TW201105736A - Liquid crystal sealing agent for liquid crystal dropping method and liquid crystal display cell using same - Google Patents

Abstract

Disclosed is a thermosetting liquid crystal sealing agent for a liquid crystal dropping method, which contains, as essential components, (a) a curable resin that is composed of an epoxy resin and a (meth)acrylated epoxy resin, (b) a polyfunctional hydrazide compound, (c) a curing accelerator, (d) an inorganic filler and (e) a silicone rubber powder that has a true specific gravity of 0.95-1.0 and an average particle diameter of 10-18 [μ m]m. The thermosetting liquid crystal sealing agent for a liquid crystal dropping method contains the silicone rubber powder (e) in an amount of 5-40% by mass relative to the liquid crystal sealing agent.

Description

201105736 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemistry that best shows the characteristics of the invention. VI. Description of the invention: [Technical field of the invention] The liquid crystal display unit thereof. The liquid crystal display unit is manufactured by a liquid crystal display unit. The present invention relates to a liquid crystal sealing agent and a liquid crystal sealing agent which is suitable for liquid crystal sealing agent by liquid crystal dropping and using the same according to the prior art - as the liquid crystal display unit (four) is enlarged, it has been used as a liquid crystal display in recent years;制造 制造 ' ' ' ' 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Specifically, the so-called liquid crystal dropping method is to apply a liquid crystal sealing agent on a liquid crystal substrate to form a (primary sealing) liquid crystal sealing agent, and then apply a circumferential sealant to the outermost periphery (the liquid crystal is dripped inside the dummy sealing inner layer, and then vacuumed). The liquid-tanned substrate of the other of the opposing liquid-phase substrates is closed by opening at atmospheric pressure, and the liquid-crystal display unit is completed by heating and hardening the sealing portion. In the manufacturing method, the liquid crystal is used. The liquid crystal sealing material used for the sealing is generally not used in the case of the 201105736 = thermosetting liquid crystal sealing agent, and the liquid heat curing type liquid crystal sealing agent cannot be used in the liquid crystal dropping method. In the case of using the conventional thermosetting liquid crystal sealing agent to perform the liquid sputum dropping method, the thermal expansion of the liquid crystal during heating and the viscosity of the liquid crystal sealing agent due to heating are lowered and under vacuum decompression, the sealing is puncture. 'And can't close the LCD. . In the method of using a liquid crystal sealing agent for photothermal curing, a liquid crystal sealing agent is applied onto a liquid crystal substrate by a dispenser or the like, and a liquid crystal is dripped on the inside of the bank, and the vacuum is bonded to the opposite side. After the substrate of one of the layers, the sealing portion was irradiated with ultraviolet rays or the like to temporarily cure the liquid crystal sealing agent at about 120 ° C for about 1 hour to produce a liquid crystal cell. However, when it is a photothermal hardening type, it is necessary to irradiate the liquid crystal sealing agent with ultraviolet rays, etc. 'But in recent years, the liquid crystal sealing portion is shielded by wiring or black matrix, and liquid crystal is used. A portion of the sealant where light is not irradiated occurs, and an unhardened portion due to light shielding of the liquid crystal seal is inserted into the liquid crystal during the heat hardening step' or a problem of liquid crystal contamination occurs. Moreover, in the design of the liquid crystal cell, it is necessary to design a restriction that the sealant is irradiated with as much light as possible. Further, deterioration of the liquid crystal or the alignment film due to the ultraviolet irradiation is a problem. Therefore, in the ultraviolet irradiation step, it takes a lot of effort to shield the liquid crystal portion by the hood so that the ultraviolet ray does not adhere to the liquid crystal. Further, as the size of the liquid crystal glass substrate is increased, there is a problem that the size of the ultraviolet irradiation device is increased or the operation cost of the ultraviolet irradiation device is increased. In view of the above, in recent years, it has been desired to realize a liquid crystal sealing agent for a thermosetting liquid crystal dropping method which can produce a liquid crystal display unit by thermal curing without using ultraviolet rays. Heretofore, there has been proposed a liquid crystal cell for a thermosetting liquid crystal dropping method. For example, in the patent document 2, it is proposed that the number of the z-bonding energy groups in the molecule is divided by the molecular weight and the value is 4 or more, and the weight of the menstrual weight is 3 to 4 parts by weight. A hardening liquid liquid sealing agent is used for the liquid helium dropping method of the hardener. The proposal becomes a low liquid crystal contamination by using this liquid crystal sealing agent. However, in the thermosetting type liquid crystal dropping method, since the thermal expansion of the liquid crystal due to heating and the pressure reduction in the vacuum are closed, the twisting causes a low viscosity to cause a low viscosity, and the liquid crystal sealing agent in the hardening process is The bank will be damaged and there is a problem of liquid crystal leakage (the problem of sealing puncture (sealed pee) 6), and the composition of the low-viscosity liquid crystal sealing agent caused by heating is still heated above the NI point, and there is dissolution to more The liquid crystal 0 which is easy to flow and the major problem causing pollution, the patent reading 2 does not clearly explain the solution to these problems. Further, in Patent Document 3, a liquid crystal sealing agent to which a gelling agent is added is proposed, and only the thermosetting liquid crystal droplets can be held in the same manner as the sealing puncture and the sealing shape. However, the 'thermally hardened liquid crystal time <hit point, that is, the addition of titanium = chemical liquid crystal sealing agent to liquid crystal contamination' is not disclosed in Patent Document 3, and it is proposed in Patent Document 4 that after coating with a thermosetting resin sealing agent