Liquid crystal sealant for liquid crystal dripping method and liquid crystal display panel using the same

Abstract

To provide a liquid crystal sealant for a liquid crystal dropping method excellent in flexibility, low moisture permeability and crushability, and a liquid crystal display cell sealed with a hardened product thereof.SOLUTION: A liquid crystal sealant for a liquid crystal dropping method contains component (A): a filler having an average particle size of 0.4 μm or less, component (B): a curable compound, and component (C): a liquid curing agent, where a content of the component (A) is 5 pts.wt. or more and 25 pts.wt. or less with respect to 100 pts.wt. of the component (B), and a viscosity at 5 rpm measured at 25°C using an E-type viscometer is 340 Pa s or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid crystal sealant for use in a liquid crystal dropping method, and a liquid crystal display cell sealed with a cured product thereof. [Background technology]

[0002] In recent years, the liquid crystal dropping method, which is highly mass-productive, has become widely used as a method for manufacturing liquid crystal display cells. In this method, liquid crystal is dropped inside a liquid crystal sealant formed on one substrate, the other substrate is bonded together under vacuum, and then the liquid crystal sealant is compressed to a specified gap (distance between the substrates) by atmospheric pressure by releasing the liquid crystal to the atmosphere, and then the liquid crystal sealant is cured by ultraviolet light or heat to manufacture a liquid crystal display cell.

[0003] However, in recent years, the increasing size and narrowing of LCD display cells has led to problems such as the liquid crystal sealant not being able to collapse to the required gap, resulting in different gaps between the center and periphery of the LCD, making it impossible to achieve the desired display characteristics.

[0004] Recently, curved displays and highly flexible displays have been developed and commercialized, and the substrates used in these displays are made of flexible materials such as plastic films instead of rigid materials such as conventional glass (Patent Document 1). With such flexible substrates, uniform atmospheric pressure is not applied to the entire substrate when forming a gap, which is one of the causes of gap defects.

[0005] Furthermore, with the introduction of flexible substrates, liquid crystal sealants are increasingly required to have the property of being able to follow the bending of the substrate, etc., i.e., remaining flexible even after curing. Liquid crystal sealants with excellent flexibility are also advantageous in terms of adhesive strength. For example, peeling and damage to equipment due to impact can be reduced. From this perspective, there is also an increasing demand for liquid crystal sealants to be flexible.

[0006] On the other hand, reducing the crosslink density of the cured product is an effective way to increase its flexibility. However, lowering the crosslink density usually results in a decrease in moisture permeability. This is thought to be because moisture penetrates through loose parts of the network. Therefore, to ensure low moisture permeability, it is necessary to achieve the contradictory properties of either increasing flexibility without lowering the crosslink density, or lowering the crosslink density without lowering moisture permeability. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-238005 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention relates to a liquid crystal sealant that can be used in flexible displays and curved displays. More specifically, the present invention aims to provide a liquid crystal sealant for a liquid crystal dropping method that has excellent flexibility, low moisture permeability, and crush resistance, and a liquid crystal display cell sealed with the cured product thereof. [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have found that a specific liquid crystal sealant for the liquid crystal dropping method has excellent crush resistance, and have arrived at the present invention. In this specification, "(meth)acrylate" means "acrylate" and / or "methacrylate".

[0010] That is, the present invention relates to the following [1] to [9]. In this application, "(Numerical value 1) to (Numerical value 2)" indicates that the upper and lower limit values ​​are included. [1] A liquid crystal sealant for a liquid crystal dropping method, comprising: component (A) a filler having an average particle size of 0.4 μm or less; component (B) a curable compound; and component (C) a liquid curing agent, The content of the component (A) is 5 parts by weight or more and 25 parts by weight or less relative to 100 parts by weight of the component (B), A liquid crystal sealant for the liquid crystal drip method with a viscosity of 340 Pa·s or less at 5 rpm measured at 25°C using an E-type viscometer. [2] The liquid crystal sealant for the liquid crystal dropping method according to the above item [1], which contains, as the component (A), one or more organic fillers selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles. [3] The liquid crystal sealant for the liquid crystal dropping method according to the above item [1] or [2], which contains a urethane (meth)acrylate as the component (B). [4] The liquid crystal sealant for a liquid crystal dropping method according to any one of items [1] to [3] above, wherein the component (C) is a compound having a thiol group. [5] The liquid crystal sealant for a liquid crystal dropping method according to any one of the preceding items [1] to [4], further comprising 0.1 to 1.0 parts by weight of a solid curing agent (D) relative to 100 parts by weight of the component (B). [6] The liquid crystal sealant for a liquid crystal dropping method according to any one of the above items [1] to [5], further comprising a component (E) of a thermal radical polymerization initiator. [7] The liquid crystal sealant for a liquid crystal dropping method according to any one of items [1] to [6], wherein the component (E) is a thermal radical polymerization initiator that does not contain an oxygen-oxygen bond (—OO—) or a nitrogen-nitrogen bond (—N═N—) in the molecule. [8] The liquid crystal sealant for a liquid crystal dropping method according to any one of items [1] to [7] above, further comprising a component (F) a photoradical polymerization initiator. [9] A liquid crystal display panel sealed with the liquid crystal sealant for the liquid crystal dropping method according to any one of the preceding items [1] to [8]. [Effects of the Invention]

[0011] The present invention can provide a liquid crystal sealant for the liquid crystal dropping method, which has excellent flexibility, low moisture permeability, and crush resistance, and a liquid crystal display cell sealed with the cured product thereof. DETAILED DESCRIPTION OF THE INVENTION

[0012] The liquid crystal sealant for liquid crystal displays of the present invention (hereinafter also simply referred to as "liquid crystal sealant") contains component (A) a filler having an average particle size of 0.4 μm or less, component (B) a curable compound, and component (C) a liquid curing agent, the content of component (A) being 5 parts by weight or more and 25 parts by weight or less per 100 parts by weight of component (B), and the viscosity at 5 rpm measured at 25°C is 340 Pa·s or less.

