KR102436297B1 - Liquid crystal sealing agent and liquid crystal display cell using the same, and manufacturing method for liquid crystal display cell - Google Patents

Abstract

(Project) This invention can be applied also to a flexible display and a curved display, Furthermore, also in general characteristics, such as low liquid-crystal contamination property and adhesive strength, the liquid crystal sealing compound for liquid crystal dropping methods excellent, and the liquid crystal display excellent in reliability to suggest a cell.
(Solution) Liquid crystal sealing agent for liquid crystal dropping methods containing at least one type of compound having a urethane bond in the molecule (A), the glass transition temperature measured by the DMA method of the cured product is 90° C. or less, and tan δ is 0.5 or more to be.

Description

A liquid crystal sealing compound, the liquid crystal display cell using the same, and the manufacturing method of a liquid crystal display cell TECHNICAL FIELD

This invention relates to the liquid crystal sealing compound used for the liquid crystal dropping method, More specifically, it can apply also to a flexible display and a curved display, Furthermore, general, such as low liquid-crystal contamination property and adhesive strength It is related with the liquid crystal sealing compound for liquid crystal dropping methods excellent also in a characteristic.

With the recent enlargement of a liquid crystal display cell, as a manufacturing method of a liquid crystal display cell, the so-called liquid crystal dropping method with higher mass productivity was proposed (refer patent document 1, patent document 2). It is the manufacturing method of the liquid crystal display cell by which a liquid crystal is sealed by bonding the other board|substrate after a liquid crystal is specifically, dripped inside the weir of the liquid crystal sealing compound formed in one board|substrate.

However, in the liquid crystal dropping method, since the liquid crystal sealing agent of a non-hardened state contacts a liquid crystal, at that time, the component of liquid crystal sealing agent melt|dissolves (elutes) in a liquid crystal, the resistance value of a liquid crystal is reduced, and the display defect of the sealing vicinity is produced There is a problem with doing it.

In order to solve this subject, the thing of the photothermal combination type is used as liquid crystal sealing compound for liquid crystal dropping methods, and it is put to practical use now (patent documents 3, 4). In the liquid crystal dropping method using this liquid crystal sealing compound, after irradiating light to the liquid crystal sealing compound pinched|interposed on a board|substrate and making it primary harden, it heats and makes secondary hardening, It is characterized by the above-mentioned. According to this method, a non-hardened liquid crystal sealing compound can be hardened|cured rapidly by light, and it is possible to suppress melt|dissolution (elution) to the liquid crystal of a liquid crystal sealing compound component. In addition, the problem of insufficient adhesive strength due to curing shrinkage during photocuring alone occurs with light curing alone, but in the case of the light and heat combined type, a stress relaxation effect is obtained by secondary curing by heating, and such a problem can be solved. has the advantage of being

When the liquid crystal sealing compound for liquid crystal dropping methods of this photothermal curing type was put to practical use, the liquid crystal dropping method became the construction method generally used.

Moreover, in the field of a liquid crystal display, development of the display which has a flexible display and a curved shape is progressing in recent years. As for the board|substrate used for such a display, a flexible thing like a plastic film is used instead of the conventional rigid thing like glass (patent document 5).

From such a background, also about the liquid crystal sealing compound for liquid crystal dropping methods, following the curvature of a board|substrate, that is, after hardening, the property of being flexible is still calculated|required.

Conventionally, development of the liquid crystal sealing compound for liquid crystal dropping methods which has a softness|flexibility from a viewpoint of an adhesive strength improvement has been performed (patent document 6). However, the liquid crystal sealing compound for liquid crystal dropping methods provided with the sufficient performance for adapting to the said flexible board|substrate is not yet implement|achieved.

Japanese Laid-Open Patent Publication No. 63-179323 Japanese Laid-Open Patent Publication No. 10-239694 Japanese Patent Publication No. 3583326 Japanese Laid-Open Patent Publication No. 2004-61925 Japanese Laid-Open Patent Publication No. 2012-238005 Japanese Laid-Open Patent Publication No. 2016-24240

This invention is applicable also to a flexible display and a curved display, Furthermore, also in general characteristics, such as low liquid-crystal contamination property and adhesive strength, the liquid crystal sealing compound for liquid crystal dropping methods excellent.

The present inventors have a specific relationship with the glass transition temperature and tan δ measured by the DMA method and containing the compound having a urethane bond in the molecule, which is a specific component, flexibility after curing of the liquid crystal sealing agent for liquid crystal dropping method , and discovered that sufficient adhesive strength was realized even in a flexible display or a curved display, leading to the present invention.

That is, the present invention relates to the following 1) to 15).

In addition, in this specification, when it describes as "(meth)acryl", it shall mean "acryl" and/or "methacryl." In addition, "liquid crystal sealing compound for liquid crystal dropping methods" may be simply described as "liquid crystal sealing compound."

Also, the superscript RTM means a registered trademark.

1) The liquid crystal sealing compound for liquid crystal dropping methods containing the compound which has a urethane bond in at least 1 type (A) molecule|numerator, the glass transition temperature measured by the DMA method of hardened|cured material is 90 degrees C or less, and tanδ is 0.5 or more.

2) Liquid crystal sealing compound for liquid crystal dropping methods as described in said 1) whose weight average molecular weight of the said component (A) is 1000 or more.

3) Liquid crystal sealing compound for liquid crystal dropping methods as described in said 1) or 2) whose said component (A) is a compound which has 3 or more ester bonds in a molecule|numerator.

4) Further, (B) Liquid crystal sealing compound for liquid crystal dropping methods in any one of said 1) - 3) containing a thermal radical polymerization initiator.

5) Furthermore, (C) Liquid crystal sealing compound for liquid crystal dropping methods in any one of said 1)-4) containing a (meth)acryl compound.

