JPWO2013047579A1 - Liquid crystal sealant and liquid crystal display cell using the same - Google Patents

Abstract

Provided is a thermosetting liquid crystal sealant which is excellent in coating workability, contact property to a counter substrate, and viscosity stability after preheating, and further excellent in adhesive strength and flexibility after curing. The liquid crystal sealant of the present invention contains (a) a solid phenol novolac resin having a softening point of 75 ° C. or lower, (b) an acrylic polymer having a core-shell structure, (c) an epoxy resin, and (d) an organic solvent. The gel time at 150 ° C. is 50 seconds or more and 200 seconds or less.

Description

  The present invention relates to a liquid crystal sealant and a liquid crystal display cell using the same.

  Today, liquid crystal display cells are used in a wide range of fields, from small displays such as mobile phones and liquid crystal monitors to large televisions, and further growth is expected in the future. There are two main methods of manufacturing this liquid crystal display cell, a liquid crystal injection method and a liquid crystal dropping method. The liquid crystal dropping method is a method of manufacturing a liquid crystal display cell by applying a liquid crystal sealant on a transparent glass substrate or plastic substrate appropriately provided with a transparent electrode and an alignment film, dropping liquid crystal inside the weir, Demand is growing from the viewpoint of shortening production tact time (time required for one process) and easy enlargement. However, there is a problem that the liquid crystal is contaminated by a process in which the uncured liquid crystal sealing agent and the liquid crystal come into contact with each other, thereby causing a problem in the quality of the liquid crystal display cell. In contrast, the liquid crystal injection method is a method in which an upper cell and a lower glass substrate are previously bonded with a liquid crystal sealant to create an empty cell, liquid crystal is injected from the injection port, and finally the injection port is sealed. In this method, it is possible to produce a high-quality liquid crystal display cell, and it is also possible to cure the liquid crystal sealant only by heat, so that it is effective particularly in the production of a small-sized liquid crystal display cell. It is a manufacturing method.

  In creating an empty cell used for the above liquid crystal injection method, a liquid crystal sealant is applied to the substrate by dispensing or screen printing, followed by preliminary overheating (precure), and then the opposite substrate is overlaid, and the liquid crystal sealant is applied. It is cured.

  The liquid crystal sealant is a curable resin composition that has a role of adhering a glass substrate or a plastic substrate and enclosing liquid crystal inside thereof. The liquid crystal sealant used in the liquid crystal dropping method is mainly a photocurable resin composition, and the liquid crystal sealant used in the liquid crystal injection method is mainly a thermosetting resin composition. That is, the characteristics required for the liquid crystal sealant differ greatly depending on the method of use. Especially for the liquid crystal sealant used in the liquid crystal injection method, it is excellent in coating workability, the thickening behavior by preheating (stable cure) is stable, and is transported in an uncured state after bonding, It is a specific problem that it is excellent in contact with the counter substrate (substrate on which the liquid crystal sealant is not applied) and has shape retention during thermosetting. Note that the contact property to the counter substrate is good when the liquid crystal sealant is sufficiently crushed and bonded to the counter substrate when the substrate is bonded to the counter substrate after preheating, and ideally the liquid crystal This is a case where contact is made in the same area as the substrate to which the sealing agent is applied. Further, the case where the contact property is poor is a case where the viscosity increase due to the preheating is too large, the liquid crystal sealant is not sufficiently crushed, and the contact area with the counter substrate is reduced.

  In addition, recent liquid crystal display cells employ a multi-processing process in which a large number of electrodes are formed on a large glass substrate, and then the upper and lower substrates are bonded together and then divided into individual liquid crystal display cells. Since the number of processed sheets is increased and the mother glass (substrate before dividing) is also enlarged, the stress applied to the liquid crystal sealant after curing is increasing. In connection with this, the further improvement of the adhesive strength property and flexibility of a liquid-crystal sealing compound is calculated | required.

For the above reasons, liquid crystal sealing agents used in the liquid crystal injection method have been vigorously developed.
For example, Patent Document 1 discloses a thermosetting liquid crystal sealing agent that is excellent in adhesiveness, moisture resistance reliability, and flexibility.
Patent Document 2 discloses a thermosetting liquid crystal sealing agent excellent in adhesiveness, moisture resistance reliability, flexibility, and thermosetting.
Patent Document 3 discloses a thermosetting liquid crystal sealing agent having excellent screen printability and moisture resistance reliability.

Japanese Patent Laid-Open No. 10-273644 Japanese Patent Laid-Open No. 11-15005 International Publication No. 2005/038519

  The present invention provides a thermosetting liquid crystal sealant that is excellent in coating workability, contact property to a counter substrate, viscosity stability after preheating, and extremely excellent in adhesive strength and flexibility after curing. Objective.

  In order to solve the above-mentioned problems, the present inventors have intensively studied and contain a phenol novolac resin having specific properties and an acrylic polymer having a core-shell structure, and further have a gel time at 150 ° C. of 50 seconds to 200 seconds. The present inventors have found that the following liquid crystal sealant solves the above-mentioned problems and completed the present invention.

