TWI690560B - Sealant for liquid crystal display element, upper and lower conduction materials and liquid crystal display element - Google Patents

Abstract

An object of the present invention is to provide a sealant for a liquid crystal display element which can obtain a cured product which can maintain excellent adhesion even when the substrate is repeatedly deformed and is resistant to impact Excellent. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.

The sealing compound for liquid crystal display elements of the present invention contains a curable resin, a polymerization initiator and/or a thermosetting agent, the storage elastic modulus of the cured product at 25°C is 2.0 GPa or less, and the loss elastic modulus of the cured product at 25°C The number is 0.1 GPa or more and 1.0 GPa or less.

Description

Sealant for liquid crystal display element, upper and lower conduction materials and liquid crystal display element

The present invention relates to a sealant for a liquid crystal display element. The sealant for a liquid crystal display element can obtain a cured product that maintains excellent adhesion even when the substrate is repeatedly deformed and has excellent impact resistance . In addition, the present invention relates to an upper and lower conduction material and a liquid crystal display element formed by using the sealant for liquid crystal display elements.

In recent years, as a manufacturing method of a liquid crystal display element, from the viewpoint of shortening the process time and optimizing the amount of liquid crystal used, the liquid crystal drip method called the drip method as disclosed in Patent Document 1 and Patent Document 2 is used. In the above method, the above-mentioned dripping method uses a photo-thermal combination hardening type sealant containing a curable resin, a photopolymerization initiator and a thermosetting agent.

Regarding the drip method, first, a rectangular sealing pattern is formed by dispensing on one of the two transparent substrates with electrodes. Then, in a state where the sealant is not cured, droplets of liquid crystal are dropped into the entire frame of the transparent substrate, immediately overlap with another transparent substrate, and the sealing portion is irradiated with ultraviolet light or the like to temporarily cure. Then, it is heated to formally harden to produce a liquid crystal display element. By bonding the substrates under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency. At present, the drip method has become the mainstream of the manufacturing method of the liquid crystal display element.

Also, in the past, glass substrates have been mainly used as substrates for liquid crystal display elements, but in recent years, polyethylene terephthalate, polycarbonate, polyolefin Flexible substrates such as amide imine have attracted attention. However, the conventional sealant has a problem that when the substrate is repeatedly deformed, the sealant cannot follow the deformation and the liquid crystal display element has a display defect.

[Prior Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2001-133794

Patent Document 2: Japanese Patent Laid-Open No. 5-295087

An object of the present invention is to provide a sealant for a liquid crystal display element which can obtain a cured product which can maintain excellent adhesion even when the substrate is repeatedly deformed and is resistant to impact Excellent. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.

The sealing compound for liquid crystal display elements of the present invention contains a curable resin, a polymerization initiator and/or a thermosetting agent, the storage elastic modulus of the cured product at 25°C is 2.0 GPa or less, and the loss elastic modulus of the cured product at 25°C The number is 0.1 GPa or more and 1.0 GPa or less.

The present invention will be described in detail below.

In order to improve the bending resistance of the cured product of the sealant for liquid crystal display elements, the inventors studied to reduce the storage elastic modulus. However, when only the storage elastic modulus is lowered, peeling or deformation may occur when the substrate is repeatedly deformed, or the impact resistance may deteriorate. Therefore, in addition to the storage elastic modulus of the hardened product at 25°C, the inventors also studied to make the loss elastic modulus of the hardened product at 25°C into a specific range. As a result, it was found that the following sealant for liquid crystal display elements can be obtained, and the present invention has been completed. The above-mentioned sealant for liquid crystal display elements can obtain excellent adhesion and impact resistance even when the substrate is repeatedly deformed. Excellent hardening.

By setting the storage elastic modulus at 25° C. and the loss elastic modulus at 25° C. of the hardened product of the sealant for liquid crystal display elements of the present invention to specific ranges, the hardened product becomes deformed even if the substrate is overturned In this case, the excellent adhesiveness can be maintained, and the impact resistance is excellent, and the following can be considered as the reason. That is, in order to maintain excellent adhesion even when the substrate is repeatedly deformed, it is necessary to make the deformation of the hardened material easier without plastic deformation, so it is preferable that the storage elastic modulus is low and the loss elastic modulus is low status. In addition, in order to be excellent in impact resistance, it is necessary to restore the shape in addition to the easier deformation of the test piece. Therefore, it is preferable that the storage elastic modulus is low and has a loss elastic modulus of a certain value or more. Based on these contents, it can be considered that this effect is exerted by setting the storage elastic modulus at 25°C and the loss elastic modulus at 25°C to specific ranges, respectively.

The upper limit of the storage elastic modulus of the cured product of the sealant for liquid crystal display elements of the present invention at 25°C is 2.0 GPa. By setting the storage elastic modulus of the cured product at 25°C to be in this range, and setting the loss elastic modulus of the cured product at 25°C to 0.1 GPa or more and 1.0 GPa or less, the sealant for a liquid crystal display element of the present invention can A cured product is obtained that can maintain excellent adhesion even when the substrate is repeatedly deformed, and has excellent impact resistance. The preferable upper limit of the storage elastic modulus of the hardened product at 25°C is 1.9 GPa, the more preferable upper limit is 1.8 GPa, and the more preferable upper limit is 1.5 GPa.

