TW201947000A - Liquid crystal display element sealing agent, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

An objective of the present invention is to provide a liquid crystal display element sealing agent such that penetration of the sealing agent by liquid crystal and pollution of the liquid crystal by the sealing agent can be suppressed, the sealing agent has excellent adhesiveness, and a liquid crystal display element having excellent display performance can be obtained. Another objective of the present invention is to provide a vertical conduction material and a liquid crystal display element formed using the liquid crystal display element sealing agent. The present invention provides a liquid crystal display element sealing agent containing a curable resin, a heat-curing agent, and soft particles having a maximum particle diameter of no less than 100% of the cell gaps in the liquid crystal display element, the curable resin being a compound having three or more epoxy groups within one molecule.

Description

Sealant for liquid crystal display element, vertical conductive material, and liquid crystal display element

The present invention relates to a sealant for a liquid crystal display device capable of suppressing the liquid crystal from being inserted into a sealant or contamination of the liquid crystal caused by the sealant, and having excellent adhesion and a liquid crystal display device having excellent display performance. The present invention also relates to a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display unit, from the viewpoints of shortening the takt time and optimizing the amount of liquid crystal used, as disclosed in Patent Documents 1 and 2 The liquid crystal dropping method using a sealant is called a dropping method.
In the dropping method, first, a sealing agent is applied to one of two transparent substrates with electrodes to form a frame-shaped sealing pattern. Next, in the state where the sealant is not hardened, a small drop of liquid crystal is dropped to the entire surface of the frame of the seal pattern, and another transparent substrate is immediately bonded, and the sealant is irradiated with light such as ultraviolet rays or heated to harden the sealant. , Thereby producing a liquid crystal display element. If substrates are to be bonded under reduced pressure, liquid crystal display elements can be manufactured with extremely high efficiency. At present, the dripping method is becoming the mainstream of manufacturing methods for liquid crystal display elements.

However, with the spread of various mobile devices with a liquid crystal panel, such as mobile phones and portable game consoles, the miniaturization of devices is the most requested issue. As a method of miniaturization, narrow edge of a liquid crystal display part can be mentioned, for example, the position of a sealing part is arrange | positioned under a black matrix (henceforth a "narrow edge design").
However, if a liquid crystal display element with a narrow edge design is manufactured by the dripping method, there are cases in which the sealant is disposed directly below the black matrix, so when the sealant is hardened by light irradiation, the irradiated light is The shielding makes it difficult for the light to reach the inside of the sealant, and the hardening of the sealant becomes insufficient. If the hardening of the sealant is insufficient, there is a problem that the uncured sealant component will elute into the liquid crystal and easily cause liquid crystal contamination.

Therefore, studies have been made to harden the sealant only by heat. However, if hardening by light irradiation is not performed, liquid crystals flow during heating and are inserted into the sealant portion in the middle of hardening. The problem of liquid crystal contamination caused by the sealant whose viscosity is reduced by heating.
Especially in recent years, with the narrow edge of the panel, the line width of the sealant to be coated is also narrowed, and the cross-sectional area of the seal after bonding is reduced. Therefore, cracks and the like of the seal pattern are liable to occur.
[Prior technical literature]
[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2001-133794 Patent Document 2: International Publication No. 02/092718

[Problems to be Solved by the Invention]

An object of the present invention is to provide a sealant for a liquid crystal display device that can suppress the liquid crystal from being inserted into a sealant or liquid crystal contamination caused by the sealant, and has excellent adhesion and a liquid crystal display device having excellent display performance. Another object of the present invention is to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
[Technical means to solve the problem]

The present invention is a sealant for a liquid crystal display element, which contains a curable resin, a thermosetting agent, and soft particles having a maximum particle size of 100% or more of the cell gap of the liquid crystal display element. The curable resin contains one molecule of Compounds of three or more epoxy groups.
The present invention is described in detail below.

In recent years, as a liquid crystal display element capable of achieving high-speed response or high contrast, a PSA (Polymer Sustained Alignment) type liquid crystal display element has attracted attention. In the PSA type liquid crystal display element, a liquid crystal composition containing a polymerizable compound is used, and the liquid crystal composition filled in the cell of the liquid crystal display element is irradiated with light or the like to polymerize the polymerizable compound in the liquid crystal composition to thereby A concave-convex shape is formed on the substrate, thereby giving a uniform pretilt angle and controlling the alignment of liquid crystal molecules. However, there is a problem that when a conventional sealing agent is used to seal a PSA type liquid crystal display element, the uneven shape formed on the substrate may be uneven, and a uniform pretilt angle may not be provided.

The inventors believe that the reason why the uneven shape formed on the substrate when sealing a PSA-type liquid crystal display element using a conventional sealant is caused by the (meth) group usually contained in the sealant as a curable resin Acrylic compounds. That is, it is considered that when the (meth) acrylic compound in the curable resin is eluted into the liquid crystal, the polymerization of the polymerizable compound in the liquid crystal also causes the polymerization of the (meth) acrylic compound, and the (meth) acrylic compound is polymerized. The part is formed into a concave-convex shape different from the target shape. Therefore, the present inventors have conducted studies on sealing PSA-type liquid crystal display elements with a sealant that does not contain a (meth) acrylic compound or reduce the content of the (meth) acrylic compound. However, when such a sealant is used, There is a problem that the liquid crystal is easily inserted into the sealant. Therefore, the present inventors have conducted research on suppressing the insertion of liquid crystal into a sealant or liquid crystal contamination caused by a sealant by blending soft particles having a maximum particle size of 100% or more of a cell gap of a liquid crystal display element. However, if a large amount of soft particles are blended in order to sufficiently suppress the insertion of liquid crystal into the sealant or the liquid crystal contamination caused by the sealant, there is a problem that the obtained sealant becomes the one with poor adhesion. Therefore, the present inventors have further studied using a compound having three or more epoxy groups in one molecule as the curable resin. As a result, it was found that it is possible to suppress the liquid crystal from being inserted into the sealant or liquid crystal contamination caused by the sealant, and a sealant for a liquid crystal display element that is excellent in adhesiveness and can obtain a liquid crystal display element with excellent display performance, has completed the present invention.
The effect of the sealant for a liquid crystal display element of the present invention in suppressing the insertion of liquid crystal into the sealant or the liquid crystal contamination caused by the sealant is particularly significant when the sealant is hardened only by heat. Moreover, the sealing compound for liquid crystal display elements of this invention can be used suitably as a sealing compound for PSA type liquid crystal display elements.

