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
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1339—Gaskets; Spacers; Sealing of 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4035—Hydrazines; Hydrazides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
  • C08L63/10—Epoxy resins modified by unsaturated compounds

Definitions

• the present invention relates to a liquid crystal sealant having good curability by heat. More specifically, the present invention relates to a liquid crystal sealing agent having good curability by heat, excellent storage stability, and excellent moisture resistance of a cured product, and a liquid crystal display cell sealed with the cured product.
• Patent Documents 1 and 2 a so-called liquid crystal dropping method with higher mass productivity has been proposed as a liquid crystal display cell manufacturing method. Specifically, it is a method of manufacturing a liquid crystal display cell in which liquid crystal is sealed by dropping a liquid crystal inside a weir of a liquid crystal sealant formed on one substrate and then bonding the other substrate.
• the liquid crystal sealant in an uncured state comes into contact with the liquid crystal. At that time, the components of the liquid crystal sealant are dissolved (eluting) in the liquid crystal to reduce the resistance value of the liquid crystal, There is a problem that a display defect occurs.
• a photothermal combination type liquid crystal sealant for a liquid crystal dropping method is currently used and put into practical use (Patent Documents 3 and 4).
• the liquid crystal dropping method using the liquid crystal sealant is characterized in that the liquid crystal sealant sandwiched between the substrates is irradiated with light to be primarily cured and then heated to be secondarily cured.
• the uncured liquid crystal sealant can be quickly cured by light, and dissolution (elution) of the liquid crystal sealant component into the liquid crystal can be suppressed.
• the problem of insufficient adhesive strength due to curing shrinkage at the time of photocuring occurs only by photocuring, but the photothermal combination type has an advantage that such problems can be solved by secondary curing by heating.
• Patent Documents 5 and 6 disclose a method using a thermal radical initiator.
• Patent Documents 7 to 9 disclose methods using polyvalent carboxylic acids as curing accelerators.
• a thermal radical initiator generates radicals little by little even at room temperature, and thus has a problem that the storage stability and work stability of the liquid crystal sealant are poor.
• a curing accelerator such as a polyvalent carboxylic acid acts as a catalyst, reacts itself, and is not taken into the cured product by a chemical bond. There is a problem of causing defects.
• liquid crystal sealants As described above, the development of liquid crystal sealants has been carried out very vigorously, but also has excellent thermal stability and good storage stability and low liquid crystal contamination. A liquid crystal sealant having the above has not been realized yet.
• the present invention relates to a liquid crystal sealant that is cured only by heating or by combined use of light and heat, and since the reaction by heat is fast, it is extremely low in contamination with liquid crystals throughout the process and has excellent storage stability and moisture resistance.
• the present invention proposes a liquid crystal sealant for a liquid crystal dropping method that is excellent in properties of cured products such as reliability.
• the inventors have one or more selected from epoxy resins, (meth) acrylated epoxy resins, and partially (meth) acrylated epoxy resins having active hydrogen in the molecule.
• a liquid crystal sealing agent containing a curable resin (however, excluding hydrogen contained in a hydroxy group as active hydrogen) has excellent thermal reactivity, and as a result, liquid crystal contamination can be suppressed.
• the inventors have found that the storage stability is excellent and have completed the present invention. That is, the present invention relates to the following 1) to 13).
• numerator, (meth) acrylated epoxy resin, and partial (meth) acrylated epoxy resin In order to avoid the trouble of describing “a curable resin composed of two or more species”, it may be described as “component (a) curable resin”.
• the liquid crystal sealant of the present invention has a high reaction rate at the time of thermosetting, the photothermal combined liquid crystal dropping method has sufficient curability even under wiring where light is difficult to reach.
• the degree of freedom can be secured and the manufacture of a highly reliable liquid crystal display panel can be facilitated, and furthermore, application to a liquid crystal dropping method in which the liquid crystal sealant is cured only by heat is also possible.
