TW201422655A - Sealing agent for liquid crystal, and liquid-crystal display cell obtained using same - Google Patents

Abstract

Proposed is a sealing agent for liquid crystals which is for use in the liquid-crystal dropping method, the sealing agent having excellent resistance to liquid-crystal penetration thereinto and being excellent also in terms of general properties required of sealing agents for liquid crystals, such as adhesion strength and the property of less fouling the liquid crystals. Use of this sealing agent for liquid crystals facilitates production of liquid-crystal display cells having exceedingly high long-term reliability. This sealing agent for liquid crystals comprises (A) a curable resin having three or more reactive functional groups per molecule and (B) a free-radical thermal polymerization initiator.

Description

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

The invention relates to a liquid crystal dense used in a liquid crystal dropping method A sealing agent and a liquid crystal display unit cell using the liquid crystal sealing agent. More specifically, the present invention relates to a liquid crystal sealing agent for a liquid crystal dropping method, and a liquid crystal display unit using the liquid crystal sealing agent, wherein the liquid crystal sealing agent is excellent in resistance to penetration of a liquid crystal into a liquid crystal sealing agent, and further, such as bonding strength. The general characteristics as the liquid crystal sealing agent are also excellent.

In recent years, as a method for producing a liquid crystal display cell, a so-called liquid crystal dropping method having higher mass productivity has been proposed (Patent Documents 1 and 2). Specifically, it is a method for producing a liquid crystal display cell in which liquid crystal is dropped on the inside of a dam formed of a liquid crystal sealing agent formed on a substrate, and then the other substrate is bonded. Then, the liquid crystal sealing agent is hardened.

However, in the liquid crystal dropping method, since the liquid crystal comes into contact with the liquid crystal sealing agent before the liquid crystal sealing agent is hardened, penetration into the liquid crystal sealing agent occurs due to the pressure caused by the liquid crystal, and in the worst case, it is sealed by the liquid crystal. The cofferdam formed by the agent may also be broken and become a problem. In the liquid crystal dropping method in which light and heat are used together, shadows such as wiring may occur, and there is a possibility that This problem can also occur when a part of the ultraviolet light is irradiated. Further, in the case where the liquid crystal sealing agent is hardened by heat only without ultraviolet irradiation, it is a problem that is particularly large. In order to solve this problem, it is necessary to increase the precision of the amount of dripping of the liquid crystal. However, even if the liquid crystal expands during the curing step of the liquid crystal sealing agent, that is, it is difficult to completely suppress the above-described infiltration phenomenon.

Moreover, for the liquid crystal sealing agent for liquid crystal dropping method, it is necessary to solve Various problems are described: general characteristics such as low liquid crystal contamination, high adhesion 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.

Patent Document 3 seeks to solve the above problems by using organic bentonite. This method has a certain effect of preventing penetration of liquid crystal, but it is difficult to say that it is sufficient.

Patent Document 4 describes a method in which a liquid crystal sealing agent using a gas phase cerium oxide (fumed silica) or a polythiol is used, and a liquid crystal sealing agent is subjected to a B-stage treatment. However, this method has the disadvantage that the steps are long and a device for this step is required.

Patent Document 5 discloses a liquid crystal sealing agent for a liquid crystal dropping method which uses a thermal radical polymerization initiator to increase the curing rate, thereby preventing penetration.

As mentioned above, although the liquid crystal sealant is being opened very aggressively A liquid crystal sealing agent which has excellent penetration resistance and is excellent in general characteristics as a liquid crystal sealing agent in terms of low liquid crystal contamination, high bonding strength, and the like.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. SHO63-179323

Patent Document 2: Japanese Laid-Open Patent Publication No. Hei 10-239694

Patent Document 3: Japanese Patent Laid-Open Publication No. 2010-14771

Patent Document 4: Japanese Laid-Open Patent Publication No. 2011-150181

Patent Document 5: International Publication No. 2011/061910

The present invention relates to a liquid crystal sealing agent used in a liquid crystal dropping method, and a liquid crystal display unit using the liquid crystal sealing agent. More specifically, a liquid crystal sealing agent for a liquid crystal dropping method and a liquid crystal sealing agent are used. The liquid crystal sealing agent is excellent in resistance to penetration of the liquid crystal into the liquid crystal sealing agent, and further excellent in general characteristics such as bonding strength as a liquid crystal sealing agent.

As a result of intensive studies, the present inventors have found the following: a liquid crystal sealing agent containing a curable resin having three or more reactive functional groups in one molecule and having excellent infiltration resistance.

Further, in the present invention, "(meth)acrylic" ("(meta)arcylic") means "acrylic acid and/or methacrylic acid", and "(meth)acrylic acid radical" means "acrylic acid sulfhydryl" And/or methacrylonitrile. Further, the "liquid crystal sealing agent for liquid crystal dropping method" may be simply referred to as "liquid crystal sealing agent".

That is, the present invention relates to the following (1) to (15).

(1) A liquid crystal sealing agent comprising: (A) a curable resin having three or more reactive functional groups in one molecule, and (B) a thermal radical polymerization initiator.

(2) The liquid crystal sealing agent according to the above (1), wherein the reactive functional group of the component (A) is a cyclic ether group and/or a (meth) acrylonitrile group.

(3) The liquid crystal sealing agent according to the above (1), wherein the reactive group equivalent (average molecular weight per reactive functional group) of the component (A) is 200 or less.