The sealing agent for liquid crystal display elements of this invention contains a curable resin.
The said curable resin contains the compound which has three or more epoxy groups in one molecule (henceforth a "three-functional or more epoxy compound"). When the sealing compound for a liquid crystal display element of the present invention contains the above-mentioned trifunctional or more epoxy compound, the liquid crystal display element can be inhibited from being inserted, and the obtained liquid crystal display element is excellent in display performance.

In terms of excellent reactivity, the obtained sealing agent for a liquid crystal display element is more excellent in suppressing the insertion of liquid crystal into the sealing agent or the effect of liquid crystal contamination caused by the sealing agent, and the above-mentioned trifunctional or more epoxy compound is preferred. It has 6 or more epoxy groups in one molecule.
In addition, in terms of excellent effect of suppressing the insertion of liquid crystal into the sealant, the above-mentioned trifunctional or more epoxy compound preferably has 3 or more epoxy groups and an isocyanuric skeleton in one molecule. Compound and / or epoxypropylamine type epoxy compound having 3 or more epoxy groups in one molecule. More preferred is a compound having three or more epoxy groups and an isocyanuric acid skeleton in one molecule.

Specific examples of the trifunctional or higher epoxy compound include a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3). . Among them, a compound represented by the following formula (1) and a compound represented by the following formula (2) are preferred, and a compound represented by the following formula (1) is more preferred.

The curable resin may contain other curable resins in addition to the trifunctional or higher functional epoxy compound. When the other curable resin is contained, a preferable lower limit of the content of the trifunctional or higher epoxy compound in 100 parts by weight of the curable resin is 50 parts by weight, and a preferable upper limit is 95 parts by weight. When the content of the above-mentioned trifunctional or more epoxy compound is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in suppressing dissolution into the liquid crystal and the effect of inserting the liquid crystal into the sealing agent. A more preferable lower limit of the content of the above-mentioned trifunctional epoxy compound is 60 parts by weight, and a more preferable upper limit is 90 parts by weight.

As the other curable resin, a monofunctional epoxy compound or a bifunctional epoxy compound can be suitably used.

As the monofunctional epoxy compound or the bifunctional epoxy compound, it is preferred that one or two epoxy groups are contained in one molecule obtained by reacting a part of the epoxy group of the multifunctional epoxy compound with (meth) acrylic acid. Partial (meth) acrylic modified epoxy resin (hereinafter also referred to as "partial (meth) acrylic modified epoxy resin"). In particular, in terms of improving the rapid curing property of the obtained sealant for a liquid crystal display element and making it more effective in suppressing the insertion of the liquid crystal into the sealant, it is preferable to modify the above-mentioned (meth) acrylic acid-modified epoxy. The resin is used in combination with the following thermal radical polymerization initiator.

Examples of the other monofunctional epoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and p-tert-butylbenzene. Glycidyl ether, glycidyl (meth) acrylate, and the like.
In the present specification, the "(meth) acrylic acid" means acrylic acid or (meth) acrylic acid, and the "(meth) acrylic acid ester" means acrylate or methacrylate.

Examples of the other bifunctional epoxy compounds include a bisphenol A type bifunctional epoxy compound, a bisphenol F type bifunctional epoxy compound, a bisphenol S type bifunctional epoxy compound, and 2,2 ' -Diallyl bisphenol A type bifunctional epoxy compound, hydrogenated bisphenol type bifunctional epoxy compound, propylene oxide addition bisphenol A type bifunctional epoxy compound, resorcinol type bifunctional epoxy compound , Biphenyl type bifunctional epoxy compound, sulfide type bifunctional epoxy compound, diphenyl ether type bifunctional epoxy compound, dicyclopentadiene type bifunctional epoxy compound, naphthalene type bifunctional epoxy compound Compounds, epoxypropylamine type bifunctional epoxy compounds, alkyl polyol type bifunctional epoxy compounds, rubber modified type bifunctional epoxy compounds, bifunctional propylene oxide ester compounds, and the like.

The sealant for liquid crystal display elements of the present invention may contain a (meth) acrylic compound having no epoxy group as the above-mentioned other curable resins, and when the PSA type liquid crystal display element is suppressed, it is prevented from being caused by dissolution into the liquid crystal. From the viewpoint of the adverse effect on the uneven shape, it is preferred that the (meth) acrylic compound not having an epoxy group is not contained.
In the present specification, the "(meth) acrylic compound" refers to a compound having a (meth) acrylfluorenyl group, and the "(meth) acrylfluorenyl" refers to acrylfluorenyl or methacrylfluorene base.

The sealing agent for liquid crystal display elements of this invention contains a thermosetting agent.
Examples of the thermosetting agent include organic acid hydrazine, imidazole derivatives, amine compounds, polyphenol compounds, and acid anhydrides. Among them, the organic acid hydrazine can be suitably used.
The said thermosetting agent can be used individually or in combination of 2 or more types.

Examples of the organic acid hydrazine include dihydrazine sebacate, dihydrazine isophthalate, dihydrazine adipate, and dihydrazine malonate.
Examples of the commercially available organic acid hydrazine include organic acid hydrazine manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazine manufactured by Ajinomoto Fine-Techno, and organic acid hydrazine manufactured by Finechem.
Examples of the organic acid hydrazine produced by the Otsuka Chemical Company include SDH, ADH, and the like.
Examples of the organic acid hydrazine produced by the Ajinomoto Fine-Techno company include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J, and the like.
Examples of the organic acid hydrazine produced by the Japanese Finechem Company include MDH and the like.

