TW201708488A - Liquid crystal sealing agent and liquid crystal display cell using the same - Google Patents

Abstract

An objective of this invention relates to a liquid crystal sealing agent for liquid crystal dropping method to be cured by heat. The provided liquid crystal sealing agent for liquid crystal dropping method has an extremely low circuit corrosion after humidity resistance test and has low liquid crystal contamination, and excellent in general characteristic such as adhesive strength and the likes, therefore capable of realize high fineness, high response, low driving voltage and long lifetime of liquid crystal display cell. The present invention provides a liquid crystal sealing agent for liquid crystal dropping method containing (A) a curable compound, wherein, a cured article obtained by thermal curing at 130 DEG C for 1 hour without exposure to ultraviolet light has a water absorption ratio of 2.0% or less based on JIS-K7209, and has a moisture permeability of 130 g/m2*24h or less based on JIS-K7129.

Description

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

The present invention relates to a liquid crystal sealing agent which is hardened by heat, and is a liquid crystal sealing agent used in a liquid crystal dropping method. More specifically, it is a liquid crystal sealing agent for liquid crystal dropping method which is extremely low in corrosion resistance after the moisture resistance test and which is excellent in general characteristics such as low liquid crystal contamination and adhesion strength.

In the method of manufacturing a liquid crystal display unit, a so-called liquid crystal dropping method with higher mass productivity has been proposed (see Patent Document 1 and Patent Document 2). Specifically, a method of manufacturing a liquid crystal display unit in which a liquid crystal is sealed by laminating liquid crystal on the inside of a dam of a liquid crystal sealing agent formed on a substrate and bonding the other substrate.

However, in the liquid crystal dropping method, the liquid crystal sealing agent in an uncured state is in contact with the liquid crystal. At this time, the components of the liquid crystal sealing agent are dissolved (dissolved) in the liquid crystal to lower the resistance value of the liquid crystal, resulting in display failure in the vicinity of the sealing. point.

In order to solve this problem, it is now used as a liquid crystal dropping method. The liquid crystal sealing agent is used in combination with light and heat (Patent Documents 3 and 4). A liquid crystal dropping method using the liquid crystal sealing agent is characterized in that a liquid crystal sealing agent held on a substrate is irradiated with light to be hardened once, and then heated and then hardened twice. According to this method, the uncured liquid crystal sealing agent can be quickly hardened by light, and dissolution (dissolution) of the liquid crystal sealing agent component in the liquid crystal can be suppressed. Further, in the case of photocuring, the problem of insufficient adhesion strength due to hardening shrinkage or the like is also caused in the case of photocuring. However, if it is a photothermal combination type, secondary hardening by heating can be obtained to obtain a relaxation stress effect. It can also solve the advantages of such a problem.

By applying the liquid crystal sealing agent for the photothermal curing type liquid crystal dropping method, the liquid crystal dropping method is a generally used method.

According to the practical use of the above liquid crystal dropping method, even a large liquid crystal display unit can be easily manufactured, and as a result, it is related to the spread of liquid crystal displays.

On the other hand, this liquid crystal dropping method sometimes has disadvantages in the quality of the liquid crystal display unit to be manufactured. First, there is a problem of defects in the driving of the liquid crystal after the moisture resistance reliability. This problem is also caused by the liquid crystal display unit manufactured by the conventional liquid crystal injection method, but is particularly remarkable in the liquid crystal display unit manufactured by the liquid crystal dropping method. In order to solve this problem, various studies have been conducted since the past. For example, a thermal radical polymerization initiator or a curing accelerator is added to increase the reaction rate or a material having low solubility in liquid crystal as a constituent component.

However, such studies have not achieved the realization of liquid crystal sealing agents for liquid crystal dropping methods which can sufficiently solve the above problems.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-63-179323

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-239694

[Patent Document 3] Japanese Patent No. 3583326

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-61925

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2004-126211

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2009-8754

[Patent Document 7] International Publication No. 2008/004455

The present invention relates to a liquid crystal sealing agent for liquid crystal dropping method which is hardened by heat, and proposes a liquid crystal sealing agent for liquid crystal dropping method, which is extremely low in corrosion resistance after moisture resistance test, and even in low liquid crystal contamination, Since the general characteristics such as the strength are also excellent, it is proposed to achieve high definition, high-speed response, low voltage drive, and long life of the liquid crystal display element.

The inventors of the present invention have found that the problem of the above-mentioned driving defects has been found to be caused by wiring corrosion after the moisture resistance test, which is caused by insufficient hardening of ultraviolet rays under the black matrix. The invention was completed almost exclusively by the moisture permeability and water absorption of the position hardened by heat.

That is, the present invention relates to the following 1) to 14). In the present specification, the term "(meth)acrylic acid" means "acrylic acid" and/or "methacrylic acid". Further, the "liquid crystal sealing agent for liquid crystal dropping method" may be described only as "liquid crystal sealing agent".

1) A liquid crystal sealing agent for a liquid crystal dropping method, which comprises (A) a curable compound, which is obtained by heat-curing only at 130 ° C for 1 hour without irradiation with ultraviolet rays, and has a water absorption measured in accordance with JIS-K7209. The rate was 2.0% or less, and the moisture permeability measured in accordance with JIS-K7129 was 130 g/m ² *24 h or less.

2) The liquid crystal sealing agent for liquid crystal dropping method according to the above 1), further comprising (B) a thermal radical polymerization initiator.

(3) The liquid crystal sealing agent for liquid crystal dropping method according to the above, wherein the component (B) thermal radical polymerization initiator does not contain an oxygen-oxygen bond (-OO-) in the molecule; A thermal radical polymerization initiator of a nitrogen-nitrogen bond (-N=N-).

(4) The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1) to 3), further comprising (C) a photoradical polymerization initiator.

(5) The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above-mentioned items 1 to 4, further comprising (D) a filler, the content of the filler in the total amount of the liquid crystal sealing agent is 20% by mass or more .