In addition, from the viewpoint of adhesion when bonding the adherend, the lower limit of the storage elastic modulus of the cured product at 25°C is preferably 1 MPa, more preferably the lower limit is 0.01 GPa, and further preferably the lower limit is 1.1 GPa .

In addition, as a hardened product for measuring the above storage elastic modulus and the loss elastic modulus described later, the following is used: After irradiating 100 mW/cm ² of ultraviolet light (wavelength 365 nm) to the sealant with a metal halide lamp for 30 seconds, at It is cured by heating at 120°C for 1 hour. In addition, this hardened|cured material means the hardened|cured material of the sealing compound used for bonding or sealing of a board|substrate etc. in a liquid crystal display element.

In addition, the storage elastic modulus and the loss elastic modulus described later can be measured by a dynamic viscoelasticity measuring device (such as "DVA-200" manufactured by IT METER AND CONTROL, etc.) in the tensile mode, with a test piece width of 5 mm and a thickness of 0.35. mm, grip width 25mm, heating rate 10°C/min, frequency 10Hz.

The hardened product of the sealant for liquid crystal display devices of the present invention has a loss elastic modulus at 25°C with a lower limit of 0.1 GPa and an upper limit of 1.0 GPa. By setting the loss elastic modulus of the hardened product at 25°C to be in this range, and setting the storage elastic modulus of the hardened product at 25°C to 2.0 GPa or less, the sealant for liquid crystal display elements of the present invention becomes even when the substrate is overturned In the case of deformation, excellent adhesion can also be maintained, and impact resistance is also excellent. The preferred lower limit of the loss elastic modulus of the hardened product at 25°C is 0.2 GPa, the preferred upper limit is 0.8 GPa, the preferred upper limit is 0.7 GPa, and the preferred upper limit is 0.3 GPa.

The sealing compound for liquid crystal display elements of this invention contains a curable resin, a polymerization initiator, and/or a thermosetting agent.

In the sealant for a liquid crystal display element of the present invention, the storage elastic modulus of the cured product at 25°C is set to 2.0 GPa or less and the loss elastic modulus of the cured product at 25°C is set to 0.1 GPa or more and 1.0 GPa or less Examples of the method include a method of using a compound having a polymerizable functional group and a rubber structure as the curable resin, or a method of blending rubber particles into a sealant. Among them, the method of using the compound having a polymerizable functional group and a rubber structure is preferable.

In addition, in this specification, a compound having a rubber structure refers to a vulcanized rubber obtained by vulcanization of raw rubber, a synthetic rubber obtained by addition polymerization and having a double bond in the molecular main chain, or using peroxide A compound with rubber elasticity such as polysiloxane rubber made by cross-linking polymethylsiloxane. The above-mentioned compound with rubber structure is characterized in that the storage elastic modulus is low and it is easy to deform, and on the other hand, the shape is easy to recover due to the high internal stress; by appropriately blending the above-mentioned rubber structure with a curable resin The compound can adjust storage elastic modulus and loss elastic modulus separately.

Examples of the polymerizable functional group possessed by the compound having the polymerizable functional group and the rubber structure include (meth)acryloyl group and epoxy group. Among them, (meth)acryloyl is preferred. In addition, it is preferable that the compound having the polymerizable functional group and the rubber structure has two or more polymerizable functional groups in one molecule.

In addition, in this specification, the "(meth)acryloyl group" means an acryloyl group or methacryloyl group.

The rubber structure of the compound having a polymerizable functional group and a rubber structure is preferably a structure having an unsaturated bond in the main chain or a structure having a polysiloxane skeleton in the main chain.

Examples of the structure having an unsaturated bond in the main chain include a structure having a skeleton obtained by polymerization of a conjugated diene in the main chain.

Examples of the skeleton obtained by the polymerization of the conjugated diene include polybutadiene skeleton, polyisoprene skeleton, styrene-butadiene skeleton, polyisobutylene skeleton, and polychloroprene skeleton. Among them, the rubber structure is more preferably a structure having a polybutadiene skeleton, a polyisoprene skeleton, or a polysiloxane skeleton.

The lower limit of the molecular weight of the compound having a polymerizable functional group and a rubber structure is preferably 500, and the upper limit is preferably 50,000. When the molecular weight of the compound having a polymerizable functional group and a rubber structure is within this range, the obtained sealant for a liquid crystal display element becomes a cured product having more excellent bending resistance. The more preferable lower limit of the molecular weight of the compound having a polymerizable functional group and a rubber structure is 1,000, and the more preferable upper limit is 30,000.

In addition, the "molecular weight" in this specification refers to the molecular weight determined from the structural formula for the compound with a determined molecular structure, and for the compound with a wide distribution of polymerization degree and the compound with an undefined modification site, Sometimes weight average molecular weight is used. In addition, the said "weight average molecular weight" is a value obtained by polystyrene conversion using the gel permeation chromatography (GPC) measurement using tetrahydrofuran as a solvent. Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).

Examples of the compound having a polymerizable functional group and a rubber structure include, for example, butadiene-acrylonitrile (ATBN) modified epoxy (meth)acrylate containing terminal amine groups and those containing terminal carboxyl groups. Butadiene-acrylonitrile (CTBN) modified epoxy (meth) acrylate, (meth) acrylic modified isoprene rubber, (meth) acrylic modified butadiene rubber, (meth) acrylic Modified polysiloxane rubber, butadiene-acrylonitrile (ATBN) modified epoxy resin containing terminal amine groups, isoprene modified epoxy resin, butadiene modified epoxy resin, containing terminal carboxyl group Polybutadiene-acrylonitrile (CTBN) modified epoxy resin, butadiene modified amine acrylate, etc. The compound having a polymerizable functional group and a rubber structure may be used alone, or two or more kinds may be used in combination.