（式中、Ｒ^５は水素原子、低級アルキル基、低級アルコキシ基、又はハロゲン原子を示し、ｒは１〜３の整数を示す。ｒが２又は３のとき、それぞれのＲ^５は同一であっても異なっていてもよい。ｓは０又は正の整数を示す。）
５）
上記成分（ｃ）のエポキシ基１当量に対する上記成分（ａ）の水酸基の当量が０．２〜１．４化学当量である上記１）乃至４）のいずれか一項に記載の液晶シール剤。
６）
上記成分（ｃ）が、ビスフェノールＡ型エポキシ樹脂である上記１）乃至５）のいずれか一項に記載の液晶シール剤。
７）
更に、（ｅ）硬化促進剤を含有する上記１）乃至６）のいずれか一項に記載の液晶シール剤。
８）
上記成分（ｅ）が、２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジンイソシアヌル酸付加物及びエポキシ樹脂アミンアダクトから選ばれる少なくとも１種である上記７）に記載の液晶シール剤。
９）
更に、（ｆ）カップリング剤を含有する上記１）乃至８）のいずれか一項に記載の液晶シール剤。
１０）
上記成分（ｆ）が、エポキシシランカップリング剤である上記９）に記載の液晶シール剤。
１１）
更に、（ｇ）無機充填剤を含有する上記１）乃至１０）のいずれか一項に記載の液晶シール剤。
１２）
上記１）乃至１１）のいずれか一項に記載の液晶シール剤を硬化して得られる硬化物でシールされた液晶表示セル。That is, the present invention relates to the following 1) to 12).
1)
(A) A solid phenol novolak resin having a softening point of 75 ° C. or less, (b) an acrylic polymer having a core-shell structure, (c) an epoxy resin, and (d) an organic solvent, and having a gel time at 150 ° C. of 50 seconds Liquid crystal sealant that is 200 seconds or longer.
2)
The liquid crystal sealant according to 1), wherein the core layer of the component (b) is a polymer of n-butyl acrylate, and the shell layer is a polymer of methyl methacrylate.
3)
1) or 2 above, wherein the component (d) is one or more organic solvents selected from the group consisting of propylene glycol diacetate, dibasic acid dimethyl ester, propylene glycol monoethyl ether acetate, and ethylene glycol dibutyl ether. Liquid crystal sealing agent as described in.
4)
The liquid crystal sealing agent according to any one of 1) to 3), wherein the component (a) is a compound represented by the following formula (1).

(In the formula, R ⁵ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and r represents an integer of 1 to 3. When r is 2 or 3, each R ⁵ is the same. And s is 0 or a positive integer.)
5)
The liquid crystal sealant according to any one of 1) to 4) above, wherein the equivalent of the hydroxyl group of the component (a) is 0.2 to 1.4 chemical equivalents relative to 1 equivalent of the epoxy group of the component (c).
6)
The liquid crystal sealant according to any one of 1) to 5), wherein the component (c) is a bisphenol A type epoxy resin.
7)
Furthermore, (e) Liquid crystal sealing agent as described in any one of said 1) thru | or 6) containing a hardening accelerator.
8)
The component (e) is at least one selected from 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct and an epoxy resin amine adduct. Liquid crystal sealing agent as described in said 7).
9)
Furthermore, (f) Liquid crystal sealing agent as described in any one of said 1) thru | or 8) containing a coupling agent.
10)
The liquid crystal sealant according to 9) above, wherein the component (f) is an epoxy silane coupling agent.
11)
Furthermore, (g) Liquid crystal sealing agent as described in any one of said 1) thru | or 10) containing an inorganic filler.
12)
A liquid crystal display cell sealed with a cured product obtained by curing the liquid crystal sealing agent according to any one of 1) to 11) above.

  The liquid crystal sealant of the present invention is excellent in contact with the counter substrate after pre-curing, very excellent in adhesive strength after curing, and excellent in moisture resistance. Therefore, a liquid crystal display cell having high reliability can be manufactured.

  The liquid crystal sealant of the present invention essentially comprises component (a) a phenol novolac resin having a softening point of 75 ° C. or less, component (b) an acrylic polymer having a core-shell structure, component (c) an epoxy resin, and component (d) an organic solvent. Contains as a component.

  The component (a) used in the present invention is a phenol novolac resin having a softening point of 75 ° C. or lower, preferably 65 ° C. or lower, more preferably 50 ° C. or lower, and is not particularly limited as long as it has this property. Although the lower limit of a softening point is not specifically limited, Preferably it is 40 degreeC or more. The softening point is measured by the ring and ball method defined in JIS K7234.

  Examples of the phenol novolac resin include bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, 4,4-biphenylphenol, 2,2,6,6-tetramethyl-4,4-biphenylphenol, 2,2 -Methylene-bis (4-methyl-6-tert-butylphenol), trishydroxyphenylmethane, pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene , Polyphenol compounds such as phenolized polybutadiene, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, allylphenols, brominated bisphenol A, vinyl Novolak resins made from various phenols such as phenol F, bisphenol S, naphthols, etc .; phenol novolac resins having a xylylene skeleton, phenol novolac resins having a dicyclopentadiene skeleton, phenol novolac resins having a fluorene skeleton, etc .; Crosslinking of various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, brominated bisphenol A, bisphenol F, bisphenol S, naphthols of any of the following formulas (2) to (4) Phenol novolak resin bonded with a group (aralkylene group); and the like.

（式中、Ｒ^１は水素原子、炭素数１〜４のアルキル基、アリル基、又はハロゲン原子を示し、ｍは１〜４の整数を示す。ｍが２以上のとき、それぞれのＲ^１は同一であっても異なっていてもよい。）

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an allyl group, or a halogen atom, and m represents an integer of 1 to 4. When m is 2 or more, each R ¹ is They may be the same or different.)

（式中、Ｒ^２及びＲ^３はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基、アリル基、又はハロゲン原子を示し、ｎ及びｐはそれぞれ独立に１〜４の整数を示す。ｎ又はｐが２以上のとき、それぞれのＲ^２及びＲ^３は同一であっても異なっていてもよい。）

(In the formula, R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an allyl group, or a halogen atom, and n and p each independently represent an integer of 1 to 4. When n or p is 2 or more, each R ² and R ³ may be the same or different.)

（式中、Ｒ^４は水素原子、炭素数１〜８のアルキル基、アリル基、ハロゲン原子、又は水酸基を示し、ｑは１〜５の整数を示す。ｑが２以上のとき、それぞれのＲ^４は同一であっても異なっていてもよい。）

(In the formula, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an allyl group, a halogen atom, or a hydroxyl group, and q represents an integer of 1 to 5. When q is 2 or more, each R ⁴ may be the same or different.)

