KR102016781B1 - Sealing agent for liquid crystal, and liquid-crystal display cell obtained using same - Google Patents

Abstract

The liquid crystal sealing agent for liquid crystal dropping methods which is excellent in the smudge resistance to liquid crystal sealing agent of liquid crystal, and also excellent in general characteristics as liquid crystal sealing agent, such as adhesive strength and low staining property to a liquid crystal, is proposed. By using the liquid crystal sealing agent of this invention, manufacture of the liquid crystal display cell excellent in long-term reliability can be made easy. The liquid crystal sealing agent of this invention contains curable resin which has three or more reactive functional groups in 1 molecule of (A), and (B) thermal radical polymerization initiator.

Description

Liquid crystal sealing agent and liquid crystal display cell using the same {SEALING AGENT FOR LIQUID CRYSTAL, AND LIQUID-CRYSTAL DISPLAY CELL OBTAINED USING SAME}

This invention relates to the liquid crystal sealing agent used for the liquid crystal dropping method, and the liquid crystal display cell using the same. More specifically, it relates to the liquid crystal sealing agent for liquid crystal dropping methods excellent in the smudge resistance to liquid crystal sealing agent to liquid crystal sealing agent, and also excellent also in general characteristics as a liquid crystal sealing agent, such as adhesive strength, and the liquid crystal display cell using the same.

As a manufacturing method of a liquid crystal display cell with the enlargement of the recent liquid crystal display cell, the so-called liquid crystal dropping method with more mass productivity is proposed (patent document 1, 2). It is the manufacturing method of the liquid crystal display cell which specifically bonds another board | substrate after dripping a liquid crystal on the inside of the bank which consists of liquid crystal sealing agents formed in one board | substrate, and hardens a liquid crystal sealing agent after that.

However, in the liquid crystal dropping method, since the liquid crystal and the liquid crystal sealing agent contact before the liquid crystal sealing agent is cured, a smudge phenomenon occurs in the liquid crystal sealing agent due to the pressure caused by the liquid crystal, and in the worst case, the dam formed of the liquid crystal sealing agent is formed. In some cases, it becomes a problem. This problem occurs when a part of the liquid crystal dropping method that uses light and heat is covered by a wiring or the like and there is a portion where sufficient ultraviolet rays are not irradiated. Moreover, when hardening liquid crystal sealing agent only by heat, without irradiating an ultraviolet-ray, it is a big problem especially. In order to solve this problem, it is necessary to increase the accuracy of the amount of dripping of the liquid crystal. However, since the liquid crystal expands during heating, which is a curing step of the liquid crystal sealing agent, it is difficult to completely suppress the above-mentioned smudge phenomenon.

Moreover, the liquid crystal sealing agent for liquid crystal dropping methods needs to solve various problems, such as general characteristics, such as low liquid crystal contamination, high adhesive strength, high moisture resistance, and high heat resistance, and workability, such as storage stability.

In order to solve this problem, various techniques have been proposed.

In patent document 3, the said subject is aimed at using organic bentonite. This method has a certain effect on the smudge of the liquid crystal, but it is difficult to say that it is sufficient.

PTL 4 describes a method of performing a B stage treatment of a liquid crystal sealing agent using a liquid crystal sealing agent using fumed silica and polythiol. However, this method has the drawback that the process becomes long and a device for the process is required.

In patent document 5, the liquid crystal sealing agent for liquid crystal dropping methods which prevents a smudge by increasing a hardening rate using a thermal radical polymerization initiator is disclosed.

As mentioned above, although the development of liquid crystal sealing agent is made very energetically, it has completed the thing which is excellent also in the general characteristics as liquid crystal sealing agent, such as low liquid crystal contamination property and high adhesive strength, even though it has excellent smudge resistance. It is not.

Japanese Laid-Open Patent Publication No. 63-179323 Japanese Patent Laid-Open No. 10-239694 Japanese Unexamined Patent Publication No. 2010-14771 Japanese Laid-Open Patent Publication 2011-150181 International Publication No. 2011/061910

The present invention relates to a liquid crystal sealing agent used in the liquid crystal dropping method, and a liquid crystal display cell using the same. More specifically, the liquid crystal sealing agent is excellent in the resistance to smudges to the liquid crystal sealing agent, and furthermore, general characteristics as a liquid crystal sealing agent such as adhesive strength. Also in the above, the liquid crystal sealing agent for liquid crystal dropping methods and the liquid crystal display cell using the same are proposed.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the liquid crystal sealing agent containing curable resin which has three or more reactive functional groups in 1 molecule has very excellent smudge resistance, and came to this invention.

In addition, "(meth) acryl" means "acryl and / or methacryl" in this specification, and "(meth) acryloyl group" means "acryloyl group and / or methacryloyl group." Moreover, the "liquid crystal sealing agent for liquid crystal dropping methods" may be described simply as "liquid crystal sealing agent."

That is, this invention relates to following (1)-(15).

(One)

(A) Liquid crystal sealing agent containing curable resin which has three or more reactive functional groups in 1 molecule, and (B) thermal radical polymerization initiator.

(2)

The liquid crystal sealing agent as described in said (1) whose reactive functional group of the said component (A) is a cyclic ether group and / or a (meth) acryloyl group.