6) Further, (D) Liquid crystal sealing compound for liquid crystal dropping methods in any one of said 1)-5) containing organic filler.

7) The liquid crystal for liquid crystal dropping method according to 6), wherein the component (D) is one or two or more organic fillers selected from the group consisting of urethane microparticles, acrylic resin microparticles, polystyrene microparticles, styrene olefin copolymer microparticles and silicone microparticles. sealant.

8) Further (E) Liquid crystal sealing compound for liquid crystal dropping methods in any one of said 1)-7) containing an inorganic filler.

9) Further, (F) Liquid crystal sealing compound for liquid crystal dropping methods in any one of said 1)-8) containing a silane coupling agent.

10) Furthermore (G) Liquid crystal sealing compound for liquid crystal dropping methods in any one of said 1)-9) containing an epoxy compound.

11) Furthermore, (H) Liquid crystal sealing compound for liquid crystal dropping methods in any one of said 1)-10) containing a thermosetting agent.

12) Liquid crystal sealing compound for liquid crystal dropping methods as described in said 11) whose said component (H) is an organic acid hydrazide compound.

13) Furthermore, (I) Liquid crystal sealing compound for liquid crystal dropping methods in any one of said 1)-12) containing radical photopolymerization initiator.

14) The liquid crystal display cell comprised by the board|substrate of 2 sheets WHEREIN: After dripping a liquid crystal inside the beam of the liquid crystal sealing compound for liquid crystal dropping methods in any one of said 1) thru|or 13) formed in one board|substrate , The other board|substrate is joined, and it hardens|cures by heat after that, The manufacturing method of the liquid crystal display cell characterized by the above-mentioned.

15) The liquid crystal display cell sealed with the hardened|cured material obtained by hardening|curing the liquid crystal sealing compound in any one of said 1)-13).

This invention is applicable also to a flexible display and a curved display, Furthermore, also in general characteristics, such as low liquid-crystal contamination property and adhesive strength, the liquid crystal sealing compound for liquid crystal dropping methods excellent.

(Form for implementing the invention)

[(A) a compound having a urethane bond in the molecule]

This invention contains (A) the compound which has a urethane bond in a molecule|numerator.

The urethane bond (-NH·CO·O-) is a functional group that contributes to the flexibility of the cured product, and can be obtained by addition reaction of a compound having an isocyanate group (-NCO) and a compound having a hydroxyl group (-OH). Further, in order to obtain a compound having a larger molecular weight and more flexibility, a dihydroxy compound may be used.

As a compound which has an isocyanate group, the compound which has a hydroxyl group, and a dihydroxy compound, the compound illustrated below is mentioned, for example.

(Compound having an isocyanate group)

As a compound which has an isocyanate group, the following diisocyanate compounds are suitable.

Chain saturated hydrocarbon isocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate; Cyclic saturated hydrocarbon isocyanate, 2,4-tolylene diisocyanate, such as dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated toluene diisocyanate , 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, 1,5-naphthalenedi Aromatic polyisocyanates, such as an isocyanate.

(Compound having a hydroxyl group)

As a compound which has a hydroxyl group, the following compounds are mentioned.

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylic rate, pentaerythritol tri(meth)acrylate, ε-caprolactone adduct of 2-hydroxyethyl(meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate.

Moreover, as a dihydroxy compound used in order to increase molecular weight, the following are mentioned, for example.

Polyetherdiol, polyesterdiol, polycaprolactonediol, polycarbonate diol.

Moreover, a component (A) can be obtained from a market as KAYARAD UX-3204, UX-4101, UX-0937 (made by Nippon Kayaku Co., Ltd.).

A component (A) can be obtained by synthesize|combining by a conventional method using the said dihydroxy compound, the compound which has an isocyanate group, and hydroxyl-group containing (meth)acrylate, for example. That is, for example, a reaction product (I) is obtained by adding a dihydroxy compound and a compound having an isocyanate group, and then a urethane (meth)acrylate is obtained by adding a hydroxyl group-containing (meth)acrylate to the reaction product (I). is obtained

As a component (A), the case where a weight average molecular weight is 1000 or more is preferable. A weight average molecular weight can be calculated|required by gel permeation chromatography (GPC) etc., for example.

The more preferable weight average molecular weights of a component (A) are 2000 or more and 15000 or less, and the especially preferable range is 2500 or more and 10000 or less.

It is preferable that the component (A) further has 3 or more ester bonds (-C(=O)O-) in the molecule. Although the ester bond also contributes to flexibility similarly to a urethane bond, higher flexibility can be provided by using together with a urethane bond.

The number of ester bonds in the molecule|numerator of a component (A) becomes like this. More preferably, it is 4 or more, Especially preferably, it is 5 or more. Although there is no upper limit in particular, about 10 or more and 175 or less are preferable from the relationship with the said molecular weight.

Such a component (A) can be obtained by using polyesterdiol, polycaprolactonediol, etc. in the said dihydroxy compound, for example. Moreover, it is available as KAYARAD UX-3204 (Nippon Kayaku Co., Ltd.) and KAYARAD UX-4101 (Nippon Kayaku Co., Ltd.) in a market.

As content of a component (A), it is preferable in the total amount of liquid crystal sealing agent that it is 10-80 mass %, More preferably, it is 20-70 mass %, and 25-60 mass % is especially preferable.

