KR20120096492A - Cationic curing liquid crystal sealant and liquid crystal display element - Google Patents

Abstract

A cationically curable liquid crystal sealant containing a cationic polymerizable compound, a photocationic polymerization initiator and / or a thermal cationic polymerization initiator supported on a dispersible microcarrier, and two substrates facing each other, The liquid crystal display element provided with the sealing agent provided between the said board | substrates, and the liquid crystal enclosed in the sealing area | region enclosed by the said sealing agent, and using the cation hardening type liquid crystal sealing agent of any one of Claims 1-5 as said sealing agent. It is preferable that the said cationically curable liquid-crystal sealing agent contains 1-30 mass% of photocationic polymerization initiators and / or thermocationic polymerization initiators which were supported by the said dispersible microcarrier with respect to the said cationically polymerizable compound.

Description

Cationic curable liquid crystal sealant, and liquid crystal display element {CATIONIC CURING LIQUID CRYSTAL SEALANT AND LIQUID CRYSTAL DISPLAY ELEMENT}

This invention relates to a liquid crystal sealing agent of a light and / or heat | fever cation hardening type more specifically with respect to a liquid crystal sealing agent.

Generally, a liquid crystal panel (liquid crystal display element) opposes a back substrate including a thin film transistor, a pixel electrode, an alignment film, and the like, and a front substrate including a color filter, an electrode, an alignment film, and the like to form a liquid crystal between both substrates. It is enclosed and constructed. And the sealing agent is used for the purpose of sticking two board | substrates together.

In recent years, in order to reduce the thickness and weight of a liquid crystal panel, or to impart flexibility, it has been studied to replace the materials of both the front substrate and the front back substrate from conventional glass to plastic. However, the sealant used conventionally was mostly developed for glass, and it was difficult to use it as it is. In the case of using a thermosetting sealing agent containing epoxy-based thermosetting resin as a main component, it is often hardened at 150 ° C. However, in the case of bonding together substrates of different temperature coefficients or thermal expansion coefficients of the upper and lower substrates, There existed a problem that a liquid crystal panel bent when cooling a panel to room temperature. For the purpose of avoiding this, a method of adding a curing catalyst such as an inorganic solid acid such as silica or an organic acid such as salicylic acid to the epoxy resin and carrying out the curing reaction at a low temperature of 40 ° C. or less has been tested. It is not

On the other hand, since the photocurable sealing agent which has an acrylate etc. as a main component does not require heat for hardening and can harden | cure in short time, it is suitable for a plastic substrate. However, since acrylate is large in shrinkage in curing, adhesiveness is weak and may be peeled off by a simple impact or the like, and there is a problem in practical use. Moreover, although the photocurable component and the thermosetting component are used together, and the photocuring sealant which completely hardens by heating (usually using heating at the time of annealing) after semi-curing by photocuring is also known, also in a plastic substrate Adhesion was weak and there was a problem practically.

On the other hand, the photocurable sealing agent (for example, refer patent document 1) which has an optical binary curing system which uses together the photocationic curability which has epoxy etc. as a main component, and the acrylate which has optical radical curability, etc., is heat-processed to hardening. Not only is it possible to cure in a short time, but also the photo-opening reaction can be used to significantly improve the adhesion between the organic protective layer of the substrate and inorganic protective layers such as SiOx. However, there also exists a problem that an ionic photocationic polymerization initiator and the acid which arises at the time of cation hardening elute in a liquid crystal, and voltage retention falls.

As a manufacturing method of the liquid crystal panel using a glass substrate, the method called the dropping method which used the photocuring thermosetting combined type sealing agent with the vacuum injection system using a thermosetting sealing agent is mainstream. In the dropping method, first, a rectangular seal pattern is formed on one side of two transparent substrates with electrodes by a dispenser. Subsequently, a small amount of liquid crystal is applied dropwise to the entire surface in the frame of the transparent substrate in the uncured state of the sealant, the other transparent substrate is overlaid under reduced pressure, and the seal portion is irradiated with ultraviolet rays to temporarily harden. Then, it heats and this hardening is performed and a liquid crystal panel is produced.

As a sealing agent for liquid crystal panels used for such a dropping method, for example, Patent Literature 2 discloses a photo-curing combination sealing agent which is photocured with a radical generated by irradiating ultraviolet rays, and further thermosets with a thermosetting agent to contain.

On the other hand, patent document 3 has proposed the sealing agent using a cationically polymerizable compound as a sealing agent which does not use a thermosetting agent. The sealant using such a cationically polymerizable compound has better storage stability than the sealant using a thermosetting agent, and has excellent low temperature fast curing property, short time required for curing, and shorten manufacturing time. And so on.

However, in the dropping method, since the sealing agent in an uncured state directly touches the liquid crystal in the process, when the sealing agent using the cationically polymerizable compound is used, the cationic polymerizable compound and the photocationic polymerization initiator are applied to the liquid crystal. In the liquid crystal display element obtained, it may elute, and there existed a problem that the disorder of the orientation of a liquid crystal, the fall of the voltage retention of a liquid crystal display element, etc. may be recognized. In particular, in recent years, liquid crystal display elements tend to use low driving voltages (low voltage liquid crystals) of liquid crystals due to low power consumption of consumers. Since this low voltage type liquid crystal has especially large dielectric constant anisotropy, it is easy to take in an impurity, and the disorder of the orientation of a liquid crystal and the fall of the voltage retention of a liquid crystal display element were remarkable.

In addition, Patent Document 4 discloses a photocationic polymerization initiator as a dispersible microcarrier that supports and supports a photocatalytic ionic salt of an onium or organometallic complex ion and a halogen-containing complex of a metal or metalloid anion. The supporting initiator for the radiation activation polymerization of the cationically polymerizable compound in the absence of a non-reactive solvent which is insoluble in the cationically polymerizable compound is known, and a photocationic curable composition using the photopolymerization initiator has been proposed.

Japanese Patent Laid-Open No. 2008-96575 Japanese Patent Application Laid-Open No. 2001-133794 Japanese Patent Application Laid-Open No. 2005-227367 Japanese Patent Application Laid-Open No. 61-278507

An object of the present invention is to provide a cationically curable liquid crystal sealant having excellent electrical properties and adhesiveness, and to provide a liquid crystal display device having excellent voltage retention using the cationically curable liquid crystal sealant.

MEANS TO SOLVE THE PROBLEM The present inventors solved the said subject by using the cationic polymerization initiator supported by the dispersible micro support as a cation curable composition.

As mentioned above, since a light or a thermal cationic polymerization initiator is an ionic compound, when it is blown into a liquid crystal, there exists a possibility that the voltage retention of the obtained liquid crystal display element may be reduced by lowering the resistance value of a liquid crystal. On the other hand, the present inventors found that elution can be greatly reduced by supporting a cationic polymerization initiator on a dispersible microcarrier, and does not cause deterioration of liquid crystal properties such as disturbance of liquid crystal orientation or reduction of voltage retention of a display element. We found that a liquid crystal sealing agent was obtained.

Moreover, by using together a basic solid substance, it discovered that the liquid crystal sealing agent which especially hardly produces the disorder of the orientation of a liquid crystal, the fall of voltage retention, or an electrode corrosion is obtained.

That is, this invention provides the cationically curable liquid crystal sealing agent containing a cationically polymerizable compound and the photocationic polymerization initiator and / or the thermocationic polymerization initiator supported on a dispersible micro support.

The present invention also provides a liquid crystal display device comprising two substrates facing each other, a sealant provided between the substrates, and a liquid crystal encapsulated in a sealing region surrounded by the sealant, and using the cation-curable liquid crystal sealant as the sealant. do.

By using the sealing agent of this invention, also in the dropping method, the liquid crystal display element which is hard to produce the disorder of the orientation of a liquid crystal, the fall of the voltage retention of a display element, etc. can be obtained.

(Dispersible microcarrier)

The cationic polymerization initiator used in the present invention is supported on a dispersible microcarrier.

The dispersible microcarrier used in the present invention is preferably granular and is within the range of 0.001 to 20 micrometers, and more preferably 0.01 to 5 micrometers, preferably less than about 50 micrometers in the largest dimension. It is preferable that it is a dispersible micromaterial having a particle diameter of 0.01-2 micrometers, and most preferably, insoluble in the organic component of the sealant, that is, inherently insoluble in the measurable amount. The larger the surface area of the dispersible microcarrier is, the more the amount of photocationic polymerization initiator to be supported is preferable. However, in general, particles having a large surface area have a small particle size and are difficult to handle. Since uniformity is impaired, the range of 0.1-10000 m <2> / g is preferable, More preferably, it is 1-5000 m <2> / g, More preferably, it is 10-2000 m <2> / g, More preferably, it is 30-1500 m <2>. / g, most preferably in the range of 30 to 1200 m 2 / g.

Specifically, silicas such as fumed silica, precipitated silica and natural silica; Diatomaceous earth; Clays such as bentonite, kaolinite, and attapulgus clay; Metal oxides, carbonates and sulfates such as aluminum, zirconium, titanium, antimony, iron, nickel, zinc, tin, copper, or mixtures thereof; Starch such as starch (ie corn starch), carbon black, graphite, diamond, polymers; Latexes such as latexes such as polystyrene, polyvinyl toluene, polyvinylpyrrolidone, polyacrylic acid, polyacrylate, polymethacrylate and the like; As pigment particles or dispersible micromaterials having a suitable size, microcarriers which may contain photocationic polymerization initiators on or in the surface thereof, such as finely crushed cellulose (ie cotton, wood), glass, etc. to be.

It is also possible to use the basic solid substance mentioned later as a dispersible micro support. However, since the basic property of a basic solid substance may inhibit the hardening reaction of a cationically polymerizable compound, a weak base is more preferable than a strong base, or the density of the basic group on the surface of a basic solid is more preferable. When the basic solid used as a support | carrier has moderate basicity, control of the delay hardening property (property which the curing reaction rate becomes slow) of a cationically polymerizable compound is possible.

In addition, the dispersible microcarrier preferably transmits light to be used, for example, ultraviolet rays.

Particularly suitable carriers are fumed silicas such as AEROSIL (Nihon Aerosol Co., Ltd.). As a metal oxide whose specific surface area of a dispersible micro support is especially large and preferable, the mesoporous body synthesize | combined using surfactant like MCM41 as a template is mentioned. In addition, the mesoporous body which produced the higher order structure of amino acids, such as an organic low molecular gel and collagen, as a template is mentioned. Examples of the mesoporous material include silica, alumina, zirconia, titania, and the like.

(Cation polymerization initiator)

The cationic polymerization initiator used in the present invention includes a photocationic polymerization initiator and a thermal cationic polymerization initiator, and these are ionic salts consisting of halogen-containing complex ions of metals or metalloids, onium cations and organometallic complex ions (hereinafter referred to as ionic salts). It is called). Specifically, group VA, Group VIA, or Group VIA atoms of the periodic table given symbols of Groups 15, 16, and 17, in particular phosphorus, antimony, bismuth, sulfur, nitrogen, and iodine atoms Is an adduct of an aromatic organic atom cation and an anion. For example, onium salts, such as an aromatic diazonium salt, an aromatic iodonium salt, and an aromatic sulfonium salt, are mentioned.

