KR102341454B1 - Sealant for liquid crystal dropping method, vertical-conduction material, liquid crystal display element, and light-shielding flexible silicone particles - Google Patents

Abstract

An object of this invention is excellent in adhesiveness, and hardly produces a liquid-crystal contamination, and it aims at providing the sealing compound for liquid crystal dropping methods which can prevent the light leakage of a liquid crystal display element. Moreover, this invention aims at providing the light-shielding flexible silicone particle|grains suitable for making the said sealing compound contain. The sealing compound for liquid crystal dropping methods which concerns on this invention contains curable resin, a polymerization initiator and/or a thermosetting agent, and light-shielding flexible particle|grains. Moreover, the light-shielding flexible silicone particle|grains which concern on this invention make silicone type particle|grains contain a light-shielding agent.

Description

Sealing agent for liquid crystal dropping method, vertical conduction material, liquid crystal display element, and light-shielding flexible silicone particle {SEALANT FOR LIQUID CRYSTAL DROPPING METHOD, VERTICAL-CONDUCTION MATERIAL, LIQUID CRYSTAL DISPLAY ELEMENT, AND LIGHT-SHIELDING FLEXIBLE SILICONE PARTICLES}

This invention is excellent in adhesiveness, and hardly produces a liquid-crystal contamination, It is related with the sealing compound for liquid crystal dropping methods which can prevent the light leakage of a liquid crystal display element. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods. Moreover, this invention relates to light-shielding flexible silicone particle|grains.

In recent years, the manufacturing method of liquid crystal display elements, such as a liquid crystal display cell, from a viewpoint of tact time shortening and optimization of the amount of liquid crystal used, from a conventional vacuum injection method, for example, is disclosed by patent document 1, patent document 2, It is changing to the liquid crystal dropping method called the dripping method using the sealing compound of the photocurable resin, a photoinitiator, a thermosetting resin, and the light and heat combination curing type containing a thermosetting agent.

In the dripping method, first, a rectangular seal pattern is formed by dispensing in one side of the transparent substrate with an electrode of 2 sheets. Next, in an uncured state, liquid crystal microdrops are dripped onto the entire surface of 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. do. Then, main hardening is performed by heating at the time of liquid crystal annealing, and a liquid crystal display element is manufactured. 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, and this dripping construction method is becoming the mainstream of the manufacturing method of a liquid crystal display element now.

By the way, in the present age in which mobile devices with various liquid crystal panels, such as a mobile phone and a portable game machine, are prevalent, size reduction of an apparatus is the most requested|required subject. As a downsizing technique, narrowing of a frame of a liquid crystal display part is mentioned, for example, arranging the position of a sealing part under a black matrix (henceforth, it is also referred to as a narrow frame design).

However, when a liquid crystal display element with a narrow frame design is manufactured by the dripping method, there is a point where light does not reach the seal part due to the black matrix, so there is a part of the photocurable resin that is not sufficiently irradiated with light and curing does not proceed. , an uncured photocurable resin eluted after the provisional curing step, and there was a problem that the liquid crystal was contaminated.

Moreover, since the conventional sealing compound was transparent or milky-white, originally even the black matrix which should suppress light leakage could not light-shield the light which permeate|transmitted sealing compound, but there existed a problem of dropping contrast.

Then, the method of providing light-shielding property to a sealing compound by adding a light-shielding agent is examined. For example, the sealing compound containing light-shielding agents, such as a titanium black type material and a carbon black type material, is disclosed by patent documents 3 - 5 as a light-shielding component.

However, after such a light-shielding agent is disperse|distributed in resin, it is easy to aggregate, and dispersion stability and adhesiveness have become a problem.

Japanese Patent Laid-Open No. 2001-133794 International Publication No. 02/092718 Japanese Laid-Open Patent Publication No. 2006-099027 Japanese Laid-Open Patent Publication No. 2005-292801 International Publication No. 2009/128470

An object of this invention is excellent in adhesiveness, and hardly produces a liquid-crystal contamination, and it aims at providing the sealing compound for liquid crystal dropping methods which can prevent the light leakage of a liquid crystal display element. 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. Moreover, an object of this invention is to provide light-shielding flexible silicone particle|grains.

This invention 1 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: For liquid crystal dropping methods containing curable resin, a polymerization initiator and/or a thermosetting agent, and light-shielding flexible particle|grains it is a seal

Moreover, this invention 2 is light-shielding flexible silicone particle|grains which make silicone type particle|grains contain a light-shielding agent.

First, the present invention 1 will be described in detail.

When this inventor pastes the board|substrate of a liquid crystal display element by mix|blending light-shielding flexible particle|grains with sealing compound, the light-shielding flexible particle|grain becomes a barrier between another sealing compound component and liquid crystal, and sealing compound elutes to a liquid crystal It was able to prevent, and it discovered that the light leakage of a liquid crystal display element could be prevented, and came to complete this invention 1.

The sealing compound for liquid crystal dropping methods of this invention 1 contains light-shielding flexible particle|grains. When the said light-shielding flexible particle|grains provide light-shielding property to sealing compound, and manufacture the role which prevents the light leakage of a liquid crystal display element, and a liquid crystal display element, it becomes a barrier between another sealing compound component and liquid crystal, and a sealing compound It has a role to prevent elution into liquid crystal. Moreover, after bonding a board|substrate by mix|blending the said light-shielding flexible particle|grain, since shift|offset|difference of the board|substrate until sealing compound hardens can be prevented, the sealing compound for liquid crystal dropping methods of this invention 1 is excellent in adhesiveness do.

As said light-shielding flexible particle|grains, what made flexible particle|grains contain a light-shielding agent is preferable.

As a method of containing the light-shielding agent in the flexible particles, for example, in the production step of the flexible particles, by dispersing a colorant such as a pigment or dye as the light-shielding agent in the raw material of the flexible particles, the colorant in the flexible particles a method of containing a colorant, a method of coating a colorant on the surface of the flexible particle after manufacturing the flexible particle having no light-shielding property, a method of absorbing the colorant into the flexible particle after manufacturing the flexible particle having no light-shielding property, etc. can be heard

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. Especially, silicone type particle|grains and vinyl type particle|grains are preferable.

It is preferable that the said silicone type particle|grain has the diorganosiloxane unit represented by following formula (1) as a repeating unit, and it is a silicone hardened|cured material which has rubber elasticity.

[Formula 1]

In formula (1), R ¹ is an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, an aryl group such as a phenyl group or a tolyl group, an alkenyl group such as a vinyl group or an allyl group, β-phenylethyl group, β -Aralkyl groups such as phenylpropyl group, hydrocarbon groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as chlorine or fluorine, epoxy groups, amino groups, mercapto groups, acryloxy groups, methacryloxy groups, etc. of reactive group-containing organic groups, and the like. It is preferable that it is 5-5000, and, as for a, it is more preferable that it is 10-1000.

The reaction mechanism of the curing reaction to form the silicon-based particles is _{a condensation reaction of a methoxysilyl group (≡SiOCH 3} ) and a hydroxysilyl group (≡SiOH), or a mercaptosilyl group (≡SiSH) and a vinylsilyl group ( the point on the ≡SiCH = CH ₂₎ include a radical reaction, or a silyl group such as a vinyl (CH = ≡SiCH that obtained from the addition reaction of ₂₎ and ≡SiH groups, but the reactivity, the reaction process of (hydrosilylation) add It is preferable to set it as a thing by reaction. That is, in the present invention, it is preferable to prepare a composition in which (a) vinyl group-containing organopolysiloxane and (b) organohydrogenpolysiloxane are subjected to an addition reaction in the presence of (c) a platinum-based catalyst to be cured.

As such a component (a), the compound etc. which are specifically, represented by following formula (2) are mentioned, for example.

[Formula 2]

In formula (2), although R<^{1> is the same as R<1>} in said formula (1), it is preferable that it does not have an aliphatic unsaturated bond. b and c are 0, 1, 2, or 3, and b+c=3, d is a positive number, e is 0 or a positive number, and 2b+e≥2.

As organohydrogenpolysiloxane of the said (b) component, the compound etc. which are represented, for example by following formula (3) are mentioned.

[Formula 3]

In the formula (3), R ² is an unsubstituted or substituted monovalent hydrocarbon group bonded to a silicon atom having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, except for an aliphatic unsaturated bond, and R an unsubstituted or a substituted monovalent hydrocarbon group in the ^second, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert- butyl group, a pentyl group, a neopentyl group, a hexyl Alkyl groups such as sil group, cyclohexyl group, octyl group, nonyl group, and decyl group; aryl groups such as phenyl group, tolyl group, xylyl group, and naphthyl group; What substituted some or all of the hydrogen atoms of a group with halogen atoms, such as fluorine, bromine, chlorine, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, etc. are mentioned. The ^{unsubstituted or substituted monovalent hydrocarbon group for R 2} is preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group. Further, f is 0.7 to 2.1, g is 0.001 to 1.0, and f+g is a positive number satisfying 0.8 to 3.0, preferably f is 1.0 to 2.0, g is 0.01 to 1.0, and f+g is 1.5 to 2.5.

Specific examples of the component (b) include compounds represented by the following formula (4).

[Formula 4]

In Formula (4), although R<^{1> is the same as R<1>} in said Formula (1), it is preferable that it does not have an aliphatic unsaturated bond. m is 0 or 1, n is 2 or 3, m+n=3, p is 0 or a positive number, q is 0 or a positive number, and 2m+q≥2.

