CN101836157A - 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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- CN101836157A CN101836157A CN200880112552A CN200880112552A CN101836157A CN 101836157 A CN101836157 A CN 101836157A CN 200880112552 A CN200880112552 A CN 200880112552A CN 200880112552 A CN200880112552 A CN 200880112552A CN 101836157 A CN101836157 A CN 101836157A
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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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- Crystallography & Structural Chemistry (AREA)
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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,, and can make technology sealant under the liquid crystal drop of liquid crystal display cells of display quality and reliability excellence even the stripping of sealant composition in liquid crystal, also can prevent to cause liquid crystal pollution with the technology of dripping.The invention still further relates to conductive material and liquid crystal display cells up and down.
Background technology
In the manufacture method of existing liquid crystal display cells, at first, 2 either party 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, adjust near the gap the sealing after, 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 manufacture method, there is following problems: cause the connecting airtight property reduction of position deviation, gap inequality, sealant and substrate etc. owing to the distortion of heating generation, perhaps residual solvent generation thermal expansion and produce bubble and cause the uneven or sealing amplitude difference in gap, perhaps the sealing and curing required time is long, perhaps pre-baking technology complexity, perhaps because of the time that solvent evaporates can be used as sealant shortens, 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.
At the problems referred to above, studied the manufacture method of the liquid crystal display cells that is called as the technology of dripping, the described technology of dripping is used the sealant that is made of curable resin composition.In the technology of dripping, at first, on of 2 transparency carriers that have an electrode, form rectangular seal pattern by serigraphy etc.Then, under the uncured state of sealant, liquid crystal droplet is dripped and coat 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.
As technology sealant under the liquid crystal drop that is used to the technology of dripping, 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 color spot etc. of liquid crystal aligning disorder and show bad problem.Reason is that in the operation of the technology of dripping, technology directly contacts liquid crystal with sealant under the liquid crystal drop of its uncured state, 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 and have used technology sealant under the liquid crystal drop of the low composition of liquid crystal dissolubility.Above-mentioned sealant is because composition is insoluble for 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 can make technology sealant under the liquid crystal drop of liquid crystal display cells of display quality and reliability excellence.
The present invention is a technology sealant under a kind of liquid crystal drop that contains curable resin and optical free radical initiating agent, described 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 described liquid crystal after placing 144 hours under-20 ℃, the absorptivity under the 405nm that described optical free radical initiating agent is measured in solvent is more than the 50mL/gcm again.
The inventor etc. concentrate on studies, found that as the optical free radical initiating agent that is used for technology usefulness sealant under the liquid crystal drop, by 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 technology sealant under the liquid crystal drop of liquid crystal display cells of display quality and reliability excellence, thereby finish the present invention.
Technology contains the optical free radical initiating agent with sealant under the liquid crystal drop of the present invention, this optical free radical initiating agent under 120 ℃ with the concentration of 4 weight % in liquid crystal fully after the dissolving, do not separate out after placing 144 hours down at-20 ℃ again from described liquid crystal.
At present, technology is used the optical free radical initiating agent low to the liquid crystal dissolubility with in the sealant in order to prevent liquid crystal pollution under liquid crystal drop.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 by 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,,, be not particularly limited as long as can dissolve above-mentioned optical free radical initiating agent and under the absorbing wavelength of measuring, not have extinction as above-mentioned solvent.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, also can react under amber light, 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 ℃ place 144 hours down after, 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 ℃.Fusing point lower limit as above-mentioned optical free radical initiating agent is not particularly limited, but under liquid crystal drop in the technology, and 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 preferred.
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 product of the oxime ester compound of following formula (1) expression, for example can enumerate IRGACUREOXE01 (Chiba refine corporate system) etc.
As the content of technology under the liquid crystal drop of the present invention with above-mentioned optical free radical initiating agent in the sealant, be not particularly limited, but preferably be limited to 0.2 weight % down, be 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.
Technology contains curable resin with sealant under the liquid crystal drop of the present invention.
