TW201502259A - Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element - Google Patents

Abstract

One purpose of the present invention is to provide a sealing agent for liquid crystal dropping methods, which has excellent bonding properties and is capable of suppressing the occurrence of seal breakage or liquid crystal contamination. Another purpose of the present invention is to provide a vertically conducting material and a liquid crystal display element, each of which is produced using the sealing agent for liquid crystal dropping methods. The present invention is a sealing agent for liquid crystal dropping methods, which is used for the production of a liquid crystal display element by a liquid crystal dropping method. This sealing agent for liquid crystal dropping methods contains a curable resin, a polymerization initiator and/or a thermal curing agent, and soft particles having a maximum particle diameter not less than 100% of the cell gap of the liquid crystal display element.

Description

Sealant for liquid crystal dropping method, upper and lower conductive materials, and liquid crystal display element

The present invention relates to a liquid crystal dropping method sealant which is excellent in adhesion and which can suppress generation of seal break or liquid crystal contamination. Moreover, the present invention relates to an upper conductive material and a liquid crystal display element which are produced by using the sealing compound for liquid crystal dropping methods.

In the past, the method of manufacturing a liquid crystal display device such as a liquid crystal display device has been changed from the prior vacuum injection method to, for example, Patent Document 1 from the viewpoints of shortening the takt time and the optimization of the liquid crystal amount. In the method disclosed in Patent Document 2, a liquid crystal dropping method called a dropping method using a photocurable resin, a photopolymerization initiator, a thermosetting resin, and a thermosetting agent for a combination of light and heat is used.

In the dropping method, a rectangular seal pattern is first formed by one drop coating on one of the two transparent substrates with electrodes. Then, the fine droplet of the liquid crystal is dropped onto the entire surface of the transparent substrate in a state where the sealant is not cured, and the other transparent substrate is immediately superposed, and the sealing portion is temporarily hardened by irradiating light such as ultraviolet rays. Thereafter, the liquid crystal is annealed at the time of liquid crystal annealing, and is finally hardened to produce a liquid crystal display element. When the substrate is bonded under reduced pressure, the liquid crystal display element can be manufactured with high efficiency. Currently, the dropping method is the mainstream of the manufacturing method of the liquid crystal display element.

In addition, in the modernization of mobile devices including mobile phones and portable game machines, such as mobile phones and portable game machines, the miniaturization of devices is the most demanding issue. As a method of downsizing, a narrow frame of the liquid crystal display unit is exemplified, and for example, an operation of arranging the position of the sealing portion under the black matrix (hereinafter also referred to as "narrow frame design") is performed.

However, when a liquid crystal display device having a narrow frame design is produced by a dropping method, a portion of the sealing portion having no light is formed by the black matrix, and thus a photocurable resin which is not hardened by light irradiation is generated. In part, the uncured sealant is in contact with the liquid crystal, and thus there is a problem that the liquid crystal is inserted into the sealant to cause a seal breakage, causing the liquid crystal to leak out; or after the temporary hardening step, the unhardened photocurable resin is eluted. Contaminated liquid crystal.

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

Patent Document 2: International Publication No. 02/092718

An object of the present invention is to provide a sealing compound for a liquid crystal dropping method which is excellent in adhesion and which can suppress generation of seal breakage or liquid crystal contamination. Further, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element which are produced by using the sealing compound for liquid crystal dropping methods.

The present invention relates to a liquid crystal dropping method sealing agent which is used in a liquid crystal display element by a liquid crystal dropping method, and is characterized in that it contains a curable resin, a polymerization initiator and/or a heat hardener, and a maximum particle. The diameter is 100% or more of soft particles of the cell gap of the liquid crystal display element.

Hereinafter, the present invention will be described in detail.

The present inventors have found that by blending soft particles having a maximum particle diameter of 100% or more of the cell gap of the liquid crystal display device, when the substrate of the liquid crystal display device is bonded, the soft particles become a component between the other sealant component and the liquid crystal. The barrier rib can suppress the occurrence of seal breakage or liquid crystal contamination caused by the flow of the liquid sealant component, thereby completing the present invention.

The sealing compound for liquid crystal dropping methods of the present invention is used for the production of a liquid crystal display element by a liquid crystal dropping method.

The sealing agent for a liquid crystal dropping method of the present invention contains soft particles (hereinafter also referred to simply as "soft particles") having a maximum particle diameter of 100% or more of the cell gap of the liquid crystal display device. The soft particles serve as a barrier between the other sealant component and the liquid crystal when the liquid crystal display element is produced, and have an effect of preventing liquid crystal from being inserted into the sealant and eluting the sealant in the liquid crystal. Moreover, by blending the above-mentioned soft particles, it is possible to prevent the substrate from being displaced until the sealant is cured after bonding the substrate.

The cell gap of the liquid crystal display element varies depending on the display element. Therefore, the cell gap of the liquid crystal display device is usually 2 μm to 10 μm.

The maximum particle diameter of the soft particles is 100% or more of the cell gap of the liquid crystal display device. When the maximum particle diameter of the soft particles is less than 100% of the cell gap of the liquid crystal display element, it is impossible to sufficiently suppress the seal breakage or the liquid crystal contamination. The maximum particle diameter of the soft particles is 100% or more of the cell gap of the liquid crystal display device, and preferably 5 μm or more.

Further, a preferred upper limit of the maximum particle diameter of the soft particles is 20 μm. When the maximum particle diameter of the soft particles exceeds 20 μm, the spring back may occur, and the obtained sealing compound for liquid crystal dropping method may be inferior in adhesion, or the obtained liquid crystal display element may have a gap defect. A more preferable upper limit of the maximum particle diameter of the above soft particles is 15 μm.

Further, the maximum particle diameter of the soft particles is preferably 2.6 times or less the cell gap. If above When the maximum particle diameter of the soft particles exceeds 2.6 times the cell gap, rebound may occur, and the obtained liquid crystal dropping method sealant may be inferior in adhesion, or the obtained liquid crystal display element may have poor gap. A more preferable upper limit of the maximum particle diameter of the soft particles is 2.2 times the cell gap, and a preferred upper limit is 1.7 times the cell gap.

Furthermore, in the present specification, the maximum particle diameter of the soft particles and the average particle diameter described below mean that the particles before being blended into the sealant are obtained by using a laser diffraction type particle size distribution analyzer. value. As the above-described laser diffraction type distribution measuring apparatus, a Mastersizer 2000 (manufactured by Malvern Co., Ltd.) or the like can be used.

In the above-mentioned soft particles, it is preferable that the content ratio of the particles having a particle diameter of 5 μm or more in the particle size distribution of the soft particles measured by the above-described laser diffraction type distribution measuring apparatus is 60% or more in terms of volume frequency. When the content ratio of the particles having a particle diameter of 5 μm or more is less than 60% by volume, the sealing fracture or liquid crystal contamination may not be sufficiently suppressed. The content ratio of the particles having a particle diameter of 5 μm or more is more preferably 80% or more.

