KR20160028404A - 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 the present invention is to provide a sealant for a liquid crystal dripping method which is excellent in adhesiveness, hardly causes liquid crystal contamination, and can prevent light leakage of a liquid crystal display element. It is another object of the present invention to provide light-shielding flexible silicon particles suitable for inclusion in the sealant. The sealing agent for a liquid crystal dropping method according to the present invention contains a curable resin, a polymerization initiator and / or a thermosetting agent, and light-shielding flexible particles. Further, the light-blocking flexible silicon particles according to the present invention contain a light-shielding agent in the silicone-based particles.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealant for a liquid crystal dripping method, a liquid crystal display device, and a light-shielding flexible silicon particle. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a sealant for a liquid crystal dripping method which is excellent in adhesiveness and rarely causes liquid crystal contamination and can prevent light leakage of a liquid crystal display element. The present invention also relates to a vertical conduction material and a liquid crystal display element manufactured using the liquid crystal drop sealing agent. Further, the present invention relates to a light-blocking flexible silicon particle.

In recent years, a method of manufacturing a liquid crystal display element such as a liquid crystal display cell has been proposed from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used, from the conventional vacuum injection system, for example, in Patent Documents 1 and 2 A liquid dropping method called a dropping method using a photo-curable resin such as a photo-curing resin such as a photo-curable resin, a photo-polymerization initiator, a thermosetting resin, and a heat curing agent.

In the dropping method, a rectangular-shaped seal pattern is formed by dispensing on one side of a transparent substrate to which two electrodes are attached. Subsequently, the sealant is left in an uncured state, and droplets of the liquid crystal are dropped onto the entire surface of the frame of the transparent substrate, the other transparent substrate is immediately superimposed, and light is irradiated to the seal portion such as ultraviolet light to perform temporary curing do. Thereafter, when the liquid crystal is annealed, the liquid crystal display device is manufactured by heating and final curing. If the substrate is bonded under a reduced pressure, the liquid crystal display element can be manufactured with a very high efficiency, and this dropping method has become the mainstream of the liquid crystal display element manufacturing method at present.

However, in the modern age in which mobile devices with various liquid crystal panels, such as mobile phones and portable game machines, are popular, miniaturization of the apparatus is a most demanded problem. As a method of miniaturization, a narrow frame of a liquid crystal display part can be exemplified. For example, a position of a seal part is arranged under a black matrix (hereinafter also referred to as a narrow frame design).

However, when a narrow-frame liquid crystal display element is manufactured by the dropping method, there is a point where light is not applied to the seal portion due to the black matrix, so that a portion of the photo- , There is a problem that uncured photocurable resin is eluted after the provisional curing process and the liquid crystal is contaminated.

In addition, since the conventional sealing agent was transparent or milky white, the light transmitting through the sealing agent can not be shielded by a black matrix originally required to suppress light leakage, and the contrast is lowered.

Thus, a method of imparting a light shielding property to a sealant by adding a light shielding agent has been studied. For example, Patent Documents 3 to 5 disclose a sealing agent containing a light-shielding agent such as a titanium black-based material or a carbon black-based material as a light-shielding component.

However, such a light-shielding agent tends to flocculate after being dispersed in a resin, and dispersion stability and adhesiveness have been a problem.

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

An object of the present invention is to provide a sealant for a liquid crystal dripping method which is excellent in adhesiveness, hardly causes liquid crystal contamination, and can prevent light leakage of a liquid crystal display element. Another object of the present invention is to provide a liquid crystal display element and a liquid crystal display device using the liquid crystal drop sealing agent. Further, the present invention aims to provide light-blocking flexible silicone particles.

The present invention 1 is a liquid crystal dripping sealing agent for use in the production of a liquid crystal display element by a liquid crystal dropping method, which comprises a curable resin, a polymerization initiator and / or a thermosetting agent, It is a sealing agent.

The present invention 2 is a light-blocking flexible silicon particle comprising a silicone-based particle containing a light-shielding agent.

First, the first aspect of the present invention will be described in detail.

The present inventors have found that when a substrate of a liquid crystal display element is bonded to a liquid crystal display element by blending a light-shielding flexible particle into a sealant, the light-shielding flexible particle becomes a barrier between the liquid composition and other sealant components, And that the light leakage of the liquid crystal display element can be prevented, and thus the present invention 1 has been completed.

The sealing agent for a liquid crystal dropping method of the present invention 1 contains light-shielding flexible particles. The light-shielding flexible particles serve to prevent the light leakage of the liquid crystal display element by imparting a light shielding property to the sealing agent, and also serve as a barrier between the liquid crystal and other sealing components when the liquid crystal display element is manufactured, And has a role of preventing elution into liquid crystals. Further, by mixing the above-mentioned light-shielding flexible particles, it is possible to prevent the substrate from shifting until the sealant is hardened after the substrate is bonded. Therefore, the sealant for liquid crystal dropping method of the present invention do.

As the light-shielding flexible particles, it is preferable that the flexible particles contain a light-shielding agent.

Examples of a method of adding a light shielding agent to the above-mentioned soft particles include a method of dispersing a colorant such as a pigment or a dye in the raw material of the soft particles as the light shielding agent, for example, A method of coating the surface of the flexible particles with a colorant after the production of the flexible particles having no light shielding property, a method of preparing the flexible particles having no light shielding property and then absorbing the colorant to the flexible particles .

Examples of the flexible particles include silicone-based particles, vinyl-based particles, urethane-based particles, fluorine-based particles, and nitrile-based particles. Among them, silicone-based particles and vinyl-based particles are preferable.

The silicone-based particles are preferably silicone-hardened products having a diorganosiloxane unit represented by the following formula (1) as a repeating unit and having rubber elasticity.

[Chemical Formula 1]

In the formula (1), R ¹ represents 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, And 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 and fluorine, and hydrocarbon groups in which a halogen atom is substituted with an epoxy group, an amino group, a mercapto group, an acryloxy group, Reactive group-containing organic groups. a is preferably from 5 to 5,000, and more preferably from 10 to 1,000.

The reaction mechanism of the curing reaction for forming the silicon-based particles may be a condensation reaction of a methoxysilyl group (≡SiOCH ₃ ) and a hydroxysilyl group (≡SiOH), or a condensation reaction of a mercapto silyl group (≡SiSH) and a vinyl silyl 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 perform the reaction. That is, in the present invention, it is preferable to make a composition for curing an addition reaction of (a) a vinyl group-containing organopolysiloxane and (b) an organohydrogenpolysiloxane in the presence of (c) a platinum catalyst.

Specific examples of such component (a) include compounds represented by the following formula (2).

(2)

In the formula (2), R ¹ is the same as R ¹ in the formula (1), but preferably has no 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?

Examples of the organohydrogenpolysiloxane as the component (b) include compounds represented by the following formula (3).

(3)

In the formula (3), R ² is an unsubstituted or substituted monovalent hydrocarbon group usually bonded to a silicon atom of 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms excluding aliphatic unsaturated bonds, 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 An aryl group such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group; an aralkyl group such as a benzyl group, a phenylethyl group and a phenylpropyl group; and an aryl group such as a phenyl group, a butyryl group, Group in which some or all of the hydrogen atoms of the group are substituted with halogen atoms such as fluorine, bromine and chlorine, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group and a trifluoropropyl group. The unsubstituted or substituted monovalent hydrocarbon group represented by R ² is preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group. F is a positive number satisfying 0.7 to 2.1, g is 0.001 to 1.0, and f + g satisfies 0.8 to 3.0, preferably 1.0 to 2.0, g is 0.01 to 1.0, and f + g is 1.5 to 2.5.

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

[Chemical Formula 4]

In the formula (4), R ¹ is the same as R ¹ in the formula (1), but preferably has no aliphatic unsaturated bond. m is 0 or 1, n is 2 or 3, and m + n = 3, p is 0 or a positive number, q is 0 or a positive number, and 2m + q?

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

The method for producing the silicone-based particles using the components (a) to (c) is not particularly limited as long as the components (a) and (b) are reacted in the presence of the component (c) For example, a method of curing the component (a) and a component (b) in a high-temperature spray dryer, a method of curing the component in an organic solvent, a method of curing the component after the emulsion is cured, and the like. In order to improve the dispersibility of the silicone-based particles, a polyorganosilsesquioxane resin may be coated on the surface of the silicon-based particles as necessary.

As described above, the light-shielding flexible particles can be produced by a method in which a coloring agent is contained in the flexible particles by dispersing a coloring agent such as a pigment or a dye in the raw material of the flexible particles as the light shielding agent in the step of producing the flexible particles . ≪ / RTI > Specifically, silicone-based particles having light shielding properties can be obtained by dispersing or dissolving colorants such as pigments or dyes in advance in the components (a) to (c) and then performing a curing reaction. When the colorant is dispersed in the components (a) to (c), it is preferable to add a surfactant or dispersant having affinity to both the silicone component and the colorant. By providing a coloring agent as a light shielding agent before the curing reaction, the coloring agent is prevented from being eluted or peeled off from the particles, and liquid crystal contamination can be suppressed.

As described above, the above-mentioned light-blocking flexible particles can be produced by preparing a flexible particle having no light-shielding property and then coating the surface of the flexible particle with a coloring agent, or after producing a flexible particle having no light- And then absorbing the colorant to the flexible particles. Specifically, the light-shielding property can be imparted by dispersing the silicone-based particles having no light-shielding property in a medium in which the coloring agent is dissolved and stirring the silicone-based particles for a predetermined period of time to fix the coloring agent to the silicone-based particles. Further, By using the same compounding device, the light-shielding property can be given by fixing the coloring agent on the surface of the silicon-based particles having no light shielding property.

A method of adsorbing a polymerizable colorant on the surface of the silicone-based particles having no light shielding property may also be used. That is, the light-shielding property can be given 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 particle having no light shielding property. Specifically, the polymer can be precipitated on the surface of the silicon-based particles by performing emulsion polymerization, so-called pre-polymerization, dispersion polymerization or the like as a monomer to be a raw material of the polymer in the presence of silicon particles having no light shielding property.

Examples of the polymer that precipitates on the surface of the silicon-based particles include polymers obtained by polymerizing acetylene and its derivatives, aniline and its derivatives, furan and its derivatives, pyrrole and its derivatives, and thiophene and its derivatives . Among them, polypyrrole having excellent black coloring property is preferable.

