CN105283803A - Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element - Google Patents

Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element Download PDF

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CN105283803A
CN105283803A CN201480032864.XA CN201480032864A CN105283803A CN 105283803 A CN105283803 A CN 105283803A CN 201480032864 A CN201480032864 A CN 201480032864A CN 105283803 A CN105283803 A CN 105283803A
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liquid crystal
methyl
mentioned
epoxy resin
sealant
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CN105283803B (en
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伊一男
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1341—Filling or closing of cells
    • G02F1/13415—Drop filling process
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/16—Materials and properties conductive

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Liquid Crystal (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Sealing Material Composition (AREA)
  • Epoxy Resins (AREA)

Abstract

One purpose of the present invention is to provide a sealing agent for liquid crystal dropping methods, which has excellent bonding properties and provides a cured product that has low water vapor permeability. Another purpose of the present invention is to provide a vertically conducting material and a liquid crystal display element, each of which is obtained using the sealing agent for liquid crystal dropping methods. The present invention is a sealing agent for liquid crystal dropping methods, which contains a curable resin and a radical polymerization initiator and/or a thermal curing agent. The curable resin contains an epoxy resin and a (meth)acrylic resin, and the amount of the epoxy resin contained in 100 parts by weight of the curable resin is 5-70 parts by weight. In addition, the epoxy resin contains 20% by weight or more of a dicyclopentadiene novolac epoxy resin.

Description

Sealant for liquid crystal dripping process, up and down conductive material and liquid crystal display cells
Technical field
The present invention relates to a kind of excellent in adhesion and sealant for liquid crystal dripping process that the moisture-penetrability of solidfied material is low.In addition, the present invention relates to and a kind ofly use this sealant for liquid crystal dripping process and the conductive material up and down made and liquid crystal display cells.
Background technology
In recent years, as the manufacture method of liquid crystal display cells, from shortening pitch time, using the optimized viewpoint of amount of liquid crystal, used as disclosed in patent documentation 1, patent documentation 2 employ photo-thermal containing curable resin, Photoepolymerizationinitiater initiater and thermal curing agents and by the liquid crystal drop under type being referred to as technique of dripping of curing type sealant.
Dripping in technique, first, one in 2 electroded transparency carriers is forming rectangular seal pattern by divider.Then, under the state that sealant is uncured, the fine droplet of liquid crystal is added drop-wise in the whole frame of transparency carrier, makes another transparency carrier overlap immediately, precuring is carried out to light such as sealing irradiation ultraviolet radiations.Then, heat and carry out main solidification, making liquid crystal display cells.By under reduced pressure carrying out the laminating of substrate, thus can with high efficiency system liquid making crystal display element, now, this technique of dripping has become the main flow of the manufacture method of liquid crystal display cells.
Universal along with tablet terminal or portable end end, liquid crystal display cells needs all the more the moisture-proof reliabilities such as the driving under hot and humid environment, for sealant, needs the performance of the immersion of the water prevented from outside further.In order to make the moisture-proof reliability of liquid crystal display cells improve, need to make the cementability of sealant and substrate etc. improve and the moisture-penetrability of the solidfied material of sealant is reduced.But, for sealant, be difficult to take into account high adhesiveness and low-moisture permeability.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2001-133794 publication
Patent documentation 2: No. 02/092718th, International Publication
Summary of the invention
Invent problem to be solved
The object of the invention is to, a kind of excellent in adhesion and sealant for liquid crystal dripping process that the moisture-penetrability of solidfied material is low is provided.In addition, the object of the invention is to, provide a kind of and use this sealant for liquid crystal dripping process and the conductive material up and down made and liquid crystal display cells.
For solving the means of problem
The present invention is a kind of sealant for liquid crystal dripping process, it is the sealant for liquid crystal dripping process containing curable resin and radical polymerization initiator and/or thermal curing agents, wherein, above-mentioned curable resin contains epoxy resin and (methyl) acrylic resin, the content of the described epoxy resin in above-mentioned curable resin 100 weight portion is 5 ~ 70 weight portions, and above-mentioned epoxy resin contains dicyclopentadiene phenolic type epoxy resin more than 20 % by weight.
Below, the present invention is described in detail.
The present inventor finds, by coordinating the dicyclopentadiene phenolic type epoxy resin of specified quantitative as curable resin, thus can obtain excellent in adhesion and that the moisture-penetrability of solidfied material is low sealant for liquid crystal dripping process, so far, complete the present invention.
Sealant for liquid crystal dripping process of the present invention contains curable resin.
Above-mentioned curable resin contains epoxy resin.
Above-mentioned epoxy resin contains dicyclopentadiene phenolic type epoxy resin.By containing above-mentioned dicyclopentadiene phenolic type epoxy resin, thus sealant for liquid crystal dripping process of the present invention can be made to have high adhesiveness and low-moisture permeability concurrently.
As above-mentioned dicyclopentadiene phenolic type epoxy resin, specifically, the compound etc. such as represented by following formula (1) can be enumerated.
[changing 1]
In formula (1), n is 1 ~ 5, is preferably 1.
As the commercially available product in above-mentioned dicyclopentadiene phenolic type epoxy resin, such as HP-7200, HP-7200L (being DIC Inc.) etc. can be enumerated.
Above-mentioned epoxy resin also can contain other epoxy resin on the basis of above-mentioned dicyclopentadiene phenolic type epoxy resin.
When containing other epoxy resin above-mentioned, the lower limit of the content of the above-mentioned dicyclopentadiene phenolic type epoxy resin in above-mentioned epoxy resin is 20 % by weight.If the content of above-mentioned dicyclopentadiene phenolic type epoxy resin is lower than 20 % by weight, then the sealant for liquid crystal dripping process of gained cannot be made to have given play to the effect having high adhesiveness and low-moisture permeability concurrently fully.The preferred lower limit of the content of above-mentioned dicyclopentadiene phenolic type epoxy resin is 25 % by weight.Above-mentioned epoxy resin is preferably only made up of above-mentioned dicyclopentadiene phenolic type epoxy resin.