  Preferable phenol novolak resins include phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, allylphenols, bisphenol F, bisphenol S, naphthols and other novolac resins made from raw materials; xylylene Phenol novolac resin having a skeleton; Phenol novolak resin having a dicyclopentadiene skeleton; Phenol novolak resin having a fluorene skeleton; Phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, brominated bisphenol A, bisphenol F Various phenols such as bisphenol S, naphthols and the like according to any one of the above formulas (2) to (4) (aralkyl Phenol novolak resin which was coupled with emission group); and the like.

  More preferred phenol novolak resins include novolak resins made from various phenols such as phenols, cresols, octylphenol, bisphenol A, bisphenol F, bisphenol S, naphthols; phenols, cresols, octylphenols, bisphenol A, And phenol novolak resins in which various phenols such as bisphenol F, bisphenol S, naphthols and the like are bonded by the crosslinking groups (aralkylene groups) of the above formulas (2) to (4).

  More preferable phenol novolak resins include phenol novolak resins made from phenol, novolak resins made from monophenols represented by cresol novolak resins made from cresols, etc .; phenols, cresols, bisphenol A, etc. And phenol novolak resins obtained by bonding various phenols of the above formulas with any of the crosslinking groups of the following formulas (5) to (9).

  A particularly preferred phenol novolak resin used in the present invention is a phenol novolak resin using monophenols as a raw material, and is represented by the following formula (1).

（式中、Ｒ^５は水素原子、低級アルキル基、低級アルコキシ基、又はハロゲン原子を示し、ｒは１〜３の整数を示す。ｒが２又は３のとき、それぞれのＲ^５は同一であっても異なっていてもよい。ｓは０又は正の整数を示す。）

(In the formula, R ⁵ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and r represents an integer of 1 to 3. When r is 2 or 3, each R ⁵ is the same. And s is 0 or a positive integer.)

  In the above formulas (1) to (9), examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl and the like. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, pentyl, hexyl, octyl and the like. Examples of the lower alkyl group include alkyl groups having 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl, preferably methyl, ethyl, n-propyl, isopropyl, C1-C4 alkyl groups, such as n-butyl, isobutyl, t-butyl, are mentioned. Examples of the lower alkoxy group include alkoxy groups having 1 to 8 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and t-butoxy, preferably methoxy, ethoxy, n-propoxy, iso C1-C4 alkoxy groups, such as propoxy and n-butoxy, are mentioned. Examples of the halogen atom include a bromine atom, a chlorine atom, and a fluorine atom. In the above formula (1), 0 or a positive integer in s is preferably 0 to 15, more preferably 0 to 10. Specifically, PN-152 (manufactured by Nippon Kayaku Co., Ltd.) or the like is easily available from the market as a commercial product.

  These phenol novolac resins are used alone or in admixture of two or more. The use amount of the phenol novolac resin used in the present invention is preferably 0.2 to 1.4 chemical equivalents as the equivalent of the hydroxyl group in the novolac resin with respect to 1 equivalent of the epoxy group of the epoxy resin in the liquid crystal sealant. Preferably it is 0.3-0.9 chemical equivalent, More preferably, it is 0.5-0.9 chemical equivalent. The amount of the novolak resin used affects the contact property of the liquid crystal sealant to the counter substrate.

  The curing agent comprising a phenol novolac resin that is preferably used in the present invention is a compound represented by the above formula (1). In the above formula (1), since the component having s = 1 or higher has a high resin viscosity, it is preferable that the component having s = 0 (binuclear body) is present, and the amount of the component present in the phenol novolac resin Usually, it is 20 to 80% by mass, preferably 25 to 70% by mass, and more preferably about 30 to 50% by mass (the rest is a component having s = 1 or more). In the reaction of a phenol novolac resin with an epoxy resin, a phenol novolac resin having three or more nuclei (for example, a compound having s = 1 in the above formula (1)) has a three-dimensional cross-linked structure, whereas a dinuclear (for example, Since the phenol novolac resin of the compound of the above formula (1) in which s = 0 is linearly cross-linked, the rigidity of the rigid structure is improved, thereby improving the adhesion to the glass substrate. Furthermore, since the phenol novolac resin suitably used in the present invention has a low resin viscosity, it is excellent in screen printability, and it becomes easy to bond the upper and lower glass substrates and form a gap when manufacturing a liquid crystal display device.

The component (b) used in the present invention is fine particles composed of two layers of a core layer made of an acrylic polymer and a shell layer also made of an acrylic polymer. The components of the acrylic polymer used for the core layer and the acrylic polymer used for the shell layer may be the same or different. As the raw material, (meth) acrylate monomers such as n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate; styrene, vinyltoluene, aromatic vinyl compounds such as α-methylstyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinylidene cyanide, 2-hydroxyethyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxyethyl fuma Rate, hydroxybutyl vinyl ether, monobutyl maleate, butoxyethyl methacrylate; and the like. Further, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, hexanediol tri (meth) Crosslinkable monomers having two or more reactive groups such as acrylates, oligoethylene di (meth) acrylate oligoethylene tri (meth) acrylates; aromatic divinyl monomers such as divinylbenzene; triallylic acid triallyl, triallyl isocyanate; Etc., and those in which one or more of these are selected can be used. Specifically, Paraloid EXL-2655 (Rohm and Haas) can be obtained from the market as a commercial product. Among these, those in which the core layer is a polymer of n-butyl acrylate and the shell layer is a polymer of methyl methacrylate are particularly preferable. This is available from the market as F-351 (Ganz Chemical Co., Ltd.).
In the present specification, meta (acrylate) means one or both of acrylate and methacrylate.