The platinum-based catalyst of component (c) is a catalyst for addition reaction of a vinyl group bonded to a silicon atom in component (a) and a hydrogen atom (SiH group) bonded to a silicon atom in component (b), for example, platinum supported carbon or silica, chloroplatinic acid, platinum-olefin complex, platinum-alcohol complex, platinum-phosphorus complex, platinum coordination compound, and the like.

As a method for producing silicone-based particles using the components (a) to (c), the component (a) and the component (b) are reacted in the presence of the component (c) to cure, and there is no particular limitation, For example, the method of hardening|curing (a) component and (b) component in high temperature spray drying, the method of hardening in an organic solvent, the method of hardening after making this into an emulsion, etc. are mentioned. Moreover, in order to make the dispersibility of a silicone type particle|grains favorable, you may coat|cover the polyorganosilsesquioxane resin on the surface of a silicone type particle|grains as needed.

As described above, the light-shielding flexible particle is a method of containing a colorant in the flexible particle by dispersing a colorant such as a pigment or dye as the light-shielding agent in the raw material of the flexible particle in the production step of the flexible particle. can be manufactured by Specifically, silicone-based particles having light-shielding properties can be obtained by dispersing or dissolving a colorant such as a pigment or dye in advance in the components (a) to (c) and then performing a curing reaction. When dispersing a coloring agent in the said (a)-(c) component, it is preferable to add surfactant or a dispersing agent which has affinity to both a silicone component and a coloring agent. By providing a colorant as a light-shielding agent before a hardening reaction, elution of a colorant from particle|grains or peeling is reduced, and liquid-crystal contamination can be suppressed.

Moreover, as above-mentioned, after the said light-shielding flexible particle|grains manufacture the flexible particle|grains which do not have light-shielding property, after manufacturing the method of coat|covering a coloring agent on the surface of the flexible particle|grains, and the flexible particle|grains which do not have light-shielding property It can manufacture also with the method of making the flexible particle|grains absorb a coloring agent. Specifically, light-shielding properties can be imparted by dispersing silicon-based particles having no light-shielding property in a medium in which a colorant is dissolved, stirring for a certain period of time to fix the colorant to the silicon-based particles, and also with a hybridizer or theta composer. Using the same complexing device, light-shielding properties can be imparted by fixing a colorant to the surface of silicon-based particles that do not have light-shielding properties.

Moreover, you may use the method of making the polymeric coloring agent adsorb|suck to the surface of the silicone type particle|grains which do not have light-shielding property. That is, light-shielding properties can be imparted by depositing a polymer having a skeleton or a functional group that absorbs light of a specific wavelength on the surface of the silicon-based particles that do not have light-shielding properties. Specifically, the polymer can be deposited on the surface of the silicone particles by subjecting the monomer used as a raw material of the polymer to emulsion polymerization, soap-free polymerization, dispersion polymerization or the like in the presence of silicon particles having no light-shielding properties.

Examples of the polymer to be deposited on the surface of the silicone particles include acetylene and its derivatives, aniline and its derivatives, furan and its derivatives, pyrrole and its derivatives, and a polymer obtained by polymerizing thiophene and its derivatives. . Among them, polypyrrole excellent in black appearance is preferable.

As the silicon-based particles having no light-shielding properties, commercially available silicone-based particles can also be used.

Examples of the commercially available silicone particles include KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (manufactured by Shin-Etsu Silicone), Torefil E-506S, EP -9215 (manufactured by Toray Dow Corning) and the like, and these can be classified and used. The silicon-type particle|grains which do not have the said light-shielding property 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 suitably.

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.

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) acrylate ) Alkyl (meth) acrylates such as acrylate and isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycerol Oxygen atom-containing (meth)acrylates such as cidyl (meth)acrylate, nitrile-containing monomers such as (meth)acrylonitrile, trifluoromethyl (meth)acrylate, pentafluoroethyl (meth)acryl Monofunctional monomers, such as fluorine-containing (meth)acrylates, such as a rate, 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 give 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)ethylene glycol di(meth)acrylate, Poly)tetramethylenedi(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 is easy to disperse|distribute uniformly, without producing 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 factor can be made low and it becomes difficult to produce problems, such as a springback. 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 chlorostyrene, triallyl (iso)cyanurate, triallyltri Monomers such as melitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ-(meth)acryloxypropyltrimethoxysilane, trimethoxysilyl styrene, and vinyltrimethoxysilane may be used. do.

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

As what is marketed among the said urethane-type particle|grains, Art Pearl (made by Negami Kogyo Co., Ltd.), dynamic beads (made by Dainichi Chemical Industry Co., Ltd.) etc. are mentioned, for example, These can be classified and used.

Light-shielding property can be provided also to the said vinyl-type particle|grains and the said urethane-type particle|grains by the method similar to the said silicone particle.

The minimum with preferable hardness of the said light-shielding flexible particle|grain is 10, and a preferable upper limit is 50. When the hardness of the said light-shielding flexible particle|grain exceeds 50, the sealing compound for liquid crystal dropping methods obtained may become inferior to adhesiveness, or a gap defect may generate|occur|produce in the liquid crystal display element obtained. A more preferable minimum of the hardness of the said light-shielding flexible particle|grain is 20, and a more preferable upper limit is 40.

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

As a light-shielding agent contained in the said flexible particle|grain, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, black dye etc. are mentioned, for example. Especially, titanium black is preferable.

The said titanium black is a substance whose transmittance with respect to the light of wavelength 370-450 nm becomes high in the vicinity of an ultraviolet region, especially compared with the average transmittance|permeability with respect to the light of wavelength 300-800 nm. That is, the titanium black is a light-shielding agent having a property of imparting light-shielding properties to light-shielding flexible particles by sufficiently shielding light of a wavelength in the visible region, while transmitting light having a wavelength in the vicinity of an ultraviolet region. Therefore, as a polymerization initiator mentioned later, the photocurable property of the sealing compound for liquid crystal dropping methods of this invention 1 by using what can start reaction with the light of the wavelength (370-450 nm) with which the transmittance|permeability of the said titanium black becomes high. can be further increased. On the other hand, as a light-shielding agent contained in the said flexible particle|grain, a substance with high insulation is preferable, and titanium black is suitable also as a light-shielding agent with high insulation.

It is preferable that the optical density per 1 micrometer (OD value) 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 better, 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 those coated with an inorganic component of Especially, the thing processed with the organic component is preferable at the point which can improve insulation more.

Moreover, since the sealing compound for liquid crystal dropping methods using titanium black as a light-shielding agent contained in the said flexible particle|grain has sufficient light-shielding property, the liquid crystal display element obtained does not leak light and has high contrast, and has excellent image display quality becomes a thing

As what is marketed among the said titanium black, 12S, 13M, 13M-C, 13R-N (all are made by Mitsubishi Materials), Tirac D (made by Ako Chemical Corporation), 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.

The minimum with a preferable primary particle diameter of the light-shielding agent contained in the said flexible particle|grain is 50 nm, and a preferable upper limit is 500 nm. When the primary particle diameter of the light-shielding agent contained in the said flexible particle|grain is less than 50 nm, a viscosity or a thix-ratio may become high, secondary aggregation may generate|occur|produce, and the dispersibility in particle|grains may fall remarkably. When the primary particle diameter of the light-shielding agent contained in the said flexible particle|grain exceeds 500 nm, the dispersibility to particle|grains may fall, or particle|grain itself may become hard and brittle. A more preferable minimum of the primary particle diameter of the light-shielding agent contained in the said flexible particle|grain is 70 nm, and a more preferable upper limit is 300 nm.

As for content of the light-shielding agent contained in the said flexible particle|grain, with respect to the whole light-shielding flexible particle|grain, a preferable minimum is 2 weight%, and a preferable upper limit is 30 weight%. When content of the light-shielding agent contained in the said flexible particle|grain is less than 2 weight%, sufficient light-shielding property may not be acquired. When content of the light-shielding agent contained in the said flexible particle|grain exceeds 30 weight%, particle|grain itself may become hard and brittle. The minimum with more preferable content of the light-shielding agent contained in the said flexible particle|grain is 5 weight%, and a more preferable upper limit is 20 weight%.

The sealing compound for liquid crystal dropping methods of this invention 1 is used for manufacture of the liquid crystal display element by a liquid crystal dropping method.

It is preferable that the said light-shielding flexible particle|grains have a largest particle diameter 100% or more of the cell gap of a liquid crystal display element. When the maximum particle diameter of the said light-shielding flexible particle|grain is less than 100% of the cell gap of a liquid crystal display element, it may become impossible to fully suppress a seal break and a liquid-crystal contamination. The largest particle diameter of the said light-shielding flexible particle|grain is 100% or more of the cell gap of a liquid crystal display element, and it is more preferable that it is 5 micrometers or more.

Moreover, the preferable upper limit of the largest particle diameter of the said light-shielding flexible particle|grain is 20 micrometers. When the maximum particle diameter of the said light-shielding flexible particle|grain exceeds 20 micrometers, a springback may be raise|generated, the sealing compound for liquid crystal dropping methods obtained will become inferior to adhesiveness, or a gap defect may generate|occur|produce in the liquid crystal display element obtained. A more preferable upper limit of the maximum particle diameter of the light-shielding flexible particle is 15 µm.

