JP2010121069A - Curable composition, liquid crystal sealing agent, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal display element in which the adhesiveness with a substrate is high and the possibility of contamination of a liquid crystal by an uncured liquid crystal sealing agent component is reduced and which is excellent in long-term stability. <P>SOLUTION: This curable composition includes (A) a compound having (meth)acryloyl group, (B) an organic acid dihydrazide compound, (C) a radiation-sensitive polymerization initiator, and (D) a compound having a structure represented by formula (1) (wherein, * represents a bond). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition useful as a sealant for liquid crystal display elements and a liquid crystal display element using the same.

  A liquid crystal display element such as a liquid crystal display cell is formed by sealing a liquid crystal between two transparent substrates with electrodes opposed to each other with a predetermined interval. Conventionally, when manufacturing a liquid crystal display cell, first, a liquid crystal injection port is provided on the outer periphery of a range in which liquid crystal is sealed by using a thermosetting sealant by screen printing on one of two transparent substrates with electrodes. Form a pattern. Next, the alignment is performed with the other transparent substrate facing each other with the spacer interposed therebetween, the two substrates are bonded together, and heated to cure the liquid crystal sealant. Next, after injecting liquid crystal from the liquid crystal injection port, the liquid crystal injection port was sealed with a sealing agent. Such a method is generally called a liquid crystal injection method.

  The liquid crystal injection method has many problems such as a large number of processes, low manufacturing efficiency, positional displacement of the substrate due to thermal strain, gap variation, and insufficient adhesion between the liquid crystal sealant and the substrate.

  As a means for solving the problems of the liquid crystal injection method, a method called a liquid crystal dropping method has been devised, and a photothermal curing combined method is becoming mainstream for curing the liquid crystal sealant. In such a liquid crystal dropping method, first, a rectangular frame serving as an outer periphery of a range in which liquid crystal is sealed is formed on one of two transparent substrates with electrodes by a liquid crystal sealant by screen printing. At this time, no liquid crystal injection port is provided. Next, liquid crystal is dropped onto the entire surface of the frame in an uncured state, and the other transparent substrate is immediately superimposed and pressure-bonded, and the liquid crystal sealant portion is irradiated with ultraviolet rays and temporarily cured. After that, the liquid crystal cell is manufactured by heating at the time of liquid crystal annealing and further curing the liquid crystal sealant.

  The liquid crystal dropping method can efficiently produce a liquid crystal cell with a small number of processes and is suitable for the production of a large panel. In addition, since temporary curing with ultraviolet rays is performed, displacement of the substrate due to thermal strain is prevented, and adhesion between the liquid crystal sealant and the substrate is improved.

However, in the liquid crystal dropping method, there is a stage where the liquid crystal sealant in an uncured state and the liquid crystal come into contact with each other. There is a problem that a failure occurs (Patent Document 1).
A curable composition in which various components are blended has been proposed for the purpose of reducing the contamination of the liquid crystal due to the components of the uncured liquid crystal sealant and improving the curability (for example, Patent Documents 2 to 7). .

  However, in recent years, there has been a demand for a narrow frame of the liquid crystal display element, and due to the narrow frame, the liquid crystal sealant is often overlapped with the black matrix and the wiring. In this part, since the liquid crystal sealant is not irradiated with ultraviolet rays, an uncured part remains in the liquid crystal sealant, and when this comes into contact with the liquid crystal, the liquid crystal sealant component is eluted and the liquid crystal is contaminated. .

JP 2001-133794 A JP 2004-37937 A JP 2003-28004 A JP 2005-263987 A JP 2005-60651 A JP 2006-30482 A JP 2006-58466 A

  The present invention has been made in view of the above-described problems, reduces the contamination of the liquid crystal, and provides sufficient curability even in a shadowed portion due to wiring or the like, and curability that can cope with narrowing of the frame. An object is to provide a composition.

  In order to achieve the above object, the present inventors have conducted intensive research, and have a compound having a (meth) acryloyl group, an organic acid dihydrazide compound, a radiation-sensitive polymerization initiator, a compound represented by the general formula (1), and any Uses epoxy curing agents, organic or inorganic particles, and silane coupling agents as ingredients, so that it has low contamination to liquid crystals and high adhesive strength that shows good curability even in shadowed areas due to wiring, etc. The present invention was completed by finding that a curable composition was obtained.