After pre-baking, the method of dropping and vacuum bonding of the day 1 and the daily untwisting liquid was carried out, but the resin composition of the liquid crystal sealing agent was not clearly indicated. In Patent Documents 5 and 6, the β-kappa ratio is considered as the B-stage treatment, and the thermosetting property of the pre-flooding 201105736 baking step is φ Φ * 〇n〇r ,, the liquid crystal sealing agent for the lower working method, However, it is necessary to stage the processing at 20 minutes + 80 in the 80C, and there is a disadvantage that the processing time becomes longer. For the β-stage processing time of 4 § 4 ε 5 0 λ, ^ 〇 is the clock, the processing > JHL degree can be increased, for example, to η η μ μ & , , c c , , , , , , , , , , , , , , , , , , , ,曰The sealant will perform the final hardening reaction at a temperature above l00t. However, it is also difficult to develop a heat-cured 3L liquid crystal drip sealant system that completely solves these problems. Liquid crystal dropping method. In addition, in recent years, it has been strongly demanded that the outer dimensions of the substrate are not increased, and the display area is larger. Therefore, the change is made to form a narrow frame edge which narrows the outer circumference of the sealing day, or narrows the width of the liquid crystal (four). The design of the liquid crystal cell. Therefore, it is required to form a liquid crystal sealing agent which is formed by finely forming a sealing width and having a sealed shape which is not easy to be disturbed in the sealing agent '" even if the sealing width is narrowed and the adhesion strength is strong. Further, a liquid crystal sealing agent having a small pot life and a small change in coating conditions of the liquid crystal sealing agent during the working time is required. In recent years, the popularity of liquid crystal televisions and the like has been increasing, and in order to improve the high-speed response of the liquid crystal, the cell gap of the liquid crystal (the gap between the two substrates filled with the liquid crystal) is narrowed. Therefore, in the vacuum bonding of the liquid crystal substrate, a liquid crystal sealing agent which is easy to narrow the cell gap is required. Further, the deterioration of the crystal seal under high-humidity conditions has become a problem for the demand for a longer life of the liquid crystal cell. In this case, a liquid crystal sealing agent having a small deterioration in adhesion strength of a liquid crystal sealing after a high temperature and high humidity test is required. As described above, it is required to realize a thermosetting liquid crystal dropping method, which is not sealed by vacuum heating, and does not have liquid crystal contamination. The adhesion strength and the strength of the 201105736 wet test are strong, and the seal coating property is excellent. A liquid crystal sealing agent for a thermosetting liquid crystal dropping method which is easy to apply at room temperature and has a narrow cell gap. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Publication No. 3955749 (Patent Document 3) Patent No. 3,976,749 [Patent Document 4] [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. 2-7-9 No. The present invention provides a liquid hardening liquid which does not require irradiation of ultraviolet rays to a liquid crystal sealing portion: 曰: a liquid crystal sealing agent for dropping a working method. Further, it provides a liquid crystal sealing agent for a thermosetting liquid crystal dropping method which is excellent in liquid crystal contamination, and has high adhesive strength after wet strength test and excellent sealing linearity, which is suitable for use at room temperature (4), and a narrow cell gap. In order to solve the aforementioned problems, the inventors of the present invention repeated the intensive research and completed the present invention. That is, the present invention relates to (1) to (8). (1) A liquid crystal sealing agent for a thermosetting liquid crystal dropping method, comprising a curable resin (4) of an epoxy resin and a (meth)acrylic epoxy resin, a polyfunctional hydrazine compound (1), and a curing accelerator (c) , inorganic filler (4) and true specific gravity of 0.95~10, average particle size of 1〇~18" Shixi oxygen rubber powder 6 201105736 Γ two as essential components, of which pre-oxygen rubber powder (seven) ... sputum daily seal 5 to 40% by mass in the agent. , 3 lining sealant: 2: t (:: loaded thermosetting liquid crystal dropping method using liquid crystal dense organic hydrogen polymer-based vinyl-containing organic polyoxan Institute and spoon-added polymer micro-powder. The liquid crystal (four) agent for a thermosetting liquid crystal dropping method according to (1) or (2), wherein the polyfunctional hydrazine compound (7) is a polyfunctional hydrazine compound having a heterotriazolium ring skeleton represented by ' (1) R1 0.

N, N, 0 R3 < -N. (1) R2 Ο (In the formula (1), at least two of the molecular skeletons K represented by the following formula (2) are independently hydrogen atoms or R to R3 (1) The group shown; , . , ~^H2Cbf 0 N. , NHc (2) (in the formula (2), n represents an integer of 1 to 6). (4) As described in the above (1) or (2) The liquid crystal sealing agent for a thermosetting liquid crystal dropping method, wherein the inorganic filler (d) is one of alumina and vermiculite. (5) The thermosetting liquid crystal dropping method according to the above (1) or (2) In the liquid crystal sealing agent, the hardening accelerator (c) is a polycarboxylic acid compound having an iso-cyanuric acid ring skeleton of the following formula (3): 7 201105736.