Moreover, it is preferable that the largest particle diameter of the said light-shielding flexible particle|grain is 2.6 times or less of a cell gap. When the maximum particle diameter of the light-shielding flexible particle exceeds 2.6 times the cell gap, springback occurs, and the resulting sealing compound for liquid crystal dropping method has poor adhesive properties, or when a gap defect occurs in the obtained liquid crystal display element there is A more preferable upper limit of the maximum particle diameter of the light-shielding flexible particle is 2.2 times the cell gap, and a more preferable upper limit is 1.7 times the cell gap.

In addition, in this specification, the maximum particle diameter of the said light-shielding flexible particle|grain and the average particle diameter mentioned later are the value obtained by measuring using the laser diffraction type particle size distribution analyzer with respect to the particle|grains before mix|blending with a sealing compound. do. As said laser diffraction type distribution measuring apparatus, Mastersizer 2000 (made by Marubansa) etc. can be used. Moreover, since the cell gap of a liquid crystal display element is not limited since it differs with a display element, The cell gap of a general liquid crystal display element is 2 micrometers - 10 micrometers.

In the particle size distribution of the light-shielding flexible particle|grains measured with the said laser diffraction type distribution analyzer, as for the said light-shielding flexible particle|grain, it is preferable that the content rate of the particle|grains with a particle diameter of 5 micrometers or more is 60 % or more by volume frequency. If the content rate of the particle|grains with a particle diameter of 5 micrometers or more is less than 60 % by volume frequency, it may become impossible to fully suppress a seal break and liquid-crystal contamination. It is more preferable that the content rate of the particle|grains with a particle diameter of 5 micrometers or more is 80 % or more.

The said light-shielding flexible particle|grains from a viewpoint of exhibiting the effect which suppresses generation|occurrence|production of a seal break and liquid-crystal contamination more to 100% or more of particle|grains of the cell gap of a liquid crystal display element 70 of the particle size distribution in the whole light-shielding flexible particle|grain It is preferable to contain % or more, and it is more preferable to be comprised only with 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 light-shielding flexible particle|grains is 2 micrometers, and a preferable upper limit is 15 micrometers. When the average particle diameter of the said light-shielding flexible particle|grain is less than 2 micrometers, the elution to the liquid crystal of a sealing compound may not fully be prevented. When the average particle diameter of the said light-shielding flexible particle|grain exceeds 15 micrometers, the sealing compound for liquid crystal dropping methods obtained may become inferior to adhesiveness, or a gap defect may generate|occur|produce in the liquid crystal display element obtained. A more preferable minimum of the average particle diameter of the said light-shielding flexible particle|grains is 4 micrometers, and a more preferable upper limit is 12 micrometers.

As said light-shielding flexible particle|grain, you may mix and use 2 or more types of light-shielding flexible particle|grains from which a largest particle diameter differs. That is, you may mix and use the light-shielding flexible particle|grains whose maximum particle diameter is less than 100% of the cell gap of a liquid crystal display element, and the light-shielding flexible particle|grains whose largest particle diameter is 100% or more of the cell gap of a liquid crystal display element.

It is preferable that the coefficient of variation (henceforth a "CV value") of the particle diameter of the said light-shielding flexible particle|grain is 30 % or less. When CV value of the particle diameter of the said light-shielding flexible particle|grain exceeds 30 %, a cell gap defect may be caused. As for CV value of the particle diameter of the said light-shielding 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 is a numerical value calculated|required by the following formula.

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

The said light-shielding flexible particle|grains can make a maximum particle diameter, an average particle diameter, and a CV value into the above-mentioned range by classifying even if it is a thing outside the above-mentioned range with a maximum particle diameter, an average particle diameter, and CV value. Moreover, since the light-shielding flexible particle|grains whose particle diameter is less than 100% of the cell gap of a liquid crystal display element do not contribute to suppression of generation|occurrence|production of a seal break or liquid-crystal contamination, and mix|blended with a sealing compound, a thixotropic value may be raised, It is preferable to remove by classification.

As a method of classifying the said light-shielding 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.

In the light-shielding flexible particles, the compressive displacement from the origin load value when a load is applied to the reversal load value is L1, and when the load value is reached from the reversal load value when the load is released to the origin When the unloading displacement up to L2 is L2, it is preferable that the recovery rate expressed by L2/L1 as a percentage is 80% or less. When the recovery rate of the said light-shielding flexible particle|grain exceeds 80 %, the function which becomes a barrier and prevents that a sealing compound elutes to a liquid crystal may fall. A more preferable upper limit of the recovery rate of the said light-shielding flexible particle|grain is 70 %, and a more preferable upper limit is 60 %.

In addition, the recovery factor of the said light-shielding 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 behavior after removing the load.

When the said light-shielding flexible particle|grains make compression 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 function which becomes a barrier that 1 g of distortion of the said light-shielding flexible particle|grain is less than 30 % and prevents that a sealing compound elutes to a liquid crystal may fall. The more preferable minimum of 1 g distortion of the said light-shielding flexible particle|grain is 40 %.

In addition, 1 g of deformation|transformation of the said light-shielding flexible particle|grain can be measured 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 light-shielding flexible particle|grains make compression displacement at the time of particle|grain destruction L4 and particle diameter Dn, it is preferable that the breaking deformation which expressed L4/Dn as a percentage is 50 % or more. The function which becomes a barrier that the breaking deformation of the said light-shielding flexible particle|grain is less than 50 % and prevents that a sealing compound elutes to a liquid crystal may fall. The more preferable minimum of the breaking deformation of the said light-shielding flexible particle|grain is 60 %.

In addition, the breaking strain of the said light-shielding flexible particle|grain can be measured by applying a load to one particle|grain using a micro compression tester, and measuring the displacement amount by which the particle|grain is destroyed. The said compressive displacement L4 is calculated by making the point at which the amount of displacement discontinuously increases with respect to the applied load as the point at which the particles are destroyed. Even if the applied load is increased, if it is not destroyed only by deformation, the breaking deformation is considered to be 100% or more.

As for the said light-shielding flexible particle|grains, a preferable minimum of a glass transition temperature is -200 degreeC, and a preferable upper limit is 40 degreeC. The glass transition temperature of the light-shielding flexible particles is -200 ℃ or higher, the lower the effect of suppressing the seal break or liquid crystal contamination, but if it is less than -200 ℃, a problem occurs in the handling of the particles, or the sealing during heating It becomes easy to crumble, and the sealing compound in the middle of hardening and a liquid crystal may contact, and liquid-crystal contamination may generate|occur|produce. When the glass transition temperature of the said light-shielding 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 light-shielding flexible particle|grain is -150 degreeC, and a more preferable upper limit is 35 degreeC.

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

It is preferable that blackening degree is 10 % or less, and, as for the said light-shielding flexible particle|grain, it is more preferable that it is 5 % or less. The lower the light-shielding property of the said light-shielding flexible particle|grain, the better, There is no minimum in particular preferable for the blackness of the said light-shielding flexible particle|grain, Usually, it is set as 0.05 % or more.

In addition, the blackening degree of the said light-shielding flexible particle|grain can be evaluated with the maximum value of the spectral transmittance in the 400-700 nm visible region full wavelength. Specifically, a flaky polymer with a thickness of 1 mm having the same composition as the particle to be evaluated is prepared as a sample for measuring the degree of blackening, and the spectral transmittance of this sample is measured using a spectrophotometer for all wavelengths in the visible region. can

As for content of the said light-shielding flexible particle|grain, with respect to 100 weight part of curable resin, a preferable minimum is 3 weight part, and a preferable upper limit is 70 weight part. When content of the said light-shielding flexible particle|grain is less than 3 weight part, it may become impossible to fully prevent the elution to the liquid crystal of a sealing compound. When content of the said light-shielding flexible particle|grain exceeds 70 weight part, the sealing compound for liquid crystal dropping methods obtained may become inferior to adhesiveness. A more preferable minimum of content of the said light-shielding flexible particle|grain is 5 weight part, a more preferable upper limit is 60 weight part, A more preferable minimum is 10 weight part, and a more preferable upper limit is 50 weight part.

The sealing compound for liquid crystal dropping methods of this invention 1 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 1 can harden 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 heating Since it becomes possible to quickly harden the sealing compound for liquid crystal dropping methods of this invention 1 only, and it is a liquid crystal display element of a narrow frame design, since generation|occurrence|production of a liquid-crystal contamination can fully be suppressed, (meth)acrylic resin and the heat mentioned later It is more preferable to contain a radical polymerization initiator.

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

In addition, in this specification, the said "(meth)acrylic resin" means a resin which has a (meth)acryloyl group, and the said "(meth)acryloyl group" means an acryloyl group or a methacryloyl group it means. 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, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, 2,2'-diallylbisphenol A 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 Epoxy 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, glycol Cydylamine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified type epoxy resin, glycidyl ester compound, bisphenol A type episulfide resin, etc. are mentioned.

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 resin, 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 a Nippon Steel Chemical Co., Ltd.) etc. are mentioned, for example.

As what is marketed among the said diphenyl ether type|mold epoxy resins, YSLV-80DE (made by a Nippon Steel Chemical Co., Ltd. make) etc. are mentioned, for example.

As what is marketed among the said dicyclopentadiene type epoxy resins, 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 the DIC company make), 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 ortho cresol 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 naphthalene phenol novolak-type epoxy resins, ESN-165S (made by the Nippon Steel Chemicals) etc. are mentioned, for example.

As what is marketed among the said glycidylamine type epoxy resins, 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 Steel Co., Ltd.), Epiclone 726 (made by DIC), Epollite 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 made by a Shin-Nittetsu Chemical Corporation), Epollide PB (made by a 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 Nippon Steel Chemical), XAC4151 (manufactured by Asahi Chemical Company), jER1031, jER1032 (all manufactured by Mitsubishi). The chemical company make), EXA-7120 (the DIC company make), TEPIC (the Nissan Chemical company make), etc. are mentioned.

