CN106797685A - Organic electro-luminescent display unit sealant - Google Patents

Organic electro-luminescent display unit sealant Download PDF

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CN106797685A
CN106797685A CN201680002382.9A CN201680002382A CN106797685A CN 106797685 A CN106797685 A CN 106797685A CN 201680002382 A CN201680002382 A CN 201680002382A CN 106797685 A CN106797685 A CN 106797685A
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methyl
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display unit
display element
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CN106797685B (en
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渡边康雄
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/10Materials in mouldable or extrudable form for sealing or packing joints or covers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/02Details
    • H05B33/04Sealing arrangements, e.g. against humidity
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2206Oxides; Hydroxides of metals of calcium, strontium or barium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2217Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224Magnesium hydroxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/006Additives being defined by their surface area
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/53Core-shell polymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02Inorganic compounds
    • C09K2200/0239Oxides, hydroxides, carbonates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0607Rubber or rubber derivatives

Abstract

Block and the organic electro-luminescent display unit sealant of tenacity excellent it is an object of the invention to provide solidfied material.The present invention is a kind of organic electro-luminescent display unit sealant, its water imbibition filler for containing cationically polymerizable compound, olefin-based rubber particles, light cationic polymerization initiator and alkaline-earth metal system and/or magnesium system, above-mentioned olefin-based rubber particles have core shell structure.

Description

Organic electro-luminescent display unit sealant
Technical field
Block and the organic electro-luminescent display unit sealant of tenacity excellent the present invention relates to solidfied material.
Background technology
Organic electroluminescent (below, also referred to as " organic EL ") display element has between mutually opposing a pair of electrodes The laminate construction of organic light emitting material is clamped with, electronics is injected from an electrode to the organic light emitting material and from another One electrode injects hole to the organic light emitting material, so as to electronics is combined and carried out with hole in organic light emitting material It is luminous.So, because organic EL display element carries out self-luminous, thus with the phase such as liquid crystal display cells for needing backlight Than, have the advantages that visibility is good, can be thinned and can DC low-voltage drive.
Constitute the organic light emitting material of organic EL display element, electrode presence easily makes characteristic bad because of moisture, oxygen etc. The problem of change.Therefore, in order to obtain the organic EL display element of practicality, it is necessary to by organic light emitting material, electrode and big air bound Realize long lifetime absolutely.As by the method for organic light emitting material, electrode and atmospheric isolation, using sealant to organic EL Display element is sealed (such as patent document 1).In the case where organic EL display element is sealed with sealant, it is Abundant suppression moisture, oxygen etc. are passed through, and are generally used in set on the layered product with organic light emitting material and are referred to as passivating film Inoranic membrane and the method that is sealed with sealant on the inoranic membrane.
In recent years, the bottom of the light instead of being sent by organic light emitting material from the substrate surface side extraction for being formed with light-emitting component The organic EL display element of portion's illumination mode, organic EL of the top light emitting mode of light is taken out from the upper surface side of organic luminous layer Display element is attracted attention.Which because aperture opening ratio is high and as low voltage drive, therefore with being conducive to long lifetime Advantage.In the organic EL display element of such top light emitting mode, due to needing to make the upper surface side of luminescent layer transparent, because This is close to carry out across the transparent moisture resistance base material such as transparent sealing resin laminated glass by the upper surface side in light-emitting component Envelope (such as patent document 2).
However, in the organic EL display element of such top light emitting mode, in order to not block the extraction direction of light and There is a problem of being configured without the space of drier, be difficult to obtain sufficient damp proof effect, lifetime.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2007-115692 publications
Patent document 2:Japanese Unexamined Patent Publication 2009-051980 publications
The content of the invention
The invention problem to be solved
Block and the organic electro-luminescent display unit use of tenacity excellent it is an object of the invention to provide solidfied material Sealant.
Means for solving the problems
The present invention is a kind of organic electro-luminescent display unit sealant, and it contains cationically polymerizable compound, alkene Hydrocarbon system rubber particles, light cationic polymerization initiator and alkaline-earth metal system and/or the water imbibition filler of magnesium system, above-mentioned olefin-based Rubber particles have core shell structure.
The present invention is described in detail below.
The present inventor etc. in order to improve the block (anti-penetrability) of organic EL display element sealant and to various suctions Humectant is studied, and is as a result found:In the situation using the alkaline-earth metal systems such as calcium oxide and/or the water imbibition filler of magnesium system Under, give play to especially excellent block.However, in the case where such water imbibition filler is used, organic EL of gained shows Show expansion in reliability test of the solidfied material of element sealant under hot and humid condition etc., existing is carrying out roller laminating work The problems such as being cracked because of bending when during sequence or using flexible base board.