[0013] The inventors have found that the viscosity of the liquid crystal sealant also affects the crushability. This is thought to be because a liquid crystal sealant with a high viscosity has a stronger resistance to atmospheric pressure when forming a gap. The viscosity measured using an E-type viscometer at 25°C and 5 rpm is preferably 340 Pa·s or less, and more preferably 330 Pa·s or less. There is no particular preferred lower limit, but in consideration of resistance to liquid crystal insertion, it is preferably 100 Pa·s or more, and more preferably 150 Pa·s or more.

[0014] In the present invention, viscosity measurements were carried out under the following conditions. 0.15 mL of liquid crystal sealant was added to the measuring cup of an E-type viscometer (RE105 manufactured by Toki Sangyo Co., Ltd.). After leaving it for 120 seconds as preheating under the conditions of a temperature of 25°C and a cone angle of 3° x R7.7, the value was measured after 180 seconds at a rotation speed of 5 rpm.

[0015] The crush resistance can be measured by measuring the gap between the substrates after lamination using an optical device or a step gauge, but in this invention, the dark interference fringes after lamination were observed as follows. After laminating a liquid crystal sealant to a glass substrate measuring 150 mm in length, 150 mm in width, and 0.5 mm in thickness, 25 main seals were dispensed on the outside of the main seals, forming a square with a line width of 1.8 mm and a length of 10 mm and a width of 10 mm. Dummy seals were dispensed on the outside of the main seals. An in-plane spacer (Hayabeads 3DS-XD 4.05 μm; manufactured by Hayakawa Rubber Co., Ltd.; gap width after lamination: 4 μm) was sprayed onto another glass substrate, which was then thermally bonded. The substrate was then bonded to the previously dispensed substrate in a vacuum using a lamination device. After 3 minutes in the atmosphere, the substrate was exposed to UV light (measurement wavelength: 365 nm) at 10,000 mJ / cm using a UV irradiator. 2 The evaluation cells were then exposed to ultraviolet light of 1000 kJ / s, and evaluation cells were prepared. The evaluation cells were observed using an interference fringe inspection lamp (FNA-35; Funatec Co., Ltd.), and the number of dark interference fringe lines inside 25 cells was counted and the average value was calculated. In this case, the average number of dark interference fringe lines is preferably 4.5 or less. A liquid crystal sealant with excellent crush resistance collapses to the height of the in-plane spacers due to atmospheric pressure, making the glass substrate flat and resulting in an average number of dark interference fringe lines of 4.5 or less, with 4.0 or less being particularly preferred. However, a liquid crystal sealant with poor crush resistance does not collapse to the height of the in-plane spacers, resulting in a difference in the gap between the liquid crystal sealant and its surroundings, resulting in the observation of many dark interference fringe lines.

[0016] The liquid crystal sealant of the present invention preferably has high flexibility and low moisture permeability. The flexibility can be evaluated by the elastic modulus. 2 After irradiation with UV light (measurement wavelength: 365 nm), the cured product is cured at 120°C for 60 minutes to a thickness of 100 μm. The modulus of elasticity measured with a universal testing machine (Shimadzu Corporation: Autograph AG-Xplus500N) at room temperature (25°C) is preferably 100 MPa or more and 3000 MPa or less, more preferably 300 MPa or more and 2500 MPa or less, and particularly preferably 400 MPa or more and 2000 MPa or less. A liquid crystal sealant within the above range is preferable because it can conform to the stress applied to the display.

[0017] Breathability: UV 3000mJ / cm 2 (Measurement wavelength: 365 nm) After irradiation, the 300 μm thick cured product was cured at 120°C for 60 minutes, and the moisture permeability was 100 g / m under conditions of 60°C and 90%. 2 24 hours or less is preferable, and 80 g / m 2 24 hours or less is more preferable, and 70 g / m 2 It is particularly preferable that the time is 24 hours or less.

[0018] [(A) Filler with an average particle size of 0.4 μm or less] Component (A) A filler having an average particle size of 0.4 μm or less (hereinafter simply referred to as component (A)) is a filler having an average particle size of 0.4 μm or less, and examples thereof include organic fillers and inorganic fillers.

[0019] In the present invention, the average particle size can be measured using a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd.; LMS-30). 。

[0020] The lower limit of the average particle size is not particularly limited, but is preferably 0.001 μm or more, more preferably 0.01 μm or more, and particularly preferably 0.1 μm or more. The upper limit is preferably 0.4 μm or less, and more preferably 0.3 μm or less. This is because dispersion is easy and gap properties are good when the particle size is within the above range.

[0021] The shape of the particles may be spherical, plate-like, or other shapes, but spherical is preferred in consideration of the gap characteristics.

[0022] The content of component (A) is preferably 5 parts by weight or more and 25 parts by weight or less, more preferably 10 parts by weight or more and 24 parts by weight or less, and particularly preferably 10 parts by weight or more and 22 parts by weight or less, relative to 100 parts by weight of the curable compound described below.