As above-mentioned curable resin, be not particularly limited, but preferably have (methyl) acryloyl group and epoxy radicals.By 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, be not particularly limited polyurethane (methyl) acrylate 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, be not particularly limited, 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) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methoxyl ethyl ester, methoxyl ethylene glycol (methyl) acrylate, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) benzyl acrylate, ethyl carbitol (methyl) acrylate, (methyl) acrylic acid phenoxy ethyl, phenoxy group diglycol (methyl) acrylate, phenoxy group polyglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, (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, be not particularly limited, for example can enumerate 1,4-butylene glycol two (methyl) acrylate, 1,3-butylene glycol 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, ammediol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diglycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, epoxypropane addition bisphenol-A two (methyl) acrylate, oxirane addition bisphenol-A two (methyl) acrylate, oxirane addition Bisphenol F two (methyl) acrylate, dihydroxymethyl bicyclopentadiene two (methyl) acrylate, 1,3-butadiene two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, the different hydrogen urea of oxirane modification acid two (methyl) acrylate, 2-hydroxy-3-methyl acryloxy propyl group two (methyl) acrylate, carbonic ester glycol two (methyl) acrylate, PTMEG two (methyl) acrylate, polyester-diol two (methyl) acrylate, polycaprolactone glycol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate 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, be not particularly limited, for example can enumerate pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, epoxypropane addition trimethylolpropane tris (methyl) acrylate, oxirane addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, the different hydrogen urea of oxirane addition 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) acryloxy ethyl phosphonic acid ester etc.
(methyl) acrylic acid epoxy ester that reaction obtains as above-mentioned making (methyl) acrylic acid and epoxy compound is not particularly limited, and for example can be according to conventional methods (methyl) acrylic acid and epoxy resin be reacted to obtain 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 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, Epicote4004 bisphenol f type epoxy resins such as (being the japan epoxy resin corporate system), bisphenol E-type epoxy resin such as R-710, 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 (エ ピ Network mouth Application) 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), the resorcinol type epoxy resin of EX-201 (long rapids fine chemistry industry corporate system) etc., Epicote YX-4000H biphenyl type epoxy resins such as (japan epoxy resin corporate systems), YSLV-50TE thioether type epoxy resin such as (Dongdu change into corporate system), YSLV-80DE biphenyl ether type epoxies such as (Dongdu change into corporate system), 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), EpiclonN-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 novolac varnish type epoxy resin such as (Dongdu change into corporate system), Epicote 630 (japan epoxy resin corporate system), Epiclon430 (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 (エ ピ ラ イ ト) 80MFA (chemical company of common prosperity society system), Denacol (デ Na コ one Le) EX-611, the how pure type epoxy resin of alkyl such as (long rapids fine chemistry industry corporate systems), 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 (long 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), Epicote1031, Epicote 1032 (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 the commercially available product 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) acrylate that isocyanates and (methyl) acrylic acid derivative reaction with hydroxyl are obtained, be not particularly limited, for example can enumerate the compound that has 2 isocyanate group with respect to 1 equivalent, (methyl) acrylic acid derivative that has hydroxyl with 2 equivalents is as catalyzer, and makes its reaction and obtain in the presence of the tin based compound.
As the isocyanates that becomes above-mentioned polyurethane (methyl) acrylate raw material, be not particularly limited, for example, can enumerate different fluorine ketone diisocyanate, 2, the 4-toluene diisocyanate, 2, the 6-toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl methane-4,4 '-diisocyanate (MDI), hydrogenation MDI, poly-MDI, 1, the 5-naphthalene diisocyanate, norbornene alkyl diisocyanate, the tolidine diisocyanate, eylylene diisocyanate (XDI), hydrogenation XDI, lysinediisocyanate, triphenylmethane triisocyanate, three (isocyanate group 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 ethylene 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, be not particularly limited, for example can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, commercially available product or ethylene glycol such as (methyl) acrylic acid 2-hydroxyl butyl ester, propylene glycol, 1, ammediol, 1, the 3-butylene glycol, 1, the 4-butylene glycol, the list of dibasic alcohol such as polyglycol (methyl) acrylate, trimethylolethane, trimethylolpropane, the list of trihydroxy alcohols such as glycerine (methyl) acrylate or two (methyl) acrylate, (methyl) acrylic acid epoxy esters such as bisphenol A modified epoxy radicals (methyl) acrylate etc.
In addition, as the commercially available product of above-mentioned polyurethane (methyl) acrylate, 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 (being industrial group's system on the root), 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, technology has at least 1 hydrogen bond functional group to the liquid crystal stripping in preferred 1 molecule of above-mentioned curable resin with sealant composition before curing under the liquid crystal drop of the present invention in order further to suppress.