(4) The liquid crystal sealing agent according to the above (1), wherein the component (A) has a molar average molecular weight of 800 or more.

(5) The liquid crystal sealing agent according to the above (1), wherein the reactive functional group of the component (A) is an acrylonitrile group.

(6) The liquid crystal sealing agent according to the above (1), wherein the component (A) contains a C1 to C4 alkylene oxide (-OR ¹ -O-) in the molecule (the above R ¹ may also have a branch) A hardening resin of a chain or a cyclic alkyl group.

(7) The liquid crystal sealing agent according to the above (1), wherein the total amount of the liquid crystal sealing agent contains 5 to 40% by mass of the component (A).

(8) The liquid crystal sealing agent according to the above (1), which further contains (C) a (meth)acrylated epoxy tree having less than 3 reactive functional groups in one molecule. Grease, and (D) thermal hardener.

(9) The liquid crystal sealing agent according to the above (8), wherein the component (C) is a (meth) acrylate of resorcinol diglycidyl ether.

(10) The liquid crystal sealing agent according to the above (8), wherein the component (D) is an organic acid cerium compound.

(11) The liquid crystal sealing agent according to the above (1), wherein the component (B) is 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane. .

(12) The liquid crystal sealing agent according to the above (1), which further contains (E) an epoxy resin having less than three reactive functional groups in one molecule.

(13) The liquid crystal sealing agent according to the above (1), further comprising (F) a decane coupling agent.

(14) A method for producing a liquid crystal display cell, wherein the liquid crystal display cell composed of two substrates is formed on one side of the substrate by any one of the above (1) to (13) After the liquid crystal is dropped on the inside of the bank formed by the liquid crystal sealing agent, the substrate on the other side is bonded, and then the liquid crystal sealing agent is cured by heat.

(15) A liquid crystal display unit cell which is sealed by a hardened substance The cured product obtained by hardening the liquid crystal sealing agent according to any one of the above (1) to (13).

The liquid crystal sealing agent of the present invention is extremely excellent in resistance to penetration of a liquid crystal into a liquid crystal sealing agent. Therefore, the manufacture of the liquid crystal display cell is easy. Moreover, since the bonding strength and the like are excellent as general characteristics of the liquid crystal sealing agent, the long-term reliability of the completed liquid crystal display cell is high. That is, the present invention can easily produce an excellent liquid crystal display unit cell.

The liquid crystal sealing agent of the present invention contains a curable resin having three or more reactive functional groups in one molecule as the component (A). Since this component has a rapid crosslinking rate (reaction speed), excellent penetration resistance can be achieved. Further, when this method is used, unlike the method of increasing the amount of the thermal radical polymerization initiator or the like to improve the reactivity, the handling ability (Handling ability) is also excellent. The processing ability refers to the ease of use of the liquid crystal sealing agent. For example, in a defoaming step of a liquid crystal sealing agent and a mixing step of a spacer agent, etc., in a step of being subjected to vacuum or heating, there is a phenomenon in which the liquid crystal sealing agent is hardened or gelled, and in the present application, The degree to which this phenomenon is likely to occur is defined as processing power. Therefore, a liquid crystal sealing agent which is hard to be hardened or gelled is regarded as a liquid crystal sealing agent having a good handling ability, and a liquid crystal sealing agent which is liable to cause hardening or gelation is regarded as a liquid crystal sealing agent having poor handling ability.

As the 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 is manufactured by Nippon Kayaku Co., Ltd.); NK ester ^RTM A -9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT , A-9550, A-DPH (above is manufactured by Shin-Nakamura Chemical Co., Ltd.); SR295, SR350, SR355, SR399, SR494, CD501, SR502, CD9021, SR9035, SR9041 (above manufactured by Sartomer Company); Denacol ^RTM EX-314, EX-411, EX-421, EX-512, EX-521, EX-611, EX-612, EX-614 (above) It is manufactured by Nagase Chemtech Co., Ltd.; jER ^RTM 152, 154, 157S70, 1031S, 1032H60, 604, 630 (above is manufactured by Mitsubishi Chemical Corporation). Furthermore, in the present specification, the superscript RTM refers to a registered trademark.

Further, it is preferred that the reactive functional group of the above component (A) is a cyclic ether And / or (meth) acrylonitrile. The cyclic ether group means a group such as an oxirane ring or a propylene oxide ring, but is preferably an oxirane ring. Further, it is particularly preferred that the reactive functional group is an acrylonitrile group.

As the component (A) at this time, 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 Kayaku Co., Ltd.); NK ester ^RTM A-9300, A-9300 -1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A -DPH (above is manufactured by Shin-Nakamura Chemical Co., Ltd.); SR295, SR350, SR355, SR399, SR494, CD501, SR502, CD9021, SR9035, SR9041 (above).

Further, the above component (A) is preferably a reactive base equivalent (per The average molecular weight of a reactive functional group is 200 or less. When the reactive group equivalent is more than 200, the density of the reactive functional group in the liquid crystal sealing agent is lowered, and the crosslinking reaction is hindered, and sufficient crosslinking speed (reaction speed) may not be obtained to obtain excellent penetration resistance. The preferred range of the reactive group equivalent is not particularly limited and is, for example, 80 to 200.