The preferable lower limit of the content of the compound having a polymerizable functional group and a rubber structure in 100 parts by weight of the entire curable resin is 20 parts by weight, and the upper limit is preferably 75 parts by weight. By setting the content of the compound having a polymerizable functional group and a rubber structure within this range, it is easy to set the storage elastic modulus and loss elastic modulus of the obtained cured product of the sealant for liquid crystal display element at 25°C, respectively It is the above range. The more preferable lower limit of the content of the compound having a polymerizable functional group and a rubber structure is 30 parts by weight, the more preferable upper limit is 70 parts by weight, and the more preferable lower limit is 51 parts by weight.

In order to adjust the storage elastic modulus and loss elastic modulus of the cured product at 25°C, or to further improve the adhesiveness when bonding the adherend or the low liquid crystal contamination, the curable resin is preferably Hardening resins other than compounds with functional groups and rubber structures. As the other curable resin, it is preferable to use other epoxy compounds or other (meth)acrylic compounds other than the compound having a polymerizable functional group and a rubber structure.

In addition, in this specification, the "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the "(meth)acrylic compound" means a compound having a (meth)acryloyl group.

Examples of the other epoxy compounds include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, and 2,2'-diene. Propyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, thioether type Epoxy resin, diphenyl ether epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, dicyclopentadiene Novolac epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol epoxy resin, glycidyl ester compound, etc.

Examples of commercially available bisphenol A epoxy resins include jER828EL and jER1004 (all manufactured by Mitsubishi Chemical Corporation), and EPICLON 850CRP (manufactured by DIC Corporation).

Examples of commercially available bisphenol F-type epoxy resins include jER806 and jER4004 (all manufactured by Mitsubishi Chemical Corporation).

Examples of commercially available bisphenol E-type epoxy resins include R710 (manufactured by Printec) and the like.

Examples of commercially available bisphenol S-type epoxy resins include EPICLON EXA1514 (manufactured by DIC).

As a commercial item among the said 2,2'- diallyl bisphenol A type epoxy resins, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

Examples of the commercially available hydrogenated bisphenol-type epoxy resins include EPICLON EXA7015 (manufactured by DIC).

Examples of the commercially available propylene oxide-added bisphenol A epoxy resin include EP-4000S (manufactured by ADEKA) and the like.

Examples of commercially available resorcinol-type epoxy resins include EX-201 (manufactured by Nagase Chemicals) and the like.

Examples of the commercially available ones of the biphenyl-type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like.

Examples of commercially available thioether epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like.

Examples of commercially available diphenyl ether-type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like.

Examples of the commercially available dicyclopentadiene-type epoxy resins include EP-4088S (made by ADEKA).

Examples of the commercially available naphthalene-type epoxy resins include EPICLON HP4032 and EPICLON EXA-4700 (all manufactured by DIC Corporation).

Examples of the commercially available phenol novolac-type epoxy resins include EPICLON N-770 (manufactured by DIC).

As a commercially available one of the above ortho-cresol novolac-type epoxy resins, for example, EPICLON N-670-EXP-S (manufactured by DIC Corporation) and the like can be cited.

Examples of the commercially available dicyclopentadiene novolac-type epoxy resins include EPICLON HP7200 (manufactured by DIC Corporation) and the like.

Examples of commercially available ones of the biphenol novolac-type epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.

Examples of the commercially available naphthol novolak-type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.).

Examples of commercially available glycidylamine-type epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation).

Examples of the commercially available alkyl polyol-type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and EPOLIGHT 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) ), DENACOL EX-611 (made by Nagase Chemical Co., Ltd.), etc.

Examples of the commercially available glycidyl ester compounds include DENACOL EX-147 (manufactured by Nagase Kasei Corporation) and the like.

As other commercially available ones among the above epoxy compounds, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 ( All are manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), etc.

In addition, the curable resin may contain a compound having an epoxy group and a (meth)acryloyl group in one molecule as the other epoxy compound. As such a compound, for example, a part of (meth)acrylic acid modified epoxy obtained by reacting a part of epoxy groups of an epoxy compound having two or more epoxy groups with (meth)acrylic acid Resin etc.

As a commercially available part of the above (meth)acrylic modified epoxy resin, for example, UVACURE1561, KRM8287 (both manufactured by DAICEL ALLNEX), etc. As the other (meth)acrylic compound, for example, a ring Oxygen (meth)acrylate, (meth)acrylate compound, amine (meth)acrylate, etc. Among them, epoxy (meth)acrylate is preferred. In addition, the above-mentioned other (meth)acrylic compounds are preferably those having two or more (meth)acryloyl groups in the molecule in terms of the degree of reactivity.

In addition, in this specification, the above-mentioned "(meth)acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" means that all the rings in the epoxy compound A compound obtained by reacting an oxy group with (meth)acrylic acid.

Examples of the epoxy (meth)acrylates include those obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of an alkaline catalyst according to a conventional method.

Examples of the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate include the same as the above-mentioned other epoxy compounds.