As the silicon-based particles having no light shielding property, commercially available silicon-based particles may be used.

Examples of commercially available silicone-based particles include KMP-594, KMP-597, KMP-598, KMP-600, KMP-601 and KMP-602 (manufactured by Shinetsu Silicones) -9215 (manufactured by Toray-Dow Corning), and the like, and they can be classified and used. The silicon-based particles having no light shielding property may be used alone or in combination of two or more.

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

The (meth) acrylic particles can be obtained by polymerizing a monomer as a raw material by a known method. Specifically, there may be mentioned, for example, suspension polymerization of monomers in the presence of a radical polymerization initiator, and seed polymerization by swelling the seed particles by absorbing the monomers to non-crosslinked seed particles in the presence of a radical polymerization initiator.

In the present specification, the term "(meth) acryl" means acryl or methacryl.

Examples of the monomer to be a raw material for forming the (meth) acrylic particles include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) (Meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (Meth) acrylate such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (Meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, nitrile-containing monomers such as (meth) acrylonitrile, Sites of such fluorine-containing (meth) the monofunctional monomers such as acrylates. Of these, alkyl (meth) acrylates are preferable in that the Tg of the homopolymer is low and the amount of deformation when a 1 g load is applied can be increased.

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

Further, in order to obtain a crosslinked structure, it is preferable to use tetramethylolmethane tetra (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, , Isocyanuric acid skeletal tri (meth) acrylate, or the like may be used. Among them, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate and the like are preferable in that the molecular weight between crosslinking points is large and the amount of deformation when a 1 g load is applied can be increased. Poly (tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate.

The amount of the crosslinking monomer to be used is preferably 1% by weight, and more preferably 90% by weight, in the whole monomer. When the crosslinking monomer is used in an amount of 1% by weight or more, the solvent resistance is increased, and problems such as swelling upon kneading with various seal raw materials are not caused, and the polymer is easily dispersed uniformly. When the amount of the crosslinkable monomer used is 90% by weight or less, the recovery rate can be lowered, and problems such as springback are less likely to occur. A more preferable lower limit of the amount of the crosslinkable monomer to be used is 3% by weight, and a more preferable upper limit is 80% by weight.

In addition to these acrylic monomers, styrene monomers such as styrene and? -Methylstyrene, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether, vinyl acetate, vinyl butyrate, vinyl laurate, Unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; halogen-containing monomers such as vinyl chloride, vinyl fluoride and chlorostyrene; and vinyl monomers such as triallyl (isocyanurate), triallyl Even when monomers such as melitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether,? - (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene and vinyltrimethoxysilane are used do.

As the vinyl-based particles, for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles, or the like may be used.

Examples of commercially available urethane-based particles include Art Pearl (manufactured by Negami Industrial Co., Ltd.) and Dynamic Beads (manufactured by Dainichi Seisakusho Co., Ltd.), which can be classified and used.

With respect to the vinyl-based particles and the urethane-based particles, light shielding properties can be imparted by the same method as that of the silicon particles.

The preferable lower limit of the hardness of the light-blocking flexible particles is 10, and the preferable upper limit is 50. [ When the hardness of the light-shielding flexible particles is more than 50, the resulting sealing agent for a liquid crystal dropping method may be poor in adhesiveness or a gap defect may occur in the obtained liquid crystal display element. A more preferable lower limit of the hardness of the light-shielding flexible particles is 20, and a more preferable upper limit is 40. [

In the present specification, the hardness of the light-blocking flexible particles means a durometer A hardness measured by a method in accordance with JIS K 6253.

Examples of the light shielding agent to be contained in the above-mentioned soft particles include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin coated carbon black and black dye. Among them, titanium black is preferable.

The titanium black is a material having a higher transmittance to light in the vicinity of the ultraviolet ray region, particularly in the wavelength range of 370 to 450 nm, as compared with the average transmittance in the wavelength range of 300 to 800 nm. That is, the titanium black is a light-shielding agent having properties of imparting light shielding properties to the light-shielding flexible particles by sufficiently shielding light having a wavelength in the visible light region while transmitting light having a wavelength in the vicinity of the ultraviolet ray region. Therefore, as a polymerization initiator to be described later, the photocurability of the sealant for a liquid crystal dropping process of the present invention 1 can be improved by using a material capable of initiating the reaction with light having a wavelength (370 to 450 nm) at which the transmittance of the titanium black becomes high Can be increased. On the other hand, as the light shielding agent to be contained in the above-mentioned flexible particles, a material having a high insulating property is preferable, and titanium black is also suitable as a light shielding agent having a high insulating property.

The titanium black preferably has an optical density (OD value) of 3 or more per 1 mu m, and more preferably 4 or more. The higher the light shielding property of the titanium black is, the better, and the preferable upper limit to the OD value of the titanium black is not particularly limited, but is usually 5 or less.

The titanium black exhibits a sufficient effect even if it is not surface-treated. However, the titanium black may be one having a surface treated with an organic component such as a coupling agent, or a titanium oxide such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide Or a titanium black coated with an inorganic component such as titanium black. Among them, it is preferable that the organic component is treated because it can further improve the insulating property.

The liquid crystal drop sealing agent using titanium black as a light-shielding agent contained in the above-mentioned flexible particles has a sufficient light-shielding property. Therefore, the obtained liquid crystal display element is excellent in image display quality without leakage of light, high contrast, .

Examples of commercially available titanium black include 12S, 13M, 13M-C and 13R-N (both manufactured by Mitsubishi Materials Corporation) and Tirac D (manufactured by Ako Kasei Co., Ltd.).

The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, and the upper limit is preferably 30 m 2 / g, more preferably 15 m 2 / g, and still more preferably 25 m 2 / g.

The lower limit of the volume resistivity of the titanium black is preferably 0.5 Ω · cm, and the upper limit thereof is preferably 3 Ω · cm. More preferably, the lower limit is 1 Ω · cm and the upper limit is 2.5 Ω · cm.

The preferred lower limit of the primary particle diameter of the light-shielding agent contained in the above-mentioned flexible particles is 50 nm, and the preferred upper limit is 500 nm. When the primary particle diameter of the light-shielding agent contained in the above-mentioned soft particles is less than 50 nm, the viscosity and the tin consumption may be increased, secondary aggregation may occur, and the dispersibility into the particles may remarkably decrease. If the diameter of the primary particles of the light-shielding agent contained in the above-mentioned flexible particles exceeds 500 nm, the dispersibility into the particles may deteriorate or the particles themselves may become hard and fragile. A more preferable lower limit of the primary particle diameter of the light-shielding agent contained in the above-mentioned flexible particles is 70 nm, and a more preferable upper limit is 300 nm.

The content of the light-shielding agent contained in the above-mentioned flexible particles is preferably 2% by weight, and more preferably 30% by weight, based on the whole light-shielding flexible particles. When the content of the light-shielding agent contained in the above-mentioned soft particles is less than 2% by weight, sufficient light shielding property may not be obtained. If the content of the light-shielding agent contained in the above-mentioned flexible particles exceeds 30% by weight, the particles themselves may be hard and fragile. A more preferable lower limit of the content of the light-shielding agent contained in the above-mentioned flexible particles is 5% by weight, and a more preferable upper limit is 20% by weight.

The sealing agent for the liquid crystal dropping method of the present invention 1 is used for the production of a liquid crystal display element by liquid crystal dropping method.

The light-blocking flexible particles preferably have a maximum particle diameter of 100% or more of the cell gap of the liquid crystal display element. When the maximum particle diameter of the light-blocking flexible particles is less than 100% of the cell gap of the liquid crystal display element, the seal brake and liquid crystal contamination may not be sufficiently suppressed. The maximum particle diameter of the light-blocking flexible particles is 100% or more of the cell gap of the liquid crystal display element, and more preferably 5 m or more.

The preferable upper limit of the maximum particle diameter of the light-blocking flexible particles is 20 占 퐉. When the maximum particle diameter of the light-shielding flexible particles exceeds 20 m, springback may be caused to result in deterioration in the adhesiveness of the resultant liquid crystal drop sealing material, or gaps may be generated in the resulting liquid crystal display element. The more preferable upper limit of the maximum particle diameter of the light-shielding flexible particles is 15 mu m.

The maximum particle diameter of the light-blocking flexible particles is preferably 2.6 times or less of the cell gap. When the maximum particle diameter of the light-shielding flexible particles exceeds 2.6 times the cell gap, springback is caused to occur, resulting in poor adhesiveness of the obtained sealing material for a liquid crystal dropping method, or in the case where a gap defect occurs in the obtained liquid crystal display element . A more preferable upper limit of the maximum particle diameter of the light-blocking flexible particles is 2.2 times the cell gap, and a more preferable upper limit is 1.7 times the cell gap.

In the present specification, the maximum particle diameter of the light-blocking flexible particles and the average particle diameter described later mean a value obtained by measuring a particle before mixing with a sealant using a laser diffraction particle size distribution measurement apparatus do. As the laser diffraction distribution measuring apparatus, a master sizer 2000 (manufactured by Maru Reflections Co., Ltd.) or the like can be used. The cell gap of the liquid crystal display element is not limited because it varies depending on the display element, but the cell gap of a general liquid crystal display element is 2 to 10 mu m.

The light-shielding flexible particles preferably have a content ratio of particles having a particle diameter of 5 占 퐉 or more among the particle size distributions of the light-shielding flexible particles measured by the laser diffraction distribution measuring apparatus to 60% or more by volumetric frequency. If the content ratio of the particles having a particle diameter of 5 占 퐉 or more is less than 60% by volume frequency, the seal brake and liquid crystal contamination may not be sufficiently suppressed. And the content ratio of the particles having a particle diameter of 5 mu m or more is more preferably 80% or more.

The above-mentioned light-shielding flexible particles should preferably be such that particles having a cell gap of 100% or more of the cell gap of the liquid crystal display element are dispersed in 70% or more of the particle size distribution in the whole light- % Or more, more preferably 100% or more of the cell gap of the liquid crystal display element.