[Glass transition temperature of cured product]

The glass transition temperature of the hardened|cured material of the liquid crystal sealing compound of this invention measured by the DMA method is 90 degrees C or less. When the glass transition temperature is low, the followability to a flexible substrate is added. In addition, the measurement conditions of DMA use, for example, a dynamic viscoelasticity measuring apparatus (DMS-6100: manufactured by SI Nanotechnology Co., Ltd.), and measure under the conditions of a frequency of 10 Hz and a temperature increase temperature of 2 degree-C/min in tension mode. . The loss coefficient tanδ is obtained from the ratio of the loss elastic modulus to the storage elastic modulus (JIS K 7244-1). Let the temperature at which the obtained loss coefficient tan-delta becomes a maximum value be a glass transition temperature.

It is difficult to achieve a glass transition temperature of 90° C. or lower only by adding the component (A), and various methods such as addition of a monofunctional compound, addition of an organic filler having flexibility, and modification of a reactive compound with a flexible bonding group, etc. method can be used.

The more preferable range of the said glass transition temperature is 85 degrees C or less, Especially preferably, it is 80 degrees C or less. Although there is no restriction|limiting in particular as a lower limit, About 0 degreeC may be sufficient.

[tanδ of cured product]

As for the hardened|cured material of the liquid crystal sealing compound of this invention, glass tan-delta measured by the DMA method is 0.5 or more. When tan-delta is 0.5 or more, the followability|trackability to a flexible board|substrate is added.

The more preferable range of the said tan-delta is 0.55 or more, Especially preferably, it is 0.57 or more. Although there is no restriction|limiting in particular as an upper limit, About 1.0 may be sufficient.

[(B) Thermal radical polymerization initiator]

The liquid crystal sealing compound of this invention may contain a thermal radical polymerization initiator as a component (B). Although the said thermal radical polymerization initiator will not be specifically limited if it is a compound which generates radicals by heating and initiates a chain polymerization reaction, An organic peroxide, an azo compound, a benzoin compound, a benzoin ether compound, an acetophenone compound, benzopinacol etc. are mentioned, Benzo pinacol is used suitably. For example, as an organic peroxide, Kayamek ^RTM A, M, R, L, LH, SP-30C, Percadox CH-50L, BC-FF, Cardox B-40ES, Percadox 14, Trigonox ^RTM 22- 70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester ^RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl ^RTM B, Percadox 16, Kayacarbon ^RTM BIC-75, AIC-75 (manufactured by Kayaqua Aqua Co., Ltd.), Permec ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC, TMH, C, V, 22, MC, Percure ^RTM AH, AL, HB, Perbutyl ^RTM H, C, ND, L, Percumyl ^RTM H, D, Peroyl ^RTM IB, IPP, Perocta ^RTM ND (Nichiyu Corporation) Manufacture) etc. are available as a commercial item. Moreover, as an azo compound, VA-044, V-070, VPE-0201, VSP-1001 (made by Wako Pure Chemical Industries, Ltd.) etc. are available as a commercial item. In addition, in this specification, the superscript RTM means a registered trademark.

Preferred as component (B) are thermal radical polymerization initiators which do not have an oxygen-oxygen bond (-O-O-) or a nitrogen-nitrogen bond (-N=N-) in the molecule. Since the thermal radical polymerization initiator having an oxygen-oxygen bond (-O-O-) or a nitrogen-nitrogen bond (-N=N-) in a molecule emits a large amount of oxygen or nitrogen at the time of radical generation, bubbles in the liquid crystal sealing agent It hardens in the state left behind, and there exists a possibility of reducing characteristics, such as adhesive strength. A benzo pinacol-based thermal radical polymerization initiator (including chemically modified benzo pinacol) is particularly suitable. Specifically, benzo pinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2-tetraphenylethane, 1,2- Diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1 ,2,2-tetra(4-methoxyphenyl)ethane, 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(triethylsiloxy)- 1,1,2,2-tetraphenylethane, 1,2-bis(t-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1 ,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1 ,1,2,2-tetraphenylethane, etc. are mentioned, Preferably 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tri Ethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1,1,2,2-tetraphenylethane, 1,2-bis(trimethylsilox) Si)-1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1,2-bis(trimethyl Siloxy)-1,1,2,2-tetraphenylethane, particularly preferably 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane.

The benzo pinacol is commercially available from Tokyo Kasei Kogyo Co., Ltd., Wako Junyaku Co., Ltd., and the like. In addition, etherification of the hydroxyl group of benzo pinacol can be synthesize|combined easily by a well-known method. In addition, silyl etherification of the hydroxyl group of benzo pinacol can be obtained by synthesizing the corresponding benzo pinacol and various silylating agents in the presence of a basic catalyst such as pyridine. Examples of the silylating agent include trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), which are commonly known trimethylsilylating agents, and triethylsilylating agents. Examples of the triethylchlorosilane (TECS) and t-butyl dimethyl silylating agent include t-butylmethylsilane (TBMS). These reagents can be easily obtained from markets such as silicone derivative manufacturers. The reaction amount of the silylating agent is preferably 1.0 to 5.0 moles per mole of the hydroxyl group of the target compound. More preferably, it is 1.5 to 3.0 times mole. When it is less than 1.0 times mole, since reaction efficiency is bad and reaction time becomes long, thermal decomposition will be accelerated|stimulated. When it is more than 5.0 times mole, separation will worsen at the time of collection|recovery, and refinement|purification will become difficult.

It is preferable that component (B) makes a particle diameter fine and disperse|distributes uniformly. If the average particle diameter is too large, 5 µm or less is preferable, since it becomes a defect factor such as inability to form a gap when bonding the upper and lower glass substrates in the production of a liquid crystal display cell with a narrow gap. Preferably it is 3 micrometers or less. In addition, although there is no problem even if it is made fine without limitation, Usually, a lower limit is about 0.1 micrometer. The particle size can be measured with a laser diffraction/scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Kikyo, Ltd.; LMS-30).

As content of a component (B), it is preferable in the total amount of liquid crystal sealing agent that it is 0.0001-10 mass %, More preferably, it is 0.0005-5 mass %, and 0.001-3 mass % is especially preferable.

