Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G85/00—General processes for preparing compounds provided for in this subclass
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

• the present invention relates to a liquid crystal sealant, and more particularly to a light and / or heat cation curable liquid crystal sealant.
• a liquid crystal panel (liquid crystal display element) has a back substrate including a thin film transistor, a pixel electrode, an alignment film, and the like facing a front substrate including a color filter, an electrode, an alignment film, and the like, and encapsulates liquid crystal between both substrates. It is configured.
• a sealing agent is used for the purpose of bonding the two substrates.
• thermosetting sealant composed mainly of an epoxy-based thermosetting resin
• it is often cured at 150 ° C, but substrates with different temperature differences between the upper and lower substrates or different thermal expansion coefficients are attached to each other.
• 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 an epoxy resin and performing a curing reaction at a low temperature of 40 ° C. or lower has been tried. Takes a long time and is not practical.
• a photocurable sealant mainly composed of acrylate or the like is suitable for a plastic substrate because it does not require heat for curing and can be cured in a short time.
• acrylate has a large cure shrinkage, its adhesiveness is weak and it may be peeled off by a simple impact or the like.
• a photo-thermosetting sealant that uses a photo-curing component and a thermo-curing component together, first semi-cured by photo-curing, and then fully cured by heating (usually using heating during annealing).
• the adhesiveness to the plastic substrate was weak and there was a problem in practical use.
• a photo-curing sealant having a light binary curing system (for example, see Patent Document 1) using a photocationic curability mainly composed of an epoxy or the like and an acrylate having a photoradical curability, heats the curing. Not only can it be cured in a short time, but the photo-ring-opening reaction can greatly improve the adhesion of the substrate to the organic protective layer and inorganic protective layers such as SiOx. it can.
• the photocationic polymerization initiator that is ionic and the acid generated during cation curing are eluted in the liquid crystal and the voltage holding ratio is lowered.
• a method for producing a liquid crystal panel using a glass substrate As a method for producing a liquid crystal panel using a glass substrate, a method called a dripping method using a photocuring thermosetting combined sealant has become mainstream as well as a vacuum injection method using a thermosetting sealant.
• the dropping method first, a rectangular seal pattern is formed on one of the two transparent substrates with electrodes by a dispenser. Next, fine droplets of liquid crystal are dropped onto the entire surface of the transparent substrate in an uncured state, and the other transparent substrate is stacked under reduced pressure, and the seal portion is irradiated with ultraviolet rays for temporary curing. Thereafter, heating is performed to perform main curing, and a liquid crystal panel is manufactured.
• Patent Document 3 proposes a sealing agent using a cationically polymerizable compound as a sealing agent that does not use a thermosetting agent. Sealing agents using such cationically polymerizable compounds are superior in storage stability compared to sealing agents using thermosetting agents, are excellent in low-temperature fast curing properties, and require a short time for curing. There are advantages such as time reduction.
• liquid crystal display elements in recent years tend to use liquid crystal display devices having a low driving voltage (low voltage type liquid crystal) due to consumer-oriented low power consumption. Since this low voltage type liquid crystal has a particularly large dielectric anisotropy, impurities are easily taken in, and the orientation of the liquid crystal is disturbed and the voltage holding ratio of the liquid crystal display element is remarkably reduced.
• Patent Document 4 discloses a dispersible microcarrier that supports and supports a photocatalytic ionic salt of an onium or organometallic complex cation and a halogen-containing complex of a metal or metalloid anion as a photocationic polymerization initiator.
• a supported initiator for radiation-activated polymerization of a cationically polymerizable compound in the absence of a non-reactive solvent that is insoluble in the cationically polymerizable compound is known, and the photoinitiator was used Photocationic curable compositions have been proposed.
• the problem to be solved by the present invention is to provide a cation curable liquid crystal sealing agent having excellent electrical properties and adhesiveness, and to provide a liquid crystal display element having an excellent voltage holding ratio using the cation curable liquid crystal sealing agent. There is to do.
• the present inventors have solved the above problems by using a cationic polymerization initiator supported on a dispersible microcarrier as a cationic curable composition.
• the light or thermal cationic polymerization initiator is an ionic compound
• the voltage holding ratio of the liquid crystal display element that can reduce the resistance value of the liquid crystal may be reduced.
• the present inventors have found that elution can be significantly reduced by supporting a cationic polymerization initiator on a dispersible microcarrier, and the liquid crystal can be used for disordered liquid crystal orientation or a decrease in voltage holding ratio of a display element. It has been found that a liquid crystal sealant that does not cause deterioration of characteristics can be obtained.
• the present invention provides a cationically curable liquid crystal sealing agent containing a cationically polymerizable compound and a photocationic polymerization initiator and / or a thermal cationic polymerization initiator supported on a dispersible microcarrier.
• the present invention also includes two substrates facing each other, a sealing agent provided between the substrates, and a liquid crystal sealed in a sealing region surrounded by the sealing material, and the cationic curing as the sealing agent Provided is a liquid crystal display element using a liquid crystal sealing agent.
• the sealant of the present invention it is possible to obtain a liquid crystal display element that is less likely to cause disorder of liquid crystal orientation or a decrease in voltage holding ratio of the display element even in the dropping method.
• the cationic polymerization initiator used in the present invention is supported on a dispersible microcarrier.
• the dispersible microcarriers used in the present invention are preferably granular and have a maximum dimension of less than about 50 micrometers, preferably in the range of 0.001 to 20 micrometers, and more preferably 0.01 to 5 micrometers. It is preferably a dispersible micromaterial that has a particle size in the meter and most preferably from 0.01 to 2 micrometers and is insoluble in the organic component of the sealant, i.e. essentially insoluble in measurable quantities.
• the range is preferably from 0.1 to 10000 m 2 / g, more preferably from 1 to 5000 m 2 / g, still more preferably from 10 to 2000 m 2 / g, because it is easy to make and inhibits the uniformity of polymerization. More preferred is 30 to 1500 m 2 / g, and most preferred is a range of 30 to 1200 m 2 / g.
• silicas such as fumed silica, precipitated silica and natural silica; diatomaceous earth; clays such as bentonite, kaolinite and attapulgus clay; aluminum, zirconium, titanium, antimony, iron, Oxides of metals such as nickel, zinc, tin, copper, carbonates and sulfates, or mixtures thereof; starches such as starch (ie corn starch), carbon black, graphite, diamond, polymers; polystyrene, polyvinyltoluene Latexes, such as latex, polyvinylprolidone, polyacrylic acid, polyacrylate, polymethacrylate, etc .; pigment particles, or dispersible micromaterials of appropriate size, with photocations on or in their surface Fine that can contain a polymerization initiator Cellulose (i.e., cotton, wood), such that carriers, for example finely ground, glass and the like.
• a polymerization initiator Cellulose (i.e., cotton,
• a basic solid substance described later as a dispersible microcarrier.
• a weak base is preferable to a strong base, or the density of basic groups on the surface of the basic solid is smaller. preferable.
• the basic solid used as the carrier has an appropriate basicity, it is possible to control the delayed curability (property of slowing the curing reaction rate) of the cationic polymerizable compound.
• the dispersible microcarriers transmit light to be used, for example, ultraviolet rays.