The preferable lower limit of the average particle diameter of the light-blocking flexible particles is 2 mu m, and the preferable upper limit is 15 mu m. When the average particle diameter of the light-blocking flexible particles is less than 2 탆, the elution of the sealant into the liquid crystal may not be sufficiently prevented in some cases. When the average particle diameter of the light-shielding flexible particles exceeds 15 mu m, the obtained sealing agent for a liquid crystal dropping method may be poor in adhesiveness or a gap defect may occur in the obtained liquid crystal display element. A more preferable lower limit of the average particle diameter of the light-blocking flexible particles is 4 탆, and a more preferable upper limit is 12 탆.

As the light-blocking flexible particles, two or more light-blocking flexible particles having different maximum particle diameters may be mixed and used. That is, the light-blocking flexible particles having a maximum particle diameter of less than 100% of the cell gap of the liquid crystal display element and the light-blocking flexible particles having a maximum particle diameter of 100% or more of the cell gap of the liquid crystal display element may be mixed and used.

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

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

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

The light-shielding flexible particles can be classified within the above-described range by classifying even the maximum particle diameter, the average particle diameter, and the CV value outside the above-described range, thereby making the maximum particle diameter, the average particle diameter, and the CV value within the above-described range. Further, the light-blocking flexible particles having a particle diameter of less than 100% of the cell gap of the liquid crystal display element do not contribute to suppression of the generation of seal break and liquid crystal contamination, and if they are added to the sealant, It is preferable to remove it by classification.

As a method of classifying the light-shielding flexible particles, for example, wet classification, dry classification, etc. may be mentioned. Among them, wet classification is preferred, and wet classification is more preferable.

The light-shielding flexible particles have a compressive displacement L1 from the original point load value when the load is applied to the reversed load value to L1, and when the load is released from the reverse load value when the load is released, Is L2, the recovery rate of L2 / L1 expressed as a percentage is preferably 80% or less. If the recovery rate of the light-shielding flexible particles exceeds 80%, the barrier function may be deteriorated to prevent the sealant from being eluted into the liquid crystal. A more preferable upper limit of the recovery rate of the light-shielding flexible particles is 70%, and a more preferable upper limit is 60%.

The recovery rate of the light-shielding flexible particles can be derived by applying a constant load (1 g) to one particle by using a micro compression tester and analyzing the recovery behavior after removing the load.

It is preferable that the light-shielding flexible particles have a 1 g strain of 30% or more in terms of L3 / Dn as a percentage when the compressive displacement when giving a load of 1 g is L3 and the particle diameter is Dn. If the 1 g deformation of the light-shielding flexible particles is less than 30%, the barrier function may be deteriorated to prevent the sealant from being eluted into the liquid crystal. A more preferred lower limit of 1 g modification of the light-shielding flexible particles is 40%.

The 1 g deformation of the light-shielding flexible particles can be measured by placing a load of 1 g per particle using a micro compression tester and measuring the amount of displacement at that time.

It is preferable that the light-shielding flexible particles have a fracture strain of 50% or more as a percentage of L4 / Dn when the compression displacement at the point of time when the particles are broken is L4 and the particle diameter is Dn. When the breaking strain of the light-blocking flexible particles is less than 50%, the barrier becomes a function to prevent the sealant from being eluted into the liquid crystal. A more preferable lower limit of the fracture strain of the light-shielding flexible particles is 60%.

The fracture strain of the light-shielding flexible particles can be measured by using a micro compression tester to load a single particle and measuring the amount of displacement at which the particle is broken. The compressed displacement L4 is calculated as the point at which the displacement amount discontinuously increases with respect to the load load as a point at which the particles are broken. It is considered that the fracture strain is 100% or more when the load is not destroyed by deforming even if the load is increased.

The light-shielding flexible particles preferably have a glass transition temperature lower limit of -200 deg. C and a preferable upper limit of 40 deg. When the glass transition temperature of the light-shielding flexible particles is -200 DEG C or higher, the effect of suppressing the seal brakes and liquid crystal contamination is better as the lower the glass transition temperature is. When the glass transition temperature is lower than -200 DEG C, problems occur in handling of the particles, And the liquid crystal is liable to collapse, so that the sealant and the liquid crystal come into contact with each other during the curing, and liquid crystal contamination may occur. When the glass transition temperature of the light-blocking flexible particles exceeds 40 캜, a gap defect may occur. A more preferable lower limit of the glass transition temperature of the light-blocking flexible particles is -150 deg. C, and a more preferable upper limit is 35 deg.

The glass transition temperature of the light-shielding flexible particles is a value measured by differential scanning calorimetry (DSC) based on JIS K 7121 "Method of measuring transition temperature of plastics".

The light-shielding flexible particles preferably have a degree of blackening of 10% or less, more preferably 5% or less. The light shielding property of the light-shielding flexible particles is preferably as low as possible. The lower limit of the blackness of the light-shielding flexible particles is not particularly limited, but is usually 0.05% or more.

Further, the degree of blackening of the light-blocking flexible particles can be evaluated as the maximum value of the spectral transmittance in the whole wavelength range of the visible light region of 400 to 700 nm. Specifically, a thin film-like polymer having the same composition as the particles to be evaluated and having a thickness of 1 mm is prepared as a sample for measuring the degree of blackness, and the spectral transmittance at the entire wavelength of the visible light region is measured for the sample using a spectrophotometer .

The content of the light-blocking flexible particles is preferably 3 parts by weight, and more preferably 70 parts by weight, based on 100 parts by weight of the curable resin. When the content of the light-blocking flexible particles is less than 3 parts by weight, the elution of the sealant into the liquid crystal may not be sufficiently prevented. When the content of the light-shielding flexible particles exceeds 70 parts by weight, the obtained sealing agent for a liquid dropping process may be poor in adhesiveness. The lower limit of the content of the light-blocking flexible particles is more preferably 5 parts by weight, more preferably 60 parts by weight, still more preferably 10 parts by weight, still more preferably 50 parts by weight.

The liquid crystal drop sealing agent of the present invention 1 contains a curable resin.

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

The liquid crystal drop sealing agent of the present invention 1 preferably contains a (meth) acrylic resin as a curable resin and a radical polymerization initiator described later as a polymerization initiator, It is possible to quickly cure the liquid crystal dropping sealant of the first aspect of the present invention, and it is possible to sufficiently suppress the occurrence of liquid crystal contamination even in a liquid crystal display element of a narrow frame design. Therefore, It is more preferable to contain a radical polymerization initiator.

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

In the present specification, the term "(meth) acrylic resin" means a resin having a (meth) acryloyl group, and the "(meth) acryloyl group" means an acryloyl group or a methacryloyl group it means. The above-mentioned "epoxy (meth) acrylate" means a compound obtained by reacting all epoxy groups in an epoxy resin with (meth) acrylic acid.

Examples of the epoxy resin as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl bisphenol A Type epoxy resin, a hydrogenated bisphenol type epoxy resin, a propylene oxide-added bisphenol A type epoxy resin, a resorcinol type epoxy resin, a biphenyl type epoxy resin, a sulfide type epoxy resin, a diphenyl ether type epoxy resin, a dicyclopentadiene type Epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolac type epoxy resin, naphthalene phenol novolak type epoxy resin, Alkylpolyol type epoxy resins, rubber modified epoxy resins, glycidyl esterification There may be mentioned water, a bisphenol A-type episulfide resins.

Examples of commercially available bisphenol A type epoxy resins include jER828EL, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation) and Epiclon 850-S (manufactured by DIC Corporation).

Examples of commercially available bisphenol F type epoxy resins include, for example, jER806 and jER4004 (all manufactured by Mitsubishi Chemical Corporation).

Examples of commercially available bisphenol S epoxy resins include Epiclon EXA1514 (manufactured by DIC Corporation) and the like.

Examples of commercially available 2,2'-diallyl bisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Yakusho Co., Ltd.) and the like.

Examples of the hydrogenated bisphenol-type epoxy resin commercially available include Epiclon EXA7015 (manufactured by DIC Corporation) and the like.

Examples of the propylene oxide-added bisphenol A type epoxy resin commercially available include EP-4000S (manufactured by ADEKA) and the like.

Examples of commercially available resorcinol-type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation) and the like.

Examples of commercially available biphenyl type epoxy resins include, for example, jERYX-4000H (manufactured by Mitsubishi Chemical Corporation).

Examples of commercially available sulfide epoxy resins include YSLV-50TE (Shin-Nittsu Co., Ltd.).

Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Shin Nittsu Chemical Co., Ltd.).

Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA) and the like.

Examples of commercially available naphthalene type epoxy resins include Epiclon HP4032 and Epiclon EXA-4700 (both manufactured by DIC).

Examples of commercially available phenol novolak epoxy resins include Epiclon N-770 (manufactured by DIC Corporation) and the like.

Examples of the commercially available orthocresol novolak type epoxy resin include Epiclon N-670-EXP-S (manufactured by DIC Corporation) and the like.

Examples of commercially available dicyclopentadiene novolak type epoxy resins include Epiclon HP7200 (manufactured by DIC Corporation) and the like.

Commercially available examples of the biphenyl novolak type epoxy resin include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.

Examples of commercially available naphthalene phenol novolak type epoxy resins include ESN-165S (Shin-Nittsu Kagaku Kagaku).

Examples of commercially available glycidylamine type epoxy resins include jER 630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Company).

Examples of commercially available products of the alkyl polyol type epoxy resin include ZX-1542 (manufactured by Shin Nittsu Chemical Co., Ltd.), Epiclon 726 (manufactured by DIC), Epolight 80MFA (manufactured by Kyowa Chemical Industry Co., Ltd.) EX-611 (manufactured by Nagase ChemteX Corporation), and the like.

Examples of the commercially available rubber-modified epoxy resin include YR-450 and YR-207 (both manufactured by Shin-Nittsu Kagaku Kagaku Kasei Co., Ltd.) and EPOLED PB (manufactured by Daicel Chemical Industries, Ltd.).

Examples of commercially available glycidyl ester compounds include, for example, Denacol EX-147 (manufactured by Nagase ChemteX).

Examples of commercially available bisphenol A episulfide resins include jERYL-7000 (manufactured by Mitsubishi Chemical Corporation) and the like.