[(C) (meth)acrylic compound]

The liquid crystal sealing agent of this invention may contain a (meth)acryl compound as a component (C). (Here, "(meth)acryl" means "acryl" and/or "methacryl." Hereinafter, the same) As a component (C), a (meth)acrylic ester compound, an epoxy (meth)acrylate compound, etc. are mentioned, for example.

In addition, the compound of a component (A) is not included in the (meth)acrylic compound of a component (C).

As a specific example of a (meth)acrylic ester compound, N-acryloyloxyethyl hexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acryl Rate, cyclohexane-1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl polyethoxy (meth) acrylate, 2-hydr Roxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate , isobornyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylic Rate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecanediol di(meth)acrylate , bisphenol A polyethoxydi(meth)acrylate, bisphenol A polypropoxydi(meth)acrylate, bisphenol F polyethoxydi(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di( meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripenta Erythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate, ditrimethylolpropanetetra(meth) ) acrylate, and monomers such as diacrylate of ester diacrylate of neopentyl glycol and hydroxypivalic acid, and diacrylate of ε-caprolactone adduct of ester of neopentyl glycol and hydroxypivalic acid. Preferably, N-acryloyloxyethyl hexahydrophthalimide, phenoxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate are mentioned.

An epoxy (meth)acrylate compound is obtained by a well-known method by reaction of an epoxy resin and (meth)acrylic acid. Although it does not specifically limit as an epoxy resin used as a raw material, A bifunctional or more than bifunctional epoxy resin is preferable, For example, resorcinol diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin. Resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, A glycidylamine type epoxy resin, a hydantoin type epoxy resin, an isocyanurate type epoxy resin, a phenol novolak type epoxy resin having a triphenolmethane skeleton, in addition to bifunctional phenols such as catechol and resorcinol and diglycidyl ethers, diglycidyl ethers of difunctional alcohols, and halides and hydrogenated substances thereof. Among these, a bisphenol A epoxy resin and resorcinol diglycidyl ether are preferable from a viewpoint of liquid-crystal contamination property. In addition, the ratio of an epoxy group and a (meth)acryloyl group is not limited, It selects suitably from a viewpoint of process suitability and liquid-crystal contamination property.

A component (C) may be used independently and may mix 2 or more types. Liquid crystal sealing compound of this invention WHEREIN: When using a component (C), it is 10-80 mass % normally in the total amount of liquid crystal sealing compound, Preferably it is 20-70 mass %.

[(D) organic filler]

The liquid crystal sealing compound of this invention may contain an organic filler as a component (D). As said organic filler, urethane microparticles|fine-particles, acrylic resin microparticles|fine-particles, polystyrene microparticles|fine-particles, styrene-olefin copolymer microparticles|fine-particles, and silicone microparticles|fine-particles are mentioned, for example. Moreover, as silicone microparticles|fine-particles, KMP-594, KMP-597, KMP-598 (made by Shin-Etsu Chemical Co., Ltd.), Torefil ^RTM E-5500, 9701, EP-2001 (made by Tore-Dow Corning) are preferable, and as urethane microparticles|fine-particles, JB- 800T, HB-800BK (Negami Kogyo Co., Ltd.), the polystyrene fine particles are preferably Lavalon ^RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (manufactured by Mitsubishi Chemical), and styrene olefin copolymer fine particles. As this, Septon ^RTM SEPS2004 and SEPS2063 are preferable.

These organic fillers may be used independently and may use 2 or more types together. Moreover, it is good also as a core-shell structure using 2 or more types. Among these, acrylic resin microparticles|fine-particles and silicone microparticles|fine-particles are preferable.

When using the acrylic resin fine particles, it is preferable that the acrylic rubber having a core-shell structure composed of two types of acrylic rubber is used, and particularly preferably, the core layer is n-butyl acrylate and the shell layer is methyl methacrylate. do. It is sold as Zephyr ^RTM F-351 by Aikako KK.

Moreover, as said silicone microparticles|fine-particles, organopolysiloxane crosslinked material powder, linear dimethylpolysiloxane crosslinked material powder, etc. are mentioned. Moreover, as a composite silicone rubber, the thing which coat|covered the silicone resin (for example, polyorganosilsesquioxane resin) on the surface of the said silicone rubber is mentioned. Among these fine particles, particularly preferred are silicone rubber of linear dimethylpolysiloxane crosslinked powder or composite silicone rubber fine particles of silicone resin-coated linear crosslinked dimethylpolysiloxane powder. These may be used independently and may use 2 or more types together. Further, preferably, the shape of the rubber powder is a spherical shape with little increase in viscosity after addition. Liquid crystal sealing agent of this invention WHEREIN: When using a component (D), it is 5-50 mass % normally in the total amount of liquid crystal sealing agent, Preferably it is 5-40 mass %.

[(E) Inorganic filler]

The liquid crystal sealing compound of this invention may contain an inorganic filler as a component (E). Examples of the inorganic filler contained in the present invention include 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, and hydroxide. Magnesium, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc. are mentioned, Preferably fused silica, crystalline silica, silicon nitride, boron nitride, Calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, and aluminum silicate are mentioned, but silica, alumina, and talc are more preferable. You may use these inorganic fillers in mixture of 2 or more types.

When the average particle diameter of the inorganic filler is too large, 2000 nm or less is suitable, and preferably 1000 nm, since it becomes a defect factor such as inability to form a gap at the time of bonding of the upper and lower glass substrates at the time of manufacturing a liquid crystal cell with a narrow gap. Below, more preferably, it is 300 nm or less. Moreover, a preferable minimum is about 10 nm, More preferably, it is about 100 nm. The particle diameter can be measured with a laser diffraction/scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Kikyo, Ltd.; LMS-30).