[0023] [Organic filler] Examples of organic fillers include urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles. Examples of silicone fine particles include KMP-594, KMP-597, and KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil RTM E-5500, 9701, and EP-2001 (manufactured by Toray Dow Corning Co., Ltd.) are preferred, JB-800T and HB-800BK (manufactured by Negami Chemical Industries Co., Ltd.) are preferred as urethane fine particles, and Rabalon is preferred as styrene fine particles. RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, and SJ6300C (manufactured by Mitsubishi Chemical) are preferred, and Septon is the styrene olefin fine particle. RTM SEPS2004 and SEPS2063 are preferred. These organic fillers may be used alone or in combination of two or more. Two or more may be used to form a core-shell structure. Among these, acrylic fine particles and silicone fine particles are preferred. When using the above acrylic fine particles, it is preferable that the acrylic fine particles are made of a core-shell structure acrylic rubber consisting of two types of acrylic rubber, and it is particularly preferable that the core layer is made of n-butyl acrylate and the shell layer is made of methyl methacrylate. RTM It is sold by Aica Kogyo Co., Ltd. as F-351. Examples of the silicone microparticles include organopolysiloxane crosslinked powder and linear dimethylpolysiloxane crosslinked powder. Examples of the composite silicone rubber include the silicone rubber whose surface is coated with a silicone resin (e.g., polyorganosilsesquioxane resin). Among these microparticles, particularly preferred are silicone rubber microparticles of linear dimethylpolysiloxane crosslinked powder or composite silicone rubber microparticles of silicone resin-coated linear dimethylpolysiloxane crosslinked powder. These may be used alone or in combination of two or more. Preferably, the rubber powder has a spherical shape, which minimizes the increase in viscosity after addition.

[0024] [Inorganic filler] Examples of inorganic fillers include silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, and asbestos, and preferred are fused silica, crystalline silica, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, and aluminum silicate, with silica, alumina, and talc being preferred. Two or more of these inorganic fillers may be mixed and used.

[0025] [(B) Curable compound] The liquid crystal sealing material of the present invention contains a curable compound as component (B) (hereinafter, also simply referred to as "component (B)"). Component (B) is not particularly limited as long as it is a compound that is cured by light, heat, or the like, but is preferably a compound having a (meth)acrylic group or an epoxy group, and particularly preferably an epoxy (meth)acrylate, a urethane (meth)acrylate, an epoxy resin, or a polybutadiene compound.

[0026] [(Meth)acrylate] Specific examples of (meth)acrylates include N-acryloyloxyethylhexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexane-1,4-dimethanol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, phenylpolyethoxy (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, and o-phenylphenol monoethoxy. ethoxy (meth)acrylate, o-phenylphenol polyethoxy (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate acrylate, tricyclodecane dimethanol (meth)acrylate, bisphenol A polyethoxydi(meth)acrylate, bisphenol A polypropoxydi(meth)acrylate, bisphenol F polyethoxydi(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(acryloxyethyl) isocyanurate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate )acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ester diacrylate of neopentyl glycol and hydroxypivalic acid, and diacrylate of an ε-caprolactone adduct of an ester of neopentyl glycol and hydroxypivalic acid.Preferred examples include o-phenylphenol monoethoxy(meth)acrylate and o-phenylphenol polyethoxy(meth)acrylate.

[0027] [Epoxy (meth)acrylate] Epoxy (meth)acrylates are obtained by a known method by reacting an epoxy resin with (meth)acrylic acid. The epoxy resin used as a raw material is not particularly limited, but is preferably a bifunctional or higher epoxy resin. Examples include dimer acid-modified epoxy resins, resorcinol diglycidyl ethers, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, bisphenol F novolac epoxy resins, alicyclic epoxy resins, aliphatic linear epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, hydantoin epoxy resins, isocyanurate epoxy resins, phenol novolac epoxy resins having a triphenolmethane skeleton, and diglycidyl ethers of bifunctional phenols such as catechol and resorcinol, diglycidyl ethers of bifunctional alcohols, and their halides and hydrogenated derivatives. Among these, bisphenol A type epoxy resin and resorcinol diglycidyl ether are preferred from the viewpoint of liquid crystal contamination. The ratio of epoxy groups to (meth)acryloyl groups is not limited, and is appropriately selected from the viewpoint of process compatibility. Partial epoxy (meth)acrylates in which some of the epoxy groups are acrylic esters are preferably used, with the acrylic ester content preferably being about 30 to 70%.

[0028] [Urethane (meth)acrylate] Urethane (meth)acrylates have a flexible skeleton specific to the urethane structure, and therefore the cured product has flexibility and low moisture permeability, and can conform to the bending of flexible displays. Therefore, urethane (meth)acrylates are preferably used as curable compounds, and it is even more preferable to use those having a polyester structure. The urethane (meth)acrylate can be obtained by reacting (a) a polyol, (b) an organic polyisocyanate, and (c) a hydroxyl group-containing (meth)acrylate to synthesize it in a conventional manner, and a catalyst such as a tin compound may be used as needed. In the synthesis of urethane (meth)acrylate, 1 equivalent of the hydroxyl group of the component (a) is preferably reacted with 1.1 to 2.0 equivalents, and particularly preferably 1.3 to 2.0 equivalents, of the isocyanate group of the component (b). The reaction temperature is preferably room temperature (25°C) to 100°C. It is preferable to react 0.95 to 1.1 equivalents of hydroxyl groups in component (c) with 1 equivalent of isocyanate groups in the reaction product of component (a) and component (b). The reaction temperature is preferably room temperature (25°C) to 100°C.