As above-mentioned hydrogen bond functional group, be not particularly limited, for example can enumerate-the OH base ,-the SH base ,-NHR base (R represents 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, easiness from importing is preferably-the OH base.
As having at least 1 hydrogen bond functional group in above-mentioned 1 molecule and having the curable resin of (methyl) acryloyl group, for example can enumerate above-mentioned polyurethane (methyl) acrylate or epoxy radicals (methyl) acrylate etc.
Technology is with in the sealant under the liquid crystal drop of the present invention, and the uncured residual component when solidifying in order to reduce as far as possible, above-mentioned curable resin are preferably has reactive basic compound 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 obtains of a part of epoxy radicals that makes compound and the reaction of (methyl) acrylic acid or make compound that the above isocyanates of two senses and (methyl) acrylic acid derivative with hydroxyl and epoxy prapanol reaction obtain etc. with 2 above epoxy radicals.
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 react in the presence of base catalyst 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, Epicote 4004 bisphenol f type epoxy resins such as (being the japan epoxy resin corporate system), bisphenol E-type epoxy resin such as R-710, 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 thioether type epoxy resin such as (Dongdu change into corporate system), YSLV-80DE biphenyl ether type epoxies such as (Dongdu change into corporate system), 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 novolac varnish type epoxy resin such as (Dongdu change into corporate system), 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 (big 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 (long 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 (long 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 product 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.
By 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 followingly obtain: the compound that has 2 isocyanate group 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, be not particularly limited, for example can enumerate different fluorine ketone diisocyanate, 2, the 4-toluene diisocyanate, 2, the 6-toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl methane-4,4 '-diisocyanate (MDI), hydrogenation MDI, poly-MDI, 1, the 5-naphthalene diisocyanate, the norbornane isocyanates, the tolidine diisocyanate, eylylene diisocyanate (XDI), hydrogenation XDI, lysinediisocyanate, triphenylmethane triisocyanate, three (isocyanate group phenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,10-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, be not particularly limited, for example can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, the commercially available product or the ethylene glycol of (methyl) acrylic acid 2-hydroxyl butyl ester etc., propylene glycol, 1, ammediol, 1, the 3-butylene glycol, 1, the 4-butylene glycol, the list of dibasic alcohol such as polyglycol (methyl) acrylate, trimethylolethane, trimethylolpropane, the list of trihydroxy alcohols such as glycerine (methyl) acrylate or two (methyl) acrylate, epoxy radicals (methyl) acrylate such as bisphenol A modified epoxy radicals (methyl) acrylate 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, be not particularly limited the compound that for example can enumerate epoxy chloropropionate alkane derivatives, ring type aliphatic epoxy resin, obtains by isocyanates and epoxy prapanol reaction etc. with epoxy radicals.
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 thioether type epoxy resin such as (Dongdu change into corporate system), YSLV-80DE biphenyl ether type epoxies such as (Dongdu change into corporate system), 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 novolac varnish type epoxy resin such as (Dongdu change into corporate system), 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 (long 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 (long 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, be not particularly limited,, for example can enumerate Celloxide (セ mouth キ サ イ De) 2021, Celloxide 2080, Celloxide3000, Eplead GT300, EHPE (being Daicel chemical company system) etc. as commercially available product.
React the compound that obtains as above-mentioned isocyanates and epoxy prapanol, be not particularly limited, for example can followingly obtain:, 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 isocyanate group.
As above-mentioned isocyanates, be not particularly limited, for example can enumerate different fluorine ketone diisocyanate, 2, the 4-toluene diisocyanate, 2, the 6-toluene diisocyanate, hexamethylene diisocyanate, the tri-methyl hexamethylene isocyanates, diphenyl methane-4,4 '-diisocyanate (MDI), hydrogenation MDI, poly-MDI, 1,5 one naphthalene diisocyanates, norbornene alkyl diisocyanate, the tolidine diisocyanate, eylylene diisocyanate (XDI), hydrogenation XDI, lysinediisocyanate, triphenylmethane triisocyanate, three (isocyanate group phenyl) thiophosphate, the tetramethylbenzene diisocyanate, 1,6,10-undecane triisocyanate etc.
In addition, as above-mentioned isocyanates, for example can enumerate chain elongation that polyvalent alcohols such as ethylene glycol, glycerine, sorbierite, trimethylolpropane, (gathering) propylene glycol, carbonic ester glycol, PTMEG, polyester-diol, polycaprolactone glycol and excessive isocyanate reaction obtain isocyanate compound.
