CN105309043A - Sealing agent for display elements - Google Patents
Sealing agent for display elements Download PDFInfo
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- CN105309043A CN105309043A CN201480030689.0A CN201480030689A CN105309043A CN 105309043 A CN105309043 A CN 105309043A CN 201480030689 A CN201480030689 A CN 201480030689A CN 105309043 A CN105309043 A CN 105309043A
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- display element
- mentioned
- monomer
- methyl
- element sealant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated 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
Abstract
The purpose of the present invention is to provide a sealing agent for display elements, which is capable of suppressing generation of an outgas, has excellent adhesion and provides a cured product that has excellent transparency. The present invention is a sealing agent for display elements, which contains a polymerization initiator and a polymerizable compound that contains a polythiol monomer having two or more thiol groups in each molecule, a polyene monomer having two or more carbon-carbon double bonds in each molecule, and a thioether oligomer that is formed by a reaction between the polythiol monomer and the polyene monomer.
Description
Technical field
The present invention relates to one can suppress escape gas (ア ウ ト ガ ス) generation and the display element sealant of the transparency excellence of cementability and solidfied material.
Background technology
In recent years, as having display element that is slim, the feature such as lightweight, low power consumption, liquid crystal display cells, organic EL display element etc. is being widely used.For these display elements, usually in the sealing etc. of liquid crystal or luminescent layer, use Photocurable resin composition.
Liquid crystal display cells manufactures by following manner usually: make 2 transparency carriers with electrode opposed across the interval of regulation, utilize sealant by its environmental seal, thus form box (セ Le), in box, inject liquid crystal from the liquid crystal injecting port being arranged at its part, and use liquid crystal injecting port sealant to be sealed by this liquid crystal injecting port.In the past, as liquid crystal injecting port sealant, progressively use the acrylic resin composition etc. of this light-cured type described in the curable epoxy resin composition of 1 liquid type or 2 liquid types, patent documentation 1 widely.But, heat for a long time under 1 liquid type curable epoxy resin composition needs high temperature usually, so productivity is poor, the curable epoxy resin composition of 2 liquid types needs time when host being mixed with curing agent, in addition, must use within the up time (pot life) after mixing, therefore especially be wanting in operability.On the other hand, although the acrylic resin composition operability of light-cured type and productivity excellence, but there is following problems: strong with the interaction of liquid crystal, therefore can pollute liquid crystal and produce irregular colour; Or because of acrylic resin remaining in the manufacture process of display element, and produce a large amount of ease gas; Or be wanting in the transparency of cementability or solidfied material.
In addition, for organic EL display element, if organic light emitting material or electrode are exposed to open-air, then its performance is sharply deteriorated, therefore in order to improve stability, the durability of organic EL display element, propose and make organic light emitting material and electrode across inorganic material film, and utilize resin molding to cover and carry out the method that seals.Such as, Patent Document 2 discloses the method forming the resin molding be made up of the resin combination of acrylic acid series on inorganic material film.In addition, in patent documentation 3, also disclose the method based on light cationic polymerization.But, also there is the problems such as the generation ease gas caused by acrylic resin in the above cases.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 6-160972 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2001-307873 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2005-336314 publication
Summary of the invention
Invent problem to be solved
The object of the invention is to, provide a kind of and can suppress the ease generation of gas and the display element sealant of the transparency excellence of cementability and solidfied material.
For solving the means of problem
The present invention is a kind of display element sealant, it contains polymerizable compound and polymerization initiator, described polymerizable compound contain the mercapto in 1 molecule with more than 2 polythiol monomer, have in 1 molecule the carbon-to-carbon double bond of more than 2 polyenic monomer and by the reaction of described polythiol monomer and described polyenic monomer and the polythioether oligomeric thing formed.
Below, the present invention is described in detail in detail.
The present inventor finds, as the polymerizable compound used in display element sealant, and be used in 1 molecule the mercapto with more than 2 polythiol monomer, have in 1 molecule the carbon-to-carbon double bond of more than 2 polyenic monomer and by the reaction of this polythiol monomer and this polyenic monomer and the polythioether oligomeric thing formed, can be obtained suppressing escaping the display element sealant of transparency excellence of the generation of gas, cementability and solidfied material thus, so far completes the present invention.
Display element sealant of the present invention can also prevent the generation of liquid crystal pollution, the infringement to organic light emitting material.
It should be noted that, in this manual, above-mentioned " display element " represents liquid crystal display cells and organic EL display element.
In display element sealant of the present invention, as polymerizable compound, containing having the polythiol monomer (being also simply called below " polythiol monomer ") of mercapto of more than 2, the polyenic monomer (being also simply called below " polyenic monomer ") in 1 molecule with the carbon-to-carbon double bond of more than 2 and the polythioether oligomeric thing (being also simply called below " polythioether oligomeric thing ") formed by the reaction of this polythiol monomer and this polyenic monomer in 1 molecule.Display element sealant of the present invention containing these compositions can suppress the generation of ease gas, forms the display element sealant of the transparency excellence of cementability and solidfied material.
As above-mentioned polythiol monomer, can enumerate such as: the aliphat polythiols such as dimercaptoethylsulfide, propanedithiol, hexa-methylene two mercaptan, decamethylene two mercaptan, the aromatic series polythiols such as toluylene-2,4-bis-mercaptan, dithio-xylene alcohol, the cyclic thioether compounds such as the multi-thioalcohol compound containing Isosorbide-5-Nitrae-dithiane ring represented by following formula (1), containing the multi-thioalcohol compound of ester bond, diethylene glycol two mercaptan, triethylene glycol two mercaptan, TEG two mercaptan, thio-diethylene glycol two mercaptan, sulfo-triethylene glycol two mercaptan, sulfo-TEG two mercaptan, three-(3-mercaptopropionyl oxygen base)-ethyl isocyanurate, TEG-bis-(3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite-four (3-mercaptopropionic acid ester), dipentaerythritol-six (3-mercaptopropionic acid ester), 4-(mercapto methyl)-3, 6-dithiaoctane-1, 8-bis-mercaptan, 4, two (mercapto methyl)-3 of 8-, 6, 9-tri-sulfo-hendecane-1, 11-bis-mercaptan, 1, 3, 4, other the polythiol monomer etc. such as 6-tetra-mercapto radical propionyl group glycoluril.These polythiol monomer may be used singly or in combination of two or more.
[changing 1]
In formula (1), l represents the integer of 1 ~ 5.