Liquid crystal sealing agent of this invention WHEREIN: When using an inorganic filler, it is 5-50 mass % normally in the total amount of liquid crystal sealing agent, Preferably it is 5-40 mass %. Since the adhesive strength with respect to a glass substrate falls and moisture-resistance reliability is also inferior when content of an inorganic filler is lower than 5 mass %, the fall of the adhesive strength after moisture absorption may also become large. Moreover, when there is more content of an inorganic filler than 50 mass %, since there is too much filler content, it may become difficult to break and gap formation of a liquid crystal cell may become impossible.

[(F) Silane Coupling Agent]

The liquid crystal sealing compound of this invention can add a silane coupling agent as a component (F), and can aim at the improvement of adhesive strength and moisture resistance.

As component (F), 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl) Ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride , 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, etc. are mentioned. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. and the like as KBM series, KBE series, and the like, they are readily available in the market. Liquid crystal sealing compound of this invention WHEREIN: When using a component (F), 0.05-3 mass % is suitable in liquid crystal sealing compound total amount.

[(G) Epoxy compound]

The liquid crystal sealing compound of this invention may contain an epoxy compound as a component (G). Although it does not specifically limit as an epoxy compound, A bifunctional or more than bifunctional epoxy compound is preferable, For example, resorcinol diglycidyl ether, bisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenolo Volac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine Epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolak type epoxy resin having triphenolmethane skeleton, diglycidyl of difunctional phenols such as catechol and resorcinol etherified substances, diglycidyl etherified substances of difunctional alcohols, halides thereof, hydrogenated substances, and the like. Among these, a bisphenol A epoxy resin and resorcinol diglycidyl ether are preferable from a viewpoint of liquid-crystal contamination property.

In addition, the compound of a component (A) is not included in the epoxy compound of a component (G).

A component (G) may be used independently and may mix 2 or more types. Liquid crystal sealing compound of this invention WHEREIN: When using a component (G), it is 5-50 mass % normally in liquid crystal sealing compound total amount, Preferably it is 5-30 mass %.

[(H) thermosetting agent]

The liquid crystal sealing compound of this invention contains a thermosetting agent as a component (H). Component (H) means a thermal curing agent that does not generate radicals by heating, unlike the component (B) thermal radical polymerization initiator. Specifically, examples of the reaction nucleophilically with a lone pair or an anion in a molecule include polyvalent amines, polyhydric phenols, and organic acid hydrazide compounds. However, the present invention is not limited thereto. Among these, an organic acid hydrazide compound is used especially suitably. For example, aromatic hydrazide terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridine dihydrazide, 1,2,4 -Benzene trihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide, etc. are mentioned. Moreover, if it is an aliphatic hydrazide compound, for example, formhydrazide, acethydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid Dihydrazide, adipic acid dihydrazide, pimeric acid dihydrazide, sebacic acid dihydrazide, 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide , iminodiacetic acid dihydrazide, N,N'-hexamethylenebis semicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3- A dihydrazide compound having a hydantoin skeleton such as bis(hydrazinocarbonoethyl)-5-isopropylhydantoin, preferably a valine hydantoin skeleton (skeleton in which the carbon atom of the hydantoin ring is substituted with an isopropyl group); Tris(1-hydrazinocarbonylmethyl)isocyanurate, tris(2-hydrazinocarbonylethyl)isocyanurate, tris(1-hydrazinocarbonylethyl)isocyanurate, tris( 3-hydrazinocarbonylpropyl)isocyanurate, bis(2-hydrazinocarbonylethyl)isocyanurate, etc. are mentioned. From the balance of curing reactivity and potential, preferably isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris(1-hydrazinocarbonylmethyl)isocyanurate, tris (1-hydrazinocarbonylethyl)isocyanurate, tris(2-hydrazinocarbonylethyl)isocyanurate, and tris(3-hydrazinocarbonylpropyl)isocyanurate, particularly preferred Preferably it is tris(2-hydrazinocarbonylethyl)isocyanurate.

A component (H) may be used independently and may mix 2 or more types. Liquid crystal sealing compound of this invention WHEREIN: When using a component (H), it is 0.1-10 mass % normally in liquid crystal sealing compound total amount, Preferably it is 1-5 mass %.

[(I) Radical Photopolymerization Initiator]

The liquid crystal sealing compound of this invention may contain an optical radical polymerization initiator as component (I). Although it will not specifically limit if it is a compound which generate|occur|produces a radical or an acid and initiates a chain polymerization reaction by irradiation of an ultraviolet-ray or visible light as an optical radical polymerization initiator, For example, For example, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone , diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1- Propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyldisulfide, etc. are mentioned. Specifically, IRGACURE ^RTM 651, 184, 2959, 127, 907, 369, 379EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE ^RTM 1173, LUCIRIN ^RTM TPO (all manufactured by BASF), Sequal ^RTM Z , BZ, BEE, BIP, BBI (all are manufactured by Seiko Chemical Co., Ltd.) and the like.

In addition, it is preferable to use what has a (meth)acryl group in a molecule|numerator from a viewpoint of liquid-crystal contamination property, for example, 2-methacryloyloxyethyl isocyanate and 1-[4-(2-hydroxyethoxy)- The reaction product of phenyl]-2-hydroxy-2-methyl-1-propan-1-one is suitably used. This compound can be prepared and obtained by the method described in International Publication No. 2006/027982.

Liquid crystal sealing compound of this invention WHEREIN: When using component (I), it is 0.001-3 mass % normally in liquid crystal sealing compound total amount, Preferably it is 0.002-2 mass %.

