CN103460121B - Sealant for one-drop fill process, vertical-conduction material, and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a sealant for a one-drop fill process, whereby uneven luminance does not occur in a panel display portion, and adhesive properties are not compromised when the sealant is applied on a hydrophobicized alignment film during manufacturing of a liquid crystal display element by a dropping process. The purpose of the present invention is also to provide a vertical-conduction material and liquid crystal display element manufactured using the sealant for a one-drop fill process. This sealant for a one-drop fill process contains a curable resin, an inorganic filler, and a polymerization initiator and/or hardener, wherein the inorganic filler is subjected to a hydrophobizing surface treatment, the M value is at least 20, and the average particle diameter is 0.3 to 1.5 [mu]m.

Description

Sealant for liquid crystal dripping process, up and down conductive material and liquid crystal display device

Technical field

The present invention relates to, in the manufacture of liquid crystal display device utilizing technique of dripping, even if cementability also can not be damaged when coating and being endowed in hydrophobic alignment films, sealant for liquid crystal dripping process that Display panel portion can not produce speck.In addition, the present invention relates to the conductive material up and down using this sealant for liquid crystal dripping process to manufacture and liquid crystal display device.

Background technology

In recent years, with regard to the manufacture method of the liquid crystal display device such as liquid crystal display (cell), from shortening pitch time, optimize the consideration such as the viewpoint that uses amount of liquid crystal, by existing vacuum injection mode, to the such as this liquid crystal drop under type transition being called as technique of dripping disclosed in patent documentation 1, wherein dripping in technique, employing the light containing light-cured resin, Photoepolymerizationinitiater initiater, heat-curing resin and thermal curing agents, heat also with the sealing agent of curing.

Dripping in technique, first, on one of 2 transparency carriers with electrode, forming rectangular seal pattern by distributing.Then, under the state that sealing agent is uncured, in the whole frame of transparency carrier, the fine droplet of liquid crystal is dripped, more overlapping with another transparency carrier immediately, carry out Procuring to light such as sealing irradiation ultraviolet radiations.Afterwards, when liquid crystal is annealed, main solidification is carried out in heating, makes liquid crystal display device.As long as under reduced pressure carry out the laminating of substrate, just can with high efficiency system liquid making crystal display element, this technique of dripping has become the main flow of the manufacture method of liquid crystal display device at present.

In addition, in the modern times that the various mobile apparatus with liquid crystal panel such as mobile telephone, portable game is universal, the miniaturization of liquid crystal terminal is the problem wishing most to realize.As the method for the miniaturization of liquid crystal end, adopt the design being reduced basket size by the narrow frame of liquid crystal panel.Such as, the design (narrow frame design) getting off to reduce the border width of liquid crystal panel by the application place of sealing agent being configured at black matrix" has been adopted.

Alignment films is formed with, to carry out tropism control to liquid crystal molecule at the pixel display part of liquid crystal panel.In above-mentioned narrow frame design, the pixel display part and the potted line that are formed with alignment films are very close, thus potted line will be positioned in alignment films.Usually, from the viewpoint of suppression to the stripping of liquid crystal, reduce liquid crystal pollution, sealing agent uses hydrophilic material, on the other hand, imparts hydrophobicity to alignment films.Therefore, when impart hydrophobic alignment films is coated with hydrophilic sealing agent and forms potted line time, applied sealing agent is ostracised in alignment films, and potted line the crooked thus interface of sealing agent and liquid crystal can occur expands sometimes.In addition, because the interface affinity of alignment films and sealing agent is low, therefore, bonding force becomes insufficient sometimes.And if be coated with sealing agent in alignment films, then to produce the special display being called as speck bad in Display panel portion sometimes.At this, speck refers to following phenomenon, and i.e., (when lighting backlight display black) during Display panel, on panel, a large amount of generation backlight is that point-like leaks through and visible bright spot, naked eyes is identified as the spot failing to show black smoothly.

At first technical literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2001-133794 publication

Summary of the invention

Invent problem to be solved

The object of the invention is to, there is provided a kind of in the manufacture of liquid crystal display device utilizing technique of dripping, even if also can not damage cementability in the alignment films coating hydrophobic property, Display panel portion can not produce the sealant for liquid crystal dripping process of speck.In addition, the object of the invention is to, the conductive material up and down and liquid crystal display device that use this sealant for liquid crystal dripping process to manufacture are provided.

For solving the method for problem

The present invention is a kind of sealant for liquid crystal dripping process, containing curable resin, inorganic filler, polymerization starter and/or thermal curing agents, implement hydrophobic surface treatment to described inorganic filler, the M value of described inorganic filler is more than 20, and median size is 0.3 ~ 1.5 μm.Below the present invention is described in detail.

In the sealing agent that liquid crystal display device uses, usually, as disclosed in Patent Document 1, in order to improve viscosity, improve based on stress dispersion effect cementability, suppress moisture-inhibiting and improve hot and humid time reliability thus coordinate inorganic filler.

The present inventor finds that the reason of Display panel portion generation speck is, inorganic filler spreads to liquid crystal from sealing agent.Namely, just formed with regard to the so narrow frame design of potted line in alignment films, because the contact interface of sealing agent and liquid crystal expands, therefore inorganic filler becomes and is easy to spread in liquid crystal, and the inorganic filler spread in liquid crystal has been upset the orientation of liquid crystal around and caused light leak.

Therefore, the present inventor finds: by being in the inorganic filler in specified range in median size, implement hydrophobic surface treatment in the mode making M value reach more than 20 to this inorganic filler, suppress inorganic filler to the diffusion of liquid crystal thus, speck improves.And, find, by the surface treatment making the M value of inorganic filler reach more than 20, the cementability of sealing agent relative to alignment films can be improved, thus complete the present invention.

Sealant for liquid crystal dripping process of the present invention contains inorganic filler.

Above-mentioned inorganic filler is not particularly limited, such as, can list: talcum, asbestos, silicon-dioxide, diatomite, montmorillonite, wilkinite, calcium carbonate, magnesiumcarbonate, aluminum oxide, polynite, zinc oxide, ferric oxide, magnesium oxide, stannic oxide, titanium oxide, magnesium hydroxide, aluminium hydroxide, granulated glass sphere, silicon nitride, barium sulfate, gypsum, Calucium Silicate powder, sericite atlapulgite, aluminium nitride etc.Wherein, preferred silicon-dioxide, talcum.

In above-mentioned silicon-dioxide; as commercially available silicon-dioxide; such as, can list: the X24 series of the Admafine of NIPSIL, Admatechs Inc. of Dong Cao Silica Inc., the SEAHOSTAR of Japanese catalyst Inc., chemical industrial company of SHIN-ETSU HANTOTAI, the spherical silicon dioxide of Denki Kagaku Kogyo kabushiki, the functional spherical silicon dioxide of Shiima electronics corporation, the micro mist spherical silicon dioxide of chemical industrial company of Japan, the functional spherical silicon dioxide etc. of East Asia Synesis Company.

In above-mentioned talcum, as commercially available talcum, such as, SG2000, NANO ACE series etc. of Japanese talcum Inc. can be listed.

In sealant for liquid crystal dripping process of the present invention, implement hydrophobic surface treatment to above-mentioned inorganic filler, M value is more than 20.If the M value of above-mentioned inorganic filler is less than 20, then the Display panel portion of the liquid crystal display device of gained easily produces speck, or, be difficult to when the coated face of sealing agent exists alignment films obtain sufficient cementability relative to alignment films.The preferred lower limit of the M value of above-mentioned inorganic filler is 22, and preferred lower limit is 23.

The upper limit of the M value of above-mentioned inorganic filler is not particularly limited, and is 99.9 in theory, and the preferred upper limit is 70, is preferredly limited to 50, and the preferred upper limit is 35 further.If the M value of above-mentioned inorganic filler is more than 50, then coordinate the viscosity of the sealing agent of inorganic filler, thixotropy index uprised, sometimes coating becomes difficulty, if the M value of above-mentioned inorganic filler is more than 70, then the aggegation of inorganic filler occurs during surface treatment sometimes.

