TWI470067B - Sealant for liquid crystal and liquid crystal display cell using the same - Google Patents

Description

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

The present invention relates to a liquid crystal sealing agent which is excellent in dispensing coating property and which can correspond to screen printing and has a viscosity of 100 Pa‧s or less, and which is not subjected to a drying step or a pre-baking step. Further, the liquid crystal does not penetrate into the liquid crystal sealing agent in the sealing portion; and the present invention relates to a liquid crystal display unit using the sealing agent.

In recent years, liquid crystal display units have also been applied to large-scale display screens such as televisions, and the demand for multi-purposes is increasing. Therefore, in order to further improve the mass productivity, the production of the liquid crystal panel is gradually increasing the size of the substrate and shortening the tap time (time per step).

In the production of a liquid crystal display device, conventionally, a liquid crystal sealing agent is applied to a glass substrate by a method such as dispensing coating or screen printing, and then sealed to form a unit in a vacuum environment. After liquid crystal is injected into the cell from a liquid crystal injection port provided in a part thereof, the liquid crystal injection port is sealed using a sealant or a sealing agent (vacuum injection method).

Further, a liquid crystal dropping method in which a liquid crystal is dropped into a crucible made of a resin and then bonded to each other to cure the resin is also put into practical use. In the liquid crystal dropping method, first, a rectangular sealing pattern composed of an uncured sealant is formed by dispensing on one of two transparent substrates with electrodes. Then, after the fine liquid droplets of the liquid crystal are dropped into the frame of the sealing pattern applied to the transparent substrate in a state where the sealing agent is not cured, the other transparent substrate is bonded immediately to form a liquid crystal cell, and the sealing pattern is formed. The part is pre-cured by irradiation with ultraviolet rays. Then, if necessary, heating is performed to perform main hardening, and a liquid crystal display unit is produced. As long as the steps of bonding the substrates to form a liquid crystal cell under reduced pressure, the liquid crystal display element can be manufactured with high efficiency, and the dropping method has gradually become the mainstream of the manufacturing method of the liquid crystal display element.

When the liquid crystal display element is manufactured by the liquid crystal dropping method, there is a problem in that the sealing pattern of the obtained liquid crystal display unit is deformed to cause a phenomenon in which the liquid crystal penetrates into the sealing pattern (infiltration phenomenon), thereby disturbing the sealing. The orientation of the liquid crystal near the pattern. The method for solving this problem is, for example, the use of a sealant having a higher viscosity than the usual user to form a seal pattern, but there is a possibility that the distribution property is deteriorated, resulting in an adverse effect such as dryness or disconnection at the time of dispensing. Further, in recent years, in order to further shorten the production time and the like, it is desirable to increase the dispensing speed or more easily form a seal pattern by screen printing, and therefore, a sealant having a lower viscosity and no penetration phenomenon is required.

In this regard, in Patent Document 1, there is a report in which the penetration of the unhardened seal pattern is increased in advance to prevent the penetration phenomenon before the step of producing the liquid crystal cell. However, there is no previous example of a liquid crystal sealing agent which is used for the liquid crystal dropping step without a pre-bake step with a low viscosity of an initial viscosity of 100 Pa‧s or less.

Further, in Patent Documents 2 and 3, there is a report of a liquid crystal sealing agent containing rubber-like polymer fine particles which is improved in liquid crystal contamination. However, in the case of the two publications, the initial viscosity is not more than 100 Pa‧s, and the rubbery polymer microparticles are used to suppress the sealant component of the light-shielding portion which is not easily irradiated with UV during photohardening. Dissolved into the liquid crystal during thermal hardening.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-275670

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-219039

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-262253

An object of the present invention is to suppress a phenomenon in which a liquid crystal penetrates into a sealant during a liquid crystal dropping method, and to provide a liquid crystal sealing agent which inhibits penetration and a liquid crystal display unit using the same.

The inventors of the present invention have found that a curable resin composition containing a silicone rubber powder can suppress the progress of liquid crystal even if the initial viscosity is 100 Pa‧s or less. Infiltration phenomenon when dripping into the method. Further, it has been found that by adding an amino decane coupling agent to the curable resin composition, the effect of further preventing the penetration phenomenon can be obtained, and by adding a spherical filler as needed, the distribution coating can be improved. The linearity of the seal at that time is completed by the present invention. In other words, the present invention relates to the following (1) to (10).

