JP5433438B2 - Liquid crystal sealing agent for thermosetting liquid crystal dropping method and liquid crystal display cell using the same - Google Patents

Description

  The present invention relates to a liquid crystal sealant and a liquid crystal display cell using the same. More specifically, the present invention relates to a liquid crystal sealant suitable for manufacturing a liquid crystal display cell by a liquid crystal dropping method and a liquid crystal display cell manufactured using the same.

  In recent years, as a method of manufacturing a liquid crystal display cell, a liquid crystal dropping method with higher mass productivity has been introduced from a conventional method of manufacturing a liquid crystal display cell by a liquid crystal vacuum injection method (see Patent Document 1). ). Specifically, the liquid crystal dropping method is to apply a liquid crystal sealing agent weir on the liquid crystal substrate (main seal), and then apply the sealing agent to the outermost circumference, apply the sealing agent (dummy seal), and then place the liquid crystal inside the inner seal. After that, the other liquid crystal substrate facing each other in a vacuum is pasted together, and then the liquid crystal is sealed by releasing to atmospheric pressure, and the sealing portion is cured by UV irradiation and heating, thereby liquid crystal display cell Is a manufacturing method to complete the process. The liquid crystal sealant used for sealing the liquid crystal in this manufacturing method is not a conventional thermosetting liquid crystal sealant, but a photothermal curing combined type liquid crystal sealant is generally used. The reason why the conventional thermosetting liquid crystal sealant is not used in the liquid crystal dropping method is that when the liquid crystal dropping method is used with the conventional thermosetting liquid crystal sealing agent, the thermal expansion of the liquid crystal during heating and the viscosity decrease due to the heating of the liquid crystal sealing agent This is because the seal is punctured and the liquid crystal cannot be sealed due to the vacuum pressure reduction.

  The photo-curing combined type liquid crystal sealant is used by applying a liquid crystal sealant weir to the liquid crystal substrate with a dispenser, etc., then dropping the liquid crystal inside the weir and attaching the other substrate facing in vacuum. After the alignment, the liquid crystal cell is manufactured by irradiating the seal portion with light such as ultraviolet rays and temporarily curing, and then thermally curing the liquid crystal sealant at about 120 ° C. for about 1 hour.

  However, with the recent narrowing of the liquid crystal cell frame, the liquid crystal seal portion is shielded from light by the wiring or the black matrix, resulting in an uncured portion that is not precured. Problems such as liquid crystal contamination caused by liquid crystal sealants that have been inserted into the liquid crystal or not temporarily cured have arisen. Therefore, in designing the liquid crystal cell, there has been a restriction that the liquid crystal cell must be designed so as not to shield the sealing agent as much as possible. In addition, since the liquid crystal and the alignment film are deteriorated by the ultraviolet irradiation, it is necessary to shield the liquid crystal portion with a light shielding mask or the like during the ultraviolet irradiation in order to prevent the deterioration. Further, as the size of the liquid crystal glass substrate is increased, the ultraviolet irradiation device is increased in size, and there is a problem that the running cost of the ultraviolet irradiation device is increased.

  In view of the above, in recent years, there has been proposed a thermosetting type liquid crystal dropping method for producing a liquid crystal display cell only by thermosetting which does not require ultraviolet irradiation even in the liquid crystal dropping method. For example, Patent Documents 2 and 3 propose a manufacturing method in which a liquid crystal sealing agent made of a thermosetting resin is applied, followed by pre-baking, and then liquid crystal dropping and vacuum bonding are performed. There is no detailed description of the composition. Similarly, Patent Document 4 proposes a method for producing a liquid crystal display element by applying a thermosetting liquid crystal sealing agent, then increasing the viscosity of the liquid crystal sealing agent by heating, dropping the liquid crystal, and vacuum bonding, and the liquid crystal sealing agent. Although it is specified that the component contains a (meth) acrylic resin, an epoxy compound, a pregel component or a solvent, the liquid crystal contamination property and liquid crystal display unevenness of the liquid crystal sealant are not specified. Patent Document 5 also proposes a method of manufacturing a liquid crystal display element by performing a liquid crystal dropping method only by thermosetting, and it is proposed that the bottom viscosity at the time of viscosity reduction during heating of the liquid crystal sealant is important. There is no specific numerical value for the bottom viscosity. In addition, a combination of thermosetting agents having different melting points is important as the liquid crystal sealant, but there is no specific indication, liquid crystal contamination property of the liquid crystal sealant, or liquid crystal display unevenness. Patent Documents 6 and 7 propose a thermosetting liquid crystal sealant for a liquid crystal dropping method in which a liquid crystal sealant is used as a B-stage process, and a pre-bake process is performed. Therefore, there is a disadvantage that the process time becomes long. In order to shorten the B stage treatment time for 20 minutes, the pre-baking treatment temperature may be increased to, for example, 100 ° C. or higher. However, in the liquid crystal sealant described above, the main curing reaction proceeds at 100 ° C. or higher. It is not preferable.

  As described above, the thermosetting type liquid crystal dripping method is realized, and it is used for the thermosetting liquid crystal dripping method that does not cause the heat seal puncture and the liquid crystal seal to be inserted into the vacuum bonded substrate and does not contaminate the liquid crystal with the liquid crystal sealant. There is a need for liquid crystal sealants that can be produced.

Japanese Patent Publication No. 8-20627 JP 2005-92043 A JP 2008-293000 A JP 2008-275670 A Japanese Patent Laid-Open No. 2005-221944 JP 2007-199710 A JP 2007-224117 A

  An object of the present invention is to provide a thermosetting liquid crystal sealing agent for a liquid crystal dropping method which does not require ultraviolet irradiation on a liquid crystal sealing portion. Furthermore, the present invention provides a liquid crystal sealant for a thermosetting liquid crystal dropping method, which has low liquid crystal contamination, strong substrate adhesive strength, excellent seal linearity, long pot life at room temperature, and easy narrowing of the cell gap. is there.

（式中、ｎ１、ｎ２は各々独立に０．５〜３の正の数（平均値）を表し、Ｒは炭素数２〜６の二価炭化水素基、Ｘ１、Ｘ２は各々独立に水素原子又は炭素数１〜６の１価炭化水素基、Ｇはグリシジル基を表す）
で表されるエポキシ樹脂（ｇ）を含有する熱硬化型液晶シール剤（但し、有機ベントナイトを含有する場合を除く）。
(２) エポキシ樹脂（ｇ）が下記一般式（２）

（式中、ｎ_１、ｎ_２は各々独立に０．５〜３の正の数（平均値）を表し、Ｒは炭素数２〜６の二価炭化水素基、Ｇはグリシジル基を表す）
で表される上記（１）に記載の熱硬化型液晶シール剤。
The present inventors have completed the present invention as a result of intensive studies to solve the above-mentioned problems.
That is, the present invention relates to the following (1) to (14).
(1) (Meth) acrylated epoxy resin (a), polyfunctional hydrazide compound (b), inorganic filler (c), curing accelerator (d), fumed silica (e), polythiol (f) and the following general Formula (1)

(In the formula, n1 and n2 each independently represent a positive number (average value) of 0.5 to 3, R is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X1 and X2 are each independently a hydrogen atom. Or a monovalent hydrocarbon group having 1 to 6 carbon atoms, G represents a glycidyl group)
A thermosetting liquid crystal sealant containing an epoxy resin (g) represented by the formula (except when it contains organic bentonite) .
(2) The epoxy resin (g) is represented by the following general formula (2)

(In the formula, n ₁ and n ₂ each independently represent a positive number (average value) of 0.5 to 3, R represents a divalent hydrocarbon group having 2 to 6 carbon atoms, and G represents a glycidyl group)
The thermosetting liquid crystal sealing agent as described in said (1) represented by these.