It should be noted that, above-mentioned M value is the hydrophobic value of performance particle powder surface, when the blending ratio of the mixed solution making water and methyl alcohol changes (when increasing methanol ratio), above-mentioned M value is the value of the percentage by volume of methyl alcohol when particle powder starts mixed liquid wetting.Specifically, can obtain as follows: the water putting into 50mL in the beaker of capacity 300mL, add inorganic filler 0.2g again, under the condition of 23 DEG C, methyl alcohol is dripped until inorganic filler is suspended from drop-burette while use magnetic stirring apparatus carries out stirring, inorganic filler is suspended in time point in solution as terminal, thus the value of the percentage by volume of the methyl alcohol of liquid mixture when can obtain terminal in beaker.Because measured value is according to the amount of inorganic filler, temperature and changing, therefore in the present invention the value under said determination condition is used as above-mentioned M value and applies.

To above-mentioned inorganic filler enforcement surface treatment chemically or physically, this inorganic filler has hydrophobic group on surface thus.

More than 20 are reached in order to make the M value of above-mentioned inorganic filler, as the functional group processed by the above-mentioned surface of hydrophobic surface treatment to inorganic filler, such as, can list: the alkyl of the carbonatomss 1 ~ 20 such as methyl, ethyl, propyl group, butyl, hexyl, cyclohexyl, octyl group, 2-ethylhexyl, dodecyl, octadecyl; The epoxy group(ing) such as glycidyl, 3,4-epoxycyclohexyls; Primary amino, secondary amino group or uncle are amino; Functional group containing alkoxyl group, vinyl, acryl, methacryloyl, thioether group, sulfydryl, isocyanate group, urea groups, pyridyl, styryl, ehter bond, ester bond, thiol group etc.

Be the method for more than 20 as making the M value of above-mentioned inorganic filler, specifically, such as can list following method: by making inorganic filler, powder body brought into physical contact with organic compound or hydrophobic inorganics, thus organifying compound or hydrophobic inorganics physical adsorption are in the method on the surface of inorganic filler; At inorganic filler near surface initiated polymerization, thus form the tectal method of polymer body accumulation on inorganic filler surface; The method etc. of the surface chemistry bonding of organifying compound and inorganic filler.Wherein, the method for the surface chemistry bonding of preferred organifying compound and inorganic filler.

As the method for the surface chemistry bonding of organifying compound and inorganic filler, such as, can list: carry out initiated polymerization using the surface of inorganic filler as basic point, form the tectal method of polymer; Use and there is the compound of functional group, and the functional groups such as the hydroxyl existed with the surface of inorganic filler carry out the method etc. of chemical bonding.Wherein, preferably use the compound with functional group, and the method for functional group's chemical bondings such as the hydroxyl existed with the surface of inorganic filler.

The compound with functional group carrying out reacting as functional groups such as the hydroxyls that the surface with above-mentioned inorganic filler exists is (following, also referred to as hydrophobic surface treatments agent), such as, can list: silicon nitrogen silane compound, silicone compounds, various silane coupling agent, various titanium coupling agent, various aluminium systems coupling agent, acid anhydrides, higher fatty acid, isocyanate compound, chloride compounds, phosphoric acid ester based compound, aldehyde cpd etc.Wherein, silane coupling agent, the silicon nitrogen silane compound such as preferred alkoxysilane compound containing trialkylsilyl group in molecular structure, chlorosilane cpd.

As the process utilizing above-mentioned silane coupling agent, above-mentioned silicon nitrogen silane compound, be preferably as follows method: in the solvent being dispersed with untreated inorganic filler, make a certain amount of silane coupling agent, silicon nitrogen silane compound is dissolved in water or the organic solvent such as the alcohols such as methyl alcohol, ethanol or acetone, vinyl acetic monomer, toluene, on the surface of inorganic filler, silane coupling agent, silicon nitrogen silane compound are reacted, then except the method for desolventizing; Make inorganic filler be scattered in silane coupling agent, silicon nitrogen silane compound reacting, then cleaning removing more than silane coupling agent, silicon nitrogen silane compound method.These methods can be carried out under the existence of the catalyzer such as amine, ammonia, acetic acid, hydrochloric acid.

In addition, as the process utilizing above-mentioned silane coupling agent, above-mentioned silicon nitrogen silane compound, while preferably untreated inorganic filler being uniformly mixed in stirrer, spraying silane coupling agent, silicon nitrogen silane compound, keep certain hour in this state, the method (hereinafter also referred to as " drying process ") of unreacted treatment agent is removed by nitrogen purge.In the method, silane coupling agent, silicon nitrogen silane compound can re-use with after solvent cut, also can directly use.The method can be carried out under the existence of the catalyzer such as amine, ammonia, acetic acid, hydrochloric acid.

In the process utilizing above-mentioned silane coupling agent, above-mentioned silicon nitrogen silane compound, can wait in the following way to suppress the M value of inorganic filler: regulate and make silane coupling agent, the weaker concn of silicon nitrogen silane compound when being diluted in solvent or regulate the addition of silane coupling agent, silicon nitrogen silane compound; Regulate make silane coupling agent, silicon nitrogen silane compound and inorganic filler surface reaction time temperature, pH.In addition, make silane coupling agent, the weaker concn of silicon nitrogen silane compound when being diluted in solvent be not particularly limited, be generally 0.01 ~ 50 % by weight, preferred lower limit is 0.1 % by weight, the preferred upper limit is 35 % by weight, preferred lower limit is 3 % by weight, and the preferred upper limit is 15 % by weight.

In addition, above-mentioned M value also can be regulated by the amount of functional groups on the surface of the inorganic filler of (untreated) before surface treatment.In this case, if identical treatment condition, then the functional group on the surface of untreated inorganic filler is more, can obtain the inorganic filler compared with high m values.

As above-mentioned silane coupling agent, such as, can list: methyltrimethoxy silane, dimethyldimethoxysil,ne, Union carbide A-162, dimethyldiethoxysilane, hexyl Trimethoxy silane, hexyl triethoxyl silane, octyl group Trimethoxy silane, octyltri-ethoxysilane, decyl Trimethoxy silane, METHYL TRICHLORO SILANE, butyl trichlorosilane, trifluoro propyl Trimethoxy silane etc. have the silane coupling agent of alkyl; Phenyltrimethoxysila,e, phenyl triethoxysilane etc. have the silane coupling agent of phenyl; 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxyl silane, 3-glycidoxypropyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc. have the silane coupling agent of epoxy group(ing); N-phenyl-3-TSL 8330, N-(2-amino-ethyl) 3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-TSL 8330,3-TSL 8330, APTES etc. have amino silane coupling agent; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyl methyl dimethoxysilane, vinyl methyl diethoxy silane, vinyl trichloro silane, allyltrichlorosilane, allyltrimethoxysilanis, allyltriethoxysilane, styryl Trimethoxy silane etc. is had to the silane coupling agent of vinyl; 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl, 3-acryloxypropyl Trimethoxy silane etc. have the silane coupling agent of (methyl) acryl; Sulfydryl and the polysulfur silane coupling agent such as 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, two (triethoxysilylpropyltetrasulfide) four thioether group, 3-Octanoylthio-1-propyl-triethoxysilicane; The ureido silane coupling agents such as 3-ureidopropyltriethoxysilane; The isocyanato silanes coupling agents etc. such as 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane.

As above-mentioned silicon nitrogen silane compound, such as, hexamethyldisilazane, dimethyl disilazane etc. can be listed.

These silane coupling agents, silicon nitrogen silane compound may be used alone, can also be 2 or more kinds in combination.

As above-mentioned hydrophobic surface treatments agent, preferred molecular weight is the surface treatment agent of less than 500.If the compound that use molecular weight is the hydrophobic surface treatments agent of less than 500 carries out surface treatment, then easily make the treated state on the surface of inorganic filler even, in addition, the aggegation between inorganic filler can be suppressed to a certain extent.The molecular weight of above-mentioned hydrophobic surface treatments agent is more preferably 100 ~ 300.

The lower limit of the median size of above-mentioned inorganic filler is 0.3 μm, and the upper limit is 1.5 μm.If the median size of above-mentioned inorganic filler is less than 0.3 μm, then the viscosity of the sealing agent of gained, thixotropy index uprise, coating becomes difficulty, therefore, or use level is restricted, and with the cementability being endowed hydrophobic alignment films on cannot play sufficient effect, or be difficult to fully obtain stress dispersion effect, the raising of water vapour permeability, the improvement effect of linear expansivity, thus fully cannot obtain the reliability of panel.In addition, under inorganic filler median size being less than to 0.3 μm implements hydrophobic surface-treated situation, will easily cause the diffusion of inorganic filler, therefore fully cannot suppress the speck produced because inorganic filler spreads in liquid crystal.If the median size of above-mentioned inorganic filler is more than 1.5 μm, then when the metal wirings such as aluminum wiring are present in the coated face of sealing agent, inorganic filler brings damage to distribution and breaks, and bad connection occurs.The preferred lower limit of the median size of above-mentioned inorganic filler is 0.4 μm, and the preferred upper limit is 1.4 μm, and preferred lower limit is 0.6 μm, and the preferred upper limit is 1.0 μm.