• a particularly suitable carrier is fumed silica, such as AEROSIL (Nippon Aerosil Co., Ltd.).
• the metal oxide having a particularly large specific surface area of the dispersible microcarrier examples include a mesoporous material synthesized using a surfactant such as MCM41 as a template.
• a surfactant such as MCM41 as a template.
• organic low molecular gels and mesoporous materials prepared using a higher order structure of amino acids such as collagen as a template can be mentioned.
• the material of the mesoporous material include silica, alumina, zirconia, titania, and the like.
• a photo cationic polymerization initiator As the cationic polymerization initiator used in the present invention, there are a photo cationic polymerization initiator and a thermal cationic polymerization initiator, which are composed of a metal- or metalloid halogen-containing complex anion, an onium cation and an organometallic complex cation.
• An ionic salt hereinafter referred to as an ionic salt.
• group VA, VIA, or VIIA atoms of the periodic table given group 15, group 16, and group 17 symbols especially phosphorus, antimony, bismuth, sulfur, nitrogen , And an adduct of an aromatic organic cation and an anion of an iodine atom.
• onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.
• the photocationic polymerization initiator used in the present invention is a photocatalytic ionic salt (hereinafter referred to as an ionic salt) comprising a halogen-containing complex anion of metal or metalloid, an onium cation and an organometallic complex cation.
• an ionic salt comprising a halogen-containing complex anion of metal or metalloid, an onium cation and an organometallic complex cation.
• onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.
• Examples of commercially available onium salts include optomer SP-150, optomer SP-151, optomer SP-170, optomer SP-171 (all manufactured by Adeka Corporation), UVE-1014 (General Electronics Co., Ltd.) ), Irgacure-261 (Ciba Geigy), Sun-Aid SI-60L, Sun-Aid SI-80L, UVI-6990 (Union Carbide), BBI-103, MPI-103, TPS-103, MDS-103, DTS- 103, NAT-103, NDS-103 (all manufactured by Midori Chemical Co., Ltd.), Sun-Aid SI-100L (all manufactured by Sanshin Chemical Industry Co., Ltd.), CI-2064, CI-2639, CI-2624, CI-2481 (all Also made by Nippon Soda Co., Ltd.), RHODORSIL PH OTOINITIATOR 2074 (manufactured by Rhone-Poulenc), CD-1012 (man
• optomer SP-150 is less likely to cause electrode corrosion due to onium salts
• optomer SP-170 is more likely to have effective curability
• RHODORSIL PHOTOINITIATOR 2074 is more preferable because it has less ionic impurities.
• the said cationic photopolymerization 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.
• the mixing ratio of the photocationic polymerization initiator is not particularly limited, but the acid generated by photoirradiation of the photocationic polymerization initiator supported on the dispersible microcarrier generally has an effect on the polymerizable compound more than usual. Since it tends to be difficult, it is preferable to increase the addition amount rather than the normal use amount. Specifically, it is preferably used in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the photocationically polymerizable compound described later.
• the curability of the sealing agent of the present invention may be insufficient. If it exceeds 20 parts by mass, the acid generated from the photocationic polymerization initiator will convert the photopolymerizable compound. Since it becomes more than the amount necessary for the reaction, there is a possibility that an acid may penetrate into the liquid crystal from the sealing agent and the electrical characteristics of the liquid crystal may be deteriorated. More preferably, it is in the range of 0.03 to 10 parts by mass.
• Thermal cationic polymerization initiator examples include: Sun-Aid SI60L, Sun-Aid SI80L, Sun-Aid SI100L, Sun-Aid SI110L, Sun-Aid SI180L (all manufactured by Sanshin Chemical Industry Co., Ltd.), CP-66, CP-77 (both are ADEKA Corporation) and the like. However, these are also used as a photocationic polymerization initiator. Further, CP-66, CP-77 (both are ADEKA Co., Ltd.), etc. The said thermal cationic polymerization initiator may be used independently and may use 2 or more types together.
• the blending ratio of the thermal cationic polymerization initiator is not particularly limited, but the acid generated by the heat of the thermal cationic polymerization initiator supported on the dispersible microcarrier generally has less effect on the polymerizable compound than usual. Since there exists a tendency, it is preferable to increase addition amount rather than normal usage-amount. Specifically, it is used in the range of 0.01 to 20 parts by weight, preferably 0.03 to 20 parts by weight, and more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the cationically polymerizable compound described later. It is preferable.
• the curability of the sealing agent of the present invention may be insufficient, and if it exceeds 20 parts by mass, the acid generated from the thermal cationic polymerization initiator will convert the cationically polymerizable compound. Since it becomes more than the amount necessary for the reaction, there is a possibility that an acid may penetrate into the liquid crystal from the sealing agent and the electrical characteristics of the liquid crystal may be deteriorated. More preferably, it is in the range of 0.03 to 10 parts by mass.
• a dispersible microcarrier carrying a cationic polymerization initiator comprises an ionic salt of a metal- or metalloid halogen-containing complex anion with an onium cation or an organometallic complex cation in a suitable solvent such as methylene chloride, methanol, It can be produced by dissolving in ethanol, propanol, 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 on the surface of the dispersible microcarrier or in the fine voids on the surface.
• a suitable solvent such as methylene chloride, methanol
• the solvent may be removed by filtration.
• a method of removing by distillation is preferable.
• a photocationic polymerization initiator that is easily decomposed it is preferably distilled off at 100 ° C. or lower, preferably 60 ° C. or lower, more preferably 40 ° C. or lower.
• lyophilization is preferably used as a drying method for removing the solvent in which the cationic polymerization initiator is dissolved.
• redispersion of the dispersible carrier material can be prevented and a fine dispersible microcarrier can be obtained.
• the finer the microcarrier the more efficiently the curing reaction of the cationic polymerizable compound can proceed.
• freeze-drying is difficult, such as when the freezing point of the solvent is low or when the solid after freezing is difficult to sublime, add water to the solvent as appropriate and dry the solvent first at the temperature at which the water freezes. The remaining frozen water may be lyophilized and removed.
• the dispersible microcarrier is preferably 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 sealing material or the liquid crystal, and the ionic cationic polymerization initiator is eluted to inhibit the insulating properties of the liquid crystal. It is preferable to wash and remove only the cationic polymerization initiator adsorbed outside the pores by some method. For this purpose, for example, the dispersible microcarrier carrying the cationic polymerization initiator may be removed with a solvent.
• the solvent to be used there is a solvent having a minimum solubility in the cationic polymerization initiator, but having an appropriate solubility that is not so large that the cationic polymerization initiator adsorbed in the pores is completely dissolved. preferable. It is necessary to select appropriately depending on the type of the dispersible carrier material and the cationic polymerization initiator. Increasing the number of washings removes the cationic polymerization initiator outside the pores, but also reduces the amount of cationic polymerization initiator inside the pores, so depending on the amount of cationic polymerization initiator remaining inside and outside the pores That is, the number of times of cleaning is determined according to curability and electrical characteristics.
• the amount of the dispersible microcarrier added is preferably in a range not exceeding 50% by mass of the cationic polymerizable compound. Specifically, it is used in the range of 0.1 to 100 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound, preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight. Part by mass is most preferred.