(6) The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above-mentioned, wherein the component (D) is (D-1) an organic filler and (D-2) an inorganic filler. mixture.

7) The liquid crystal dense method for liquid crystal dropping method according to any one of the above 1) to 6) In the sealing agent, the content of the inorganic filler in the total amount of the liquid crystal sealing agent of the component (D-2) is 20% by mass or more.

The liquid crystal sealing agent for liquid crystal dropping methods of any one of the above-mentioned 1 (1), wherein the component (A) curable compound is an epoxy (meth) acrylate compound.

The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above-mentioned, wherein the component (A) curable compound is an epoxy (meth) acrylate compound and an epoxy compound. mixture.

(10) The liquid crystal sealing agent for liquid crystal dropping method according to any one of the above 1) to (9), further comprising (E) a heat curing agent.

(11) The liquid crystal sealing agent for liquid crystal dropping method according to the above 10), wherein the component (E) thermal curing agent is an organic acid bismuth.

The liquid crystal sealing agent for liquid crystal dropping methods as described in any one of the above-mentioned 1) to 11) further contains (F) a decane coupling agent.

And a liquid crystal display unit manufacturing method comprising the liquid crystal according to any one of the above 1) to 12) formed on a substrate in a liquid crystal display unit comprising two substrates. After dropping the liquid crystal into the inside of the bank of the liquid crystal sealing agent for the dropping method, the other substrate is bonded, and then hardened by light and/or heat.

(14) A liquid crystal display unit which is obtained by curing a liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above 1) to 12).

The liquid crystal sealing agent for liquid crystal dropping method of the invention can be It is extremely useful as a liquid crystal sealing agent for liquid crystal display elements, because the wiring corrosion is minimized and the liquid crystal contamination is low and the strength is excellent.

Fig. 1 is a view showing the hardening width of the light shielding portion. A liquid crystal sealing agent to which 1 w% of 5 μm glass fibers were added was applied to the center of the etched chromium-plated glass substrate, and the black matrix substrate was bonded as a counter substrate, and fixed by a jig (before ultraviolet irradiation). Further, after irradiating ultraviolet rays of 3,000 mJ/cm ² from the side of the glass substrate which was etched with chromium, the two substrates which were bonded were peeled off, and the portion which was shielded from light under the chrome was confirmed by a microscope, and the hardened width of the light-shielding portion was measured.

The liquid crystal sealing agent of the present invention contains (A) a curable compound.

The component (A) is not particularly limited as long as it is polymerized by light or heat, and examples thereof include a curable compound having a (meth)acryl fluorenyl group and a curable compound having an epoxy group.

Examples of the curable compound having a (meth)acryl fluorenyl group include (meth) acrylate and epoxy (meth) acrylate. Examples of the (meth) acrylate include benzyl methacrylate, cyclohexyl methacrylate, glyceryl dimethacrylate, glyceryl triacrylate, EO-modified glyceryl triacrylate, and neopentyl alcohol acrylate. And trimethylolpropane triacrylate, propylene (propylene oxyethyl) trimeric isocyanate, dipentaerythritol hexaacrylate, fluoroethanolamine triacrylate, and the like. The epoxy group (meth) acrylate can be obtained by a known method by reacting an epoxy compound with (meth)acrylic acid. Become the original The epoxy compound is not particularly limited, and is preferably a bifunctional or higher epoxy compound, and examples thereof include a bisphenol A epoxy compound, a bisphenol F epoxy compound, and a bisphenol S epoxy compound. Phenolic novolac type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolak type epoxy compound, bisphenol F novolak type epoxy compound, alicyclic epoxy compound, aliphatic chain epoxy Compound, glycidyl ester type epoxy compound, glycidyl amine type epoxy compound, intramethylene urea type epoxy compound, trimeric isocyanate type epoxy compound, phenol novolac type epoxy compound having a trisphenol methane skeleton And other diglycidyl ethers of difunctional phenols such as catechol and resorcin, diglycidyl ethers of difunctional alcohols, and halides, hydrides thereof and the like. Among these, an epoxy compound having a resorcinol skeleton is preferable from the viewpoint of liquid crystal contamination, and is, for example, resorcinol diglycidyl ether. Further, the ratio of the epoxy group to the (meth) acrylonitrile group is not limited, and can be appropriately selected from the viewpoints of step suitability and liquid crystal contamination.

Therefore, a curable compound having a (meth)acryl fluorenyl group is preferably a (meth)acryloxy group and a resilience compound having a resorcinol skeleton, for example, resorcinol diglycidyl ether. Acrylate, methacrylate of resorcinol diglycidyl ether.

The curable compound having an epoxy group may, for example, be an epoxy compound. The epoxy compound is not particularly limited, and is preferably a bifunctional or higher epoxy compound, and examples thereof include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, and a phenol. Novolak type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolac type epoxidation , bisphenol F novolak type epoxy compound, alicyclic epoxy compound, aliphatic chain epoxy compound, glycidyl ester type epoxy compound, glycidyl amine type epoxy compound, beta-urea urea type Epoxy compound, trimeric isocyanate type epoxy compound, phenol novolac type epoxy compound having a trisphenol methane skeleton, bisglycidyl etherate of other difunctional phenols, diglycidyl ether of difunctional alcohol a halide, a hydride, or the like. Among these, a bisphenol type epoxy compound and a novolac type epoxy compound are preferable from the viewpoint of liquid crystal contamination.

A curable compound having a (meth) acryloxy group and a curable compound having an epoxy group may be used in combination of two or more kinds, and a (meth) acrylated epoxy compound and an epoxy compound may be used in combination. One of the best.

The content of the component (A) in the liquid crystal sealing agent of the present invention is usually from 30 to 75% by mass, preferably from 40 to 65% by mass. Further, in particular, when the epoxy compound and the (meth)acrylated epoxy compound are used in combination, the content of the epoxy compound in the component (A) is usually from 3 to 30% by mass, preferably from 5 to 20% by mass, more preferably It is 8 to 15% by mass.