It should be noted that, in this manual, the median size of above-mentioned inorganic filler refers to, is in the D50 value of the size-grade distribution of the particle of dispersion state in sealant for liquid crystal dripping process of the present invention, and above-mentioned median size can use particles distribution instrument described later to measure.

The CV value of the particle diameter of above-mentioned inorganic filler is not particularly limited, and the preferred upper limit is 40%.If the CV value of the particle diameter of above-mentioned inorganic filler is more than 40%, then the liquid crystal display device generation gap of gained is bad sometimes.

It should be noted that, the median size of above-mentioned inorganic filler and CV value, can, by make inorganic filler be present in solvent that inorganic filler easily disperses, particles distribution instrument (such as, Particle Sizing Systems Inc.) be used to measure.

The content of above-mentioned inorganic filler is relative to curable resin 100 weight part, and preferred lower limit is 5 weight parts, and the preferred upper limit is 40 weight parts.If the amount of above-mentioned inorganic filler is less than 5 weight parts, then sometimes cannot obtain the regulating effect of sufficient stress dispersion effect, linear expansivity.If more than 40 weight parts, then the viscosity of the sealing agent of gained, thixotropy index uprise, and sometimes distribute and become difficulty.The preferred lower limit of the use level of above-mentioned inorganic filler is 10 weight parts, and the preferred upper limit is 30 weight parts.

Sealant for liquid crystal dripping process of the present invention, in the scope not hindering effect of the present invention, in order to the object of carrying out finely tuning etc. to viscosity, can coordinate implement above-mentioned hydrophobic surface treatment and the M value that obtains be more than 20 inorganic filler beyond other inorganic fillers and/or organic filler.

As above-mentioned organic filler, such as, polyester micropartical, polyurethane particulate, vinyl polymer particulate, (methyl) acrylic polymers particulate etc., core-shell particles etc. can be enumerated.

The content of above-mentioned organic filler is relative to curable resin 100 weight part, and preferred lower limit is 5 weight parts, the preferred upper limit is 30 weight parts.If the content of above-mentioned organic filler is less than 5 weight parts, then sometimes cannot obtain sufficient stress dispersion effect.If the content of above-mentioned organic filler is more than 30 weight parts, then the viscosity of the sealing agent of gained uprises, and coating sometimes becomes difficulty.The preferred upper limit of the content of above-mentioned organic filler is 20 weight parts.

Sealant for liquid crystal dripping process of the present invention contains curable resin.

Above-mentioned curable resin is preferably containing having the resin of unsaturated double-bond and having the resin of epoxy group(ing).As the resin with unsaturated double-bond, the resin with (methyl) acryl, the resin etc. that there is allylic resin, there is vinyl can be listed.Wherein, the resin with (methyl) acryl is preferably used.

The above-mentioned resin with (methyl) acryl is not particularly limited; such as, can list: reacted by compound and (methyl) vinylformic acid making to have hydroxyl and the ester cpds obtained, complete (methyl) acrylic modified epoxy resin making (methyl) vinylformic acid and epoxy compounds react and obtain, carbamate (methyl) acrylate etc. that obtains by making to have (methyl) acrylic acid derivative of hydroxyl and isocyanate reaction.

It should be noted that; in this manual; above-mentioned (methyl) acryl represents acryloxy or methacryloxy; above-mentioned (methyl) acrylate represents acrylate or methacrylic ester, and above-mentioned (methyl) vinylformic acid represents acrylic or methacrylic acid.In addition, in this manual, above-mentioned (methyl) acrylic modified epoxy resin completely represents the compound that the whole epoxy group(ing) in epoxy resin and (methyl) vinylformic acid are reacted.

The ester cpds being reacted by the compound and above-mentioned (methyl) vinylformic acid that make to have hydroxyl and obtained is not particularly limited, and as the ester cpds of simple function, such as, can list: (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl ester, (methyl) stearyl acrylate ester, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 2-methoxy acrylate, methoxyl group ethylene glycol (methyl) acrylate, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) benzyl acrylate, ethyl carbitol (methyl) acrylate, (methyl) acrylate, phenoxy group glycol ether (methyl) acrylate, phenoxy group polyoxyethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, (methyl) vinylformic acid 2,2,2-trifluoro ethyl ester, (methyl) vinylformic acid 2,2,3,3-tetrafluoro propyl ester, (methyl) vinylformic acid 1H, 1H, 5H-octafluoro pentyl ester, imide (methyl) acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, the different tetradecane ester of (methyl) vinylformic acid, (methyl) vinylformic acid 2-butoxyethyl, (methyl) vinylformic acid 2-phenoxy ethyl, (methyl) vinylformic acid dicyclopentenyloxyethyl methacrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) dimethylaminoethyl acrylate ester, 2 (methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acrylyl oxy-ethyl 2-hydroxypropylphthalate, glycidyl (methyl) acrylate, 2-(methyl) acrylyl oxy-ethyl phosphoric acid ester etc.

In addition, in above-mentioned ester cpds, as the ester cpds of 2 officials' energy, such as, can list: BDO two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, decamethylene-glycol two (methyl) acrylate, 2-normal-butyl-2-ethyl-1,3-PD two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene oxide addition dihydroxyphenyl propane two (methyl) acrylate, ethyleneoxide addition dihydroxyphenyl propane two (methyl) acrylate, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid two (methyl) acrylate, 2-hydroxyl-3-(methyl) acryloxypropyl (methyl) acrylate, carbonate diol two (methyl) acrylate, polyether glycol two (methyl) acrylate, polyester glycol two (methyl) acrylate, PC glycol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate etc.

In addition, in above-mentioned ester cpds, can above ester cpds as 3 officials, such as, can list: tetramethylolmethane three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, propylene oxide addition trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, own lactones modification trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, glycerol three (methyl) acrylate, propylene oxide addition glycerol three (methyl) acrylate, three (methyl) acryloyl ethyl phosphoric acid ester etc.

By complete (methyl) acrylic modified epoxy resin making above-mentioned (methyl) vinylformic acid and epoxy compounds react and obtain, such as, send as an envoy to epoxy resin and (methyl) vinylformic acid can be enumerated to react under the existence of basic catalyst according to usual method and the material etc. that obtains.

As the raw material epoxy resin for the synthesis of above-mentioned (methyl) acrylic modified epoxy resin completely, such as, can list: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2, 2 '-diallyl bisphenol type epoxy resin, A Hydrogenated Bisphenol A type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, Resorcinol type epoxy resin, biphenyl type epoxy resin, thioether-type epoxy resin, phenylbenzene ether type epoxy, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy, ortho-cresol phenol aldehyde type epoxy resin, dicyclopentadiene phenolic type epoxy resin, biphenyl phenol aldehyde type epoxy resin, naphthol novolac type epoxy resin, glycidyl amine type epoxy resin, alkyl polyols type epoxy resin, modified rubber type epoxy resin, glycidyl ester cpds, bisphenol A-type episulfide resin etc.

As commercially available above-mentioned bisphenol A type epoxy resin, such as, Epikote828EL, Epikote1004 (being Mitsubishi Chemical Ind's system), Epiclon850-S (DIC Inc.) etc. can be listed.

As commercially available above-mentioned bisphenol f type epoxy resin, such as, Epikote806, Epikote4004 (being Mitsubishi Chemical Ind's system) etc. can be listed.

As commercially available above-mentioned bisphenol-s epoxy resin, such as, EpiclonEXA1514 (DIC Inc.) etc. can be listed.

As commercially available above-mentioned 2,2 '-diallyl bisphenol type epoxy resin, such as, can list RE-810NM (Japanese chemical drug Inc.) etc.

As commercially available above-mentioned A Hydrogenated Bisphenol A type epoxy resin, such as, EpiclonEXA7015 (DIC Inc.) etc. can be listed.

As commercially available above-mentioned propylene oxide addition bisphenol A type epoxy resin, such as, EP-4000S (ADEKA Inc.) etc. can be listed.