で表される上記（１）に記載の熱硬化型液晶シール剤。
(４) 多官能ヒドラジド化合物（ｂ）が下記一般式（４）

｛式中、Ｒ^１〜Ｒ^３は各々独立して水素原子又は式（５）で表される基であり、Ｒ^１〜Ｒ^３の少なくとも何れか２つは式（５）で表される基を示し、ｎは１〜６の整数を示す｝
で表されるイソシアヌル環骨格を有する多官能ヒドラジド化合物である上記（１）乃至（３）のいずれか一項に記載の熱硬化型液晶シール剤。 (3) The epoxy resin (g) is represented by the following general formula (3)

The thermosetting liquid crystal sealing agent as described in said (1) represented by these.
(4) The polyfunctional hydrazide compound (b) is represented by the following general formula (4)

{Wherein R ^{1 to} R ³ are each independently a hydrogen atom or a group represented by the formula (5), and at least any two of R ^{1 to} R ³ are groups represented by the formula (5) And n represents an integer of 1 to 6}
The thermosetting liquid crystal sealing agent according to any one of (1) to (3), which is a polyfunctional hydrazide compound having an isocyanuric ring skeleton represented by:

｛式中、Ｔ^１〜Ｔ^３は各々独立して水素原子又は上記式（７）で表される基であり、Ｔ^１〜Ｔ^３の少なくとも何れか２つは式（７）で表される基を示し、ｎは１〜６の整数を示す｝
で表されるイソシアヌル環骨格を有する多価カルボン酸化合物である上記（１）乃至（５）のいずれか一項に記載の熱硬化型液晶シール剤。 (5) The thermosetting liquid crystal sealing agent according to any one of (1) to (4), wherein the inorganic filler (c) is alumina and / or silica.
(6) The curing accelerator (d) is represented by the following general formula (6)

{Wherein T ^{1 to} T ³ are each independently a hydrogen atom or a group represented by the above formula (7), and at least any two of T ^{1 to} T ³ are represented by the formula (7) Represents a group, and n represents an integer of 1 to 6}
The thermosetting liquid crystal sealing agent according to any one of (1) to (5), which is a polyvalent carboxylic acid compound having an isocyanuric ring skeleton represented by:

(7) The thermosetting liquid crystal sealing agent according to any one of (1) to (6), wherein the fumed silica (e) is contained in an amount of 0.5 to 7% by mass based on the total amount of the liquid crystal sealing agent. .
(8) The thermosetting liquid crystal sealing agent according to any one of (1) to (7), wherein the polythiol (f) is contained in an amount of 0.5 to 5% by mass based on the total amount of the liquid crystal sealing agent.
(9) The thermosetting liquid crystal sealing agent as described in any one of (1) to (8) above, which contains a coupling agent.
(10) Any of the above (1) to (9), wherein the viscosity is 100 to 500 Pa · s when measured at 25 ° C. under the condition of 5 rpm using a conical plate type rotational viscometer (E type viscometer) The thermosetting liquid crystal sealing agent according to any one of the above.
(11) The liquid crystal sealant was heated at 80 to 110 ° C. for 3 to 15 minutes to be B-staged, then cooled to 25 ° C., and then heated from 30 ° C. to 120 ° C. at a temperature increase of 18 ° C./min. In the dynamic viscoelasticity measurement, the complex viscosity at 40 ° C. is 1000 to 10,000 Pa · s, and the minimum value of the complex viscosity is in the range of 1 to 1000 Pa · s. The thermosetting liquid crystal sealing agent according to any one of (1) to (10) above.

(12) Ratio η _{0.5 of} viscosity η _0.5 measured under the condition of 0.5 rpm at 25 ° C. using an E-type viscometer and viscosity η _5.0 measured under the condition of _5.0 rpm at 25 ° C. The thermosetting liquid crystal sealing agent according to any one of (1) to (11) above, wherein / η _5.0 is 1.2 to _3.0 .
(13) A liquid crystal display cell sealed with a cured product of the liquid crystal sealant according to any one of (1) to (12) above.
(14) With the liquid crystal sealing agent according to any one of (1) to (12), a step of forming a seal pattern on one substrate, a step of prebaking the formed pattern, and a frame of the prebaked pattern A method for producing a liquid crystal display cell comprising: a step of laminating a liquid crystal in the substrate and bonding the other substrate so as to enclose the liquid crystal; and a step of thermally curing the sealing agent after the bonding step .

  With the liquid crystal sealant of the present invention, it is possible to more efficiently perform a thermosetting liquid crystal dropping method that does not require ultraviolet irradiation to the liquid crystal seal portion. In addition, the liquid crystal sealant of the present invention has low liquid crystal contamination, strong adhesive strength, excellent seal linearity, and a long pot life at room temperature. Manufacturing a liquid crystal cell having a high narrow cell gap is facilitated. As a result, a high-reliability and high-quality liquid crystal cell can be produced with a high yield.

Hereinafter, the present invention will be described in detail.
The heat-curable liquid crystal sealant of the present invention is applied with a liquid crystal sealant on one liquid crystal display substrate and then thickened or precured by heating (pre-baking) before being bonded to the counter liquid crystal display substrate (B stage). The liquid crystal sealant is suitable for a thermosetting liquid crystal dropping method in which a liquid crystal display element is produced by performing liquid crystal dropping and substrate pasting to be cured by heating.

（式中、ｎ１、ｎ２は各々独立に０．５〜３の正の数（平均値）を表し、Ｒは炭素数２〜６の二価炭化水素基、Ｘ１、Ｘ２は各々独立に水素原子又は炭素数１〜６の１価炭化水素基、Ｇはグリシジル基を表す）
で表されるエポキシ樹脂（ｇ）（ＡＯ付加ビスＳエポキシ樹脂（ｇ）ともいう）を含有する。 The liquid crystal sealant of the present invention has the following general formula (1)

(In the formula, n1 and n2 each independently represent a positive number (average value) of 0.5 to 3, R is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X1 and X2 are each independently a hydrogen atom. Or a monovalent hydrocarbon group having 1 to 6 carbon atoms, G represents a glycidyl group)
The epoxy resin (g) represented by (AO addition bis S epoxy resin (g)) is contained.

（式中、ｎ１、ｎ２は各々独立に０．５〜３の正の数（平均値）を表し、Ｒは炭素数２〜６の二価炭化水素基、好ましくは炭素数２〜３のアルキレン基、Ｇはグリシジル基を表す）で表される。 Preferably, the epoxy resin (g) is represented by the following general formula (2)

(In the formula, n1 and n2 each independently represents a positive number (average value) of 0.5 to 3, and R is a divalent hydrocarbon group having 2 to 6 carbon atoms, preferably alkylene having 2 to 3 carbon atoms. Group, G represents a glycidyl group).