(In the formula (3), T: to r are each independently a nitrogen atom or a molecular skeleton represented by the following formula (4), and at least one of T to r: represents a formula (4) of the formula (4) in the formula (4). (2) A thermosetting liquid crystal dropping method liquid crystal sealing agent containing a polythiol compound as described in the above (1) or (7), wherein the thermosetting liquid crystal dropping method liquid crystal sealing agent according to the above (1) or (7), The (8)-type display unit is sealed by the cured product of the crystal sealant according to the above (1) or (2). The liquid crystal sealing agent of the present invention does not require ultraviolet irradiation on the liquid crystal sealing portion. The thermosetting liquid crystal dropping method is possible, because the liquid crystal contamination is low, the adhesion strength after the adhesion strength and the moisture resistance test is strong, and the sealing linearity is excellent. 纟 The application period of the room temperature is long, and the liquid crystal cell of the narrow cell gap is manufactured. It is easy to manufacture, and high-reliability and high-quality liquid crystal display unit manufacturing system has high yield and can be produced. 8 201105736 [Embodiment] The present invention will be described in detail. The thermosetting liquid crystal dropping method of the present invention is used for crystal sealing. Agent Also referred to as "liquid crystal sealant", it contains hardened tree sap (a) gg 醯肼 compound (b), hardening accelerator (c), inorganic filler (4) and true specific gravity of 0.H 〇, average The particle size is 】]~18", the rubber powder (e) is used as an essential component, wherein the stone oxide rubber powder (e) contains 5 to 40% by mass of the liquid crystal sealing agent. Liquid crystal sealing shot, as the above-mentioned curable resin (small epoxy resin and (meth)acrylic epoxy resin. (Here, "(meth)acrylic" means "acrylic" A "methacrylic acid" The sclerosing resin (a) used in the present invention preferably has low contamination to a liquid crystal, low solubility, and low resin viscosity. Examples of suitable epoxy resins include bisphenol A type. Epoxy resin, double-check F-type epoxy resin 'double-brewed s-type epoxy resin, 胄 乙 院 加 加 双 双 帛 帛 帛 、 、 、 、 、 、 纷 纷 纷 纷 纷 纷 纷 纷 纷 、 、 、 、 、 Epoxy resin, bisphenol A novolac type epoxy resin 'bisphenol f novolac type epoxy resin, resorcinol diminal Ether, alicyclic epoxy resin, aliphatic lock epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, intramethylene urea resin, isomeric cyanate ring Oxygen resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin having a trisphenol methane skeleton, and diglycidyl ether compound of difunctional phenol, difunctional alcohol The diglycidyl ether compound, etc. The epoxy resin may be used singly or in combination of two or more kinds. Among these, 'from the viewpoint of liquid crystal contamination and viscosity, it is more 201105736 which is a bisphenol A type ring. Oxygen resin, bisphenol plus double 酴 s type epoxy resin, benzophenanthrene glutamate, epoxy epoxide is called benzene dioxin diglycidide shouted. ^ Water glycerin, which is especially good (methicone) The acidified epoxy resin is obtained by epoxy resin. The epoxy group is also epoxy-based epoxy resin or the (meth)acrylic acid of the ring earthworm (methane). The composition is reacted with the intention of / less than 4 liters of acrylated epoxy resin. (Methyl) Molybdenum) - officially w μ AW 岬义化娘虱 resin is preferably a compound having a (meth) propyl sulfhydryl group... may also be a "(methyl) acrylonitrile group and The structure of the epoxy group. At this time, the ratio of the epoxy group/(meth)acryl fluorenyl group is not selected from the viewpoints of the process suitability and viewpoint. Further, the (meth)acrylic acid % milk tree may be used singly or in combination of two or more. The epoxy resin of the raw material of the (meth)acrylic epoxy resin is particularly limited, and it is preferably an epoxy resin which is wrapped in (four) must be A, for example

A pair of A-type epoxy resin, bisphenol F oxy resin 'epoxy Ethylene addition type... type II ring ^ ^ 1 rolling tree, phenol novolac type II! ":, A (10) varnish epoxy Resin, Shuangpan A (four) varnish show her bismuth, bisphenol F novolac type epoxy resin, resorcinol diester ring epoxy resin 'aliphatic lock epoxy resin, shrinking wide: S曰 type ring resin , Glycidylamine type epoxy resin, B-urea urea type = tree ': Iso-trimer acid vinegar type epoxy resin 'bicyclic bismuth diene type epoxy: ear burial type epoxy resin, with three The phenyl age of the courtyard skeleton (four) clear ... oxygen oxide resin 'and difunctional diglycidyl (four), two 10 201105736 digol alcohol diglycidyl ether, etc., preferably bisphenol A type epoxy tree month s, bisphenol F type epoxy resin, resorcinol diglycidyl ether, of which more preferably is a separate - a succinyl ether. From the viewpoint of hardenability, the (meth)acrylated % oxygen resin is preferably an acrylated epoxy resin obtained by reacting an epoxy resin with acrylic acid. More preferably, it is an acrylic acid addition product of a bisphenol F type epoxy resin or an acrylic acid addition product of a m-diphenol diglycidyl ether. The curable resin of the % oxy-lipid and the (meth) acrylated epoxy resin (<the content in the liquid; 曰^ sealant is usually 30 to 70% by mass, preferably 4 〇 to 6 〇 里When the content of % is less than 30% by mass, the reaction at the time of thermosetting is slow, and when the liquid crystal cell is produced by the liquid Ba dropping method, the sealed bank is sealed by the liquid crystal::: and the sealing resin is low in viscosity, and sealing puncture occurs. If the content is as large as 70% by mass, sufficient adhesive strength is not obtained. Further, the content of the epoxy resin in the hardened tree (a) is usually 3 to 30 mass%/◦, preferably 5 to ^. 〇 , , , , , , , 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 The liquid-day sealant of the moon 含有 month contains a polyfunctional ruthenium compound (b). The compound (b) refers to a compound having two or more rutheniums in the molecule, as a specific example thereof. Examples thereof include dioxonium oxalate, dimercapto-malonate, hexamethylenediamine, diammonium pimelate, and octanoic acid. , azelaic acid diterpene, - .> diterpene, ~ acid diterpene, twelve burning two leave a # _ /, alkane oxime, maleic acid diterpenoid, fumaric acid diterpenoid , '醯肼, tartaric acid diterpenes, malate diterpenoids, meta-phenylene ... fight, for stupid dicarboxylic acid two brewing, 2,6-cacocarboxylic acid two brewing, 4,4_ 11 201105736 diphenyl Bismuth, 14-naphthoquinone dioxime, 2,6-pyridinium dihydrazide q, 2,4-benzenetriazole, pyromellitic tetraruthenium, 1,4,5, 8-naphthoic acid tetra An anthracene compound of a phthalic acid carbendazim skeleton such as hydrazine, 1, 3-bis(indolylethyl)-5-isopropylhydantoin, and the above formula (丨) Tris(丨-mercaptocarbonylmethyl)isocyanate, tris(2-mercaptocarbonylethyl)isocyanate, tris(3-mercaptocarbonylpropyl)isocyanate And bis(2-fluorenylcarbonylethyl)isocyanate, etc., may be used alone or in combination of two or more. Among these polyfunctional ruthenium compounds, adipic acid is preferred. Diterpene, diammonium isophthalate, 1,3-bis(decylcarbonylethyl)_5_isopropylhydantoin, (dibudecylcarbonylmethyl)isocyanate, tris(2-cyanocarbonylethyl)isocyanate, tris(3-mercaptocarbonylpropyl)isocyanate, double (2 _ mercaptocarbonyl: group) isocyanurate' is more preferably a tris(diphenylmethyl) isocyanurate or a tris(2-mercaptoethyl) differently represented by the formula (1) Cyanuric acid vinegar, tris(3-mercaptocarbonylpropyl)isocyano cyanide, bis(2- mercaptocarbonylethyl)isocyanuric acid, etc. The polyfunctional hydrazone compound is particularly exemplified by three (2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The diameter is fine and the branches are scattered. If the average particle diameter is too large, it is more than 2 in the case where the liquid crystal cell is formed in a narrow gap, and it is a failure to form a gap or the like when the upper and lower glass substrates are bonded together. The particle size of the hardener is preferably determined by a snow-emitting-scattering-scattering particle size distribution analyzer (manufactured by Dry Enterprise: us-30). In addition, "June-style club SEIS_ is prone to agglomeration, so it is preferable that the average particle diameter is too small to be extremely small (for example, 12 201105736). In the liquid crystal sealing agent of the present invention, For the total amount of the curable resin (3) of the epoxy resin and the (meth) propylene S under-epoxidized epoxy resin (1), the compounding ratio of the polyfunctional oxime compound (b) is 5 to 70 mass. When the amount of the component (b) is less than 5 parts by mass, the heat hardening reaction is insufficient, and the adhesive force and the glass transition point become low. On the other hand, if the amount of the component (b) is more than the mass part, the hardening is performed. The liquid crystal sealant of the present invention contains a hardening accelerator (c) as a hardening accelerator (c), as long as the adhesive remains, and the adhesive strength is lowered, and the pot life is also deteriorated. The reaction-promoting property is high, and the contamination of the liquid crystal is low. The storage period of the liquid crystal sealing agent is not deteriorated during normal temperature storage, and is not limited, and examples thereof include the iso-cyanuric acid ring represented by the above formula (3). Skeletal polycarboxylic acid or hydrazine Oxy-resin amine adducts, etc. These may be used alone or in combination of two or more. Among these curing accelerators, (1) (1) Acid ester, tris(2-stable ethyl)isocyanuric acid, S-(3-carboxypropyl)isocyanate, bis(2-indenyl)isocyanuric acid More preferably, it is a tris(3-hydroxypropyl) iso-cyanuric acid vinegar. The hardening accelerator (c) 'in order to become a quick-hardening latent hardening accelerator' is preferably a fine particle size and a uniform particle size. If the average particle diameter is too large, it is a major cause of failure in forming a gap between the upper and lower glass substrates when the liquid crystal cell is formed in a narrow gap. Therefore, it is preferably 3...the lower is 2&quot In addition, if the storage stability at room temperature is too small, the lower limit of the average particle diameter of the hardening accelerator is usually about 1 " m. 13 201105736 In the present invention, the hardening accelerator (c) accounts for liquid crystal. The content of the sealant is preferably from 0.1 to 10% by mass, more preferably from 3 to 8% by mass. If the content is less than 0.1% by mass, then When the content is more than 1% by mass, the stability at room temperature is deteriorated. The inorganic filler (d) used in the present invention may, for example, be alumina or vermiculite. Metal oxides such as talc, clay, bentonite, organic bentonite, barium titanate, titanium oxide, cobalt oxide, magnesium oxide, nickel oxide, cerium oxide, carbonates such as calcium carbonate and magnesium carbonate, barium sulfate, calcium sulfate For example, a metal hydroxide such as a sulfate, aluminum hydroxide or magnesium hydroxide, or a bismuth citrate such as calcium citrate, aluminum citrate or bismuth ruthenate may be used singly or in combination of two or more. Among the inorganic fillers, at least one of alumina and vermiculite is particularly preferred. The inorganic filler (d) used in the present invention preferably has an average particle diameter of 3 vm or less. When the average particle diameter is more than 3 #m, the formation of the gap occurs when the upper and lower glass substrates are bonded during the production of the liquid crystal cell. The lower limit of the average particle diameter of the inorganic filler is usually about 〇·〇1 V m. The content of the inorganic filler used in the present invention in the liquid crystal sealing agent is usually from 1 to 4% by mass, preferably from 2 to 30% by mass. If the content of the inorganic filler is less than / in the mass. Further, the adhesion strength to the glass substrate is lowered, and the moisture resistance reliability is also poor, so that the adhesion strength after moisture absorption is greatly lowered. Further, when the amount of the filler of the inorganic filler is more than 40% by mass, the content of the filler is too large, so that the seal does not easily collapse and the gap of the liquid crystal cell cannot be formed. The silicone rubber powder used in the present invention (the magic system refers to a rubbery polyoxyl resin obtained by crosslinking a polyoxyalkylene oxide, for example, a vinyl group-containing organic polyfluorene 14 201105736 • an alkane and an organic hydrogen polyoxyalkylene oxide The fine powder of the addition polymer, etc. These may be used singly or in combination of two or more. Among these, the oxime oxygen rubber powder is preferably a vinyl group-containing dimethyl polyoxane. The fine powder of the addition polymer of the methyl hydrogen polyoxyalkylene. Specific examples thereof include hydrazine, ^-52-875 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. The true specific gravity of the powder (6) is preferably 95 to 1. When the true specific gravity is larger than 丨.〇, the rubber particles become hard, and when the liquid crystal cell is fabricated, the gap is formed when the upper and lower glass substrates are bonded together: If the true specific gravity is less than 〇95, the sealing of the liquid crystal will easily occur when the unit is fabricated. The true specific gravity can be obtained by liquid immersion method using the isopropanol method (Archimeder method). The average particle diameter of the rubber powder (e) is preferably 10 to 18/zm, more preferably in~^ Wenma 10 1 5#m. If the average particle size is larger than 18/zm, the seal will not easily collapse. The average + 卞3 祖仏 is less than 1 〇" m, especially in the production of 5# in. 