KR102323647B1 - Sealant for one-drop fill process, vertically conducting material, and liquid crystal display element - Google Patents

Abstract

An object of this invention is to provide the sealing compound for liquid crystal dropping methods compatible with suppression of a seal break and liquid-crystal contamination, and suppression of the gap defect by springback. Moreover, this invention aims at providing the vertical conduction material and liquid crystal display element manufactured using the sealing compound for liquid crystal dropping methods. This invention is a sealing compound for liquid crystal dropping methods used for manufacture of the liquid crystal display element by a liquid crystal dropping method, Comprising: Curable resin, a polymerization initiator and/or thermosetting agent, and flexible particle|grains are contained, The said flexible particle|grains are particle size distribution WHEREIN: It is the sealing compound for liquid crystal dropping methods whose mode particle diameter is 1.07 times or more of a median particle diameter.

Description

Sealant for liquid crystal dropping method, vertical conduction material, and liquid crystal display element {SEALANT FOR ONE-DROP FILL PROCESS, VERTICALLY CONDUCTING MATERIAL, AND LIQUID CRYSTAL DISPLAY ELEMENT}

This invention relates to the sealing compound for liquid crystal dropping methods which are compatible with suppression of a seal break and liquid-crystal contamination, and suppression of the gap defect by springback. Moreover, this invention relates to the vertical conduction material and liquid crystal display element manufactured using the sealing compound for liquid crystal dropping methods.

In recent years, the manufacturing method of liquid crystal display elements, such as a liquid crystal display cell, from a viewpoint, such as tact time shortening and optimization of the amount of liquid crystal used, from a conventional vacuum injection method, as disclosed by patent document 1 and patent document 2, for example. The liquid crystal dropping method called the dripping method using the sealing compound of the same light-heat combined use hardening type is becoming mainstream.

In the dripping method, first, a rectangular seal pattern is formed with a dispenser in one side of the transparent substrate with an electrode of 2 sheets. Next, in a state in which the sealing compound is not cured, microdroplets of the liquid crystal are dripped onto the entire surface inside the frame of the transparent substrate, the other transparent substrate is immediately superimposed, and the sealing portion is irradiated with light such as ultraviolet rays to perform temporary curing. Conduct. Then, at the time of liquid crystal annealing, it heats and performs main hardening, and produces a liquid crystal display element. When bonding of a board|substrate is made to perform under reduced pressure, a liquid crystal display element can be manufactured with very high efficiency.

By the way, in the present age in which mobile devices equipped with various liquid crystal panels, such as a mobile phone and a portable game machine, are widespread, size reduction of an apparatus is the most requested|required subject. As a method of downsizing, narrow frame-ization of a liquid crystal display part is mentioned, for example, arrange|positioning the position of a sealing part under a black matrix is implemented (henceforth "narrow frame design").

However, when a liquid crystal display element of a narrow frame design is manufactured by a dripping method, since there is a point where light does not reach the seal part due to the black matrix, a portion of the photocurable resin that is not sufficiently irradiated with light and does not cure occurs. And, since the uncured sealing compound is in contact with the liquid crystal, the liquid crystal enters the sealing compound, a seal break occurs, the liquid crystal leaks, or the uncured photocurable resin is eluted after the provisional curing step, and the liquid crystal is contaminated There was a problem that there was

Japanese Patent Laid-Open No. 2001-133794 International Publication No. 02/092718

An object of this invention is to provide the sealing compound for liquid crystal dropping methods compatible with suppression of a seal break and liquid-crystal contamination, and suppression of the gap defect by springback. Moreover, this invention aims at providing the vertical conduction material and liquid crystal display element which are manufactured using the sealing compound for liquid crystal dropping methods.

The present invention is a sealing agent for a liquid crystal dropping method used for production of a liquid crystal display element by a liquid crystal dropping method, comprising a curable resin, a polymerization initiator and/or a thermosetting agent, and flexible particles, the flexible particles having a particle size distribution WHEREIN: It is the sealing compound for liquid crystal dropping methods 1.07 times or more of a median particle diameter of a mode particle diameter.

Hereinafter, the present invention will be described in detail.

The present inventors examined suppressing generation|occurrence|production of a seal break and a liquid-crystal contamination by mix|blending flexible particle|grains with the sealing compound for liquid crystal dropping methods, and making the flexible particle|grain become a barrier between another sealing compound component and a liquid crystal.

However, when such a flexible particle|grain was mix|blended, the cell gap defect by springback may generate|occur|produce in the liquid crystal display element obtained.

Then, as a result of earnest examination, the present inventors achieve both suppression of seal break and liquid crystal contamination and suppression of gap defect by springback by mix|blending flexible particle whose mode particle diameter is larger than a specific value more than a median particle diameter in a particle size distribution as a result of earnest examination It found out that the sealing compound for liquid crystal dropping methods that can be done was obtained, and came to complete this invention.

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

The sealing compound for liquid crystal dropping methods of this invention contains a flexible particle|grain.

When the said flexible particle|grain manufactures a liquid crystal display element, it becomes a barrier between another sealing compound component and a liquid crystal, and has a role which prevents that a liquid crystal enters a sealing compound and a sealing compound elutes to a liquid crystal. Moreover, after bonding a board|substrate by mix|blending the said flexible particle|grain, shift|offset|difference of a board|substrate until sealing compound hardens can be prevented.

The said flexible particle|grain is a particle size distribution. WHEREIN: A mode particle diameter is 1.07 times or more of a median particle diameter. When the mode particle diameter of the said flexible particle|grain is 1.07 times or more of a median particle diameter, suppression of a seal break and a liquid-crystal contamination, and suppression of the cell gap defect by springback are compatible. In particle size distribution, as for the said flexible particle|grain, it is preferable that a mode particle diameter is larger than 1.07 times of a median particle diameter, and it is more preferable that it is larger than 1.10 times.

In addition, in this specification, the mode particle diameter in the said flexible particle|grain, a median particle diameter, a largest particle diameter, a minimum particle diameter, and an average particle diameter are a value obtained by measuring a particle size distribution using a Coulter-type particle size distribution analyzer. means As the Coulter-type distribution measuring device, Multisizer 4 (manufactured by Beckman Coulter), etc. can be used, specifically, 0.1 g of particles are added to 10 g of methanol to mix well, and ultrasonic dispersion is performed for 5 minutes. A particle dispersion liquid is prepared, and the obtained particle dispersion liquid is injected into the beaker containing electrolyte solution "ISOTON II" (made by Beckman Coulter) in a sample stand with a dropper until the indicated concentration of a measuring apparatus becomes 5%. By setting it as this concentration, a measured value with reproducibility can be obtained. The measurement is performed twice, and the arithmetic mean of the calculated values is used.

The "moderate particle diameter" means a particle diameter representing the maximum frequency of particle size distribution by volume frequency, and in the particle size distribution measured using the Coulter-type particle size distribution measuring apparatus, a data processing computer system (Beckman - It is computable using the apparatus which connected the Coulter company make). In the measuring apparatus, the pore diameter of the aperture is set to 50 μm, the range of the measurement range 1 to 30 μm is divided by 300, the frequency value is calculated on a volume basis, and the particle diameter showing the maximum frequency can be calculated. have.

The "median particle diameter" means a particle diameter when the volume of particles larger than the particle diameter occupies 50% of the volume of all particles in the particle size distribution by volume frequency, and the Coulter-type particle size distribution measuring device In the particle size distribution measured using In the measuring apparatus, the pore diameter of the aperture is set to 50 µm, the range of the measurement range 1 to 30 µm is divided by 300, the frequency value is calculated on a volume basis, and the volume integral ratio is 50% from the smaller one. The particle diameter can be calculated as the median particle diameter.