で表されるエチレンオキサイド付加ビスフェノールＳ型エポキシ樹脂である。
本発明で用いられるＡＯ付加ビスＳエポキシ樹脂（ｇ）は、原料となるビスフェノールＳ化合物にアルキレンオキサイドを付加させ、次いで得られた化合物の水酸基をエピハロヒドリンと反応させて得られる。該エポキシ樹脂（ｇ）の原料となるビスフェノールＳ化合物としてはビスフェノールＳ、又は、ハロゲン若しくはＣ１−Ｃ４アルキル置換ビスフェノールＳ等を挙げることが出来、好ましいのは、ビスフェノールＳである。ビスフェノールＳ化合物に付加させるアルキレンオキサイドとしては、一般式（１）のＲに対応するアルキレンオキサイドであれば特に制限はない。通常エチレンオキサイド、プロピレンオキサイド、テトラメチレンオキサイド、メチルエチレンオキサイド、ヘキサメチレンオキサイド等の炭素数２〜６のアルキレンオキサイド、好ましくは炭素数２−３のアルキレンオキサイドを挙げることができ、耐熱性、機械強度の観点からエチレンオキサイドが好ましい。同様に付加するアルキレンオキサイドはフェノール１当量につきアルキレンオキサイド０．５〜３当量が好ましく、更に好ましくは１．０〜１．５当量である。エピハロヒドリンとしては特に限定はしないが、エピクロルヒドリン、β−メチルエピクロルヒドリン、エピブロモヒドリン、β−メチルエピブロモヒドリン等が挙げられるが、好ましいのはエピクロルヒドリンである。 More preferably, the epoxy resin (g) is represented by the following general formula (3):

It is an ethylene oxide addition bisphenol S type epoxy resin represented by these.
The AO-added bis S epoxy resin (g) used in the present invention is obtained by adding alkylene oxide to a raw material bisphenol S compound and then reacting the hydroxyl group of the obtained compound with epihalohydrin. Examples of the bisphenol S compound used as a raw material for the epoxy resin (g) include bisphenol S, halogen, or C1-C4 alkyl-substituted bisphenol S, and bisphenol S is preferred. The alkylene oxide to be added to the bisphenol S compound is not particularly limited as long as it is an alkylene oxide corresponding to R in the general formula (1). Usually, mention may be made of alkylene oxides having 2 to 6 carbon atoms such as ethylene oxide, propylene oxide, tetramethylene oxide, methylethylene oxide, hexamethylene oxide, etc., preferably alkylene oxides having 2 to 3 carbon atoms, heat resistance, mechanical strength From the viewpoint of, ethylene oxide is preferable. Similarly, the alkylene oxide added is preferably 0.5 to 3 equivalents, more preferably 1.0 to 1.5 equivalents of alkylene oxide per equivalent of phenol. Although it does not specifically limit as an epihalohydrin, Although epichlorohydrin, (beta) -methylepichlorohydrin, epibromohydrin, (beta) -methylepibromohydrin, etc. are mentioned, Epichlorohydrin is preferable.

  The content of the AO-added bis S epoxy resin (g) in the liquid crystal sealant is usually 5 to 20% by mass, preferably 7 to 15% by mass, based on the total amount of the liquid crystal sealant. When the content of the epoxy resin (g) is in the above range, curing is quick and appropriate adhesive strength can be obtained. When the amount of the epoxy resin (g) is too small, the adhesive strength is weakened. When the amount is too large, the curing is slowed down, and seal puncture is likely to occur.

The liquid crystal sealing agent of the present invention contains a (meth) acrylated epoxy resin (a). In the present invention, the term “(meth) acryl” means “acryl” and / or “methacryl”.
The (meth) acrylated epoxy resin (a) used in the present invention preferably has low contamination and solubility in liquid crystals and low resin viscosity.

  The (meth) acrylated epoxy resin (a) is a resin obtained by reaction of an epoxy resin and (meth) acrylic acid (or a salt or ester thereof, etc.), such as an epoxy acrylate resin or an epoxy resin (meth) acrylate. Also called. Usually, all of the epoxy groups are (meth) acrylated, but within the scope of achieving the effects of the present invention, the epoxy group of the epoxy resin is reacted with less than an equivalent amount of (meth) acrylic acid component intentionally. A partial (meth) acrylated epoxy resin leaving an epoxy group may be used. The (meth) acrylation rate is preferably 50 to 100%, more preferably 70 to 100%, and most preferably 100% with respect to the total epoxy groups. The (meth) acrylated epoxy resin (a) is preferably a compound in which a bifunctional or higher polyfunctional epoxy resin is (meth) acryloylated. In addition, as described above, instead of a total (meth) acrylated epoxy resin, a partially (meth) acrylated epoxy resin (a resin having a structure having both a (meth) acryloyl group and an epoxy group in one molecule) may be used. In this case, the ratio of the epoxy group to the (meth) acryloyl group is not limited and is appropriately selected from the viewpoint of process compatibility and liquid crystal contamination. The (meth) acrylated epoxy resin may be used alone or in combination of two or more.

Although it does not specifically limit as an epoxy resin used as the raw material of (meth) acrylated epoxy resin (a), The epoxy resin more than bifunctional is preferable. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, ethylene oxide-added bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy. Resin, bisphenol F novolac type epoxy resin, resorcin diglycidyl ether, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, Dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin having triphenolmethane skeleton, Other, diglycidyl ethers of bifunctional phenols, bifunctional alcohols diglycidyl ethers of and the like. Bifunctional epoxy resins such as bisphenol epoxy resin (for example, bisphenol A type epoxy resin or bisphenol F type epoxy resin), resorcin diglycidyl ether, 1,6 hexanediol diglycidyl ether are preferable. Among them, bisphenol F type epoxy resin, resorcin diglycidyl ether, or 1,6 hexanediol diglycidyl ether is preferable, and bisphenol F type epoxy resin or resorcin diglycidyl ether is more preferable.
The (meth) acrylated epoxy resin (a) is preferably an acrylated epoxy resin obtained by reaction of an epoxy resin (preferably a bifunctional epoxy resin) and acrylic acid from the viewpoint of curability. Further preferred are acrylic acid adducts of bisphenol F type epoxy resins and / or acrylic acid adducts of resorcin diglycidyl ether. Most preferred is an acrylic acid adduct of resorcin diglycidyl ether.

The content of the (meth) acrylated epoxy resin (a) in the liquid crystal sealant is usually 30 to 70% by mass, preferably 40 to 60% by mass, based on the total amount of the liquid crystal sealant. When the content is less than 30% by mass, the reaction at the time of thermosetting is delayed, and the seal weir is sealed puncture due to the thermal expansion of the liquid crystal and the lowering of the viscosity of the sealing resin when the liquid crystal cell is formed by the liquid crystal dropping method. When the content is more than 70% by mass, sufficient adhesive strength cannot be obtained.
As the (meth) acrylated epoxy resin (a), the liquid crystal sealing agent of the present invention containing an acrylic acid adduct of resorcin diglycidyl ether is more preferable, and the content of the acrylic acid adduct is (meth) acrylated epoxy resin. It is 40-100 mass% with respect to the total amount of (a), Preferably it is 50-100%.

The liquid crystal sealant of the present invention contains a polyfunctional hydrazide compound (b).
As a polyfunctional hydrazide compound (b), what has two or more hydrazide groups in a molecule | numerator can be mentioned, Preferably a 2-4 functional hydrazide compound is mentioned. Specific examples thereof include, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanediohydrazide, hexadecane maleic dihydrazide, Dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4-bisbenzenedihydrazide, 1,4-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzenetrihydrazide, pyromellitic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydride Hydrazide compounds having a valine hydantoin skeleton such as razide, 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) ) Isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate, and these may be used alone or in admixture of two or more.

｛式中、Ｒ^１〜Ｒ^３は各々独立して水素原子又は式（５）で表される基を示し、Ｒ^１〜Ｒ^３の少なくとも何れか２つは式（５）で表される基であり、ｎは１〜６、好ましくは１〜３の整数を示す｝
で表されるイソシアヌル環骨格を有する多官能ヒドラジド化合物である。 Among these polyfunctional hydrazide compounds, preferred are 2-3 functional hydrazide compounds. More specifically, C3-C5 aliphatic dicarboxylic acid dihydrazide such as adipic acid dihydrazide, phthalic acid dihydrazide such as isophthalic acid dihydrazide, 1,3 such as 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin -Bis (hydrazinocarbono C1-C5 alkyl) -5-C1-C5 alkyl hydantoin, and tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3 -Hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate and the like bis or tris (hydrazinocarbonyl C1-C6 alkyl) isocyanurate. Among these, preferred hydrazide compounds include bis or tris (hydrazinocarbonyl C1-C6 alkyl) isocyanurate. The isocyanurate has the following general formula (4)

{Wherein R ^{1 to} R ³ each independently represent a hydrogen atom or a group represented by Formula (5), and at least any two of R ^{1 to} R ³ are groups represented by Formula (5). And n represents an integer of 1 to 6, preferably 1 to 3}
It is a polyfunctional hydrazide compound which has the isocyanuric ring skeleton represented by these.