The liquid crystal sealing agent of the present invention is a cured product which is thermally cured at 130 ° C for 1 hour without irradiation with ultraviolet rays, and has a water absorption ratio of 2.0% or less as measured according to JIS-K7209 (D method) (wherein the test condition is 60 ° C). 90% of the environment). The moisture absorbed by the liquid crystal sealing agent is used to promote the decomposition of the organic matter in the liquid crystal sealing agent, and even to transport the decomposition products and impurity ions out of the liquid crystal sealing agent.

The water absorption rate is preferably 1.8% or less, more preferably 1.6% or less.

The liquid crystal sealing agent of the present invention is a cured product which is thermally cured only at 130 ° C for 1 hour without irradiation with ultraviolet rays, and has a moisture permeability of 130 g/m ² *24 h or less as measured according to JIS-K7129 (method A). Because the moisture that penetrates the liquid crystal sealant has a great influence on the wiring corrosion. Further, if Lyssy L80-5000 manufactured by Systech illinois Co., Ltd. is used, it can be measured in accordance with JIS-K7129 (method A). The test temperature was set at 60 °C.

The moisture permeability is preferably 110 g/m ² *24 h or less, more preferably 90 g/m ² *24 h or less.

In the liquid crystal sealing agent of the present invention, (B) a thermal radical polymerization initiator can be used to increase the hardening speed and the degree of hardening.

The thermal radical polymerization initiator is not particularly limited as long as it is a compound which initiates a chain reaction by heating to generate a radical, and examples thereof include an organic peroxide, an azo compound, and a benzoin compound. A benzoin ether compound, an acetophenone compound, tetraphenyl-1,2-ethylene bromide (benzopinacol), etc., tetraphenyl-1,2-ethanediol is suitably used. For example, as an organic peroxide, the following commercial products can be obtained: Kayamek ^RTM A, M, R, L, LH, SP-30C, Perkadox CH-50L, BC-FF, Cadox B-40ES, Perkadox 14, Trigonox ^RTM 22-70E, 23-C70, 121, 121-50E, 121-LS 50E, 21-LS50E, 42, 42LS, Kayaester ^RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl ^RTM B, Perkadox 16, Kayacarbon ^RTM BIC-75, AIC-75 (made by AKZO Co., Ltd.), Permek ^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, Percumyl ^RTM H, D, Peroyl ^RTM IB, IPP, Perocta ^RTM ND, (Nippon Oil Co., Ltd.) System) and so on.

Further, as the azo compound, the following commercially available products: VA-044, V-070, VPE-0201, VSP-1001 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like can be obtained. In this specification, the superscript RTM means a registered trademark.

The component (B) is preferably a thermal radical polymerization initiator which does not have an oxygen-oxygen bond (-O-O-) or a nitrogen-nitrogen bond (-N=N-) in the molecule. A thermal radical polymerization initiator having an oxygen-oxygen bond (-OO-) or a nitrogen-nitrogen bond (-N=N-) in a molecule generates a large amount of oxygen or nitrogen when generating a radical, so that it is liquid crystal The sealant is hardened in the state of remaining bubbles, and has the property of lowering the strength and the like. A tetraradyl-1,2-ethanediol-based thermal radical polymerization initiator (including a tetraphenyl-1,2-ethanediol chemically modified) is particularly suitable. Specifically, for example, tetraphenyl-1,2-ethanediol, 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-tetrakis(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetrakis(4-methoxyphenyl)ethane, 1,2- Bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(triethyldecyloxy)-1,1,2,2-tetraphenyl Alkane, 1,2-bis(t-butyldimethylamyloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylphosphonium-1,1 , 2,2-tetraphenylethane, 1-hydroxy-2-triethyl decyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyl dimethyl Alkyloxy-1,1,2,2-tetraphenylethane, etc., preferably 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethyl decyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethyloxyl-1,1,2, 2-tetraphenylethane, 1,2-bis(trimethylhydrazine Oxyl)-1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane, 1, 2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, especially good 1,2-bis(trimethyldecyloxy)-1,1,2,2 - Tetraphenylethane.

The above tetraphenyl-1,2-ethanediol is commercially available from Tokyo Chemical Industry Co., Ltd., and Wako Pure Chemical Industries Co., Ltd. Further, the hydroxy etherification of tetraphenyl-1,2-ethanediol can be easily synthesized by a known method. Further, the hydroxy decyl etherification of tetraphenyl-1,2-ethanediol can be achieved by making the corresponding tetraphenyl-1,2-ethanediol and various thiolation agents alkaline in pyridine It is synthesized by the method of heating under the medium. The thiolating agent may, for example, be trimethylchlorodecane (TMCS), hexamethyldioxane (HMDS) or N,O-bis(trimethylhydrazine) which is a commonly known trimethyl hydrazide. Trifluoroacetamide (BSTFA) or triethylchlorodecane (TECS) as a triethyl decylating agent, third butyl methyl decane (TBMS) as a third butyl dimethyl hydrazylating agent Wait. These reagents can be easily obtained by a hydrazine derivative manufacturer or the like. The reaction amount of the thiolating agent is preferably 1.0 to 5.0 moles per mole of the hydroxyl group of the target compound. More preferably 1.5 to 3.0 times Mo. If it is less than 1.0 times mole, the reaction efficiency is poor, and the reaction time becomes long, so that thermal decomposition is promoted. If it is more than 5.0 times mole, the separation becomes poor at the time of recovery, or the purification becomes difficult.

The component (B) is preferably finely divided in particle diameter and uniformly dispersed. When the average particle diameter is too large, when a liquid crystal display unit having a narrow gap is produced, the gap between the upper and lower glass substrates cannot be smoothly performed. Therefore, it is preferably 5 μm or less, more preferably 3 μm or less. Further, it may be fined even if it is not completely reduced, but the lower limit is usually about 0.1 μm. The particle size system can be laser diffraction/scattering particle size distribution analyzer (dry type) Limited company Seishin enterprise system; LMS-30) determination.

The content of the component (B) is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass, and particularly preferably 0.001 to 3% by mass, based on the total amount of the liquid crystal sealing agent.

