleton and an alkoxysilyl group are bonded via a hydroxy group on the inorganic filler surface. . By performing such surface treatment, the compatibility between the inorganic filler (I) and the resin is improved, and the moisture resistance and the adhesion are improved.

  If necessary, monomers and / or oligomers of (meth) acrylic acid ester may be used in the liquid crystal sealing agent of the present invention. Examples of the monomer or oligomer of (meth) acrylic acid ester include a reaction product of dipentaerythritol and (meth) acrylic acid, and a reaction product of dipentaerythritol / caprolactone and (meth) acrylic acid.

In the liquid crystal sealing agent of the present invention, additives such as a curing accelerator such as an organic acid and imidazole, a pigment, a leveling agent, an antifoaming agent, and a solvent can be further added, if necessary.
Examples of the curing accelerator include organic acids and imidazoles.
As an organic acid, although an organic carboxylic acid, an organic phosphoric acid, etc. are mentioned, the case where it is an organic carboxylic acid is preferable. Specifically, aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, thiodipropionic acid And cyclohexanedicarboxylic acid, tris (2-carboxymethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, tris (2-carboxypropyl) isocyanurate, bis (2-carboxyethyl) isocyanurate and the like. .
In addition, as an imidazole compound, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 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′-methylimidazole (1 ′ )) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl-4-methylimidazole (1 ′)) Ethyl-s-triazine, 2,4-diamino-6 (2′- Methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2: 3 adduct of 2-methylimidazole isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethyl Examples include imidazole, 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, it is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the liquid crystal sealing agent.

As an example of the method for obtaining the liquid crystal sealing agent of the present invention, the following methods are available.
First, the component (A), the component (C), and if necessary, the component (D) and the component (F) are mixed and stirred, and then heated to 90 ° C. After heating and dissolving the photo radical polymerization initiator (component (B-2)) there, it cools to room temperature, adds a heat radical polymerization initiator (B-1), and it is a silane as needed. After adding a coupling agent (component (H)), an inorganic filler (component (I)), a thermosetting agent (component (G)), an organic filler (component (E)), etc. and stirring, a 3-roll mill is used. The liquid crystal sealing agent of the present invention can be produced by dispersing it and filtering it through a metal mesh.

In the liquid crystal display cell of the present invention, a pair of substrates having predetermined electrodes formed on the substrates is disposed opposite to each other at a predetermined distance, the periphery is sealed with the liquid crystal sealing agent of the present invention, and liquid crystal is sealed in the gap. is there. The type of liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a combination of light transmitting property to at least one of glass, quartz, plastic, silicon and the like. As the manufacturing method, after adding a spacer (space control material) such as glass fiber to the liquid crystal sealing agent of the present invention, the liquid crystal sealing agent is applied to one of the pair of substrates using a dispenser or a screen printing apparatus. After curing, temporary curing is performed at 80 to 120 ° C., if necessary. Thereafter, liquid crystal is dropped on the inner side of the ridge of the liquid crystal sealing agent, the other glass substrate is superposed in vacuum, and the gap is taken out. After forming the gap, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C. for 1 to 2 hours. In the case of using as a light and heat combination type, the liquid crystal sealing agent portion is irradiated with ultraviolet light by an ultraviolet light irradiator and light curing is performed. The ultraviolet irradiation dose is preferably 500 to 10000 mJ / cm ² , more preferably 1000 to 6000 mJ / cm ² . Thereafter, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C. for 1 to 2 hours, as necessary. The liquid crystal display cell of the present invention thus obtained is free from display defects due to liquid crystal contamination, and is excellent in adhesion and moisture resistance. As a spacer, glass fiber, a silica bead, a polymer bead etc. are mention | raise | lifted, for example. The diameter varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount thereof used is usually about 0.1 to 4% by mass, preferably 0.5 to 2% by mass, and more preferably about 0.9 to 1.5% by mass with respect to 100% by mass of the liquid crystal sealing agent of the present invention is there.