Examples of the commercially available epoxy (meth)acrylates include epoxy (meth)acrylates manufactured by DAICEL ALLNEX, epoxy (meth)acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd., Epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase Chemicals, etc.

Examples of the epoxy (meth)acrylates manufactured by DAICEL ALLNEX include: EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3708, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX63182, etc.

Examples of the epoxy (meth)acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020.

Examples of the epoxy (meth)acrylates manufactured by the Kyoeisha Chemical Company include EPOXYESTER M-600A, EPOXYESTER 40EM, EPOXYESTER 70PA, EPOXYESTER 200PA, EPOXYESTER 80MFA, EPOXYESTER 3002M, EPOXYESTER 3002A, EPOXYESTER 1600A, EPOXYESTER 3000M , EPOXYESTER 3000A, EPOXYESTER 200EA, EPOXYESTER 400EA, etc.

Examples of the epoxy (meth)acrylate produced by the Nagase Chemical Company include DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, DENACOL ACRYLATE DA-911, and the like.

Examples of the monofunctional ones in the (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , Isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Isobornyl meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl acetate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Methacrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbitol ( Methacrylic acid ester, (meth)acrylic acid 2,2,2-trifluoroethyl ester, (meth)acrylic acid 2,2,3,3-tetrafluoropropyl ester, (meth)acrylic acid 1H,1H,5H -Octafluoropentyl ester, amide imine (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyl Oxyethyl succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-hydroxypropylphthalic acid 2-(meth)acryloyloxyethyl ester, phosphoric acid 2 -(Meth)acrylic acid ethyl ester, glycidyl (meth)acrylate, etc.

In addition, examples of the two functions in the (meth)acrylate compound include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylate. , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di (Meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol Alcohol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanurate di(meth)acrylate, (meth) 2-Hydroxy-3-(meth)acrylic propyl acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth) ) Acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.

In addition, examples of the trifunctional or higher among the (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate and ethylene oxide addition trimethylolpropane tri(methyl ) Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanurate Acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, phosphate tri (meth) Acryloyloxyethyl, di(trimethylolpropane) tetra(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dixin Pentaerythritol hexa(meth)acrylate, etc.

The above-mentioned (meth)acrylic acid amine ester can be obtained, for example, by using 1 equivalent of an isocyanate compound having 2 isocyanate groups in the presence of a catalyst amount of tin-based compound, and 2 equivalents of a (meth)acrylic acid derivative having a hydroxyl group Obtained through the reaction.

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenyl Methane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), Hydrogenated XDI, ionic acid diisocyanate, triphenylmethane triisocyanate, thiophosphoric acid tris(isocyanatophenyl), tetramethyl xylylene diisocyanate, 1,6,11-undecane triisocyanate, etc. .

In addition, as the above-mentioned isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyol with an excessive amount of isocyanate compound can also be used.

Examples of the above-mentioned polyols include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

Examples of the (meth)acrylic acid derivatives having hydroxyl groups include hydroxyalkyl mono(meth)acrylates, mono(meth)acrylates of glycols, and mono(meth)acrylic acid of triols. Ester or di(meth)acrylate, epoxy (meth)acrylate, etc.

Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate and the like.

Examples of the above-mentioned glycols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.

Examples of the triols include trimethylolethane, trimethylolpropane, and glycerin.

Examples of the epoxy (meth)acrylate include bisphenol A epoxy acrylate.

Examples of the commercially available among the above-mentioned (meth)acrylate amine esters include: (meth)acrylic acid amine esters manufactured by Toya Synthetic Corporation, DAICEL ALLNEX (meth)acrylic acid amine esters, manufactured by Negami Industry Co., Ltd. Amino (meth)acrylate, Amino (meth)acrylate manufactured by Shin Nakamura Chemical Industry Company, Amino (meth)acrylate manufactured by Kyoeisha Chemical Company, etc.

Examples of the amine (meth)acrylate manufactured by the above-mentioned East Asia Synthesizer include M-1100, M-1200, M-1210, and M-1600. Examples of the amine (meth)acrylates manufactured by DAICEL ALLNEX include: EBECRYL 210, EBECRYL 220, EBECRYL 230, EBECRYL 270, EBECRYL 1290, EBECRYL 2220, EBECRYL 4827, EBECRYL 4842, EBECRYL 4858, EBECRYL 5129, EBECRYL 6700, EBECRYL 8402, EBECRYL 8803, EBECRYL 8804, EBECRYL 8807, EBECRYL 9260, etc.

Examples of the amine (meth)acrylates produced by the above-mentioned Kinshang Industrial Company include: ARTRESIN UN-330, ARTRESIN SH-500B, ARTRESIN UN-1200TPK, ARTRESIN UN-1255, ARTRESIN UN-3320HB, ARTRESIN UN-7100, ARTRESIN UN-9000A, ARTRESIN UN-9000H, etc.

Examples of the amine (meth)acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U -10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000 , UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, etc.

Examples of the amine (meth)acrylate manufactured by the Kyoeisha Chemical Company include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA -306T etc.

The above curable resins may be used alone or in combination of two or more.

The sealant for a liquid crystal display element of the present invention preferably has a content ratio of (meth)acryloyl group in the total of (meth)acryloyl group and epoxy group in the curable resin set to 50 mole% or more And below 95 mol%.