(3)

The liquid crystal sealing agent as described in said (1) or (2) whose reactive group equivalent (molecular weight per 1 reactive functional group) of the said component (A) is 200 or less.

(4)

The liquid crystal sealing agent in any one of said (1)-(3) whose molar average molecular weight of the said component (A) is 800 or more.

(5)

The liquid crystal sealing agent in any one of said (1)-(4) whose reactive functional group of the said component (A) is acryloyl group.

(6)

Wherein the component (A) is a curable resin containing a C1 ~ C4 alkylene oxide (-OR ¹ -O-) (wherein R ¹ represents a chain which may have a branched or cyclic alkylene group) in the molecule The liquid crystal sealing agent in any one of (1)-(5).

(7)

The liquid crystal sealing agent in any one of said (1)-(6) containing 5-40 mass% of said components (A) in the total amount of liquid crystal sealing agent.

(8)

Furthermore, the liquid crystal sealing agent in any one of said (1)-(7) containing (C) (meth) acrylated epoxy resin which has less than three reactive functional groups in 1 molecule, and (D) thermosetting agent.

(9)

Liquid crystal sealing agent as described in said (8) whose said component (C) is (meth) acrylic ester of resorcin diglycidyl ether.

10

Liquid crystal sealing agent as described in said (8) or (9) whose said component (D) is an organic acid hydrazide compound.

(11)

Liquid crystal sealing agent in any one of said (1)-(10) whose said component (B) is 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane,

(12)

Furthermore, the liquid crystal sealing agent in any one of said (1)-(11) containing the epoxy resin which has less than 3 reactive functional groups in (E) 1 molecule.

(13)

Furthermore, the liquid crystal sealing agent in any one of said (1)-(12) containing (F) silane coupling agent.

(14)

Liquid crystal display cell comprised by two board | substrates WHEREIN: After dropping a liquid crystal inside the bank formed of the liquid crystal sealing agent in any one of said (1)-(13) formed in one board | substrate, the other board | substrate The manufacturing method of the liquid crystal display cell which bonds and cures the said liquid crystal sealing agent by heat after that.

(15)

The liquid crystal display cell sealed with the hardened | cured material obtained by hardening | curing the liquid crystal sealing agent in any one of said (1)-(13).

The liquid crystal sealing agent of this invention is very excellent in the tolerance to the smudge of a liquid crystal. Therefore, the manufacturing of the liquid crystal display cell is facilitated. Moreover, since the general characteristics as liquid crystal sealing agents, such as adhesive strength, are also excellent, the completed liquid crystal display cell is a thing with long term reliability. That is, this invention makes it easy to manufacture the outstanding liquid crystal display cell.

The liquid crystal sealing agent of this invention contains curable resin which has three or more reactive functional groups in 1 molecule as a component (A). Since this component has a high crosslinking rate (reaction rate), excellent smudge resistance can be realized. Moreover, when this method is used, unlike the method of improving the reactivity by increasing the quantity of a thermal radical polymerization initiator etc., it is also excellent in handling property. Handling property means the ease of use of a liquid crystal sealing agent. For example, there is a phenomenon that the liquid crystal sealing agent is cured or gelled in a process of being placed under vacuum or applying heat such as a defoaming step of a liquid crystal sealing agent or a mixing step of a spacer agent, and handling of the occurrence of this phenomenon is easy in the present application. Defined as last name. Therefore, what hardens | cures or gelatinizes is used as the liquid-crystal sealing agent with good handling property, and what makes it easy to produce hardening or gelling is set as the liquid-crystal sealing agent with poor handling property.

As component (A), for example, KAYARAD ^RTM PET-30, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA-12, GPO-303, TMPTA, THE-330, TPA-320 , TPA-330, D-310, D-330, RP-1040, UX-5000, DPHA-40H (above, manufactured by Nippon Gunpowder Co., Ltd.), NK ester ^RTM A-9300, A-9300-1CL, A-GLY- 9E, A-GLY-20E, A-TMM-3, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH (above, Shinnakamura Chemical Industry Co., Ltd.), SR295, SR350, SR355, SR399, SR494, CD501, SR502, CD9021, SR9035, SR9041 (above, manufactured by Satomer), Denacol ^RTM EX-314, EX-411, EX-421, EX- 512, EX-521, EX-611, EX-612, EX-614 (above, manufactured by Nagase Chemtex Corporation), jER ^RTM 152, 154, 157 S70, 1031S, 1032H60, 604, 630 (above, manufactured by Mitsubishi Chemical Corporation ), And the like. In addition, superscript RTM in this specification means a registered trademark.

Moreover, it is preferable that the reactive functional group of the said component (A) is a cyclic ether group and / or a (meth) acryloyl group. Although a cyclic ether group shows groups, such as an oxirane ring and an oxetane ring, it is preferable when it is an oxirane ring. Moreover, especially preferably, it is a case where a reactive functional group is acryloyl group.

As the component (A) in this case, for example, KAYARAD ^RTM PET-30, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA-12, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, D-310, D-330, RP-1040, UX-5000, DPHA-40H (above, manufactured by Nippon Gunpowder Co., Ltd.), NK ester ^RTM A-9300, A-9300-1CL, A -GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH And Shin Nakamura Chemical Industry Co., Ltd.), SR295, SR350, SR355, SR399, SR494, CD501, SR502, CD9021, SR9035, SR9041 (above, manufactured by Satomer).

