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
  • G02F1/1341—Filling or closing of cells
• • 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
  • G02F1/1345—Conductors connecting electrodes to cell terminals
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/16—Solid spheres
  • C08K7/18—Solid spheres inorganic
• • 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
  • G02F1/1341—Filling or closing of cells
  • G02F1/13415—Drop filling process
• • 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
  • G02F2202/00—Materials and properties
  • G02F2202/28—Adhesive materials or arrangements

Definitions

• the present invention can cause bright spot unevenness in the panel display part without damaging the adhesiveness even when applied on an alignment film imparted with hydrophobicity. It is related with the sealing agent for liquid crystal dripping construction methods without any. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.
• Liquid crystal dripping method called a dripping method using a light- and heat combined curing-type sealant containing a light-sensitive resin, a photopolymerization initiator, a thermosetting resin, and a thermosetting agent.
• a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing.
• a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame with the sealant being uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays to perform temporary curing. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.
• a design for reducing the size of a casing by narrowing the frame of a liquid crystal panel has been performed.
• a design is performed to reduce the frame width of the liquid crystal panel by disposing the application position of the sealing agent under the black matrix.
• An alignment film is formed on the pixel display portion of the liquid crystal panel to control the alignment of liquid crystal molecules.
• the pixel display portion on which the alignment film is formed and the seal line are very close to each other, and the seal line is positioned on the alignment film.
• a hydrophilic sealant is used, while the alignment film is imparted with hydrophobicity. Therefore, when a hydrophilic sealant is applied onto the hydrophobic alignment film to form a seal line, the applied sealant is repelled on the alignment film, and the interface between the sealant and the liquid crystal expands. In this way, the seal line may be distorted. Moreover, since the interface affinity between the alignment film and the sealing agent is low, the adhesive force may be insufficient.
• bright spot unevenness means that when a panel is displayed (when the backlight is turned on and displayed in black), many bright spots appear where the backlight is punctuated on the panel, and black display is observed with the naked eye. A phenomenon in which sweetened unevenness is recognized.
• the present invention can cause bright spot unevenness in the panel display part without damaging the adhesiveness even when applied on an alignment film imparted with hydrophobicity.
• An object of the present invention is to provide a sealing agent for a liquid crystal dropping method without any problems.
• an object of this invention is to provide the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.
• the present invention is a liquid crystal dropping method sealant containing a curable resin, an inorganic filler, a polymerization initiator and / or a thermosetting agent, and the inorganic filler is subjected to a hydrophobic surface treatment. And a liquid crystal dropping method sealing agent having an M value of 20 or more and an average particle size of 0.3 to 1.5 ⁇ m.
• the present invention is described in detail below.
• the sealant used in the liquid crystal display element is usually improved in viscosity, improved adhesiveness due to stress dispersion effect, and reliability at high temperature and high humidity by suppressing moisture permeability.
• An inorganic filler is blended for the purpose of improving the effect, improving the linear expansion coefficient, and the like.
• the present inventor has found that the cause of the bright spot unevenness generated in the panel display part is due to the inorganic filler diffused from the sealant into the liquid crystal. That is, in a narrow frame design in which a seal line is formed on the alignment film, the contact interface between the sealant and the liquid crystal is expanded, so that the inorganic filler is easily diffused in the liquid crystal and spreads in the liquid crystal.
• the inorganic filler disturbs the orientation of the surrounding liquid crystal and causes light to escape.
• the present inventor has applied an inorganic filler liquid crystal to the inorganic filler having an average particle diameter within a specific range by subjecting the inorganic filler to a hydrophobic surface treatment so that the M value is 20 or more. It was found that the unevenness of the bright spot was improved by suppressing the diffusion to the surface. Furthermore, it discovered that the adhesiveness of the sealing agent with respect to alignment film can also be improved by the surface treatment which makes M value of an inorganic filler 20 or more, and came to complete this invention.
• the sealing agent for liquid crystal dropping method of the present invention contains an inorganic filler.
• the inorganic filler is not particularly limited.
• talc asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, water
• examples thereof include magnesium oxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, and aluminum nitride.
• silica and talc are preferable.
• silica examples include NIPSIL manufactured by Tosoh Silica, Admafine manufactured by Admatechs, Seahoster manufactured by Nippon Shokubai Co., Ltd., X24 series manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Denki Kagaku Kogyo Co., Ltd. Spherical silica, functional spherical silica manufactured by Cima Electronics Co., Ltd., fine powder spherical silica manufactured by Fuso Chemical Industry Co., Ltd., functional spherical silica manufactured by Toagosei Co., Ltd., and the like.
• talc examples include SG2000 manufactured by Nippon Talc Co., Ltd., NANO ACE series, and the like.
• the inorganic filler is subjected to a hydrophobic surface treatment and has an M value of 20 or more.
• M value of the inorganic filler has an M value of less than 20, bright spot unevenness is likely to occur in the panel display portion of the liquid crystal display element obtained, or the alignment film has an alignment film on the coated surface of the sealing agent. On the other hand, sufficient adhesion cannot be obtained.
• the minimum with a preferable M value of the said inorganic filler is 22, and a more preferable minimum is 23.
• the upper limit of the M value of the inorganic filler is not particularly limited and is theoretically 99.9, but a preferable upper limit is 70, a more preferable upper limit is 50, and a further preferable upper limit is 35. If the M value of the inorganic filler exceeds 50, the viscosity or thixotropic index of the sealing agent containing the inorganic filler may increase, making it difficult to apply, and the M value of the inorganic filler may be 70. If it exceeds, aggregation of the inorganic filler may occur during the surface treatment.
• the M value is a value representing the hydrophobicity of the particle powder surface.