Technology preferably also contains thermal curing agents with sealant under the liquid crystal drop of the present invention.
As above-mentioned thermal curing agents, be not particularly limited, for example can enumerate amines, polyhydric phenol based compound, acid anhydrides etc.
As above-mentioned amines, can enumerate the compound that has 1 above primary amino radical～uncle's amino in 1 molecule.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, be not particularly limited, for example can enumerate 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, be not particularly limited, for example can enumerate Epicure YH-306, YH-307 (being the japan epoxy resin corporate system) etc.
Above-mentioned thermal curing agents can use separately, and also two or more kinds may be used.Wherein, based on the viewpoint of curability at low temperatures and excellent storage stability, preferred dihydrazide compound.
Use level as above-mentioned thermal curing agents is not particularly limited, 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, technology has the possibility of variation under the liquid crystal drop of the present invention with the storage stability of sealant, 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.
Technology preferably also contains silane coupling agent with sealant under the liquid crystal drop of the present invention.Above-mentioned silane coupling agent mainly has as the effect that is used for the bonding auxiliary agent that technology usefulness sealant and liquid crystal display cells substrate under the liquid crystal drop of the present invention is bonding well.
As above-mentioned silane coupling agent, be not particularly limited, for example can enumerate gamma-amino propyl trimethoxy silicane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-methoxy propoxyl group propyl trimethoxy silicane, γ-isocyanate group propyl trimethoxy silicane etc.Above-mentioned silane coupling agent can use separately, and also two or more kinds may be used.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 of the display quality that does not reduce the liquid crystal display cells that utilizes the technology manufacturing of dripping, use.
Use level as above-mentioned silane coupling agent is not particularly limited, 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., technology can contain filling agent with sealant under the liquid crystal drop of the present invention.
As above-mentioned filling agent, be not particularly limited, for example can enumerate organic fillers such as inorganic fillers such as talcum, asbestos, silicon dioxide, zeyssatite, clay, bentonitic clay, lime carbonate, magnesium carbonate, aluminium oxide, smectite, zeyssatite, magnesium oxide, titanium dioxide, magnesium hydroxide, aluminium hydroxide, beaded glass, barium sulphate, gypsum, calcium silicate, talcum, beaded glass, sericite atlapulgite, bentonitic clay or polyester micropartical, polyurethane particulate, polyvinyl particulate, acrylate copolymer particulate.
Use level as above-mentioned filling agent is not particularly limited, but with respect to the above-mentioned curable resin of 100 weight portions, preferred lower limit is 1 weight portion, and 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 under the liquid crystal drop of the present invention technology with the operability such as illustrative of sealant.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.
Technology is used E type viscosity meter with sealant under the liquid crystal drop of the present invention, 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 not particularly limited with the E type viscosity meter of the viscosity of sealant under the liquid crystal drop of the present invention as measuring, and for example can enumerate Bo Lefei corporate system " DV-III ".
As the method that is used to make technology usefulness sealant under the liquid crystal drop of the present invention, be not particularly limited, can enumerate 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 the ionic adsorption solid.
Technology is below 600,000 mPas with sealant owing to viscosity under the liquid crystal drop of the present invention, 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 make the liquid crystal display cells of high quality image under the situation that does not cause liquid crystal pollution.
Cooperate electrically conductive microparticle by technology under liquid crystal drop of the present invention in sealant, can make conductive material up and down.The technology under the liquid crystal drop of the invention described above of containing also is one of the present invention with the conductive material up and down of sealant and electrically conductive microparticle.
As above-mentioned electrically conductive microparticle, be not particularly limited, 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 elasticity of resin particle excellence, does not damage ground such as transparency carrier and conducts electricity connections, so preferably.
Using technology 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 dripping liquid crystal droplet and coat in the whole frame of transparency carrier under the uncured state such as sealant under liquid crystal drop of the present invention, at once the operation that overlaps with another transparency carrier; The operation that technology under the liquid crystal drop of the present invention is solidified with the light of seal pattern part irradiation ultraviolet radiation of sealant etc. etc. temporarily; And the seal pattern that will temporarily solidify heating, make the operation of seal pattern itself curing that constitutes with sealant etc. by technology under the liquid crystal drop of the present invention etc.
