WO2014192881A1 - Sealing agent for liquid crystal display elements, vertically conducting material, liquid crystal display element and production method of sealing agent for liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a sealing agent for liquid crystal display elements which has excellent adhesiveness, and low moisture permeability of the cured product. A further purpose of the present invention is to provide a vertically conducting material formed using said sealing agent for liquid crystal display elements, a liquid crystal display element, and a production method of the sealing agent for liquid crystal display elements. This sealing agent for liquid crystal display elements contains a particle-dispersed curable resin comprising (meth)acrylic acid ester polymer particles dispersed in a curable resin, and a radical polymerization initiator and/or a thermosetting agent, wherein the particle-dispersed curable resin is formed in that the (meth)acrylic acid ester polymer particles, in a state dispersed in a dispersion medium, are dispersed in a curable resin, and the dispersion medium is thereafter removed.

Description

Sealant for liquid crystal display element, vertical conduction material, liquid crystal display element, and method for producing liquid crystal display element sealant

The present invention relates to a sealant for a liquid crystal display device having excellent adhesiveness and low moisture permeability of a cured product. Moreover, this invention relates to the manufacturing method of the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements, and this liquid crystal display element.

In recent years, as a method for manufacturing a liquid crystal display element, a curable resin, a photopolymerization initiator, and a heat as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a curing agent is used.

In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. . Thereafter, the film is heated and subjected to main curing to produce a liquid crystal display element. A liquid crystal display element can be manufactured with extremely high efficiency by bonding the substrates under a reduced pressure, and this dropping method is currently the mainstream method for manufacturing liquid crystal display elements.

With the widespread use of tablets and mobile devices, liquid crystal display elements are increasingly required to have moisture resistance reliability in driving in high-temperature and high-humidity environments, and the performance of sealing agents to prevent water from entering from the outside. Is further demanded. In order to improve the moisture resistance reliability of the liquid crystal display element, it is necessary to improve the adhesiveness between the sealing agent and the substrate and to reduce the moisture permeability of the cured product of the sealing agent. However, it has been difficult to achieve both high adhesiveness and low moisture permeability in the sealing agent.

JP 2001-133794 A International Publication No. 02/092718

An object of this invention is to provide the sealing compound for liquid crystal display elements which is excellent in adhesiveness and the moisture permeability of hardened | cured material is low. Moreover, an object of this invention is to provide the manufacturing method of the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements, and this sealing compound for liquid crystal display elements.

The present invention includes a particle-dispersed curable resin in which (meth) acrylic acid ester polymer particles are dispersed in a curable resin, a radical polymerization initiator and / or a thermosetting agent, and the particle-dispersed curable resin. Is a sealing agent for a liquid crystal display device in which (meth) acrylic acid ester polymer particles dispersed in a dispersion medium are dispersed in a curable resin, and then the dispersion medium is removed.
The present invention is described in detail below.

The present inventor considered blending (meth) acrylic acid ester polymer particles in order to achieve both high adhesion of the sealing agent for liquid crystal display elements and low moisture permeability of the cured product. However, when the (meth) acrylic acid ester polymer particles are blended directly into the sealing agent for liquid crystal display elements, the (meth) acrylic acid ester polymer particles cannot be sufficiently dispersed in the sealing agent, With a sealant in which the dispersion of the (meth) acrylate polymer particles is insufficient, it is impossible to achieve both high adhesiveness and low moisture permeability of the cured product.
Therefore, as a result of intensive studies, the present inventors have dispersed (meth) acrylic acid ester polymer particles dispersed in a dispersion medium in a curable resin, and then removed the dispersion medium to obtain (meth) acrylic acid. By preparing a particle-dispersed curable resin in which ester polymer particles are dispersed in a curable resin, and mixing the particle-dispersed curable resin with other sealant components, (meth) acrylic acid is contained in the sealant. It has been found that ester polymer particles can be sufficiently dispersed, and as a result, it is possible to obtain a sealing agent for a liquid crystal display device having excellent adhesion and low moisture permeability of a cured product, thereby completing the present invention. It came to.

The sealing agent for liquid crystal display elements of the present invention contains a particle-dispersed curable resin in which (meth) acrylic ester polymer particles are dispersed in a curable resin.
The particle-dispersed curable resin is obtained by dispersing (meth) acrylic acid ester polymer particles dispersed in a dispersion medium in a curable resin and then removing the dispersion medium.
In the present specification, the “(meth) acryl” means acryl or methacryl.

Examples of the dispersion medium in which the (meth) acrylic acid ester polymer particles are dispersed include water, acetone, methanol, ethanol, and the like.

The (meth) acrylate polymer particles dispersed in the dispersion medium are preferably obtained by polymerizing a (meth) acrylate monomer in the dispersion medium. Examples of the method for polymerizing the (meth) acrylic acid ester monomer include suspension polymerization, emulsion polymerization, and dispersion polymerization. Among these, emulsion polymerization in the presence of a surfactant is preferable, and since it is not necessary to remove the surfactant after polymerization, the emulsion polymerization in the presence of a reactive surfactant is more preferable. preferable.

Examples of the (meth) acrylic acid ester monomer used as the raw material for the (meth) acrylic acid ester polymer particles include linear or branched aliphatic alkyl alcohols having 1 to 18 carbon atoms or alicyclic rings. (Meth) acrylic acid esters which are ester compounds of the formula alkyl alcohol and (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid and polypropylene glycol or polyethylene Hydroxyl group-containing unsaturated monomers such as monoester with glycol, epoxy group-containing unsaturated monomers such as glycidyl (meth) acrylate, (meth) acryloylaziridine, (meth) acryloyloxyethylaziridine Aziridinyl group-containing unsaturated monomers such as 2-isopropenyl Oxazoline group-containing unsaturated monomers such as -2-oxazoline and 2-vinyl-2-oxazoline, (meth) acrylic acid and ethylene glycol, 1,3-butylene glycol, 1,6-hexane glycol, neopentyl Polyfunctional (meth) acrylic acid esters containing two or more polymerizable unsaturated groups in the molecule such as an ester with a polyhydric alcohol such as glycol, polyethylene glycol, polypropylene glycol and trimethylolpropane; Examples include allyl acrylate. Among them, the reactive surfactant and the (meth) acrylic acid ester polymer particles are firmly bonded, so that epoxy group-containing unsaturated monomers, aziridinyl group-containing unsaturated monomers, oxazoline groups Containing unsaturated monomers are preferred. Moreover, since a moderate crosslinked structure can be introduce | transduced into a (meth) acrylic acid ester type polymer particle, polyfunctional (meth) acrylic acid esters and (meth) acrylic acid allyl are also preferable.
These (meth) acrylic acid ester monomers may be used alone or in combination of two or more.