Among the above-mentioned epoxy (meth) acrylates, commercially available ones include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL40, EBRY LRDXECRY63182 manufactured by Daicel LRDXECRY63182 (all, EBECRYL3800 by Daicel LRDXECRYL3800) ), 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 Company), Denacol Acrylate DA-141, and denacol acrylate DA-314 and denacol acrylate DA-911 (all manufactured by Nagase Chemtex Corporation).

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

As a monofunctional thing among the ester compounds obtained by making the compound which has a hydroxyl group react with the said (meth)acrylic acid, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4 -Hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) ) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3- Tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl ( Meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, iso Myristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethyl Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acrylo A yloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth)acrylate, 2-(meth)acryloyloxyethyl phosphate, etc. are mentioned.

As a bifunctional thing among the said ester compound, 1, 4- butanediol di (meth) acrylate, 1, 3- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, , 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene Glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth) Acrylate, dimethyloldicyclopentadienyldi(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, neopentylglycol di(meth)acrylate, ethylene oxide-modified isocyanuric acid di(meth)acryl Rate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylic a rate, polycaprolactone di(meth)acrylate, polybutadienediol di(meth)acrylate, etc. are mentioned.

As a trifunctional or more than trifunctional thing of the said ester compound, for example, pentaerythritol tri(meth)acrylate, trimethylol propane tri(meth)acrylate, propylene oxide addition trimethylol propane tri(meth)acrylate, ethylene oxide addition Trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipenta Erythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, tris (meth)acryloyloxyethyl phosphate etc. are mentioned.

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

As isocyanate used as the raw material of the said urethane (meth)acrylate, For example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate , diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI) , hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate, and the like.

Moreover, as said isocyanate, For example, polyols, such as ethylene glycol, glycerol, sorbitol, trimethylol propane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactonediol, and an excess isocyanate A chain-extended isocyanate compound obtained by the reaction of can also be used.

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 -Commercial products such as hydroxybutyl (meth)acrylate and 2-hydroxybutyl (meth)acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene Mono(meth)acrylates of dihydric alcohols such as glycol, mono(meth)acrylates or di(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin, bisphenol A type epoxy acrylate, etc. of epoxy (meth)acrylate, and the like.

Among the urethane (meth) acrylates, commercially available ones include, 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, ArtResin UN-7 UN-9000A, ArtResin UN-7 Allnex Co., Ltd. Art Resin UN-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Kogyo), 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 made by Shin-Nakamura Chemical Industries) Manufacture), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all are the Kyoeisha Chemicals make), etc. are mentioned.

The (meth) acrylic resin is, in terms of suppressing the adverse effect of a liquid crystal preferably has a hydrogen-bonding units, 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 because of high reactivity.

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

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)acrylic-modified epoxy resin means a resin which has each 1 or more epoxy group and (meth)acryloyl group in 1 molecule, For example, a resin which has 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 partial (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 becomes high, a liquid-crystal contamination may be 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 1 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 largest particle diameter of the said light-shielding 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 light-shielding flexible particle, the effect of suppressing the occurrence of springback, which is likely to be caused by the light-shielding flexible particle, is further improved. can be made excellent.

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

As described above, since the radical polymerization initiator has a significantly faster curing rate than the thermal curing agent, by using the radical polymerization initiator, the occurrence of seal break and liquid crystal contamination is suppressed, and further, by the light-shielding flexible particles Springback, which tends to occur, can also be suppressed.

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

As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Especially, the polymeric azo initiator which consists of a polymeric azo compound is preferable.

In addition, in this specification, a polymeric azo initiator has an azo group, and produces|generates the radical which can harden a (meth)acryloyloxy group with heat|fever means the compound whose number average molecular weight is 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 polymer azo initiator is less than 1000, the polymer azo initiator may adversely affect the liquid crystal. When the number average molecular weight of the said polymeric azo initiator exceeds 300,000, mixing with curable resin may become difficult. A more preferable lower limit of the number average molecular weight of the polymer azo initiator is 5000, a more preferable upper limit is 100,000, a still more preferable lower limit 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.

As said polymeric azo initiator, what has a structure in which units, such as polyalkylene oxide and polydimethylsiloxane, couple|bonded, through an azo group is mentioned, for example.

As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, it is preferable to have a polyethylene oxide structure. Examples of such a polymer azo initiator include a polycondensate of 4,4'-azobis(4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis(4-cyanopentanoic acid). ) and a polycondensate of polydimethylsiloxane having a terminal amino group, and the like, and specifically, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.) manufacture) and the like.

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, IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACUREOXE01, DAROCUR TPO (all manufactured by BASF Japan), benzoinmethyl ether, benzoin ethyl ether Ether, benzoin isopropyl ether (all above, the Tokyo Chemical Industry make) etc. are mentioned.

Moreover, as said polymerization initiator, a cationic polymerization initiator can also be used. As said cationic polymerization initiator, a photocationic polymerization initiator can be used suitably. The said photocationic polymerization initiator will not be specifically limited if it generate|occur|produces a protonic acid or a Lewis acid by light irradiation, The thing of an ionic photo-acid generating type may be sufficient, and a nonionic photo-acid generating 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. logistics, and the like.

As what is marketed among the said photocationic polymerization initiators, Adeka Optomer SP-150, Adeka Optomer 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. When content of the said polymerization initiator is less than 0.1 weight part, the sealing compound for liquid crystal dropping methods obtained 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. hydrazide, malonic acid dihydrazide, etc. are mentioned, As what is commercially available, For example, Amicure VDH, Amicure UDH (all are made by Ajinomoto Fine Techno), SDH, IDH, ADH (all are made by Otsuka Chemical Co., Ltd.) manufacture), MDH (made by Nippon Finechem Corporation), etc. are mentioned.

As for content of the said thermosetting agent, with respect to 100 weight part of said curable resin, 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 1 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 an isocyanuric ring structure, an epoxy resin amine adduct, etc. are mentioned, for example, Specifically, For example, tris (2-carboxymethyl) iso Anurate, 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 1 contains a filler for the purpose of the improvement of a viscosity, the adhesive improvement by a stress dispersion effect, the improvement of a linear expansion coefficient, 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. , glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, aluminum nitride, and other inorganic fillers, polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, core shell acrylate copolymer microparticles Organic fillers, such as these, etc. 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 5 weight%, and a preferable upper limit is 70 weight%. When content of the said filler is less than 5 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 10 weight%, and a more preferable upper limit is 50 weight%.

It is preferable that the sealing compound for liquid crystal dropping methods of this invention 1 contains a silane coupling agent. The said silane coupling agent mainly has a role as an adhesion|attachment adjuvant for bonding a sealing compound, a board|substrate, etc. favorably.

The said silane coupling agent is excellent in the effect of improving the adhesiveness of 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 suitably used 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%.

In addition to the said light-shielding flexible particle|grain, the sealing compound for liquid crystal dropping methods of this invention 1 may contain the light-shielding agent of the state which is not made to contain in a flexible particle|grain. As said light-shielding agent, the thing similar to the light-shielding agent made to contain the above-mentioned flexible particle|grains can be used.

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 still more preferable upper limit is 60 weight%.

The sealing compound for liquid crystal dropping methods of this invention 1 further, as needed, spacers, such as a reactive diluent for viscosity adjustment, polymer beads for panel gap adjustment, an antifoamer, a leveling agent, a polymerization inhibitor, another coupling agent, etc. may contain additives.

The method of manufacturing the sealing compound for liquid crystal dropping methods of this invention 1 is not specifically limited, For example, using mixers, such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, three rolls, , the method of mixing curable resin, a polymerization initiator and/or a thermosetting agent, light-shielding 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 1 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|operativity 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.

It is preferable that OD value is 2 or more, and, as for the sealing compound for liquid crystal dropping methods of this invention 1, it is more preferable that it is 3 or more. The higher the light-shielding property of the sealing compound for liquid crystal dropping methods of this invention 1, the better, and although there is no upper limit in particular preferable for the OD value of the sealing compound for liquid crystal dropping methods of this invention 1, Usually, it is set to 6 or less.

By mix|blending electroconductive microparticles|fine-particles with the sealing compound for liquid crystal dropping methods of this invention 1, a vertical conduction material can be manufactured. The vertical conduction material containing the sealing compound for liquid crystal dropping methods of such this invention 1, 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 them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.

The liquid crystal display element formed using the sealing compound for liquid crystal dropping methods of this invention 1, 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, for example, two transparent substrates, such as a glass substrate with electrodes, such as an ITO thin film, and a polyethylene terephthalate substrate, are prepared, and the liquid crystal of this invention 1 in one of them. A step of forming a rectangular seal pattern by screen printing, dispenser application, etc. of the sealing compound for the dropping method, and the liquid crystal dropping method sealing compound of the present invention 1 in an uncured state to apply small droplets of liquid crystal to the entire frame of the transparent substrate The method etc. which have a process which apply|coats dropwise to a surface and overlaps the other board|substrate immediately, and the process of heating and hardening the sealing compound for liquid crystal dropping methods of this invention 1 are mentioned. Moreover, before the process of heating and hardening the sealing compound for liquid crystal dropping methods of this invention 1, you may perform the process of irradiating lights, such as an ultraviolet-ray, to a seal pattern part, and temporarily hardening a sealing compound.