In view of the effect of suppressing the occurrence of seal breakage or liquid crystal contamination, the soft particles preferably contain 100% or more of the cell gap of the liquid crystal display element of 70% or more of the particle size distribution of all the soft particles, and more preferably Preferably, it is composed only of particles of 100% or more of the cell gap of the liquid crystal display element.

A preferred lower limit of the average particle diameter of the soft particles is 2 μm, and a preferred upper limit is 15 μm. When the average particle diameter of the soft particles is less than 2 μm, the elution of the sealant into the liquid crystal may not be sufficiently suppressed. When the average particle diameter of the soft particles exceeds 15 μm, the obtained sealing compound for liquid crystal dropping methods may be inferior in adhesion, or the obtained liquid crystal display element may have a gap defect. The average particle size of the above soft particles is better The limit is 4 μm, and the upper limit is more preferably 12 μm.

As the soft particles, if the maximum particle diameter of all the soft particles is within the above range, two or more kinds of soft particles having the largest particle diameter may be used in combination. In other words, soft particles having a maximum particle diameter of less than 100% of the cell gap of the liquid crystal display element and soft particles having a maximum particle diameter of 100% or more of the cell gap of the liquid crystal display element may be used in combination.

The coefficient of variation of the particle diameter of the soft particles (hereinafter also referred to as "CV value") is preferably 30% or less. When the CV value of the particle diameter of the soft particles exceeds 30%, the cell gap may be defective. The CV value of the particle diameter of the soft particles is more preferably 28% or less.

In the present specification, the CV value of the particle diameter means a value obtained by the following formula.

CV value (%) of particle size = (standard deviation of particle diameter / average particle diameter) × 100

When the soft particles have a maximum particle diameter, an average particle diameter, or a CV value exceeding the above range, the maximum particle diameter, the average particle diameter, or the CV value may be within the above range by classification. Further, the soft particles having a particle diameter of less than 100% of the cell gap of the liquid crystal display element do not contribute to suppression of occurrence of seal breakage or liquid crystal contamination, and if blended into the sealant, there is a case where the thixotropic value is increased. Jia is removed by grading.

As a method of classifying the above-mentioned soft particles, for example, methods such as wet classification and dry classification can be mentioned. Among them, wet classification is preferred, and wet sieve classification is preferred.

In the soft particles, the compression displacement of the origin load value to the reverse load value when the load is applied is L1, and when the reverse load value when the load is released to the origin load value is L2, The recovery rate of L2/L1 is preferably 80% or less in percentage. When the recovery rate of the soft particles exceeds 80%, the barrier layer is formed to prevent elution of the sealant to the liquid crystal. The situation in which the function is declining. The upper limit of the recovery ratio of the above soft particles is 70%, and the upper limit is preferably 60%.

Further, the recovery rate of the soft particles can be derived by applying a fixed load (1 g) to one particle using a micro compression tester and analyzing the recovery behavior after removing the load.

In the soft particles, the compression displacement when a load of 1 g is applied is L3, and when the particle diameter is Dn, the strain of L3/Dn expressed by a percentage is preferably 30% or more. When the 1 g strain of the soft particles is less than 30%, there is a case where the barrier is formed and the function of preventing the sealing agent from eluting into the liquid crystal is lowered. A more preferred lower limit of the 1 g strain of the soft particles is 40%.

Further, the 1 g strain of the soft particles can be derived by applying a load of 1 g to one particle using a micro compression tester and measuring the amount of displacement at this time.

In the soft particles, the compression displacement when the particles are broken is L4, and when the particle diameter is Dn, the strain at which L4/Dn is broken is preferably 50% or more. When the strain at break of the soft particles is less than 50%, there is a case where the barrier is formed and the function of preventing the sealant from eluting into the liquid crystal is lowered. A more preferable lower limit of the strain of the soft particles is 60%.

Further, the strain at break of the soft particles can be derived by applying a load to one particle using a micro compression tester and measuring the displacement amount of the particle breakage. The compression displacement L4 is calculated at the time when the displacement amount is discontinuously increased under the load load, and is set as the time at which the particle is broken. It is considered that the strain at break is 100% or more even when the load is increased and the deformation is not broken.

A preferred lower limit of the glass transition temperature of the soft particles is -200 ° C, and preferably the upper limit is 40 ° C. The lower the glass transition temperature of the soft particles, the better the seal breakage or the liquid crystal contamination, but if it is less than -200 ° C, there is a case where the operability as a particle A problem arises, or the sealant is easily disintegrated during the heating process, and the sealant in the hardening process comes into contact with the liquid crystal to cause liquid crystal contamination. When the glass transition temperature of the soft particles exceeds 40 ° C, a gap defect may occur. A more preferred lower limit of the glass transition temperature of the soft particles is -150 ° C, and a more preferred upper limit is 35 ° C.

Further, the glass transition temperature of the soft particles indicates a value measured by differential scanning calorimetry (DSC) based on "Method for measuring the transfer temperature of plastics" of JIS K 7121.

Examples of the soft particles include polyfluorene-based particles, vinyl particles, urethane-based particles, fluorine-based particles, and nitrile-based particles. Among them, polyfluorene-based particles and vinyl-based particles are preferred.

From the viewpoint of dispersibility in the resin, the polyfluorinated particles are preferably polyoxyethylene rubber particles.

For example, KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (Shin-Etsu Silicones Co., Ltd.), TORAYFIL, and the like are commercially available. E-506S, EP-9215 (manufactured by Dow Corning Toray Co., Ltd.), etc., can be used for classification. These polyoxygenated particles may be used singly or in combination of two or more.

As the vinyl-based particles, (meth)acrylic particles can be suitably used.

The (meth)acrylic acid particles can be obtained by polymerizing a monomer which is a raw material by a known method. Specifically, for example, a method of suspending polymerization of a monomer in the presence of a radical polymerization initiator; in the presence of a radical polymerization initiator, by absorbing monomer by non-crosslinked particles, A method in which a plurality of particles are swollen and subjected to seed polymerization.

Furthermore, in the present specification, the above-mentioned "(meth)acrylic acid" means acrylic or nail Acrylic acid.

Examples of the monomer to form the raw material of the (meth)acrylic acid particles include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Butyl acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, ( (meth)acrylic acid alkyl esters such as stearyl methacrylate, cyclohexyl (meth) acrylate, isodecyl (meth) acrylate; or 2-hydroxyethyl (meth) acrylate; a (meth) acrylate containing an oxygen atom such as glyceryl acrylate, polyoxyethylene (meth) acrylate, or glycidyl (meth) acrylate; or a nitrile containing monomer such as (meth) acrylonitrile Or a monofunctional monomer such as a fluorine-containing (meth) acrylate such as trifluoromethyl (meth)acrylate or pentafluoroethyl (meth)acrylate. Among them, the (meth)acrylic acid alkyl esters are preferred because the Tg of the homopolymer is low and the amount of deformation when a load of 1 g is applied can be increased.

In the present specification, the term "(meth)acrylate" means acrylate or methacrylate.