(1) A liquid crystal sealing agent comprising (a) a polyoxyxene rubber powder and having a viscosity at 25 ° C measured by an E-type viscometer of 100 Pa ‧ or less.

(2) The liquid crystal sealing agent according to (1) above, which further comprises (b) an amino decane coupling agent.

(3) The liquid crystal sealing agent according to (1) above, which further comprises (c) a spherical filler.

(4) The liquid crystal sealing agent according to any one of (1) to (3) above which further comprises (d) a photocurable resin.

(5) The liquid crystal sealing agent according to the above (4), wherein (d) a photocurable resin is an epoxy acrylate.

(6) The liquid crystal sealing agent according to any one of (1) to (5) above which further comprises (e) a photoradical polymerization initiator.

(7) The liquid crystal sealing agent according to any one of the above (1) to (6), further comprising (f) a thermosetting resin and/or (g) a heat curing agent.

(8) The liquid crystal sealing agent according to the above (7), wherein (f) the thermosetting resin-based epoxy resin, and the component (g) the thermosetting agent is hydrazide.

(9) The liquid crystal sealing agent according to any one of the above (1), wherein the (h) inorganic filler having an average particle diameter of 3 μm or less is further contained.

(10) A liquid crystal display unit which is obtained by curing the cured liquid crystal sealing agent according to any one of the above (1) to (9).

In other words, the liquid crystal sealing agent of the present invention has a low viscosity and does not undergo a pre-baking step, and has an excellent effect of preventing liquid crystal from penetrating into the sealant during the liquid crystal dropping method. Therefore, by using this sealant, it is easy to manufacture a liquid crystal display panel which can shorten the time taken for dispensing coating and screen printing.

Hereinafter, the present invention will be described in detail.

The polyoxyxylene rubber powder used in the liquid crystal sealing agent of the present invention is not particularly limited as long as it is composed of a polymer having a repeating of a decane bond as a main chain. The polyoxynian powder is generally classified into a resin powder and a rubber powder according to the modulus of elasticity, and is particularly preferably a rubber powder having impact absorption properties from the viewpoint of suppressing penetration of liquid crystal into the sealant. The polyoxyethylene rubber powder coated on the surface without a crosslinked polymer or the like is preferred. Further, in the present invention, the polyoxyxene rubber is preferably one having a structure obtained by crosslinking a polyoxyalkylene oxide, and the polyoxyalkylene oxide is preferably a linear dimethyl polyoxyalkylene. Further, since the sealant is heat-treated at the time of manufacture and use, it is preferable to have heat resistance.

When the average particle diameter of the polyoxyxene rubber powder (a) used in the liquid crystal sealing agent of the present invention is too large, when a liquid crystal cell having a narrow gap is produced, a gap cannot be formed smoothly when the upper and lower glass substrates are bonded together. Since it is a cause of failure, it is usually 3 μm or less, and preferably 2 μm or less. Further, similarly, the maximum particle diameter is usually 8 μm or less, and preferably 5 μm or less. Also, in order to form a gap well, it is preferable to exhibit rubber elasticity at -50 ° C to 250 ° C. In addition, it is also preferable in terms of liquid crystal contamination. KMP-594 is made by Shin-Etsu Chemical Co., Ltd. The amount of use of the liquid crystal sealing agent of the present invention is usually from 1 to 20% by mass, and preferably from about 5 to 15% by mass, based on 100% by mass of the liquid crystal sealing agent of the present invention. If more is added, the shaking property is increased to lower the coatability.

The polyoxyxylene rubber powder (a) used in the liquid crystal sealing agent of the present invention is preferably used in combination with the amino decane coupling agent (b). By using these together, since the impact resistance is improved, it is possible to prevent the liquid crystal from penetrating into the sealant.