• the particle powder It is the value of the volume percentage of methanol when it begins to get wet with the liquid mixture. Specifically, 50 mL of water is placed in a 300 mL beaker, 0.2 g of inorganic filler is further added, and methanol is suspended from the burette while stirring with a magnetic stirrer at 23 ° C. It is dripped until it becomes cloudy, and it can be calculated
• the inorganic filler By subjecting the inorganic filler to a chemical or physical hydrophobic surface treatment, the inorganic filler has a hydrophobic group on the surface.
• examples of the functional group to be treated on the surface of the inorganic filler by the hydrophobic surface treatment include a methyl group, an ethyl group, a propyl group, and a butyl group.
• a method for setting the M value of the inorganic filler to 20 or more specifically, for example, by bringing the inorganic filler and a fine powder of an organic compound or a hydrophobic inorganic substance into physical contact with each other, A method of physically adsorbing organic compounds or hydrophobic inorganic substances on the surface, a method of causing a polymerization reaction near the surface of the inorganic filler to form a coating layer on which the polymer is deposited, and an inorganic filling And a method of chemically bonding an organic compound to the surface of the agent.
• a method in which an organic compound is chemically bonded to the surface of the inorganic filler is preferable.
• Examples of the method for chemically bonding an organic compound to the surface of the inorganic filler include, for example, a method of forming a polymer coating layer by causing a polymerization reaction from the surface of the inorganic filler as a base point, and an inorganic compound using a compound having a functional group.
• Examples thereof include a method of chemically bonding with a functional group such as a hydroxyl group present on the surface of the filler.
• a method of chemically bonding with a functional group such as a hydroxyl group present on the surface of the inorganic filler using a compound having a functional group is preferable.
• Examples of the compound having a functional group that reacts with a functional group such as a hydroxyl group present on the surface of the inorganic filler include, for example, a silazane compound, a siloxane compound, various silane coupling agents, Examples include various titanium coupling agents, various aluminum coupling agents, acid anhydrides, higher fatty acids, isocyanate compounds, acid chloride compounds, phosphate ester compounds, and aldehyde compounds. Of these, silane coupling agents such as alkoxysilane compounds and chlorosilane compounds and silazane compounds are preferred.
• a certain amount of the silane coupling agent or the silazane compound is mixed with alcohols such as water, methanol, ethanol, A method of removing the solvent after dissolving it in an organic solvent such as acetone, ethyl acetate, or toluene and reacting the surface of the inorganic filler with a silane coupling agent or silazane compound, or inorganic to the silane coupling agent or silazane compound A method of removing and washing excess silane coupling agent and silazane compound after dispersing and reacting the filler is preferred. These methods may be performed in the presence of a catalyst such as amines, ammonia, acetic acid and hydrochloric acid.
• a catalyst such as amines, ammonia, acetic acid and hydrochloric acid.
• the silane coupling agent or the silazane compound is sprayed while stirring and mixing the untreated inorganic filler in a mixer, and is kept for a certain period of time, and is not reacted.
• a method of removing the treatment agent by nitrogen purge or the like (hereinafter also referred to as “dry method”) is also preferable.
• the silane coupling agent and the silazane compound may be diluted with a solvent or used as they are. This method may be performed in the presence of a catalyst such as amines, ammonia, acetic acid and hydrochloric acid.
• the dilution concentration when the silane coupling agent or the silazane compound is diluted in a solvent is not particularly limited, but is usually 0.01 to 50% by weight, a preferable lower limit is 0.1% by weight, and a preferable upper limit is 35% by weight.
• a more preferred lower limit is 3% by weight, and a more preferred upper limit is 15% by weight.
• the M value can also be adjusted by the amount of functional groups on the surface of the inorganic filler before surface treatment (untreated). In this case, an inorganic filler having a higher M value can be obtained as the number of functional groups on the surface of the untreated inorganic filler increases under the same processing conditions.
• silane coupling agent examples include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, and decyl.
• Ureidosilane coupling agents such as 3-ureidopropyltriethoxysilane, and isocyanate silane coupling agents such as 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.
• Examples include run coupling agents.
• Examples of the silazane compound include hexamethyldisilazane and dimethyldisilazane. These silane coupling agents and silazane compounds may be used alone or in combination of two or more.
• the hydrophobic surface treating agent preferably has a molecular weight of 500 or less.
• the molecular weight of the hydrophobic surface treating agent is more preferably 100 to 300.
• the lower limit of the average particle diameter of the inorganic filler is 0.3 ⁇ m, and the upper limit is 1.5 ⁇ m.
• the average particle size of the inorganic filler is less than 0.3 ⁇ m, the viscosity and thixotropic index of the resulting sealing agent are increased and application becomes difficult, so the blending amount is limited and hydrophobicity is imparted. Insufficient effect on adhesion to alignment film, stress dispersion effect, improvement of moisture permeability and improvement of linear expansion coefficient are difficult to obtain, and panel reliability may not be obtained sufficiently. .
• an inorganic filler having an average particle size of less than 0.3 ⁇ m when a hydrophobic surface treatment is applied to an inorganic filler having an average particle size of less than 0.3 ⁇ m, the inorganic filler tends to diffuse, and thus the inorganic filler is diffused in the liquid crystal and generated. Bright spot unevenness cannot be sufficiently suppressed. If the average particle size of the inorganic filler exceeds 1.5 ⁇ m, when metal wiring such as aluminum wiring is present on the coating surface of the sealing agent, the inorganic filler damages the wiring and breaks, resulting in poor connection. To do.
• the preferable lower limit of the average particle diameter of the inorganic filler is 0.4 ⁇ m, the preferable upper limit is 1.4 ⁇ m, the more preferable lower limit is 0.6 ⁇ m, and the more preferable upper limit is 1.0 ⁇ m.
• the average particle size of the inorganic filler is a D50 value in the particle size distribution of the particles dispersed in the sealing agent for liquid crystal dropping method of the present invention. Can be measured.
• the CV value of the particle diameter of the inorganic filler is not particularly limited, the preferable upper limit is 40%. When the CV value of the particle diameter of the inorganic filler exceeds 40%, a gap defect may occur in the obtained liquid crystal display element.