That is, the present invention provides the following curable composition, a liquid crystal sealant comprising the same, and a liquid crystal display device using the same.
1. (A) Compound having (meth) acryloyl group (B) Organic acid dihydrazide compound,
(C) a radiation sensitive polymerization initiator, and
(D) the following formula (1),

（式（１）中、「＊」は結合手であることを示す。）
で表される構造を有する化合物を含有することを特徴とする、硬化性組成物。
２．（Ｄ）成分が、
下記式

(In formula (1), “*” indicates a bond.)
A curable composition comprising a compound having a structure represented by:
2. (D) component is
Following formula

（上記式中、Ｒはそれぞれ独立に、水素原子、炭素数３〜３０の第二級もしくは第三級のアルキル基、炭素数５〜１２の環状アルキル基、アリル基、炭素数７〜３０のアルアルキル基または炭素数２〜３０のアシル基である。）のいずれかで表される化合物である、上記１に記載の硬化性組成物。
３．（Ｄ）成分が、Ｎ−ヒドロキシコハク酸イミド、Ｎ-ヒドロキシ−５−ノルボルネン−２，３−ジカルボキシイミド、Ｎ−ヒドロキシフタルイミド、Ｎ−アセトキシフタルイミド、Ｎ−ベンゾキシフタルイミド、Ｎ−ヒドロキシ−１，８−ナフタルイミドまたはトリヒドロキシイミドシアヌル酸である上記２記載の硬化性組成物。
４．（Ｃ）感放射線性重合開始剤が、Ｏ−アシルオキシム化合物およびアセトフェノン化合物よりなる群から選択される少なくとも１種を含有する上記１に記載の硬化性組成物。
５．さらに、（Ｅ）有機粒子、或いは無機粒子のいずれか、またはその両方を含有する上記１〜４のいずれか１項に記載の硬化性組成物。
６．さらに、（Ｆ）１分子中に３個以上のエポキシ基を有し、かつ（メタ）アクリロイル基を有しないエポキシ樹脂を含有する上記１〜５のいずれか１項に記載の硬化性組成物。
７．さらに、（Ｇ）シランカップリング剤を含有する上記１〜６のいずれか１項に記載の硬化性組成物。
８．上記１〜７のいずれか１項に記載の硬化性組成物からなる液晶シール剤。
９．上記８に記載の液晶シール剤を用いて製造された液晶表示素子。

(In the above formula, each R is independently a hydrogen atom, a secondary or tertiary alkyl group having 3 to 30 carbon atoms, a cyclic alkyl group having 5 to 12 carbon atoms, an allyl group, or a group having 7 to 30 carbon atoms. The curable composition according to 1 above, which is a compound represented by any one of an aralkyl group and an acyl group having 2 to 30 carbon atoms.
3. Component (D) is N-hydroxysuccinimide, N-hydroxy-5-norbornene-2,3-dicarboximide, N-hydroxyphthalimide, N-acetoxyphthalimide, N-benzoxyphthalimide, N-hydroxy-1 The curable composition according to 2 above, which is 1,8-naphthalimide or trihydroxyimide cyanuric acid.
4). (C) The curable composition according to 1 above, wherein the radiation-sensitive polymerization initiator contains at least one selected from the group consisting of an O-acyloxime compound and an acetophenone compound.
5). Furthermore, (E) The curable composition of any one of said 1-4 containing either an organic particle or an inorganic particle, or both.
6). Furthermore, (F) The curable composition of any one of said 1-5 containing the epoxy resin which has 3 or more epoxy groups in 1 molecule, and does not have a (meth) acryloyl group.
7). Furthermore, (G) The curable composition of any one of said 1-6 containing a silane coupling agent.
8). A liquid crystal sealant comprising the curable composition according to any one of 1 to 7 above.
9. 9. A liquid crystal display device produced using the liquid crystal sealant according to 8.

ADVANTAGE OF THE INVENTION According to this invention, the sclerosing | hardenable property which shows the favorable sclerosis | hardenability can be provided even if it is a part which is low in the stain | pollution property with respect to a liquid crystal and becomes a shadow by wiring etc.
ADVANTAGE OF THE INVENTION According to this invention, when manufacturing a liquid crystal display element by a liquid crystal dropping method, a particularly useful liquid crystal sealing agent can be provided.

I. Curable composition The curable composition of this invention (henceforth the composition of this invention) may contain the following component (A)-(G). Among the following components, (A) to (D) are essential components, and (E) to (G) are optional components to be blended as necessary.
(A) (meth) acrylate compound (B) organic acid dihydrazide compound (C) radiation sensitive polymerization initiator (D) compound having a structure represented by the following formula (1)

（式（１）中、「＊」は結合手であることを示す。）
（Ｅ）有機粒子、あるいは無機粒子
（Ｆ）１分子中に３個以上のエポキシ基を有し、かつ（メタ）アクリロイル基を有しないエポキシ樹脂
（Ｇ）シランカップリング剤

(In formula (1), “*” indicates a bond.)
(E) Organic particles or inorganic particles (F) Epoxy resin having three or more epoxy groups in one molecule and having no (meth) acryloyl group (G) Silane coupling agent

  The curable composition of the present invention uses a compound having a structure represented by the general formula (1) (hereinafter referred to as the component (D)), so that the ultraviolet ray is weakly scattered at a shielding portion that is not directly irradiated with ultraviolet rays by a wiring or a black matrix. Even so, the crosslinking reaction of the (meth) acryloyl group proceeds and high liquid crystal stain resistance can be imparted. Here, “high sensitivity” means that the absorption coefficient of ultraviolet rays is large and radicals can be generated even with weak light.