As the liquid crystal sealing agent of the present invention, (C) a photoradical polymerization initiator can be used, and a liquid crystal sealing agent of a photothermal type can be used.

The photoradical polymerization initiator is not particularly limited as long as it generates a radical by irradiation with ultraviolet light or visible light, and is not particularly limited, but examples thereof include benzyl dimethyl acetal. , 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, diphenyl ketone, 2-ethyl hydrazine, 2-hydroxy-2-methyl propyl benzene, 2-methyl-[4- (methylthio)phenyl]-2-morpholinyl-1-propane, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyl Sulfur ether and the like. Specifically, for example, IRGACURE ^RTM 651, 184, 2959, 127, 907, 369, 379 EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE ^RTM 1173, and LUCIRIN ^RTM TPO (all of which are manufactured by BASF Corporation) ), SEIKUOL ^RTM Z, BZ, BEE, BIP, BBI (any one is manufactured by Seiko Chemical Co., Ltd.).

Further, from the viewpoint of liquid crystal contamination, it is preferred to use a (meth)acrylic group in the molecule, and for example, 2-methylpropenyloxyethyl isocyanate and 1-[4-(2-hydroxyethyl) are preferably used. A reaction product of oxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one. This compound can be produced by the method described in International Publication No. 2006/027982.

Moreover, it is preferable from the viewpoint of improving the curability of the light-shielding portion which is not sufficiently irradiated to the light due to the wiring or the black matrix, and the absorption coefficient at 350 nm measured in acetonitrile is 500 ml ‧ g ^-1 ‧ cm or more. For example, IRGACURE ^RTM 651907, 369, 379EG, 819, 784, OXE01, OXE02, LUCIRIN ^RTM TPO (any of which is manufactured by BASF Corporation), diethyl thioxanthone, benzophenone, and the like.

The content of the component (C) photoradical polymerization initiator which can be used in the liquid crystal sealing agent of the present invention in the liquid crystal sealing agent is usually from 0.1 to 20% by mass based on the total amount of the liquid crystal sealing agent of the present invention. It is preferably 0.2 to 15% by mass.

The liquid crystal sealing agent of the present invention can use (D) a filler to increase the strength of the bonding. The filler may be (D-1) an organic filler, or may be a (D-2) inorganic filler or a mixture thereof, but it is preferably a mixture of the two, respectively.

In the total amount of the liquid crystal sealing agent, the content of the (D) filler is usually from 5 to 70% by mass, preferably from 10 to 60% by mass. Further, when the content of the filler (D) is 20% by mass or more, the effects of the present invention can be particularly remarkably exhibited, and particularly preferably 20 to 50% by mass.

The component (D-1) organic filler may, for example, be a urethane microparticle, an acryl microparticle, a styrene microparticle, a styrene olefin microparticle, or a polyoxynium microparticle. Further, the polysiloxane particles are preferably KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), Torayfil ^RTM E-5500, 9701, EP-2001 (manufactured by Dow Corning Toray Co., Ltd.), and an amine group. The formate microparticles are preferably JB-800T, HB-800BK (Kenwon Industrial Co., Ltd.), and the styrene microparticles are Rabalon ^RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (Mitsubishi Chemical) Preferably, the styrene olefin microparticles are preferably Septon ^RTM SEPS2004 or SEPS2063.

These organic fillers may be used singly or in combination of two or more. Two or more types can be used as the core-shell structure. Among these, acrylic fine particles and polyoxynized fine particles are preferred.

When the acrylic fine particles are used, an acrylic rubber having a core-shell structure composed of two types of acrylic rubber is preferable, and a particularly preferred core layer is n-butyl acrylate and the shell layer is methyl methacrylate. This is a Zefiac ^RTM F-351 sold by AICA Industries, Inc.

Further, the polyfluorene fine particles may be, for example, an organic polyoxyalkylene crosslinked product powder or a linear dimethyl polyoxyalkylene crosslinked product powder. The composite polyoxyxene rubber may, for example, be coated with a polyoxyxylene compound (for example, a polyorganosilsesquioxane compound) on the surface of the above polyoxyxene rubber. Among these fine particles, a polyfluorene rubber or a polyxanium compound which is a linear dimethylpolyoxyalkylene crosslinked powder is coated with a linear polydimethylene oxide crosslinked powder. Rubber particles. These may be used alone or in combination of two or more. Further, it is preferable that the shape of the rubber powder is a spherical shape having less viscosity and viscosity after the addition. In the liquid crystal sealing agent of the present invention, when the component (D) is used, it is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the liquid crystal sealing agent.

The inorganic filler of the component (D-2) may, for example, be cerium oxide, cerium carbide, cerium nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, oxidation. Magnesium, zirconia, aluminum hydroxide, magnesium hydroxide, calcium citrate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably melted Dioxane Huayu, crystalline cerium oxide, cerium nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium citrate, aluminum citrate, preferably mica , alumina, talc. These inorganic fillers can be used by mixing two or more types.

When the average particle diameter of the inorganic filler is too large, when a liquid crystal cell having a narrow gap is formed, the gap may not be formed smoothly when the upper and lower glass substrates are bonded together. Therefore, it is suitably 2000 nm or less, preferably 1000 nm or less. More preferably, it is 300 nm or less. A preferred lower limit is about 10 nm, and more preferably about 100 nm. The particle size was measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by Seishine Co., Ltd.; LMS-30).

When an inorganic filler is used in the liquid crystal sealing agent of the present invention, it may be about 10 to 50% by mass in the total amount of the liquid crystal sealing agent, but when it is 20% by mass or more, the effect of the present invention is more remarkable. Very good is 20 to 50% by mass.

The liquid crystal sealing agent of the present invention may contain (E) a heat hardener.