• the average particle size and CV value of the inorganic filler are measured using a particle size distribution meter (for example, manufactured by Particle Sizing Systems) by dispersing the inorganic filler in a solvent in which the inorganic filler is easily dispersed. Can do.
• the content of the inorganic filler is preferably 5 parts by weight and preferably 40 parts by weight with respect to 100 parts by weight of the curable resin.
• the content of the inorganic filler is less than 5 parts by weight, a sufficient stress dispersion effect and a linear expansion coefficient adjustment effect may not be obtained. If it exceeds 40 parts by weight, the viscosity or thixotropic index of the resulting sealant may increase, making dispensing difficult.
• the more preferable lower limit of the blending amount of the inorganic filler is 10 parts by weight, and the more preferable upper limit is 30 parts by weight.
• the sealing agent for liquid crystal dropping method of the present invention has been subjected to the above hydrophobic surface treatment for the purpose of finely adjusting the viscosity, etc. within a range not impairing the effects of the present invention, and the M value is 20 or more.
• the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, (meth) acrylic polymer fine particles, and core shell particles.
• the content of the organic filler is preferably 5 parts by weight and preferably 30 parts by weight with respect to 100 parts by weight of the curable resin. If the content of the organic filler is less than 5 parts by weight, a sufficient stress dispersion effect may not be obtained. When content of the said organic filler exceeds 30 weight part, the viscosity of the sealing agent obtained may become high and application
• the upper limit with more preferable content of the said organic filler is 20 weight part.
• the sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
• the curable resin preferably contains a resin having an unsaturated double bond and a resin having an epoxy group.
• the resin having an unsaturated double bond include a resin having a (meth) acryloyl group, a resin having an allyl group, and a resin having a vinyl group. Of these, a resin having a (meth) acryloyl group is preferably used.
• the resin having the (meth) acryloyl group is not particularly limited. For example, an ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and an epoxy compound are reacted.
• Examples include completely (meth) acryl-modified epoxy resins obtained by the above, urethane (meth) acrylates obtained by reacting isocyanates with (meth) acrylic acid derivatives having a hydroxyl group, and the like.
• the (meth) acryloyl group means an acryloyloxy group or a methacryloyloxy group
• the (meth) acrylate means an acrylate or a methacrylate
• the (meth) acryl is an acrylic. Or methacryl.
• the complete (meth) acryl-modified epoxy resin represents a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid.
• the ester compound obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group is not particularly limited, and examples of monofunctional compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) ) Acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, Lahydrofurfuryl (meth) acrylate, benzyl
• Examples of the bifunctional compound of the ester compounds include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
• those having three or more functional groups include, for example, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added tri Methylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane Tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene N'okishido added glycer
• an epoxy resin and (meth) acrylic acid are used in the presence of a basic catalyst according to a conventional method. And the like obtained by reacting with.
• Examples of the epoxy resin used as a raw material for synthesizing the complete (meth) acryl-modified epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallyl bisphenol A.
• Type epoxy resin hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy Resin, phenol novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin Naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, bisphenol A type episulfide resins.
• Examples of commercially available bisphenol A type epoxy resins include Epicoat 828EL, Epicoat 1004 (all manufactured by Mitsubishi Chemical Corporation), Epicron 850-S (manufactured by DIC Corporation), and the like. As what is marketed among the said bisphenol F type epoxy resins, Epicoat 806, Epicoat 4004 (all are Mitsubishi Chemical Corporation make) etc. are mentioned, for example. As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example. Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
• Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel Chemical Co., Ltd.).
• Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
• Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
• Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
• Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
• epiclone HP7200 made by DIC
• examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
• examples of commercially available naphthalenephenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel Chemical Co., Ltd.).
• Examples of commercially available glycidylamine epoxy resins include Epicoat 630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
• alkyl polyol type epoxy resins examples include ZX-1542 (manufactured by Nippon Steel Chemical Co., Ltd.), Epicron 726 (manufactured by DIC Corporation), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX- 611 (manufactured by Nagase ChemteX Corporation).
• Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corp.), and the like.
• Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
• Examples of commercially available bisphenol A type episulfide resins include Epicoat YL-7000 (manufactured by Mitsubishi Chemical Corporation).
• epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031, Epicoat 1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.) and the like.
• the completely (meth) acryl-modified epoxy resin obtained by reacting the (meth) acrylic acid with an epoxy compound include, for example, resorcinol type epoxy resin (“EX-201” manufactured by Nagase ChemteX Corporation). ) 360 parts by weight, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 210 parts by weight of acrylic acid are refluxed and stirred at 90 ° C. while feeding air, and reacted for 5 hours. Thus, a completely acrylic-modified resorcinol type epoxy resin can be obtained.
• resorcinol type epoxy resin (“EX-201” manufactured by Nagase ChemteX Corporation).
• the urethane (meth) acrylate obtained by reacting the isocyanate with a (meth) acrylic acid derivative having a hydroxyl group is, for example, a (meth) acrylic acid derivative 2 having a hydroxyl group with respect to 1 equivalent of a compound having two isocyanate groups.
• the equivalent weight can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
• the isocyanate used as a raw material for the urethane (meth) acrylate is not particularly limited.
• MDI 4'
• the isocyanate used as the raw material of the urethane (meth) acrylate is not particularly limited.
• ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone Chain-extended isocyanate compounds obtained by reacting polyols such as diols with excess isocyanate can also be used.
• the hydroxyl group-containing (meth) acrylic acid derivative used as a raw material for the urethane (meth) acrylate is not particularly limited.
• Commercial products such as (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and other products such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol
• the urethane (meth) acrylate includes, for example, 134 parts by weight of trimethylolpropane, 0.2 part by weight of BHT as a polymerization inhibitor, 0.01 part by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate.