Examples of the rubber particles include silicone rubber particles, butadiene rubber particles, isoprene rubber particles, nitrile rubber particles, styrene rubber particles, and acrylic rubber particles. Among them, at least one selected from the group consisting of silicone rubber particles, butadiene rubber particles, and isoprene rubber particles is preferable.

The preferred lower limit of the average particle diameter of the rubber particles is 0.1 μm, and the preferred upper limit is 5 μm. By setting the average particle diameter of the rubber particles in this range, it is easy to set the storage elastic modulus and loss elastic modulus of the obtained cured product of the sealant for a liquid crystal display element at 25° C. to the above ranges. The more preferable lower limit of the average particle diameter of the rubber particles is 0.5 μm, and the more preferable upper limit is 3 μm.

In addition, in this specification, the average particle diameter of the rubber particles refers to a value obtained by measuring the particles before blending into the sealant using a laser diffraction type particle size distribution measuring device. As the laser diffraction type particle size distribution measuring device, Mastersizer 2000 (manufactured by Malvern) or the like can be used. The average particle diameter of the rubber particles refers to the average particle diameter of 10 particles obtained by observing the particles contained in the sealant at a magnification of 10,000 with a scanning electron microscope. As the scanning electron microscope, a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation) or the like can be used.

The preferable lower limit of the content of the rubber particles in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight. By setting the content of the rubber particles in this range, it is easy to set the storage elastic modulus and loss elastic modulus of the obtained cured product of the sealant for a liquid crystal display element at 25° C. to the above ranges. The more preferable lower limit of the content of the rubber particles is 20 parts by weight, and the more preferable upper limit is 50 parts by weight.

The sealing agent for liquid crystal display elements of the present invention contains a polymerization initiator and/or a thermosetting agent.

Examples of the polymerization initiator include radical polymerization initiators and cationic polymerization initiators.

Examples of the radical polymerization initiator include a thermal radical polymerization initiator that generates radicals by heating, and a photo radical polymerization initiator that generates radicals by light irradiation.

等。 Examples of the photo radical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, acetylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, 9-oxygen sulfur

Wait.

Examples of commercially available photo-radical polymerization initiators include photo-radical polymerization initiators manufactured by BASF Corporation, photo-radical polymerization initiators manufactured by Tokyo Chemical Industry Co., Ltd., and the like.

Examples of the photo-radical polymerization initiator manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, LUCIRIN TPO, and the like.

Examples of the photo-radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

These photo radical polymerization initiators may be used alone or in combination of two or more.

Examples of the thermal radical polymerization initiator include those composed of an azo compound, an organic peroxide, and the like. Among them, a polymer azo initiator composed of a polymer azo compound is preferred.

In addition, in this specification, the polymer azo compound refers to a radical having an azo group, which is generated by heat and can harden the (meth)acryloyloxy group, and has a number average molecular weight of 300 or more Compound.

The preferred lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 1,000, and the preferred upper limit is 300,000. By setting the number average molecular weight of the above-mentioned polymer azo compound within this range, it is possible to prevent adverse effects on the liquid crystal and to easily mix it into the curable resin. The more preferable lower limit of the number average molecular weight of the polymer azo compound is 5000, the more preferable upper limit is 100,000, the more preferable lower limit is 10,000, and the more preferable upper limit is 90,000.

In addition, in this specification, the said number average molecular weight is the value measured by the gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and it is calculated by polystyrene conversion. Examples of the column when measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).

Examples of the polymer azo compound include a structure having a plurality of units such as polyalkylene oxide or polydimethylsiloxane bonded via an azo group.

The polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide is bonded via an azo group is preferably a polyethylene oxide structure.

Specific examples of the polymer azo compound include, for example, a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'-a Polycondensates of bis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amine groups.

Examples of the commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.).

In addition, examples of commercially available azo compounds that are not polymers include V-65 and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.).

Examples of the organic peroxides include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.

As the above cationic polymerization initiator, a photo cationic polymerization initiator can be preferably used. The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generation type or a nonionic photoacid generation type.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halide salts, and aromatic osmium salts, iron-propadiene complexes, and titanocene complexes. Organic metal complexes such as aryl silanol-aluminum complexes, etc.

Examples of commercially available photo-cationic polymerization initiators include Adeka Optomer SP-150 and Adeka Optomer SP-170 (all manufactured by ADEKA).

The above polymerization initiator may be used alone or in combination of two or more.

Regarding the content of the polymerization initiator, with respect to 100 parts by weight of the curable resin, the lower limit is preferably 0.1 part by weight, and the upper limit is preferably 30 parts by weight. When the content of the polymerization initiator is 0.1 part by weight or more, the obtained sealing compound for liquid crystal display elements becomes more excellent in curability. When the content of the polymerization initiator is 30 parts by weight or less, the obtained sealing compound for liquid crystal display elements becomes more excellent in storage stability. The more preferable lower limit of the content of the polymerization initiator is 1 part by weight, the more preferable upper limit is 10 parts by weight, and the more preferable upper limit is 5 parts by weight.

Examples of the thermosetting agent include organic acid hydrazine, imidazole derivatives, amine compounds, polyphenol compounds, acid anhydrides, and the like. Among them, it is preferable to use solid organic acid hydrazine.

Examples of the solid organic acid hydrazine include 1,3-bis(hydrazinocarbonylethyl)-5-isopropylhydantoin, sebacic acid dihydrazide, and isophthalic acid dihydrazide. , Adipic acid dihydrazide, malonic acid dihydrazide and so on.