Next, the present invention 2 will be described in detail.

The light-shielding flexible silicone particle|grains of this invention 2 make silicone type particle|grains contain a light-shielding agent. The light-shielding flexible silicone particle|grains of this invention 2 can be used suitably as light-shielding flexible particle|grains contained in the sealing compound for liquid crystal dropping methods of this invention 1. That is, when this inventor bonds the board|substrate of a liquid crystal display element by mix|blending the light-shielding flexible silicone particle with sealing compound, the light-shielding flexible silicone particle becomes a barrier between another sealing compound component and a liquid crystal, and a sealing compound It was discovered that it can prevent eluting to a liquid crystal and the light leakage of a liquid crystal display element can be prevented, and came to complete this invention 2.

As a method of containing the light-shielding agent in the silicone-based particles, for example, in the manufacturing step of the silicone-based particles, a colorant such as a pigment or dye as the light-shielding agent is dispersed in the raw material of the silicone-based particles, and the like. a method of containing silicone particles having no light-shielding property and then coating the surface of the silicone particles with a colorant, or a method of absorbing a colorant into the silicone-based particles after preparing silicone particles having no light-shielding properties, etc. can be heard

It is preferable that the said silicone type particle|grain has the diorganosiloxane unit represented by following formula (1) as a repeating unit, and it is a silicone hardened|cured material which has rubber elasticity.

[Formula 5]

In formula (1), R ¹ is an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, an aryl group such as a phenyl group or a tolyl group, an alkenyl group such as a vinyl group or an allyl group, β-phenylethyl group, β -Aralkyl groups such as phenylpropyl group, hydrocarbon groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as chlorine or fluorine, epoxy groups, amino groups, mercapto groups, acryloxy groups, methacryloxy groups, etc. of reactive group-containing organic groups, and the like. It is preferable that it is 5-5000, and, as for a, it is more preferable that it is 10-1000.

The curing mechanism of the silicone-based particles is _{a condensation reaction between a methoxysilyl group (≡SiOCH 3} ) and a hydroxysilyl group (≡SiOH), or a mercaptosilyl group (≡SiSH) and a vinylsilyl group (≡SiCH=CH _{2 )} ) and the addition reaction of a vinylsilyl group (≡SiCH=CH ₂ ) and ≡SiH group, but in terms of reactivity and reaction process, (hydrosilylation) addition reaction it is preferable That is, in the present invention, it is preferable to prepare a composition in which (a) vinyl group-containing organopolysiloxane and (b) organohydrogenpolysiloxane are subjected to an addition reaction in the presence of (c) a platinum-based catalyst to be cured.

As such a component (a), the compound etc. which are specifically, represented by following formula (2) are mentioned, for example.

[Formula 6]

In formula (2), although R<^{1> is the same as R<1>} in said formula (1), it is preferable that it does not have an aliphatic unsaturated bond. b and c are 0, 1, 2, or 3, and b+c=3, d is a positive number, e is 0 or a positive number, and 2b+e≥2.

As organohydrogenpolysiloxane of the said (b) component, the compound etc. which are represented, for example by following formula (3) are mentioned.

[Formula 7]

In the formula (3), R ² is an unsubstituted or substituted monovalent hydrocarbon group bonded to a silicon atom having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, except for an aliphatic unsaturated bond, and R an unsubstituted or a substituted monovalent hydrocarbon group in the ^second, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert- butyl group, a pentyl group, a neopentyl group, a hexyl Alkyl groups such as sil group, cyclohexyl group, octyl group, nonyl group, and decyl group; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; What substituted some or all of the hydrogen atoms of a group with halogen atoms, such as fluorine, bromine, chlorine, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, etc. are mentioned. The ^{unsubstituted or substituted monovalent hydrocarbon group for R 2} is preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group. Further, f is 0.7 to 2.1, g is 0.001 to 1.0, and f+g is a positive number satisfying 0.8 to 3.0, preferably f is 1.0 to 2.0, g is 0.01 to 1.0, and f+g is 1.5 to 2.5.

Specific examples of the component (b) include compounds represented by the following formula (4).

[Formula 8]

In Formula (4), although R<^{1> is the same as R<1>} in said Formula (1), it is preferable that it does not have an aliphatic unsaturated bond. m is 0 or 1, n is 2 or 3, m+n=3, p is 0 or a positive number, q is 0 or a positive number, and 2m+q≥2.

The platinum-based catalyst of component (c) is a catalyst for addition reaction of a vinyl group bonded to a silicon atom in component (a) and a hydrogen atom (SiH group) bonded to a silicon atom in component (b), for example, platinum supported carbon or silica, chloroplatinic acid, platinum-olefin complex, platinum-alcohol complex, platinum-phosphorus complex, platinum coordination compound, and the like.

As a method for producing silicone-based particles using the components (a) to (c), the component (a) and the component (b) are reacted in the presence of the component (c) to cure, and there is no particular limitation, For example, the method of hardening|curing (a) component and (b) component in high temperature spray drying, the method of hardening in an organic solvent, the method of hardening after making this into an emulsion, etc. are mentioned. Moreover, in order to further make the dispersibility of a silicone type particle|grains favorable, you may coat|cover the polyorganosilsesquioxane resin on the surface of a silicone type particle|grains as needed.

As described above, the light-shielding flexible silicone particles can be produced by dispersing a colorant such as a pigment or dye as the light-shielding agent in the raw material of the silicone-based particles, or by a method of containing a colorant in the silicone-based particles. . Specifically, silicone-based particles having light-shielding properties can be obtained by dispersing or dissolving a colorant such as a pigment or dye in advance in the components (a) to (c) and then performing a curing reaction. When dispersing a coloring agent in the said (a)-(c) component, it is preferable to add surfactant or a dispersing agent which has affinity to both a silicone component and a coloring agent. By providing a colorant as a light-shielding agent before a hardening reaction, elution of a colorant from particle|grains or peeling is reduced, and liquid-crystal contamination can be suppressed.

In addition, as described above, the light-shielding flexible silicone particles can be prepared by manufacturing silicone-based particles that do not have light-shielding properties, and then coating the surface of the silicone-based particles with a colorant, or by producing silicone-based particles that do not have light-shielding properties. It can also be manufactured by the method of making the silicone type particle|grains absorb a coloring agent later. Specifically, light-shielding properties can be imparted by dispersing silicon-based particles having no light-shielding property in a medium in which a colorant is dissolved, stirring for a certain period of time to fix the colorant to the silicon-based particles, and also with a hybridizer or theta composer. Using the same complexing device, light-shielding properties can be imparted by fixing a colorant to the surface of silicon-based particles that do not have light-shielding properties.

Moreover, you may use the method of making the polymeric coloring agent adsorb|suck to the surface of the silicone type particle|grains which do not have light-shielding property. That is, light-shielding properties can be imparted by depositing a polymer having a skeleton or a functional group that absorbs light of a specific wavelength on the surface of the silicon-based particles that do not have light-shielding properties. Specifically, the polymer can be deposited on the surface of the silicone particles by subjecting the monomer used as a raw material of the polymer to emulsion polymerization, soap-free polymerization, dispersion polymerization or the like in the presence of silicon particles having no light-shielding properties.

Examples of the polymer to be deposited on the surface of the silicone particles include acetylene and its derivatives, aniline and its derivatives, furan and its derivatives, pyrrole and its derivatives, and a polymer obtained by polymerizing thiophene and its derivatives. . Among them, polypyrrole excellent in black appearance is preferable.

As the silicon-based particles having no light-shielding properties, commercially available silicone-based particles can also be used.

Examples of the commercially available silicone particles include KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (manufactured by Shin-Etsu Silicone), Torefil E-506S, EP -9215 (manufactured by Toray Dow Corning) and the like, and these can be classified and used. The silicon-type particle|grains which do not have the said light-shielding property may be used independently and 2 or more types may be used together.

Examples of the light-shielding agent contained in the silicon-based particles include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Especially, titanium black is preferable.

The said titanium black is a substance whose transmittance with respect to the light of wavelength 370-450 nm becomes high in the vicinity of an ultraviolet region, especially compared with the average transmittance|permeability with respect to the light of wavelength 300-800 nm. That is, the titanium black is a light-shielding agent having a property of imparting light-shielding properties to light-shielding flexible silicone particles by sufficiently shielding light of a wavelength in the visible region, while transmitting light having a wavelength in the vicinity of an ultraviolet region. Therefore, for example, as a polymerization initiator used for the sealing compound for liquid crystal dropping methods, the liquid crystal dropping by using what can start reaction with the light of the wavelength (370-450 nm) with which the transmittance|permeability of the said titanium black becomes high. The photocurability of the sealing compound for construction methods can be increased more. On the other hand, when using for the sealing compound for liquid crystal dropping methods, etc., as a light-shielding agent contained in the said silicon-type particle|grains, a material with high insulation is preferable, and titanium black is suitable also as a light-shielding agent with high insulation.

It is preferable that the optical density (OD value) per 1 micrometer of the said titanium black is 3 or more, and it is more preferable that it is 4 or more. The higher the light-shielding property of the titanium black, the better, 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 those coated with an inorganic component of Especially, the thing processed with the organic component is preferable at the point which can improve insulation more.

Moreover, when the light-shielding flexible silicone particle which contained titanium black in the said silicon-type particle|grains as a light-shielding agent is used for the sealing compound for liquid crystal dropping methods, for example, that the sealing compound for liquid crystal dropping methods has sufficient light-shielding property It becomes and the liquid crystal display element obtained does not leak light, has high contrast, and has the outstanding image display quality.