  More preferably tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate or bis (2-hydrazinocarbonylethyl) isocyanate And, more preferably, tris (2-hydrazinocarbonylethyl) isocyanurate.

In order to make the polyfunctional hydrazide compound (b) a latent curing agent for rapid curing, it is preferable that the particle size is finely dispersed uniformly. The average particle size is preferably 4 μm or less, and more preferably 3 μm or less, because if the average particle size is too large, it becomes a cause of defects such as failure to form a gap when the upper and lower glass substrates are bonded together during the production of a narrow gap liquid crystal cell. The particle size of the curing agent was measured with a laser diffraction / scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .: LMS-30). In addition, since it will become easy to raise | generate aggregation if an average particle diameter is too small, it is preferable to prepare so that it may not become extremely small (for example, 0.1 micrometer or less).
Therefore, a preferable average particle diameter is 0.2 μm or more and 4 μm or less, more preferably 0.5 μm or more and 3 μm or less, and further preferably 0.8 μm or more and 2.5 μm or less.

  The content of the polyfunctional hydrazide compound (b) in the liquid crystal sealing agent of the present invention is usually 5 parts by mass to 100 parts by mass in total of the (meth) acrylated epoxy resin (a) and the epoxy resin (g). About 60 parts by mass, preferably 10 to 40 parts by mass, and more preferably 15 to 35 parts by mass. When the polyfunctional hydrazide compound (b) is within this range, the thermosetting reaction proceeds sufficiently in a short time and exhibits excellent adhesion, and the glass transition point of the cured sealant is high, and the heat resistance is excellent. When the amount of the component (b) is too small, the thermosetting reaction becomes insufficient, the adhesive force is weak, and the glass transition point is lowered. On the other hand, if the amount of component (b) is too large, the curing agent remains, the adhesive strength is lowered, and the pot life is also deteriorated. Therefore, it is preferable to select according to the composition within the above range.

As the inorganic filler (c) used in the present invention, alumina, silica, talc, clay, bentonite, barium titanium acid, titanium oxide, cobalt oxide, magnesium oxide, nickel oxide, metal oxides such as zirconium oxide, Carbonates such as calcium carbonate and magnesium carbonate, sulfates such as barium sulfate and calcium sulfate, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, silicates such as calcium silicate, aluminum silicate and zirconium silicate These may be used alone or in combination of two or more. Of these inorganic fillers, alumina and / or silica are particularly preferable.

  The average particle size of the inorganic filler (c) used in the present invention is preferably 3 μm or less. If the average particle size is larger than 3 μm, it will hinder the gap formation when the upper and lower glass substrates are bonded together during the production of the liquid crystal cell. The lower limit of the average particle size of the inorganic filler is usually about 0.01 μm. The thickness is preferably about 10 nm to 500 nm, more preferably about 20 nm to 250 nm, and still more preferably about 30 to 200 nm. Content in the liquid crystal sealing agent of the inorganic filler (c) used by this invention is 3-20 mass% normally with respect to the total amount of a liquid crystal sealing agent, Preferably it is 5-15 mass%. When content of an inorganic filler (c) is in the said range, the adhesive strength with respect to a glass substrate is high, and it is excellent also in moisture resistance. If the content of the inorganic filler (c) is too small, the adhesive strength to the glass substrate is lowered, the moisture resistance reliability is also inferior, and the reliability of the adhesive strength after moisture absorption is lost. In addition, when the content of the inorganic filler is too large, it is difficult to form a gap in the liquid crystal cell because the seal is difficult to be broken, and there is a possibility that the production efficiency is lowered, such as the formation of an accurate cell gap is not performed, and the yield is lowered. is there.

｛式中、Ｔ^１〜Ｔ^３は各々独立して水素原子又は上記式（７）で表される基であり、Ｔ^１〜Ｔ^３の少なくとも何れか２つは式（７）で表される基を示し、ｎは１〜６の整数を示す｝
で表されるイソシアヌル環骨格を有する多価カルボン酸化合物である。
具体的には、トリス（１−カルボキシメチル）イソシアヌレート、トリス（２−カルボキシエチル）イソシアヌレート、トリス（３−カルボキシプロピル）イソシアヌレート、ビス（２−カルボキシエチル）イソシアヌレートがあげられ、中でもトリス（３−カルボキシプロピル）イソシアヌレートが好ましい。 The liquid crystal sealing agent of the present invention contains a curing accelerator (d) in order to promote the curability of the thermosetting reaction. The curing accelerator (d) is not limited as long as it has high thermosetting reaction accelerating property during heating, low contamination to liquid crystal, and does not deteriorate the pot life of the liquid crystal sealant during normal temperature storage. Examples thereof include polyvalent carboxylic acids and epoxy resin amine adducts.
These may be used alone or in combination of two or more. Among these curing accelerators, preferred are
The following general formula (6)

{Wherein T ^{1 to} T ³ are each independently a hydrogen atom or a group represented by the above formula (7), and at least any two of T ^{1 to} T ³ are represented by the formula (7) Represents a group, and n represents an integer of 1 to 6}
It is a polyvalent carboxylic acid compound which has the isocyanuric ring skeleton represented by these.
Specific examples include tris (1-carboxymethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, tris (3-carboxypropyl) isocyanurate, and bis (2-carboxyethyl) isocyanurate. (3-Carboxypropyl) isocyanurate is preferred.

  In order to make the curing accelerator (d) a latent curing accelerator for rapid curing, it is preferable to make the particle size fine and uniformly disperse. The average particle size is preferably 4 μm or less, and more preferably 3 μm or less, because if the average particle size is too large, it becomes a cause of defects such as failure to form a gap when the upper and lower glass substrates are bonded together during the production of a narrow gap liquid crystal cell. The lower limit is usually 0.5 μm or more, preferably 1 μm or more, for convenience of handling.

  In the present invention, the content of the curing accelerator (d) in the liquid crystal sealant is usually 1 to 20% by mass, preferably 3 to 15% by mass, more preferably 5%, based on the total amount of the liquid crystal sealant. ˜15 mass%. When the content is too small, the curability is deteriorated and seal puncture occurs, and when the content is too large, the room temperature storage stability and the linearity of the seal are deteriorated.

The liquid crystal sealant of the present invention contains fumed silica (e). By adding fumed silica, the thixotropy of the resin composition is increased, and the applicability, workability, and seal puncture resistance of the liquid crystal sealant can be appropriately adjusted. The fumed silica used in the present invention includes anhydrous amorphous silica fine particles obtained by hydrolyzing silicon tetrachloride as a raw material at a high temperature, and the surfaces of the anhydrous amorphous silica fine particles are hexamethyldisilazane and methylchlorosilane. Hydrophobic fumed silica that has been surface-treated with styrene and silicone oils can be mentioned, and hydrophobic fumed silica is preferred. The average primary particle diameter of the fumed silica contained in the present invention is 0.07 μm or less. Preferably it is 2 nm-70 nm, More preferably, it is about 4 nm-50 nm, More preferably, it is about 6 nm-25 nm.
Moreover, content in the liquid-crystal sealing compound of the fumed silica contained is 0.5-7 mass%, Preferably it is 1-5 mass%. When the content of fumed silica is this content, preferable thixotropic properties can be obtained. When the content of fumed silica is too small, seal puncture is likely to occur during heating, and when the content is too large, the dispensing performance of the sealant is deteriorated.