In addition, the content of the above-mentioned dicyclopentadiene phenolic type epoxy resin in curable resin 100 weight portion is preferably lower than 70 weight portions.If the content of above-mentioned dicyclopentadiene phenolic type epoxy resin is more than 70 weight portions, then the viscosity of the sealant for liquid crystal dripping process of gained becomes too high, and coating is deteriorated sometimes.The content of above-mentioned dicyclopentadiene phenolic type epoxy resin is more preferably below 30 weight portions, more preferably below 10 weight portions.
As other epoxy resin above-mentioned, can enumerate such as: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2, 2 '-diallyl bisphenol type epoxy resin, bisphenol-A epoxy resin, epoxypropane addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether-type epoxy resin, diphenyl ether type epoxy, dicyclopentadiene-type epoxy resin beyond dicyclopentadiene phenolic type, naphthalene type epoxy resin, phenol novolak type epoxy, orthoresol phenol aldehyde 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, epihydric alcohol ester compound, bisphenol A-type episulfide resin etc.These epoxy resin may be used singly or in combination of two or more.
As the commercially available product in above-mentioned bisphenol A type epoxy resin, such as jER828, jER1004 (being Mitsubishi Chemical Ind's system), EPICLON850CRP (DIC Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned bisphenol f type epoxy resin, such as jER806, jER4004, jERYL983U (being Mitsubishi Chemical Ind's system) can be enumerated.
As the commercially available product in above-mentioned bisphenol-s epoxy resin, such as EPICLONEXA1514 (DIC Inc.) etc. can be enumerated.
As above-mentioned 2, the commercially available product in 2 '-diallyl bisphenol type epoxy resin, can enumerate such as RE-810NM (Japanese chemical drug Inc.) etc.
As the commercially available product in above-mentioned bisphenol-A epoxy resin, such as EPICLONEXA7015 (DIC Inc.), jERYX8000 (Mitsubishi Chemical Ind's system) etc. can be enumerated.
As the commercially available product in above-mentioned epoxypropane addition bisphenol A type epoxy resin, such as EP-4000S (ADEKA Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned resorcinol type epoxy resin, such as EX-201 (NagaseChemtex Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned biphenyl type epoxy resin, such as jERYX-4000H (Mitsubishi Chemical Ind's system) etc. can be enumerated.
As the commercially available product in above-mentioned thioether-type epoxy resin, such as YSLV-50TE (aurification Inc. is lived by Nippon Steel) etc. can be enumerated.
As the commercially available product in above-mentioned diphenyl ether type epoxy, such as YSLV-80DE (aurification Inc. is lived by Nippon Steel) etc. can be enumerated.
As the commercially available product in the dicyclopentadiene-type epoxy resin beyond above-mentioned dicyclopentadiene phenolic type, such as EP-4088S (ADEKA Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned naphthalene type epoxy resin, such as EPICLONHP4032, EPICLONEXA-4700 (being DIC Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned phenol novolak type epoxy, such as EPICLONN-770 (DIC Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned orthoresol phenol aldehyde type epoxy resin, such as EPICLONN-670-EXP-S (DIC Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned biphenyl phenol aldehyde type epoxy resin, such as NC-3000P (Japanese chemical drug Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned naphthol novolac type epoxy resin, such as ESN-165S (aurification Inc. is lived by Nippon Steel) etc. can be enumerated.
As the commercially available product in above-mentioned glycidyl amine type epoxy resin, such as jER630 (Mitsubishi Chemical Ind's system), EPICLON430 (DIC Inc.), TETRAD-X (Mitsubishi Gas Chemical Inc.) etc. can be enumerated.
As the commercially available product in abovementioned alkyl polyol type epoxy resin, such as ZX-1542 (aurification Inc. is lived by Nippon Steel), EPICLON726 (DIC Inc.), EPOLIGHT80MFA (chemistry Inc. of common prosperity company), DENACOLEX-611 (NagaseChemtex Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned modified rubber type epoxy resin, such as YR-450, YR-207 (be Nippon Steel and live aurification Inc.), EPOLEADPB (Daicel chemical industrial company system) etc. can be enumerated.
As the commercially available product in above-mentioned epihydric alcohol ester compound, such as DENACOLEX-147 (NagaseChemtex Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned bisphenol A-type episulfide resin, such as jERYL-7000 (Mitsubishi Chemical Ind's system) etc. can be enumerated.
As other commercially available products in above-mentioned epoxy resin, such as YDC-1312, YSLV-80XY, YSLV-90CR (be Nippon Steel and live aurification Inc.), XAC4151 (Asahi Kasei Corporation's system), jER1031, jER1032 (being Mitsubishi Chemical Ind's system), EXA-7120 (DIC Inc.) etc. can be enumerated.
In addition, as other epoxy resin above-mentioned, can containing the resin in 1 molecule with epoxy radicals and (methyl) acryloxy.As such compound, part (methyl) acrylic modified epoxy resin etc. that a part of epoxy radicals can enumerated in the compound such as making to have more than 2 epoxy radicals is reacted with (methyl) acrylic acid and obtained.Above-mentioned part (methyl) acrylic modified epoxy resin (methyl) not described later acrylic resin, but as epoxy resin.
It should be noted that, part (methyl) acrylic modified epoxy resin obtained by making a part of epoxy radicals of above-mentioned dicyclopentadiene phenolic type epoxy resin and (methyl) acrylic acid react can being used.