  The liquid crystal sealing material of the present invention is excellent in reactivity, and crosslinks between molecules are rapidly made by heat, so that the elution of the component into the liquid crystal is extremely small, and the display defect of the liquid crystal display cell can be reduced. It is possible. Moreover, since it is excellent also in storage stability, it is suitable for manufacture of a liquid crystal display cell. Furthermore, since the cured product is excellent in various cured product characteristics such as adhesive strength, heat resistance, moisture resistance, etc., it is possible to create a liquid crystal display cell excellent in reliability by using the liquid crystal sealing agent of the present invention. is there. Moreover, the liquid crystal display cell produced using the liquid-crystal sealing compound of this invention also satisfies the characteristic required as a liquid crystal display cell that a voltage holding ratio is high and an ion density is low.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. In the following description, "part" and "%" are based on mass unless otherwise specified.

[Reference synthesis example 1]
[Synthesis of epoxy acrylate of bisphenol F epoxy resin]
Dissolve 68.9 g of bisphenol F-type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDF-8170C, epoxy equivalent 160 g / eq) in 66.7 g of toluene, add 1500 ppm of dibutylhydroxytoluene as a polymerization inhibitor to this, and adjust to 60 ° C The temperature rose. Thereafter, 31.1 g of acrylic acid was added and the temperature was further raised to 80 ° C. 1500 ppm of trimethyl ammonium chloride as a reaction catalyst was added thereto, followed by stirring at 98 ° C. for about 30 hours. The resulting reaction solution was washed with water and toluene was distilled off to obtain an epoxy acrylate of bisphenol F epoxy.

[Reference synthesis example 2]
[Synthesis of epoxy acrylate of resorcin diglycidyl ether]
In 266.8 g of toluene was dissolved 181.2 g of resorcin diglycidyl ether (manufactured by Nagase ChemteX Co., Ltd.), 0.8 g of dibutylhydroxytoluene as a polymerization inhibitor was added thereto, and the temperature was raised to 60 ° C. Thereafter, 117.5 g of acrylic acid of 100% equivalent of epoxy group is added and the temperature is further raised to 80 ° C. 0.6 g of trimethyl ammonium chloride as a reaction catalyst is added to this and stirred at 98 ° C. for about 30 hours, A reaction solution was obtained. The reaction solution was washed with water and toluene was distilled off to obtain 293 g of the desired epoxy acrylate of resorcin diglycidyl ether.

[Reference synthesis example 3]
[Synthesis of 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane]
100 parts (0.28 mol) of commercially available benzopinacol (manufactured by Tokyo Kasei Co., Ltd.) was dissolved in 350 parts of dimethyl formaldehyde. 32 parts (0.4 mole) of pyridine as a base catalyst and 150 parts (0.58 mole) of BSTFA (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silylating agent were added thereto, and the temperature was raised to 70 ° C. and stirred for 2 hours. The resulting reaction solution was cooled and, while stirring, 200 parts of water was added to precipitate the product and deactivate the unreacted silylating agent. The precipitated product was separated by filtration and thoroughly washed with water. The resulting product was then dissolved in acetone, recrystallized by adding water and purified. 105.6 parts (yield 88.3%) of the target 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane were obtained.
As a result of analysis by HPLC (high performance liquid chromatography), the purity was 99.0% (area percentage).

(Preparation of sealing agent for liquid crystal dropping method)
[Examples 1 to 5, Comparative Examples 1 to 10]
After mixing and stirring each component (component (A), component (C) and, if necessary, component (D), component (F) in the proportions shown in Table 1 below, the mixture was heated to 90 ° C.) According to the above, the photo radical polymerization initiator (component (B-2)) is dissolved by heating and cooled to room temperature, and the thermal radical polymerization initiator (B-1) is added, and the silane coupling agent (if necessary) Component (H), inorganic filler (component (I)), thermosetting agent (component (G)), organic filler (component (E)), (meth) acrylic acid monomer, etc. are added and stirred, 3 It disperse | distributed with this roll mill, it filtered with metal mesh (635 mesh), and prepared the sealing agent Examples 1-5 for liquid crystal dropping methods similarly, in the ratio shown in the following Table 2, Comparative Examples 1-10. Was prepared.

