JP6452194B2 - Liquid crystal sealant and liquid crystal display cell using the same - Google Patents

Description

  The present invention relates to a liquid crystal sealing agent used in a liquid crystal dropping method. In more detail, while having sufficient insertion resistance of liquid crystal to the liquid crystal sealant, it is highly reliable because it has excellent workability, low liquid crystal contamination, and particularly low water vapor permeability and low water absorption. The present invention relates to a liquid crystal sealant for a liquid crystal dropping method that enables production of a display cell.

  Along with the recent increase in size of liquid crystal display cells, a so-called liquid crystal dropping method with higher mass productivity has been proposed as a method for manufacturing liquid crystal display cells (Patent Document 1 and Patent Document 2). Specifically, it is a method of manufacturing a liquid crystal display cell in which liquid crystal is dropped inside a weir of a liquid crystal sealant formed on one substrate, the other substrate is bonded, and then the liquid crystal sealant is cured.

  Liquid crystal sealing agents for liquid crystal dropping methods (hereinafter referred to as sealing agents) are required to have excellent low water vapor permeability (hereinafter referred to as low moisture permeability) and low water absorption. This is because the moisture permeability and water absorption of the sealant contribute to the reliability of the liquid crystal cell, particularly the long-term durability of the liquid crystal display function under high temperature and high humidity. Currently, the technology trend is to apply low-voltage drive using low-power consumption semiconductors such as negative-type liquid crystals and oxide semiconductors as liquid crystal materials, mainly in small or medium-size liquid crystal displays. It is widely known that the moisture resistance is lower than that of the liquid crystal. In general, negative liquid crystals have high water absorption, so that they have low durability under high temperature and high humidity, and are easily affected by the moisture permeability and water absorption of the sealant. Further, in low voltage driving, the lower limit of the allowable value for lowering the resistance value of the liquid crystal material is higher than before, and higher reliability is required for the sealant.

  Further, a high glass transition point (hereinafter referred to as Tg) is required for the sealant. This is an accelerated test condition: high temperature test 80 ° C., heat cycle test −20 ° C. to 60 ° C., high temperature and high humidity test 60 ° C. 90% RH, heat shock test −20 ° C. × 30 minutes to 60 ° C. × 30 minutes, pressure cooker This is because the sealant having a low Tg in the test of 120 ° C. × 2 atm or the like affects the reliability of the liquid crystal cell due to a change in mechanical properties.

In order to solve these problems, various technologies have been proposed.
In patent document 3, the sealing agent which has high Tg using an epoxy resin, a (meth) acrylic resin, and an acrylic polymer is disclosed. However, there is no description about moisture permeability, and since the acrylic polymer used in the technology has high moisture permeability, it is easy to permeate moisture, so that high reliability of the liquid crystal cell cannot be obtained.
In patent document 4, although the technique of the sealing agent with low moisture permeability is disclosed, there is no description regarding Tg and water absorption. A sealing agent having a low Tg or a high water absorption causes functional failure of the liquid crystal display cell such as display unevenness and response speed delay with time in an acceleration test.

  As described above, the liquid crystal sealant is developed very vigorously, but has a high Tg and excellent insertion resistance, low liquid crystal contamination, low moisture permeability, and low water absorption. The liquid crystal sealant has not yet been completed.

JP-A 63-179323 JP-A-10-239694 JP 2013-76967 A JP2013-218168A

  The present invention relates to a liquid crystal sealant used in a liquid crystal dropping method, and more specifically, a liquid crystal having a high Tg and excellent in insertion resistance, workability, low moisture permeability, low water absorption, and low liquid crystal contamination. A liquid crystal sealant for a dripping method is proposed.

As a result of intensive studies, the present inventors have found that a liquid crystal sealing agent for a liquid crystal dropping method containing a (meth) acrylic compound having a specific skeleton has insertion resistance, workability, low moisture permeability, low water absorption, and low liquid crystal. The present inventors have found that it is excellent in contamination, and have arrived at the present invention.
In the present specification, “(meth) acryl” means “acryl and / or methacryl”, and “(meth) acryloyl group” means “acryloyl group and / or methacryloyl group”. Further, “liquid crystal sealing agent for liquid crystal dropping method” may be simply referred to as “liquid crystal sealing agent” or “sealing agent”.

（式中、Ｒ^１はそれぞれ独立して、水素原子または炭素数１〜４の炭化水素基を表し、Ｒ^２はそれぞれ独立して、炭素数１〜５の炭化水素基を表し、ｍおよびｎは平均の繰り返し数を表し、ｍ＋ｎは０〜１２であり、Ｒ^３は炭素数３〜２０のシクロアルキレン基、またはシクロアルキリデン基をそれぞれ表す。）
２）
成分（Ａ）のＲ^２が、それぞれ独立して、炭素数２または３の炭化水素基である上記１）に記載の液晶滴下工法用液晶シール剤。
３）
さらに（Ｃ）エポキシ基を有する化合物を含有する上記１）または２）に記載の液晶滴下工法用液晶シール剤。
４）
さらに（Ｄ）熱硬化剤を含有する上記１）乃至３）の何れか一項に記載の液晶滴下工法用液晶シール剤。
５）
さらに（Ｅ）フィラーを含有する上記１）乃至４）の何れか一項に記載の液晶滴下工法用液晶シール剤。
６）
前記成分（Ｅ）の平均粒子径が８μｍ以下である上記５）に記載の液晶滴下工法用液晶シール剤。
７）
前記成分（Ｅ）が、ウレタン微粒子、アクリル微粒子、シリコーン微粒子、スチレン微粒子、スチレンオレフィン微粒子の群から選択される１または２以上のフィラーである上記５）または６）に記載の液晶滴下工法用液晶シール剤。
８）
粘弾性測定装置を使用し昇温速度２℃／ｍｉｎで測定したＴｇが１００℃以上である上記１）乃至７）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
９）
６０℃９０％ＲＨ条件下で測定した膜厚１００μｍの硬化膜の透湿度が１５０ｇ／ｍ^２・ｄａｙ以下である上記１）乃至８）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
１０）
２枚の基板により構成される液晶表示セルにおいて、一方の基板に形成された上記１）乃至９）の何れか一項に記載の液晶滴下工法用液晶シール剤の堰の内側に液晶を滴下した後、もう一方の基板を貼り合わせ、その後、熱により硬化することを特徴とする液晶表示セルの製造方法。
１１）
上記１）乃至１０）の何れか一項に記載の液晶滴下工法用液晶シール剤を硬化せしめて得られる硬化物でシールされた液晶表示セル。 That is, the present invention relates to the following 1) to 11).
1)
(A) A liquid crystal sealing agent for a liquid crystal dropping method comprising a (meth) acrylic compound having a cycloalkylene group or a cycloalkylidene group represented by the following general formula (1), and (B) a radical polymerization initiator.

