JP6021697B2 - Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element - Google Patents

Description

In the production of a liquid crystal display element by a dropping method, 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.

In recent years, a method for manufacturing a liquid crystal display element such as a liquid crystal display cell has been developed from a conventional vacuum injection method in view of shortening tact time and optimizing the amount of liquid crystal used, for example, photocuring as disclosed in Patent Document 1. 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.
In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, 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.

By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and portable game machines are widespread, downsizing of liquid crystal terminals is the most demanded issue. As a technique for reducing the size of a liquid crystal terminal, a design for reducing the size of a casing by narrowing the frame of a liquid crystal panel has been performed. For example, a design (narrow frame design) is performed to reduce the frame width of the liquid crystal panel by disposing the application position of the sealing agent under a 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. In the above-mentioned narrow frame design, 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. Usually, from the viewpoint of suppressing elution into the liquid crystal and reducing liquid crystal contamination, 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. Furthermore, when the sealing agent is applied on the alignment film, a special display defect called bright spot unevenness may occur in the panel display portion. Here, 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.

JP 2001-133794 A

In the production of a liquid crystal display element by a dropping method, 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. Moreover, 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 which is silica having an M value of 20 or more and an average particle size of 0.3 to 1.5 μm.
The present invention is also a liquid crystal dropping method sealing agent containing a curable resin, an inorganic filler, a polymerization initiator and / or a thermosetting agent, wherein the inorganic filler is a hydrophobic surface treatment. The M value is 20 or more, the average particle size is 0.3 to 1.5 μm, and the polymerization initiator is a sealing agent for liquid crystal dropping method containing a thermal radical polymerization initiator.
The present invention is described in detail below.

As disclosed in Patent Document 1, 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. Inorganic fillers are blended for the purpose of improving the effect and improving the linear expansion coefficient.
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.
In view of this, 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. For example, 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. Of these, silica and talc are preferable.

Examples of commercially available silica 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.
Examples of commercially available talc include SG2000 manufactured by Nippon Talc Co., Ltd., NANO ACE series, and the like.

In the sealing agent for liquid crystal dropping method of the present invention, the inorganic filler is subjected to a hydrophobic surface treatment and has an M value of 20 or more. When 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 more preferable lower limit of the M value of the inorganic filler is 22, and the more preferable lower limit 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. When the mixing ratio of the mixed liquid of water and methanol is changed (when the methanol ratio is increased), 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 | required as a value of the volume percentage of methanol of the liquid mixture in the beaker in an end point by making the end point the inorganic filler suspended in the solution. Since the measured value varies depending on the amount and temperature of the inorganic filler, in the present invention, the value under the measurement condition is applied as the M value.

By subjecting the inorganic filler to a chemical or physical hydrophobic surface treatment, the inorganic filler has a hydrophobic group on the surface.
In order to make the M value of the inorganic filler 20 or more, 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. An hexyl group, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, a lauryl group, a stearyl group, etc., an alkyl group having 1 to 20 carbon atoms, a glycidyl group, an epoxy group such as a 3,4-epoxycyclohexyl group, 1 Class, secondary or tertiary amino group, alkoxyl group, vinyl group, acryloyl group, methacryloyl group, sulfide group, mercapto group, isocyanate group, ureido group, pyridyl group, styryl group, ether bond, ester bond And a functional group containing a thiol group.

As 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. Of these, 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. Among these, 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 (hereinafter also referred to as a hydrophobic surface treatment agent) 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.

As the treatment with the silane coupling agent or the silazane compound, in a solvent in which an untreated inorganic filler is dispersed, 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.

In addition, as the treatment with the silane coupling agent or the silazane compound, 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. In this method, 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.