As above-mentioned part (methyl) acrylic modified epoxy resin, specifically, such as can obtain as described below: make phenol novolak type epoxy (DIC Inc., " N-770 ") 190g is dissolved in toluene 500mL, in this solution, add triphenylphosphine 0.1g and make uniform solution, under return stirring, acrylic acid 35g was dripped with 2 hours in the solution of gained, then return stirring is carried out further 6 hours, then toluene is removed, obtain part acrylic acid modified phenol phenol aldehyde type epoxy resin that the epoxy radicals of 50 % by mole and acrylic acid reacts and obtain thus (now, 50% there occurs part acrylic acid modification).
As the commercially available product in above-mentioned part (methyl) acrylic modified epoxy resin, can enumerate such as UVACURE1561 (DaicelAllnex Inc.).
The lower limit of the content of the above-mentioned epoxy resin in above-mentioned curable resin 100 weight portion is 5 weight portions, the upper limit is 70 weight portions.If the content of above-mentioned epoxy resin is lower than 5 weight portions, then the content of above-mentioned dicyclopentadiene phenolic type epoxy resin tails off, and therefore, the sealant for liquid crystal dripping process of gained becomes and cannot have high adhesiveness and low-moisture permeability concurrently.If the content of above-mentioned epoxy resin is more than 70 weight portions, then becomes and easily liquid crystal pollution occurs.The preferred lower limit of the content of above-mentioned epoxy resin is 10 weight portions, the preferred upper limit is 65 weight portions, preferred lower limit is 15 weight portions, the preferred upper limit is 60 weight portions.
In addition, the preferred lower limit of the content of in above-mentioned curable resin 100 weight portion, except above-mentioned part (methyl) acrylic modified epoxy resin epoxy resin is 3 weight portions, the preferred upper limit is 59 weight portions.If the content of the epoxy resin except above-mentioned part (methyl) acrylic modified epoxy resin is lower than 3 weight portions, then the tailing off of content of above-mentioned dicyclopentadiene phenolic type epoxy resin, the sealant for liquid crystal dripping process of gained becomes and cannot have high adhesiveness and low-moisture permeability concurrently sometimes.If the content of the epoxy resin except above-mentioned part (methyl) acrylic modified epoxy resin more than 59 weight portions, then produces liquid crystal pollution sometimes.The preferred lower limit of the content of above-mentioned epoxy resin is 5 weight portions, the preferred upper limit is 30 weight portions, the preferred upper limit is 20 weight portions.
Above-mentioned curable resin contains (methyl) acrylic resin.
Above-mentioned (methyl) acrylic resin can be enumerated such as: the ester compounds obtained by making (methyl) acrylic acid react with the compound with hydroxyl, by epoxy (methyl) acrylate that makes (methyl) acrylic acid and epoxy compound react and obtain, reacted by (methyl) acrylic acid derivative making isocyanates and have a hydroxyl and carbamate (methyl) acrylate etc. that obtains.
It should be noted that, in this manual, above-mentioned (methyl) acrylic resin refers to the resin with (methyl) acryloyl group, and above-mentioned (methyl) acryloyl group refers to acryloyl group or methacryl.In addition, above-mentioned (methyl) acrylate refers to acrylate or methacrylate.Epoxy (methyl) acrylate that whole epoxy radicals that above-mentioned epoxy (methyl) acrylate refers to epoxy compound and (methyl) acrylic acid react and obtains.
Wherein, dicyclopentadiene phenolic type epoxy (methyl) acrylate that whole epoxy radicals that above-mentioned (methyl) acrylic resin preferably contains above-mentioned dicyclopentadiene phenolic type epoxy resin is reacted with (methyl) acrylic acid.
As the ester compounds of the simple function in above-mentioned ester compounds, can enumerate such as: (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxy butyl ester, (methyl) acrylic acid-2-hydroxy butyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-methoxy acrylate, methoxyl ethylene glycol (methyl) acrylate, (methyl) acrylic acid-2-ethoxy ethyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) benzyl acrylate, ethyl carbitol (methyl) acrylate, (methyl) acrylate, phenoxy group diethylene glycol (methyl) acrylate, phenoxy group polyglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, (methyl) acrylic acid 2,2,2-trifluoro ethyl ester, (methyl) acrylic acid 2,2,3,3-tetrafluoro propyl ester, (methyl) acrylic acid 1H, 1H, 5H-octafluoro pentyl ester, acid imide (methyl) acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) n-octyl, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, the different myristin of (methyl) acrylic acid, (methyl) acrylic acid-2-butoxyethyl, (methyl) acrylic acid-2-phenoxy ethyl, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylate, 2-(methyl) acryloyl-oxyethyl succinic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid ester, 2-(methyl) acryloyl-oxyethyl-2-hydroxypropylphthalate, (methyl) glycidyl acrylate, 2-(methyl) acryloyl-oxyethyl phosphate etc.
As the ester compounds of 2 officials' energy in above-mentioned ester compounds, can enumerate such as: BDO two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-decanediol 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, polyglycol two (methyl) acrylate, epoxypropane addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) acrylate, 1,3-BDO 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, PTMEG two (methyl) acrylate, polyester-diol two (methyl) acrylate, polycaprolactone glycol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate etc.
Can above ester compounds as 3 officials in above-mentioned ester compounds, can enumerate such as: pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, epoxypropane addition trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, pentaerythrite four (methyl) acrylate, glycerine three (methyl) acrylate, epoxypropane addition glycerine three (methyl) acrylate, three (methyl) acryloyl-oxyethyl phosphate etc.
As above-mentioned epoxy (methyl) acrylate, can enumerate and such as according to conventional method, epoxy resin and (methyl) acrylic acid be reacted under the existence of base catalyst and epoxy (methyl) acrylate etc. that obtains.
With regard to the epoxy compound as the raw material for the synthesis of above-mentioned epoxy (methyl) acrylate, the epoxy resin identical with above-mentioned epoxy resin can be used.
