CN102007447A - Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element - Google Patents
Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element Download PDFInfo
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- CN102007447A CN102007447A CN2009801129799A CN200980112979A CN102007447A CN 102007447 A CN102007447 A CN 102007447A CN 2009801129799 A CN2009801129799 A CN 2009801129799A CN 200980112979 A CN200980112979 A CN 200980112979A CN 102007447 A CN102007447 A CN 102007447A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
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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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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
- G02F2202/023—Materials and properties organic material polymeric curable
- G02F2202/025—Materials and properties organic material polymeric curable thermocurable
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Abstract
Disclosed is a sealing agent for use in a liquid crystal dropping process, which enable the production of a liquid crystal display element having reduced unevenness in color and high image quality even when the liquid crystal display element is produced by a dropping process. The sealing agent comprises a resin having a (meth)acryl group and a polymeric azo initiator.
Description
Technical field
The present invention relates to a kind of utilization and drip technology when making liquid crystal display cells, can make technology sealant under the liquid crystal drop of liquid crystal display cells of the few high quality image of color spot.In addition, also relate to a kind ofly when utilizing the vacuum injection mode to make liquid crystal indicator, can make the liquid crystal panel sealing compound of the liquid crystal display cells of the few high quality image of color spot.
Background technology
At present, liquid crystal display cells such as liquid crystal display are to use the following technology that is called as the vacuum injection mode to make, described method is: make 2 electroded transparency carriers opposed across the interval of regulation, seal around it with sealant, form the unit, in the unit, inject liquid crystal from being arranged on its a part of liquid crystal injecting port, use sealant or sealing compound to seal described liquid crystal injecting port.
In the vacuum injection mode, at first, on any, use the Thermocurable sealant to form the seal pattern that is provided with liquid crystal injecting port, under 60～100 ℃, carry out preliminary drying, make the solvent seasoning in the sealant by serigraphy at 2 electroded transparency carriers.Then, insert sept, and make 2 plate bases opposed, aim at and make the two applying, under 110～220 ℃, carry out 10～90 minutes hot pressing, behind near the gap the adjustment sealing, in baking oven, heated 10～120 minutes down, make sealant lead curing at 110～220 ℃.Then, inject liquid crystal, use sealing compound encapsulated liquid crystals inlet at last, make liquid crystal display cells from liquid crystal injecting port.
But in recent years, the method of making liquid crystal indicators such as liquid crystal display is from shortening the productive temp time, will using viewpoint such as amount of liquid crystal optimization to consider, just from above-mentioned vacuum injection mode change into gradually for example patent documentation 1, the patent documentation 2 disclosed used by contain photo-curable acryl resin and Photoepolymerizationinitiater initiater, and the liquid crystal drop that is known as the technology of dripping of the sealant that also constitutes with the resin combination of curing type of the light of heat-curable epoxy resin and thermal polymerization, heat under mode.
Under the liquid crystal drop in the mode, at first on one of them of 2 electroded substrates, form seal pattern.Then, the state uncured with sealant drops in small liquid crystal drop in the whole frame of substrate, and another substrate is overlapped, return to normal pressure after, the sealing irradiation ultraviolet radiation is carried out the curing (precuring operation) of acryl resin.Thereafter, the curing of epoxy resin is carried out in heating, makes liquid crystal display cells.
But now, the various mobile devices that have liquid crystal panel such as portable phone, portable game are popularized gradually, and equipment miniaturization becomes the problem of the most urgent research.As the method for miniaturization, can enumerate the narrow frame (narrow-frame) of liquid crystal display part and change, for example the position of sealing is formulated under the black matrix (below be also referred to as narrow frame design).
Yet, when dripping technology by narrow frame design, because black matrix, make sealing exist rayed less than the place, therefore produce and fully do not carry out rayed and the part of uncured acryl resin, liquid crystal is polluted in uncured acryl resin stripping after the precuring operation, has the problem that causes the liquid crystal display inequality.
In addition, for to black matrix sealing down also irradiates light reliably, the back side of the substrate that also proposes to associate is the method for array side irradiates light, still on array base palte, also exist metal wiring, transistor etc., sealing exist rayed less than the place.
At such problem, solidify in order after rayed, to make uncured acryl resin reliably, also proposed to use low-molecular-weight superoxide or azo-compound the method that is combined with as the sealant of the composition that makes the acryl resin heat curing.If use this sealant, the heating in the time of then can annealing by liquid crystal makes at the uncured acryl resin of precuring operation solidifies.But there are the following problems,, because of low-molecular-weight superoxide or azo-compound produce color spot to the liquid crystal stripping around sealing, can not obtain the liquid crystal display cells of high quality images that is.
On the other hand, be vacuum injection mode when making liquid crystal indicator utilizing prior art, exist with above-mentioned liquid crystal drop under the identical problem of situation of mode.That is, when utilizing the vacuum injection mode to make liquid crystal indicator, the liquid crystal panel that is used for sealing liquid crystal contacts with liquid crystal with uncured state with sealing compound.At this, liquid crystal panel is not being shone the sufficient light time with sealing compound, still can produce color spot around the mouth-sealed portion, can not obtain the liquid crystal display cells of high quality images.
Patent documentation 1: TOHKEMY 2001-133794 communique
Patent documentation 2: Japanese kokai publication hei 5-295087 communique
Summary of the invention
In view of above-mentioned present situation, a kind ofly drip technology when making liquid crystal display cells even the object of the present invention is to provide in utilization, also can make technology sealant under the liquid crystal drop of liquid crystal display cells of the few high quality image of color spot.In addition, also provide a kind of when utilizing the vacuum injection mode to make liquid crystal indicator, can make the liquid crystal panel sealing compound of the liquid crystal display cells of the few high quality image of color spot.
The invention provides technology sealant under a kind of liquid crystal drop that contains resin with (methyl) acryloyl group and polymeric azo initiating agent.
The invention provides a kind of resin with (methyl) acryloyl group and liquid crystal panel sealing compound of polymeric azo initiating agent of containing.
The present invention below is described in detail in detail.
Found that of wholwe-hearted research such as the inventor: contain that technology does not have harmful effect with sealant azo initiator self when carrying out heat curing to liquid crystal under the liquid crystal drop of resin with (methyl) acryloyl group and polymeric azo initiating agent; and by making the resin solidification of uncured having (methyl) acryloyl group; can make the liquid crystal display cells of the few high quality image of color spot, until having finished the present invention.
Technology contains the polymeric azo initiating agent with sealant under the liquid crystal drop of the present invention.
Technology is with in the sealant under the liquid crystal drop of the present invention, by using this initiating agent, even for because of rayed such as black matrix less than the hermetic unit in place, also can make its curing reliably, therefore few generation liquid crystal pollution by heat.
So-called polymeric azo initiating agent in this instructions is meant that the molecular weight that has azo group and can make the generation free radical that (methyl) acryloyl group solidifies by heat is at the compound more than 300.
And above-mentioned polymeric azo initiating agent also decomposes the generation free radical by rayed usually, therefore also can be used as the optical free radical initiating agent and works.
The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiating agent is 1000, preferred upper limit is 300,000.When the number-average molecular weight less than 1000 of above-mentioned polymeric azo initiating agent, the polymeric azo initiating agent can produce harmful effect to liquid crystal sometimes, when surpassing 300,000, is difficult to sometimes and has the mixed with resin of (methyl) acryloyl group.Be limited to 5000 under the number-average molecular weight of above-mentioned polymeric azo initiating agent is preferred, be limited to 100,000 on preferred, be limited to 10,000 under most preferred, be limited to 90,000 on most preferred.