Further, in addition to the above (meth) acrylic acid ester monomer, other copolymerizable monomers may be used as long as the object of the present invention is not impaired.
Examples of the other copolymerizable monomers include styrene, vinyl toluene, acrylonitrile, methacrylonitrile, vinyl acetate, divinylbenzene, diallyl phthalate and the like. Among these, divinylbenzene and diallyl phthalate are preferable because an appropriate cross-linked structure can be introduced into the (meth) acrylic acid ester polymer particles.

The surfactant has a role as an emulsifier in the emulsion polymerization.
As described above, a reactive surfactant is preferably used as the surfactant because it does not need to be removed after polymerization.
The reactive surfactant is a water-soluble or acid-soluble product obtained by polymerizing a polymerizable monomer component containing an unsaturated carboxylic acid in the presence of an alkyl mercaptan having 6 to 18 carbon atoms. A water-dispersible terminal alkyl group-containing polymer and / or a salt thereof is preferable.

The unsaturated carboxylic acid has a role of imparting hydrophilicity to the terminal alkyl group-containing polymer and a role of introducing a functional group capable of reacting with an epoxy resin into the (meth) acrylic acid ester polymer particles. .

Examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and half-esterified products of these unsaturated dicarboxylic acids. Etc. These unsaturated carboxylic acids may be used alone or in combination of two or more.

The polymerizable monomer component may contain other polymerizable monomer in addition to the unsaturated carboxylic acid.
The other polymerizable monomer is not particularly limited as long as it has copolymerizability with the unsaturated carboxylic acid, and examples thereof include styrene, vinyl toluene, α-methyl styrene, chloromethyl styrene, styrene sulfone. Styrene derivatives such as acids and salts thereof, (meth) acrylamide derivatives such as (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, , Synthesized by esterification reaction of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like with an alcohol having 1 to 18 carbon atoms. Acrylic esters, 2-hydroxyethyl (meth) acrylate, 2-hydro (meth) acrylate Hydroxy group-containing (meth) acrylic acid esters such as cypropyl, (meth) acrylic acid and polypropylene glycol or polyethylene glycol monoester, ethyl (meth) acrylate 2-ethyl sulfonate and salts thereof, vinyl sulfonic acid and its A salt, vinyl acetate, (meth) acrylonitrile, etc. are mentioned. These other polymerizable monomers may be used alone or in combination of two or more.
The type and amount of the other polymerizable monomer are appropriately adjusted in consideration of the acid value of the obtained terminal alkyl group-containing polymer.

The alkyl mercaptan used as a raw material for the terminal alkyl group-containing polymer has a role of imparting surface activity by introducing an alkyl group into the terminal of the terminal alkyl group-containing polymer.

The lower limit of the carbon number of the terminal alkyl group-containing polymer is 6 and the upper limit is 18. When the number of carbon atoms of the alkyl mercaptan is less than 6, storage stability and stability during emulsion polymerization are deteriorated. When the number of carbon atoms of the alkyl mercaptan exceeds 18, adverse effects due to unreacted substances occur.
Specific examples of the alkyl mercaptan include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, cetyl mercaptan, stearyl mercaptan and the like. These alkyl mercaptans may be used alone or in combination of two or more.

The amount of the alkyl mercaptan used is preferably 2 parts by weight and preferably 300 parts by weight with respect to 100 parts by weight of the polymerizable monomer component. If the amount of the alkyl mercaptan used is less than 2 parts by weight, the surface activity may not be sufficiently imparted. When the amount of the alkyl mercaptan used exceeds 300 parts by weight, an adverse effect due to unreacted substances occurs.

Examples of the method for producing the terminal alkyl group-containing polymer include bulk polymerization, solution polymerization, and suspension polymerization.
When the terminal alkyl group-containing polymer is produced, it is preferable to use a polymerization initiator of preferably 1 mol or less, more preferably 0.1 mol or less with respect to 1 mol of the alkyl mercaptan.
The preferred polymerization temperature for producing the terminal alkyl group-containing polymer is usually 50 to 150 ° C., and the preferred polymerization time is 1 to 8 hours.

The terminal alkyl group-containing polymer has an acid value of 200 or more. When the acid value of the terminal alkyl group-containing polymer is less than 200, the (meth) acrylic acid ester polymer particles may not be sufficiently imparted with reactivity with an epoxy resin.
Although there is no particular upper limit on the acid value of the terminal alkyl group-containing polymer, the substantial upper limit is 500.

The minimum with a preferable number average molecular weight of the said terminal alkyl group containing polymer is 300, and a preferable upper limit is 7000. By using a terminal alkyl group-containing polymer having an acid value of 200 or more in which the number average molecular weight of the terminal alkyl group-containing polymer is in this range, the (meth) acrylic acid ester polymer particles are reacted with an epoxy resin. It is possible to sufficiently impart properties. The more preferable lower limit of the number average molecular weight of the terminal alkyl group-containing polymer is 1000, and the more preferable upper limit is 4000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).

A salt obtained by neutralizing a part or all of the carboxyl groups of the terminal alkyl group-containing polymer with a neutralizing agent has an excellent emulsifying effect when performing emulsion polymerization.
Examples of the neutralizing agent include alkali metal compounds such as sodium hydroxide and potassium hydroxide, alkaline earth metal compounds such as calcium hydroxide and calcium carbonate, ammonia, monomethylamine, dimethylamine, trimethylamine, and mono Examples include water-soluble organic amines such as ethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and diethylenetriamine. Of these, ammonia and low boiling point amines such as monomethylamine, dimethylamine, and trimethylamine are preferable.