Moreover, it is preferable that the said component (A) is 200 or less reactive group equivalent (molecular weight per 1 reactive functional group). When the reactive group equivalent is larger than 200, the crosslinking reaction may be inhibited by decreasing the density of the reactive functional group in the liquid crystal sealing agent, and sufficient crosslinking rate (reaction rate) may not be obtained in order to obtain excellent smudge resistance. Although the preferable range of reactive group equivalent is not specifically limited, For example, 80-200.

Preferred components (A) are, for example, KAYARAD ^RTM PET-30, DPHA, DPCA-20, DPCA-30, DPEA-12, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, D- 310, D-330, RP-1040, UX-5000, DPHA-40H (above, manufactured by Nippon Gunpowder Co., Ltd.), NK ester ^RTM A-9300, A-9300-1CL, A-TMM-3, A-TMM-3LM -N, A-TMPT, AD-TMP, A-TMMT, A-9550, A-DPH (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), SR295, SR350, SR355, SR399, SR494, SR9041 (above, manufactured by Satomer) ), And the like.

Moreover, it is preferable that the said component (A) is 800 or more in molar average molecular weight. When the molar average molecular weight of component (A) is lower than 800, since it becomes easy to melt | dissolve in a liquid crystal like a solvent, when liquid crystal sealing agent contacts a liquid crystal in the state before hardening, it may contaminate a liquid crystal and may degrade display performance. . Although the preferable range of molar average molecular weight is not specifically limited, For example, 800-10000.

As preferable component (A), KAYARAD ^RTM DPCA-20 (molar average molecular weight 807), DPCA-30 (molar average molecular weight 921), DPEA-12 (molar average molecular weight 1191) (all are the Nippon Kayaku Co., Ltd. product) etc. are mentioned, for example. Can be mentioned.

The component (A) is preferred if a curable resin containing a C1 ~ C4 alkylene oxide (-OR ¹ -O-) in the molecule. Here, R ¹ represents a chain or cyclic alkylene group which may have a branch.

Examples of C1-C4 alkylene oxides include methylene oxide, ethylene oxide, n-propylene oxide, i-propylene oxide, n-butylene oxide, sec-butylene oxide and the like. Among these, ethylene oxide and n-propylene oxide are preferable, and ethylene oxide is particularly preferable.

Specifically, KAYARAD ^RTM DPEA-12 (made by Nippon Kayaku Co., Ltd.) is mentioned.

It is preferable that the content rate in the liquid crystal sealing compound total amount of a component (A) is 5-40 mass%. When the content ratio is too large, the adhesive shrinkage to the glass substrate may decrease due to the increase in curing shrinkage, and when too small, the effect of the present invention, that is, excellent smudge resistance may not be realized. As content rate, More preferably, it is 10-30 mass%, Especially preferably, it is the case of 10-25 mass%.

The thermal radical polymerization initiator as the component (B) is not particularly limited as long as it generates a radical by heating and initiates a chain polymerization reaction, but the organic peroxide, azo compound, benzoin compound, benzoin ether compound, acetophenone compound, Benzo pinacol etc. are mentioned, A benzo pinacol is used preferably. For example, the organic peroxides include kayammex ^RTM A, M, R, L, LH, SP-30C, Parkadox CH-50L, BC-FF, Cardox B-40ES, Parkadox 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, Parkadox 16, Kayacarbon ^RTM BIC-75, AIC-75 (above, manufactured by Kayaku Akzo Co., Ltd.), Pamec ^RTM N, H, S, F, D, G, Pahexa ^RTM H, HC, Far TMH, C, V, 22, MC, Parkour ^RTM AH, AL, HB, Pabutyl ^RTM H, C, ND, L, Pacumyl ^RTM H, D, Faroyl ^RTM IB, IPP, Paoctata ^RTM ND, (above, Nichiyu Co., Ltd.) etc. can be obtained as a commercial item. Moreover, as an azo compound, VA-044, V-070, VPE-0201, VSP-1001 (above, Wako Pure Chemical Industries Ltd. make) etc. can be obtained as a commercial item.

Preferred as the component (B) is a benzopinacol-based thermal radical polymerization initiator (including chemically modified benzopinacol). Specifically, benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2-tetraphenylethane, 1,2-dipe Oxy-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-tetraphenylethane, 1,2-bis (t-butyldimethylsiloxy) -1,1,2,2-tetraphenylethane, 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, etc. are mentioned, Preferably 1-hydroxy-2- trimethylsiloxy-1,1,2,2- tetraphenylethane, 1-hydroxy-2-triethyl Siloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1,1,2,2-tetraphenylethane, 1,2-bis ( Dimethylsiloxy) -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, and particularly preferably 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane.