As what is marketed among the said titanium black, 12S, 13M, 13M-C, 13R-N (all are made by Mitsubishi Materials), Tirac D (made by Ako Chemical Corporation), 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.

A preferable lower limit of the primary particle diameter of the light-shielding agent contained in the silicon-based particles is 50 nm, and a preferable upper limit thereof is 500 nm. When the primary particle diameter of the light-shielding agent contained in the silicone-based particles is less than 50 nm, secondary aggregation is intense, and the dispersibility in the silicone particles may be remarkably reduced. When the primary particle diameter of the light-shielding agent contained in the silicon-based particles exceeds 500 nm, the silicon particles may be hard and brittle. A more preferable lower limit of the primary particle diameter of the light-shielding agent contained in the silicon-based particles is 70 nm, and a more preferable upper limit thereof is 300 nm.

As for content of the light-shielding agent contained in the said silicone type particle|grain, with respect to the whole light-shielding flexible silicone particle|grains, a preferable minimum is 2 weight%, and a preferable upper limit is 30 weight%. When content of the light-shielding agent contained in the said silicone type particle|grain is less than 2 weight%, sufficient light-shielding property may not be acquired. When content of the light-shielding agent contained in the said silicone type particle|grain exceeds 30 weight%, a silicone particle may become hard and brittle. The minimum with more preferable content of the light-shielding agent contained in the said silicone type particle|grains is 5 weight%, and a more preferable upper limit is 20 weight%.

When using the said light-shielding flexible silicone type particle|grains for the sealing compound for liquid crystal dropping methods, it is preferable that the largest particle diameter is 100% or more of the cell gap of a liquid crystal display element. When the largest particle diameter of the said light-shielding flexible silicone type particle|grain is less than 100% of the cell gap of a liquid crystal display element, it may become impossible to fully suppress a seal break and a liquid-crystal contamination. The largest particle diameter of the said light-shielding flexible silicone type particle|grain is 100% or more of the cell gap of a liquid crystal display element, and it is more preferable that it is 5 micrometers or more.

Moreover, the preferable upper limit of the largest particle diameter of the said light-shielding flexible silicone type particle|grain is 20 micrometers. When the maximum particle diameter of the said light-shielding flexible silicone type particle|grain exceeds 20 micrometers, when it uses for the sealing compound for liquid crystal dropping methods, a springback will be raised, and the sealing compound for liquid crystal dropping methods obtained will become inferior in adhesiveness, or the liquid crystal display element obtained In some cases, a gap defect may occur. A more preferable upper limit of the maximum particle diameter of the light-shielding flexible silicone-based particles is 15 µm.

Moreover, it is preferable that the largest particle diameter of the said light-shielding flexible silicone type particle|grain is 2.6 times or less of a cell gap. When the maximum particle diameter of the light-shielding flexible silicone particles exceeds 2.6 times the cell gap, springback occurs when used in the sealing compound for the liquid crystal dropping method, and the sealing compound for the liquid crystal dropping method obtained has poor adhesiveness, or obtained A gap defect may generate|occur|produce in a liquid crystal display element. A more preferable upper limit of the maximum particle diameter of the light-shielding flexible silicone particles is 2.2 times the cell gap, and a more preferable upper limit is 1.7 times the cell gap.

In addition, in the present specification, the maximum particle diameter of the light-shielding flexible silicone-based particles and the average particle diameter to be described later are the values obtained by measuring the particles before mixing with the sealing agent using a laser diffraction type particle size distribution analyzer. it means. As said laser diffraction type distribution measuring apparatus, Mastersizer 2000 (made by Marubansa) etc. can be used. Moreover, since the cell gap of a liquid crystal display element is not limited since it differs with a display element, The cell gap of a general liquid crystal display element is 2 micrometers - 10 micrometers.

In the light-shielding flexible silicone-based particles, the content ratio of particles having a particle diameter of 5 µm or more in the particle size distribution of the light-shielding flexible silicone-based particles measured by the laser diffraction distribution analyzer is preferably 60% or more in terms of volume frequency. When the content rate of the particle|grains of 5 micrometers or more particle diameter is less than 60 % by volume frequency, when it uses for the sealing compound for liquid crystal dropping methods, it may become impossible to fully suppress a seal break and a liquid-crystal contamination. It is more preferable that the content rate of the particle|grains with a particle diameter of 5 micrometers or more is 80 % or more.

The said light-shielding flexible silicone type particle|grains from a viewpoint of exhibiting the effect which suppresses generation|occurrence|production of a seal break and liquid-crystal contamination more when it uses for the sealing compound for liquid crystal dropping methods more than 100% of the cell gap of a liquid crystal display element, difference It is preferable to contain 70% or more of the particle size distribution in the whole optically flexible silicone type particle|grain, and it is more preferable to be comprised only with 100% or more of particle|grains of the cell gap of a liquid crystal display element.

The preferable minimum of the average particle diameter of the said light-shielding flexible silicone type particle|grains is 2 micrometers, and a preferable upper limit is 50 micrometers. When the average particle diameter of the said light-shielding flexible silicone type particle|grain is less than 2 micrometers and it uses for the sealing compound for liquid crystal dropping methods, the elution to the liquid crystal of a sealing compound may not fully be prevented. When the average particle diameter of the light-shielding flexible silicone particles exceeds 50 µm, when used in the sealing compound for the liquid crystal dropping method, the sealing compound for the liquid crystal dropping method obtained has poor adhesiveness, or there is a gap defect in the liquid crystal display element obtained may or may not occur. A more preferable lower limit of the average particle diameter of the light-shielding flexible silicone particles is 4 µm, a more preferable upper limit is 15 µm, and a more preferable upper limit is 12 µm.

As said light-shielding flexible silicone type particle|grains, you may mix and use 2 or more types of light-shielding flexible silicone type particle|grains from which a largest particle diameter differs. That is, when using for the sealing compound for liquid crystal dropping methods, light-shielding flexible silicone type particle|grains whose maximum particle diameter is less than 100% of the cell gap of a liquid crystal display element, and light-shielding property whose largest particle diameter is 100% or more of the cell gap of a liquid crystal display element You may mix and use flexible silicone type particle|grains.

It is preferable that the coefficient of variation (henceforth a "CV value") of the particle diameter of the said light-shielding flexible silicone type particle|grain is 30 % or less. When CV value of the particle diameter of the said light-shielding flexible silicone type particle|grain exceeds 30 % and it uses for the sealing compound for liquid crystal dropping methods, a cell gap defect may be caused. As for the CV value of the particle diameter of the said light-shielding flexible silicone type particle|grain, it is more preferable that it is 28 % or less. In addition, in this specification, the CV value of a particle diameter is a numerical value calculated|required by the following formula.

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

The light-shielding flexible silicone particles, by classifying the maximum particle diameter, average particle diameter, or CV value even if it is outside the above-mentioned range, the maximum particle diameter, average particle diameter, or CV value can be within the above-mentioned range. Moreover, when using for the sealing compound for liquid crystal dropping methods, the light-shielding flexible silicone type particle|grains whose particle diameter is less than 100% of the cell gap of a liquid crystal display element does not contribute to suppression of generation|occurrence|production of a seal break or liquid crystal contamination, and to a sealing compound Since a thixotropic value may be raised when mix|blending, it is preferable to remove by classification.

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

In the light-shielding flexible silicone particles, the compressive displacement from the origin load value when a load is applied to the reversal load value is L1, and from the reversal load value when the load is released to the origin load value. When the unloading displacement until the time of unloading is L2, it is preferable that the recovery rate expressed by L2/L1 as a percentage is 80% or less. When the recovery factor of the said light-shielding flexible silicone type particle|grain exceeds 80 %, when it uses for the sealing compound for liquid crystal dropping methods, it becomes a barrier and the function which prevents that a sealing compound elutes to a liquid crystal may fall. A more preferable upper limit of the recovery rate of the said light-shielding flexible silicone type particle|grains is 70 %, and a more preferable upper limit is 60 %.

In addition, the recovery factor of the said light-shielding flexible silicone type 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 behavior after the load is removed.

When the said light-shielding flexible silicone particle|grains make compressive displacement at the time of applying a load of 1 g L3, and make a particle diameter Dn, it is preferable that 1 g deformation|transformation which expressed L3/Dn as a percentage is 30 % or more. When 1 g of strain of the said light-shielding flexible silicone type particle|grain is less than 30 %, when it uses for the sealing compound for liquid crystal dropping methods, it becomes a barrier and the function which prevents that a sealing compound elutes to a liquid crystal may fall. The more preferable minimum of 1 g distortion of the said light-shielding flexible silicone type particle|grain is 40 %.

In addition, 1 g of deformation|transformation of the said light-shielding flexible silicone type particle|grain can be measured 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.

The light-shielding flexible silicone particles preferably have a breaking strain expressed by L4/Dn as a percentage of 50% or more when the compressive displacement at the time the particles are broken is L4 and the particle diameter is Dn. When the breaking strain of the said light-shielding flexible silicone type particle|grain is less than 50 %, when it uses for the sealing compound for liquid crystal dropping methods, it becomes a barrier and the function which prevents that a sealing compound elutes to a liquid crystal may fall. The more preferable minimum of the breaking deformation of the said light-shielding flexible silicone type particle|grain is 60 %.