The lower limit of the content of the thermosetting agent is preferably 1 part by weight and the upper limit of 50 parts by weight is preferable with respect to 100 parts by weight of the curable resin. By setting the content of the above-mentioned thermosetting agent to be in this range, it is possible to obtain a more excellent thermosetting property without deteriorating the coatability and the like of the obtained sealing agent for a liquid crystal display element. A more preferable upper limit of the content of the heat curing agent is 30 parts by weight.

The sealing agent for liquid crystal display elements of the present invention preferably contains a polymerization initiator.
Examples of the polymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.
Among them, it is preferable to include a radical polymerization initiator as the polymerization initiator. The rebound of the following soft particles is affected not only by the maximum particle size of the soft particles, but also by the hardening speed of the sealant. Compared with the thermosetting agent, the above radical polymerization initiator can significantly increase the curing speed. Therefore, by using it in combination with the above-mentioned soft particles, it is possible to suppress the occurrence of rebound which is easily caused by the above-mentioned soft particles. The display element is more excellent in gap retention.

Examples of the radical polymerization initiator include a thermal radical polymerization initiator that generates radicals by heating, a photo radical polymerization initiator that generates radicals by light irradiation, and the like. Among them, a thermal radical polymerization initiator is preferred. As described above, it is particularly preferable that the obtained (meth) acrylic acid is improved in terms of the rapid curing property of the obtained sealant for a liquid crystal display element and is more excellent in suppressing the insertion of liquid crystal into the sealant. The modified epoxy resin is used in combination with the above-mentioned thermal radical polymerization initiator.

Examples of the thermal radical polymerization initiator include an azo compound, an organic peroxide, and the like. Among them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter also referred to as an "azo initiator") is preferable, and an initiator composed of a polymer azo compound is more preferable. Initiator (hereinafter also referred to as "polymer azo initiator").
These thermal radical polymerization initiators may be used alone or in combination of two or more kinds.
In addition, in the present specification, the "polymer azo compound" refers to a radical having an azo group and generating a radical capable of reacting with a (meth) acrylfluorenyl group by heat, and having a number average molecular weight of 300 or more. Compound.

A preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 1,000, and a preferable upper limit is 300,000. When the number average molecular weight of the above-mentioned polymer azo compound is within this range, adverse effects on the liquid crystal can be prevented, and it can be easily mixed into the curable resin. A more preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 5000, a more preferable upper limit is 100,000, a further preferable lower limit is 10,000, and a more preferable upper limit is 90,000.
In the present specification, the number average molecular weight is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and is a value determined by polystyrene conversion. Examples of the column when the number-average molecular weight measured in terms of polystyrene is measured by GPC include Shodex LF-804 (manufactured by Showa Denko).

Examples of the polymer azo compound include a structure having a plurality of units such as polyalkylene oxide or polydimethylsiloxane bonded via an azo group.
As the polymer azo compound having a structure in which a plurality of units such as a polyalkylene oxide are bonded via an azo group, a polymer having a polyethylene oxide structure is preferred.
Specific examples of the polymer azo compound include a polycondensate of 4,4'-azobis (4-cyanovaleric acid) and a polyalkylene glycol, or 4,4'-couple A polycondensate of nitrogen bis (4-cyanovaleric acid) and polydimethylsiloxane having a terminal amine group, and the like.
Examples of the commercially available polymer azo initiator include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical).
Examples of non-polymeric azo initiators include V-65 and V-501 (both manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.).

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

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

Examples of the photo-radical polymerization initiator include benzophenone compounds, acetophenone compounds, fluorenylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and 9-oxysulfur. Compounds etc.
Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -1-butanone, 2- (dimethylamino) -2-((4-methylphenyl) methyl) -1- (4- (4- Phenyl) phenyl) -1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (2,4,6-trimethylbenzyl) ) Phenylphosphine oxide, 2-methyl-1- (4-methylthienyl) -2- Phenylpropane-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propane-1-one, 1- (4- (benzene Thio) phenyl) -1,2-octanedione 2- (O-benzylideneoxime), 2,4,6-trimethylbenzylidenediphenylphosphine oxide, and the like.
The photoradical polymerization initiator may be used alone or in combination of two or more kinds.

As said cationic polymerization initiator, a photocationic polymerization initiator can be used suitably.
The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generation type or a nonionic photoacid generation type.
Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halide salts, and aromatic sulfonium salts, fluorene-arene complexes, titanocene complexes, and aromatic compounds. Organometallic complexes such as silyl alcohol-aluminum complexes.

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

These photocationic polymerization initiators may be used alone or in combination of two or more kinds.

The content of the polymerization initiator relative to 100 parts by weight of the curable resin, a preferred lower limit is 0.01 parts by weight, and a preferred upper limit is 10 parts by weight. When the content of the polymerization initiator is within this range, the obtained sealing agent for a liquid crystal display element becomes a liquid crystal display element which suppresses liquid crystal contamination and is more excellent in storage stability or hardenability. A more preferable lower limit of the content of the polymerization initiator is 0.1 part by weight, and a more preferable upper limit is 5 parts by weight.

The sealant for liquid crystal display elements of the present invention can be suitably used for sealing liquid crystal between substrates of a PSA type liquid crystal display element.
The sealant for liquid crystal display elements of the present invention contains soft particles having a maximum particle size of 100% or more of the cell gap of the liquid crystal display element (hereinafter also simply referred to as "soft particles"). The above-mentioned soft particles have a function of becoming a barrier between other sealant components and the liquid crystal when manufacturing a liquid crystal display element, and prevent the liquid crystal from being inserted into the sealant and the sealant from being eluted to the liquid crystal. In addition, by blending the above-mentioned soft particles, the substrate can be prevented from being shifted before the sealant is cured after the substrate is bonded.
The cell gap of a liquid crystal display element is not limited because it varies depending on the display element, but usually the cell gap of a liquid crystal display element is 2 μm or more and 10 μm or less.

