CN101836157B - Sealing material for liquid crystal dispensing method, transfer material and liquid crystal displays - Google Patents
Sealing material for liquid crystal dispensing method, transfer material and liquid crystal displays Download PDFInfo
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- CN101836157B CN101836157B CN2008801125524A CN200880112552A CN101836157B CN 101836157 B CN101836157 B CN 101836157B CN 2008801125524 A CN2008801125524 A CN 2008801125524A CN 200880112552 A CN200880112552 A CN 200880112552A CN 101836157 B CN101836157 B CN 101836157B
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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
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Abstract
The invention aims at providing a sealing material for liquid crystal dispensing method which dose not contaminate a liquid crystal when used in the production of liquid crystal displays by the dispenser method even if a component of the sealing material is dissolved in the liquid crystal and which makes it possible to produce liquid crystal displays excellent in display quality and reliability. A sealing material for liquid crystal dispensing method which contains both a curable resin and a photo-radical initiator, wherein the photo-radical initiator is one which does not precipitate from a liquid crystal as tested by dissolving the initiator completely in the liquid crystal in a concentration of 4wt% at 120 DEG C and allowing the resulting solution to stand at -20 DEG C for 144 hours and which exhibits an absorptivity of 50mL/gm or above as determined at 405nm in a solvent.
Description
Technical field
When the present invention relates to make liquid crystal display cells with the technology of dripping, even the stripping of sealant composition in liquid crystal, also can prevent to cause liquid crystal pollution, and the technology of can making under the liquid crystal drop of display quality and the liquid crystal display cells of reliability excellence is used sealant.The invention still further relates to conductive material and liquid crystal display cells up and down.
Background technology
In the manufacturing approach of existing liquid crystal display cells; At first; 2 arbitrary sides that have the transparency carrier of electrode; Utilize serigraphy to form the seal pattern that is provided with the liquid crystal injecting port that has used thermosetting encapsulants, under 60～100 ℃, carry out preroast again, make the solvent seasoning in the sealant.Then, make 2 substrates across dividing plate opposed and alignment fit, 110～220 ℃ of following hot pressing 10～90 minutes, behind near the gap the adjustment sealing, in baking oven,, make sealant curing itself in 110～220 ℃ of heating 10～120 minutes down.At last, inject liquid crystal, use sealing compound encapsulated liquid crystals inlet at last, make liquid crystal display cells from liquid crystal injecting port.
But; In this manufacturing approach, have following problems: the distortion that produces owing to heating causes that position deviation, gap are uneven, the connecting airtight property reduction of sealant and substrate etc., perhaps residual solvent generation thermal expansion and produce bubble and cause the gap uneven or seal amplitude difference; Perhaps the sealing and curing required time is long; Perhaps the prebake curing process is complicated, and the time that perhaps can be used as sealant because of solvent evaporates shortens, and it is consuming time etc. perhaps to inject liquid crystal.Especially in large-scale liquid crystal watch showing device in recent years, injecting liquid crystal very consuming time is serious problem.
To the problems referred to above, studied the manufacturing approach of the liquid crystal display cells that is called as the technology of dripping, the said technology of dripping is used the sealant that is made up of curable resin composition.In the technology of dripping, at first, on of 2 transparency carriers that have an electrode, form rectangular seal pattern through serigraphy etc.Then, under the uncured state of sealant, liquid crystal droplet is dripped and coats in the whole frame of transparency carrier, overlapping with another transparency carrier at once, again the sealant irradiation ultraviolet radiation is solidified temporarily.Then, heating when liquid crystal is annealed as required, and then be cured, make liquid crystal display cells.If adhesive substrates under reduced pressure then can be with high efficiency system liquid making crystal display element.Expectation this technology of dripping from now on becomes the main flow of LCD device preparation method.
Use sealant as the liquid crystal drop that is used to the technology of dripping is technological down, owing to can obtain high adhesiveness, so use epoxy resin usually as the thermosetting composition.But, utilize in the liquid crystal display cells that the technology of dripping makes, have to be easy to generate to result from the disorderly color spot of liquid crystal aligning etc. and show bad problem.Reason is that in the operation of the technology of dripping, the liquid crystal drop of its uncured state technology down directly contacts liquid crystal with sealant, and before the sealant full solidification, the stripping of sealant composition is in liquid crystal.
In order to address the above problem, for example patent documentation 1, patent documentation 2 disclose to use technology under the liquid crystal drop of the low composition of liquid crystal dissolubility have been used sealant.Above-mentioned sealant is because composition is insoluble from liquid crystal, so do not produce liquid crystal pollution.But, even state sealant in the use and utilize the technology of dripping to make under the situation of liquid crystal display cells, also cause liquid crystal pollution in fact sometimes, can't make that color spot is few, the liquid crystal display cells of high quality images.
Patent documentation 1: No. the 3583326th, patent
Patent documentation 2: TOHKEMY 2001-133794 communique
Summary of the invention
The object of the present invention is to provide when making liquid crystal display cells with the technology of dripping; Even the stripping of sealant composition is in liquid crystal; Also can prevent to cause liquid crystal pollution, and the technology of can making under the liquid crystal drop of the excellent liquid crystal display cells of display quality and reliability is used sealant.
The present invention is a kind of technological down sealant of using of liquid crystal drop that contains curable resin and optical free radical initiating agent; Said optical free radical initiating agent under 120 ℃ with the concentration of 4 weight % in liquid crystal fully after the dissolving; Do not separate out from said liquid crystal after 144 hours-20 ℃ of held, the absorptivity under the 405nm that said optical free radical initiating agent is measured in solvent is more than the 50mL/gcm again.
The inventor etc. concentrate on studies; The result finds as being used for technological optical free radical initiating agent with sealant under the liquid crystal drop; Through using the optical free radical initiating agent high to the liquid crystal dissolubility; Promptly can obtain to prevent causing liquid crystal pollution, and can realize that the liquid crystal drop of the liquid crystal display cells that display quality and reliability are excellent is technological down and use sealant, thereby accomplish the present invention.
Liquid crystal drop of the present invention down technology contains the optical free radical initiating agent with sealant, and this optical free radical initiating agent fully after the dissolving, is not being separated out from said liquid crystal after 144 hours-20 ℃ of held in liquid crystal with the concentration of 4 weight % under 120 ℃ again.
At present, under liquid crystal drop the technology with sealant in, use the optical free radical initiating agent low to the liquid crystal dissolubility in order to prevent liquid crystal pollution.But, even the problem of using above-mentioned optical free radical initiating agent also can't fully prevent liquid crystal pollution is arranged.
The inventor can prevent liquid crystal pollution through using the optical free radical initiating agent high to the liquid crystal dissolubility.
Be limited to 50mL/gcm under the absorptivity at the 405nm place that above-mentioned optical free radical initiating agent is measured in solvent.Absorptivity is during less than 50mL/gcm, and the sealant cures of utilizing luminous ray to carry out is insufficient.The preferred lower limit of above-mentioned absorptivity is 70mL/gcm.Above-mentioned absorptivity has high and reactive more high more tendency, so there is not the special upper limit.
Need to prove, as above-mentioned solvent, as long as can dissolve above-mentioned optical free radical initiating agent and under the absorbing wavelength of measuring, not have extinction, not special the qualification.Particularly, can use acetonitrile, methyl alcohol etc.
The preferred not absorbing wavelength of above-mentioned optical free radical initiating agent is the above light of 500nm.Above-mentioned optical free radical initiating agent absorbs the light time of the above wavelength of 500nm, under amber light, also can react, and the operability of sealant is poor sometimes.