〇 _ _ 1 The early gap of the gap, liquid crystal sealing puncture is easy to occur. If the average particle size is in the above range, even if the cell gap is H " Yang: can ensure the gap, and can be manufactured without occurrence The average particle diameter of the sealing puncture of the mono-oxygen rubber powder can be obtained from a photograph of an electron microscope. Ben: Mingzhong, the rubber powder (the content in the liquid crystal sealing agent is ～40% by mass, preferably 1〇) ~ If the content is less than 5% by mass, the sealing of the liquid crystal cell will occur when the liquid crystal cell is manufactured, and the viscosity of the liquid crystal sealing agent is lowered, and the weather is θ or leaked. When it is more than 40% by mass, the dot seal of the liquid crystal sealing agent, a > J扪 viscosity becomes excessive, and cannot be coated. 15 201105736 Adding a igneous stone in the liquid crystal sealing agent of the present invention... adding a tree: Second, you can add igneous stone. With the coating and operation of liquid daily sealant In addition, the igneous stone used for the dying is exemplified by the puncture property of four people. As the raw material of the present invention, the water is used as a raw material, and the raw material is a fine particle at a high temperature. a hydrophobic fushed stone surface-treated with hexamethyldioxane, smoldering methyl decane, or polyoxyxene oil. When the above-mentioned slashed stone and stalker are added to the liquid crystal sealing agent of the present invention , V, granules u are preferably G·°7"m or less. Further, the added igneous vermiculite (including the above-mentioned hydrophobic sputum 矽-) is preferably 0.5 in the liquid daily sealing agent. ～10% by mass. The liquid crystal sealing agent of the present invention may contain a polythiol compound for improving hardenability. The term "polythiol compound" refers to a compound having two or more thiol groups in the molecule, and as a specific example of the compound of the sulphate, for example, it can be exemplified by a thiophene s.基丙院, U3—三骑基丙院, 1>4_二敌基丁烧, U—二疏基己院,双(2_基基ethyl) sulfide, 1,2-double (2一Benzyl ethyl thio) ethene, 1) 5-dioxalyl + oxapentane, u-di-diyl-3,6-dioxaoctane, 2,2-dimercaptopropane <, 3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2ιylmethyl-adimercaptopropane, 2-mercaptomethyl-1,4-didecylbutane, 2 (2_decylethylthio η,3_dimercaptopropane, anthracene, 2_bis(2-hydrylethylthio)_3_mercaptopropane, 1' 1,1-tris(indenyl)propane, four (mercaptopurine) decanediol bis(2-mercaptoacetate), ethylene glycol bis(3- mercaptopropionate), 丨'4-butanediol 16 201105736 . Double (2-mercaptoethyl) Acid ester), 1,4-butanediol bis(3-mercaptopropionate), tri-propyl mercapto-propanol tris(2-sulfoacetate), tri-methylpropanol tris(3_sparse base Propionate) 'Pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3- mercaptopropionate), 1,1 -didecylcyclohexane, 1,4-didecylcyclohexane, 1, 3-diylcyclohexane, 1,2-dimercaptocyclohexane, dipentaerythritol hexa(3-mercaptopropionate), dipentaerythritol hexa(2-mercaptoacetate), 1,2-di Benzobenzene, 1,3-diweiry-2-propanol, 2,3-diyl-1-propanol, 1,2-diyl-1,3-butanediol, hydroxydecyl-three (mercaptoethylsulfanyl) decane, hydroxyethylthiomethyl-tris(decylethylthio)decane, ethylene glycol bis(3-mercaptopropionate), propylene glycol bis (3 — Mercaptopropionate, butanediol bis(3-mercaptopropionate), octanediol bis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), ethylene glycol Bis(4-mercaptobutyrate), propylene glycol bis(4-mercaptobutyrate), butanediol bis(4-mercaptobutyrate), octanediol bis(4-mercaptobutyrate), three Methylolpropane tris(4-mercaptobutyrate), pentaerythritol tetrakis(4-mercaptobutyrate), ethylene glycol bis(6-mercaptovalerate), C Alcohol bis(6-mercapto valerate), butane diol bis(6-M valerate), octanediol bis(6-mercapto valerate), trimethylolpropane tris(6-毓Pentavalerate, pentaerythritol tetrakis(6-mercapto valerate), 1,6-hexanedithiol, 1,9-nonanedithiol, 1,1 fluorene-dithiol, 4,4' - bis(indenylmethyl)phenyl sulfide, 2,4'-bis(indolyl)phenyl sulfide, 2,4,4'-tris(decylmethyl)phenyl sulfide, 2,2 ',4,4'-tetrakis(fluorenylmethyl) stupyl sulfide, 1,3,5-tris[2-(3-mercaptopropoxy)ethyl]-1,3, 5-trin -2, 4, 6(1H, 3H,5H)-trione, 1,3,5-tris(3-mercaptobutoxyethyl)-1, 3, 5-trian-2, 4, 6 (1H,3H, 5H)-trione, pentaerythritol tetrakis(3-mercaptobutyrate), 17 201105736 1,4-bis(3-succinyl decyloxy) butyl, etc. can be used alone or in combination More than two kinds of people use. Among these polythiol compounds, tris(tetra)propanyltris(3-mercaptopropionic acid vinegar), pentaerythritol tetrakis(3-mercaptopropionic acid from (a), diquaternary stilbene hexapropylpropane (tetra)), l 3, 5-tris[2_(3,ylpropenyloxy)ethyl]_1,3,5-tris- 2,4,6(砒311,51〇_trione, 135 tris(3-sulfanyl) Butoxyethyl ", .-tri-heart" (1) Gong Li: diketone, pentaerythritol tetrakis (3, butyl acetoate), from the viewpoint of liquid crystal contamination and room temperature storage stability, especially good for 2 H bis (3' butylbutoxyethyl ketone, pentaerythritol tetrakis(3-propylbutyric acid) having a mercaptan structure. The content of the polythiol compound in the liquid helium sealant is usually from about 1 to 2. The mass %, preferably 0.3 to the core amount % is more preferably °·5 to 1 〇 mass %. If the content is less than the U quality, the hardness is poor: the sealing is puncture, and the content is multi-sided. %, the room > m preserves the stability. The liquid crystal sealing agent of the present invention may be added with an & agent in order to improve the adhesion strength. The coupling agent used has no right J τ ' and has a special limitation. Jiawei contains 矽=元 coupling agent. Examples of the zebra calcining coupler include 3-glycidoxypropyl propyl methacrylate, 3-glycidoxypropylmethyldimethoxy sylvestre, 3%, oxypropyl acrylate Propylmethyldimethoxyl, 2_(3,[epoxycyclohexyl)ethyl-methoxydecane, Ν-phenyl-physicopropylpropyltrimethoxy oxime HC2-amino B Base) 3-aminopropylmethyldimethoxycarbazide, ν_(2-aminoethyl) 3-aminopropyltrimethoxy(tetra), 3-aminopropyltriethoxy sulphate, 3 - benzyl propyl trimethoxy zeoxime, ethylene trimethoxy hydride, (2 (vinylbenzylamino) ethyl) 3 -aminopropyl tridecyloxydecane salt 18 201105736 acid salt, 3 a decane coupling agent such as methacryloxypropyltrimethoxy decane, 3-apropylpropyl decyloxydecane or 3-chloropropyltrimethoxy decane, or isopropyl (N- Ethylaminoethylamino) titanate, isopropyl triisostearate