Examples of other commercially available epoxy resins include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Shin Nittsu Kagaku Kagaku), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 EXA-7120 (manufactured by DIC Corporation), and TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 (all manufactured by Daicel Alnex Co., Ltd.), which are commercially available from among the above epoxy (meth) Epoxy ester M-600A, Epoxy ester 40EM, Epoxy ester 70PA, Epoxy ester (manufactured by Shin-Nakamura Chemical Co., Ltd.), EA-1010, EA-1020, EA-5323, EA-5520, EA- Epoxy ester 300 M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA- 141, Denacol acrylate DA-314, Denacol acrylate DA-911 (all manufactured by Nagase Chemtech), and the like.

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

Examples of the monofunctional ester compound obtained by reacting a compound having a hydroxyl group in (meth) acrylic acid include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isobutyl (meth) acrylate, Acrylates such as stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (Meth) acrylate, benzyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy dicarboxylic acid (Meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, Acrylate such as propyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) (Meth) acrylate, isopropyl (meth) acrylate, isopropyl (meth) acrylate, isopropyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (Meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acryloyloxyethyl succinic acid, 2- (meth) (Meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, and the like.

Examples of the bifunctional functional group in the ester compound include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di 2-ethyl-1,3-propanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, (Meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di Diethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene oxide adduct bisphenol A di (meth) acrylate, ethylene oxide adduct bisphenol A di (meth) acrylate, ethylene oxide adduct bisphenol F di Acrylate, dimethyl Diethylene glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-ethylhexyl glycoldi (meth) acrylate, (Meth) acrylate, polycarbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone Acrylate, lactone (meth) acrylate, and polybutadiene diol di (meth) acrylate.

(Meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide addition trimethylolpropane tri (meth) acrylate, ethylene oxide adduct Trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, ethylene oxide added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) (Meth) acrylate, trimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide addition glycerin tri (Meth) acryloyloxyethyl phosphate, and the like.

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

Examples of the isocyanate as a raw material of the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate , MDI, hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornadiisocyanate, tolylidine diisocyanate, xylylene diisocyanate (XDI), diphenylmethane-4,4'-diisocyanate , Hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, and 1,6,10-undecane triisocyanate.

Examples of the isocyanate include polyols such as ethylene glycol, glycerin, sorbitol, trimethylol propane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol and polycaprolactone diol, and excess isocyanate Chain extended isocyanate compound obtained by the reaction of the chain extender can also be used.

Examples of the (meth) acrylic acid derivative having a hydroxyl group which is a raw material of the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like; and aromatic hydrocarbons such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, Mono (meth) acrylate or di (meth) acrylate of a trivalent alcohol such as mono (meth) acrylate of a dihydric alcohol such as glycol, etc .; trimethylol ethane, trimethylol propane or glycerin; bisphenol A type epoxy acrylate Epoxy (meth) acrylate, and the like.

Examples of commercially available urethane (meth) acrylate include M-1100, M-1200, M-1210 and M-1600 (all manufactured by TOAGOSEI CO., LTD.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (all manufactured by Daicel Alnex), ARTICLE UN-9000H, ARTICLE UN- U-122P, U-108A, U-340P, U (all manufactured by Negami Industrial Co., Ltd.), Art Resin UN- 4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-4000 (all manufactured by Shin-Nakamura Chemical Industries Co., Ltd.), UA-4400, UA-340P, UA-3HA, UA-7200, U-2061BA, U-10H, U-122A, U- (All manufactured by Kyoeisha Chemical Co., Ltd.), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA- And the like.

The (meth) acrylic resin preferably has a hydrogen-bonding unit such as an -OH group, an -NH- group, or an -NH ₂ group in view of suppressing an adverse influence on a liquid crystal. It is preferable that the (meth) acrylic resin has 2 to 3 (meth) acryloyl groups in the molecule for reasons of high reactivity.

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

Examples of the epoxy resin include an epoxy resin as a raw material for synthesizing the epoxy (meth) acrylate, a partial (meth) acryl-modified epoxy resin, and the like.

In the present specification, the term "part (meth) acrylic modified epoxy resin" means a resin having at least one epoxy group and at least one (meth) acryloyl group in one molecule. For example, a resin having two or more epoxy groups Can be obtained by reacting a part of the epoxy group with (meth) acrylic acid.

Examples of commercially available partial (meth) acrylic-modified epoxy resins include UVACURE 1561 (manufactured by Daicel Alnex).

When the epoxy resin is contained as the curable resin, the preferable upper limit of the ratio of the epoxy group to the total amount of the (meth) acryloyl group and the epoxy group in the whole curable resin is 50 mol%. When the ratio of the epoxy groups is more than 50 mol%, the solubility of the sealant for a liquid crystal dripping method obtained in the liquid crystal becomes high, causing liquid crystal contamination, and the obtained liquid crystal display element may have poor display performance. A more preferable upper limit of the ratio of the epoxy groups is 20 mol%.

The sealant for liquid crystal dropping method of the present invention 1 contains a polymerization initiator and / or a thermosetting agent.

Among them, it is preferable to contain a radical polymerization initiator as a polymerization initiator. The springback is influenced not only by the maximum particle diameter of the light-blocking flexible particles but also by the curing rate of the sealant. Since the radical polymerization initiator can remarkably accelerate the curing rate as compared with the thermosetting agent, the use of the radical polymerization initiator in combination with the light-shielding flexible particles makes it possible to suppress the occurrence of springback, which is likely to occur by the light- It can be made excellent.

Examples of the radical polymerization initiator include a thermal radical polymerization initiator that generates a radical by heating, and a photo radical polymerization initiator that generates a radical by light irradiation.

As described above, since the curing rate of the radical polymerization initiator is remarkably faster than that of the thermosetting agent, the use of the radical polymerization initiator suppresses occurrence of seal break and liquid crystal contamination, It is possible to suppress springback which is likely to occur.

Among them, the obtained liquid sealant sealant can be quickly cured by heat, so that the radical polymerization initiator preferably contains a thermal radical polymerization initiator.

Examples of the thermal radical polymerization initiator include azo compounds, organic peroxides, and the like. Among them, a polymeric azo initiator comprising a polymeric azo compound is preferable.

In the present specification, the polymer azo initiator means a compound having an azo group and having a number average molecular weight of 300 or more, which produces a radical capable of curing the (meth) acryloyloxy group by heat.

The preferred lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferred upper limit is 300,000. If the number average molecular weight of the polymeric azo initiator is less than 1000, the polymeric azo initiator may adversely affect the liquid crystal. If the number average molecular weight of the polymeric azo initiator exceeds 30,000, mixing with a curable resin may become difficult. A more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, a more preferable upper limit is 100,000, a more preferable lower limit is 10,000, and a more preferable upper limit is 90,000.

In the present specification, the number average molecular weight is a value obtained by conducting gel permeation chromatography (GPC) and calculating by polystyrene conversion. As a column for measuring the number average molecular weight by polystyrene conversion by GPC, for example, Shodex LF-804 (manufactured by Showa Denko K.K.) can be mentioned.

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

As the polymeric azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded through the azo group, it is preferable that the polymeric azo initiator has a polyethylene oxide structure. Examples of such a polymeric azo initiator include a polycondensation product of 4,4'-azobis (4-cyanopentanoic acid) and a polyalkylene glycol, 4,4'-azobis (4-cyanopentanoic acid And VPD-0601, VPE-0601, VPS-0501, and VPS-1001 (all of which are manufactured by Wako Pure Chemical Industries, Ltd.), and polycondensates of polydimethylsiloxane having terminal amino groups, and specific examples thereof include VPE- And the like.

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, peroxydicarbonate, and the like.

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

Examples of commercially available photoradical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACUREOXE 01, DAROCUR TPO (all from BASF Japan), benzoin methyl ether, Ether, and benzoin isopropyl ether (all of which are manufactured by TOKYO CHEMICAL INDUSTRIES, LTD.).

As the polymerization initiator, a cation polymerization initiator may also be used. As the cationic polymerization initiator, a photocathon polymerization initiator can be suitably used. The photo cationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generator type or a nonionic photoacid generator type.

Examples of the photocathione polymerization initiator include an onium salt such as an aromatic diazonium salt, an aromatic halonium salt and an aromatic sulfonium salt, an iron-allene complex, a titanocene complex, an organometallic complex such as an aryl silanol- And logistics.

Examples of commercially available photocathione polymerization initiators include ADEKA OPTOMER SP-150 and ADEKA OPTOMER SP-170 (all manufactured by ADEKA).

The content of the polymerization initiator is preferably 0.1 part by weight, and more preferably 30 parts by weight, based on 100 parts by weight of the curable resin. When the content of the polymerization initiator is less than 0.1 part by weight, the obtained sealing agent for dropwise addition may not be sufficiently cured. If the content of the polymerization initiator is more than 30 parts by weight, the storage stability of the resultant liquid crystal drip sealing agent may be lowered. A more preferable lower limit of the content of the polymerization initiator is 1 part by weight, and a more preferable upper limit is 10 parts by weight, and a more preferable upper limit is 5 parts by weight.

Examples of the heat curing agent include organic acid hydrazide, imidazole derivatives, amine compounds, polyhydric phenol compounds, and acid anhydrides. Among them, solid organic acid hydrazide is suitably used.

The solid organic acid hydrazide includes, for example, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, (All manufactured by Ajinomoto Fine Techno Co., Ltd.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Industries, Ltd.), and the like, and commercially available products include, for example, Amicure VDH, Amicure UDH ), MDH (manufactured by Nippon Fine Chemicals), and the like.

The content of the thermosetting agent is preferably 1 part by weight, and more preferably 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the thermosetting agent is less than 1 part by weight, the obtained liquid crystal dropping sealant may not be sufficiently thermally cured. If the content of the thermosetting agent exceeds 50 parts by weight, the viscosity of the resultant liquid crystal drop sealing agent becomes excessively high and the coating property may be deteriorated. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.

The sealant for liquid crystal dropping method of the present invention 1 preferably contains a curing accelerator. By using the curing accelerator, the sealant can be sufficiently cured even without heating at a high temperature.

Examples of the curing accelerator include polycarboxylic acids having an isocyanuric ring skeleton and epoxy resin amine adducts. Specific examples thereof include tris (2-carboxymethyl) iso (2-carboxyethyl) isocyanurate, tris (3-carboxypropyl) isocyanurate, and bis (2-carboxyethyl) isocyanurate.