• the liquid-crystal sealing compound of this invention is 1 type (s) or 2 or more types selected from the epoxy resin which has active hydrogen in a component (a) molecule
• the curable resin which consists of is contained.
• hydrogen contained in the hydroxy group is excluded.
• a hydroxy group generally has a large acid dissociation constant (pKa) and also has a weak nucleophilicity of the hydroxy group itself, so that it is difficult to function as a catalyst.
• pKa acid dissociation constant
• a normal epoxy acrylate has a secondary hydroxy group, but does not function as a reaction catalyst during heat curing.
• the curable resin has a functional group that reacts with light or heat such as a (meth) acryloyl group or an epoxy group, the amount of the curable resin taken into the cured product and dissolved in the liquid crystal can be dramatically reduced. The display characteristics of the liquid crystal display element are not impaired.
• (meth) acryl means one or both of “acryl” and “methacryl”.
• (meth) acryloyl means one or both of “acryloyl” and “methacryloyl”.
• the active hydrogen examples include active hydrogen contained in a carboxy group, a sulfanyl group, an amino group, a sulfo group, a phospho group, and the like. That is, as the component (a), for example, a (meth) acrylated epoxy resin and a partial (meth) acrylated epoxy resin having a carboxy group, a sulfanyl group, an amino group, a sulfo group, a phospho group or the like in the molecule, and a molecule Examples thereof include a curable resin containing one or more selected from epoxy resins having a carboxy group, a thiol group, an amino group, a sulfo group, a phospho group, and the like.
• a carboxy group is particularly preferable because of its function as a catalyst and ease of synthesis.
• an epoxy resin having an amino group amine-modified bisphenol A type epoxy acrylate EBECRYL 3703 (manufactured by Daicel Cytec Co., Ltd.) and the like are easily available as commercial products.
• the component (a) curable resin is preferably a (meth) acrylated epoxy resin rather than an epoxy resin or a partially (meth) acrylated epoxy resin. Since the (meth) acrylated epoxy resin reacts quickly by light, it is possible to further suppress dissolution in the liquid crystal.
• This curable resin can be obtained, for example, by reacting an acid anhydride, a polyvalent carboxylic acid, or the like with a (meth) acrylated epoxy resin obtained by a known reaction between an epoxy resin and (meth) acrylic acid. .
• epoxy resin (meth) acrylic acid having a predetermined equivalent ratio
• catalyst for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.
• a polymerization inhibitor for example, methoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.
• an esterification reaction is performed at 80 ° C. to 110 ° C. to obtain a (meth) acrylated epoxy resin.
• the obtained (meth) acrylated epoxy resin is reacted with an acid anhydride by the method described in, for example, JP-A-49-2601, JP-A-3-143911, JP-A-5-32746, A (meth) acrylated epoxy resin having active hydrogen in the molecule can be obtained.
• the epoxy resin used as a raw material is not particularly limited, but a bifunctional or higher functional epoxy resin is preferable, for example, resorcinol diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type.
• resorcinol diglycidyl ether, bisphenol A type epoxy resin, and bisphenol F type epoxy resin are preferable, and resorcinol diglycidyl ether is particularly preferable.
• the content of component (a) is preferably 5 to 50 parts by mass, preferably 5 to 30 parts by mass, when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass. Particularly preferred. If the amount of the component (a) is too small, sufficient thermosetting property cannot be obtained. On the other hand, if the amount is too large, the liquid crystal sealant has a high viscosity, which restricts the blending of other components.
• thermosetting agent that is the component (b) used in the liquid crystal sealing agent of the present invention is not particularly limited, and examples thereof include polyvalent amines, polyhydric phenols, hydrazide compounds, and the like. Compounds are particularly preferably used.
• the aromatic hydrazide terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzenetrihydrazide, 1,4,5,8-naphthoic acid examples include tetrahydrazide and pyromellitic acid tetrahydrazide.