(Photocationic polymerization initiator)

The photocationic polymerization initiator used in the present invention is a photocatalyst ionic salt (hereinafter referred to as ionic salt) composed of a halogen containing anion of a metal or metalloid, an onium cation and an organometallic complex ion. Specifically, aromatics of Group VA, Group VIA, or Group VIA atoms, in particular phosphorus, antimony, sulfur, nitrogen, and iodine atoms, given the symbols of Group 15, Group 16, and Group 17 It is an adduct of organic atom cations and anions. For example, onium salts, such as an aromatic diazonium salt, an aromatic iodonium salt, and an aromatic sulfonium salt, are mentioned. Examples of commercially available ones of these onium salts include Optomer SP-150, Optomer SP-151, Optomer SP-170, Optomer SP-171 (all of which are manufactured by Kadeka Corporation), UVE-1014 (General Electronics) (Manufactured), Irgacure 261 (manufactured by Chiba Co., Ltd.), Sanade SI-60L, Sanade SI-80L, UVI6990 (manufactured by Union Carbide), BBI? 103, MPI? 103, TPS? 103, MDS? 103 , DTS-103, NAT-103, NDS-103 (all made by Midori Chemical Co., Ltd.), Sanade SI-100L (all made by Sanshin Chemical Co., Ltd.), CI-2064, CI-2639, CI-2624, CI-2481 (all Nippon Soda Co., Ltd., RHODORSIL PHOTOINITIATOR 2074 (made by Ron pullangsa), CD-1012 (made by Satomer company), etc. are mentioned. Among them, Optomer SP-150 is unlikely to cause electrode corrosion by onium salts, Optomer SP-170 easily obtains effective curability, and RHODORSIL PHOTOINITIATOR 2074 is more preferable because of less ionic impurities.

The said photocationic polymerization initiator may be used independently and may use 2 or more types together. Moreover, you may use together sensitizers, such as anthracene type and a thioxanthone type as needed.

Moreover, although it does not specifically limit as a compounding ratio of the said photocationic polymerization initiator, Generally the acid which the photocationic polymerization initiator supported by the dispersible microcarrier by light irradiation has a tendency which is less likely to act on a polymeric compound than usual. It is preferable to increase the addition amount rather than the normal amount of use. It is preferable to use specifically in the range of 0.01-20 mass parts with respect to 100 mass parts of photocationic polymeric compounds mentioned later. If it is less than 0.01 mass part, the sclerosis | hardenability of the sealant of this invention may become inadequate, and when it exceeds 20 mass parts, since the acid which generate | occur | produced in the photocationic polymerization initiator will be more than the quantity required to react a photopolymerizable compound, liquid crystal from a sealing agent There is a possibility that the acid penetrates the acid and deteriorates the electrical characteristics of the liquid crystal. More preferably, it is 0.03-10 mass parts.

(Thermal Cationic Polymerization Initiator)

Examples of commercially available initiators that generate acids by heat in the cationic polymerization initiator include acid aid SI60L, acid aid SI80L, acid aid SI100L, acid aid SI110L, and acid aid SI180L (all manufactured by Sanshin Chemical Co., Ltd.), CP-66, CP-77 (all are the same). However, these can also be used as a photocationic polymerization initiator. In addition, CP-66, CP-77 (all of them are available).

The said thermocationic polymerization initiator may be used independently and may use 2 or more types together. Moreover, although it does not specifically limit as a compounding ratio of the said thermocationic polymerization initiator, Generally, since the acid which the thermocationic polymerization initiator supported by the dispersible microcarrier generate | occur | produces by heat tends to have an inability to act on a polymeric compound more than usual, It is preferable to increase the addition amount rather than normal usage. Specifically, it is preferable to use 0.01-20 mass parts with respect to 100 mass parts of cationically polymerizable compounds mentioned later, Preferably it is 0.03-20 mass parts, More preferably, it is 0.1-20 mass parts. If it is less than 0.01 mass part, the hardenability of the sealant of this invention may become inadequate, and when it exceeds 20 mass parts, since the acid which generate | occur | produced in the thermal cationic polymerization initiator will be more than the quantity required to react a cationically polymerizable compound, There is a possibility that the acid penetrates into the liquid crystal, thereby deteriorating the electrical characteristics of the liquid crystal. More preferably, it is 0.03-10 mass parts.

(Support method)

The dispersible microcarrier carrying a cationic polymerization initiator may be a metal or metalloid-containing halogen-containing anion and an ionic salt of an onium cation and an organometallic cation with a suitable solvent such as methylene chloride, methanol, ethanol, propanol, It can be prepared by dissolving in acetone, water, nitromethane, toluene, xylene or the like or a mixed solvent thereof and mixing this solution with an appropriate amount of a dispersible carrier material. By removing the solvent, the photocationic polymerization initiator is supported in the fine pores on the surface or the surface of the dispersible microcarrier. Although the solvent may be removed by filtration, since the ionic salt dissolved in the solvent may flow out without being effectively supported on silica, a method of removing by solvent is preferable. Moreover, when using the photocationic polymerization initiator which is easy to decompose, it is preferable to distill at 100 degrees C or less, Preferably it is 60 degrees C or less, More preferably, it is 40 degrees C or less.

In the above, it is preferable to use lyophilization as a drying method of removing the solvent which melt | dissolved the cationic polymerization initiator. Thereby, reaggregation of a dispersible carrier material can be prevented and a fine dispersible microcarrier can be obtained. The finer the microcarrier, the more effectively the curing reaction of the cationically polymerizable compound can proceed. When freeze-drying is difficult, such as when the freezing point of the solvent is low or when the solid after freezing is difficult to sublimate, add water to the solvent properly, dry the solvent first at a temperature at which the water freezes, and freeze the remaining frozen water. You may dry and remove.

The dispersible microcarrier is porous, and the supported cationic polymerization initiator is preferably supported in the pores of the carrier. This is because the cationic polymerization initiator adsorbed outside the pores is highly likely to come into contact with the resin component of the sealant or the liquid crystal, and the ionic cationic polymerization initiator elutes to inhibit the insulation of the liquid crystal. It is preferable to wash and remove only the cationic polymerization initiator adsorbed out of the pores by any method. For that purpose, for example, the dispersible microcarrier carrying the cationic polymerization initiator may be removed with a solvent. As a solvent to be used, it is preferable that there is minimal solubility in a cationic polymerization initiator, but has a suitable solubility that the dissolving power is not too large so that all of the cationic polymerization initiator adsorbed in the pores is dissolved. It is necessary to select suitably according to the kind of dispersible carrier material and cationic polymerization initiator. When the number of washing is increased, the number of cationic polymerization initiators other than the pores is removed, but the amount of cationic polymerization initiators in the pores is also reduced.

(Addition amount)

If the dispersible microcarrier is added in an excessively large amount, the cationically polymerizable compound may thicken to reduce handling properties such as the drawability of the sealant. Therefore, it is preferable that the addition amount of a dispersible micro support does not exceed 50 weight% of a cationically polymerizable compound. Specifically, 0.1-50 mass parts is used with respect to 100 mass parts of cationically polymerizable compounds, 0.1-50 mass parts is preferable, 1-30 mass parts is more preferable, 3-10 mass parts is the most preferable.

In addition, since it is preferable to use a cation polymerization initiator in the range of 0.1-20 mass parts with respect to 100 mass parts of cationically polymerizable compounds as mentioned above, the usage-amount of a dispersible microcarrier is used inverting from the quantity of the supported cationically polymerizable initiator. It is desirable to.

On the other hand, the supported amount varies depending on the surface shape and surface area of the dispersible microcarrier. For example, when a large amount of the polymerization initiator is supported on a dispersible microcarrier having a small surface area, the polymerization initiator is laminated in multiple layers on the hollow structure surface of the dispersible microcarrier. As a polymerization initiator, adsorption force becomes weak, and there exists a possibility that the said polymerization initiator may melt | dissolve or disperse | distribute to the said polymeric compound side. This is a cause of contamination to the liquid crystal and also of deterioration of the electrical properties, which is undesirable. In addition, it also differs depending on whether the opening of the hollow structure is large and opened or bottleneck type. For example, in the case where the opening of the hollow structure is opened out, it is impossible to support a large amount for the above reason, but there is an advantage that the acid generated from the polymerization initiator acts effectively on the polymerization of the polymerizable compound. have. On the contrary, in the bottle neck type, even if the polymerization initiator is supported in large quantities, there is little possibility that the carrier will flow out from the carrier to the polymerizable compound side, but the amount of diffusion of generated acid will also decrease, and the reaction may not proceed efficiently. have. Although the influence of the property of a dispersible microcarrier is mentioned in detail, generally, the support amount of the said polymerization initiator with respect to a dispersible microcarrier is represented by the supported amount represented by the addition amount / surface area of a dispersible microcarrier, and is 1x10 <^-7>. It is preferable that it is -1g / m <2>, 1 * 10 <^-6> g / m <2> is more preferable, 1 * 10 <^-6> -1 * 10 <^-2> g / m <2> is more preferable, and 1 * 10 <^{-5> is} 1 × 10 ⁻³ g / m 2 is most preferred.

The latter is estimated to correspond to 1/10 to 100 layers in terms of the average number of stacked layers of the polymerization initiator molecules per unit area.

It is confirmed that the supported cationic polymerization initiator is difficult to re-elute. Specifically, as a result of the experiment of re-eluting the supported cationic polymerization initiator with acetone, 30 to 60% by mass of cationic polymerization was irrespective of the type of the dispersible microcarrier to be used and irrespective of the amount of the supported cationic polymerization initiator. It was suggested that the initiator was re-eluted into the solution (B), and therefore 70-40 mass% of the cationic polymerization initiator was bound to the silica with sufficient binding force (see reference experiments described later). The cationically polymerizable compound to be used has a lower solubility than acetone. Therefore, the cationic polymerization initiator once supported is estimated to maintain a stable state with little re-elution in the cationically polymerizable compound.

(Particle size)

The dispersible microcarrier has a size of about several hundred nanometers of primary particles, but aggregates to form secondary aggregates of several hundred nanometers to several micrometers. In order to fully exhibit the catalytic function of the cationic polymerization initiator supported on the dispersible microcarrier, it is preferable to disperse to the size of a primary particle as much as possible.

(How to add)

The dispersible microcarrier carrying the cationic polymerization initiator is added to the cationically polymerizable compound which is a dispersion medium in the form of powder, and stirred by a mixer, a screw extruder or the like, or kneading such as a three roll, kneader, twin screw extruder or the like. Can be dispersed. It is also preferable to use a bead mill or the like in order to obtain a finely dispersed state. Specifically, by stirring together the photocationic polymerization initiator supported on the dispersible microcarrier, the photocationic polymerizable compound described below, and microbeads, which are stirred particles (media), the particles collide with the aggregated particles and shear through the stirred particles. (Iii) By giving energy and dispersing the aggregated particles, a finer dispersed state can be obtained.