The preferred lower limit of 10 hours half life temperatures of above-mentioned polymeric azo initiating agent is that 50 ℃, preferred upper limit are 90 ℃.When 50 ℃ of 10 hours half life temperature deficiencies of above-mentioned polymeric azo compound, technology is with the storage-stable variation of sealant under the resulting sometimes liquid crystal drop.When 10 hours half life temperatures of above-mentioned polymeric azo compound surpassed 90 ℃, technology needed high temperature and long-time with the curing of sealant under the liquid crystal drop of the present invention, and the productivity of counter plate is influential sometimes.
Above-mentioned polymeric azo initiating agent for example can be enumerated has the azo initiator that is combined with the structure of unit such as a plurality of dimethyl silicone polymers or polyoxygenated alkene across azo group.
As the structure that is combined with unit such as a plurality of polyoxygenated alkene, preferably has the structure of polyethylene oxide structure.
As this polymeric azo initiating agent, for example can enumerate: 4, the condensed polymer or 4 of 4 '-azo two (4-cyanopentanoic acid) and poly alkylene glycol, 4 '-azo two (4-cyanopentanoic acid) and terminal condensed polymer with amino dimethyl silicone polymer etc. for example can be enumerated VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (being the system with the pure pharmaceutical worker's industry of light society) etc. particularly.
In addition, above-mentioned polymeric azo compound can also preferably use the polymeric azo compound of following general formula (I) expression described in TOHKEMY 2008-50572 communique or the TOHKEMY 2003-12784 communique.
In the formula (I), R
12, R
13, R
22And R
23Represent independently that respectively carbon number is 1～10 alkyl or cyano group, a and b are respectively 0～4 number independently, A
11And A
12Be macromolecular chain, Y
11And Y
12Respectively be independently-CO-O-,-O-CO-,-NH-CO-,-CO-NH-,-O-or-S-.
In the above-mentioned general formula (I), R
12, R
13, R
22And R
23The carbon number of expression is that 1～10 alkyl can be enumerated: methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, isobutyl, amyl group, isopentyl, tertiary pentyl, hexyl, cyclohexyl, cyclohexyl methyl, cyclohexyl ethyl, heptyl, different heptyl, uncle's heptyl, n-octyl, iso-octyl, uncle's octyl group, 2-ethylhexyl, n-nonyl, positive decyl etc.
In the above-mentioned general formula (I), A
11And A
12Port リ オ キ シ レ Application), polymethylene chain, polyether chain, polyester chain, polysiloxane chain, poly-(methyl) acrylate chains, polystyrene-vinyl acetate chain, polyamide chains, polyimide chain, polyurethane chain, polyureas chain, polypeptied chain etc. there is no particular limitation for the macromolecular chain of expression, for example can enumerate poly suboxygen base chain (Japanese:.Wherein, preferred Y
11For-O-CO-, Y
12Be the compound of-CO-O-, A
11And A
12When the macromolecular chain of expression is polyether chain and polyester chain, cheap especially and manufacturing easily, therefore more preferably.
In the above-mentioned general formula (I), A
11And A
12In the polymeric azo compound for polyether chain, the compound of following general formula (II) expression provide dissolubility good, control the molecular weight and the dispersed high grafting pigment of polymerization initiator easily, therefore more preferably.
In the formula (II), R
12, R
13, R
22, R
23, a is identical with above-mentioned general formula (I) with b, R
11And R
21Independent respectively expression carbon number is 1～24 alkyl, Z
11, Z
12, Z
21And Z
22The alkylidene of representing carbon number 1～4 respectively independently, m, n, s and t are respectively 0～1000 number independently, and m+n sum, s+t sum are respectively more than 2 independently.
In the above-mentioned general formula (II), Z
11, Z
12, Z
21And Z
22The carbon number of expression is that 1～4 alkylidene can be enumerated: methylene, ethylidene, trimethylene, propylidene (Japanese: プ ロ ピ レ Application), propylidene (Japanese: プ ロ ピ リ デ Application), isopropylidene (Japanese: イ ソ プ ロ ピ リ デ Application), tetramethylene, butylidene, isobutylene, ethyl ethylidene, dimethyl ethylidene etc., R
11And R
21The carbon number of expression is that 1～24 alkyl can be enumerated: methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, isobutyl, amyl group, isopentyl, tertiary pentyl, hexyl, cyclohexyl, cyclohexyl methyl, cyclohexyl ethyl, heptyl, different heptyl, uncle's heptyl, n-octyl, iso-octyl, uncle's octyl group, 2-ethylhexyl, n-nonyl, positive decyl, lauryl, stearyl, docosyl etc.For R
11And R
21The carbon number of expression is 1～24 alkyl, because carbon number is 1～4 o'clock, provide dispersed high grafting pigment, and the esterification of the compound of an end of chain polymer with hydroxyl and azodicarboxy acid compound is reactive high, therefore preferably.
The A of the polymeric azo compound of above-mentioned general formula (I) expression
11And A
12In the material of polyester chain, the dissolubility of the compound of following formula (III) expression is good, have excellent water-resistance, and is therefore preferred.
In the formula (III), R
12, R
13, R
22, R
23, a is identical with above-mentioned general formula (I) with b, Z
13And Z
23Represent independently that respectively carbon number is 1～18 alkylidene, R
31And R
41The alkyl of representing hydrogen atom or carbon number 1～24 respectively independently, p and u are respectively 1～1000 number independently.
In the above-mentioned general formula (III), Z
13, Z
23プ ロ ピ レ Application), propylidene (Japanese: プ ロ ピ リ デ Application), isopropylidene (Japanese: イ ソ プ ロ ピ リ デ Application), tetramethylene, butylidene, isobutylene, ethyl ethylidene, dimethyl ethylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji, 1 carbon number of expression is that 1～18 alkylidene can be enumerated: methylene, ethylidene, trimethylene, propylidene (Japanese:, 4-penta 2 bases, inferior decyl, inferior undecyl, 1,4-undecane two bases, inferior dodecyl, 1,11-heptadecane two bases, inferior octadecyl etc., R
31And R
41The carbon number of expression is that 1～24 alkyl can be enumerated as the R in the above-mentioned general formula (II)
11And R
21Illustrative alkyl.For R
31And R
41The carbon number of expression is 1～24 alkyl, because carbon number is 1～4 o'clock, provide esterification reactive high of compound that an end of dispersed high grafting pigment and chain polymer has hydroxyl and azodicarboxy acid compound, therefore preferably.
In the above-mentioned general formula (III), p and u are 20～100 o'clock, provide esterification reactive high of compound that an end of dispersed high grafting pigment and chain polymer has hydroxyl and azodicarboxy acid compound, therefore preferably.
There is no particular limitation for the content of the above-mentioned polymeric azo initiating agent under the liquid crystal drop of the present invention in the technology usefulness sealant; but resin 100 weight portions of above-mentioned with respect to having (methyl) acryloyl group; preferred be limited to 0.1 weight portion down, be limited to 30 weight portions on preferably.When above-mentioned polymeric azo initiating agent contain quantity not sufficient 0.1 weight portion the time, the above-mentioned sometimes polymerization with resin of (methyl) acryloyl group can not fully be carried out.When the content of above-mentioned polymeric azo initiating agent surpassed 30 weight portions, technology uprised with the viscosity of sealant under the liquid crystal drop that obtains, and sometimes the coating operability was produced harmful effect.Be limited to 0.5 weight portion under the content of above-mentioned polymeric azo initiating agent is preferred, be limited to 10 weight portions on preferred.