• aliphatic hydrazide compound examples include form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, 1,4- Cyclohexane dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis (hydrazinocarbono Hydantoin skeleton such as ethyl) -5-isopropylhydantoin, preferably valine hydanto
• Examples of the compound represented by the above (1) include tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris. (3-hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate, and the like can be mentioned, but the structure of the formula (1) is not limited thereto.
• isophthalic acid dihydrazide isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate and tris (3-hydrazinocarbonylpropyl) isocyanurate, particularly preferably tris (2-hydrazinocarbonylethyl) isocyanurate.
• component (b) is preferably 1 part by mass to 20 parts by mass, more preferably 2 parts by mass to 15 parts by mass, when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass. Yes, two or more may be used in combination.
• the liquid crystal sealant of the present invention is selected from an epoxy resin, a (meth) acrylated epoxy resin, and a partially (meth) acrylated epoxy resin having no active hydrogen in the molecule as the component (c). Or you may contain the curable resin (However, the hydrogen contained in a hydroxyl group is remove
• the component (c) used in the present invention preferably has low contamination and solubility in liquid crystals.
• suitable epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy.
• Resin phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, hydantoin type epoxy Resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having triphenolmethane skeleton, other diglycidyl ethers of difunctional phenols, diglycidyl ether of difunctional alcohols Things, and their halides, but hydrogenated product or the like, but is not limited thereto.
• the (meth) acryloylated epoxy resin and the partial (meth) acryloylated epoxy resin can be obtained by a known reaction between an epoxy resin and (meth) acrylic acid.
• epoxy resin, (meth) acrylic acid having a predetermined equivalent ratio catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.), and a polymerization inhibitor (for example, methoquinone)
• catalyst for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.
• a polymerization inhibitor for example, methoquinone
• hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc. and an esterification reaction is carried out at 80 °
• An epoxy resin more than bifunctional is preferable, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolac type epoxy resin , Cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin , Phenol novolac type epoxy resins having a triphenolmethane skeleton, other diglycidyl ethers of difunctional phenols, diglycidyl ethers of difunctional alcohols, and These halides, hydrogenated product and the like.
• bisphenol type epoxy resin and novolac type epoxy resin are more preferable from the viewpoint of liquid crystal contamination.
• the ratio of the epoxy group to the (meth) acryloyl group is not limited, and is appropriately selected from the viewpoint of process compatibility and liquid crystal contamination.
• the amount used is appropriately determined in consideration of the workability and physical properties of the liquid crystal sealant obtained.
• the total amount of the liquid crystal sealant is 100 parts by mass, it is preferably 20 parts by mass to 80 parts by mass, and more preferably 30 parts by mass to 70 parts by mass.
• the component (d) silane coupling agent can be used to improve adhesive strength and moisture resistance reliability.
• silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl)
• the component (e) inorganic filler can be used to improve the adhesive strength and improve the moisture resistance reliability.
• this (e) inorganic filler fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, Aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably fused silica, crystalline silica, nitriding Silicon, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, more silicate, aluminum silicate, more
• the average particle size is too large, it becomes a cause of defects such as failure to form a gap when laminating the upper and lower glass substrates when manufacturing a narrow gap liquid crystal cell, and therefore 3 ⁇ m or less is appropriate, and preferably 2 ⁇ m or less.
• the particle size can be measured with a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).
• the content of the inorganic filler (e) that can be used in the liquid crystal sealant of the present invention in the liquid crystal sealant is usually 3 parts by mass to 60 parts by mass when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass. Yes, preferably 5 to 50 parts by mass.
• the content of the inorganic filler is too large, the liquid crystal cell may not be able to form a gap because it is difficult to be crushed.
• the liquid crystal sealant of the present invention may contain a component (f) a photoradical polymerization initiator in order to obtain a photothermal combination curable liquid crystal sealant.
• the radical photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals by UV or visible light irradiation and initiates a chain polymerization reaction.
• benzyl dimethyl ketal 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, Benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine
• An oxide etc. can be mentioned. From the viewpoint of liquid crystal contamination, it is preferable to use those having a (meth) acryloyl group in the molecule.