Further, since it has a crosslinked structure, tetramethylol methane tetra(meth)acrylate, tetramethylol methane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate can also be used. , trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerin Di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)tetramethylene di(meth)acrylate, 1 a polyfunctional monomer such as 4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate or isomeric cyanuric acid tris(meth)acrylate. Among them, the molecular weight between the cross-linking points is large and can be increased The amount of deformation when a large load of 1 g is applied is preferably (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)tetramethylene di(methyl) Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate.

The lower limit of the amount of the crosslinkable monomer used in all the monomers is preferably 1% by weight, and preferably the upper limit is 90% by weight. When the amount of the crosslinkable monomer used is 1% by weight or more, the solvent resistance is improved, and when it is kneaded with various sealant materials, problems such as swelling do not occur, and it is easy to uniformly disperse. When the amount of the crosslinkable monomer used is 90% by weight or less, the recovery rate can be lowered, and problems such as rebound can be less likely to occur. A more preferred lower limit of the amount of the crosslinkable monomer used is 3% by weight, and a more preferred upper limit is 80% by weight.

Further, in addition to the acrylic monomers, styrene monomers such as styrene and α-methylstyrene; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, etc. may be used. Vinyl ethers; or vinyl acetates such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate; or unsaturated hydrocarbons such as ethylene, propylene, isoprene, butadiene; a halogen-containing monomer such as vinyl chloride, vinyl fluoride or chlorostyrene; (iso)triallyl cyanurate, triallyl 1,2,4-benzenetricarboxylate, divinylbenzene, ortho-benzene Diallyl formate, diallyl acrylamide, diallyl ether, γ-(meth) propylene methoxypropyltrimethoxy decane, trimethoxydecyl styrene, vinyl trimethoxy Monomers such as decane.

Further, as the vinyl-based particles, for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles or the like can be used.

For example, the product of the above-mentioned amine ester-based particles may be, for example, Art-pearl (manufactured by Kokusai Kogyo Co., Ltd.), DAIMIC BEAZ (manufactured by Dainipsu Seika Co., Ltd.), and the like.

A preferred lower limit of the hardness of the soft particles is 10, and a preferred upper limit is 50. When the hardness of the soft particles exceeds 50, the obtained sealing compound for liquid crystal dropping method may be inferior in adhesion, or the obtained liquid crystal display element may have a gap defect. The lower limit of the hardness of the above soft particles is preferably 20, and the upper limit is more preferably 40.

Further, the hardness of the above soft particles in the present specification means the hardness A hardness measured by the method according to JIS K 6253.

The content of the soft particles is preferably 3 parts by weight, and preferably 70 parts by weight, based on 100 parts by weight of the curable resin. When the content of the soft particles is less than 3 parts by weight, the sealing agent may not be sufficiently prevented from being eluted into the liquid crystal. When the content of the soft particles exceeds 70 parts by weight, the obtained sealing compound for liquid crystal dropping methods may be inferior in adhesion. A more preferred lower limit of the content of the soft particles is 5 parts by weight, more preferably 60 parts by weight, still more preferably 10 parts by weight, and still more preferably 50 parts by weight.

The sealing compound for liquid crystal dropping methods of this invention contains a hardening resin.

The curable resin preferably contains a (meth)acrylic resin.

In the sealing compound for liquid crystal dropping methods of the present invention, in order to allow rapid curing, it is preferred to contain a (meth)acrylic resin as a curable resin and to contain a radical polymerization initiator as a polymerization initiator. The liquid crystal display device for a liquid crystal dropping method of the present invention can be rapidly cured by heating, and the liquid crystal display element having a narrow frame design can sufficiently suppress the occurrence of liquid crystal contamination, and more preferably contains a (meth)acrylic resin and the following. Thermal radical polymerization initiator.

More preferably, the curable resin contains an epoxy (meth) acrylate.

Furthermore, in the present specification, the above-mentioned "(meth)acrylic resin" means having (a) The resin of the acrylonitrile group, the above-mentioned "(meth)acryl fluorenyl group" means an acryl fluorenyl group or a methacryl fluorenyl group. Moreover, the above-mentioned "epoxy (meth) acrylate" means a compound obtained by reacting all of the epoxy groups in the epoxy resin with (meth)acrylic acid.

Examples of the epoxy resin to be used as a raw material for synthesizing the above epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin, and 2 , 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolac type epoxy Resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, epoxy propyl amine type epoxy resin, alkyl polyol type epoxy resin A rubber-modified epoxy resin, a glycidyl ester compound, a bisphenol A-type episulfide resin, or the like.

The commercially available ones of the bisphenol A type epoxy resins include, for example, jER828EL, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), and EPICLON 850-S (manufactured by DIC Corporation).

The commercially available one of the bisphenol F-type epoxy resins may, for example, be jER806 or jER4004 (all manufactured by Mitsubishi Chemical Corporation).

The commercially available one of the bisphenol S-type epoxy resins is, for example, EPICLON EXA1514 (manufactured by DIC Corporation).

The commercially available one of the 2,2'-diallyl bisphenol A type epoxy resins is, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

As a commercially available one of the above hydrogenated bisphenol type epoxy resins, for example, EPICLON can be cited. EXA7015 (manufactured by DIC Corporation) and the like.

The commercially available one of the above-mentioned propylene oxide-added bisphenol A-type epoxy resins is, for example, EP-4000S (manufactured by Adeka Co., Ltd.).

The commercially available one of the resorcinol-type epoxy resins is, for example, EX-201 (manufactured by Nagase Chemtex Co., Ltd.).

As a commercial item of the above-mentioned biphenyl type epoxy resin, jERYX-4000H (made by Mitsubishi Chemical Corporation), etc. are mentioned, for example.

For example, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) or the like can be mentioned as a commercially available one of the above-mentioned thioether type epoxy resins.

For example, YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like can be cited as a commercially available one of the above-mentioned diphenyl ether type epoxy resins.

The commercially available one of the above-mentioned dicyclopentadiene type epoxy resins is, for example, EP-4088S (manufactured by Adeka Co., Ltd.).

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

As a commercial item of the above-mentioned phenol novolak type epoxy resin, EPICLON N-770 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item of the above-mentioned o-cresol novolac type epoxy resin, EPICLON N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.

The commercially available one of the above-mentioned dicyclopentadiene novolac type epoxy resins is exemplified by EPICLON HP7200 (manufactured by DIC Corporation).

As a commercially available one of the above-mentioned biphenol novolak type epoxy resins, for example, NC-3000P can be cited. (made by Nippon Kayaku Co., Ltd.), etc.

For example, ESN-165S (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like are mentioned as a commercial product of the above-mentioned naphthol-based novolak-type epoxy resin.

For example, jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like are mentioned as a commercially available one of the above-mentioned epoxy propylamine type epoxy resins.

For example, 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.) are listed as a commercial product of the above-mentioned alkyl polyol type epoxy resin. ), DENACOL EX-611 (manufactured by Nagase Chemtex), and the like.

For example, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (manufactured by Daicel Co., Ltd.), and the like are mentioned as a commercially available one of the rubber-modified epoxy resins.

The commercially available one of the above-mentioned glycidyl ester compounds is, for example, DENACOL EX-147 (manufactured by Nagase Chemtex Co., Ltd.).