Cationic Polymerizable Compound

The cationically polymerizable compound used in the present invention is not particularly limited as long as it is a known conventional compound having an epoxy group, an oxetanyl group, and a vinyl ether group, which are generally used as a polymerizable compound capable of cationic polymerization in the presence of the cationic polymerization initiator. . However, since the compound which has an oxetanyl group is small in the amount of hydroxyl groups produced | generated by superposition | polymerization, since it is disadvantageous in adhesiveness with plastics, it is more preferable to refrain from using a small amount.

As a cationically polymerizable compound which has one or more epoxy groups in 1 molecule, For example, bisphenol-A epoxy resin (brand name "Epiclon 850CRP", "Epiclon 850S", "Epiclon 1050", "Epiclon 1050" made by DIC Corporation) 1055 "), Bisphenol F type epoxy resin (brand name" Epiclon 830CRP "made by DIC Corporation," Epiclon 830 ", bisphenol S type epoxy resin (brand name" Epiclon EXA1514 "made by DIC Corporation), hydrogenated bisphenol type epoxy resin (DIC Brand name "Epiclon EXA7015" made by company, Propylene oxide addition bisphenol A type epoxy resin (brand name "EP-4000S" made by Asahi Denka Co., Ltd.), resorcinol type epoxy resin (brand name "EX-201" made by Nagase ChemteX Corporation) , Biphenyl type epoxy resin (brand name "Epicoat YX-4000H" made by Japan epoxy resin company), dicyclopentadiene type epoxy resin (brand name "EP-4088S made by Asahi Denka Corporation), naphthalene type epoxy resin (product made by DIC Corporation) costume Name "Epiclon HP4032", "Epiclon EXA-4700", phenol novolak-type epoxy resin (brand name "Epiclon N-770" made by DIC Corporation), orthocresol novolak-type epoxy resin (trade name "Epi Corporation made by DIC Corporation" Biphenyl novolak-type epoxy resins, such as clone N-670-EXP-S ") and NC-3000P (made by Nihon Kayaku Co., Ltd.), naphthalene phenol novolak-type epoxy resins, such as ESN-165S (made by Totogsei Co., Ltd.), and epi Coat 630 (made in Japan epoxy resin company), rubber modified type epoxy resin (brand name "PB3600" made by Daiserugagaku Corporation), bisphenol A type episulfide resin (brand name "epi coat YL-7000" made by Japan epoxy resin company) And alicyclic epoxy resins (trade names "Celoxide 2021", "Celoxide 2080", "Celoxide 3000", "EHPE" manufactured by Daiserugaku Co., Ltd.) and the like.

As a commercial item of the cationically polymerizable compound which has the said 1 or more vinyl ether group, 4-vinyloxy butanol (brand name "Vinyl-4-hydroxybutylether" by BASF Corporation), triethylene glycol divinyl ether (brand name "Rapi-Cure by ISP company") DVE-3 '), 1, 4- cyclohexane dimethanol divinyl ether (brand name "CHDVE" by Nippon Carbide Industries, Ltd.) etc. are mentioned.

As a cationically polymerizable compound which has 1 or more oxetanyl group in 1 molecule, 3-ethyl-3- (phenoxymethyl) oxetane (brand name "OXT-211" by Toagosei Co., Ltd.), 3-ethyl is mentioned, for example. 3- (cyclohexyl) methyl oxetane (trade name "CHOX" by Toagosei Co., Ltd.) etc. are mentioned. Examples of the compound having two or more oxetane rings include 1,4-bis [{(3-ethyloxetane-1 yl) methoxy} methyl] benzene (trade name "OXT-121" manufactured by Toagosei Co., Ltd.), 1,3- Bis [(3-ethyloxetane-3 yl) methoxy] benzene (brand name "OXT-223" made by Toagosei Co., Ltd.), bis [1-ethyl (3-oxetanyl)] methyl ether (brand name of Toagosei Co., Ltd. make "OXT-221"), phenol novolak oxetane (brand name "PNOX-1009" made by Toagosei Co., Ltd.), 4,4'-bis [{(3-ethyloxetane-1 yl) methoxy} methyl] biphenyl (Trade name "OXBP" by the Ubegosan Co., Ltd.) is mentioned.

Among the above cationically polymerizable compounds, the cohesive force is obtained by the use of the interaction between the aromatic rings and is advantageous for adhesion, and therefore, the polymerizable compound having an epoxy group having an aromatic ring is particularly preferable. Specifically, bisphenol A type epoxy resin (brand name "Epiclon 850CRP", "Epiclon 850S", "Epiclon 1050", "Epiclon 1055", "Epiclon 4822" by DIC Corporation), bisphenol F type epoxy resin (Trade name "Epiclon 830CRP", "Epiclon 830" by DIC Corporation), etc. are mentioned.

In particular, since a viscosity is low and the dilution effect with the compound represented by General formula (1) is also high, bisphenol-A epoxy resin (brand name "Epiclon 850CRP" made by DIC Corporation), bisphenol F-type epoxy resin (brand name "made by DIC Corporation" Epiclonal 830CRP '') is particularly preferred.

When using as a sealing agent for liquid crystal displays, it is preferable to use a hydrogenated bisphenol-type epoxy resin from a viewpoint of reducing the contamination with respect to a liquid crystal. Specifically (brand name "Epiclon EXA7015" made in DIC Corporation, brand name "Epicoat YX-8000" made in Japan epoxy resin company, "Epicoat YX-8034", brand name "EX-216L" made by Nagase Chemtex Corporation) are mentioned Can be.

The cationically polymerizable compound of the present invention may be used in combination with a radical curable composition (hereinafter referred to as a radical curable composition).

(Composition of Radical Curing System)

A radical curable composition is a composition containing a radically polymerizable compound and a radical polymerization initiator. As a radically polymerizable compound, if it is a well-known conventional compound which has a (meth) acryloyl group generally used in the field of UV hardening, there will be no restriction | limiting in particular, When using for liquid crystal panel sealing, a thing which is hard to mix with a liquid crystal is more preferable. Can be used. However, in order to avoid excessive hardening shrinkage, (meth) acrylates, such as dipentaerythritol penta, hexaacrylate, and pentaerythritol tetraacrylate, which have large hardening shrinkage, are preferably avoided by using a small amount. Moreover, since the radically polymerizable compound which has a carboxylic acid group may react with an epoxy group during storage, and may raise a composition viscosity rapidly, it is preferable to avoid it by using a small amount.

Epoxy (meth) acrylate, ethyl oxide, propylene oxide, cyclic compounds obtained by modifying polyester (meth) acrylate and epichlorohydrin having an ester bond in the main chain structure and having at least two (meth) acryloyl groups (Meth) acrylate modified with lactone or the like can also be preferably used. However, when the acrylate having a urethane group is combined with a cationic curing system, curing inhibition by the urethane group occurs, so it is preferable to avoid using a small amount.

As a specific example of the (meth) acrylate used by this invention, the glycerin monomethacrylate (brand name "Blemmer GLM" by Nippon Yushi Corporation) and acryloyloxyethyl phthalate (made by Kyoeisha Chemical Co., Ltd.) are mentioned, for example. Brand name "HOA-MPE"), benzyl (meth) acrylate (brand name "biscoat # 160" made by Osaka Yuki Chemical Co., Ltd.), nonylphenoxy polyethylene glycol acrylate (brand name "Aronix M111" made by Toagosei Corporation, " Aronix M113 "," Aronix M117 "), ECH modified phenoxyacrylate (brand name" Aronix M5700 "made by Toagosei Corporation), EO modified succinic acid acrylate (brand name" HOA-MS "made by Kyoeisha Chemical Co., Ltd.) ), (Meth) acrylic, such as EO modified phosphate methacrylate (brand name "P-1M" made by Kyoeisha Chemical Co., Ltd.), rosin modified epoxy acrylate (brand name "beam set 101" by Arakawa Chemical Co., Ltd.) Having one diary ( Meta) acrylate, bis (acryloylethyl) hydroxyethyl isocyanurate (trade name "Aronix M215" made by Toagosei Co., Ltd.), EO modified bisphenol A diacrylate (brand name "ADPE-150" made by Nippon Yushi Corporation) ), PO modified bisphenol A diacrylate (brand name "ADBP-200" made by Nippon Oil Industries, Ltd.), ECH modified bisphenol A type acrylate (brand name "DICLITE UE8200" made by DIC Chemical Corporation), ECH modified phthalic acid diacrylate (Nagase Brand name "DA-721" made by Kasei Co., Ltd., ECH modified hexahydrophthalic acid diacrylate (brand name "DA-722" made by Nagase Kasei Co., Ltd.), and tricyclodecane dimethanol diacrylate (brand name "made by Daiseru UCB company" IRR214 "), rosin modified ester acrylate (brand name" beam set 115B "made by Arakawa Chemical Co., Ltd.), EO modified phosphoric acid dimethacrylate (brand name" P-2M "by Kyoeisha Chemical Co., Ltd.), tris (acrylo) Monooxyethyl) Cyanurate (brand name "Aronix M315" made by Doagosei Co., Ltd.), dimethylol propane tetraacrylate (brand name "Aronix M408" made by Doagosei Co., Ltd.), dipentaerythritol hexaacrylate (brand name "made by Nippon Kayaku Corporation" Kaya rad DPHA), two or more (meth) acrylo, such as caprolactone modified dipentaerythritol hexaacrylate (brand name Kaya rad DPCA-30, Kaya rad DPCA-120 by Nihon Kayaku Co., Ltd.) (Meth) acrylate etc. which have a diary are mentioned.

Especially among the said radically polymerizable compounds, the (meth) acrylate modified with lactone and the (meth) acrylate modified with rosin are especially preferable because it makes the curable composition soft and adhesiveness favorable. Specifically, lactone modified hydroxy pivalate neopentyl glycol diacrylate (brand name "HX620" made by Nippon Kayaku Co., Ltd.), lactone modified BPA epoxy phthalate ester diacrylate (brand name "Ebecryl 3708" made by Daicel Cytec Co., Ltd.) And rosin-modified epoxy acrylate (trade name "Beamset 101" manufactured by Arakawa Chemical Co., Ltd.).

The usage-amount of the said radically polymerizable compound will not be specifically limited if it is a range which does not impair the range of this invention. Specifically, it is preferable that it is the range of 20-70 mass%.

Moreover, as a radical photoinitiator, benzophenone, 2, 2- diethoxy acetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, etc. can be used, for example. have. These radical photopolymerization initiators may be used independently and may use 2 or more types together.