• the cationic polymerization initiator is preferably used in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound as described above, the amount of the dispersible microcarrier used is the supported cation. It is preferable to use by calculating back from the amount of the polymerizable initiator.
• the optimum amount of the loading 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 a multilayer on the surface of the hollow structure of the dispersible microcarrier.
• the polymerization initiator of the layer becomes weaker in adsorption force, the polymerization initiator may be dissolved or dispersed on the polymerizable compound side. This is undesirable because it causes contamination of the liquid crystal and causes deterioration of electrical characteristics. Furthermore, it differs depending on whether the opening portion of the hollow structure is largely open to the outside or the bottleneck type. For example, when the opening of the hollow structure is opened to the outside, it is not possible to support a large amount for the above reasons, but there is an advantage that the acid generated from the polymerization initiator effectively acts on the polymerization of the polymerizable compound. .
• the amount of the polymerization initiator supported on the dispersible microcarrier is the amount expressed by the addition amount / the surface area of the dispersible microcarrier.
• the latter is estimated to correspond to 1/10 to 100 layers in terms of the average number of layers of the polymerization initiator molecules per unit area.
• the supported cationic polymerization initiator is difficult to re-elute. Specifically, as a result of an experiment in which the supported cationic polymerization initiator was re-eluted with acetone, 30-60, regardless of the type of the dispersible microcarrier used and the supported amount of the cationic polymerization initiator to be supported. It was suggested that mass% of the cationic polymerization initiator re-eluted into the solution (B), and therefore 70 to 40% by mass of the cationic polymerization initiator was bound to the silica with sufficient bonding strength. (See reference experiment below).
• the cationically polymerizable compound to be used is less soluble than acetone. Therefore, it is estimated that the cationic polymerization initiator supported on one end hardly remains in the cationically polymerizable compound and remains stable.
• Some dispersible microcarriers have a primary particle size of about several tens of nanometers, but often aggregate to form secondary aggregates of several hundred nm to several ⁇ m. In order to sufficiently exhibit the catalytic function of the cationic polymerization initiator supported on the dispersible microcarrier, it is desirable to disperse to the size of the primary particles as much as possible.
• a dispersible microcarrier carrying a cationic polymerization initiator is added to a cationically polymerizable compound as a dispersion medium in the form of powder and stirred by a mixer or a screw extruder, or a three-roll, kneader, biaxial extruder, etc. It can be dispersed by kneading. In order to obtain a finer dispersion state, it is also preferable to use a bead mill or the like.
• the photocationic polymerization initiator supported on the dispersible microcarrier, the photocationic polymerizable compound described later, and the microbeads that are the stirring particles (media) are stirred together, and the stirring particles are passed through.
• the stirring particles are passed through.
• (Cationically polymerizable compound) As the cationically polymerizable compound used in the present invention, known and commonly used epoxy groups, oxetanyl groups and vinyl ether groups which are generally used as polymerizable compounds capable of cationic polymerization in the presence of the cationic polymerization initiator. If it is a compound, there will be no limitation in particular. However, a compound having an oxetanyl group is preferably used only in a small amount because it is disadvantageous in adhesiveness to plastic because the amount of hydroxyl group produced by polymerization is small.
• Examples of the cationically polymerizable compound having one or more epoxy groups in one molecule include bisphenol A type epoxy resins (trade names “Epicron 850CRP”, “Epicron 850S”, “Epicron 1050”, “Epicron” manufactured by DIC Corporation).
• Examples of commercially available cationically polymerizable compounds having one or more vinyl ether groups include 4-vinyloxybutanol (trade name “Vinyl-4-hydroxybutyether” manufactured by BASF) and triethylene glycol divinyl ether (manufactured by ISP). Trade name “Rapi-Cure DVE-3”), 1,4-cyclohexanedimethanol divinyl ether (trade name “CHDVE” manufactured by Nippon Carbide Industries, Ltd.), and the like.
• Examples of the cationically polymerizable compound having one or more oxetanyl groups in one molecule include 3-ethyl-3- (phenoxymethyl) oxetane (trade name “OXT-211” manufactured by Toagosei Co., Ltd.), 3-ethyl -3- (cyclohexyl) methyloxetane (trade name “CHOX” manufactured by Toa Gosei Co., Ltd.) and the like.
• 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 (trade name “OXT-223” manufactured by Toa Gosei Co., Ltd.), bis [1-ethyl (3-oxetanyl)] methyl ether (product of Toa Gosei Co., Ltd.) Name “OXT-221”), phenol novolac oxetane (trade name “PNOX-1009” manufactured by Toa Gosei Co., Ltd.), 4,4′-bis [ ⁇ (3-ethyloxetane-1-yl) methoxy ⁇ methyl] biphenyl (Ube) Product name “OX
• a polymerizable compound having an epoxy group having an aromatic ring is particularly preferable because cohesive force is obtained by utilizing the interaction between aromatic rings, which is advantageous for adhesion.
• bisphenol A type epoxy resin trade names “Epicron 850CRP”, “Epicron 850S”, “Epicron 1050”, “Epicron 1055”, “Epicron 4822”, manufactured by DIC Corporation
• bisphenol F type epoxy resin (DIC) Trade name “Epicron 830CRP”, “Epicron 830” manufactured by the company.
• bisphenol A type epoxy resin (trade name “Epiclon 850CRP” manufactured by DIC) and bisphenol F type epoxy resin (manufactured by DIC) (Trade name “Epiclon 830CRP”) is particularly preferred.
• DIC bisphenol F type epoxy resin
• 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).
• a radical curable composition hereinafter referred to as a radical curable composition
• the radical curable composition is a composition containing a radical polymerizable compound and a radical polymerization initiator.
• the radical polymerizable compound is not particularly limited as long as it is a known and commonly used compound having a (meth) acryloyl group as commonly used in the field of UV curing, but when used for a liquid crystal panel seal, Those that are difficult to mix with liquid crystal can be used more preferably.
• (meth) acrylate such as dipentaerythritol penta, hexaacrylate, pentaerythritol tetraacrylate and the like, which are considered to have large curing shrinkage.
• the radically polymerizable compound which has a carboxylic acid group may react with an epoxy group during storage and may increase the viscosity of the composition rapidly, it is preferable to use only a small amount.
• Polyester (meth) acrylate having an ester bond in the main chain structure and having at least two (meth) acryloyl groups, epoxy (meth) acrylate obtained by modification with epichlorohydrin, ethyl oxide, propylene oxide, A (meth) acrylate modified with a cyclic lactone or the like can also be preferably used.
• an acrylate having a urethane group is used in combination with a cationic curing system, curing inhibition by the urethane group occurs, so it is preferable to use only a small amount.
• (meth) acrylate used in the present invention include, for example, glycerin monomethacrylate (trade name “Blemmer GLM” manufactured by NOF Corporation), acryloyloxyethyl phthalate (trade name “HOA-MPE” manufactured by Kyoeisha Chemical Co., Ltd.).
• (meth) acrylate modified with lactone and (meth) acrylate modified with rosin are particularly preferable because they make the curable composition flexible and improve adhesion.
• lactone-modified hydroxypivalate neopentyl glycol diacrylate (trade name “HX620” manufactured by Nippon Kayaku Co., Ltd.)