  The component (c) used in the present invention is not particularly limited as long as it is a compound having a glycidyl group. Specific examples include, for example, bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; 4,4′-biphenylphenol diglycidyl ether; 2,2 ′, 6,6′-tetramethyl-4 , 4′-biphenylphenol diglycidyl ether; glycidyl ether of 2,2′-methylene-bis (4-methyl-6-tert-butylphenol); trishydroxyphenylmethane triglycidyl ether; pyrogallol triglycidyl ether; diisopropylidene skeleton A glycidyl ether of phenol having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; a phenol, cresol, ethylphenol, butylphenol , Octylphenols, bisphenol A, bisphenol F, bisphenol S, novolak resins made from various phenols such as naphthols, xylylene skeleton-containing phenol novolac resins, dicyclopentadiene skeleton-containing phenol novolac resins, fluorene skeleton-containing phenol novolac resins, etc. Glycidyl etherified products of various novolak resins of the above; alicyclic epoxy resins having an aliphatic skeleton such as cyclohexane; heterocyclic epoxy resins having a heterocyclic ring such as isocyanuric ring, hydantoin ring; brominated bisphenol A, brominated bisphenol F, Epoxy resin obtained by glycidylation of brominated phenols such as brominated bisphenol S, brominated phenol novolak, brominated cresol novolak, etc .; N, N-diglycidyl N, N-diglycidyl aniline; phenyl glycidyl ether; resorcinol diglycidyl ether; 1,6-hexanediol diglycidyl ether; trimethylolpropane triglycidyl ether; polypropylene glycol diglycidyl ether; The epoxy resin generally manufactured and sold such as ', 4' epoxycyclo) hexylmethylhexanecarboxylate, hexahydrophthalic anhydride diglycidyl ester; Preferably, bisphenol A type epoxy resin, bisphenol F type epoxy resin, N, N-diglycidyl-o-toluidine, N, N-diglycidylaniline, (3,4-4 ′ ′, 4′epoxycyclo) hexylmethylhexanecarboxylate Hexahydrophthalic anhydride diglycidyl ester, more preferably bisphenol A type epoxy resin. These epoxy resins may be used as a mixture of two or more. Moreover, although the said epoxy resin has a liquid thing and a solid thing, it can also be mixed and used suitably according to desired viscosity.

  The epoxy equivalent of the epoxy resin used in the present invention is preferably 230 or less, more preferably 210 or less, and still more preferably 190 or less. If it is 230 or more, the reactivity with the curing agent is inferior, and workability is also problematic. The total amount of chlorine in the liquid epoxy resin used in the present invention is preferably 1500 ppm or less, more preferably 1200 or less, and still more preferably 1000 or less. When the total chlorine amount is 1500 or more, corrosion of the ITO electrode of the liquid crystal cell becomes significant. The epoxy equivalent is measured by JIS K7236, and the total chlorine content is measured by a hydrolysis method.

  The component (d) used in the present invention is added for the purpose of reducing the viscosity in order to improve workability. Examples of the organic solvent that can be used include alcohol solvents, ether solvents, acetate solvents, and dibasic acid dimethyl esters. These may be used alone or in combination of two or more in any ratio. May be used.

  Examples of the alcohol solvent include alkyl alcohols such as ethanol and isopropyl alcohol; 3-methyl-3-methoxybutanol, 3-methyl-3-ethoxybutanol, 3-methyl-3-n-propoxybutanol, and 3-methyl. -3-Isopropoxybutanol, 3-methyl-3-n-butoxysibutanol, 3-methyl-3-isobutoxysibutanol, 3-methyl-3-sec-butoxybutanol, 3-methyl-3-tert-butoxy Alkoxy alcohols such as sibutanol; and the like.

  Examples of ether solvents include monohydric alcohol ether solvents, alkylene glycol monoalkyl ether solvents, alkylene glycol dialkyl ether solvents, dialkylene glycol alkyl ether solvents, trialkylene glycol alkyl ether solvents, and the like.

  Examples of the monohydric alcohol ether solvent include 3-methyl-3-methoxybutanol methyl ether, 3-methyl-3-ethoxybutanol ethyl ether, 3-methyl-3-n-butoxysibutanol ethyl ether, 3-methyl Examples include -3-isobutoxysibutanol propyl ether, 3-methyl-3-sec-butoxybutanol-isopropyl ether, and 3-methyl-3-tert-butoxybutanol-n-butyl ether.

  Examples of the alkylene glycol monoalkyl ether solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene Glycol mono-sec-butyl ether, propylene glycol mono-tert-butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl Ete , Ethylene glycol monobutyl -sec- butyl ether, and ethylene glycol monobutyl -tert- butyl ether.

  Examples of the alkylene glycol dialkyl ether solvent include propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol diisopropyl ether, propylene glycol di-n-butyl ether, propylene glycol diisobutyl ether, propylene glycol di-sec- Butyl ether, propylene glycol di-tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol diisopropyl ether, ethylene glycol di-n-butyl ether, ethylene glycol diisobutyl ether, ethylene glycol di-se - butyl ether, ethylene glycol di -tert- butyl ether, and ethylene glycol dibutyl ether.

  Dialkylene glycol alkyl ether solvents include, for example, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol diisopropyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol diisobutyl. Ether, dipropylene glycol di-sec-butyl ether, dipropylene glycol di-tert-butyl ether, diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol diisopropyl ether, diethylene glycol di-n-butyl ether, diethylene glycol diisobuty Ether, diethylene glycol di -sec- butyl ether, diethylene glycol di -tert- butyl ether, and the like.

  Trialkylene glycol alkyl ether solvents include, for example, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tridipropylene glycol dipropyl ether, tripropylene glycol diisopropyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol diisobutyl ether. , Tripropylene glycol di-sec-butyl ether, tripropylene glycol di-tert-butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol diisopropyl ether, triethylene glycol di-n- Butyl ether, triethyl Glycol diisobutyl ether, triethylene glycol di -sec- butyl ether, triethylene alkylene glycol dialkyl ethers such as triethylene glycol di -tert- butyl ether, and the like.