Therefore, the result that the present inventor etc. is furtherd investigate finds:By be applied in combination as resinous principle sun from Sub- polymerizable compound and the olefin-based rubber particles with core shell structure, and make the water suction of the alkaline-earth metal system and/or magnesium system Property filler dispersion, the excellent organic EL display element of block and toughness both of which such that it is able to obtain solidfied material seals Agent.So that complete the present invention.
Organic EL display element sealant of the invention contains cationically polymerizable compound.
As above-mentioned cationically polymerizable compound, can enumerate with such as epoxy radicals, oxetanylmethoxy, vinyl ether group Deng the compound as cationic polymerizable group.
As above-mentioned cationically polymerizable compound, the preferably compound with epoxy radicals.Wherein, it is preferably selected from double The epoxy resin of phenol skeleton, the epoxy resin of tool novolak skeleton, the epoxy resin with naphthalene skeleton and with two rings penta At least a kind epoxy resin in the epoxy resin of diene skeleton, the more preferably epoxy resin with bisphenol backbone, further preferably Bisphenol A type epoxy resin, bisphenol f type epoxy resin.
In addition, as above-mentioned cationically polymerizable compound, going out from the viewpoint of the generation for suppressing ease gas (ア ウ ト ガ ス) Hair, can contain the compound shown in following formula (1) and/or the compound shown in following formula (2).
[changing 1]
In formula (1), R1~R18For hydrogen atom, halogen atom or the alkyl of oxygen atom or halogen atom can be included, it Can be identical respectively, it is also possible to it is different.X is bonding arm, oxygen atom, the alkylidene of carbon number 1~5, Epoxide carbonyl, carbon number 2~5 Alkylene oxide group carbonyl or secondary amino group.
[changing 2]
In formula (2), R19~R21It is the alkylidene of the carbon number 2~10 of straight-chain or branched, they can be identical respectively, Can also be different.E1~E3Separately represent following formula (3-1) or following formula (3-2) shown in organic group.
[changing 3]
In formula (3-1), R22It is hydrogen atom or methyl.
As the compound shown in the compound shown in above-mentioned formula (1) and/or above-mentioned formula (2), following formula is preferably selected from In the compound shown in compound, following formula (4-2) shown in (4-1) and the compound shown in following formula (4-3) at least 1 kind.
[changing 4]
As commercially available product in above-mentioned cationically polymerizable compound, can enumerate for example:EPICLON EXA- 830LVP (DIC company systems);JER 4005P (Mitsubishi Chemical Ind's system);Celloxide 8000, Celloxide 2021P are ( Be Daicel company system), TEPIC-VL (Nissan Chemical company system) etc..
Organic EL display element sealant of the invention contains olefin-based rubber particles.
Above-mentioned olefin-based rubber particles have core shell structure.
By containing the above-mentioned olefin-based rubber particles with core shell structure, so that the organic EL display element of gained is used The tenacity excellent of the solidfied material of sealant.In addition, olefin-based rubber particles due to compared with other rubber particles decomposability it is low, because And also there is the effect of the generation for suppressing ease gas.
From the viewpoint of the dispersiveness in above-mentioned cationically polymerizable compound, above-mentioned olefin-based rubber particles preferably have There is the stratum nucleare comprising conjugated diene rubber and carry the tree of the segment of the compound of polymerism unsaturated double-bond comprising having The shell of fat.
As above-mentioned conjugated diene rubber, such as butadiene rubber, SBR styrene butadiene rubberses, isoamyl two can be enumerated Alkene rubber, neoprene etc..Wherein, preferred butadiene rubber.
In addition, the glass transition temperature (Tg) of above-mentioned conjugated diene rubber is preferably less than 0 DEG C.
As the above-mentioned compound with polymerism unsaturated double-bond, can enumerate such as (methyl) acrylic compounds, Styrenic, acrylonitrile compounds etc..Wherein, preferred (methyl) acrylic compounds.
It is explained, in this specification, above-mentioned " (methyl) Bing Xi Suan ﹡ " refers to Bing Xi Suan ﹡ and/or Jia base Bing Xi Suan ﹡.