Moreover, the maleimide compound which has photoinitiation property can also be used. As a specific example of the maleimide compound which has photoinitiation ability, the maleimide compound of Unexamined-Japanese-Patent No. 2000-19868 and Unexamined-Japanese-Patent No. 2004-070297 is mentioned, for example.

Examples of the radical thermal polymerization initiators include peroxide or azo initiators. Examples of the peroxide thermal polymerization initiator include 3,5,5-trimethylhexanoyl peroxide (trade name: Peroyl355, manufactured by Nichi Corporation), 2,4-dichlorobenzoyl peroxide (trade name: Naper CS, Nichi Corporation Diacyl peroxides, such as is), isobutyl peroxide (brand name: peroyl IB, Nichi Corporation), dilauroyl peroxide (brand name: perroyl L, Nichi Corporation); Di (3-methyl-3-methoxybutyl) peroxydicarbonate (brand name: Peroyl SOP, Nichiyu Corporation), di-2-methoxybutyl peroxydicarbonate (brand name: Peroyl MBP, Nichiyu Corporation), di 2-ethylhexyl peroxydicarbonate (brand name: peroyl OPP, Nichiyu Corporation), di-2-ethoxyethyl peroxydicarbonate (brand name: Peroyl EEP, Nichiyu Corporation), diisopropyl peroxydicarbonate (brand name) : Peroxydicarbonates, such as a peroyl IPP and Nichi Corporation, and a bis- (4-t-butyl cyclohexyl) peroxydicarbonate (brand name: perroyl TCP, Nichi Corporation); t-butyl peroxy pivalate (brand name: perbutyl PV, Nichi Corporation), t-hexyl peroxy pivalate (brand name: perhexyl PV, Nichi Corporation), t-butyl peroxy neodecanoate (brand name: Perbutyl ND, Nichi oil company, t-hexyl peroxy neodecanoate (brand name: perhexyl ND, Nichi oil company), t-hexyl peroxy isopropyl monocarbonate (brand name: perhexyl I, Nichi oil company) , 1-cyclohexyl-1-methylethyl peroxy neodecanoate (trade name: percycloND, Nichiyu Co., Ltd.), 1,1,3,3-tetramethylbutyl peroxy neodecanoate (brand name: perocta ND, Nichiyu Corporation), cumyl peroxy neodecanoate (brand name: Percumyl ND, Nichiyu Corporation), (α, α'-bis-neodecanoyl peroxy) diisopropylbenzene (brand name: diper ND And peroxy esters, such as Nichi Oil Co., Ltd., etc. are mentioned.

As an azo thermal polymerization initiator, it is 2,2'- azobis (4-methoxy-2, 4- dimethylvaleronitrile) (brand name: V-70, made by Wako Pure Chemical Industries, Ltd.), 2,2 ', for example. -Azobis (2-cyclopropyl propionitrile) (brand name: V-68, the product made by Wako Pure Chemical Industries, Ltd.), 2,2'- azobis (2, 4- dimethylvaleronitrile) (brand name: V-65, Waco Azonitrile compounds such as Junyaku Corporation); 2,2'-azobis (2-methyl-N-phenylpropionamidine) (trade name: VA-545, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [N- (4-chlorophenyl) -2 -Methylpropionamidine] dihydrochloride (trade name: VA-546, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [N- (4-hydroxyphenyl) -2-methylpropionamidine] dihydrochloride (Brand name: VA-548, product made by Wako Pure Chemical Industries, Ltd.), 2,2'- azobis [N- (4-aminophenyl) -2-methylpropionamidine] tetrahydrochloride (brand name: VA-500, product of Wako Pure Chemical Industries, Ltd.) Agent), 2,2'-azobis [2-methyl-N- (phenylmethyl) -propionamidine] dihydrochloride (trade name: VA-552, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis ( 2-methyl-N-propenylpropionamidine) dihydrochloride (trade name: VA-553, manufactured by Wakojunyaku Corporation), 2,2'-azobis (2-methylpropionamidine) dihydrochloride (brand name: V -50, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine Azoamidine compounds such as dihydrochloride (trade name: VA-558, manufactured by Wako Pure Chemical Industries, Ltd.); 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (trade name: V-041, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (trade name: V-044, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (4,5,6,7 -Tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride (trade name: V-054, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (3,4, 5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride (trade name: V-058, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (5-hydroxy-3,4 And cyclic amidine compounds such as 5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride (trade name: V-059, manufactured by Wako Pure Chemical Industries, Ltd.), and the like.

The said radical photoinitiator may be used independently and may use 2 or more types together. Moreover, although it does not specifically limit as a compounding ratio of the said radical polymerization initiator, A preferable minimum is 0.1 mass part and a preferable upper limit is 20 mass parts with respect to 100 mass parts of curable compositions. If it is less than 0.1 mass part, the sclerosis | hardenability of the sealant of this invention may become inadequate, and when it exceeds 10 mass parts, the radical photoinitiator which cannot fully react may remain in large quantities, and may elute to a liquid crystal. The minimum with more preferable is 0.3 mass part, and a more preferable upper limit is 10 mass parts.

In addition, when using together a radical curing system and a cation curing system, the compound which has group of both a radically polymerizable group and a cationically polymerizable group can also be used. As a polymeric compound which has group of both a radically polymerizable group and a cationically polymerizable group, for example, in a commercially available BPF epoxy half acrylate and BPA epoxy half acrylate (brand name "UVa1561" by Daicel Cytec Co., Ltd.) and one molecule The compound in which one part of the epoxy groups of the compound which has two or more epoxy groups was made to react (meth) acrylic acid, and was (meth) acryloylated is mentioned.

Especially, BPA epoxy half acrylate and BPF epoxy half acrylate have a high dilution effect, and are more preferable.

In this invention, if it uses the radical hardening system and cation hardening system together, specifically, the composition which the epoxy group coexisted as a (meth) acryloyl group as a radical photocuring system and a cation hardening system in the said composition, The epoxy group is more preferably cationic polymerization and the (meth) acryloyl group by radical polymerization and curing, and can be firmly adhered to the substrate. In this case, in order to advance superposition | polymerization more efficiently, it is preferable to use together the radical polymerization initiator which radically polymerizes the (meth) acryloyl group with the cationic polymerization initiator which carries out cationic polymerization of an epoxy group in the said curable composition.

The cation curable adhesive of this invention can further reduce metal corrosion by using a basic solid substance together.

(Basic solid material)

The basic solid substance used by this invention can be used if it is a compound of the solid which has a function which neutralizes or captures an acid. Since the polymerization reaction of the cationically polymerizable compound is generated by the acid generated from the cationic polymerization initiator, it is necessary to neutralize and supplement the excess acid after the polymerization has sufficiently proceeded by the acid. Since the basic solid substance in this invention is used in the state contained in the adhesive agent, there exists a possibility to inhibit cationic polymerization. Thus, basic solid materials are required to be substantially insoluble in the cationically polymerizable compound. It is preferable that the solubility of a basic solid substance is 0.02 mass part or less with respect to 100 mass parts of cationically polymerizable compounds. If the solubility of a basic solid substance is high, the generated acid will immediately be trapped by a basic solid substance and superposition | polymerization of a cationically polymerizable compound will not progress and adhesive performance cannot fully be exhibited.

In addition, the particle size of the basic solid material is preferably finer in order to prevent the generated acid from leaking from the adhesive to the outside. Since the particle size has a physical limit, when the particles of the basic solid substance to be used do not aggregate and remain as primary particles, the particle size is preferably 0.01 to 50 µm, more preferably 0.01 to 5 µm, and 0.01 to 1 µm. More preferred. When the particles of the basic solid substance to be used aggregate to form secondary particles, the size of the secondary particles is preferably in the above range. Moreover, when using as a basic solid substance for the sealing agent of a liquid crystal display, 0.01-2 micrometers is preferable from the limitation of the board | substrate spacing of two sheets.

Examples of the inorganic basic solid substance include various inorganic salts (carbonates, phosphates, carboxylates, etc.), metal oxides, metal sulfides, metal nitrides, basic clay minerals, and the like, and basic surfaces of these inorganic solids. Specific examples of the inorganic salts include calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, magnesium bicarbonate, zinc carbonate, calcium phosphate and phosphoric acid. Magnesium, sodium phosphate, potassium phosphate, barium phosphate, sodium citrate, potassium citrate, calcium citrate, magnesium citrate, magnesium oxalate, sodium oxalate, potassium oxalate, sodium tartrate, potassium tartrate, basic as glass oxide, alumina (active Alumina), zeolite, titanium oxide, zinc oxide, silica gel, tin oxide, zirconium oxide, magnesium oxide, calcium oxide, basic zinc sulfide as metal sulfide, basic titanium nitride as metal nitride, basic talc as clay mineral, metal hydroxide Basic magnesium hydroxide etc. can be mentioned as an example.

In the present invention, as the basic solid substance, basic glass beads, basic titanium oxide, basic zinc oxide, basic silica gel, basic tin oxide, basic zirconium oxide, basic titanium nitride, basic zinc sulfide, and the like are, for example, precursors thereof. Phosphorus metal oxides, metal nitrides and metal sulfides can be made basic by treating them with a nitrogen compound such as a silane coupling agent having a basic group such as an organic amino group or hexamethyldisilazane. However, this invention is not limited to these.

As an organic basic solid substance, the polymer synthesize | combined by superposing | polymerizing the monomer which has a basic functional group (for example, an organic amino group, a nitrogen atom containing heterocyclic group, a weak acid strong base functional group, etc.) contains a basic functional group on the surface of an organic polymer bead. The thing which carried out the coupling process with the compound and the said polymer beads coated with the said polymers are mentioned. The present invention is not limited to these. The organic basic solid substance can be synthesized by various methods, and a commercially available organic basic solid substance can also be used. Specifically, the epamine (made by Nihon Shokubai Co., Ltd.) of polyethyleneimine can be illustrated.

In the present invention, as the basic solid substance, basic clay minerals such as talc or basic functional groups can be easily introduced, and can be reproduced by surface treatment, have sufficient surface area, high safety, and easy availability. Calcium carbonate, barium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, magnesium bicarbonate, glass beads, alumina (active alumina), zeolite, titanium oxide, zinc oxide, silica, In addition, polymers having a basic functional group (for example, an organic amino group, a nitrogen atom-containing heterocyclic group, a weak acid strong base functional group, etc.), a surface of an organic polymer bead coupled with a basic functional group-containing compound, and the polymer beads Beads coated with polymers are preferred. Especially, the silica which introduce | transduced basic viscosity minerals, such as talc, and a basic functional group is preferable.

Since basicity which a basic solid has may inhibit the hardening reaction of a cationically polymerizable compound, weak base is more preferable than strong base, or the density of the basic group on the surface of a basic solid is more preferable. This is because it is preferable that the base of the basic solid gradually neutralizes the remaining acid after the acid generated by the cationic polymerization initiator sufficiently generates a curing reaction of the cationically polymerizable compound.