In addition, the breaking strain of the said light-shielding flexible silicone type particle|grain can be measured 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 is calculated by setting 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. When the applied load is only deformed and does not break even when the load is increased, the breaking deformation is considered to be 100% or more.

As for the said light-shielding flexible silicone type particle|grains, a preferable minimum of a glass transition temperature is -200 degreeC, and a preferable upper limit is 40 degreeC. The glass transition temperature of the light-shielding flexible silicone particles is -200 ℃ or higher, the lower the effect of suppressing the seal break or liquid crystal contamination, but if it is less than -200 ℃, a problem occurs in the handling of the particles, or the sealing during heating It becomes easy to crumble, and the sealing compound and liquid crystal in the middle of hardening may contact, and liquid-crystal contamination may generate|occur|produce. When the glass transition temperature of the said light-shielding flexible silicone particle|grain exceeds 40 degreeC, a gap defect may generate|occur|produce. The minimum with a more preferable glass transition temperature of the said light-shielding flexible particle|grain is -150 degreeC, and a more preferable upper limit is 35 degreeC. In addition, the glass transition temperature of the said light-shielding flexible silicone type particle|grain shows the value measured by differential scanning calorimetry (DSC) based on "the transition temperature measuring method of plastics" of JISK7121.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in adhesiveness and hardly produces a liquid-crystal contamination, and the sealing compound for liquid crystal dropping methods which can prevent the light leakage of a liquid crystal display element can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element manufactured using the sealing compound for liquid crystal dropping methods can be provided. Moreover, according to this invention, light-shielding flexible silicone particle|grains can be provided.

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

(Preparation of light-shielding flexible particle A)

500 g of methylvinylsiloxane having a viscosity of 600 cP (compound represented by the following formula (5)), 20 g of methylhydrogenpolysiloxane having a viscosity of 30 cP (a compound represented by the following formula (6)), and titanium black (Mitsubishi Mute) 26 g (manufactured by Real, "13M") was put into a 1 liter capacity glass beaker, and stirred and mixed at 2000 rpm using a homomixer.

Next, 1 g of polyoxyethylene (additional mole number = 9 moles) octylphenyl ether and 150 g of water were added and stirring was continued at 6000 rpm. As a result, phase inversion occurred and thickening was confirmed, but further as it was. As a result of adding 329 g of water while stirring at 3000 rpm, an O/W emulsion was obtained.

[Formula 9]

[Formula 10]

Next, this emulsion was transferred to a glass flask equipped with a stirring device by means of an anchor-type stirring blade, and 1 g of a toluene solution (platinum content 0.05%) of a chloroplatinic acid-olefin complex (platinum content 0.05%) and polyoxyethylene (addition The number of moles = 9 moles) A mixture of 1 g of octylphenyl ether was added, and reaction was performed for 12 hours. As a result, a dispersion (hereinafter also referred to as "silicone rubber spherical fine particle aqueous dispersion-1") was obtained, but this dispersion liquid The average particle diameter of the particles in the mixture was measured using a Coulter counter (manufactured by Coulter Electronics), and as a result, it was 10 µm. As a result of drying several g of this dispersion at room temperature, elastic rubber powder was obtained.

In a 3 liter glass flask, 2290 g of water, 580 g of silicone rubber spherical fine particle aqueous dispersion-1, and 60 g of aqueous ammonia (concentration of 28% by weight) were put into a 3 liter glass flask, the water temperature was set to 10°C, and the blade rotation speed was 200 rpm Stirring was performed by an anchor-type stirring blade under the conditions of Although pH of the liquid at this time was 11.2, methyltrimethoxysilane 65g was dripped at this liquid over 20 minutes, liquid temperature was maintained at 5-15 degreeC in the meantime, and after stirring for 4 hours, 55- The liquid obtained by heating to 60 degreeC and stirring continuously for 1 hour was made into the cake-like thing of about 30% of water using the pressure filter.

Next, this cake-like substance was dried at the temperature of 105 degreeC in a hot-air circulation dryer, and the obtained dried substance was pulverized by the jet mill. Then, the light-shielding flexible particle|grains A which are light-shielding flexible silicone particle|grains containing a light-shielding agent were obtained by adjusting a predetermined particle diameter and a largest particle diameter by classification operation.

500 g of methylvinylsiloxane having a viscosity of 600 cP (compound represented by the following formula (5)), 20 g of methylhydrogenpolysiloxane having a viscosity of 30 cP (a compound represented by the following formula (6)), and titanium black (Mitsubishi Mute) 26 g (manufactured by Real, "13M") was put into a 1 liter capacity glass beaker, and to a solution obtained by stirring and mixing at 2000 rpm using a homomixer, a toluene solution of chloroplatinic acid-olefin complex (platinum content 0.05%) A liquid mixture was prepared in which 1 g was added.

The obtained liquid mixture was poured onto a batt previously coated with Teflon (registered trademark), the height was adjusted so that the thickness after curing was 1 mm, and reacted at room temperature for 24 hours to obtain a sheet. The obtained sheet was cut, and the sample for a 1 mm-thick flaky blackening degree measurement which has the same composition as the light-shielding flexible particle|grain A was obtained.

"Maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature" of the obtained light-shielding flexible particle A, for measuring the degree of blackening measured using UV-3600 (manufactured by Shimadzu Corporation) "Blackening degree" of the sample, and using a micro compression tester (manufactured by Shimadzu Corporation, "PCT-200"), the fine particles were compressed at a compression rate of 0.28 mN in a diamond-made cylindrical smooth cross-section having a diameter of 50 µm. Table 1 shows the "recovery rate", "1 g strain", and "breaking strain" measured under the conditions of /sec, the origin load value of 1.0 mN, and the reversal load value of 10 mN.

(Production of light-shielding flexible particles B)

The same reaction as for light-shielding flexible A is performed except that the usage-amount of titanium black (Mitsubishi Materials, "13M") was 52 g, and as flexible particles containing a light-shielding agent, tea which is a light-shielding flexible silicone particle The sample for the measurement of the flaky blackening degree of thickness 1mm which has the photoluminescent flexible particle|grain B and the light-shielding flexible particle|grain B and the same composition was manufactured.

About the obtained light-shielding flexible particle|grain B, it carried out similarly to the light-shielding flexible particle A, and measured "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "blackening degree" , "recovery rate", "1 g strain", and "breaking strain" are shown in Table 1.

(Preparation of light-shielding flexible particle C)

The reaction similar to the said "production of the light-shielding flexible particle|grain A" was performed using only methylvinylsiloxane and methylhydrogenpolysiloxane without adding titanium black, and silicone type particle|grains were obtained.

20 g of the obtained silicone particles and 210 g of water were put into a 1 liter separable flask, and stirred and dispersed. Separately, a solution in which 3 g of polyvinylpyrrolidone was dissolved in 50 g of water was prepared, added to the separable flask, and stirred for 30 minutes.

Then, 10 g of pyrrole, 5.3 g of water peroxide (15 weight%), and 24.4 g of sulfuric acid (5 weight%) were added, and stirring was performed for 30 minutes. Then, 0.08 g of iron sulfate heptahydrate was dissolved in 1 g of water and added to the separable flask. After that, stirring was continued for 12 hours at room temperature, and the particles were washed several times with water. After drying this dispersion liquid at room temperature, the predetermined particle diameter and the largest particle diameter were adjusted by classification operation, and the light-shielding flexible particle|grain C which is a light-shielding flexible silicone particle|grain was obtained.

About the obtained light-shielding flexible particle|grain C, it carried out similarly to light-shielding flexible particle A, and measured "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "recovery rate" , "1 g deformation", and "breaking deformation" are shown in Table 1. In addition, about the light-shielding flexible particle|grain C, since the sample for a blackening degree measurement could not be manufactured, the measurement of blackening degree was not performed.

(Preparation of light-shielding flexible particle D)

50 g of polytetramethylene glycol diacrylate, 950 g of ethylhexyl methacrylate, and 50 g of titanium black (manufactured by Mitsubishi Materials, “13M”) were put into a 3 liter glass beaker, and a homomixer was used. and stirred and mixed at 2000 rpm. Furthermore, 40 g of benzoyl peroxide was added to this liquid mixture, and it mixed with the stirring blade until it melt|dissolved uniformly (Hereinafter, the obtained liquid mixture is also called "monomer liquid mixture").

The monomer mixture was put into a reaction kiln in which 5 kg of a 1 wt% aqueous solution of polyvinyl alcohol was charged, and stirred for 2 to 4 hours to adjust the particle size so that the monomer droplets became a predetermined particle size. After this, reaction was performed in 85 degreeC nitrogen atmosphere for 9 hours, and the polymer particle was obtained. After wash|cleaning the obtained polymer particle several times with hot water, classification operation was performed and the particle diameter and the largest particle diameter were adjusted. Moreover, after performing solvent substitution with methanol for several times, it dried at 30 degreeC under reduced pressure with a vacuum dryer for 12 hours, and the light-shielding flexible particle|grain D was obtained.

A part of the monomer mixture was poured onto a bat that had been previously coated with Teflon (registered trademark), the height was adjusted so that the thickness after curing was 1 mm, and reacted at 85° C. for 20 hours to obtain a sheet. The obtained sheet was cut, and the sample for a 1 mm-thick flaky blackening degree measurement which has the light-shielding flexible particle|grain D and the same composition was obtained.

About the obtained light-shielding flexible particle|grain D, "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "blackening degree" measured in the same way as light-shielding flexible particle A , "recovery rate", "1 g strain", and "breaking strain" are shown in Table 1.