The amine decane coupling agent (b) which can be used in the liquid crystal sealing agent of the present invention can be generally used, and is not particularly limited. For example: aminopropyltrimethoxydecane, aminopropyltriethoxydecane, dimethylaminopropyltrimethoxydecane, diethylaminopropyltrimethoxydecane, dipropylamino Propyltrimethoxydecane, dibutylaminopropyltrimethoxydecane, monobutylaminopropyltrimethoxydecane, dioctylaminopropyltrimethoxydecane, dibutylaminopropyl Dimethoxydecane, dibutylaminopropyl monomethoxydecane, dimethylaminophenyltrimethoxydecane, trimethoxydecyl-γ-propylphenylamine, trimethoxydecylalkyl - γ-propylbenzylamine, trimethoxydecyl-γ-propyl piperidine, trimethoxydecyl-γ-propylmorpholine, trimethoxydecyl-γ-propylimidazole, and the like. These may be used alone or in combination of two or more. When the liquid crystal sealing agent of the present invention is 100% by mass as a whole, the content of the amino decane coupling agent in the liquid crystal sealing agent is about 0 to 3% by mass.

The initial viscosity of the liquid crystal sealing agent in the present invention is 100 Pa‧s or less. When the initial viscosity is 100 Pa·s or less, the distribution coating property is excellent and can correspond to screen printing, which is greatly related to the productivity of the panel and has an effective influence.

The spherical filler (c) which can be used in the liquid crystal sealing agent of the present invention may, for example, be silica, silica gel, hollow glass, carbon black or high molecular polyethylene. In the case of a spherical shape, since the agitation pressure can be applied as a whole regardless of the direction, it can be stably settled. Further, the filler usually has an average particle diameter of about 0.001 μm to 100 μm, and preferably 0.01 μm to 10 μm. By adding a spherical filler of this size, the shaking of the resin can be reduced. By this, it is possible to perform stable dispensing coating to improve the linearity of the seal. In the foregoing, since it is easily dispersed in the resin, it is more preferable that the surface is hydrophobized. A submicron spherical cerium oxide powder x-24-9163A manufactured by Shin-Etsu Chemical Co., Ltd. can be obtained from the market. When the liquid crystal sealing agent of the present invention is 100% by mass as a whole, the amount thereof is usually from 0 to 10% by mass, and preferably from about 1 to 5% by mass. If more is added, the effect of the polyoxymethylene rubber powder and the amino decane coupling agent is low, and the penetration property is poor.

The photocurable resin (d) which can be used in the liquid crystal sealing agent of the present invention is not particularly limited as long as it has low elution property into the liquid crystal, and examples thereof include, for example, urethane acrylate (A). A compound having an acrylonitrile group as a functional group, such as an acrylate or an epoxy (meth) acrylate. Specifically, for example, benzyl methacrylate, cyclohexyl methacrylate, glycerin dimethacrylate, glycerol trimethacrylate, EO modified glycerin triacrylate, pentaerythritol acrylate, trimethylolpropane three Acrylate, propylene (propylene oxyethyl) isocyanurate, dipentaerythritol hexaacrylate, fluoroglycolol triacrylate, and the like. Further, from the viewpoint of liquid crystal contamination, epoxy (meth) acrylate resin is particularly preferable. The epoxy (meth) acrylate resin can be obtained by subjecting acrylic acid or methacrylic acid to an esterification reaction with an epoxy resin having at least two epoxy groups in the molecule. This synthesis reaction can generally be carried out by a known method. For example, adding a predetermined equivalent ratio of acrylic acid or methacrylic acid to a epoxy resin, and a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, and three Triphenyl stibine, etc., with polymerization inhibitors (eg, p-methoxyphenol, hydroquinone, methylhydroquinone, thiophene (phenothiazine), dibutylhydroxytoluene, etc.), for example, an esterification reaction at 80 to 110 °C. Further, examples of the epoxy resin having at least two epoxy groups in the molecule include a bisphenol A type epoxy resin, an alkyl substituted bisphenol A type epoxy resin, and an alkylene oxide addition bisphenol A type epoxy resin. Resin, bisphenol F epoxy resin, alkyl substituted bisphenol F epoxy resin, alkylene oxide addition bisphenol F epoxy resin, bisphenol S epoxy resin, alkyl substituted bisphenol S ring Oxygen resin, alkylene oxide addition bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, epoxy Propylamine type epoxy resin, dicyclopentadiene type epoxy resin, polyfluorene modified epoxy resin, amine ester modified epoxy resin, rubber modified epoxy resin, etc., with bisphenol A type epoxy Resin, alkyl substituted bisphenol A epoxy resin, alkylene oxide addition bisphenol A epoxy resin, bisphenol F epoxy resin, alkyl substituted bisphenol F epoxy resin, alkylene oxide addition A bisphenol F type epoxy resin, a bisphenol S type epoxy resin, an alkyl substituted bisphenol S type epoxy resin, and an alkylene oxide addition bisphenol S type epoxy resin are preferred. In the liquid crystal sealing agent of the present invention, when the liquid crystal sealing agent of the present invention is 100% by mass as a whole, the content of the photocurable resin (d) in the liquid crystal sealing agent is about 0 to 80% by mass.