The liquid crystal sealant of the present invention contains a polythiol compound (f) in order to improve curability. Examples of the polythiol compound include compounds having 2 or more, preferably 2 to 6, more preferably 3 to 4 thiol groups in the molecule.
Examples of the polythiol compound (f) include the following (1) to (3).
(1) Di- or trimercapto C1-C5 alkanes such as methanedithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1 , 2,3-trimercaptopropane, etc.
(2) 3 to 5 mercapto C3-C4 acyl groups obtained by a reaction of a 3-5 valent branched C3-C5 alcohol or dimer thereof and a mercapto C3-C4 fatty acid having a mercapto group at the 2-position or 3-position. ~ 6 mercapto C3-C4 fatty acid esters such as trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) ), Pentaerythritol tetrakis (3-mercaptobutyrate), etc.
(3) 1,3,5-tris {2- (3-mercapto C2-C5 acyloxy) ethyl} -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, for example 1 , 3,5-tris {2- (3-mercaptopropionyloxy) ethyl} -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris ( 3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like.

These may be used alone or in combination of two or more. Among these polythiol compounds, preferred are mercapto C3- having 3 to 6 mercapto C3-C4 acyl groups of the above (2) having a secondary thiol structure from the viewpoint of liquid crystal contamination and room temperature storage stability. C4 fatty acid ester or 1,3,5-tris {2- (3-mercapto C2-C5 acyloxy) ethyl} -1,3,5-triazine-2,4,6 (1H, 3H, 5H of (3) above ) -Trione, more preferably 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione or pentane Erythritol tetrakis (3-mercaptobutyrate) is preferred.
The content of the polythiol compound with respect to the total amount of the liquid crystal sealant is usually 0.1 to 5% by mass, preferably 0.3 to 3% by mass, and more preferably 0.5 to 2.5% by mass.
If the content of the polythiol compound is too small, the curability deteriorates and seal puncture occurs. On the other hand, if the content is too large, the room temperature storage stability deteriorates.

In the liquid crystal sealing agent of the present invention, a coupling agent may be added in order to improve the adhesive strength. Usually, the coupling agent may be omitted, but is preferably included. Although there is no special limitation in the coupling agent to be used, it is preferable to contain a silane coupling agent.
Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3 -Black Propyl methyl dimethoxy silane, 3-chloropropyl trimethoxysilane and the like.
Other coupling agents include isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, neoalkoxy tri ( titanium coupling agents such as p-N- (β-aminoethyl) aminophenyl) titanate, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxy zirconate, neoalkoxy tris neodecanoyl zirconate, Neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-amino) Phenyl) zirconate, ammonium zirconium carbonate, Al- acetylacetonate, Al- methacrylate, zirconium or the like Al- propionate, or aluminum-based coupling agents. These may be used alone or in combination of two or more.

Of these coupling agents, a silane coupling agent is preferred, and an aminosilane coupling agent or an epoxysilane coupling agent is more preferred. A silane coupling agent containing an epoxy group is most preferable, and more specifically, a glycidoxy C1-C4 alkyl tri-C1-C3 alkoxy silane or a glycidoxy C1-C4 alkyl di-C1-C3 alkoxy C1-C3 alkyl silane may be mentioned. it can. Among the silane coupling agents containing an epoxy group, glycidoxy C1-C4 alkyl tri-C1-C3 alkoxysilane is more preferable.
By using a coupling agent, a liquid crystal sealant having excellent moisture resistance reliability and little decrease in adhesive strength after moisture absorption can be obtained. The content of the coupling agent relative to the total amount of the liquid crystal sealant is 0 to 3% by mass, preferably about 0.05 to 3% by mass.

An organic filler may be added to the liquid crystal sealant of the present invention as long as it does not affect the properties of the liquid crystal sealant. Although it is not usually used in the present invention, it may be added as necessary. Examples of the organic filler include polymer beads and swelling type fillers. These organic fillers may be used alone or in combination of two or more.
The average particle diameter of the added organic filler is 5 μm or less, preferably 2 μm or less. When the average particle size is larger than 5 μm, it becomes difficult to form a cell gap. Moreover, the addition amount of the organic filler that can be added is preferably 20% by mass or less in the liquid crystal sealant. When the amount is more than 20% by mass, the viscosity becomes high and it becomes difficult to form a cell gap.

If necessary, the liquid crystal sealant of the present invention may further contain additives such as pigments, leveling agents and antifoaming agents. These addition amounts are 0-10 mass% with respect to the total amount of a liquid-crystal sealing compound, Preferably it is about 0-5 mass%.
In addition, it is not usually necessary to add an organic solvent to the liquid crystal sealant of the present invention, but it can be added depending on circumstances.
In addition, the liquid crystal sealing agent of the present invention is a thermosetting liquid crystal sealing agent, and pre-curing or thickening (B-stage) before liquid crystal dropping can be performed by pre-baking without irradiation with ultraviolet rays or the like. Usually, it does not require a photopolymerization initiator or the like that is required when photocuring is used in combination.

A preferred liquid crystal sealant composition of the present invention is as follows.
In the following, component (a) is a (meth) acrylated epoxy resin (a), component (g) is an AO-added bis-S epoxy resin (g), component (b) is a polyfunctional hydrazide compound (b), (c) ) Component means inorganic filler (c), (d) component means curing accelerator (d), (e) component means fumed silica (e), (f) component means polythiol (f),% and parts Are mass% and mass part, and the ratio of each component is the ratio to the total amount of the liquid crystal sealant unless otherwise specified.
Preferred composition of the liquid crystal sealant of the present invention:
(A) component; 30 to 70%, preferably 40 to 60%,
(G) component; 5 to 20%, preferably 7 to 15%
(B) Component: 5 parts to 60 parts, preferably 10 parts to 40 parts, more preferably 15 parts to 35 parts (c) component, based on 100 parts in total of the components (a) and (g); 20%, preferably 5-15%
Component (d): 1 to 20%, preferably 3 to 15%, more preferably 5 to 15%
(E) component; 0.5-7%, preferably 1-5%
Component (f): 0.1 to 5%, preferably 0.3 to 3%, more preferably 0.5 to 2.5%
Coupling agent: 0 to 3%, preferably 0.05 to 3%
Other additives; 0-10%, preferably 0-5%

  In order to obtain the liquid crystal sealant of the present invention, the components required in the above-mentioned sealant of the present invention may be mixed uniformly and suitably, but preferably the (meth) acrylated epoxy resin (a) and AO Addition bis S epoxy resin (g), preferably further a coupling agent and, if necessary, the above-mentioned other additives are added and mixed uniformly (preferably dissolved and mixed), and then added to the polyfunctional hydrazide compound ( b), an inorganic filler (c), a curing accelerator (d) and fumed silica (e), and a polythiol (f) and other optional components as appropriate, and a known mixing device such as a three-roll, sand mill, It is preferable to mix uniformly by a ball mill or the like. It is preferable to perform a filtration treatment to remove foreign substances after mixing is completed.