Additives, such as hardening accelerators, such as an organic acid and imidazole, a radical polymerization inhibitor, a pigment, a leveling agent, an antifoamer, and a solvent, can be mix|blended with the liquid crystal sealing compound of this invention as needed further.

[curing accelerator]

As said hardening accelerator, an organic acid, imidazole, etc. are mentioned.

Examples of the organic acid include organic carboxylic acid and organic phosphoric acid, but the organic carboxylic acid is preferable. Specifically, aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenonetetracarboxylic acid, and furandicarboxylic acid, succinic acid, adipic acid, dodecane diacid, sebacic acid, thiodipropionic acid, and cyclohexane Dicarboxylic acid, tris(2-carboxymethyl)isocyanurate, tris(2-carboxyethyl)isocyanurate, tris(2-carboxypropyl)isocyanurate, bis(2-carboxyethyl)isocyanurate and the like.

Examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1- Benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyano Ethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'- Undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl-4-methylimidazole (1')) ethyl-s-triazine, 2 ,4-diamino-6(2'-methylimidazole (1'))ethyl-s-triazine-isocyanuric acid adduct, 2:3 adduct of 2-methylimidazoleisocyanuric acid, 2 -Phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl- 2-phenyl-3,5-dicyanoethoxymethylimidazole etc. are mentioned.

Liquid crystal sealing compound of this invention WHEREIN: When using a hardening accelerator, it is 0.1-10 mass % normally in the total amount of liquid crystal sealing agent, Preferably it is 1-5 mass %.

[Radical polymerization inhibitor]

The radical polymerization inhibitor is not particularly limited as long as it is a compound that prevents polymerization by reacting with radicals generated from a radical photopolymerization initiator or a thermal radical polymerization initiator. A quinone type, piperidine type, hindered phenol type, nitroso type, etc. is available. Specifically, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2 ,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-methoxypiperidine-1-oxyl, 2,2,6, 6-tetramethyl-4-phenoxypiperidine-1-oxyl, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t -Butyl-4-ethylphenol, 2,6-di-t-butylcresol, stearyl β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylene Bis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6- t-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl], 2,4, 8,10-tetraoxaspiro[5,5]undecane, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenylpropionate)methane], 1 ,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-sec-triazine-2,4,6-(1H,3H,5H)trione, parame Toxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, aluminum salt of N-nitrosophenylhydroxyamine, trade name ADEKA STAB LA-81, brand name ADEKA STAB LA-82 (Adeka Co., Ltd.) manufacture), etc., but are not limited thereto. Among these, naphthoquinone, hydroquinone, and nitroso piperazine radical polymerization inhibitors are preferable, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-t-butyl-P- Cresol and Polystop 7300P (manufactured by Hakuto Corporation) are more preferred, and Polystop 7300P (manufactured by Hakuto Corporation) is most preferred.

As content of a radical polymerization inhibitor, 0.0001-1 mass % is preferable in the liquid crystal sealing compound total amount of this invention, 0.001-0.5 mass % is more preferable, 0.01-0.2 mass % is especially preferable.

As an example of the method of obtaining the liquid crystal sealing compound of this invention, there exists the method shown next. First, (A) component, (C)component, (G)component, and (I)component are heat-dissolved as needed. Then, after cooling to room temperature, (B) component, (D) component, (E) component, (F) component, (H) component, an antifoaming agent, a leveling agent, a solvent, etc. are added as needed, and a well-known mixing apparatus The liquid crystal sealing compound of this invention can be manufactured by mixing uniformly with, for example, a 3-axis roll, a sand mill, a ball mill, etc. and filtering with a metal mesh.

The liquid crystal display cell of this invention arrange|positions a pair of board|substrates which formed the predetermined electrode on the board|substrate opposingly at a predetermined space|interval, the periphery is sealed with the liquid crystal sealing agent of this invention, and liquid crystal is enclosed in the gap. The kind of liquid crystal to be enclosed is not specifically limited. Here, the substrate is constituted by a combination substrate in which at least one of which is made of glass, quartz, plastic, silicon, or the like, has light transmittance. As the manufacturing method, after adding spacers (gap control material), such as glass fiber, to the liquid crystal sealing compound of this invention using a dispenser or a screen printing apparatus, the said liquid crystal sealing compound is apply|coated to one of the said pair of board|substrates. After that, if necessary, temporary curing is performed at 80 to 120°C. Then, a liquid crystal is dripped inside the beam of the said liquid crystal sealing compound, the other glass substrate is mutually overlapped in vacuum, and a gap is formed. After gap formation, the liquid crystal display cell of this invention can be obtained by hardening|curing at 90-130 degreeC for 1 hour - 2 hours. Moreover, when using as a photothermal combination type|mold, an ultraviolet-ray is irradiated to a liquid crystal sealing compound part with an ultraviolet irradiation machine, and it is photocured. The amount of ultraviolet irradiation is preferably 500 to 6000 mJ/cm 2 , more preferably 1000 to 4000 mJ/cm 2 . Then, the liquid crystal display cell of this invention can be obtained by hardening|curing at 90-130 degreeC for 1-2 hours as needed. Thus, the liquid crystal display cell of this invention obtained does not have the display defect by liquid-crystal contamination, and is excellent in adhesiveness and moisture-resistance reliability. Examples of the spacer include glass fibers, silica beads, and polymer beads. Although the diameter changes depending on the objective, it is 2-8 micrometers normally, Preferably it is 4-7 micrometers. The usage-amount is 0.1-4 mass parts normally with respect to 100 mass parts of liquid crystal sealing compound of this invention, Preferably it is 0.5-2 mass parts, More preferably, it is about 0.9-1.5 mass parts.