[0029] Specific examples of (a) polyols include tricyclodecane dimethanol, hydrogenated polybutadiene polyol, dimer diol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20-icosanediol, and 1-methyl-1,8-octanediol. Examples of the diols (a-1) include 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A poly(n≒2-20)ethoxydiol, and bisphenol A poly(n≒2-20)propoxydiol, and polyester polyols (a-2) which are reaction products of these diols (a-1) with dibasic acids or their anhydrides (e.g., succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid, or anhydrides thereof). Preferred are polyester polyols and polyols having an aromatic ring, and particularly preferred are polyester polyols having an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring; and aromatic heterocycles such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring; and preferably a benzene ring or a naphthalene ring. The component (a) may be used alone or in combination of two or more.

[0030] Specific examples of (b) organic polyisocyanates include tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-cyclohexylmethane diisocyanate, xylylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, trimethylhexamethylene diisocyanate, dimeryl diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-diphenylene diisocyanate, etc. Preferred examples include tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0031] Specific examples of (c) hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,4-butanediol (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, pentaerythritol tri(meth)acrylate, an ε-caprolactone adduct of 2-hydroxyethyl (meth)acrylate, and 2-hydroxy-3-phenyloxypropyl (meth)acrylate. Preferred examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and polyethylene glycol mono(meth)acrylate.

[0032] The lower limit of the weight average molecular weight of the urethane (meth)acrylate in terms of polystyrene measured by GPC is preferably 1000 or more, more preferably 2000 or more, particularly preferably 3000 or more, and most preferably 4000 or more. The upper limit is preferably 10000 or less, more preferably 8000 or less, particularly preferably 7000 or less, and most preferably 6000 or less. By being in the above range, the viscosity of the liquid crystal sealant can be in an appropriate range while maintaining good flexibility and moisture permeability.

[0033] [Epoxy resin] In a preferred embodiment of the present invention, component (B) contains an epoxy resin. The epoxy resin is not particularly limited, but is preferably a bifunctional or higher functional epoxy resin, such as dimer acid-modified epoxy resin, resorcinol diglycidyl ether, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, alicyclic epoxy resin, aliphatic linear epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, hydantoin epoxy resin, isocyanurate epoxy resin, phenol novolac epoxy resin having a triphenolmethane skeleton, and diglycidyl ethers of bifunctional phenols such as catechol and resorcinol, diglycidyl ethers of bifunctional alcohols, and their halides and hydrogenated derivatives. Of these, bisphenol A epoxy resin and resorcinol diglycidyl ether are preferred from the viewpoint of liquid crystal contamination resistance.

[0034] [Polybutadiene compounds] In addition, it is also a preferred embodiment of the present invention to use a polybutadiene compound having an epoxy group or a (meth)acrylic group in component (B). Polybutadiene compounds having an epoxy group are commercially available, for example, as JP-100 and JP-200 manufactured by Nippon Soda Co., Ltd. Polybutadiene compounds having a (meth)acrylic group are commercially available, for example, as TEAI-1000 and TE-2000 manufactured by Nippon Soda Co., Ltd. From the viewpoint of reducing liquid crystal contamination, the lower limit of the number average molecular weight of these polybutadiene compounds is preferably 500, more preferably 750, and particularly preferably 1000. From the viewpoint of handleability, the upper limit of the number average molecular weight is preferably 10000, more preferably 8000, and particularly preferably 6000.

[0035] The component (B) may be any of the above materials, or may be a mixture of two or more of them. The component (B) preferably accounts for 50 to 95 mass % of the total amount of the liquid crystal sealant, and more preferably 70 to 90 mass %.

[0036] [(C) Liquid hardener] The liquid crystal sealing material of the present invention contains a liquid curing agent (hereinafter simply referred to as "component (C)") as component (C). The liquid curing agent is a curing agent that is liquid at 25°C. Examples of component (C) include amine compounds, ketimine compounds, imidazole compounds, and compounds having a thiol group, with thiol group being preferred. These liquid curing agents preferably do not contain solvents to prevent contamination of the liquid crystal. Furthermore, from the viewpoint of achieving both good curability and usable life, the exothermic heat initiation temperature during curing is preferably 90°C or higher and 150°C or lower, more preferably 110°C or higher and 130°C or lower.

[0037] Examples of amine compounds include Fujicure 7000, Fujicure 7001, and Fujicure 7000 manufactured by T&K TOKA Corporation; examples of ketimine compounds include ADEKA Hardener EH-235R-2 manufactured by ADEKA Corporation, TMA K13 and TMA K22 manufactured by Tsuno Group Co., Ltd., and jER Cure H3 and jER Cure H30 manufactured by Mitsubishi Chemical Corporation; and examples of imidazole compounds include ADEKA Hardener EH-2021 manufactured by ADEKA Corporation, and these are all commercially available products.