Technology 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 under the liquid crystal drop of use the invention described above.
According to the present invention, can provide technology sealant under a kind of liquid crystal drop, 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 the liquid crystal display cells of display quality and reliability excellence.
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, make uniform solution.In this solution under reflux stirring after splashing into 72g acrylic acid in 2 hours, and then reflux and stirred 8 hours.
Then, remove toluene, obtain the acrylic acid epoxy base ester (1) (the complete modification product 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, make uniform solution.After splashing into 54g acrylic acid in 2 hours, and then reflux and stirred 6 hours under in this solution, reflux stirring.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, make uniform solution.In this solution under reflux stirring after splashing into 54g acrylic acid in 2 hours, and then carry out refluxing in 6 hours and stir.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, make uniform solution.In this solution, in reflux stirring down after splashing into 36g acrylic acid in 2 hours, and then reflux and stirred 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, adds the 0.1g triphenylphosphine again in this solution, makes uniform solution to make 157g biphenyl ether type epoxy.In this solution, reflux to stir down after splashing into 36g acrylic acid in 2 hours, and then reflux and stirred 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, the hydrochloric acid content that is consumed by epoxy radicals with the KOH titration.
(embodiment 1)
Cooperate the synthetic partially modified resin (2) of 100 weight portions, 2 weight portion optical free radical initiating agents (the Chiba corporate system of refining, IRGACURE OXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions are as spherical silicon dioxide (the Admatechs corporate system of filling agent, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403), with planetary stirring apparatus (Thinky corporate system, the experienced too youth of あ わ と り) after the stirring, evenly mix with ceramic three-roller, obtain technology sealant under the liquid crystal drop.
(embodiment 2)
Cooperate the synthetic epoxy acrylate (1) of 50 weight portions, the partially modified resin (4) that 50 weight portions are synthetic, 2 weight portion optical free radical initiating agents (the Chiba corporate system of refining, IRGACUREOXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions are as spherical silicon dioxide (the Admatechs corporate system of filling agent, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403), with planetary stirring apparatus (Thinky corporate system, the experienced too youth of あ わ と り) after the stirring, evenly mix with ceramic three-roller, obtain technology sealant under the liquid crystal drop.
(embodiment 3)
Cooperate the synthetic partially modified resin (2) of 100 weight portions, 5 weight portion optical free radical initiating agents (the Chiba corporate system of refining, IRGACURE OXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions are as spherical silicon dioxide (the Admatechs corporate system of filling agent, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403), with planetary stirring apparatus (Thinky corporate system, the experienced too youth of あ わ と り) after the stirring, evenly mix with ceramic three-roller, obtain technology sealant under the liquid crystal drop.
(embodiment 4)
Cooperate the synthetic epoxy acrylate (1) of 50 weight portions, the partially modified resin (4) that 50 weight portions are synthetic, 0.5 weight portion optical free radical initiating agent (the Chiba corporate system of refining, IRGACUREOXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions are as spherical silicon dioxide (the Admatechs corporate system of filling agent, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403), with planetary stirring apparatus (Thinky corporate system, the experienced too youth of あ わ と り) after the stirring, evenly mix with ceramic three-roller, obtain technology sealant under the liquid crystal drop.
(embodiment 5)
Cooperate the synthetic epoxy acrylate (1) of 50 weight portions, the partially modified resin (4) that 50 weight portions are synthetic, 5 weight portion optical free radical initiating agents (the Chiba corporate system of refining, IRGACUREOXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 22 weight portions are as spherical silicon dioxide (the Admatechs corporate system of filling agent, SO-C1) and 8 weight portion talcums and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403), with planetary stirring apparatus (Thinky corporate system, the experienced too youth of あ わ と り) after the stirring, evenly mix with ceramic three-roller, obtain technology sealant under the liquid crystal drop.
(embodiment 6)
Cooperate the synthetic epoxy acrylate (1) of 50 weight portions, the partially modified resin (4) that 50 weight portions are synthetic, 2 weight portion optical free radical initiating agents (the Chiba corporate system of refining, IRGACUREOXEO1), 5 weight portions are as the adipic dihydrazide of thermal curing agents, 30 weight portions are as spherical silicon dioxide (the Admatechs corporate system of filling agent, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403), with planetary stirring apparatus (Thinky corporate system, the experienced too youth of あ わ と り) after the stirring, mix with ceramic three-roller homogeneous, obtain technology sealant under the liquid crystal drop.