Examples of the commercially available solid organic acid hydrazide include organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazide manufactured by Finechem Japan, and organic acid hydrazide manufactured by Ajinomoto Fine-Techno. .

Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.

Examples of the organic acid hydrazide manufactured by the Japanese Finechem Company include MDH and the like.

Examples of the organic acid hydrazide manufactured by the Ajinomoto Fine-Techno Company include AMICURE VDH, AMICURE VDH-J, and AMICURE UDH.

The above-mentioned thermosetting agents may be used alone or in combination of two or more.

Regarding the content of the above-mentioned thermosetting agent, with respect to 100 parts by weight of the above-mentioned curable resin, the lower limit is preferably 1 part by weight, and the upper limit is preferably 50 parts by weight. When the content of the thermosetting agent is 1 part by weight or more, the obtained sealing compound for liquid crystal display elements becomes more excellent in thermosetting properties. By setting the content of the thermosetting agent to 50 parts by weight or less, the obtained sealant for liquid crystal display elements becomes more excellent in coatability. The upper limit of the content of the above-mentioned thermosetting agent is more preferably 30 parts by weight.

The sealant for liquid crystal display elements of the present invention preferably contains a filler in order to achieve an increase in viscosity, a further increase in adhesiveness due to a stress dispersion effect, an improvement in linear expansion rate, and an improvement in moisture resistance of a cured product.

As the above-mentioned filler, an inorganic filler or an organic filler can be used.

Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, Magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc.

Examples of the organic filler include polyester fine particles, polyurethane fine particles, ethylene polymer fine particles, acrylic polymer fine particles, and the like.

The preferable lower limit of the content of the filler in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight. By setting the content of the filler in this range, it is possible to suppress the deterioration of coating properties and the like, and to further exert effects such as improvement of adhesiveness. The more preferable lower limit of the content of the filler is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.

In order to further improve adhesiveness, the sealing compound for liquid crystal display elements of the present invention preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly has a role as an adhesion aid for good adhesion of the sealant to the substrate and the like.

As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like are preferably used.

The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 0.1 part by weight, and the preferable upper limit is 20 parts by weight. By setting the content of the above-mentioned silane coupling agent within this range, the generation of liquid crystal contamination can be suppressed, and the effect of improving adhesion can be further exerted. The lower limit of the content of the silane coupling agent is more preferably 0.5 part by weight, and the upper limit is more preferably 10 parts by weight.

The sealing compound for liquid crystal display elements of this invention may contain a light-shielding agent. By containing the above-mentioned light-shielding agent, the sealing agent for liquid crystal display elements of this invention can be used suitably as a light-shielding sealing agent.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferred.

The above-mentioned titanium black is a material that has a higher transmittance in the vicinity of the ultraviolet region, especially light in the wavelength range of 370 nm to 450 nm, compared to the average transmittance for light of wavelengths of 300 nm to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent which has light-shielding properties for the sealing agent for liquid crystal display elements of the present invention by sufficiently shielding light of wavelengths in the visible light region, and on the other hand, has the property of transmitting light of wavelengths near the ultraviolet region . The light-shielding agent contained in the sealing compound for liquid crystal display elements of the present invention is preferably a material with high insulation, and titanium black is also preferable as a light-shielding agent with high insulation.

The titanium black mentioned above exerts sufficient effects even if the surface is untreated, but it can also be treated with organic components such as coupling agents on the surface, or through silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, oxidation Titanium black with surface treatment such as those coated with inorganic components such as magnesium. Among them, those treated with an organic component are preferable in terms of further improving insulation.

In addition, the liquid crystal display element manufactured by using the sealing agent for liquid crystal display elements of the present invention containing the above titanium black as a light-shielding agent has sufficient light-shielding properties, so it can achieve light leakage without high contrast, and has excellent Liquid crystal display element of image display quality.

Examples of the commercially available titanium black mentioned above include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Chemical Corporation.

Examples of the titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13R-N, and 14M-C.

Examples of the titanium black manufactured by Ako Chemical Co., Ltd. include Tilack D and the like.

The preferable lower limit of the specific surface area of the titanium black is 13 m ² /g, the preferable upper limit is 30 m ² /g, the more preferable lower limit is 15 m ² /g, and the more preferable upper limit is 25 m ² /g.

In addition, the preferable lower limit of the volume resistance of the above titanium black is 0.5Ω‧cm, the preferred upper limit is 3Ω‧cm, the more preferred lower limit is 1Ω‧cm, and the more preferred upper limit is 2.5Ω‧cm.

The primary particle diameter of the light-shielding agent is not particularly limited as long as the distance between the substrates of the liquid crystal display element is not exceeded, but the preferred lower limit is 1 nm, and the preferred upper limit is 5 μm. By setting the primary particle size of the light-shielding agent within this range, it is possible to achieve a more excellent coating property without greatly increasing the viscosity or the shakeability of the obtained sealant for liquid crystal display elements. The preferred lower limit of the primary particle size of the above-mentioned opacifier is 5 nm, the preferred upper limit is 200 nm, the preferred lower limit is 10 nm, and the preferred upper limit is 100 nm.

In addition, the primary particle diameter of the said sunscreen can be measured using a particle size distribution meter (for example, "NICOMP 380ZLS" by PARTICLE SIZING SYSTEMS).