Examples of the emulsion polymerization method for obtaining the (meth) acrylic acid ester polymer particles include, for example, the terminal alkyl group-containing polymer and / or a salt thereof together with the polymerizable monomer component and the dispersion medium. Examples of the polymerization method include mixing, a monomer dropping method, a pre-emulsion method, a seed polymerization method, and a multistage polymerization method.
A preferable polymerization temperature for the above emulsion polymerization is 0 to 100 ° C., and a more preferable polymerization temperature is 50 to 80 ° C. The preferred polymerization time for the emulsion polymerization is 1 to 10 hours.

As for the usage-amount of the said surfactant, a preferable minimum is 0.5 weight part and a preferable upper limit is 10 weight part with respect to 100 weight part of said (meth) acrylic acid ester monomers. If the amount of the reactive surfactant used is less than 0.5 parts by weight, the emulsifying effect may not be sufficiently exhibited. When the usage-amount of the said reactive surfactant exceeds 10 weight part, it may become easy to produce a bubble.

A polymerization catalyst may be used when performing the emulsion polymerization.
Examples of the polymerization catalyst include hydrogen peroxide, peracetic acid, di-t-butyl peroxide, 4,4′-azobis (4-cyanopentanoic acid), and the like.

The upper limit with preferable glass transition temperature of the said (meth) acrylic-ester type polymer particle is 20 degreeC. When the glass transition temperature of the (meth) acrylic acid ester polymer particles exceeds 20 ° C., the obtained cured product of the sealing agent for liquid crystal display elements may be inferior in toughness. A more preferable upper limit of the glass transition temperature of the (meth) acrylic acid ester polymer particles is 0 ° C.
The lower limit of the glass transition temperature of the (meth) acrylic acid ester polymer particles is not particularly limited, but the substantial lower limit is −80 ° C.

The minimum with a preferable average particle diameter of the said (meth) acrylic-ester type polymer particle is 0.01 micrometer, and a preferable upper limit is 10 micrometers. When the average particle diameter of the (meth) acrylic acid ester polymer particles is less than 0.01 μm, the obtained cured product of the sealing agent for liquid crystal display elements may be inferior in adhesiveness. When the average particle diameter of the (meth) acrylic acid ester polymer particles exceeds 10 μm, the moisture permeability of the cured product of the obtained sealing agent for liquid crystal display elements becomes high, and display defects may occur in the liquid crystal display elements. . The minimum with a more preferable average particle diameter of the said (meth) acrylic-ester type polymer particle is 0.1 micrometer, and a more preferable upper limit is 8 micrometers.
In addition, in this specification, the said average particle diameter means the average value of the particle diameter of 10 particle | grains observed by the magnification of 10,000 times using the scanning electron microscope. As the scanning electron microscope, S-4300 (manufactured by Hitachi High-Technologies Corporation) or the like can be used.

The preferable lower limit of the content of the (meth) acrylate polymer particles in 100 parts by weight of the particle-dispersed curable resin is 5 parts by weight, and the preferable upper limit is 50 parts by weight. If the content of the (meth) acrylic acid ester polymer particles is less than 5 parts by weight, the effect of improving the adhesive strength of the cured product of the obtained sealing agent for liquid crystal display elements may not be sufficiently exhibited. When the content of the (meth) acrylic acid ester polymer particles exceeds 50 parts by weight, the viscosity becomes too high, and the obtained sealing agent for liquid crystal display elements may be inferior in coatability. The minimum with more preferable content of the said (meth) acrylic-ester type polymer particle is 10 weight part, and a more preferable upper limit is 30 weight part.

Examples of the curable resin in which the (meth) acrylic ester polymer particles are dispersed include an epoxy resin and a (meth) acrylic resin. Among these, an epoxy resin is preferably used. That is, the particle-dispersed curable resin is preferably a particle-dispersed epoxy resin in which (meth) acrylic ester polymer particles are dispersed in an epoxy resin.
In the present specification, the “(meth) acrylic resin” means a compound having a (meth) acryloyl group, and the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2,2′-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, and propylene oxide-added bisphenol A. Type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, di Cyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphthalenephenol novolac epoxy resin, glycidyl amide Type epoxy resins, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, bisphenol A type episulfide resins. These epoxy resins may be used independently and 2 or more types may be used in combination.

Examples of commercially available bisphenol A type epoxy resins include jER828, jER1004 (all manufactured by Mitsubishi Chemical Corporation), and Epicron 850-S (manufactured by DIC).
As what is marketed among the said bisphenol F-type epoxy resins, jER806, jER4004 (all are the Mitsubishi Chemical company make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include jERYX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available bisphenol A type episulfide resins include jERYL-7000 (manufactured by Mitsubishi Chemical Corporation).
Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 (all Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation) and the like.

Examples of the (meth) acrylic resin include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and an epoxy (meta) obtained by reacting (meth) acrylic acid with an epoxy compound. ) Urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with acrylate or isocyanate.
In the present specification, the term “(meth) acrylate” means acrylate or methacrylate, and the term “epoxy (meth) acrylate” means that all epoxy groups of an epoxy compound are reacted with (meth) acrylic acid. It may be that in which some epoxy groups of the epoxy compound are reacted with (meth) acrylic acid.
As the (meth) acrylic resin, a methacrylic resin is preferable because the moisture permeability of the cured product of the obtained sealing agent can be further lowered.

Examples of the monofunctional compounds of the ester compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethylcal Tall (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl ( (Meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (Meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethyl Aminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl ( And (meth) acrylate and 2- (meth) acryloyloxyethyl phosphate.

Examples of the bifunctional ester compound include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (me ) Acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyl di (meth) acrylate, 1,3 -Butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di ( (Meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate Polybutadiene di (meth) acrylate.