The "maximum particle diameter" is, in the particle size distribution measured using the Coulter-type particle size distribution analyzer, as the particle diameter increases from the mode particle diameter, the volume frequency decreases continuously, so that the particle is not detected. Let the previous particle diameter be the largest particle diameter. In addition, since it is highly likely that it is a flock|aggregate that the volume frequency was detected discontinuously, it excludes from the maximum particle diameter.

The "minimum particle diameter" is set to 1.05 µm, which is the lower limit of detection in the 50 µm aperture to be used, regardless of the sample to be measured.

The said "average particle diameter" is the particle size distribution measured using the said Coulter-type particle size distribution analyzer. WHEREIN: It is computable using the apparatus which connected the computer system for data processing (made by Beckman Coulter). Measurement apparatus WHEREIN: The pore diameter of an aperture shall be 50 micrometers, the range of 1-30 micrometers may be divided|segmented by 300, and an average particle diameter can be computed on a volume basis.

"D90" to be described later means a particle diameter when the volume of particles larger than the particle diameter occupies 10% of the volume of all particles in the particle size distribution by volume frequency, and the Coulter-type particle size distribution measuring device is The particle size distribution measured using the WHEREIN: It is computable using the apparatus to which the computer system for data processing (made by Beckman Coulter) was connected. The measuring apparatus WHEREIN: The pore diameter of an aperture shall be 50 micrometers, the range of the measurement range 1-30 micrometers is divided|segmented by 300, The particle diameter of 90% from the one with a smaller volume integral ratio can be computed as D90.

In the flexible particle, in order to more effectively suppress seal break and liquid crystal contamination and suppress cell gap defects due to springback, in particle size distribution, it is preferable that D90 in the cumulative distribution is less than 1.40 times the median particle diameter, It is more preferable that it is less than 1.35 times.

From the viewpoint of more effectively suppressing seal break and liquid crystal contamination and suppressing cell gap defects due to springback, the flexible particle is a particle size distribution from the smallest particle size to a particle size smaller than the median particle size by 2 µm. When the ratio of the frequency is W (%) and the ratio of the volume frequency from a particle diameter 2 µm larger than the median particle diameter to the maximum particle diameter is Z (%), it is preferable that W/Z≥1.1, and W/Z It is more preferable that ≥1.2.

From the viewpoint of more effectively suppressing seal break and liquid crystal contamination and suppressing cell gap defects due to springback, the flexible particle is a particle size distribution from a particle size smaller than the median particle size by 2 µm to the median particle size. When the ratio of the frequency is X (%) and the ratio of the volume frequency from the median particle diameter to the particle diameter 2 µm larger than the median particle diameter is Y (%), it is preferable that X+Y≥60, and X+Y≥70 more preferably.

From the viewpoint of more effectively suppressing seal break and liquid crystal contamination and suppression of cell gap defects due to springback, the flexible particles have a particle size distribution from a particle size larger than the median particle size by 2 μm to the maximum particle size. It is preferable that the sum of the frequencies, ie, the Z is less than 10% of the total, and the sum of the volume frequencies from the minimum particle diameter to a particle diameter 2 µm smaller than the median particle diameter, ie, the W is less than 20% of the total.

As a method of making the mode particle diameter of the said flexible particle 1.07 times or more of a median particle diameter, for example, a method of classifying flexible particles whose mode particle diameter is less than 1.07 times the median particle diameter, or two or more types from which a particle size distribution differs The method of mixing flexible particle|grains, etc. are mentioned.

As a method of classifying the said flexible particle|grain, methods, such as wet classification and dry classification, are mentioned, for example. Especially, wet classification is preferable and wet sieve classification is more preferable.

Specifically, for example, the method of sieving the slurry which disperse|distributed the flexible particle|grains in the suitable dispersion medium using the high-precision sieve etc. with which the mesh was uniformly equipped is used preferably.

As for the said flexible particle|grain, it is preferable that a largest particle diameter is 100% or more of the cell gap of a liquid crystal display element, and it is 5-50 micrometers. When the largest particle diameter of the said flexible particle|grain is less than 100% of the cell gap of a liquid crystal display element, or it is less than 5 micrometers, it may become impossible to fully suppress a seal break and a liquid-crystal contamination. When the largest particle diameter of the said flexible particle|grain exceeds 50 micrometers, a springback may be raised, the sealing compound for liquid crystal dropping methods obtained will become inferior to adhesiveness, or a gap defect may arise in the liquid crystal display element obtained. A more preferable upper limit of the largest particle diameter of the said flexible particle|grain is 12 micrometers, and a more preferable upper limit is 15 micrometers.

Moreover, it is preferable that the largest particle diameter of the said flexible particle|grain is 2.6 times or less of a cell gap. When the maximum particle diameter of the said flexible particle|grain exceeds 2.6 times of a cell gap, a springback may be raise|generated, the sealing compound for liquid crystal dropping methods obtained will become a thing inferior in adhesiveness, or a gap defect may arise in the liquid crystal display element obtained. A more preferable upper limit of the maximum particle diameter of the flexible particle is 2.2 times the cell gap, and a more preferable upper limit is 1.7 times the cell gap.

In addition, since the cell gap of a liquid crystal display element changes with display elements, it is although it is not limited, The cell gap of a general liquid crystal display element is 2-10 micrometers.

As for the said flexible particle, it is preferable that the content rate of the particle|grains of a particle diameter of 5 micrometers or more in the particle size distribution of the flexible particle measured with the said Coulter-type distribution analyzer is 60 % or more by volume frequency. When the content rate of the particle|grains of 5 micrometers or more of particle diameter is less than 60 % by volume frequency, it may become impossible to fully suppress a seal break and a liquid-crystal contamination. As for the content rate of the particle|grains with a particle diameter of 5 micrometers or more, it is more preferable that it is 80 % or more.

The said flexible particle|grains, from a viewpoint of exhibiting the effect which suppresses generation|occurrence|production of a seal break and liquid-crystal contamination more, contain 100% or more of particle|grains of the cell gap of a liquid crystal display element 70% or more of the particle size distribution in the whole flexible particle|grain It is preferable, and it is more preferable that it consists only of 100% or more of particle|grains of the cell gap of a liquid crystal display element.

The minimum with preferable average particle diameter of the said flexible particle|grain is 2 micrometers, and a preferable upper limit is 15 micrometers. When the average particle diameter of the said flexible particle|grain is less than 2 micrometers, generation|occurrence|production of a seal break or a liquid-crystal contamination may not fully be suppressed. When the average particle diameter of the said flexible particle|grain exceeds 15 micrometers, the sealing compound for liquid crystal dropping methods obtained may become a thing inferior in adhesiveness, or a gap defect may arise in the liquid crystal display element obtained. The minimum with a more preferable average particle diameter of the said flexible particle|grain is 4 micrometers, a more preferable upper limit is 12 micrometers, and a more preferable minimum is 5 micrometers.

It is preferable that the coefficient of variation (henceforth a "CV value") of the particle diameter of the said flexible particle|grain is 30 % or less. When CV value of the particle diameter of the said flexible particle|grain exceeds 30 %, a cell gap defect may be caused. As for CV value of the particle diameter of the said flexible particle|grain, it is more preferable that it is 28 % or less.

In addition, in this specification, the CV value of a particle diameter refers to the numerical value calculated|required by the following formula in the particle size distribution measured using the said Coulter type particle size distribution measuring apparatus.