As commercially available above-mentioned Resorcinol type epoxy resin, such as, EX-201 (Nagase Chemtex Inc.) etc. can be listed.

As commercially available above-mentioned biphenyl type epoxy resin, such as, EPIKOTE YX-4000H (Mitsubishi Chemical Ind's system) etc. can be listed.

As commercially available above-mentioned thioether-type epoxy resin, such as, YSLV-50TE (chemical company of Nippon Steel system) etc. can be listed.

As commercially available above-mentioned phenylbenzene ether type epoxy, such as, YSLV-80DE (chemical company of Nippon Steel system) etc. can be listed.

As commercially available above-mentioned dicyclopentadiene-type epoxy resin, such as, EP-4088S (ADEKA Inc.) etc. can be listed.

As commercially available above-mentioned naphthalene type epoxy resin, such as, EPICLON HP4032, EPICLON EXA-4700 (being DIC Inc.) etc. can be listed.

As commercially available above-mentioned phenol novolak type epoxy, such as, EPICLON N-770 (DIC Inc.) etc. can be listed.

As commercially available above-mentioned ortho-cresol phenol aldehyde type epoxy resin, such as, EPICLONN-670-EXP-S (DIC Inc.) etc. can be listed.

As commercially available above-mentioned dicyclopentadiene phenolic type epoxy resin, such as, EPICLON HP7200 (DIC Inc.) etc. can be listed.

As commercially available above-mentioned biphenyl phenol aldehyde type epoxy resin, such as, NC-3000P (Japanese chemical drug Inc.) etc. can be listed.

As commercially available above-mentioned naphthol novolac type epoxy resin, such as, ESN-165S (chemical company of Nippon Steel system) etc. can be listed.

As commercially available above-mentioned glycidyl amine type epoxy resin, such as, EPIKOTE630 (Mitsubishi Chemical Ind's system), EPICLON430 (DIC Inc.), TETRAD-X (Mitsubishi Gas Chemical Inc.) etc. can be listed.

As commercially available abovementioned alkyl polyol type epoxy resin, such as, ZX-1542 (chemical company of Nippon Steel system), EPICLON726 (DIC Inc.), EPOLIGHT80MFA (chemical company of common prosperity society system), DENACOL EX-611 (Nagase Chemtex Inc.) etc. can be listed.

As commercially available above-mentioned modified rubber type epoxy resin, such as, YR-450, YR-207 (being chemical company of Nippon Steel system), EPOLEAD PB (Daicel Inc.) etc. can be listed.

As commercially available above-mentioned glycidyl ester cpds, such as, DENACOLEX-147 (Nagase Chemtex Inc.) etc. can be listed.

As commercially available above-mentioned bisphenol A-type episulfide resin, such as, EPIKOTEYL-7000 (Mitsubishi Chemical Ind's system) etc. can be listed.

As other the commercially available products in above-mentioned epoxy resin, such as, can list: YDC-1312, YSLV-80XY, YSLV-90CR (being chemical company of Nippon Steel system), XAC4151 (Asahi Kasei Corporation's system), EPIKOTE1031, EPIKOTE1032 (being Mitsubishi Chemical Ind's system), EXA-7120 (DIC Inc.), TEPIC (Nissan Chemical Inc.) etc.

As complete (methyl) acrylic modified epoxy resin by making above-mentioned (methyl) vinylformic acid and epoxy compounds react and obtain, specifically, such as, can by making Resorcinol type epoxy resin (Nagase Chemtex Inc. while feeding air, " EX-201 ") 360 weight parts, as p methoxy phenol 2 weight part of stopper, as triethylamine 2 weight part of catalysts, and vinylformic acid 210 weight part carries out return stirring at 90 DEG C, make their reactions 5 hours and obtain complete acrylic acid modified Resorcinol type epoxy resin.

As commercially available above-mentioned (methyl) acrylic modified epoxy resin completely, such as, can list: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 (being Daicel cytec Inc.), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (being chemical industrial company of Xin Zhong village system), EpoxyesterM-600A, Epoxyester40EM, Epoxyester70PA, Epoxyester200PA, Epoxyester80MFA, Epoxyester3002M, Epoxyester3002A, Epoxyester1600A, Epoxyester3000M, Epoxyester3000A, Epoxyester200EA, Epoxyester400EA (being chemical company of common prosperity society system), DENACOL ACRYLATEDA-141, DENACOL ACRYLATEDA-314, DENACOL ACRYLATEDA-911 (being Nagase Chemtex Inc.) etc.

Make to have (methyl) acrylic acid derivative of hydroxyl and above-mentioned isocyanate reaction and carbamate (methyl) acrylate obtained, such as, can, by relative to compound 1 equivalent with 2 isocyanate group, (methyl) acrylic acid derivative 2 equivalent with hydroxyl be made to react under the tin based compound of catalytic amount exists and obtain.

The isocyanic ester becoming the raw material of above-mentioned carbamate (methyl) acrylate is not particularly limited, such as, can list: isophorone diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, ditan-4, 4 '-vulcabond (MDI), hydrogenation MDI, aggretion type MDI, 1, 5-naphthalene diisocyanate, norbornene alkyl diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenation XDI, lysinediisocyanate, triphenylmethane triisocyanate, tri o cresyl thiophosphate (4-phenyl isocyanate), tetramethyl-xylylene diisocyanate, 1, 6, 10-undecane triisocyanate etc.

In addition, the isocyanic ester becoming the raw material of above-mentioned carbamate (methyl) acrylate is not particularly limited, such as, also can use by the polyvalent alcohols such as ethylene glycol, glycerol, Sorbitol Powder, TriMethylolPropane(TMP), (gathering) propylene glycol, carbonate diol, polyether glycol, polyester glycol, PC glycol and the reaction of excessive isocyanic ester and the isocyanate compound after the chain extension obtained.

That become the raw material of above-mentioned carbamate (methyl) acrylate, that have hydroxyl (methyl) acrylic acid derivative is not particularly limited, such as, can list: the commercially available products such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid 2-hydroxy ester; List (methyl) acrylate of the dibasic alcohol such as ethylene glycol, propylene glycol, 1,3-PD, 1,3 butylene glycol, BDO, polyoxyethylene glycol; List (methyl) acrylate of the trivalent alcohols such as trimethylolethane, TriMethylolPropane(TMP), glycerine or two (methyl) acrylate; Complete (methyl) acrylated epoxy such as (methyl) Acryrylic acid modified bisphenol A epoxy resin etc. completely.

Above-mentioned carbamate (methyl) acrylate can obtain in the following way, specifically, such as, add TriMethylolPropane(TMP) 134 weight part, the BHT0.2 weight part as stopper, dibutyl tin dilaurate 0.01 weight part as catalysts and isophorone diisocyanate 666 weight part, their reactions 2 hours are made while return stirring at 60 DEG C, then, add 2-hydroxy ethyl methacrylate 51 weight part, while feeding air, return stirring at 90 DEG C, makes their reactions 2 hours.

As commercially available above-mentioned carbamate (methyl) acrylate, such as, can list: M-1100, M-1200, M-1210, M-1600 (being East Asia Synesis Company system), Ebecryl230, Ebecryl270, Ebecryl4858, Ebecryl8402, Ebecryl8804, Ebecryl8803, Ebecryl8807, Ebecryl9260, Ebecryl1290, Ebecryl5129, Ebecryl4842, Ebecryl210, Ebecryl4827, Ebecryl6700, Ebecryl220, Ebecryl2220 (being Daicel cytec Inc.), ARTRESIN UN-9000H, ARTRESIN UN-9000A, ARTRESIN UN-7100, ARTRESIN UN-1255, ARTRESIN UN-330, ARTRESIN UN-3320HB, ARTRESIN UN-1200TPK, ARTRESIN SH-500B (being Gen Shang industrial system), 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 (being chemical industrial company of Xin Zhong village system), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (being chemical company of common prosperity society system) etc.

Above-mentioned have more than 50 % by weight of the resin of (methyl) acryl, is preferably the compound at least in 1 molecule with 1 OH base.Above-mentioned to have more than 50 % by weight of the resin of (methyl) acryl be the compound at least in 1 molecule with 1 OH base, and sealing agent can be suppressed thus to the stripping of liquid crystal.

As the compound at least in above-mentioned 1 molecule with 1 OH base, consider from viewpoints such as the easnesses synthesized, particularly preferably complete (methyl) acrylic modified epoxy resin.