Since the liquid crystal sealing compound of this invention has very favorable thermosetting property, it hardens|cures rapidly in the heating process in the liquid crystal dropping method, the hardened|cured material is excellent in adhesiveness, and liquid-crystal contamination property is favorable, this invention It is possible to create the liquid crystal display cell excellent in reliability by using the liquid crystal sealing compound of .

(Example)

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to an Example. In addition, unless otherwise stated, "part" and "%" in the text are based on mass.

[Synthesis Example 1: Synthesis of All Acrylates of Bisphenol A Type Epoxy Resin]

282.5 g of bisphenol A epoxy resin (product name: YD-8125, manufactured by Shin-Nittetsu Chemical Co., Ltd.) was dissolved in 266.8 g of toluene, 0.8 g of dibutylhydroxytoluene as a polymerization inhibitor was added thereto, and heated to 60° C. warmed up Thereafter, 117.5 g of acrylic acid equivalent to 100% of the epoxy group was added, the temperature was further raised to 80°C, and 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, followed by stirring at 98°C for about 30 hours to obtain a reaction solution. By washing this reaction liquid with water and distilling off toluene, 395 g of the target bisphenol A epoxy acrylate was obtained.

[Synthesis Example 2: Synthesis of partial acrylated bisphenol A epoxy resin]

836 g of bisphenol A epoxy resin (RE-310S by Nippon Kayaku Co., Ltd.) was melt|dissolved in 1000 g of toluene, 3 g of dibutylhydroxytoluene was added to this as a polymerization inhibitor, and it heated up to 60 degreeC. Then, 165 g of 50% equivalent of epoxy group acrylic acid (manufactured by Nippon Shokubai) and 5 g of a 40% aqueous solution of tripropylammonium hydroxide as a reaction catalyst are added, stirred at 98°C for about 10 hours, and the reaction solution got By washing this reaction liquid with water and distilling off toluene, 995 g of the target partially acrylated bisphenol A epoxy resin was obtained.

[Synthesis Example 3: Synthesis of partial acrylated bisphenol F-type epoxy resin]

495 g of bisphenol F-type epoxy resin (RE-304S by Nippon Kayaku Co., Ltd.) was melt|dissolved in 600 g of toluene, 1.8 g of dibutylhydroxytoluene was added to this as a polymerization inhibitor, and it heated up to 60 degreeC. Thereafter, 105 g of acrylic acid equivalent to 50% of the epoxy group (manufactured by Nippon Shokubai Co., Ltd.) and 3 g of a 40% aqueous solution of tripropylammonium hydroxide as a reaction catalyst are added, stirred at 98° C. for about 10 hours, and the reaction solution got 594 g of the target partially acrylated bisphenol F-type epoxy resin was obtained by washing this reaction liquid with water and distilling off toluene.

[Synthesis Example 4: Synthesis of 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane]

100 parts (0.28 mol) of commercially available benzopinacol (manufactured by Tokyo Kasei) was dissolved in 350 parts of dimethylformaldehyde. 32 parts (0.4 mol) of pyridine as a base catalyst and 150 parts (0.58 mol) of BSTFA (made by Shin-Etsu Chemical Co., Ltd.) as a silylating agent were added to this, and it heated up to 70 degreeC, and stirred for 2 hours. While cooling and stirring the obtained reaction liquid, 200 parts of water was put, the product was precipitated, and the unreacted silylating agent was deactivated. The precipitated product was separated by filtration, and then sufficiently washed with water. Next, the obtained product was dissolved in acetone, recrystallized by adding water, and purified. 105.6 parts (yield: 88.3%) of the target 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane were obtained.

[Preparation of Examples 1 to 6 and Comparative Examples 1 to 3]

Component (A), epoxy compound (component (G)), and radical photopolymerization initiator (component (I)) are added to (meth)acrylic compound (component (C)) in a ratio shown in Table 1 below, and heated at 90°C dissolved. Cool to room temperature, thermal radical polymerization initiator (component (B)), organic filler (component (D)), inorganic filler (component (E)), thermal curing agent (component (H)), silane coupling agent (component (F) )) etc. were added and stirred, it was disperse|distributed with the 3-axis roll mill, it filtered with a metal mesh (635 mesh), and the sealing compound for liquid crystal dropping methods (Examples 1-6, Comparative Examples 1-3) was prepared.

[Evaluation of Examples 1 to 6 and Comparative Examples 1 to 3]

[Method for measuring glass transition temperature and mechanical loss coefficient tanδ]

The liquid crystal sealing agent prepared in Examples and Comparative Examples was sandwiched with a polyethylene terephthalate (PET) film into a thin film having a thickness of 100 μm, and 3000 mJ/cm After irradiating UV light for 30 seconds), it was put into an oven at 120° C. for 40 minutes to cure. After peeling off PET film after hardening and obtaining a sealing compound cured film, this was cut into the rectangular shape of 50 mm x 5 mm, and it was set as the sample piece. This sample piece was measured in the tensile mode of a dynamic viscoelasticity measuring device (DMS-6100: manufactured by SI Nanotechnology Co., Ltd.) under the conditions of a frequency of 10 Hz and a temperature rising temperature of 2° C./min, and the ratio of the loss elastic modulus and the storage elastic modulus (JIS K 7244-1), the loss coefficient tan δ is obtained. The temperature at which the obtained loss coefficient tan δ becomes the maximum value was made into the glass transition temperature.