As simple function (methyl) acrylic compounds in above-mentioned (methyl) acrylic compounds, example can be enumerated Such as:(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (first Base) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid is different pungent Ester, (methyl) n-octyl, the different nonyl ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) lauryl Ester, the different myristin of (methyl) acrylic acid, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid Isobornyl thiocyanoacetate, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (first Base) propylene 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) propylene Sour 2- methoxy acrylates, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 2- butoxyethyls, (methyl) third Olefin(e) acid 2- phenoxy ethyls, methoxy ethyl glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, benzene Epoxide diethylene glycol (methyl) acrylate, phenoxy group polyethylene glycol (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, Ethyl carbitol (methyl) acrylate, (methyl) acrylic acid 2,2,2- trifluoro ethyl esters, (methyl) acrylic acid 2,2,3,3- tetra- Fluorine propyl ester, (methyl) acrylic acid 1H, 1H, 5H- octafluoro pentyl ester, acid imide (methyl) acrylate, (methyl) acrylic acid dimethyl Amino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, 2- (methyl) acryloyl-oxyethyls butanedioic acid, 2- (methyl) third Alkene trimethylammonium hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl -2- hydroxypropyl phthalates, (methyl) glycidyl acrylate, 2- (methyl) acryloyl-oxyethyl phosphate etc..
It is explained, in this manual, above-mentioned " (methyl) acrylate " refers to acrylate or methacrylate, Above-mentioned " (methyl) acryloyl group " refers to acryloyl group or methylacryloyl.
As 2 functions (methyl) acrylic compounds in above-mentioned (methyl) acrylic compounds, can enumerate for example 1,3- butanediols two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate, 1,6- hexane diols two (methyl) acrylate, 1,9- nonanes glycol two (methyl) acrylate, 1,10- decanediols two (methyl) acrylate, (methyl) acrylate of 2- normal-butyl -2- ethyl -1,3- propane diols two, DPG two (methyl) acrylate, three Propane diols two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethyl two Alcohol 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 bicyclopentadiene two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Ethyleneoxide addition isocyanuric acid two (methyl) acrylate, 2- hydroxyls -3- (methyl) acryloxypropyl (methyl) third Olefin(e) acid ester, carbonate diol two (methyl) acrylate, PTMEG two (methyl) acrylate, polyester-diol two (methyl) third Olefin(e) acid ester, polycaprolactone glycol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate etc..
As more than 3 functions in above-mentioned (methyl) acrylic compounds (methyl) acrylic compounds, can enumerate For example:Pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, the hydroxyl first of expoxy propane addition three Base propane three (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, caprolactone modification three Hydroxymethyl-propane three (methyl) acrylate, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, glycerine three (methyl) Acrylate, expoxy propane addition glycerine three (methyl) acrylate, three (methyl) acryloyl-oxyethyl phosphates, Ji Wusi Alcohol four (methyl) acrylate, two (trihydroxy methyl) propane four (methyl) acrylate, dipentaerythritol five (methyl) acrylic acid Ester, dipentaerythritol six (methyl) acrylate etc..
As above-mentioned styrenic, such as styrene, AMS, divinylbenzene etc. can be enumerated.
As aforesaid propylene nitrile based compound, such as acrylonitrile, methacrylonitrile etc. can be enumerated.
As long as above-mentioned olefin-based rubber particles are the olefin-based rubber particles with above-mentioned core shell structure, then can be comprising 2 laminar structures of above-mentioned stratum nucleare and above-mentioned shell, or also with intermediate layer 3 between above-mentioned stratum nucleare and above-mentioned shell Multilayer structure making more than layer.
The preferred lower limit of the average grain diameter of above-mentioned olefin-based rubber particles is 10nm, the preferred upper limit is 2000nm.It is logical Crossing makes the average grain diameter of above-mentioned olefin-based rubber particles for more than 10nm, so that the organic EL display element sealant of gained Solidfied material toughness more preferably.It is below 2000nm by making the average grain diameter of above-mentioned olefin-based rubber particles, so that shell The covering rate of layer is uprised, and transparent more excellent when making to be used as surfacing.Above-mentioned olefin-based rubber particles it is flat The preferred upper limit of equal particle diameter is 300nm, and the further preferred upper limit is 100nm.
It is explained, the average grain diameter of above-mentioned olefin-based rubber particles can be surveyed using such as laser diffraction formula size distribution Determine device etc. to be measured.As above-mentioned laser diffraction formula particle size distribution device, it is possible to use Mastersizer 2000 (Malvern company systems) etc..
Relative to the above-mentioned weight portion of cationically polymerizable compound 100, the content of above-mentioned olefin-based rubber particles it is preferred Lower limit for 5.0 weight portions, the preferred upper limit be 80 weight portions.By making the content of above-mentioned olefin-based rubber particles be 5.0 weights More than amount part, so that the toughness of the solidfied material of the organic EL display element sealant of gained is more excellent.By making above-mentioned alkene The content of hydrocarbon system rubber particles is below 80 weight portions, so that the solidfied material of the organic EL display element sealant of gained Block is more excellent.The preferred lower limit of the content of above-mentioned olefin-based rubber particles is 10 weight portions, the preferred upper limit is 70 weight portions.
Organic EL display element sealant of the invention contains light cationic polymerization initiator.