The benzopinacol is commercially available from Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., and the like. Moreover, the compound which etherified the hydroxyl group of benzopinacol can be easily synthesize | combined by a well-known method. Moreover, the compound which silyl-etherylated the hydroxy group of benzo pinacol can be synthesize | combined and obtained by the method of heating the corresponding benzo pinacol and various silylating agents under basic catalysts, such as a pyridine. Examples of the silylating agent include trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA), and triethyl, which are generally known trimethylsilylating agents. Triethylchlorosilane (TECS) which is a silylating agent, t-butylmethylsilane (TBMS) which is a t-butyldimethylsilylating agent, etc. are mentioned. These reagents are readily available on the market such as silicone derivative makers. As reaction amount of a silylating agent, 1.0-5.0 times mole is preferable with respect to 1 mol of hydroxyl groups of a target compound. More preferably, it is 1.5-3.0 times mole. When less than 1.0 molar, reaction efficiency is bad and reaction time becomes long, and thermal decomposition is accelerated | stimulated. When more than 5.0 times mole, separation will worsen or it will become difficult at the time of collection | recovery.

The liquid crystal sealing agent of this invention may contain the (meth) acrylic-ized epoxy resin which has less than three reactive functional groups in 1 molecule as a component (C). Component (C) can be obtained by well-known reaction of the epoxy resin and (meth) acrylic acid which have less than 3 reactive functional groups in 1 molecule. For example, (meth) acrylic acid and a catalyst (e.g., benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstyrene, etc.) in a predetermined equivalent ratio to the epoxy resin, and a polymerization inhibitor (For example, metoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) is added, and it is obtained by performing esterification reaction at 80-110 degreeC, for example. Although it does not specifically limit as an epoxy resin used as a raw material, A bifunctional or more functional epoxy resin is preferable, For example, diglycidyl ether of resorcinol (resorcin), bisphenol A type epoxy resin, bisphenol F type epoxy resin , Bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, others The diglycidyl ether compound of bifunctional phenols, the diglycidyl ether compound of bifunctional alcohols, those halides, hydrogenated substance, etc. are mentioned. Among them, diglycidyl ethers of bisphenol type epoxy resins, novolac type epoxy resins and resorcinol (resorcin) are more preferable from the viewpoint of liquid crystal contamination.

In addition, content of a component (C) is appropriately determined in consideration of workability and physical properties of the liquid crystal sealing agent, and is usually about 10 to 60% by mass in the liquid crystal sealing agent, preferably 20 to 50% by mass.

The liquid crystal sealing agent of this invention may contain a thermosetting agent as a component (D). This component (D) is different from the thermal radical polymerization initiator which is the said component (B), and means the thermosetting agent which does not generate a radical. Specifically, nucleophilic reaction is carried out by an unshared electron pair or an anion in a molecule, and examples thereof include polyvalent amines, polyhydric phenols, and organic acid hydrazide compounds. However, it is not limited to these. Of these, organic acid hydrazide 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- Benzene trihydrazide, 1,4,5,8-naphtho-acid tetrahydrazide, pyromellitic acid tetrahydrazide, etc. are mentioned. Moreover, if it is an aliphatic hydrazide compound, for example, form hydrazide, acethydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydra Gide, adipic dihydrazide, pimelic acid dihydrazide, sebacic acid dihydrazide, 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, imino diacetic acid dihai Dragizide, N, N'-hexamethylenebis semicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis (hydrazino Dihi having a hydantoin skeleton such as carbonoethyl) -5-isopropylhydantoin, preferably a valinhydantoin skeleton (skeleton in which the carbon atom of the hydantoin ring is substituted with an isopropyl group) Rajide compounds, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanur Elate, bis (2-hydrazinocarbonylethyl) isocyanurate, etc. are mentioned. In the balance of curing reactivity and latentness, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2- Hydrazinocarbonylethyl) isocyanurate and tris (3-hydrazinocarbonylpropyl) isocyanurate, and particularly preferably malonic acid dihydrazide.

It is preferable that it is 0.1-10 mass% in the total amount of a liquid crystal sealing agent, and, as for the content rate of a component (D), it is more preferable that it is 1-5 mass%.

The liquid crystal sealing agent of this invention can further improve the adhesive strength by containing the epoxy resin which has less than three reactive functional groups in 1 molecule as a component (E). As component (E), it is preferable that contamination with a liquid crystal and solubility are low. Examples of preferred epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, diglycidyl ethers of resorcinol (resorcin), phenol novolac type epoxy resins, and cresol novolac types. Epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy Resins, isocyanurate-type epoxy resins, diglycidyl ether compounds of other bifunctional phenols, diglycidyl ether compounds of difunctional alcohols, and their halides and hydrogenated substances.

The content rate of component (E) is suitably determined in consideration of the workability and physical properties of the liquid crystal sealing agent, and is usually about 5 to 30 mass% in the total amount of the liquid crystal sealing agent, and preferably 5 to 20 mass%.

The liquid crystal sealing agent of this invention can further add a silane coupling agent as a component (F), and can aim at the improvement of adhesive strength and moisture resistance. Examples of the component (F) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl). Ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride , 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, and the like. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. etc. as KBM series, KBE series, etc., it is easily available on the market.

It is preferable that the content rate of component (F) is 0.05-3 mass% in the total amount of liquid crystal sealing agent.

In addition to the above components, the liquid crystal sealing agent of the present invention may be, for example, a photopolymerization initiator, a radical polymerization inhibitor, an inorganic filler, rubber fine particles, a curing accelerator such as an organic acid or an imidazole compound, an organic filler, or a pigment, a leveling agent, an antifoaming agent, a solvent, or the like. The additive of can be mix | blended.