In the treatment with the silane coupling agent or the silazane compound, adjusting the dilution concentration when the silane coupling agent or the silazane compound is diluted in a solvent, the addition amount of the silane coupling agent or the silazane compound, the silane coupling agent The M value of the inorganic filler can be controlled by adjusting the temperature and pH when the silazane compound is reacted with the surface of the inorganic filler. The dilution concentration in the case of diluting the silane coupling agent or the silazane compound in a solvent is not particularly limited, but is usually 0.01 to 50% by weight, the preferred lower limit is 0.1% by weight, and the preferred 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.

Examples of the silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, and decyl. Silane coupling agents having an alkyl group such as trimethoxysilane, methyltrichlorosilane, butyltrichlorosilane, and trifluoropropyltrimethoxysilane, and silane coupling agents having a phenyl group such as phenyltrimethoxysilane and ferriethoxysilane. 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Silane coupling agents having an epoxy group such as (poxycyclohexyl) ethyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- ( 2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, silane coupling agents having an amino group such as 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrichlorosilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltrime Silane coupling agents having a vinyl group such as xysilane, and silane cups having a (meth) acryloyl group such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. Ring agents, mercapto and sulfur silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-octanoylthio-1-propyltriethoxysilane, Ureidosilane coupling agents such as 3-ureidopropyltriethoxysilane, and isocyanates such as 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane A silane coupling agent etc. are mentioned.
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. When the surface treatment is performed using a hydrophobic surface treatment compound having a molecular weight of 500 or less, the surface treatment state of the inorganic filler can be easily made uniform, and aggregation of the inorganic fillers can be relatively suppressed. The molecular weight of the hydrophobic surface treatment agent is more preferably 100 to 300.

The lower limit of the average particle diameter of the inorganic filler is 0.3 μm, and the upper limit is 1.5 μm. When the average particle size of the inorganic filler is less than 0.3 μm, 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. . In addition, when a hydrophobic surface treatment is applied to an inorganic filler having an average particle size of less than 0.3 μm, 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 μm, 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 μm, the preferable upper limit is 1.4 μm, the more preferable lower limit is 0.6 μm, and the more preferable upper limit is 1.0 μm.
In the present specification, 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.

Although 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. When 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. You may mix | blend other inorganic fillers and / or organic fillers other than a certain inorganic filler.
Examples of 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 | coating may become difficult. The minimum with more preferable content of the said organic filler is 5 weight part, and a more preferable upper limit 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. Examples of 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.
In the present specification, the (meth) acryloyl group means an acryloyloxy group or a methacryloyloxy group, the (meth) acrylate means an acrylate or a methacrylate, and the (meth) acryl is an acrylic. Or methacryl. In the present specification, 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 (meta ) 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 (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meta ) Acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) ) Acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, cyclo Xyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) ) Acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyl Roxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, etc. The

Among the ester compounds, examples of the bifunctional compound include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyl di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate Diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate Rate, polybutadiene di (meth) acrylate.

Among the above ester compounds, 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 glycerin tri (meth) acrylate, tris (meth) acryloyl ethyl phosphate, and the like.

As a complete (meth) acryl-modified epoxy resin obtained by reacting the (meth) acrylic acid with an epoxy compound, for example, 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 that is 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.