  Examples of the acetate solvent include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-sec- Butyl ether acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol mono-tert-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monopropyl ether acetate, Lopylene glycol mono-n-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono-tert-butyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3- Ethoxybutyl acetate, 3-methyl-3-propoxybutyl acetate, 3-methyl-3-isopropoxybutyl acetate, 3-methyl-3-n-butoxyethyl acetate, 3-methyl-3-isobutoxybutyl acetate, 3 -Alkylene glycol monoalkyl ether acetates such as methyl-3-sec-butoxy butyl acetate and 3-methyl-3-tert-butoxy butyl acetate; Glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, tripropylene glycol diacetate, butyl acetate and the like.

Examples of the dibasic acid dimethyl ester include esters represented by CH ₃ OCO — (— CH ₂ —) _n —COOCH ₃ (n = 2 to 4). Specific examples of such esters include dimethyl glutarate, dimethyl adipate, and dimethyl succinate. Moreover, you may mix these 2 or more types. A mixture of dimethyl glutarate, dimethyl adipate, and dimethyl succinate can also be obtained from the market as Rhodia Solve RPDE (manufactured by Rhodia Nikka Co., Ltd.).

Among these organic solvents, propylene glycol diacetate, propylene glycol monoethyl ether acetate, dibasic acid dimethyl ester, and ethylene glycol dibutyl ether are preferable, and propylene glycol diacetate, propylene glycol monoethyl ether acetate, and rhodia are more preferable. Solv RPDE, ethylene glycol dibutyl ether. This is because of compatibility with the component (b). Component (b) has the property of absorbing organic solvents and resins and swelling them little by little. For this reason, depending on the selection of the organic solvent, it becomes a liquid crystal sealant with poor storage stability. Organic solvents such as propylene glycol diacetate, propylene glycol monoethyl ether acetate, rhodiasolve RPDE, and ethylene glycol dibutyl ether have sufficient ability to dissolve component (a), component (c), etc., but component (b) It is inferior in compatibility with. Therefore, insufficient dissolution of the resin component does not cause insoluble components to precipitate or cause layer separation, and the component (b) is swollen during storage, and properties such as the viscosity of the liquid crystal sealant are improved. There is no change.
The boiling point of the organic solvent is preferably in the range of 150 to 230 ° C. When the boiling point is lower than 150 ° C., the increase in viscosity during screen printing of the liquid crystal sealant is large and the use time is shortened. When the boiling point is higher than 230 ° C., the solvent does not volatilize when the solvent is dried, and air bubbles are caught in the liquid crystal sealant after the main curing, or the cured physical properties are deteriorated.

  The amount of the organic solvent used can be any amount necessary to adjust the viscosity (for example, 15 to 60 Pa · s (25 ° C.)) that the liquid crystal sealing agent can be applied by a method such as dispensing or screen printing. Usually, it uses so that the non-volatile component in a liquid-crystal sealing compound may be 70 mass% or more, Preferably it is 85-95 mass%.

  The liquid crystal sealant of the present invention has a property that the gel time at 150 ° C. is 50 seconds or more and 200 seconds or less. When the gel time at 150 ° C. is longer than 200 seconds, the liquid crystal sealant cures slowly, so that the liquid crystal sealant leaks due to the difference between the internal pressure and the external pressure of the liquid crystal sealant during heat press, or the seal width due to capillary action. Inconveniences such as being disturbed are likely to occur. Conversely, if it is shorter than 50 seconds, the storage stability of the liquid crystal sealant itself is affected. A more preferable gel time is 70 seconds or more and 200 seconds or less, still more preferably 100 seconds or more and 200 seconds or less, and particularly preferably 100 seconds or more and 150 seconds or less. In the present specification, gel time means an automatic gelling tester (manufactured by Iyo Denshi), a measurement temperature of 150 ° C., a 0.4 mL liquid crystal sealant placed in a measurement part, and an attached Teflon (registered) It is defined as the time until the torque sensor detects a torque of 70 gcm by rotating the needle made by the trademark) at 100 rpm and stirring the liquid crystal sealant.

  The liquid crystal sealing agent of the present invention may further contain a curing accelerator as a component (e) for the purpose of improving thermal reactivity. Examples of the curing accelerator (e) used in the present invention include imidazoles; imidazoles, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, oxalic acid, and the like. Salts with polyvalent carboxylic acids; amides such as dicyandiamide; salts of the amides with phenols, the above polyvalent carboxylic acids or phosphinic acids; 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as -7; salts of the diaza compounds with phenols, the above polyvalent carboxylic acids, or phosphinic acids; phosphines such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate; 2,4,6-tris Phenols such as aminomethylphenol; amine adducts and the like. Specifically, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2 -Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-methylimidazo) (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole and the like.

  Among these curing accelerators, preferred are salts of imidazoles and polyvalent carboxylic acids, and amine adducts. Particularly preferred is 2,4-diamino-6- [2′-methylimidazolyl- (1 ′). ] -Ethyl-s-triazine isocyanuric acid adduct, epoxy resin amine adduct. Since these curing accelerators are difficult to dissolve in solvents and have high potential, the pot life of the liquid crystal sealing agent is long, and further, when heated at 100 ° C. or higher, it cures quickly. This is because the liquid crystal sealant is prevented from leaking due to the stress due to the difference between the external pressure and the external pressure. These compounds can be obtained from the market as MY-H (manufactured by Ajinomoto Fine Techno Co., Ltd.) and 2MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd.). As for the addition amount of a hardening accelerator, 0.5-20 mass parts is preferable with respect to 100 mass parts of epoxy resins, More preferably, it is 1-18 mass parts.

  These curing accelerators are preferably used in the form of latent curing accelerators because they have advantages such as improved workability (extension of pot life). Latent curing accelerators are solid at room temperature and have the property of dissolving when heated and reacting as curing accelerators for the first time. For example, microcapsule-type curing accelerators in which these curing accelerators are made into microcapsules And a solid dispersion type curing accelerator (for example, imidazoles) which is difficult to dissolve in a solvent or an epoxy resin, and an amine adduct.