Although it will not specifically limit, if it is a compound which generate | occur | produces a radical and an acid by irradiation of an ultraviolet-ray or visible light, and starts a chain polymerization reaction as said photoinitiator, For example, 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 And 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyl disulfide and the like. Specifically, IRGACURE ^RTM 651, 184, 2959, 127, 907, 396, 379EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE ^RTM 1173, LUCIRIN ^RTM TPO (above, manufactured by BASF), Sheikhol ^RTM Z, BZ, BEE, BIP, BBI (above, Seiko Chemical Co., Ltd.) etc. are mentioned.

Moreover, it is preferable to use what has a (meth) acryl group in a molecule | numerator from a liquid-crystal contamination viewpoint, For example, 2-methacryloyl oxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2methyl-1-propan-1-one The reaction product is used preferably. This compound can be manufactured and obtained by the method of international publication 2006/027982.

The content rate in liquid crystal sealing agent total amount at the time of using a photoinitiator is 0.001-3 mass% normally, Preferably it is 0.002-2 mass%.

The radical polymerization inhibitor is not particularly limited as long as it is a compound that prevents polymerization by reacting with a radical generated from a photopolymerization initiator, a thermal radical polymerization initiator, or the like, and is not limited to quinone, piperidine, hindered phenol, and nitroso. Can be used. Specifically, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6, -tetramethylpiperidine-1-oxyl, 2 , 2,6,6, -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) propionate, 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'-hydroxy Nylpropionate) 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, thiodiphenylamine, aluminum salt of N-nitrosophenylhydroxyamine, trade name adecastab LA-81, trade name adecastab LA -82 (manufactured by Adeka Co., Ltd.) and the like, but are not limited thereto. Of these, naphthoquinone-based, hydroquinone-based and nitroso-based piperazine-based radical polymerization inhibitors are preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-P- Cresol and polystop 7300P (made by Hakuto Co., Ltd.) are more preferable, and polystop 7300P (made by Hakuto Co., Ltd.) is the most preferable.

The method of adding a radical polymerization inhibitor at the time of synthesize | combining the (meth) acrylated epoxy resin which is a component (C), or the method of dissolving in the epoxy resin which is a component (C) which is (meth) acrylic epoxy resin and / or a component (E) is have. In order to acquire a more effective effect, it is preferable to add and melt | dissolve with respect to a component (C) and / or a component (E).

As content rate of a radical polymerization inhibitor, 0.0001-1 mass% is preferable in the liquid crystal sealing agent total amount of this invention, 0.001-0.5 mass% is more preferable, 0.01-0.2 mass% is especially preferable.

As the inorganic filler, fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, hydroxide Magnesium, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos and the like, and preferably fused silica, crystalline silica, silicon nitride, boron nitride, carbonate Calcium, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, more preferably fused silica, crystalline silica, alumina, talc. You may use these inorganic fillers in mixture of 2 or more type. When the average particle diameter is too large, 3 m or less is suitable, and preferably 2 m or less, because it causes defects such as gap formation when bonding the upper and lower glass substrates at the time of manufacturing the narrow gap liquid crystal cell. It is as follows. The particle diameter can be measured by a laser diffraction scattering particle size distribution analyzer (dry) (manufactured by Seishin Co., Ltd .; LMS-30).

When using an inorganic filler in the liquid crystal sealing agent of this invention, it is 5-50 mass% normally in the total amount of a liquid crystal sealing agent, Preferably it is 5-40 mass%. When the content rate of an inorganic filler is lower than 5 mass%, since the adhesive strength with respect to a glass substrate falls and since moisture resistance reliability is inferior, the fall of the adhesive strength after moisture absorption may also become large. On the other hand, when the content rate of an inorganic filler is more than 50 mass%, since filler content is too large, it may not be easily crushed and the gap formation of a liquid crystal cell may become impossible.

As said rubber microparticles | fine-particles, a natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), butyl rubber (IIR), nitrile rubber (NBR), ethylene propylene Rubber (EPM, EP), chloroprene rubber (CR), acrylic rubber (ACM, ANM), chlorosulfonated polyethylene rubber (CSM), urethane rubber (PUR), silicone rubber (Si, SR), fluorine rubber (FKM, FPM ), Polysulfide rubber (thiocol) and the like, may be used alone or may be a core shell structure using two or more kinds. Moreover, you may use 2 or more types together. Among these, acrylic rubber and silicone rubber are preferable.

When using an acrylic rubber, it is preferable when it is an acrylic rubber of the core shell structure which consists of two types of acrylic rubber, It is especially preferable that a core layer is n-butylacrylate and a shell layer is methyl methacrylate. It is sold by Aika Kogyo Co., Ltd. as Zephyr ^RTM F-351.

Moreover, as said silicone rubber, organopolysiloxane crosslinked powder, a linear dimethyl polysiloxane crosslinked powder, etc. are mentioned. Moreover, as a composite silicone rubber, what coat | covered the silicone resin (for example, polyorgano silsesquioxane resin) on the surface of the said silicone rubber is mentioned. Especially preferable among these rubber fine particles are silicone rubber of linear dimethylpolysiloxane crosslinked powder or composite silicone rubber fine particles of silicone resin coated linear dimethylpolysiloxane crosslinked powder. These may be used independently and may use 2 or more types together. In addition, preferably, the shape of the rubber powder is preferably a spherical form with little viscosity increase after addition.