In addition, consider from the high viewpoint of reactivity, the above-mentioned resin with (methyl) acryl is preferably in molecule the material with 2 ~ 3 (methyl) acryloxies.

As the above-mentioned resin with epoxy group(ing), can use and become for the synthesis of the identical material of the epoxy resin of the above-mentioned raw material of (methyl) acrylic modified epoxy resin completely.

In addition, the above-mentioned resin with epoxy group(ing) such as, also can be the compound in 1 molecule with (methyl) acryl and epoxy group(ing).As such compound, such as, the part acrylic acid modified epoxy etc. obtained by making a part of epoxy group(ing) of the compound with more than 2 epoxy group(ing) and (methyl) vinylformic acid react can be listed.

It should be noted that, above-mentioned curable resin can only containing the resin in above-mentioned 1 molecule with (methyl) acryl and epoxy group(ing).

Above-mentioned part acrylic acid modified epoxy, such as, can obtain by making epoxy resin and (methyl) vinylformic acid carry out reacting under the existence of basic catalyst according to usual method.Specifically, such as, can obtain in the following way: make phenol novolak type epoxy N-770 (DIC Inc.) 190g be dissolved in toluene 500mL, triphenylphosphine 0.1g is added in this solution, make uniform solution, in this solution, vinylformic acid 35g was dripped through 2 hours under return stirring, and then carry out 6 hours reflux stirrings, then, removing toluene, the part acrylic acid modified phenol phenol aldehyde type epoxy resin (in this case, 50% part propylene acidifying) that the epoxy group(ing) of 50 % by mole and vinylformic acid react and obtains can be obtained thus.

As commercially available above-mentioned part acrylic acid modified epoxy, such as, UVACURE1561 (Daicel cytec Inc.) can be listed.

Sealant for liquid crystal dripping process of the present invention, preferably to coordinate in the mode that molar ratio computing reaches 50:50 ~ 95:5 with the ratio of (methyl) acryl of curable resin and epoxy group(ing) and above-mentionedly has the resin of (methyl) acryl and the above-mentioned resin with epoxy group(ing).

Sealant for liquid crystal dripping process of the present invention contains polymerization starter and/or thermal curing agents.

As above-mentioned polymerization starter, such as, optical free radical polymerization starter, hot radical polymerization starter, light cationic polymerization initiators etc. can be listed.

When above-mentioned curable resin contain above-mentioned there is the resin of (methyl) acryl, sealant for liquid crystal dripping process of the present invention is preferably containing optical free radical polymerization starter or hot radical polymerization starter.

Above-mentioned optical free radical polymerization starter is not particularly limited; such as, can be suitable for using benzophenone based compound, methyl phenyl ketone based compound, acylphosphine oxide based compound, two luxuriant titanium sub-group compounds, oxime ester based compound, benzoin ether based compound, thioxanthone etc.

In addition, as commercially available above-mentioned optical free radical polymerization starter, such as, can list: IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACUREOXE01, LUCIRIN TPO (being BASF Japan Inc.), benzoin methylether, ethoxybenzoin, benzoin iso-propylether (more than, be Tokyo and change into industrial's system) etc.Wherein, wide from the viewpoint of absorbing wavelength region, be suitably IRGACURE651, IRGACURE907, benzoin iso-propylether and LUCIRIN TPO.These optical free radical polymerization starters can be used alone also that two or more kinds may be used.

The content of above-mentioned optical free radical polymerization starter is not particularly limited, and relative to above-mentioned resin 100 weight part with (methyl) acryl, preferred lower limit is 0.1 weight part, and the preferred upper limit is 10 weight parts.If the content of above-mentioned optical free radical polymerization starter is less than 0.1 weight part, then the light of the sealant for liquid crystal dripping process of gained overlaps and cannot carry out fully.If the content of above-mentioned optical free radical polymerization starter is more than 10 weight parts, then unreacted optical free radical polymerization starter remains in a large number, and the weathering resistance of the sealant for liquid crystal dripping process of gained can be deteriorated sometimes.The preferred lower limit of the content of above-mentioned optical free radical polymerization starter is 1 weight part, and the preferred upper limit is 5 weight parts.

Above-mentioned hot radical polymerization starter is not particularly limited, and such as, can list superoxide, azo-compound etc.

As commercially available above-mentioned hot radical polymerization starter, such as, can list: V-30, V-501, V-601, VPE-0201 (being pure pharmaceutical worker's industry Inc. with light), Perbutyl O, Perhexyl O, Perbutyl PV (being You company to manufacture) etc.

The content of above-mentioned hot radical polymerization starter is not particularly limited, and relative to above-mentioned resin 100 weight part with (methyl) acryl, preferred lower limit is 0.01 weight part, and the preferred upper limit is 10 weight parts.If the content of above-mentioned hot radical polymerization starter is less than 0.01 weight part, then sometimes overlaps and fully do not carry out or react becoming slow.If the content of above-mentioned hot radical polymerization starter is more than 10 weight parts, then package stability reduces sometimes.The preferred lower limit of the content of above-mentioned hot radical polymerization starter is 0.5 weight part, and the preferred upper limit is 5 weight parts.

As above-mentioned azo-compound, polymeric azo initiator can be used.Polymeric azo initiator refers to, having azo-group and generating the molecular weight of free radical that (methyl) acrylic can be made to solidify by heat is the compound of more than 300.It should be noted that, above-mentioned polymeric azo initiator usually also can be decomposed by rayed, produce free radical, therefore also can play a role as optical free radical polymerization starter.

The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiator is 1000, and the preferred upper limit is 300,000.If the number-average molecular weight of above-mentioned polymeric azo initiator is less than 1000, then polymeric azo initiator can carry out detrimentally affect in feeding crystal zone sometimes, if more than 300,000, then sometimes become difficulty to the mixing in the resin with (methyl) acrylic.The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiator is 5000, and the preferred upper limit is 100,000, and preferred lower limit is 10,000 further, and the preferred upper limit is 90,000 further.As such polymeric azo initiator, such as, can 4 be listed, the polycondensate, 4 of 4 '-azo two (4-cyanopentanoic acid) and polyalkylene glycol, 4 '-azo two (4-cyanopentanoic acid) and the polycondensate etc. of polydimethylsiloxane with terminal amino group, as commercially available product, such as, can list: VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (being pure pharmaceutical worker's industry Inc. with light) etc.

When above-mentioned curable resin contain above-mentioned there is the resin of epoxy group(ing), sealant for liquid crystal dripping process of the present invention is preferably containing light cationic polymerization initiators or thermal curing agents.

As long as above-mentioned smooth cationic polymerization initiators is produced protonic acid by rayed or lewis acidic material is not particularly limited, can be ionic photic sour generation type, also can be the photic sour generation type of nonionic.Specifically, such as, can list: the organometallic complex classes etc. such as the salts such as aromatic diazonium salt, aromatic halonium salts, aromatic series sulfonium salt, iron-allene complex thing, two titanocene complexes, aryl-silane alcohol-aluminium complex.These light cationic polymerization initiators can be used alone, and also two or more kinds may be used.

As commercially available above-mentioned smooth cationic polymerization initiators, such as, can list: Adekaoptomer SP-150, Adeka optomer SP-170 (being ADEKA Inc.), UVE-1014 (General Electric Corporation's system), CD-1012 (Sartomer Inc.), RD-2074 (Rhodia Inc.) etc.

The content of above-mentioned smooth cationic polymerization initiators is not particularly limited, and relative to above-mentioned resin 100 weight part with epoxy group(ing), preferred lower limit is 0.1 weight part, and the preferred upper limit is 10 weight parts.If the content of above-mentioned smooth cationic polymerization initiators is less than 0.1 weight part, then have the cationoid polymerisation of time positively charged ion repeatability compound fully to carry out, or the curing reaction of the sealing agent of gained became slow.If the content of above-mentioned smooth cationic polymerization initiators is more than 10 weight parts, then the curing reaction of the sealing agent of gained becomes too fast, and operability reduces sometimes, or the sealing agent of gained becomes uneven cured article.The preferred lower limit of the content of above-mentioned smooth cationic polymerization initiators is 0.5 weight part.

Above-mentioned thermal curing agents is not particularly limited, and such as, can list: organic acid hydrazides, imdazole derivatives, amine compound, polyvalent alcohol based compound, acid anhydrides etc.Wherein, be solid-state organic acid hydrazides under being suitable for using normal temperature.