The heat hardener is different from the above component (B) thermal radical polymerization initiator, and means a heat hardener which does not generate heat by heating. Specifically, the reaction can be carried out nucleophilically by a non-covalent electron pair or an anion in the molecule, and examples thereof include polyamines, polyhydric phenols, and organic acid hydrazine compounds. However, it is not subject to such restrictions. Among these, the organic acid hydrazine compound is particularly preferably used. For example, an aromatic cerium diterpene terephthalate, diammonium isophthalate, dioxane 2,6-pyridinium dichloride, 2,6-pyridine dioxime, 1,2,4-benzene Triterpenoids, tetrakisole of 1,4,5,8-naphthoic acid, tetraterpene tetrabenzoate Hey. Further, in the case of an aliphatic hydrazine compound, for example, formazan, ethyl hydrazine, cesium propionate, bismuth oxalate, diammonium malonate, diterpene succinate, diammonium glutarate, Dioxane adipate, diammonium pimelate, diterpene sebacate, 1,4-cyclohexanedioxime, diterpenic tartrate, diterpene malate, diimine diacetate肼, N, N'-hexamethylene bis-half carbamazepine, triterpenoid citrate, trimethyl hydrazine acetate, triterpene Cyclohexane tricarboxylate, 1,3-bis(decylcarbonylethyl) -5-isopropyl acetyl carbazide or the like having a carbendazim skeleton, preferably having a guanyl carbendazim skeleton (a skeleton in which a carbon atom of the uremic urea ring is substituted by an isopropyl group) Anthraquinone compound, ginseng (1-mercaptocarbonylmethyl)trimeric isocyanate, ginseng (2-mercaptocarbonylethyl)trimeric isocyanate, ginseng (1-fluorenylcarbonylethyl)trimeric isocyanate, ginseng (3- Mercaptocarbonylpropyl)trimeric isocyanate, bis(2-mercaptocarbonylethyl)trimeric isocyanate, and the like. From the balance between hardening reactivity and potential, it is preferred to di-isophthalic acid dithizone, diammonium malonate, diammonium adipate, ginseng (1-mercaptocarbonylmethyl) trimeric Cyanic acid, ginseng (1-mercaptocarbonylethyl) trimer isocyanate, ginseng (2-mercaptocarbonylethyl) trimer isocyanate, ginseng (3-mercaptocarbonylpropyl) trimeric isocyanate, especially good ginseng ( 2-mercaptocarbonylethyl)trimeric isocyanate.

The component (E) may be used singly or in combination of two or more. When the component (E) is used in the liquid crystal sealing agent of the present invention, it is usually from 0.1 to 10% by mass, preferably from 1 to 5% by mass, based on the total amount of the liquid crystal sealing agent.

The liquid crystal sealing agent of the present invention may contain a decane coupling agent as the component (F) to improve the strength or moisture resistance.

The component (F) may, for example, be 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane or 3-epoxypropoxy group. Propylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-(2- Aminoethyl) 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethyl Oxydecane, 3-thiolpropyltrimethoxydecane, vinyltrimethoxydecane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxydecane Hydrochloride, 3-methacryloxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, and the like. These decane coupling agents are KBM series and KBE series sold by Shin-Etsu Chemical Co., Ltd., etc., and can be easily obtained from the market. When the component (F) is used in the liquid crystal sealing agent of the present invention, it is preferably 0.05 to 3% by mass in the total amount of the liquid crystal sealing agent.

The liquid crystal sealing agent of the present invention may further contain an additive such as an organic acid or an imidazole hardening accelerator, a radical polymerization inhibitor, a pigment, a leveling agent, an antifoaming agent, a solvent, or the like as needed.

The hardening accelerator may, for example, be an organic acid or an imidazole.

The organic acid may, for example, be an organic carboxylic acid or an organic phosphoric acid, and is preferably an organic carboxylic acid. Specific examples thereof include aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, and furan dicarboxylic acid, and succinic acid. Diacid, dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, gin(2-carboxymethyl)trimeric isocyanate, ginseng (2-carboxyethyl)trimeric isocyanate, Reference to (2-carboxypropyl) trimeric isocyanate, bis(2-carboxyethyl) trimeric isocyanate, and the like.

Further, examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzene. Methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl -2-undecylimidazole, 2,4-diamino-6(2'-methylimidazolium(1'))ethyl-s-three 2,4-diamino-6(2'-undecenyl imidazolium (1')) ethyl-s-three 2,4-Diamino-6(2'-ethyl-4-methylimidazolium (1'))ethyl-s-three 2,4-Diamino-6(2'-methylimidazolium(1'))ethyl-s-three /Trimeric isocyanate adduct, 2:3 adduct of 2-methylimidazolium tripolyisocyanate, 2-phenylimidazole trimer isocyanate adduct, 2-phenyl-3,5 - Dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the like.

When a hardening accelerator is used in the liquid crystal sealing agent of the present invention, it is usually from 0.1 to 10% by mass, preferably from 1 to 5% by mass, based on the total amount of the liquid crystal sealing agent.

The radical polymerization inhibitor is not particularly limited as long as it reacts with a radical generated by a photoradical polymerization initiator or a thermal radical polymerization initiator to inhibit polymerization, and a lanthanoid system can be used. Piperidine, hindered phenol, nitroso, and the like. Specifically, for example, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxide (2) , 2,6,6-tetramethylpiperidine-1-oxyl), 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxide, 2,2,6,6-tetramethyl-4 -methoxypiperidine-1-oxide, 2,2,6,6-tetramethyl-4-phenoxypiperidine-1-oxide, hydroquinone, 2-methylhydroquinone, 2-methyl Oxyhydrohydroquinone, p-benzoquinone, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl cresol, stearyl beta-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-sulfur Bis--3-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1- Dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy]ethyl], 2,4,8,10-tetraoxaspiro[ 5,5]undecane, fluorene-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenylpropionate)methane, 1,3,5-para (3',5'-di-t-butyl-4'-hydroxybenzyl)-second-three -2,4,6-(1H,3H,5H)trione, p-methoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N-nitrosophenylhydroxylamine The aluminum salt, trade name Adekastab LA-81, trade name Adek stab LA-82 (made by Adeka Co., Ltd.), etc. are not limited to these. Among these, a naphthoquinone-based, hydroquinone-based or nitroso-piperidin-based radical polymerization inhibitor is preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di- The third butyl-P-cresol and the Polystop 7300P (manufactured by Berton Co., Ltd.) are more preferable, and Polystop 7300P (manufactured by Berton Co., Ltd.) is most preferable.