In the above-mentioned optical free radical initiating agent, the preferred upper limit of fusing point is 85 ℃.When the fusing point of above-mentioned optical free radical initiating agent surpasses 85 ℃, make its under 120 ℃ with the concentration of 4 weight % in liquid crystal fully after the dissolving, again-20 ℃ of held after 144 hours, the optical free radical initiating agent is separated out from liquid crystal, and liquid crystal pollution takes place sometimes.The fusing point of above-mentioned optical free radical initiating agent more preferably on be limited to 80 ℃.As the fusing point lower limit of above-mentioned optical free radical initiating agent, not special qualification the, but under liquid crystal drop in the technology, the operation that has uncured at normal temperatures sealant to contact with liquid crystal in order to be suppressed at stripping in the liquid crystal as far as possible, is limited to 30 ℃ under preferably.
As above-mentioned optical free radical initiating agent, for example can enumerate oxime ester compound.Particularly, for example can enumerate 1 of following formula (1) expression, 2-acetyl caproyl 1-[4-(thiophenyl)-2-(O-benzene first oxime)] etc.As the commercially available article of the oxime ester compound of following formula (1) expression, for example can enumerate IRGACUREOXE01 (Chiba refine corporate system) etc.
Down technology is with the content of above-mentioned optical free radical initiating agent in the sealant as liquid crystal drop of the present invention, and not special qualification the, but be limited to 0.2 weight % under preferred is limited to 10 weight % on preferably.The content of above-mentioned optical free radical initiating agent is during less than 0.2 weight %, solidifies insufficiently sometimes, but when surpassing 10 weight %, produces liquid crystal pollution sometimes, and perhaps the bonding force for substrate reduces.Above-mentioned optical free radical initiator content more preferably be limited to 1.0 weight % down, be limited to 5.0 weight % on more preferably.
Liquid crystal drop of the present invention technology down contains curable resin with sealant.
As above-mentioned curable resin, not special the qualification, but preferably have (methyl) acryloyl group and epoxy radicals.Through having above-mentioned functional group, can be used as the two steps curing of carrying out photocuring, heat curing when technology is with sealant under the existing liquid crystal drop.
In addition, in the above-mentioned curable resin, have under the situation of (methyl) acryloyl group and epoxy radicals, epoxy radicals is 40 moles of % with respect to the preferred upper limit of the ratio of the total amount of (methyl) acryloyl group and epoxy radicals.When surpassing 40 moles of %, the dissolubility raising to liquid crystal causes producing at panel the pollution of spot sometimes.Be limited to 30 moles of % more preferably.
As above-mentioned curable resin; Not special the qualification, polyurethane (methyl) acrylic ester that for example can enumerate ester compounds that (methyl) acrylic acid and the compound reaction with hydroxyl are obtained, make (methyl) acrylic acid epoxy ester that (methyl) acrylic acid and epoxy compound reaction obtain, isocyanates and (methyl) acrylic acid derivative with hydroxyl is reacted obtain etc.
React the ester compounds that obtains as above-mentioned making (methyl) acrylic acid and compound with hydroxyl; Not special the qualification; Compound as simple function; For example can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid Lauryl Ester, (methyl) stearyl acrylate base ester, (methyl) IBOA, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methoxyl ethyl ester, methoxyl monoethylene glycol (methyl) acrylic ester, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) benzyl acrylate, ethyl carbitol (methyl) acrylic ester, (methyl) acrylic acid phenoxy ethyl, phenoxy group diglycol (methyl) acrylic ester, phenoxy group polyglycol (methyl) acrylic ester, methoxy poly (ethylene glycol) (methyl) acrylic ester, (methyl) acrylic acid 2; 2; 2-tetrafluoro ethyl ester, (methyl) acrylic acid 2; 2; 3; 3-tetrafluoro propyl ester, (methyl) acrylic acid 1H; 1H, 5H-octafluoro pentyl ester, (methyl) acrylic acid polyurethane, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid n-octyl, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) acrylic acid myristyl ester, (methyl) acrylic acid 2-butoxy ethyl ester, (methyl) acrylic acid 2-phenoxy ethyl, (methyl) acrylic acid dicyclo dialkylene ester, (methyl) isodecyl acrylate, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid dimethylamino ethyl ester, 2-(methyl) acryloxy ethyl succinic acid, 2-(methyl) acryloxy ethyl hexahydrobenzene dioctyl phthalate, phthalic acid 2-(methyl) acryloxy ethyl 2-hydroxy propyl ester, (methyl) glycidyl acrylate, phosphoric acid 2-(methyl) acryloxy ethyl ester etc.
In addition; Above-mentioned making (methyl) acrylic acid reacts in the ester compounds that obtains with the compound with hydroxyl; Ester compounds as two senses; Not special the qualification; For example can enumerate 1; 4-butylene glycol two (methyl) acrylic ester, 1; 3-butylene glycol two (methyl) acrylic ester, 1; 6-hexanediol two (methyl) acrylic ester, 1; 9-nonanediol two (methyl) acrylic ester, 1; 10-decanediol two (methyl) acrylic ester, 2-normal-butyl-2-ethyl-1, ammediol two (methyl) acrylic ester, DPG two (methyl) acrylic ester, tripropylene glycol two (methyl) acrylic ester, polypropylene glycol two (methyl) acrylic ester, ethylene glycol bisthioglycolate (methyl) acrylic ester, diglycol two (methyl) acrylic ester, tetraethylene glycol two (methyl) acrylic ester, polyglycol two (methyl) acrylic ester, epoxypropane addition bisphenol-A two (methyl) acrylic ester, oxirane addition bisphenol-A two (methyl) acrylic ester, oxirane addition Bisphenol F two (methyl) acrylic ester, dihydroxymethyl bicyclopentadiene two (methyl) acrylic ester, 1,3-butadiene two (methyl) acrylic ester, neopentyl glycol two (methyl) acrylic ester, the different hydrogen urea acid of oxirane modification two (methyl) acrylic ester, 2-hydroxy-3-methyl acryloxy propyl group two (methyl) acrylic ester, carbonic ester glycol two (methyl) acrylic ester, PTMEG two (methyl) acrylic ester, polyester-diol two (methyl) acrylic ester, polycaprolactone glycol two (methyl) acrylic ester, polybutadiene diol two (methyl) acrylic ester etc.
In addition; Above-mentioned making (methyl) acrylic acid reacts in the ester compounds that obtains with the compound with hydroxyl; As the ester compounds more than the trifunctional; Not special the qualification for example can be enumerated pentaerythrite three (methyl) acrylic ester, trimethylolpropane tris (methyl) acrylic ester, epoxypropane addition trimethylolpropane tris (methyl) acrylic ester, oxirane addition trimethylolpropane tris (methyl) acrylic ester, caprolactone modification trimethylolpropane tris (methyl) acrylic ester, the different hydrogen urea acid of oxirane addition three (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester, two trimethylolpropane four (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, glycerine three (methyl) acrylic ester, epoxypropane addition glycerine three (methyl) acrylic ester, three (methyl) acryloxy ethyl phosphonic acid ester etc.
(methyl) acrylic acid epoxy ester that reaction obtains as above-mentioned making (methyl) acrylic acid and epoxy compound, not special the qualification for example can be according to conventional methods reacted (methyl) acrylic acid and epoxy resin and obtained in the presence of base catalyst.