(In the formula, each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, each R ² independently represents a hydrocarbon group having 1 to 5 carbon atoms, m and n Represents an average number of repetitions, m + n is 0 to 12, and R ³ represents a cycloalkylene group having 3 to 20 carbon atoms or a cycloalkylidene group.
2)
The liquid crystal sealing agent for liquid crystal dropping method according to 1) above, wherein R ^{2 of} component (A) is independently a hydrocarbon group having 2 or 3 carbon atoms.
3)
Furthermore, (C) Liquid crystal sealing agent for liquid crystal dropping methods as described in said 1) or 2) containing the compound which has an epoxy group.
4)
Furthermore, (D) Liquid crystal sealing agent for liquid crystal dropping methods as described in any one of said 1) thru | or 3) containing a thermosetting agent.
5)
Furthermore, (E) The liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said 1) thru | or 4) containing a filler.
6)
The liquid crystal sealing agent for a liquid crystal dropping method according to 5) above, wherein the average particle diameter of the component (E) is 8 μm or less.
7)
Liquid crystal for liquid crystal dropping method according to 5) or 6) above, wherein the component (E) is one or more fillers selected from the group consisting of urethane fine particles, acrylic fine particles, silicone fine particles, styrene fine particles, and styrene olefin fine particles. Sealing agent.
8)
The liquid crystal sealant for a liquid crystal dropping method according to any one of 1) to 7) above, wherein Tg measured at a temperature elevation rate of 2 ° C./min using a viscoelasticity measuring device is 100 ° C. or higher.
9)
The liquid crystal sealant for liquid crystal dropping method according to any one of 1) to 8) above, wherein the moisture permeability of a cured film having a film thickness of 100 μm measured at 60 ° C. and 90% RH is 150 g / m ² · day or less. .
10)
In a liquid crystal display cell constituted by two substrates, the liquid crystal was dropped inside the liquid crystal sealing agent weir for liquid crystal dropping method according to any one of 1) to 9) formed on one substrate. Then, another substrate is bonded together, and then cured by heat, a method for producing a liquid crystal display cell.
11)
A liquid crystal display cell sealed with a cured product obtained by curing the liquid crystal sealing agent for a liquid crystal dropping method according to any one of 1) to 10) above.

  The liquid crystal sealant of the present invention is very excellent in low moisture permeability and low water absorption. Moreover, it has high Tg. Therefore, the completed liquid crystal display cell has high long-term reliability. That is, the present invention enables production of an excellent liquid crystal display cell.

The liquid-crystal sealing compound of this invention contains the (meth) acryl compound (component (A)) represented by the said Formula (1).
In the above (1), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, each R ² independently represents a hydrocarbon group having 1 to 5 carbon atoms, m And n represents an average number of repetitions, m + n is 0 to 12, and R ³ represents a cycloalkylene group having 3 to 20 carbon atoms or a cycloalkylidene group.

R ¹ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

R ² is preferably an ethylene group, an n-propylene group, an i-propylene group or an n-butylene group, more preferably an ethylene group (carbon number 2 hydrocarbon group) or an n-propylene group (number 3 carbon atoms). Hydrocarbon group).

  The m + n is 0-12. Since m and n are averages of the number of repetitions, they may be decimal numbers. A more preferable range of m + n is 0.4 to 12, and a particularly preferable range is 2 to 10.

R ³ is not particularly limited as long as it is a cycloalkylene group having 3 to 20 carbon atoms or a cycloalkylidene group. Here, the cycloalkylene group having 3 to 20 carbon atoms is bonded with two carbons of the cycloalkane having 3 to 20 carbon atoms, and the cycloalkylidene group having 3 to 20 carbon atoms is the number of carbon atoms. It is bonded to one carbon of 3 to 20 cycloalkanes. Examples of the cycloalkane are preferably cyclopentane, cyclohexane, cyclododecane, tricyclodecane, isobornane, isophorone, and adamantane. Cyclohexane, tricyclodecane, and isophorone are particularly preferable because of easy material availability.
Moreover, the said C3-C20 cycloalkylene group or cycloalkylidene group may have a 1 or 2 or more substituent. Examples of the substituent include a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, A methyl group is preferred.

The (meth) acrylic compound (component (A)) contained in the liquid crystal sealant of the present invention reacts, for example, bisphenol Z with alkylene oxide (alkylene oxide) or alkylene carbonate (alkylene carbonate), and then (meth) By carrying out a dehydration condensation reaction in the presence of acrylic acid and an acid catalyst, a compound in which R ³ is a cyclohexylidene group can be obtained. In addition, when (meth) acrylic acid is reacted in the presence of bisphenol Z and a catalyst, it is possible to synthesize those having m + n of 0. In the present invention, bisphenol Z is available from Honshu Chemical Industry Co., Ltd. In the reaction of bisphenol Z and alkylene oxide, 0.5 to 24 mol of alkylene oxide is reacted with 1 mol of bisphenol Z. In the reaction of bisphenol Z and alkylene carbonate, 2 to 5 mol of alkylene carbonate is reacted with 1 mol of bisphenol Z. Alkylene oxide or alkylene carbonate may be used alone or in combination of two or more.

  Specific examples of the alkylene oxide include alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. Specific examples of the alkylene carbonate include alkylene carbonates such as ethylene carbonate (ethylene carbonate) and propylene carbonate (propylene carbonate, butylene carbonate (butylene carbonate)).

  The reaction of bisphenol Z with alkylene oxide or alkylene carbonate is carried out under an alkali catalyst such as sodium hydroxide or potassium hydroxide for a reaction time of 1 to 48 hours and a reaction temperature of 90 ° C to 200 ° C. In the reaction of bisphenol Z and alkylene oxide, 0.01 to 5% by mass of an alkali catalyst is used with respect to 100% by mass of the reaction mixture. In the reaction of bisphenol Z and alkylene carbonate, 0.01 to 0.5 mol of alkali catalyst is used with respect to 1 mol of bisphenol Z.

  In the dehydration condensation reaction between a reaction product of bisphenol Z and alkylene oxide or alkylene carbonate (hereinafter referred to as bisphenol Z reaction product) and (meth) acrylic acid, (meth) acrylic acid is 0.1 -10 mol is used. As a reaction solvent in the dehydration condensation reaction, an azeotropic solvent capable of distilling off water generated in the reaction can be used. The azeotropic solvent here has a boiling point of 60 to 130 ° C. and can be easily separated from water, and in particular, non-reactive organic solvents such as benzene, toluene, n-hexane, n-heptane, and cyclohexane. It is desirable to use one kind or a mixture of two or more kinds.

  The reaction time in the dehydration condensation reaction may be in the range of 1 to 24 hours, and the reaction temperature may be in the range of 60 to 150 ° C. However, the reaction time is preferably 75 to 120 ° C from the viewpoint of shortening the reaction time and preventing polymerization.

  Usually, a commercially available (meth) acrylic acid used as a raw material is already added with a polymerization inhibitor such as p-methoxyphenol, but a polymerization inhibitor may be added again during the reaction. Examples of such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, Examples include phenothiazine. The amount of its use is 0.01-1 mass% with respect to the reaction mixture.

  The acid catalyst used in the dehydration condensation reaction can be arbitrarily selected from known ones such as sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and the amount used is 1 mole of (meth) acrylic acid. It is 0.01-10 mol% with respect to it, Preferably it is 1-5 mol%.

  5-70 mass% is preferable in the total amount of a liquid-crystal sealing compound, and, as for the content rate of a component (A), 20-50 mass% is still more preferable.

  Examples of the radical polymerization initiator (B) contained in the liquid crystal sealing agent of the present invention include a thermal radical polymerization initiator and a photo radical polymerization initiator. These may be used alone or in combination.

The thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction, but there are organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, benzopinacols, and the like. And benzopinacol is preferably used. For example, examples of the organic peroxide include Kayamek ^RTM A, M, R, L, LH, SP-30C, Parkadox CH-50L, BC-FF, Kadox B-40ES, Parkadox 14, Trigonox ^RTM 22-70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kaya Ester ^RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl ^RTM B, Parkardox 16 , Kayacaron ^RTM BIC-75, AIC-75 (manufactured by Kayaku Akzo Co., Ltd.), Permec ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC, Pat TMH, C, V, 22, MC, Percure ^RTM AH, AL, HB, Perbutyl ^RTM H, C, ND, L, Parkmill ^{RT M} H, D, Peroyl ^RTM IB, IPP, Perocta ^RTM ND, is available as such is a commercially available product (manufactured by NOF Co., Ltd.). Moreover, as an azo compound, VA-044, V-070, VPE-0201, VSP-1001 (made by Wako Pure Chemical Industries Ltd.), etc. are available as a commercial item. In the present specification, the superscript RTM means a registered trademark. Moreover, in the liquid-crystal sealing compound of this invention, a thermal radical polymerization initiator may be used independently and may be used in mixture of multiple types.