Hereinafter, each component will be described.
(A) a compound having a (meth) acryloyl group (hereinafter also referred to as component (A)),
The compound having a (meth) acryloyl group is a component that undergoes radical polymerization.

Examples of the compound having a (meth) acryloyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and isobutyl (meth). Acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxy Ethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2,2,2, -trifluoroethyl (meth) acrylate, 2 , 2,3,3, -tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H, -octafluoropentyl (meth) acrylate, imide (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n -Butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl ( Acrylate), isononyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2- Hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propane Diol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene Xoxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) Acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylol Propane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) Acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri ( Examples include meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, and tris (meth) acryloyloxyethyl phosphate. Of these, (meth) acrylate compounds having an aromatic ring can be preferably used.
Examples of commercially available compounds having such a (meth) acryloyl group include VR-77LC (manufactured by Showa Polymer Co., Ltd.), EB3700 (manufactured by Daicel Cytec Co., Ltd.), and the like.
In addition, a urethane (meth) acrylate compound obtained by reacting a polyol compound with a compound having an isocyanate group and a (meth) acryloyl group can also be used.

  The blending amount of the component (A) in the composition of the present invention is preferably 0.1 to 90% by weight, more preferably 1 to 80% by weight, particularly preferably when the entire composition is 100% by weight. 5 to 60% by weight. When the blending amount of the component (A) is in the range of 0.1 to 90% by weight, an appropriate hardness can be obtained particularly when irradiated with ultraviolet rays, and displacement due to heat hardly occurs.

(B) Organic acid dihydrazide compound An organic acid dihydrazide compound (hereinafter also referred to as component (B)) is blended to crosslink an epoxy group-containing compound and to exhibit effects of adhesion and hardness, and as an epoxy curing agent. Function. The organic acid dihydrazide compound itself undergoes a crosslinking reaction with the epoxy group and is incorporated into the crosslinked polymer. These organic acid dihydrazide compounds preferably have a melting point or a softening point temperature of 100 ° C. or higher according to the ring and ball method (based on JIS K2207).

  In addition, the active hydrogen of the amine contained in the organic acid dihydrazide compound causes a thermal nucleophilic addition reaction to the (meth) acryloyl group of the other component having the (meth) acryloyl group in the composition of the present invention. The curability of the inventive composition is improved. Since the organic acid dihydrazide compound exhibits thermal reaction characteristics with respect to both the (A) component (meth) acrylate compound and / or the (F) component epoxy compound, the organic acid dihydrazide compound functions as a compatibilizing component of both components, and is a liquid crystal display. The panel reliability such as the display characteristics of the panel and the adhesion reliability is improved.

The upper limit of the melting point or the softening point temperature by the ring and ball method is not particularly limited, but is usually 250 ° C. or lower.
Specific examples of the organic acid dihydrazide compound having a melting point or a softening point temperature by the ring and ball method of 100 ° C. or higher include, for example, adipic acid dihydrazide (melting point 181 ° C.), 1,3-bis (hydrazinocarboethyl) -5. -Organic acid dihydrazide such as isopropyl hydantoin (melting point: 120 ° C). The organic acid dihydrazide compound used in the present invention is preferably one that has been subjected to a purification treatment by a water washing method, a recrystallization method, or the like.

As an example of a commercial item of the above-mentioned (B) ingredient, Amicure VDH, VDH-J, UDH, UDH-J (Ajinomoto Fine Techno Co., Ltd. product) etc. are mentioned, for example.
An organic acid dihydrazide compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The blending amount of the component (B) in the composition of the present invention is 0.1 to 60% by weight, preferably 1 to 50% by weight, more preferably 5 when the solid content of the composition is 100% by weight. ~ 30% by weight. When the blending amount of the component (B) is 0.1 to 60% by weight, particularly sufficient hardness and adhesiveness are obtained, and exudation to liquid crystal due to unreacted substances in the cured product (hereinafter also referred to as liquid crystal contamination) Can be prevented.