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

As for the said flexible particle|grain, even if a largest particle diameter, an average particle diameter, and a CV value are things outside the above-mentioned range, by classifying by the above-mentioned method, a largest particle diameter, an average particle diameter, and a CV value will be in the above-mentioned range. can In addition, since flexible particles having a particle diameter of less than 100% of the cell gap of the liquid crystal display element do not contribute to the suppression of seal break or liquid crystal contamination, and may increase the thixotropic value when blended with a sealing agent, it is removed by classification it is preferable

The flexible particles have a compression displacement from the origin load value when a load is applied to the reversal load value as L1, and from the reversal load value when the load is released to the origin load value. When unloading displacement is L2, it is preferable that the recovery factor which expressed L2/L1 as a percentage is 80 % or less. When the recovery rate of the said flexible particle|grain exceeds 80 %, the effect which suppresses generation|occurrence|production of a seal break and a liquid-crystal contamination may not fully be exhibited. A more preferable upper limit of the recovery rate of the said flexible particle|grain is 70 %, and a more preferable upper limit is 60 %.

In addition, the recovery rate of the said flexible particle|grain can be derived|led-out by applying a fixed load (1g) to one particle|grain using a micro compression tester, and analyzing the recovery|restoration behavior after removing the load.

When the said flexible particle|grains make compressive displacement when a load of 1 g is applied to L3, and makes a particle diameter Dn, it is preferable that the 1 g deformation|transformation which showed L3/Dn as a percentage is 30 % or more. The effect which suppresses generation|occurrence|production of a seal break or liquid-crystal contamination as 1 g distortion of the said flexible particle|grain being less than 30 % may not fully be exhibited. The more preferable minimum of 1 g deformation|transformation of the said flexible particle|grain is 40 %.

In addition, 1 g of deformation|transformation of the said flexible particle|grain can be derived|led-out by applying a load of 1 g to one particle|grain using a micro compression tester, and measuring the amount of displacement at that time.

When the said flexible particle|grains make the compressive displacement at the time of particle|grains fracture|rupture L4 and particle diameter Dn, it is preferable that the breaking deformation which showed L4/Dn as a percentage is 50 % or more. The effect which suppresses generation|occurrence|production of a seal break or liquid-crystal contamination as the breaking strain of the said flexible particle|grain is less than 50 % may not fully be exhibited. The more preferable minimum of the fracture deformation|transformation of the said flexible particle|grain is 60 %.

In addition, the breaking deformation of the said flexible particle|grain can be derived|led-out by applying a load to one particle|grain using a micro compression tester, and measuring the displacement amount by which the particle|grain breaks. The said compressive displacement L4 computes the time point at which the displacement amount discontinuously increases with respect to the applied load as the time point at which the particle|grains are broken. In the case where it only deforms and does not break even when the applied load is increased, the breaking deformation is considered to be 100% or more.

As for the said flexible particle|grain, a preferable minimum of a glass transition temperature is -200 degreeC, and a preferable upper limit is 40 degreeC. The lower the glass transition temperature of the flexible particles, the better the seal break and liquid crystal contamination properties, but if it is less than -200 ° C, there is a problem in handling as particles, or the sealing agent is easily crushed during heating, and the sealing agent during curing and Liquid crystal may come into contact and liquid crystal contamination may occur. When the glass transition temperature of the said flexible particle|grain exceeds 40 degreeC, a gap defect may generate|occur|produce. The minimum with a more preferable glass transition temperature of the said flexible particle|grain is -150 degreeC, and a more preferable upper limit is 35 degreeC.

In addition, the glass transition temperature of the said flexible particle|grain shows the value measured by differential scanning calorimetry (DSC) based on "the transition temperature measuring method of plastics" of JISK7121.

As said flexible particle|grains, silicone type particle|grains, vinyl type particle|grains, urethane type particle|grains, fluorine type particle|grains, nitrile type particle|grains, etc. are mentioned, for example. Among them, silicon-based particles and vinyl-based particles are preferable.

The silicone-based particles are preferably silicone rubber particles from the viewpoint of dispersibility in the resin.

Among the silicon-based particles, commercially available ones include, for example, KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (manufactured by Shin-Etsu Chemical Co., Ltd.), Torefil E-506S, EP. -9215 (manufactured by Toray Dow Corning), etc., and these can be used by adjusting them so that the mode particle diameter is 1.07 times or more of the median particle diameter by classification, mixing, or the like. The said silicon-type particle|grains may be used independently and 2 or more types may be used together.

As said vinyl-type particle|grains, (meth)acrylic particle|grains are used preferably.

The said (meth)acrylic particle|grains can be obtained by polymerizing the monomer used as a raw material by a well-known method. Specific examples include a method of suspension polymerization of a monomer in the presence of a radical polymerization initiator, a method of swelling the seed particles by absorbing the monomer into the non-crosslinked seed particles in the presence of a radical polymerization initiator, and seed polymerization, and the like. When the mode particle diameter of the obtained particle|grains is less than 1.07 times of a median particle diameter, it adjusts so that it may become 1.07 times or more of a median particle diameter by classification, mixing, etc.

In addition, in this specification, the said "(meth)acryl" means acryl or methacryl.

As a monomer used as a raw material for forming the (meth)acrylic particles, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl ( Meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) Alkyl (meth) acrylates such as acrylate and isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycy Oxygen atom-containing (meth)acrylates such as dil (meth)acrylate, nitrile-containing monomers such as (meth)acrylonitrile, trifluoromethyl (meth)acrylate, pentafluoroethyl (meth)acrylate Monofunctional monomers, such as fluorine-containing (meth)acrylates, such as these, are mentioned. Among them, alkyl (meth)acrylates are preferable because the homopolymer has a low Tg and can increase the amount of deformation when a load of 1 g is applied.

In addition, in this specification, the said "(meth)acrylate" means an acrylate or a methacrylate.

Moreover, in order to have a crosslinked structure, tetramethylol methane tetra (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane di (meth) acrylate, trimethylol propane tri (meth) acryl Rate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylic rate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and polyfunctional monomers such as isocyanuric acid skeleton tri(meth)acrylate. Among them, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly) ethylene glycol di(meth)acrylate, (poly) ) Tetramethylene di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate are preferable.

As for the usage-amount of the said crosslinkable monomer, in the whole monomer, a preferable minimum is 1 weight%, and a preferable upper limit is 90 weight%. When the usage-amount of the said crosslinkable monomer is 1 weight% or more, solvent resistance improves and it becomes easy to disperse|distribute uniformly, without raising problems, such as swelling, when it kneads|mixed with various sealing compound raw materials. When the usage-amount of the said crosslinkable monomer is 90 weight% or less, a recovery rate can be made low, and problems, such as a springback, do not occur easily. The more preferable lower limit of the usage-amount of the said crosslinkable monomer is 3 weight%, and a more preferable upper limit is 80 weight%.

In addition to these acrylic monomers, styrene-based monomers such as styrene and α-methylstyrene, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether, vinyl acetate, vinyl butyrate, vinyl laurate, Acid vinyl esters such as vinyl stearate, unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene, halogen-containing monomers such as vinyl chloride, vinyl fluoride, and chlorstyrene, triallyl (iso)cyanurate, triallyltri Monomers such as melitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ-(meth)acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, and vinyltrimethoxysilane may be used. do.

Moreover, as said vinyl particle, you may use polydivinylbenzene particle|grains, polychloroprene particle|grains, butadiene rubber particle|grains, etc., for example.

Examples of commercially available urethane-based particles include Art Pearl (manufactured by Negami Kogyo Co., Ltd.) and Dynamic Beads (manufactured by Daiichi Seijo Kogyo Co., Ltd.). These particles have a median particle diameter in the mode of particle size by classification, mixing, or the like. It can be used by adjusting it to be 1.07 times or more of the diameter.

A preferable minimum of the hardness of the said flexible particle|grain is 10, and a preferable upper limit is 50. When the hardness of the said flexible particle|grain exceeds 50, the sealing compound for liquid crystal dropping methods obtained may become a thing inferior in adhesiveness, or a gap defect may arise in the liquid crystal display element obtained. A more preferable minimum of the hardness of the said flexible particle|grain is 20, and a more preferable upper limit is 40.

In addition, in this specification, the hardness of the said flexible particle|grain means the durometer A hardness measured by the method based on JISK6253.