Technology contains the resin with (methyl) acryloyl group under the liquid crystal drop of the present invention with sealant.
There is no particular limitation for above-mentioned resin with (methyl) acryloyl group, for example can enumerate: the ester compounds by compound with hydroxyl and the reaction of (methyl) acrylic acid are obtained, epoxy (methyl) acrylate by (methyl) acrylic acid and epoxy compound being reacted obtain, (methyl) propenoic methyl carbamate by (methyl) acrylic acid derivative with hydroxyl and isocyanate reaction are obtained.
For being not particularly limited by the ester compounds that the reaction of compound with hydroxyl and above-mentioned (methyl) acrylic acid is obtained, the ester compounds of simple function for example can be enumerated: (methyl) 2-Hydroxy ethyl acrylate, (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) lauryl acrylate, (methyl) stearyl acrylate acid esters, (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 tetrahydrofuran ester, (methyl) benzyl acrylate, ethyl carbitol (methyl) acrylate, (methyl) acrylic acid phenoxy ethyl, phenoxy group diethylene glycol (methyl) acrylate, phenoxy group polyglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, 2,2,2-trifluoroethyl (methyl) acrylate, 2,2,3,3-tetrafluoro propyl group (methyl) acrylate, 1H, 1H, 5H-octafluoro amyl group (methyl) acrylate, acid imide (methyl) acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid n-octyl, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, the different myristin of (methyl) acrylic acid, (methyl) acrylic acid-2-butoxy ethyl ester, (methyl) acrylic acid-2-phenoxy ethyl, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) isodecyl acrylate, diethylamino ethyl (methyl) acrylate, dimethyl aminoethyl (methyl) acrylate, 2-(methyl) acryloxy ethyl succinic acid, 2-(methyl) acryloxy ethyl six hydrogen phthalandiones, 2-(methyl) acryloxy ethyl-2-hydroxypropyl phthalate ester, (methyl) glycidyl acrylate, 2-(methyl) acryloxy ethyl phosphonic acid ester etc.
In addition, dual functional ester compounds for example can be enumerated: 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 (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyglycol two (methyl) acrylate, epoxypropane addition bisphenol-A two (methyl) acrylate, oxirane addition bisphenol-A two (methyl) acrylate, oxirane addition Bisphenol F two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxirane modification isocyanuric acid two (methyl) acrylate, 2-hydroxyl-3-(methyl) acryloxy propyl group (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, the above ester compounds of trifunctional for example can be enumerated: 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, oxirane addition isocyanuric acid three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, double 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.
Epoxy (methyl) acrylate that reaction obtains for above-mentioned (methyl) acrylic acid by making and epoxy compound is not particularly limited, and for example can enumerate by epoxy resin and (methyl) acrylic acid are reacted the compound that obtains etc. in the presence of base catalyst according to conventional method.
The epoxy compound that becomes the raw material that is used for synthetic above-mentioned epoxy (methyl) acrylate is not particularly limited, as commercially available compound, for example can enumerate EPICOAT828EL, EPICOAT1004 bisphenol A type epoxy resins such as (all being the japan epoxy resin corporate system); EPICOAT806, EPICOAT4004 bisphenol f type epoxy resins such as (all being the japan epoxy resin corporate system); EPICLON EXA1514 bisphenol-s epoxy resins such as (big Japanese ink 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 ink 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 (Nagase Chemtex corporate systems); EPICOATYX-4000H biphenyl type epoxy resins such as (japan epoxy resin corporate systems); YSLV-50TE (Dongdu changes into corporate system) sulfides type epoxy resin; YSLV-80DE ether type epoxies such as (Dongdu change into corporate system); EP-4088S dicyclopentadiene type epoxy resin such as (rising sun electrification corporate systems); EPICLONHP4032, EPICLON EXA-4700 naphthalene type epoxy resin such as (all being big Japanese ink corporate system); EPICLON N-770 phenol novolak type epoxy resin such as (big Japanese ink corporate systems); EPICLON N-670-EXP-S o-cresol phenolic epoxy varnish such as (big Japanese ink corporate systems); EPICLON HP 7200 dicyclopentadiene novolaks type epoxy resin such as (big Japanese ink corporate systems); NC-3000P biphenyl phenolic resin varnish type epoxy resins such as (Japanese chemical drug corporate systems); ESN-165S naphthalenes such as (Dongdu change into corporate system) phenol novolak type epoxy resin, EPICOAT 630 (japan epoxy resin corporate system), EPICLON 430 (big Japanese ink corporate system), TETRAD-X glycidyl group amine type epoxy resin such as (Mitsubishi's aerochemistry corporate systems); ZX-1542 (Dongdu changes into corporate system), EPICLON 726 (big Japanese ink corporate system), EPOLIGHT 80MFA (chemical company of common prosperity society system), DENACOL EX-611 alkyl polyols type epoxy resin such as (Nagase Chemtex corporate systems); YR-450, YR-207 (all being that Dongdu changes into corporate system), EPOLEAD PB modified rubber type epoxy resin such as (Daicel chemical company systems); DENACOL EX-147 epihydric alcohol ester compounds such as (Nagase Chemtex corporate systems); EPICOAT YL-7000 bisphenol A-type episulfide resins such as (japan epoxy resin corporate systems); Also have YDC-1312, YSLV-80XY, YSLV-90CR (all being that Dongdu changes into corporate system), XAC4151 (Asahi Chemical Industry's corporate system), EPICOAT 1031, EPICOAT 1032 (all being the japan epoxy resin corporate system), EXA-7120 (big Japanese ink corporate system), TEPIC (daily output chemical company system) etc. in addition.
Epoxy (methyl) the acrylate concrete example that the reaction of above-mentioned (methyl) acrylic acid by making and epoxy compound obtains as can by the limit send into the air limit under 90 ℃ to resorcinol type epoxy resin (EX-201, Nagase Chemtex corporate system) 360 weight portions, as p methoxy phenol 2 weight portions of polymerization inhibitor, as stirrings that reflux of triethylamine 2 weight portions, acrylic acid 210 weight portions of catalysts, it is reacted obtained in 5 hours.
In addition, as the commercially available product of above-mentioned epoxy (methyl) acrylate, for example can enumerate: EBECRYL 3700, EBECRYL 3600, EBECRYL 3701, EBECRYL 3703, EBECRYL 3200, EBECRYL 3201, EBECRYL 3600, EBECRYL 3702, EBECRYL 3412, EBECRYL 860, EBECRYL RDX 63182, EBECRYL 6040, EBECRYL 3800 (all being Daicel cytec corporate system), EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD, EMA-1020 (all being Xin Zhong village chemical industrial company system), epoxy-ester M-600A, epoxy-ester 40EM, epoxy-ester 70PA, epoxy-ester 200PA, epoxy-ester 80MFA, epoxy-ester 3002M, epoxy-ester 3002A, epoxy-ester 1600A, epoxy-ester 3000M, epoxy-ester 3000A, epoxy-ester 200EA, epoxy-ester 400EA (all being chemical company of common prosperity society system), DENACOL acrylate DA-141, DENACOL acrylate DA-314, DENACOL acrylate DA-911 (all being Nagase Chemtex corporate system) etc.