Above-mentioned solid-state organic acid hydrazides is not particularly limited, such as, can 1 be listed, 3-bis-(3-hydrazine-3-oxo-propyll)-5-(1-methylethyl) glycolylurea, sebacic dihydrazide, different O-phthalic acid dihydrazide, adipic dihydrazide, acid dihydrazide etc., as commercially available product, such as, AMICURE VDH, AMICURE UDH (being aginomoto FINE-TECHNO Inc.), SDH, IDH (being great mound chemical company system), ADH (Japanese Finechem Inc.) etc. can be listed.

The content of above-mentioned thermal curing agents is not particularly limited, and relative to above-mentioned resin 100 weight part with epoxy group(ing), preferred lower limit is 0.1 weight part, and the preferred upper limit is 50 weight parts.If the content of above-mentioned thermal curing agents is less than 0.1 weight part, then thermofixation sometimes cannot be carried out fully, or reaction became slow.If the content of above-mentioned thermal curing agents is more than 50 weight parts, then the viscosity of the sealing agent of gained uprises sometimes, and coating becomes difficulty.The preferred lower limit of the content of above-mentioned thermal curing agents is 1 weight part, and the preferred upper limit is 30 weight parts.

Sealant for liquid crystal dripping process of the present invention is preferably containing silane coupling agent.Above-mentioned silane coupling agent mainly plays the effect of bonding auxiliary agent.

Above-mentioned silane coupling agent is not particularly limited, and such as, is suitable for using 3-TSL 8330,3-mercaptopropyi Trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane etc.

Sealant for liquid crystal dripping process of the present invention, can also as required and containing for adjusting viscosity reactive diluent, regulate thixotropic thixotropic agent, the polymer bead curing catalyst such as thing, 3-rubigan-1,1-dimethyl urea, defoamer, flow agent, stopper, other additives etc. at equal intervals for adjusting range sheet separation.

As the method manufacturing sealant for liquid crystal dripping process of the present invention, such as, following method can be listed: use the mixing machine such as homogeneous dispersion machine, homogenizer, universal mixer, planetary-type mixer, kneader, three rollers, by the method etc. of the mixing such as curable resin, inorganic filler, polymerization starter and/or thermal curing agents, the silane coupling agent that adds as required.Now, in order to remove contained ionic impurity, can with ionic adsorption solid contact.

With regard to sealant for liquid crystal dripping process of the present invention, use E type viscometer 25 DEG C, the preferred lower limit of viscosity that measures under the condition of 1.0rpm is 100Pas, the preferred upper limit is 400Pas.If above-mentioned viscosity is less than 100Pas, then sometimes liquid crystal cannot be kept.If above-mentioned viscosity is more than 400Pas, then coating is deteriorated sometimes.The preferred lower limit of above-mentioned viscosity is 200Pas, and the preferred upper limit is 350Pas.

The preferred upper limit of the thixotropy index of sealant for liquid crystal dripping process of the present invention is 1.5.If the thixotropy index of sealant for liquid crystal dripping process of the present invention is more than 1.5, then the variation such as coating sometimes.The preferred upper limit of the thixotropy index of sealant for liquid crystal dripping process of the present invention is 1.3.The lower limit of the thixotropy index of sealant for liquid crystal dripping process of the present invention is not particularly limited, but is not less than 1.0 in fact.

It should be noted that, in this manual, above-mentioned " thixotropy index " refers to, use E type viscometer 25 DEG C, the viscosity that measures of the condition of 0.5rpm is divided by using E type viscometer 25 DEG C, the viscosity that measures under the condition of 5.0rpm and the value that obtains.

By coordinating electrically conductive microparticle in sealant for liquid crystal dripping process of the present invention, thus upper and lower conductive material can be manufactured.This conductive material up and down containing sealant for liquid crystal dripping process of the present invention and electrically conductive microparticle is also one of the present invention.

Above-mentioned electrically conductive microparticle is not particularly limited, and can use Metal Ball, be formed with the particulate of conductive metal layer on the surface of resin particle.Wherein, the particulate being formed with conductive metal layer on the surface of resin particle can utilize the elasticity of the excellence of resin particle, thus can carry out conduction and connect when distribution connecting portion in not wounded substrate, therefore preferably.

Sealant for liquid crystal dripping process of the present invention can also as required and containing opacifying property tinting material, for viscosity adjustment reactive diluent, regulate thixotropic thixotropic agent, polymer bead thing, curing catalyst, defoamer, flow agent, stopper, other additives etc. at equal intervals for adjusting range sheet separation.

The liquid crystal display device of sealant for liquid crystal dripping process of the present invention and/or upper and lower conductive material of the present invention is used also to be one of the present invention.

As the method manufacturing liquid crystal display device of the present invention, such as, the method etc. with following operation can be listed, described operation comprises: on one of 2 transparency carriers with electrode such as ito thin film, utilize silk screen printing, divider coating etc., make sealant for liquid crystal dripping process of the present invention etc. form the operation of the seal pattern of rectangular shape; Under the state that sealant for liquid crystal dripping process of the present invention etc. is uncured, in the frame coating transparency carrier that the fine droplet of liquid crystal is dripped whole, and operation overlapping with another transparency carrier immediately; To light such as the seal pattern partial illumination ultraviolets of sealant for liquid crystal dripping process of the present invention etc., make the operation of sealing agent Procuring; And the sealing agent after Procuring is heated, make the operation that it formally solidifies.

The effect of invention

According to the present invention, can be provided in the manufacture of the liquid crystal display device utilizing the process implementing that drips, though when applied in the alignment films of hydrophobic property also can not damage cementability, sealant for liquid crystal dripping process that Display panel portion can not produce speck.In addition, according to the present invention, the conductive material up and down and liquid crystal display device that use this sealant for liquid crystal dripping process to manufacture can also be provided.

Embodiment

Below, the present invention will be described in more detail to enumerate embodiment, but the present invention is not limited in these embodiments.

(embodiment 1)

(surface treatment of inorganic filler)

Silicon dioxide granule (Japanese catalyst Inc., " KEP-30 ", median size 0.3 μm, M value are 0) 10 weight parts as inorganic filler are scattered in be dissolved with in ethanol 100 weight part of triethoxyl silane 5 weight part, react 1 hour under the backflow of ethanol, obtain methyl process silicon-dioxide (M value 34).

(preparation of sealing agent)

Mating part acrylic modified epoxy resin (Daicel cytec Inc., " EBECRYL1561 ") 20 weight parts, completely Acryrylic acid modified bisphenol A epoxy resin (Daicel cytec Inc., " EBECRYL3700 ") 40 weight parts, optical free radical polymerization starter (BASF Japan Inc., " IRGACURE651 ") 1 weight part, be heated to 80 DEG C make their dissolve after, use planetary whipping appts to carry out stirring and obtaining mixture.

Then, coordinate methyl process silicon-dioxide 6 weight part as the gained of inorganic filler, adipic dihydrazide (Japanese Finechem Inc., " ADH ") 5 weight parts as thermal curing agents and 3-glycidoxypropyltrime,hoxysilane 1 weight part as silane coupling agent, after using planetary whipping appts to stir, use three ceramic rollers to disperse, obtain sealing agent.

(embodiment 2)

In " (surface treatment of inorganic filler) ", use silicon dioxide granule (Japanese catalyst Inc., " KEP-50 ", median size be 0.5 μm, M value be 0) as inorganic filler, in addition, carry out the operation identical with embodiment 1, methyl process silicon-dioxide (M value is 31).

Use methyl process silicon-dioxide 7 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 3)

In " (surface treatment of inorganic filler) ", use silicon dioxide granule (Japanese catalyst Inc., " KEP-100 ", median size be 1.0 μm, M value be 0) as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain methyl process silicon-dioxide (M value is 30).

Use methyl process silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 4)

In embodiment 3, together with thermal curing agents, coordinate polymeric azo compound (with light pure pharmaceutical worker's industry Inc., " VPE0201 ") 5 weight parts as hot radical polymerization starter, in addition, carry out the operation identical with embodiment 3, obtain sealing agent.

(embodiment 5)

In " (surface treatment of inorganic filler) ", use silicon dioxide granule (Japanese catalyst Inc., " KEP-150 ", median size be 1.5 μm, M value be 0) as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain methyl process silicon-dioxide (M value 26).