(embodiment 7)
Cooperate the synthetic epoxy acrylate (1) of 50 weight portions, the partially modified resin (4) that 25 weight portions are synthetic, the partially modified resin (5) that 25 weight portions are synthetic, 2 weight portion optical free radical initiating agents (the Chiba corporate system of refining, IRGACURE OXEO1), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions are as spherical silicon dioxide (the Admatechs corporate system of filling agent, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403), with planetary stirring apparatus (Thinky corporate system, the experienced too youth of あ わ と り) after the stirring, evenly mix with ceramic three-roller, obtain technology sealant under the liquid crystal drop.
(embodiment 8)
Cooperate the synthetic epoxy acrylate (1) of 50 weight portions, the partially modified resin (4) that 25 weight portions are synthetic, the partially modified resin (5) that 25 weight portions are synthetic, 2 weight portion optical free radical initiating agents (the Chiba corporate system of refining, IRGACURE OXEO1), 10 weight portions are as the sebacic dihydrazide of thermal curing agents, 30 weight portions are as spherical silicon dioxide (the Admatechs corporate system of filling agent, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403), with planetary stirring apparatus (Thinky corporate system, the experienced too youth of あ わ と り) after the stirring, evenly mix with ceramic three-roller, obtain technology sealant under the liquid crystal drop.
(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, obtain technology sealant under the liquid crystal drop.
(comparative example 2)
Cooperate the synthetic epoxy acrylate (1) of 50 weight portions, the partially modified resin (3) that 50 weight portions are synthetic, 2 weight portion optical free radical initiating agents (the Chiba corporate system of refining, DAROCURETPO), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions are as spherical silicon dioxide (the Admatechs corporate system of filling agent, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403), with planetary stirring apparatus (Thinky corporate system, the experienced too youth of あ わ と り) after the stirring, evenly mix with ceramic three-roller, obtain technology sealant under the liquid crystal drop.
(comparative example 3)
Cooperate the synthetic epoxy acrylate (1) of 50 weight portions, the partially modified resin (4) that 50 weight portions are synthetic, 5 weight portion optical free radical initiating agents (the Chiba corporate system of refining, DAROCURE1173), 16 weight portion thermal curing agents (aginomoto fine chemistry corporate system, Amicure VDH), 30 weight portions are as spherical silicon dioxide (the Admatechs corporate system of filling agent, SO-C1) and 2 weight portion silane coupling agents (chemical company of SHIN-ETSU HANTOTAI system, KBM403), with planetary stirring apparatus (Thinky corporate system, the experienced too youth of あ わ と り) after the stirring, evenly mix with ceramic three-roller, obtain technology sealant under the liquid crystal drop.
(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, obtain technology sealant under the liquid crystal drop.
(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, obtain technology sealant under the liquid crystal drop.
The evaluation of＜optical free radical initiating agent 〉
The optical free radical initiating agent that is used for embodiment and comparative example is carried out following evaluation.
The results are 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 sample 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, be 1[cm if the pond is long], 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]
The technology evaluation of sealant under the＜liquid crystal drop 〉
Technology under the liquid crystal drop of making in embodiment 1～8 and the comparative example 1～5 is carried out following evaluation with sealant.
The results are shown in table 3.
(1) evaluation of curable
With glass holding liquid crystal display element sealant.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)
Alignment films with have the one side of the substrate of transparency electrode, in the mode of describing the rectangle frame with divider coating of liquid crystalline display element sealant.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 of 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, technology sealant 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 from causing liquid crystal pollution, and can make the liquid crystal display cells of display quality and reliability excellence.
Claims (5)
1. technology sealant under the liquid crystal drop is characterized in that,
It is to contain technology sealant under the liquid crystal drop of curable resin and optical free radical initiating agent,
Described optical free radical initiating agent be under 120 ℃ with the concentration of 4 weight % in liquid crystal fully after the dissolving, again at-20 ℃ of optical free radical initiating agents of not separating out after placing 144 hours down from described liquid crystal,
The absorptivity at the 405nm place that described optical free radical initiating agent is measured in solvent is more than the 50mL/gcm.
2. technology sealant under the liquid crystal drop as claimed in claim 1 is characterized in that the optical free radical initiating agent is 1,2-acetyl caproyl 1-[4-(thiophenyl)-2-(O-benzoyl oxime)].