For example, jERYL-7000 (manufactured by Mitsubishi Chemical Corporation) or the like can be mentioned as a commercially available product of the bisphenol A-type cyclic thioether resin.

Other commercially available ones of the above-mentioned epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, and jER1032 ( All are manufactured by Mitsubishi Chemical Corporation, EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

As a commercial one of the above-mentioned epoxy (meth)acrylate, for example, the following are mentioned: EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX63182 (all manufactured by Daicel-ALLNEX), EA-1010, EA -1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (both manufactured by Kyoei Chemical Co., Ltd.), Denacol Acrylate DA-141, Denacol Acrylate DA-314 , Denacol Acrylate DA-911 (all manufactured by Nagase Chemtex) and the like.

Examples of the (meth)acrylic resin other than the epoxy (meth) acrylate include an ester compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, and a (meth) group having a hydroxyl group. An urethane (meth) acrylate obtained by reacting an acrylic acid derivative with an isocyanate.

As a monofunctional one in the ester compound obtained by reacting the compound having a hydroxyl group with the above (meth)acrylic acid, for example, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate may be mentioned. , 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, isooctyl (meth)acrylate , lauryl (meth)acrylate, stearyl (meth)acrylate, isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, A Oxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (A) Acrylate, (methyl) Phenoxyethyl acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ( 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, hydrazine Imine (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, isodecyl (meth)acrylate, isomyristyl (meth)acrylate, 2-butoxy (meth)acrylate Ethyl ethyl ester, 2-phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, diethylaminoethyl (meth)acrylate , dimethylaminoethyl (meth) acrylate, 2-(methyl) propylene methoxyethyl succinate, 2-(methyl) propylene methoxyethyl hexahydrophthalate, o-benzene 2-(methyl)propenyloxyethyl 2-dipropyl propyl dicarboxylate, glycidyl (meth)acrylate, 2-(phosphoric acid) Yl) ethyl group, Bing Xixi.

Examples of the bifunctional ones of the above ester compounds include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, and 1,6-hexane. Alcohol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol 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(methyl) Acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide addition bisphenol A Acrylate, ethylene oxide addition bisphenol A di(meth) acrylate, ethylene oxide addition bisphenol F di(meth) acrylate, dimethylol dicyclopentadienyl (Meth) acrylate, 1,3-butanediol di(meth) acrylate, neopentyl glycol II (Meth) acrylate, ethylene oxide modified di(meth) acrylate, 2-hydroxy-3-(meth) propylene methoxy propyl (meth) acrylate, carbonate Glycol di(meth)acrylate, polyether diol di(meth) acrylate, polyester diol di(meth) acrylate, polycaprolactone diol di(meth) acrylate, polybutylene Diene glycol di(meth)acrylate or the like.

Examples of the trifunctional or higher functional group of the ester compound include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and propylene oxide addition trimethylolpropane. Tris(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide plus Formed tris (meth) acrylate cyanide, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bis (trimethylolpropane) tetra ( Methyl) acrylate, neopentyl alcohol tetra(meth) acrylate, glycerol tri(meth) acrylate, propylene oxide addition glycerol tri(meth) acrylate, tris((meth) propylene hydride) Oxyethyl) ester and the like.

The above-mentioned amine ester (meth) acrylate can be obtained, for example, by reacting 2 equivalents of a (meth)acrylic acid derivative having a hydroxyl group with 1 equivalent of a compound having 2 isocyanate groups in the presence of a catalytic amount of a tin-based compound.

Examples of the isocyanate which is a raw material of the above amine ester (meth) acrylate include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and the like. Methylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, poly MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate , decyl diisocyanate (XDI), hydrogenated XDI, diazonic acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, 1,6, 10-undecane triisocyanate and the like.

Further, as the above isocyanate, for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, polyether diol, polyester diol, poly A chain extended isocyanate compound obtained by reacting a polyol such as caprolactone diol with an excess of isocyanate.

Examples of the (meth)acrylic acid derivative having a hydroxyl group which is a raw material of the above amine ester (meth) acrylate include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. , commercially available products such as 4-hydroxybutyl (meth)acrylate and 2-hydroxybutyl (meth)acrylate, or ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-butane a mono (meth) acrylate of a glycol such as an alcohol, 1,4-butanediol or polyethylene glycol; a monohydric alcohol of a triol such as trimethylolethane, trimethylolpropane or glycerol Epoxy (meth) acrylate such as acrylate or di(meth) acrylate, bisphenol A epoxy acrylate or the like.

The commercially available ones of the above-mentioned amine ester (meth) acrylates include, for example, M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL 230, EBEORY L270, and EBECRYL. 4858, EBECRYL 8402, EBECRYL 8804, EBECRYL 8803, EBECRYL 8807, EBECRYL 9260, EBECRYL 1290, EBECRYL 5129, EBECRYL 4842, EBECRYL 210, EBECRYL 4827, EBECRYL 6700, EBECRYL 220, EBECRYL 2220 (all manufactured by DAICEL-ALLNEX), Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Gensal Industries, Inc.), 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 Xinzhongcun Chemical Industry Co., Ltd. Manufacturing), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.).

The (meth)acrylic resin preferably has a hydrogen bonding unit such as a -OH group, a -NH- group or a -NH ₂ group in terms of suppressing adverse effects on the liquid crystal.

Further, in terms of the degree of reactivity, the (meth)acrylic resin preferably has 2 to 3 (meth) acrylonitrile groups in the molecule.

In order to improve the adhesiveness of the obtained sealing compound for liquid crystal dropping methods, the said curable resin may further contain an epoxy resin.

Examples of the epoxy resin include an epoxy resin or a partial (meth)acrylic modified epoxy resin which is a raw material for synthesizing the above epoxy (meth)acrylate.

In the present specification, the above-mentioned partial (meth)acrylic acid-modified epoxy resin means one or more epoxy groups and one or more (meth)acryl fluorenyl groups in one molecule. The resin can be obtained, for example, by reacting a partial epoxy group of a resin having two or more epoxy groups with (meth)acrylic acid.

The commercially available one of the above-mentioned partial (meth)acrylic acid-modified epoxy resins is, for example, UVAGURE 1561 (manufactured by DAICEL-ALLNEX Co., Ltd.).

In the case where the epoxy resin is contained as the curable resin, the upper limit of the ratio of the epoxy group to the total amount of the (meth)acryl fluorenyl group and the epoxy group in the entire curable resin is 50 mol. ear%. When the ratio of the epoxy group exceeds 50 mol%, the solubility of the obtained sealing compound for liquid crystal dropping methods in the liquid crystal becomes high, and liquid crystal contamination is caused. This causes the obtained liquid crystal display element to be inferior in display performance. A more preferable upper limit of the ratio of the above epoxy groups is 20 mol%.

The sealant for liquid crystal dropping method of the present invention contains a polymerization initiator and/or a heat hardener.

Among them, it is preferred to contain a radical polymerization initiator as a polymerization initiator. The rebound is affected not only by the maximum particle size of the soft particles described above, but also by the rate of hardening of the sealant. Since the radical polymerization initiator can significantly accelerate the curing rate as compared with the thermal curing agent, it can be used in combination with the above-mentioned soft particles to suppress the occurrence of rebound which is easily caused by the soft particles. .