The content of the curing accelerator is preferably 0.1 part by weight, and more preferably 10 parts by weight, based on 100 parts by weight of the curable resin. If the content of the curing accelerator is less than 0.1 parts by weight, the resulting sealant for liquid crystal dropping treatment may not be sufficiently cured, or heating at high temperature may be required for curing. When the content of the curing accelerator is more than 10 parts by weight, the obtained sealing agent for dropwise addition of a liquid crystal may have poor adhesiveness.

The sealing agent for a liquid crystal dropping method of the present invention 1 preferably contains a filler for the purpose of improving the viscosity, improving the adhesion due to the stress dispersion effect, improving the coefficient of linear expansion, improving moisture resistance of the cured product, and the like.

Examples of the filler include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, magnesium hydroxide, aluminum hydroxide , Inorganic fillers such as glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay and aluminum nitride; inorganic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, core shell acrylate copolymer fine particles And the like. These fillers may be used alone or in combination of two or more.

The content of the filler is preferably 5% by weight, and more preferably 70% by weight, based on the total weight of the liquid crystal drop sealing agent. If the content of the filler is less than 5% by weight, effects such as improvement in adhesion may not be sufficiently exhibited. When the content of the filler exceeds 70% by weight, the viscosity of the resultant liquid seal agent for a drip feed can be increased and the coating property may be deteriorated. A more preferable lower limit of the content of the filler is 10% by weight, and a more preferable upper limit is 50% by weight.

It is preferable that the sealing agent for a liquid crystal dropping method of the present invention 1 contains a silane coupling agent. The silane coupling agent serves mainly as an adhesion assisting agent for favorably bonding a sealant and a substrate.

The silane coupling agent is excellent in the effect of improving adhesion of a substrate or the like and is capable of inhibiting the outflow of the curable resin into the liquid crystal by chemical bonding with the curable resin, Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane and the like are suitably used Is used. These silane coupling agents may be used alone or in combination of two or more.

The content of the silane coupling agent is preferably 0.1% by weight, and more preferably 20% by weight, based on the total weight of the liquid crystal drop sealing agent. If the content of the silane coupling agent is less than 0.1% by weight, the effect of blending the silane coupling agent may not be sufficiently exhibited. If the content of the silane coupling agent is more than 20% by weight, the obtained sealant for dropwise addition may contaminate the liquid crystal. A more preferable lower limit of the content of the silane coupling agent is 0.5% by weight, and a more preferable upper limit is 10% by weight.

The sealing agent for a liquid crystal dropping method of the present invention 1 may contain, in addition to the light-shielding flexible particles, a light-shielding agent not contained in the flexible particles. As the light-shielding agent, the same light-shielding agent as that contained in the above-described flexible particles can be used.

The content of the light-shielding agent is preferably 5% by weight, and more preferably 80% by weight, based on the total weight of the liquid crystal drop sealing agent. If the content of the light-shielding agent is less than 5% by weight, sufficient light-shielding properties may not be obtained. If the content of the light-shielding agent exceeds 80% by weight, the resulting liquid crystal dipping method sealant may adhere to the substrate and the strength after curing may deteriorate, or the image-forming property may deteriorate. A more preferable lower limit of the content of the light shielding agent is 10% by weight, and a more preferable upper limit is 70% by weight. A more preferable lower limit is 30% by weight, and a more preferable upper limit is 60% by weight.

The sealing agent for a liquid crystal dropping method of the present invention 1 may further contain a reactive diluent for viscosity adjustment, a spacer such as polymer beads for adjusting the panel gap, a defoaming agent, a leveling agent, a polymerization inhibitor, Of an additive.

The method for manufacturing the liquid crystal dropping method sealant of the first aspect of the present invention is not particularly limited and a method for producing the sealant for a liquid crystal dropping method of the present invention is not particularly limited and, for example, , A method of mixing an additive such as a curable resin, a polymerization initiator and / or a thermosetting agent, a light-shielding flexible particle, and a silane coupling agent added as needed.

The preferable lower limit of the viscosity measured at 25 캜 and 1 rpm using an E-type viscometer in the liquid crystal drop sealing method of the present invention 1 is 50,000 Pa · s, and the preferable upper limit is 500,000 Pa · s . When the viscosity is less than 50,000 Pa · s or more than 500,000 Pa · s, the workability when the liquid crystal drop sealing agent is applied to a substrate or the like may be deteriorated. A more preferred upper limit of the viscosity is 400,000 Pa 占 퐏.

The sealant for a liquid crystal dropping method of the present invention 1 preferably has an OD value of 2 or more, more preferably 3 or more. The higher the light shielding property of the sealant for a liquid crystal drop method of the present invention 1 is, the higher the higher the better. The upper limit for the OD value of the liquid crystal drop sealer of the present invention 1 is not particularly limited, but is usually 6 or less.

The upper and lower conductive materials can be produced by blending the conductive fine particles in the liquid crystal drop sealing agent of the first invention. The sealing agent for a liquid crystal dropping method of the present invention 1 and the upper and lower conductive materials containing the conductive fine particles are also one of the present invention.

As the conductive fine particles, for example, a metal ball, a conductive fine metal particle formed on the surface of the resin fine particle, or the like can be used. Among them, the conductive metal layer formed on the surface of the resin fine particles is preferable because conductive connection is possible without damaging the transparent substrate or the like due to excellent elasticity of the resin fine particles.

The liquid crystal display device using the liquid crystal drop sealing material of the first invention or the vertical conduction material of the present invention is also one of the present invention.

As a method of producing the liquid crystal display element of the present invention, for example, two transparent substrates such as a glass substrate or a polyethylene terephthalate substrate having an electrode such as an ITO thin film are prepared, A step of forming a rectangular seal pattern by a screen printing or a dispenser application of a sealant for a dropping process, a sealant for a liquid crystal dropping process according to the first aspect of the invention, and the like, And a method of heating and curing the sealing agent for a liquid crystal dropping method of the present invention 1, and the like. Before the step of heating and curing the liquid crystal dropping method sealant of the first aspect of the present invention, a step of irradiating light such as ultraviolet rays to the seal pattern part to cure the sealant may be performed.

Next, the second aspect of the present invention will be described in detail.

The light-blocking flexible silicon particles of the second invention are formed by containing a light shielding agent in the silicon-based particles. The light-blocking flexible silicone particles of the second invention can be suitably used as the light-shielding flexible particles contained in the liquid crystal drop sealing agent of the first invention. That is, the inventor of the present invention has found that when the substrate of the liquid crystal display element is bonded by blending the light-shielding flexible silicon particles to the sealing agent, the light-blocking flexible silicon particles become a barrier between the liquid crystal element and other sealant components, The liquid crystal display element can be prevented from being eluted with the liquid crystal and the light leakage of the liquid crystal display element can be prevented, and thus the present invention 2 has been completed.

Examples of the method for containing the light-shielding agent in the silicone-based particle include a method of dispersing the coloring agent in the silicone-based particle by dispersing a coloring agent such as a pigment or a dye in the raw material of the silicon- A method of coating the surface of the silicone-based particles with a coloring agent after the silicone-based particles having no light-shielding property are prepared, a method of absorbing the coloring agent in the silicone-based particles after the silicone- .

The silicone-based particles are preferably silicone-hardened products having a diorganosiloxane unit represented by the following formula (1) as a repeating unit and having rubber elasticity.

[Chemical Formula 5]

In the formula (1), R ¹ represents 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, And 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 and fluorine, and hydrocarbon groups in which a halogen atom is substituted with an epoxy group, an amino group, a mercapto group, an acryloxy group, Reactive group-containing organic groups. a is preferably from 5 to 5,000, and more preferably from 10 to 1,000.

The curing mechanism of the silicone-based particles is preferably a condensation reaction of a methoxysilyl group (≡SiOCH ₃ ) with a hydroxysilyl group (≡SiOH) or a condensation reaction of a mercapto silyl group (≡SiSH) with a vinyl silyl group (≡SiCH═CH ₂ ) Or an addition reaction of a vinylsilyl group (≡SiCH═CH ₂ ) with an ≡SiH group, and the like. However, the addition of a (hydrosilylation) addition reaction in terms of reactivity and reaction process . That is, in the present invention, it is preferable to make a composition for curing an addition reaction of (a) a vinyl group-containing organopolysiloxane and (b) an organohydrogenpolysiloxane in the presence of (c) a platinum catalyst.

Specific examples of such component (a) include compounds represented by the following formula (2).

[Chemical Formula 6]

In the formula (2), R ¹ is the same as R ¹ in the formula (1), but preferably has no 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?

Examples of the organohydrogenpolysiloxane as the component (b) include compounds represented by the following formula (3).

(7)

In the formula (3), R ² is an unsubstituted or substituted monovalent hydrocarbon group usually bonded to a silicon atom of 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms excluding aliphatic unsaturated bonds, 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 An aryl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group, an aralkyl group such as a benzyl group, a phenylethyl group or a phenylpropyl group, or an aryl group such as a phenyl group, a butyryl group, Group in which some or all of the hydrogen atoms of the group are substituted with halogen atoms such as fluorine, bromine and chlorine, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group and a trifluoropropyl group. The unsubstituted or substituted monovalent hydrocarbon group represented by R ² is preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group. F is a positive number satisfying 0.7 to 2.1, g is 0.001 to 1.0, and f + g satisfies 0.8 to 3.0, preferably 1.0 to 2.0, g is 0.01 to 1.0, and f + g is 1.5 to 2.5.

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

[Chemical Formula 8]

In the formula (4), R ¹ is the same as R ¹ in the formula (1), but preferably has no aliphatic unsaturated bond. m is 0 or 1, n is 2 or 3, and m + n = 3, p is 0 or a positive number, q is 0 or a positive number, and 2m + q?

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

The method for producing the silicone-based particles using the components (a) to (c) is not particularly limited as long as the components (a) and (b) are reacted in the presence of the component (c) For example, a method of curing the component (a) and a component (b) in a high-temperature spray dryer, a method of curing the component in an organic solvent, a method of curing the component after the emulsion is cured, and the like. In order to further improve the dispersibility of the silicone-based particles, the surface of the silicon-based particles may be coated with a polyorganosilsesquioxane resin, if necessary.