• the mixture can be reacted at 60 ° C. with stirring under reflux for 2 hours, and then 51 parts by weight of 2-hydroxyethyl acrylate is added, and the mixture is refluxed and stirred at 90 ° C. while feeding air, and reacted for 2 hours.
• urethane (meth) acrylates include, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), Evecryl 230, Evekril 270, Evekril 4858.
• 50% by weight or more of the resin having the (meth) acryloyl group is a compound having at least one OH group in one molecule.
• 50% by weight or more of the resin having the (meth) acryloyl group is a compound having at least one OH group in one molecule, elution of the sealant into the liquid crystal can be suppressed.
• the compound having at least one OH group in one molecule is particularly preferably a complete (meth) acryl-modified epoxy resin from the viewpoint of ease of synthesis and the like.
• the resin having a (meth) acryloyl group preferably has 2 to 3 (meth) acryloyloxy groups in the molecule from the viewpoint of high reactivity and the like.
• the same epoxy resin as a raw material for synthesizing the complete (meth) acryl-modified epoxy resin can be used.
• the resin having an epoxy group may be, for example, a compound having a (meth) acryloyl group and an epoxy group in one molecule.
• a compound having a (meth) acryloyl group and an epoxy group in one molecule examples include a partially acrylic-modified epoxy resin obtained by reacting a part of the epoxy group of a compound having two or more epoxy groups with (meth) acrylic acid.
• the curable resin may contain only a resin having a (meth) acryloyl group and an epoxy group in the one molecule.
• the partially acrylic modified epoxy resin can be obtained, for example, by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. Specifically, for example, 190 g of phenol novolac type epoxy resin N-770 (manufactured by DIC) is dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine is added to this solution to obtain a uniform solution, and 35 g of acrylic acid is added to this solution. Was added dropwise under reflux stirring for 2 hours, and further reflux stirring was performed for 6 hours. Next, by removing toluene, a partially acrylic modified phenol novolac type epoxy resin in which 50 mol% of the epoxy groups reacted with acrylic acid was obtained. (In this case 50% partially acrylated).
• UVACURE1561 As what is marketed among the said partial acrylic modified epoxy resins, UVACURE1561 (made by Daicel Cytec) is mentioned, for example.
• the sealing agent for liquid crystal dropping method of the present invention is a resin having the above (meth) acryloyl group so that the molar ratio of (meth) acryloyl group to epoxy group of the curable resin is 50:50 to 95: 5. It is preferable to blend the resin having the epoxy group.
• the sealing agent for liquid crystal dropping method of the present invention contains a polymerization initiator and / or a thermosetting agent.
• the polymerization initiator include a photo radical polymerization initiator, a thermal radical polymerization initiator, and a photo cationic polymerization initiator.
• the sealing compound for liquid crystal dropping methods of this invention contains a photoradical polymerization initiator or a thermal radical polymerization initiator.
• the photo radical polymerization initiator is not particularly limited.
• a benzophenone compound, an acetophenone compound, an acyl phosphine oxide compound, a titanocene compound, an oxime ester compound, a benzoin ether compound, a thioxanthone, or the like is preferably used. Can do.
• Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACUREOXE01, Lucin TPO (all from BASF M Examples include ether, benzoin ethyl ether, benzoin isopropyl ether (all of which are manufactured by Tokyo Chemical Industry Co., Ltd.). Of these, IRGACURE651, IRGACURE907, benzoin isopropyl ether, and lucillin TPO are preferred because of their wide absorption wavelength range. These radical photopolymerization initiators may be used alone or in combination of two or more.
• a preferable minimum is 0.1 weight part and a preferable upper limit is 10 weight part with respect to 100 weight part of resin which has the said (meth) acryloyl group.
• the content of the radical photopolymerization initiator is less than 0.1 parts by weight, the photopolymerization of the obtained liquid crystal dropping method sealing agent may not sufficiently proceed.
• the content of the photo radical polymerization initiator exceeds 10 parts by weight, a large amount of unreacted photo radical polymerization initiator remains, and the weather resistance of the obtained liquid crystal dropping method sealing agent may deteriorate.
• the minimum with more preferable content of the said radical photopolymerization initiator is 1 weight part, and a more preferable upper limit is 5 weight part.
• the thermal radical polymerization initiator is not particularly limited, and examples thereof include peroxides and azo compounds.
• examples of commercially available thermal radical polymerization initiators include V-30, V-501, V-601, VPE-0201 (all manufactured by Wako Pure Chemical Industries, Ltd.), perbutyl O, perhexyl O, Examples include perbutyl PV (both manufactured by NOF Corporation).
• a preferable minimum is 0.01 weight part and a preferable upper limit is 10 weight part with respect to 100 weight part of resin which has the said (meth) acryloyl group. If the content of the thermal radical polymerization initiator is less than 0.01 parts by weight, the polymerization may not proceed sufficiently or the reaction may become too slow. When content of the said thermal radical polymerization initiator exceeds 10 weight part, storage stability may fall.
• the minimum with more preferable content of the said thermal radical polymerization initiator is 0.5 weight part, and a more preferable upper limit is 5 weight part.
• a polymer azo initiator may be used as the azo compound.
• the high molecular azo initiator means a compound having an azo group and a radical-generating molecular weight of 300 or more that can cure a (meth) acryl group with heat.
• the said polymeric azo initiator decomposes
• the preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. If the number average molecular weight of the polymer azo initiator is less than 1000, the polymer azo initiator may adversely affect the liquid crystal, and if it exceeds 300,000, mixing with a resin having a (meth) acryl group may occur. It can be difficult.
• the more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
• polymeric azo initiators examples include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) with terminal groups.
• examples of commercially available products include polycondensates of polydimethylsiloxane having an amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all of which are Wako Pure Chemical Industries). Yakuhin Kogyo Co., Ltd.).
• the sealing compound for liquid crystal dropping methods of this invention contains a photocationic polymerization initiator or a thermosetting agent.