• lactone-modified BPA epoxy phthalate ester diacrylate (trade name “Evecryl 3708” manufactured by Daicel Cytec Co., Ltd.)
• Rosin-modified epoxy acrylate trade name “Beamset 101” manufactured by Arakawa Chemical Co., Ltd.
• the amount of the radical polymerizable compound used is not particularly limited as long as it does not impair the scope of the present invention. Specifically, it is preferably in the range of 20 to 70% by mass.
• radical photopolymerization initiators examples include benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, and thioxanthone. These radical photopolymerization initiators may be used alone or in combination of two or more.
• a maleimide compound having photoinitiating ability can also be used. Specific examples of the maleimide compound having photoinitiating ability include maleimide compounds described in, for example, JP-A Nos. 2000-19868 and 2004-070297.
• radical thermal polymerization initiators examples include peroxide-based or azo-based initiators.
• peroxide thermal polymerization initiator examples include 3,5,5-trimethylhexanoyl peroxide (trade name: Parroyl 355, manufactured by NOF Corporation), 2,4-dichlorobenzoyl peroxide (trade name: Nyper).
• Diacyl peroxides such as CS, manufactured by NOF Corporation, isobutyl peroxide (trade name: Parroyl IB, manufactured by NOF Corporation), dilauroyl peroxide (trade name: Parroyl L, manufactured by NOF Corporation); Methyl-3-methoxybutyl) peroxydicarbonate (trade name: Parroyl SOP, manufactured by NOF Corporation), di-2-methoxybutyl peroxydicarbonate (trade name: Parroyl MBP, manufactured by NOF Corporation), Di-2 -Ethylhexyl peroxydicarbonate (trade name: Parroyl OPP, manufactured by NOF Corporation), di-2-ethoxyethyl peroxydicarbonate (Trade name: Parroyl EEP, manufactured by NOF Corporation), diisopropyl peroxydicarbonate (trade name: Parroyl IPP, manufactured by NOF Corporation), bis- (4-t-butylcyclohexyl) peroxydicarbonate (trade name) Per
• azo thermal polymerization initiator for example, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (trade name: V-70, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′- Azobis (2-cyclopropylpropionitrile) (trade name: V-68, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2,4-dimethylvaleronitrile) (trade name: V-65, Wako Pure) 2,2'-azobis (2-methyl-N-phenylpropionamidine) (trade name: VA-545, manufactured by Wako Pure Chemical Industries), 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 ] Drochloride (trade name: VA-548, 2,
• the radical polymerization initiators may be used alone or in combination of two or more. Moreover, it is although it does not specifically limit as a mixture ratio of this radical polymerization initiator, A preferable minimum is 0.1 mass part with respect to 100 mass parts of curable compositions, and a preferable upper limit is 20 mass parts. If it is less than 0.1 parts by mass, the curability of the sealing agent of the present invention may be insufficient. If it exceeds 10 parts by mass, a large amount of radical polymerization initiator that cannot be reacted remains in the liquid crystal. There is a possibility of melting. A more preferred lower limit is 0.3 parts by mass, and a more preferred upper limit is 10 parts by mass.
• a compound having both radical polymerizable groups and cationic polymerizable groups can also be used.
• the polymerizable compound having both radical polymerizable group and cationic polymerizable group include commercially available BPF epoxy half acrylate and BPA epoxy half acrylate (trade name “UVa1561” manufactured by Daicel Cytec Co., Ltd.) Examples thereof include compounds in which a part of the epoxy group of a compound having a plurality of epoxy groups is reacted with (meth) acrylic acid to form (meth) acryloyl. Among them, BPA epoxy half acrylate and BPF epoxy half acrylate are more preferable because of high dilution effect.
• a combination of a radical curing system and a cationic curing system specifically, a (meth) acryloyl group as a radical curing system and an epoxy group as a cationic curing system coexist in the composition.
• the epoxy group can be cationically polymerized and the (meth) acryloyl group can be radically polymerized and cured by light irradiation or heat treatment, so that it can be firmly bonded to the substrate.
• a cationic polymerization initiator that cationically polymerizes an epoxy group and a radical polymerization initiator that radically polymerizes a (meth) acryloyl group are used in the curable composition. Is preferred.
• the cationic curable adhesive of the present invention can further reduce metal corrosivity by using a basic solid substance in combination.
• Basic solid substance As the basic solid substance used in the present invention, any solid compound having a function of neutralizing or capturing an acid can be used. Since the polymerization reaction of the cationic polymerizable compound is caused 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 with the acid. Since the basic solid substance in the present invention is used in the state of being included in the adhesive, it may inhibit cationic polymerization. Accordingly, the basic solid substance is required to be substantially insoluble in the cationic polymerizable compound. The solubility of the basic solid substance is preferably 0.02 parts by mass or less with respect to 100 parts by mass of the cationic polymerizable compound.
• the particle size of the basic solid substance is preferably fine in order to prevent the generated acid from leaking from the adhesive to the outside. Since the size of the particles is physically limited, when the basic solid material particles to be used are not agglomerated and remain primary particles, the particle size is preferably 0.01 to 50 ⁇ m, preferably 0.01 to 5 ⁇ m. More preferred is 0.01 to 1 ⁇ m. When the particles of the basic solid substance to be used are aggregated to form secondary particles, the size of the secondary particles is preferably in the above range. Further, when used as a basic solid substance for a sealing material of a liquid crystal display, 0.01 to 2 ⁇ m is preferable because of the limitation of the distance between two substrates.
• inorganic basic solid materials various inorganic salts (carbonates, phosphates, carboxylates, etc.), metal oxides, metal sulfides, metal nitrides, basic clay minerals, etc., and these inorganic solid surfaces are basic What was processed etc. are mentioned.
• glass beads alumina (activated alumina), zeolite, titanium oxide, zinc oxide, silica gel, tin oxide, zircon oxide, magnesium oxide, calcium oxide, metal sulfide Group of zinc sulfide, basic titanium nitride as a metal nitride, basic talc as clay minerals, magnesium hydroxide of the basic and the like as a metal hydroxide.
• basic solid substances basic glass beads, basic titanium oxide, basic zinc oxide, basic silica gel, basic tin oxide, basic zircon oxide, basic titanium nitride, basic zinc sulfide
• the precursor metal oxide, metal nitride, metal sulfide is treated with a silane coupling agent having a basic group such as an organic amino group or a nitrogen compound such as hexamethyldisilazane. It can be basic. However, the present invention is not limited to these.
• Organic basic solid substance can be synthesized by various methods, and a commercially available organic basic solid substance can also be used. Specific examples include polyethyleneimine epomine (manufactured by Nippon Shokubai Co., Ltd.).
• a basic clay mineral such as talc or a basic functional group
• a basic solid substance a basic clay mineral such as talc or a basic functional group
• Coupling treated with functional group-containing compound and beads coated with the polymer beads are preferred.
• basic viscosity minerals such as talc and silica into which basic functional groups are introduced are preferable. Since the basicity of the basic solid may inhibit the curing reaction of the cationic polymerizable compound, a weak base is preferable to a strong base, or a lower density of basic groups on the surface of the basic solid is preferable. . This is because it is desirable that the basic solid base gradually neutralizes the remaining acid after the acid generated by the cationic polymerization initiator has sufficiently caused the curing reaction of the cationic polymerizable compound.