As the thermal radical polymerization initiator, preferred is a thermal radical polymerization initiator having no oxygen-oxygen bond (—O—O—) or nitrogen-nitrogen bond (—N═N—) in the molecule. A thermal radical polymerization initiator having an oxygen-oxygen bond (—O—O—) or a nitrogen-nitrogen bond (—N═N—) in the molecule emits a large amount of oxygen or nitrogen when a radical is generated. There exists a possibility that it hardens | cures in the state which left the bubble inside, and characteristics, such as adhesive strength, may be reduced. Particularly preferred are benzopinacol-based thermal radical polymerization initiators (including those obtained by chemically modifying benzopinacol). Specifically, benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy- 1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra (4-methylphenyl) ethane, 1,2-diphenoxy-1,1,2,2-tetra (4-methoxyphenyl) ethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, 1,2-bis (triethylsiloxy) -1,1,2,2-tetraphenyl Ethane, 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, 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane, and the like are preferable, and preferably 1- Hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethyl Siloxy-1,1,2,2-tetraphenylethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylsiloxy- 1,1,2,2-tetraphenylethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, especially The Mashiku 1, 2- bis (trimethylsiloxy) -1,1, 2,2-tetraphenyl ethane.
The benzopinacol is commercially available from Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd. Moreover, etherification of the hydroxy group of benzopinacol can be easily synthesized by a known method. Moreover, silyl etherification of the hydroxy group of benzopinacol can be obtained by synthesizing by a method in which the corresponding benzopinacol and various silylating agents are heated under a basic catalyst such as pyridine. Examples of silylating agents include trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) and triethylsilylating agents, which are generally known trimethylsilylating agents. Examples of triethylchlorosilane (TECS) and t-butyldimethylsilylating agent include t-butylmethylsilane (TBMS). These reagents can be easily obtained from markets such as silicon derivative manufacturers. The reaction amount of the silylating agent is preferably 1.0 to 5.0 times mol for 1 mol of the hydroxyl group of the target compound. More preferably, it is 1.5-3.0 times mole. When the amount is less than 1.0 times mol, the reaction efficiency is poor and the reaction time is prolonged, so that thermal decomposition is promoted. When the amount is more than 5.0 times mol, separation may be deteriorated during collection or purification may be difficult.

  It is preferable that the thermal radical polymerization initiator has a fine particle size and is uniformly dispersed. The average particle size is preferably 5 μm or less, more preferably 3 μm or less, because if the average particle size is too large, it becomes a cause of defects such as inability to successfully form a gap when the upper and lower glass substrates are bonded together during the production of a narrow gap liquid crystal display cell. . Moreover, although it does not matter even if it makes it infinitely small, usually a minimum is about 0.1 micrometer. The particle size can be measured by a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).

  As content of a thermal radical polymerization initiator, it is preferable that it is 0.0001-10 mass% in the total amount of a liquid-crystal sealing compound, More preferably, it is 0.0005-5 mass%, 0.001-3 mass % Is particularly preferred. When the content of the thermal radical polymerization initiator is lower than 0.0005% by mass, the reactivity is insufficient and liquid crystal leaks (a phenomenon in which the liquid crystal material enters the sealant due to a pressure difference between the inside and outside of the cell) and a seal path (pressure inside and outside the cell) Due to the difference, a phenomenon in which the liquid crystal material passes through the sealant is likely to occur. On the other hand, if the content of the thermal radical polymerization initiator is higher than 5% by mass, the stability of the sealing agent is impaired. This is because the viscosity is likely to increase with time, that is, the pot life (pot life) is shortened, which affects the productivity.

The photo radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by light irradiation and initiates a chain polymerization reaction, but such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc. Benzoins; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, di Ethoxyacetophenone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, oligo [2-hydroxy-2-methyl-1- [4- (1-Me Acetophenones such as 2-vinylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2 Thioxanthones such as chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone; 2,4 , 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, diphenyl- (2,4,6-trimethyl) Examples thereof include phosphine oxides such as (tilbenzoyl) phosphine oxide, a reaction product of a radical polymerization initiator having a hydroxyl group and a compound having a (meth) acryloyl group. Preferably, they are acetophenones, more preferably 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and 2-isocyanatoethyl (meth) acrylate. It is a reaction product. In addition, in the liquid-crystal sealing compound of this invention, radical photopolymerization initiator may be used independently and may be used in mixture of multiple types.
The above-mentioned radical photopolymerization initiator can be easily obtained from the market. For example, IRGACURE ^RTM 651, 184, 2959, 127, 907, 369, 379EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE Examples thereof include ^RTM 1173, LUCIRIN ^RTM TPO (all manufactured by BASF), Seikol ^RTM Z, BZ, BEE, BIP, and BBI (all manufactured by Seiko Chemical Co., Ltd.).

  As content of radical photopolymerization initiator, it is preferable that it is 0.0001-10 mass% in the total amount of a liquid-crystal sealing compound, More preferably, it is 0.0005-5 mass%, 0.001-3 mass % Is particularly preferred. When the content of the photo radical initiator is lower than 0.0001% by mass, the reactivity is insufficient, and in particular, the light-shielding part curability deteriorates. In recent years, high-definition displays are progressing mainly in small and medium displays. The TFT wiring density is gradually increased, and the light beam for curing the sealing agent is not irradiated to the light shielding portion under the wiring, so that the sealing agent is in an uncured state, and liquid crystal leak and a seal pass are likely to occur. In addition, when the content of the photo radical initiator is higher than 10% by mass, the content of the curable resin or the inorganic or organic filler is relatively lowered, the Tg is decreased, the moisture permeability is increased, and the reliability of the cell is impaired. . In addition, the generated decomposition product of the photo radical initiator is eluted into the liquid crystal, which affects the cell driving.

  The liquid crystal sealant of the present invention preferably contains (C) a compound having an epoxy group. Although it does not specifically limit as a compound which has the said (C) epoxy group, The epoxy compound which has an aromatic ring is preferable.

  Examples of the epoxy compound having an aromatic ring include epoxy compounds having a phenyl skeleton such as styrene oxide and phenyl glycidyl ether, biphenyl glycidyl ether, biphenyl diglycidyl ether, p-tert-butylphenyl glycidyl ether, 3, 3 ′, 5, 5 Epoxy compounds having a biphenyl skeleton such as' -tetramethyl-4,4'-bis (glycidyloxy) -1,1'-biphenyl, biphenyl aralkyl type epoxy compounds, phenol novolac type epoxy compounds, cresol novolak type epoxy compounds, etc. Bisphenol A type epoxy compound such as novolac type epoxy compound, bisphenol A diglycidyl ether, brominated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, Bisphenol F type epoxy compounds such as bisphenol F diglycidyl ether, bisphenol S type diglycidyl ether, bisphenol S type epoxy compounds such as brominated bisphenol S diglycidyl ether, bisphenol E type epoxy compounds such as bisphenol E diglycidyl ether, ether Bisphenol O type epoxy compounds such as bisphenol O diglycidyl ether having a bond, bisphenol AF type epoxy compounds such as bisphenol AF diglycidyl ether having a fluorine atom, bisphenol Z diglycidyl ether having an alicyclic ring, bisphenol TMC diglycidyl ether, etc. Bisphenol Z type epoxy compound, bisphenol TMC type epoxy compound, bisphenol A having an aromatic group as a substituent Bisphenol AP type epoxy compounds such as diglycidyl ether, bisphenol BP diglycidyl ether, bisphenol PH diglycidyl ether, bisphenol BP type epoxy compound, bisphenol PH type epoxy compound, 1,3-bis (4′-glycidyloxyphenyl) adamantane , Epoxy compounds having an adamantane skeleton such as 2,2-bis (4′-glycidyloxyphenyl) adamantane, epoxy compounds having a fluorene skeleton such as bisphenylfluorenedin glycidyl ether and bisphenylfluorene ethanol glycidyl ether, glycidyloxynaphthalene 1,6-bis (2,3-epoxypropan-1-yloxy) naphthalene, binaphthalene glycidyl ether, binaphthalenediglycidyl ether And epoxy compounds having a naphthalene skeleton such as binaphthol ethanol diglycidyl ether. Bisphenol type epoxy resins are preferred, and bisphenol A type epoxy compounds, bisphenol E type epoxy compounds, bisphenol F type epoxy compounds, bisphenol O type epoxy compounds, and bisphenol S type epoxy compounds are more preferred.