Use methyl process silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 6)

In " (surface treatment of inorganic filler) ", use silicon dioxide granule (Japanese catalyst Inc., " KEP-100 ", median size be 1.0 μm, M value be 0) as inorganic filler, 3-TSL 8330 is used to replace Union carbide A-162, in addition, carry out the operation identical with embodiment 1, obtain amino process silicon-dioxide (M value is 23).

Use amino process silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 7)

In " (surface treatment of inorganic filler) ", use silicon dioxide granule (Japanese catalyst Inc., " KEP-100 ", median size be 1.0 μm, M value be 0) as inorganic filler, 3-glycidoxypropyltrime,hoxysilane 3.5 weight part is used to replace Union carbide A-162 5 weight part, in addition, carry out the operation identical with embodiment 1, obtain epoxy finishes silicon-dioxide (M value is 20).

Use epoxy finishes silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 8)

In " (surface treatment of inorganic filler) ", use silicon dioxide granule (Japanese catalyst Inc., " KEP-100 ", median size be 1.0 μm, M value be 0) as inorganic filler, 3-glycidoxypropyltrime,hoxysilane is used to replace Union carbide A-162, in addition, carry out the operation identical with embodiment 1, obtain epoxy finishes silicon-dioxide (M value is 25).

Use epoxy finishes silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 9)

The use level of epoxy finishes silicon-dioxide is changed to 2 weight parts, in addition, carries out the operation identical with embodiment 8, obtain sealing agent.

(embodiment 10)

The use level of epoxy finishes silicon-dioxide is changed to 30 weight parts, in addition, carries out the operation identical with embodiment 8, obtain sealing agent.

(embodiment 11)

In " (surface treatment of inorganic filler) ", use talc particles (Japanese talcum Inc., " SG-2000 ", median size be 1.0 μm, M value be 0) as inorganic filler, 3-glycidoxypropyltrime,hoxysilane is used to replace Union carbide A-162, in addition, carry out the operation identical with embodiment 1, obtain epoxy finishes talcum (M value is 24).

The use level of epoxy finishes silicon-dioxide is changed to 10 weight parts, has also coordinated epoxy finishes talcum 5 weight part produced as inorganic filler, in addition, carried out the operation identical with embodiment 8, obtain sealing agent.

(embodiment 12)

In " (surface treatment of inorganic filler) ", use silicon dioxide granule " AdmafineSO-E3 " (Admatechs Inc., median size be 1.0 μm, M value be 0) as inorganic filler, 3-glycidoxypropyltrime,hoxysilane 10 weight part is used to replace Union carbide A-162 5 weight part, in addition, carry out the operation identical with embodiment 1, obtain epoxy finishes silicon-dioxide (M value 25).

Use epoxy finishes silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 13)

The use level of 3-glycidoxypropyltrime,hoxysilane is changed to 10 weight parts, in addition, carries out the operation identical with embodiment 7, obtain epoxy finishes silicon-dioxide (M value is 34).

Use epoxy finishes silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 14)

The use level of 3-glycidoxypropyltrime,hoxysilane is changed to 30 weight parts, in addition, carries out the operation identical with embodiment 7, obtain epoxy finishes silicon-dioxide (M value is 57).

Use epoxy finishes silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 15)

In " (surface treatment of inorganic filler) ", use talc particles (Japanese talcum Inc., " D-600 ", median size be 0.6 μm, M value be 0) as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain methyl process talcum (M value is 29).

Use methyl process talcum 10 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 16)

In " (surface treatment of inorganic filler) ", use talc particles (Japanese talcum Inc., " SG-2000 ", median size be 1.0 μm, M value be 0) as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain methyl process talcum (M value 25).

Use methyl process talcum 10 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent and liquid crystal display device.

(embodiment 17)

In " (surface treatment of inorganic filler) ", use talc particles (Japanese talcum Inc., " SG-2000 ", median size be 1.0 μm, M value be 0) as inorganic filler, add this talc particles 100 weight part in a in a henschel mixer, while carrying out heating at 150 DEG C, the mixture of spray water 5 weight part and hexamethyldisilazane 10 weight part is while methyl process is carried out in stirring on one side, obtains methyl process talcum (M value is 40).

Use methyl process talcum 10 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 18)

Use level 5 weight part of 3-glycidoxypropyltrime,hoxysilane is changed to 4 weight parts, in addition, carries out the operation identical with embodiment 11, obtain epoxy finishes talcum (M value is 20).

Use epoxy finishes talcum 10 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 19)

Epoxy finishes talcum (M value is 24) 10 weight parts that use is carried out the operation identical with embodiment 11 and obtained, as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 20)

The use level of epoxy finishes talcum is changed to 2 weight parts, in addition, carries out the operation identical with embodiment 19, obtain sealing agent.

(embodiment 21)

The use level of epoxy finishes talcum is changed to 30 weight parts, in addition, carries out the operation identical with embodiment 19, obtain sealing agent.

(embodiment 22)

The use level of 3-glycidoxypropyltrime,hoxysilane is changed to 10 weight parts, in addition, carries out the operation identical with embodiment 11, obtain epoxy finishes talcum (M value is 30).

Use epoxy finishes talcum 10 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 23)

The use level of 3-glycidoxypropyltrime,hoxysilane is changed to 30 weight parts, in addition, carries out the operation identical with embodiment 11, obtain epoxy finishes talcum (M value is 75).

Use epoxy finishes talcum 10 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(embodiment 24)

Use 3-TSL 8330 to replace 3-glycidoxypropyltrime,hoxysilane, in addition, carry out the operation identical with embodiment 11, obtain amino process talcum (M value is 23).

Use amino process talcum 10 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 1)

In " (surface treatment of inorganic filler) ", use silicon dioxide granule (Japanese catalyst Inc., " KEP-250 ", median size be 2.5 μm, M value be 0) as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain methyl process silicon-dioxide (M value is 24).

Use methyl process silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 2)

Use methyl process silicon-dioxide (chemical industrial company of SHIN-ETSU HANTOTAI system, " X24-9163A ", median size are 0.08 μm, M value be 38) 5 weight parts as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 3)

The use level of methyl process silicon-dioxide is changed to 10 weight parts, in addition, carries out the operation identical with comparative example 2, obtain sealing agent.

(comparative example 4)

Use untreated " KEP-50 " 7 weight part as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 5)

Use untreated " KEP-100 " 15 weight part as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 6)

In " (surface treatment of inorganic filler) ", " HPS1000 (East Asia Synesis Company system, median size are 1.0 μm, M value be 0) is as inorganic filler; in addition; carry out the operation identical with embodiment 1, obtain methyl process silicon-dioxide (M value is 15) to use silicon dioxide granule.

Use methyl process silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 7)

The use level of 3-glycidoxypropyltrime,hoxysilane is changed to 1 weight part, in addition, carries out the operation identical with embodiment 7, obtain epoxy finishes silicon-dioxide (M value is 13).

Use epoxy finishes silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 8)

The use level of 3-glycidoxypropyltrime,hoxysilane is changed to 5 weight parts, in addition, carries out the operation identical with embodiment 12, obtain epoxy finishes silicon-dioxide (M value is 17).

Use epoxy finishes silica 15 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 9)

In " (surface treatment of inorganic filler) ", use silicon dioxide granule " AdmafineSO-C1 " (Admatechs Inc., median size be 0.25 μm, M value be 0) as inorganic filler, 3-glycidoxypropyltrime,hoxysilane 0.2 weight part is used to replace Union carbide A-162 5 weight part, in addition, carry out the operation identical with embodiment 1, obtain epoxy finishes silicon-dioxide (M value is 3).

Use epoxy finishes silicon-dioxide 5 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 10)

In " (surface treatment of inorganic filler) ", use silicon dioxide granule " AdmafineSO-25H " (Admatechs Inc., median size be 0.5 μm, M value be 0) as inorganic filler, 3-glycidoxypropyltrime,hoxysilane 10 weight part is used to replace Union carbide A-162 5 weight part, in addition, carry out the operation identical with embodiment 1, epoxy finishes silicon-dioxide (M value is 15).

Use epoxy finishes silicon-dioxide 7 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 11)

In " (surface treatment of inorganic filler) ", use silicon dioxide granule " AdmafineSO-C2 " (Admatechs Inc., median size be 0.5 μm, M value be 0) as inorganic filler, 3-glycidoxypropyltrime,hoxysilane 0.2 weight part is used to replace Union carbide A-162 5 weight part, in addition, carry out the operation identical with embodiment 1, obtain epoxy finishes silicon-dioxide (M value is 5).