As represented by above-mentioned formula (1) containing 1, the multi-thioalcohol compound of 4-dithiane ring, specifically, can list such as 2,5-dimercapto methyl isophthalic acid, 4-dithiane, 2,5-dimercapto ethyl-Isosorbide-5-Nitrae-dithiane, 2,5-dimercapto propyl group-1,4-dithiane, 2,5-dimercapto butyl-Isosorbide-5-Nitrae-dithiane etc.
In above-mentioned polythiol monomer, in order to make the display element sealant of gained excellent in transparent, preferably containing the polythiol monomer of ester bond.
As the above-mentioned polythiol monomer containing ester bond, specifically, such as trimethylolpropane tris (3-mercaptopropionic acid ester), three-[(3-mercaptopropionyl oxygen base)-ethyl]-isocyanuric acid esters, pentaerythrite four mercaptoacetate, pentaerythrite four (3-mercaptopropionic acid ester), TEG two (3-mercaptopropionic acid ester) etc. can be enumerated.
Wherein, preferred trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite-four (3-mercaptopropionic acid ester), dipentaerythritol-six (3-mercaptopropionic acid ester), containing 1, the multi-thioalcohol compound of 4-dithiane ring, more preferably trimethylolpropane tris (3-mercaptopropionic acid ester), dipentaerythritol-six (3-mercaptopropionic acid ester), 2,5-dimercapto-methyl-1,4-dithiane.
In addition, above-mentioned polythiol monomer is preferably containing the monomer (3 officials can polythiol monomer) above of mercapto in 1 molecule with more than 3.
Can above polythiol monomer as above-mentioned 3 officials, preferably there is the monomer of 3 ~ 20 mercaptos in 1 molecule, more preferably containing the monomer in 1 molecule with 3 ~ 8 mercaptos.
The preferred lower limit of the content of the above-mentioned polythiol monomer in overall 100 weight portions of above-mentioned polymerizable compound is 5 weight portions, the preferred upper limit is 40 weight portions.If the content of above-mentioned polythiol monomer is lower than 5 weight portions, then coating is deteriorated sometimes.If the content of above-mentioned polythiol monomer is more than 40 weight portions, then sometimes cannot suppress the generation of ease gas fully.The preferred lower limit of the content of above-mentioned polythiol monomer is 10 weight portions, and the preferred upper limit is 35 weight portions.
As above-mentioned polyenic monomer, (methyl) allyl compound, (methyl) acrylic compounds, divinylbenzene etc. can be enumerated such as.These polyenic monomers may be used singly or in combination of two or more.
It should be noted that, in this manual, above-mentioned " (methyl) pi-allyl " refer to pi-allyl or methacrylic, and above-mentioned " (methyl) acrylic compounds " refers to acrylic compounds or methacrylic.
As above-mentioned (methyl) allyl compound, can enumerate such as: triallyl cyanurate, triallyl isocyanurate, isocyanuric acid trimethyl allyl ester, diallyl maleate, diallyl adipate, diallyl phthalate, triallyltrimelitate, pyromellitic acid four allyl ester, glycerol diallyl ether, trimethylolpropane allyl ether, pentaerythrite, diallyl ether, 1, 3-diallyl-5-glycidyl isocyanurate, 1, 3, 4, 6-tetraallyl glycoluril, 1, 3, 4, 6-tetraallyl-3a-methyl glycoluril, 1, 3, 4, 6-tetraallyl-3a, 6a-dimethylglycoluril etc.Wherein, preferred triallyl cyanurate, triallyl isocyanurate, 1,3,4,6-tetraallyl glycoluril.
As above-mentioned (methyl) acrylic compounds; as long as be the compound in 1 molecule with acryloyl group or methacryl more than 2; just being not particularly limited, can enumerating such as: epoxy (methyl) acrylate obtained by the reaction of (methyl) acrylic acid and epoxy compounds, the ester compounds obtain by making (methyl) acrylic acid react with the compound with hydroxyl, to be reacted by (methyl) acrylic acid derivative making isocyanates and there is hydroxyl and carbamate (methyl) acrylate etc. that obtains.
It should be noted that, it is in this manual, above-mentioned that " " refer to acrylate or methacrylate, above-mentioned " epoxy (methyl) acrylate " represents the compound making the whole epoxy radicals in epoxy compounds and (methyl) acrylic acid react and obtain to (methyl) acrylate.
Above-mentioned epoxy (methyl) acrylate is not particularly limited, and can enumerate such as: epoxy (methyl) acrylate obtained by making (methyl) acrylic acid and epoxy compounds react under the existence of base catalyst according to conventional methods.
With regard to the epoxy compounds of the raw material as above-mentioned epoxy (methyl) acrylate, can list such as: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2, 2 '-diallyl bisphenol type epoxy compounds, A Hydrogenated Bisphenol A type epoxy compounds, expoxy propane addition bisphenol A type epoxy compound, resorcinol type epoxy compounds, biphenyl type epoxy compound, thioether-type epoxy compounds, diphenyl ether type epoxy compounds, dicyclopentadiene type epoxy compound, naphthalene type epoxy compounds, phenol novolak type epoxy compounds, orthoresol novolak type epoxy compound, dicyclopentadiene phenolic type epoxy compounds, biphenyl novolak type epoxy compound, naphthalene phenol novolak type epoxy compounds, glycidyl amine epoxy compound, alkyl polyols type epoxy compounds, modified rubber type epoxy compounds, epihydric alcohol ester compound, bisphenol A-type episulfide compound etc.
In the ester compounds obtained by making above-mentioned (methyl) acrylic acid react with the compound with hydroxyl, as the ester compounds of 2 officials' energy, can enumerate such as: BDO two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-decanediol two (methyl) acrylate, 2-normal-butyl-2-ethyl-1,3-PD two (methyl) acrylate, DPG 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, polyethylene glycol two (methyl) acrylate, expoxy propane addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid two (methyl) acrylate, 2-hydroxyl-3-(methyl) acryloxypropyl (methyl) acrylate, carbonate diol two (methyl) acrylate, PTMEG two (methyl) acrylate, polyester-diol two (methyl) acrylate, polycaprolactone glycol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate etc.
In addition, in above-mentioned ester compounds, can above ester compounds as 3 officials, can enumerate such as: pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, expoxy propane addition trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, pentaerythrite four (methyl) acrylate, glycerol three (methyl) acrylate, expoxy propane addition glycerol three (methyl) acrylate, three (methyl) acryloyl-oxyethyl phosphate etc.
In addition, above-mentioned polyenic monomer is preferably containing the monomer (3 officials can polyenic monomer) above in 1 molecule with more than 3 carbon-to-carbon double bonds.