(Handling test)
After mixing 0.15 g of a 5 μm spacer (PF-50S: manufactured by Nippon Electric Glass Co., Ltd.) with 15 g of each prepared sealing agent for liquid crystal dropping method, the pressure reduction degree of -0.1 MPa for 10 minutes at 500 rpm and 1500 rpm of revolution. Vacuum stirring defoamed. As a vacuum stirring defoaming device, a vacuum stirring defoaming mixer VMX-360: manufactured by EME Co., Ltd. was used. It was placed under an atmosphere of 23 ° C., and the time for gelation was measured, and the evaluation was made according to the following criteria. The results are shown in Table 1 (Example) and Table 2 (Comparative Example).
○: not gelled for 72 hours or more Δ: gelled in 24 hours or more and less than 72 hours ×: gelled in less than 24 hours

(Creating a liquid crystal cell for evaluation)
An alignment film liquid (PIA-5540-05A; manufactured by Chisso Corporation) was applied to a substrate with a transparent electrode, baked, and subjected to rubbing treatment. The main seal and the dummy seal were dispensed so that the line width after bonding the obtained liquid crystal sealing agent on this substrate was 1 mm, and then the microdroplets of liquid crystal (JC-5015LA; made by Chisso Corporation) were used as a seal pattern It dripped in the frame. Furthermore, an in-plane spacer (Natco Spacer KSEB-525F; made by Natco Co., Ltd .; gap width 5 μm after bonding) is dispersed onto another rubbing-treated substrate, thermally fixed, and the other in a vacuum using a bonding device And the liquid crystal dripped substrate of. Open to the atmosphere to form a gap, mask only in the seal pattern frame, irradiate UV rays of 3000 mJ / cm ^{2 with} a UV irradiator, then place in an oven and thermally cure at 120 ° C for 1 hour to evaluate a liquid crystal test cell for evaluation Created.

  The liquid crystal alignment disorder in the vicinity of the seal of the prepared liquid crystal cell for evaluation was observed with a polarization microscope, and the liquid crystal alignment in the vicinity of the seal was evaluated according to the criteria shown below. The results are shown in Table 1 (Example) and Table 2 (Comparative Example).

(Evaluation of liquid crystal alignment near the seal)
◎: The alignment disorder of the liquid crystal is less than 0.2 mm from the seal.
Good: The alignment disorder of the liquid crystal is 0.2 mm or more and less than 0.4 mm from the seal.
B: Alignment disorder of the liquid crystal is 0.4 mm or more and less than 0.6 mm from the seal.
X: Alignment disorder of liquid crystal is 0.6 mm or more and less than 1.0 mm from the seal.

(Liquid crystal resistivity)
About 100 mg of each sealant was applied to the bottom of a 10 ml vial, and then 10 times the amount of liquid crystal (MLC-6866-100: manufactured by Merck Ltd.) was added. After heating at 120 ° C. for 60 minutes, it was cooled at room temperature for 30 minutes. Each supernatant was separated by decantation to adjust the measurement sample liquid crystal. The measurement sample liquid crystal made the value after applied voltage 10V240 seconds into a specific resistance value with a digital super-high resistance meter (R8340: made by Advantest Co., Ltd.), and compared with the value without a sealing agent (blank liquid crystal). In comparison, the index of decline was determined from the following equation.

(Formula 1)
Decrease index = −Log (y / x) (Expression 1)
x: specific resistance value of blank liquid crystal y: specific resistance value of sample liquid crystal

○: less than 1.5 △: 1.5 or more and less than 2.0 ×: 2.0 or more

(Adhesive strength test)
To 1 g of the obtained sealing agent, 0.01 g of 5 μm glass fiber (PF-50S: manufactured by Nippon Electric Glass Co., Ltd.) is added as a spacer, and mixed and stirred. This sealing agent is applied on a 10 mm × 25 mm glass substrate by screen printing to a portion with a line width of 0.8 mm and a length of 10 mm from a side to 5 mm, and 10 mm × 20 mm glass on the sealing agent The pieces are pasted together so that one side is offset by 5 mm, and after sandwiching both ends with a clip, it is photocured by UV irradiation of 3000 mJ / cm ² and placed in an oven at 120 ° C. for 1 hour to further thermoset The The peel adhesive strength was measured so that the 5 mm gap part of the glass piece was peeled up from the bottom with a bond tester (SS-30WD: manufactured by Nishijin Trading Co., Ltd.). The results are shown in Table 1 (Example) and Table 2 (Comparative Example).
(Evaluation of adhesion strength test)
:: strength is 2.5 kg or more ○: strength is 2.0 kg or more and less than 2.5 kg Δ: strength is 1.5 kg or more and less than 2.0 kg ×: strength is less than 1.5 kg

(Evaluation of liquid crystal alignment near seal after moisture resistance test)
The liquid crystal cell for evaluation described above was put in a constant temperature and humidity tester (HPAV-8-20 manufactured by Isuzu Seisakusho Co., Ltd.) for 48 hours at a temperature of 60 ° C. and a humidity of 90% atmosphere, and left standing for 30 minutes at room temperature for cooling. The liquid crystal alignment disorder in the vicinity of the seal was observed with a polarization microscope, and the liquid crystal alignment in the vicinity of the seal was evaluated according to the criteria shown below. The results are shown in Table 1 (Example) and Table 2 (Comparative Example).