  Among these curing accelerators, the average particle size of the solid dispersion type latent curing accelerator is preferably 6 μm or less, more preferably 4 μm or less, and even more preferably about 3 μm or less as measured by a laser method. When a latent curing accelerator having an average particle size of more than 6 μm is used, it is difficult to apply the dispenser, and the shape after application is not uniform, and therefore the seal shape after sealing is not uniform. Moreover, the rough coarseness of a filler is confirmed in the seal | sticker part after sealing of the liquid-crystal sealing compound which uses a hardening accelerator with an average particle diameter larger than 6 micrometers.

  The liquid crystal sealant of the present invention may contain a coupling agent as the component (f) for the purpose of further improving the adhesive strength. Examples of the 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-aminopropylmethyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-ku Silane coupling agents such as ropropylmethyldimethoxysilane and 3-chloropropyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetra Titanium coupling agents such as isopropyldi (dioctylphosphite) titanate and neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neo Alkoxy zirconate, neoalkoxy tris neodecanoyl zirconate, neoalkoxy tris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxy tris (eth Zirconium-based coupling agents such as N-diaminoethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate; aluminum-based coupling agents such as Al-acetylacetonate, Al-methacrylate, Al-propionate; etc. Of these, silane coupling agents are preferred, and epoxy silane coupling agents are more preferred. 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. Specifically, Sila Ace S-510 (manufactured by Chisso Corporation) is available from the market.

  In the liquid crystal sealant of the present invention, the component (g) inorganic filler can be used to improve adhesive strength and moisture resistance reliability. As this (g) inorganic filler, fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide , Aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably fused silica, crystalline silica, Silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, more preferably fused silica, crystalline silica, aluminum Na, talc. Two or more of these inorganic fillers may be mixed and used. If the average particle size is too large, it becomes a cause of defects such as inability to form a gap when the upper and lower glass substrates are bonded together when manufacturing a narrow gap liquid crystal cell. Therefore, 3 μm or less is appropriate, and preferably 2 μm or less. . The particle size can be measured by a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).

  The content in the liquid crystal sealant of the component (g) inorganic filler that can be used in the liquid crystal sealant of the present invention is usually 10 to 60 parts by mass, when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass, Preferably it is 20-50 mass parts. When the content of the inorganic filler is less than 10 parts by mass, the adhesion strength to the glass substrate is lowered, and the moisture resistance reliability is inferior. On the other hand, when the content of the inorganic filler is more than 60 parts by mass, the liquid crystal cell may not be able to form a gap due to being hardly crushed.

  The liquid crystal sealant of the present invention may further contain additives such as organic fillers, pigments, leveling agents, and antifoaming agents as necessary.

  An example of a method for obtaining the liquid crystal sealant of the present invention is the following method. First, component (a), component (c), and component (d) are dissolved and mixed, and if necessary, component (f), component (g), organic filler, antifoaming agent, leveling agent, etc. are added thereto. , Uniformly mixed with a known mixing device, for example, a three roll, sand mill, ball mill, etc., and then component (b) and component (e) are added and mixed uniformly with a three roll or planetary mixer. The liquid crystal sealing agent of the present invention can be produced by filtering with a mesh.

  The liquid crystal display cell of the present invention is a cell in which a pair of substrates having predetermined electrodes formed on a substrate are arranged opposite to each other at a predetermined interval, the periphery is sealed with the liquid crystal sealant of the present invention, and the liquid crystal is sealed in the gap. is there. The kind of liquid crystal to be sealed is not particularly limited. Here, the substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicon, etc. and having light transmission properties. As a manufacturing method thereof, after adding a spacer (gap control material) such as glass fiber to the liquid crystal sealant of the present invention, the liquid crystal sealant was applied to one of the pair of substrates using a dispenser, a screen printing apparatus or the like. Then, temporary hardening is performed for 3 to 30 minutes at the temperature of 80-120 degreeC as needed. Thereafter, the other glass substrate is overlaid and a gap is formed while heating. After forming the gap, an empty cell can be obtained by curing at 100 to 180 ° C. for 30 minutes to 3 hours. The liquid crystal display cell of the present invention can be obtained by injecting liquid crystal in a vacuum from a break (injection port) of the liquid crystal sealant provided in advance in this empty cell. The liquid crystal display cell of the present invention thus obtained is excellent in adhesiveness and flexibility, and is extremely resistant to impacts such as dropping. It is also excellent in moisture resistance reliability. Examples of the spacer include glass fiber, silica beads, and polymer beads. The diameter varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount used is usually 0.1 to 4 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.

  The liquid crystal sealant of the present invention is very excellent in workability. That is, the coating workability by dispensing, screen printing, etc. is good, and it is easily used because it quickly rises to a certain viscosity during preliminary overheating and then stabilizes. Furthermore, since the contact with the counter substrate is excellent, the substrates do not peel off during transportation, and the thermosetting property is very good, and the substrate is cured quickly in the heating step. Therefore, the uncured component does not remain, and the elution of the constituent components into the liquid crystal is extremely small, so that display defects of the liquid crystal display cell can be reduced. Furthermore, since the cured product is excellent in various cured product characteristics such as adhesive strength, heat resistance, and moisture resistance, it is possible to produce a liquid crystal display cell with excellent reliability by using the liquid crystal sealant of the present invention. is there. In addition, the liquid crystal display cell prepared using the liquid crystal sealant of the present invention satisfies the characteristics required for a liquid crystal display cell having a high voltage holding ratio and a low ion density.

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

[Preparation of liquid crystal sealant]
Each resin component (component (a), component (c)) and organic solvent (component (d)) were mixed and dissolved by heating in the proportions shown in Table 1 below. After cooling to room temperature, a coupling agent (component (f), inorganic filler (component (g))) or the like is added as necessary, and an acrylic polymer having a core-shell structure (component (b)), if necessary Then, a curing accelerator (component (e)) was added, mixed uniformly with three rolls and filtered through a metal mesh to prepare liquid crystal sealants of Examples 1 to 8 and Comparative Examples 1 to 4.