Can above polyenic monomer as above-mentioned 3 officials, preferably there is the monomer of 3 ~ 20 carbon-to-carbon double bonds in 1 molecule, more preferably there is the monomer of 3 ~ 8 carbon-to-carbon double bonds in 1 molecule.
The preferred lower limit of the content of the above-mentioned polyenic monomer in overall 100 weight portions of above-mentioned polymerizable compound is 5 weight portions, the preferred upper limit is 40 weight portions.If the content of above-mentioned polyenic monomer is lower than 5 weight portions, then coating is deteriorated sometimes.If the content of above-mentioned polyenic monomer is more than 40 weight portions, then the unreacted reactant of polyenic monomer remains and ease gas occurs sometimes.The preferred lower limit of the content of above-mentioned polyenic monomer is 10 weight portions, the preferred upper limit is 35 weight portions.
As the mixing ratio of above-mentioned polythiol monomer and above-mentioned polyenic monomer, the mercapto of preferred above-mentioned polythiol monomer and the mol ratio of the carbon-to-carbon double bond of above-mentioned polyenic monomer are with mercapto: the scope of carbon-to-carbon double bond=3:1 ~ 1:3 coordinates, more preferably with mercapto: the scope of carbon-to-carbon double bond=2:1 ~ 1:2 coordinates.
In display element sealant of the present invention, as above-mentioned polymerizable compound, preferably on the basis of above-mentioned polyenic monomer, also contain polyenoid oligomer.By containing above-mentioned polyenoid oligomer, thus effect and the coating of the generation suppressing ease gas can be improved.
It should be noted that, in this manual, above-mentioned " polyenoid oligomer " not included in above-mentioned " polyenic monomer ".
As the polyenic monomer from above-mentioned polyenoid oligomer, above-mentioned (methyl) allyl compound (methyl) acrylic compounds, divinylbenzene etc. can be enumerated.
As the method manufacturing above-mentioned polyenoid oligomer, can enumerate such as: make above-mentioned polyenic monomer under the existence of polymerization initiator described later etc., carry out the method etc. of reacting.As above-mentioned polymerization initiator, Photoepolymerizationinitiater initiater, thermal polymerization can be enumerated, preferably use thermal polymerization.
The preferred lower limit of the weight average molecular weight of above-mentioned polyenoid oligomer is 300, the preferred upper limit is 20,000.If the weight average molecular weight of above-mentioned polyenoid oligomer is lower than 300, then the effect of the generation of suppression ease gas sometimes cannot be made to improve fully.If the weight average molecular weight of above-mentioned polyenoid oligomer is more than 20,000, then the viscosity of the display element sealant of gained becomes too high and coating is deteriorated sometimes.The preferred lower limit of the weight average molecular weight of above-mentioned polyenoid oligomer is 400, the preferred upper limit is 4000.
It should be noted that, in this manual, above-mentioned " weight average molecular weight " utilizes gel permeation chromatography (GPC) to measure, and is the value obtained by polystyrene conversion.Making used pillar as when utilizing GPC to measure weight average molecular weight based on polystyrene conversion, such as ShodexLF-804 (Showa electrician Inc.) etc. can be enumerated.
The preferred lower limit of the content of the above-mentioned polyenoid oligomer in overall 100 weight portions of above-mentioned polymerizable compound is 30 weight portions, the preferred upper limit is 90 weight portions.If the content of above-mentioned polyenoid oligomer is lower than 30 weight portions, then sometimes cannot give play to the effect of the generation suppressing ease gas further fully.If the content of above-mentioned polyenoid oligomer is more than 90 weight portions, then the viscosity of the display element sealant of gained becomes too high and coating is deteriorated sometimes.The preferred lower limit of the content of above-mentioned polythioether oligomeric thing is 35 weight portions, the preferred upper limit is 80 weight portions.
For display element sealant of the present invention, by containing above-mentioned polythioether oligomeric thing, thus the viscosity of display element sealant is moderately uprised, not easily inequality occurs when application.
Above-mentioned polythioether oligomeric thing obtains as follows: by making above-mentioned polythiol monomer and reaching the above-mentioned polyenic monomer of the scope of 3:1 ~ 1:3 relative to above-mentioned polythiol monomer, under the existence of polymerization initiator, utilize illumination to penetrate or heat and carry out polyaddition reaction, obtaining in the reactive mixture in polymer form thus.As above-mentioned polymerization initiator, Photoepolymerizationinitiater initiater, thermal polymerization can be enumerated, preferably use thermal polymerization.
It should be noted that, above-mentioned polythioether oligomeric thing can contain unreacted mercapto, unreacted carbon-to-carbon double bond, also can not contain unreacted mercapto, unreacted carbon-to-carbon double bond.Namely, can be the polythioether oligomeric thing not containing mercapto, the unreacted carbon-to-carbon double bond polyaddition reaction of above-mentioned polythiol monomer and above-mentioned polyenic monomer being carried out fully and obtains, also can be the polythioether oligomeric thing containing unreacted mercapto, unreacted carbon-to-carbon double bond obtained by making reaction stop in the way of this polyaddition reaction.
As above-mentioned thermal polymerization, be not particularly limited, be suitable for using hot radical polymerization initiator.
As above-mentioned hot radical polymerization initiator, the hot radical polymerization initiator such as comprising azo-compound, organic peroxide etc. can be enumerated.
As above-mentioned azo-compound, such as 2 can be enumerated, 2 '-azo two (2,4-methyl pentane nitrile), azodiisobutyronitrile etc.
As above-mentioned organic peroxide, can enumerate such as: benzoyl peroxide, ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxy dicarbonate etc.
In addition, as above-mentioned Photoepolymerizationinitiater initiater, can use and the Photoepolymerizationinitiater initiater identical as the Photoepolymerizationinitiater initiater enumerated listed by the polymerization initiator contained by display element sealant of the present invention described later.
In the polyaddition reaction of above-mentioned polythiol monomer and polyenic monomer, when the molal quantity (molal quantity of the molal quantity/carbon-to-carbon double bond of mercapto) of the mercapto of the polythiol monomer for the molal quantity of the carbon-to-carbon double bond of polyenic monomer is less than 0.15, usually, in the reactant mixture of gained, polyenic monomer remains with the form of unreacted component.
It should be noted that, for display element sealant of the present invention, can being in the polyaddition reaction of above-mentioned polythiol monomer and polyenic monomer, making to contain polymerization initiator in the mixture of polythiol monomer and polyenic monomer and the polythioether oligomeric thing obtain by making reaction stop in the way of polyaddition reaction and the display element sealant that obtains.
In addition, for above-mentioned polythioether oligomeric thing, the polythioether oligomeric thing produced in advance can be mixed with polythiol monomer and polyenic monomer.