The epoxy compound that is used for the raw material of synthetic above-mentioned (methyl) acrylic acid epoxy ester; As commercially available epoxy compound; For example can enumerate the how pure type epoxy resin of alkyl, YR-450, YR-207 (be Dongdu and change into corporate system), Eplead (エ Port リ one De) PB modified rubber type epoxy resin such as (Daicel chemical company systems), Denacol EX-147 glycidyl ester compounds such as (the rapids fine chemistry industry corporate systems of length), Epicote YL-7000 bisphenol A-type episulfide resins such as (japan epoxy resin corporate systems), other YDC-1312, YSLV-80XY, YSLV-90CR (be Dongdu and change into corporate system), XAC4151 (Asahi Chemical Industry's corporate system), Epicote1031, Epicote 1032 (being the japan epoxy resin corporate system), EXA-7120 (Japanese black liquid corporate system greatly), TEPIC (producing chemical company's system daily) etc. such as resorcinol type epoxy resin that Epicote (エ ピ コ one ト) 828EL, Epicote 1004 bisphenol A type epoxy resins such as (being the japan epoxy resin corporate system), Epicote 806, bisphenol E-type epoxy resin such as Epicote4004 bisphenol f type epoxy resin, R-710 such as (being the japan epoxy resin corporate system), Epiclon EXA1514 (big Japanese black liquid corporate system) wait bisphenol-s epoxy resin, RE-810NM (Japanese chemical drug corporate system) 2,2 '-diallyl bisphenol type epoxy resin of etc.ing, Epiclon (エ ピ Network mouth Application) EXA7015 (big Japanese black liquid corporate system) to wait A Hydrogenated Bisphenol A type epoxy resin, EP-4000S (rising sun electrification corporate system) to wait epoxypropane addition bisphenol A type epoxy resin, EX-201 (long rapids fine chemistry industry corporate system) to wait, Epicote YX-4000H (japan epoxy resin corporate system) biphenyl type epoxy resin of etc.ing, epoxy resin such as type such as YSLV-50TE (Dongdu the changes into corporate system) thioether of etc.ing, ether type epoxy such as YSLV-80DE (Dongdu the changes into corporate system) biphenyl of etc.ing, EP-4088S dicyclopentadiene-type epoxy resin such as (rising sun electrification corporate systems), Epiclon HP4032, Epiclon EXA-4700 (being the black liquid corporate system of big Japan) the naphthalene type epoxy resin of etc.ing, EpiclonN-770 phenolic resin varnish type epoxy resins such as (Japanese black liquid corporate systems greatly), Epiclon N-670-EXP-S o-cresol phenolic epoxy varnish such as (Japanese black liquid corporate systems greatly), Epiclon HP7200 bicyclopentadiene phenolic resin varnish type epoxy resins such as (Japanese black liquid corporate systems greatly), NC-3000P biphenyl phenolic resin varnish type epoxy resins such as (Japanese chemical drug corporate systems), ESN-165S naphthol novolacs such as (Dongdu change into corporate system) varnish type epoxy resin, Epicote 630 (japan epoxy resin corporate system), Epiclon430 (Japanese black liquid corporate system greatly), TETRAD-X glycidyl group amine type epoxy resin such as (gas chemical company of Mitsubishi systems), ZX-1542 (Dongdu changes into corporate system), Epiclon 726 (passable Japanese black liquid corporate system), Epolight (エ ピ ラ イ ト) 80MFA (chemical company of common prosperity society system), Denacol (デ Na コ one Le) EX-611, (the rapids fine chemistry industry corporate system of Chang).
In addition; As the commercially available article of above-mentioned (methyl) acrylic acid epoxy ester, for example can enumerate Ebecryl (エ ベ Network リ Le) 3700, Ebecryl 3600, Ebecryl 3701, Ebecryl 3703, Ebecryl3200, Ebecryl 3201, Ebecryl 3702, Ebecryl 3412, Ebecryl 860, EbecrylRDX63182, Ebecryl 6040, Ebecryl 3800 (being Daicel UCB. S.A. (BE) Bruxelles Belgium system), EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD, EMA-1020 (being Xin Zhong village chemical industrial company system), Epoxyester (エ Port キ シ エ ス テ Le) M-600A, Epoxyester 40EM, Epoxyester 70PA, Epoxyester 200PA, Epoxyester 80MFA, Epoxyester 3002M, Epoxyester 3002A, Epoxyester 1600A, Epoxyester 3000M, Epoxyester 3000A, Epoxyester 200EA, Epoxyester 400EA (being chemical company of common prosperity society system), Denacolacrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911 (being long rapids fine chemistry industry corporate system) etc.
As above-mentioned polyurethane (methyl) acrylic ester that isocyanates and (methyl) acrylic acid derivative reaction with hydroxyl are obtained; Not special the qualification; For example can enumerate the compound that has 2 NCOs with respect to 1 equivalent; (methyl) acrylic acid derivative that has hydroxyl with 2 equivalents is as catalyzer, and in the presence of the tin based compound, makes its reaction and obtain.
As the isocyanates that becomes above-mentioned polyurethane (methyl) acrylic ester raw material; Not special the qualification; For example; Can enumerate different fluorine ketone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl methane-4; 4 '-diisocyanate (MDI), hydrogenation MDI, gather MDI, 1; 5-naphthalene diisocyanate, norbornene alkyl diisocyanate, tolidine diisocyanate, eylylene diisocyanate (XDI), hydrogenation XDI, LDI, triphenylmethane triisocyanate, three (NCO phenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate etc.
In addition; As above-mentioned isocyanates, for example also can use the chain elongation that obtains by polyvalent alcohols such as monoethylene glycol, glycerine, sorbierite, trimethylolpropane, (gathering) propylene glycol, carbonic ester glycol, PTMEG, polyester-diol, polycaprolactone glycol and excessive isocyanate reaction isocyanate compound.
As above-mentioned (methyl) acrylic acid derivative with hydroxyl; Not special the qualification; For example can enumerate commercially available article such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester or monoethylene glycol, propylene glycol, 1; Ammediol, 1; 3-butylene glycol, 1, (methyl) acrylic acid epoxy esters such as list (methyl) acrylic ester of trihydroxy alcohols such as the list of dibasic alcohol such as 4-butylene glycol, polyglycol (methyl) acrylic ester, trimethylolethane, trimethylolpropane, glycerine or two (methyl) acrylic ester, bisphenol A modified epoxy radicals (methyl) acrylic ester etc.
In addition; As the commercially available article of above-mentioned polyurethane (methyl) acrylic ester, for example can enumerate M-1100, M-1200, M-1210, M-1600 (being East Asia Synesis Company system), Ebecryl (エ ベ Network リ Le) 230, Ebecryl 270, Ebecryl 4858, Ebecryl 8402, Ebecryl8804, Ebecryl 8803, Ebecryl 8807, Ebecryl 9260, Ebecryl 1290, Ebecryl 5129, Ebecryl 4842, Ebecryl 210, Ebecryl 4827, Ebecryl 6700, Ebecryl 220, Ebecryl2220 (being Daicel UCB. S.A. (BE) Bruxelles Belgium system), Artresin (ア one ト レ ジ Application) UN-9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (be root and attend industrial group's 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 Xin Zhong village chemical industrial company system), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I etc.
In addition, liquid crystal drop of the present invention is technological down to have at least 1 hydrogen bond property functional group to the liquid crystal stripping in preferred 1 molecule of above-mentioned curable resin with sealant composition before curing in order further to suppress.
As above-mentioned hydrogen bond property functional group; Not special the qualification; For example can enumerate-OH base ,-the SH base ,-NHR base (R representes aromatic series or aliphatic hydrocarbon and derivant thereof) ,-the COOH base ,-functional group such as NHOH base and be present in intramolecular-NHCO-,-NH-,-CONHCO-,-residues such as NH-NH-; Wherein, the easy property from importing is preferably-the OH base.
As having at least 1 hydrogen bond property functional group in above-mentioned 1 molecule and having the curable resin of (methyl) acryloyl group, for example can enumerate above-mentioned polyurethane (methyl) acrylic ester or epoxy radicals (methyl) acrylic ester etc.