[Geltime]
Using an automatic gelation tester (manufactured by Iyo Denshi), in a measurement temperature of 150 ° C. atmosphere, 0.4 mL of the prepared liquid crystal sealant is put in the measurement part, and the attached Teflon (registered trademark) needle is rotated at 100 rpm. The time until the torque sensor detected a torque of 70 gcm was defined as the gel time. The results are shown in Table 1.

[Viscosity measurement]
The viscosity at 25 ° C. and 10 rpm was measured with an E-type viscometer (VISCONIC EHD type, cone 3 ° × R14: manufactured by Tokyo Seiki Co., Ltd.). The results are shown in Table 1.

[Thixo ratio]
Viscosity of 10 rpm and 1 rpm at 25 ° C. was measured with an E-type viscometer (VISCONIC EHD type, cone 3 ° × R14: manufactured by Tokyo Seiki Co., Ltd.). did. The results are shown in Table 1.

[Storage stability test]
The liquid crystal sealant thus prepared was stored in an atmosphere of 25 ° C. for 48 hours, and the viscosity at 25 ° C. and 10 rpm was measured with an E-type viscometer (VISCONIC EHD type, cone 3 ° × R14: manufactured by Tokyo Seiki Co., Ltd.). The increase in viscosity from the viscosity was calculated and used as the rate of increase after 48 hours. The calculation formula was {(viscosity after 48 hours−initial viscosity) / (initial viscosity)} × 100. The results are shown in Table 1.

[Adhesion test]
A liquid crystal sealant obtained by adding 1% by mass of 5 μm glass fiber (PF-50S: manufactured by Nippon Electric Glass Co., Ltd.) to a cleaned glass substrate with an ITO film of 1.5 cm × 3 cm with respect to the liquid crystal sealant is 5 μm. It apply | coated so that the diameter when crushing to thickness might be set to 0.8-1.2 mm. Pre-heat for 10 minutes on a hot plate set at 90 ° C, and use a glass substrate with an ITO film of 1.5 cm x 3 cm as a counter substrate in a cross shape so that the ITO surface side is the liquid crystal sealant side Bonding, binder clip No. At 155 (manufactured by Lion Office Equipment), two places were fixed and the substrate was fixed. This test piece was put into an electric dryer set at 150 ° C. and cooled to room temperature. The strength in the tensile direction was measured at a speed of 3.3 mm / sec in a tensile mode of a bond tester (SS-30WD: manufactured by Seishin Shoji). The strength was converted to the unit area of the seal and used as the adhesive strength. The criteria for evaluation are as follows. The results are shown in Table 1.
○: Adhesive strength is 16 MPa or more Δ ... Adhesive strength is 10 MPa or more and less than 16 MPa x ... Adhesive strength is less than 10 MPa

[Moisture resistance test]
A test piece was prepared in the same procedure as in the above [Adhesion test]. Thereafter, the sample was placed in a constant temperature and humidity chamber (HPAV-80-20: manufactured by Isuzu Seisakusho) set at 60 ° C. and 90% for 12 hours and then cooled at room temperature to obtain a test specimen for measurement. The strength in the tensile direction was measured at a speed of 3.3 mm / sec in the tensile mode of a bond tester (SS-30WD manufactured by Seishin Shoji). The strength was converted to the unit area of the seal and defined as the moisture-resistant adhesive strength. The criteria for evaluation are as follows. The results are shown in Table 1.
○: Moisture-resistant adhesive strength is 16 MPa or more Δ ... Moisture-resistant adhesive strength is 10 MPa or more and less than 16 MPa x ... Moisture-resistant adhesive strength is less than 10 MPa

[Contact to counter substrate]
A liquid crystal sealant is applied on a 5 cm × 5 cm glass substrate in a pattern with an injection port so that the cross-sectional area is 5000 μm ² with a dispenser, and solvent drying (precure) is performed for 10 minutes with an electric dryer set at 90 ° C. It was. After cooling the substrate to a room temperature atmosphere, a 5 cm × 5 cm counter glass substrate was overlaid, a 10 kg weight was placed for 30 seconds, the crushability of the liquid crystal sealant was observed with an optical microscope, and the width of the liquid crystal sealant was measured. The measurement is performed from two directions of the glass substrate side coated with the liquid crystal sealant and the counter substrate, and by comparing the width of the liquid crystal sealant on the side coated with the liquid crystal sealant and the width of the liquid crystal sealant on the counter substrate side, The degree of collapse was evaluated. The criteria for evaluation are as follows. The results are shown in Table 1.
A: The width of the counter glass substrate is 70% or more of the width of the substrate coated with the liquid crystal sealant. B: The width of the counter glass substrate is 40% or more and less than 70% of the width of the substrate coated with the liquid crystal sealant. ... the width of the counter glass substrate is 10% or more and less than 40% of the width of the substrate coated with the liquid crystal sealant x ... the width of the counter glass substrate is less than 10% of the width of the substrate coated with the liquid crystal sealant or not at all Not touching

[Leaking property test of liquid crystal sealant components after pressing]
A liquid crystal sealant is applied on a 5 cm × 5 cm glass substrate in a pattern with an injection port so that the cross-sectional area is 5000 μm ² with a dispenser, and solvent drying (precure) is performed for 10 minutes with an electric dryer set at 90 ° C. It was. After cooling the substrate to the room temperature atmosphere, a 5 cm × 5 cm counter glass substrate was overlaid, and the four sides were bonded with a binder clip no. 155 (manufactured by Lion Office Equipment) and put in an electric dryer set at 150 ° C. for 60 minutes. After cooling the substrate to room temperature, the state of the liquid crystal sealant on the substrate was observed with an optical microscope. In this test, the presence or absence of the resin component leaching (presence or absence of phase separation between the resin component and the filler component) is confirmed from the influence of curability and the like. The criteria for evaluation are as follows. The results are shown in Table 1.
○: No resin component exudation ×: Resin component exudation