The maximum particle diameter of the soft particles is 100% or more of the cell gap of the liquid crystal display element. By making the maximum particle diameter of the soft particles 100% or more of the cell gap of the liquid crystal display element, it is possible to suppress the liquid crystal from being inserted into the sealant or liquid crystal contamination caused by the sealant. The maximum particle diameter of the soft particles is preferably more than 100% of the cell gap of the liquid crystal display element. The maximum particle diameter of the soft particles is preferably 5 μm or more.
A preferable upper limit of the maximum particle diameter of the soft particles is 20 μm. When the maximum particle diameter of the soft particles is 20 μm or less, springback can be suppressed, and the obtained liquid crystal display element becomes more excellent in gap retention. A more preferable upper limit of the maximum particle diameter of the soft particles is 15 μm.
Furthermore, the maximum particle diameter of the soft particles is preferably 260% or less of the cell gap. By setting the maximum particle diameter of the soft particles to 260% or less of the cell gap and suppressing springback, the obtained liquid crystal display element becomes more excellent in gap retention. The more preferable upper limit of the maximum particle diameter of the soft particles is 220% of the cell gap, and the more preferable upper limit is 170% of the cell gap.
In addition, in this specification, the maximum particle diameter of the said soft particle and the following average particle diameter are the values obtained by measuring the particle | grains before mixing with a sealant using the laser diffraction type particle size distribution measuring device. . As the laser diffraction type particle size distribution measuring device, Mastersizer 2000 (manufactured by Malvern) can be used. In addition, the maximum particle diameter of the soft particles and the following average particle diameters refer to the maximum value of the particle diameters of ten particles observed with the scanning electron microscope at a magnification of 10,000 times to the particles included in the sealant, and average value. As the scanning electron microscope, a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies) can be used.
In addition, in a liquid crystal display element, as long as soft particles whose shape is deformed due to being crushed by the bonded substrate are confirmed in the hardened material of the sealant, the maximum particle diameter of the soft particles can be said to be a liquid crystal display element. More than 100% of the cell gap.

It is preferable that the content ratio of the particles having a particle size of 5 μm or more in the particle size distribution of the soft particles measured by the laser diffraction type distribution measuring device is 60% or more by volume frequency. When the content ratio of the particles having a particle diameter of 5 μm or more is 60% or more by volume frequency, the effect of suppressing the insertion of liquid crystal into the sealant or the liquid crystal contamination caused by the sealant is more excellent. The content ratio of particles having a particle diameter of 5 μm or more is more preferably 80% or more.

The above-mentioned soft particles are preferably 70% by volume frequency in the particle size distribution of the soft particles measured by the above-mentioned laser diffraction type distribution measuring device. the above. By making the content ratio of the particles of 100% or more of the cell gap of the liquid crystal display element 70% or more by volume frequency, it becomes more excellent in suppressing the liquid crystal from being inserted into the sealant or the liquid crystal contamination caused by the sealant. The content of the soft particles is preferably 100% or more of the cell gap of the liquid crystal display device, and the content ratio of the particles is 100% by volume frequency, that is, only the particles of 100% or more of the cell gap of the liquid crystal display device are included.

A preferable lower limit of the average particle diameter of the soft particles is 2 μm, and a preferable upper limit is 15 μm. When the average particle diameter of the soft particles is 2 μm or more, the effect of suppressing the liquid crystal insertion into the sealant or the liquid crystal contamination caused by the sealant is more excellent. By making the average particle diameter of the said soft particle 15 micrometers or less, the liquid crystal display element obtained will become the thing which is more excellent in gap | interval retention. A more preferable lower limit of the average particle diameter of the soft particles is 4 μm, and a more preferable upper limit is 12 μm.

As the soft particles, as long as the overall maximum particle diameter is in the above range, two or more kinds of soft particles having different maximum particle diameters may be mixed and used. That is, soft particles whose maximum particle diameter is less than 100% of the cell gap of the liquid crystal display element and soft particles whose maximum particle diameter is 100% or more of the cell gap of the liquid crystal display element can be mixed and used.

The coefficient of variation (hereinafter also referred to as "CV value") of the particle diameter of the soft particles is preferably 30% or less. By making the CV value of the particle diameter of the said soft particle 30% or less, the obtained liquid crystal display element becomes the thing which is more excellent in gap | interval retention. The CV value of the particle size of the soft particles is more preferably 28% or less, and even more preferably 15% or less.
In addition, in this specification, the said "CV value of a particle diameter" means the value calculated | required by the following formula.
CV of particle size (%) = (standard deviation of particle size / average particle size) × 100

Even if the maximum particle size, average particle size, or CV value of the soft particles is outside the above range, the maximum particle size, average particle size, or CV value can be set within the above range by classification. In addition, soft particles whose particle size does not reach 100% of the cell gap of the liquid crystal display element cannot be helpful because of the suppression of liquid crystal insertion into the sealant or the liquid crystal pollution caused by the sealant. If blended in the sealant, Since the thixotropic value is increased, it is preferably removed by classification in advance.
Examples of the method for classifying the soft particles include methods such as wet classification and dry classification. Among them, wet classification is preferred, and wet sieve classification is more preferred.

It is preferable that the compression displacement of the soft particles from the load value from the origin to a specific reverse load value when the load is applied is set to L1, and the unloading displacement from the reverse load value to the load value from the origin when the load is released is set. When it is L2, the response rate of L2 / L1 expressed as a percentage is 80% or less. When the response rate of the soft particles is 80% or less, the effect of suppressing the liquid crystal from being inserted into the sealant or the liquid crystal contamination caused by the sealant is more excellent. The more preferable upper limit of the response rate of the soft particles is 70%, and the more preferable upper limit is 60%.
The response rate of the soft particles is substantially 5% or more.
The response rate of the soft particles can be derived by analyzing the response of a particle using a micro compression tester to a certain load (1 g) and removing the load.