Liquid crystal drop of the present invention is technological down with in the sealant, the uncured residual component when solidifying in order to reduce as far as possible, and above-mentioned curable resin is preferably the compound that has reactive base more than 2 in 1 molecule.
In addition, as above-mentioned curable resin, can use the compound that has different reactive functional groups in 1 molecule.As above-claimed cpd, for example can enumerate the compound that has at least one epoxy radicals and (methyl) acryloyl group in 1 molecule respectively.
As having the compound of at least 1 epoxy radicals in above-mentioned 1 molecule respectively with (methyl) acryloyl group; For example, the compound that a part of epoxy radicals that makes the compound with 2 above epoxy radicals and the reaction of (methyl) acrylic acid obtain or make compound that the above isocyanates of two senses and (methyl) acrylic acid derivative with hydroxyl and epoxy prapanol reaction obtain etc.
The compound that a part of epoxy radicals that makes above-mentioned compound with 2 above epoxy radicals and the reaction of (methyl) acrylic acid obtain for example can make epoxy resin and (methyl) acrylic acid in the presence of base catalyst, react according to conventional methods and obtain.
As above-mentioned compound with 2 above epoxy radicals; For example can enumerate Epicote 828EL, Epicote 1004 bisphenol A type epoxy resins such as (being the japan epoxy resin corporate system), Epicote 806, bisphenol E-type epoxy resin such as Epicote 4004 bisphenol f type epoxy resin, R-710 such as (being the japan epoxy resin corporate system), Epiclon EXA1514 bisphenol-s epoxy resins such as (big Japanese black liquid corporate systems), RE-810NM 2,2 '-propenyl bisphenol A type epoxy resins such as (Japanese chemical drug corporate systems), Epiclon EXA7015 A Hydrogenated Bisphenol A type epoxy resin such as (big Japanese black liquid corporate systems), EP-4000S epoxypropane addition bisphenol A type epoxy resins such as (rising sun electrification corporate systems), EX-201 resorcinol type epoxy resin such as (long rapids fine chemistry industry corporate systems), Epicote YX-4000H biphenyl type epoxy resins such as (japan epoxy resin corporate systems), YSLV-50TE thioethers such as (Dongdu change into corporate system) type epoxy resin, YSLV-80DE biphenyl such as (Dongdu change into corporate system) ether type epoxy, EP-4088S dicyclopentadiene-type epoxy resin such as (rising sun electrification corporate systems), Epiclon HP4032, EpiclonEXA-4700 naphthalene type epoxy resin such as (being the black liquid corporate system of big Japan), Epiclon N-770 phenolic resin varnish type epoxy resins such as (big Japanese black liquid corporate systems), Epiclon N-670-EXP-S o-cresol phenolic epoxy varnish such as (big Japanese black liquid corporate systems), Epiclon HP7200 bicyclopentadiene phenolic resin varnish type epoxy resins such as (big Japanese black liquid corporate systems), NC-3000P biphenyl phenolic resin varnish type epoxy resins such as (Japanese chemical drug corporate systems), ESN-165S naphthol novolacs such as (Dongdu change into corporate system) varnish type epoxy resin, Epicote 630 (japan epoxy resin corporate system), Epiclon 430 (big Japanese black liquid corporate system), TETRAD-X glycidyl group amine type epoxy resin such as (gas chemical company of Mitsubishi systems), ZX-1542 (Dongdu changes into corporate system), Epiclon 726 (Da Japanese black liquid corporate system), Epolight 80MFA (chemical company of common prosperity society system), Denacol (デ Na コ one Le) EX-611 alkyl polyols type epoxy resin such as (Chang rapids fine chemistry industry corporate systems), YR-450, YR-207 (be Dongdu and change into corporate system), Eplead PB modified rubber type epoxy resin such as (Daicel chemical company systems), Denacol EX-147 glycidyl ester compounds such as (Chang rapids fine chemistry industry corporate systems), Epicote YL-7000 bisphenol A-type episulfide resins such as (japan epoxy resin corporate systems), YDC-1312 in addition, YSLV-80XY, YSLV-90CR (be Dongdu and change into corporate system), XAC4151 (Asahi Chemical Industry's corporate system), Epicote 1031, Epicote 1032 (being the epoxy resin corporate system), EXA-7120 (big Japanese black liquid corporate system), TEPIC (daily output chemical company system) etc.
The commercially available article of the compound that obtains as a part of epoxy radicals of above-mentioned compound with 2 above epoxy radicals and the reaction of (methyl) acrylic acid for example can be enumerated Ebecryl 1561 (Daicel UCB. S.A. (BE) Bruxelles Belgium system) etc.
Through making the isocyanates more than above-mentioned two senses react the compound that obtains with (methyl) acrylic acid derivative with hydroxyl and epoxy prapanol; For example can obtain as follows: the compound that has 2 NCOs with respect to 1 equivalent; (methyl) acrylic acid derivative with hydroxyl and epoxy prapanol with 1 equivalent of respectively doing for oneself are catalyzer, it is reacted in the presence of the tin based compound and obtain.
As the isocyanates more than above-mentioned two senses; Not special the qualification; For example can enumerate different fluorine ketone diisocyanate, 2; 4-toluene diisocyanate, 2; 6-toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl methane-4, gather MDI, 1,5-naphthalene diisocyanate, norbornane isocyanates, tolidine diisocyanate, eylylene diisocyanate (XDI), hydrogenation XDI, LDI, triphenylmethane triisocyanate, three (NCO phenyl) thiophosphate, tetramethylxylene diisocyanate, 1 at 4 '-diisocyanate (MDI), hydrogenation MDI; 6,10-undecane triisocyanate etc.
In addition; As the isocyanates more than above-mentioned two senses, for example also can make chain elongation that polyalcohols such as spent glycol, glycerine, sorbierite, trimethylolpropane, (gathering) propylene glycol, carbonic ester glycol, PTMEG, polyester-diol, polycaprolactone glycol and excessive isocyanate reaction obtain isocyanate compound.
As above-mentioned (methyl) acrylic acid derivative with hydroxyl; Not special the qualification; For example can enumerate commercially available article or monoethylene glycol, the propylene glycol, 1 of (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester etc.; Ammediol, 1; 3-butylene glycol, 1, epoxy radicals (methyl) acrylic ester such as list (methyl) acrylic ester of trihydroxy alcohols such as the list of dibasic alcohol such as 4-butylene glycol, polyglycol (methyl) acrylic ester, trimethylolethane, trimethylolpropane, glycerine or two (methyl) acrylic ester, bisphenol A modified epoxy radicals (methyl) acrylic ester etc.
In addition, sealant of the present invention can also contain the compound with epoxy radicals except that containing above-mentioned curable resin with (methyl) acryloyl group.
As above-mentioned compound with epoxy radicals, not special the qualification for example can be enumerated epoxy chloropropionate alkane derivatives, ring type aliphatic epoxy resin, reacted the compound that obtains etc. by isocyanates and epoxy prapanol.