• the cation coupling type liquid crystal sealing agent of this invention can also mix a well-known and usual silane coupling agent.
• silane coupling agents a silane coupling agent having a polymerizable group such as a (meth) acryloyl group or an epoxy group is copolymerized with a radical curable or cationic curable compound to obtain high adhesion. Is particularly preferable.
• silane coupling agent having a polymerizable group examples include 3- (meth) acryloyloxypropyltrimethoxysilane, 3-epoxyoxypropyltrimethoxysilane, and the like.
• examples of commercially available silane coupling agents having such a polymerizable group include, for example, trade names “KBM503”, “KBE503”, “KBM502”, “KBE502”, “KBM5102”, and “KBM5103” manufactured by Shin-Etsu Chemical Co., Ltd. , “KBM403” and the like.
• the amount used is preferably in the range of 0.1 to 10% by mass, particularly preferably in the range of 1 to 5% by mass with respect to the total amount of the curable composition. If the ratio of the silane coupling agent is less than 0.1% by mass, a sufficient adhesion effect may not be obtained, and if it exceeds 10% by mass, phase separation may occur. A more preferred lower limit is 0.5 parts by mass, and a more preferred upper limit is 5 parts by mass.
• the filler can be appropriately blended in addition to the dispersible microcarrier carrying the cationic polymerizable compound in the present invention.
• the filler is added for the purpose of improving the adhesiveness of the sealing agent of the present invention due to the stress dispersion effect and improving the linear expansion coefficient.
• talc 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 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.
• the blending ratio of the filler is not particularly limited, but as a blending amount including the dispersible microcarrier of the present invention, a preferred lower limit is 1 part by weight and a preferred upper limit is 100 parts by weight with respect to 100 parts by weight of the curable composition. Part. When the amount is less than 1 part by mass, the effect of adding the filler is hardly obtained. When the amount exceeds 100 parts by mass, the handling property such as the drawability of the sealing agent of the present invention may be deteriorated. A more preferred lower limit is 5 parts by mass, and a more preferred upper limit is 50 parts by mass.
• the cation curable liquid crystal sealant of the present invention has a viscosity of 100 Pa ⁇ s or higher measured at 25 ° C. and 2 sec ⁇ 1 using an E type viscometer, and the liquid crystal for producing a liquid crystal display element by a dropping method described later is used. More preferably, it can be used as a sealant.
• it is less than 100 Pa ⁇ s, when the liquid crystal display element is manufactured by the dropping method, the shape of the seal pattern formed on the transparent substrate cannot be maintained, and the sealing agent component is eluted in the liquid crystal, resulting in liquid crystal contamination. May end up.
• a more preferred lower limit is 100 Pa ⁇ s, and a more preferred upper limit is 5000 Pa ⁇ s.
• the drawing property of the sealant of the present invention is not sufficient, and it may be difficult to produce a liquid crystal display element by a dropping method.
• the E-type viscometer for measuring the viscosity is not particularly limited, and, for example, “DV-III” manufactured by Brookfield can be used.
• the cation curable liquid crystal sealant of the present invention can be used as a sealant for sealing an injection port after injecting a liquid crystal material into the liquid crystal panel, in addition to the sealant for producing a liquid crystal panel.
• the liquid crystal panel for example, after applying the photocationic curable liquid crystal sealant of the present invention to either the front or back substrate provided with a thin film transistor, pixel electrode, alignment film, color filter, electrode, etc.
• the other substrate is bonded, and light is irradiated from the substrate surface side of the substrate or from the side surface of the substrate to cure the photocurable composition for a liquid crystal panel seal of the present invention.
• the injection port is sealed with a sealant, whereby a liquid crystal panel can be produced.
• the liquid crystal panel has a liquid crystal dropping method, that is, a step of forming a seal pattern on one of two transparent substrates with electrodes using the photocationic curable liquid crystal sealant of the present invention, and a fine droplet of liquid crystal. It can be obtained by performing the step of dropping and applying to the entire surface of the seal pattern frame, the step of overlaying and bonding the other transparent substrate through the seal pattern, and the step of irradiating the seal pattern with light in this order. .
• a liquid crystal dropping method that is, a step of forming a seal pattern on one of two transparent substrates with electrodes using the photocationic curable liquid crystal sealant of the present invention, and a fine droplet of liquid crystal. It can be obtained by performing the step of dropping and applying to the entire surface of the seal pattern frame, the step of overlaying and bonding the other transparent substrate through the seal pattern, and the step of irradiating the seal pattern with light in this order. .
• the photocationic curable liquid crystal sealant of the present invention does not cure immediately after being irradiated with ultraviolet rays, but exhibits a delayed curing property of curing after maintaining a viscous fluid state for a while, two transparent substrates with electrodes
• a step of forming a seal pattern using the photocationic curable liquid crystal sealant of the present invention a step of irradiating the seal pattern with light, and a drop of liquid crystal are applied to the entire surface of the seal pattern frame. It is also possible to obtain the above-described process and the process of superimposing the other transparent substrate and bonding them together via the seal pattern in this order.
• Examples of the cationic curable liquid crystal sealing agent exhibiting delayed curing include the cationic polymerizable compound and a composition of the compound and a reaction retarding agent. Although it does not specifically limit as this reaction retarder, For example, a polyol compound etc. can be used. By containing the reaction retarder, the pot life and the curing time after the cationic curable liquid crystal sealing agent of the present invention is irradiated with light or heat-treated can be controlled.
• aliphatic polyols are preferable, and examples of such aliphatic polyols include (poly) alkylene glycols and glycerins such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and butylene glycol. , Polyglycerin, pentaerythritol, polycaprolactone polyol, crown ether and the like.
• the kind of the photocationic polymerization initiator supported on one dispersible microcarrier is not particularly limited, and those described above can be used.
• the cation curable liquid crystal sealant of the present invention is preferably applied using a dispenser or by a screen printing method. In that case, it is common to apply to a line width of 0.08 to 2 mm and a line height of 5 to 50 ⁇ m.
• the light used for curing the photocationically curable liquid crystal sealing agent of the present invention is preferably ultraviolet light or visible light, and particularly preferably light having a wavelength of 300 nm to 400 nm.
• the light source for example, a high-pressure mercury lamp, a metal halide lamp, or the like can be used. When the illuminance of the light source is 500 W / m 2 or more, it is preferable that curing is quick. If the light quantity to be irradiated is 20000 J / m 2 or more in terms of the integrated light quantity, it can be cured well.
• the photocationic curable liquid crystal sealant of the present invention shows good photocurability even in an air atmosphere, but when photocured in an inert gas atmosphere such as nitrogen, it can be cured with a small amount of accumulated light. Since it is possible, it is more preferable.
• Adeka optomer SP150 of ADEKA Corporation was used as a photocationic polymerization initiator.
• SP150 is a propion carbonate solution having a solid content concentration of 50%, and the amount (parts by mass) described later is a part by mass including a solvent.
• 1 part by mass of a cationic photopolymerization initiator “SP150” was added to 20 parts by mass of acetone and dissolved.