When producing above-mentioned polythioether oligomeric thing in advance, become polythiol monomer and the polyenic monomer of the raw material of above-mentioned polythioether oligomeric thing, can be identical with the polythiol monomer contained by above-mentioned display element sealant of the present invention and polyenic monomer, also can be different.
The preferred lower limit of the weight average molecular weight of above-mentioned polythioether oligomeric thing is 500.If the weight average molecular weight of above-mentioned polythioether oligomeric thing is lower than 500, then the effect of inequality when sometimes cannot give play to the application of the display element sealant preventing gained fully.The weight average molecular weight of above-mentioned polythioether oligomeric thing more preferably above 1500, more preferably more than 2000.
In addition, the preferred upper limit of the weight average molecular weight of above-mentioned polythioether oligomeric thing is 40,000.If the weight average molecular weight of above-mentioned polythioether oligomeric thing is more than 40,000, then the viscosity of the display element sealant of gained becomes too high, and coating is poor.The preferred upper limit of the weight average molecular weight of above-mentioned polythioether oligomeric thing is 10,000, preferably the upper limit is 8000 further.
The preferred lower limit of the content of the above-mentioned polythioether oligomeric thing in overall 100 weight portions of above-mentioned polymerizable compound is 30 weight portions.If the content of above-mentioned polythioether oligomeric thing is lower than 30 weight portions, then cannot suppress the generation of gas of escaping fully, or the effect of inequality when cannot give play to the application of the display element sealant preventing gained fully.The preferred lower limit of the content of above-mentioned polythioether oligomeric thing is 35 weight portions, further preferred lower limit is 40 weight portions.
In addition, the preferred upper limit of the content of the above-mentioned polythioether oligomeric thing in overall 100 weight portions of above-mentioned polymerizable compound is 90 weight portions.If the content of above-mentioned polythioether oligomeric thing is more than 90 weight portions, then the viscosity of the display element sealant of gained becomes too high and coating variation sometimes.The preferred upper limit of the content of above-mentioned polythioether oligomeric thing is 80 weight portions.
Content during preferred display element sealant of the present invention is overall, polythiol monomer is 5 ~ 40 % by weight, and the content of polyenic monomer is 5 ~ 40 % by weight, and the content of polythioether oligomeric thing is 30 ~ 90 % by weight.By making the content of above-mentioned polythiol monomer, above-mentioned polyenic monomer and above-mentioned polythioether oligomeric thing for this scope, thus in the various aspects of the transparency suppressing the effect of generation of ease gas, coating, cementability and solidfied material, all can give play to sufficient effect.
Display element sealant of the present invention, in the scope not hindering object of the present invention, can contain other polymerizable compounds beyond above-mentioned polythiol monomer, above-mentioned polyenic monomer, above-mentioned polyenoid oligomer and above-mentioned polythioether oligomeric thing.
As other polymerizable compounds above-mentioned, as long as utilize light or heat to be cured the polymerizable compound of reaction, just be not particularly limited, can enumerate such as the epoxy compounds of the raw material of above-mentioned epoxy (methyl) acrylate, partly (methyl) acrylated epoxy compound etc.
It should be noted that, above-mentioned in this manual " partly (methyl) acrylated epoxy compound " refers in 1 molecule, have the epoxy radicals of more than 1 and the compound of 1 (methyl) acryloyl group.In addition, in this manual, above-mentioned " (methyl) acryloyl group " refers to acryloyl group or methacryl.
Above-mentioned part (methyl) acrylated epoxy compound such as obtains by making 1 epoxy radicals had in 1 molecule in the epoxy compounds of more than 2 epoxy radicals react with (methyl) acrylic acid.
Display element sealant of the present invention contains polymerization initiator.
As above-mentioned polymerization initiator, such as Photoepolymerizationinitiater initiater, above-mentioned thermal polymerization can be enumerated, be suitable for using Photoepolymerizationinitiater initiater.
For above-mentioned polymerization initiator, the preferred lower limit of molecular weight is 250, the preferred upper limit is 1500.By using molecular weight to be the polymerization initiator of 250 ~ 1500, thus display element sealant of the present invention can become sealant more excellent in the effect of the generation of suppression ease gas.If the molecular weight of above-mentioned polymerization initiator is lower than 250, then sometimes become the reason that ease gas occurs.If the molecular weight of above-mentioned polymerization initiator is more than 1500, then solidification becomes insufficient sometimes.Wherein, from the view point of the generation reducing ease gas, the preferred lower limit of the molecular weight of above-mentioned polymerization initiator is 300, the preferred upper limit is 1050, further preferred lower limit is 348, the further preferred upper limit is 790.
As above-mentioned Photoepolymerizationinitiater initiater, can enumerate such as: there is the compound of acylphosphine oxide skeleton, there is the heavy compound of alpha-aminoacetophenone skeleton (original text: heavy compound), there is the compound of benzil ketals skeleton, there is the compound of alpha-hydroxyacetophenone skeleton, there is the compound of benzoin skeleton, there is the compound of oxime ester skeleton, there is the compound, organic peroxide, azo-compound, oligomer compounds etc. of two luxuriant titanium skeletons.These Photoepolymerizationinitiater initiaters may be used singly or in combination of two or more.Wherein, from the view point of photo-curable; preferably be selected from least one in the compound with acylphosphine oxide skeleton, the heavy compound with alpha-aminoacetophenone skeleton, the compound with benzil ketals skeleton, the compound with alpha-hydroxyacetophenone skeleton, the compound with benzoin skeleton, the compound with oxime ester skeleton, the compound with two luxuriant titanium skeletons and oligomer compounds, be more preferably the compound and/or oligomer compounds with acylphosphine oxide skeleton.
At this, the above-mentioned compound with acylphosphine oxide skeleton refers to, the part of acylphosphine oxide is replaced to the compound after other groups.The above-mentioned compound with alpha-aminoacetophenone skeleton refers to, the part of alpha-aminoacetophenone is replaced to the compound after other groups.The above-mentioned compound with benzil ketals skeleton refers to, the part of alpha-dihydroxy-acetophenone is replaced to the compound after other groups.The above-mentioned compound with alpha-hydroxyacetophenone skeleton refers to, the part beyond the hydroxyl of α-monohydroxy acetophenone is replaced to the compound after other groups.The above-mentioned compound with benzoin skeleton refers to, the part of benzoin is replaced to the compound after other groups.The above-mentioned compound with oxime ester skeleton refers to, the part of N-acetyl group dimethyl oxime is replaced to the compound after other groups.The above-mentioned compound with two luxuriant titanium skeletons refers to, the parts of two luxuriant titaniums is replaced to the compound after other groups.Above-mentioned organic peroxide refers to the compound with peroxy.Above-mentioned azo-compound refers to the compound with azo group.