As above-mentioned epoxy chloropropionate alkane derivatives; For example can enumerate Epicote 828EL, Epicote1004 bisphenol A type epoxy resins such as (being the japan epoxy resin corporate system), Epicote 806, Epicote4004 bisphenol f type epoxy resins such as (being the japan epoxy resin corporate system), Epiclon EXA1514 bisphenol-s epoxy resins such as (big Japanese black liquid corporate systems), RE-810NM 2,2 '-diallyl bisphenol type epoxy resin such as (Japanese chemical drug corporate systems), Epiclon EXA7015 A Hydrogenated Bisphenol A type epoxy resin such as (big Japanese black liquid corporate systems), EP-4000S epoxypropane addition bisphenol A type epoxy resins such as (rising sun electrification corporate systems), EX-201 resorcinol type epoxy resin such as (long rapids fine chemistry industry corporate systems), Epicote YX-4000H biphenyl type epoxy resins such as (japan epoxy resin corporate systems), YSLV-50TE thioethers such as (Dongdu change into corporate system) type epoxy resin, YSLV-80DE biphenyl such as (Dongdu change into corporate system) ether type epoxy, EP-4088S dicyclopentadiene-type epoxy resin such as (rising sun electrification corporate systems), Epiclon HP4032, Epiclon EXA-4700 naphthalene type epoxy resin such as (being the black liquid corporate system of big Japan), Epiclon N-770 phenolic resin varnish type epoxy resins such as (big Japanese black liquid corporate systems), Epiclon N-670-EXP-S o-cresol phenolic epoxy varnish such as (big Japanese black liquid corporate systems), Epiclon HP7200 bicyclopentadiene phenolic resin varnish type epoxy resins such as (big Japanese black liquid corporate systems), NC-3000P biphenyl phenolic resin varnish type epoxy resins such as (Japanese chemical drug corporate systems), ESN-165S naphthol novolacs such as (Dongdu change into corporate system) varnish type epoxy resin, Epicote630 (japan epoxy resin corporate system), Epiclon 430 (big Japanese black liquid corporate system), TETRAD-X glycidyl group amine type epoxy resin such as (gas chemical company of Mitsubishi systems), ZX-1542 (Dongdu changes into corporate system), Epiclon 726 (big Japanese black liquid corporate system), Epolight 80MFA (chemical company of common prosperity society system), Denacol EX-611 alkyl polyols type epoxy resin such as (passable rapids fine chemistry industry corporate systems), YR-450, YR-207 (be Dongdu and change into corporate system), Eplead PB modified rubber type epoxy resin such as (Daicel chemical company systems), Denacol EX-147 glycidyl ester compounds such as (Chang rapids fine chemistry industry corporate systems), Epicote YL-7000 bisphenol A-type episulfide resins such as (japan epoxy resin corporate systems), other YDC-1312, YSLV-80XY, YSLV-90CR (be Dongdu and change into corporate system), XAC4151 (Asahi Chemical Industry's corporate system), Epicote 1031, Epicote1032 (being the japan epoxy resin corporate system), EXA-7120 (big Japanese black liquid corporate system), TEPIC (daily output chemical company system) etc.
In addition; As above-mentioned ring type aliphatic epoxy resin; Not special the qualification as commercially available article, for example can be enumerated Celloxide (セ mouth キ サ イ De) 2021, Celloxide 2080, Celloxide3000, Eplead GT300, EHPE (being Daicel chemical company system) etc.
React the compound that obtains as above-mentioned isocyanates and epoxy prapanol; Not special the qualification; For example can obtain as follows:, as catalyzer, in the presence of the tin based compound, make its reaction and obtain with 2 equivalent epoxy prapanols with respect to compound with 2 NCOs.
As above-mentioned isocyanates; Not special the qualification; For example can enumerate different fluorine ketone diisocyanate, 2; 4-toluene diisocyanate, 2; 6-toluene diisocyanate, hexamethylene diisocyanate, tri-methyl hexamethylene isocyanates, diphenyl methane-4, gather MDI, 1,5 one naphthalene diisocyanate, norbornene alkyl diisocyanate, tolidine diisocyanate, eylylene diisocyanate (XDI), hydrogenation XDI, LDI, triphenylmethane triisocyanate, three (NCO phenyl) thiophosphate, tetramethylbenzene diisocyanate, 1 at 4 '-diisocyanate (MDI), hydrogenation MDI; 6,10-undecane triisocyanate etc.
In addition; As above-mentioned isocyanates, for example can enumerate chain elongation that polyvalent alcohols such as monoethylene glycol, glycerine, sorbierite, trimethylolpropane, (gathering) propylene glycol, carbonic ester glycol, PTMEG, polyester-diol, polycaprolactone glycol and excessive isocyanate reaction obtain isocyanate compound.
Liquid crystal drop of the present invention technology down preferably also contains thermal curing agents with sealant.
As above-mentioned thermal curing agents, not special the qualification for example can be enumerated amines, polyhydric phenol based compound, acid anhydrides etc.
As above-mentioned amines, can enumerate and have 1 above primary amino radical in 1 molecule～the amino compound of uncle.Particularly; For example can enumerate aromatic amine, glyoxal ethylines, 1 such as m-phenylene diamine, diaminodiphenyl-methane, dihydrazide compounds such as imidazolinium compounds such as imidazolium compoundss such as 2-methylimidazole, 1-cyano ethyl-glyoxal ethyline, glyoxal ethyline quinoline, sebacic dihydrazide, isophthalic dihydrazide, Amicure (ア ミ キ ユ ア) PN-23, Amicure MY-24, Amicure VDH amine adduct class, dicyandiamides etc. such as (being aginomoto fine chemistry corporate system).
As above-mentioned polyhydric phenol based compound; Not special the qualification for example can be enumerated Epicure (エ ピ キ ユ ア) 170, Epicure YL6065 polyphenol compounds such as (being the japan epoxy resin corporate system), Epicure MP402FPI phenolic varnish type phenolics such as (japan epoxy resin corporate systems).
As above-mentioned acid anhydrides, not special the qualification for example can be enumerated Epicure YH-306, YH-307 (being the japan epoxy resin corporate system) etc.
Above-mentioned thermal curing agents can use separately, also can be also with more than 2 kinds.Wherein, based on the viewpoint of curability at low temperatures and excellent storage stability, preferred dihydrazide compound.
As the use level of above-mentioned thermal curing agents, not special qualification the, but with respect to the above-mentioned curable resin of 100 weight portions preferably is limited to 1 weight portion down, is limited to 100 weight portions on preferably.The use level of above-mentioned thermal curing agents is during less than 1 weight portion, and the curing of above-mentioned curable resin becomes insufficient, when surpassing 100 weight portions; The technological down storage stability with sealant of liquid crystal drop of the present invention has the possibility of variation; In addition, when forming solidfied material, might moisture-proof reduce.The use level of above-mentioned thermal curing agents more preferably on be limited to 20 weight portions.
Liquid crystal drop of the present invention technology down preferably also contains silane coupling agent with sealant.Above-mentioned silane coupling agent mainly have as be used for liquid crystal drop of the present invention down technology with the effect of the bonding well bonding auxiliary agent of sealant and liquid crystal display cells substrate.
As above-mentioned silane coupling agent, not special the qualification for example can be enumerated gamma-amino propyl trimethoxy silicane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-methoxy propoxyl group propyl trimethoxy silicane, γ-NCO propyl trimethoxy silicane etc.Above-mentioned silane coupling agent can use separately, also can be also with more than 2 kinds.Need to prove that above-mentioned γ-methoxy propoxyl group propyl trimethoxy silicane is the compound with epoxy radicals, but can in the scope of the degree that does not reduce the display quality that utilizes the technological liquid crystal display cells of making that drips, use.
As the use level of above-mentioned silane coupling agent, not special qualification the, but with respect to the above-mentioned curable resin of 100 weight portions preferably is limited to 0.1 weight portion down, is limited to 10 weight portions on preferably.The use level of above-mentioned silane coupling agent might can not be given full play to performance during less than 0.1 weight portion, and when surpassing 10 weight portions, remaining silane coupling agent stripping might reduce display quality in liquid crystal.The use level of above-mentioned silane coupling agent more preferably be limited to 0.5 weight portion down, be limited to 3 weight portions on more preferably.
In addition, in order to improve cementability that the stress dispersion effect obtains, to improve linear expansivity etc., liquid crystal drop of the present invention technology down can contain filling agent with sealant.