Examples of the ester compound having three or more functional groups include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri. (Meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide De additional glycerin tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, and the like.

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

As an epoxy compound used as a raw material for synthesize | combining the said epoxy (meth) acrylate, the thing similar to the epoxy resin which disperse | distributes the (meth) acrylic acid ester type polymer particle mentioned above can be used.

As what is marketed among the said epoxy (meth) acrylate, as what all the epoxy groups of the epoxy compound reacted with (meth) acrylic acid, for example, Evecryl 860, Evecryl 3200, Evecril 3201, Evecryl 3412, Evecryl 3600, Evecril 3700, Evecril 3701, Evecril 3702, Evecril 3800, Evecril 3800, Evecril 6040, Evecryl RDX63182 (all manufactured by Daicel Ornex), EA-1010, EA-1020, EA-5323, EA-5520, EA- CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Epoxy ester M-600A, Epoxy ester 40EM, Epoxy ester 70PA, Epoxy ester 200PA, Poxyester 80MFA, Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911 (all manufactured by Nagase ChemteX Corporation) and the like.
Moreover, as what is marketed among the said epoxy (meth) acrylate, as a thing with which some epoxy groups of the epoxy compound reacted with (meth) acrylic acid, UVACURE1561 (made by Daicel Ornex) is mentioned, for example. It is done.

The urethane (meth) acrylate is obtained, for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of a compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound. Can do.

Examples of the isocyanate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), and hydrogenated MDI. , Polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethyl Examples include xylene diisocyanate and 1,6,10-undecane triisocyanate.

In addition, as an isocyanate that is a raw material of the urethane (meth) acrylate, polyols such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like Chain-extended isocyanate compounds obtained by reaction with excess isocyanate can also be used.

Examples of the (meth) acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Commercial products such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, mono (meth) acrylates of trihydric alcohols such as polyethylene glycol, trimethylolethane And mono (meth) acrylate or di (meth) acrylate of a trivalent alcohol such as trimethylolpropane and glycerin, and epoxy acrylate such as bisphenol A-modified epoxy acrylate.

Commercially available urethane (meth) acrylates include, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), Evecryl 230, Evekril 270, Evekril 4858. , Evecril 8402, Evecril 8804, Evecril 8803, Evecril 8807, Evecril 9260, Evecryl 1290, Evecril 5129, Evecril 4842, Evecril 4827, Evecril 4827, Evecril 6700, Evecril 220, Evecryl 22B Resin UN-9000H, Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-33 0HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Kogyo Co., Ltd.), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA- 7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600, AT-600, UA- 306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.) It is.

The (meth) acrylic resin preferably has a hydrogen-bonding unit such as —OH group, —NH— group, —NH ₂ group and the like from the viewpoint of suppressing adverse effects on the liquid crystal. (Meth) acrylate is particularly preferred.
The (meth) acrylic resin preferably has 2 to 3 (meth) acryloyl groups in the molecule because of its high reactivity.

As a method for producing the particle-dispersed curable resin, for example, the emulsion of the (meth) acrylic acid ester polymer particles obtained by the emulsion polymerization described above is mixed with the curable resin, and the mixture is subjected to normal pressure or reduced pressure. Examples thereof include a method of removing the dispersion medium while stirring under.

As what is marketed among the said particle | grain dispersion | distribution curable resin, the Acre Reset BP series (made by Nippon Shokubai Co., Ltd.) etc. are mentioned, for example.

The preferable lower limit of the content of the particle-dispersed curable resin in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 2 parts by weight, and the preferable upper limit is 30 parts by weight. If the content of the particle-dispersed curable resin is less than 2 parts by weight, the effect of improving the adhesive strength of the cured product of the obtained sealing agent for liquid crystal display elements may not be sufficiently exhibited. If the content of the particle dispersion curable resin exceeds 30 parts by weight, liquid crystal contamination may occur. A more preferable lower limit of the content of the particle dispersion curable resin is 5 parts by weight, and a more preferable upper limit is 20 parts by weight.

The sealant for a liquid crystal display element of the present invention is a blend of a curable resin in which particles are not dispersed (hereinafter also referred to as “other curable resin”) in addition to the above-mentioned particle dispersion curable resin. There may be.
As said other curable resin, what was mentioned as curable resin which disperse | distributes the said (meth) acrylic-ester type polymer particle can be used. Especially, the said (meth) acrylic resin is preferable. That is, it is preferable that the sealing compound for liquid crystal display elements of the present invention contains a particle dispersion curable resin, a (meth) acrylic resin, a radical polymerization initiator and / or a thermosetting agent. As the (meth) acrylic resin used as the other curable resin, a methacrylic resin is preferable because the moisture permeability of the cured product of the obtained sealant can be further reduced. Moreover, as a (meth) acrylic resin used as said other curable resin, an epoxy (meth) acrylate is used suitably.

The sealing agent for liquid crystal display elements of this invention contains a radical polymerization initiator and / or a thermosetting agent.
Examples of the radical polymerization initiator include photo radical polymerization initiators, thermal radical polymerization initiators, and the like, and the sealing agent for liquid crystal display elements of the present invention contains a thermal radical polymerization initiator as the radical polymerization initiator. Is preferred.

Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, and the like.

Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACUREOXE01, and Lucirin TPO (all manufactured by BASF 30, manufactured by BASF 30 SPEEDCURE EMK (manufactured by Nippon Sebel Hegner), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all of which are manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.

Examples of the thermal radical polymerization initiator include azo compounds and peroxides. Among these, a polymer azo initiator composed of a polymer azo compound is preferable.
In the present specification, the polymer azo initiator means a compound having an azo group and generating a radical capable of curing a (meth) acryloyloxy group by heat and having a number average molecular weight of 300 or more. .

The preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo initiator is less than 1000, the polymer azo initiator may adversely affect the liquid crystal. When the number average molecular weight of the polymeric azo initiator exceeds 300,000, mixing with the curable resin may be difficult. The more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).

Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable. Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples include polycondensates of polydimethylsiloxane having a terminal amino group.