The thixotropy index in the liquid crystal sealant of the present invention is preferably 1.2 to 3.0. More preferably, it is 1.5-2.5. In the present invention, the thixotropy index is determined by using an E-type viscometer with a viscosity η _5.0 measured at _5.0 rpm at 25 ° C. and a viscosity η _0.5 measured at 0.5 rpm at 25 ° C. The ratio η _0.5 / η _5.0 . When the thixotropy index is within this range, there is no sagging of the sealing agent after application (being unable to maintain a uniform seal shape), and the phenomenon that the sealing agent oozes out to electrical wiring during pre-baking and the final Even when the viscosity is temporarily reduced during heating for curing, seal puncture does not occur. If the thixotropy index is too small, the sealing agent after application will sag and it will not be possible to maintain a uniform seal shape, and the phenomenon that the resin will bleed out into the electrical wiring during pre-baking will occur. If the thixotropy index is too large, the sealant will not be able to maintain its linearity at the time of application, and the defoaming property will be poor, so that it is easy to cause seal breakage due to bubbles.
The thixotropy is adjusted by using nano-sized particles such as fumed silica used in the present invention, layered fillers such as talc, fine-particle fillers or amorphous materials, or polar substances having a strong intermolecular force (for example, hydrogen bonding). A resin coupling agent having a functional functional group) or the like can be mixed into the sealant. In the present invention, since the fumed silica used functions to adjust the thixotropy, usually no other thixotropy adjusting agent is required. However, other thixotropy adjusting agents may be used in combination as necessary.

As for the viscosity of 25 degreeC in the 5 rpm measurement of the cone-plate type rotational viscometer (E type rotational viscometer) of the liquid-crystal sealing compound of this invention, 100-500 Pa.s is preferable. When the viscosity at 25 ° C. is 100 Pa · s or more, the liquid crystal sealant is not inserted into the liquid crystal after bonding, and when it is 500 Pa · s or less, the application property of the liquid crystal sealant is good. The viscosity is more preferably about 200 to 450 Pa · s, and more preferably about 250 to 400 Pa · s. When the viscosity is within this range, the coating property of the sealant is good, and there is no fear that the liquid crystal sealant is inserted into the liquid crystal after the substrates are bonded.
This viscosity measurement uses a conical plate type rotational viscometer RE-105U (manufactured by Toki Sangyo Co., Ltd.). A liquid crystal sealant sample amount of 0.15 ml is used as a cone plate 1 ° 34 × R12, rotation speed 5 rpm, temperature. The viscosity was measured 3 minutes after the start of rotation under the condition of 25 ° C.

  The liquid crystal sealant of the present invention is heated at 80 to 110 ° C. for 3 to 15 minutes to form a B stage, then cooled to 25 ° C., and then at a temperature increase of 18 ° C./min. In the measurement of dynamic viscoelasticity when the temperature is raised, the complex viscosity at 40 ° C. is in the range of 1000 to 10000 Pa · s, more preferably 1500 to 5000 Pa · s, and the minimum value of the complex viscosity is 1 It is preferable when it is in the range of ~ 1000 Pa · s, more preferably 10 to 500 Pa · s. When the minimum value of the complex viscosity is within the above range, there is no occurrence of seal puncture during heating, and a cell gap after cell formation is easily produced. If the minimum value of the complex viscosity is too low, seal puncture occurs during heating. Moreover, if the minimum value of the complex viscosity is too high, there is no cell gap after cell formation. Furthermore, when the complex viscosity at 40 ° C. is within the above range, the liquid crystal sealant is not inserted even in a low temperature range (for example, room temperature (about 25 ° C.) to 60 ° C.), and the cell gap collapses well. It is. If the complex viscosity at 40 ° C. is too low, the liquid crystal can be easily inserted into the sealant at a low temperature range. Conversely, if it is too high, the cell gap collapses and the prebaking process margin becomes narrow. The dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring device Rheosol-G5000 (manufactured by UBM Co., Ltd.) with a liquid crystal sealant sample amount of 0.4 ml placed on a parallel plate and measured under the condition of a frequency of 1 Hz.

In the liquid crystal display cell of the present invention, a pair of substrates on which predetermined electrodes are formed are arranged to face 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. The kind of liquid crystal to be sealed is not particularly limited. Any substrate can be used as long as it can be used as a substrate for a liquid crystal display cell. For example, a substrate made of glass, quartz, plastic, silicon, or the like that is usually used at present can be mentioned.
The liquid crystal display cell of the present invention is the liquid crystal sealant of the present invention, the step of forming a seal pattern on one substrate, the step of pre-baking the formed pattern, putting the liquid crystal in the frame of the pre-baked pattern, and the other substrate Can be manufactured by passing through the steps of laminating the liquid crystal so as to enclose the liquid crystal, and the step of thermosetting the sealing agent after the laminating step. Furthermore, necessary steps may be added. The liquid crystal display cell of the present invention is usually preferably produced by a method called a thermosetting liquid crystal dropping method.

The liquid crystal dropping method is a method of introducing liquid crystal into the pattern frame by dropping liquid crystal, and is currently widely performed. In the conventional liquid crystal dropping method, the sealing agent is cured by using both light and heat. However, the thermosetting liquid crystal dropping method is a method in which the main seal is cured only by thermosetting. The manufacturing method of the liquid crystal display cell by the thermosetting liquid crystal dropping method will be described more specifically. First, a spacer (gap control material) such as glass fiber is added to and mixed with the liquid crystal sealing agent of the present invention. 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 3 to 6 μm. The amount used is usually 0.1 to 4 parts by weight, preferably 0.5 to 2 parts by weight, more preferably about 0.9 to 1.5 parts by weight with respect to 100 parts by weight of the liquid crystal sealant of the present invention. is there.
A liquid crystal sealant containing a spacer is applied to one side of the substrate by a dispenser or the like to form a weir (main seal), and then the sealant is preheated (prebaked) by a heating device such as a hot plate or oven. Heating can usually be performed by heating a substrate coated with a sealant. The liquid crystal sealant is precured by this preheating. This preheating (prebaking) is usually performed at 80 to 110 ° C. for 3 to 15 minutes. This heating is preferably performed so that the complex viscosity of the liquid crystal sealant at 40 ° C. falls within the range of 1000 to 10,000 Pa · s in the dynamic viscoelasticity measurement of the liquid crystal sealant after heating.
Thereafter, in order to keep the liquid crystal sealing substrate in a vacuum, a sealant is further applied to the outermost periphery (dummy seal). Then, the liquid crystal is dropped inside the weir of the inner seal, the other glass substrate is overlaid in a vacuum, and then released to atmospheric pressure, so that the gap is made. The dummy sealant for holding the liquid crystal sealing substrate in a vacuum does not come into contact with the liquid crystal and is cut off after completion of the liquid crystal cell. Even if the same liquid crystal sealant is used, another UV curable type is used. A sealant, a visible light curable sealant, or a thermosetting sealant may be used. The dummy seal may be cured by heating or light irradiation as necessary after the gap is formed.
The substrate on which the gap has been formed is heated at 90 to 130 ° C. for 1 to 2 hours, and the dummy seal is cut off to obtain the liquid crystal display cell of the present invention. 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.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. In addition, this invention is not limited at all by the following examples.
Synthesis Example 1 [Synthesis of All Acrylate of Resorcin Diglycidyl Ether]
Resorcin diglycidyl ether resin was dissolved in toluene, and dibutylhydroxytoluene was added thereto as a polymerization inhibitor, and the temperature was raised to 60 ° C. Thereafter, acrylic acid with 100% equivalent of epoxy group was added, the temperature was further raised to 80 ° C., trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C. for about 50 hours. The obtained reaction solution was washed with water, and toluene was distilled off to obtain an epoxy acrylate of resorcin.