As preferred component (A), 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 is manufactured by Nippon Kayaku 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 Industry Co., Ltd.); SR295, SR350, SR355, SR399, SR494 , SR9041 (above is manufactured by Shadobu Co., Ltd.).

Further, the component (A) is preferably a molar average molecular weight of 800 or more. When the molar average molecular weight of the component (A) is less than 800, since it is easily dissolved in the liquid crystal like a solvent, when the liquid crystal sealing agent comes into contact with the liquid crystal in a state before hardening, the liquid crystal may be contaminated to exhibit display performance. Deterioration. The preferred range of the molar average molecular weight is not particularly limited, and is, for example, 800~ 10000.

Preferred examples of the component (A) include KAYARAD ^RTM DPCA-20 (mole average molecular weight 807), DPCA-30 (mole average molecular weight 921), and DPEA-12 (mole average molecular weight 1191) (both Made by Nippon Chemical Co., Ltd.).

The component (A) is preferably a curable resin containing a C1 to C4 alkylene oxide (-OR ¹ -O-) in its molecule. Here, R ¹ above represents an alkylene group which may have a branched chain or a cyclic chain.

Examples of the C1 to C4 alkylene oxides include methylene oxide, ethylene oxide, n-propylene oxide, isopropylene oxide, n-butylene oxide, and second butylene oxide. Among them, ethylene oxide and n-propylene oxide are preferred, and ethylene oxide is particularly preferred.

Specifically, KAYARAD ^RTM DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.) can be cited.

The content of the component (A) in the total amount of the liquid crystal sealing agent is preferably 5~ 40% by mass. When the content is too large, it is particularly preferably 10, and the hardening shrinkage becomes large. Therefore, the bonding strength to the glass substrate may be lowered. When the content is too small, the effect of the present invention may not be achieved, that is, excellent penetration resistance. The content is more preferably 10 to 30% by mass and not more than 25% by mass.

The component (B), which is a thermal radical polymerization initiator, is not particularly limited, and may be a compound which generates a radical by heating and initiates a chain polymerization reaction, and examples thereof include an organic peroxide, an azo compound, and a benzoin compound. As the benzoin ether compound, the acetophenone compound, the benzopinacol or the like, benzopinacol can be preferably used. For example, as an organic peroxide, the following organic peroxides are commercially available: Kayamek ^RTM A, M, R, L, LH, SP-30C, Perkadox CH-50L, BC-FF, Cadox B-40ES , Perkadox14, 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, Perkadox16, Kayacarvone ^RTM BIC-75, AIC-75 (above manufactured by KAYAKU AKZO CO., LTD.); Permek ^RTM N, H, S, F, D, G , Perhexa ^RTM H, HC, paTMH, C, V, 22, MC, Percure ^RTM AH, AL, HB, Perbutyl ^RTM H, C, ND, L, Percumyl ^RTM H, D, Peroyl ^RTM IB, IPP, Perocta ^RTM ND (The above is manufactured by NOF CORPORATION). Further, as the azo compound, the following azo compounds can be obtained in the form of a commercially available product: VA-044, V-070, VPE-0201, VSP-1001 (The above is Wako Pure Chemical Co., Ltd. (Wako Pure Chemical Co., Ltd.) Industries, Ltd.), etc.

The component (B) is preferably a benzopinacol-based thermal radical polymerization initiator (including an initiator which is chemically modified with 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-tetrakis(4-methoxyphenyl)ethane, 1,2-bis(trimethylhydrazine) Oxy)-1,1,2,2-tetraphenylethane, 1,2-bis(triethyldecyloxy)-1,1,2,2-tetraphenylethane, 1,2- Bis(t-butyldimethylformane)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenyl Ethylethane, 1-hydroxy-2- Triethyl decyloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethyloxy-1,1,2,2-tetraphenyl Ethane or the like, preferably 1-hydroxy-2-trimethylphosphonium-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethyldecyloxy-1,1 , 2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethyloxy-1,1,2,2-tetraphenylethane, and 1,2-double (three Methyl decyloxy)-1,1,2,2-tetraphenylethane, further preferably 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethyl Alkane, and 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, particularly preferably 1,2-bis(trimethyldecyloxy)-1 1,2,2-tetraphenylethane.

The above benzopinacol is marketed by Tokyo Chemical Industry Co., Ltd. and Wako Pure Chemical Industries Co., Ltd. Further, a compound obtained by etherifying a hydroxyl group of benzopinacol can be easily synthesized by a known method. Further, a compound obtained by subjecting a hydroxyl group of benzopinacol to oxime etherification can be obtained by a method in which a corresponding benzopinacol and various alkylating agents are heated under an alkaline catalyst such as pyridine. And synthetically obtained. Examples of the decylating agent include trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), and N, O-bis (trimethyl) which are generally known as trimethyl sulfonating agents. N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA), and triethyl chloroalkylating agent (TRIS), triethyl chlorosilane (TECS), tert-butyl dimethyl decane The agent is tributyl methylsilane (TBMS) or the like. Such reagents are readily available on the market from hydrazine derivatives manufacturers and the like. The reaction amount of the decylating agent is preferably 1.0 to 5.0 moles per mole of the hydroxyl group of the target compound. Further preferably, it is 1.5 to 3.0 times Mo. Since the reaction efficiency is less than 1.0 times Moule The deterioration is caused, and the reaction time becomes long, and therefore, thermal decomposition is promoted. If it is more than 5.0 times the mole, the separation is deteriorated at the time of recovery, and the purification becomes difficult.