As what is marketed among the said bisphenol A type epoxy resins, Epicoat 828EL, Epicoat 1004 (all are the Mitsubishi Chemical company make), Epiklon 850-S (made by DIC company), etc. are mentioned, for example.
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.
As what is marketed among the said 2,2'- diallyl bisphenol A type epoxy resins, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said propylene oxide addition bisphenol A type epoxy resins, EP-4000S (made by ADEKA) etc. are mentioned, for example.
As what is marketed among the said resorcinol type epoxy resins, EX-201 (made by Nagase ChemteX Corporation) etc. are mentioned, for example.
As what is marketed among the said biphenyl type epoxy resins, Epicoat YX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.
As what is marketed among the said sulfide type epoxy resins, YSLV-50TE (made by Nippon Steel Chemical Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said diphenyl ether type epoxy resins, YSLV-80DE (made by Nippon Steel Chemical Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said dicyclopentadiene type epoxy resins, EP-4088S (made by ADEKA) etc. are mentioned, for example.
As what is marketed among the said naphthalene type | mold epoxy resins, Epicron HP4032, Epicron EXA-4700 (all are the products made from DIC) etc. are mentioned, for example.
As what is marketed among the said phenol novolak-type epoxy resins, Epicron N-770 (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said ortho cresol novolak-type epoxy resins, Epicron N-670-EXP-S (made by DIC) etc. are mentioned, for example.
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
As what is marketed among the said biphenyl novolak-type epoxy resins, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said naphthalene phenol novolak-type epoxy resins, ESN-165S (made by Nippon Steel Chemical Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said glycidylamine type epoxy resins, Epicoat 630 (made by Mitsubishi Chemical Corporation), Epicron 430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemical Co., Inc.) etc. are mentioned, for example.
Examples of commercially available alkyl polyol type epoxy resins 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 (all manufactured by Nippon Steel Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Chemical Industries, Ltd.), and the like.
As what is marketed among the said glycidyl ester compounds, Denacol EX-147 (made by Nagase ChemteX Corporation) etc. is mentioned, for example.
As what is marketed among the said bisphenol A type | mold episulfide resin, Epicoat YL-7000 (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.
Other commercially available 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, and Epicoat. 1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.) and the like.

As a complete (meth) acryl-modified epoxy resin obtained by reacting the (meth) acrylic acid with an epoxy compound, specifically, 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.

Among the above-mentioned completely (meth) acryl-modified epoxy resins, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3702, Manufactured), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA , Epoxy ester 200PA, epoxy ester 80 FA, Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA- 314, Denacol acrylate DA-911 (all manufactured by Nagase ChemteX Corporation) and the like.

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 the raw material of the urethane (meth) acrylate is not particularly limited. For example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4 , 4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethanetri Isocyanate, tris (isocyanatephenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triiso Aneto and the like.

Moreover, the isocyanate used as the raw material of the urethane (meth) acrylate is not particularly limited. For example, 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 (meth) acrylic acid derivative having a hydroxyl group, which is a raw material for the urethane (meth) acrylate, is not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Commercial products such as (meth) acrylate and 2-hydroxybutyl (meth) acrylate, and two products such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol Mono (meth) acrylates of divalent alcohols, mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, fully (meth) acrylic modified bisphenol A type epoxy resins, etc. Complete (Meth) acrylic-modified epoxy resin.

Specifically, 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. for 2 hours with stirring under reflux, 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.

Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei Co., Ltd.), Evekril 230, Evekril 270, and Evekril 4858. , Evekril 8402, Evekrill 8804, Evekrill 8803, Evekrill 8807, Evekrill 9260, Evekrill 1290, Evekril 5129, Evekril 4842, Evekril 4827, Evekril 6700, Evekril 220, Evekyle Rine Tech Co., Ltd. UN-9000H, Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-332 HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Kogyo Co., Ltd.), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA- 7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600, AT-600, UA- 306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.) That.

It is preferable that 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. When 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.
In addition, the resin having the (meth) acryloyl group is preferably one having 2 to 3 (meth) acryloyloxy groups in the molecule from the viewpoint of high reactivity and the like.

As the resin having an epoxy group, 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. Examples of such a compound 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, 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).

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 (meth) acryloyl group so that the molar ratio of the (meth) acryloyl group and the 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.
Examples of the polymerization initiator include a photo radical polymerization initiator, a thermal radical polymerization initiator, and a photo cationic polymerization initiator.

When the said curable resin contains the resin which has the said (meth) acryloyl group, it is preferable that 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. For example, 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.

Although content of the said radical photopolymerization initiator is not specifically limited, 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. When 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. When 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).

Although content of the said thermal radical polymerization initiator is not specifically limited, 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.

As the azo compound, a polymer azo initiator may be used. 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. In addition, since the said polymeric azo initiator decomposes | disassembles also by light irradiation normally and generate | occur | produces a radical, it can function also as a photoradical polymerization initiator.