• the photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. May be.
• onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts
• organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes.
• photocationic polymerization initiators may be used independently and 2 or more types may be used together.
• photocationic polymerization initiators examples include, for example, Adekaoptomer SP-150, Adekaoptomer SP-170 (all manufactured by ADEKA), UVE-1014 (manufactured by General Electric), CD-1012 (manufactured by Sartomer), RD-2074 (manufactured by Rhodia) and the like.
• a preferable minimum is 0.1 weight part and a preferable upper limit is 10 weight part with respect to 100 weight part of resin which has the said epoxy group.
• the content of the photocationic polymerization initiator is less than 0.1 parts by weight, the cationic polymerization of the photocationic polymerizable compound does not proceed sufficiently, or the curing reaction of the resulting sealant becomes too slow. There is. If the content of the cationic photopolymerization initiator is more than 10 parts by weight, the curing reaction of the resulting sealing agent becomes too fast, and workability is reduced, or the resulting sealing agent becomes a non-uniform cured product. There are things to do.
• the minimum with more preferable content of the said photocationic polymerization initiator is 0.5 weight part.
• thermosetting agent is not specifically limited, For example, organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned. Among these, organic acid hydrazide solid at room temperature is preferably used.
• the solid organic acid hydrazide is not particularly limited, and examples thereof include 1,3-bis (hydrazinocarboethyl-5-isopropylhydantoin), sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
• Examples of commercially available products include Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.), SDH, IDH (all manufactured by Otsuka Chemical Co., Ltd.), ADH (manufactured by Nippon Finechem Co., Ltd.), and the like.
• thermosetting agent is not specifically limited, A preferable minimum is 0.1 weight part and a preferable upper limit is 50 weight part with respect to 100 weight part of resin which has the said epoxy group. If the content of the thermosetting agent is less than 0.1 parts by weight, the thermosetting may not proceed sufficiently or the reaction may become too slow. When content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing agent obtained may become high and coating may become difficult.
• the minimum with more preferable content of the said thermosetting agent is 1 weight part, and a more preferable upper limit is 30 weight part.
• the sealing agent for liquid crystal dropping method of the present invention preferably contains a silane coupling agent.
• the silane coupling agent mainly has a role as an adhesion assistant.
• the silane coupling agent is not particularly limited, and for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are preferably used.
• the sealing agent for the liquid crystal dropping method of the present invention further includes a reactive diluent for adjusting the viscosity, a thixotropic agent for adjusting the thixotropy, a spacer such as a polymer bead for adjusting the panel gap, if necessary. It may contain a curing accelerator such as -P-chlorophenyl-1,1-dimethylurea, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other additives.
• a curing accelerator such as -P-chlorophenyl-1,1-dimethylurea
• Examples of the method for producing the sealant for the liquid crystal dropping method of the present invention include, for example, a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a three-roll mixer, etc. And a method of mixing an agent, a polymerization initiator and / or a thermosetting agent, and a silane coupling agent added as necessary. At this time, in order to remove the ionic impurities contained, it may be brought into contact with an ion-adsorbing solid.
• the sealing agent for liquid crystal dropping method of the present invention has a preferable lower limit of 100 Pa ⁇ s and a preferable upper limit of 400 Pa ⁇ s as measured with an E-type viscometer at 25 ° C. and 1.0 rpm. If the viscosity is less than 100 Pa ⁇ s, the liquid crystal may not be retained. When the viscosity exceeds 400 Pa ⁇ s, applicability may be deteriorated. A more preferable lower limit of the viscosity is 200 Pa ⁇ s, and a more preferable upper limit is 350 Pa ⁇ s.
• the preferable upper limit of the thixotropic index is 1.5.
• the more preferable upper limit of the thixotropic index of the sealing agent for liquid crystal dropping method of the present invention is 1.3.
• the lower limit of the thixotropic index of the sealing agent for liquid crystal dropping method of the present invention is not particularly limited, but is not substantially less than 1.0.
• the “thixotropic index” means a viscosity measured at 25 rpm at 25 ° C. using an E type viscometer, and 5.0 rpm at 25 ° C. using an E type viscometer. It means the value divided by the viscosity measured under the conditions.
• a vertical conduction material can be produced by blending conductive fine particles with the sealant for the liquid crystal dropping method of the present invention.
• Such a vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.
• the conductive fine particles are not particularly limited, and metal balls, those obtained by forming a conductive metal layer on the surface of resin fine particles, and the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particle is preferable because the conductive connection is possible without damaging the wiring connection portion on the substrate due to the excellent elasticity of the resin fine particle.
• the sealing agent for the liquid crystal dropping method of the present invention is further provided with a light-shielding colorant, a reactive diluent for viscosity adjustment, a thixotropic agent for adjusting thixotropy, and a panel gap adjustment, if necessary.
• a spacer such as polymer beads, a curing accelerator, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other additives may be contained.
• the liquid crystal display element using the sealing compound for liquid crystal dropping method of the present invention and / or the vertical conduction material of the present invention is also one aspect of the present invention.
• one of two transparent substrates with electrodes, such as an ITO thin film is formed into a rectangular shape by screen printing, dispenser application, etc. of the liquid crystal dropping method sealing agent of the present invention.
• a step of forming a seal pattern of the present invention a step of applying a liquid crystal micro-droplet on the entire surface of a transparent substrate in an uncured state with the liquid crystal dropping method sealing agent of the present invention uncured, and immediately overlaying the other transparent substrate And the process of irradiating light, such as ultraviolet rays, to seal pattern parts, such as the sealant for liquid crystal dropping methods of the present invention, and temporarily hardening the sealant, and the process of heating and temporarily hardening the temporarily hardened sealant And the like.
• irradiating light such as ultraviolet rays
• the present invention in the production of a liquid crystal display element by a dropping method, even if it is applied on an alignment film imparted with hydrophobicity, bright spot unevenness occurs in the panel display part without impairing the adhesion. It is possible to provide a sealant for a liquid crystal dropping method that does not occur. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.