The liquid crystal sealing agent of the present invention may also contain no in one molecule A (meth)acrylated epoxy resin having three reactive functional groups as component (C). The component (C) can be obtained by a well-known reaction of an epoxy resin having less than three reactive functional groups in one molecule with (meth)acrylic acid. For example, a specific equivalent ratio of (meth)acrylic acid, a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, and triphenyl) is added to the epoxy resin. And the like, and a polymerization inhibitor (for example, methoxyphenol, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.), and obtained by, for example, esterification at 80 to 110 ° C . The epoxy resin is not particularly limited as the raw material, and is preferably a bifunctional or higher epoxy resin, and examples thereof include di-epoxypropyl ether of resorcinol (resorcin) and bisphenol. A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type ring Oxygen resin, carbendazim type epoxy resin, isocyanurate type epoxy resin, diethylene oxide propyl ether compound of difunctional phenol, diepoxypropyl etherate of difunctional alcohol , and the like, halides, hydrides, and the like. Among them, from the viewpoint of liquid crystal contamination, a bisphenol type epoxy resin, a novolac type epoxy resin, and a di-epoxypropyl ether of resorcin (Resorcin) are more preferable.

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

The liquid crystal sealing agent of the present invention may further contain a heat curing agent as a Minute (D). This component (D) is different from the above-mentioned component (B), that is, a thermal radical polymerization initiator, and is a thermosetting agent which does not generate a radical. Specifically, it is a component which reacts nucleophilically by an unshared electron pair or an anion in the molecule, and examples thereof include polyamines, polyhydric phenols, and organic acid hydrazine compounds. However, it is not limited to these. Among them, an organic acid hydrazine compound is particularly preferably used. For example, an aromatic hydrazine, p-xylylene phthalate, m-xylylene hydrazine, 2,6-naphthoic acid diterpene, 2,6-pyridine dihydrazine, 1,2,4-benzenetriazole, Bismuth, tetrakis(superfines) of 1,4,5,8-naphthoate and tetraterpenoids of pyromellitic acid. Further, examples of the aliphatic hydrazine compound include formazan, ethyl hydrazine, cesium propionate, bismuth oxalate, diammonium malonate, diterpene succinate, and bismuth glutarate. Bismuth, diammonium adipate, diammonium pimelate, diterpene sebacate, 1,4-cyclohexanedioxime, diterpenic tartrate, diterpene malate, iminodiacetic acid Diterpenoid, N, N'-hexamethylene diamine urea, triterpenoid citrate, trimethyl hydrazine acetate, triterpene Cyclohexane tricarboxylate, 1,3-bis(decylcarbonyl) a base having a carbendazim skeleton, preferably a guanamine carbendazim skeleton (a skeleton in which a carbon atom of the uremone ring is substituted with an isopropyl group) Bismuth compound; tris(1-mercaptocarbonylmethyl)isocyanurate, tris(2-mercaptocarbonylethyl)isocyanurate, tris(3-mercaptocarbonylpropyl)isocyanurate Ester, bis(2-mercaptocarbonylethyl)isocyanurate, and the like. From the standpoint of the balance between the hardening reactivity and the latent potential, it is preferably meta-xylylene hydrazine, diammonium malonate, diterpene adipate, tris(1-mercaptocarbonylmethyl) isocyanide. Uric acid ester, tris(2-mercaptocarbonylethyl)isocyanurate, tris(3-mercaptocarbonylpropyl)isocyanurate, particularly preferably diammonium malonate.

The content of the component (D) in the total amount of the liquid crystal sealing agent is preferably from 0.1 to 10% by mass, and more preferably from 1 to 5% by mass.

The liquid crystal sealing agent of the present invention may further comprise a molecule An epoxy resin having less than three reactive functional groups is used as the component (E) to improve the bonding strength. The component (E) is preferably one which is less polluting or solubility to liquid crystals. Examples of suitable epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and diepoxypropyl groups of resorcinol (Resorcin). Ether, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain Epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, ethyl uret urea type epoxy resin, isocyanurate type epoxy resin, and dicyclic bisphenol An oxypropyl etherate, a di-epoxypropyl ether compound of a difunctional alcohol, a halide, a hydride or the like.

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

The liquid crystal sealing agent of the present invention may further be added with a decane coupling agent. For the component (F), it is intended to improve the bonding strength and moisture resistance. As the component (F), 3-glycidoxypropyltrimethoxydecane, 3-glycidoxymethyldimethoxydecane, 3-glycidoxymethyldiethoxyl Baseline, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3 - mercaptopropyltrimethoxydecane, vinyltrimethoxydecane, N-(2-(vinylbenzylamino)ethyl)-3-aminopropyltrimethoxydecane hydrochloride, 3-methyl C Ethyloxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, and the like. These decane coupling agents are sold in the KBM series, the KBE series, etc., by Shin-Etsu Chemical Co., Ltd., etc., and thus can be easily obtained from the market.

The content of the component (F) is preferably from 0.05 to 3% by mass based on the total amount of the liquid crystal sealing agent.

The liquid crystal sealing agent of the present invention may be blended in addition to the above components. For example, a photopolymerization initiator, a radical polymerization inhibitor, an inorganic filler, a rubber fine particle, a hardening accelerator such as an organic acid or an imidazole compound, an organic filler, or an additive such as a pigment, a leveling agent, an antifoaming agent, or a solvent.