As above-mentioned filling agent; Not special the qualification for example can be enumerated organic fillers such as inorganic filler such as talcum, asbestos, silicon dioxide, zeyssatite, clay, bentonitic clay, lime carbonate, magnesium carbonate, aluminium oxide, smectite, zeyssatite, magnesium oxide, titanium dioxide, magnesium hydroxide, hydrate of aluminium, beaded glass, barium sulphate, gypsum, calcium silicate, talcum, beaded glass, sericite atlapulgite, bentonitic clay or polyester micropartical, polyurethane particulate, polyvinyl particulate, acrylate copolymer particulate.
As the use level of above-mentioned filling agent, not special the qualification, but with respect to the above-mentioned curable resin of 100 weight portions, preferred lower limit is 1 weight portion, the preferred upper limit is 100 weight portions.The use level of above-mentioned filling agent might can not be given full play to performance during less than 1 weight portion, when surpassing 100 weight portions, might not reduce technological operability such as illustrative with sealant liquid crystal drop of the present invention under.The more preferably lower limit of the use level of above-mentioned filling agent is 10 weight portions, and more preferably the upper limit is 50 weight portions.
Liquid crystal drop of the present invention technology down uses E type viscosity meter with sealant, is 600,000 mPas 25 ℃ of viscosity upper limits of measuring down.When above-mentioned viscosity surpassed 600,000 mPas, illustrative was insufficient, can't make liquid crystal display cells with the technology of dripping.The preferred lower limit of above-mentioned viscosity is 100,000 mPas, and more preferably the upper limit is 450,000 mPas.
Technology is with the E type viscosity meter of the viscosity of sealant down as measuring liquid crystal drop of the present invention, and not special the qualification for example can be enumerated Bo Lefei corporate system " DV-III ".
As being used to make technological method under the liquid crystal drop of the present invention with sealant; Not special the qualification can be enumerated the method for the existing known method hybrid regulatory of utilization quantitative above-mentioned curable resin, optical free radical initiating agent and the above-mentioned thermal curing agents that cooperates as required, silane coupling agent etc. etc.At this moment, in order to remove contained ionic impurity, it is contacted with ionic adsorption property solid.
Liquid crystal drop of the present invention technology down uses sealant because viscosity is below 600,000 mPas, so illustrative is also excellent.In addition, above-mentioned curable resin is owing to containing the optical free radical initiating agent high to above-mentioned liquid crystal dissolubility, so when making liquid crystal display cells with the technology of dripping, can under the situation that does not cause liquid crystal pollution, make the liquid crystal display cells of high quality image.
Cooperate electrically conductive microparticle through technology under liquid crystal drop of the present invention in sealant, conductive material about can making.The technological down conductive material up and down with sealant and electrically conductive microparticle of liquid crystal drop that contains the invention described above also is one of the present invention.
As above-mentioned electrically conductive microparticle, not special the qualification can use metal ball, form the particulate of conductive metal layer etc. on the resin particle surface.Wherein, the particulate that forms conductive metal layer on resin particle surface can utilize the excellent elasticity of resin particle, does not damage ground such as transparency carrier and conducts electricity connections, so preferably.
Using technological under the liquid crystal drop of the present invention also is one of the present invention with sealant and/or the liquid crystal display cells that conductive material became of the present invention up and down.
As the method for making liquid crystal display cells of the present invention; For example can enumerate following method, it comprises following operation: technology utilizes serigraphy, divider coating etc. to form the operation of rectangular seal patterns with sealant etc. have on of transparency carrier of electrode liquid crystal drop of the present invention 2 of ito thin films etc. under; Technology is with under the uncured state such as sealant liquid crystal droplet being dripped and coating in the whole frame of transparency carrier the operation that overlaps with another transparency carrier at once under liquid crystal drop of the present invention; To the following technology operation of solidifying of liquid crystal drop of the present invention temporarily with the light of the seal pattern part irradiation ultraviolet radiation of sealant etc. etc.; And the seal pattern that will temporarily solidify heating, make by the liquid crystal drop of the present invention operation etc. of the seal pattern curing that constitutes with sealant etc. of technology down itself.
The liquid crystal drop of use the invention described above technology down also is one of the present invention with sealant and/or the liquid crystal display cells that conductive material became of the present invention up and down.
According to the present invention; The technological sealant of using under a kind of liquid crystal drop can be provided, when making liquid crystal display cells, even the stripping of sealant composition is in liquid crystal with the technology of dripping; Also can prevent to cause liquid crystal pollution, and can make display quality and the excellent liquid crystal display cells of reliability.
Embodiment
Below, provide embodiment and illustrate in greater detail the present invention, but the present invention also only is not limited to following embodiment.
< synthesizing of curable resin >
(synthesizing of acrylic acid epoxy ester (1))
170g bisphenol A type epoxy resin 850CRP (big Japanese black liquid corporate system) is dissolved in the 500mL toluene, in this solution, adds the 0.1g triphenylphosphine again, process uniform solution.In this solution under the refluxing and stirring after splashing into 72g acrylic acid in 2 hours, and then refluxing and stirring 8 hours.
Then, remove toluene, obtain the acrylic acid epoxy base ester (1) (the complete modification article of 850CRP) that whole epoxy radicals change into acryloyl group.
(the bisphenol E-type acrylic acid epoxy ester resin (synthesizing of partially modified resin (2)) that the reaction of a part of epoxy radicals and acrylic acid is obtained)
163g bisphenol E-type epoxy resin R-710 (Mitsui Chemicals corporate system) is dissolved in the 500mL toluene, in this solution, adds the 0.1g triphenylphosphine again, process uniform solution.In this solution under the refluxing and stirring after splashing into 54g acrylic acid in 2 hours, and then refluxing and stirring 6 hours.Remove toluene, obtain the epoxy radicals of 75 moles of % and the bisphenol E-type acrylic acid epoxy ester resin (partially modified resin (2)) that the acrylic acid reaction obtains.
Need to prove that degree of modification is measured with following method: make resin dissolves behind hydrochloric acid-dioxane solutions, the hydrochloric acid content that is consumed by epoxy radicals with the KOH titration.
(the Bisphenol F type acrylic acid epoxy ester resin (synthesizing of partially modified resin (3)) that the reaction of a part of epoxy radicals and acrylic acid is obtained)
156g bisphenol f type epoxy resin 830CRP (big Japanese black liquid corporate system) is dissolved in the 500mL toluene, in this solution, adds the 0.1g triphenylphosphine again, process uniform solution.In this solution under the refluxing and stirring after splashing into 54g acrylic acid in 2 hours, and then carry out 6 hours refluxing and stirring.Remove toluene, obtain the epoxy radicals of 75 moles of % and the Bisphenol F type epoxy acrylate resin (partially modified resin (3)) that the acrylic acid reaction obtains.
Need to prove that degree of modification is measured with following method: make resin dissolves behind hydrochloric acid-dioxane solutions, the hydrochloric acid content that is consumed by epoxy radicals with the KOH titration.
(the bisphenol E-type epoxy acrylate resin (synthesizing of partially modified resin (4)) that the reaction of a part of epoxy radicals and acrylic acid is obtained)
163g bisphenol E-type epoxy resin R-710 (Mitsui Chemicals corporate system) is dissolved in the 500mL toluene, adds the 0.1g triphenylphosphine at this solution again, process uniform solution.In this solution, under the refluxing and stirring after splashing into 36g acrylic acid in 2 hours, and then refluxing and stirring 6 hours.Remove toluene, obtain the epoxy radicals of 50 moles of % and the bisphenol E-type epoxy acrylate resin (partially modified resin (4)) that the acrylic acid reaction obtains.