The soft particles are preferably such that the compression displacement when applying a load of 1 g is set to L3 and the particle diameter is set to Dn, and the 1 g strain of L3 / Dn expressed as a percentage is 30% or more. By setting the strain of 1 g of the soft particles to 30% or more, the effect of suppressing the liquid crystal from being inserted into the sealant or the liquid crystal contamination caused by the sealant is more excellent. The lower limit of the 1 g strain of the soft particles is preferably 40%.
The 1 g strain of the soft particles can be derived by applying a 1 g load to one particle using a micro compression tester and measuring the amount of displacement.

It is preferable that when the compression displacement of the soft particles at the time point when the particles are broken is L4 and the particle diameter is Dn, the breaking strain of L4 / Dn expressed as a percentage is 50% or more. By setting the destruction strain of the soft particles to 50% or more, the effect of suppressing the liquid crystal insertion into the sealant or the liquid crystal contamination caused by the sealant is more excellent. A more preferable lower limit of the breaking strain of the soft particles is 60%.
The breaking strain of the soft particles can be derived by measuring a displacement amount by which a particle is broken by applying a load to the particle using a micro compression tester. The compression displacement L4 is calculated by taking the point in time when the amount of displacement increases discontinuously with respect to the load load as the point in time when the particles are destroyed. In the case where only deformation occurs without breaking even when the load is increased, the breaking strain is considered to be 100% or more.

The preferable lower limit of the glass transition temperature of the soft particles is -200 ° C, and the preferable upper limit is 40 ° C. The lower the glass transition temperature of the above-mentioned soft particles, the better the viewpoint of suppressing the insertion of liquid crystal into the sealant or the liquid crystal contamination caused by the sealant. The operability of the particles is -200 ° C or higher Become more excellent. By setting the glass transition temperature of the soft particles to 40 ° C. or lower, the obtained liquid crystal display element becomes more excellent in gap retention. A more preferable lower limit of the glass transition temperature of the soft particles is -150 ° C, and a more preferable upper limit is 35 ° C.
The glass transition temperature of the above-mentioned soft particles is a value measured by differential scanning calorimetry (DSC) based on "Method for Measuring the Transition Temperature of Plastics" based on JIS K 7121.

Examples of the soft particles include polysiloxane-based particles, ethylene-based particles, urethane-based particles, fluorine-based particles, and nitrile-based particles. Among these, polysiloxane particles and vinyl particles are preferred.

As said silicone particle | grains, a silicone rubber particle is preferable from a viewpoint of the dispersibility in resin.
Examples of commercially available ones of the above-mentioned polysiloxane particles include KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Torayfil E-506S, EP-9215 (both manufactured by Toray Dow Corning), etc. can be used by classifying them. These polysiloxane particles may be used alone or in combination of two or more.

As the vinyl-based particles, (meth) acrylic particles can be suitably used.
The (meth) acrylic particles can be obtained by polymerizing a monomer serving as a raw material by a known method. Specifically, for example, a method of suspension polymerization of a monomer in the presence of a radical polymerization initiator; and a method of absorbing monomers by non-crosslinked seed particles in the presence of a radical polymerization initiator A method of swelling seed particles to perform seed polymerization and the like.
In the present specification, the "(meth) acrylic acid" refers to acrylic acid or methacrylic acid.

As a monomer which becomes a raw material for forming the said (meth) acrylic particle, a monofunctional monomer can be used.
Examples of the monofunctional monomer include an alkyl mono (meth) acrylate, a mono (meth) acrylate containing an oxygen atom, a mono (meth) acrylate containing a nitrile group, and a mono (methyl) containing a fluorine atom. Based) acrylate.
Examples of the mono (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (methyl) (Hexyl) hexyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearin (meth) acrylate Esters, cyclohexyl (meth) acrylate, isofluorenyl (meth) acrylate, and the like.
Examples of the oxygen atom-containing mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and (meth) Glycidyl acrylate, etc.
Examples of the nitrile group-containing mono (meth) acrylic monomer include (meth) acrylonitrile and the like.
Examples of the fluorine atom-containing mono (meth) acrylate include trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate.
Among them, an alkyl mono (meth) acrylate is preferred because the glass transition temperature of the homopolymer is low and the amount of deformation when a load of 1 g can be increased.
In addition, in this specification, the "(meth) acrylate" means an acrylate or a methacrylate.

Moreover, in order to have a crosslinked structure, you may use a polyfunctional monomer as said monomer.
Examples of the polyfunctional monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dinepentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (Meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) butylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isotricyanic acid skeleton tri (meth) acrylate, and the like. Among these, (poly) ethylene glycol di (meth) acrylate and (poly) propylene glycol di are preferred because they have a large molecular weight between the crosslinking points and can increase the amount of deformation when a load of 1 g is applied. (Meth) acrylate, (poly) butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylic acid ester.

A preferable lower limit of the use amount of the polyfunctional monomer in the entire monomer is 1% by weight, and a preferable upper limit is 90% by weight. When the amount of the polyfunctional monomer used is 1% by weight or more, the solvent resistance of the soft particles is improved, and problems such as swelling do not occur when mixed with other sealant components, and it becomes easy to uniformly disperse. When the amount of the polyfunctional monomer used is 90% by weight or less, the response rate of the soft particles can be reduced, and problems such as springback are difficult to occur. A more preferable lower limit of the use amount of the above-mentioned polyfunctional monomer is 3% by weight, and a more preferable upper limit is 80% by weight.

Further, as the monomers, in addition to the acrylic monomers, for example, styrene monomers, vinyl ethers, vinyl esters, unsaturated hydrocarbons, halogen atom-containing monomers, or (iso) trimers can be used. Triallyl cyanate, triallyl 1,2,4-benzenetricarboxylate, divinylbenzene, diallyl phthalate, diallyl allylamine, diallyl ether, 3 -(Meth) acrylic methoxypropyltrimethoxysilane, vinyltrimethoxysilane and other monomers.
Examples of the styrene-based monomer include styrene, α-methylstyrene, and trimethoxysilylstyrene.
Examples of the vinyl ethers include methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether.
Examples of the vinyl esters include vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, and the like.
Examples of the unsaturated hydrocarbon include ethylene, propylene, isoprene, and butadiene.
Examples of the halogen atom-containing monomer include vinyl chloride, vinyl fluoride, and chlorostyrene.