• 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl]- The reaction product with 2-hydroxy-2methyl-1-propan-1-one is preferably used.
• This compound can be obtained by the method described in International Publication No. 2006/027982.
• the content of the component (f) photopolymerization initiator that can be used in the liquid crystal sealant of the present invention in the liquid crystal sealant is usually 0.5 parts by mass when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass. -20 parts by mass, preferably 1-15 parts by mass.
• a monomer or oligomer of (meth) acrylic acid ester may be used as necessary.
• Such monomers and oligomers include, for example, a reaction product of dipentaerythritol and (meth) acrylic acid, a reaction product of dipentaerythritol / caprolactone and (meth) acrylic acid, etc., but has a contamination property to liquid crystals. If it is low, it will not be restricted in particular.
• liquid crystal sealing agent of the present invention if necessary, additives such as curing accelerators such as organic acids and imidazoles, organic fillers, pigments, leveling agents, antifoaming agents, and solvents can be blended.
• curing accelerators such as organic acids and imidazoles
• organic fillers such as organic acids and imidazoles
• pigments such as pigments, leveling agents, antifoaming agents, and solvents
• An example of a method for obtaining the liquid crystal sealant of the present invention is the following method. First, the component (c) and the component (f) are heated and dissolved in the component (a) as necessary. Next, after cooling to room temperature, component (b) is added, and if necessary, component (d), component (e), and organic filler, antifoaming agent, leveling agent, solvent, etc. are added,
• the liquid crystal sealant of the present invention can be produced by uniformly mixing with a three-roll, sand mill, ball mill or the like and filtering with a metal mesh.
• the liquid crystal display cell of the present invention is a cell in which a pair of substrates having predetermined electrodes formed on a substrate are arranged opposite to each other at a predetermined interval, the periphery is sealed with the liquid crystal sealant of the present invention, and the liquid crystal is sealed in the gap. is there.
• the kind of liquid crystal to be sealed is not particularly limited.
• the substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicon, etc. and having light transmission properties.
• a spacer spacer (gap control material) such as glass fiber
• the liquid crystal sealant is applied to one of the pair of substrates using a dispenser or a screen printing device.
• the liquid crystal display cell of the present invention can be obtained by curing at 90 ° C. to 130 ° C. for 1 to 2 hours.
• the liquid crystal sealant is irradiated with ultraviolet rays by an ultraviolet irradiator and photocured.
• Ultraviolet irradiation amount is preferably 500mJ / cm 2 ⁇ 6000mJ / cm 2, more preferably 1000mJ / cm 2 ⁇ 4000mJ / cm 2.
• the liquid crystal display cell of the present invention can be obtained by curing at 90 ° C. to 130 ° C. for 1 to 2 hours.
• the liquid crystal display cell of the present invention thus obtained is free from display defects due to liquid crystal contamination and has excellent adhesion and moisture resistance reliability.
• the spacer include glass fiber, silica beads, and polymer beads.
• the diameter varies depending on the purpose, but is usually 2 ⁇ m to 8 ⁇ m, preferably 4 ⁇ m to 7 ⁇ m.
• the amount used is usually 0.1 to 4 parts by weight, preferably 0.5 to 2 parts by weight, more preferably 0.9 to 1 part by weight with respect to 100 parts by weight of the liquid crystal sealant of the present invention. About 5 parts by mass.
• the liquid crystal sealant of the present invention has a very good thermosetting property and quickly cures in the heating step in the liquid crystal dropping method. Accordingly, the elution of the constituent components into the liquid crystal is extremely small, and display defects of the liquid crystal display cell can be reduced. Moreover, since it is excellent also in storage stability, it is suitable for manufacture of a liquid crystal display cell. Furthermore, since the cured product is excellent in various cured product characteristics such as adhesive strength, heat resistance, and moisture resistance, it is possible to produce a liquid crystal display cell with excellent reliability by using the liquid crystal sealant of the present invention. is there. In addition, the liquid crystal display cell prepared using the liquid crystal sealant of the present invention satisfies the characteristics required for a liquid crystal display cell having a high voltage holding ratio and a low ion density.