• the photocationic polymerization initiator (A) supported on the dispersible microcarrier (hereinafter referred to as the supported photocationic polymerization initiator ( A)) was obtained.
• the characteristic X-ray intensity ratio of silica and sulfur using a fluorescent X-ray analyzer estimate the content of the photocationic polymerization initiator from the sulfur content, and the content of the initiator (photocationic polymerization initiator) ) / (Supporting mass of silica + photocation polymerization initiator) was 28% by mass. Therefore, the supported amount of the photocationic polymerization initiator with respect to silica calculated from the value obtained from the fluorescent X-ray analyzer is 1.3 ⁇ 10 ⁇ 3 g / m 2 .
• the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur. (Loaded mass of photocationic polymerization initiator) / (silica + photocationic polymerization initiator) was 12% by mass. Accordingly, the supported amount of the photocationic polymerization initiator with respect to silica calculated from this content ratio is 4.5 ⁇ 10 ⁇ 4 g / m 2 .
• the silica-supported thermal cationic polymerization initiator after centrifugation was stirred in 100 parts by mass of ultrapure water, and water was removed with a centrifuge. This was repeated a total of 4 times, and the silica-supported thermal cationic polymerization initiator after centrifugation was vacuum dried at room temperature to obtain a supported thermal cationic polymerization initiator (C).
• C thermal cationic polymerization initiator
• MCM41 which is a mesoporous silica material
• a surfactant docosyltrimethylammonium chloride (C22TMACl)
• C22TMACl docosyltrimethylammonium chloride
• mesoporous material (c) excluding the template mesoporous material (c) excluding the template.
• the pore diameter and surface area of the mesoporous material were measured with an N2 adsorption device (Autosorb). The pore diameter was 4.6 nm and the specific surface area was 1080 m 2 / g.
• a photocationic polymerization initiator “SP150” 1 part by weight of a photocationic polymerization initiator “SP150” was dissolved in a mixed solvent composed of 16 parts by weight of acetone and 4 parts by weight of water.
• 1 part by mass of the mesoporous material (c) was added to the solution of “SP150” and dispersed in the solution using an ultrasonic disperser.
• the dispersion solution was vacuum-dried while maintaining the temperature at 0 ° C. or lower, and acetone was distilled off, followed by vacuum drying. After acetone is distilled off, it is vacuum-dried while the water is frozen, and so-called freeze-drying is performed.
• the following washing was performed. 20 parts by mass of the silica-supported photocationic polymerization initiator was stirred in 100 parts by mass of an ethyl acetate solution, and the ethyl acetate was removed with a centrifuge. This was repeated a total of 4 times, and then the silica-supported photocationic polymerization initiator after centrifugation was stirred in 100 parts by mass of ultrapure water, and water was removed with a centrifuge.
• the silica-supported photocationic polymerization initiator after centrifugation was vacuum dried at room temperature to obtain a supported photocationic polymerization initiator (D).
• the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur. (Loaded mass of photocationic polymerization initiator) / (silica + photocationic polymerization initiator) The supported mass) was 18% by mass. Accordingly, the supported amount of the photocationic polymerization initiator with respect to silica calculated from this content ratio is 2.0 ⁇ 10 ⁇ 4 g / m 2 .
• This is designated as a supported photocationic polymerization initiator (E).
• the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur. (Loaded mass of photocationic polymerization initiator) / (silica + photocationic polymerization initiator) ) was 62%. Accordingly, the supported amount of the photocationic polymerization initiator with respect to silica calculated from this content ratio is 5.4 ⁇ 10 ⁇ 3 g / m 2 .
• the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur. (Loaded mass of photocationic polymerization initiator) / (silica + photocationic polymerization initiator) The supported mass) was 4% by mass. Therefore, the supported amount of the photocationic polymerization initiator with respect to silica calculated from this content is 3.9 ⁇ 10 ⁇ 5 g / m 2 .
• the following washing was performed to remove the initiator adsorbed outside the pores from the supported photocationic polymerization initiator after drying.
• 20 parts by mass of the silica-supported photocationic polymerization initiator was stirred in 100 parts by mass of an ethyl acetate solution, and the ethyl acetate was removed with a centrifuge. This was repeated a total of 4 times, and then the silica-supported photocationic polymerization initiator after centrifugation was stirred in 100 parts by mass of ultrapure water, and water was removed with a centrifuge. This was repeated a total of 4 times, and the supported photocationic polymerization initiator after centrifugation was vacuum dried at room temperature to obtain a supported photocationic polymerization initiator (G).
• G supported photocationic polymerization initiator
• the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur. (Loaded mass of photocationic polymerization initiator) / (silica + photocationic polymerization initiator) The supported mass) was 2% by mass. Therefore, the supported amount of the photocationic polymerization initiator with respect to silica calculated from this content ratio is 4.1 ⁇ 10 ⁇ 4 g / m 2 .
• the content ratio of the photocationic polymerization initiator is determined from the intensity ratio of the characteristic X-rays of silica and sulfur. (Loaded mass of photocationic polymerization initiator) / (silica + photocationic polymerization initiator) The supported mass) was 0.1% by mass. Therefore, the supported amount of the photocationic polymerization initiator with respect to silica calculated from this content is 9.3 ⁇ 10 ⁇ 7 g / m 2 .
• Example 1 2 parts by weight of the supported photocationic polymerization initiator (A) is added to 22 parts by weight of an epoxy monomer “EXA850crp” manufactured by DIC Corporation, and mixed using a rotating / revolving mixer-THINKY AR250 to obtain a sealing agent (A). It was. At this time, the cationic polymerization initiator is 2.5 parts by mass and the dispersible microcarrier is 6.5 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound.
• the liquid crystal of Example 1 using the sealant (A) exhibited the same voltage holding ratio as that of the liquid crystal of Reference Example 2 alone.
• Comparative Example 1 in which the photocationic polymerization initiator and silica were separately added to the epoxy monomer without being supported on silica, and Comparative Example 2 in which only the photocationic polymerization initiator was added were lower than the voltage holding ratio of Reference Example 2. It was suggested that the cationic photopolymerization initiator was eluted in the liquid crystal. Note that the voltage holding ratio of Reference Example 1 in which only the epoxy monomer is added is also lower than the voltage holding ratio of only the liquid crystal of Reference Example 2. This suggests that the epoxy monomer itself also contains a factor that decreases the voltage holding ratio.
• Example 1 of the present application is higher than the voltage holding ratio of Reference Example 1, and from this, the initiation of photocationic polymerization carried on the dispersible microcarrier (of Example 1) of the present invention is started. It is suggested that the agent can also adsorb impurities and the like present in the monomer.
• Example 2 70 parts of epoxy monomer “EXA850crp” manufactured by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether “Denacol EX-212-L” manufactured by Nagase ChemteX Corporation, and silane system manufactured by Shin-Etsu Chemical Co., Ltd. 5 parts of the coupling agent “KBM403” was added and mixed using a rotating / revolving mixer THINKY AR250 until uniform. Next, 9 parts by mass of the supported photocationic polymerization initiator (B) was added and kneaded with three rolls to obtain a sealing agent (B). At this time, the cationic polymerization initiator is 1.1 parts by mass and the dispersible microcarrier is 7.9 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound.