  Moreover, the epoxy compound which modified the said epoxy compound with the alkylene oxide for the purpose of improving liquid-crystal contamination | pollution property can also be used suitably. As the alkylene oxide modification, ethylene oxide modification is particularly preferable, and as the modified epoxy compound, an ethylene oxide modified bisphenol S type epoxy compound is preferable. This is because the modification with alkylene oxide causes a difference in SP value (solubility parameter) with the liquid crystal material, which makes it difficult to cause liquid crystal contamination.

  For the purpose of improving reactivity, a compound in which the epoxy compound has an allyl group can also be suitably used. When using the epoxy compound which has an allyl group, it is preferable to use primary thiol or secondary thiol together, and use of secondary thiol is particularly preferable. Secondary thiols are readily available as commercial products, Karenz MT PE1 pentaerythritol tetrakis (3-mercaptobutyrate), Karenz MT BD1 (1,4-bis (3-mercaptobutyryloxy) butane), Karenz MT NR1 (1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione) (all Showa Denko KK) Manufactured). The blending amount of the thiol is 0.01-2 mol / eq. With respect to the allyl group equivalent of the epoxy compound. Is preferable, and 0.05 to 1 mol is particularly preferable. 0.01 mol / eq. If the amount is less than 1, the reactivity is low, so the effect of high crosslinking cannot be expected. In addition, 2 mol / eq. If it is more than the range, the stability deteriorates and the pot life is impaired.

  It is preferable that the content rate of the compound (C) which has an epoxy group is 1-30 mass% in the total amount of a liquid-crystal sealing compound, More preferably, it is 3-20 mass%, 5-15 mass% is especially preferable.

  The liquid crystal sealant of the present invention preferably contains a thermosetting agent as component (D). Unlike the component (B) radical polymerization initiator, the thermosetting agent (D) means a thermosetting agent that does not generate radicals.

  Specifically, it reacts nucleophilically with an unshared electron pair or an anion in the molecule, and examples thereof include polyvalent amines, polyhydric phenols, and organic acid hydrazide compounds. However, it is not limited to these. Of these, organic acid hydrazide compounds are particularly preferably used. For example, the aromatic hydrazide terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzenetrihydrazide, 1,4,5,8-naphthoic acid Examples thereof include tetrahydrazide and pyromellitic acid tetrahydrazide. Examples of aliphatic hydrazide compounds include form hydrazide, 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-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis ( Hydantoin skeletons such as hydrazinocarbonoethyl) -5-isopropylhydantoin, preferably valine hydantoin skeleton (the carbon atom of the hydantoin ring is Dihydrazide compounds having a skeleton substituted with a propyl group), tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate and the like can be mentioned. Preferably, from the balance of curing reactivity and latency, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris ( 2-hydrazinocarbonylethyl) isocyanurate and tris (3-hydrazinocarbonylpropyl) isocyanurate, particularly preferably tris (2-hydrazinocarbonylethyl) isocyanurate and isophthalic acid dihydrazide.

  0.1-10 mass% is preferable in the total amount of a liquid-crystal sealing compound, and, as for the content rate of a component (D) thermosetting agent, 1-5 mass% is still more preferable.

  The liquid crystal sealing agent of the present invention preferably contains (E) a filler. It does not specifically limit as a component (E), An organic filler and / or an inorganic filler can be used.

Examples of the organic filler include urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles. The silicone fine particles are preferably KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil ^RTM E-5500, 9701, EP-2001 (manufactured by Toray Dow Corning Co., Ltd.), and urethane fine particles. Are JB-800T and HB-800BK (Negami Kogyo Co., Ltd.), and styrene fine particles are preferably Lavalon ^RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (manufactured by Mitsubishi Chemical Corporation), and styrene olefin fine particles As Septon ^RTM SEPS2004 and SEPS2063, it is preferable.
These organic fillers may be used alone or in combination of two or more. Moreover, it is good also as a core-shell structure using 2 or more types. Of these, acrylic fine particles and silicone fine particles are preferable.
When the above acrylic fine particles are used, it is preferable that the acrylic rubber has a core-shell structure composed of two kinds of acrylic rubbers, and particularly preferably a core layer is n-butyl acrylate and a shell layer is methyl methacrylate. This is sold by Aika Industries as Zefiac ^RTM F-351.
Examples of the silicone fine particles include crosslinked organopolysiloxane powders and linear dimethylpolysiloxane crosslinked powders. Examples of the composite silicone rubber include those obtained by coating the surface of the silicone rubber with a silicone resin (for example, polyorganosilsesquioxane resin). Among these fine particles, a silicone rubber of a linear dimethylpolysiloxane crosslinked powder or a composite silicone rubber fine particle of a silicone resin-coated linear dimethylpolysiloxane crosslinked powder is particularly preferable. These may be used alone or in combination of two or more. Preferably, the rubber powder has a spherical shape with little viscosity increase after addition. In the liquid crystal sealing agent of the present invention, when an organic filler is used, it is usually 5 to 50% by mass, preferably 5 to 40% by mass, in the total amount of the liquid crystal sealing agent.

Examples of the inorganic filler include fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, and aluminum hydroxide. , Magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably fused silica, crystalline silica, silicon nitride, nitriding Boron, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, more preferably fused silica, crystalline silica, aluminum It is a talc. These inorganic fillers may be used in combination of two or more. If the average particle size is too large, it becomes a cause of defects such as inability to form a gap when the upper and lower glass substrates are bonded together when manufacturing a narrow gap liquid crystal cell. Therefore, 3 μm or less is appropriate, and preferably 2 μm or less. . The particle size can be measured by a laser diffraction / scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).
In the liquid crystal sealing agent of the present invention, when an inorganic filler is used, it is usually 5 to 50% by mass, preferably 5 to 40% by mass, in the total amount of the liquid crystal sealing agent. When the content of the inorganic filler is lower than 5% by mass, the adhesive strength to the glass substrate is lowered, and the moisture resistance reliability is inferior, so that the decrease in the adhesive strength after moisture absorption may be increased. Moreover, when there is more content of an inorganic filler than 50 mass%, since there is too much filler content, it may become difficult to collapse and it will become impossible to form the gap of a liquid crystal cell.

  The filler used in the present invention is preferably an organic filler, and particularly preferably silicone fine particles and core-shell structured acrylic fine particles. The average particle size is preferably from 0.01 to 10 μm, particularly preferably from 0.1 to 8 μm. In order to improve the anti-insertion performance of the liquid crystal material, it is preferable to use a filler having a larger particle size. However, an organic filler having an average particle size that is too large is used as a gap in the bonding of the upper and lower glass substrates when the liquid crystal cell is manufactured. Although it follows and deforms, a gap defect is likely to occur due to the repulsive force stored by the filler in a subsequent process.