As above-mentioned epoxy (methyl) acrylate, specifically, such as can obtain as described below: at 90 DEG C, while send into air, while carry out return stirring to resorcinol type epoxy resin (NagaseChemtex Inc., " EX-201 ") 360 weight portions, p methoxy phenol 2 weight portion as polymerization inhibitor, triethylamine 2 weight portion as catalysts, acrylic acid 210 weight portion, and make their reactions 5 hours, obtain resorcinol type epoxy acrylate thus.
As the commercially available product in above-mentioned epoxy (methyl) acrylate, such as EBECRYL860 can be enumerated, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 (being DaicelAllnex Inc.), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (being chemical industrial company of Xin Zhong village system), epoxy-ester M-600A, epoxy-ester 40EM, epoxy-ester 70PA, epoxy-ester 200PA, epoxy-ester 80MFA, epoxy-ester 3002M, epoxy-ester 3002A, epoxy-ester 1600A, epoxy-ester 3000M, epoxy-ester 3000A, epoxy-ester 200EA, epoxy-ester 400EA (being chemistry Inc. of common prosperity company), DENACOLACRYLATEDA-141, DENACOLACRYLATEDA-314, DENACOLACRYLATEDA-911 (being NagaseChemtex Inc.) etc.
Carbamate (methyl) acrylate obtained above by making isocyanates react with (methyl) acrylic acid derivative with hydroxyl, such as by make to have 2 isocyanate group compound 1 equivalent, and (methyl) acrylic acid derivative 2 equivalent with hydroxyl react under the tin based compound of catalytic amount exists and obtain.
With regard to the isocyanates of the raw material as above-mentioned carbamate (methyl) acrylate, can enumerate such as: isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl methane-4, 4 '-diisocyanate (MDI), hydrogenation MDI, aggretion type MDI, 1, 5-naphthalene diisocyanate, norbornene alkyl diisocyanate, tolidine diisocyanate, XDI (XDI), hydrogenation XDI, lysinediisocyanate, triphenylmethane triisocyanate, three (isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate, 1, 6, 10-undecane triisocyanate etc.
In addition, for the isocyanates of the raw material as carbamate (methyl) acrylate obtained above by making isocyanates react with (methyl) acrylic acid derivative with hydroxyl, the reaction by the polyvalent alcohols such as ethylene glycol, glycerine, D-sorbite, trimethylolpropane, (gathering) propylene glycol, carbonate diol, PTMEG, polyester-diol, polycaprolactone glycol and excessive isocyanates can also be used and the isocyanate compound of the chain elongation that obtains
Just as the raw material of above-mentioned carbamate (methyl) acrylate, there is (methyl) acrylic acid derivative of hydroxyl, can enumerate such as: (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxy butyl ester, the commercially available products such as (methyl) acrylic acid-2-hydroxy butyl ester, or ethylene glycol, propylene glycol, 1, ammediol, 1, 3-butylene glycol, 1, 4-butylene glycol, list (methyl) acrylate of the dibasic alcohol such as polyglycol, trimethylolethane, trimethylolpropane, list (methyl) acrylate of the trihydroxy alcohols such as glycerine or two (methyl) acrylate, the epoxy acrylates etc. such as bisphenol A modified epoxy acrylate.
As above-mentioned carbamate (methyl) acrylate, specifically, such as can obtain as described below: add trimethylolpropane 134 weight portion, the BHT0.2 weight portion as polymerization inhibitor, dibutyl tin laurate 0.01 weight portion as catalysts, isophorone diisocyanate 666 weight portion, while carry out return stirring to it at 60 DEG C, while make it react 2 hours, then, add acrylic acid 2-hydroxyl ethyl ester 51 weight portion, while send into air, while carry out return stirring to it and make it react 2 hours at 90 DEG C, obtain thus.
As the commercially available product in above-mentioned carbamate (methyl) acrylate, such as M-1100 can be enumerated, 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 DaicelUCB Inc.), ArtresinUN-9000H, ArtresinUN-9000A, ArtresinUN-7100, ArtresinUN-1255, ArtresinUN-330, ArtresinUN-3320HB, ArtresinUN-1200TPK, ArtresinSH-500B (being Gen Shang industrial group 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 chemistry Inc. of common prosperity company) etc.
From the dysgenic aspect suppressed liquid crystal, above-mentioned (methyl) acrylic resin preferably has-OH base ,-NH-base ,-NH 2the hydrogen bond unit such as base, from the easiness etc. of synthesis, are particularly preferably epoxy (methyl) acrylate.
In addition, above-mentioned (methyl) acrylic resin preferably has 2 ~ 3 (methyl) acryloyl groups in the molecule from the aspect that reactivity is high.
Sealant for liquid crystal dripping process of the present invention contains radical polymerization initiator and/or thermal curing agents.
As above-mentioned radical polymerization initiator, optical free radical polymerization initiator, hot radical polymerization initiator etc. can be enumerated.
As above-mentioned optical free radical polymerization initiator, such as benzophenone based compound, acetophenone based compound, acylphosphine oxide based compound, two luxuriant titanium sub-group compounds, oxime ester based compound, benzoin ether based compound, thioxanthones based compound etc. can be enumerated.
As the commercially available product in above-mentioned optical free radical polymerization initiator, such as IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACUREOXE01, LucirinTPO (being BASFJapan Inc.), NCI-930 (ADEKA Inc.), SPEEDCUREEMK (DKSHJAPAN Inc.), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (be Tokyo and change into industrial group's system) etc. can be enumerated.
As above-mentioned hot radical polymerization initiator, such as superoxide, azo-compound etc. can be enumerated.Wherein, the polymeric azo initiating agent of polymeric azo compound is preferably comprised.
It should be noted that, in this manual, polymeric azo initiating agent refers to: there is azo group and be heated and generate the free radical that (methyl) acryloxy can be made to solidify, number-average molecular weight is the compound of more than 300.