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. Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) and terminal. Examples thereof include polycondensates of polydimethylsiloxane having an amino group, and examples of commercially available products include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.). Yakuhin Kogyo Co., Ltd.).

When the said curable resin contains the resin which has the said epoxy group, it is preferable that 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. Specific examples include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts, and organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. . These photocationic polymerization initiators may be used independently and 2 or more types may be used together.

Examples of commercially available photocationic polymerization initiators include, for example, Adekaoptomer SP-150, Adekaoptomer SP-170 (all manufactured by ADEKA), UVE-1014 (manufactured by General Electronics), CD -1012 (manufactured by Sartomer), RD-2074 (manufactured by Rhodia) and the like.

Although content of the said photocationic polymerization initiator is not specifically limited, 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. When 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.

The said 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 normal temperature 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, and malonic acid dihydrazide. 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. .

Although content of the said 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.
Although the said silane coupling agent is not specifically limited, For example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane etc. are used suitably.

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.

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.

In the sealing agent for liquid crystal dropping method of the present invention, the preferable upper limit of the thixotropic index is 1.5. When the thixotropic index of the sealing agent for liquid crystal dropping method of the present invention exceeds 1.5, applicability and the like may be deteriorated. 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.
In the present specification, 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.

Liquid crystal dropping method of the present invention 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. For example, 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.

As a method for producing the liquid crystal display element of the present invention, for example, 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 the 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.

According to 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.

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

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 μm, M value 0) as inorganic fillers 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).

(Preparation of sealant)
Partial acrylic modified epoxy resin (Daicel Cytec, "EBECRYL 1561") 20 parts by weight, fully acrylic modified bisphenol A type epoxy resin (Daicel Cytec, "EBECRYL 3700") 40 parts by weight, photo radical polymerization initiator (BASF Japan) 1 part by weight, manufactured by “IRGACURE 651”) was dissolved by heating at 80 ° C. and then stirred using a planetary stirrer to obtain a mixture.
Next, 6 parts by weight of the methyl-treated silica obtained as an inorganic filler, 5 parts by weight of adipic acid dihydrazide (manufactured by Nippon Finechem Co., “ADH”) as a thermosetting agent, and 3-glycid as a silane coupling agent After blending 1 part by weight of xylpropyltrimethoxysilane and stirring with a planetary stirrer, the mixture was dispersed with three ceramic rolls to obtain a sealant.

(Example 2)
In “(Surface treatment of inorganic filler)”, Examples were used except that silica particles (manufactured by Nippon Shokubai Co., Ltd., “KEP-50”, average particle size 0.5 μm, M value 0) were used as the inorganic filler. 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)”, Examples were used except that silica particles (manufactured by Nippon Shokubai Co., Ltd., “KEP-100”, average particle diameter 1.0 μm, 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.

(Example 5)
In “(Surface treatment of inorganic filler)”, Examples were used except that silica particles (manufactured by Nippon Shokubai Co., Ltd., “KEP-150”, average particle size 1.5 μm, 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.

(Example 6)
In “(Surface treatment of inorganic filler)”, silica particles (“KEP-100” manufactured by Nippon Shokubai Co., Ltd., average particle size 1.0 μm, M value 0) are used as the inorganic filler, 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 (“KEP-100” manufactured by Nippon Shokubai Co., Ltd., average particle size 1.0 μm, M value 0) are used as the inorganic filler, and methyl triethoxysilane 5 weight 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 instead 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 size 1.0 μm, M value 0) are used as the inorganic filler, and replaced with methyltriethoxysilane. Except that 3-glycidoxypropyltrimethoxysilane was used, the same operation as in Example 1 was performed to obtain an epoxy-treated silica (M value 25).
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 diameter 1.0 μm, M value 0) are 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 μm, M value 0) was used as the inorganic filler, and methyltriethoxysilane 5 An 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.