The photopolymerization initiator is not particularly limited, and may be a compound which generates a radical or an acid by irradiation with ultraviolet light or visible light to initiate chain polymerization, and examples thereof include benzoin dimethyl ketal. , 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethyl hydrazine, 2-hydroxy-2-methylpropiophenone, 2-methyl-[4-(A Thio)phenyl]-2-morpholinyl-1-propane, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, Camphorquinone, 9-fluorenone, diphenyl Disulfide and the like. Specifically, IRGACURE ^RTM 651, 184, 2959, 127, 907, 396, 379 EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE ^RTM 1173, LUCIRIN ^RTM TPO (above, manufactured by BASF Corporation); SEIKUOL ^RTM Z, BZ, BEE, BIP, BBI (above manufactured by Seiko Chemical Co., Ltd.) and the like.

Further, from the viewpoint of liquid crystal contamination, it is preferred to use a photopolymerization initiator having a (meth)acryl group in the molecule, and for example, 2-methylpropene oxime can be preferably used. The reaction product of oxyethyl isocyanate with 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one. This compound can be obtained by the method described in International Publication No. 2006/027982.

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

The radical polymerization inhibitor is not particularly limited and is The radical generated by the photopolymerization initiator or the thermal radical polymerization initiator or the like may be reacted to inhibit polymerization, and a guanidine, piperidine, hindered phenol, or nitroso group may be used. Specific examples thereof include naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidin-1-oxyl, 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-yloxy, 2,2,6,6-tetramethyl-4-methoxypiperidin-1-yl, 2, 2,6,6-tetramethyl-4-phenoxypiperidin-1-yloxy, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, p-benzoquinone, butylated hydroxy fennel Ether, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-t-butyl-m-cresol, β-(3,5-di-t-butyl-4-hydroxyl Phenyl) stearyl laurate, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6- Third butyl phenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy]ethyl], 2,4,8,10-tetraoxaspiro[5,5]undecane, tetra- [Methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenylpropionate)methane, 1,3,5-tris(3',5'-di- Tributyl-4'-hydroxybenzyl)-second triazine-2,4,6-(1H,3H,5H)trione, p-methoxyphenol, 4-methoxy-1-naphthol, Thiodiphenylamine N- nitrosophenyl hydroxylamine aluminum salt, tradename ADEKASTAB LA-81, trade name, ADEKASTAB LA-82 (Adeka Corp. as above (ADEKA Corporation) manufactured by Made, etc., but not limited to these. Among them, a radical polymerization inhibitor of a naphthoquinone type, a hydroquinone type, or a nitroso piperazine type is preferable, and a naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di- Tributyl-p-cresol, Polystop 7300P (manufactured by Hakuto Co., Ltd.), and most preferably Polystop 7300P (manufactured by Berton Co., Ltd.).

The radical polymerization inhibitor has the following method: when the component (C) is a (meth)acrylated epoxy resin; or dissolved in the component (C), a (meth)acrylated epoxy resin and/or Ingredient (E) is an epoxy resin. In order to obtain a more effective effect, it is preferably added to the component (C) and/or the component (E) and dissolved. The content of the radical polymerization inhibitor is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, particularly preferably 0.01 to 0.2% by mass, based on the total amount of the liquid crystal sealing agent of the present invention.

Examples of the inorganic filler include molten cerium oxide and crystal two. Cerium oxide, tantalum carbide, tantalum nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesia, zirconia, aluminum hydroxide, magnesium hydroxide, cesium Calcium acid, aluminum niobate, lithium aluminum niobate, zirconium silicate, antimony bismuth, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably molten cerium oxide, crystalline cerium oxide, cerium nitride, nitrogen Boron, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium citrate, aluminum citrate, further preferably molten cerium oxide, crystalline cerium oxide, aluminum oxide, talc. Two or more kinds of these inorganic fillers may be used in combination. When the average particle diameter is too large, the problem that the gap cannot be formed smoothly when the upper and lower glass substrates are bonded together when the liquid crystal cell having a narrow gap is formed is preferably 3 μm or less, preferably 2 μm or less. Laser diffraction/scatter A particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co. Ltd.; LMS-30) was used to measure the particle diameter.

In the liquid crystal sealing agent of the present invention, when the inorganic filler is used, the total amount of the liquid crystal sealing agent is usually 5 to 50% by mass, preferably 5 to 40% by mass. When the content of the inorganic filler is less than 5% by mass, the bonding strength to the glass substrate is lowered, and the moisture resistance reliability is also poor, and therefore, the decrease in the bonding strength after moisture absorption may become large. On the other hand, when the content of the inorganic filler is more than 50% by mass, the filler content is excessive, and therefore, it may be difficult to crush and the gap of the liquid crystal cell may not be formed.

Examples of the rubber fine particles include natural rubber (NR) and Pentadiene 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), polyurethane rubber (PUR), silicone rubber (Si, SR), fluororubber (FKM, FPM), polysulfide rubber (thiokol), etc., may be individual rubber particles or two or more core-shell structures. In addition, two or more types may be used in combination. Among them, acrylic rubber and silicone rubber are preferred.