[Measurement of modulus of elasticity]

About the liquid crystal sealing compound manufactured by the Example and the comparative example, 3000 mJ/cm<2> (100mW) by the metal halide lamp (made by Ushio Denki Co., Ltd.) to what was pinched|interposed on the polyethylene terephthalate (PET) film and made into a 100-micrometer-thick thin film. After curing by irradiating an ultraviolet ray of /cm 2 for 30 seconds), and then putting it in an oven at 120 ° C. for 40 minutes to cure, peeling off the PET film to obtain a sealing cured film, and then a dumbbell-shaped test piece (total length 75 mm, total length) 10 mm in width, 50 mm in length of a narrow parallel part, 5 mm in width, and 0.1 mm in thickness) were cut into the sample piece. The obtained test piece was subjected to a tensile test using a Tensilon universal testing machine (manufactured by A&D, RTG-1210) at room temperature (22°C) at a test rate of 3 mm/min, and within the proportional limit. The modulus of elasticity was calculated from the results of tensile stress and strain.

[Breaking point extension]

About the liquid crystal sealing compound manufactured by the Example and the comparative example, 3000 mJ/cm<2> (100mW) by the metal halide lamp (made by Ushio Denki Co., Ltd.) to what was pinched|interposed on the polyethylene terephthalate (PET) film and made into a 100-micrometer-thick thin film. After curing by irradiating an ultraviolet ray of /cm 2 for 30 seconds), and then putting it in an oven at 120 ° C. for 40 minutes to cure, peeling off the PET film to obtain a sealing cured film, and then a dumbbell-shaped test piece (total length 75 mm, total length) 10 mm in width, 50 mm in length of a narrow parallel part, 5 mm in width, and 0.1 mm in thickness) were cut into the sample piece. The obtained test piece was subjected to a tensile test using a Tensilon universal testing machine (manufactured by A&D, RTG-1210) at room temperature (22°C) at a test rate of 3 mm/min, and The elongation was computed from the increase amount of distance.

[Bending Test]

By the method similar to the elastic modulus measuring method, the sealing compound cured film was produced, 50 mm in length, 5 mm in width, and rectangular shape of thickness 0.1mm were cut out, and it was set as the sample piece. The obtained sample piece was bent so that it might become 25 mm in length for half, and it fixed for 10 second. The thing in which the test piece was not cracked was evaluated as (circle) and the thing in which the test piece was cracked was made into x.

[Adhesive strength]

About the liquid crystal sealing compound manufactured by the Example and the comparative example, 3000 mJ/cm<2> (100mW) by the metal halide lamp (made by Ushio Denki Co., Ltd.) to what was pinched|interposed on the polyethylene terephthalate (PET) film and made into a 100-micrometer-thick thin film. /cm 2 for 30 seconds) was irradiated and cured, and then put into an oven at 120° C. for 40 minutes to cure. By the method similar to the elastic modulus measuring method, the sealing compound cured film was produced, 50 mm in length, 5 mm in width, and rectangular shape of thickness 0.1mm were cut out, and it was set as the sample piece. The obtained sample piece was bent so that it might become 25 mm in length for half, and it fixed for 10 second. Observing the sample, the test piece did not crack and did not peel off the PET film was evaluated as ○, the test piece did not crack and the PET film peeled off, △, and the test piece cracked and the PET film peeled off as ×.

From the result of Table 1, containing the compound which has a urethane bond in a molecule|numerator, the glass transition temperature measured by the DMA method of hardened|cured material is 90 degrees C or less, and the liquid crystal sealing compound of this invention whose tan δ is 0.5 or more is low elastic modulus, Moreover, the elongation to a fracture|rupture point was also large, therefore, also in a bending test and an adhesion test, compared with the liquid crystal sealing compound of a comparative example, it was confirmed to show a favorable result.

Since the liquid crystal sealing compound of this invention is applicable also to a flexible display and a curved display, and is excellent also in general characteristics, such as adhesive strength, a highly reliable liquid crystal display element can be implement|achieved.

Claims (8)

Component (A) containing at least (A) a compound having a urethane bond in the molecule, (B) a thermal radical polymerization initiator, (C) a (meth)acrylic compound, (H) a thermal curing agent, and (I) a radical radical polymerization initiator Content of 25-60 mass % in the total amount of liquid crystal sealing agent, content of component (C) is 10-70 mass % in the total amount of liquid crystal sealing agent, The glass transition temperature measured by the DMA method of hardened|cured material is 90 It is °C or less, and tan-delta is 0.5 or more liquid crystal sealing compound for liquid crystal dropping methods. According to claim 1,
The liquid crystal sealing compound for liquid crystal dropping methods whose weight average molecular weights of the said component (A) are 1000 or more. According to claim 1,
The liquid crystal sealing compound for liquid crystal dropping methods whose said component (A) is a compound which has 3 or more ester bonds in a molecule|numerator. According to claim 1,
Furthermore, the liquid crystal sealing compound for liquid crystal dropping methods containing at least 1 sort(s) chosen from the group which consists of (D) organic filler, (E) inorganic filler, (F) silane coupling agent, and (G) epoxy compound. 5. The method of claim 4,
contains at least the component (D),
The liquid crystal sealing compound for liquid crystal dropping methods whose said component (D) is 1 or 2 or more organic fillers chosen from the group which consists of urethane microparticles|fine-particles, acrylic resin microparticles|fine-particles, polystyrene microparticles|fine-particles, styrene olefin copolymer microparticles|fine-particles, and silicone microparticles|fine-particles. According to claim 1,
The liquid crystal sealing compound for liquid crystal dropping methods whose said component (H) is an organic acid hydrazide compound. The liquid crystal display cell comprised by the board|substrate of 2 sheets WHEREIN: Liquid crystal is dripped inside the weir of the liquid crystal sealing compound for liquid crystal dropping methods in any one of Claims 1-6 formed in one board|substrate. The manufacturing method of the liquid crystal display cell characterized by bonding together the other board|substrate, and hardening|curing with a heat|fever after that. The liquid crystal display cell sealed with the hardened|cured material obtained by hardening|curing the liquid crystal sealing compound for liquid crystal dropping methods in any one of Claims 1-6.