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

Examples of commercially available thermal radical polymerization initiators include perbutyl O, perhexyl O, perbutyl PV (all manufactured by NOF Corporation), V-30, V-501, V-601, VPE-0201. VPE-0401, VPE-0601 (both manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

The minimum with preferable content of the said radical polymerization initiator in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 0.01 weight part, and a preferable upper limit is 10 weight part. When the content of the radical polymerization initiator is less than 0.01 parts by weight, the obtained sealing agent for liquid crystal display elements may not be sufficiently cured. When content of the said radical polymerization initiator exceeds 10 weight part, storage stability may fall.

Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among these, solid organic acid hydrazide is preferably used.

Examples of the solid organic acid hydrazide include 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like. Examples of such products include SDH (manufactured by Nippon Finechem Co., Ltd.), ADH (manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like.

The preferable lower limit of the content of the thermosetting agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 1 part by weight, and the preferable upper limit is 50 parts by weight. When the content of the thermosetting agent is less than 1 part by weight, the sealing agent for liquid crystal display elements of the present invention may not be sufficiently cured. When content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal display elements of this invention will become high, and coating property may deteriorate. The minimum with more preferable content of the said thermosetting agent is 1.5 weight part, and a more preferable upper limit is 30 weight part.

The sealing agent for liquid crystal display elements of the present invention may further contain a filler for the purpose of improving the adhesiveness by the stress dispersion effect, improving the linear expansion coefficient, and the like.
Examples of the filler include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, and hydroxide. Examples include inorganic fillers such as aluminum, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, and aluminum nitride, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles. It is done.

The minimum with preferable content of the said filler in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 5 weight part, and a preferable upper limit is 70 weight part. When the content of the filler is less than 5 parts by weight, effects such as improvement of adhesiveness may not be sufficiently exhibited. When the content of the filler exceeds 70 parts by weight, the viscosity of the obtained sealing agent for liquid crystal display elements becomes too high, and coatability may be deteriorated. The minimum with more preferable content of the said filler is 10 weight part, and a more preferable upper limit is 60 weight part.

The sealing agent for liquid crystal display elements of the present invention may contain a silane coupling agent.
As the silane coupling agent, for example, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane and the like are preferably used. These may be used independently and 2 or more types may be used together.

The minimum with preferable content of the said silane coupling agent in 100 weight part of sealing agents for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 20 weight part. When the content of the silane coupling agent is less than 0.1 parts by weight, the effect of blending the silane coupling agent may not be sufficiently exhibited. When content of the said silane coupling agent exceeds 20 weight part, the sealing compound for liquid crystal display elements obtained may cause liquid-crystal contamination. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 10 weight part.

The sealing agent for liquid crystal display elements of the present invention may contain a light shielding agent. By containing the said light shielding agent, the sealing compound 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. Of these, titanium black is preferable.

Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing a light shielding property to the sealing agent for liquid crystal display elements of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region. A shading agent. Therefore, by using the photo radical polymerization initiator or the photo cationic polymerization initiator that can start the reaction with light having a wavelength (370 to 450 nm) at which the transmittance of the titanium black is high, the liquid crystal of the present invention is used. The photocurability of the sealant for display elements can be further increased. On the other hand, the light shielding agent contained in the liquid crystal display element sealant of the present invention is preferably a highly insulating material, and titanium black is also preferred as the highly insulating light shielding agent.
The titanium black preferably has an optical density (OD value) per μm of 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black is not particularly limited, but is usually 5 or less.

The above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.

Examples of commercially available titanium black include 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), 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.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.

The primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5 μm. When the primary particle diameter of the light-shielding agent is less than 1 nm, the viscosity and thixotropy of the obtained sealing agent for liquid crystal display elements is greatly increased, and workability may be deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5 μm, the applicability of the obtained sealing agent for liquid crystal display elements to the substrate may be deteriorated. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.

The preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. If the content of the light shielding agent is less than 5 parts by weight, sufficient light shielding properties may not be obtained. When the content of the light-shielding agent exceeds 80 parts by weight, the adhesion of the obtained sealing agent for liquid crystal display elements to the substrate and the strength after curing may be lowered, or the drawing property may be lowered. The more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.

The sealing agent for liquid crystal display elements of the present invention preferably further contains flexible particles having a maximum particle size of 100% or more of the cell gap of the liquid crystal display element and 5 μm to 20 μm. By blending the flexible particles with the sealing agent, when the substrates of the liquid crystal display element are bonded together, the flexible particles are crushed by the substrate bonding pressure in the sealing agent to partially form a stationary dam. By doing so, it is possible to effectively suppress the occurrence of seal break and liquid crystal contamination due to the flow of the liquid sealant component.

The sealing agent for liquid crystal display elements of the present invention further comprises a spacer such as a reactive diluent for adjusting the viscosity, a thixotropic agent for adjusting the thixotropy, a polymer bead for adjusting the panel gap, if necessary. Other known additives such as a curing accelerator such as -P-chlorophenyl-1,1-dimethylurea, an antifoaming agent, a leveling agent, and a polymerization inhibitor may be contained.

A polymerizable monomer component containing an unsaturated carboxylic acid is polymerized in the presence of an alkyl mercaptan having 6 to 18 carbon atoms, and a water-soluble or water-dispersible terminal alkyl group-containing polymer having an acid value of 200 or more and Step 1 for obtaining a reactive surfactant which is a salt thereof, (meth) acrylic acid ester polymer by emulsion polymerization of (meth) acrylic acid ester monomer in the presence of the reactive surfactant Step 2 for obtaining particles, Step 3 for obtaining a particle-dispersed epoxy resin by dispersing the (meth) acrylic ester polymer particles in an epoxy resin, and at least the particle-dispersed epoxy resin and (meth) acrylic resin And a process 4 for mixing a radical polymerization initiator and / or a thermosetting agent is also one aspect of the present invention.

Examples of the mixing method in Step 4 include, for example, a particle-dispersed epoxy resin prepared in advance in Steps 1 to 3, a (meth) acrylic resin, a radical polymerization initiator and / or a thermosetting agent, as necessary. Examples thereof include a method of mixing the silane coupling agent added in accordance with a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll.