(Other component silane coupling agent)

Moreover, in order to improve adhesiveness, you may mix the well-known silane coupling agent with the cation curable liquid crystal sealing agent of this invention. Among such silane coupling agents, silane coupling agents having a polymerizable group such as a (meth) acryloyl group or an epoxy group are particularly preferable because they can be copolymerized with a radical curing system or a cationic curing system compound to obtain high adhesiveness.

As a silane coupling agent which has a polymeric group, 3- (meth) acryloyloxypropyl trimethoxysilane, 3-epoxyoxypropyl trimethoxysilane, etc. are mentioned, for example. As a commercial item of the silane coupling agent which has such a polymeric group, For example, brand names "KBM503", "KBE503", "KBM502", "KBE502", "KBM5102", "KBM5103", "KBM403" made by Shin-Etsu Chemical Co., Ltd., etc. are mentioned, for example. Can be mentioned.

As for the usage-amount when using the said silane coupling agent together, it is preferable to use in the range of 0.1-10 mass% with respect to the amount of all curable compositions, and the range of 1-5 mass% is especially preferable. When the ratio of a silane coupling agent is less than 0.1 mass%, sufficient adhesive effect may not be acquired, and there exists a possibility that phase separation may be carried out in the quantity exceeding 10 mass%. The minimum with more preferable is 0.5 mass part, and a more preferable upper limit is 5 mass parts.

(Other ingredients)

A well-known additive and filler can also be suitably added to the cation-curable liquid-crystal sealing agent of this invention according to the objectives, such as viscosity adjustment and storage stability.

For example, a filler can be mix | blended suitably other than the dispersible micro support which carried the cationically polymerizable compound in this invention. By mix | blending a filler, it adds for the purpose of the improvement of the adhesiveness of the sealing agent of this invention by the stress dispersion effect, the improvement of a linear expansion rate, etc. For example, talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, magnesium oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, barium sulfate, gypsum, calcium silicate And inorganic fillers such as talc, glass beads, sericite activated clay, bentonite, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.

Although the compounding ratio of the said filler is not specifically limited, As a compounding quantity containing the dispersible microcarrier of this invention, a preferable minimum with respect to 100 mass parts of said curable compositions is 1 mass part, and a preferable upper limit is 100 mass parts. If it is less than 1 mass part, the effect which added the filler can hardly be acquired, and when it exceeds 100 mass parts, there exists a possibility that handling property, such as the drawing property of the seal agent of this invention, may be reduced. A minimum with more preferable 5 mass parts and a more preferable upper limit are 50 mass parts.

(Viscosity)

The cation-curable liquid-crystal sealing agent of this invention is more preferable as a liquid crystal sealing agent for manufacture of the liquid crystal display element by the dropping method mentioned later that the viscosity measured at 25 degreeC and 2sec- ¹ using an E-type viscosity meter is 100 Pa.s or more. Can be used. When it is less than 100 Pa.s, when manufacturing a liquid crystal display element by the dropping method, the shape of the seal pattern formed on the transparent substrate cannot be maintained, and a sealant component may elute in a liquid crystal, and liquid crystal contamination may arise. The minimum with more preferable is 100 Pa.s, and a more preferable upper limit is 5000 Pa.s. When it exceeds 5000 Pa.s, the drawing property of the sealant of this invention may not be enough, and manufacture of the liquid crystal display element by a dropping method may become difficult. It does not specifically limit as E-type viscometer which measures a viscosity at this time, For example, "DV-III" made from Brookfield, etc. can be used.

(Liquid crystal seal agent)

The cation-curable liquid crystal sealing agent of the present invention can be used as a sealing agent for sealing an injection hole after injecting a liquid crystal material into a liquid crystal panel, in addition to the sealing agent when preparing a liquid crystal panel.

The liquid crystal panel is coated with the photocationic curable liquid crystal sealant of the present invention on any one of the substrate surfaces of the front or rear substrate provided with, for example, a thin film transistor, a pixel electrode, an alignment film, a color filter, an electrode, and the like. One board | substrate is stuck, light is irradiated from the board surface side of the said board | substrate, or the side surface of the said board | substrate, and the photocurable composition for liquid crystal panel seals of this invention is hardened. Next, after inject | pouring a liquid crystal into the obtained liquid crystal cell, a liquid crystal panel can be created by sealing an injection hole with a sealing agent.

In addition, the liquid crystal panel has a liquid crystal dropping method, that is, a step of forming a seal pattern on one side of two transparent substrates with an electrode using the photocationic curable liquid crystal sealant of the present invention, and a small amount of liquid crystal in the seal pattern range. It can obtain by carrying out the process of dripping-coating on the whole inner surface, the process of laminating | stacking the other transparent substrate through the said seal pattern, and the process of irradiating light to the said seal pattern in this order.

When the photocationic curable liquid crystal sealing agent of the present invention does not cure immediately after irradiating ultraviolet rays, but exhibits delayed curing properties such as curing after maintaining the state of a viscous fluid for a while, one of two transparent substrates with electrodes The process of forming a seal pattern using the photocationic curable liquid crystal sealing agent of this invention, the process of light-irradiating to the said seal pattern, the process of dripping and applying a minute amount of liquid crystal to the whole surface in the said seal pattern range, and the other It can also be obtained by superimposing the transparent substrates and bonding them through the seal pattern in this order.

Examples of the cationically curable liquid crystal sealing agent that exhibits delayed curing properties include the cationically polymerizable compound and a composition of the compound and the reaction retardant. Although it does not specifically limit as said reaction retardant, For example, a polyol compound etc. can be used. By containing the said reaction retardant, the pot life and hardening time after irradiating light or heat-processing to the cationically curable liquid crystal sealing agent of this invention can be controlled. It is preferable that it is an aliphatic polyol among the said polyol compounds, As this aliphatic polyol, (poly) alkylene glycol, glycerin, polyglycerol, such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, butylene glycol, for example And the like using pentaerythritol, polycaprolactone polyol, crown ether, and the like. The kind of photocationic polymerization initiator supported on one dispersible micro support is not specifically limited, The above-mentioned thing can be used.

In order to form the cationically curable liquid crystal sealant of the present invention on the substrate surface, it is preferable to apply by using a dispenser or to apply by screen printing. In that case, it is common to apply | coat at line width 0.08-2 mm and line height 5-50 micrometers.

Ultraviolet rays or visible rays are preferable, and the light of the wavelength used for hardening the photocationic curable liquid crystal sealing agent of this invention is especially preferable, The light of the wavelength of 300 nm-400 nm is preferable. As a light source, a high pressure mercury lamp, a metal halide lamp, etc. can be used, for example. If the illuminance of the said light source is 500 W / m <2> or more, hardening is fast and it is preferable. The amount of light to be irradiated can be cured satisfactorily if it is 20000 J / m <2> or more in conversion light quantity. Moreover, although the photocationic curable liquid-crystal sealing agent of this invention shows favorable photocurability also in an air atmosphere, since it can harden | cure with a small amount of accumulated light, when photocuring in inert gas atmosphere, such as nitrogen, it is more preferable.

[Example]

Hereinafter, an Example and a comparative example demonstrate this invention concretely. Moreover, evaluation about adhesiveness and voltage retention was performed as follows.

(Production Example 1 Manufacturing method of photocationic polymerization initiator supported on a dispersible microcarrier)

As a photocationic polymerization initiator, Adeka Optomer SP150 manufactured by Adeka Corporation was used. Moreover, SP150 is a propion carbonate solution of 50% of solid content concentration, and the usage-amount (mass part) mentioned later was made into the mass part containing a solvent.

1 mass part photocationic polymerization initiator "SP150" was added and dissolved in 20 mass parts acetone. Subsequently, 1 mass part of silica "Aerosil300 surface areas 300 m <2> / g" by Nippon Air Products Co., Ltd. was added to the said acetone solution of "SP150", and it disperse | distributed in the solution by the ultrasonic disperser. Then, this dispersion solution is vacuum-dried at room temperature (20-25 degreeC), acetone is distilled off, and the photocationic polymerization initiator (A) supported on the dispersible micro support (henceforth called a supported photocationic polymerization initiator (A)). Got. In calculation, the loading amount of the photocationic polymerization initiator on silica was 0.5 g (0.5% by mass since NV. 50%) / (1 g × 300 m 2 /g)=1.7×10 ⁻³ g / m 2. Using a fluorescence X-ray analyzer, the intensity ratio of the characteristic X-rays of silica and sulfur was determined, the content of the photocationic polymerization initiator was estimated from the content of sulfur, and the content ratio of the present initiator (supported mass of the photocationic polymerization initiator) / (silica + The supported mass of the photocationic polymerization initiator) was 28%. Therefore, the supported amount of the photocationic polymerization initiator with respect to silica calculated from the value calculated | required by the fluorescent X-ray analyzer is 1.3x10 <^-3> g / m <2>.

(Production Example 2 Method for producing a photocationic polymerization initiator supported on a dispersible microcarrier)

1 mass part photocationic polymerization initiator "SP150" was added and melt | dissolved in the mixed solvent which consists of 16 mass parts acetone and 4 mass parts water. Subsequently, 1 mass part of silica "Aerosil300 specific surface areas 300 m <2> / g" made from Nippon Air Corporation was added to the said "SP150" solution, and it disperse | distributed in the solution by the ultrasonic disperser. The dispersion solution was vacuum dried while maintaining the temperature at 0 ° C. or lower, and the acetone was distilled off, and vacuum drying was continued as it was at room temperature. After acetone is distilled off, it is vacuum-dried while water is frozen, and what is called freeze-drying is performed. The following washing | cleaning was performed in order to remove the initiator which adsorbed in addition to the pore by the said silica carrying photocationic polymerization initiator after drying. 20 mass parts of the silica-supported photocationic polymerization initiators were dispersed and stirred in 100 mass parts of ethyl acetate solution, and ethyl acetate was removed by a centrifugal separator. This was repeated four times in total, and then the silica-supported photocationic polymerization initiator after centrifugation was stirred in 100 parts by mass of ultrapure water, and water was removed by a centrifugal separator. This was repeated four times in total, and the silica-supported photocationic polymerization initiator after centrifugation was vacuum dried at room temperature to obtain a supported photocationic polymerization initiator (B).

When the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur using a fluorescent X-ray analyzer, (supported mass of the photocationic polymerization initiator) / (supported mass of the silica + photocationic polymerization initiator) is It was 12 mass%. Therefore, the supported amount of the photocationic polymerization initiator with respect to the silica calculated from this content rate is 4.5x10 <^-4> g / m <2>.