Use epoxy finishes silicon-dioxide 7 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 12)

The use level of 3-glycidoxypropyltrime,hoxysilane is changed to 1 weight part, in addition, carries out the operation identical with embodiment 11, obtain epoxy finishes talcum (M value is 14).

Use epoxy finishes talcum 10 weight part of gained as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

(comparative example 13)

Use untreated " SG-2000 " 10 weight part as inorganic filler, in addition, carry out the operation identical with embodiment 1, obtain sealing agent.

It should be noted that, in embodiment and comparative example, the M value of the inorganic filler of use derives as follows.

Under the environment of 23 DEG C, the ion exchanged water of inorganic filler 0.2g and 50mL is added the beaker of capacity 300mL.While using the solution in magnetic stirrer beaker, drip methyl alcohol until inorganic filler is suspended from drop-burette.Now, be suspended the time point of state in the solution as terminal by visual using becoming inorganic filler, the value of the methyl alcohol percentage by volume of the liquid mixture in beaker during terminal is set to M value.

< evaluates >

Following evaluation is carried out to the sealing agent obtained by each embodiment and each comparative example.Show the result in table 1 ~ 3.

(1) viscosity and thixotropy index

For the sealing agent obtained by each embodiment and each comparative example, use E type viscometer (BROOKFIELD Inc., " DV-III "), measure 25 DEG C, viscosity under the condition of 1.0rpm.

In addition, similarly operate, to 25 DEG C, viscosity under the condition of 0.5rpm and 25 DEG C, 5.0rpm condition under viscosity measure, the viscosity be used in 25 DEG C, measuring under the condition of 0.5rpm, divided by 25 DEG C, the viscosity that measures under the condition of 5.0rpm, derives thixotropy index.

(2) coating

Spacer particulate (ponding chemical industrial company system, " Micropearl SI-H050 ", 5.0 μm) 1 weight part is made to be dispersed in sealing agent 100 weight part obtained by each embodiment and each comparative example, to be filled in syringe and to carry out deaeration, on one of 2 sheet glass substrates, divider is used to be coated with in the mode making the line width of the sealing agent after laminating reach 1mm.

Opticmicroscope is used to confirm the sealing agent after coating, interrupt there is not sealing under surface covered 100mm/ second, sealing the average evaluation attenuated is " ◎ ", interrupt there is not sealing under surface covered 60mm/ second, seal situation about attenuating, and, do not occur to seal under 100mm/ second and interrupt but partly observe that to seal the average evaluation attenuated be "○", surface covered 60mm/ lower part second is observed sealing and attenuated but the average evaluation that interrupts do not occur to seal for " △ ", be "×" by there is the average evaluation that sealing interrupts under surface covered 60mm/ second, thus the coating of sealing agent is evaluated.

(3) cementability

Spacer particulate (ponding chemical industrial company system, " Micropearl SP205 ", 5.0 μm) 3 weight parts are dispersed in sealing agent 100 weight part obtained by each embodiment and each comparative example.The central part being formed with the corning glass 1737 (20mm × 50mm × 1.1mmt) of transparency electrode (ITO) on surface gets the sealing agent being dispersed with spacer particulate of denier.The amount of sealing agent is, is extruded the amount expanding and reach about 3mm by the glass of homotype overlapping on it.For the glass substrate after laminating, use the high-pressure mercury light irradiation 30 seconds 100mW/cm with the strainer intercepting below 350nm light ²ultraviolet, make sealant cures.Afterwards, at 120 DEG C, carry out heating in 1 hour, obtain adhesive test sheet.For the adhesive test sheet of gained, tonometer is used to be measured bonding strength by planar stretch test method(s).

In addition, above-mentioned corning glass 1737 is coated with imide resin (Nissan Chemical Inc., " #7492 ") by spin-coating method, be used at 80 DEG C and burn till and define the substrate of alignment films after preroasting, at 230 DEG C, carry out operation same as described above to make adhesive test sheet, similarly carry out operation to measure bonding strength.

(4) distribution is damaging

Prepare that there is the glass substrate being configured with the pattern of the aluminum wiring of 100 width 50 μm on the thick non-alkali glass of 0.7mm and the glass substrate be made up of the non-alkali glass that the 0.7mm not configuring distribution is thick.

On the distribution of glass substrate being configured with aluminum wiring, the mode of 1mm is reached with the sealed width with direction at a right angle, the direction of aluminum wiring and after crimping, be coated with the sealing agent obtained by each embodiment and each comparative example, laminating does not configure the glass substrate of distribution, crimps with the pressure of 0.5MPa.Afterwards, the high pressure mercury vapour lamp with the strainer intercepting below 350nm light is used, to sealing agent partial illumination 30 seconds 100mW/cm ²ultraviolet, then at 120 DEG C heat 1 hour, make sealant cures.

After making sealant cures, measure the conduction of each aluminum wiring, thus outage (ratio of the distribution broken occurs in 100) is evaluated.

(5) speck

Spacer particulate (ponding chemical industrial company system, " Micropearl SP205 ", 5.0 μm) 3 weight parts are dispersed in sealing agent 100 weight part obtained by each embodiment and each comparative example.On of 2 alkali-free glass substrates of the alignment films after being formed with friction treatment and ITO electrode, to describe the mode of rectangular frame, divider is utilized to be coated with the sealing agent being dispersed with spacer particulate.Then, drip liquid crystal (Merck Inc., " ZLI-4792 "), another 1 plate base of fitting, use high pressure mercury vapour lamp with the strainer intercepting below 350nm light with 100mW/cm ²irradiate and make sealant cures in 30 seconds, then, heat 1 hour at 120 DEG C, produce liquid crystal display device.

By the liquid crystal display device modularization of gained, make it show black and use backlight from back side illuminaton light, carry out visual, by the whole average evaluation of speck of not observing above of the panel at liquid crystal display device for " ◎ ", speck will be observed but the actual average evaluation using the level belonging to no problem is "○" near sealing agent only around panel, display part at panel being observed speck on a large scale, belongs to the average evaluation of the actual level used to be "×", thus evaluates speck.

(6) gap is uneven

The liquid crystal display device obtained for operating in the same manner as " (5) speck ", is evaluated by the bad inequality caused in gap by visual.In addition, measure panel gap, counter plate central authorities and sealing agent near gap inequality evaluate.Above all target gap is obtained and the average evaluation of not observing gap inequality is "○" by whole for panel, by panel periphery higher than the gap of central part and can the average evaluation of gap inequality that causes thus of visual confirmation be "×", thus gap inequality be evaluated.

(7) irregular colour

At 60 DEG C, under the environment of 95%RH, the liquid crystal display device obtained operating in the same manner as " (5) speck " is placed 300 hours, 500 hours and 1000 hours, the irregular colour that liquid crystal around visual observation sealing produces, the whole face of placement liquid crystal panel after 1000 hours still do not existed completely the average evaluation of irregular colour for " ◎ ", by placement after 500 hours whole of liquid crystal panel without irregular colour, but observing average evaluation uneven slightly is after 1000 hours "○", by placement after 300 hours whole of liquid crystal panel without irregular colour, but observe average evaluation uneven slightly after 500 hours for " △ ", be "×" by the average evaluation observing irregular colour after 300 hours, thus irregular colour is evaluated.

Table 1

Table 2

Table 3

Utilizability in industry

According to the present invention, may be provided in the manufacture of the liquid crystal display device utilizing technique of dripping, even if cementability also can not be damaged when coating and being endowed in hydrophobic alignment films, sealant for liquid crystal dripping process that Display panel portion can not produce speck.In addition, according to the present invention, the conductive material up and down and liquid crystal display device that use this sealant for liquid crystal dripping process to manufacture can be provided.

Claims (3)

1. a sealant for liquid crystal dripping process, it contains curable resin, inorganic filler, polymerization starter and/or thermal curing agents, and the feature of described sealant for liquid crystal dripping process is,

Hydrophobic surface treatment is implemented to described inorganic filler, the M value of described inorganic filler is more than 20, median size is 0.3 ~ 1.5 μm,

Relative to described curable resin 100 weight part, containing described inorganic filler 5 ~ 40 weight part.

2. a conductive material about, is characterized in that, containing sealant for liquid crystal dripping process according to claim 1 and electrically conductive microparticle.

3. a liquid crystal display device, is characterized in that, uses sealant for liquid crystal dripping process described in claim 1 or upper and lower conductive material according to claim 2 and makes.