(Example 13)
Epoxy-treated silica (M value 34) was obtained in the same manner as in Example 7 except that the blending 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.

(Example 14)
Epoxy-treated silica (M value 57) was obtained in the same manner as in Example 7 except that the blending 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)
Example 1 except that “talc particles (manufactured by Nippon Talc Co., Ltd.,“ D-600 ”, average particle size 0.6 μm, M value 0)” was used as the inorganic filler in “(Surface treatment of 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 μm, 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 size 1.0 μm, 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.

(Example 18)
An epoxy-treated talc (M value 20) was obtained by performing the same operation as in Example 11 except that the blending amount 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 sealing agent 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.

(Example 22)
Except having changed the compounding quantity of 3-glycidoxypropyl trimethoxysilane into 10 weight part, operation similar to Example 11 was performed and the epoxy process talc (M value 30) was obtained.
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 23)
Except having changed the compounding quantity of 3-glycidoxypropyl trimethoxysilane into 30 weight part, operation similar to Example 11 was performed and the epoxy process talc (M value 75) was obtained.
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 operation 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.

(Comparative Example 1)
In “(Surface treatment of inorganic filler)”, Examples were used except that silica particles (manufactured by Nippon Shokubai Co., Ltd., “KEP-250”, average particle diameter 2.5 μm, M value 0) were used as the inorganic filler. In the same manner as in Example 1, methyl-treated silica (M value 24) 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.

(Comparative Example 2)
Sealing was carried out in the same manner as in Example 1 except that 5 parts by weight of methyl-treated silica (“X24-9163A”, average particle diameter 0.08 μm, M value 38) manufactured by Shin-Etsu Chemical Co., Ltd. was used as the inorganic filler. An agent was obtained.

(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.

(Comparative 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.

(Comparative 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.

(Comparative 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 μm, 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.

(Comparative Example 7)
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.

(Comparative Example 8)
Epoxy-treated silica (M value 17) was obtained in the same manner as in Example 12 except that the blending 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.

(Comparative Example 9)
In “(Surface treatment of inorganic filler)”, silica particles “Admuffin SO-C1” (manufactured by Admatechs, average particle diameter of 0.25 μm, M value 0) was used as the inorganic filler, and methyltriethoxysilane 5 An epoxy-treated silica (M value 3) was obtained in the same manner as in Example 1 except that 0.2 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 5 parts by weight of the obtained epoxy-treated silica was used as the inorganic filler.

(Comparative Example 10)
In “(Surface Treatment of Inorganic Filler)”, silica particles “Admafine SO-25H” (manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm, M value 0) was used as the inorganic filler, and methyltriethoxysilane 5 An epoxy-treated silica (M value 15) was obtained by performing the same operation 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 7 parts by weight of the obtained epoxy-treated silica was used as the inorganic filler.

(Comparative Example 11)
In “(Surface treatment of inorganic filler)”, silica particles “Admuffin SO-C2” (manufactured by Admatechs, average particle size 0.5 μm, M value 0) was used as the inorganic filler, and methyltriethoxysilane 5 Except having used 0.2 weight part of 3-glycidoxypropyl trimethoxysilane instead of the weight part, operation similar to Example 1 was performed and the epoxy process silica (M value 5) was obtained.
A sealing agent was obtained in the same manner as in Example 1 except that 7 parts by weight of the obtained epoxy-treated silica was used as the inorganic filler.

(Comparative Example 12)
Except having changed the compounding quantity of 3-glycidoxypropyl trimethoxysilane into 1 weight part, operation similar to Example 11 was performed and the epoxy process talc (M value 14) was obtained.
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.

(Comparative Example 13)
A sealing agent was obtained in the same manner as in Example 1 except that 10 parts by weight of untreated “SG-2000” was used as the inorganic filler.

In addition, 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.

<Evaluation>
The following evaluation was performed about the sealing agent obtained by each Example and each comparative example. The results are shown in Tables 1-3.