(Production Example 3 Method for Producing Thermocation Polymerization Initiator Supported on Dispersible Microcarrier)

1 mass part of thermal cationic polymerization initiator "acid aid SI100L" was added and melt | dissolved in the mixed solvent which consists of 16 mass parts acetone and 4 mass parts water. Subsequently, 1 mass part of silica "Aerosil300 specific surface areas 300 m <2> / g" by the Nippon Aerosol Co., Ltd. was added to the said "SI100L" solution, and it disperse | distributed in the solution by the ultrasonic disperser. The dispersion solution was vacuum dried while maintaining the temperature at 0 ° C. or lower, and the acetone was distilled off, and vacuum drying was continued as it was at room temperature. After acetone is distilled off, it is vacuum-dried while water is frozen, and what is called freeze-drying is performed. The following washing | cleaning was performed in order to remove the initiator adsorbed other than a pore from the said silica carrying thermal cationic polymerization initiator after drying. 20 mass parts of the silica-supported thermocationic polymerization initiators were dispersed and stirred in 100 mass parts of ethyl acetate solution, and ethyl acetate was removed by a centrifugal separator. This was repeated four times in total, and then the silica-supported thermocationic polymerization initiator after centrifugation was stirred in 100 parts by mass of ultrapure water, and water was removed by a centrifugal separator. This was repeated four times in total, and the silica-supported thermocationic polymerization initiator after centrifugation was vacuum dried at room temperature to obtain a supported thermocationic polymerization initiator (C).

Using a fluorescence X-ray analyzer, the content ratio of the thermal cationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur, and the (supporting mass of the thermal cationic polymerization initiator) / (supporting mass of the silica + thermal cationic polymerization initiator) is , 9%. Therefore, the supported amount of the thermal cationic polymerization initiator with respect to the silica calculated from this content ratio is 3.3x10 <^-4> g / m <2>.

(Production Example 4 Manufacturing method of photocationic polymerization initiator supported on a dispersible microcarrier)

For the first time, MCM41, a mesoporous body of silica, was adjusted. As a template, 7.3 parts by mass of a surfactant and docosyltrimethylammonium chloride (C22TMACl) were added to 60 parts by mass of ion-exchanged water, completely dissolved at 60 ° C, and then 24 parts by mass of 10% (w / w) sulfuric acid aqueous solution was added. It was a liquid. 10 parts by mass of water glass (SiO ₂ , 36-38%, Na ₂ O, 17-19%) and 20 mL of ion-exchanged water were added to make a liquid b. While maintaining a liquid at 60-65 degreeC and stirring vigorously, b liquid was added to it, pH of the reaction liquid was adjusted to 8.5 with 10% (w / w) sulfuric acid, and it stirred for 5 to 8 hours then. Next, this liquid mixture was transferred to a 250 ml autoclave and heat-treated at 105 degreeC for 2 to 5 days. The reaction solution was vacuum filtered to obtain about 9 g of crude product. The crude product was air dried at 45 ° C. for 24 hours and calcined for 6 hours in an electric furnace at 550 ° C. to obtain approximately 4.5 g of mesoporous body (c) from which the template was removed. The pore diameter and surface area of the mesoporous body were measured by N2 adsorption apparatus (Autosorb). The pore diameter was 4.6 nm and specific surface area 1080 m 2 / g.

1 mass part photocationic polymerization initiator "SP150" was added and melt | dissolved in the mixed solvent which consists of 16 mass parts acetone and 4 mass parts water. Subsequently, 1 mass part of said mesoporous bodies (c) were added to the said "SP150" solution, and it disperse | distributed in solution by the ultrasonic disperser. The dispersion solution was vacuum dried while keeping the dispersion solution at 0 ° C. or lower, and acetone was distilled off, followed by vacuum drying. After acetone is distilled off, it is vacuum-dried while water is frozen, and what is called freeze-drying is performed. The following washing | cleaning was performed in order to remove the initiator adsorbed other than a pore from the silica supported photocationic polymerization initiator after drying. 20 mass parts of the silica-supported photocationic polymerization initiators were stirred in 100 parts by weight of an ethyl acetate solution, and ethyl acetate was removed by a centrifugal separator. This was repeated four times in total, and then, the silica-supported photocationic polymerization initiator after centrifugation was stirred in 100 parts by mass of ultrapure water, and water was removed by a centrifugal separator. This was repeated four times in total, and the silica-supported photocationic polymerization initiator after centrifugation was vacuum dried at room temperature to obtain a supported photocationic polymerization initiator (D).

When the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur using a fluorescent X-ray analyzer, (supported mass of the photocationic polymerization initiator) / (supported mass of the silica + photocationic polymerization initiator) is , 18%. Therefore, the supported amount of the photocationic polymerization initiator with respect to the silica calculated from this content ratio is 2.0x10 <^-4> g / m <2>.

(Production Example 5 Manufacturing Method of Photocationic Polymerization Initiator Supported on Dispersible Microcarrier)

2 mass parts photocationic polymerization initiator "SP150" was added and melt | dissolved in the mixed solvent which consists of 16 mass parts acetone and 4 mass parts water. Subsequently, 1 mass part of silica "Aerosil300" by the Nippon Aerosol Co., Ltd. was added to the said "SP150" solution, and it disperse | distributed in the solution by the ultrasonic disperser. The dispersion was vacuum dried while maintaining the dispersion solution at 0 ° C. or lower, and the acetone was distilled off, and vacuum drying was continued at room temperature as it was, followed by freeze drying. This is referred to as a supported photocationic polymerization initiator (E).

When the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur using a fluorescent X-ray analyzer, (supported mass of the photocationic polymerization initiator) / (supported mass of the silica + photocationic polymerization initiator) is , 62%. Therefore, the supported amount of the photocationic polymerization initiator with respect to the silica calculated from this content ratio is 5.4x10 <^-3> g / m <2>.

(Production Example 6 Method for producing photocationic polymerization initiator supported on a dispersible microcarrier)

0.2 mass part photocationic polymerization initiator "SP150" was added and melt | dissolved in the mixed solvent which consists of 16 mass parts acetone and 4 mass parts water. Subsequently, 1 mass part of MCM41 of manufacture example 4 was added to the solution of "SP150", and it disperse | distributed in solution by the ultrasonic disperser. The dispersion solution was vacuum dried while keeping the dispersion solution at 0 ° C. or lower, and the acetone was distilled off, and vacuum drying was continued as it was, followed by freeze drying. This is referred to as a supported photocationic polymerization initiator (F).

When the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur using a fluorescent X-ray analyzer, (supported mass of the photocationic polymerization initiator) / (supported mass of the silica + photocationic polymerization initiator) is , 4%. Therefore, the supported amount of the photocationic polymerization initiator with respect to the silica calculated from this content rate is 3.9x10 <^-5> g / m <2>.

(Manufacture example 7 manufacturing method of photocationic polymerization initiator supported on a dispersible micro support)

1 mass part photocationic polymerization initiator "SP150" was added and melt | dissolved in the mixed solvent which consists of 16 mass parts acetone and 4 mass parts water. Subsequently, 1 mass part of silica "Aerosil OX50 (specific surface area 50m <2> / g)" by the Nippon Aerosol Co., Ltd. was added to the said "SP150" solution, and it disperse | distributed in the solution by the ultrasonic disperser. The dispersion solution was vacuum dried while keeping the dispersion solution at 0 ° C. or lower, and the acetone was distilled off, and vacuum drying was continued as it was, followed by freeze drying. The following washing | cleaning was performed in order to remove the initiator which adsorbed other than pore from the supported photocationic polymerization initiator after drying. 20 mass parts of the said silica supported photocationic polymerization initiators were stirred in 100 mass parts of ethyl acetate solutions, and ethyl acetate was removed by the centrifuge. This was repeated four times in total, and then, the silica-supported photocationic polymerization initiator after centrifugation was stirred in 100 parts by mass of ultrapure water, and water was removed by a centrifugal separator. This was repeated four times in total, and the supported photocationic polymerization initiator after centrifugation was vacuum dried at room temperature to obtain a supported photocationic polymerization initiator (G).

When the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur using a fluorescent X-ray analyzer, (supported mass of the photocationic polymerization initiator) / (supported mass of the silica + photocationic polymerization initiator) is , 2%. Therefore, the supported amount of the photocationic polymerization initiator with respect to the silica calculated from this content ratio is 4.1x10 <^-4> g / m <2>.

(Manufacture example 8 manufacturing method of photocationic polymerization initiator supported on a dispersible micro support)

0.02 mass part photocationic polymerization initiator "SP150" was added and melt | dissolved in the mixed solvent which consists of 64 mass parts acetone and 16 mass parts water. Subsequently, 5 mass parts of MCM41 of manufacture example 4 was added to the said "SP150" solution, and it disperse | distributed in solution by the ultrasonic disperser. The dispersion solution was vacuum dried while keeping the dispersion solution at 0 ° C. or lower, and the acetone was distilled off, and vacuum drying was continued as it was, followed by freeze drying. This is referred to as a supported photocationic polymerization initiator (H).

When the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur using a fluorescent X-ray analyzer, (supported mass of the photocationic polymerization initiator) / (supported mass of the silica + photocationic polymerization initiator) is , 0.1%. Therefore, the loading amount of the photocationic polymerization initiator with respect to the silica computed from this content rate is 9.3x10 <^-7> g / m <2>.

(Example 1)

2 mass parts of supported photocationic polymerization initiator (A) was added to 22 mass parts of DIC Corporation epoxy monomer "EXA850crp", it mixed using the rotating revolving mixer-THINKY AR250, and it was set as the sealing agent (A).

At this time, 2.5 mass parts of cationic polymerization initiators are 6.5 mass parts with respect to 100 mass parts of cationically polymerizable compounds.

(Measurement of Evaluation Method Voltage Retention Rate)

It added to 20 mass parts of DIC Corporation liquid crystal "PA-0211CA033" in 1 mass part of sealing agents (A), and stored it at 120 degreeC for 1 hour. This was taken out to room temperature and left still, and the liquid crystal and the sealing agent (A) were phase-separated. The upper liquid crystal part was taken out, and the voltage retention was measured. As for the voltage retention, the liquid crystal cell whose GAP between two glass substrates with an ITO electrode is 5 micrometers is prepared, the initial voltage which is 23 degreeC and 5V AC is applied to the liquid crystal cell which injected the above-mentioned liquid crystal, 64 kV, The voltage ratio before and after the frame time of 200 Hz and 2000 Hz was calculated, and multiplied by 100 to obtain the voltage retention.

The results are shown in Table 1.

(Comparative Example 1)

1 mass part photocationic polymerization initiator "SP150" was mixed with 22 mass parts epoxy monomer "EXA850crp", and then 1 mass part of silica "Aerosil300" was added and mixed, and it was set as the sealing agent (H1).

According to the said evaluation method, the voltage retention was measured. The results are shown in Table 1.

(Comparative Example 2)

1 mass part photocationic polymerization initiator "SP150" was mixed with 22 mass parts epoxy monomers "EXA850crp", and it was set as sealing agent (H2).

According to the said evaluation method, the voltage retention was measured. The results are shown in Table 1.

Reference Example 1

It added to 20 mass parts liquid crystal "PA-0211CA033" in 1 mass part of epoxy monomer "EXA850crp", and stored it at 120 degreeC for 1 hour. When this was taken out to room temperature and left to stand, the liquid crystal and the epoxy monomer were phase separated, and the liquid crystal parts such as upper were taken out. The voltage retention of the collected liquid crystal was measured. The results are shown in Table 1.