A vertical conducting material can be produced by blending conductive fine particles with the liquid crystal display element sealant of the present invention. If such a vertical conduction material is used, the electrodes can be reliably conductively connected.
The vertical conduction material containing the sealing agent for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.

As said electroconductive fine particles, what formed the conductive metal layer on the surface of a metal ball, resin microparticles | fine-particles etc. can be used, for example. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.

The liquid crystal display element using the sealing agent for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.
As a method for producing the liquid crystal display element of the present invention, for example, the liquid crystal display element sealant of the present invention is applied to one of two substrates having an ITO thin film by screen printing, dispenser application, etc. The step of forming the seal pattern, the step of applying the liquid crystal microdrops on the entire surface of the frame of the seal pattern, and superposing the other substrate under vacuum, the liquid crystal display element sealant of the present invention is irradiated with light such as ultraviolet rays Examples of the method include a step of irradiating and temporarily curing the sealant, and a step of heating and temporarily curing the temporarily cured sealant.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which is excellent in adhesiveness and has low moisture permeability of hardened | cured material can be provided. Moreover, according to this invention, the manufacturing method of the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements, and this sealing compound for liquid crystal display elements can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Production of reactive surfactant A)
A flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 180 parts by weight of isopropyl alcohol as a solvent, heated to 81 ° C. while being blown with nitrogen, and refluxed for 10 minutes. Thereafter, 53.6 parts by weight of acrylic acid as unsaturated carboxylic acid, 16.5 parts by weight of lauryl methacrylate, 91 parts by weight of polyethylene glycol monomethacrylate, 13.7 parts by weight of n-dodecyl mercaptan as alkyl mercaptan, and polymerization A polymerizable monomer mixture obtained by mixing 0.4 parts by weight of 2,2-azobisisobutyronitrile (AIBN) as an initiator was dropped into the flask over 2 hours. After completion of the dropwise addition, the mixture was refluxed for 1 hour to obtain a solution of a terminal alkyl group-containing polymer (reactive surfactant A) having a solid content of 49.1% by weight.
The resulting reactive surfactant A had an acid value of 239 and a number average molecular weight of 2300.

(Production of reactive surfactant B)
As the unsaturated carboxylic acid, the solid content was 49.5% by weight in the same manner as “(Production of Reactive Surfactant A)” except that acrylic acid was not used and the blending amount of methacrylic acid was 70 parts by weight. Solution of the terminal alkyl group-containing polymer (reactive surfactant B).
The resulting reactive surfactant B had an acid value of 256 and a number average molecular weight of 2,100.

(Production of reactive surfactant C)
The terminal alkyl group having a solid content of 49.6% by weight was the same as “(Production of reactive surfactant A)” except that 18 parts by weight of stearyl mercaptan was used in place of n-dodecyl mercaptan as the alkyl mercaptan. A solution of the containing polymer (reactive surfactant C) was obtained.
The resulting reactive surfactant C had an acid value of 630 and a number average molecular weight of 2800.

(Preparation of particle dispersion curable resin A)
4.1 parts by weight of the resulting reactive surfactant A solution, 85 parts by weight of ethyl acrylate, 10 parts by weight of ethyl methacrylate, and 5 parts by weight of glycidyl methacrylate as a (meth) acrylate monomer Part, 0.5% by weight of 28% ammonia water, and 36 parts by weight of ion exchange water were mixed and stirred to obtain a pre-emulsion.
A flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 63 parts by weight of water, heated to 70 ° C. while blowing nitrogen gas, and 4,4 ′ as a polymerization catalyst. -After adding 8 parts by weight of a 5% aqueous solution of ammonia-neutralized azobis (4-cyanopentanoic acid), the resulting pre-emulsion was dropped from the dropping funnel over 3.5 hours. The temperature during dropping of the pre-emulsion was maintained at 70 to 75 ° C. After the dropping was completed, the polymerization was terminated by stirring for 2 hours at the same temperature, and a (meth) acrylate polymer emulsion having a nonvolatile content of 46% by weight was obtained. Obtained. After completion of dropping, the dropping funnel was washed with water, and the washing liquid was added to the flask. The obtained (meth) acrylic acid ester polymer had a glass transition temperature of −8 ° C. and an average particle size of 0.2 μm.
A flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with the obtained (meth) acrylic ester polymer emulsion, and water was added to give a nonvolatile content concentration of 30 wt. After adjusting to%, 184 parts by weight of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “jER828”) was added as an epoxy resin and stirred. Next, the temperature was raised to 70 ° C., and the pressure was gradually reduced to 50 mmHg to remove water. Thereafter, the mixture is heated at 130 ° C. to completely remove water, and the carboxyl group in the reactive surfactant A and the epoxy resin are pre-reacted so that the content of (meth) acrylate polymer particles is 20% by weight. Particle dispersion curable resin A which is a particle dispersion epoxy resin was obtained.

(Preparation of particle dispersion curable resin B)
(Meta) In the same manner as “(Preparation of particle-dispersed curable resin A)” except that 3 parts by weight of the reactive surfactant B solution was used instead of the reactive surfactant A solution. A particle-dispersed curable resin B which is a particle-dispersed epoxy resin having an acrylic ester polymer particle content of 20% by weight was obtained.
The (meth) acrylate polymer particles obtained in the particle-dispersed curable resin B had a glass transition temperature of −32 ° C. and an average particle size of 0.2 μm.

(Preparation of particle dispersion curable resin C)
In the same manner as “(Preparation of particle-dispersed curable resin A)” except that 3 parts by weight of the solution of the reactive surfactant C was used instead of the solution of the reactive surfactant A, (Meta) A particle-dispersed curable resin C which is a particle-dispersed epoxy resin having an acrylic ester polymer particle content of 20% by weight was obtained.
The (meth) acrylate polymer particles obtained in the particle-dispersed curable resin C had a glass transition temperature of −20 ° C. and an average particle size of 0.2 μm.