[0038] Examples of compounds having a thiol group include methanedithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-trimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, bis(2-mercaptoethyl)sulfide, 1,2-bis(2-mercaptoethylthio)ethane, 1,5-dimercapto-3-oxapentane, 1,8-dimercapto-3,6- Dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, 2-(2-mercaptoethylthio)-1,3-dimercaptopropane, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,1,1-tris(mercaptomethyl)propane, tetrakis(mercaptomethyl)methane, ethylene Ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(2-mercaptoacetate), 1,4-butanediol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate) Dipentaerythritol hexakis(3-mercaptopropionate), 1,1-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, dipentaerythritol hexakis(3-mercaptopropionate), dipentaerythritol hexakis(2-mercaptoacetate), 1,2-dimercaptobenzene, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-Butanediol, Hydroxyethyl-tris(mercaptoethylthiomethyl)methane, Hydroxyethylthiomethyl-tris(mercaptoethylthio)methane, 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), trimethylolpropane tris(4-mercaptobutyrate), pentaerythritol tetrakis(4-mercaptobutyrate), ethylene glycol bis(6-mercaptovalerate), propylene glycol bis(6-mercaptovalerate), butanediol bis(6-mercaptovalerate), octa Trimethylolpropane bis(6-mercaptovalerate), trimethylolpropane tris(6-mercaptovalerate), pentaerythritol tetrakis(6-mercaptovalerate), 1,6-hexanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 4,4'-bis(mercaptomethyl)phenyl sulfide, 2,4'-bis(mercaptomethyl)phenyl sulfide, 2,4,4'-tri(mercaptomethyl)phenyl sulfide, 2,2',4,4'-tetra(mercaptomethyl) Examples of suitable mercaptobutyryloxy compounds include phenyl sulfide, 1,3,5-tris[2-(3-mercaptopropionyloxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptobutyrate), and 1,4-bis(3-mercaptobutyryloxy)butane, which may be used alone or in combination of two or more. Among these, preferred are trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), 1,3,5-tris[2-(3-mercaptopropionyloxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione and pentaerythritol tetrakis(3-mercaptobutyrate) are preferred, and from the viewpoints of liquid crystal contamination prevention and storage stability at room temperature, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and pentaerythritol tetrakis(3-mercaptobutyrate), which have a secondary thiol structure, are particularly preferred. These compounds having a thiol group may be produced by known methods, or commercially available compounds may be used. RTM PE1, BD1, NR1, trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate) (all manufactured by Showa Denko K.K.), polythiol RTM 340M (manufactured by Toray Fine Chemicals Co., Ltd.), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.), and the like.

[0039] Compounds having three or more thiol groups per molecule are also preferred. Examples include 2,4,4'-tri(mercaptomethyl)phenyl sulfide, 2,2',4,4'-tetra(mercaptomethyl)phenyl sulfide, 1,3,5-tris[2-(3-mercaptopropionyloxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptobutyrate), and 1,4-bis(3-mercaptobutyryloxy)butane. This is because improved crosslink density can improve heat resistance and other properties. Furthermore, when used in liquid crystal display cells, in particular, it can suppress elution into the liquid crystal, achieving high reliability.

[0040] The above-mentioned materials may be used alone or in combination as component (C). The content of component (C) is preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, and particularly preferably 4 to 6 parts by weight, per 100 parts by weight of component (B).

[0041] [(D) Solid hardener] The liquid crystal sealing material of the present invention contains a solid curing agent (hereinafter simply referred to as "component (D)") as component (D). The solid curing agent is a curing agent that is solid at 25°C. By adding a certain amount of component (D), it is possible to improve the curability of the liquid crystal sealant while suppressing adverse effects on the gap property. Examples of component (D) include, but are not limited to, compounds having a carboxy group bonded to an aromatic ring in the molecule, polyamines, polyphenols, and organic acid hydrazides. Examples include aromatic hydrazides such as terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridine dihydrazide, 1,2,4-benzenetrihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, and pyromellitic acid tetrahydrazide. Furthermore, examples of aliphatic hydrazides include formhydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, sebacic acid dihydrazide, 1,4-cyclohexane dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N,N'-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, and 1,3 Examples of the dihydrazide include dihydrazides having a hydantoin skeleton such as -bis(hydrazinocarbonoethyl)-5-isopropylhydantoin, preferably a valine hydantoin skeleton (a skeleton in which the carbon atoms of the hydantoin ring are substituted with isopropyl groups), tris(1-hydrazinocarbonylmethyl)isocyanurate, tris(2-hydrazinocarbonylethyl)isocyanurate, tris(1-hydrazinocarbonylethyl)isocyanurate, tris(3-hydrazinocarbonylpropyl)isocyanurate, and bis(2-hydrazinocarbonylethyl)isocyanurate. In view of the balance between curing reactivity and latency, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris(1-hydrazinocarbonylmethyl)isocyanurate, tris(1-hydrazinocarbonylethyl)isocyanurate, tris(2-hydrazinocarbonylethyl)isocyanurate, and tris(3-hydrazinocarbonylpropyl)isocyanurate are preferred.

[0042] Component (D) may be used alone or in combination of two or more types. Component (D) is preferably added in an amount of 0.1 to 1.0 parts by weight, more preferably 0.2 to 0.8 parts by weight, and particularly preferably 0.2 to 0.6 parts by weight, per 100 parts by weight of component (B). Furthermore, it is preferable to reduce the particle size of component (D) using a jet mill or the like. Specifically, it is preferable for the average particle size to be 3.0 μm or less, more preferably 2.5 μm or less, and particularly preferably 2.0 μm or less.

[0043] [(E) Thermal radical polymerization initiator] The liquid crystal sealing material of the present invention contains (E) a thermal radical polymerization initiator (hereinafter also simply referred to as "component (E)"), which can improve the curing rate and curability. Component (E) is not particularly limited as long as it is a compound that generates radicals upon heating and initiates a chain polymerization reaction, but examples include organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, benzopinacol, etc., and benzopinacol is preferably used. For example, an organic peroxide is Kayamec RTM A, M, R, L, LH, SP-30C, Perkadox CH-50L, BC-FF, Kadox B-40ES, Perkadox 14, Trigonox RTM 22-70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl RTM B, Percadox 16, Kayacarvone RTM BIC-75, AIC-75 (manufactured by Kayaku Akzo Co., Ltd.), Permec RTM N, H, S, F, D, G, Perhexa RTM H,HC,TMH,C,V,22,MC,Percure RTM AH, AL, HB, Perbutyl RTM H, C, ND, L, Park Mill RTM H., D., Parloyle RTMIB, IPP, Perocta RTM ND (manufactured by NOF Corporation) and other products are available commercially.