As the above-mentioned compound with acylphosphine oxide skeleton; can enumerate such as: 2; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide (BASFJapan Inc., " LUCILINTPO "), two (2; 4,6-trimethylbenzoyl) phenyl phosphine oxide (BASFJapan Inc., " IRGACURE819 ") etc.
As the above-mentioned compound with alpha-aminoacetophenone skeleton, can enumerate such as: 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino propane-1-ketone (BASFJapan Inc., " IRGACURE907 "), 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butanone (BASFJapan Inc., " IRGACURE369 "), 1, 2-(dimethylamino)-2-((4-aminomethyl phenyl) methyl)-1-(4-(4-morpholinyl) phenyl)-1-butanone (BASFJapan Inc., " IRGACURE379 ") etc.
As the above-mentioned compound with benzil ketals skeleton, can enumerate such as: 2,2-dimethoxy-1,2-diphenylethane-1-ketone (BASFJapan Inc., " IRGACURE651 ") etc.
As the above-mentioned compound with alpha-hydroxyacetophenone skeleton, can enumerate such as: 2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl-propiono)-benzyl) phenyl)-2-methyl-propan-1-ketone (BASFJapan Inc., " IRGACURE127 ") etc.
As the above-mentioned compound with oxime ester skeleton; can enumerate such as: 1-(4-(phenyl) phenyl)-1,2-octanedione 2-(O-benzoyl oxime) (BASFJapan Inc., " IRGACUREOXE01 "), O-acetyl group-1-(6-(2-toluyl)-9-ethyl-9H-carbazole-3-base) acetophenone oxime (BASFJapan Inc., " IRGACUREOXE02 ") etc.
As the above-mentioned compound with two luxuriant titanium skeletons, can enumerate such as: two (η 5-2,4-cyclopentadiene-1-base)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-base)-phenyl) titanium (BASFJapan Inc., " IRGACURE784 ") etc.
The oligomer compounds listed as above-mentioned Photoepolymerizationinitiater initiater, from the view point of the generation reducing ease gas, preferred degree of polymerization is the compound of 2 ~ 10, in addition, from the view point of not easily there is the gas that escapes, preferably there is the hydrogen bond such as hydroxyl, amino (original text: water acid Knot conjunction property) functional group.
Specifically, can enumerate such as: oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) propane) (Lamberti Inc., " ESACUREKIP150 ", " ESACURE1 "), Macrogol 200-two (β-4 (4-(2-dimethylamino-2-benzyl) bytyry phenyl) piperazine) (IGM Inc., " Omnipol910 "), (2-carboxymethoxythioxanthone)-(polytetramethylene glycol 250) diester (IGM Inc., " OmnipolTX "), (Carboxvmethoxv methoxy base benzophenone)-(polyethylene glycol 250) diester (IGM Inc., " OmnipolBP ") etc.
Content 100 weight portions overall relative to above-mentioned polymerizable compound of above-mentioned polymerization initiator, preferred lower limit is 0.1 weight portion, the preferred upper limit is 5 weight portions.If the content of above-mentioned polymerization initiator is lower than 0.1 weight portion, then the curing reaction of the display element sealant of gained is insufficient sometimes carries out.If the content of above-mentioned polymerization initiator is more than 5 weight portions, then curing reaction becomes too fast, and operability declines sometimes, or the solidfied material of the display element sealant of gained becomes uneven.The preferred lower limit of the content of above-mentioned polymerization initiator is 0.5 weight portion, the preferred upper limit is 4 weight portions.
Display element sealant of the present invention can contain thermal curing agents.
The solidfied material that above-mentioned thermal curing agents is preferably after solidification is transparent thermal curing agents, can enumerate such as mercaptan compound, imdazole derivatives, amines, polyalcohol based compound, acid anhydrides etc.As thermal curing agents commercially available in above-mentioned thermal curing agents, such as HN-2200, HN-2000, HN-5500, MHAC-P (be Hitachi and change into Inc.), FUJICURE7000, FUJICURE7001, FUJICURE7002, Tohmide410-N, Tohmide215-70X, Tohmide423, Tohmide437, TohmideTXC-636-A (being T & KTOKA Inc.), MEH-8000H, MEH-8005 (be bright and change into Inc.) etc. can be enumerated.
Display element sealant of the present invention can contain cementability imparting agent.
As above-mentioned cementability imparting agent, silane coupler, titanium coupling agent, the aluminum coupling agents etc. such as such as 3-methacryloxypropyl trimethoxy silane, 3-glycidoxy-propyltrimethoxy silane, 3-glycidoxypropyl diethoxy silane, N-(amino-ethyl) TSL 8330, mercaptopropyi trimethoxy silane can be enumerated.These cementability imparting agents can be used alone, and also two or more kinds may be used.
Display element sealant of the present invention can contain stabilizer for the object of anti-oxidation etc.
As aforementioned stable agent, such as 2 can be enumerated, 2 '-di-2-ethylhexylphosphine oxide-(4-methyl-6-tert-butylphenol), 4,4 '-Ding pitches base two-(the 6-tert-butyl group-3-methylphenol), 2,2 '-di-2-ethylhexylphosphine oxide-(4-ethyl-6-tert-butyl phenol) etc.These stabilizers can be used alone, and also two or more kinds may be used.
Display element sealant of the present invention can also contain the additives such as filler, curing accelerator, plasticizer, surfactant, fire retardant, antistatic agent, defoamer, levelling agent, ultraviolet absorption material, organic solvent in the scope not hindering object of the present invention.
As the method manufacturing display element sealant of the present invention, can enumerate such as by polythiol monomer, polyenic monomer, polythioether oligomeric thing, polymerization initiator and polyenoid oligomer, cementability imparting agent etc. added as required, utilize the method etc. that mixer mixes equably.
For display element sealant of the present invention, use conical rotary type viscosimeter 20 DEG C, the preferred lower limit of viscosity that records under the condition of 20rpm is 0.4Pas, the preferred upper limit is 40Pas.If above-mentioned viscosity is lower than 0.4Pas, then sometimes there is composition inequality in the display element sealant of gained, or application becomes difficulty, or the display characteristic of the display element of gained is deteriorated.If above-mentioned viscosity is more than 40Pas, then application sometimes becomes difficulty.The preferred lower limit of above-mentioned viscosity is 0.5Pas, the preferred upper limit is 35Pas, preferred lower limit is 1Pas, the further preferred upper limit is further 25Pas.