Above-mentioned by making (methyl) propenoic methyl carbamate that (methyl) acrylic acid derivative with hydroxyl and isocyanate reaction obtain for example can be by in the presence of the tin based compound of catalytic amount, (methyl) acrylic acid derivative 2 equivalents with hydroxyl are reacted with it and obtain with respect to compound 1 equivalent with 2 isocyanate group.
The isocyanates that becomes above-mentioned raw material by making (methyl) propenoic methyl carbamate that (methyl) acrylic acid derivative with hydroxyl and isocyanate reaction obtain is not particularly limited, for example can enumerate: isophorone diisocyanate, 2, the 4-toluene diisocyanate, 2, the 6-toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl methane-4,4 '-diisocyanate (MDI), hydrogenation MDI, polymeric MDI, 1, the 5-naphthalene diisocyanate, norbornene alkyl diisocyanate, the tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenation XDI, Lycine diisocyanate (Japanese: リ ジ Application ジ イ ソ シ ア ネ one ト), triphenylmethane triisocyanate, three (isocyanato-phenyl) thiophosphate, tetramethylbenzene dimethyl diisocyanate, 1,6,10-undecane triisocyanate etc.
In addition, the isocyanates that becomes above-mentioned raw material by making (methyl) propenoic methyl carbamate that (methyl) acrylic acid derivative with hydroxyl and isocyanate reaction obtain is not particularly limited, for example also can use chain elongation that the reaction by polyvalent alcohols such as ethylene glycol, glycerine, D-sorbite, trimethylolpropane, (gathering) propylene glycol, carbonic ester glycol, PTMEG, polyester-diol, polycaprolactone glycol and excessive isocyanates obtains isocyanate compound.
(methyl) acrylic acid derivative with hydroxyl that becomes above-mentioned raw material by making (methyl) propenoic methyl carbamate that (methyl) acrylic acid derivative with hydroxyl and isocyanate reaction obtain is not particularly limited, for example can enumerate: (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-2-hydroxy propyl ester, (methyl) acrylic acid-4-hydroxyl butyl ester, (methyl) acrylic acid-commercially available product or ethylene glycol such as 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, epoxy acrylates such as bisphenol A modified epoxy acrylate etc.
Above-mentioned by making (methyl) propenoic methyl carbamate concrete example that (methyl) acrylic acid derivative with hydroxyl and isocyanate reaction obtain as can be by adding trimethylolpropane 134 weight portions, BHT 0.2 weight portion, dibutyl tin dilaurate 0.01 weight portion, isophorone diisocyanate 666 weight portions as catalysts as polymerization inhibitor, under 60 ℃, reflux to stir and make its reaction 2 hours, and then adding 2-Hydroxy ethyl acrylate 51 weight portions, the air limit is sent on the limit obtained its reaction in 2 hours 90 ℃ of stirrings that reflux down.
As the commercially available product of above-mentioned (methyl) propenoic methyl carbamate, for example can enumerate: M-1100, M-1200, M-1210, M-1600 (all being East Asia Synesis Company system), EBECRYL 230, EBECRYL 270, EBECRYL 4858, EBECRYL 8402, EBECRYL 8804, EBECRYL 8803, EBECRYL 8807, EBECRYL 9260, EBECRYL 1290, EBECRYL 5129, EBECRYL 4842, EBECRYL 210, EBECRYL 4827, EBECRYL 6700, EBECRYL 220, EBECRYL 2220 (all being Daicel cytec corporate system), Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all 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 (all 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.
Above-mentioned resin with (methyl) acryloyl group produces the harmful effect aspect from inhibition to liquid crystal to be considered, preferably have-the OH base ,-the NH-base ,-NH
2Hydrogen bond unit such as base are considered from synthetic aspects such as easy degree, preferred especially epoxy (methyl) acrylate.
In addition, above-mentioned resin with (methyl) acryloyl group considers preferably to have 2～3 (methyl) acryloyl groups from the high aspect of reactivity molecule.
For improving tackiness, technology also preferably contains the resin with epoxy with sealant under the liquid crystal drop of the present invention.
Above-mentioned resin with epoxy radicals is not particularly limited, and as commercially available product, for example can enumerate: EPICOAT 828EL, EPICOAT 1004 bisphenol A type epoxy resins such as (all being the japan epoxy resin corporate system); EPICOAT 806, EPICOAT 4004 bisphenol f type epoxy resins such as (all being the japan epoxy resin corporate system); EPICLON EXA1514 bisphenol-s epoxy resins such as (big Japanese ink 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 ink 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 (Nagase Chemtex corporate systems); EPICOAT YX-4000H biphenyl type epoxy resins such as (japan epoxy resin corporate systems); YSLV-50TE (Dongdu changes into corporate system) sulfides type epoxy resin; YSLV-80DE 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 (all being big Japanese ink corporate system); EPICLON N-770 phenol novolak type epoxy resin such as (big Japanese ink corporate systems); EPICLON N-670-EXP-S o-cresol phenolic epoxy varnish such as (big Japanese ink corporate systems); EPICLON HP 7200 dicyclopentadiene novolaks type epoxy resin such as (big Japanese ink corporate systems); NC-3000P biphenyl phenolic resin varnish type epoxy resins such as (Japanese chemical drug corporate systems); ESN-165S naphthalenes such as (Dongdu change into corporate system) phenol novolak type epoxy resin, EPICOAT 630 (japan epoxy resin corporate system), EPICLON 430 (big Japanese ink corporate system), TETRAD-X glycidyl group amine type epoxy resin such as (Mitsubishi's aerochemistry corporate systems); ZX-1542 (Dongdu changes into corporate system), EPICLON 726 (big Japanese ink corporate system), EPOLIGHT 80MFA (chemical company of common prosperity society system), DENACOL EX-611 alkyl polyols type epoxy resin such as (Nagase Chemtex corporate systems); YR-450, YR-207 (all being that Dongdu changes into corporate system), EPOLEAD PB modified rubber type epoxy resin such as (Daicel chemical company systems); DENACOL EX-147 epihydric alcohol ester compounds such as (Nagase Chemtex corporate systems); EPICOAT YL-7000 bisphenol A-type episulfide resins such as (japan epoxy resin corporate systems); Also have YDC-1312, YSLV-80XY, YSLV-90CR (all being that Dongdu changes into corporate system), XAC4151 (Asahi Chemical Industry's corporate system), EPICOAT 1031, EPICOAT 1032 (all being the japan epoxy resin corporate system), EXA-7120 (big Japanese ink corporate system), TEPIC (daily output chemical company system) etc. in addition.
In addition, above-mentioned resin with epoxy radicals for example can be the compound that has (methyl) acryloyl group and epoxy radicals in 1 molecule.This compound for example can be enumerated the compound that a part of epoxy radicals and the reaction of (methyl) acrylic acid by making the compound with 2 above epoxy radicals obtain etc.
By above-mentioned a part of epoxy radicals with compound of 2 above epoxy radicals is for example obtained by epoxy resin and (methyl) acrylic acid are reacted in the presence of base catalyst according to a conventional method with the compound that the reaction of (methyl) acrylic acid obtains.Particularly, phenol novolak type epoxy resin N-770 (big Japanese ink corporate system) 190g is dissolved in the 500mL toluene, in this solution, add the 0.1g triphenylphosphine, make uniform solution, after under reflux stirring, acrylic acid 35g being splashed into this solution with 2 hours, reflux again and stirred 6 hours, then can obtain the epoxy radicals of 50mol% and the phenolic varnish type solid modified epoxy (50% part propylene acidifying at this moment) of (methyl) acrylic acid reaction gained by removing toluene.