As for content of the said flexible particle|grain, a preferable minimum is 15 weight part with respect to 100 weight part of curable resin, and a preferable upper limit is 50 weight part. When content of the said flexible particle|grain is less than 15 weight part, it may become impossible to fully prevent the elution to the liquid crystal of a sealing compound. When content of the said flexible particle|grain exceeds 50 weight part, the sealing compound for liquid crystal dropping methods obtained may become inferior to applicability|paintability and adhesiveness. A more preferable minimum of content of the said flexible particle|grain is 20 weight part, and a more preferable upper limit is 40 weight part.

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

It is preferable that the said curable resin contains a (meth)acrylic resin.

Since the sealing compound for liquid crystal dropping methods of this invention can be hardened quickly, it is preferable to contain (meth)acrylic resin as curable resin, and to contain the radical polymerization initiator mentioned later as a polymerization initiator, and only heating Since it becomes possible to quickly harden the sealing compound for liquid crystal dropping methods of the present invention, and even a liquid crystal display element of a narrow frame design, generation of liquid crystal contamination can be sufficiently suppressed, (meth)acrylic resin and a thermal radical polymerization initiator described later It is more preferable to contain.

It is more preferable that the said curable resin contains epoxy (meth)acrylate.

In addition, in this specification, the said "(meth)acrylic resin" means resin which has a (meth)acryloyl group, and the said "(meth)acryloyl group" means an acryloyl group or a methacryloyl group do. In addition, the said "epoxy (meth)acrylate" means the compound which made all the epoxy groups in an epoxy resin react with (meth)acrylic acid.

As an epoxy resin used as a raw material for synthesizing the epoxy (meth)acrylate, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and 2,2'-diallylbisphenol A type Epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin Resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol novolak type epoxy resin, glycy dilamine-type epoxy resins, alkyl polyol-type epoxy resins, rubber-modified epoxy resins, glycidyl ester compounds, bisphenol A-type episulfide resins, and the like.

As what is marketed among the said bisphenol A epoxy resins, jER828EL, jER1001, jER1004 (all are made by Mitsubishi Chemical Corporation), Epiclone 850-S (made by DIC Corporation), etc. are mentioned, for example.

As what is marketed among the said bisphenol F-type epoxy resins, jER806, jER4004 (all are Mitsubishi Chemical Corporation make) etc. are mentioned, for example.

As what is marketed among the said bisphenol S-type epoxy resins, Epiclon EXA1514 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said 2,2'- diallylbisphenol A epoxy resins, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

As what is marketed among the said hydrogenated bisphenol-type epoxy resins, Epiclon EXA7015 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said propylene oxide addition bisphenol A epoxy resins, EP-4000S (made by ADEKA) etc. are mentioned, for example.

As what is marketed among the said resorcinol type epoxy resin, EX-201 (made by Nagase Chemtex) etc. is mentioned, for example.

As what is marketed among the said biphenyl type epoxy resin, jERYX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

As what is marketed among the said sulfide-type epoxy resins, YSLV-50TE (made by the Nippon Tetsu Sumikin Chemical Company) etc. are mentioned, for example.

As what is marketed among the said diphenyl ether type|mold epoxy resin, YSLV-80DE (made by a Nippon-Tsumikin Chemical company) etc. are mentioned, for example.

As what is marketed among the said dicyclopentadiene type epoxy resin, EP-4088S (made by ADEKA) etc. are mentioned, for example.

As what is marketed among the said naphthalene type epoxy resins, Epiclon HP4032, Epiclon EXA-4700 (all are made by DIC Corporation), etc. are mentioned, for example.

As what is marketed among the said phenol novolak-type epoxy resins, Epiclon N-770 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said orthocresol novolak-type epoxy resins, Epiclon N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, Epiclon HP7200 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said biphenyl novolak-type epoxy resins, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

As what is marketed among the said naphthalenephenol novolak-type epoxy resins, ESN-165S (made by Nippon-Tsumikin Chemical Co., Ltd.) etc. are mentioned, for example.

As what is marketed among the said glycidylamine type epoxy resin, jER630 (made by Mitsubishi Chemical Corporation), Epiclone 430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemicals), etc. are mentioned, for example.

As what is marketed among the said alkyl polyol type epoxy resins, For example, ZX-1542 (made by Nippon-Tsumikin Chemicals), Epiclone 726 (made by DIC), Eporite 80MFA (made by Kyoeisha Chemicals), Denacol EX-611 (manufactured by Nagase Chemtex) and the like.

As what is marketed among the said rubber-modified epoxy resins, YR-450, YR-207 (all are the Shin-Nittetsu Sumikin Chemicals make), Epolide PB (made by Daicel), etc. are mentioned, for example.

As what is marketed among the said glycidyl ester compound, Denacol EX-147 (made by Nagase Chemtex) etc. is mentioned, for example.

As what is marketed among the said bisphenol A episulfide resins, jERYL-7000 (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Shin-Nittetsu Chemical Co., Ltd.), XAC4151 (all manufactured by Asahi Chemical Co., Ltd.), jER1031, jER1032 (all manufactured by Mitsubishi). Chemical company make), EXA-7120 (made by DIC company), TEPIC (made by Nissan Chemical company), etc. are mentioned.

Among the above-mentioned epoxy (meth) acrylates, commercially available ones include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBRYECRYL603 manufactured by DYCELL EBECRYL3800 (all manufactured by Daicel EBECRYL3800, EBRY ALL EBECRYL3800) , EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA , Epoxy ester 80MFA, Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Dena Chole acrylate DA-314 and denacol acrylate DA-911 (all are made by Nagase Chemtex Corporation), etc. are mentioned.

As other (meth)acrylic resins other than the said epoxy (meth)acrylate, for example, an ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group, an isocyanate compound A (meth)acrylic acid derivative having a hydroxyl group is reacted The urethane (meth)acrylate etc. obtained by making it are mentioned are mentioned.

Among the ester compounds obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group, monofunctional ones include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl ( Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, iso Nonyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate , bicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate , 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylic rate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl ( Meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl 2-hydroxypropylphthalate, 2-(meth)acryloyloxy Ethyl phosphate, glycidyl (meth)acrylate, etc. are mentioned.

Among the ester compounds, the bifunctional ones include, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di ( Meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol Di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate , Ethylene oxide addition bisphenol F di(meth)acrylate, dimethyloldicyclopentadienyldi(meth)acrylate, ethylene oxide-modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3-(meth)acrylo Iloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, poly Butadienediol di(meth)acrylate, etc. are mentioned.

Among the ester compounds, trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, capro Lactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide addition isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide addition glycerin tri (meth) acrylate, pentaerythritol tri ( Meth) acrylate, tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Erythritol hexa(meth)acrylate etc. are mentioned.

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

As an isocyanate compound used as a raw material of the said urethane (meth)acrylate, For example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate , diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogen Added XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, tetramethylxylene diisocyanate, 1,6,11- undecane triisocyanate, etc. are mentioned.

Moreover, as said isocyanate compound, For example, Reaction of polyols, such as ethylene glycol, glycerol, sorbitol, trimethylol propane, propylene glycol, carbonate diol, polyetherdiol, polyesterdiol, polycaprolactonediol, and an excess isocyanate compound A chain-extended isocyanate compound obtained by

As the (meth)acrylic acid derivative having a hydroxyl group as a raw material of the urethane (meth)acrylate, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxy Hydroxyalkyl mono(meth)acrylates such as hydroxybutyl (meth)acrylate and 2-hydroxybutyl (meth)acrylate; ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol; Mono(meth)acrylates of dihydric alcohols such as 1,4-butanediol and polyethylene glycol, mono(meth)acrylates or di(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin; and epoxy (meth)acrylates such as bisphenol A epoxy acrylate.