The liquid crystal sealant of the present invention preferably has a Tg of 100 ° C. or higher. This is because the smaller the change in mechanical properties under the accelerated test of the liquid crystal cell, the better the reliability. The following conditions are exemplified as the acceleration test conditions for the liquid crystal cell.
High temperature test: 80 ° C
Heat cycle test: -20 ° C to 60 ° C
High temperature and high humidity test: 60 ° C 90% RH
Heat shock test: −20 ° C. × 30 minutes to 60 ° C. × 30 minutes Pressure cooker test: 120 ° C. × 2 atm

  Examples of methods for measuring Tg include DSC (differential scanning calorimetry) method, TMA (thermomechanical analysis) method, and DMA (dynamic viscoelasticity measurement) method. The DMA method is preferred, and the temperature obtained by reading the value of the tan δ peak top obtained by measurement under the conditions of a temperature rising rate of 2 to 5 ° C./min and a measurement tension of 10 to 4000 mN is used as Tg.

The liquid crystal sealant of the present invention preferably has a moisture permeability of 150 g / m ² · day or less of a cured film having a film thickness of 100 μm measured at 60 ° C. and 90% RH. If the moisture permeability of the sealant is high, the reliability of the liquid crystal cell tends to be lowered. This is because the sealant with high moisture permeability transmits moisture in the atmosphere over time in the acceleration test and affects the driving of the liquid crystal display cell such as display unevenness and a decrease in response speed. The reliability of the liquid crystal cell can be confirmed by looking at VHR (voltage holding ratio), afterimages when the liquid crystal cell is driven, and display unevenness.

  There are two types of liquid crystal materials: positive liquid crystal materials with a positive Δε (dielectric anisotropy) and negative liquid crystal materials with a negative Δε. Although it is known to decrease, negative liquid crystal materials have been found to be more affected. This is because the negative liquid crystal material has a high water absorption of 2 to 3 times that of the positive liquid crystal material. Negative type liquid crystal material is a material that is expected to be used in future liquid crystal displays together with photo-alignment film polyimide, and there is a strong demand from the market to reduce the moisture permeability of sealants in order to improve the reliability of liquid crystal cells. Performance.

  Examples of the method for measuring moisture permeability include a moisture sensor (Lyssy) method, a cup method, and an infrared sensor (Mocon) method. From the standpoint of sample preparation and measurement, the moisture sensitive sensor method is preferred, and the measurement conditions are a temperature of 40 ° C. or 60 ° C. and a humidity of 90% RH or 95% RH. For the sample, a cured film obtained by spreading a sealant sandwiched between release films with a desktop laminator to a film thickness of about 100 μm and curing with light and / or heat is used.

  A silane coupling agent can be added to the liquid crystal sealing agent of the present invention for the purpose of improving adhesive strength and moisture resistance. As silane coupling agents, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 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-black Propyl methyl dimethoxy silane, 3-chloropropyl trimethoxy silane, and the like. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. as KBM series, KBE series, etc., they are easily available from the market. The content of the silane coupling agent in the liquid crystal sealant is preferably 0.05 to 3% by mass of the liquid crystal sealant of the present invention.

  In the liquid crystal sealant of the present invention, reactive compounds other than the component (A) and the component (C) may be used in consideration of viscosity, adhesion to an adherend, Tg, liquid crystal contamination, and the like. Specific examples include (meth) acrylates, oxetane compounds, and alicyclic epoxy resins. Examples of the (meth) acrylates include monofunctional (meth) acrylates, bifunctional (meth) acrylates, and three or more in the molecule. These are polyfunctional (meth) acrylates having a (meth) acryloyl group, polyester (meth) acrylates, epoxy (meth) acrylates, and the like.

  Examples of monofunctional (meth) acrylates include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and cyclohexyl (meth) acrylate. (Meth) acrylate having a heterocyclic ring such as alicyclic (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, benzyl (meth) acrylate, Ethoxy-modified cresol (meth) acrylate, propoxy-modified cresol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, o-phenylphenol (meth) acrylate , O-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate, p-phenylphenol polyethoxy ( (Meth) acrylates having aromatic rings such as meth) acrylate, o-phenylbenzyl acrylate, p-phenylbenzyl acrylate, carbazole (poly) ethoxy (meth) acrylate, carbazole (poly) propoxy (meth) acrylate, (poly) caprolactone (Meth) acrylates having a heterocyclic ring such as modified carbazole (meth) acrylate, naphthyl (meth) acrylate, naphthyl (poly) ethoxy (meth) acrylate, naphthyl (polyethylene) ) Propoxy (meth) acrylate, (poly) caprolactone modified naphthyl (meth) acrylate, binaphthol (meth) acrylate, binaphthol (poly) ethoxy (meth) acrylate, binaphthol (poly) propoxy (meth) acrylate, (poly) caprolactone modified binaphthol (Meth) acrylates having condensed rings such as (meth) acrylate, naphthol (meth) acrylate, naphthol (poly) ethoxy (meth) acrylate, naphthol (poly) propoxy (meth) acrylate, (poly) caprolactone modified naphthol (meth) acrylate Acrylate, imide (meth) acrylate having an imide ring structure, butanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylate having a hydroxyl group such as dipropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, butoxyethyl ( (Meth) acrylate, caprolactone (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, octafluoropentyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, Isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate (Meth) acrylate having an alkyl group such as lauryl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, etc. Examples thereof include (meth) acrylates of polyhydric alcohols.

  Examples of the bifunctional (meth) acrylate include (meth) acrylate having a heterocycle such as hydropivalaldehyde-modified trimethylolpropane di (meth) acrylate, (poly) ethoxy-modified bisphenol A di (meth) acrylate, and (poly) propoxy Modified bisphenol A di (meth) acrylate, (poly) ethoxy modified bisphenol F di (meth) acrylate, (poly) propoxy modified bisphenol F di (meth) acrylate, (poly) ethoxy modified bisphenol S di (meth) acrylate, (poly ) Propoxy-modified bisphenol S di (meth) acrylate, hexahydrophthalic acid di (meth) acrylate, bisphenoxy (poly) ethoxyfluorene and other (meth) acrylates, biphenyldimethanol di (me ) (Meth) acrylate having a heterocyclic ring such as acrylate, binaphthol di (meth) acrylate, binaphthol (poly) ethoxydi (meth) acrylate, binaphthol (poly) propoxy di (meth) acrylate, (poly) caprolactone modified binaphthol di (meth) (Meth) acrylate having condensed ring such as acrylate, bisphenol full orange (meth) acrylate, bisphenoxymethanol full orange (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, bisphenoxycaprolactone full orange (meth) acrylate, etc. Acrylates of isocyanates such as (meth) acrylates having polycyclic aromatics, diacrylated isocyanurates, 1,4-butanediol di (meth) acrylates (Meth) acrylate having a linear methylene structure such as 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, Cyclodecane dimethanol (meth) acrylate and other alicyclic (meth) acrylates, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, etc. Examples thereof include di (meth) acrylates of polyhydric alcohols.