In the compound that a part of epoxy radicals by making above-mentioned compound with 2 above epoxy radicals and the reaction of (methyl) acrylic acid obtain, commercially available product for example can be enumerated EBECRYL 1561 (Daicel cytec corporate system).
Containing with sealant in technology under the liquid crystal drop of the present invention under the situation of above-mentioned resin with epoxy radicals, is that 50: 50～95: 5 mode cooperates resin with (methyl) acryloyl group and the resin with epoxy radicals with the ratio of (methyl) acryloyl group and epoxy radicals preferably.When the ratio of (methyl) acryloyl group 50% when following, when the thermal polymerization that utilizes azo initiator finishes, still have a lot of uncured epoxy resin compositions, therefore pollute liquid crystal sometimes.When the ratio of (methyl) acryloyl group 95% when above, can not produce sufficient adhesive power sometimes.
Contain with sealant in technology under the liquid crystal drop of the present invention under the situation of above-mentioned resin with epoxy radicals, preferably further contain the epoxy thermosetting agent.Above-mentioned epoxy thermosetting agent is not particularly limited, and for example can enumerate: organic acid hydrazides, imdazole derivatives, amines, polyhydric phenol based compound, acid anhydrides etc.Wherein preferably use the organic acid hydrazides of solid.
Above-mentioned solid organic acid hydrazides is not particularly limited, and for example can enumerate: sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, malonic acid hydrazides and other AJICURE VDH, AJICURE UDH (being aginomoto Microtechnic system) etc.
There is no particular limitation for the content of above-mentioned epoxy thermosetting agent, but with respect to above-mentioned resin 100 weight portions with epoxy radicals, preferably is limited to 1 weight portion down, is limited to 50 weight portions on preferably.When above-mentioned epoxy thermosetting agent contain quantity not sufficient 1 weight portion the time, almost can not obtain containing the effect of thermal curing agents.When the content of above-mentioned epoxy thermosetting agent surpassed 50 weight portions, technology can uprise with the viscosity of sealant under the liquid crystal drop of the present invention, damages coating etc. sometimes.The content of above-mentioned epoxy thermosetting agent more preferably on be limited to 30 weight portions.
As mentioned above; technology, not only makes above-mentioned resin heat curing with (methyl) acryloyl group, and can make its photocuring by using above-mentioned polymeric azo initiating agent with sealant under the liquid crystal drop of the present invention; as required, can also contain Photoepolymerizationinitiater initiater.There is no particular limitation for above-mentioned Photoepolymerizationinitiater initiater, as commercially available product, for example can enumerate: Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 819, Irgacure 651, Irgacure 369, Irgacure 379, Irgacure OXE01 (being the Ciba corporate system), benzoin styrax methyl ether, benzoin ethylether, benzoin isopropyl ether, Lucirin TPO (BASF Japanese firm system) etc.
There is no particular limitation for the content of above-mentioned Photoepolymerizationinitiater initiater, but preferably be limited to 0.1 weight portion down with respect to above-mentioned resin 100 weight portions with (methyl) acryloyl group, is limited to 10 weight portions on preferably.Above-mentioned Photoepolymerizationinitiater initiater contain quantity not sufficient 0.1 weight portion the time, can not make under the liquid crystal drop of the present invention technology with sealant photocuring fully sometimes.When the content of above-mentioned Photoepolymerizationinitiater initiater surpassed 10 weight portions, storage-stable reduced sometimes.
Technology can also contain the light-proofness colorant with sealant under the liquid crystal drop of the present invention.
By containing above-mentioned light-proofness colorant, technology is painted with sealant under the liquid crystal drop of the present invention.Thus, under the situation that the narrowed width of black mask and sealant overflow under the black mask laterally, the light that also can prevent to carry on the back illuminator spills and reduces contrast from sealant.
Technology is when adding above-mentioned light-proofness colorant in the sealant under existing liquid crystal drop, hinders rayed sometimes and damages curable.But technology by containing above-mentioned resin and polymeric azo initiating agent with (methyl) acryloyl group, can utilize heat to make its curing reliably with sealant under the liquid crystal drop of the present invention.
And so-called " light-proofness " is meant the light of the wavelength 370～800nm that covers more than 80% in this instructions.
Above-mentioned light-proofness colorant so long as under the liquid crystal drop of the present invention after giving curing technology just be not particularly limited with the few colorant of the impurity in sealant light-proofness and the liquid crystal.Above-mentioned light-proofness colorant preference such as black pigment or multiple pigment and/or dyestuff with the complementary colors relation that after mixing, becomes black.
Above-mentioned black pigment is not particularly limited, and for example can enumerate: iron oxide, titanium are black, nigrosine, cyanine are black, fullerene, carbon black, resin-coating type carbon black etc.Above-mentioned black pigment can use separately also and can more than 2 kinds and use.Wherein, consider the black and/or carbon black of preferred titanium from insulativity, operability aspect.
Above-mentioned carbon black so long as the few carbon black of the stripping of impurity in liquid crystal just there is no particular limitation, for example can use known carbon blacks such as channel black, dim, furnace black, pyrolytic carbon black.Wherein, consider from the viewpoint of insulativity, the preferred surface grafting grafting carbon black, surface be insulated coating carbon black that inorganics or insulativity organism coat and/or the acidic black of the surface having been implemented oxidation processes.It is low that this carbon black and the carbon black that is untreated are compared electric conductivity, when therefore technology is used sealant under being used for liquid crystal drop of the present invention, can obtain sewing less and liquid crystal display cells that reliability is high of electric current.
Above-mentioned titanium is black, and there is no particular limitation, as concrete commercially available product, for example can enumerate 12S, 13M, 13MC, 13R-N (more than be Mitsubshi Materials Corp's system), テ イ ラ Star Network D (red fringe changes into corporate system) etc.In addition, can also use that the black surface of above-mentioned titanium to have been carried out titanium that inorganic constituents such as the black or oxidized silicon of the titanium of coupling agent treatment, titanium dioxide, germanium oxide, aluminium oxide, zirconia, magnesium oxide coat black etc.
The multiple organic pigment that becomes the complementary colors relation of black when having above-mentioned mixing is not particularly limited, and for example can enumerate: condensation polycyclic pigment such as phthalocyanine pigment such as azo class pigment such as insoluble azo colour, dissolubility AZO pigments or copper phthalocyanine blue pigment, copper halide phthalocyanine color, sulfonated copper phthalocyanine pigment, metal-free phthalocyanine, different metal phthalocyanine color or amino anthraquinones pigment, indanthrene pigment, isoindolinone pigment, quinacridone pigment, triazine dioxin pigment, purple cyclic ketones pigment, perylene dye etc.Wherein, preferably use copper halide phthalocyanine color or condensation polycyclic pigment.The auxiliary coloring components that these organic pigments also can be used as above-mentioned black pigment uses.
The multiple dyestuff that becomes the complementary colors relation of black when having above-mentioned mixing is not particularly limited, and for example can enumerate: cyanine class dyestuff, phthalocyanine (Japanese: class dyestuff メ タ シ ア ニ Application), alkalescence cyanines (Japanese: ロ one ダ シ ア ニ Application) class dyestuff, Oxonol (Japanese: class dyestuff オ キ ソ ノ one Le), styryl dye, substrate styrene (Japanese: ベ one ス ス チ リ Le) class dyestuff, the benzo pyran dyestuff, quinolizine class dyestuff, the Coumarins dyestuff, the thiazoles dyestuff, indanthrene dyes, the pyranthrone dyestuff, anthraquinone carbazoles dyestuff En Kun oxazole class dyestuff, indigo, thioindigo class dyestuff, the pyrazolone azo dyes, γ-sour azo dyes, H-acid azo dyes, triallyl methane class dyestuff oxazine class dyestuff etc.The auxiliary coloring components that these dyestuffs also can be used as above-mentioned black pigment uses.