Among the urethane (meth) acrylates that are commercially available, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toa Synthetic Corporation), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803 , EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (all manufactured by Daicel Olnes), Atresin UN-9000H, Atresin UN-9000H, Atresin UN-9000H Resin UN-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Industries), U-122P, U-108A, U-340P, U- 4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Industries) ), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all of which are manufactured by Kyoeisha Chemical Corporation) and the like.

The (meth) acrylic resin is, in terms of suppressing the adverse effect on the liquid crystal, it is preferable to have a hydrogen bond Castle unit such as -OH group, -NH- group, -NH ₂ group. Moreover, it is preferable that the said (meth)acrylic resin has 2-3 (meth)acryloyl groups in a molecule|numerator from a high reactivity viewpoint.

The said curable resin may contain an epoxy resin for the purpose of improving the adhesiveness of the sealing compound for liquid crystal dropping methods obtained, etc.

As said epoxy resin, the epoxy resin used as a raw material for synthesizing the said epoxy (meth)acrylate, a partially (meth)acrylic-modified epoxy resin, etc. are mentioned, for example.

In addition, in this specification, the said partially (meth)acryl-modified epoxy resin means a resin each having one or more epoxy groups and (meth)acryloyl groups in one molecule, for example, a resin having two or more epoxy groups. It can be obtained by reacting a part of the epoxy group with (meth)acrylic acid.

As what is marketed among the said partially (meth)acrylic-modified epoxy resins, UVACURE1561 (made by Daicel Allnex) etc. is mentioned, for example.

When the said epoxy resin is contained as said curable resin, the preferable upper limit of the ratio of the epoxy group with respect to the total amount of the (meth)acryloyl group in the said curable resin whole is 50 mol%. When the ratio of the said epoxy group exceeds 50 mol%, the solubility with respect to the liquid crystal of the sealing compound for liquid crystal dropping methods obtained increases, liquid-crystal contamination is raised, and the liquid crystal display element obtained may become inferior in display performance. The more preferable upper limit of the ratio of the said epoxy group is 20 mol%.

The sealing compound for liquid crystal dropping methods of this invention contains a polymerization initiator and/or a thermosetting agent.

Especially, it is preferable to contain a radical polymerization initiator as a polymerization initiator. Springback is influenced not only by the influence of the particle size distribution of the said flexible particle|grain but also by the curing rate of a sealing compound. Since the radical polymerization initiator can significantly speed up the curing rate compared to the thermal curing agent, by using it in combination with the flexible particles, the effect of suppressing the occurrence of springback, which is likely to be caused by the flexible particles, can be made more excellent. have.

As said radical polymerization initiator, the thermal radical polymerization initiator which generate|occur|produces a radical by heating, a radical photopolymerization initiator which generate|occur|produces a radical by light irradiation, etc. are mentioned.

As described above, the radical polymerization initiator has a significantly faster curing rate compared to the thermal curing agent, so by using the radical polymerization initiator, the occurrence of seal break and liquid crystal contamination is suppressed, and the flexible particles are easily generated by blending the Springback can also be suppressed more effectively.

Especially, since the sealing compound for liquid crystal dropping methods obtained can be hardened quickly by a heat|fever, a thermal radical polymerization initiator is preferable.

As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among them, a polymer azo initiator composed of a polymer azo compound is preferable.

In addition, in this specification, a polymeric azo initiator means an azo group and a number average molecular weight which produces|generates the radical which can harden a (meth)acryloyloxy group by heat|fever is 300 or more compound means 300 or more.

The preferable lower limit of the number average molecular weight of the said polymeric azo initiator is 1000, and a preferable upper limit is 300,000. When the number average molecular weight of the said polymeric azo initiator is less than 1000, a polymeric azo initiator may exert a bad influence on a liquid crystal. When the number average molecular weight of the said polymeric azo initiator exceeds 300,000, mixing with respect to curable resin may become difficult. A more preferable minimum of the number average molecular weight of the said polymeric azo initiator is 5000, a more preferable upper limit is 100,000, a more preferable minimum is 10,000, and a more preferable upper limit is 90,000.

In addition, in this specification, the said number average molecular weight is a value calculated|required by polystyrene conversion by measuring by gel permeation chromatography (GPC). As a column at the time of measuring the number average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko Co., Ltd.) etc. are mentioned, for example.

Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.

The polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group preferably has a polyethylene oxide structure. As such a polymer azo initiator, for example, a polycondensate of 4,4'-azobis(4-cyanopentanoic acid) and polyalkylene glycol, 4,4'-azobis(4-cyanopentanoic acid) and Polycondensate of polydimethylsiloxane having a terminal amino group, etc. are mentioned, Specifically, For example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.) etc. are mentioned. can be heard

Moreover, as an example of azo initiators other than a polymeric azo initiator, V-65, V-501 (all are made by Wako Pure Chemical Industries, Ltd.) etc. are mentioned, for example.

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkylperoxide, peroxyester, diacylperoxide, and peroxydicarbonate.

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

Among the radical photopolymerization initiators, commercially available ones include, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all manufactured by BASF), benzo Inmethyl ether, benzoin ethyl ether, benzoin isopropyl ether (all are the Tokyo Chemical Industry make) etc. are mentioned.

You may use a cationic polymerization initiator as said polymerization initiator.

As said cationic polymerization initiator, a photocationic polymerization initiator can be used preferably. The said photocationic polymerization initiator will not be specifically limited if a protonic acid or a Lewis acid is generated by light irradiation, An ionic photo-acid generation type may be sufficient, and a nonionic photo-acid generation type may be sufficient as it.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts and aromatic sulfonium salts, iron-allene complexes, titanocene complexes, and organometallic complexes such as arylsilanol-aluminum complexes. and the like.

As what is marketed among the said photocationic polymerization initiators, Adeka Optoma SP-150, Adeka Optoma SP-170 (all are made by ADEKA Corporation), etc. are mentioned, for example.

As for content of the said polymerization initiator, with respect to 100 weight part of said curable resin, a preferable minimum is 0.1 weight part, and a preferable upper limit is 30 weight part. The sealing compound for liquid crystal dropping methods obtained as content of the said polymerization initiator is less than 0.1 weight part may not fully be hardened. When content of the said polymerization initiator exceeds 30 weight part, the storage stability of the sealing compound for liquid crystal dropping methods obtained may fall. A more preferable lower limit of the content of the polymerization initiator is 1 part by weight, a more preferable upper limit is 10 parts by weight, and a still more preferable upper limit is 5 parts by weight.

As said thermosetting agent, organic acid hydrazide, an imidazole derivative, an amine compound, polyhydric phenol type compound, an acid anhydride etc. are mentioned, for example. Among them, solid organic acid hydrazide is preferably used.

Examples of the solid organic acid hydrazide include 1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, and adipic acid dihydrazide. drazide, malonic acid dihydrazide, etc. are mentioned, As what is marketed, For example, Amicure VDH, Amicure UDH (all are made by Ajinomoto Fine Techno), SDH, IDH, ADH (all are made by Otsuka Chemical Co., Ltd.) , MDH (manufactured by Nippon Fine Cam), and the like.

As for content of the said thermosetting agent, with respect to 100 weight part of said curable resins, a preferable minimum is 1 weight part, and a preferable upper limit is 50 weight part. When content of the said thermosetting agent is less than 1 weight part, the sealing compound for liquid crystal dropping methods obtained may not fully be thermosetting. When content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained may become high too much, and applicability|paintability may worsen. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.

It is preferable that the sealing compound for liquid crystal dropping methods of this invention contains a hardening accelerator. By using the said hardening accelerator, even if it does not heat at high temperature, a sealing compound can fully be hardened.