(Preparation of particle dispersion curable resin D)
The content of the (meth) acrylate polymer particles is the same as “(Preparation of particle dispersion curable resin A)” except that the amount of the bisphenol A-type epoxy resin is changed to 874 parts by weight. A particle-dispersed curable resin D, which is a 5% by weight particle-dispersed epoxy resin, was obtained.
The (meth) acrylate polymer particles obtained in the particle-dispersed curable resin D had a glass transition temperature of −8 ° C. and an average particle size of 0.2 μm.

(Preparation of particle dispersion curable resin E)
The content of the (meth) acrylate polymer particles is the same as “(Preparation of particle dispersion curable resin A)” except that the amount of the bisphenol A-type epoxy resin is changed to 46 parts by weight. A particle-dispersed curable resin E, which is a 50% by weight particle-dispersed epoxy resin, was obtained.
The (meth) acrylic acid ester polymer particles obtained in the particle-dispersed curable resin E had a glass transition temperature of −8 ° C. and an average particle size of 0.2 μm.

(Preparation of particle dispersion curable resin F)
Except for using 184 parts by weight of ethyl methacrylate (Mitsubishi Rayon Co., Ltd.) instead of 184 parts by weight of bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., “jER828”), “(Particle Dispersion Curable Resin A In the same manner as in “Preparation”, a particle-dispersed curable resin F, which is a particle-dispersed methacrylic resin having a content of (meth) acrylate polymer particles of 20% by weight, was obtained.
The (meth) acrylate polymer particles obtained in the particle-dispersed curable resin F had a glass transition temperature of −8 ° C. and an average particle size of 0.2 μm.

(Preparation of particle dispersion curable resin G)
The content of the (meth) acrylic acid ester polymer particles is 20% in the same manner as “(Preparation of particle dispersion curable resin A)” except that the stirring time after completion of the pre-emulsion dropping is changed to 30 minutes. % Particle dispersion curable resin G which is a particle dispersion epoxy resin was obtained.
The (meth) acrylate polymer particles obtained in the particle-dispersed curable resin G had a glass transition temperature of −8 ° C. and an average particle size of 0.05 μm.

(Preparation of particle dispersion curable resin H)
The content of the (meth) acrylic acid ester polymer particles is 20% in the same manner as “(Preparation of particle dispersion curable resin A)” except that the stirring time after completion of the pre-emulsion dropping is changed to 4 hours. % Particle dispersion curable resin H which is a particle dispersion epoxy resin was obtained.
The glass transition temperature of the (meth) acrylic acid ester polymer particles obtained in the particle-dispersed curable resin H was −8 ° C., and the average particle size was 0.5 μm.

(Preparation of particle dispersion curable resin I)
(Meth) acrylic acid ester-based polymer as in “(Preparation of particle-dispersed curable resin A)”, except that 1.5 parts by weight of sodium dodecyl sulfate was used instead of the reactive surfactant A solution. A polymer emulsion was obtained. Next, by decanting with water, sodium dodecyl sulfate was removed from the (meth) acrylic acid ester polymer emulsion, and the (meth) acrylic acid ester polymer emulsion from which the sodium dodecyl sulfate was removed was used. Preparation of curable resin A) ”was carried out to obtain a particle-dispersed curable resin I which is a particle-dispersed epoxy resin having a content of (meth) acrylic ester polymer particles of 20% by weight.
The (meth) acrylate polymer particles obtained in the particle-dispersed curable resin I had a glass transition temperature of −20 ° C. and an average particle size of 0.2 μm.

(Example 1)
15 parts by weight of particle dispersion curable resin A, 45 parts by weight of bisphenol A type epoxy methacrylate as (meth) acrylic resin, 1.5 parts by weight of IRGACURE 651 (manufactured by BASF Japan) as a radical polymerization initiator, and malonic acid dihydrazide 5 as a thermosetting agent Part by weight, 32 parts by weight of silica as a filler, and 1.5 parts by weight of γ-glycidoxypropyltrimethoxysilane as a silane coupling agent, a planetary stirrer (Shinky Co., “Awatori Nertaro”) After using and mixing, the liquid crystal display element sealant of Example 1 was prepared by further mixing using three rolls.

(Examples 2 to 12, Comparative Examples 1 and 2)
The sealants for liquid crystal display elements of Examples 2 to 12 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 except that the materials having the blending ratios shown in Tables 1 and 2 were used.
In Comparative Example 2, (meth) acrylic acid ester polymer particles and an epoxy resin were directly mixed in advance, and then the resulting mixture was mixed with other components.

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

(1) Adhesiveness 1% by weight of a silica spacer (Sekisui Chemical Co., Ltd., “SI-H055”) was added to each liquid crystal display element sealant obtained in the Examples and Comparative Examples, and two ITO films After irradiating 3000 mJ / cm ² of ultraviolet rays with a metal halide lamp, the glass test piece (30 × 40 mm) with a fine drop was applied to one of the attached glass test pieces and the other glass test piece was laminated in a cross shape. An adhesion test piece was obtained by heating at 120 ° C. for 60 minutes. A tensile test (5 mm / sec) was performed by placing chucks above and below the adhesion test piece. The case where the value obtained by dividing the obtained measured value (kgf) by the cross-sectional area (cm ² ) of seal application is 60 kgf / cm ² or more is “◯”, and is 30 kgf / cm ² or more and less than 60 kgf / cm ² Was evaluated as “Δ”, and “x” when 0 kgf / cm ² or more and less than 30 kgf / cm ² .

(2) Moisture resistance of the cured product Each of the sealing agents for liquid crystal display elements obtained in Examples and Comparative Examples was coated on a smooth release film with a coater to a thickness of 200 to 300 μm. Subsequently, after irradiating 3000 mJ / cm < ² > of ultraviolet-rays with a metal halide lamp, the film for moisture permeability measurement was obtained by heating at 120 degreeC for 60 minutes. A moisture permeation test cup is prepared by a method according to JIS Z 0208 for moisture proof packaging materials (cup method), and the obtained moisture permeation measuring film is attached to an oven at a temperature of 80 ° C. and a humidity of 90% RH. The moisture permeability was measured. The case where the obtained moisture permeability value is less than 50 g / m ² · 24 hr is “◯”, and the case where it is 50 g / m ² · 24 hr or more and less than 70 g / m ² · 24 hr is “Δ”, 70 g / m ^The case where it was ² · 24 hours or more was evaluated as “x”, and the moisture resistance of the cured product was evaluated.