The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiating agent is 1000, the preferred upper limit is 300,000.If the number-average molecular weight of above-mentioned polymeric azo initiating agent is lower than 1000, then polymeric azo initiating agent brings harmful effect to liquid crystal sometimes.If the number-average molecular weight of above-mentioned polymeric azo initiating agent is more than 300,000, then sometimes become difficulty to the mixing in curable resin.The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiating agent is 5000, the preferred upper limit is 100,000, and preferred lower limit is 10,000 further, preferably the upper limit is 90,000 further.
It should be noted that, in this manual, above-mentioned number-average molecular weight utilizes gel permeation chromatography (GPC) to carry out measuring and the value obtained by polystyrene conversion.As the chromatographic column during number-average molecular weight measured by GPC based on polystyrene conversion, such as ShodexLF-804 (Showa electrician Inc.) etc. can be enumerated.
As above-mentioned polymeric azo initiating agent, can enumerate such as: have make the structure of the unit bondings such as multiple polyalkylene oxide or dimethyl silicone polymer by azo group, polymeric azo initiating agent.
As the above-mentioned polymeric azo initiating agent with the structure making the unit bondings such as multiple polyalkylene oxides by azo group, preferably there is the polymeric azo initiating agent of polyethylene oxide structure.As such polymeric azo initiating agent, such as 4 can be enumerated, the condensed polymer of 4'-azo two (4-cyanopentanoic acid) and poly alkylene glycol, 4,4'-azos two (4-cyanopentanoic acid) and the condensed polymer etc. of dimethyl silicone polymer with terminal amino group.
As above-mentioned organic peroxide, such as ketone peroxide, ketal peroxide, hydroperoxides, dialkyl peroxide, peroxyester, diacyl peroxide, peroxy dicarbonate etc. can be enumerated.
As the commercially available product in above-mentioned hot radical polymerization initiator, such as PERBUTYLO, PERHEXYLO, PERBUTYLPV (being You Inc.), V-30, V-501, V-601, VPE-0201, VPE-0401, VPE-0601 (being pure pharmaceutical worker's industry Inc. with light) etc. can be enumerated.
Content preferred lower limit for above-mentioned curable resin 100 weight portion of above-mentioned radical polymerization initiator is 0.01 weight portion, the preferred upper limit is 10 weight portions.If the content of above-mentioned radical polymerization initiator is lower than 0.01 weight portion, then the sealant for liquid crystal dripping process of gained sometimes cannot be made to solidify fully.If the content of above-mentioned radical polymerization initiator is more than 10 weight portions, then storage-stable reduces sometimes.
As above-mentioned thermal curing agents, such as organic acid hydrazides, imdazole derivatives, amines, polyhydric phenol based compound, acid anhydrides etc. can be enumerated.Wherein, the organic acid hydrazides that suitable use is solid-state.
As above-mentioned solid-state organic acid hydrazides, such as 1 can be enumerated, two (diazanyl carbon the ethyl)-5-isopropyl hydantoins (1 of 3-, 3-PVC ス (ヒ De ラ ジ ノ カ Le ボ ノ エ チ Le)-5-イ ソ プ ロ ピ Le ヒ ダ Application ト イ Application), sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, acid dihydrazide etc., as commercially available product, such as can list SDH (Japanese FINECHEM Inc.), ADH (great mound chemical company system), AMICUREVDH, AMICUREVDH-J, AMICUREUDH (being AJINOMOTOFINE-TECHNO Inc.) etc.
Content preferred lower limit for above-mentioned curable resin 100 weight portion of above-mentioned thermal curing agents is 1 weight portion, the preferred upper limit is 50 weight portions.If the content of above-mentioned thermal curing agents is lower than 1 weight portion, then sealant for liquid crystal dripping process of the present invention sometimes cannot be made to solidify fully.If the content of above-mentioned thermal curing agents is more than 50 weight portions, then the viscosity of sealant for liquid crystal dripping process of the present invention uprises sometimes, and coating is deteriorated.The preferred upper limit of the content of above-mentioned thermal curing agents is 30 weight portions.
Sealant for liquid crystal dripping process of the present invention is preferably containing curing accelerator.Solidify fully to make above-mentioned dicyclopentadiene phenolic type epoxy resin, and need to heat at a higher temperature, but by using above-mentioned curing accelerator, even if thus at high temperature do not heat, also it can be made to solidify fully, the effect having high adhesiveness and low-moisture permeability concurrently can have been given play to fully.
As above-mentioned curing accelerator, such as imidazoles system curing accelerator, mercaptan system curing accelerator, tertiary amine system curing accelerator etc. can be enumerated.Wherein, and aspect that viscosity escalating rate of room temperature under low fast from curing rate, preferably containing imidazoles system curing accelerator and/or mercaptan system curing accelerator.
As above-mentioned imidazoles system curing accelerator, such as 1-cyano ethyl-2-phenylimidazole, 2,4-diamido-6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine, 2-phenyl-4-methyl-5-hydroxymethylimidazole etc. can be enumerated.
As above-mentioned mercaptan system curing accelerator, such as tri-thiol acetic acid trihydroxy methyl propyl ester, tri-thiol acetic acid trihydroxy methyl ethyl ester etc. can be enumerated.
Content preferred lower limit for above-mentioned curable resin 100 weight portion of above-mentioned curing accelerator is 1 weight portion, the preferred upper limit is 10 weight portions.If the content of above-mentioned curing accelerator is lower than 1 weight portion, then the sealant for liquid crystal dripping process of gained does not solidify fully sometimes, or needs to make it solidify at high temperature to heat.If the content of above-mentioned curing accelerator is more than 10 weight portions, then the cementability of the sealant for liquid crystal dripping process of gained is deteriorated sometimes.