As described above, the light-shielding flexible silicon particles can be produced by a method in which a coloring agent is contained in the silicone-based particles by dispersing a coloring agent such as a pigment or a dye in the raw material of the silicone-based particles as the light-shielding agent . Specifically, silicone-based particles having light shielding properties can be obtained by dispersing or dissolving colorants such as pigments or dyes in advance in the components (a) to (c) and then performing a curing reaction. When the colorant is dispersed in the components (a) to (c), it is preferable to add a surfactant or dispersant having affinity to both the silicone component and the colorant. By providing a coloring agent as a light shielding agent before the curing reaction, the coloring agent is prevented from being eluted or peeled off from the particles, and liquid crystal contamination can be suppressed.

As described above, the above-mentioned light-blocking flexible silicone particles can be obtained by preparing a silicone-based particle having no light shielding property and then coating the surface of the silicone-based particle with a coloring agent, or a method of producing silicone- And then absorbing the coloring agent to the silicone-based particles. Specifically, the light-shielding property can be imparted by dispersing the silicone-based particles having no light-shielding property in a medium in which the coloring agent is dissolved and stirring the silicone-based particles for a predetermined period of time to fix the coloring agent to the silicone-based particles. Further, By using the same compounding device, the light-shielding property can be given by fixing the coloring agent on the surface of the silicon-based particles having no light shielding property.

A method of adsorbing a polymerizable colorant on the surface of the silicone-based particles having no light shielding property may also be used. That is, the light-shielding property can be given 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 particle having no light shielding property. Specifically, the polymer can be precipitated on the surface of the silicon-based particles by performing emulsion polymerization, so-called pre-polymerization, dispersion polymerization or the like as a monomer to be a raw material of the polymer in the presence of silicon particles having no light shielding property.

Examples of the polymer that precipitates on the surface of the silicon-based particles include polymers obtained by polymerizing acetylene and its derivatives, aniline and its derivatives, furan and its derivatives, pyrrole and its derivatives, and thiophene and its derivatives . Among them, polypyrrole having excellent black coloring property is preferable.

As the silicon-based particles having no light shielding property, commercially available silicon-based particles may be used.

Examples of commercially available silicone-based particles include KMP-594, KMP-597, KMP-598, KMP-600, KMP-601 and KMP-602 (manufactured by Shinetsu Silicones) -9215 (manufactured by Toray-Dow Corning), and the like, and they can be classified and used. The silicon-based particles having no light shielding property may be used alone or in combination of two or more.

Examples of the light-shielding agent to be contained in the silicone-based particles include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black and resin-coated carbon black. Among them, titanium black is preferable.

The titanium black is a material having a higher transmittance to light in the vicinity of the ultraviolet ray region, particularly in the wavelength range of 370 to 450 nm, as compared with the average transmittance in the wavelength range of 300 to 800 nm. That is, the titanium black is a light-shielding agent having a property of shielding light-shielding flexible silicon particles by sufficiently shielding light having a wavelength in the visible light region while transmitting light having a wavelength in the vicinity of the ultraviolet ray region. Accordingly, for example, by using a polymerizable initiator for use in a liquid crystal drop sealing agent which can initiate a reaction with light having a wavelength (370 to 450 nm) at which the transmittance of the titanium black becomes high, The photocurability of the sealing agent for the process can be further increased. On the other hand, when used as a sealant for a liquid crystal dropping method, a material having high insulating properties is preferable as a light shielding agent contained in the silicone-based particles, and titanium black is also suitable as a light shielding material having high insulating properties.

The titanium black preferably has an optical density (OD value) of 3 or more per 1 mu m, and more preferably 4 or more. The higher the light shielding property of the titanium black is, the better, and the preferable upper limit to the OD value of the titanium black is not particularly limited, but is usually 5 or less.

The titanium black exhibits a sufficient effect even if it is not surface-treated. However, the titanium black may be one having a surface treated with an organic component such as a coupling agent, or a titanium oxide such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide Or a titanium black coated with an inorganic component such as titanium black. Among them, it is preferable that the organic component is treated because it can further improve the insulating property.

When a light-shielding flexible silicone particle containing titanium black as the light-shielding agent in the silicone-based particles is used for a liquid crystal dropping sealant, for example, the liquid crystal dropping sealant has a sufficient shading property The obtained liquid crystal display element is free from light leakage, has a high contrast, and has excellent image display quality.

Examples of commercially available titanium black include 12S, 13M, 13M-C and 13R-N (both manufactured by Mitsubishi Materials Corporation) and Tirac D (manufactured by Ako Kasei Co., Ltd.).

The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, and the upper limit is preferably 30 m 2 / g, more preferably 15 m 2 / g, and still more preferably 25 m 2 / g.

The lower limit of the volume resistivity of the titanium black is preferably 0.5 Ω · cm, and the upper limit thereof is preferably 3 Ω · cm. More preferably, the lower limit is 1 Ω · cm and the upper limit is 2.5 Ω · cm.

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

The content of the light-shielding agent contained in the silicone-based particles is preferably 2% by weight, and more preferably 30% by weight, based on the total amount of the light-blocking flexible silicon particles. When the content of the light-shielding agent contained in the silicone-based particles is less than 2% by weight, sufficient light-shielding properties may not be obtained. When the content of the light-shielding agent contained in the silicone-based particles exceeds 30% by weight, the silicone particles may be hard and easily broken. The lower limit of the content of the light-shielding agent contained in the silicone-based particles is more preferably 5% by weight, and still more preferably 20% by weight.

When the light-blocking flexible silicone-based particles are used in a sealant for liquid crystal dropping method, the maximum particle diameter is preferably 100% or more of the cell gap of the liquid crystal display element. If the maximum particle diameter of the light-blocking flexible silicone-based particles is less than 100% of the cell gap of the liquid crystal display element, the seal brake and liquid crystal contamination may not be sufficiently suppressed. The maximum particle diameter of the light-blocking flexible silicone-based particles is 100% or more of the cell gap of the liquid crystal display element, and more preferably 5 m or more.

The preferable upper limit of the maximum particle diameter of the light-blocking flexible silicone-based particles is 20 占 퐉. When the maximum particle diameter of the light-blocking flexible silicone-based particles is more than 20 m, springback is caused in the case of being used for a sealant for a liquid crystal dropping method, resulting in poor adhesion of the obtained sealant for a liquid crystal dropping method, A gap defect may occur in some cases. The more preferable upper limit of the maximum particle diameter of the light-blocking flexible silicone-based particles is 15 탆.

The maximum particle diameter of the light-blocking flexible silicone-based particles is preferably 2.6 times or less of the cell gap. When the maximum particle diameter of the light-blocking flexible silicone-based particles exceeds 2.6 times the cell gap, springback is caused in the case where it is used for a sealant for a liquid crystal dropping method, and the obtained sealant for a liquid crystal dropping method is poor in adhesiveness, A gap defect may occur in the liquid crystal display element. A more preferable upper limit of the maximum particle diameter of the light-blocking flexible silicone-based particles is 2.2 times the cell gap, and a more preferable upper limit is 1.7 times the cell gap.

In the present specification, the maximum particle diameter of the light-blocking flexible silicone-based particles and the average particle diameter described later are values obtained by measuring a particle before being blended with a sealant using a laser diffraction particle size distribution measurement apparatus as it means. As the laser diffraction distribution measuring apparatus, a master sizer 2000 (manufactured by Maru Reflections Co., Ltd.) or the like can be used. The cell gap of the liquid crystal display element is not limited because it varies depending on the display element, but the cell gap of a general liquid crystal display element is 2 to 10 mu m.

The light-blocking flexible silicone-based particles preferably have a content ratio of particles having a particle diameter of 5 占 퐉 or more among the particle size distributions of the light-blocking flexible silicone-based particles measured by the laser diffraction distribution measuring device at 60% or more by volume frequency. If the content ratio of the particles having a particle diameter of 5 占 퐉 or more is less than 60% by volume frequency, the seal brake or the liquid crystal contamination may not be sufficiently suppressed when used for a liquid crystal drop sealing agent. And the content ratio of the particles having a particle diameter of 5 mu m or more is more preferably 80% or more.

The above-mentioned light-blocking flexible silicone-based particles are preferably used in an amount of 100% or more of the cell gap of the liquid crystal display element from the viewpoint of exerting an effect of suppressing occurrence of seal break and liquid crystal contamination when used in a liquid crystal drop sealing agent. Is preferably contained in an amount of not less than 70% of the particle size distribution in the whole of the photopolymerizable silicone-based particles, and more preferably, it is composed of only particles having a cell gap of not less than 100% of the cell gap of the liquid crystal display element.

The preferable lower limit of the average particle diameter of the light-blocking flexible silicone-based particles is 2 占 퐉, and the preferable upper limit is 50 占 퐉. When the average particle diameter of the light-blocking flexible silicone-based particles is less than 2 占 퐉, elution of the sealant into the liquid crystal can not be sufficiently prevented in the case of using it for a liquid crystal drop sealing agent. When the average particle diameter of the light-blocking flexible silicone-based particles exceeds 50 탆, the obtained liquid crystal drop sealing agent becomes poor in adhesiveness when used in a liquid crystal drop sealing agent, or the resulting liquid crystal display element has a gap defect Or may occur. A more preferable lower limit of the average particle diameter of the light-blocking flexible silicone-based particles is 4 占 퐉, a more preferable upper limit is 15 占 퐉, and a more preferable upper limit is 12 占 퐉.

As the light-blocking flexible silicone-based particles, two or more light-blocking flexible silicone-based particles having different maximum particle diameters may be mixed and used. That is, when used in a sealant for a liquid crystal dropping method, a light-shielding flexible silicone-based particle having a maximum particle diameter of less than 100% of the cell gap of the liquid crystal display element and a light- The flexible silicon-based particles may be mixed and used.

The variation coefficient of the particle diameter of the light-blocking flexible silicon-based particles (hereinafter also referred to as " CV value ") is preferably 30% or less. When the CV value of the particle diameter of the light-blocking flexible silicone-based particles is more than 30%, a cell gap defect may occur in the case of being used for a liquid crystal drop sealing agent. The CV value of the particle diameter of the light-blocking flexible silicone-based particles is more preferably 28% or less. In the present specification, the CV value of the particle diameter is a value obtained by the following formula.