When rubber fine particles are used in the liquid crystal sealing agent of this invention, it is 5-50 mass% normally in the total amount of a liquid crystal sealing agent, Preferably it is 5-40 mass%.

An organic acid, imidazole, etc. are mentioned as said hardening accelerator.

Organic carboxylic acid, organic phosphoric acid, etc. are mentioned as an organic acid, However, In the case of organic carboxylic acid, it is preferable. Specifically, aromatic carboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, and furandicarboxylic acid, succinic acid, adipic acid, dodecaneic acid, sebacic acid, thiodi Propionic acid, cyclohexanedicarboxylic acid, tris (2-carboxymethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, tris (2-carboxypropyl) isocyanurate, bis (2-carboxy Ethyl) isocyanurate, and the like.

Moreover, as an imidazole compound, 2-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl-4- methyl imidazole, 1 -Benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-sia Noethyl-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: 3 addition of 2, 4- diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, and 2-methylimidazole isocyanuric acid Water, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1- Cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole and the like.

When using a hardening accelerator in the liquid crystal sealing agent of this invention, it is 0.1-10 mass% normally in the total amount of a liquid crystal sealing agent, Preferably it is 1-5 mass%.

There is a method shown next as an example of the method of obtaining the liquid crystal sealing agent of this invention. First, (meth) acrylated epoxy resin which has less than 3 reactive functional groups in 1 molecule which is component (C) to curable resin which has 3 or more reactive functional groups in 1 molecule which is component (A), component (E) The epoxy resin which has less than 3 reactive functional groups in phosphorus 1 molecule is heat-mixed, and after cooling to room temperature, the thermal radical polymerization initiator which is a component (B), and the thermosetting agent which is a component (D) as needed, and a component (F) phosphorus Liquid crystal sealing agent of this invention by adding a silane coupling agent, an antifoamer, a leveling agent, a solvent, etc., uniformly mixing by a well-known mixing apparatus, for example, 3 rolls, a sand mill, a ball mill, etc., and filtering by a metal mesh. Can be prepared.

The liquid crystal display cell of this invention arrange | positions a pair of board | substrates which provided the predetermined electrode in the board | substrate at predetermined intervals, seals the circumference with the liquid crystal sealing agent of this invention, and liquid crystal was enclosed in the clearance gap. The kind of liquid crystal enclosed is not specifically limited. Here, the board | substrate is comprised with the board | substrate of the combination which has light transmittance in at least one which consists of glass, quartz, a plastic, silicon, etc. By the manufacturing method, after adding the spacer (gap control material), such as glass fiber, to the liquid crystal sealing agent of this invention, the liquid crystal sealing agent was apply | coated to one of the pair of board | substrates using a dispenser, a screen printing apparatus, etc. Then, temporary hardening is performed at 80-120 degreeC as needed. Then, liquid crystal is dripped inside the bank which consists of this liquid crystal sealing agent, and the other glass substrate is piled up in vacuum, and gap gap is performed. After gap formation, the liquid crystal display cell of this invention can be obtained by hardening at 90-130 degreeC for 1-2 hours. The liquid crystal display cell of this invention obtained in this way does not have the display defect by liquid crystal contamination, and is excellent in adhesiveness and moisture resistance reliability. As a spacer, glass fiber, silica beads, polymer beads, etc. are mentioned, for example. Although the diameter changes with the objective, it is 2-8 micrometers normally, Preferably it is 4-7 micrometers. The content is usually 0.1 to 4% by mass, preferably 0.5 to 2% by mass, and more preferably about 0.9 to 1.5% by mass relative to 100% by mass of the liquid crystal sealing agent of the present invention.

The liquid crystal sealing agent of this invention has very favorable resistance to the smudge of a liquid crystal, and does not produce the phenomenon which a liquid crystal permeates and a seal | sticker deteriorates also in the bonding process of a board | substrate and a heating process in a liquid crystal dropping method. Therefore, the manufacture of a stable liquid crystal display cell is possible. Moreover, since the speed | rate which curable resin crosslinks is fast, the elution of the structural component to the liquid crystal is also very small and it is possible to reduce the display defect of a liquid crystal display cell. Moreover, since it is excellent also in storage stability, it is suitable for manufacture of a liquid crystal display cell. Moreover, since the hardened | cured material is excellent also in various hardened | cured material characteristics, such as adhesive strength, heat resistance, and moisture resistance, it is possible to manufacture the liquid crystal display cell excellent in reliability by using the liquid crystal sealing agent of this invention. Moreover, the liquid crystal display cell manufactured using the liquid crystal sealing agent of this invention also satisfy | fills the characteristic required as a liquid crystal display cell with high voltage retention and low ion density.

Example

Hereinafter, although an Example and an Example demonstrate this invention further in detail, this invention is not limited to an Example. In addition, "part" and "%" are mass references | standards in a body unless there is particular notice.

Synthesis Example 1

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

100 parts (0.28 mol) of commercially available benzopinacol (made by Tokyo Chemical) was dissolved in 350 parts of dimethylformaldehyde. 32 parts (0.4 mol) of pyridine as a base catalyst and 150 parts (0.58 mol) of BSTFA (made by Shin-Etsu Chemical Co., Ltd.) were added as a silylating agent, and it heated up to 70 degreeC, and stirred for 2 hours. The reaction solution was cooled, 200 parts of water was added while stirring to precipitate the product, and the unreacted silylating agent was deactivated. The precipitated product was filtered off and washed with water sufficiently. The product obtained was then dissolved in acetone, purified by addition of water and recrystallized. 105.6 parts (yield 88.3%) of 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).