Examples of the radical polymerization initiator include a thermal radical polymerization initiator which generates a radical by heating, a photoradical polymerization initiator which generates a radical by light irradiation, and the like.

As described above, since the radical polymerization initiator has a significantly faster curing rate than the thermosetting agent, the use of the radical polymerization initiator can suppress the occurrence of seal breakage or liquid crystal contamination, and can also suppress the above-mentioned softness. The rebound of particles is easy to produce.

Among them, since the liquid crystal dropping method obtained by heat can be rapidly hardened by a sealant, it is preferred that the above radical polymerization initiator contains a thermal radical polymerization initiator.

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 comprising a polymer azo compound is preferred.

In the present specification, the term "polymer azo initiator" means a number average molecular weight of a radical having an azo group and which generates a radical which hardens a (meth) propylene oxime by heat. The above compounds.

A preferred lower limit of the number average molecular weight of the above polymer azo initiator is 1000, and a preferred upper limit is 300,000. When the number average molecular weight of the above polymer azo initiator is less than 1,000, the polymer azo initiator may adversely affect the liquid crystal. When the number average molecular weight of the above polymer azo initiator is more than 300,000, it may become difficult to mix into the curable resin. The lower limit of the number average molecular weight of the above polymer azo initiator is 5,000, more preferably 100,000, and still more preferably 10,000, and further preferably 90,000.

In the present specification, the above-mentioned number average molecular weight is measured by gel permeation chromatography (GPC) and is determined by polystyrene conversion. As a column for measuring the number average molecular weight in terms of polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) or the like can be mentioned.

The polymer azo initiator is, for example, a structure in which a plurality of units such as a polyalkylene oxide or a polydimethyl siloxane are bonded via an azo group.

The polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group is preferably a polyethylene oxide structure. As such a polymer azo initiator, for example, a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and a polyalkylene glycol, or 4,4'-azo may be mentioned. a polycondensate of bis(4-cyanovaleric acid) and polydimethyl methoxy oxane having an amine group at the terminal, and specific examples thereof include VPE-0201, VPE-0401, VPE-0601, and VPS-0501. VPS-1001, V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

Examples of the organic peroxide include ketone peroxide and peroxyketal. Hydroperoxide, dialkyl peroxide, peroxyester, dinonyl peroxide, peroxydicarbonate, and the like.

Examples of the photoradical polymerization initiator include a benzophenone compound, an acetophenone compound, a fluorenyl phosphine oxide compound, a titanocene compound, an oxime ester compound, and a benzoin ether compound. 9-oxygen sulfur Wait.

As a commercially available one of the above photoradical polymerization initiators, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, DAROCUR TPO, Lucirin TPO (both Manufactured by BASF Japan, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.).

As the above cationic polymerization initiator, a photocationic polymerization initiator can be suitably used. The photocationic polymerization initiator is not particularly limited as long as it is 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 an anthracene salt such as an aromatic diazo sulfonium salt, an aromatic halo sulfonium salt or an aromatic sulfonium salt, an iron-aromatic hydrocarbon complex, and a titanocene complex. An organic metal complex such as an aryl stanol-aluminum complex or the like.

The commercially available ones of the above-mentioned photocationic polymerization initiators include, for example, Adeka Optomer SP-150 and Adeka Optomer SP-170 (all manufactured by ADEKA Co., Ltd.).

The content of the polymerization initiator is preferably 0.1 part by weight, and preferably 30 parts by weight, based on 100 parts by weight of the curable resin. If the above aggregation When the content of the initiator is less than 0.1 part by weight, the obtained sealing compound for liquid crystal dropping methods may not be sufficiently cured. When the content of the polymerization initiator is more than 30 parts by weight, the storage stability of the obtained sealing compound for liquid crystal dropping method may be lowered. A more preferred lower limit of the content of the above polymerization initiator is 1 part by weight, more preferably 10 parts by weight, and still more preferably 5 parts by weight.

Examples of the above-mentioned thermosetting agent include an organic acid hydrazine, an imidazole derivative, an amine compound, a polyphenol compound, and an acid anhydride. Among them, a solid organic acid hydrazine can be suitably used.

Examples of the solid organic acid hydrazine include 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin, bismuth sebacate, and bismuth isophthalate. In the case of a commercial product, for example, Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), SDH, IDH, and ADH (all of them are large). Manufactured by a chemical company, MDH (manufactured by JAPAN FINECHEM Co., Ltd.), etc.

The content of the above-mentioned thermosetting agent is preferably 1 part by weight, and preferably 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned thermosetting agent is less than 1 part by weight, the obtained sealing compound for liquid crystal dropping methods may not be sufficiently thermally cured. When the content of the above-mentioned heat-hardening agent is more than 50 parts by weight, the viscosity of the obtained sealing compound for liquid crystal dropping methods may become too high, and coatability may deteriorate. A more preferable upper limit of the content of the above-mentioned thermosetting agent is 30 parts by weight.

The sealing agent for liquid crystal dropping methods of the present invention preferably contains a hardening accelerator. By using the above-described hardening accelerator, the sealant can be sufficiently cured even if it is not heated at a high temperature.

Examples of the hardening accelerator include an iso-cyanuric acid ring skeleton. Specific examples of the polyvalent carboxylic acid or the epoxy resin amine adduct include, for example, tris(2-carboxymethyl) isocyanurate or tris(2-carboxyethyl) isocyanurate. , tris(3-carboxypropyl) isocyanurate, bis(2-carboxyethyl) isocyanurate, and the like.

The content of the hardening accelerator is preferably 0.1 parts by weight, and preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the hardening accelerator is less than 0.1 part by weight, the obtained sealing compound for liquid crystal dropping method may not be sufficiently cured, or heating at a high temperature may be required in order to cure it. When the content of the above-mentioned hardening accelerator exceeds 10 parts by weight, the obtained sealing compound for liquid crystal dropping methods may be inferior in adhesion.

The sealing agent for liquid crystal dropping methods of the present invention preferably contains a filler in order to improve the viscosity, improve the adhesion due to the stress dispersion effect, improve the linear expansion ratio, and improve the moisture resistance of the cured product.

Examples of the filler include talc, asbestos, cerium oxide, diatomaceous earth, bentonite, bentonite, calcium carbonate, magnesium carbonate, aluminum oxide, montmorillonite, zinc oxide, iron oxide, magnesium oxide, and tin oxide. , titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, tantalum nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, aluminum nitride and other inorganic fillers, or polyester microparticles, polyurethane microparticles, ethylene An organic filler such as a base polymer microparticle, an acrylic polymer microparticle, or a core-shell acrylate copolymer microparticle. These fillers may be used singly or in combination of two or more.