(C) Radiation-sensitive polymerization initiator The radiation-sensitive polymerization initiator used in the present invention (hereinafter also referred to as component (C)) includes an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, a benzophenone compound, and the like. Can do.
Specific examples of the O-acyloxime compound include etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.
Of these O-acyloxime compounds, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) can be mentioned as a preferable example.
These O-acyloxime compounds can be used alone or in admixture of two or more.
Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.
Specific examples thereof include α-aminoketone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl). ) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like;
Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4 -(2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like;
Of these acetophenone compounds, α-aminoketone compounds are preferred, especially 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-dimethylamino-2- (4-methylbenzyl). -1- (4-Morpholin-4-yl-phenyl) -butan-1-one is preferred.
Specific examples of the biimidazole compound include, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1, And 2'-biimidazole.
Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole is preferred, especially 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole Is preferred.
In the curable composition of the present invention, when a biimidazole compound is used as the (C) radiation-sensitive polymerization initiator, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as “amino”) is used to sensitize it. System sensitizer ") can be added.
Examples of such amino sensitizers include 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone. Of these amino sensitizers, 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amino sensitizers can be used alone or in admixture of two or more.
Furthermore, when a biimidazole compound and an amino sensitizer are used in combination, a thiol compound can be added as a hydrogen radical donor. The biimidazole compound is sensitized and cleaved by an amino sensitizer to generate an imidazole radical, but as it is, high polymerization initiating ability is not expressed, and the curable composition of the present invention is formed as a liquid crystal display element spacer. In some cases, the obtained spacer has an unfavorable shape such as a reverse taper shape. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, hydrogen radicals are donated from the thiol compound to the imidazole radical, so that the imidazole radical is converted to neutral imidazole. In addition, a component having a sulfur radical having a high polymerization initiating ability is generated, and better curability can be generated.
Examples of such thiol compounds include aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole; 3-mercaptopropionic acid, 3-mercapto Aliphatic monothiol compounds such as methyl propionate; bifunctional or higher functional aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate).
Of these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.
By using a biimidazole compound and an amino sensitizer in combination with a thiol compound, good curability can be expressed and adhesion to the substrate becomes good.

  Examples of commercially available compounds having an O-acyloxime ester structure include Irgacure OXE02 (manufactured by Ciba Specialty Chemicals Co., Ltd.), N-1919 (manufactured by Adeka Corporation), and the like. Examples of commercially available acetophenone compounds include Irgacure 369, Irgacure 379 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and the like.

  (C) The radiation sensitive polymerization initiator of a component may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, you may combine an appropriate sensitizer and a chain transfer agent.

  The blending amount of the component (C) in the curable composition of the present invention is 0.01 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 100% by weight. Is 1 to 10% by weight. When the blending amount of component (C) is 0.01 to 20% by weight, particularly sufficient hardness and dimensional stability can be obtained, and liquid crystal contamination can be prevented.

Component (D) By providing component (D) in the curable resin composition of the present invention, a curable composition for a liquid crystal sealant that exhibits good curability even in a shadowed portion due to wiring or the like is provided. it can.
The component (D) is a compound having a structure represented by the above formula (1), and more specific compounds are compounds represented by the following formulas (2-1) to (2-8). is there.
In the formula, each R is independently a hydrogen atom, a secondary or tertiary alkyl group having 3 to 30 carbon atoms, a cyclic alkyl group having 5 to 12 carbon atoms, an allyl group, or an aralkyl group having 7 to 30 carbon atoms. Or it is a C2-C30 acyl group. )
Examples of the secondary or tertiary alkyl group having 3 to 30 carbon atoms represented by R in the following formula include isopropyl group, 2-butyl group, t-butyl group, 2-pentyl group, t-pentyl group and the like. ;
Examples of the cyclic alkyl group having 5 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group;
Examples of the aralkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group and cinnamyl group;
Examples of the acyl group having 2 to 30 carbon atoms include acetyl group, propionyl group, butyryl group, benzoyl group, acetylacetyl group (acetonylcarbonyl group), cyclohexylcarbonyl group, acryloyl group, methoxycarbonyl group, and benzyloxycarbonyl group. , Can be mentioned respectively. R in the above formula is preferably a hydrogen atom, acetyl group, benzoyl group, allyl group, benzyl group or t-butyl group.

As the component (D) contained in the curable resin composition of the present invention, compounds represented by the above formulas (2-1) to (2-8) can be preferably used. As a more specific example, N-hydroxysuccinimide, N-hydroxy-5-norbornene-2,3-dicarboximide, N-hydroxyphthalimide, N-acetoxyphthalimide, N-benzoxyphthalimide, N-hydroxy-1,8-naphthalimide or Trihydroxyimido cyanuric acid is more preferably used, and N-hydroxysuccinimide, N-hydroxyphthalimide, N-acetoxyphthalimide, N-hydroxy-1,8-naphthalimide or trihydroxyimide cyanuric acid is particularly preferable.
In the curable resin composition of this invention, (D) component can be used individually by 1 type or in mixture of 2 or more types.
The blending amount of the component (D) in the curable composition of the present invention is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, when the entire curable composition is 100% by weight. More preferably, it is 1 to 3% by weight. When the blending amount of the component (D) is 0.01 to 10% by weight, good curability can be exhibited even in a portion shaded by wiring or the like.

(E) Organic Particles or Inorganic Particles The curable composition of the present invention contains either organic particles or inorganic particles, or both (hereinafter also referred to as “component (E)”). Adhesive strength can be increased by containing either organic particles or inorganic particles, or both.

  As the organic particles, solid particles such as acrylic fine particles are preferably used. Examples of the acrylic fine particles include a methyl methacrylate polymer, a copolymer of methacrylic acid and an alkyl compound, and among these, commercially available ones include, for example, Zefiac F-320, F-301, F -340, F-325, F-351 (manufactured by Gantz Kasei Co., Ltd.) and the like.