There is no particular limitation for the particle diameter of above-mentioned light-proofness colorant, and the preferred lower limit of primary particle is that 10nm, preferred upper limit are 500nm.If the particle diameter of above-mentioned light-proofness colorant is beyond this scope the time, in the technology of dripping of the present invention with the dispersed variation in the sealant.
There is no particular limitation for the content of above-mentioned light-proofness colorant, is 5 weight portions with respect to the technology of dripping of the present invention with the general assembly (TW) 100 weight portion preferred lower limit of sealant, and preferred upper limit is 50 weight portions.When above-mentioned light-proofness colorant contain quantity not sufficient 5 weight portions the time, sometimes can not obtain sufficient light-proofness, when surpassing 50 weight portions, technology reduces or the reduction of drawing property the adaptation of substrate or the intensity after the curing with sealant under the liquid crystal drop of the present invention sometimes.Be limited to 10 weight portions under the content of above-mentioned light-proofness colorant preferred, be limited to 40 weight portions on preferred.
The technology of dripping of the present invention except that above-mentioned light-proofness colorant, can also contain pigment (organic pigment, inorganic pigment) or dyestuff etc. as auxiliary coloring components with sealant.For example when above-mentioned black pigment is rubescent black, present auxiliary coloring components by interpolation as the blueness of red complementary colors, can make above-mentioned light-proofness colorant present better black.
Technology more preferably 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 gluing auxiliary agent that technology usefulness sealant and liquid crystal display cells substrate under the liquid crystal drop is good gluing.
Above-mentioned silane coupling agent is not particularly limited, to improve effect good because with the tackiness of glass substrate etc., can therefore preferably use for example gamma-amino propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-isocyanato-propyl trimethoxy silicane etc. by preventing to flow in the liquid crystal with the curable resin chemical bond is incompatible.These silane coupling agents both can use separately, also can be also with two or more.
For improving the tackiness that produced by the stress dispersion effect, improving linear expansivity etc., technology can also contain filling agent with sealant under the liquid crystal drop of the present invention.
There is no particular limitation for above-mentioned filling agent, for example can enumerate: talcum, asbestos, silicon dioxide, zeyssatite, smectite, bentonitic clay, lime carbonate, magnesium carbonate, aluminium oxide, polynite, zeyssatite, zinc paste, iron oxide, magnesium oxide, tin oxide, titanium dioxide, magnesium hydroxide, aluminium hydroxide, beaded glass, silicon nitride, barium sulphate, gypsum, calcium silicate, talcum, beaded glass, the sericite atlapulgite, bentonitic clay, inorganic fillers such as aluminium nitride, or polyester micropartical, polyurethane particulate, the polyvinyl particulate, organic fillers such as acrylate copolymer particulate.
Technology with sealant as required under the liquid crystal drop of the present invention, the polymer microbeads that can also contain the reactive diluent that is useful on the viscosity adjustment, adjust thixotropic thixotropic agent, is used to adjust panel gap is thing, 3-rubigan-1 uniformly-spaced, curing accelerators such as 1-dimethyl urea, defoamer, levelling agent, polymerization inhibitor, other adjuvant etc.
There is no particular limitation for the manufacture method of sealing material for liquid crystal display device of the present invention, for example can enumerate and utilize present known method with above-mentioned resin with (methyl) acryloyl group, polymeric azo initiating agent, and the method for mixing such as the adjuvant that cooperates as required etc.
Cooperate electrically conductive microparticle by technology under liquid crystal drop of the present invention in sealant, can make conductive material up and down.
There is no particular limitation for above-mentioned electrically conductive microparticle, can use Metal Ball for example, be formed with material of conductive metal layer etc. on the surface of resin particle.Wherein, form the material of conductive metal layer owing to can utilize the resin particle excellent elasticity on the surface of resin particle, ground such as lesion electrode does not realize that conduction connects, and is therefore preferred.
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 of conductive material manufacturing up and down of the present invention.
The manufacture method of liquid crystal display cells of the present invention for example can be enumerated method that includes following operation etc., described operation is: by serigraphy, distribute coating etc. with technology under the liquid crystal drop of the present invention with printing such as sealant or be coated on the side with the substrate of 2 plate electrodes such as ito thin film, the operation of formation seal pattern; The fine droplet of liquid crystal dripped to be coated in the frame of seal pattern, makes the overlapping operation of another substrate in a vacuum; With the operation that technology under the liquid crystal drop of the present invention is made its precuring with light such as irradiation ultraviolet radiation such as sealants; And heat the operation that makes the seal pattern that constitutes with sealant etc. by technology under the liquid crystal drop of the present invention lead curing.
Using technology under the aforesaid liquid crystal drop of the present invention also is one of the present invention with sealant and/or the liquid crystal display cells of conductive material manufacturing up and down of the present invention.
Contain and above-mentionedly have the resin of (methyl) acryloyl group and the liquid crystal panel of above-mentioned polymeric azo initiating agent also is one of the present invention with sealing compound.
Utilizing prior art is vacuum injection mode when making liquid crystal indicator, and with above-mentioned identical when utilizing that mode is made liquid crystal indicator under the liquid crystal drop, liquid crystal panel contacts with liquid crystal with uncured state when encapsulated liquid crystals with sealing compound.At this moment, liquid crystal panel is not shone the sufficient light time with sealing compound, around mouth-sealed portion, still producing color spot, can not obtain the liquid crystal display cells of high quality image.If liquid crystal panel of the present invention with the sealant of sealing compound when utilizing the vacuum injection mode to make liquid crystal indicator, can be made the liquid crystal display cells of the few high quality image of color spot.Particularly under the situation of the ultraviolet panel designs of underexpose, extremely effective.
Liquid crystal panel of the present invention is identical with technology usefulness sealant under the liquid crystal drop of the present invention with sealing compound, can contain resin with epoxy radicals, epoxy thermosetting agent, Photoepolymerizationinitiater initiater, light-proofness colorant, silane coupling agent, filling agent, various adjuvants etc.
According to the present invention, provide a kind of utilization to drip technology when making liquid crystal display cells, also can make technology sealant under the liquid crystal drop of liquid crystal display cells of the few high quality image of color spot.In addition, also provide a kind of when utilizing the vacuum injection mode to make the liquid crystal display cells device, can make the liquid crystal panel sealing compound of the liquid crystal display cells of the few high quality image of color spot.
Description of drawings
Fig. 1 is shown schematically in the figure that utilizes mode under the liquid crystal drop to make the order of liquid crystal display cells in embodiment, the comparative example.
Fig. 2 is shown schematically in the figure that utilizes the vacuum injection mode to make the order of liquid crystal display cells in embodiment, the comparative example.
Embodiment
Below, enumerate embodiment and illustrate in greater detail mode of the present invention, but the present invention has more than and is defined in these embodiment.
(synthesizing of epoxy acrylate (EX-201 modification product))
120g EX-201 (resorcinol type epoxy resin) is dissolved in the 500mL toluene, in this solution, adds the 0.1g triphenyl phasphine and make uniform solution.Dripped 70g acrylic acid with 2 hours under reflux stirring in this solution after, stirring 8 hours again refluxes.Then, by remove toluene obtain all epoxy radicals all modification become the epoxy acrylate (EX-201 modification product) of acryloyl group.