In addition, the photoradical polymerization initiator (e) which can be used in the liquid crystal sealing agent of the present invention is not particularly limited as long as it is a radical polymerization initiator, and examples thereof include benzyldimethylketal. , 1-hydroxycyclohexyl phenyl ketone, diethylthioxanthone, benzophenone, 2-ethyl hydrazine, 2-hydroxy-2-methylpropiophenone, 2-methyl-[4 -(Methylthio)phenyl]-2-morpholinyl-1-propane, 2,4,6-trimethylbenzylidenediphenylphosphine oxide, and the like. In addition, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one or 2-isocyanatoethyl methacrylate can also be used. A reaction product of 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one.

In the liquid crystal sealing agent of the present invention, the compounding ratio of the photoradical polymerization initiator component (e) to the photocurable resin (d) is usually 0.01 to 20 by mass based on 100 parts by mass of the component (d). It is preferably 5 to 15 parts by mass. If the amount of the radical generating type photoradical polymerization initiator is less than 0.01 parts by mass, the photohardening reaction is insufficient, and if it is more than 20 parts by mass, the amount of the initiator is excessive, and the initiator causes contamination of the liquid crystal or The deterioration of the properties of the cured resin is a problem.

In the liquid crystal sealing agent of the present invention, a thermosetting resin (f) and/or a thermosetting agent (g) may also be contained. By using the thermosetting resin (f) and/or the thermosetting agent (g), the liquid crystal contamination property is improved. In addition, the reliability of the subsequent strength and heat and humidity resistance test is improved.

The thermosetting resin (f) which can be used in the liquid crystal sealing agent of the present invention is not particularly limited, and is preferably a bifunctional or higher epoxy resin, for example, a bisphenol A epoxy resin or a bisphenol F epoxy resin. Bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A phenolic type epoxy resin, bisphenol F phenolic type epoxy resin, alicyclic epoxy resin, aliphatic Chain epoxy resin, glycidyl ester epoxy resin, epoxy propyl amine epoxy resin, hydantoin epoxy resin, isocyanurate epoxy resin, with trisphenol methane The skeleton phenol novolak type epoxy resin, and other di-epoxy propyl ether compounds of difunctional phenols, diepoxypropyl ether compounds of difunctional alcohols, and halides, hydrides and the like. Among these, from the viewpoint of liquid crystal contamination, a bisphenol epoxy resin or a novolac epoxy resin is preferred.

Further, the amount of the hydrolyzable chlorine of the thermosetting resin which can be used in the liquid crystal sealing agent of the present invention is preferably 600 ppm or less. When the amount of hydrolyzable chlorine is more than 600 ppm, there is a possibility that the liquid crystal sealing agent has a problem with the contamination of the liquid crystal. The amount of hydrolyzable chlorine can be quantified by, for example, dissolving about 0.5 g of the epoxy resin in 20 mL of the second. The dioxane was refluxed for 5 minutes in 5 mL of a 1N KOH/ethanol solution, and then titrated with a 0.01 N silver nitrate solution. The content of such an epoxy resin in the liquid crystal sealing agent is about 5 to 50% by mass.