When an acrylic rubber is used, it is preferably an acrylic rubber having a core-shell structure composed of two kinds of acrylic rubbers, and particularly preferably, the core layer is n-butyl acrylate and the shell layer is methyl methacrylate. Such a rubber is sold under the trade name Zefiakku ^RTM F-351 by AICA Kogyo Co., Ltd.

Further, as the above-mentioned silicone rubber, an organic polyoxane crosslinker is exemplified. Powder, linear dimethyl polyoxyalkylene crosslinked powder, and the like. Further, examples of the composite silicone rubber include a silicone resin (for example, a polyorganosilsesquioxane resin) coated on the surface of the above-described silicone rubber. Among these rubber fine particles, a composite oxirane rubber in which a linear dimethylpolysiloxane crosslinked powder of a fluorinated rubber or a oxime resin is coated with a linear dimethyl polyoxyalkylene crosslinked powder is particularly preferred. particle. These may be used alone or in combination of two or more. Further, it is preferable that the shape of the rubber powder is a spherical shape having a small increase in viscosity after the addition.

In the liquid crystal sealing agent of the present invention, when the rubber fine particles are used, the total amount of the liquid crystal sealing agent is usually 5 to 50% by mass, preferably 5 to 40% by mass.

Examples of the curing accelerator include an organic acid and an imidazole.

The organic acid may, for example, be an organic carboxylic acid or an organic phosphoric acid, and is preferably an organic carboxylic acid. Specific examples thereof include aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, and furan dicarboxylic acid; succinic acid and hexanic acid; Acid, dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, tris(2-carboxymethyl)isocyanurate, tris(2-carboxyethyl)isocyanuric acid An acid ester, tris(2-carboxypropyl)isocyanurate, bis(2-carboxyethyl)isocyanurate or the like.

Further, examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1- Benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- 2-undecylimidazole, 2,4-diamino-6-(2'-methylimidazolium (1')) ethyl-s-triazine, 2,4-diamino-6-(2' -undecyl imidazolium (1')) ethyl-s-triazine, 2,4-diamino-6-(2'-ethyl-4-methylimidazolium (1')) ethyl-all three Oxazine, 2,4-diamino-6-(2'-methylimidazolium (1'))ethyl - a homotriazine/isocyanuric acid adduct, a 2:3 adduct of 2-methylimidazoisocyanuric acid, a 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-di Hydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the like.

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

As an example of a method of obtaining the liquid crystal sealing agent of the present invention, there is The method shown below. First, in the component (A), that is, a curable resin having three or more reactive functional groups in one molecule, the component (C) has less than three reactive functional groups in one molecule, if necessary (A) The acrylated epoxy resin, the component (E) is heated and mixed with an epoxy resin having less than 3 reactive functional groups in one molecule, and after cooling to room temperature, the component (B) is added as a thermal radical polymerization initiation. And a component (D), a heat hardener, a component (F), a decane coupling agent, an antifoaming agent, a leveling agent, a solvent, etc., using a well-known mixing apparatus, such as a three-roll mill, sanding. The liquid crystal sealing agent of the present invention can be produced by uniformly mixing a machine, a ball mill or the like and filtering it with a metal mesh.

The liquid crystal display unit cell of the present invention is formed on the substrate with a specific The pair of substrates of the electrodes are arranged to face each other at a specific interval, and the liquid crystal display cell is sealed by sealing the liquid crystal sealant of the present invention with a liquid crystal sealing agent in the gap. The type of the liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a combination substrate which is made of glass, quartz, plastic, tantalum or the like and at least one of which has light transmissivity. In the liquid crystal display unit of the present invention, a spacer such as a glass fiber (gap control material) is added to the liquid crystal sealing agent of the present invention, and then one of the pair of substrates is used. The liquid crystal sealing agent is applied by a dispenser, a screen printing device, or the like, and then pre-cured at 80 to 120 ° C as needed. Thereafter, the liquid crystal was dropped onto the inside of the bank formed of the liquid crystal sealing agent, and the other glass substrate was superposed in a vacuum to cause a gap to be generated. After the gap is formed, it is cured at 90 to 130 ° C for 1 to 2 hours, whereby the liquid crystal display cell of the present invention can be obtained. The liquid crystal display cell of the present invention thus obtained does not exhibit display defects due to liquid crystal contamination, and is excellent in adhesion and moisture resistance reliability. Examples of the spacer include glass fibers, cerium oxide beads, and polymer beads. The diameter varies depending on the purpose, and is usually 2 to 8 μm, preferably 4 to 7 μm. The amount of the liquid crystal sealing agent of the present invention is usually 0.1 to 4% by mass, preferably 0.5 to 2% by mass, and more preferably 0.9 to 1.5% by mass, based on 100% by mass of the liquid crystal sealing agent of the present invention.

The liquid crystal sealing agent of the present invention has excellent resistance to liquid crystal infiltration For example, in the bonding step and the heating step of the substrate in the liquid crystal dropping method, liquid crystal infiltration and sealing collapse do not occur. Therefore, a stable liquid crystal display cell can be produced. Further, since the curable resin is rapidly crosslinked, the constituent components are rarely eluted into the liquid crystal, and the display failure of the liquid crystal display cell can be reduced. Moreover, since it is excellent in storage stability, it is suitable for the manufacture of a liquid crystal display cell. Further, since the cured product has excellent properties such as adhesion strength, heat resistance, and moisture resistance, the liquid crystal display unit having excellent reliability can be produced by using the liquid crystal sealing agent of the present invention. Further, the liquid crystal display cell produced by using the liquid crystal sealing agent of the present invention has a high voltage holding ratio and a low ion density, and is sufficiently required as a liquid crystal display unit cell.