Examples of the inorganic fine particles include particles containing silica, alumina, zirconium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate, talc, montmorillonite and the like as main components, and particles containing silica and alumina as main components are preferable.
The shape of the inorganic fine particles may be any of a spherical shape, a rod shape, a plate shape, a fiber shape, and an indeterminate shape, and these may be a solid shape, a hollow shape, or a porous shape.
The number average particle size of the inorganic fine particles is usually 0.001 to 10 μm, preferably 0.01 to 5 μm. If it exceeds 10 μm, there is a possibility that the gap formation for bonding the glass substrates during the production of the liquid crystal cell will not be successful. Here, the number average particle diameter of the inorganic fine particles is measured by a laser light diffraction method. The inorganic fine particles may be directly added to and mixed with other components in powder form, or the solvent dispersion may be added to and mixed with other components to distill off the solvent.

  Examples of commercially available inorganic fine particles include Admafine SO-E1, SO-E2, SO-E3, SO-E4, SO-E5, SE3200-SEJ (manufactured by Admatechs Co., Ltd.), SS01, SS03. , SS15, SS35 (manufactured by Osaka Kasei Co., Ltd.) and the like. An inorganic fine particle may be used individually by 1 type, and may be used in combination of 2 or more type.

  The inorganic fine particles may be surface-treated with a silane coupling agent or the like. By performing such a surface treatment, compatibility with other components can be improved, and dispersibility and mechanical strength in the composition can be improved.

The compounding amount of the organic particles in the curable composition of the present invention is 0.1 to 50% by weight, preferably 1 to 40% by weight when the entire curable composition is 100% by weight. When the blending amount is 0.1 to 50% by weight, a sufficient gelling action is exhibited, the fluidity of the seal part is reduced during heating, and deformation and tearing of the seal part can be prevented.
Moreover, the compounding quantity of the inorganic particle in the curable composition of this invention is 1-50 weight% when the whole curable composition is 100 weight%, Preferably it is 5-40 weight%, More preferably, it is 10 ~ 30% by weight. When the blending amount of the inorganic particles is 1 to 50% by weight, it is possible to easily form a gap for bonding the glass substrates when manufacturing the liquid crystal cell.
Further, the organic particles and the inorganic particles can be used as a mixture, and the blending amount of the organic particles and the inorganic particles is 2 to 50% by weight when the entire curable composition is 100% by weight, Preferably it is 5 to 40 weight%, More preferably, it is 10 to 30 weight%. When the blending amount is 2 to 50% by weight, it is possible to particularly increase the adhesive strength.

(F) Epoxy Compound An epoxy compound (hereinafter also referred to as “component (F)”) is a compound having at least one epoxy group in one molecule, and is a component that reacts and cures by heating. By blending the component (F), the tensile adhesive strength is improved. Examples of the component (F) include an aliphatic compound having an epoxy group, an alicyclic compound having an epoxy group, an aromatic compound having an epoxy group, and the like. An aromatic compound having an epoxy group is preferred.

Specific examples of the aliphatic compound having an epoxy group include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and polyethylene glycol. Diglycidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ethers; polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Polyglycidyl ethers; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; glycidyl of higher fatty acids Esters; epoxidized soybean oil; butyl epoxy stearate, epoxy stearic octyl, epoxidized linseed oil, epoxy polybutadiene, and the like.
Commercially available aliphatic compounds having an epoxy group include SR-NPG, SR-16H, SR-PG, SR-TPG (above, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.); PG-202, PG-207 (above, Toto Kasei) EX-610U, EX-1610-P (manufactured by Nagase ChemteX Corporation) and the like.

Specific examples of the alicyclic compound having an epoxy group include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3. , 4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl- 3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl- 3 ', 4'-epoxy Rhohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), di (3,4) of ethylene glycol 4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxycyclohexahydrophthalic acid dioctyl, epoxycyclohexahydrophthalic acid di-2-ethylhexyl, and the like.
Examples of commercially available alicyclic compounds having an epoxy group include Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-400, Epolide. 401, epolide 403 (manufactured by Daicel Chemical Industries, Ltd.) and the like.

  Examples of the aromatic compound having an epoxy group include compounds having an aromatic ring structure in the main skeleton and having two or more epoxy groups. Examples of the aromatic ring structure of such a compound include a bisphenol A type structure, a bisphenol F type structure, a novolac type structure, a naphthalene skeleton, an anthracene skeleton structure, and a fluorene skeleton.

  As commercial products of aromatic compounds having an epoxy group, JER806, JER828, YL980 (above, manufactured by Japan Epoxy Resin Co., Ltd.); YD-127, YD-128, YDF-170, YDF-175S, YDPN-638, YDCN- 701 (manufactured by Toto Kasei Co., Ltd.); EPICLON 830, EPICLON 850, EPICLON 835, EPICLON HP-4032D (manufactured by DIC);

  The blending amount of the component (F) in the curable composition of the present invention is 1 to 90% by weight, preferably 5 to 80% by weight, more preferably 5 when the entire curable composition is 100% by weight. ~ 60% by weight. When the blending amount of the component (F) is 1 to 90% by weight, positional displacement due to heat is particularly difficult to occur, and the adhesive strength can be further increased.