[0044] In addition, commercially available azo compounds include VA-044, 086, V-070, VPE-0201, and VSP-1001 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0045] A preferred component (E) is a thermal radical polymerization initiator that does not have an oxygen-oxygen bond (-OO-) or a nitrogen-nitrogen bond (-N=N-) in the molecule. Thermal radical polymerization initiators that have an oxygen-oxygen bond (-OO-) or a nitrogen-nitrogen bond (-N=N-) in the molecule emit large amounts of oxygen or nitrogen when generating radicals, and therefore may cure with air bubbles remaining in the liquid crystal sealant, resulting in reduced adhesive strength, reduced moisture permeability, and reduced properties in humid and hot environments. Benzopinacol-based thermal radical polymerization initiators (including chemically modified benzopinacol) are particularly suitable. Specifically, benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, 1,2 -Bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(t-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane Examples thereof include 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1,1,2,2-tetraphenylethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane, preferably 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane, and particularly preferably 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. The benzopinacol mentioned above is commercially available from Tokyo Chemical Industry Co., Ltd., Fujifilm Wako Pure Chemical Industries, Ltd., and other companies. The hydroxy group of benzopinacol can be easily etherified by well-known methods. The hydroxy group of benzopinacol can be silyl-etherified by heating the corresponding benzopinacol with various silylating agents in the presence of a basic catalyst such as pyridine. Examples of silylating agents include commonly known trimethylsilylating agents such as trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), and N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), as well as triethylsilylating agents such as triethylchlorosilane (TECS), and t-butyldimethylsilylating agents such as t-butylmethylsilane (TBMS). These reagents are readily available commercially from silicon derivative manufacturers and other sources. The reaction amount of the silylating agent is preferably 1.0 to 5.0 moles per mole of hydroxy group in the target compound, more preferably 1.5 to 3.0 moles. If the molar ratio is less than 1.0, the reaction efficiency will be poor and the reaction time will be longer, which will promote thermal decomposition. If the molar ratio is more than 5.0, separation will be poor during recovery and purification will be difficult.

[0046] The content of the component (E) is preferably 0.0001 to 5 mass %, more preferably 0.0005 to 3 mass %, and particularly preferably 0.001 to 1 mass %, of the total amount of the liquid crystal sealing material of the present invention.

[0047] [(F) Photoradical polymerization initiator] The liquid crystal sealing material of the present invention may contain a photoradical polymerization initiator (hereinafter simply referred to as "component (F)") as component (F). The photoradical polymerization initiator is not particularly limited as long as it is a compound that generates radicals or acids and initiates a chain polymerization reaction when irradiated with ultraviolet light or visible light. Examples of the photoradical polymerization initiator include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, and diphenyl disulfide. Specific examples include IRGACURE RTM 651, 184, 2959, 127, 907, 369, 379EG, 819, 784, 754, 500, OXE01, OXE02, OXE03, OXE04, DAROCURE RTM 1173, LUCIRIN RTM TPO (both manufactured by BASF), Seikuol RTM Z, BZ, BEE, BIP, BBI (all manufactured by Seiko Chemical Co., Ltd.), Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), etc. Among these, preferred is IRGACURE, an oxime ester initiator. RTM OXE01, OXE02, OXE03, OXE04, and the thioxanthone initiator Kayacure DETX-S. Furthermore, the combined use of an oxime ester initiator and a thioxanthone initiator is preferred because it allows both instant curing and curing in light-shielded areas and also allows curing under visible light. When the component (F) is used in the liquid crystal sealant of the present invention, it is usually 0.001 to 3 mass %, preferably 0.005 to 2 mass %, of the total amount of the liquid crystal sealant.

[0048] [(O) Other ingredients] The liquid crystal sealing material of the present invention may further contain additives such as a curing accelerator, a silane coupling agent, a radical polymerization inhibitor, a pigment, a leveling agent, an antifoaming agent, and a solvent, if necessary. [Curing accelerator] The reactivity of the liquid crystal sealing material of the present invention can be further improved by adding a curing accelerator, such as an organic acid or imidazole. Examples of the organic acid include organic carboxylic acids and organic phosphoric acids, with organic carboxylic acids being preferred. Specific examples include aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenonetetracarboxylic acid, and furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, tris(2-carboxymethyl)isocyanurate, tris(2-carboxyethyl)isocyanurate, tris(2-carboxypropyl)isocyanurate, and bis(2-carboxyethyl)isocyanurate. Furthermore, examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6(2'-methylimidazole(1'))ethyl-s-triazine, 2,4-diamino-6(2'-undecylimidazole(1'))ethyl-s-triazine, and 2,4-diamino-6(2'-undecylimidazole(1')). '))ethyl-s-triazine, 2,4-diamino-6(2'-ethyl-4-methylimidazole(1'))ethyl-s-triazine, 2,4-diamino-6(2'-methylimidazole(1'))ethyl-s-triazine·isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2:3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the like. When a curing accelerator is used in the liquid crystal sealing material of the present invention, the amount thereof is preferably 0.1 to 10 mass %, more preferably 1 to 5 mass %, of the total amount of the liquid crystal sealing material.

[0049] [Silane coupling agents] Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, and 3-chloropropyltrimethoxysilane. These silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. and other companies under the names KBM series and KBE series, and are therefore readily available on the market. When a silane coupling agent is used in the liquid crystal sealant of the present invention, the amount thereof is preferably 0.05 to 3 mass % based on the total amount of the liquid crystal sealant.