As said hardening accelerator, polyhydric carboxylic acid which has isocyanuric ring skeleton, an epoxy resin amine adduct, etc. are mentioned, for example, Specifically, For example, tris (2-carboxymethyl) isocyanu is mentioned, for example. Late, tris(2-carboxyethyl)isocyanurate, tris(3-carboxypropyl)isocyanurate, bis(2-carboxyethyl)isocyanurate, etc. are mentioned.

As for content of the said hardening accelerator, with respect to 100 weight part of said curable resin, a preferable minimum is 0.1 weight part, and a preferable upper limit is 10 weight part. When content of the said hardening accelerator is less than 0.1 weight part, the sealing compound for liquid crystal dropping methods obtained may not fully harden|cure, or in order to harden|cure it, the heating at high temperature may be needed. When content of the said hardening accelerator exceeds 10 weight part, the sealing compound for liquid crystal dropping methods obtained may become inferior to adhesiveness.

It is preferable that the sealing compound for liquid crystal dropping methods of this invention contains a filler for the purpose of the improvement of a viscosity, the adhesive improvement by a stress dispersion effect, the improvement of a coefficient of linear expansion, the moisture resistance improvement of hardened|cured material, etc.

Examples of the filler include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, Inorganic fillers such as glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride, polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, core-shell acrylate copolymer microparticles Organic fillers, such as these are mentioned. These fillers may be used independently and may be used in combination of 2 or more type.

As for content of the said filler, with respect to the whole sealing compound for liquid crystal dropping methods, a preferable minimum is 10 weight%, and a preferable upper limit is 70 weight%. When content of the said filler is less than 10 weight%, effects, such as an adhesive improvement, may not fully be exhibited. When content of the said filler exceeds 70 weight%, the viscosity of the sealing compound for liquid crystal dropping methods obtained may become high, and applicability|paintability may worsen. The more preferable lower limit of content of the said filler is 20 weight%, and a more preferable upper limit is 60 weight%.

It is preferable that the sealing compound for liquid crystal dropping methods of this invention contains a silane coupling agent. The said silane coupling agent mainly has a role as an adhesion|attachment adjuvant for adhering a sealing compound, a board|substrate, etc. favorably.

The said silane coupling agent is excellent in the effect of improving adhesiveness with a board|substrate etc., and since it can suppress the outflow of curable resin into a liquid crystal by chemically bonding with curable resin, for example, N-phenyl-3- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, etc. are preferably used do. These silane coupling agents may be used independently and may be used in combination of 2 or more type.

As for content of the said silane coupling agent, with respect to the whole sealing compound for liquid crystal dropping methods, a preferable minimum is 0.1 weight%, and a preferable upper limit is 20 weight%. When content of the said silane coupling agent is less than 0.1 weight%, the effect by mix|blending a silane coupling agent may not fully be exhibited. When content of the said silane coupling agent exceeds 20 weight%, the sealing compound for liquid crystal dropping methods obtained may contaminate a liquid crystal. A more preferable lower limit of content of the said silane coupling agent is 0.5 weight%, and a more preferable upper limit is 10 weight%.

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

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 preferable.

The titanium black is a substance having a higher transmittance in the vicinity of an ultraviolet region, particularly in the light of a wavelength of 370 to 450 nm, compared with the average transmittance for light having a wavelength of 300 to 800 nm. That is, the titanium black is a light-shielding agent having a property of transmitting light of a wavelength in the vicinity of an ultraviolet region while providing light-shielding property to the sealing compound for liquid crystal dropping method of the present invention by sufficiently shielding light of a wavelength in the visible region. . As a light-shielding agent contained in the sealing compound for liquid crystal dropping methods of this invention, a substance with high insulation is preferable, and titanium black is preferable also as a light-shielding agent with high insulation.

It is preferable that the optical density (OD value) per 1 micrometer is 3 or more, and, as for the said titanium black, it is more preferable that it is 4 or more. The higher the light-shielding property of the titanium black, the more preferable, and there is no upper limit particularly preferable for the OD value of the titanium black;

Although the said titanium black exhibits sufficient effect even if it is not surface-treated, the thing whose surface is treated with organic components, such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. Surface-treated titanium black, such as one coated with an inorganic component of Among these, those treated with an organic component are preferred from the viewpoint of further improving insulation.

Moreover, since the liquid crystal display element manufactured using the sealing compound for liquid crystal display elements of this invention containing the said titanium black as a light-shielding agent has sufficient light-shielding property, there is no light leakage and has high contrast, excellent image display quality It is possible to realize a liquid crystal display device having

As what is marketed among the said titanium black, 12S, 13M, 13M-C, 13R-N, 14M-C (all are made by Mitsubishi Materials), Tillac D (made by Ako Chemical Co., Ltd.) etc. are mentioned, for example.

A preferable lower limit of the specific surface area of the titanium black is 13 m2/g, a preferable upper limit is 30 m2/g, a more preferable lower limit is 15 m2/g, and a more preferable upper limit is 25 m2/g.

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

Although the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the cell gap of a liquid crystal display element, A preferable lower limit is 1 nm, and a preferable upper limit is 5 micrometers. When the primary particle diameter of the said light-shielding agent is less than 1 nm, the viscosity and thixotropy of the sealing compound for liquid crystal dropping methods obtained may increase greatly, and workability|operativity may worsen. When the primary particle diameter of the said light-shielding agent exceeds 5 micrometers, the applicability|paintability with respect to the board|substrate of the sealing compound for liquid crystal dropping methods obtained may worsen. A more preferable lower limit of the primary particle diameter of the light-shielding agent is 5 nm, a more preferable upper limit is 200 nm, a more preferable lower limit is 10 nm, and a more preferable upper limit is 100 nm.

As for content of the said light-shielding agent, with respect to the whole sealing compound for liquid crystal dropping methods, a preferable minimum is 5 weight%, and a preferable upper limit is 80 weight%. When content of the said light-shielding agent is less than 5 weight%, sufficient light-shielding property may not be acquired. When content of the said light-shielding agent exceeds 80 weight%, the adhesiveness to the board|substrate of the sealing compound for liquid crystal dropping methods obtained, and the intensity|strength after hardening may fall, or drawing property may fall. A more preferable lower limit of content of the said light-shielding agent is 10 weight%, a more preferable upper limit is 70 weight%, A more preferable minimum is 30 weight%, and a more preferable upper limit is 60 weight%.

The sealing compound for liquid crystal dropping methods of this invention, spacers, such as a reactive diluent for viscosity adjustment, polymer beads for panel gap adjustment, and an antifoamer, a leveling agent, a polymerization inhibitor, other coupling agents, etc. as needed further You may contain an additive.

The method of manufacturing the sealing compound for liquid crystal dropping methods of this invention is not specifically limited, For example, sclerosis|hardenability using mixers, such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll The method of mixing resin, a polymerization initiator and/or a thermosetting agent, flexible particle|grains, and additives, such as a silane coupling agent added as needed, etc. are mentioned.

The minimum with preferable viscosity measured on 25 degreeC and 1 rpm conditions using the E-type viscometer in the sealing compound for liquid crystal dropping methods of this invention is 50,000 Pa.s, and a preferable upper limit is 500,000 Pa.s. When the said viscosity is less than 50,000 Pa.s or exceeds 500,000 Pa.s, workability at the time of apply|coating the sealing compound for liquid crystal dropping methods to a board|substrate etc. may worsen. A more preferable upper limit of the viscosity is 400,000 Pa·s.

A vertical conduction material can be manufactured by mix|blending electroconductive microparticles|fine-particles with the sealing compound for liquid crystal dropping methods of this invention. The vertical conduction material containing the sealing compound for liquid crystal dropping methods of this invention and electroconductive fine particles is also one of this invention.

As the conductive fine particles, for example, metal balls or those in which a conductive metal layer is formed on the surface of the resin fine particles can be used. Among these, those in which a conductive metal layer is formed on the surface of the resin fine particles are preferable in that conductive connection is possible without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.