(G) Silane Coupling Agent A silane coupling agent is preferably used because the effect of improving the durability of the adhesive strength of the curable composition of the present invention can be expressed (improved or improved).
As the silane coupling agent, those having an epoxy group and those having a (meth) acryloyl group are preferable.
A silane coupling agent may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the silane coupling agent having an epoxy group include γ-glycidoxypropyltrimethoxysilane. Examples of commercially available products of these silane coupling agents include SH6040 (manufactured by Toray Dow Corning Co., Ltd.), KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.), and the like.
Examples of the silane coupling agent having a (meth) acryloyl group include γ-methacryloxypropyltrimethoxysilane. Examples of commercially available products of these silane coupling agents include SZ6030 (manufactured by Toray Dow Corning Co., Ltd.), KBM-503, KBM-5103 (manufactured by Shin-Etsu Silicone Co., Ltd.), and the like.

  The compounding amount of the component (G) in the curable composition of the present invention is 0.001 to 15% by weight, preferably 0.01 to 10% by weight, when the entire curable composition is 100% by weight. More preferably, it is 0.1 to 5% by weight. When the amount of component (G) is 0.001 to 15% by weight, sufficient adhesion durability is obtained.

Other components Other components can be mix | blended with the curable composition of this invention in the range which does not impair the effect of this invention. Examples of such additives include radiation sensitive polymerization initiators other than the component (C), partially (meth) acryloylated epoxy resins, reactive (meth) acrylic polymers, sensitizers, chain transfer agents, and antifoaming agents. Agents, ion scavengers, water absorbing agents, leveling agents, spacers, and the like.

<Method for producing curable composition>
In the curable composition of the present invention, the components (A) to (D) and, if necessary, the components (E) to (G) are put in a container and sufficiently mixed using a stirrer such as a planetary stirrer. Thereafter, it can be produced by defoaming under vacuum.

<Curing method and curing conditions of curable composition>
The curable composition of the present invention can be cured by ultraviolet irradiation or by heating.
When the curable composition of the present invention is used as a liquid crystal sealant and a liquid crystal dropping method is used, it is generally cured by further heating after ultraviolet irradiation.
The wavelength of light used for curing the curable composition of the present invention is not particularly limited, but is preferably 350 to 700 nm in consideration of damage to the alignment film and the liquid crystal. Irradiation dose is preferably 500~10,000mJ / cm ^2, more preferably a 1,000~3,000mJ / cm ^2.
Although it does not specifically limit as temperature of thermosetting, Preferably curing temperature is 70 degreeC or more and less than 200 degreeC, More preferably, it is 100 degreeC or more and less than 150 degreeC. Moreover, as hardening time, Preferably it is 20 minutes or more and less than 3 hours, More preferably, it is 30 minutes or more and less than 2 hours.

II. Liquid crystal sealant The liquid crystal sealant is used to bond the two glass substrates of the liquid crystal display element to protect the inside and prevent the liquid crystal from flowing out.
The liquid-crystal sealing compound of this invention consists of the said curable composition of this invention, It is characterized by the above-mentioned. Therefore, the liquid crystal sealant of the present invention has liquid crystal stain resistance, dark part curability, tensile adhesive strength, and the like, and is useful for the production of liquid crystal display elements (liquid crystal display cells) by a liquid crystal dropping method.

  The viscosity of the liquid crystal sealant of the present invention is not particularly limited, but is preferably 10 to 1,000 Pa · s, more preferably 100 to 500 Pa · s, from the viewpoint of dispensing properties and shape preservation properties.

III. Liquid crystal display element The liquid crystal display element of this invention is manufactured using the liquid-crystal sealing compound of the said invention. Therefore, according to the present invention, it is possible to obtain a liquid crystal display element having excellent resistance to liquid crystal contamination and tensile adhesion, and excellent long-term stability and reliability.

The structure of the liquid crystal display element of the present invention will be described with reference to the schematic view of one embodiment of the liquid crystal display element of the present invention shown in FIG.
As shown in FIG. 1, the liquid crystal display element 1 includes a liquid crystal sealant and a liquid crystal 22 with a spacer 18 sandwiched between two glass substrates 10 provided with a transparent electrode 14, an alignment film 12, and a color filter 16. It has a structure to hold.
The two glass substrates 10 are bonded together by the liquid crystal sealing agent 20, and at the same time, the liquid crystal 22 is sealed and held in a space surrounded by the glass substrate 10 and the liquid crystal sealing agent 20. As can be seen from FIG. 1, the liquid crystal sealant 20 is in direct contact with the liquid crystal 22, so that the specific resistance of the liquid crystal 22 is reduced when components in the uncured liquid crystal sealant 20 may be dissolved in the liquid crystal 22. As a result, the long-term stability and reliability of the liquid crystal display element 1 are impaired.
Since the liquid crystal display element of the present invention uses the above-described liquid crystal sealant of the present invention, the uncured liquid crystal sealant component is prevented from dissolving in the liquid crystal, and thus has excellent long-term stability and reliability. Yes.