Need to prove that degree of modification is measured with following method: make resin dissolves behind hydrochloric acid-dioxane solutions, the hydrochloric acid content that is consumed by epoxy radicals with the KOH titration.
(the biphenyl ether type epoxy acrylate resin (synthesizing of partially modified resin (5)) that the reaction of a part of epoxy radicals and acrylic acid is obtained)
(YSLV-80DE (chemical company of Nippon Steel system) is dissolved in the 500mL toluene, in this solution, adds the 0.1g triphenylphosphine again, processes uniform solution to make 157g biphenyl ether type epoxy.In this solution, under the refluxing and stirring after splashing into 36g acrylic acid in 2 hours, and then refluxing and stirring 6 hours.Remove toluene, obtain the epoxy radicals of 50 moles of % and the bisphenol E-type epoxy acrylate resin (partially modified resin (5)) that the acrylic acid reaction obtains.
Need explanation, degree of modification is measured with following method: make resin dissolves behind hydrochloric acid-dioxane solutions, with the KOH titration by the hydrochloric acid content of epoxy radicals consumption.
(embodiment 1)
Cooperate the synthetic partially modified resin (2) of 100 weight portions, 2 weight portion optical free radical initiating agents (Chiba refine corporate system, IRGACURE OXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
(embodiment 2)
Cooperate the synthetic partially modified resin (4) of the synthetic epoxy acrylate (1) of 50 weight portions, 50 weight portions, 2 weight portion optical free radical initiating agents (Chiba refine corporate system, IRGACUREOXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
(embodiment 3)
Cooperate the synthetic partially modified resin (2) of 100 weight portions, 5 weight portion optical free radical initiating agents (Chiba refine corporate system, IRGACURE OXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
(embodiment 4)
Cooperate the synthetic partially modified resin (4) of the synthetic epoxy acrylate (1) of 50 weight portions, 50 weight portions, 0.5 weight portion optical free radical initiating agent (Chiba refine corporate system, IRGACUREOXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
(embodiment 5)
Cooperate the synthetic partially modified resin (4) of the synthetic epoxy acrylate (1) of 50 weight portions, 50 weight portions, 5 weight portion optical free radical initiating agents (Chiba refine corporate system, IRGACUREOXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 22 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 8 weight portion talcums and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
(embodiment 6)
Cooperate the synthetic partially modified resin (4) of the synthetic epoxy acrylate (1) of 50 weight portions, 50 weight portions, 2 weight portion optical free radical initiating agents (Chiba refine corporate system, IRGACUREOXEO1), 5 weight portions as the adipic dihydrazide of thermal curing agents, 30 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Mix with ceramic three-roller homogeneous, the technology that obtains under the liquid crystal drop is used sealant.
(embodiment 7)
Cooperate the synthetic partially modified resin (5) of the synthetic epoxy acrylate (1) of 50 weight portions, 25 weight portions synthetic partially modified resin (4), 25 weight portions, 2 weight portion optical free radical initiating agents (Chiba refine corporate system, IRGACURE OXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
(embodiment 8)
Cooperate the synthetic partially modified resin (5) of the synthetic epoxy acrylate (1) of 50 weight portions, 25 weight portions synthetic partially modified resin (4), 25 weight portions, 2 weight portion optical free radical initiating agents (Chiba refine corporate system, IRGACURE OXEO1), 10 weight portions as the sebacic dihydrazide of thermal curing agents, 30 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
(comparative example 1)
Cooperate the synthetic partially modified resin (2) of 100 weight portions, 2 weight portion optical free radical initiating agents (Chiba refine corporate system, DAROCURETPO), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
(comparative example 2)
Cooperate the synthetic partially modified resin (3) of the synthetic epoxy acrylate (1) of 50 weight portions, 50 weight portions, 2 weight portion optical free radical initiating agents (Chiba refine corporate system, DAROCURETPO), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
(comparative example 3)
Cooperate the synthetic partially modified resin (4) of the synthetic epoxy acrylate (1) of 50 weight portions, 50 weight portions, 5 weight portion optical free radical initiating agents (Chiba refine corporate system, DAROCURE1173), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
(comparative example 4)
Cooperate the synthetic partially modified resin (2) of 100 weight portions, 2 weight portion optical free radical initiating agents (Chiba refine corporate system, IRGACURE819), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions spherical silicon dioxide (Admatechs corporate system, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) as filling agent; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
(comparative example 5)
Cooperate the synthetic partially modified resin (2) of 100 weight portions, 2 weight portion optical free radical initiating agents (Chiba refine corporate system, IRGACURE379), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), as the spherical silicon dioxide (Admatechs corporate system, SO-C1) and the 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403) of 30 weight portion filling agents; After planetary stirring apparatus (Thinky corporate system, あ わ と り practice too youth) stirring; Evenly mix with ceramic three-roller, the technology that obtains under the liquid crystal drop is used sealant.
< evaluation of optical free radical initiating agent >
Optical free radical initiating agent to being used for embodiment and comparative example carries out following evaluation.
The result is shown in table 1 and table 2.
(1) the deliquescent evaluation of the liquid crystal of optical free radical initiating agent
In glass sample preparation bottle, add the 0.5g liquid crystal, be the optical free radical initiating agent of the ormal weight of 4 weight % with respect to this liquid crystal.Cover the lid of appearance bottle, put into 120 ℃ of baking ovens, placed 1 hour.Take out from baking oven after 1 hour, placed the precipitation state of visual inspection optical free radical initiating agent 144 hours at-20 ℃.
Need to prove,, use MLC-6609 (VA, Merck & Co., Inc.'s system) and ZN-5001LA (TN, Chisso Corporation's system) respectively as liquid crystal.
(2) mensuration of the absorptivity of optical free radical initiating agent
About DAROCUR ETPO and IRGACURE OXE01, the solution that 1 mole of above-mentioned substance of 1L acetonitrile dissolving is obtained is put into the 1cm quartz cell, use the absorptivity under the spectrophotometric determination 405nm.
About DAROCURE 1173, IRGACURE 819 and IRGACURE 379, the solution that 1 mole of above-mentioned substance of 1L dissolve with methanol is obtained is put into the 1cm quartz cell, use the absorptivity under the spectrophotometric determination 405nm.
Need to prove that if pond length is 1 [cm], volumetric molar concentration is c [mol/L], molar absorptivity is ε [L/molcm], then according to the rule of lambert-beer, and molar absorptivity=ε cl.
[table 1]
| The optical free radical initiating agent | Absorptivity | Fusing point |
| DAROCURE?TPO | 165mL/gcm (in the acetonitrile) | 88-92℃ |
| IRGACURE?OXE01 | (101.6ml/gcm in the acetonitrile) | 40-42℃ |
| DAROCURE?1173 | 0ml/gm (in the methyl alcohol > | 4℃ |
| IRGACURE?819 | 899ml/gcm (in the methyl alcohol) | 127-133℃ |
| IRGACURE?379 | 280ml/gcm (in the methyl alcohol) | 110-114℃ |
[table 2]
< technological down the evaluation of liquid crystal drop>with sealant
Carry out following evaluation to the liquid crystal drop of making in embodiment 1～8 and the comparative example 1～5 is technological down with sealant.
The result is shown in table 3.
(1) evaluation of curable
Use sealant with glass holding liquid crystal display element.Under this state, irradiates light, making wavelength is that the exposure of the light of 405nm is 3000mJ/cm
2Need to prove, during irradiation, use the 400nm cutoff filter.Then, measure the reaction rate of acryloyl group with the analytical approach of using FT-IR.The reaction rate of acryloyl group is " * " less than 50% sample, and 50～70% sample is " △ ", and the sample above 70% is " zero ".