The liquid crystal display element which has the sealing compound for liquid crystal dropping methods of this invention, or the vertical conduction material of this invention is also one of this invention.

As a method of manufacturing the liquid crystal display element of this invention, in one of two transparent substrates, such as a glass substrate with electrodes, such as an ITO thin film, and a polyethylene terephthalate board|substrate, for example, the sealing compound for liquid crystal dropping methods of this invention A step of forming a rectangular seal pattern by screen printing, dispenser application, etc., the liquid crystal dropping method of the present invention is applied dropwise to the entire surface within the rim of the transparent substrate in an uncured state, The method etc. which have the process of directly overlapping another board|substrate, and the process of heating and hardening the sealing compound for liquid crystal dropping methods of this invention are mentioned. Moreover, before the process of heating and hardening the sealing compound for liquid crystal dropping methods of this invention, you may perform the process of irradiating lights, such as an ultraviolet-ray, to a sealing pattern part, and temporarily hardening a sealing compound.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods compatible with suppression of a seal break and liquid-crystal contamination, and suppression of the gap defect by springback can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited only to these Examples.

In addition, the sealing agent for organic electroluminescent display elements of an Example and a comparative example shall be used for manufacture of the organic electroluminescent display element whose cell gap is 5 micrometers.

(Preparation of flexible particle A)

Silicone rubber particles (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KMP-601") are dispersed in methanol, wet sieved through a sieve of 8 µm mesh, and then passed through the sieve to recover and dry, which is a classification treatment product of silicone rubber particles Flexible particle A was obtained. As a sieve, a polyimide film having very high precision holes obtained by performing ultra-high precision micromachining with a laser was used.

About the obtained flexible particle|grain A, the mode particle diameter measured using the Coulter-type distribution analyzer (the Beckman Coulter company make, "Multisizer 4"), the median particle diameter, the largest particle diameter, the minimum particle diameter, and an average particle diameter, D90, CV value of particle diameter, ratio of volume frequency from minimum particle diameter to particle diameter 2 μm smaller than median particle diameter W, ratio of volume frequency from median particle diameter to particle diameter 2 μm small to median particle diameter Table 1 shows X, the ratio Y of the volume frequency from the median particle diameter to the particle diameter 2 μm larger than the median particle diameter, and the ratio Z of the volume frequency from the particle diameter 2 μm larger than the median particle diameter to the maximum particle diameter.

For the measurement by the Coulter-type distribution measuring device, 0.1 g of particles are added to 10 g of methanol, mixed well, and ultrasonic dispersion is performed for 5 minutes to prepare a particle dispersion, and an electrolyte solution "ISOTON II" in a sample stand (Beckman · The obtained particle dispersion liquid was inject|poured into the beaker containing Coulter (made by Coulter) with the dropper until the display density|concentration of a measuring apparatus became 5 %. The measurement was performed twice, and the arithmetic mean of the calculated values was used.

(Preparation of flexible particle B)

Silicone rubber particles (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KMP-601") were dispersed in methanol and wet sieved through a sieve of 8 µm mesh to recover what passed through the sieve, and then wet sieve through a sieve of 5 µm mesh Then, what remained on the sieve was collect|recovered and dried, and the flexible particle|grain B which is a classification process product of silicone rubber particle|grains was obtained. As a sieve, a polyimide film having very high precision holes obtained by performing ultra-high precision micromachining with a laser was used.

About the obtained flexible particle|grain B, it carried out similarly to the flexible particle|grain A, and measured the mode particle diameter, a median particle diameter, a largest particle diameter, a minimum particle diameter, an average particle diameter, D90, CV value of a particle diameter, W, X, Y and Z is shown in Table 1.

(Preparation of flexible particle C)

Silicone rubber particles (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KMP-601") are dispersed in methanol, wet sieved through a sieve of 10 μm mesh, and the sieve passed through the sieve is recovered and dried, which is a classification treatment product of silicone rubber particles Flexible particle C was obtained. As a sieve, a polyimide film having very high precision holes obtained by performing ultra-high precision micromachining with a laser was used.

About the obtained flexible particle|grain C, it carried out similarly to the flexible particle|grain A, and measured the mode particle diameter, a median particle diameter, a largest particle diameter, a minimum particle diameter, an average particle diameter, D90, CV value of a particle diameter, W, X, Y, and Z is shown in Table 1.

(Preparation of flexible particle D)

Silicon rubber particles (manufactured by Shin-Etsu Chemical Industries, Ltd., "KMP-601") were fed by a precision air classifier (manufactured by Nisshin Engineering, "Turbo Classifier TC-15") at a feed rate of 5 kg/h and a rotational speed of 10000 rpm. was classified to obtain flexible particles D.

About the obtained flexible particle|grain D, it carried out similarly to the flexible particle|grain A, and measured the mode particle diameter, a median particle diameter, a largest particle diameter, a minimum particle diameter, an average particle diameter, D90, CV value of a particle diameter, W, X, Y, and Z is shown in Table 1.

(Preparation of flexible particle E)

55 parts by weight of silicone resin particles (manufactured by Momentive Performance Materials, "Tospearl 1100") and 45 parts by weight of silicone resin particles (manufactured by Momentive Performance Materials, "Tospearl 2000B") in a powder mixer ( It stirred and mixed uniformly using the Nippon Cokes Industry Co., Ltd. make, "FM mixer (FM5RC/I)"), and the flexible particle|grain E was obtained.

About the obtained flexible particle|grain E, it carried out similarly to the flexible particle|grain A, and measured the mode particle diameter, a median particle diameter, a largest particle diameter, a minimum particle diameter, an average particle diameter, D90, CV value of a particle diameter, W, X, Y and Z is shown in Table 1.

(Preparation of flexible particle F)

75 parts by weight of polytetramethylene glycol diacrylate, 21 parts by weight of styrene, and 4 parts by weight of benzoyl peroxide were mixed and uniformly dissolved to obtain a monomer mixture. The obtained monomer liquid mixture was put into a reaction kiln containing a 1 wt% polyvinyl alcohol aqueous solution, and stirred for 2 to 4 hours to adjust the particle size of the monomer droplets to a predetermined particle size. Next, reaction was performed in 85 degreeC nitrogen atmosphere for 9 hours, and the unclassified polymer particle was obtained. The obtained finely divided polymer particles were washed several times with hot water and dried. Then, it disperse|distributed in methanol, wet sieve classification was carried out with the sieve of a 10 micrometers mesh, what passed through the sieve was collect|recovered, it was made to dry, and the flexible particle|grain F which is a classification processing product of vinyl type particle|grains was obtained. As a sieve, a polyimide film having very high precision holes obtained by performing ultra-high precision micromachining with a laser was used.

About the obtained flexible particle|grain F, it carried out similarly to the flexible particle|grain A, and measured the mode particle diameter, a median particle diameter, a largest particle diameter, a minimum particle diameter, an average particle diameter, D90, CV value of a particle diameter, W, X, Y and Z is shown in Table 1.

(Preparation of flexible particle G)

75 parts by weight of polytetramethylene glycol diacrylate, 21 parts by weight of styrene, and 4 parts by weight of benzoyl peroxide were mixed and uniformly dissolved to obtain a monomer mixture. The obtained monomer liquid mixture was put into a reaction kiln containing a 1 wt% polyvinyl alcohol aqueous solution, and stirred for 2 to 4 hours to adjust the particle size of the monomer droplets to a predetermined particle size. Next, reaction was performed in 85 degreeC nitrogen atmosphere for 9 hours, and the unclassified polymer particle was obtained. The obtained finely divided polymer particles were washed several times with hot water and dried. Then, it disperse|distributed in methanol, wet sieve classification was carried out with the sieve of an 8-micrometer mesh, what passed through a sieve was collect|recovered, it was made to dry, and the flexible particle|grain G which is a classification processing product of vinyl type particle|grains was obtained. As a sieve, a polyimide film having very high precision holes obtained by performing ultra-high precision micromachining with a laser was used.