The liquid crystal display element of the present invention is preferably manufactured by a liquid crystal dropping method. An outline of a manufacturing process of a liquid crystal display element by a liquid crystal dropping method will be described with reference to FIG.
On one glass substrate, a frame of a liquid crystal sealing agent that surrounds a range in which liquid crystal is sealed is formed using a dispenser. The line width and film thickness of the liquid crystal sealing agent are usually about 0.1 to 5 mm and 0.1 to 20 μm, respectively, preferably 0.5 to 3 mm and 1 to 10 μm. Examples of the liquid crystal sealant dispenser used in this case include SHOTminiSL (manufactured by Musashi Engineering Co., Ltd.).
Without curing the liquid crystal sealant, after dropping the liquid crystal into the frame of the liquid crystal sealant and removing bubbles, etc., the other glass substrate is bonded, the two glass substrates are pressure-bonded, and the liquid crystal is sealed To do.
Next, ultraviolet rays are irradiated to temporarily cure the liquid crystal sealant. The ultraviolet rays used at this time are preferably those having a wavelength of 200 to 700 nm, and more preferably those having a wavelength of 350 to 700 nm in consideration of damage to the alignment film and the liquid crystal. As the ultraviolet light source, a high-pressure mercury lamp, a metal halide lamp, an LED, or the like is preferably used.
Thereafter, the substrate is heated at 70 to 200 ° C., preferably 90 to 150 ° C., for 10 minutes to 5 hours, preferably 30 minutes to 2 hours to perform liquid crystal annealing, and at the same time, the liquid crystal sealant is fully cured to obtain liquid crystal. A display element is obtained.
<Example>

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.

Production Example Synthesis of Urethane Acrylate (Component (A); Glycerin-AOI) 75.4 parts of 2-isocyanatoethyl acrylate (Karenz AOI manufactured by Showa Denko KK) in a vessel equipped with a stirrer, and dibutyltin dilaurate 0.1 24.6 parts of glycerin (purified glycerin manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was added dropwise at 10 ° C. for 1 hour, and then stirred at 60 ° C. for 4 hours. Liquid.
When the amount of residual isocyanate of the product in this reaction liquid was measured by FT-IR, it was 0.1 mass% or less, and it was confirmed that the reaction was carried out almost quantitatively. Moreover, it confirmed that a urethane bond and an acryloyl group (polymerizable unsaturated group) were included in the molecule | numerator.
As a result, 100 parts of glycerin-AOI was obtained.

Example 1
The components shown in Example 1 in Table 1 below were weighed into a container and thoroughly mixed using a planetary stirrer (Awatori Nertaro, manufactured by Shinky Corporation). Thereafter, defoaming was performed under vacuum to produce a curable composition.

Examples 2-11 and Comparative Examples 1-4
Each curable composition was produced in the same manner as in Example 1 except that the composition shown in Table 1 was used.

<Characteristic evaluation of cured product>
The following characteristics were evaluated when the curable compositions obtained in the above Examples and Comparative Examples were cured. The obtained results are shown in Tables 1 and 2.

1. Tensile bond strength [Glass]
Take the curable composition in the center of the slide glass, apply 4.5μm spacer particles thinly around the curable composition with a brush, and stack the other slide glass into a cross and press. And a uniform thickness. This was irradiated with ultraviolet rays (500 mW / cm ² , 3000 mJ / cm ² ) and then left at 120 ° C. for 1 hour to obtain a sample for measuring tensile adhesive strength. This sample was measured for adhesive strength (N / cm ² ) with a tensile tester. It can be said that the larger the value of the adhesive strength, the better the adhesiveness.

2. Change of liquid crystal phase transition temperature 0.025 g of the curable composition was put in a sample bottle (inner diameter 10 mm), and then 0.075 g of liquid crystal (MLC-6608 manufactured by Merck & Co., Inc.) was put. The sample bottle was irradiated with ultraviolet rays (3000 mJ / cm ² ) from the bottom and then left at 120 ° C. for 1 hour. After allowing to cool to 25 ° C, the supernatant of the liquid crystal was taken out and subjected to DSC measurement (temperature increase rate 2 ° C / min). The amount of change was determined from the difference between the measured phase transition temperature and the phase transition temperature of the untreated liquid crystal (blank), and evaluated according to the following evaluation criteria.
○: The difference (change amount) is less than 0.5 ° C. with respect to the blank. Δ: The difference (change amount) is 0.5 ° C. or more and less than 1.0 with respect to the blank. 1.0 ℃ or higher

4). Dark part sclerosis | hardenability What prepared the light-shielding process (1) for the whole slide glass, and what processed the light-shielding process (2) half. A curable composition is spot-coated on the central part of (1), and (2) is bonded together (at this time, the center of the sealing agent is placed at the boundary between the shielding part and non-shielding part of (2)). After sufficient compression, after irradiation with ultraviolet rays (3000mJ / cm ^2), to stand for 1 hour at 120 ° C.. Two glass slides were peeled off, IR measurement was performed on the inside of 0.5 mm from the non-shielding part and the shielding part end, the acrylic reaction rate was calculated from the following formula, and evaluated according to the following evaluation criteria.