titanate, titanium di(dioctyl pyrophosphate)oxyacetate, tetraisopropyl-(one octyl) Chia acid filling g) titanate, fresh alkoxy III (p_N-(y3 - aminoethyl) amine stupid a titanium-based coupling agent such as titanate, zr-acetamidine acetonide, Zr-mercapto acrylate, zr-propionate, neoalkoxy zirconium neoalkoxytrimethylene decanoate, Neoalkoxytris(decanedecyl)benzenesulfonyl zirconate, neoalkoxytris(ethylideneethylamine)zirconate, neoalkoxybis(m-aminophenyl) The ergic acid ester, the ammonium carbonate hydrazine, the A1_acetamidine acetonide, the A1-mercapto acrylate, the A1_propionate, or the like, or the aluminum-based coupling agent may be used alone or in combination of two or more. Preferably, it is a 7-burning coupling agent', more preferably an amine-based money-based, a coupling agent or an epoxy-based oxime coupling agent. By using a coupling agent, excellent resistance to the material and adhesion after moisture absorption can be obtained. Reduce the liquid crystal sealant. The coupling agent accounts for about 0.05 to 3% by mass of the liquid crystal sealing agent. ^ + Poor LCD seal ^ ^ π 7 muscle day diced dog plus organic filler. The organic filler may, for example, be a polymer bead or a core-shell type acrylic rubber filler. These fillers may be used singly or in combination of two or more kinds, and the organic filler to be added is specifically filled with 2 # m or less. The average particle diameter is larger than 30% by mass of the mass of the organic filler which can be added. When the average particle diameter is 5 μm or less, it is preferable to form a cell gap. The addition amount is preferably such that the inorganic filler (d) is more than 3% by mass, the viscosity is high and 19 201105736 is difficult. Forming a cell gap. In the liquid crystal sealing agent of the present invention, it is more suitable to blend a photoradical polymerization initiator, a thermal radical generator, a J organic granule, a pigment, a leveling agent, and a defoaming agent. Additives such as the agent. The liquid crystal sealing agent of the present invention, for example, β ^ fine is composed of a hardening enthalpy (a) in a phthalocyanine resin and a (meth) acrylated % oxy-resin. It is known that it is suitable to add a multi-g month t醯肼 compound (b), a hardening accelerator (c), an inorganic filler (d), a milklan gum powder (e), and other optional components such as igneous vermiculite. The human σ device, for example, a 3-roll mill, a sand mill, a ball mill, or the like is uniformly mixed, and after the end of the combination, in order to remove the foreign matter, it is preferable to apply a filtering treatment. The unit is configured to be relatively grounded at intervals of the buckles > A pair of substrates having a designated electrode, which is sealed with a liquid crystal sealing agent of the present invention by a ruthenium, and a liquid crystal is injected into the gap. That is, the hardened material of the sealant is sealed. The type of the liquid crystal to be sealed is not particularly limited. Here, the substrate is made of a substrate made of glass, quartz, plastic, or Shiki. / Method for manufacturing a liquid crystal display unit by a thermosetting liquid crystal dropping method In the liquid crystal sealing agent of the present invention, a spacer (gap control material) such as glass fiber is added to the liquid crystal sealing agent. Examples of the spacer include, for example, glass fibers, vermiculite beads, polymer beads, etc. Depending on the purpose, it is usually 2 to bm, preferably 3 to 6/m. The amount used is '1 to 4 parts by mass relative to the ι by mass of the liquid crystal sealing agent of the present invention. Preferably, the amount of 〇. 5 to 2 parts by mass is more preferably about 5 parts by mass. The liquid crystal sealing agent mixed with the spacer is coated on one side of the substrate by a distribution benefit, etc., in the shape of 20 201105736 (Main seal) 'In order to close the liquid crystal substrate Hold the sealant (false seal) in the vacuum and apply it to the outermost circumference for one week. Then, the liquid crystal is dropped on the inside of the sealed bank, and the other glass substrate is vacuumed in the vacuum, at atmospheric pressure. The opening is opened to create a gap. The dummy sealant for holding the liquid crystal sealing substrate in a vacuum is not in contact with the liquid crystal and is cut off after the liquid crystal single s is completed, so that it can be used in close proximity to the liquid crystal (four) (four), or Use other uv hardening type sealant, visible light hardening type sealant or heat hardening type sealant. After forming a vacuum gap, 'When using UV curing type sealant or visible light hardening type seal in false seal, UV irradiation machine Or the visible light irradiation device irradiates the dummy sealing portion with ultraviolet rays or visible light to photoharden the dummy sealing portion. When the photohardenable sealant is not used in the dummy seal, the light irradiation step 1 is omitted from the base where the gap will be formed! The liquid crystal of the present invention can be obtained by heating at 9 〇 13 rc for 2 hours. The liquid crystal display unit of the present invention thus obtained is free from display defects due to liquid crystal contamination, and is excellent in adhesion and moisture resistance reliability. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. Further, the present invention is not limited by the following examples. Synthesis Example 1 [Synthesis of a full acrylate of resorcinol diglycidyl ether]: Dissolving a m-glycidyl ether resin in a stupid compound, and adding a butyl group to the stupid compound as a polymerization inhibitor The agent is heated up to 6 〇t. Then, 100% equivalent of acrylic acid of the epoxy group was added, and the temperature was raised to 8 (rc), and the vaporized trimethylammonium of the reaction catalyst was added thereto, and the mixture was stirred at 98 t for about 50 hours. The obtained reaction liquid was washed with water to take off toluene. 