For display element sealant of the present invention, the average transmittance of the visible ray of preferred consolidation thing in the region of wavelength 380 ~ 780nm is more than 80%.By making the average transmittance of above-mentioned visible ray be more than 80%, thus can be suitable in the purposes needing the transparency.The average transmittance of above-mentioned visible ray is more preferably more than 95%.
It should be noted that, for the above-mentioned solidfied material that will measure the average transmittance of visible ray, by irradiating 2000mJ/cm to display element sealant of the present invention
2ultraviolet method and obtain.
For display element sealant of the present invention, weight reduction rates when being heated to 130 DEG C to the solidfied material of thickness 100 μm with programming rate 10 DEG C/min is preferably less than 0.15%.Above-mentioned weight reduction rates can be considered ease gas generating capacity, therefore, by being less than 0.15%, thus can become the sealant be inhibited to the harmful effect of display element.Above-mentioned weight reduction rates is more preferably less than 0.1%.
It should be noted that, for the solidfied material that will measure above-mentioned weight reduction rates, by irradiating 2000mJ/cm to the display element sealant of the present invention after being coated with in the mode making thickness reach 100 μm
2ultraviolet method and obtain.
As the curing penetrated by illumination when making display element sealant cures of the present invention, the wavelength and 300 ~ 3000mJ/cm that such as irradiate 300 ~ 400nm can be enumerated
2the method etc. of light of accumulated light.
As the light source for irradiating light to display element sealant of the present invention, such as low pressure mercury lamp, medium pressure mercury lamp, high-pressure mercury lamp, ultrahigh pressure mercury lamp, excimer laser, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp, sodium vapor lamp, Halogen lamp LED, xenon lamp, LED, fluorescent lamp, sunlight, electron beam illuminating device etc. can be enumerated.These light sources can be used alone, and also two or more kinds may be used.
As the method for display element sealant of the present invention being irradiated to light, irradiate while such as various light source can be enumerated, interval time successively the irradiating of difference, irradiate and the combination irradiation etc. successively irradiated simultaneously, also can use arbitrary illuminating method.
Display element sealant of the present invention can be used as by the face of display element, whole, above, below or the sealant of environmental seal, sealing-in agent or be used for by be arranged at display element peristome sealing sealing compound, wherein, be preferred for whole of display element sealing.
It should be noted that, in this manual, above-mentioned " whole face " not refers to necessary 100% of the face with display element, and refers to the sealing surface of the necessity needed for display element.In addition, above-mentioned " above " refers to the side of appearing light, i.e. the face of visuognosis side.
Display element sealant of the present invention such as can be used for organic EL display element sealing-in agent, organic EL display element sealant, sealing-in agent used for liquid crystal display element, sealing material for liquid crystal display device, electrochromism substrate sealing-in agent, electrochromism substrate sealant, Electronic Paper sealing-in agent, Electronic Paper sealant etc.
Invention effect
According to the present invention, can provide a kind of and can suppress the ease generation of gas and the display element sealant of the transparency excellence of cementability and solidfied material.
Embodiment
Below enumerate embodiment to be described in more detail the present invention, but the present invention is not limited in these embodiments.
(making of polythioether oligomeric thing)
As shown in table 1, use mixer (new eastern scientific company system, " Three-OneMotorHEIDONBLH300 ") using the trimethylolpropane tris (3-mercaptopropionic acid ester) as multi-thioalcohol compound, triallyl isocyanurate as polyenic compounds and as thermal polymerization 2,2 '-azo two (2,4-methyl pentane nitrile) mix according to the mix proportion shown in table 1, thus obtain reactant mixture.The reactant mixture of gained is poured in poor solvent, collects the oligomer that there occurs precipitation, solvent is removed under vacuo, obtains polythioether oligomeric thing A ~ C thus.
For the polythioether oligomeric thing A ~ C of gained, utilize and use ShodexLF-804 (Showa electrician Inc.) to measure the weight average molecular weight based on polystyrene conversion as the gel permeation chromatography (GPC) of pillar.Show the result in table 1.
(embodiment 1 ~ 11, comparative example 1 ~ 5)
According to the mix proportion described in table 2,3, each material use mixer (new eastern scientific company system, " Three-OneMotorHEIDONBLH300 ") is mixed, prepares the display element sealant of embodiment 1 ~ 11 and comparative example 1 ~ 5 thus.
(evaluation)
For each display element sealant of gained in embodiment and comparative example, evaluate according to following method.Show the result in table 2,3.
(1) viscosity
Use conical rotary type viscosimeter (Dong Ji industry companies system, " TV-22 type "), 20 DEG C, under the condition of 20rpm to embodiment and comparative example in the viscosity of each display element sealant of gained measure.
(2) coating
Coating when using each display element sealant obtained in distributor (Musashi high-tech company system, " SHOTMASTER300 ") application embodiment on the glass substrate and comparative example is evaluated.Dispenser nozzle is fixed as 400 μm, nozzle gap be fixed as 30 μm, ejection press solidly be decided to be 300kPa and carry out application time, can without the style of calligraphy characterized by hollow strokes (か The れ) or turned-down edge (ダ レ) carry out application average evaluation be "○", the average evaluation that will there occurs the style of calligraphy characterized by hollow strokes or turned-down edge is " △ ", larger application fracture will occur or application is uneven or cannot the average evaluation of application be "×" completely.
(3) escape gas generating capacity
Use rod coaters to carry out application to each display element sealant obtained in embodiment and comparative example and reach 100 μm to make the thickness after application, use ultra high pressure mercury light irradiation 2000mJ/cm
2ultraviolet and form film.
Use apparatus for thermal analysis (SeikoInstruments Inc., " TG/DTA6200 ") to measure weight reduction rates when the film of gained is heated to 130 DEG C with programming rate 10 DEG C/min, it can be used as ease gas generating capacity.
(4) cementability
Use micropipette that each display element sealant obtained in embodiment and comparative example is coated with 0.05g on the glass substrate.This substrate is fitted according to the Thickness Mode reaching 50 μm with the other glass substrate being configured with distance piece, uses high voltage mercury lamp radiation 2000mJ/cm
2ultraviolet, make bonding force test sample.For the bonding force test sample of gained, use EZGRAPH (Inc. of Shimadzu Seisakusho Ltd.), under the condition of peeling rate 5mm/min, carry out disbonded test, determine bonding force."○" that to be the average evaluation of more than 1.0N/cm by bonding force be, be "×" by bonding force lower than the average evaluation of 1.0N/cm, thus cementability is evaluated.