• Example 1 Surface treatment of inorganic filler 10 parts by weight of silica particles (“KEP-30” manufactured by Nippon Shokubai Co., Ltd., average particle size 0.3 ⁇ m, M value 0) as an inorganic filler are dispersed in 100 parts by weight of ethanol in which 5 parts by weight of methyltriethoxysilane is dissolved. And reacted for 1 hour under reflux of ethanol to obtain methyl-treated silica (M value 34).
• silica particles (“KEP-30” manufactured by Nippon Shokubai Co., Ltd., average particle size 0.3 ⁇ m, M value 0) as an inorganic filler are dispersed in 100 parts by weight of ethanol in which 5 parts by weight of methyltriethoxysilane is dissolved. And reacted for 1 hour under reflux of ethanol to obtain methyl-treated silica (M value 34).
• Partial acrylic modified epoxy resin (Daicel Cytec, "EBECRYL1561”) 20 parts by weight, fully acrylic modified bisphenol A type epoxy resin (Daicel Cytec, “EBECRYL3700”) 40 parts by weight, radical photopolymerization initiator (BASF) 1 part by weight (manufactured by Japan, “IRGACURE 651”) was blended and dissolved by heating at 80 ° C., followed by stirring using a planetary stirring device to obtain a mixture.
• BASF radical photopolymerization initiator
• Example 2 In “(Surface treatment of inorganic filler)”, except that silica particles (manufactured by Nippon Shokubai Co., Ltd., “KEP-50”, average particle size 0.5 ⁇ m, M value 0) were used as inorganic fillers, Examples In the same manner as in Example 1, methyl-treated silica (M value 31) was obtained. A sealing agent was obtained in the same manner as in Example 1 except that 7 parts by weight of the obtained methyl-treated silica was used as the inorganic filler.
• Example 3 In “(Surface treatment of inorganic filler)”, except that silica particles (manufactured by Nippon Shokubai Co., Ltd., “KEP-100”, average particle diameter: 1.0 ⁇ m, M value: 0) were used as the inorganic filler. In the same manner as in Example 1, methyl-treated silica (M value 30) was obtained. A sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained methyl-treated silica was used as the inorganic filler.
• Example 4 In Example 3, a seal was made in the same manner as in Example 3 except that 5 parts by weight of a polymer azo compound (manufactured by Wako Pure Chemical Industries, Ltd., “VPE0201”) was blended as a thermal radical polymerization initiator together with the thermosetting agent. An agent was obtained.
• a polymer azo compound manufactured by Wako Pure Chemical Industries, Ltd., “VPE0201”
• Example 5 In “(Surface treatment of inorganic filler)”, Examples were used except that silica particles (“KEP-150” manufactured by Nippon Shokubai Co., Ltd., average particle size 1.5 ⁇ m, M value 0) were used as the inorganic filler. In the same manner as in Example 1, methyl-treated silica (M value 26) was obtained. A sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained methyl-treated silica was used as the inorganic filler.
• silica particles (“KEP-150” manufactured by Nippon Shokubai Co., Ltd., average particle size 1.5 ⁇ m, M value 0) were used as the inorganic filler.
• M value 26 methyl-treated silica
• a sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained methyl-treated silica was used as the inorganic filler.
• Example 6 In “(Surface treatment of inorganic filler)”, silica particles (“KEP-100” manufactured by Nippon Shokubai Co., Ltd., average particle diameter 1.0 ⁇ m, M value 0) are used as inorganic fillers, and replaced with methyltriethoxysilane. In the same manner as in Example 1 except that 3-aminopropyltrimethoxysilane was used, amino-treated silica (M value 23) was obtained. A sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained amino-treated silica was used as the inorganic filler.
• Example 7 In “(Surface treatment of inorganic filler)”, silica particles (manufactured by Nippon Shokubai Co., Ltd., “KEP-100”, average particle diameter 1.0 ⁇ m, M value 0) were used as the inorganic filler, and methyl triethoxysilane 5 wt.
• An epoxy-treated silica (M value 20) was obtained in the same manner as in Example 1 except that 3.5 parts by weight of 3-glycidoxypropyltrimethoxysilane was used in place of the parts.
• a sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained epoxy-treated silica was used as the inorganic filler.
• Example 8 In “(Surface treatment of inorganic filler)”, silica particles (“KEP-100” manufactured by Nippon Shokubai Co., Ltd., average particle diameter 1.0 ⁇ m, M value 0) are used as inorganic fillers, and replaced with methyltriethoxysilane. In the same manner as in Example 1 except that 3-glycidoxypropyltrimethoxysilane was used, epoxy-treated silica (M value 25) was obtained. A sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained epoxy-treated silica was used as the inorganic filler.
• Example 9 A sealing agent was obtained in the same manner as in Example 8 except that the amount of the epoxy-treated silica was changed to 2 parts by weight.
• Example 10 A sealing agent was obtained in the same manner as in Example 8 except that the amount of the epoxy-treated silica was changed to 30 parts by weight.
• Example 11 In “(Surface treatment of inorganic filler)”, talc particles (manufactured by Nippon Talc Co., Ltd., “SG-2000”, average particle size 1.0 ⁇ m, M value 0) were used as the inorganic filler, and replaced with methyltriethoxysilane. In the same manner as in Example 1 except that 3-glycidoxypropyltrimethoxysilane was used, an epoxy-treated talc (M value 24) was obtained. A sealing agent was obtained in the same manner as in Example 8 except that the amount of the epoxy-treated silica was changed to 10 parts by weight and that 5 parts by weight of the prepared epoxy-treated talc was further blended as an inorganic filler.