21 201105736 epoxy acrylate was obtained. Example 1 and 2, Comparative Examples 1 to 3: The acrylic acid epoxy resin, epoxy resin, and stone stalk coupling agent described in Table 1 were mixed. A resin liquid is obtained. Next, it is obtained by using a machine, a polyfunctional ruthenium compound, a hardening promotion, a ruthenium oxide rubber powder, and a polythiol compound to obtain a liquid crystal sealing agent. In Example 2, a hybrid helmet filler, a polyfunctional hydrazine compound, a hardening accelerator, and a silicone rubber were mixed to obtain a liquid crystal sealing agent. In the comparison, inorganic filler was mixed; polyfunctional hydrazine compound, hardening promotion a liquid crystal encapsulant is obtained by using a thiol compound as a liquid crystal encapsulant. In the comparison, an inorganic filler, a polyfunctional ruthenium compound, a ruthenium oxide rubber powder, and a polythiol compound are mixed to obtain a liquid crystal. Sealing agent. Compare the inorganic filler 'polyfunctional bismuth compound' hardening accelerator with a liquid crystal sealant. [Table 1] Acrylate epoxy resin 氺1 epoxy resin 氺2 Multifunctional 醯肼Compound 13 Hardening Accelerator 14 Example 1 180 20 61 Example 2 180 20 61 ~~30 - Comparative Example 1 180 20 61 ~ '30~~ Comparative Example 2 180 20 -----. Comparative Example 3 180 20 — 61 I~l3~ 0 Inorganic filler 氺5 13 13 13 13' Antimony rubber powder A Wood 6 Oxygen rubber rubber powder B 氺7 * Xiyuan coupling agent 18 J10 110 110 ~ΊΤΓ^ ^ΞΙΙ 3 Polythiol compound Wood 9 7 Again, the \CZ components in Table 7 1 ---------- are the numerical mass parts in Table 1 below. The one shown. 22 1 1 · The stupid diphenol condensate All- acrylate of glyceryl ether (manufactured by Nippon Chemical Co., Ltd. 201105736 by Synthetic Co., Ltd.: Synthesis Example 1) * 2 : m-diphenol diglycidyl ether (RGE-HH, manufactured by Nippon Kayaku Co., Ltd.) 〇氺3: three (2 - mercaptocarbonylethyl) isomeric cyanurate (HCIC) finely pulverized product (manufactured by FINECHEM, Japan: finely pulverized by a jet mill to an average particle of _ 1. 5 # m).氺4: Tris(3-carboxypropyl)iso-cyanurate (C3-CIC acid) pulverized product (\W Chemical Industry Co., Ltd.: finely pulverized by a jet mill to an average particle size 1. 5 # m) * 5 : Spherical vermiculite (manufactured by Shin-Etsu Chemical Co., Ltd.: χ24_9ΐ63Α; primary average particle size ll〇nm). *6: Neodymium rubber powder A (fine powder of an addition polymer of vinyl-containing dimethylpolysiloxane and methylhydrogenpolysiloxane), manufactured by Shin-Etsu Chemical Industrial Co., Ltd.: KMP-598; The average average particle size is 13# m, and the true specific gravity is 97. 97). *7. Oxygenated rubber powder B (fine powder of an addition polymer of a vinyl group-containing dimethyl polysiloxane and a mercapto hydrogen polyoxyalkylene, manufactured by Shin-Etsu Chemical Co., Ltd.: KMP-594; Particle size 5 / / m, true specific gravity 〇 97). ^ 8·3 % oxypropoxypropyltrimethoxydecane (manufactured by Chiss Co., Ltd.: Sila-Ace S-510). : Pentaerythritol tetrakis(3 - thioglycolic acid vinegar) (made by Zhaomao Electric Co., Ltd.:

Karenz MT PE1). Determination of the true specific gravity of Shixi oxygen rubber powder: The true specific gravity of Shixiqi Rubber Sheng Powder is difficult to pass. , s 里 系 由 由 在 在 在 在 在 在 在 在 在 在 在 在 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定. Measurement of Average Particle Diameter: Diameter The average particle size of the silicone rubber powder was determined from the photograph of the electron microscope. The liquid crystal cell for evaluation: Each of the liquid crystal sealing agents of the examples and the comparative examples! In the gram, add the glass fiber of the diameter of 5 "111 as a spacer, mix and stir off = fill the syringe. Further, an alignment film solution (pia-5540-05A; manufactured by CHiss Co., Ltd.) was applied onto a glass substrate with an IT〇 transparent electrode, and baked, and subjected to rubbing treatment. In the substrate, a liquid crystal sealing agent of the examples and the comparative examples previously filled in the device was applied using a dispenser (SHOTMASTER 3GO: manufactured by Musashi Engineering Co., Ltd.), and a sealing pattern and a dummy sealing pattern were applied. A small drop of JC_5()15LA; manufactured by CHlss Co., Ltd.) was dropped into the frame of the seal pattern. On the other glass substrate that has been rubbed, the in-plane spacer (Nat〇Cospacer-525F; 〇) Co., Ltd. was produced; the gap width after bonding was 5 "m), and the heat-fixing was used. The apparatus to be bonded was bonded to the substrate on which the liquid crystal was dropped in the vacuum, and the gap was formed by opening the atmosphere, and then 12 (the TC was supplied in the box to heat-harden for 1 hour) to prepare a liquid crystal test cell for evaluation. The density of the liquid crystal cell for evaluation and the liquid crystal alignment disorder (evaluation of liquid crystal contamination) were observed by a polarizing microscope, and it was shown in Table 2. In addition, the liquid crystal characteristic evaluation apparatus was used (〇ms_nk3: Central Precision Machinery Co., Ltd. The gap between the liquid crystal cells produced was measured, and the results of the evaluation of the gap of the cell 24 201105736 were shown in Table 2. The sealing shape, liquid crystal alignment disorder, and liquid crystal were the following four grades. Evaluation of the seal shape: 〇· The linearity of the seal is not disordered. 厶: The deformation of the seal is seen. 'The liquid crystal is closed without problems. The liquid crystal is inserted into the seal, and the liquid crystal can be closed. Level Χχ : The sealing system is broken and the unit cannot be formed. Evaluation of the liquid crystal cell gap: 〇·The cell gap is 5 ym uniformly in the cell. △: There is no gap of about 5 · 5 μ m in the cell. X: There is no gap of 6 or more in the cell. The seal is broken and the cell cannot be formed. Evaluation of liquid crystal alignment: 〇: There is no disorder in the alignment of the liquid crystal in the vicinity of the seal. △: Near the seal The alignment of the liquid crystal is slightly disordered. x : The alignment of the liquid crystal in the vicinity of the seal is disordered. XX : The seal is broken and the unit cannot be formed. [Table 2]