For sealant for liquid crystal dripping process of the present invention, for objects such as the improvement of the cementability brought by stress dispersion effect, the improvement of linear expansivity, filler can also be contained.
As above-mentioned filler, the inorganic fillers such as such as talcum, asbestos, silicon dioxide, zeyssatite, terre verte, bentonitic clay, calcium carbonate, magnesium carbonate, aluminium oxide, smectite, zinc paste, iron oxide, magnesium oxide, tin oxide, titanium dioxide, magnesium hydroxide, aluminium hydroxide, beaded glass, silicon nitride, barium sulphate, gypsum, calcium silicate, sericite atlapulgite, aluminium nitride can be enumerated, the organic fillers such as polyester micropartical, polyurethane particulate, polyvinyl particulate, acrylic polymers particulate.
The preferred lower limit of the content of the above-mentioned filler in sealant for liquid crystal dripping process 100 weight portion of the present invention is 5 weight portions, the preferred upper limit is 70 weight portions.If the content of above-mentioned filler is lower than 5 weight portions, then sometimes the effects such as the improvement of cementability cannot be given play to fully.If the content of above-mentioned filler is more than 70 weight portions, then the viscosity of the sealant for liquid crystal dripping process of gained becomes too high sometimes, and coating is deteriorated.The preferred lower limit of the content of above-mentioned filler is 10 weight portions, the preferred upper limit is 60 weight portions.
Sealant for liquid crystal dripping process of the present invention contains silane coupling agent.
As above-mentioned silane coupling agent, suitable use is 3-TSL 8330,3-mercaptopropyi trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-isocyanates propyl trimethoxy silicane etc. such as.They can be used alone, and also two or more kinds may be used.
The preferred lower limit of the content of the above-mentioned silane coupling agent in sealant for liquid crystal dripping process 100 weight portion of the present invention is 0.1 weight portion, the preferred upper limit is 20 weight portions.If the content of above-mentioned silane coupling agent is lower than 0.1 weight portion, then sometimes cannot give play to fully by the effect coordinating silane coupling agent to bring.If the content of above-mentioned silane coupling agent is more than 20 weight portions, then the sealant for liquid crystal dripping process of gained can cause liquid crystal pollution sometimes.The preferred lower limit of the content of above-mentioned silane coupling agent is 0.5 weight portion, the preferred upper limit is 10 weight portions.
Sealant for liquid crystal dripping process of the present invention can contain opacifier.By containing above-mentioned opacifier, thus sealant for liquid crystal dripping process of the present invention can be suitable for being used as shading sealant.
As above-mentioned opacifier, can enumerate such as iron oxide, titanium is black, nigrosine, cyanine are black, fullerene, carbon black, resin coating cap-type carbon black etc.Wherein, titanium is preferably black.
Above-mentioned titanium is black, with it to compared with the average transmittance of the light of wavelength 300 ~ 800nm, its near ultraviolet range, the particularly material that uprises of the transmissivity of the light of wavelength 370 ~ 450nm.That is, above-mentioned titanium is black is the opacifier with following character: by covering the light of the wavelength of visible region fully, and gives light-proofness to sealant for liquid crystal dripping process of the present invention, on the other hand, makes the Transmission light of the wavelength near ultraviolet range.Thus, as above-mentioned optical free radical polymerization initiator, above-mentioned smooth cationic polymerization initiators, by using the light of the wavelength (370 ~ 450nm) utilizing the black transmissivity of above-mentioned titanium to uprise and can the material of initiation reaction, thus the photo-curable of sealant for liquid crystal dripping process of the present invention can be made further to increase.In addition, on the other hand, as the opacifier contained by sealant for liquid crystal dripping process of the present invention, the material that preferred insulativity is high, as the opacifier that insulativity is high, preferred titanium is black.
Black for above-mentioned titanium, the optical concentration (OD value) of every 1 μm is preferably more than 3, is more preferably more than 4.The light-proofness that above-mentioned titanium is black is more high better, and the preferred upper limit of OD value institute that above-mentioned titanium is black is not particularly limited, but is generally less than 5.
Black for above-mentioned titanium, even not surface treated titanium is black, also can give play to sufficient effect, also can use: the titaniums after surface treatment such as the titanium that the inorganic constituents such as titanium black, surperficial oxidized silicon, titanium dioxide, germanium oxide, aluminium oxide, zirconia, magnesium oxide of surface after the organic principle process such as coupling agent covers is black are black.Wherein, preferred by the black aspect from insulativity can be improved further of the titanium after organic principle process.
In addition, the liquid crystal display cells manufactured containing the black sealant for liquid crystal dripping process of the present invention as opacifier of above-mentioned titanium is used to have sufficient light-proofness, therefore, it is possible to realize there is no spilling of light and there is high-contrast and there is the liquid crystal display cells of excellent display quality of image.
Commercially available product in black as above-mentioned titanium, can enumerate such as 12S, 13M, 13M-C, 13R-N (being Mitsubishi Material Company's system), TilackD (red fringe changes into Inc.) etc.
The preferred lower limit of the specific surface area that above-mentioned titanium is black is 13m 2/ g, the preferred upper limit are 30m 2/ g, preferred lower limit are 15m 2/ g, the preferred upper limit are 25m 2/ g.
In addition, the preferred lower limit of the volume resistance that above-mentioned titanium is black is 0.5 Ω cm, the preferred upper limit is 3 Ω cm, preferred lower limit is 1 Ω cm, the preferred upper limit is 2.5 Ω cm.