The content of the above filler is preferably 10% by weight, and preferably 70% by weight, based on the entire sealing agent for liquid crystal dropping method. When the content of the filler is less than 10% by weight, the effect of improving the adhesion or the like may not be sufficiently exhibited. If the above fill When the content of the agent exceeds 70% by weight, the viscosity of the obtained sealing compound for liquid crystal dropping methods is increased, and the coatability is deteriorated. A more preferred lower limit of the content of the above filler is 20% by weight, and a more preferred upper limit is 60% by weight.

The sealing agent for liquid crystal dropping method of the present invention preferably contains a decane coupling agent. The above-described decane coupling agent has a function as a secondary binder for mainly adhering a sealant to a substrate or the like.

The decane coupling agent is excellent in adhesion to a substrate or the like, and can be chemically bonded to the curable resin to suppress the flow of the curable resin into the liquid crystal. For example, N-phenyl-3 can be suitably used. -Aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-isocyanatepropylpropane Trimethoxy decane and the like. These decane coupling agents may be used singly or in combination of two or more.

The content of the above-mentioned decane coupling agent is preferably 0.1% by weight, and preferably 20% by weight, based on the entire sealing agent for liquid crystal dropping method. When the content of the above decane coupling agent is less than 0.1% by weight, the effect of blending the decane coupling agent may not be sufficiently exhibited. When the content of the above decane coupling agent exceeds 20% by weight, the obtained liquid crystal dropping method sealant may contaminate the liquid crystal. A more preferred lower limit of the content of the above decane coupling agent is 0.5% by weight, and a more preferred upper limit is 10% by weight.

The sealing agent for liquid crystal dropping methods of this invention may also contain an opacifier. The sealing agent for liquid crystal dropping methods of the present invention can be suitably used as a light-shielding sealant by containing the above-mentioned sunscreen 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 titanium black is higher in transmittance in the vicinity of the ultraviolet region, particularly light having a wavelength of 370 to 450 nm, than the average transmittance of light having a wavelength of 300 to 800 nm. In other words, the titanium black has a light-shielding agent which imparts light-shielding property to the sealing compound for liquid crystal dropping methods of the present invention by sufficiently shielding light of a wavelength in the visible light region, and has a wavelength near the ultraviolet region. Light passes through. The light-shielding agent contained in the sealing compound for liquid crystal dropping methods of the present invention is preferably a material having high insulating properties, and is preferably a titanium black as a light-shielding agent having high insulating properties.

The titanium black preferably has an optical density (OD value) of 1 or more per 1 μm, more preferably 4 or more. The higher the light blocking property of the titanium black, the better, and the OD value of the titanium black has no particularly preferable upper limit, and is usually 5 or less.

The titanium black described above can exert sufficient effects even if it is not surface-treated, but can be used as a surface treatment agent such as a coupling agent or a surface of cerium oxide, titanium oxide, cerium oxide, aluminum oxide, zirconium oxide or magnesium oxide. A surface treated titanium black such as an inorganic component. Among them, in terms of further improving the insulating property, it is preferred to be treated by an organic component.

Moreover, the liquid crystal display element manufactured by the sealing compound for liquid crystal dropping methods of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding property, so that light leakage can be achieved, high contrast ratio, and excellent image display. Quality liquid crystal display elements.

For example, 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Co., Ltd.), Tilack D (manufactured by Ako Chemical Co., Ltd.), and the like are mentioned.

A preferred lower limit of the specific surface area of the above titanium black is 13 m ² /g, preferably an upper limit of 30 m ² /g, a more preferred lower limit of 15 m ² /g, and a more preferred upper limit of 25 m ² /g.

Moreover, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω. Cm, preferably the upper limit is 3Ω. Cm, the lower limit is 1Ω. Cm, the upper limit is better 2.5Ω. Cm.

The primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display device. A preferred lower limit is 1 nm, and a preferred upper limit is 5 μm. When the primary particle diameter of the above-mentioned sunscreen agent is less than 1 nm, the viscosity or the shakeability of the obtained sealing compound for liquid crystal dropping methods may be greatly increased, and the workability may be deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5 μm, the coating property of the obtained liquid crystal dropping method sealing agent on the substrate may be deteriorated. A more preferred lower limit of the primary particle diameter of the above-mentioned opacifier is 5 nm, more preferably an upper limit of 200 nm, further preferably a lower limit of 10 nm, and further preferably an upper limit of 100 nm.

The content of the above-mentioned light-shielding agent is preferably 5% by weight, and preferably 80% by weight, based on the entire sealing agent for liquid crystal dropping method. When the content of the above-mentioned sunscreen agent is less than 5% by weight, sufficient light-shielding properties may not be obtained. When the content of the above-mentioned light-shielding agent exceeds 80% by weight, the adhesion between the obtained liquid crystal dropping method sealing agent to the substrate and the strength after curing may be lowered, or the drawability may be lowered. A more preferred lower limit of the content of the above-mentioned opacifier is 10% by weight, more preferably 70% by weight, still more preferably 30% by weight, and still more preferably 60% by weight.

The sealing agent for liquid crystal dropping method of the present invention may further contain a reactive diluent for adjusting the viscosity, a spacer such as a polymer bead for adjusting the gap of the panel, an antifoaming agent, a leveling agent, and a polymerization inhibitor. Additives such as other coupling agents.

The method for producing the sealing compound for a liquid crystal dropping method of the present invention is not particularly limited, and examples thereof include a mixer using a homogeneous phase disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill. A method of mixing an additive such as a curable resin, a polymerization initiator, and/or a thermosetting agent, soft particles, and a decane coupling agent to be added as needed.

The lower limit of the viscosity of the sealant for liquid crystal dropping method of the present invention measured by using an E-type viscometer at 25 ° C and 1 rpm is 50,000 Pa. s, the upper limit is preferably 500,000 Pa. s. If the above viscosity is less than 50,000 Pa. s or more than 500,000 Pa. s, the workability when the liquid crystal dropping method sealing agent is applied to a substrate or the like may be deteriorated. The upper limit of the above viscosity is 400,000 Pa. s.

The upper and lower conductive materials can be produced by blending conductive fine particles into the sealing compound for liquid crystal dropping method of the present invention. Moreover, such a sealing agent containing the liquid crystal dropping method of the present invention and the conductive fine particles upper and lower conductive materials are also one of the inventions.

The conductive fine particles are not particularly limited, and a metal ball or a conductive metal layer formed on the surface of the resin fine particles can be used. Among them, it is preferable that the conductive metal layer is formed on the surface of the resin fine particles by the excellent elasticity of the resin fine particles, and the conductive connection can be performed without damaging the transparent substrate or the like.

Further, the liquid crystal display element obtained by using the sealing compound for liquid crystal dropping method of the present invention or the conductive material for the upper and lower sides of the present invention is also one of the inventions.

As a method of producing the liquid crystal display device of the present invention, for example, a method having the following steps: one of two transparent substrates such as a glass substrate with an electrode such as an ITO film or a polyethylene terephthalate substrate; a step of forming a rectangular seal pattern by screen printing, a dispenser, or the like according to the sealing compound for liquid crystal dropping method of the present invention, and liquid crystal in the state in which the sealing compound for liquid crystal dropping method of the present invention is not cured. The step of applying a small droplet onto the entire surface of the frame of the transparent substrate and immediately superposing the other substrate; and heating the sealing agent for liquid crystal dropping method of the present invention to harden it. Further, before the step of curing the sealing agent for liquid crystal dropping method of the present invention, the portion of the seal pattern may be irradiated with ultraviolet light or the like. A step of temporarily hardening the sealant.