  Polyfunctional (meth) acrylates include polyfunctional (meth) acrylates having an isocyanurate ring such as tris (acryloxyethyl) isocyanurate, (poly) caprolactone-modified tris (acryloxyethyl) isocyanurate, pentaerythritol tri (meta) ) Acrylate, pentaerythritol tetra (meth) acrylate, (poly) ethoxy modified pentaerythritol tetra (meth) acrylate, (poly) propoxy modified pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, (poly) caprolactone Modified dipentaerythritol penta (meth) acrylate, (poly) ethoxy modified dipentaerythritol penta (meth) acrylate, (poly) propoxy modified dipen Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (poly) caprolactone modified dipentaerythritol hexa (meth) acrylate, (poly) ethoxy modified dipentaerythritol hexa (meth) acrylate, (poly) propoxy modified di Pentaerythritol hexa (meth) acrylate, polypentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, (poly) ethoxy modified trimethylolpropane tri (meth) acrylate, (poly) propoxy modified trimethylolpropane tri ( Multifunctional polyfunctional alcohols such as (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate ) Acrylic, polyfunctional (meth) acrylates containing phosphorus such as tri (meth) acrylate, polyfunctional (meth) acrylates having aromatic properties such as trimethylolpropane benzoate (meth) acrylate, 2,2,2-tris Examples include acid-modified polyfunctional (meth) acrylates such as acryloyloxymethyl succinic acid and polyfunctional (meth) acrylates having a silicone skeleton such as silicone hexa (meth) acrylate.

  Examples of the urethane (meth) acrylate include diol compounds (for example, 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, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentane Diol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypropoxydiol Polycarbonate or the like) or a reaction product of these diol compounds and dibasic acid or anhydride thereof (for example, succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid or anhydrides thereof). Polyester diol and organic polyisocyanate (eg, chain saturated hydrocarbon isocyanate such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate) , Norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylate Cyclic saturated hydrocarbon isocyanates such as diisocyanate and hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate, 6 -Aromatic polyisocyanates such as isopropyl-1,3-phenyl diisocyanate and 1,5-naphthalene diisocyanate) and then a reaction product in which a hydroxyl group-containing (meth) acrylate is added.

  Examples of the polyester (meth) acrylate include a polyester diol which is a reaction product of a diol compound and a dibasic acid or an anhydride thereof, and a reaction product of (meth) acrylic acid.

  Examples of the epoxy (meth) acrylate include a reaction product of the epoxy compound listed in the component (C) and (meth) acrylic acid. Further, not all epoxy groups and (meth) acrylic acid may have reacted, and partial epoxy acrylates having an epoxy group and (meth) acrylate group of 1: 9 to 9: 1 are also preferably used.

  As the oxetane compound, a compound having a ring structure is preferable. For example, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3-phenoxymethyloxetane, 1,4 -Bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyloxetane-3 -Yl) methoxy] benzene, 4,4'-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl, 2,2'-bis [(3-ethyl-3-oxetanyl) methoxy] biphenyl, 3, 3 ′, 5,5′-tetramethyl [4,4′-bis (3-ethyloxetane-3-yl) methoxy] biphenyl, 2,7-bis [(3-ethylox Oxetane compounds having an aromatic ring such as tan-3-yl) methoxy] naphthalene, 4,4′-bis [(1-ethyl-3-oxetanyl) methyl] thiodibenzenethioether acid, 3 (4), 8 (9 ) -Bis [(1-ethyl-3-oxetanyl) methoxymethyl] -tricyclo [5.2.2.12.6] decane and other oxetane compounds, heterogeneous products such as a reaction product of CIC acid and oxetane alcohol An oxetane compound having a ring is exemplified.

  Examples of the alicyclic epoxy resin include compounds represented by the following formulas (2) to (18).

（ｐは平均の繰り返し数であり１〜４を表す。）

(P is the average number of repetitions and represents 1 to 4)

  In addition to the above components, the liquid crystal sealing agent of the present invention can contain additives such as radical polymerization inhibitors, curing accelerators such as organic acids and imidazole compounds, pigments, leveling agents, antifoaming agents, and solvents.

The radical polymerization inhibitor is not particularly limited as long as it is a compound that prevents polymerization by reacting with radicals generated from a photopolymerization initiator, a thermal radical polymerization initiator, etc., and is not limited to quinone, piperidine, hinders. A dophenol type, a nitroso type, etc. can be used. Specifically, 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, 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'-methylene (4-ethyl-6-tert-butylphenol), 4,4′-thiobis-3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3 , 9-bis [1,1-dimethyl-2- [β- (3-tert-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-tris (3 ′, 5′- Di-t-butyl-4′-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, paramethoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N-nitroso Examples include, but are not limited to, an aluminum salt of phenylhydroxyamine, trade name ADK STAB LA-81, trade name ADK STAB LA-82 (manufactured by Adeka Corporation), and the like. Of these, naphthoquinone, hydroquinone, and nitroso piperazine radical polymerization inhibitors are preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-P-cresol, Polystop 7300P (Hakuto Co., Ltd.) Company-made) is more preferred, and Polystop 7300P (made by Hakuto Co., Ltd.) is most preferred.
There are methods for adding radical polymerization inhibitors when synthesizing component (A) (meth) acrylate and methods for dissolving in component (A) (meth) acrylate and / or component (C) epoxy resin. In order to obtain an effective effect, it is preferable to add the component (A) (meth) acrylate and / or component (C) to the curable resin having an epoxy group and dissolve it.
The content of the radical polymerization inhibitor is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and 0.01 to 0.2% by mass in the total amount of the liquid crystal sealant of the present invention. Is particularly preferred.

Examples of the curing accelerator include organic acids and imidazoles.
Examples of the organic acid include organic carboxylic acids and organic phosphoric acids, but organic carboxylic acids are preferred. Specifically, aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, 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, bis (2-carboxyethyl) isocyanurate and the like. .
Examples of imidazole compounds include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 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, 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-dihydroxymethyl Examples include imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole.
In the liquid crystal sealant of the present invention, when a curing accelerator is used, it is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the liquid crystal sealant.

  An example of a method for obtaining the liquid crystal sealant of the present invention is the following method. First, the component (A) is heated and mixed with the component (A) as necessary, cooled to room temperature, and then the component (B), if necessary, the component (D), the component (E), and a radical polymerization inhibitor. The liquid crystal sealant of the present invention is added by adding an antifoaming agent, a leveling agent, a solvent, etc., mixing uniformly with a known mixing device such as a three roll, sand mill, ball mill, etc., and filtering through a metal mesh. Can be manufactured.

  The liquid crystal display cell of the present invention is a cell in which a pair of substrates having predetermined electrodes formed on a substrate are arranged opposite to each other at a predetermined interval, the periphery is sealed with the liquid crystal sealant of the present invention, and the liquid crystal is sealed in the gap. is there. The kind of liquid crystal to be sealed is not particularly limited. Here, the substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicon, etc. and having light transmission properties. As a manufacturing method thereof, after adding a spacer (gap control material) such as glass fiber to the liquid crystal sealant of the present invention, the liquid crystal sealant is applied to one of the pair of substrates using a dispenser or a screen printing device. Then, if necessary, temporary curing is performed at 80 to 120 ° C. Thereafter, a liquid crystal is dropped inside the weir of the liquid crystal sealant, and the other glass substrate is overlaid in a vacuum to create a gap. After forming the gap, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C. for 0.5 to 2 hours. The liquid crystal display cell of the present invention thus obtained has no display defects due to liquid crystal contamination, and has excellent adhesion and moisture resistance reliability. Examples of the spacer include glass fiber, silica beads, polymer beads and the like. The 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% by mass, preferably 0.5 to 2% by mass, and more preferably about 0.9 to 1.5% by mass with respect to 100% by mass of the liquid crystal sealant of the present invention. is there. Since the addition of the spacer can be expected to improve the adhesive strength between the sealing agent and the substrate, the liquid crystal leakage property, the liquid crystal contamination property, and the like, the addition amount is preferably adjusted in view of the physical properties to be expressed.