The preferable lower limit of the content of the above-mentioned opacifier in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. By setting the content of the above-mentioned light-shielding agent within this range, the effect of improving the light-shielding property can be further achieved without reducing the adhesion, strength after curing, and drawability of the obtained sealant for liquid crystal display elements. The more preferable lower limit of the content of the above-mentioned sunscreen agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the more preferable lower limit is 30 parts by weight, and the more preferable upper limit is 60 parts by weight.

The sealant for liquid crystal display elements of the present invention may further contain additives such as a stress relaxation agent, a reactive diluent, a shaker, a spacer, a hardening accelerator, a defoaming agent, a leveling agent, and a polymerization inhibitor, if necessary.

As a method of manufacturing the sealing agent for liquid crystal display elements of the present invention, for example, a blender such as a homogenous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill can be used to harden the resin. , Polymerization initiators and/or thermal hardeners, and silane coupling agents and other additives added as needed, such as mixing methods.

By mixing conductive fine particles into the sealant for liquid crystal display elements of the present invention, a vertical conduction material can be manufactured. Such a top-to-bottom conductive material containing the sealing compound for liquid crystal display elements of the present invention and conductive fine particles is also one of the present invention.

As the conductive fine particles, a metal ball, a conductive metal layer formed on the surface of the resin fine particles, or the like can be used. Among them, a conductive metal layer formed on the surface of the resin microparticles can be used for conductive connection without damaging the transparent substrate or the like due to the excellent elasticity of the resin microparticles, which is preferable.

A liquid crystal display element using the sealing compound for liquid crystal display elements of the present invention or the upper and lower conduction materials of the present invention is also one of the present invention.

The sealing compound for liquid crystal display elements of this invention can be used suitably for manufacturing a liquid crystal display element by the liquid crystal dropping method.

As a method of manufacturing the liquid crystal display element of the present invention by the liquid crystal dropping method, for example, the following methods can be cited.

First, a step of forming a rectangular seal pattern on a substrate by screen printing, dispenser coating, or the like to form a sealant for a liquid crystal display element of the present invention is performed. Then, in the uncured state of the sealant for liquid crystal display elements of the present invention, the step of dropping the liquid crystal coated droplets on the entire frame of the transparent substrate and immediately overlapping it with another substrate is performed. After that, the steps of irradiating ultraviolet light or the like to the sealing pattern portion of the sealant for liquid crystal display element of the present invention to temporarily cure the sealant, and the step of heating the temporarily hardened sealant to formally harden, can be carried out as described above Step by step method to obtain a liquid crystal display element.

As the above substrate, a flexible substrate is preferred.

Examples of the flexible substrate include plastic substrates made of polyethylene terephthalate, polyester, poly(meth)acrylate, polycarbonate, polyether satin, and polyimide. Moreover, the sealing compound for liquid crystal display elements of this invention can also be used when attaching a normal glass substrate.

A transparent electrode made of indium oxide, etc., an alignment film made of polyimide, etc., an inorganic ion shielding film, etc. are usually formed on the substrate.

According to the present invention, it is possible to provide a sealant for a liquid crystal display element which can obtain a cured product which can maintain excellent adhesiveness even when the substrate is repeatedly deformed and has excellent impact resistance. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.

Hereinafter, the present invention will be described in further detail with examples, but the present invention is not limited to these examples.

(Synthesis Example 1)

To the reaction flask, 15 parts by weight of a butadiene-acrylonitrile copolymer containing terminal amine groups ("ATBN 1300X16" manufactured by Ube Kosei Corporation) and bisphenol A epoxy acrylate ("DAICEL ALLNEX Corporation") were added. EBECR YL3700") 60 parts by weight. Then, the mixture in the reaction flask was stirred at 120° C. for 3 hours to carry out a reaction, thereby obtaining butadiene-acrylonitrile (ATBN) modified epoxy acrylate containing terminal amine groups as a polymerizable functional group and rubber Structured compounds.

(Synthesis Example 2)

To the reaction flask, 3550 parts by weight of butadiene-acrylonitrile copolymer ("CTBN1300X8" manufactured by Ube Kosei Corporation) containing terminal carboxyl groups and 400 parts by weight of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Corporation) were added 10. 10 parts by weight of p-methoxyphenol as a polymerization inhibitor and 10 parts by weight of triethylamine as a reaction catalyst. Then, while feeding air into the reaction flask, while stirring at 110°C under reflux for 5 hours, the mixture in the reaction flask was reacted to obtain modified epoxy acrylic acid containing butadiene-acrylonitrile (CTBN) containing terminal carboxyl groups. Ester as a compound with a polymerizable functional group and a rubber structure.

(Synthesis Example 3)

To the reaction flask were added 72 parts by weight of acrylic acid, 312 parts by weight of bisphenol F diglycidyl ether, 0.3 parts by weight of p-methoxyphenol as a polymerization inhibitor, and 0.3 parts by weight of triethylamine as a reaction catalyst. Then, the mixture in the reaction flask was reacted while heating to 90°C using a heating mantle and stirring for 5 hours, thereby obtaining a part of acrylic-modified bisphenol F-type epoxy resin.

(Examples 1 to 10 and Comparative Examples 1 to 4)

Using a planetary mixer (Thinky Co., Ltd. manufactured by Thinky) to mix the materials of the blending ratios described in Tables 1 and 2, and then using a three-roll mill to mix, thereby preparing Examples 1 to 10. , And the sealants for liquid crystal display elements of Comparative Examples 1 to 4.