3. technology sealant under the liquid crystal drop as claimed in claim 1 or 2 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.
4. conductive material about in the of a kind is characterized in that, contains technology sealant and electrically conductive microparticle under claim 1, the 2 or 3 described liquid crystal drops.
5. a liquid crystal display cells is characterized in that, technology forms with sealant and/or the described conductive material up and down of claim 4 under use claim 1, the 2 or 3 described liquid crystal drops.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007277596 | 2007-10-25 | ||
| JP2007-277596 | 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 true CN101836157A (en) | 2010-09-15 |
| CN101836157B 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) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105814480A (en) * | 2014-08-01 | 2016-07-27 | Dic株式会社 | Liquid crystal display device |
| CN105814479A (en) * | 2014-07-23 | 2016-07-27 | Dic株式会社 | Liquid crystal display device |
| CN107710061A (en) * | 2016-01-26 | 2018-02-16 | 积水化学工业株式会社 | Shading sealant, upper and lower conductive material and liquid crystal display cells used for liquid crystal display element |
| CN108239508A (en) * | 2016-12-27 | 2018-07-03 | 日本化药株式会社 | Photocurable resin composition, sealant, electronic component and liquid crystal display |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5287012B2 (en) * | 2008-02-25 | 2013-09-11 | Ｊｓｒ株式会社 | Curable composition, liquid crystal sealant, and liquid crystal display element |
| CN102197334B (en) * | 2009-05-15 | 2014-11-05 | 积水化学工业株式会社 | Sealant for liquid crystal dropping process, vertically conducting 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 |
| WO2012002028A1 (en) * | 2010-06-28 | 2012-01-05 | 株式会社Adeka | 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 |
| WO2018225543A1 (en) * | 2017-06-06 | 2018-12-13 | 日本化薬株式会社 | Compound and photocurable composition using same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3742000B2 (en) * | 2000-11-30 | 2006-02-01 | 富士通株式会社 | Press machine |
| KR101228430B1 (en) * | 2002-11-06 | 2013-02-01 | 니폰 가야꾸 가부시끼가이샤 | 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 |
| KR101369022B1 (en) * | 2006-03-29 | 2014-02-28 | 세키스이가가쿠 고교가부시키가이샤 | Sealing material for liquid-crystal dropping process, vertical-conduction material, and liquid-crystal display element |
| TW200831541A (en) * | 2006-12-28 | 2008-08-01 | Jsr Corp | Sealant for liquid crystal display device and liquid crystal display device |
-
2008
- 2008-10-10 JP JP2008548789A patent/JP4427085B2/en active Active
- 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
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105814479A (en) * | 2014-07-23 | 2016-07-27 | Dic株式会社 | Liquid crystal display device |
| CN105814479B (en) * | 2014-07-23 | 2017-03-29 | Dic株式会社 | Liquid crystal indicator |
| CN105814480A (en) * | 2014-08-01 | 2016-07-27 | Dic株式会社 | Liquid crystal display device |
| CN105814480B (en) * | 2014-08-01 | 2020-01-07 | Dic株式会社 | Liquid crystal display device having a plurality of pixel electrodes |
| CN107710061A (en) * | 2016-01-26 | 2018-02-16 | 积水化学工业株式会社 | Shading sealant, upper and lower conductive material and liquid crystal display cells used for liquid crystal display element |
| CN107710061B (en) * | 2016-01-26 | 2022-01-28 | 积水化学工业株式会社 | Light-shielding sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN108239508A (en) * | 2016-12-27 | 2018-07-03 | 日本化药株式会社 | Photocurable resin composition, sealant, electronic component and liquid crystal display |
| CN108239508B (en) * | 2016-12-27 | 2021-09-28 | 日本化药株式会社 | Liquid crystal sealing agent for liquid crystal dropping method and liquid crystal display unit |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101486619B1 (en) | 2015-01-26 |
| CN101836157B (en) | 2012-07-18 |
| JP4427085B2 (en) | 2010-03-03 |
| TWI463225B (en) | 2014-12-01 |
| KR20100086486A (en) | 2010-07-30 |
| TW200921222A (en) | 2009-05-16 |
| JPWO2009054276A1 (en) | 2011-03-03 |
| WO2009054276A1 (en) | 2009-04-30 |
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