(Reference Example 2)

The voltage retention of only liquid crystal "PA-0211CA033" was measured. The results are shown in Table 1.

As shown in Table 1, the liquid crystal of Example 1 using the sealing agent (A) showed the voltage retention equivalent to the liquid crystal of the reference example 2. However, Comparative Example 1, in which only the photocationic polymerization initiator and silica were added to the epoxy monomer separately and only the photocationic polymerization initiator, without supporting the silica, was lower than the voltage retention of Reference Example 2, and the photocationic polymerization initiator was eluted to the liquid crystal. It was suggested.

Moreover, the voltage retention of the reference example 1 which added only the epoxy monomer also falls below the voltage retention of the liquid crystal of the reference example 2. From this, it is suggested that the epoxy monomer itself also includes a factor for lowering the voltage retention. However, the voltage retention shown in Example 1 of the present application is higher than that of Reference Example 1, and from this, the photocationic polymerization initiator supported on the dispersible microcarrier of Example 1 of the present invention is an impurity present in the monomer. It is suggested that it can also adsorb | suck etc.

[Table 1]

(Example 2)

70 parts of epoxy monomer "EXA850crp" made by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether "Denacol EX-212-L" made by Nagase Chemtex Co., Ltd., Shin-Etsu Chemical Co., Ltd. The silane coupling agent "KBM403" made by Shikisha Corporation was mixed with 5 parts and it used until it became uniform using the rotating revolving mixer THINKY AR250. Next, 9 mass parts of supported photocationic polymerization initiators (B) were added, it knead | mixed with 3 rolls and it was set as the sealing agent (B). At this time, with respect to 100 mass parts of cationically polymerizable compounds, a cationic polymerization initiator is 1.1 mass parts and a dispersible micro support is 7.9 mass parts.

On 5 sheets of glass substrate "RZ-B107N1N" with ITO by EHC company, the 5% ethanol dispersion liquid of spacer-"LH11S" by Hayakawa Rubber Co., Ltd. was sprayed. Next, the sealing agent (B) was apply | coated by the dispenser to one glass substrate with ITO so that the sealing agent width of the liquid crystal panel finally obtained may be set to about 1 mm. The sealing agent (B) was apply | coated so that it might become a rectangular drawing line so that an electrode may be put inside and surrounds it. Then, 500 W / m <2> ultraviolet-rays were irradiated to the said sealant (B) part for 20 second using the high pressure metal halide lamp. Before the curing reaction of the sealant (B) is terminated, a suitable amount of liquid crystal "PA-0211CA033" made by DIC Corporation is added dropwise to the inside of the rectangular sealant (B), and the bonding is performed by facing the glass substrate sprayed with a spacer and bonding. Made. The voltage retention was measured after hold | maintaining this liquid crystal panel in the constant temperature and humidity tank of 60 degreeC and 90% of humidity for 480 hours. The voltage retention was 23 DEG C and an initial voltage of 5 V AC was applied at 64 mA, and the voltage ratio before and after the frame time of 167 Hz was determined, and multiplied by 100. The results are shown in Table 2.

Example 3

70 parts of epoxy monomer "EXA850crp" made by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether "Denacol EX-212-L" made by Nagase Chemtex Co., Ltd., Shin-Etsu Chemical Co., Ltd. The silane coupling agent "KBM403" made by Shikisha Corporation was mixed with 5 parts and it used until it became uniform using the rotating revolving mixer THINKY AR250. Next, 9 mass parts of supported thermal cationic polymerization initiators (C) were added, it knead | mixed with 3 rolls and it was set as the sealing agent (C). At this time, the cationic polymerization initiator is 0.8 parts by mass and the dispersible microcarrier is 8.2 parts by mass based on 100 parts by mass of the cationically polymerizable compound.

On 5 sheets of glass substrate "RZ-B107N1N" with ITO by EHC company, the 5% ethanol dispersion liquid of spacer-"LH11S" by Hayakawa Rubber Co., Ltd. was sprayed. Next, the sealing agent (C) was apply | coated by the dispenser to one glass substrate with ITO so that the sealing agent (C) width of the liquid crystal panel finally obtained may be set to about 1 mm. The sealing agent (C) was apply | coated so that it might become a rectangular drawing line so that an electrode may be put inside and surrounds it. It was heat treated at 120 ° C. for 60 seconds. Before completion of the curing reaction of the sealant (C), an appropriate amount of liquid crystal "PA-0211CA033" made by DIC was added dropwise to the inside of the rectangular sealant (C), and the bonding was performed by facing the glass substrate sprayed with a spacer. Made a panel. This panel was processed at 120 degreeC for 1 hour, and hardening of the sealing agent (C) was accelerated | stimulated.

Voltage retention was measured like Example 2, and the result was shown in Table 2.

(Example 4)

70 parts of epoxy monomer "EXA850crp" made by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether "Denacol EX-212-L" made by Nagase Chemtex Co., Ltd., Shin-Etsu Chemical Co., Ltd. The silane coupling agent "KBM403" made by Shikisha Corporation was mixed with 5 parts and it used until it became uniform using the rotating revolving mixer THINKY AR250. Next, 9 mass parts of supported photocationic polymerization initiators (D) were added, it knead | mixed with 3 rolls and it was set as the sealing agent (D). At this time, the cationic polymerization initiator is 1.6 parts by mass and the dispersible microcarrier is 7.4 parts by mass based on 100 parts by mass of the cationically polymerizable compound.

Voltage retention was measured like Example 2, and the result was shown in Table 2.

(Example 5)

70 parts of epoxy monomer "EXA850crp" made by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether "Denacol EX-212-L" made by Nagase Chemtex Co., Ltd., Shin-Etsu Chemical Co., Ltd. The silane coupling agent "KBM403" made by Shikisha Corporation was mixed with 5 parts and it used until it became uniform using the rotating revolving mixer THINKY AR250. Next, 9 mass parts of supported photocationic polymerization initiators (E) were added, it knead | mixed with 3 rolls and it was set as the sealing agent (E). At this time, the cationic polymerization initiator is 5.6 parts by mass and the dispersible microcarrier is 3.4 parts by mass based on 100 parts by mass of the cationically polymerizable compound.

Voltage retention was measured like Example 2, and the result was shown in Table 2.

Example 6

70 parts of epoxy monomer "EXA850crp" made by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether "denacol EX-212-L" made by Nagase Chemtex Co., Ltd., Shin-Etsu Chemical Co., Ltd. The silane coupling agent "KBM403" made by Shikisha Corporation was mixed with 5 parts and it used until it became uniform using the rotating revolving mixer THINKY AR250. Next, 9 mass parts of supported photocationic polymerization initiators (F) were added, it knead | mixed with 3 rolls and it was set as the sealing agent (F). At this time, a cationic polymerization initiator is 0.4 mass part with respect to 100 mass parts of cationically polymerizable compounds, and a dispersible micro support is 8.6 mass parts.

Voltage retention was measured like Example 2, and the result was shown in Table 2.

(Example 7)

70 parts of epoxy monomer "EXA850crp" made by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether "Denacol EX-212-L" made by Nagase Chemtex Co., Ltd., Shin-Etsu Chemical Co., Ltd. The silane coupling agent "KBM403" made by Shikisha Corporation was mixed with 5 parts and it used until it became uniform using the rotating revolving mixer THINKY AR250. Next, 9 mass parts of supported photocationic polymerization initiators (G) were added, it knead | mixed with 3 rolls and it was set as the sealing agent (G). At this time, the cationic polymerization initiator is 0.2 parts by mass and the dispersible microcarrier is 8.8 parts by mass based on 100 parts by mass of the cationically polymerizable compound.

Voltage retention was measured like Example 2, and the result was shown in Table 2.

(Example 8)

70 parts of epoxy monomer "EXA850crp" made by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether "Denacol EX-212-L" made by Nagase Chemtex Co., Ltd., Shin-Etsu Chemical Co., Ltd. The silane coupling agent "KBM403" made by Shikisha Corporation was mixed with 5 parts and it used until it became uniform using the rotating revolving mixer THINKY AR250. Next, 9 mass parts of supported photocationic polymerization initiators (H) were added, it knead | mixed with 3 rolls and it was set as the sealing agent (H). At this time, the cationic polymerization initiator is 0.01 parts by mass and the microcarrier is 8.8 parts by mass based on 100 parts by mass of the cationically polymerizable compound.

Voltage retention was measured similarly to Example 2, and the result was shown in Table 2.

[Table 2]

(Example 9)

Epoxy monomer "Epicoat 828" made from 10 parts by weight of Japan epoxy resin, 2 parts by weight of supported photocationic polymerization initiator (A), 10 parts by weight of "Epicoat 807", 2.5 parts by weight of Mitsubishi Chemical Co., Ltd. It added to "PTMG1000", mixed using the rotating revolving mixer THINKY AR250, and set it as the sealing agent (I).

Two glass substrates RS-B107M1N (with rubbing completed alignment film, with ITO) made by EHC were prepared, and 5% ethanol dispersion liquid of spacer-"LH11S" made by Hayakawa Rubber Co., Ltd. was sprayed on one of them. Next, the said sealing agent (I) was further apply | coated to the outer glass | board part of the board | substrate with a seal width of about 1 mm in rectangular shape on one glass substrate using the dispenser. Thereafter, 500 W / m 2 ultraviolet light was irradiated to the sealant portion for 40 seconds using a high pressure metal halide lamp. Next, an appropriate amount of liquid crystal "PA-0211CA033" made by DIC Corporation was added dropwise to the inside of the spherical sealant on the substrate, and the rubbing directions of the two glass substrates were orthogonal to be bonded to each other to prepare a cell. The cell was returned to the atmosphere, and the space between the substrates became the size of the spacer, and left for 1 hour until the sealant (I) was delayed and cured to produce a TN type liquid crystal panel.

The liquid crystal panel was fitted with the optical axis aligned between two orthogonal polarizing plates, and the liquid crystal display element was created. When the voltage was not applied, the display was transparent to show a bright display. When the voltage was applied, the electrode portion of the cell did not pass light, resulting in a dark display, showing a good display state.

(Comparative Example 3)

10 parts by weight of epoxy monomer `` epicoat 828 '' made by 10 parts by weight of Japan epoxy resin resin, 10 parts by weight of `` epicoat 807 '', 2.5 parts by weight of Mitsubishi Chemical Co., Ltd. PTMG1000 ", and it mixed using the rotating revolving mixer THINKY AR250, and was made into the sealing agent (H3).