The content of the radical polymerization inhibitor is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, even more preferably 0.01 to 0.2% by mass, based on the total amount of the liquid crystal sealing agent of the present invention.

As an example of the method for producing the liquid crystal sealing agent of the present invention, the following methods are shown. First, the component (A) and the component (C) as needed are heated and dissolved. After cooling to room temperature, the component (F) is added as needed, and (B) component, (D) component, (E) component, antifoaming agent, leveling agent, solvent, etc. are further added as needed, and it is known. The mixing device such as a three-roll mill, a sand mill, a ball mill or the like is uniformly mixed and filtered by a metal mesh, whereby the liquid crystal sealing agent of the present invention can be produced.

In the liquid crystal display unit of the present invention, a pair of substrates on which a predetermined electrode has been formed are disposed to face each other at a predetermined interval, and the liquid crystal sealing agent of the present invention is sealed around the liquid crystal sealing agent of the present invention. The type of the liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a substrate having a combination of light transmittance of at least one surface made of glass, quartz, plastic, orium. After the liquid crystal sealing agent of the present invention is added with a spacer such as a glass fiber (gap control material), the liquid crystal sealing agent is applied to one of the pair of substrates by using a dispenser or a screen printing device. Temporary hardening is carried out at 80 to 120 ° C as needed. Thereafter, liquid crystal was dropped on the inside of the bank of the liquid crystal sealing agent, and the other glass substrate was superposed in a vacuum to perform gap formation. After the gap is formed, it is cured at 90 to 130 ° C for 1 to 2 hours, whereby the liquid crystal display unit of the present invention is obtained. Further, when it is used as a photothermal type, the liquid crystal sealing agent portion is irradiated with ultraviolet rays by an ultraviolet ray irradiator to be photocured. Based ultraviolet irradiation amount is preferably 500 to 10000mJ / cm ^2, more preferably to 1000 based 6000mJ / cm ² of irradiation amount is preferred. Thereafter, the liquid crystal display unit of the present invention is obtained by hardening at 90 to 130 ° C for 1 to 2 hours as needed. The liquid crystal display unit of the present invention obtained in this manner 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 particles, polymer particles or the like. The diameter varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount thereof to be used is usually from 0.1 to 4% by mass, preferably from 0.5 to 2% by mass, more preferably from 0.9 to 1.5% by mass, based on 100% by mass of the liquid crystal sealing agent of the present invention.

The liquid crystal sealing agent of the invention has the function of reducing wiring corrosion The effect. This result eliminates drive defects after the moisture resistance test. Further, it is excellent in low liquid crystal contamination, and the cured product is excellent in various cured properties such as adhesion strength and heat resistance. From the above, by using the liquid crystal sealing agent of the present invention, a liquid crystal display unit having excellent reliability can be realized. Further, the liquid crystal display unit produced by using the liquid crystal sealing agent of the present invention sufficiently satisfies the characteristics necessary for the liquid crystal display unit because of high voltage holding ratio and low ion density.

[Examples]

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

[Synthesis Example 1] [Synthesis of a full acrylate of resorcinol diglycidyl ether] [step 1]

5,500 g of resorcin, 37,000 g of epichlorohydrin, and 500 g of tetramethylammonium chloride were placed in a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, and dissolved under stirring, and the temperature was raised to 70 °C. Then, 4000 g of sodium hydroxide in the form of tablets was added in portions over a period of 100 minutes, and then reacted at 70 ° C for 1 hour. After completion of the reaction, 15000 g of water was added and washed with water, and then excess epichlorohydrin or the like was distilled off from the oil layer under reduced pressure at 130 °C. 22200 g of methyl isobutyl ketone was added to the residue, dissolved, and the temperature was raised to 70 °C. After stirring, 1000 g of a 30% aqueous sodium hydroxide solution was added, and the reaction was carried out for 1 hour, and then washed with water 5550 g three times, and the methyl isobutylate was distilled off under reduced pressure at 180 ° C. The base ketone produced 10,550 g of resorcinol diglycidyl ether. The epoxy equivalent of the obtained epoxy compound was 129 g/eq.

[Step 2]

181.2 g of resorcinol diglycidyl ether obtained in the above Synthesis Example 1 was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene was further added as a polymerization inhibitor, and the temperature was raised to 60 °C. Thereafter, 117.5 g of acrylic acid having an epoxy group equivalent of 100% was added, and the mixture was further heated to 80 ° C, and 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C for about 30 hours. The obtained reaction liquid was washed with water, and toluene was distilled off, whereby 253 g of the acrylate compound as the intended meta- benzenediol diglycidyl ether was obtained.

[Synthesis Example 2] [Synthesis of all-acrylates of bisphenol A epoxy compounds]

282.5 g of a bisphenol A type epoxy compound (product name: YD-8125, manufactured by Nippon Steel Chemical Co., Ltd.) was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene was added thereto as a polymerization inhibitor, and the temperature was raised to 60 ° C. Thereafter, 117.5 g of an acrylic acid having an epoxy equivalent of 100% was added, and the mixture was further heated to 80 ° C, and 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C for about 30 hours to obtain a reaction. liquid. The reaction liquid was washed with water, and toluene was distilled off to obtain 395 g of an acrylate compound of the intended bisphenol A type epoxy compound.