In addition, as the vinyl-based particles, for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles, and the like can also be used.

Examples of the commercially available amine ester-based particles include Artpearl (manufactured by Negami Industry Co., Ltd.) and Daimic beaz (manufactured by Daihichi Shoyo Kogyo Co., Ltd.), and these can be classified and used.

A preferable lower limit of the hardness of the soft particles is 3, and a preferable upper limit is 50. By making the hardness of the said soft particle into this range, the obtained liquid crystal display element will become the thing which is more excellent in gap | interval retention. The lower limit of the hardness of the soft particles is more preferably 10, the upper limit is more preferably 40, and the more preferable lower limit is 20.
In addition, in this specification, the said "hardness of a soft particle" is a value of the hardness A hardness measured by the method based on JISK 6253.

A preferable lower limit of the content of the soft particles in the sealant for a liquid crystal display element of the present invention is 5 wt%, and a preferable upper limit is 60 wt%. When the content of the soft particles is 5% by weight or more, the effect of suppressing the insertion of liquid crystal into the sealant or contamination of the liquid crystal by the sealant is more excellent. By setting the content of the soft particles to 60% by weight or less, the obtained sealing agent for a liquid crystal display element becomes more excellent in adhesiveness. The more preferable lower limit of the content of the soft particles is 10% by weight, the more preferable upper limit is 50% by weight, the more preferable lower limit is 20% by weight, and the more preferable upper limit is 40% by weight.

In order to improve the viscosity, improve the adhesion by the effect of stress dispersion, improve the linear expansion ratio, etc., the sealing agent for a liquid crystal display element of the present invention preferably contains a filler.

As the filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, and iron oxide. , Magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, and the like.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
These fillers may be used alone or in combination of two or more.

A preferable lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 10 parts by weight, and a preferable upper limit is 70 parts by weight. When the content of the filler is in this range, effects such as improvement in adhesiveness and the like are not deteriorated without deteriorating coatability and the like. A more preferable lower limit of the content of the filler is 20 parts by weight, and a more preferable upper limit is 60 parts by weight.

The sealing agent for liquid crystal display elements of this invention may contain a silane coupling agent. The above-mentioned silane coupling agent mainly functions as a bonding aid for adhering a sealant to a substrate and the like well.

As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanate can be suitably used. Acid propyltrimethoxysilane and the like. These silane coupling agents are excellent in improving the adhesion to a substrate and the like, and can prevent the curable resin from flowing into the liquid crystal by chemically bonding with the curable resin.
These silane coupling agents may be used alone or in combination of two or more kinds.

A preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 0.1 part by weight, and a preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is in this range, liquid crystal contamination is suppressed and the effect of improving adhesion is more excellent. A more preferable lower limit of the content of the silane coupling agent is 0.3 part by weight, and a more preferable upper limit is 5 parts by weight.

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

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

Compared with the average transmittance for light having a wavelength of 300 nm to 800 nm, the titanium black is a substance having a higher transmittance for light in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 nm to 450 nm. That is, the above-mentioned titanium black is a light-shielding agent having properties such that the light-shielding property is provided to the sealant for a liquid crystal display element of the present invention by sufficiently shielding light of a wavelength in the visible light region, and the wavelength near the ultraviolet region is provided. The light is transmitted. Therefore, by using light having a wavelength (370 nm or more and 450 nm or less) capable of increasing the transmittance of the titanium black, the starter of the reaction is used as the photoradical polymerization initiator or the photocationic polymerization initiator. Can further increase the photocurability of the sealant for a liquid crystal display element of the present invention. On the other hand, as the light-shielding agent contained in the sealant for a liquid crystal display element of the present invention, a substance having a high insulating property is preferable, and as a light-shielding agent having a high insulating property, titanium black is also suitable.
The titanium black preferably has an optical density (OD value) of 3 or more per 1 μm, and more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black does not have a particularly preferable upper limit, but it is usually 5 or less.

The above titanium black exhibits sufficient effects even if it is not surface-treated, but it can also be treated with organic components such as coupling agents on the surface, or silicon oxide, titanium oxide, germanium oxide, alumina, zirconia, magnesium oxide, etc. Surface-treated titanium black, such as those coated with inorganic components. Among them, those treated with an organic component are preferred in terms of further improving the insulation properties.
In addition, the liquid crystal display element manufactured by using the sealant for liquid crystal display elements of the present invention in which the above-mentioned titanium black is used as a light-shielding agent has sufficient light-shielding properties, so there is no leakage of light and a high contrast ratio can be achieved. Liquid crystal display element with excellent image display quality.

As a marketer among the above-mentioned titanium blacks, for example, titanium black manufactured by Mitsubishi Materials Co., Ltd., titanium black manufactured by Akagi Kasei Co., Ltd., and the like can be cited.
Examples of the titanium black manufactured by the Mitsubishi Materials company include 12S, 13M, 13M-C, 13R-N, and 14M-C.
Examples of the titanium black manufactured by the Akagi Chemical Industry Company include Tilack D and the like.

The preferred lower limit of the specific surface area of the titanium black is 13 m ² / g, the preferred upper limit is 30 m ² / g, the more preferred lower limit is 15 m ² / g, and the more preferred upper limit is 25 m ² / g.
In addition, the preferable lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferable upper limit is 3 Ω · cm, the more preferable lower limit is 1 Ω · cm, and the more preferable upper limit is 2.5 Ω · cm.