According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method which is excellent in adhesion and which can suppress generation of seal breakage or liquid crystal contamination. Moreover, according to the present invention, the upper and lower conductive materials and the liquid crystal display element produced by using the sealing compound for liquid crystal dropping methods can be provided.

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

(Production of polymer particle A)

750 g of polytetramethylene glycol diacrylate, 250 g of styrene, and 40 g of benzamidine peroxide were mixed and uniformly dissolved to obtain a monomer mixture liquid. The monomer mixture obtained was placed in a reaction vessel to which a 1% by weight aqueous solution of polyvinyl alcohol was added and stirred for 2 to 4 hours, whereby the particle size was adjusted so that the droplets of the monomer became a specific particle diameter. Then, the reaction was carried out for 9 hours under a nitrogen atmosphere at 85 ° C to obtain polymer particles A. The obtained particles are washed several times with hot water. Thereafter, large particles having a specific particle diameter or more are separated by a classification operation using a sieve, and then dried.

The polymer particles A obtained had a maximum particle diameter of 11.4 μm, an average particle diameter of 7.8 μm, a CV value of 26.9% of the particle diameter, and a glass transition temperature (Tg) of 33 °C. In addition, a cylindrical compression end surface of a diameter of 50 μm made of diamond was used at a compression speed of 0.28 mN/sec, an origin load value of 1.0 mN, and a reverse load value of 10 mN using a micro compression tester ("PCT-200" manufactured by Shimadzu Corporation). The recovery rate of the polymer particles A obtained by measuring the fine particles was 76%, the strain of 1 g was 36%, and the strain at break was 65%.

(Production of Polymer Particle B)

600 g of polytetramethylene glycol diacrylate, 400 g of ethylhexyl methacrylate, and 40 g of benzamidine peroxide were mixed and uniformly dissolved to obtain a monomer mixture liquid. The monomer mixture obtained was placed in a reaction vessel to which a 1% by weight aqueous solution of polyvinyl alcohol was added and stirred for 2 to 4 hours, whereby the particle size was adjusted so that the droplets of the monomer became a specific particle diameter. Then, the reaction was carried out for 9 hours under a nitrogen atmosphere at 85 ° C to obtain polymer particles B. The obtained particles are washed several times with hot water. Thereafter, large particles having a specific particle diameter or more are separated by a classification operation using a sieve, and then dried.

The polymer particles B obtained had a maximum particle diameter of 11.7 μm, an average particle diameter of 8.2 μm, a CV value of particle size of 25.9%, and a glass transition temperature (Tg) of 15 °C. Further, the recovery ratio of the polymer particles B measured in the same manner as the polymer particles A was 70%, the strain of 1 g was 42%, and the strain at break was 58%.

(Production of polymer particle C)

400 g of polytetramethylene glycol diacrylate, 600 g of styrene, and 40 g of benzamidine peroxide were mixed and uniformly dissolved to obtain a monomer mixture liquid. The monomer mixture obtained is put into a reaction vessel to which 5 kg of a 1% by weight aqueous solution of polyvinyl alcohol is added and stirred for 2 to 4 hours, thereby performing particle size adjustment so that the droplets of the monomer become specific particle diameters. . Then, the reaction was carried out for 9 hours under a nitrogen atmosphere at 85 ° C to obtain polymer particles C. The obtained particles are washed several times with hot water. Thereafter, large particles having a specific particle diameter or more are separated by a classification operation using a sieve, and then dried.

The obtained polymer particles C had a maximum particle diameter of 12.2 μm, an average particle diameter of 8.0 μm, a CV value of the particle diameter of 27.0%, and a glass transition temperature (Tg) of 62 °C. Further, the recovery ratio of the polymer particles C measured in the same manner as the polymer particles A was 78%, the strain of 1 g was 32%, and the strain at break was 55%.

(Production of polymer particle D)

500 g of polytetramethylene glycol diacrylate, 450 g of styrene, 50 g of divinylbenzene, and 40 g of benzamidine peroxide were mixed and uniformly dissolved to obtain a monomer mixture liquid. The monomer mixture obtained was placed in a reaction vessel to which a 1% by weight aqueous solution of polyvinyl alcohol was added and stirred for 2 to 4 hours, whereby the particle size was adjusted so that the droplets of the monomer became a specific particle diameter. Then, the reaction was carried out for 9 hours under a nitrogen atmosphere at 85 ° C to obtain polymer particles D. The obtained particles are washed several times with hot water. Thereafter, large particles having a specific particle diameter or more are separated by a classification operation using a sieve, and then dried.

The obtained polymer particles D had a maximum particle diameter of 11.5 μm, an average particle diameter of 8.1 μm, a particle diameter of C8.1 of 28.1%, and a glass transition temperature (Tg) of 25 °C. Further, the recovery ratio of the polymer particles D measured in the same manner as the polymer particles A was 76%, the strain of 1 g was 28%, and the strain at break was 55%.

(Production of polymer particles E)

300 g of polytetramethylene glycol diacrylate, 700 g of n-octyl acrylate, and 40 g of benzamidine peroxide were mixed and uniformly dissolved to obtain a monomer mixture liquid. The monomer mixture obtained was placed in a reaction vessel to which a 1% by weight aqueous solution of polyvinyl alcohol was added and stirred for 2 to 4 hours, whereby the particle size was adjusted so that the droplets of the monomer became a specific particle diameter. Then, the reaction was carried out for 9 hours under a nitrogen atmosphere at 85 ° C to obtain polymer particles E. Wash the obtained particles with hot water Several times. Thereafter, large particles having a specific particle diameter or more are separated by a classification operation using a sieve, and then dried.

The obtained polymer particles E had a maximum particle diameter of 11.5 μm, an average particle diameter of 8.1 μm, a particle diameter of C8.1 of 28.1%, and a glass transition temperature (Tg) of -60 °C. Further, the recovery ratio of the polymer particles E measured in the same manner as the polymer particles A was 40%, the strain of 1 g was 52%, and the strain at break was 62%.

(Production of polymer particles F)

The polymer particles were produced by the same operation as the polymer particles E. The polymer particles F having a particle diameter different from E are obtained by the adjustment of the particle diameter at the time of the reaction and the classification operation by the sieve after the rinsing.

The polymer particles F had a maximum particle diameter of 8.0 μm, an average particle diameter of 5.5 μm, a particle diameter of CIR of 29.1%, and a glass transition temperature (Tg) of -60 °C. Further, the recovery ratio of the polymer particles F measured in the same manner as the polymer particles A was 40%, the strain of 1 g was 60%, and the strain at break was 62%.

(Production of polymer particle G)

The polymer particles were produced by the same operation as the polymer particles A. The polymer particles G having a particle diameter different from that are obtained by the adjustment of the particle diameter at the time of the reaction and the classification operation by the sieve after the rinsing.