[Synthesis Example 3] Synthesis of [1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane]

Commercially available tetraphenyl-1,2-ethanediol (Tokyo Chemical Industry Co., Ltd. 100 parts (0.28 moles) dissolved in 350 parts of dimethylformaldehyde. To this was added 32 parts (0.4 mol) of pyridine as an alkali catalyst, and 150 parts (0.58 mol) of BASFA (manufactured by Shin-Etsu Chemical Co., Ltd.) as a thiolizing agent, and the temperature was raised to 70 ° C, and stirred for 2 hours. . The obtained reaction liquid was cooled, and while stirring, 200 parts of water was added to precipitate a product, and the unreacted thiolation agent was deactivated. After the precipitated product was separated by filtration, it was sufficiently washed with water. Then, the obtained product was dissolved in acetone, and water was added thereto to recrystallize and purify. The object of 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane was obtained in an amount of 105.6 parts (yield: 88.3%).

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

[Modification of Examples 1 to 5 and Comparative Examples 1 to 4]

A photoradical polymerization initiator (ingredient (C)) is added to the curable compound (component (A)) such as the compound synthesized in Synthesis Example 1 and the compound synthesized in Synthesis Example 2 at a ratio shown in the following Table 1 to Dissolved by heating at 90 °C. Cooling to room temperature, adding a thermal radical polymerization initiator (ingredient (B)), a decane coupling agent (ingredient (F)), a thermosetting agent (ingredient (E)), and an organic filler (ingredient (D-1) ), an inorganic filler (component (D-2)), etc., after stirring, dispersed in a three-roll mill, and filtered through a metal mesh (635 mesh) to prepare a sealant for liquid crystal dropping method (Examples 1 to 5, Comparative Example) 1 to 4).

[Water absorption rate measurement]

The liquid crystal sealing agent produced in the examples and the comparative examples was sandwiched between polyparaphenylene The ethylene formate (PET) film was placed in a 130 ° C oven for 1 hour as a film having a thickness of 100 μm, and was hardened. After hardening, the PET film was peeled off to obtain a sealant cured film, which was cut into 20 mm × 50 mm. Short note shape as a sample piece. The obtained sample piece was subjected to stabilization for 24 hours under the conditions of 25° C. and 50% RH according to JIS-K7209 D method, and then the initial weight was measured, and after absorbing water for 24 hours under conditions of 60° C. and 90% RH. The weight was measured as the weight after water absorption. After the measurement, the water absorption rate was calculated according to the following formula.

Water absorption rate (%) = ((weight after water absorption (g) - initial weight (g)) / initial weight (g)) × 100 (%)

[Transparent moisture measurement]

A sealant cured film was produced by the same method as the water absorption rate, and cut into a square shape of 90 mm × 90 mm to prepare a sample piece. This sample piece was subjected to measurement of moisture permeability at a temperature of 60 ° C according to a moisture permeability measuring device Lyssy L80-5000 manufactured by Systech Illinois Co., Ltd. of JIS-K7129 A.

[Evaluation of electrode corrosion in high temperature and high humidity test]

Using the liquid crystal sealing agent produced in the examples and the comparative examples, a liquid crystal cell for evaluation having a cell gap of 5 μm was produced, and the occurrence of electrode corrosion in the high temperature and high humidity test was confirmed. The test methods are shown below.

0.02 g of a glass fiber having a diameter of 5 μm was added as a spacer to 2 g of each of the liquid crystal sealing agents, and the mixture was stirred and defoamed, and filled in a 5 ml syringe. The glass substrate with the ITO transparent electrode is filled in advance with a dispenser (SHOTMASTER 300: manufactured by Takeshi Engineering Co., Ltd.). The liquid crystal sealing agent of the syringe was applied to a rectangular seal pattern of 30 mm × 40 mm, and then fine droplets of liquid crystal (MLC-3007: manufactured by Merk Co., Ltd.) were dropped into the seal pattern frame. On the other ITO glass substrate, an in-plane spacer (Natocospacer KSEB-525F: manufactured by Natoco Co., Ltd.: 5 μm wide after bonding) was placed and heat-sealed, using a bonding apparatus in a vacuum and the previous one. After bonding the substrates dropped into the liquid crystal, the atmosphere is connected to form a gap. In order to make it difficult to irradiate the sealant with the ultraviolet ray-shielding portion, the metal halide lamp (manufactured by Ushio Electric Co., Ltd.) is irradiated with ultraviolet rays having a low irradiation amount of 500 mJ/cm 2 (5 seconds at 100 mW/cm 2 ) to semi-harden the seal pattern. Further, the film was further placed in an oven at 130 ° C for 1 hour to thermally cure the seal pattern to prepare a liquid crystal cell for evaluation. In a state where a sine wave voltage of 10 V and 100 Hz was applied by a Function Generator (FG-281: manufactured by TEXIO, Technology Co., Ltd.), the obtained liquid crystal cell for evaluation was placed in a high-temperature and high-humidity condition of 60 ° C and 90% RH for 240 hours, and then borrowed. The evaluation sealing portion was observed by a microscope, and evaluation of electrode corrosion was performed in accordance with the following criteria.

○: No corrosion of the ITO electrode was observed in the peripheral portion of the seal.

△: Corrosion of the ITO electrode was slightly observed in the peripheral portion of the seal.

×: Corrosion of the ITO electrode was observed in the peripheral portion of the seal.

[Liquid Crystal Pollution Evaluation]

For each liquid crystal sealing agent manufactured in the examples and the comparative examples, about 100 mg of the sealant was applied to the bottom of a 10 ml vial, and then, liquid crystal (MLC- was added from above, 10 times the amount of each of the applied sealants. 3007: Merk Co., Ltd.). The resulting vial was heated, maintained at 130 ° C for 1 hour, and then cooled to room temperature for 30 minutes. The supernatant of each liquid crystal was separated by decantation, and the resistance value was measured by a digital ultra-high resistance meter (R8340: manufactured by Advantest Co., Ltd.) as a specific resistance with respect to the value of the liquid crystal without the sealant. The value is determined based on the following criteria.