• Examples 1 to 3 Comparative Examples 1 to 4
• Each curable resin component (components (a) and (c)) was mixed and stirred at the ratio shown in Table 1 below, and then heated and dissolved at 90 ° C.
• the photo radical polymerization initiator (component (f)) was heated and dissolved therein, and then cooled to room temperature.
• a silane coupling agent (component (d)), an inorganic filler (component (e)), a thermosetting agent ( Component (b)) was added and stirred, and then dispersed with a three-roll mill and filtered through a metal mesh (635 mesh) to prepare sealants for liquid crystal dropping methods of Examples 1 to 3.
• the curable resin component (component (c)) was heated at 90 ° C. at the ratio shown in Table 1 below.
• the photo radical polymerization initiator (component (f)) was heated and dissolved therein, and then cooled to room temperature.
• a silane coupling agent (component (d)), an inorganic filler (component (e)), a thermosetting agent ( Component (b)) and a curing accelerator were added, stirred, dispersed with a three-roll mill, and filtered through a metal mesh (635 mesh) to prepare sealing agents for liquid crystal dropping methods of Comparative Examples 1 to 4. .
• the evaluation test was carried out by the following method.
• the obtained liquid crystal sealant was sandwiched between polyethylene terephthalate (PET) films and a thin film with a thickness of 100 ⁇ m was irradiated with 3000 mJ / cm 2 of ultraviolet rays by a UV irradiator, and then put into an oven and thermally cured at 120 ° C. for 1 hour. After curing, the PET film was peeled off to obtain a sample. After measuring the weight of the sample, the sample was left in an environment of 60 ° C. and 90% RH for 12 hours and weighed again. Table 1 shows the weight change rate (%) with respect to the initial weight.
• an in-plane spacer (NATOCO SPACER KSEB-525F; manufactured by NATCO; gap width of 5 ⁇ m after bonding) is sprayed and thermally fixed on another rubbing-treated substrate, and the substrate is first vacuumed using a bonding apparatus. The liquid crystal dripped substrate was attached. After opening the atmosphere to form a gap, masking only the seal pattern frame, irradiating with 50 mJ / cm 2 of UV light with a UV irradiator, putting it in an oven and thermosetting at 120 ° C. for 1 hour, liquid crystal test cell for evaluation It was created.
• NATOCO SPACER KSEB-525F manufactured by NATCO; gap width of 5 ⁇ m after bonding
• the complex viscosity was measured with a dynamic viscoelasticity measuring device (Rhesol-G5000, manufactured by UBM Co., Ltd.).
• the setting of the dynamic viscoelasticity measuring apparatus is as follows. Cone: Parallel cone with a diameter of 20 mm, frequency: 1 Hz, distortion angle: 3 deg.
• the measurement temperature was raised from 30 ° C. to 120 ° C. at a rate of 18 ° C./min, and then maintained at 120 ° C.
• Table 1 shows the time when the viscosity reached 10,000 Pa ⁇ s.
• Comparative Example 1 that does not contain a curing accelerator component is inferior in curability, and as a result, alignment failure occurs in the panel display characteristics.
• those using CIC acid, dodecanedioic acid, or a thermal radical initiator as a curing accelerator have improved the curability, but have problems with liquid crystal contamination and moisture-resistant adhesion.
• Examples 1 to 3 it is confirmed that other characteristics are at a usable level while improving the curability. In particular, Examples 1 and 2 show very excellent results in all characteristics.
• the liquid crystal sealing agent of the present invention is excellent in workability because of its excellent storage stability and curability, and it is excellent in liquid crystal contamination, moisture-resistant adhesion, and panel display characteristics because of its high liquid crystal display cell performance. It can be said that reliability can be realized.
• the liquid crystal sealant of the present invention is excellent in workability, it enables stable production of liquid crystal display cells and contributes to ensuring long-term reliability of the liquid crystal display cells.

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• 2011
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