Synthesis Example 2

[Synthesis of Total Acrylate of Resorcinic Diglycidyl Ether]

181.2 g of resorcinin diglycidyl ether (EX-201: Nagase Chemtex Co., Ltd.) was dissolved in 266.8 g of toluene, 0.8 g of dibutylhydroxytoluene was added to this as a polymerization inhibitor, and it heated up to 60 degreeC. Then, 117.5 g of 100% equivalent of acrylic acid of an epoxy group was added, it heated up to 80 degreeC again, 0.6 g of trimethylammonium chloride which is a reaction catalyst was added to this, and it stirred at 98 degreeC for about 30 hours, and obtained the reaction liquid. The reaction solution was washed with water and toluene was distilled off to obtain 293 g of epoxy acrylate of the desired resorcinin diglycidyl ether. The reactive group equivalent of the obtained epoxy acrylate is 183 in theory.

[Examples 1-5, Comparative Example 1]

The components (A), (C) and (E) of the amounts shown in the following Table 1 were heated and mixed, and after cooling, the components (B), (D), (F) and (other components) were added and stirred Then, it disperse | distributed with three roll mills, it filtered by the metal mesh (635 mesh), and prepared the liquid crystal sealing agent of Examples 1-5. Moreover, the material shown in Table 1 was mix | blended by the same process, and the liquid crystal sealing agent of the comparative example 1 was prepared.

A-1: ethylene oxide modified dipentaerythritol hexaacrylate (made by Nippon Gunpowder Co., Ltd .: DPEA-12)

(Number of reactive functional groups: 6, molar average molecular weight: 1107, molecular weight per 1 reactive functional group: 185)

A-2: caprolactone modified (2 mol) dipentaerythritol hexaacrylate (made by Nippon Gunpowder Co., Ltd .: DPCA-20)

(Number of reactive functional groups: 6, molar average molecular weight: 807, molecular weight per 1 reactive functional group: 134)

A-3: caprolactone modified (6 mol) dipentaerythritol hexaacrylate (made by Nippon Gunpowder Co., Ltd .: DPCA-60)

(Number of reactive functional groups: 6, molar average molecular weight: 1263, molecular weight per 1 reactive functional group: 211)

A-4: pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd .: PET-30)

(Number of reactive functional groups: 3, molar average molecular weight: 298, molecular weight per 1 reactive functional group: 99)

B-1: 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane

(Synthesis example 1 finely ground to an average particle diameter of 1.9 mu m in a jet mill)

C-1: Total acrylate of resorcin diglycidyl ether (synthesis example 2)

D-1: tris (2-hydrazinocarbonylethyl) isocyanurate finely ground product

(Product manufactured by Nippon Finechem Co., Ltd .: finely ground with HCIC and jet mill with an average particle diameter of 1.5 μm)

E-1: Ethylene oxide addition bisphenol S type epoxy resin (synthesis | combined by the method of patent 4211942)

F-1: 3-glycidoxypropyltrimethoxysilane (Tosoh Co., Ltd. make: Silor Ace S-510)

F-2: N-2 (aminoethyl) 3-aminopropyl triethoxysilane (Shin-Etsu Chemical Co., Ltd. make: KBM-603)

O-1: spherical silica (Shin-Etsu Chemical Co., Ltd. make: X-24-9163A; primary average particle diameter: 110 nm)

O-2: Silicone rubber powder Shin-Etsu Chemical Industry Co., Ltd. make: KMP-594; Primary mean particle diameter 3 μm, specific gravity 0.97, Shore A hardness 30)

(Fine powder of addition polymer of vinyl group-containing dimethylpolysiloxane and methylhydrogenpolysiloxane,

O-3: tris (3-carboxyethyl) isocyanurate

(Manufactured by Shikoku Kasei Kogyo Co., Ltd .: finely pulverized with an average particle diameter of 1.5 µm using CIC acid and a jet mill)

The following evaluation was performed about the liquid crystal sealing agent prepared in Examples 1-5 and the comparative example 1. The results are summarized in Table 2.

[Evaluation of Sim Resistance of Liquid Crystals]

1 g of glass fibers having a diameter of 5 µm was added to each of 100 g of the liquid crystal sealing agent as a spacer, mixed stirring and defoaming was performed, and the syringe was filled. The liquid crystal sealing agent filled in this syringe was apply | coated to the glass substrate in which the ITO transparent electrode was formed using the dispenser (SHOTMASTER300: Musashi Engineering Co., Ltd.), and the seal pattern and the dummy seal pattern were formed. Next, the micro droplet of liquid crystal (MLC-3007; Merck Corporation make) was dripped in the frame of the seal pattern. Furthermore, in-plane spacers (Natoco spacer KSEB-525F; manufactured by Natoko Co., Ltd .; gap width 5 μm after bonding) are spread and heat-bonded to a glass substrate that has undergone another rubbing treatment, and the front liquid crystal in vacuum using a bonding apparatus. It bonded together with the board | substrate which finished dripping. After opening to air to form a gap, it was left to stand for 10 minutes, and it put into 120 degreeC oven, and heat-hardened for 1 hour. Then, the interface of a seal and a liquid crystal was observed with the polarization microscope, and it evaluated according to the following criteria. The results are shown in Table 2.