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

The light-blocking flexible silicone-based particles can be classified within the above-described range by classifying even the maximum particle diameter, the average particle diameter, and the CV value outside the above-described range, thereby making the maximum particle diameter, the average particle diameter, and the CV value within the above-described range. When used in a sealant for a liquid crystal dropping method, the light-blocking flexible silicone-based particles having a particle diameter of less than 100% of the cell gap of the liquid crystal display element do not contribute to suppression of occurrence of seal breakage or liquid crystal contamination, It is preferable to remove by the classification because there is a case where the tin value is increased when it is blended.

As a method of classifying the light-blocking flexible silicon-based particles, for example, wet classification, dry classification, etc. may be mentioned. Among them, wet classification is preferred, and wet classification is more preferable.

The light-shielding flexible silicone-based particles have a compressive displacement L1 from the original point load value to the reversed load value when the load is applied to L1, and from the reverse load value when the load is released to the original point load value When the secondary displacement is L2, it is preferable that the recovery rate expressed by the percentage of L2 / L1 is 80% or less. When the recovery rate of the light-blocking flexible silicone-based particles is more than 80%, the function of preventing the sealant from being eluted into the liquid crystal may be deteriorated due to a barrier when used in a liquid crystal drop sealing agent. A more preferable upper limit of the recovery rate of the light-blocking flexible silicone-based particles is 70%, and a more preferable upper limit is 60%.

The recovery rate of the light-blocking flexible silicone-based particles can be derived by applying a constant load (1 g) to one particle by using a micro compression tester and analyzing the recovery behavior after removing the load.

The light-shielding flexible silicone-based particles preferably have a 1 g strain of 30% or more as expressed by a percentage of L3 / Dn when the compression displacement when a load of 1 g is applied is L3 and the particle diameter is Dn. When the 1 g deformation of the light-blocking flexible silicone-based particles is less than 30%, the function of preventing the sealant from being eluted into the liquid crystal may be lowered as a barrier in the case of being used for a liquid crystal drop sealing agent. A more preferable lower limit of 1 g modification of the light-blocking flexible silicone-based particles is 40%.

The 1 g deformation of the light-blocking flexible silicone-based particles can be measured by applying a load of 1 g per particle using a micro compression tester and measuring the amount of displacement at that time.

The light-shielding resilient flexible silicon-based particles preferably have a fracture strain of 50% or more expressed as a percentage of L4 / Dn when the compressive displacement at the point of time at which the particles are broken is L4 and the particle diameter is Dn. When the breaking strain of the light-blocking flexible silicone-based particles is less than 50%, the barrier function becomes a barrier when used for a liquid crystal drop sealing agent, and the function of preventing the sealant from being eluted into liquid crystal may be lowered. The lower limit of the fracture strain of the light-blocking flexible silicone-based particles is more preferably 60%.

The fracture strain of the light-blocking flexible silicone-based particles can be measured by using a micro compression tester to load a particle and measuring the amount of displacement at which the particle is broken. The compressed displacement L4 is calculated by taking the point at which the amount of displacement becomes discontinuous with respect to the load load as the point at which the particle is destroyed. If it is deformed even when the load load is large but is not destroyed, the fracture strain is considered to be 100% or more.

The light-blocking flexible silicone-based particles preferably have a glass transition temperature lower limit of -200 deg. C and a preferable upper limit of 40 deg. When the glass transition temperature of the light-shielding flexible silicon particles is -200 DEG C or higher, the effect of suppressing the seal break and liquid crystal contamination is better as the lower the glass transition temperature is. When the glass transition temperature is lower than -200 DEG C, And the liquid crystal is liable to collapse, so that the sealant and the liquid crystal come into contact with each other during the curing, and liquid crystal contamination may occur. When the glass transition temperature of the light-blocking flexible silicon particles exceeds 40 캜, a gap defect may occur. A more preferable lower limit of the glass transition temperature of the light-blocking flexible particles is -150 deg. C, and a more preferable upper limit is 35 deg. The glass transition temperature of the light-blocking flexible silicone-based particles is a value measured by differential scanning calorimetry (DSC) based on JIS K 7121 "Method of measuring transition temperature of plastics".

According to the present invention, it is possible to provide a sealing agent for a liquid crystal dripping method which is excellent in adhesiveness, hardly causes liquid crystal contamination, and can prevent light leakage of the liquid crystal display element. Further, according to the present invention, it is possible to provide a liquid crystal display device and a liquid crystal display device using the liquid crystal dropping sealant. Further, according to the present invention, light-blocking flexible silicon particles can be provided.

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

(Production of light-shielding flexible particle A)

, 500 g of a methylvinylsiloxane having a viscosity of 600 cP (compound represented by the following formula (5)), 20 g of a methylhydrogenpolysiloxane having a viscosity of 30 cP (compound represented by the following formula (6) Quot; 13M " manufactured by REAL Inc.) was placed in a 1-liter glass beaker, and the mixture was stirred and mixed at 2000 rpm using a homomixer.

Subsequently, 1 g of polyoxyethylene octylphenyl ether (addition mole number = 9 mols) and 150 g of water were added and stirring was continued at 6000 rpm. As a result, phase change was observed and the viscosity was confirmed. While stirring at 3000 rpm, 329 g of water was added to obtain an O / W type emulsion.

[Chemical Formula 9]

[Chemical formula 10]

Subsequently, this emulsion was transferred to a glass flask equipped with an agitator with an anchor-type stirring wing, and 1 g of a toluene solution of a chloroplatinic acid-olefin complex (platinum content: 0.05%) and polyoxyethylene (Hereinafter also referred to as " silicone rubber spherical fine particle water dispersion 1 ") was obtained as a result of a reaction for 12 hours, Was measured using a Coulter counter (manufactured by Coulter Electronics Co., Ltd.) as a result of measurement, and the number of g of the dispersion was dried at room temperature to obtain an elastic rubber powder.

In a 3-liter glass flask, 2290 g of water, 580 g of the silicone rubber spherical fine particle water dispersion-1 and 60 g of ammonia water (concentration 28% by weight) were charged and the water temperature was set to 10 캜, , Stirring was carried out by an anchor type stirring wing under the conditions of The pH of the solution was 11.2. To this solution, 65 g of methyltrimethoxysilane was added dropwise over 20 minutes, the temperature of the solution was maintained at 5 to 15 占 폚, further stirred for 4 hours, The mixture was heated to 60 占 폚 and stirred for 1 hour. The obtained solution was made into a cake-like material having a water content of about 30% by using a pressure filter.

Then, the cake form was dried in a hot air circulating dryer at a temperature of 105 ° C, and the obtained dried material was crushed by a jet mill. Thereafter, a predetermined particle diameter and a maximum particle diameter were adjusted by a classifying operation to obtain light-shielding flexible particles A which were light-blocking flexible silicon particles containing a light-shielding agent.

, 500 g of a methylvinylsiloxane having a viscosity of 600 cP (compound represented by the following formula (5)), 20 g of a methylhydrogenpolysiloxane having a viscosity of 30 cP (compound represented by the following formula (6) (Platinum content: 0.05%) of chloroplatinic acid-olefin complex was added to a solution obtained by mixing 26 g of a polyvinyl alcohol solution (" 13M " 1 g was added to prepare a mixed solution.

The resultant mixed solution was poured into a bath previously coated with Teflon (registered trademark), the height was adjusted so that the thickness after curing became 1 mm, and the reaction was carried out at room temperature for 24 hours to obtain a sheet. The obtained sheet was cut to obtain a sample for measuring the degree of blackness on the flake having a thickness of 1 mm and the same composition as the light-shielding flexible particle A was obtained.

The measurement of the degree of blackening of the obtained light-shielding flexible particle A using the "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", and UV-3600 (manufactured by Shimadzu Corporation) Microparticles were compressed at a compression speed of 0.28 mN (diameter) at a circumferential smoothed end face of a diamond-made diameter of 50 占 퐉 using a "blackening degree" of the sample and a micro compression tester ("PCT-200" quot; 1 g deformation " and " fracture strain " measured under the conditions of an initial load of 1.0 mN / sec, an origin load of 1.0 mN and an inverse load of 10 mN are shown in Table 1.

(Production of light-shielding flexible particle B)

Except that the amount of titanium black used ("13M" manufactured by Mitsubishi Materials Corporation) was changed to 52 g, the same reaction as that of the light-shielding flexible A was carried out. As the flexible particles containing the light- Light-sensitive flexible particles B, and light-shielding flexible particles B were prepared.

The "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "degree of blackening" , "Recovery rate", "1 g strain" and "fracture strain" are shown in Table 1.

(Production of light-shielding flexible particles C)

Except that titanium black was not added and only methylvinylsiloxane and methylhydrogenpolysiloxane were used, and the same reaction as in the above-mentioned "production of light-shielding flexible particles A" was carried out to obtain silicon-based particles.

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

Subsequently, 10 g of pyrrole, 5.3 g of water (15% by weight) and 24.4 g of sulfuric acid (5% by weight) were added and stirred for 30 minutes. Then, 0.08 g of iron sulfate heptahydrate was dissolved in 1 g of water and added to the separable flask. Thereafter, stirring was continued at room temperature for 12 hours, and the particles were washed several times with water. After the dispersion was dried at room temperature, a predetermined particle diameter and a maximum particle diameter were adjusted by a classifying operation to obtain light-shielding flexible particles C as light-blocking flexible silicon particles.

The "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "recovery rate" , &Quot; 1 g strain ", and " fracture strain " are shown in Table 1. Further, since the samples for measuring the degree of blackening were not prepared for the light-shielding flexible particles C, the degree of blackening was not measured.

(Preparation of light-shielding flexible particles D)

50 g of polytetramethylene glycol diacrylate, 950 g of ethylhexyl methacrylate, and 50 g of titanium black ("13M" manufactured by Mitsubishi Materials Co., Ltd.) were charged into a 3-liter glass beaker, and using a homomixer And the mixture was stirred at 2000 rpm. Further, 40 g of benzoyl peroxide was added to this mixed solution and mixed with stirring wing until uniformly dissolved (hereinafter, the obtained mixed solution was also referred to as " monomer mixture solution ").