• Example 12 In “(Surface Treatment of Inorganic Filler)”, silica particles “Admuffin SO-E3” (manufactured by Admatechs, average particle size 1.0 ⁇ m, M value 0) was used as the inorganic filler, and methyltriethoxysilane 5 Epoxy-treated silica (M value 25) was obtained in the same manner as in Example 1 except that 10 parts by weight of 3-glycidoxypropyltrimethoxysilane was used instead of parts by weight. A sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained epoxy-treated silica was used as the inorganic filler.
• Epoxy-treated silica (M value 34) was obtained in the same manner as in Example 7 except that the amount of 3-glycidoxypropyltrimethoxysilane was changed to 10 parts by weight.
• a sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained epoxy-treated silica was used as the inorganic filler.
• Epoxy-treated silica (M value 57) was obtained in the same manner as in Example 7 except that the amount of 3-glycidoxypropyltrimethoxysilane was changed to 30 parts by weight.
• a sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained epoxy-treated silica was used as the inorganic filler.
• Example 15 In “(Surface treatment of inorganic filler)”, Example 1 was used except that talc particles (manufactured by Nippon Talc Co., Ltd., “D-600”, average particle diameter 0.6 ⁇ m, M value 0) were used as the inorganic filler. The same procedure was carried out to obtain methyl-treated talc (M value 29). A sealing agent was obtained in the same manner as in Example 1 except that 10 parts by weight of the obtained methyl-treated talc was used as the inorganic filler.
• Example 16 In “(Surface treatment of inorganic filler)”, Example 1 was used except that talc particles (manufactured by Nippon Talc Co., Ltd., “SG-2000”, average particle size 1.0 ⁇ m, M value 0) were used as the inorganic filler. The same procedure was carried out to obtain methyl-treated talc (M value 25). A sealing agent and a liquid crystal display device were obtained in the same manner as in Example 1 except that 10 parts by weight of the obtained methyl-treated talc was used as the inorganic filler.
• Example 17 In “(Surface treatment of inorganic filler)”, talc particles (manufactured by Nippon Talc Co., Ltd., “SG-2000”, average particle diameter 1.0 ⁇ m, M value 0) are used as inorganic fillers, and the talc particles are used in a Henschel mixer. 100 parts by weight was added and heated at 150 ° C., while stirring and spraying with a mixture of 5 parts by weight of water and 10 parts by weight of hexamethyldisilazane, methyl treatment was performed to obtain methyl-treated talc (M value 40). . A sealing agent was obtained in the same manner as in Example 1 except that 10 parts by weight of the obtained methyl-treated talc was used as the inorganic filler.
• Epoxy-treated talc (M value 20) was obtained in the same manner as in Example 11 except that 5 parts by weight of 3-glycidoxypropyltrimethoxysilane was changed to 4 parts by weight.
• a sealing agent was obtained in the same manner as in Example 1 except that 10 parts by weight of the obtained epoxy-treated talc was used as the inorganic filler.
• Example 19 A sealing agent was obtained in the same manner as in Example 1 except that 10 parts by weight of an epoxy-treated talc (M value 24) obtained by performing the same operation as in Example 11 was used as the inorganic filler.
• Example 20 A sealant was obtained in the same manner as in Example 19 except that the amount of the epoxy-treated talc was changed to 2 parts by weight.
• Example 21 A sealant was obtained in the same manner as in Example 19 except that the amount of the epoxy-treated talc was changed to 30 parts by weight.
• Epoxy-treated talc (M value 30) was obtained in the same manner as in Example 11 except that the amount of 3-glycidoxypropyltrimethoxysilane was changed to 10 parts by weight.
• a sealing agent was obtained in the same manner as in Example 1 except that 10 parts by weight of the obtained epoxy-treated talc was used as the inorganic filler.
• Epoxy-treated talc (M value 75) was obtained in the same manner as in Example 11 except that the amount of 3-glycidoxypropyltrimethoxysilane was changed to 30 parts by weight.
• a sealing agent was obtained in the same manner as in Example 1 except that 10 parts by weight of the obtained epoxy-treated talc was used as the inorganic filler.
• Example 24 Except that 3-aminopropyltrimethoxysilane was used instead of 3-glycidoxypropyltrimethoxysilane, the same procedure as in Example 11 was performed to obtain an amino-treated talc (M value 23). A sealing agent was obtained in the same manner as in Example 1 except that 10 parts by weight of the amino-treated talc obtained was used as the inorganic filler.
• Example 2 Sealing was carried out in the same manner as in Example 1 except that 5 parts by weight of methyl-treated silica (manufactured by Shin-Etsu Chemical Co., Ltd., “X24-9163A”, average particle size 0.08 ⁇ m, M value 38) was used as the inorganic filler. An agent was obtained.
• methyl-treated silica manufactured by Shin-Etsu Chemical Co., Ltd., “X24-9163A”, average particle size 0.08 ⁇ m, M value 38
• Comparative Example 3 A sealing agent was obtained in the same manner as in Comparative Example 2 except that the amount of methyl-treated silica was changed to 10 parts by weight.
• Example 4 A sealant was obtained in the same manner as in Example 1 except that 7 parts by weight of untreated “KEP-50” was used as the inorganic filler.
• Example 5 A sealant was obtained in the same manner as in Example 1 except that 15 parts by weight of untreated “KEP-100” was used as the inorganic filler.
• Example 6 In “(Surface treatment of inorganic filler)”, the same procedure as in Example 1 was performed except that silica particles “HPS1000 (manufactured by Toagosei Co., Ltd., average particle size: 1.0 ⁇ m, M value: 0) were used as the inorganic filler. Thus, methyl-treated silica (M value 15) was obtained. A sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained methyl-treated silica was used as the inorganic filler.
• Epoxy-treated silica (M value 13) was obtained in the same manner as in Example 7 except that the amount of 3-glycidoxypropyltrimethoxysilane was changed to 1 part by weight.
• a sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained epoxy-treated silica was used as the inorganic filler.