About the obtained flexible particle|grain G, it carried out similarly to the flexible particle|grain A, and measured the mode particle diameter, a median particle diameter, a largest particle diameter, a minimum particle diameter, an average particle diameter, D90, CV value of a particle diameter, W, X, Y and Z is shown in Table 1.

(Example 1)

As a curable resin, 70 parts by weight of a bisphenol A epoxy acrylate (manufactured by Daicel Allnex, "EBECRYL3700") and 30 parts by weight of a bisphenol F-type epoxy resin (manufactured by Mitsubishi Chemical, "jER806") as a thermal radical polymerization initiator 7 parts by weight of a polymer azo initiator (manufactured by Wako Pure Chemical Industries, Ltd., "VPE-0201"), 8 parts by weight of sebacic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd., "SDH") as a thermosetting agent, and 30 parts by weight of flexible particles A , 10 parts by weight of silica (manufactured by Adomatex, “Adomafine SO-C2”) as a filler, and 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-403” as a silane coupling agent) ) 1 weight part was mix|blended, and after stirring with the planetary stirring apparatus (The Sinki company make, "Awatori Rentaro"), it was made to mix uniformly with a ceramic 3-stage roll, and the sealing compound for liquid crystal dropping methods was obtained.

(Examples 2 to 10, Comparative Examples 1 to 4)

According to the blending ratios shown in Tables 2 and 3, each material was prepared in the same manner as in Example 1, mixed using a planetary stirrer (“Awatori Rentaro” manufactured by Sinki Corporation), and then further using a 3-stage roll By mixing, the sealing compound for liquid crystal dropping methods of Examples 2-10 and Comparative Examples 1-4 was prepared.

In addition, the "KMP-601 unclassified product" used in Comparative Example 1 was used as it is without classifying silicone rubber particles (manufactured by Shin-Etsu Chemical Co., Ltd., "KMP-601"), and the "KMP-600 unclassified product" used in Comparative Example 2 was used. ' indicates that silicone rubber particles (manufactured by Shin-Etsu Chemical Industries, Ltd., "KMP-600") were used without classification, and "9701 unclassified product" used in Comparative Example 3 is silicone elastomer composite particles (manufactured by Toray Dow Corning, "9701 cosmetic powder") was used as it is without classification, and the mode particle diameter, median particle diameter, maximum particle diameter, minimum particle diameter, average particle diameter, D90, particle diameter measured in the same manner as flexible particle A for each The CV values, W, X, Y and Z of are shown in Table 1.

<Evaluation>

The following evaluation was performed about each sealing compound for liquid crystal dropping methods obtained by the Example and the comparative example.

(cell gap)

With respect to 100 parts by weight of each sealing compound for liquid crystal dropping method obtained in Examples and Comparative Examples, 1 part by weight of spacer particles having an average particle diameter of 4.7 µm (“Micropearl SI”, manufactured by Sekisui Chemical Industry Co., Ltd.) with a planetary stirring device uniformly After dispersing and filling a syringe for dispensers ("PSY-10E", manufactured by Musashi Engineering, Inc.) with the obtained sealing compound, and a defoaming treatment, with a dispenser (manufactured by Musashi Engineering, "SHOTMASTER300"), two ITO thin films A sealing compound (main seal) was applied to one side of this attached transparent electrode substrate so as to draw a rectangular edge, and a sealing compound (dummy seal) was further applied to the outer periphery in order to keep the cell in a vacuum. . Then, the microdroplet of TN liquid crystal (the Chisso company make, "JC-5001LA") was drip-coated with the liquid crystal dropping device, and the other transparent substrate was bonded together under the vacuum of 5 Pa with the vacuum bonding device. After irradiating a 100 mW/cm<2> ultraviolet-ray for 30 second using the high-pressure mercury-vapor lamp to the cell after bonding together, it heated at 125 degreeC for 60 minutes, the sealing compound was thermosetted, and the liquid crystal display element was obtained.

The cell gap of the obtained liquid crystal display element was measured, and when the inside of a cell was 4-5 micrometers uniformly, "double-circle", when a 4-5 micrometers gap was obtained in almost the whole in a cell, "circle", 4 to in a cell The cell gap was evaluated as “Δ” when there were many or wide portions in which a gap of 5 μm was not obtained, and “×” when a cell could not be formed. The results are shown in Tables 2 and 3.

(Liquid crystalline contamination)

About the liquid crystal display element obtained by the evaluation of the said "(cell gap)", the display unevenness generated in the liquid crystal (especially the corner part) around the seal part was visually observed, and when there was no display unevenness at all, "double-circle", display unevenness was Liquid-crystal staining property was evaluated by making "○" when there was almost no case, "(triangle|delta)" for the case where display nonuniformity was clearly confirmed, and the case where severe display nonuniformity was confirmed or the case where a cell could not be formed as "x". The results are shown in Tables 2 and 3.

(Evaluation of the flexible particle taken out from the sealing compound)

After putting 0.5 weight part of each sealing compound for liquid crystal dropping methods obtained by the Example and the comparative example into 30 weight part of ethanol and stirring at 35 degreeC for 1 hour, the flexible microparticles|fine-particles were taken out from the sealing compound by filtering.

Modest particle diameter, median particle diameter, maximum particle diameter, minimum particle diameter, average particle diameter, particle diameter which carried out similarly to said "(preparation of flexible particle A)" and measured about the flexible particle taken out from each sealing compound Table 4 shows the CV values of W, X, Y and Z.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods compatible with suppression of a seal break and liquid-crystal contamination, and suppression of the gap defect by springback can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.

Claims (9)

As a sealing compound for liquid crystal dropping methods used for manufacture of the liquid crystal display element by a liquid crystal dropping method,
Curable resin, a polymerization initiator and/or a thermosetting agent, and flexible particle|grains are contained,
The said flexible particle|grain is 1.07 times or more of a median particle diameter in particle size distribution. The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. The method of claim 1,
Flexible particle is particle size distribution. WHEREIN: D90 in cumulative distribution is less than 1.40 times of a median particle diameter, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. 3. The method according to claim 1 or 2,
For flexible particles, in the particle size distribution, W (%) is the ratio of the volume frequency from the minimum particle diameter to the particle diameter 2 μm smaller than the median particle diameter, and the volume frequency from the particle diameter 2 μm larger than the median particle diameter to the maximum particle diameter. When the ratio of is made into Z (%), it is W/Z≥1.1, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. 3. The method according to claim 1 or 2,
For flexible particles, in the particle size distribution, the ratio of the volume frequency from a particle diameter 2 µm smaller than the median particle diameter to the median particle diameter is X (%), and the volume frequency from the median particle diameter to a particle diameter 2 μm larger than the median particle diameter It is X+Y≥60 when ratio is made into Y (%), The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. 3. The method according to claim 1 or 2,
In the particle size distribution of flexible particles, the sum of the volume frequencies from the particle diameter 2 μm larger than the median particle diameter to the maximum particle diameter is less than 10% of the total, and from the minimum particle diameter to a particle diameter 2 μm smaller than the median particle diameter The total of the volume frequency of is less than 20% of the whole, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. 3. The method according to claim 1 or 2,
A flexible particle|grain is 100% or more of a maximum particle diameter of the cell gap of a liquid crystal display element, and it is 5-50 micrometers, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. 3. The method according to claim 1 or 2,
A light-shielding agent is contained, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. The sealing compound for liquid crystal dropping methods of Claim 1 or 2, and electroconductive fine particles are contained, The vertical conduction material characterized by the above-mentioned. It has the sealing compound for liquid crystal dropping methods of Claim 1 or 2, The liquid crystal display element characterized by the above-mentioned.