Acrylic reaction rate = {1- (acrylic peak area after curing / standard peak area after curing) / (acrylic peak area before curing / standard peak area before curing)} × 100

○: Acrylic reaction rate of 0.5 mm from the end of the shielding part is 50% or more Δ: Acrylic reaction rate of 0.5 mm part from the end of the shielding part is 30% or more and less than 50% The acrylic reaction rate of the part is less than 30%

The compositions in Tables 1 and 2 represent the following.
A component A-1: EB3700: Daicel Cytec Co., Ltd. bisphenol A-containing epoxy acrylate A-2: Glycerin-AOI: synthesized in Production Example 1 B component Amicure UDH-J: Ajinomoto Fine Techno Co., Ltd. C Component C-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)
Product name "Irgacure OXE02", manufactured by Ciba Specialty Chemicals)
C-2: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one
(Product name "Irgacure 379", manufactured by Ciba Specialty Chemicals)
C-3: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole C-4: 4,4′-bis (diethylamino) benzophenone C-5: 2-mercaptobenzothiazole D component D-1: N-hydroxyphthalimide D-2: N-hydroxysuccinimide D-3: N-acetoxyphthalimide D-4: trihydroxyimino cyanuric acid D-5 : N-hydroxy-5-norbornene-2,3-dicarboximide / E component inorganic particles Admafine SO-E3: Silica fine particle organic particles manufactured by Admatechs Co., Ltd. Zefiac F325: PMMA particles manufactured by Ganz Kasei Co., Ltd., average Particle size 0.5μm
F component EX-1610-P: a polyfunctional epoxy compound (weight average molecular weight (GPC): 760) manufactured by Nagase ChemteX Corporation
・ G component
SH6040: Toray Dow Corning Co., Ltd. silane coupling agent; γ-glycidoxypropyltrimethoxysilane

Since the liquid crystal sealant of the present invention is sufficiently cured even in a portion not directly irradiated with ultraviolet rays overlapping with a wiring, a black matrix, etc. due to a recent demand for a narrower frame, the liquid crystal sealant has high adhesion to the substrate and is an uncured liquid crystal The possibility of liquid crystal contamination due to the sealant component is reduced, and a liquid crystal display element having excellent long-term stability can be provided.
ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal sealing agent useful in the liquid crystal dropping system which can manufacture a liquid crystal display element efficiently with few processes can be provided.

It is a cross-sectional schematic diagram of the liquid crystal display element of this invention. It is a figure which shows the outline | summary of the liquid crystal dropping method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Liquid crystal display element 10 Glass substrate 12 Alignment film 14 Transparent electrode 16 Color filter 18 Spacer 20 Liquid crystal sealing agent 22 Liquid crystal

Claims (9)

(A) Compound having (meth) acryloyl group (B) Organic acid dihydrazide compound (C) Radiation sensitive polymerization initiator, and (D) Formula (1)

(In formula (1), “*” indicates a bond.)
A curable composition comprising a compound having a structure represented by:
(D) component is
Following formula

(In the above formula, each R is independently a hydrogen atom, a secondary or tertiary alkyl group having 3 to 30 carbon atoms, a cyclic alkyl group having 5 to 12 carbon atoms, an allyl group, or a group having 7 to 30 carbon atoms. An aralkyl group or an acyl group having 2 to 30 carbon atoms.)
The curable composition of Claim 1 which is a compound represented by either. Component (D) is N-hydroxysuccinimide, N-hydroxy-5-norbornene-2,3-dicarboximide, N-hydroxyphthalimide, N-acetoxyphthalimide, N-benzoxyphthalimide, N-hydroxy-1 The curable composition according to claim 2, which is 1,8-naphthalimide or trihydroxyimide cyanuric acid.   (C) The curable composition of Claim 1 in which a radiation sensitive polymerization initiator contains at least 1 sort (s) selected from the group which consists of an O-acyl oxime compound and an acetophenone compound. The curable composition according to any one of claims 1 to 4, further comprising (E) either organic particles or inorganic particles, or both.   Furthermore, (F) The curable composition of any one of Claims 1-5 containing the epoxy resin which has 3 or more epoxy groups in 1 molecule, and does not have a (meth) acryloyl group. .   Furthermore, (G) The curable composition of any one of Claims 1-6 containing a silane coupling agent.   The liquid-crystal sealing compound which consists of a curable composition of any one of Claims 1-7.   The liquid crystal display element manufactured using the liquid-crystal sealing compound of Claim 8.

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