The component (g) which can be used in the liquid crystal sealing agent of the present invention is not particularly limited, and a solid organic hydrazine is preferably used. For example, salicylate, benzamidine, naphthalene-1,4-dicarboxylic acid diterpene, diterpene bismuthate, diterpene bismuthate, 2,6-naphthoic acid Diterpene, dioxonium 2,6-pyridinedicarboxylate, triterpenoid 1,2,4-benzenetricarboxylic acid, tetraterpene tetramethylenetetracarboxylate, tetraterpene tetracarboxylic acid Wait. Further, examples of the aliphatic hydrazine compound include formazan, acetamidine, acetonide, bismuth oxalate, diammonium malonate, diterpene succinate, diammonium glutarate, and hexahydrate. Bismuth diacid, dinonyl pimelate, diammonium 1,4-cyclohexanedicarboxylate, diterpene tartrate, diterpene malate, diimine diimide, N,N' - hexamethylene double (semi-calendar), triterpene citrate, nitrogen tris(acetonitrile), cyclohexane tricarboxylic acid A diterpenoid having an allantoin skeleton, such as 1,3-bis(hydrazinocarbonoethyl-5-isopropylhydantoin) From the viewpoint of the balance between the hardening reactivity and the latent property, for example, a bifunctional diterpene is preferable, and particularly, for example, diterpenic acid diterpenoid is preferable.

When the average particle diameter of the ruthenium compound is too large, when a liquid crystal cell having a narrow gap is produced, the gap between the upper and lower glass substrates cannot be formed smoothly, and therefore, it is usually 3 μm or less and 2 μm or less. It is better. Further, similarly, the maximum particle diameter is usually 8 μm or less, and preferably 5 μm or less. This particle size was measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by SEISHIN Co., Ltd., LMS-30).

In the liquid crystal sealing agent of the present invention, the content of the thermosetting agent (g) is preferably from 0.20 to 0.80, preferably from 0.4 to 0.6, with respect to the epoxy equivalent of the epoxy group of the epoxy resin of the component (f). good.

Further, the inorganic filler (h) which can be used in the liquid crystal sealing agent of the present invention may, for example, be a molten cerium oxide, a crystalline cerium oxide, a cerium carbide, a cerium nitride, a boron nitride, a calcium carbonate, a magnesium carbonate, a barium sulfate, or a sulfuric acid. Calcium, mica, talc, clay, alumina, magnesia, zirconia, aluminum hydroxide, magnesium hydroxide, calcium citrate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber , molybdenum disulfide, asbestos, etc., with molten cerium oxide, crystalline cerium oxide, tantalum nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium citrate Aluminum citrate is preferred, and molten cerium oxide, crystalline cerium oxide, aluminum oxide, and talc are more preferable. These inorganic fillers It can be used in combination of 2 or more types. When the average particle diameter is too large, when a liquid crystal cell having a narrow gap is produced, it is a problem that a gap or the like cannot be formed smoothly when the upper and lower glass substrates are bonded. Therefore, it is usually 3 μm or less, and preferably 2 μm or less. The particle size was measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by SEISHIN Co., Ltd., LMS-30).

The content of the inorganic filler which can be used in the liquid crystal sealing agent in the present invention is usually from 5 to 40% by mass, and preferably from 15 to 30% by mass. When the content of the inorganic filler is less than 5% by mass, the adhesion strength to the glass substrate is lowered, and the moisture resistance reliability is also poor, so that the adhesion strength after moisture absorption is also largely lowered. Further, when the content of the inorganic filler is more than 40% by mass, since the content of the filler is too large, it is difficult to form a gap of the liquid crystal cell.

In order to increase the bonding strength, the liquid crystal sealing agent of the present invention may contain a decane coupling agent other than the amine decane coupling agent. The decane coupling agent may, for example, be 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropylmethyldi Methoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, N-phenyl-γ-aminopropyltrimethoxydecane, N-2-(aminoethyl) 3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3 - mercaptopropyltrimethoxydecane, vinyltrimethoxydecane, N-(2-(vinylbenzylamino)ethyl)-3-aminopropyltrimethoxydecane hydrochloride, 3-methyl A decane coupling agent such as acryloxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane or 3-chloropropyltrimethoxydecane. These decane coupling agents may be used in combination of two or more kinds. Among these, in order to obtain better bonding strength and shakeability, it is preferred to use two kinds of decane coupling agents in combination. By using a decane coupling agent, a liquid crystal sealing agent having a strong adhesive strength is obtained. When the liquid crystal sealing agent of the present invention is 100% by mass as a whole, the content of the decane coupling agent is usually about 0 to 3% by mass.