The primary particle diameter of the above-mentioned 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 element. The lower limit is preferably 1 nm, and the upper limit is preferably 5000 nm. By making the primary particle diameter of the said light-shielding agent into this range, it can be made into the thing which is more excellent in light-shielding property, without deteriorating the coating property of the obtained sealing compound for liquid crystal display elements. The lower limit of the primary particle diameter of the above-mentioned sunscreen is more preferably 5 nm, the more preferable upper limit is 200 nm, the more preferable lower limit is 10 nm, and the more preferable upper limit is 100 nm.
The primary particle diameter of the light-shielding agent can be measured by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

A preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and a preferable upper limit is 80 parts by weight. When the content of the light-shielding agent is within this range, it is possible to exhibit more excellent light-shielding properties without significantly reducing the adhesiveness, strength after hardening, and drawability of the obtained sealant for a liquid crystal display element. A more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a more preferable lower limit is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.

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

The method for manufacturing the sealant for liquid crystal display elements of the present invention is not particularly limited, and for example, a method of mixing additives such as a curable resin, a thermosetting agent, soft particles, and a silane coupling agent, if necessary, using a mixer.
Examples of the mixer include a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll kneader.

By mixing conductive fine particles into the sealant for a liquid crystal display element of the present invention, a vertical conductive material can be manufactured. In addition, the sealant for a liquid crystal display element of the present invention and the conductive material for the upper and lower conductive particles are also one aspect of the present invention.

As the conductive fine particles, metal balls, those having a conductive metal layer formed on the surface of the resin fine particles, and the like can be used. Among them, those having a conductive metal layer formed on the surface of the resin fine particles are preferable in terms of being able to achieve conductive connection without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.

In addition, a liquid crystal display element formed by using the sealant for liquid crystal display elements of the present invention or the upper-lower conductive material of the present invention is also one aspect of the present invention.
As the liquid crystal display element of the present invention, a liquid crystal display element with a narrow edge design is preferred. Specifically, the width of the frame portion around the liquid crystal display portion is preferably 2 mm or less.
In addition, when the liquid crystal display element of the present invention is manufactured, the coating width of the sealant for a liquid crystal display element of the present invention is preferably 1 mm or less.

As a method for manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method can be suitably used. Specifically, for example, a method having the following steps can be mentioned.
First, the following steps are performed: on one of two transparent substrates having an electrode such as an ITO film and an alignment film, the sealant for a liquid crystal display element of the present invention is coated by screen printing, dispenser application, or the like to form a frame-shaped substrate. Seal pattern. Next, the following steps are performed: in a state where the sealant for a liquid crystal display element of the present invention is not hardened, minute droplets of a liquid crystal composition containing a polymerizable compound are added dropwise and applied to a frame of a sealing pattern of a substrate, and overlapped under vacuum. Another transparent substrate. Thereafter, a step is performed in which the sealant for a liquid crystal display element of the present invention is hardened by heating. Further, the following steps are performed: polymerizing a polymerizable compound in the liquid crystal composition by light irradiation or the like under a voltage applied state to form a concave-convex shape on the substrate; and by the method including the above steps, a PSA type liquid crystal display can be obtained element. In addition, before the step of hardening the sealant for a liquid crystal display element of the present invention by the above-mentioned heating, a step of temporarily hardening the sealant by light irradiation may be performed, but the sealant for a liquid crystal display element of the present invention suppresses liquid crystal The effect of the liquid crystal contamination caused by the insertion into the sealant or by the sealant is particularly significant in the case where the sealant is hardened only by heat.
[Effect of the invention]

According to the present invention, it is possible to provide a sealant for a liquid crystal display device that can suppress the liquid crystal from being inserted into a sealant or liquid crystal contamination caused by the sealant, and has excellent adhesion and can obtain a liquid crystal display device with excellent display performance. Furthermore, according to the present invention, it is possible to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

Examples are described below to further describe the present invention, but the present invention is not limited to these examples.

(Synthesis of Partial Acrylic Modified Diphenyl Ether Epoxy Resin)
On one side, 1000 parts by weight of a diphenyl ether type epoxy resin (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., "YSLV80DE"), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, 229 parts by weight of acrylic acid and acrylic acid were refluxed at 90 ° C. while being fed into the air, and the reaction was allowed to proceed for 5 hours. In order to adsorb ionic impurities in the reaction, 100 parts by weight of the obtained resin was filtered through a column filled with 10 parts by weight of a natural combination of quartz and kaolin ("Sillitin V85" manufactured by Hoffmann Mineral) to obtain a portion of acrylic acid. Modified diphenyl ether epoxy resin.

(Synthesis of resorcinol epoxy acrylate)
On one side, 1000 parts by weight of a resorcinol-type epoxy resin ("DENACOL EX-201" manufactured by Nagase Kasei Corporation), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, and triethylamine as a reaction catalyst 2 parts by weight and 649 parts by weight of acrylic acid were refluxed and stirred at 90 ° C for 5 hours, and air was introduced while reacting them. In order to adsorb ionic impurities in the reaction, 100 parts by weight of the obtained resin was filtered through a column filled with 10 parts by weight of a natural combination of quartz and kaolin ("Sillitin V85" manufactured by Hoffmann Mineral) to obtain m-benzene. Diphenol epoxy acrylate.

(Grading of polysiloxane rubber particles)
Silicone rubber particles ("KMP-601" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were dispersed in methanol, and a particle size in the range of 5 to 8 μm was obtained by using a 8 μm mesh sieve and a 5 μm mesh sieve. Wet sieve classification. The classified particles are recovered and then dried to obtain a classified processed product of silicone rubber particles. The sieve system uses a highly precise hole obtained by performing ultra-high precision micro-processing on a polyimide film using a laser.
With respect to the obtained graded processed product of silicone rubber particles, the maximum particle diameter measured by a laser diffraction particle size distribution measuring device (manufactured by Malvern, "Mastersizer-2000") was 8 μm.
In addition, a wet sieve classification was performed using a 6 μm mesh sieve and a 3 μm mesh sieve so that the particle size was in the range of 3 to 6 μm. In addition, the classification of the silicone rubber particles was obtained in the same manner. Processed product (maximum particle size 6 μm).
Furthermore, a wet sieve classification was performed using a 3 μm mesh sieve so that the particle size was in the range of 3 μm or less. In addition, a classification product of silicone rubber particles (maximum particle size: 3 μm) was obtained in the same manner. ).