[0050] [Radical polymerization inhibitor] The radical polymerization inhibitor is not particularly limited as long as it is a compound that reacts with radicals generated from a photoradical polymerization initiator, a thermal radical polymerization initiator, or the like to prevent polymerization, and can be a quinone-based, piperidine-based, hindered phenol-based, nitroso-based, etc. Specific examples include naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-methoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-phenoxypiperidine-1-oxyl, and hydroquinone. , 2-methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butylcresol, stearyl β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol) ol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl], 2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenylpropionate)methane], 1,3,5-trimethyl- Examples of suitable antibacterial agents include, but are not limited to, this(3',5'-di-t-butyl-4'-hydroxybenzyl)-sec-triazine-2,4,6-(1H,3H,5H)trione, paramethoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, aluminum salt of N-nitrosophenylhydroxyamine, and Adeka STAB LA-81 (trade name) and Adeka STAB LA-82 (trade name) (manufactured by Adeka Corporation).Of these, naphthoquinone-based, hydroquinone-based, nitroso-based, and piperazine-based radical polymerization inhibitors are preferred, naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, and Polystop 7300P (manufactured by Hakuto Co., Ltd.) are more preferred, and Polystop 7300P (manufactured by Hakuto Co., Ltd.) is most preferred. The content of the radical polymerization inhibitor is preferably 0.0001 to 1 mass %, more preferably 0.001 to 0.5 mass %, and particularly preferably 0.005 to 0.2 mass %, based on the total amount of the liquid crystal sealing material of the present invention.

[0051] An example of a method for obtaining the liquid crystal sealant of the present invention is the following method: First, the curable compound, photoradical initiator, thermal radical initiator, and radical polymerization inhibitor are heated and dissolved at 90°C, and then cooled to room temperature, and a silane coupling agent, curing agent, curing accelerator, filler, antifoaming agent, leveling agent, solvent, etc. are added, and the mixture is uniformly mixed using a known mixing device such as a three-roll mill, sand mill, or ball mill, and then filtered through a metal mesh, thereby producing the liquid crystal sealant of the present invention.

[0052] A liquid crystal display cell manufactured using the liquid crystal sealant of the present invention comprises a pair of substrates, each having a predetermined electrode formed thereon, arranged opposite each other at a predetermined distance, the periphery of which is sealed with the liquid crystal sealant of the present invention, and a liquid crystal sealed in the gap. The type of liquid crystal to be sealed is not particularly limited. Here, the substrates are a combination of substrates made of glass, quartz, plastic, silicon, or the like, at least one of which is optically transparent. The manufacturing method involves adding a spacer (gap control material) such as glass fiber to the liquid crystal sealant of the present invention, applying the liquid crystal sealant to one of the pair of substrates using a dispenser or screen printing device, and then temporarily curing at 80 to 120°C, if necessary. Liquid crystal is then dropped inside the weir of the liquid crystal sealant, and the other glass substrate is placed on top of it in a vacuum to form a gap. After gap formation, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130°C for 30 minutes to 2 hours. When used as a combined photothermal and photothermal type, the liquid crystal sealant is photocured by irradiating it with ultraviolet light using an ultraviolet irradiator. The ultraviolet irradiation dose is preferably 500 to 6000 mJ / cm 2 , more preferably 1000 to 4000 mJ / cm 2 The preferred irradiation dose is 365 nm (measurement wavelength). Thereafter, if necessary, curing is performed at 90 to 130°C for 30 minutes to 2 hours to obtain the liquid crystal display cell of the present invention. The liquid crystal display cell of the present invention obtained in this manner is free from display defects due to liquid crystal contamination and has excellent adhesiveness and moisture-resistant reliability. Examples of spacers include glass fiber, silica beads, and polymer beads. Their diameter varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount used is usually 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, and more preferably about 0.9 to 1.5 parts by mass, per 100 parts by mass of the liquid crystal sealant of the present invention. [Example]

[0053] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" in the text are based on mass.

[0054] [Synthesis Example 1] A flask equipped with a thermometer, condenser, and stirrer was charged with 776.99 g of a polyester polyol (P-2012, manufactured by Kuraray Co., Ltd., hydroxyl value 54.6 mg KOH / g) of methylpentanediol, adipic acid, and isophthalic acid, and 131.68 g of toluene diisocyanate (Coronate T-100, manufactured by Tosoh Corporation, molecular weight 174.2) and reacted at 80 °C. The isocyanate content was determined by back titration with hydrochloric acid after adding excess amine. The value was confirmed to be within ±2% of the residual isocyanate content calculated from the calculated value. Next, 0.6 g of methoquinone (polymerization inhibitor), 90.43 g of 2-hydroxyethyl acrylate (molecular weight 116.1), and 0.3 g of dibutyltin dilaurate (catalyst) were added, and the mixture was stirred at 80 °C. The isocyanate group absorption spectrum (at 2280 cm) was measured by infrared absorption spectroscopy. -1 The reaction was continued until the methyl group disappeared, yielding a urethane acrylate oligomer having a weight-average molecular weight of 6,300.

[0055] [Synthesis Example 2] 100 parts (0.28 mol) of commercially available benzopinacol (Tokyo Chemical Industry Co., Ltd.) was dissolved in 350 parts of dimethylformaldehyde. 32 parts (0.4 mol) of pyridine as a base catalyst and 150 parts (0.58 mol) of BSTFA (Shin-Etsu Chemical Co., Ltd.) as a silylating agent were added, and the mixture was heated to 70°C and stirred for 2 hours. The resulting reaction solution was cooled and, while stirring, 200 parts of water was added to precipitate the product and deactivate the unreacted silylating agent. The precipitated product was separated by filtration and thoroughly washed with water. The resulting product was then dissolved in acetone, recrystallized with water, and purified. 105.6 parts of the desired 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane were obtained (yield 88.3%).