After irradiating 100 mW/cm ² of ultraviolet light (wavelength 365 nm) for 30 seconds with a metal halogen lamp to the obtained sealant for each liquid crystal display element, it was heated at 120° C. for 1 hour to obtain a cured product. Using a dynamic viscoelasticity measuring device ("DVA-200" manufactured by IT METER AND CONTROL), the test piece was tested under the conditions of test piece width 5mm, thickness 0.35mm, grip width 25mm, heating rate 10°C/min, frequency 10Hz The obtained hardened material measures the storage elastic modulus and the loss elastic modulus. Tables 1 and 2 show the storage elastic modulus and loss elastic modulus of each hardened product at 25°C.

<evaluation>

The following evaluation was performed about each sealing compound for liquid crystal display elements obtained in the Example and the comparative example. The results are shown in Tables 1 and 2.

(One-sided bending test)

After irradiating 100 mW/cm ² of ultraviolet light (wavelength 365 nm) for 30 seconds with a metal halide lamp to each liquid crystal display element sealant obtained in Examples and Comparative Examples, it was heated at 120° C. for 1 hour to produce a film with a thickness of 300 μm. Use it as a test piece. Each obtained test piece was wound on a SUS rod of 30 mm in diameter, and the state of each test piece when it was fixed with tape ("Fabric tape 601S" manufactured by Sekisui Chemical Industry Co., Ltd.) was visually observed.

As a result, the case where the peeling of the test piece and the tape was not confirmed was evaluated as "○", and the case where the test piece was confirmed to be peeled but the tape was still partially fixed was evaluated as "△", and both the test piece and the tape were confirmed to be peeled. The situation is evaluated as "×". In this test, it is better to deform the test piece more easily, so it is more advantageous if the storage elastic modulus is low.

(Left and right bending test)

For the five test pieces produced in the same manner as the above "(One-sided bending test)", the following operation is performed at a rate of 20 times per minute for 10 minutes, that is, it is made about 10 along the long side with the test piece The arc of the double-diameter roller is bent 90 degrees and then returns to a flat shape, and then bent 90 degrees in the opposite direction and then returned to a flat shape, and then the state of each test piece is visually observed. As a result, the case where no deformation was confirmed for all 5 test pieces was evaluated as "○", and the case where 1 or more and 3 or less test pieces were confirmed to be deformed was evaluated as "△", and 4 or more test pieces were evaluated The case where deformation was confirmed was evaluated as "×". In this test, it is necessary to prevent plastic deformation of the test piece, so it is more advantageous when the loss elastic modulus is low.

(Impact resistance test)

For the 5 test pieces made in the same way as the above "(One-sided bending test)", each test piece was placed on the floor, and a 100g weight was dropped from a height of 50cm onto each test piece, and then Visually observe the state of each test piece.

As a result, the case where no cracks or ruptures were confirmed for all 5 test pieces was evaluated as "○", and the case where 1 or more and 3 or less test pieces were confirmed to be cracked or broken was evaluated as "△", and When 4 or more test pieces were confirmed to be cracked or broken, they were evaluated as “×”. In this test, the deformation of the test piece is required to be easier and the shape is restored after the deformation, so it is more advantageous when the storage elastic modulus is low and the loss elastic modulus is high.

[Industry availability]

According to the present invention, it is possible to provide a sealant for a liquid crystal display element which can obtain a cured product which can maintain excellent adhesiveness even when the substrate is repeatedly deformed and has excellent impact resistance. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.

Claims (6)

A sealant for liquid crystal display elements, containing a curable resin, a polymerization initiator and/or a thermosetting agent, characterized in that the storage elastic modulus of the cured product at 25°C is 2.0 GPa or less, and the cured product is at 25°C The loss elastic modulus is 0.1 GPa or more and 1.0 GPa or less, the curable resin contains a compound having a polymerizable functional group and a rubber structure, and 100 parts by weight of the entire curable resin has a polymerizable functional group and a rubber structure The content of the compound is 20 parts by weight or more and 75 parts by weight or less. For example, in the sealant for liquid crystal display elements of claim 1, the above rubber structure has a structure having an unsaturated bond in the main chain or a structure having a polysiloxane skeleton in the main chain. As for the sealant for liquid crystal display elements of claim 1 or 2, the content of the compound having the polymerizable functional group and the rubber structure in 100 parts by weight of the entire curable resin is 51 parts by weight or more and 70 parts by weight Below. As for the sealing compound for liquid crystal display elements of Claim 1 or 2, the said curable resin contains epoxy (meth)acrylate. A vertical conduction material, which contains a sealant for liquid crystal display elements and conductive fine particles, the sealant for liquid crystal display elements contains a curable resin, a polymerization initiator, and/or a thermosetting agent, and the hardening of the sealant for liquid crystal display elements The storage elastic modulus of the product at 25°C is 2.0 GPa or less, and the loss elastic modulus of the cured product at 25°C is 0.1 GPa or more and 1.0 GPa or less. The curable resin contains a compound having a polymerizable functional group and a rubber structure, The content of the compound having the polymerizable functional group and the rubber structure in 100 parts by weight of the entire curable resin is 20 parts by weight or more and 75 parts by weight or less. A liquid crystal display element which uses the liquid of items 1, 2, 3 or 4 of the patent application The crystal display element is made of the sealing compound or the patent application item 5 upper and lower conduction materials.