(2) display panels evaluation (color spot evaluation)
In alignment films and the one side that has the substrate of transparency electrode, use sealant with divider coating of liquid crystalline display element with the mode of describing box.Then, splash into liquid crystal (Merck & Co., Inc.'s system, " ZN-5001LA "), behind another substrate of fitting, the irradiation high-pressure sodium lamp is with 100mW/cm
2Shone 30 seconds, and made its curing.At this moment, use the 400nm cutoff filter.Then, under 120 ℃, make its heat curing 1 hour, make display panels.
For the display panels (the sample number is 5) of gained, near the liquid crystal aligning race conditio the sealant behind the firm making display panels is confirmed in visual inspection.Judge the orientation disorder situation with the color spot of display part,, estimate with following 4 grades according to the degree of color spot: ◎ (not having color spot fully), zero (micro-color spot is arranged), △ (a small amount of color spot is arranged), * (a large amount of color spots are arranged).Need to prove, be evaluated as ◎, zero display panels is the practical no problem rank fully that goes up.[table 3]
Utilizability on the industry
According to the present invention; The technological sealant of using under a kind of liquid crystal drop can be provided, and it is when making liquid crystal display cells with the technology of dripping, even the stripping of sealant composition is in liquid crystal; Also can prevent to cause liquid crystal pollution, and can make display quality and the excellent liquid crystal display cells of reliability.
Claims (4)
1. the following technology of liquid crystal drop is used sealant, it is characterized in that,
It is the technological down sealant of using of liquid crystal drop that contains curable resin and optical free radical initiating agent,
Said optical free radical initiating agent be under 120 ℃ with the concentration of 4 weight % in liquid crystal fully after the dissolving, the optical free radical initiating agent of not separating out after 144 hours-20 ℃ of held again from said liquid crystal,
The absorptivity at the 405nm place that said optical free radical initiating agent is measured in solvent is more than the 50mL/gcm,
Said optical free radical initiating agent is 1,2-acetyl caproyl 1-[4-(thiophenyl)-2-(O-benzoyl oxime)].
2. liquid crystal drop as claimed in claim 1 down technology is used sealant, it is characterized in that curable resin has (methyl) acryloyl group and epoxy radicals, and epoxy radicals is 40 moles below the % with respect to the ratio of the total amount of (methyl) acryloyl group and epoxy radicals.
3. conductive material about in the of a kind is characterized in that, contains under claim 1 or the 2 described liquid crystal drops technological with sealant and electrically conductive microparticle.
4. a liquid crystal display cells is characterized in that, use claim 1 or 2 described liquid crystal drops technology down form with sealant and/or the described conductive material up and down of claim 4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-277596 | 2007-10-25 | ||
| JP2007277596 | 2007-10-25 | ||
| PCT/JP2008/068481 WO2009054276A1 (en) | 2007-10-25 | 2008-10-10 | Sealing material for liquid crystal dispensing method, transfer material and liquid crystal displays |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101836157A CN101836157A (en) | 2010-09-15 |
| CN101836157B true CN101836157B (en) | 2012-07-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801125524A Active CN101836157B (en) | 2007-10-25 | 2008-10-10 | Sealing material for liquid crystal dispensing method, transfer material and liquid crystal displays |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4427085B2 (en) |
| KR (1) | KR101486619B1 (en) |
| CN (1) | CN101836157B (en) |
| TW (1) | TWI463225B (en) |
| WO (1) | WO2009054276A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009230095A (en) * | 2008-02-25 | 2009-10-08 | Jsr Corp | Curable composition, liquid crystal sealing agent and liquid crystal display element |
| KR101093469B1 (en) | 2009-05-15 | 2011-12-13 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for use in liquid crystal dropping process, vertical-conduction material, and liquid crystal display element |
| KR20100137972A (en) * | 2009-06-24 | 2010-12-31 | 삼성전자주식회사 | Sealant, liquid crystal display having the same and method of fabricating the same |
| CN102439089B (en) * | 2010-06-28 | 2015-05-06 | 株式会社艾迪科 | Curable resin composition |
| JP6138563B2 (en) * | 2013-04-16 | 2017-05-31 | 積水化学工業株式会社 | Oxime ester initiator, curable resin composition, sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| JP5685346B1 (en) * | 2013-05-15 | 2015-03-18 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
| US20170058160A1 (en) * | 2014-07-23 | 2017-03-02 | DIC Corporation (Tokyo) | Liquid crystal display device |
| EP3176633B1 (en) * | 2014-08-01 | 2019-04-03 | DIC Corporation | Liquid crystal display device |
| JP6918693B2 (en) * | 2016-01-26 | 2021-08-11 | 積水化学工業株式会社 | Light-shielding sealant for liquid crystal display elements, vertical conductive materials, and liquid crystal display elements |
| JP6338745B1 (en) * | 2016-12-27 | 2018-06-06 | 日本化薬株式会社 | Photocurable resin composition and sealant for electronic parts |
| JPWO2018225543A1 (en) * | 2017-06-06 | 2020-04-09 | 日本化薬株式会社 | Compound and photocurable composition using the same |
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|---|---|---|---|---|
| JP2005292801A (en) * | 2004-03-09 | 2005-10-20 | Sekisui Chem Co Ltd | Light shielding sealing agent for liquid crystal display element, vertical conducting material, and liquid crystal display element |
| CN1711300A (en) * | 2002-11-06 | 2005-12-21 | 日本化药株式会社 | Sealing material for liquid crystal and liquid crystal display cell using same |
| JP2007171774A (en) * | 2005-12-26 | 2007-07-05 | Shin Etsu Chem Co Ltd | Sealing agent composition for liquid crystal display element |
| WO2007114184A1 (en) * | 2006-03-29 | 2007-10-11 | Sekisui Chemical Co., Ltd. | Sealing material for liquid-crystal dropping process, vertical-conduction material, and liquid-crystal display element |
| JP2008179797A (en) * | 2006-12-28 | 2008-08-07 | Jsr Corp | Sealing agent for liquid crystal display element, and liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3742000B2 (en) * | 2000-11-30 | 2006-02-01 | 富士通株式会社 | Press machine |
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- 2008-10-10 CN CN2008801125524A patent/CN101836157B/en active Active
- 2008-10-10 WO PCT/JP2008/068481 patent/WO2009054276A1/en active Application Filing
- 2008-10-10 KR KR1020107011041A patent/KR101486619B1/en active IP Right Grant
- 2008-10-24 TW TW097140762A patent/TWI463225B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711300A (en) * | 2002-11-06 | 2005-12-21 | 日本化药株式会社 | Sealing material for liquid crystal and liquid crystal display cell using same |
| JP2005292801A (en) * | 2004-03-09 | 2005-10-20 | Sekisui Chem Co Ltd | Light shielding sealing agent for liquid crystal display element, vertical conducting material, and liquid crystal display element |
| JP2007171774A (en) * | 2005-12-26 | 2007-07-05 | Shin Etsu Chem Co Ltd | Sealing agent composition for liquid crystal display element |
| WO2007114184A1 (en) * | 2006-03-29 | 2007-10-11 | Sekisui Chemical Co., Ltd. | Sealing material for liquid-crystal dropping process, vertical-conduction material, and liquid-crystal display element |
| JP2008179797A (en) * | 2006-12-28 | 2008-08-07 | Jsr Corp | Sealing agent for liquid crystal display element, and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4427085B2 (en) | 2010-03-03 |
| JPWO2009054276A1 (en) | 2011-03-03 |
| CN101836157A (en) | 2010-09-15 |
| TWI463225B (en) | 2014-12-01 |
| TW200921222A (en) | 2009-05-16 |
| KR20100086486A (en) | 2010-07-30 |
| WO2009054276A1 (en) | 2009-04-30 |
| KR101486619B1 (en) | 2015-01-26 |
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