[0056] [Examples 1 to 18, Comparative Examples 1 to 9] The component curable compound, photoradical initiator, thermal radical initiator, and radical polymerization inhibitor were heated and dissolved at 90°C in the proportions shown in Tables 1 and 2 below, then cooled to room temperature, and a silane coupling agent, curing agent, curing accelerator, and filler were added and stirred, then dispersed using a three-roll mill and filtered through a metal mesh (635 mesh) to prepare a liquid crystal sealant.

[0057] [evaluation] [viscosity] 0.15 mL of liquid crystal sealant was added to the measuring cup of an E-type viscometer (RE105 manufactured by Toki Sangyo Co., Ltd.). After preheating for 120 seconds at a temperature of 25°C and a cone angle of 3° x R7.7, the value was measured after 180 seconds at a rotation speed of 5 rpm. The results are shown in Tables 1 and 2. [Interference fringe test] After bonding liquid crystal sealant to a glass substrate measuring 150mm long, 150mm wide, and 0.5mm thick, 25 main seals were dispensed to form a square with a line width of 1.8mm, 10mm long, and 10mm wide, and dummy seals were dispensed on the outside of them. Another glass substrate was sprayed with in-plane spacers (Hayabeads 3DS-XD 4.05μm; manufactured by Hayakawa Rubber Co., Ltd.; gap width after bonding was 4μm), thermally bonded, and then bonded to the substrate with the previously dispensed sealant in a vacuum using a bonding device. After 3 minutes in the atmosphere, a UV irradiator was used to irradiate the substrate with 10,000mJ / cm of UV light (measurement wavelength: 365nm). 2 An evaluation cell was prepared by irradiating the light with ultraviolet light. The evaluation cells were observed using an interference fringe inspection lamp (FNA-35; Funatec Co., Ltd.), and the number of dark interference fringe lines inside 25 cells was counted and the average value was calculated. The results are shown in Tables 1 and 2. Elasticity Modulus The liquid crystal sealant produced in the examples and comparative examples was sandwiched between polyethylene terephthalate (PET) films to form a thin film with a thickness of 100 μm, and then irradiated with UV light at 3000 mJ / cm 2After irradiating the specimen with ultraviolet light (measurement wavelength: 365 nm), the specimen was placed in an oven and thermally cured at 120°C for 60 minutes. After curing, the PET film was peeled off to obtain a sample. The specimen was subjected to a tensile test at room temperature (25°C) at a test speed of 5 mm / min using a Tensilon universal testing machine (A&D Co., Ltd., RTG-1210). The results are shown in Tables 1 and 2. [Moisture permeability] The liquid crystal sealant produced in the examples and comparative examples was sandwiched between polyethylene terephthalate (PET) films to form a thin film with a thickness of 300 μm, and then irradiated with a UV irradiator at 3000 mJ / cm 2 After irradiating with ultraviolet light (measurement wavelength: 365 nm), the sample was placed in an oven and thermally cured at 120°C for 60 minutes. After curing, the PET film was peeled off to obtain a sample. The moisture permeability of the sample at 60°C and 90% humidity was measured using a moisture permeability measuring device (Lyssy: L80-5000). The results are shown in Tables 1 and 2.

[0058] [Table 1]

[0059] [Table 2]

[0060] TIFF0007736491000003.tif129168

[0061] From the results of Tables 1 and 2, it was confirmed that the liquid crystal sealant of the present invention has an average number of interference fringes of 4.5 or less, and is excellent in crush resistance. It was also confirmed that the liquid crystal sealant of the present invention has both flexibility and low moisture permeability. [Industrial Applicability]

[0062] The liquid crystal sealant of the present invention has excellent crush resistance and is compatible with flexibility and low moisture permeability, and is therefore useful as a liquid crystal sealant particularly for thin liquid crystal displays and curved liquid crystal displays.

Claims

1. A liquid crystal sealant for a liquid crystal dropping method, comprising: component (A) a filler having an average particle diameter of 0.4 μm or less as measured in a dry state using a laser diffraction / scattering particle size distribution analyzer; component (B) a curable compound; component (C) a liquid curing agent; and component (D) a solid curing agent, The content of the component (A) is 5 parts by weight or more and 25 parts by weight or less relative to 100 parts by weight of the component (B), The content of the component (D) is 0.1 parts by weight or more and 1.0 parts by weight or less relative to 100 parts by weight of the component (B), A liquid crystal sealant for a liquid crystal dropping method, having a viscosity of 340 Pa·s or less when measured at 5 rpm at 25°C using an E-type viscometer.

2. 2. The liquid crystal sealant for a liquid crystal dropping method according to claim 1, wherein the component (A) contains one or more organic fillers selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles.

3. The liquid crystal sealant for a liquid crystal dropping method according to claim 1 or 2, wherein the component (B) contains a urethane (meth)acrylate.

4. The liquid crystal sealant for a liquid crystal dropping method according to any one of claims 1 to 3, wherein the component (C) is a compound having a thiol group.

5. The liquid crystal sealant for a liquid crystal dropping method according to claim 1 , further comprising a component (E) of a thermal radical polymerization initiator.

6. 6. The liquid crystal sealant for a liquid crystal dropping method according to claim 5, wherein the component (E) is a thermal radical polymerization initiator that does not contain an oxygen-oxygen bond (—O—O—) or a nitrogen-nitrogen bond (—N═N—) in the molecule.

7. The liquid crystal sealant for a liquid crystal dropping method according to claim 1 , further comprising a component (F) a photoradical polymerization initiator.

8. A liquid crystal display panel sealed with the liquid crystal sealant for a liquid crystal dropping method according to claim 1 .

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