The polymer particles G had a maximum particle diameter of 4.5 μm, an average particle diameter of 3.1 μm, a particle diameter of C9.0 of 29.0%, and a glass transition temperature (Tg) of 35 °C. Further, the recovery ratio of the polymer particles G measured in the same manner as the polymer particles A was 42%, the strain of 1 g was 50%, and the strain at break was 52%.

(Example 1)

70 parts by weight of bisphenol A type epoxy acrylate ("EBECRYL 3700" manufactured by DAICEL-ALLNEX Co., Ltd.) and 30 parts by weight of bisphenol F type epoxy resin ("JER806" manufactured by Mitsubishi Chemical Corporation) , a polymer azo initiator as a thermal radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., "VPE-0201"), 7 parts by weight, as a thermal hardener, azelaic acid diterpene (Otsuka Chemical Co., Ltd.) Manufactured, "SDH"), 8 parts by weight, 30 parts by weight of polymer particles A as soft particles, 10 parts by weight of cerium oxide ("Admafine SO-C2" manufactured by Admatechs Co., Ltd.) as a filler, and decane coupling agent 1 part by weight of 3-glycidoxypropyltrimethoxydecane ("KBM-403", manufactured by Shin-Etsu Silicones Co., Ltd.) was blended, and a planetary stirring device (manufactured by Thinky Co., Ltd., "Defoaming Taro" was used. After stirring, the ceramic three-roll mill was uniformly mixed to obtain a sealing agent for liquid crystal dropping method.

(Examples 2 to 15, Comparative Examples 1, 2)

According to the blending ratios shown in Table 1, the materials were mixed using a planetary mixer ("Defoaming Taro" manufactured by Thinky Corporation) in the same manner as in Example 1, and then mixed using a three-roll mill. The sealants for liquid crystal dropping methods of Examples 2 to 15 and Comparative Examples 1 and 2 were prepared.

<evaluation>

Each of the sealing compounds for liquid crystal dropping methods obtained in the examples and the comparative examples was subjected to the following evaluation. The results are shown in Table 1.

(adhesive)

In the case of 100 parts by weight of each of the sealing compounds for liquid crystal dropping methods obtained in the examples and the comparative examples, spacer particles having an average particle diameter of 5 μm (manufactured by Sekisui Chemical Co., Ltd., "Micropearl SP-" 2050") 1 part by weight is uniformly dispersed by a planetary stirring device, and a very small amount is placed in the central portion of Corning glass 1737 (20 mm × 50 mm × thickness 0.7 mm), and the same type of glass is superposed thereon to make the liquid crystal dropping method sealed. The agent was spread out and heated at 120 ° C for 1 hour to thermally harden the sealant to obtain a test piece.

The strength of the subsequent test piece was measured using a tensiometer. The bonding strength is ² or more of the circumstances 270N / cm is set to "○" will be followed by strength of 250N / cm ² or more and less than 270N / cm ² of the case is set to "△", the bonding strength less than 250N / cm ² In the case of "X", the adhesion is evaluated.

(liquid crystal contamination)

1 part by weight of the spacer particles ("Micropearl SP-2050" manufactured by Sekisui Chemical Co., Ltd.) having an average particle diameter of 5 μm was used for planetary stirring with respect to 100 parts by weight of each of the sealing compounds for liquid crystal dropping methods obtained in the examples and the comparative examples. The apparatus was uniformly dispersed, and the obtained sealant was filled in a syringe for dripping ("PSY-10E" manufactured by Musashi Engineering Co., Ltd.), and subjected to a defoaming treatment, and then a dispenser (manufactured by Musashi Engineering Co., Ltd., "SHOTMASTER") was used. 300") The sealant was applied so as to form a rectangular frame on the transparent electrode substrate with the ITO film. Then, a fine droplet of TN liquid crystal (Chisso Co., Ltd., "JC-5001LA") was dropped by a liquid crystal dropping device, and another transparent substrate was bonded by a vacuum bonding apparatus under a vacuum of 5 Pa. The bonded unit was heated at 120 ° C for 1 hour to thermally cure the sealant to obtain a liquid crystal display element (cell gap 5 μm).

Visually observing the display unevenness of the liquid crystal (especially the corner portion) around the sealing portion of the obtained liquid crystal display element, and setting "no ○○" at all without display unevenness, and substantially no display unevenness In the case of "○", the case where display unevenness is rarely generated is set to "△", and will be In some cases, the display unevenness is set to "Δ×", the case where the display unevenness is confirmed is set to "X", and the case where the display unevenness is confirmed is "××", and the liquid crystal contamination property is evaluated.

[Industrial availability]

According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method which is excellent in adhesion and which can suppress generation of seal breakage or liquid crystal contamination. Moreover, according to the present invention, the upper and lower conductive materials and the liquid crystal display element produced by using the sealing compound for liquid crystal dropping methods can be provided.

Claims (10)

A liquid crystal dropping method sealing agent for producing a liquid crystal display element by a liquid crystal dropping method, comprising: a curable resin, a polymerization initiator, and/or a thermosetting agent, and a maximum particle diameter of 100% or more of soft particles of the cell gap of the liquid crystal display element. The sealant for a liquid crystal dropping method according to the first aspect of the invention, wherein the content of the soft particles is from 3 to 70 parts by weight based on 100 parts by weight of the curable resin. The sealant for a liquid crystal dropping method according to the first or second aspect of the invention, wherein, for the soft particles, the compression load at the origin load value to the reverse load value when the load is applied is L1, and the load is released. When the unloading displacement of the reverse load value to the origin load value is L2, the recovery rate of L2/L1 is expressed as a percentage of 80% or less. The sealant for a liquid crystal dropping method according to the first, second or third aspect of the invention, wherein the soft particle has a compression displacement when a load of 1 g is applied as L3, and when the particle diameter is Dn, a percentage is expressed as L3/ The strain of 1 g of Dn is 30% or more. The sealing agent for liquid crystal dropping methods of claim 1, 2, 3 or 4, wherein the glass transition temperature of the soft particles is -200 to 40 °C. The sealant for a liquid crystal dropping method according to the first, second, third, fourth or fifth aspect of the patent application, wherein, for the soft particles, the compression displacement when the particles are broken is L4, and when the particle diameter is Dn, the percentage is It means that the strain at break of L4/Dn is 50% or more. The sealant for liquid crystal dropping methods of the first, second, third, fourth, fifth or sixth aspect of the patent application, wherein the coefficient of variation of the particle diameter of the soft particles is 30% or less. For example, the sealing agent for liquid crystal dropping method of the first, second, third, fourth, fifth, sixth or seventh paragraph of the patent application, It contains an opacifier. A top-bottom conductive material comprising a sealing agent for liquid crystal dropping method and conductive fine particles of the first, second, third, fourth, fifth, sixth, seventh or eighth aspect of the patent application. A liquid crystal display element manufactured by using a sealing compound for liquid crystal dropping method of the first, second, third, fourth, fifth, sixth, seventh or eighth aspect of the patent application or a conductive material for upper and lower parts of the ninth application.