Synthesis Example 2 [Synthesis of ethylene oxide-added bisphenol S type epoxy resin]
Ethylene oxide-added bisphenol S (manufactured by Nikka Chemical Co., Ltd .; trade name SEO-2, melting point 183 ° C., purity 99.5%) in a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, epichlorohydrin 370 parts by mass, 185 parts by mass of dimethyl sulfoxide and 5 parts by mass of tetramethylammonium chloride were added and dissolved under stirring, and the temperature was raised to 50 ° C. Next, 60 parts by mass of flaky sodium hydroxide was added in portions over 100 minutes to carry out the reaction, and then the reaction was further carried out at 50 ° C. for 3 hours. After completion of the reaction, 400 parts by mass of water was added to the reaction solution 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 parts by mass of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Thereto was added 10 parts by mass of a 30% aqueous sodium hydroxide solution with stirring, and the reaction was carried out for 1 hour, followed by washing with water three times. Distilling off methyl isobutyl ketone under reduced pressure at 180 ° C. using a rotary evaporator. Then, 212 parts by mass of an ethylene oxide-added bisphenol S-type epoxy resin was obtained. The epoxy equivalent of the obtained epoxy resin was 238 g / eq, and the viscosity at 25 ° C. was 113400 mPa · s (crystallized when left at room temperature).

Examples 1 and 2, Comparative Examples 1, 2 and 3
An acrylated epoxy resin, an epoxy resin, and a silane coupling agent described in Table 1 were mixed to obtain a resin liquid. Next, in order to obtain the liquid crystal sealing agents of Examples 1 and 2 and Comparative Example 1, three inorganic fillers, polyfunctional hydrazide compounds, hydrophobic fumed silica, curing accelerators and polythiol compounds were added to this resin liquid. The liquid crystal sealants of Examples 1 and 2 and Comparative Example 1 were obtained by kneading with a roll. In order to obtain the liquid crystal sealant of Comparative Example 2, the liquid crystal sealant of Comparative Example 2 was obtained by the same production method as Example 2 except that fumed silica was not added to Example 2. In order to obtain the liquid crystal sealant of Comparative Example 3, the liquid crystal sealant of Comparative Example 3 was obtained by the same production method as in Example 1 except that no polythiol compound was added to Example 1.

The numerical values in Table 1 are parts by mass.
* 1: All acrylated bisphenol F epoxy resin (Nippon Kayaku Co., Ltd .: R94200)
* 2: Total acrylate of resorcin diglycidyl ether (Nippon Kayaku Co., Ltd .: Synthesis Example 1)
* 3: Ethylene oxide-added bisphenol S epoxy resin (Nippon Kayaku Co., Ltd .: RE-203: Synthesis Example 2)
* 4: Bisphenol A type epoxy resin (Nippon Kayaku Co., Ltd .: RE310S)
* 5: Tris (2-hydrazinocarbonylethyl) isocyanurate finely pulverized product (manufactured by Nippon Finechem Co., Ltd .: HCIC finely pulverized with a jet mill to an average particle size of 1.5 μm)
* 6: Tris (3-carboxypropyl) isocyanurate pulverized product (manufactured by Shikoku Kasei Kogyo Co., Ltd .: C3-CIC acid finely pulverized to a mean particle size of 1.5 μm with a jet mill)
* 7: Spherical alumina (manufactured by CI Kasei Co., Ltd .: Nanotech Alumina SPC; primary average particle size 50 nm)
* 8: Hydrophobic fumed silica (manufactured by Tokuyama Corporation: PM-20L; average primary particle size 12 nm)
* 9: 3-Glycidoxypropyltrimethoxysilane (manufactured by Chisso Corporation: Silaace S-510)
* 10: Pentaerythritol tetrakis (3-mercaptobutyrate) (Showa Denko KK: Karenz MT PE1)

Measurement of Viscosity at 25 ° C. Using a cone-plate rotational viscometer RE-105U (manufactured by Toki Sangyo Co., Ltd.), a liquid crystal sealant sample amount of 0.15 ml was used using a cone plate (cone angle standard: 1 ° 34 × R12). The viscosity was measured 3 minutes after the start of rotation under the conditions of a rotation speed of 5 rpm and a temperature of 25 ° C.

Measurement of dynamic viscoelasticity A dynamic viscoelasticity measuring device Rheosol-G5000 (manufactured by UBM Co., Ltd.) was used, and a liquid crystal sealant sample amount of 0.4 ml was placed on a parallel plate and measured under conditions of a frequency of 1 Hz.

Preparation of liquid crystal cell for evaluation 1 g of 5 μm glass fiber was added as a spacer to 100 g of each of the liquid crystal sealants of Examples and Comparative Examples, mixed and defoamed, and filled into a syringe.
An alignment film solution (PIA-5540-05A; manufactured by Chisso Corporation) was applied to a glass substrate with an ITO transparent electrode, fired, and rubbed. The main seal pattern was applied using a dispenser (SHOTMASTER 300: manufactured by Musashi Engineering Co., Ltd.) with the liquid crystal sealants of Examples and Comparative Examples previously filled in the syringe on this substrate. The heating (pre-baking) of each substrate coated with the main seal pattern was carried out at the temperatures and times described in Table 1 pre-baking temperatures and times (Example 1 and Comparative Example 1 were 110 ° C., 7 minutes; Example 2 and Comparative Example 2 were carried out at 105 ° C. for 6 minutes; Comparative Example 3 was carried out at 120 ° C. for 6 minutes. Thereafter, a dummy seal pattern was applied, and then fine droplets of liquid crystal (JC-5015LA; manufactured by Chisso Corporation) were 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, thermally fixed, and in a vacuum using a bonding apparatus. The substrate was bonded to the liquid crystal dripped substrate. After opening to the atmosphere and forming a gap, the main seal portion was shielded with a light shielding mask so that ultraviolet light was not irradiated, and only the dummy seal portion was irradiated with 2000 mJ / cm 2 of ultraviolet light to cure the dummy seal portion. Then, it put into 120 degreeC oven and heat-hardened for 1 hour, and produced the liquid crystal test cell for evaluation.

  Table 2 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. Further, Table 2 shows the results of measuring the gap of the prepared liquid crystal cell using a liquid crystal characteristic evaluation apparatus (OMS-NK3: manufactured by Chuo Seiki Co., Ltd.). The evaluation criteria for the seal shape, the liquid crystal alignment disorder, and the liquid crystal cell gap were the following four levels, respectively.

Evaluation standard 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 Criteria for Liquid Crystal Cell Gap: The cell has a uniform cell gap of 5 μm.
(Triangle | delta): The location of the cell gap exceeding 5.5 micrometers exists in a cell.
X: A gap of 6 μm or more exists in the cell.
XX: The seal is broken and a cell cannot be formed.
Evaluation of liquid crystal alignment (circle): There is no disorder of liquid crystal alignment 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.

Table 2
Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3
Seal shape ○ ○ ○ ×× ○
Liquid crystal cell gap ○ ○ ○ ×× ○
Liquid crystal alignment ○ ○ × ×× ×

Liquid crystal sealant adhesive strength test 1 g of 5 μm glass fiber is added as a spacer to 100 g of liquid crystal sealant and mixed and stirred. This liquid crystal sealant was applied onto a 50 mm × 50 mm glass substrate, and a 1.5 mm × 1.5 mm glass piece was bonded onto the liquid crystal sealant, and cured in an oven at 120 ° C. for 1 hour. The shear adhesive strength of the glass piece was measured using a bond tester (SS-30WD: manufactured by Seishin Shoji Co., Ltd.). The results are shown in Table 3.

Pot life Using a conical plate type rotational viscometer RE-105U (manufactured by Toki Sangyo Co., Ltd.), 0.15 ml of a liquid crystal sealant sample was corn plate 1 ° 34 × R12, rotation speed 5 rpm, temperature 25 ° C. The viscosity was measured 3 minutes after the start of rotation. The pot life was calculated by changing the viscosity after 1 day storage at 25 ° C. Table 3 shows the rate of increase in viscosity (%) relative to the initial viscosity.