The liquid crystal cell was produced by changing from sealing agent (B) to sealing agent (H3) and making the other conditions like Example 2. That is, two glass substrates RS-B107M1N (with rubbing oriented film, with ITO) by EHC Corporation were prepared, and 5% ethanol dispersion liquid of spacer-"LH11S" by Hayakawa Rubber Co., Ltd. was sprayed on one of them. Next, the said sealing agent (H3) was apply | coated to one more glass substrate in the shape of a rectangle with a seal width of about 1 mm in the outer edge part of a board | substrate using a dispenser. Thereafter, 500 W / m 2 ultraviolet light was irradiated to the sealant portion for 40 seconds using a high pressure metal halide lamp. Subsequently, an appropriate amount of liquid crystal "PA-0211CA033" made by DIC Corporation was added dropwise to the inside of the spherical phase seal agent (H3) on the substrate, and the rubbing directions of the two glass substrates were orthogonal to be bonded to each other to prepare a cell. . This cell was returned to the atmosphere, and the space | interval between board | substrates was compressed to the size of the spacer, and it was left to stand for 1 hour until the sealing agent (H3) delayed-hardening after that, and the TN type liquid crystal panel was produced.

As in Example 9, the liquid crystal display device was fabricated by fitting the optical axis between two orthogonal polarizing plates. However, unlike Example 2, an opaque portion appeared at the periphery of the sealant in the state where no voltage was applied, and dark indication of a part of the electrode portion appeared gray when voltage was applied.

The sealing agent produced by the method of this invention by the comparison of Example 9 and the comparative example 3 showed that liquid crystal contamination was low. This is considered to be because the amount of the photocationic polymerization initiator which leaks from a sealing agent and contaminates a liquid crystal is small.

(Re-elutation of reference experiment-supported photocationic polymerization initiator)

One part of the supported photocationic polymerization initiator (A) obtained in Production Example 1 was added to 24 parts of acetone, shaken for 30 minutes with an ultrasonic cleaner, a solution (B) was prepared, and redissolved in the solution (B). The quantity of the photocationic polymerization initiator was measured, and it was set as "the amount of the polymerization initiator eluted." It is evaluated that the amount of photocationic polymerization initiator remaining without eluting is the amount of polymerization initiator supported on silica with sufficient bonding force. The results are shown in Table 3.

The supported amount of the dispersible microcarrier and the supported photocationic polymerization initiator to be used under the conditions described above were appropriately changed to prepare other supported photocationic polymerization initiators. Similarly, "the amount of the polymerization initiator eluted" was measured. The results are shown in Table 3.

In Table 3, "the total amount of polymerization initiators" refers to the mass of the photocationic polymerization initiator used for the supported photocationic polymerization initiator (A) and other photocationic polymerization initiators. Therefore, (the amount of the polymerization initiator eluted) / (the amount of the total polymerization initiator) has shown the ratio of the mass of the photocationic polymerization initiator re-eluted to the solution (B), ie, acetone.

As a result, 30 to 60% of the photocationic polymerization initiator is re-dissolved in the solution (B) irrespective of the type of the dispersible microcarrier to be used and regardless of the amount of the supported photocationic polymerization initiator. It was suggested that 40% of the photocationic polymerization initiator is bonded to silica with sufficient bonding force.

[Table 3]

Preparation Example 9 Adjustment of Basic Solid Material (1)

The basic solid substance (1) was produced by introducing a basic functional group onto the surface of the fumed silica. As fumed silica, R976S manufactured by Nippon Aerosol Co., Ltd. was used. Production conditions are described below. The mass ratio of the composition of each Example was put together in Table 4.

(Gamma) -aminopropyl triethoxysilane (LS3150, Shin-Etsu Chemical Co., Ltd.) which is a silane coupling agent was melt | dissolved in the solution which consists of 1800 mass parts of ethyl alcohol and 200 mass parts of water. Dissolution amount is shown in Table 4.

Fumed silica (100 parts by mass of R976S manufactured by Nippon Aerosol Co., Ltd.) was immersed in the solution and mixed for 10 minutes by an ultrasonic dispersion device.The solution was heat-treated for 1.5 hours on a hot plate heated to 150 ° C to obtain powder.

In order to remove the unreacted substance and the polymer of the silane coupling agent which is not bound to the fumed silica surface, 100 parts by mass of this powder is dispersed in 2000 parts by mass of ethyl alcohol, shaken with an ultrasonic treatment device for 10 minutes, and then centrifuged to remove the powder. Got. This washing was repeated twice more. This powder was dried at 80 ° C. for 4 hours by hot air to obtain a basic solid substance (1).

[Table 4]

(Example 10)

100 parts by mass of the sealing agent (D) described in Example 4 was used, and 2.5 parts by weight of the basic solid substance (1) was mixed using a rotary revolving mixer THINKY AR250 to obtain a sealing agent (J).

(Example 11)

Using 100 parts by mass of the sealant (D) described in Example 4, 20 parts by mass of commercially available talc and `` Microlite (manufactured by Takehara Chemical Co., Ltd.) '' were mixed using a rotating revolution mixer THINKY AR250, (K) was obtained.

(Evaluation pH of the extraction water)

PH measurement of the extraction water from an adhesive agent was performed as follows. After irradiating an ultraviolet-ray to an adhesive agent, in order to quantify the acid which arose from the photo-acid generator which extrudes from the adhesive to the outside, the ultraviolet-ray-exposed adhesive agent was immersed in ultrapure water, and the pH was measured. In order to perform this measurement, 0.5 g of said adhesive agent was put into the glass container of 4.2 cm <2> of low areas, the lid of the glass container was taken out, and the ultraviolet-ray of 500W / m <2> intensity was irradiated 20000J / m <2> from the upper side. Immediately thereafter, 5 g of ultrapure water was poured into the glass container, and the lid was covered and left standing in a thermostat kept at 80 ° C for 1 hour, and then cooled to room temperature (23 ° C) to measure pH. The results are shown in Table 5.

[Table 5]

As a result, the pH of the extract water is 5 or more, indicating that the basic solid substance neutralizes or captures the acid generated in the photoacid generator.

(Evaluation example Promotion test of electrode corrosion)

The acceleration test of electrode corrosion was done about the sealing agents (J) and (K) of Examples 10 and 11.

The said sealing agent (J) and (K) were apply | coated to the cell with a blaze electrode so that the film thickness might be set to 10 micrometers, and it irradiated and hardened | cured by ultraviolet-ray (strength 50mW / cm <2>) for 40 sec.

(The electrode is made of chromium, the electrode width is 10㎛)

The bladder-shaped electrodes are divided into two systems to oppose each other, and are combined so that the bladders overlap each other, and the electrode spacing of each other is 10 占 퐉. After applying a DC voltage of 10 V between the electrodes, the electrode was maintained for 3 days in an environment of 60 ° C.-90% and the electrode corrosion was accelerated. Then, the electrode was observed with an optical microscope. It was set as "(circle)" when the slight electrode corrosion generate | occur | produced, and "x" when the electrode corrosion occurred. The results are shown in Table 6.

TABLE 6

As a result, the use of the sealants (J) and (K) did not produce any electrode corrosion. This result indicates that the basic solid substance neutralizes or captures the acid generated from the photoacid generator.

Example 12 Preparation of Liquid Crystal Panel by Dropping Method

Two glass substrates RS-B107M1N (with rubbing completed alignment film, with ITO) made by EHC were prepared, and 5% ethanol dispersion liquid of spacer-"LH11S" made by Hayakawa Rubber Co., Ltd. was sprayed on one of them. Next, the sealant (J) produced in Example 10 was applied to one glass substrate in a rectangular shape with a seal width of about 1 mm to the outer edge of the substrate by using a dispenser, using a high pressure metal halide lamp. Ultraviolet rays of 500 W / m 2 were irradiated to the sealant portion for 40 seconds. Subsequently, an appropriate amount of liquid crystal "PA-0211CA033" made by DIC Corporation was added dropwise under vacuum to the inside of the rectangular sealant on the substrate, and the rubbing directions of two glass substrates were orthogonal to be bonded to each other to prepare a cell. This cell was returned to atmospheric pressure, and the TN type liquid crystal panel was produced.

The liquid crystal panel was fitted with the optical axis aligned between two orthogonal polarizing plates, and the liquid crystal display element was created. When the voltage was not applied, the display was transparent, and the display was clear. When the voltage was applied, the electrode portion of the cell did not pass the light to become dark display, showing a good display state.

<Voltage retention test>

On 5 sheets of glass substrate "RZ-B107N1N" with ITO by EHC company, the 5% ethanol dispersion liquid of spacer-"LH11S" by Hayakawa Rubber Co., Ltd. was sprayed. Next, about 1 mm width | variety is provided so that two liquid crystal injection openings may be provided in the outer periphery of a board | substrate using the dispenser using the sealant (J) or (K) of Examples 10 and 11 on one more glass substrate with ITO. After application | coating with the two glass substrates, they are bonded together, and it irradiates 500 W / m <2> ultraviolet-rays to the said sealant part for 40 second using a high pressure metal halide lamp in nitrogen atmosphere, and a 2-blood cell was made. Made. After inject | pouring the liquid crystal "PA-0211CA033" by DIC Corporation under vacuum in 2 blood cells, masking that the said liquid crystal composition does not directly contact an ultraviolet-ray, 2 blood is sealed with a sealing agent (J) or (K), In a nitrogen atmosphere, 500 W / m <2> ultraviolet-ray was re-examined for 40 second using the high pressure metal halide lamp, and the liquid crystal panel was produced.

The 60 degreeC 90% RH wet heat exposure test was done for the liquid crystal panel produced by said method, and the voltage retention after 120 hours was measured. The voltage retention was 24 degreeC, and applied the voltage of 64 kV of the initial voltage of 5 V to the liquid crystal panel, and computed the value which multiplied 100 by the voltage ratio before and after the frame time of 167 kPa.

[Table 7]

Claims (6)

A cationically curable liquid crystal sealing agent comprising a cationic polymerizable compound and a photocationic polymerization initiator and / or a thermal cationic polymerization initiator supported on a dispersible microcarrier. The method of claim 1,
A cationically curable liquid crystal sealing agent containing 1 to 30% by mass of a photocationic polymerization initiator and / or a thermal cationic polymerization initiator supported on the dispersible microcarrier with respect to the cationically polymerizable compound. The method according to claim 1 or 2,
The cationically curable liquid crystal sealing agent having a surface area of the dispersible microcarrier in a range of 1 to 5000 m 2 / g. 4. The method according to any one of claims 1 to 3,
A cation-curable liquid crystal sealant, wherein the amount of the photocationic and / or thermocationic polymerization initiator supported on the dispersible microcarrier is in the range of 1 × 10 ⁻⁶ g / m 2 to 1 g / m 2. 5. The method according to any one of claims 1 to 4,
A cation curable liquid crystal sealant containing a basic solid substance. Two substrates facing each other, the sealant provided between the said board | substrate, and the liquid crystal enclosed in the sealing area | region enclosed by the said sealing agent, Comprising: The cationically curable liquid crystal sealing agent as described in any one of Claims 1-5 as said sealant The liquid crystal display element characterized by using.