(synthesizing of part propylene acidylate epoxy acrylate (the partially modified product of N-770))
190g N-770 (phenol novolak type epoxy resin) is dissolved in the 500mL toluene, in this solution, adds the 0.1g triphenyl phasphine and make uniform solution, in this solution reflux stir under with behind 2 hours Dropwise 35 g acrylic acid, stirring 6 hours again refluxes.Then, by removing the part propylene acidylate epoxy acrylate (the partially modified product of N-770) that epoxy radicals modification that toluene obtains 50 moles of % becomes acryloyl group.
(embodiment 1～10, and comparative example 1～3)
Press the described match ratio of table 1, after each material is mixed with planetary stirring machine (Thinky corporate system " あ わ と り Practice is the youth too "), with triple-roller mill it is mixed again, prepare technology sealant under the liquid crystal drop of embodiment 1～10, comparative example 1～3 thus.
As shown in Figure 1, on the substrate that is formed with transparency electrode and alignment films,, be coated with technology sealant under the resulting liquid crystal drop with divider to describe the mode of square-shaped frame, in addition, get technology sealant under the resulting liquid crystal drop ready in the inside of square-shaped frame.Then the fine droplet of liquid crystal (Chisso corporate system " JC-5004LA ") is dripped and be coated in the frame of whole transparent base, overlapping in a vacuum other the substrate that is formed with transparency electrode and alignment films, after removing vacuum, use high-pressure mercury-vapor lamp with 100mW/cm to the housing sealing
230 seconds of irradiation ultraviolet radiation.At this moment, technology under the liquid crystal drop after getting ready is not formed mask with the mode that sealant shines UV.Carry out liquid crystal annealing in 1 hour at 120 ℃ then, make technology sealant heat curing under the liquid crystal drop simultaneously, obtain liquid crystal display cells.
＜estimate
To embodiment 1～10, and comparative example 1～3 under the liquid crystal drop that obtains technology with sealant, reach liquid crystal display cells and carry out following evaluation.The result is illustrated in the table 1.
(panel shows uneven evaluation)
To the liquid crystal display cells that obtains, the color spot that technology produces with the liquid crystal around the sealant under the liquid crystal drop after visualization is got ready under "on" position and the non-power status.Its result will not have the average evaluation of color spot to be " ◎ " fully; Almost there is not the average evaluation of color spot to be " zero "; There is the average evaluation of a small amount of color spot to be " △ "; There is the average evaluation of a lot of color spots to be " * ".
(adhesive strength evaluation)
With respect to sealant 100 weight portions of technology under the liquid crystal drop that obtains, with mean grain size is that polymer microbeads (ponding chemical industrial company system " Micro-Pearl SP ") 3 weight portions of 5 μ m make its dispersion make uniform liquid with planetary stirring apparatus, get denier in the corning glass 1737 (central portion of 20mm * 50mm * 1.1mmt), the glass of homotype is in the above overlapping, the extruding liquid crystal technology of dripping makes its diffusion with sealant, with 100mW/cm
220 seconds of irradiation ultraviolet radiation.Heated 1 hour down at 120 ℃ then, obtain the adhesive test sheet.This test film is measured adhesive strength with tensiometer, and (comparative unit is N/cm
2).
[table 1]
(embodiment 11～15, and comparative example 4～5)
Press the described match ratio of table 2, each material is mixed with planetary stirring machine (Thinky corporate system " あ わ と り Practice is the youth too "), prepare the liquid crystal panel sealing compound of embodiment 11～15, comparative example 4～5 thus.
As shown in Figure 2, on the substrate that is formed with transparency electrode and alignment films, in the interrupted mode of the part of square-shaped frame, with technology sealant under the liquid crystal drop of divider coating embodiment 1, then, overlapping other the substrate that is formed with transparency electrode and alignment films is forced into sealant and forms predetermined gap, carry out 1 hour heat treated at 120 ℃, obtain the preflood dummy cell of liquid crystal.Then, make dummy cell be vacuum state after, liquid crystal (Chisso corporate system " JC-5004LA ") with after the interrupted place of the part of square-shaped frame contacts, is returned to normal pressure, placed 2 hours, obtain the unit that inside is full of liquid crystal thus.
Then, with embodiment 11～15, and the sealing compound of comparative example 4～5, with the part of square-shaped frame interrupted local use resulting liquid crystal panel with the sealing compound sealing after, to this sealing compound with high-pressure mercury-vapor lamp with 100mW/cm
230 seconds of irradiation ultraviolet radiation.Carry out liquid crystal annealing in 1 hour at 120 ℃ then, make the sealing compound heat curing simultaneously, obtain liquid crystal display cells.In addition, at this moment, to sealing compound not irradiation ultraviolet radiation, under 120 ℃ of conditions of carrying out the annealing of 1 hour liquid crystal, also obtain liquid crystal display cells.
＜estimate
To embodiment 11～15, and comparative example 4～5 in the liquid crystal display cells that obtains, carry out panel by the following method and show uneven evaluation.The result is illustrated in the table 2.
(panel shows uneven evaluation)
To the liquid crystal display cells that obtains, the color spot that the liquid crystal under "on" position and non-power status around the visualization mouth-sealed portion produces.Its result will not have the average evaluation of color spot to be " ◎ " fully; Almost there is not the average evaluation of color spot to be " zero "; There is the average evaluation of a small amount of color spot to be " △ "; There is the average evaluation of a lot of color spots to be " * ".
[table 2]
(reference example 1～5)
Press the described match ratio of table 3, after each material is mixed with planetary stirring machine (Thinky corporate system " あ わ と り Practice is the youth too "), with triple-roller mill it is mixed again, prepare technology sealant under the liquid crystal drop of reference example 1～5 thus.
＜estimate
To technology sealant under the liquid crystal drop that in reference example 1～5, obtains, estimate OD value and curable in order to following method.And then, use the method identical to estimate panel and show uneven with embodiment.
The results are shown in table 3.
(mensuration of optical density (OD value))
Technology is with adding silicon dioxide spacer thing (ponding chemical industrial company system, the Micro-Pearl SI) 1g of diameter 5 μ m among the sealant 100g as sept mixing stirring under the liquid crystal drop that obtains.
The adding that obtains is had technology is coated on sealant on the glass substrate of 50mm * 50mm under the liquid crystal drop of sept, the glass substrate of same specification is overlapped on this substrate, apply load, crush, form homogeneous thickness to the diameter of sept.Secondly, use metal halide lamp with 100mW/cm
230 seconds of irradiation ultraviolet radiation.Then, in baking oven, under 120 ℃, carry out solidifying in 1 hour, obtain the working sample of shading sealant.Use KONICA corporate system PDA-100 to measure optical density (OD value) to the sample that obtains.
(evaluation of curable)
Technology under the liquid crystal drop is clipped between 2 polyethylene terephthalate films with sealant, and the thickness that makes sealant is about 5 μ m, makes sample.Use high-pressure mercury-vapor lamp with 100mW/cm to this sample
2Irradiation ultraviolet radiation carries out thermal treatment in 1 hour after 30 seconds under 120 ℃.When after thermal treatment, peeling off the polyethylene terephthalate film, will be on the two sides not the average evaluation of residual pleat be " zero ", be " * " with the average evaluation of arbitrary residual pleat.