If the primary particle size of above-mentioned opacifier be liquid crystal display cells substrate between distance below, be not particularly limited, but preferred lower limit be 1nm, the preferred upper limit is 5 μm.If the primary particle size of above-mentioned opacifier is lower than 1nm, then the viscosity of the sealant for liquid crystal dripping process of gained or thixotropy significantly increase, and workability is deteriorated sometimes.If the primary particle size of above-mentioned opacifier is more than 5 μm, then the sealant for liquid crystal dripping process of gained is deteriorated to the coating of substrate sometimes.The preferred lower limit of the primary particle size of above-mentioned opacifier is 5nm, the preferred upper limit is 200nm, preferred lower limit is 10nm, the further preferred upper limit is further 100nm.
The preferred lower limit of the content of the above-mentioned opacifier in sealant for liquid crystal dripping process 100 weight portion of the present invention is 5 weight portions, the preferred upper limit is 80 weight portions.If the content of above-mentioned opacifier is lower than 5 weight portions, then sometimes cannot obtain sufficient light-proofness.If the content of above-mentioned opacifier is more than 80 weight portions, then the sealant for liquid crystal dripping process of gained reduces the intensity after the adaptation of substrate, solidification sometimes, or illustrative declines.The preferred lower limit of the content of above-mentioned opacifier is 10 weight portions, the preferred upper limit is 70 weight portions, preferred lower limit is 30 weight portions, the further preferred upper limit is further 60 weight portions.
Sealant for liquid crystal dripping process of the present invention also can as required containing the reactive diluent for adjusting viscosity, for adjusting thixotropic thixotropic agent, polymer microbeads other known adjuvants such as thing, defoamer, levelling agent, polymerization inhibitor at equal intervals for adjusting panel gap.
As manufacturing the method for sealant for liquid crystal dripping process of the present invention, can enumerate and such as utilize the mixer such as homogenous disperse machine, homogeneous mixer, universal mixer, planetary-type mixer, kneader, 3 roller machines to carry out the method etc. mixed curable resin, radical polymerization initiator and/or thermal curing agents, the silane coupling agent etc. that adds as required.
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.If use this upper and lower conductive material, then can reliably inter-electrode conductive be connected.
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.
As above-mentioned electrically conductive microparticle, the electrically conductive microparticle etc. such as defining conductive metal layer on the surface of Metal Ball, resin particle can be used.Wherein, from relying on the excellent resilience of resin particle, and can realize when not damaging transparency carrier etc. that conduction connects in set out, preferably define the electrically conductive microparticle of conductive metal layer on the surface of resin particle.
Use sealant for liquid crystal dripping process of the present invention or upper and lower conductive material of the present invention and the liquid crystal display cells made is one of the present invention.
As the method manufacturing liquid crystal display cells of the present invention, the method etc. such as with following operation can be enumerated: by the coating such as serigraphy, divider coating sealant for liquid crystal dripping process of the present invention on one in 2 substrates with ito thin film etc., form the operation of rectangular seal pattern; Being dripped by the fine droplet of liquid crystal is coated in the whole frame of seal pattern, makes the operation of another substrate overlap under vacuo; The light such as sealant for liquid crystal dripping process irradiation ultraviolet radiation of the present invention are made to the operation of sealant precuring; And the sealant after precuring is heated and makes the operation of its main solidification.
Invention effect
According to the present invention, a kind of excellent in adhesion and sealant for liquid crystal dripping process that the moisture-penetrability of solidfied material is low can be provided.In addition, according to the present invention, can provide a kind of and use this sealant for liquid crystal dripping process and the conductive material up and down made and liquid crystal display cells.
Embodiment
Below, enumerate embodiment and in further detail the present invention is described, but the present invention is not merely defined in these embodiments.
(embodiment 1)
Utilize planetary stirring machine (THINKY Inc., " あ わ と り Practice Taro "), using dicyclopentadiene phenolic type epoxy resin (the DIC Inc. as curable resin, " EPICLONHP-7200 ") 5 weight portions, as bisphenol type epoxy methacrylate 95 weight portion of (methyl) acrylic resin, as diphenyl (2,4,6-trimethoxybenzoy) phosphine oxide (the BASFJapan Inc. of optical free radical polymerization initiator, " LucirinTPO ") 1.5 weight portions, as acid dihydrazide (the Japanese Finechem Inc. of thermal curing agents, " MDH ") 1.1 weight portions, as 2-undecyl imidazole 0.2 weight portion of curing accelerator, as talcum (the Japanese talcum Inc. of filler, " NANOACED-600F ") 10 weight portions, and as 3-glycidoxypropyltrime,hoxysilane (the CHISSO Inc. of silane coupling agent, " S510 ") 1.5 weight portions mixing after, utilize three-roller to mix further, prepare the sealant for liquid crystal dripping process of embodiment 1 thus.
(embodiment 2 ~ 15, comparative example 1 ~ 9)
Use each material of the match ratio recorded in table 1 ~ 3, in addition, operate similarly to Example 1, prepare the sealant for liquid crystal dripping process of embodiment 2 ~ 15, comparative example 1 ~ 9.
< evaluates >
Following evaluation has been carried out to the sealant for liquid crystal dripping process obtained in embodiment and comparative example.Show the result in table 1 ~ 3.
(1) coating
The each sealant for liquid crystal dripping process obtained in each embodiment and each comparative example is filled in the syringe (Musashi Engineering Inc., " PSY-10E ") of point adapted, carries out deaeration process.Then, use divider (Musashi Engineering Inc., " SHOTMASTER300 "), one in the transparent electrode substrate of 2 band ito thin films is coated with sealant in the mode depicting rectangular frame.Then, the fine droplet of coating TN liquid crystal (CHISSO Inc., " JC-5001LA ") of dripping with liquid crystal dripping device, to fit another transparency carrier with vacuum forming apparatus under the decompression of 5Pa.With metal halide lamp, 3000mJ/cm is irradiated to the unit after laminating 2ultraviolet, then, at 120 DEG C heat 60 minutes, make sealant heat curing thus, for each sealant, respectively make 100 liquid crystal display cells.Observe the liquid crystal display cells of gained, by the liquid crystal display cells occurring to break at sealing be that the situation of 0 is set to " ◎ ", the situation that is 1 ~ 3 by the liquid crystal display cells occurring to break at sealing is set to "○", the situation that is 4 ~ 10 by the liquid crystal display cells that broken string occurs at sealing is set to " △ ", by the liquid crystal display cells that broken string occurs at sealing is is that the situation of more than 11 is set to "×", thus coating is evaluated.