• Epoxy-treated silica (M value 17) was obtained in the same manner as in Example 12 except that the amount of 3-glycidoxypropyltrimethoxysilane was changed to 5 parts by weight.
• a sealing agent was obtained in the same manner as in Example 1 except that 15 parts by weight of the obtained epoxy-treated silica was used as the inorganic filler.
• Epoxy-treated talc (M value 14) was obtained in the same manner as in Example 11 except that the amount of 3-glycidoxypropyltrimethoxysilane was changed to 1 part by weight.
• a sealing agent was obtained in the same manner as in Example 1 except that 10 parts by weight of the obtained epoxy-treated talc was used as the inorganic filler.
• M value of the inorganic filler used in the Example and the comparative example was derived as follows. Under a 23 ° C. atmosphere, 0.2 g of inorganic filler and 50 mL of ion-exchanged water were placed in a 300 mL beaker. While stirring the solution in the beaker with a magnetic stirrer, methanol was added dropwise from the burette until the inorganic filler was suspended. At this time, the point in time when the inorganic filler was visually suspended in the solution was defined as the end point, and the methanol volume percentage value of the liquid mixture in the beaker at the end point was defined as the M value.
• Viscosity and thixotropic index About the sealant obtained in each Example and each Comparative Example, conditions of 25 ° C. and 1.0 rpm using an E-type viscometer (“DV-III” manufactured by Brookfield) The viscosity at was measured. Similarly, the viscosity under the conditions of 25 ° C. and 0.5 rpm and the viscosity under the conditions of 25 ° C. and 5.0 rpm are measured, and the viscosity measured under the conditions of 25 ° C. and 0.5 rpm is 25 ° C., 5. The thixotropic index was derived by dividing by the viscosity measured at 0 rpm.
• Adhesiveness 3 parts by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SP205”, 5.0 ⁇ m) were dispersed in 100 parts by weight of the sealant obtained in each Example and each Comparative Example.
• a very small amount of the sealing agent in which the spacer fine particles were dispersed was taken in the center of Corning glass 1737 (20 mm ⁇ 50 mm ⁇ 1.1 mmt) having a transparent electrode (ITO) formed on the surface.
• the amount of the sealing agent was set to an amount of about 3 mm ⁇ by overlapping the same type of glass on top of it and spreading it.
• the sealing agent was cured by irradiating the bonded glass substrate with 100 mW / cm 2 of ultraviolet light for 30 seconds using a high-pressure mercury lamp with a filter that cuts light of 350 nm or less. Then, it heated at 120 degreeC for 1 hour, and obtained the adhesion test piece. About the obtained adhesion test piece, the adhesive strength was measured by a plane tensile test method using a tension gauge. Further, an imide resin (manufactured by Nissan Chemical Co., Ltd., “# 7492”) was applied to the above-mentioned Corning glass 1737 by spin coating, prebaked at 80 ° C., and then baked at 230 ° C. to form an alignment film as described above. Similarly, an adhesive test piece was prepared, and the adhesive strength was measured in the same manner.
• Wiring damage property It consists of a glass substrate having a pattern in which 100 pieces of aluminum wiring having a width of 50 ⁇ m are arranged on a non-alkali glass having a thickness of 0.7 mm, and a non-alkali glass having a thickness of 0.7 mm in which no wiring is arranged.
• a glass substrate was prepared. Apply the sealant obtained in each example and each comparative example on the glass substrate wiring on which the aluminum wiring is arranged so as to be in a direction perpendicular to the direction of the aluminum wiring and to have a seal width of 1 mm after crimping. Then, a glass substrate on which no wiring was arranged was bonded and pressure-bonded at a pressure of 0.5 MPa.
• the sealant part was irradiated with 100 mW / cm 2 of ultraviolet light for 30 seconds using a high-pressure mercury lamp with a filter that cuts light of 350 nm or less, and then heated at 120 ° C. for 1 hour to cure the sealant. .
• the continuity of each aluminum wiring was measured and the disconnection rate (ratio of disconnected wiring in 100 wires) was evaluated.
• Bright spot unevenness 3 parts by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SP205”, 5.0 ⁇ m) were dispersed in 100 parts by weight of the sealant obtained in each Example and each Comparative Example.
• a sealant in which spacer fine particles were dispersed was applied with a dispenser so as to draw a rectangular frame on one of two non-alkali glass substrates on which a rubbing-treated alignment film and ITO electrodes were formed.
• liquid crystal (Merck, “ZLI-4792”) is dropped, and the other substrate is bonded, and a high-pressure mercury lamp with a filter that cuts light of 350 nm or less is irradiated at 100 mW / cm 2 for 30 seconds. Then, the sealant was cured, and further heated at 120 ° C. for 1 hour to produce a liquid crystal display element.
• the obtained liquid crystal display element is modularized and displayed in black, light is applied from the back side with a backlight and visually observed, and when bright spot unevenness is not confirmed over the front surface of the liquid crystal display element panel, ⁇ ⁇ '' The bright spot unevenness was confirmed in the vicinity of the sealant around the panel, but it was a level where there was no problem in practical use. Brightness unevenness was evaluated with “ ⁇ ” as the level.
• Gap unevenness For the liquid crystal display device obtained in the same manner as “(5) Bright spot unevenness”, the unevenness due to the gap defect was visually evaluated. Moreover, the panel gap was measured and the gap difference of the panel center and sealant vicinity was evaluated. “ ⁇ ” indicates that the target gap was obtained across the front of the panel, and no gap unevenness was observed, and the panel periphery was higher than the gap at the center, and the gap unevenness due to that was confirmed visually. Gap unevenness was evaluated as “ ⁇ ”.
• the present invention in the production of a liquid crystal display element by a dropping method, even if it is applied on an alignment film imparted with hydrophobicity, bright spot unevenness occurs in the panel display part without impairing the adhesion. It is possible to provide a sealant for a liquid crystal dropping method that does not occur. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.

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• 2012
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