[Examples]

Hereinafter, the present invention will be described in more detail by way of experimental examples and examples. However, the invention is not limited to the embodiments. In addition, as long as there is no special record, the "parts" and "%" in this article are the quality benchmarks.

(Synthesis Example 1)

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

100 parts (0.28 mol) of commercially available benzopinacol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 350 parts of dimethylformamide. Thereto, 32 parts of pyridine (0.4 mol) was added as a base catalyst, and BSTFA (manufactured by Shin-Etsu Chemical Co., Ltd.) 150 parts (0.58 mol) was used as a decylating agent, and the temperature was raised to 70 ° C, followed by stirring for 2 hours. The obtained reaction liquid was cooled, and while stirring, 200 parts of water was added to precipitate a product and deactivate the unreacted decylating agent. The precipitated product was filtered, separated, and washed thoroughly. Then, the obtained product was dissolved in acetone, and after adding water, it was recrystallized and purified. 105.6 parts of the desired 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane (yield 88.3%) was obtained.

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

(Synthesis Example 2)

[Synthesis of a full acrylate of resorcinol diepoxypropyl ether]

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

(Examples 1 to 5, Comparative Example 1)

The components (A), (C), and (E) in the amounts shown in Table 1 below were heated and mixed, and after cooling, the components (B), (D), (F), and (other components) were added and stirred. Thereafter, the film was dispersed by a three-roll mill and filtered with a metal mesh (635 mesh) to prepare liquid crystal sealants of Examples 1 to 5. Further, according to the same procedure, the materials shown in Table 1 were blended, and the liquid crystal sealing agent of Comparative Example 1 was prepared.

A-1: Ethylene oxide modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.: DPEA-12)

(Reactive functional group number: 6, molar average molecular weight: 1107, average molecular weight per 1 reactive functional group: 185)

A-2: Caprolactone upgrading (2 mol) dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.: DPCA-20)

(Reactive functional group number: 6, molar average molecular weight: 807, average molecular weight per 1 reactive functional group: 134)

A-3: Caprolactone upgrading (6 mol) dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.: DPCA-60)

(Reactive functional group number: 6, molar average molecular set: 1263, average molecular weight per 1 reactive functional group: 211)

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

(Reactive functional group number: 3, molar average molecular weight: 298, average molecular weight per 1 reactive functional group: 99)

B-1:1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane (Synthesis Example 1 was finely ground to a mean particle size by a jet mill) 1.9μm)

C-1: all-acrylate of resorcinol diepoxypropyl ether (Synthesis Example 2)

D-1: tris(2-mercaptocarbonylethyl)isocyanurate finely divided product

(Manufactured by Japan FINECHEM Co., Ltd.: HCIC, finely ground to a uniform particle size of 1.5 μm by a jet mill)

E-1: ethylene oxide addition bisphenol S type epoxy resin (synthesized by the method described in Japanese Patent No. 4211942)

F-1: 3-glycidoxypropyltrimethoxydecane (manufactured by Chisso Corporation: Sila-Ace S-510)

F-2: N-2-(aminoethyl)-3-aminopropyltriethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-603)

O-1: spherical cerium oxide (manufactured by Shin-Etsu Chemical Co., Ltd.: X-24-9163A; primary average particle diameter is 110 nm)

O-2: niobium oxide rubber powder (manufactured by Shin-Etsu Chemical Co., Ltd.: KMP-594; primary average particle size of 3 μm, specific gravity of 0.97, Shore A hardness For 30)

(fine powder of addition polymer of vinyl-containing dimethyl polysiloxane and methyl hydrogen polyoxyalkylene)

O-3: tris(3-hydroxyethyl)isocyanurate

(Manufactured by Shikoku Chemical Industry Co., Ltd.: CIC acid, finely ground to a uniform particle size of 1.5 μm by a jet mill)

The liquid crystal sealing agents prepared in Examples 1 to 5 and Comparative Example 1 were subjected to the following evaluations. The results are summarized in Table 2.

[Evaluation of penetration resistance of liquid crystal]

To 100 g of each of the liquid crystal sealing agents, 1 g of glass fibers having a diameter of 5 μm was added as a spacer, and the mixture was stirred and defoamed, and filled in a syringe. The liquid crystal sealing agent filled in the syringe was applied onto a glass substrate with an ITO transparent electrode using a dispenser (SHOTMASTER 300: manufactured by Musashi Engineering Inc.) to form a seal pattern and a simulated seal. pattern. Then, fine droplets of liquid crystal (MLC-3007; manufactured by Merck Ltd.) were dropped into the frame of the seal pattern. Further, on a glass substrate which had been subjected to rubbing treatment, a planar spacer (Natoco Spacer KSEB-525F; manufactured by Natoco Co., Ltd.; gap width after bonding) of 5 μm was spread, and thermal bonding was carried out using a bonding apparatus in a vacuum. It is bonded to the substrate on which the previous liquid crystal has been dropped. After opening in the air to form a gap, it was allowed to stand for 10 minutes, and put into a 120 ° C oven for heat hardening for 1 hour. Thereafter, the interface between the seal and the liquid crystal was observed by a polarizing microscope, and the evaluation was performed in accordance with the following criteria. The results are shown in Table 2.