(Evaluation of liquid crystal alignment near the seal)
◎: The alignment disorder of the liquid crystal is less than 0.2 mm from the seal.
Good: The alignment disorder of the liquid crystal is 0.2 mm or more and less than 0.4 mm from the seal.
B: Alignment disorder of the liquid crystal is 0.4 mm or more and less than 0.6 mm from the seal.
X: Alignment disorder of liquid crystal is 0.6 mm or more and less than 1.0 mm from the seal.

From the results in Tables 1 and 2, Examples 1 to 5 in which the thermal radical polymerization initiator and the two types of polymerization inhibitors were added showed good handling, a narrow liquid crystal alignment poor area near the seal, and high adhesive strength. The For Comparative Examples 1 to 10 in which one type of polymerization inhibitor is used, all properties of the handling property which is an essential characteristic for the liquid crystal sealing agent, the liquid crystal contamination test in the vicinity of the seal after the initial and moisture resistance test, and the liquid crystal resistivity There was nothing to meet.
From this, it can be said that the present invention is a liquid crystal sealing agent excellent in liquid crystal staining property, adhesive strength and liquid crystal staining property after a moisture resistance test, and also excellent in reliability of a liquid crystal display cell manufactured using this. .

  The liquid crystal sealing material of the present invention has extremely small influence on the liquid crystal display characteristics, and thus enables high definition, high speed response, low voltage drive, and long life of the liquid crystal display element. Moreover, since it is excellent in adhesive strength and moisture resistance reliability, manufacture of a highly reliable liquid crystal display element is realizable.

Claims (14)

Hydroquinone, which contains (A) two or more radical polymerization inhibitors, (B) a radical polymerization initiator and (C) (meth) acrylated epoxy compound, and (A) two or more radical polymerization inhibitors A liquid crystal sealing agent for liquid crystal dropping method comprising a polymerization inhibitor having free radicals as an essential component . The liquid crystal sealing agent for a liquid crystal dropping method according to claim 1 , wherein the radical polymerization initiator (B) is a thermal radical polymerization initiator (B-1). (B-1) The liquid crystal dropping method according to claim 2 , wherein the thermal radical polymerization initiator does not contain an oxygen-oxygen bond (-O-O-) and a nitrogen-nitrogen bond (-N = N-) in the molecule. Sealant. The liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 3 , further comprising (D) urethane (meth) acrylate. Furthermore, (E) The liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of the Claims 1 thru | or 4 containing the organic filler. The liquid crystal sealing agent for liquid crystal dropping method according to claim 5 , wherein the component (E) is a rubber fine particle. The liquid crystal sealing agent for liquid crystal dropping method according to claim 6 , wherein the component (E) is one or more rubber fine particles selected from the group consisting of acrylic rubber, styrene rubber, styrene olefin rubber and silicone rubber. The liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 4 , wherein the radical polymerization initiator (B) is a radical photopolymerization initiator (B-2). The liquid crystal sealing compound for liquid crystal dropping method according to any one of claims 1 to 8 , further comprising (F) a curable compound having an epoxy group and (G) a thermosetting agent. The liquid crystal sealing compound for liquid crystal dropping method according to claim 9 , wherein the component (G) is an organic acid hydrazide. Furthermore, (H) The liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of the Claims 1 thru | or 10 containing a silane coupling agent. The liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 11 , further comprising (I) an inorganic filler. A liquid crystal display cell constituted by two substrates, after dropping a liquid crystal inside the edge of the liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 12 formed on one of the substrates A method of manufacturing a liquid crystal display cell comprising laminating the other substrate and then curing it by light and / or heat. A liquid crystal display cell sealed with a cured product obtained by curing the liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 12 .