(1) Viscosity and thixotropic index About the sealing agent 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.

(2) Coating properties 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SI-H050”, 5.0 μm) is dispersed in 100 parts by weight of the sealant obtained in each Example and each Comparative Example, The syringe was filled and defoamed, and applied to one of the two glass substrates with a dispenser so that the line width of the sealing agent after bonding was 1 mm.
The sealant after application is confirmed with an optical microscope. When the application speed is 100 mm / sec and there is no seal breakage or seal thinness, “◎”, at the application speed of 60 mm / sec, there is no seal breakage or seal thinness, and 100 mm / sec. In the case where no seal breakage occurred, “◯” indicates a case where seal thinness was observed in part, and “△” indicates a case where seal thinness was observed in part at an application speed of 60 mm / sec but no seal breakage occurred. The coating property of the sealant was evaluated with “X” when the seal was broken at a coating speed of 60 mm / sec.

(3) Adhesiveness 3 parts by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SP205”, 5.0 μm) 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 mmΦ 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 the alignment film as described above. Similarly, an adhesive test piece was prepared, and the adhesive strength was measured in the same manner.

(4) Wiring damage property It consists of a glass substrate having a pattern in which 100 pieces of aluminum wiring having a width of 50 μm 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. Thereafter, 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. .
After curing the sealant, the continuity of each aluminum wiring was measured and the disconnection rate (ratio of disconnected wiring in 100 wires) was evaluated.

(5) Bright spot unevenness 3 parts by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SP205”, 5.0 μm) 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. Next, 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.
When 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.

(6) 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 “×”.

(6) Color unevenness The liquid crystal display device obtained in the same manner as “(5) Bright spot unevenness” was allowed to stand in an environment of 60 ° C. and 95% RH for 300 hours, 500 hours, and 1000 hours. The color unevenness generated in the liquid crystal around the seal portion is visually observed, and “◎” indicates that there is no color unevenness over the entire surface of the liquid crystal panel even after being left for 1000 hours. However, “◯” indicates a case where slight unevenness is recognized after 1000 hours, and “no” indicates that there is no color unevenness over the entire surface of the liquid crystal panel after standing for 300 hours, but a case where slight unevenness is observed after 500 hours. The case where the color unevenness was recognized after “Δ” and 300 hours was evaluated as “X”, and the color unevenness was evaluated.

According to 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.

Claims (5)

A liquid crystal dropping method sealing agent containing a curable resin, an inorganic filler, a polymerization initiator and / or a thermosetting agent,
The inorganic filler is silica having a hydrophobic surface treatment, an M value of 20 or more, and an average particle diameter of 0.3 to 1.5 μm,
The content of the inorganic filler is 5 parts by weight or more with respect to 100 parts by weight of the curable resin,
The said curable resin contains the partial acrylic modified epoxy resin which has a (meth) acryloyl group and an epoxy group in 1 molecule, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. The sealing agent for liquid crystal dropping method according to claim 1, wherein the polymerization initiator contains a thermal radical polymerization initiator. A liquid crystal dropping method sealing agent containing a curable resin, an inorganic filler, a polymerization initiator and / or a thermosetting agent,
The inorganic filler has a hydrophobic surface treatment, has an M value of 20 or more, and an average particle size of 0.3 to 1.5 μm,
The content of the inorganic filler is 5 parts by weight or more with respect to 100 parts by weight of the curable resin,
The polymerization initiator contains a thermal radical polymerization initiator,
The said curable resin contains the partial acrylic modified epoxy resin which has a (meth) acryloyl group and an epoxy group in 1 molecule, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. A vertical conduction material comprising the sealing agent for liquid crystal dropping method according to claim 1, 2 or 3, and conductive fine particles. A liquid crystal display element comprising the sealing agent for a liquid crystal dropping method according to claim 1, 2 or 3, and / or the vertical conduction material according to claim 4.