(5) transparency (average transmittance of visible ray) of solidfied material
The each display element sealant obtained in embodiment and comparative example is held in PET resin film, irradiates 2000mJ/cm
2ultraviolet, produce the transmissivity test sample of thickness 100 μm.Tou She for gained is Shuaied Measuring and is surely used sample, uses spectrophotometer (Inc. of Hitachi, " U-3000 ", condition 300 ~ 800nm), measures the average transmittance of the visible ray under wavelength 380 ~ 780nm.
(6) display performance of display element
(6-1) display performance of liquid crystal display cells
(making of liquid crystal display cells)
Prepare thickness
iTO electrode after surface filming, further, utilize spin-coating method by thickness
alignment films coat surface and the glass substrate (long 25mm, wide 25mm, thick 0.7mm) 2 obtained, a substrate uses heat-curable epoxy resin (periphery sealing-in agent), and utilizes silk screen printing and carry out printed patterns in the mode being designed with Liquid crystal pour oral area.Then, the substrate having carried out pattern printing is kept 3 minutes at 80 DEG C, thus carried out preparing dry and periphery sealing-in agent to the welding of substrate, then return room temperature.Then, another substrate scatters the distance piece of 5 μm, then makes each baseplate-laminating, utilize the crimping that the hot pressing being heated to 130 DEG C is carried out 2 hours, thus periphery sealing-in agent is solidified, obtain empty box.After vacuum draw is carried out to the box of the sky of gained, liquid crystal (MERCK Inc., " ZLI-4792 ") is injected by inlet, use each display element sealant obtained in embodiment and comparative example to be sealed by inlet, use high voltage mercury lamp radiation 3000mJ/cm
2ultraviolet, make sealant cures.Then, at 120 DEG C, carry out the annealing of 1 hour liquid crystal, produce liquid crystal display cells.
(orientation disorder of liquid crystal display cells)
Utilize the voltage of AC3.5V, under the show state of halftoning, make the liquid crystal display cells of gained drive, utilize the orientation disorder of the liquid crystal near polarized light microscope observing inlet.Situation to orientation disorder unconfirmed is set to "○", is set to " △ " by confirming lower than the situation of the orientation disorder of 1mm, the situation of the obvious orientation disorder (dark uneven) that there is more than 1mm is set to "×", thus the display performance of liquid crystal display cells is evaluated.
(6-2) display performance of organic EL display element
(being configured with the making of the substrate of the duplexer comprising organic light emitting material)
Will on glass substrate (long 25mm, wide 25mm, thick 0.7mm) with
thickness object that ITO electrode film forming is obtained as substrate.Acetone, alkaline aqueous solution, ion exchange water, isopropyl alcohol is utilized to carry out the ultrasonic washing of 15 minutes to aforesaid substrate respectively, then the washing utilizing the isopropyl alcohol boiled to carry out 10 minutes, utilizes UV-ozone cleaning machine (Japanese LASER electronics corporation system, " NL-UV253 ") to carry out pre-treatment (original text: straight pre-treatment) in addition.
Then, this substrate is fixed on the substrate geometrical clamp of vacuum deposition apparatus, N is put in the crucible of biscuiting, N '-two (1-naphthyl)-N, N '-diphenylbenzidine (α-NPD) 200mg, puts into three (oxine) aluminium (Alq in the crucible of other different biscuitings
3) 200mg, be decompressed to 1 × 10 by vacuum chamber
-4pa.Then, the crucible being placed with α-NPD is heated, make α-NPD with evaporation rate
be piled up in substrate, make thickness
hole transmission layer film forming.Then, to being placed with Alq
3crucible heat, with
evaporation rate make thickness
organic light emitting material film forming.Then, the substrate being formed with hole transmission layer and organic light emitting material is moved in other vacuum deposition apparatus, steam in this vacuum in the tungsten resistance heating ship in device and put into lithium fluoride 200mg, in another tungsten ship, put into aluminum steel 1.0g.Then, 2 × 10 are decompressed to by the evaporator of vacuum deposition apparatus
-4pa, make lithium fluoride with
evaporation rate formed
film, then with
speed aluminium is formed
film.Make to return normal pressure in evaporator by nitrogen, the substrate that will be configured with the duplexer of the organic light emitting material comprising 10mm × 10mm takes out.
(utilizing the covering of inorganic material film A)
For the substrate being configured with the duplexer comprising organic light emitting material of gained, the mask of the peristome with 13mm × 13mm is set in the mode of the entirety covering this duplexer, utilizes plasma CVD method to form inorganic material film A.
Plasma CVD method carries out under the following conditions: use SiH
4respective flow, as unstrpped gas, is set to 10sccm and 200sccm by gas and nitrogen, RF power is set to 10W (frequency 2.45GHz), chamber indoor temperature is set to 100 DEG C, cavity pressure is set to 0.9Torr.
The thickness of the inorganic material film A of the silicon nitride formed about 0.2 μm.
(formation of resin protection film)
The substrate being configured with the duplexer after being covered by inorganic material film A is set in vacuum plant, be arranged in the heating ship in vacuum plant (adding Hot ボ ー ト) each display element sealant 0.5g putting into embodiment and comparative example and obtain, be decompressed to 10Pa, comprising the part of quadrangle of 11mm × 11mm of duplexer, at 200 DEG C, display element sealant is heated, carry out vacuum evaporation in the mode making thickness reach 0.5 μm.Then, use the ultraviolet of high voltage mercury lamp radiation wavelength 365nm under vacuum conditions, reach 3000mJ/cm to make exposure
2, thus make display element sealant cures and form resin protection film.
(utilizing the covering of inorganic material film B)
To cover the mode being formed with the entirety of the resin protection film of the 11mm × 11mm of the substrate of resin protection film; setting has the mask of the peristome of 12mm × 12mm; utilize plasma CVD method to form inorganic material film B, thus obtain display element (organic EL display element).
For plasma CVD method, carry out under the following conditions: use SiH
4respective flow, as unstrpped gas, is set to SiH by gas and nitrogen
4gas 10sccm, nitrogen 200sccm, and RF power is set to 10W (frequency 2.45GHz), cavity temperature is set to 100 DEG C, cavity pressure is set to 0.9Torr.
The thickness of the inorganic material film B of the silicon nitride formed is about 1 μm.
(luminance of organic EL display element)
By made each organic EL display element 60 DEG C, expose 100 hours under the condition of 90%RH after, apply the voltage of 3V, visualization luminance (presence or absence of luminous and blackspot, the delustring of pixel periphery), blackspot, periphery delustring and average evaluation luminous is equably "○" will do not had, by find blackspot, periphery delustring average evaluation be " △ ", average evaluation non-light emitting portion obviously expanded is "×", thus evaluates the display performance of organic EL display element.