(Circle): The smudge of a liquid crystal is not observed by liquid crystal sealing agent.

(Triangle | delta): The smudge of a liquid crystal is observed weakly by liquid crystal sealing agent.

X: The smudge of a liquid crystal is observed by liquid crystal sealing agent.

[Pollution Assessment for Liquid Crystals]

1 g of glass fibers having a diameter of 5 µm was added to each of 100 g of the liquid crystal sealing agent as a spacer, mixed stirring and defoaming was performed, and the syringe was filled. The liquid crystal sealing agent filled in this syringe was apply | coated to the glass substrate in which the ITO transparent electrode was formed using the dispenser (SHOTMASTER300: Musashi Engineering Co., Ltd.), and the seal pattern and the dummy seal pattern were formed. Next, the micro droplet of liquid crystal (MLC-3007; Merck Corporation make) was dripped in the frame of the seal pattern. Furthermore, in-plane spacers (Natoco spacer KSEB-525F; manufactured by Natoko Co., Ltd .; gap width 5 μm after bonding) are spread and heat-bonded to a glass substrate that has undergone another rubbing treatment, and the front liquid crystal in vacuum using a bonding apparatus. It bonded together with the board | substrate which finished dripping. After opening to air to form a gap, it was left to stand for 10 minutes, and it put into 120 degreeC oven, and heat-hardened for 1 hour. Then, the interface of a seal and a liquid crystal was observed with the polarization microscope, and it evaluated according to the following criteria. The results are shown in Table 2.

(Circle): Discoloration or a foreign material is not observed in the liquid crystal of liquid crystal sealing agent vicinity.

(Triangle | delta): Discoloration or a foreign material is observed weakly in the liquid crystal of liquid crystal sealing agent vicinity.

X: Discoloration or a foreign material is observed by the liquid crystal near liquid crystal sealing agent.

[Adhesive Strength Evaluation]

1 g of glass fibers having a diameter of 3 µm was added to 100 g of the liquid crystal sealing agent as a spacer, and mixing and stirring were performed. This liquid crystal sealing agent was apply | coated on the glass substrate of 50 mm x 50 mm, the glass piece of 1.5 mm x 1.5 mm was bonded on this liquid crystal sealing agent, and it put into the 120 degreeC oven, and hardened | cured for 1 hour. The shear adhesive strength of this glass piece was measured using the bond tester (SS-30WD: the Seishin Corporation make). The results are shown in Table 2.

From the result of Table 2, it was confirmed that Examples 1-5 improved the smudge resistance of the liquid crystal compared with the comparative example 1 which does not add the component (A).

Industrial availability

The liquid crystal sealing agent of this invention is excellent in the smudge resistance of liquid crystal to the liquid crystal sealing agent, Furthermore, it is excellent also in general characteristics as liquid crystal sealing agent, such as adhesive strength, and can manufacture the liquid crystal display cell excellent in long-term reliability easily. .

Claims (15)

(A) Curable resin which has 6 or more (meth) acryloyl groups as a reactive functional group in 1 molecule, (B) thermal radical polymerization initiator, and (C) (meth) acrylated epoxy which has less than 3 reactive functional groups in 1 molecule The liquid crystal sealing agent containing resin and whose said component (C) is the (meth) acrylic ester of resorcin diglycidyl ether. The method of claim 1,
Liquid crystal sealing agent whose reactive group equivalent (molecular weight per 1 reactive functional group) of the said component (A) is 200 or less. The method of claim 1,
Liquid crystal sealing agent whose molar average molecular weight of the said component (A) is 800 or more. The method of claim 1,
The component (A) is C1 ~ C4 alkyl in the molecule, alkylene oxide (-OR ¹ -O-) a curable resin containing a (wherein R ¹ represents an alkylene or cyclic which may have a branch), the liquid crystal A permanent system. The method of claim 1,
Liquid crystal sealing agent containing 5-40 mass% of said components (A) in the total amount of liquid crystal sealing agent. The method of claim 1,
Furthermore, (D) liquid crystal sealing agent containing a thermosetting agent. The method of claim 6,
Liquid crystal sealing agent whose said component (D) is an organic acid hydrazide compound. The method of claim 1,
Liquid crystal sealing agent whose said component (B) is 1,2-bis (trimethylsiloxy) -1,1,2,2- tetraphenylethane. The method of claim 1,
Furthermore, (E) liquid crystal sealing agent containing the epoxy resin which has less than 3 reactive functional groups in 1 molecule. The method of claim 1,
Furthermore, (F) liquid crystal sealing agent containing a silane coupling agent. In the liquid crystal display cell comprised by two board | substrates, after dropping a liquid crystal inside the bank consisting of the liquid crystal sealing agent in any one of Claims 1-10 formed in one board | substrate, the other board | substrate is The manufacturing method of the liquid crystal display cell bonded together and hardening the said liquid crystal sealing agent with heat after that. The liquid crystal display cell sealed with the hardened | cured material obtained by hardening | curing the liquid crystal sealing agent of any one of Claims 1-10. delete delete delete