• One glass substrate “RZ-B107N1N” with ITO manufactured by EHC was sprayed with 5% ethanol dispersion of spacer “LH11S” manufactured by Hayakawa Rubber.
• the sealing agent (B) was applied to another glass substrate with ITO with a dispenser so that the sealing liquid width of the finally obtained liquid crystal panel was about 1 mm.
• the sealing agent (B) was applied so as to form a rectangular drawing line so as to surround the electrode inside.
• the sealant (B) was irradiated with ultraviolet rays of 500 W / m 2 for 20 seconds using a high-pressure metal halide lamp.
• liquid crystal “PA-0211CA033” manufactured by DIC Corporation is dropped inside the rectangular sealant (B), and the spacer is made to face the sprayed glass substrate.
• a laminated liquid crystal panel was prepared. This liquid crystal panel was held in a constant temperature and humidity chamber at a temperature of 60 ° C. and a humidity of 90% for 480 hours, and then the voltage holding ratio was measured. The voltage holding ratio was obtained by applying an initial voltage of 5 V AC at 23 ° C. for 64 microseconds, obtaining a voltage ratio before and after a frame time of 167 milliseconds, and multiplying this by 100. The results are shown in Table 2.
• Example 3 70 parts of epoxy monomer “EXA850crp” manufactured by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether “Denacol EX-212-L” manufactured by Nagase ChemteX Corporation, and silane system manufactured by Shin-Etsu Chemical Co., Ltd. 5 parts of the coupling agent “KBM403” was added and mixed using a rotating / revolving mixer THINKY AR250 until uniform. Next, 9 parts by mass of a supported thermal cationic polymerization initiator (C) was added and kneaded with three rolls to obtain a sealing agent (C).
• C supported thermal cationic polymerization initiator
• the cationic polymerization initiator is 0.8 part by mass and the dispersible microcarrier is 8.2 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound.
• One glass substrate “RZ-B107N1N” with ITO manufactured by EHC was sprayed with 5% ethanol dispersion of spacer “LH11S” manufactured by Hayakawa Rubber.
• the sealing agent (C) was applied to another glass substrate with ITO with a dispenser so that the width of the sealing agent (C) of the finally obtained liquid crystal panel was about 1 mm.
• the sealing agent (C) was applied so as to form a rectangular drawing line so as to surround the electrode inside. This was heat-treated at 120 ° C. for 60 seconds.
• Example 4 70 parts of epoxy monomer “EXA850crp” manufactured by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether “Denacol EX-212-L” manufactured by Nagase ChemteX Corporation, and silane system manufactured by Shin-Etsu Chemical Co., Ltd. 5 parts of the coupling agent “KBM403” was added and mixed using a rotating / revolving mixer THINKY AR250 until uniform. Next, 9 parts by mass of the supported photocationic polymerization initiator (D) was added and kneaded with three rolls to obtain a sealing agent (D).
• D supported photocationic polymerization initiator
• the cationic polymerization initiator is 1.6 parts by mass and the dispersible microcarrier is 7.4 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound.
• the voltage holding ratio was measured in the same manner as in Example 2, and the results are shown in Table 2.
• Example 5 70 parts of epoxy monomer “EXA850crp” manufactured by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether “Denacol EX-212-L” manufactured by Nagase ChemteX Corporation, and silane system manufactured by Shin-Etsu Chemical Co., Ltd. 5 parts of the coupling agent “KBM403” was added and mixed using a rotating / revolving mixer THINKY AR250 until uniform. Next, 9 parts by mass of the supported photocationic polymerization initiator (E) was added and kneaded with three rolls to obtain a sealant (E).
• E supported photocationic polymerization initiator
• the cationic polymerization initiator is 5.6 parts by mass and the dispersible microcarrier is 3.4 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound.
• the voltage holding ratio was measured in the same manner as in Example 2, and the results are shown in Table 2.
• Example 6 70 parts of epoxy monomer “EXA850crp” manufactured by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether “Denacol EX-212-L” manufactured by Nagase ChemteX Corporation, and silane system manufactured by Shin-Etsu Chemical Co., Ltd. 5 parts of the coupling agent “KBM403” was added and mixed using a rotating / revolving mixer THINKY AR250 until uniform. Next, 9 parts by mass of the supported photocationic polymerization initiator (F) was added and kneaded with three rolls to obtain a sealant (F).
• F supported photocationic polymerization initiator
• the cationic polymerization initiator is 0.4 parts by mass and the dispersible microcarrier is 8.6 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound.
• the voltage holding ratio was measured in the same manner as in Example 2, and the results are shown in Table 2.
• Example 7 70 parts of epoxy monomer “EXA850crp” manufactured by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether “Denacol EX-212-L” manufactured by Nagase ChemteX Corporation, and silane system manufactured by Shin-Etsu Chemical Co., Ltd. 5 parts of the coupling agent “KBM403” was added and mixed using a rotating / revolving mixer THINKY AR250 until uniform. Next, 9 parts by mass of the supported photocationic polymerization initiator (G) was added and kneaded with three rolls to obtain a sealing agent (G).
• G supported photocationic polymerization initiator
• the cationic polymerization initiator is 0.2 parts by mass and the dispersible microcarrier is 8.8 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound.
• the voltage holding ratio was measured in the same manner as in Example 2, and the results are shown in Table 2.
• Example 8 70 parts of epoxy monomer “EXA850crp” manufactured by DIC Corporation, 30 parts of 1,6-hexanediol diglycidyl ether “Denacol EX-212-L” manufactured by Nagase ChemteX Corporation, and silane system manufactured by Shin-Etsu Chemical Co., Ltd. 5 parts of the coupling agent “KBM403” was added and mixed using a rotating / revolving mixer THINKY AR250 until uniform. Next, 9 parts by mass of the supported photocationic polymerization initiator (H) was added and kneaded with three rolls to obtain a sealant (H).
• H supported photocationic polymerization initiator
• the cationic polymerization initiator is 0.01 part by mass and the microcarrier is 8.8 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound.
• the voltage holding ratio was measured in the same manner as in Example 2, and the results are shown in Table 2.
• Example 9 2 parts by weight of supported cationic photopolymerization initiator (A) 10 parts by weight of epoxy monomer “Epicoat 828”, 10 parts by weight “Epicoat 807”, 2.5 parts by weight of Mitsubishi Chemical Corporation It added to company "PTMG1000", it mixed using the rotation-revolution mixer THINKY AR250, and it was set as the sealing agent (I).
• Two glass substrates RS-B107M1N (with a rubbed alignment film and with ITO) made by EHC were prepared, and one of them was sprayed with a 5% ethanol dispersion of a spacer “LH11S” made by Hayakawa Rubber.
• the sealing agent (I) was applied to another glass substrate in a rectangular shape with a seal width of about 1 mm on the outer edge of the substrate using a dispenser. Thereafter, the sealant part was irradiated with ultraviolet rays of 500 W / m 2 for 40 seconds using a high-pressure meta-hara lamp. Next, an appropriate amount of liquid crystal “PA-0211CA033” manufactured by DIC Corporation is dropped inside the rectangular upper sealant on the substrate under vacuum, and the rubbing directions of the two glass substrates are orthogonalized to produce a bonded cell. did.