The monomer mixture was introduced into a reaction flask charged with 5 kg of a 1 wt% aqueous solution of polyvinyl alcohol and stirred for 2 to 4 hours to adjust the particle diameter so that the monomer droplets had a predetermined particle diameter. Thereafter, the reaction was carried out in a nitrogen atmosphere at 85 캜 for 9 hours to obtain polymer particles. The polymer particles thus obtained were washed several times with hot water and classified, and the particle diameters and the maximum particle diameters were adjusted. Further, after the solvent substitution with methanol several times, the light-shielding flexible particles D were obtained by drying under reduced pressure at 30 DEG C for 12 hours in a vacuum dryer.

A part of the monomer mixture was poured into a bath previously coated with Teflon (registered trademark), the height was adjusted so that the thickness after curing became 1 mm, and the reaction was carried out at 85 캜 for 20 hours to obtain a sheet. The resulting sheet was cut to obtain a sample for measuring the degree of blackness on the flake having a thickness of 1 mm and the same composition as the light-shielding flexible particles D.

The "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "degree of blackening" , "Recovery rate", "1 g strain" and "fracture strain" are shown in Table 1.

(Preparation of light-shielding flexible particles E)

The same operations as those of the light-shielding flexible particles D were conducted except that 400 g of polytetramethylene glycol diacrylate and 600 g of styrene were used instead of 50 g of polytetramethylene glycol diacrylate and 950 g of ethylhexyl methacrylate , A sample for measuring the degree of blackness on a flake having a thickness of 1 mm and the same composition as the light-shielding flexible particle E and the light-shielding flexible particle E was prepared.

The "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature" and "degree of blackening", which were measured in the same manner as for light- , "Recovery rate", "1 g strain" and "fracture strain" are shown in Table 1.

(Preparation of light-shielding flexible particles F)

The same operation as that of the light-shielding flexible particles D was carried out except that 750 g of polytetramethylene glycol diacrylate and 250 g of styrene were used instead of 50 g of polytetramethylene glycol diacrylate and 950 g of ethylhexyl methacrylate , A sample for measuring the degree of blackness on a flake having a thickness of 1 mm and the same composition as the light-shielding flexible particles F and the light-shielding flexible particles F was prepared.

The "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "degree of blackening" , "Recovery rate", "1 g strain" and "fracture strain" are shown in Table 1.

(Production of light-shielding flexible particle G)

The same procedure as that of the light-shielding flexible particle A was conducted except that the maximum particle diameter was adjusted to 5 m or less at the time of classifying to obtain light-shielding flexible particles G.

The "maximum particle diameter", "average particle diameter", "CV value of particle diameter", "glass transition temperature", "degree of blackening" , "Recovery rate", "1 g strain" and "fracture strain" are shown in Table 1.

Since the particle composition is the same as that of the light-shielding flexible particle A, the same sample as that obtained for the light-shielding flexible particle A was used as the sample for measuring the degree of blackening.

(Production of non-light-shrinkable flexible particle A)

The same reaction as in the light-shielding flexible particle A was carried out except that no titanium black was added, and as the flexible particles not containing a light-shielding agent, the non-light-deflecting flexible particle A and the thickness 1 having the same composition as the non- Mm in thickness was prepared.

Average particle diameter ", " CV value of particle diameter ", " glass transition temperature ", " degree of blackening ", " , "Recovery rate", "1 g strain" and "fracture strain" are shown in Table 1.

(Example 1)

, 70 parts by weight of bisphenol A type epoxy acrylate ("Ebecryl 3700" manufactured by Daicel-Ornex Co., Ltd.) as a curable resin, 30 parts by weight of bisphenol F type epoxy resin ("jER806" manufactured by Mitsubishi Chemical Corporation) 7 parts by weight of a polymeric azo initiator ("VPE-0201" manufactured by Wako Pure Chemical Industries, Ltd.) as an initiator, 8 parts by weight of sebacic acid dihydrazide ("SDH" , 10 parts by weight of silica (Admafine SO-C2, manufactured by Admatechs Co., Ltd.) and 3 parts by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Shinetsu Silicones Co., Ltd.) KBM-403 ") were mixed and stirred with a planetary stirring apparatus (" Awatolian Taro "manufactured by Singkis), followed by homogeneous mixing with three rolls of ceramic to obtain a liquid sealant sealing agent.

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

Each material was mixed in the same manner as in Example 1, using a planetary-type stirring device ("Awatolian Taro" manufactured by Singkis Co., Ltd.) according to the blending ratio shown in Table 2, To prepare liquid sealant sealants of Examples 2 to 14 and Comparative Examples 1 to 3.

<Evaluation>

The following evaluations were carried out for each liquid crystal drop sealing agent obtained in Examples and Comparative Examples. The results are shown in Table 2.

(Adhesive property)

1 part by weight of spacer particles having an average particle diameter of 5 占 퐉 ("Micropearl SP-2050", manufactured by Sekisui Chemical Co., Ltd.) were added to 100 parts by weight of each sealant for liquid crystal dropping process obtained in Examples and Comparative Examples, (20 mm x 50 mm x 0.7 mm thick), and the same type of glass was superimposed thereon to spread the sealant for liquid crystal dropping process so as to widen the glass rod and spread it at 120 DEG C For 1 hour to thermally cure the sealant to obtain an adhesive test piece.

The adhesive strength of the obtained adhesive test piece was measured using a tension gauge. , The case where the bonding strength was 270 N / cm 2 or more was evaluated as &quot; &quot;, the case where the bonding strength was less than 250 N / cm 2 and less than 270 N / cm 2 was evaluated as & .

(Light shielding)

1 part by weight of spacer particles having an average particle diameter of 5 占 퐉 ("Micropearl SP-2050", manufactured by Sekisui Chemical Co., Ltd.) were added to 100 parts by weight of each sealant for liquid crystal dropping process obtained in Examples and Comparative Examples, Uniformly dispersed on a glass substrate of 50 mm x 50 mm, and a glass substrate of the same shape was superimposed thereon. Next, the sealant was thermally cured by heating at 120 DEG C for 1 hour to obtain a test piece for OD value measurement. The OD value was measured using a PDA-100 (manufactured by Konica Corp.) for the obtained OD value measurement test piece. &Quot;? &Quot;, OD value of 3 or more were evaluated as? Was evaluated as &quot; DELTA &quot;, and when it was less than 2, it was evaluated as &quot; x &quot;

(Liquid crystal contamination)

One part by weight of spacer particles ("Micropearl SP-2050", manufactured by Sekisui Chemical Co., Ltd.) having an average particle diameter of 5 탆 was added to 100 parts by weight of each liquid crystal drop sealing material obtained in Examples and Comparative Examples by a planetary stirring device (Manufactured by Musashi Engineering Co., Ltd., "PSY-10E") was filled with the sealing agent obtained, and the resulting sealing agent was filled in a dispensing syringe A sealant was applied so that a rectangular frame was formed on the attached transparent electrode substrate. Subsequently, a small droplet of a TN liquid crystal ("JC-5001LA" manufactured by Toso Co., Ltd.) was dropwise applied with a liquid crystal dropping device and the other transparent substrate was bonded under vacuum of 5 Pa by a vacuum bonding apparatus. The bonded cells were heated at 120 DEG C for 1 hour to thermally cure the sealant to obtain a liquid crystal display device (cell gap of 5 mu m).

With respect to the obtained liquid crystal display element, the display irregularities occurring in the liquid crystal (particularly at the corners) around the seal portion were visually observed, and the case where there was no display irregularity was &quot; OO &quot;, the case where there was little display irregularity was & , A case where slight display unevenness occurred, and a case where a severe display unevenness was confirmed as &quot; x &quot;, to evaluate the liquid crystal staining property.

Industrial availability

According to the present invention, it is possible to provide a sealing agent for a liquid crystal dripping method which is excellent in adhesiveness, hardly causes liquid crystal contamination, and can prevent light leakage of the liquid crystal display element. Further, according to the present invention, it is possible to provide a liquid crystal display device and a liquid crystal display device using the liquid crystal dropping sealant. Further, according to the present invention, light-blocking flexible silicon particles can be provided.

Claims (12)

As a sealant for a liquid crystal dropping method used in the production of a liquid crystal display element by a liquid crystal dropping method,
A curable resin, a polymerization initiator and / or a thermosetting agent, and a light-
Wherein the sealant is a liquid sealant. The method according to claim 1,
Wherein the light-blocking flexible particles have a maximum particle diameter of 100% or more of the cell gap of the liquid crystal display element. 3. The method according to claim 1 or 2,
The light-shielding flexible particles have a compressive displacement L1 from the original point load value when the load is applied to the reverse load value to L1, and from the reverse load value when the load is released to the original point load value Wherein a recovery ratio of L2 / L1 expressed as a percentage is 80% or less when the load displacement of the roller is L2. The method according to claim 1, 2, or 3,
The light-shielding flexible particles have a 1 g strain of 30% or more in terms of L3 / Dn as a percentage when the compression displacement when giving a load of 1 g is L3 and the particle diameter is Dn, Sealing system for construction method. The method according to claim 1, 2, 3, or 4,
Wherein the light-shielding flexible particles have a glass transition temperature of -200 to 40 占 폚. The method of claim 1, 2, 3, 4, or 5,
The light-shielding flexible particles have a fracture strain of 50% or more, expressed as a percentage of L4 / Dn, when the compression displacement at the point of time when the particles are broken is L4 and the particle diameter is Dn. . The method of claim 1, 2, 3, 4, 5, or 6,
The light-shielding flexible particles have a coefficient of variation of particle diameter of 30% or less. The method of claim 1, 2, 3, 4, 5, 6, or 7,
A sealant for a liquid crystal dropping process characterized by further comprising a light shielding agent in addition to the light shielding flexible particles. A liquid crystal drop sealing agent according to any one of claims 1, 2, 3, 4, 5, 6, 7, and 8, and a conductive fine particle Upper and lower conduction material. A sealing agent for a liquid crystal dropping method according to any one of claims 1, 2, 3, 4, 5, 6, 7, and 8 or an upper and lower conductive material according to claim 9 And the liquid crystal display element is manufactured. A light-shading flexible silicon particle characterized by comprising a silicone-based particle containing a light-shielding agent. 12. The method of claim 11,
Wherein the average particle diameter is 2 to 50 占 퐉.