○: Infiltration of liquid crystal was not observed in the liquid crystal sealing agent.

△: A little penetration of liquid crystal was observed in the liquid crystal sealing agent.

X: Infiltration of liquid crystal was observed in the liquid crystal sealing agent.

[For the pollution evaluation of liquid crystal]

To 100 g of each of the liquid crystal sealing agents, 1 g of glass fibers having a diameter of 5 μm was added as a spacer, and the mixture was stirred and defoamed, and filled in a syringe. The liquid crystal sealing agent filled in the syringe was applied onto a glass substrate with an ITO transparent electrode using a dispenser (SHOTMASTER 300: manufactured by Musashi Hi-Tech Co., Ltd.) to form a seal pattern and a dummy seal pattern. Then, fine droplets of liquid crystal (MLC-3007; manufactured by Merck & Co., Ltd.) were dropped into the frame of the seal pattern. Further, on a glass substrate which had been subjected to rubbing treatment, a planar spacer (Natoco Spacer KSEB-525F; manufactured by Natoco Co., Ltd.; gap width after bonding) of 5 μm was spread, and thermal bonding was carried out using a bonding apparatus in a vacuum. It is bonded to the substrate on which the previous liquid crystal has been dropped. After opening in the air to form a gap, it was allowed to stand for 10 minutes, and put into a 120 ° C oven for heat hardening for 1 hour. Thereafter, the interface between the seal and the liquid crystal was observed by a polarizing microscope, and the evaluation was performed in accordance with the following criteria. The results are shown in Table 2.

○: No discoloration or foreign matter was observed in the liquid crystal in the vicinity of the liquid crystal sealing agent.

△: A slight discoloration or foreign matter was observed in the liquid crystal in the vicinity of the liquid crystal sealing agent.

X: Discoloration or foreign matter was observed in the liquid crystal in the vicinity of the liquid crystal sealing agent.

[Composition Strength Evaluation]

To 100 g of the liquid crystal sealing agent, 1 g of glass fibers having a diameter of 3 μm was added as a spacer and mixed and stirred. Apply this liquid crystal sealant to 50 On a glass substrate of mm × 50 mm, a glass piece of 1.5 mm × 1.5 mm was attached to the liquid crystal sealing agent, and the film was placed in an oven at 120 ° C for 1 hour. The shear bond strength of the glass piece was measured using a Bond Tester (SS-30WD: manufactured by Sejin Corporation). The results are shown in Table 2.

From the results of Table 2, it was confirmed that the penetration resistance of the liquid crystals in Examples 1 to 5 was improved as compared with Comparative Example 1 in which the component (A) was not added.

[Industrial availability]

The liquid crystal sealing agent of the present invention is excellent in resistance to penetration of a liquid crystal into a liquid crystal sealing agent, and is excellent as a general property of a liquid crystal sealing agent, such as a bonding strength, and can easily produce a liquid crystal display cell excellent in long-term reliability.

Claims (15)

A liquid crystal sealing agent comprising: (A) a curable resin having three or more reactive functional groups in one molecule, and (B) a thermal radical polymerization initiator. The liquid crystal sealing agent according to claim 1, wherein the reactive functional group of the component (A) is a cyclic ether group and/or a (meth) acryl group. The liquid crystal sealing agent according to claim 1, wherein the reactive group equivalent (average molecular weight per reactive functional group) of the component (A) is 200 or less. The liquid crystal sealing agent according to claim 1, wherein the component (A) has a molar average molecular weight of 800 or more. The liquid crystal sealing agent according to claim 1, wherein the reactive functional group of the component (A) is an acrylonitrile group. The liquid crystal sealing agent according to claim 1, wherein the component (A) contains a C1 to C4 alkylene oxide (-OR ¹ -O-) in the molecule (the aforementioned R ¹ represents a chain which may also have a branch or A cyclic resin of a cyclic alkyl group. The liquid crystal sealing agent according to claim 1, wherein the total amount of the liquid crystal sealing agent contains 5 to 40% by mass of the component (A). The liquid crystal sealing agent according to claim 1, further comprising (C) a (meth)acrylated epoxy resin having less than three reactive functional groups in one molecule, and (D) a thermal curing agent. The liquid crystal sealing agent according to claim 8, wherein the component (C) is a (meth) acrylate of resorcinol diglycidyl ether. The liquid crystal sealing agent according to claim 8, wherein the component (D) is an organic acid cerium compound. The liquid crystal sealing agent according to claim 1, wherein the component (B) is 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane. The liquid crystal sealing agent according to claim 1, which further contains (E) an epoxy resin having less than 3 reactive functional groups in one molecule. The liquid crystal sealing agent according to claim 1, which further contains (F) a decane coupling agent. A liquid crystal sealing agent according to any one of claims 1 to 13, wherein a liquid crystal sealing agent according to any one of claims 1 to 13 is formed on a substrate formed on one side of a liquid crystal display cell composed of two substrates. After the liquid crystal is dropped on the inside of the formed weir, the substrate on the other side is bonded, and then the liquid crystal sealing agent is cured by heat. A liquid crystal display unit cell obtained by curing a liquid crystal sealing agent according to any one of claims 1 to 13 which is obtained by hardening a liquid crystal sealing agent according to any one of claims 1 to 13.