In the liquid crystal sealing agent of the present invention, an organic filler, an additive such as a pigment, a leveling agent, an antifoaming agent, or a solvent may be further blended as needed.

In order to obtain the liquid crystal sealing agent of the present invention, first, the component (e) and the component (f) are dissolved and dissolved as needed in the component (d). Next, a decane coupling agent is mixed in the mixture, and a predetermined amount of the component (a), the component (b), the component (c), the component (g), the component (h), and the organic filler as needed, and defoaming are added. After the agent, the solvent, the leveling agent, and the like are uniformly mixed by a conventional mixing device, such as a three-roll mill, a sand mixer, a ball mill, etc., and filtered by a metal mesh, the liquid crystal sealing agent of the present invention can be obtained. .

In the liquid crystal display unit of the present invention, the liquid crystal display unit is formed by arranging a predetermined interval between the substrate and a predetermined interval, and sealing the periphery with the sealant of the present invention, and sealing the liquid crystal in the gap. The type of the liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a substrate including glass, quartz, plastic, tantalum, or the like, and at least one of which has a combination of light transmissivity. In the method of the method, for example, when a liquid crystal instillation method is used, a spacer (gap control material) such as glass fiber is added to the liquid crystal sealing agent of the present invention, and then one of the pair of substrates is used for distribution. The liquid crystal sealing agent is applied to a device or a screen printing device or the like. Next, liquid crystal was dropped on the inside of the liquid crystal sealing agent, and another glass substrate was superposed in a vacuum to form a gap. After the gap is formed, the liquid crystal sealing portion is irradiated with ultraviolet rays by an ultraviolet ray irradiator to perform photocuring. Ultraviolet irradiation amount is preferably 500mJ / cm ² to ^{6000mJ / cm 2, 1000mJ / cm} 2 to 4000mJ / cm ² irradiation amount of more preferably. Then, it is cured at 90 to 130 ° C for 1 to 2 hours as needed, whereby the liquid crystal display unit of the present invention can be obtained. 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. The spacer may, for example, be glass fiber, cerium oxide beads, polymer beads or the like. The diameter varies depending on the purpose, and is usually 2 to 8 μm, and preferably 4 to 7 μm. The amount of use of the liquid crystal sealing agent of the present invention is usually 0.1 to 4 parts by mass, more preferably 0.5 to 2 parts by mass, still more preferably about 0.9 to 1.5 parts by mass.

(Example)

The invention is illustrated in more detail below by way of examples. In the examples, "parts" means mass parts, and "%" means mass%.

(Modulation of sealant for liquid crystal dropping method)

Each of the resin components was mixed and stirred at a ratio shown in the following table, and then the photopolymerization initiator was heated and dissolved. Then, a filler, a thickener, and the like are appropriately added and stirred. Then, it was dispersed by a three-roll mill, and filtered by a metal mesh (manufactured by Kansai Gold Co., Ltd., material SVS316, twilling, mesh size: 635 mesh) to prepare a liquid crystal dropping method. Sealants.

(manufacturing unit by evaluation coating, evaluation)

5 μm of glass fiber (PF-50S, manufactured by Nippon Electric Glass Co., Ltd.) which is used as a gap material in the prepared liquid crystal dropping method sealant, and filled in a syringe, defoamed, and dispensed by a dispenser (MUSASHI) SHOTMASTER 300, manufactured by the company, is applied to the glass substrate by drawing a rectangular shape. For the sealant-coated substrate thus obtained, an appropriate amount of liquid crystal was dropped into a sealing frame, and placed in a vacuum bonding apparatus, and another substrate was laminated in a vacuum. After returning to atmospheric pressure, the linearity was confirmed with the naked eye. In terms of linearity, any one that has no broken line and undulation and has a fixed line width is ○, one of which has a broken line or undulation, or one whose line width is not fixed is △, and any one of broken line or undulation And the line width is not fixed, it is ×. After further observation for 10 minutes, the occurrence of seal rupture was ×, and those who had infiltrated but not ruptured were Δ, and those who did not penetrate or rupture were ○.