  The liquid crystal sealant of the present invention has very good resistance to liquid crystal insertion, and causes a phenomenon that the liquid crystal is inserted or the seal is broken in the substrate bonding process and heating process in the liquid crystal dropping method. Absent. Therefore, a stable liquid crystal display cell can be produced. Moreover, since the speed at which the curable resin is cross-linked is high, the elution of the constituent components into the liquid crystal is extremely small, and display defects of the liquid crystal display cell can be reduced. Moreover, since it is excellent in coating workability, it is suitable for manufacturing a liquid crystal display cell. Furthermore, since the cured product is excellent in various cured product properties such as adhesive strength, heat resistance, particularly low moisture permeability, low water absorption, and moisture resistance, the use of the liquid crystal sealant of the present invention enables excellent liquid crystal properties. Display cells can be created. In addition, the liquid crystal display cell prepared using the liquid crystal sealant of the present invention satisfies the characteristics required for a liquid crystal display cell having a high voltage holding ratio and a low ion density.

  EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention still in detail, this invention is not limited to an Example. Unless otherwise specified, “part” and “%” in the text are based on mass.

[Synthesis Example 1: Synthesis of bisphenol Z-type diethoxydiacrylate]
In a flask equipped with a stirrer, a reflux tube and a thermometer, 268.4 g (1.0 mol) of bisphenol Z (Honshu Chemical Industry Co., Ltd.), 220.2 g (2.5 mol) of ethylene carbonate, and potassium carbonate 41.5 g (0.3 mol) and toluene 2000 ml were charged and reacted at 110 ° C. for 12 hours.
After the reaction, the resulting reaction solution was washed with water and 1% NaOH aqueous solution, and then washed with water until the washing water became neutral. The solvent after the water-washed solution was distilled off under reduced pressure using a rotary evaporator to obtain 300.0 g of a 2 mol reactant of ethylene oxide of bisphenol Z.
Subsequently, in a flask equipped with a stirrer, a reflux tube, a thermometer, and a water separator, 182.7 g (0.5 mol) of an ethylene oxide 2 mol reaction product of bisphenol Z, and 86.5 g (2.4 mol) of acrylic acid. Then, 0.95 g of paratoluenesulfonic acid, 0.87 g of hydroquinone, 917.4 g of toluene and 393.2 g of cyclohexane were charged, and the reaction was carried out at a reaction temperature of 95 to 105 ° C. while azeotropically distilling the produced water with the solvent. After the reaction, the reaction solution was neutralized with 25% NaOH aqueous solution, washed with 200 g of 15% by mass saline solution three times, and the solvent was distilled off under reduced pressure to obtain bisphenol Z type diethoxydiacrylate. The bisphenol Z-type diethoxydiacrylate is a compound of the above formula (1) in which R ¹ is a hydrogen atom, R ² is ethylene, R ³ is cyclohexylidene, and m = 1 and n = 1 are the main. It is a component compound.

[Synthesis Example 2: Synthesis of 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane]
In a flask equipped with a stirrer, a reflux tube and a thermometer, 100 parts (0.28 mol) of commercially available benzopinacol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 350 parts of dimethylformaldehyde. To this was added 32 parts (0.4 mol) of pyridine as a base catalyst and 150 parts (0.58 mol) of BSTFA (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silylating agent, and the mixture was heated to 70 ° C. and stirred for 2 hours. The obtained reaction solution was cooled and stirred while adding 200 parts of water to precipitate the product and deactivate the unreacted silylating agent. The precipitated product was separated by filtration and thoroughly washed with water. Subsequently, the obtained product was dissolved in acetone, recrystallized by adding water and purified. 105.6 parts (yield 88.3%) of the target 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane were obtained.
As a result of analysis by HPLC (high performance liquid chromatography), the purity was 99.0% (area percentage).

[Synthesis Example 3: Synthesis of acrylated resorcin diglycidyl ether]
In a flask equipped with a stirrer, a reflux tube and a thermometer, 181.2 g of resorcin diglycidyl ether (product name: Denacol EX-201, manufactured by Nagase ChemteX Corporation) was dissolved in 266.8 g of toluene and polymerized. As an inhibitor, 0.8 g of dibutylhydroxytoluene was added, and the temperature was raised to 60 ° C. Thereafter, 117.5 g of acrylic acid with 100% equivalent of epoxy group was added and the temperature was further raised to 80 ° C., 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, A reaction solution was obtained. This reaction solution was washed with water and toluene was distilled off to obtain 253 g of the desired resorcin diglycidyl ether epoxy acrylate (acrylated resorcin diglycidyl ether).

[Synthesis Example 4: Synthesis of epoxy acrylate of bisphenol F type epoxy resin]
In a flask equipped with a stirrer, a reflux tube and a thermometer, 312.4 g of a bisphenol F type epoxy resin (product name: Epototo YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was dissolved in 266.8 g of toluene. To this was added 0.8 g of dibutylhydroxytoluene as a polymerization inhibitor, and the temperature was raised to 60 ° C. Thereafter, 144.1 g of acrylic acid with 100% equivalent of epoxy group was added and the temperature was further raised to 80 ° C., 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, A reaction solution was obtained. The reaction solution was washed with water and toluene was distilled off to obtain 410 g of the desired bisphenol F type epoxy acrylate (acrylated bisphenol F type epoxy resin).

[Synthesis Example 5: Synthesis of 4,4′-EO-modified bisphenol S-type epoxy resin]
In a flask equipped with a stirrer, a reflux tube and a thermometer, 4,4′-bis (2-hydroxyethyloxy) diphenylsulfone (manufactured by Nikka Chemical; trade name SEO-2, melting point 183 ° C., purity 99.5) %) 169 g, epichlorohydrin 370 g, dimethyl sulfoxide 185 g and tetramethylammonium chloride 5 g were added and dissolved under stirring, and the temperature was raised to 50 ° C. Next, 60 g of flaky sodium hydroxide was added in portions over 100 minutes, followed by a post-reaction at 50 ° C. for 3 hours. After completion of the reaction, 400 g of water was added and washed with water. Excess epichlorohydrin and the like were distilled off from the oil layer under reduced pressure at 130 ° C. using a rotary evaporator. To the residue, 450 g of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 10 g of 30% aqueous sodium hydroxide was added and reacted for 1 hour, followed by washing with water three times. Methyl isobutyl ketone was distilled off at 180 ° C. under reduced pressure using a rotary evaporator. , 4'-EO modified bisphenol S type epoxy resin 212g was obtained. The epoxy equivalent of the obtained epoxy resin was 238 g / eq.

  The liquid crystal dropping method sealant and cured product of the present invention were obtained with the compositions as shown in the following examples. Moreover, the evaluation method and evaluation criteria for the resin composition and the cured film were as follows.

[Evaluation method]
[Water permeability]
A sealant is dropped onto a PET separator (PET38AL-5, manufactured by Lintec Corporation), covered with the same PET separator, spread using a desktop laminator, the film thickness is adjusted to 100 μm, and heated at 120 ° C. for 1 hr. A test piece was prepared by curing. The obtained test piece was measured for moisture permeability with a Lyssy water vapor permeability meter L80-5000 (manufactured by Systech Illinois), 60 ° C. × 90% RH.

[Water absorption]
A test piece was prepared in the same manner as the above sample, and the cured film was cut into a width of 20 mm and a length of 50 mm, and the mass change after 24 hours was confirmed under the condition of 60 ° C. and 90% RH, and the water absorption was calculated. .
Water absorption rate = (mass after water absorption-mass before water absorption) / mass before water absorption

[Glass transition point Tg]
A test piece was prepared in the same manner as the sample, and the Tg point was measured with a viscoelasticity measurement system EXSTAR DMS-6000 (manufactured by Hitachi High-Tech Science Co., Ltd.), a tensile mode, a frequency of 1 Hz, and a temperature increase of 2 ° C./min. The tan δ peak top was defined as Tg.