Using thixotropy value the E-type viscometer, the ratio of the viscosity eta _5.0 measured at 5.0rpm conditions in viscosity eta _0.5 and 25 ° C. as measured under the conditions of 0.5rpm at 25 ° C. eta _0. Calculated from ₅ / η _5.0 . The results are shown in Table 3.

As shown in Tables 2 and 3, the liquid crystal sealing agents of Examples 1 and 2 according to the present invention can accurately gap by the liquid crystal dropping method, do not disturb the liquid crystal alignment, and have excellent adhesiveness. In addition, since it is a sealant with little change in viscosity and good workability, it is suitable for a thermosetting liquid crystal dropping method. In addition, since there is no disorder in the alignment of the liquid crystal, it can be seen that the contamination with the liquid crystal sealant is remarkably low.
On the other hand, in the comparative example, in the comparative example 2, the viscosity drop at the time of heating is remarkable and the liquid crystal cell cannot be formed. In the comparative examples 1 and 3, the liquid crystal alignment is disturbed, and the liquid crystal sealing agent is contaminated with liquid crystal. Is recognized. In Comparative Example 3, the curability was further insufficient and sufficient adhesive strength was not obtained. Therefore, none of the comparative examples satisfy all the evaluation items.

Production of Liquid Crystal Display Cell for Projection Display Device Production of a liquid crystal display cell for a projection display device using the sealant of the present invention will be described as a preferred embodiment according to the present invention. In a liquid crystal display cell for a projection display device, a TFT substrate on which a TFT (Thin Film Transistor) and a pixel electrode are formed and a counter substrate on which the counter electrode is formed are spaced apart from each other via the sealant of the present invention. Are arranged to face each other.
A specific method of disposing the TFT substrate and the counter substrate so as to face each other with a predetermined gap will be described. On the TFT substrate and the counter substrate, an alignment film obtained by applying polyimide, baking and rubbing, or an alignment film obtained by obliquely depositing inorganic material such as SiO2 or directional sputtering is formed. ing.
The main seal pattern is applied using a dispenser with the liquid crystal sealant of the embodiment filled in the syringe in the same manner as the production of the evaluation liquid crystal cell on the TFT substrate. The heating (pre-baking) of each substrate coated with the main seal pattern was carried out at the temperatures and times described in the pre-baking temperatures and times shown in Table 1 (110 ° C. for 7 minutes in Example 1 and Comparative Examples 1 and 3). Example 2 and Comparative Example 2 were carried out at 105 ° C. for 6 minutes. Thereafter, a dummy seal pattern is applied, and then a liquid crystal microdrop is dropped into the frame of the seal pattern. Further, the counter substrate and the TFT substrate on which the liquid crystal has been dropped are bonded together in a vacuum using a bonding apparatus. After opening the atmosphere to form a gap, the main seal portion is shielded from light with a light-shielding mask so that ultraviolet light is not irradiated, and only the dummy seal portion is irradiated with ultraviolet light at 2000 mJ / cm 2 to cure the dummy seal portion. Thereafter, it is placed in an oven at 120 ° C. and cured by heating for 1 hour to produce a liquid crystal display cell for a projection display device. In the liquid crystal display cell for a projection display device, the in-plane spacer is not used because the spacer existing in the region contributing to display is enlarged and visually recognized.

  The liquid crystal display cell for the projection type display device prepared by the above method has the same seal shape and liquid crystal orientation as the evaluation liquid crystal cell described above, has a good seal linearity, has a low liquid crystal contamination property, and is uniform. It becomes a cell gap.

Claims (14)

(Meth) acrylated epoxy resin (a), polyfunctional hydrazide compound (b), inorganic filler (c), curing accelerator (d), fumed silica (e), polythiol (f) and the following general formula (1) )

(In the formula, n1 and n2 each independently represent a positive number (average value) of 0.5 to 3, R is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X1 and X2 are each independently a hydrogen atom. Or a monovalent hydrocarbon group having 1 to 6 carbon atoms, G represents a glycidyl group)
A thermosetting liquid crystal sealant containing an epoxy resin (g) represented by the formula (except when it contains organic bentonite) .
The epoxy resin (g) is represented by the following general formula (2)

(In the formula, n ₁ and n ₂ each independently represent a positive number (average value) of 0.5 to 3, R represents a divalent hydrocarbon group having 2 to 6 carbon atoms, and G represents a glycidyl group)
The thermosetting liquid crystal sealing agent of Claim 1 represented by these. The epoxy resin (g) is represented by the following general formula (3)

The thermosetting liquid crystal sealing agent of Claim 1 represented by these. The polyfunctional hydrazide compound (b) is represented by the following general formula (4)

{Wherein R ^{1 to} R ³ are each independently a hydrogen atom or a group represented by the formula (5), and at least any two of R ^{1 to} R ³ are groups represented by the formula (5) And n represents an integer of 1 to 6}
The thermosetting liquid crystal sealing agent according to any one of claims 1 to 3, which is a polyfunctional hydrazide compound having an isocyanuric ring skeleton represented by formula (1).   The thermosetting liquid crystal sealing agent according to any one of claims 1 to 4, wherein the inorganic filler (c) is alumina and / or silica. The curing accelerator (d) is represented by the following general formula (6)

{Wherein T ^{1 to} T ³ are each independently a hydrogen atom or a group represented by the above formula (7), and at least any two of T ^{1 to} T ³ are represented by the formula (7) Represents a group, and n represents an integer of 1 to 6}
The thermosetting liquid crystal sealing agent according to claim 1, which is a polyvalent carboxylic acid compound having an isocyanuric ring skeleton represented by:   The thermosetting liquid crystal sealing agent according to any one of claims 1 to 6, wherein the fumed silica (e) is contained in an amount of 0.5 to 7% by mass based on the total amount of the liquid crystal sealing agent.   The thermosetting liquid crystal sealing agent according to any one of claims 1 to 7, wherein the polythiol (f) is contained in an amount of 0.5 to 5% by mass based on the total amount of the liquid crystal sealing agent.   The thermosetting liquid crystal sealant according to any one of claims 1 to 8, further comprising a coupling agent.   10. The viscosity according to claim 1, wherein the viscosity is 100 to 500 Pa · s when measured under a condition of 5 rpm at 25 ° C. using a conical plate type rotational viscometer (E type viscometer). Thermosetting liquid crystal sealant.   When the liquid crystal sealant is heated to 80 to 110 ° C. for 3 to 15 minutes to form a B stage, then cooled to 25 ° C., and then heated from 30 ° C. to 120 ° C. under a temperature increase of 18 ° C./min. The complex viscosity at 40 ° C. is 1000 to 10000 Pa · s and the minimum value of the complex viscosity is in the range of 1 to 1000 Pa · s in the dynamic viscoelasticity measurement. The thermosetting liquid crystal sealing agent as described in any one of thru | or 10. Ratio η _0.5 / η _{5 of} viscosity η _0.5 measured under the condition of 0.5 rpm at 25 ° C. using an E-type viscometer and viscosity η _5.0 measured under the condition of _5.0 rpm at 25 ° C. _The thermosetting liquid crystal sealant according to any one of claims 1 to 11, wherein 0.0 is 1.2 to 3.0.   The liquid crystal display cell sealed with the hardened | cured material of the liquid-crystal sealing compound as described in any one of Claims 1 thru | or 12.   A liquid crystal sealant according to any one of claims 1 to 12, wherein a step of forming a seal pattern on one substrate, a step of prebaking the formed pattern, putting liquid crystal in a frame of the prebaked pattern, and the other A method for producing a liquid crystal display cell, comprising: a step of bonding the substrate in such a manner as to enclose a liquid crystal; and a step of thermally curing the sealant after the bonding step.