○: 5.0×10 ¹² or more

△: 5.0 × 10 ¹¹ or more, less than 5.0 × 10 ¹²

×: not up to 5.0×10 ¹¹

[Evaluation of shading degree of shading]

As shown in Fig. 1, a liquid crystal sealing agent containing 1 w% of glass fibers of 3 μm was applied to the center of a glass substrate which was etched with chromium, and a black matrix substrate was used as a counter substrate, and fixed by a jig (UV). Before irradiation). Further, ultraviolet rays of 3000 mJ/cm ^{2 were} irradiated from the side of the glass substrate which was etched with chromium, and then the two bonded substrates were peeled off, and the portion which was shielded from light under the chrome was confirmed by a microscope, and the hardened width of the light-shielding portion was measured.

○: 30 μm or more

△: 10 μm or more and less than 30 μm

×: less than 10 μm

A-1: total acrylate of resorcinol diglycidyl ether (Synthesis Example 1)

A-2: Total acrylate of bisphenol A type epoxy resin (Synthesis Example 2)

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

A-4: Bisphenol A type epoxy resin (manufactured by Nippon Chemical Co., Ltd.: RE-310S)

A-5: Bisphenol A type epoxy resin high molecular weight body (Nippon Steel Corporation: YD-012)

A-6: Ethylene oxide modified bisphenol S type epoxy resin (synthesized by the method described in Japanese Patent No. 4211942)

B-1:1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane (Synthesis Example 3 was pulverized by a jet mill to an average of 1.9 μm)

B-2: polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyethylene glycol (molecular weight: 2000) (manufactured by Wako Pure Chemical Industries Co., Ltd.: VPE-0201)

C-1: 2-methacryloyloxyethyl isocyanate and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one Reaction product (synthesized by the method described in International Publication No. 2006/027982)

C-2: 1,2-octanedione, 1-[4-(phenylsulfanyl)-2-(O-benzhydrylhydrazine)] (manufactured by BASF: IRGACURE OXE-01

C-3: 2,4-diethylthiaxanthone (manufactured by Nippon Chemical Co., Ltd.: DETX-S)

D-1-1: Polymethacrylate organic fine particles (manufactured by AICA Industrial Co., Ltd.: F-351S)

D-2-1: Spherical cerium oxide (manufactured by Shin-Etsu Chemical Co., Ltd.: X-24-9163A)

D-2-2: Spherical cerium oxide (manufactured by Tokuyama Co., Ltd.: Sunseal SSP-07DM)

E-1: ginseng (2-mercaptocarbonylethyl) trimer isocyanate finely pulverized product (manufactured by Japan Finechem Co., Ltd.: HCIC, finely pulverized to 1.5 μm by a jet mill)

F-1: 3-glycidoxypropyltrimethoxydecane (manufactured by JNC Co., Ltd.: Sila-Ace S-510)

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

O-1: nitroso piperidine derivative (made by Bodong Co., Ltd.: Polystop 7300P)

O-2: ginseng (3-carboxyethyl) trimeric isocyanate (manufactured by Shikoku Chemical Industry Co., Ltd.: CIC acid, finely pulverized by a jet mill to an average particle diameter of 1.5 μm)

As is apparent from the results of Table 1, Examples 1 to 5 in which the water absorption rate and the moisture permeability of the cured product hardened by heat were not more than a certain degree were not corroded, and the liquid crystal contamination was also excellent. On the other hand, the liquid crystal sealing agent described in the comparative example has wiring corrosion and has a problem in long-term reliability of the liquid crystal display unit. From this fact, the invention of the present invention is a liquid crystal sealing agent excellent in reliability after the moisture resistance test, and the liquid crystal display unit manufactured using the liquid crystal sealing agent is also excellent in reliability.

[Industry use possibility]

Since the liquid crystal sealing agent of the present invention has an extremely small influence on the liquid crystal display characteristics, it is possible to achieve high definition of the liquid crystal display element, high-speed response, low voltage driving, and long life. Further, since the strength and the moisture resistance reliability are excellent, the production of the liquid crystal display element having high reliability can be realized.

Claims (14)

A liquid crystal sealing agent for a liquid crystal dropping method, which comprises (A) a curable compound, which is obtained by heat-curing only at 130 ° C for 1 hour without irradiating ultraviolet rays, and the water absorption rate measured according to JIS-K7209 It is 2.0% or less, and the moisture permeability measured according to JIS-K7129 is 130 g/m ² *24h or less. The liquid crystal sealing agent for liquid crystal dropping method according to claim 1, further comprising (B) a thermal radical polymerization initiator. The liquid crystal sealing agent for liquid crystal dropping method according to claim 1 or 2, wherein the component (B) thermal radical polymerization initiator does not contain an oxygen-oxygen bond (-OO-) in the molecule; A thermal radical polymerization initiator of a nitrogen-nitrogen bond (-N=N-). The liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 3, further comprising (C) a photoradical polymerization initiator. The liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 4, further comprising (D) a filler, the content of the filler in the total amount of the liquid crystal sealing agent being 20% by mass or more . The liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 5, wherein the component (D) is (D-1) an organic filler and (D-2) an inorganic filler. mixture. The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the first aspect of the invention, wherein the content of the component (D-2) inorganic filler in the total amount of the liquid crystal sealing agent is 20% by mass. the above. The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the first aspect of the invention, wherein the component (A) curable compound is an epoxy (meth) acrylate compound. The liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 7, wherein the component (A) curable compound is an epoxy (meth) acrylate compound and an epoxy compound. mixture. The liquid crystal sealing agent for liquid crystal dropping method according to any one of claims 1 to 9 further contains (E) a heat hardening agent. The liquid crystal sealing agent for a liquid crystal dropping method according to claim 10, wherein the component (E) thermal curing agent is an organic acid bismuth. The liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 11, further comprising (F) a decane coupling agent. A method of manufacturing a liquid crystal display unit, comprising the steps of: in the liquid crystal display unit comprising two substrates, the liquid crystal according to any one of claims 1 to 12 formed on a substrate After dropping the liquid crystal into the inside of the bank of the liquid crystal sealing agent for the dropping method, the other substrate is bonded, and then hardened by light and/or heat. A liquid crystal display unit is obtained by curing a cured product obtained by curing a liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 12.