[Printability test]
The prepared liquid crystal sealant was printed and applied to a glass substrate with a screen printer (LS-150: manufactured by Neurong Precision Industrial Co., Ltd.). This was confirmed visually. The presence or absence of fading, breakage of the liquid crystal sealant, etc. was observed. The criteria for evaluation are as follows. The results are shown in Table 1.
○ ... Fuzzy, no cut × ... Fuzzy, cut

[Dispensing test]
The prepared liquid crystal sealant was filled and defoamed in a syringe, and then applied onto a glass substrate at 30 mm / sec with a dispenser (Shot Master 300: manufactured by Musashi Engineering Co., Ltd.), and the shape was visually confirmed. The presence or absence of fading, breakage of the liquid crystal sealant, etc. was observed. The criteria for evaluation are as follows. The results are shown in Table 1.
○ ... Fuzzy, no cut × ... Fuzzy, cut

[Specific resistance measurement test]
After applying about 100 mg of the liquid crystal sealant prepared on the bottom of the 10 mL sample bottle uniformly, solvent drying (precure) was performed for 10 minutes with an electric dryer set at 90 ° C. Thereafter, it was cured for 60 minutes with an electric dryer set at 150 ° C. After cooling to room temperature, liquid crystal (MLC-6866-100: manufactured by Merck & Co., Inc.) was added 10 times the amount of liquid crystal sealant. After heating for 24 hours in an electric dryer set at 90 ° C., the mixture was cooled for 30 minutes. Each supernatant was separated by decantation, and the specific resistance value was measured with a digital ultrahigh resistance meter (R8340: manufactured by Advantest Corporation). The criteria for evaluation are as follows. The results are shown in Table 1.
○ ・ ・ ・ Specific resistance value is 1.0 × 10E + 12 or more × ・ ・ ・ Specific resistance value is less than 1.0 × 10E + 12 Note that the specific resistance value “1.0E + 12” represents “1.0 × 10 ¹² ”. The same applies to other descriptions.

[Water absorption rate]
The liquid crystal sealant prepared on a 5 cm × 7 cm glass substrate was applied using an applicator having a clearance of 25 μm. Solvent drying was performed for 10 minutes with an electric dryer set at 90 ° C., and cured for 60 minutes with an electric dryer set at 150 ° C. Calculate the water absorption rate from the weight change between the liquid crystal sealant that was cooled to room temperature and the liquid crystal sealant immediately after curing after being put in a constant temperature and humidity chamber (HPAV-80-20: Isuzu Seisakusho) set at 60 ° C and 90% for 24 hours. did. The calculation formula was {(weight of sealant after water absorption−weight of sealant before water absorption) / (weight of sealant before water absorption)} × 100. The results are shown in Table 1.

From the results shown in Table 1, the liquid crystal sealant of the present invention was excellent in printability, dispensing property, and contact property to the counter substrate, and was excellent in workability when manufacturing a liquid crystal panel. In addition, the seal shape was not disturbed after bonding and pressing, and showed excellent values for adhesion, moisture-proof adhesion, and liquid crystal contamination. On the other hand, as for the comparative example, even if it is excellent in printability and dispensing property, the contact property to the counter substrate is poor, the workability is good but the adhesiveness is poor, or the bleeding occurs after pressing. was there.
Therefore, it can be said that the liquid crystal sealant of the present invention is a highly reliable sealant with no problem in workability throughout the process.

  The liquid crystal sealant of the present invention is excellent in coating workability, contact property to the counter substrate, viscosity stability after preliminary overheating, and extremely excellent in adhesive strength and flexibility after curing. Therefore, a highly reliable liquid crystal display cell can be easily manufactured.

Claims (12)

  (A) A solid phenol novolak resin having a softening point of 75 ° C. or less, (b) an acrylic polymer having a core-shell structure, (c) an epoxy resin, and (d) an organic solvent, and having a gel time at 150 ° C. of 50 seconds Liquid crystal sealant that is 200 seconds or longer.   The liquid crystal sealant according to claim 1, wherein the core layer of the component (b) is a polymer of n-butyl acrylate, and the shell layer is a polymer of methyl methacrylate.   The component (d) is one or more organic solvents selected from the group consisting of propylene glycol diacetate, dibasic acid dimethyl ester, propylene glycol monoethyl ether acetate, and ethylene glycol dibutyl ether. Liquid crystal sealing agent as described in 2. The liquid crystal sealant according to any one of claims 1 to 3, wherein the component (a) is a compound represented by the following formula (1).

(In the formula, R ⁵ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and r represents an integer of 1 to 3. When r is 2 or 3, each R ⁵ is the same. And s is 0 or a positive integer.)   5. The liquid crystal sealant according to claim 1, wherein an equivalent of the hydroxyl group of the component (a) is 0.2 to 1.4 chemical equivalents relative to 1 equivalent of the epoxy group of the component (c).   The liquid crystal sealant according to any one of claims 1 to 5, wherein the component (c) is a bisphenol A type epoxy resin.   Furthermore, the liquid-crystal sealing compound as described in any one of Claims 1 thru | or 6 containing (e) hardening accelerator.   The component (e) is at least one selected from 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct and an epoxy resin amine adduct. The liquid crystal sealing agent according to claim 7.   Furthermore, the liquid-crystal sealing compound as described in any one of Claims 1 thru | or 8 containing a coupling agent (f).   The liquid crystal sealant according to claim 9, wherein the component (f) is an epoxy silane coupling agent.   Furthermore, the liquid-crystal sealing compound as described in any one of Claims 1 thru | or 10 containing (g) inorganic filler.   The liquid crystal display cell sealed with the hardened | cured material obtained by hardening | curing the liquid-crystal sealing compound as described in any one of Claims 1 thru | or 11.