(2) cementability
The silicon dioxide spacer thing (ponding chemical industrial company system, " SI-H055 ") of 1 % by weight is coordinated in each sealant for liquid crystal dripping process obtained in embodiment and comparative example, 2 are dropped in in the alkali glass test film (30 × 40mm) of ito film with small drop, and to fit another glass test sheet with crosswise thereon, with metal halide lamp, 3000mJ/cm is irradiated to gained laminating thing 2ultraviolet, then at 120 DEG C heat 60 minutes, obtain adhesive test sheet thus.This adhesive test sheet the fixture configured up and down and carry out tension test (5mm/sec).The measured value (kgf) obtained is amassed (cm divided by sealing coated sections 2) value that obtains is 60kgf/cm 2above average evaluation is " ◎ ", will be 40kgf/cm 2above and less than 60kgf/cm 2average evaluation be "○", will be 10kgf/cm 2above and less than 40kgf/cm 2average evaluation be " △ ", by less than 10kgf/cm 2average evaluation be "×", thus cementability to be evaluated.
(3) moisture-proof of solidfied material
In level and smooth mold release film, utilize coating machine that each sealant for liquid crystal dripping process obtained in embodiment and comparative example is applied to thickness 200 ~ 300 μm.Then, metal halide light irradiation 3000mJ/cm is utilized 2ultraviolet after, at 120 DEG C heat 60 minutes, obtain moisture permeability mensuration film thus.Utilize the method for the moisture permeability test method (agar diffusion method) of the water vapor proof barrier packaging material according to JISZ0208, make moisture permeability test cup, the moisture permeability mensuration film of gained is installed, and puts in the baking oven of temperature 80 DEG C of humidity 90%RH, thus determine moisture permeability.By the value of the moisture permeability of gained lower than 50g/m 2the situation of 24 hours is set to " ◎ ", will will be 50g/m 2more than 24 hours and lower than 70g/m 2the situation of 24 hours is set to "○", will will be 70g/m 2more than 24 hours and lower than 100g/m 2the situation of 24 hours is set to " △ ", will will be 100g/m 2the situation of more than 24 hours is set to "×", thus have rated the moisture-proof of solidfied material.
(4) display performance (the color spot evaluation of the liquid crystal display cells after the laggard row cutting of hot and humid lower keeping) of liquid crystal display cells
The sealant for liquid crystal dripping process obtained in each embodiment and comparative example is filled in the syringe (Musashi Engineering Inc., " PSY-10E ") of point adapted, has carried out deaeration process.Then, with divider (Musashi Engineering Inc., " SHOTMASTER300 "), be coated with sealant with in the transparent electrode substrate of ito thin film in the mode describing rectangular frame at 2.Then, the fine droplet of coating TN liquid crystal (CHISSO Inc., " JC-5001LA ") of dripping with liquid crystal dripping device, to fit another transparency carrier with vacuum forming apparatus under the decompression of 5Pa.Metal halide lamp is used to irradiate 3000mJ/cm to the unit after laminating 2ultraviolet, then at 120 DEG C heat 60 minutes, make sealant heat curing thus, for each sealant, respectively make 5 liquid crystal display cells.After the liquid crystal display cells of gained is preserved 36 hours under the environment of temperature 80 DEG C, humidity 90%RH, implement the voltage driven of AC3.5V, the sealant periphery of visualization medium tone (original text: Zhong Inter Tone).The average evaluation of color spot will be can't see completely for " ◎ " at sealant periphery, slightly can see that compared with the average evaluation of light color spot be "○", being " △ " compared with the average evaluation of heavy colour spot clearly by existence, just seeing that the average evaluation of color spot is "×" by when not being energized.
Utilizability in industry
According to the present invention, a kind of excellent in adhesion and sealant for liquid crystal dripping process that the moisture-penetrability of solidfied material is low can be provided.In addition, according to the present invention, can provide a kind of and use this sealant for liquid crystal dripping process and the conductive material up and down made and liquid crystal display cells.

Claims (7)

1. a sealant for liquid crystal dripping process, is characterized in that, containing curable resin, radical polymerization initiator and/or thermal curing agents, wherein,
Described curable resin contains epoxy resin and (methyl) acrylic resin,
The content of the described epoxy resin in described curable resin 100 weight portion is 5 ~ 70 weight portions, and described epoxy resin contains dicyclopentadiene phenolic type epoxy resin more than 20 % by weight.
2. sealant for liquid crystal dripping process according to claim 1, is characterized in that, containing curing accelerator.
3. sealant for liquid crystal dripping process according to claim 2, is characterized in that, curing accelerator contains imidazoles system curing accelerator and/or mercaptan system curing accelerator.
4. the sealant for liquid crystal dripping process according to any one of claims 1 to 3, is characterized in that, (methyl) acrylic resin contains dicyclopentadiene phenolic type epoxy (methyl) acrylate.
5. the sealant for liquid crystal dripping process according to any one of Claims 1 to 4, is characterized in that, containing opacifier.
6. a conductive material about, is characterized in that, containing the sealant for liquid crystal dripping process according to any one of Claims 1 to 5 and electrically conductive microparticle.
7. a liquid crystal display cells, is characterized in that, uses the sealant for liquid crystal dripping process according to any one of claim 1 ~ 5 or upper and lower conductive material according to claim 6 to manufacture.
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