Utilizability in industry
According to the present invention, can provide a kind of and can suppress the ease generation of gas and the display element sealant of the transparency excellence of cementability and solidfied material.
Claims (11)
1. a display element sealant, is characterized in that, containing polymerizable compound and polymerization initiator,
Described polymerizable compound contain the mercapto in 1 molecule with more than 2 polythiol monomer, have in 1 molecule the carbon-to-carbon double bond of more than 2 polyenic monomer and by the reaction of described polythiol monomer and described polyenic monomer and the polythioether oligomeric thing formed.
2. display element sealant according to claim 1, is characterized in that, polythiol monomer contains the monomer of the mercapto in 1 molecule with more than 3.
3. display element sealant according to claim 1 and 2, is characterized in that, polyenic monomer contains the monomer of the carbon-to-carbon double bond in 1 molecule with more than 3.
4. the display element sealant according to any one of claims 1 to 3, is characterized in that, containing polyenoid oligomer.
5. the display element sealant according to any one of Claims 1 to 4, is characterized in that, the weight average molecular weight of polythioether oligomeric thing is 500 ~ 40,000.
6. the display element sealant according to any one of Claims 1 to 5, is characterized in that, the content of the polythioether oligomeric thing in overall 100 weight portions of polymerizable compound is more than 30 weight portions.
7. the display element sealant according to any one of claim 1 ~ 6, it is characterized in that, during display element is overall with sealant, the content of polythiol monomer is 5 ~ 40 % by weight, the content of polyenic monomer is 5 ~ 40 % by weight, and the content of polythioether oligomeric thing is 30 ~ 90 % by weight.
8. the display element sealant according to any one of claim 1 ~ 7, is characterized in that, the molecular weight of polymerization initiator is 250 ~ 1500.
9. the display element sealant according to any one of claim 1 ~ 8, is characterized in that, use conical rotary type viscosimeter 20 DEG C, the viscosity that records under the condition of 20rpm is 0.4 ~ 40Pas.
10. the display element sealant according to any one of claim 1 ~ 9, is characterized in that, the average transmittance of the visible ray of its solidfied material in the region of wavelength 380 ~ 780nm is more than 80%.
11. display element sealants according to any one of claim 1 ~ 10, is characterized in that, the weight reduction rates when solidfied material of its thickness 100 μm is heated to 130 DEG C with programming rate 10 DEG C/min is for less than 0.15%.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
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| JP2013-115382 | 2013-05-31 | ||
| JP2013115380 | 2013-05-31 | ||
| JP2013115381 | 2013-05-31 | ||
| JP2013-115381 | 2013-05-31 | ||
| JP2013-115380 | 2013-05-31 | ||
| JP2013115382 | 2013-05-31 | ||
| JP2014024517 | 2014-02-12 | ||
| JP2014-024517 | 2014-02-12 | ||
| PCT/JP2014/064292 WO2014192880A1 (en) | 2013-05-31 | 2014-05-29 | Sealing agent for display elements |
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| CN105309043A true CN105309043A (en) | 2016-02-03 |
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|---|---|
| JP (2) | JP5785331B2 (en) |
| KR (1) | KR20160015207A (en) |
| CN (1) | CN105309043A (en) |
| TW (1) | TW201504346A (en) |
| WO (1) | WO2014192880A1 (en) |
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| CN110168442A (en) * | 2017-07-14 | 2019-08-23 | 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 |
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| CN105579898B (en) * | 2013-11-13 | 2017-07-21 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, up and down conductive material and liquid crystal display cells |
| JP2016183231A (en) * | 2015-03-26 | 2016-10-20 | 四国化成工業株式会社 | Resin composition comprising glycoluril compound |
| WO2016194871A1 (en) * | 2015-06-02 | 2016-12-08 | 積水化学工業株式会社 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
| JP6496214B2 (en) * | 2015-08-19 | 2019-04-03 | 積水化学工業株式会社 | Sealant for display element |
| JP6595848B2 (en) * | 2015-08-28 | 2019-10-23 | 積水化学工業株式会社 | Sealant for display element |
| JP6769894B2 (en) * | 2016-03-01 | 2020-10-14 | 積水化学工業株式会社 | Curable resin composition and sealant for display elements |
| WO2024090339A1 (en) * | 2022-10-25 | 2024-05-02 | デンカ株式会社 | Photocurable resin composition for display device, and display device |
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| JP2627598B2 (en) | 1992-06-12 | 1997-07-09 | 新豊 劉 | camera |
| JP2001307873A (en) | 2000-04-21 | 2001-11-02 | Toppan Printing Co Ltd | Organic electroluminescence display element and its manufacturing method |
| JP2002285156A (en) * | 2001-03-26 | 2002-10-03 | Sharp Corp | Liquid crystal display cell, agent for sealing liquid crystal injection opening and liquid crystal composition |
| JP2004107450A (en) * | 2002-09-17 | 2004-04-08 | Sekisui Chem Co Ltd | Photocurable resin for sealing agent, liquid-crystal display element or organic electroluminescent element |
| JP2005336314A (en) | 2004-05-26 | 2005-12-08 | Sekisui Chem Co Ltd | Photocurable resin composition |
| JP2005336404A (en) * | 2004-05-28 | 2005-12-08 | Sekisui Chem Co Ltd | Photocurable resin composition, liquid crystal inlet sealing agent, and liquid crystal display cell |
| JP2007065349A (en) * | 2005-08-31 | 2007-03-15 | Sekisui Chem Co Ltd | Liquid crystal injection hole sealing agent and liquid crystal cell |
| US8440736B2 (en) * | 2008-04-07 | 2013-05-14 | University Of Southern Mississippi | Photocuable thiol-ene low gas permeability membranes |
| JP5682062B2 (en) * | 2008-10-30 | 2015-03-11 | ナガセケムテックス株式会社 | Curable composition |
| US8823154B2 (en) * | 2009-05-08 | 2014-09-02 | The Regents Of The University Of California | Encapsulation architectures for utilizing flexible barrier films |
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2014
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- 2014-05-29 JP JP2014528730A patent/JP5785331B2/en active Active
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| CN110168442A (en) * | 2017-07-14 | 2019-08-23 | 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 |
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| JPWO2014192880A1 (en) | 2017-02-23 |
| KR20160015207A (en) | 2016-02-12 |
| TW201504346A (en) | 2015-02-01 |
| JP5785331B2 (en) | 2015-09-30 |
| JP6427070B2 (en) | 2018-11-21 |
| JP2015187993A (en) | 2015-10-29 |
| WO2014192880A1 (en) | 2014-12-04 |
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