[Creation of liquid crystal cell for evaluation]
As a spacer, 1 g of 5 μm glass fiber is added to each 100 g of the liquid crystal sealants of Examples 1 to 3 and Comparative Examples 1 and 2, mixed and defoamed, and filled into a syringe. An alignment film solution (PIA-5540-05A; manufactured by JNC Petrochemical Co., Ltd.) was applied to a glass substrate with an ITO transparent electrode, baked, and rubbed. Using this dispenser (SHOTMASTER 300: manufactured by Musashi Engineering Co., Ltd.), the liquid crystal sealants of Examples and Comparative Examples previously filled in a syringe on this substrate were applied with a seal pattern and a dummy seal pattern, and then liquid crystal (JC-5015LA A fine droplet of JNC Petrochemical Co., Ltd.) was dropped into the frame of the seal pattern. Further, an in-plane spacer (NATOCO SPACER KSEB-525F; manufactured by NATCO; gap width of 5 μm after bonding) is sprayed on another glass substrate that has been subjected to rubbing treatment, heat-adhered, and in a vacuum using a vacuum bonding apparatus. Then, the substrate was bonded to the liquid crystal dripped substrate. Then, after opening to the atmosphere and forming a gap, it was put into an oven at 120 ° C. and cured by heating for 1 hour to prepare a liquid crystal test cell for evaluation.

Table 1 shows the results of observation of the seal shape and liquid crystal alignment disorder of the prepared liquid crystal cell for evaluation with a polarizing microscope. Moreover, the gap of the produced liquid crystal cell is shown in Table 1 as a result of measurement using a liquid crystal characteristic evaluation apparatus (OMS-NK3: manufactured by Chuo Seiki Co., Ltd.). The evaluation of the seal shape, liquid crystal alignment disorder, and the gap of the liquid crystal cell was made into the following four stages.
The seal shape is an evaluation related to the coating workability, and the evaluation of the liquid crystal alignment is an evaluation related to the liquid crystal contamination. The liquid crystal cell gap can also be confirmed for insertion resistance.

[Evaluation of seal shape]
○: There is no disturbance in the linearity of the seal.
[Delta]: Deformation of the seal is recognized, but there is no problem in sealing the liquid crystal.
X: A level at which liquid crystal is inserted into the seal and a problem may occur in sealing the liquid crystal.
XX: The seal is broken and a cell cannot be formed.

[Evaluation of liquid crystal cell gap]
A: The cell gap is uniformly 5 μm.
Δ: There is a place where a gap of about 5.5 μm is not formed in the cell.
X: There is a place where a gap of 6 μm or more does not appear in the cell.
XX: The seal is broken and a cell cannot be formed.

[Evaluation of liquid crystal alignment]
○: There is no alignment disorder in the vicinity of the seal.
Δ: There is a slight disorder in the alignment of the liquid crystal in the vicinity of the seal.
X: There is disorder in alignment of liquid crystal in the vicinity of the seal.
XX: The seal is broken and a cell cannot be formed.

[Examples 1 to 3]
A liquid crystal sealant was produced using the components (A) and (B) in the amounts shown in Table 1. The manufacturing method is as follows.
First, as the component (A) and the component (C), the compound obtained in Synthesis Example 1, the epoxy resin, and the acrylate monomer are heated and mixed, and after cooling to room temperature, the component (B) radical generator and the component (D) heat Addition of curing agent, component (E) filler, silane coupling agent, polymerization inhibitor, curing accelerator, kneading with three rolls, and filtration with a metal mesh (635 mesh), liquid crystal sealing agent of the present invention Manufactured.
[Comparative Example 1]
A liquid crystal sealant was produced using the components (B) in the amounts shown in Table 1. The manufacturing method is as follows.
First, an epoxy resin and an acrylate monomer are heated and mixed as the compound obtained in Synthesis Example 3 and component (C), cooled to room temperature, then component (B) radical generator, component (D) thermosetting agent, component (E). ) Filler, silane coupling agent, polymerization inhibitor and curing accelerator were added, kneaded with three rolls, and filtered with a metal mesh (635 mesh) to produce the liquid crystal sealant of the present invention.
[Comparative Example 2]
A liquid crystal sealant was produced using the components (B) in the amounts shown in Table 1. The manufacturing method is as follows.
First, an epoxy resin and an acrylate monomer are heated and mixed as the compound obtained in Synthesis Example 4 and component (C), cooled to room temperature, then component (B) radical generator, component (D) thermosetting agent, component (E ) Filler, silane coupling agent, polymerization inhibitor and curing accelerator were added, kneaded with three rolls, and filtered with a metal mesh (635 mesh) to produce the liquid crystal sealant of the present invention.

  As shown in Table 1, while the liquid crystal sealants of Examples 1 to 3 have sufficient insertion resistance, they have excellent coating workability, low liquid crystal contamination, high Tg, moisture permeability and water absorption rate. It was confirmed that this was an excellent sealant.

  The liquid crystal sealant for the liquid crystal dropping method of the present invention is excellent in application workability such as dispensing and screen printing and has low liquid crystal contamination, while having good resistance to liquid crystal insertion. Furthermore, since it is a liquid crystal sealing agent for a liquid crystal dropping method having excellent moisture permeability and water absorption, a liquid crystal display cell having excellent long-term reliability can be easily produced.

Claims (11)

(A) represented by the following general formula (1) you express by (meth) acrylic compound, liquid crystal sealing material for a liquid crystal dropping process containing (B) a radical polymerization initiator.

(In the formula, each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, each R ² independently represents a hydrocarbon group having 1 to 5 carbon atoms, m and n Represents an average number of repetitions, m + n is 0 to 12, and R ³ represents cyclohexylidene. ) The liquid crystal sealing agent for a liquid crystal dropping method according to claim 1, wherein R ^{2 of the} component (A) is each independently a hydrocarbon group having 2 or 3 carbon atoms.   Furthermore, the liquid-crystal sealing compound for liquid crystal dropping methods of Claim 1 or 2 containing the compound which has (C) an epoxy group.   Furthermore, (D) The liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of Claims 1 thru | or 3 containing a thermosetting agent.   Furthermore, the liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of Claims 1 thru | or 4 containing (E) filler. The liquid crystal sealant for a liquid crystal dropping method according to claim 5, wherein the average particle size of the component (E) is 8 μm or less.   The liquid crystal seal for a liquid crystal dropping method according to claim 5 or 6, wherein the component (E) is one or more fillers selected from the group consisting of urethane fine particles, acrylic fine particles, silicone fine particles, styrene fine particles, and styrene olefin fine particles. Agent.   The liquid crystal sealant for a liquid crystal dropping method according to any one of claims 1 to 7, wherein Tg measured by using a viscoelasticity measuring device at a heating rate of 2 ° C / min is 100 ° C or higher. The liquid crystal sealant for a liquid crystal dropping method according to any one of claims 1 to 8, wherein a moisture permeability of a cured film having a thickness of 100 µm measured under a condition of 60 ° C and 90% RH is 150 g / m ² · day or less.   After a liquid crystal is dripped inside the liquid crystal sealing agent weir for liquid crystal dropping method according to any one of claims 1 to 9, which is formed on one substrate in a liquid crystal display cell constituted by two substrates. A method for producing a liquid crystal display cell, characterized in that the other substrate is bonded and then cured by heat. The liquid crystal display cell sealed with the hardened | cured material obtained by hardening the liquid crystal sealing agent for liquid crystal dropping methods as described in any one of Claims 1 thru | or 9 .