[table 3]
Utilizability on the industry
According to the present invention, when providing a kind of utilization to drip technology manufacturing liquid crystal display cells, can make the sealant for liquid crystal dripping process of the liquid crystal display cells of the few high quality image of color spot. In addition, also provide a kind of when utilizing the vacuum injection mode to make the liquid crystal display cells device, can make the liquid crystal panel sealing compound of the liquid crystal display cells of the few high quality image of color spot.
Claims (according to the modification of the 19th of treaty)
1. technology sealant under the liquid crystal drop is characterized in that,
Contain resin with (methyl) acryloyl group and number-average molecular weight and be 5000～100,000 polymeric azo initiating agent.
2. technology sealant under the liquid crystal drop according to claim 1 is characterized in that,
The polymeric azo initiating agent has dimethyl silicone polymer unit or polyoxygenated alkene unit.
3. technology sealant under the liquid crystal drop according to claim 1 and 2 is characterized in that,
Also contain resin and epoxy thermosetting agent with epoxy radicals.
4. according to technology sealant under claim 1, the 2 or 3 described liquid crystal drops, it is characterized in that,
Also contain Photoepolymerizationinitiater initiater.
5. according to technology sealant under claim 1,2, the 3 or 4 described liquid crystal drops, it is characterized in that,
Also contain the light-proofness colorant.
6. conductive material about in the of a kind is characterized in that,
Contain technology sealant and electrically conductive microparticle under claim 1,2,3, the 4 or 5 described liquid crystal drops.
7. a liquid crystal panel sealing compound is characterized in that,
Contain resin and polymeric azo initiating agent with (methyl) acryloyl group.
8. a liquid crystal display cells is characterized in that,
Used technology sealant and/or the described conductive material up and down of claim 6 under claim 1,2,3, the 4 or 5 described liquid crystal drops.
9. a liquid crystal display cells is characterized in that,
Used the described liquid crystal panel sealing compound of claim 7.
Claims (9)
1. technology sealant under the liquid crystal drop is characterized in that,
Contain resin and polymeric azo initiating agent with (methyl) acryloyl group.
2. technology sealant under the liquid crystal drop according to claim 1 is characterized in that,
The polymeric azo initiating agent has dimethyl silicone polymer unit or polyoxygenated alkene unit.
3. technology sealant under the liquid crystal drop according to claim 1 and 2 is characterized in that,
Also contain resin and epoxy thermosetting agent with epoxy radicals.
4. according to technology sealant under claim 1, the 2 or 3 described liquid crystal drops, it is characterized in that,
Also contain Photoepolymerizationinitiater initiater.
5. according to technology sealant under claim 1,2, the 3 or 4 described liquid crystal drops, it is characterized in that,
Also contain the light-proofness colorant.
6. conductive material about in the of a kind is characterized in that,
Contain technology sealant and electrically conductive microparticle under claim 1,2,3, the 4 or 5 described liquid crystal drops.
7. a liquid crystal panel sealing compound is characterized in that,
Contain resin and polymeric azo initiating agent with (methyl) acryloyl group.
8. a liquid crystal display cells is characterized in that,
Used technology sealant and/or the described conductive material up and down of claim 6 under claim 1,2,3, the 4 or 5 described liquid crystal drops.
9. a liquid crystal display cells is characterized in that,
Used the described liquid crystal panel sealing compound of claim 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008109201 | 2008-04-18 | ||
| JP2008-109201 | 2008-04-18 | ||
| PCT/JP2009/057568 WO2009128470A1 (en) | 2008-04-18 | 2009-04-15 | Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102007447A true CN102007447A (en) | 2011-04-06 |
| CN102007447B CN102007447B (en) | 2013-01-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980112979.9A Active CN102007447B (en) | 2008-04-18 | 2009-04-15 | Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP4616404B2 (en) |
| KR (1) | KR101194202B1 (en) |
| CN (1) | CN102007447B (en) |
| TW (1) | TW200949393A (en) |
| WO (1) | WO2009128470A1 (en) |
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| CN103764707A (en) * | 2011-08-18 | 2014-04-30 | 积水化学工业株式会社 | Epoxy compound, epoxy compound mixture, curable composition, and connecting structure |
| WO2017031775A1 (en) * | 2015-08-25 | 2017-03-02 | 深圳市华星光电技术有限公司 | Branched organosilicon material and method for preparing liquid crystal display panel |
| CN110325904A (en) * | 2017-07-14 | 2019-10-11 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
| TWI682024B (en) * | 2014-05-23 | 2020-01-11 | 日商積水化學工業股份有限公司 | Sealant for liquid crystal dropping method, upper and lower conduction materials, and liquid crystal display element |
| TWI690560B (en) * | 2016-12-27 | 2020-04-11 | 日商積水化學工業股份有限公司 | Sealant for liquid crystal display element, upper and lower conduction materials and liquid crystal display element |
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| US8362151B2 (en) * | 2002-05-31 | 2013-01-29 | Elsicon, Inc. | Hybrid polymer materials for liquid crystal alignment layers |
| JP2012088412A (en) * | 2010-10-18 | 2012-05-10 | Sekisui Chem Co Ltd | Light-shielding sealing agent for liquid crystal display element, vertical conducting material and liquid crystal display element |
| WO2012077572A1 (en) * | 2010-12-09 | 2012-06-14 | 積水化学工業株式会社 | Sealing material for liquid-crystal dropping process, material for vertical conduction, and liquid-crystal display element |
| CN103026292B (en) | 2011-04-05 | 2014-03-05 | 积水化学工业株式会社 | Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element |
| JP5926617B2 (en) * | 2011-06-01 | 2016-05-25 | 積水化学工業株式会社 | Light-shielding sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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| US6074628A (en) * | 1997-04-25 | 2000-06-13 | Procter & Gamble | Hairspray compositions containing silicon block copolymers |
| JP2000298352A (en) * | 1999-04-14 | 2000-10-24 | Jsr Corp | Material for electronic parts and method for using same |
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| 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 |
| KR101049998B1 (en) * | 2006-09-07 | 2011-07-19 | 미쓰이 가가쿠 가부시키가이샤 | Liquid crystal sealing agent, method for manufacturing liquid crystal display panel using the liquid crystal sealing agent, and liquid crystal display panel |
| WO2008102550A1 (en) * | 2007-02-20 | 2008-08-28 | Mitsui Chemicals, Inc. | Curable resin composition for sealing liquid crystal, and method for production of liquid crystal display panel using the same |
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2009
- 2009-04-15 CN CN200980112979.9A patent/CN102007447B/en active Active
- 2009-04-15 WO PCT/JP2009/057568 patent/WO2009128470A1/en active Application Filing
- 2009-04-15 JP JP2009516789A patent/JP4616404B2/en active Active
- 2009-04-15 KR KR1020107018271A patent/KR101194202B1/en active IP Right Grant
- 2009-04-17 TW TW98112732A patent/TW200949393A/en unknown
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2010
- 2010-10-14 JP JP2010231631A patent/JP2011059700A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2011059700A (en) | 2011-03-24 |
| TWI379133B (en) | 2012-12-11 |
| KR20110007091A (en) | 2011-01-21 |
| TW200949393A (en) | 2009-12-01 |
| KR101194202B1 (en) | 2012-10-25 |
| JPWO2009128470A1 (en) | 2011-08-04 |
| WO2009128470A1 (en) | 2009-10-22 |
| JP4616404B2 (en) | 2011-01-19 |
| CN102007447B (en) | 2013-01-23 |
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