Example 1 Example 2 t匕Comparative Example 1 Comparative Example 2 f-sealing shape 〇〇 XX ... flat 乂 1 1 1J ύ vy ί night crystal unit gap 〇〇〇〇 vy 2 night crystal alignment 〇〇 △ X —— XX As shown in Table 2, the liquid crystal sealing agent of the embodiment of the present invention can be applied to a thermosetting liquid crystal dropping method. In Comparative Example 1, since the particle size of the diarrhea rubber was small, the insertion of the liquid crystal into the seal or the sway of the seal line occurred. In Comparative Example 25, 201105736, the hardening was insufficient and the contamination of the liquid crystal with the resin could not be suppressed. In Comparative Example 3, a breakage of the seal occurred, and the unit could not be produced. Liquid crystal sealant adhesion strength test [Adhesive strength (12 (rc i after hardening)] · Add 1 g of 5 # m glass fiber as a spacer in a liquid crystal sealant, and mix and stir. The liquid crystal sealing agent was coated on a glass substrate of 5 mm×50 mm, and a glass piece of 1·5_χ1·5_ was attached to the liquid crystal sealing agent, and put into a 12 〇t oven for 1 hour to be hardened. Using a bonding tester ( SS_30WD: manufactured by Nishijin Co., Ltd.) to measure the shear adhesion strength of the glass sheet. Table 3 shows the adhesion strength (12 (rci after hardening) results. Liquid crystal sealant moisture adhesion strength test [adhesive strength (after PCT) )]: The same test sample (7) as the above-mentioned liquid crystal sealant adhesion strength test was produced. The test sample was placed in a pressure cook test (PCT) machine under the conditions of 121: (2, 2 A air pressure and humidity 1%). The shear bond strength of the sample after the 2G hour elapsed was measured by using a bonding tester (SS-30WD: manufactured by Sejin Corporation) for 20 hours (TPC-411: manufactured by TABAI ESPEC Co., Ltd.). Intensity (after pCT . The results are applicable period (the initial value of the viscosity increase rate):

The viscosity of the obtained liquid crystal sealing agent (manufactured by Toki Sangyo Co., Ltd.) was measured at 25 t, and the viscosity (hereinafter also referred to as M-day post-point) was measured, and the viscosity immediately after the production was calculated (hereinafter also The increase rate (applicable period) from the "initial viscosity". The value of the initial viscosity (pa s) and the value of the pot life (%) are shown in 纟3. Further, the pot life is a value calculated by the following formula (5) 26 201105736. • (5) Applicable period = (1 post-viscosity - initial viscosity) / (initial viscosity) χ 100 · [Table 3]

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 383 390 412 320 250 7% 5°/〇6% 7% 6°/〇) 55MPa 50MPa 45MPa 40MPa 45MPa 35MPa 40MPa 30MPa 15MPa 30MPa As shown in Table 3 Illustratively, the liquid crystal sealant of the embodiment of the present invention is an initial initial viscosity (Pa · s) (25 ° C / 5 rpm) application period increase rate) 1.2 (TC1 small day 13⁄43⁄4. pani ......... ........ A sealant which is excellent in moisture resistance and has little change in viscosity and has good workability. INDUSTRIAL APPLICABILITY The liquid crystal sealing agent for a thermosetting liquid crystal dropping method of the present invention can be used. Used in the manufacture of liquid crystal display unit. [Simple description of the diagram] Benefit 0 [Description of main component symbols] None 0 27

Claims (1)

201105736 VII. Patent application scope: 1·-hardening resin for liquid crystal sealing agent for liquid crystal sealing agent for liquid crystal dropping method and (meth)acrylated epoxy resin (a), 22 醯肼 compound (b) ), hardening accelerator (c), inorganic filler ^da) and = official weight is .... 0' average particle size is! . ～18 oxygen embossing (4) as an essential component' wherein the diarrhea rubber powder (4) contains 5 to 40% by mass of the sealant. /日曰2·For example, the liquid crystal sealing agent for the thermosetting liquid crystal dropping method of the first application of the patent scope: the crushed oxygen rubber powder (4) is an organic compound having a vinyl group and an organic cerium A fine powder of the addition polymer. Machine ^ 3 · For example, the liquid crystal sealing agent for the thermosetting liquid crystal dropping method of claim 1 or 2, wherein the multi-official anti-time is dripped, and the compound (b) is , f isocyanate ring skeleton represented by formula (1) - &, R1 ', R ' g 醯肼 compound: 〇(1) Formula (only 1 to R3 name - 61⁄2 丄 molecule 1, ～ middle: at least two of the hydrogen atoms or the sub-months represented by the following formula (2): a group represented by the formula (2): In the integer formula (2) of 'NK 0 6 , η represents 28 (2) ? 01105736 4 · Liquid crystal sealing agent for thermosetting liquid crystal dropping method according to claim 1 or 2 'in which inorganic filler (d) Any one of alumina and vermiculite. 5. Liquid crystal sealant for thermosetting liquid crystal dropping method according to claim 1 or 2, wherein the hardening accelerator (c) has the following formula ( 3) The polycarboxylic acid compound of the isomeric polycyanate ring skeleton shown: In the formula (3) of 0, τ to T3 are each independently a hydrogen atom or a molecular skeleton represented by the following formula (4), and at least two of ^ to T3 represent a group represented by the formula (4): In the formula (4), η represents an integer of 1 to 6. 6. A liquid crystal sealing agent for a thermosetting liquid crystal dropping method according to claim 2 or 2, which contains a polythiol compound. 7. A liquid crystal sealing agent for a thermosetting liquid crystal dropping method according to the scope of patent application 帛i or 2, which contains a coupling agent. 8. A liquid crystal display unit sealed by a cured product of a liquid crystal sealing agent as described in claim 2 or 2. 29 201105736 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemistry that best shows the characteristics of the invention. VI. Description of the invention: [Technical field of the invention] The liquid crystal display unit thereof. The liquid crystal display unit is manufactured by a liquid crystal display unit. The present invention relates to a liquid crystal sealing agent and a liquid crystal sealing agent which is suitable for liquid crystal sealing agent by liquid crystal dropping and using the same according to the prior art - as the liquid crystal display unit (four) is enlarged, it has been used as a liquid crystal display in recent years;制造 制造 ' ' ' ' 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Specifically, the so-called liquid crystal dropping method is to apply a liquid crystal sealing agent on a liquid crystal substrate to form a (primary sealing) liquid crystal sealing agent, and then apply a circumferential sealant to the outermost periphery (the liquid crystal is dripped inside the dummy sealing inner layer, and then vacuumed). The liquid-tanned substrate of the other of the opposing liquid-phase substrates is closed by opening at atmospheric pressure, and the liquid-crystal display unit is completed by heating and hardening the sealing portion. In the manufacturing method, the liquid crystal is used. Liquid crystal sealing material used for sealing, generally not)