(1) Bisphenol A type epoxy acrylate: R-93100 (manufactured by Nippon Kayaku Co., Ltd.)

(2) Reactive reaction of resorcinol diepoxypropyl ether with acrylic acid

(3) Methacrylate modified epoxy acrylate: RM-93100 (manufactured by Nippon Kayaku Co., Ltd.)

(4) Resorcinol diepoxypropyl ether

(5) Phenol aralkyl type epoxy resin: YDF-8170C (manufactured by Tohto Kasei Co., Ltd.)

(6) Phenol aralkyl type epoxy resin: EPPN501H (manufactured by Nippon Kayaku Co., Ltd.)

(7) 1-[4-(2-Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one: Irgacure 2959 (manufactured by Ciba Specialty Chemical Co., Ltd.)

(8) N-2-(Aminoethyl)-3-aminopropyltrimethoxydecane: KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603)

(9) 3-glycidoxypropyltrimethoxydecane: SILA-ACE S-510 (manufactured by CHISSO Co., Ltd.)

(10) Diterpenic acid diterpene: IDH-S (manufactured by Otsuka Chemical Co., Ltd.)

(11) 1,3-bis(carboxyethyl)-5-isopropyl allantoin: AMICURE VDH (Ajinomoto Fine Techno Co., Ltd.)

(12) Polyoxyethylene rubber powder: KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(13) Polyoxyl composite powder: KMP-600 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(14) Core-shell type acrylic copolymer: F-351S (manufactured by GANZ Kasei Co., Ltd.)

(15) Sub-micron spherical filler: X-24-9163A (manufactured by Shin-Etsu Chemical Co., Ltd.)

(16) Alumina: SPC-AL (manufactured by C. I. Chemical Co., Ltd.)

(17) Rubber: Paraloid EXL-2655 (made by Osaka Chemical Industry Co., Ltd.)

(18) Cerium oxide: SP-1B (made by Fuso Chemical Industry Co., Ltd.)

※Polyoxime composite powder: spherical powder coated on the surface of polyoxyxene rubber powder by polyoxynoxy resin

(industrial availability)

As described above, the liquid crystal sealing agent of the present invention has excellent initializability because of its low initial viscosity, and also has excellent properties in penetrability in liquid crystal infiltration into the sealant. On the other hand, the liquid crystal sealing agent of the comparative example is excellent in the penetration property of the liquid crystal infiltrating into the sealing agent because of the high initial viscosity, but the linearity is poor, and it does not satisfy any characteristic as the liquid crystal sealing agent of the present invention. . Therefore, the liquid crystal sealing agent of the present invention is excellent in the workability of the substrate coating and the penetration property in the liquid crystal dropping method through the steps, and can be said to have high reliability.

Claims (9)

A liquid crystal sealing agent comprising (a) a polyoxyxene rubber powder and (d) a photocurable resin, and the viscosity at 25 ° C measured by an E-type viscometer is 100 Pa. s the following. The liquid crystal sealing agent of claim 1, wherein (d) the photocurable resin is an epoxy acrylate. The liquid crystal sealing agent of claim 1, wherein the (b) amino decane coupling agent is further contained. The liquid crystal sealing agent of claim 3, wherein the (c) spherical filler is further contained. The liquid crystal sealing agent of claim 4, wherein the (e) photoradical polymerization initiator is further contained. The liquid crystal sealing agent of claim 5, wherein the (f) thermosetting resin and/or (g) thermal hardener are further included. The liquid crystal sealing agent of claim 6, wherein (f) a thermosetting resin-based epoxy resin, and (g) a thermal curing agent is an organic hydrazine. The liquid crystal sealing agent of claim 7, wherein the (h) inorganic filler having an average particle diameter of 3 μm or less is further contained. A liquid crystal display unit which is a cured product obtained by hardening a liquid crystal sealing agent according to any one of claims 1 to 8.