(Production of light-shielding flexible particles E)

Instead of 50 g of polytetramethylene glycol diacrylate and 950 g of ethylhexyl methacrylate, except having used 400 g of polytetramethylene glycol diacrylate and 600 g of styrene, operation similar to light-shielding flexible particle|grain D is performed And the light-shielding flexible particle|grain E and the sample for a 1 mm-thick flaky blackening degree measurement which has the same composition as the light-shielding flexible particle|grain E were manufactured.

About the obtained light-shielding flexible particle|grain E, it carried out similarly to light-shielding flexible particle|grain A, and measured "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "blackening degree" , "recovery rate", "1 g strain", and "breaking strain" are shown in Table 1.

(Production of light-shielding flexible particles F)

Instead of 50 g of polytetramethylene glycol diacrylate and 950 g of ethylhexyl methacrylate, except having used 750 g of polytetramethylene glycol diacrylate and 250 g of styrene, operation similar to light-shielding flexible particle|grain D is performed And the light-shielding flexible particle|grain F and the light-shielding flexible particle|grain F and the sample for a 1 mm-thick flaky blackening degree measurement which have the same composition were manufactured.

About the obtained light-shielding flexible particle|grain F, it carried out similarly to light-shielding flexible particle|grain A, and measured "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "blackening degree" , "recovery rate", "1 g strain", and "breaking strain" are shown in Table 1.

(Production of light-shielding flexible particles G)

At the time of classification, except having adjusted so that the largest particle diameter might be set to 5 micrometers or less, operation similar to the light-shielding flexible particle|grain A was performed, and the light-shielding flexible particle|grain G was obtained.

About the obtained light-shielding flexible particle|grain G, it carried out similarly to light-shielding flexible particle|grain A, and measured "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "blackening degree" , "recovery rate", "1 g strain", and "breaking strain" are shown in Table 1.

In addition, since a particle composition was the same as that of the light-shielding flexible particle|grain A, the thing similar to what was obtained about the light-shielding flexible particle|grain A was used for the sample for a blackening degree measurement.

(Preparation of non-light-shielding flexible particle A)

A thickness 1 having the same composition as the non-light-shielding flexible particle A and the non-light-shielding flexible particle A as flexible particles which perform the same reaction as that of the light-shielding flexible particle A, and do not contain a light-shielding agent, except that titanium black is not added A sample for measuring the degree of blackening in the shape of a mm flake was prepared.

About the obtained non-light-shielding flexible particle|grain A, it carried out similarly to light-shielding flexible particle A, and measured "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "blackening degree" , "recovery rate", "1 g strain", and "breaking strain" are shown in Table 1.

(Example 1)

As a curable resin, 70 parts by weight of a bisphenol A epoxy acrylate (manufactured by Daicel Allnex, "Ebecryl 3700") and 30 parts by weight of a bisphenol F-type epoxy resin (manufactured by Mitsubishi Chemical, "jER806"), and thermal radical polymerization 7 parts by weight of a polymer azo initiator (manufactured by Wako Pure Chemical Industries, Ltd., "VPE-0201") as an initiator, and 8 parts by weight of sebacane dihydrazide (manufactured by Otsuka Chemicals, "SDH") as a thermosetting agent, light-shielding flexible particles 30 parts by weight of A, and 10 parts by weight of silica (manufactured by Admatex, "Adma Fine SO-C2") as a filler, and 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone, Inc., as a silane coupling agent, "KBM-403") 1 weight part was mix|blended, and after stirring with the planetary stirring apparatus (The Thinky company make, "Awatori Rentaro"), it was made to mix uniformly with three ceramic rolls, and the sealing compound for liquid crystal dropping methods was obtained.

(Examples 2 to 14, Comparative Examples 1 to 3)

According to the compounding ratio shown in Table 2, each material was carried out in the same manner as in Example 1, and mixed using a planetary stirring device (“Awatori Rentaro” manufactured by Sinki Co., Ltd.), and then further using 3 rolls By mixing, the sealing compound for liquid crystal dropping methods of Examples 2-14 and Comparative Examples 1-3 was prepared.

<Evaluation>

The following evaluation was performed about each sealing compound for liquid crystal dropping methods obtained by the Example and the comparative example. The results are shown in Table 2.

(Adhesive)

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 5 μm (“Micro Pearl SP-2050” manufactured by Sekisui Chemical Industry Co., Ltd.) in a planetary stirring device By uniformly disperse|distributing by, a trace amount is taken in the central part of Corning glass 1737 (20mm x 50mm x thickness 0.7mm), glass of the same type is superimposed on it, and the sealing compound for liquid crystal dropping methods is spread out and spread, and 120 degreeC was heated for 1 hour to thermoset the sealing compound, and an adhesion test piece was obtained.

About the obtained adhesion test piece, adhesive strength was measured using the tension gauge. When the adhesive strength is 270 N/cm 2 or more, “○”, when the adhesive strength is 250 N/cm 2 or more and less than 270 N/cm 2 “Δ”, and when the adhesive strength is less than 250 N/cm 2 “×”, the adhesiveness was evaluated.

(light-shielding)

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 5 μm (“Micro Pearl SP-2050” manufactured by Sekisui Chemical Industry Co., Ltd.) in a planetary stirring device This was uniformly dispersed by the method, applied on a 50 mm x 50 mm glass substrate, and a glass substrate of the same shape was superposed thereon. Next, it heated at 120 degreeC for 1 hour, the sealing compound was thermosetted, and the test piece for OD value measurement was obtained. The OD value was measured using a PDA-100 (manufactured by Konica Co., Ltd.) for the obtained test piece for OD value measurement, "○○" when the OD value was 3 or more, "○" when the OD value was 2.5 or more and less than 3, "○", 2 or more 2.5 The case where it was less than "(triangle|delta)" and the case of less than 2 were made into "x", and light-shielding property was evaluated.

(Liquid contamination)

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 5 μm (“Micro Pearl SP-2050” manufactured by Sekisui Chemical Industry Co., Ltd.) with a planetary stirring device After uniformly dispersing, the obtained sealing compound is filled in a syringe for dispensing (Musashi Engineering Co., Ltd., "PSY-10E"), and a defoaming treatment is performed, and then the ITO thin film is discharged with a dispenser (Musashi Engineering Co., Ltd., "SHOTMASTER300") A sealing compound was applied to the attached transparent electrode substrate as if drawing a rectangular frame. Then, the microdroplet of TN liquid crystal (the Thixo company make, "JC-5001LA") was drip-coated by the liquid crystal dropping device, and the other transparent substrate was bonded together under the vacuum of 5 Pa with the vacuum bonding device. The cell after bonding was heated at 120 degreeC for 1 hour, the sealing compound was thermosetted, and the liquid crystal display element (5 micrometers of cell gaps) was obtained.

About the obtained liquid crystal display element, the display nonuniformity which generate|occur|produces in the liquid crystal (especially a corner part) around a seal|sticker part is observed visually, and "○○" when there is no display nonuniformity at all, and "○" when there is almost no display nonuniformity. , the case where a slight display nonuniformity generate|occur|produced was made into "Δ", and the case where severe display nonuniformity was confirmed was made into "x", and liquid-crystal contamination property was evaluated.

Industrial Applicability

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in adhesiveness and hardly produces a liquid-crystal contamination, and can provide the sealing compound for liquid crystal dropping methods which can prevent the light leakage of a liquid crystal display element. Moreover, according to this invention, the vertical conduction material and liquid crystal display element manufactured using the sealing compound for liquid crystal dropping methods can be provided. Moreover, according to this invention, light-shielding flexible silicone particle|grains can be provided.

Claims (12)

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 light-shielding flexible particle|grains are contained,
In the light-shielding flexible particles, the compressive displacement from the origin load value when a load is applied to the reversal load value is L1, and when the load value is reached from the reversal load value when the load is released When unloading displacement to to is made L2, the recovery factor which showed L2/L1 as a percentage is 80 % or less, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. 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 light-shielding flexible particle|grains are contained,
The said light-shielding flexible particle|grains make compression displacement when a load of 1 g is applied to L3, and when a particle diameter is made into Dn, 1 g deformation|transformation which expressed L3/Dn as a percentage is 30% or more, The liquid crystal characterized by the above-mentioned Sealing agent for the drip method. 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 light-shielding flexible particle|grains are contained,
The said light-shielding flexible particle|grains make the compressive displacement at the time of particle|grain destruction L4, and when the particle diameter is Dn, the breaking deformation expressed by L4/Dn as a percentage is 50% or more, The seal for liquid crystal dropping method characterized by the above-mentioned my. 4. The method of claim 1, 2 or 3,
A light-shielding flexible particle|grain is 100% or more of a largest particle diameter of the cell gap of a liquid crystal display element, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. 4. The method of claim 1, 2 or 3,
Glass transition temperature of light-shielding flexible particle|grains is -200-40 degreeC, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. 4. The method of claim 1, 2 or 3,
Light-shielding flexible particle|grains are 30 % or less of the coefficient of variation of a particle diameter, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. 4. The method of claim 1, 2 or 3,
In addition to light-shielding flexible particle|grains, it further contains a light-shielding agent, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. The sealing compound for liquid crystal dropping methods of Claim 1, 2, or 3, and electroconductive fine particles are contained, The vertical conduction material characterized by the above-mentioned. It is manufactured using the sealing compound for liquid crystal dropping methods of Claim 1, 2, or 3, The liquid crystal display element characterized by the above-mentioned. delete delete delete