(3) Display performance of liquid crystal display element (evaluation of color unevenness of liquid crystal display element driven after storage under high temperature and high humidity)
Each liquid crystal display element sealant obtained in Examples and Comparative Examples was filled in a dispensing syringe (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.) and subjected to defoaming treatment. Next, using a dispenser (“SHOTMASTER 300” manufactured by Musashi Engineering Co., Ltd.), a sealing agent was applied so as to draw a rectangular frame on one of the two transparent electrode substrates with an ITO thin film. Subsequently, fine droplets of TN liquid crystal (manufactured by Chisso Corporation, “JC-5001LA”) were applied dropwise with a liquid crystal dropping device, and the other transparent substrate was bonded with a vacuum laminating device under a reduced pressure of 5 Pa. The cells after bonding are irradiated with 3000 mJ / cm ² ultraviolet rays with a metal halide lamp and then heated at 120 ° C. for 60 minutes to thermally cure the sealing agent, thereby producing five liquid crystal display elements for each sealing agent. did. The obtained liquid crystal display element was stored for 36 hours in an environment of a temperature of 80 ° C. and a humidity of 90% RH, and then driven with a voltage of AC 3.5 V, and the periphery of the halftone sealant was visually observed. The case where no color unevenness was observed at all around the sealant part was evaluated as “◯”, the case where slightly light color unevenness was observed as “Δ”, and the case where clear dark color unevenness was observed as “X”.

(4) Using a coating dispenser (manufactured by Musashi Engineering Co., Ltd., “SHOTMASTER300”), each of the sealing agents for liquid crystal display elements obtained in Examples and Comparative Examples is used for TN alignment film SE7492 (manufactured by Nissan Chemical Co., Ltd.). The coating property when applied to a glass substrate with attached was evaluated. When dispensing with a dispensing nozzle of 400 μm, a nozzle gap of 30 μm, and a coating pressure of 300 kPa, “◎” indicates that the coating can be applied without fading, and “○” indicates that the coating can be applied with little fading. The coating property was evaluated as “Δ” when it occurred and “x” when it could not be applied at all.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which is excellent in adhesiveness and has low moisture permeability of hardened | cured material can be provided. Moreover, according to this invention, the manufacturing method of the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements, and this sealing compound for liquid crystal display elements can be provided.

Claims (12)

1. A particle-dispersed curable resin in which (meth) acrylic acid ester polymer particles are dispersed in a curable resin, a radical polymerization initiator and / or a thermosetting agent,
   The particle dispersion curable resin is obtained by dispersing (meth) acrylic acid ester polymer particles dispersed in a dispersion medium in a curable resin and then removing the dispersion medium. Seal for element.
2. 2. The sealant for a liquid crystal display element according to claim 1, wherein the particle-dispersed curable resin is a particle-dispersed epoxy resin in which (meth) acrylic ester polymer particles are dispersed in an epoxy resin.
3. The sealing agent for liquid crystal display elements according to claim 1 or 2, comprising a particle-dispersed curable resin, a (meth) acrylic resin, a radical polymerization initiator and / or a thermosetting agent.
4. The methacrylic resin is contained as a (meth) acrylic resin, The sealing compound for liquid crystal display elements of Claim 3 characterized by the above-mentioned.
5. The (meth) acrylic acid ester polymer particles dispersed in a dispersion medium are obtained by polymerizing a (meth) acrylic acid ester monomer in the dispersion medium. Item 5. The sealing agent for liquid crystal display elements according to item 1, 2, 3 or 4.
6. 6. The sealing agent for a liquid crystal display element according to claim 5, wherein the method of polymerizing the (meth) acrylic acid ester monomer is emulsion polymerization in the presence of a reactive surfactant.
7. The reactive surfactant is a water-soluble or water having an acid value of 200 or more obtained by polymerizing a polymerizable monomer component containing an unsaturated carboxylic acid in the presence of an alkyl mercaptan having 6 to 18 carbon atoms. 7. The sealing agent for liquid crystal display elements according to claim 6, which is a dispersible terminal alkyl group-containing polymer and / or a salt thereof.
8. The sealing agent for liquid crystal display elements according to claim 1, 2, 3, 4, 5, 6 or 7, further comprising a thermal radical polymerization initiator as the radical polymerization initiator.
9. 9. The sealing agent for liquid crystal display elements according to claim 1, comprising a light-shielding agent.
10. A vertical conducting material comprising the sealing agent for a liquid crystal display element according to claim 1, 2, 3, 4, 6, 7, 8, or 9 and conductive fine particles.
11. A liquid crystal display element manufactured using the sealing agent for a liquid crystal display element according to claim 1, 2, 3, 4, 5, 6, 7, 8, or 9, or the vertical conduction material according to claim 10. .
12. A polymerizable monomer component containing an unsaturated carboxylic acid is polymerized in the presence of an alkyl mercaptan having 6 to 18 carbon atoms, and a water-soluble or water-dispersible terminal alkyl group-containing polymer having an acid value of 200 or more and Step 1 for obtaining a reactive surfactant which is / or a salt thereof,
    Step 2 of emulsion-polymerizing a (meth) acrylate monomer in the presence of the reactive surfactant to obtain (meth) acrylate polymer particles,
    Step 3 of dispersing the (meth) acrylic acid ester polymer particles in an epoxy resin to obtain a particle-dispersed epoxy resin, and
    The manufacturing method of the sealing compound for liquid crystal display elements characterized by having the process 4 which mixes the said particle-dispersed epoxy resin, a (meth) acrylic resin, and a radical polymerization initiator and / or a thermosetting agent at least.