• the cell was returned to the atmosphere, and the interval between the substrates became the size of the spacer, and was allowed to stand for 1 hour until the sealant (I) was delayed cured to produce a TN type liquid crystal panel.
• This liquid crystal panel was sandwiched between two orthogonal polarizing plates with the optical axis aligned, to prepare a liquid crystal display element. When no voltage was applied, the display appeared transparent and bright, and when the voltage was applied, the electrode portion of the cell did not transmit light and dark display, indicating a good display state.
• two EHC glass substrates RS-B107M1N (with a rubbed alignment film, with ITO) were prepared, and one of them was sprayed with a 5% ethanol dispersion of a spacer “LH11S” manufactured by Hayakawa Rubber. .
• the sealing agent (H3) was applied to another glass substrate in a rectangular shape with a seal width of about 1 mm on the outer edge of the substrate using a dispenser. Thereafter, the sealant part was irradiated with ultraviolet rays of 500 W / m 2 for 40 seconds using a high pressure meta-hara lamp.
• Example 9 An opaque portion appeared in the periphery of the sealant without applying a voltage, and when the voltage was applied, a dark display of a part of the electrode portion appeared gray.
• a comparison between Example 9 and Comparative Example 3 showed that the sealant produced by the method of the present invention had little liquid crystal contamination. This is presumably because the amount of the photocation polymerization initiator that leaks from the sealing agent and contaminates the liquid crystal is small.
• the other supported photocationic polymerization initiators were prepared by appropriately changing the dispersible microcarriers used under the same conditions as described above and the supported amount of the photocationic polymerization initiator to be supported. Similarly, “eluting amount of polymerization initiator” was measured. The results are shown in Table 3.
• Total amount of polymerization initiator in Table 3 represents the mass of the photocationic polymerization initiator used in the supported photocationic polymerization initiator (A) and other photocationic polymerization initiators. Therefore, (eluting amount of polymerization initiator) / (total amount of polymerization initiator) indicates a ratio of mass of the photocationic polymerization initiator re-eluted in the solution (B), that is, acetone. From this result, 30 to 60% of the photocationic polymerization initiator was re-eluted into the solution (B) regardless of the type of the dispersible microcarrier used and the amount of the photocationic polymerization initiator to be supported. Therefore, it was suggested that 70 to 40% of the photocationic polymerization initiator was bound to the silica with a sufficient binding force.
• the basic solid substance (1) was prepared by introducing basic functional groups on the surface of fumed silica.
• fumed silica R976S manufactured by Nippon Aerosil Co., Ltd. was used.
• the production conditions will be described below.
• the mass ratio of the composition of each example is summarized in Table-1.
• ⁇ -aminopropyltriethoxysilane LS3150, Shin-Etsu Chemical Co., Ltd.
• the dissolution amount is shown in Table-1.
• Fumed silica (100 parts by mass of R976S manufactured by Nippon Aerosil Co., Ltd.) was immersed in the solution and mixed for 10 minutes with an ultrasonic dispersing device. This solution was heated on a hot plate heated to 150 ° C. for 1.5 hours. The powder was obtained by processing. In order to remove the unreacted material and / or the polymer of the silane coupling agent not bonded to the fumed silica surface, 100 parts by mass of this powder was dispersed in 2000 parts by mass of ethyl alcohol and 10 minutes by an ultrasonic treatment apparatus. After shaking, the powder was obtained by centrifugation. This washing was repeated two more times. This powder was dried with hot air at 80 ° C. for 4 hours to obtain a basic solid substance (1).
• Example 10 100 parts by mass of the sealant (D) described in Example 4 was mixed with 2.5 parts by mass of the basic solid substance (1) using a rotating / revolving mixer THINKY AR250, and the sealant (J )
• Example 11 Using 100 parts by mass of the sealant (D) described in Example 4, 20 parts by mass of this and a commercially available talc “Microlite (manufactured by Takehara Chemical Industry Co., Ltd.)” were used using a rotating / revolving mixer THINKY AR250. And mixed to obtain a sealant (K).
• the pH of the extracted water from the adhesive was measured as follows. After irradiating the adhesive with ultraviolet rays, in order to quantify the acid generated from the photoacid generator leached out from the adhesive, the adhesive irradiated with ultraviolet rays was immersed in ultrapure water and the pH was measured. In order to perform this measurement, 0.5 g of the adhesive is put into a glass container having a bottom area of 4.2 cm 2 , the lid of the glass container is removed, and ultraviolet rays having an intensity of 500 W / m 2 are applied from above to 20000 J / m 2. Irradiated.
• the pH of the extracted water was 5 or more, indicating that the basic solid substance neutralized or captured the acid generated from the photoacid generator.
• Electrode corrosion acceleration test For the sealing agents (J) and (K) of Examples 10 and 11, an electrode corrosion acceleration test was performed.
• the sealing agents (J) and (K) were applied to a comb-tooth electrode cell with an applicator so as to have a film thickness of 10 ⁇ m, and cured by irradiation with ultraviolet rays (intensity 50 mW / cm 2) for 40 seconds.
• the comb electrode is made of chromium, and the electrode width is 10 ⁇ m.
• the comb-shaped electrodes are divided into two systems and are opposed to each other, and are combined so that the comb teeth are nested, and the distance between the electrodes is 10 ⁇ m.
• Example 12 Liquid crystal panel production by dripping method
• Two glass substrates RS-B107M1N with a rubbed alignment film and with ITO
• ITO ionization film
• a spacer “LH11S” made by Hayakawa Rubber
• the sealant (J) produced in Example 10 was applied to another glass substrate in a rectangular shape with a seal width of about 1 mm on the outer edge of the substrate using a dispenser, and a high-pressure meta-hara lamp was used. Then, the sealant part was irradiated with UV of 500 W / m 2 for 40 seconds.
• liquid crystal “PA-0211CA033” manufactured by DIC Corporation is dropped inside the rectangular sealant on the substrate under vacuum, and a bonding cell is produced by making the rubbing directions of the two glass substrates orthogonal to each other. did.
• This cell was returned to atmospheric pressure to produce a TN type liquid crystal panel.
• This liquid crystal panel was sandwiched between two orthogonal polarizing plates with the optical axis aligned, to prepare a liquid crystal display element. When no voltage was applied, the display appeared transparent and bright, and when the voltage was applied, the electrode portion of the cell did not transmit light and dark display, indicating a good display state.
• a liquid crystal “PA-0211CA033” manufactured by DIC Corporation was injected into a two-hole cell under vacuum, and the liquid crystal composition was masked so as not to be directly exposed to ultraviolet rays. Then, two holes were used with a sealant (J) or (K) Was sealed and re-irradiated with a UV light of 500 W / m 2 for 40 seconds using a high-pressure metal halide lamp in a nitrogen atmosphere to prepare a liquid crystal panel.
• the liquid crystal panel produced by the above method was subjected to a 60 ° C. and 90% RH wet heat exposure test, and the voltage holding ratio after 120 hours was measured. The voltage holding ratio was calculated by applying an initial voltage of 5 V AC to the liquid crystal panel at 24 ° C. for 64 microseconds and multiplying the voltage ratio before and after the frame time of 167 milliseconds by 100.

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