(Examples 1 to 10, Comparative Examples 1 to 3)
In accordance with the blending ratios described in Table 1, the materials were mixed using a planetary mixer ("Defoaming Taro" manufactured by Thinky), and then mixed using a three-roll kneader to prepare Examples 1 to 10. 3. Sealants for liquid crystal display elements of Comparative Examples 1 to 3.

＜ Evaluation ＞
The following evaluations were performed about each sealing agent for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Table 1.

(Adherence)
With respect to 100 parts by weight of each of the sealants for liquid crystal display elements obtained in the examples and comparative examples, 1 part by weight of spacer particles having an average particle diameter of 5 μm (made by Sekisui Chemical Industry Co., Ltd., "Micropearl" SP-2050 ") dispersed evenly. Take the trace amount of the sealant in which the spacer particles are dispersed to the center of the glass substrate (20 mm × 50 mm × thickness 0.7 mm), and superimpose the same type of glass substrate on it. The sealant for a liquid crystal display element was pushed out and heated at 120 ° C. for 1 hour to harden the sealant, thereby obtaining a subsequent test piece.
Using the tensiometer, the adhesive strength of the obtained adhesive test piece was measured. A case where the bonding strength is 200 N / cm ² or more is "0", a case where the bonding strength is 150 N / cm ² or more and less than 200 N / cm ² is "Δ", and a bonding strength is less than 150. The case of N / cm ² was set to “×” to evaluate the adhesiveness.

(Anti-insertion)
With respect to 100 parts by weight of each of the sealants for liquid crystal display elements obtained in the examples and comparative examples, 1 part by weight of spacer particles having an average particle diameter of 5 μm (made by Sekisui Chemical Industry Co., Ltd., "Micropearl" SP-2050 ") dispersed evenly. The sealant in which the spacer particles are dispersed is filled in a syringe for dispensing (manufactured by Musashi Hi-Tech Corporation, "PSY-10E") and subjected to a defoaming treatment. Using a dispenser (manufactured by Musashi Hi-Tech Co., Ltd., "SHOTMASTER300"), the defoamed sealant was applied to a glass substrate having an ITO film and an alignment film in a rectangular frame. Then, a liquid crystal composition (MLC-6883 (manufactured by Merck)) containing a polymerizable compound was added dropwise by a liquid crystal dropping device, and 1% by weight of bis (2-methacrylic acid) biphenyl 4,4'-diyl ester was added. And the winner). Another glass substrate having an ITO film and an alignment film was superimposed on the glass substrate on which the liquid crystal composition was dropped and applied with the sealant for a liquid crystal display element of the present invention, and then a vacuum bonding device was used under a vacuum of 5 Pa. Bonding was performed to obtain a unit. The obtained unit was heated at 120 ° C for 1 hour to harden the sealant. Next, a mercury lamp was used to irradiate 100 mW / cm ² of ultraviolet light (wavelength 313 nm) for 50 seconds under a voltage applied state, and the polymerizable compound in the liquid crystal composition was polymerized to form an uneven shape, thereby obtaining a liquid crystal display element (cell gap 5 μm).
For each of the obtained liquid crystal display elements, the shape of the sealing pattern was observed. Set the shape of the seal pattern not disturbed by the internal liquid crystal to "◎", set the shape of the seal pattern slightly disturbed to "0", and set the shape of the seal pattern to be greatly disturbed but the liquid crystal does not break through the seal pattern. The value was "Δ", and the liquid crystal penetrated the seal pattern and was exposed to the outside as "X" to evaluate the anti-insertion property.

(Display performance of liquid crystal display elements)
Each of the obtained liquid crystal display elements was visually confirmed in the same manner as the evaluation of the "(insertion prevention property)" described above to be in the vicinity of the sealant after applying a voltage for 100 hours under an environment of 60 ° C and 90% RH. The liquid crystal alignment is disordered (uneven display).
The display unevenness of the liquid crystal display element was not observed at all, and was set to "0". The display unevenness was observed near the sealant of the liquid crystal display element (peripheral portion), and was set to "Δ". The case where the peripheral portion extends to the central portion is set to "x" to evaluate the display performance of the liquid crystal display element.
In addition, the liquid crystal display element evaluated as "0" is a level which is completely practical without problems. The liquid crystal display element of "Δ" is a level that may cause problems depending on the display design. The liquid crystal display element of "×" is intolerable. Practical level.

[Table 1]

[Industrial availability]

According to the present invention, it is possible to provide a sealant for a liquid crystal display device that can suppress the liquid crystal from being inserted into a sealant or liquid crystal contamination caused by the sealant, and has excellent adhesion and can obtain a liquid crystal display device with excellent display performance. Furthermore, according to the present invention, it is possible to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

no

no

Claims (6)

A sealant for a liquid crystal display element, comprising: a curable resin, a thermosetting agent, and soft particles having a maximum particle diameter of 100% or more of a cell gap of the liquid crystal display element; The curable resin includes a compound having three or more epoxy groups in one molecule. The sealant for a liquid crystal display device according to claim 1, wherein the compound having three or more epoxy groups in one molecule has three or more epoxy groups and an isocyanuric skeleton in one molecule ) Compounds and / or epoxypropylamine type epoxy compounds having 3 or more epoxy groups in one molecule. The sealant for a liquid crystal display device according to claim 2, wherein the compound having three or more epoxy groups in one molecule is a compound having three or more epoxy groups and an isocyanuric acid skeleton in one molecule. . The sealant for a liquid crystal display element according to 2 or 3, which is used for sealing liquid crystal between substrates of a PSA type liquid crystal display element. A vertical conduction material comprising the sealant for liquid crystal display elements and conductive fine particles according to claim 1, 2, 3, or 4. A liquid crystal display element is obtained by using the sealant for liquid crystal display elements according to claim 1, 2, 3, or 4 or the top-to-bottom conduction material according to claim 5.