As long as above-mentioned light cationic polymerization initiator is to produce Bronsted acid or lewis acidic cation poly- using light irradiation Initiator is closed, is then not particularly limited, acid type can be produced for ionic light, or nonionic light produces acid type.
The light cationic polymerization initiator of acid type is produced as above-mentioned ionic light, can enumerate such as anionicsite by BF4 -、PF6 -、SbF6 -Or (BX4)-(wherein, X represents the phenyl replaced by the fluorine of at least more than 2 or trifluoromethyl) is constituted Aromatic series sulfonium salt, aromatic iodonium salts, aromatic diazonium salt, aromatic series ammonium salt or (2,4- cyclopentadiene -1- bases) ((1- Methylethyl) benzene)-Fe salt etc..
As above-mentioned aromatic series sulfonium salt, can enumerate for example:The double hexafluorophosphates of double (4- (diphenyl sulfonium) phenyl) thioethers, The double tetrafluoroborates of double (4- (diphenyl sulfonium) phenyl) thioethers pair hexafluoro antimonates, double (4- (diphenyl sulfonium) phenyl) thioethers, Double (4- (diphenyl sulfonium) phenyl) thioether four (pentafluorophenyl group) borates, diphenyl -4- (thiophenyl) phenyl sulfonium hexafluorophosphoric acid Salt, diphenyl -4- (thiophenyl) phenyl sulfonium hexafluoro antimonate, diphenyl -4- (thiophenyl) phenyl sulfonium tetrafluoroborate, two (pentafluorophenyl group) borate of phenyl -4- (thiophenyl) phenyl sulfonium four, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro-antimonic acid Salt, triphenylsulfonium tetrafluoroborate, triphenylsulfonium four (pentafluorophenyl group) borate, double (4- (two (4- (2- '-hydroxyethoxies Base)) phenyl sulfonium) phenyl) thioether double hexafluorophosphate, double (4- (two (4- (2- hydroxyl-oxethyls)) phenyl sulfoniums) phenyl) sulphur It is the double tetrafluoroborates of the double hexafluoro antimonates of ether, double (4- (two (4- (2- hydroxyl-oxethyls)) phenyl sulfoniums) phenyl) thioethers, double (4- (two (4- (2- hydroxyl-oxethyls)) phenyl sulfoniums) phenyl) thioether four (pentafluorophenyl group) borate etc..
As above-mentioned aromatic iodonium salts, such as diphenyl iodine hexafluorophosphate, diphenyl iodine hexafluoro antimony can be enumerated Hydrochlorate, diphenyl iodine tetrafluoroborate, diphenyl iodine four (pentafluorophenyl group) borate, double (dodecylphenyl) iodine six Fluorophosphate, double (dodecylphenyl) iodine hexafluoro antimonates, double (dodecylphenyl) iodine tetrafluoroborates, double (ten Dialkyl phenyl organic) iodine four (pentafluorophenyl group) borate, 4- aminomethyl phenyls -4- (1- Methylethyls) phenyl-iodide hexafluoro phosphorus Hydrochlorate, 4- aminomethyl phenyls -4- (1- Methylethyls) phenyl-iodide hexafluoro antimonate, 4- aminomethyl phenyls -4- (1- methyl Ethyl) phenyl-iodide tetrafluoroborate, 4- aminomethyl phenyls -4- (1- Methylethyls) phenyl-iodide four (pentafluorophenyl group) boric acid Salt etc..
As above-mentioned aromatic diazonium salt, can enumerate for example phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoro antimonate, Phenyldiazonium tetrafluoroborate, phenyldiazonium four (pentafluorophenyl group) borate etc..
As above-mentioned aromatic series ammonium salt, such as 1- benzyls -2- cyanopyridines hexafluorophosphate, 1- benzyls can be enumerated Base -2- cyanopyridines hexafluoro antimonate, 1- benzyl -2- cyanopyridines tetrafluoroborate, 1- benzyl -2- cyano group Pyridine four (pentafluorophenyl group) borate, 1- (naphthyl methyl) -2- cyanopyridines hexafluorophosphate, 1- (naphthyl first Base) -2- cyanopyridines hexafluoro antimonate, 1- (naphthyl methyl) -2- cyanopyridines tetrafluoroborate, 1- (naphthyls Methyl) -2- cyanopyridines four (pentafluorophenyl group) borate etc..
As above-mentioned (2,4- cyclopentadiene -1- bases) ((1- Methylethyls) benzene)-Fe salt, can enumerate for example (2, 4- cyclopentadiene -1- bases) ((1- Methylethyls) benzene)-Fe (II) hexafluorophosphate, (2,4- cyclopentadiene -1- bases) ((1- Methylethyls) benzene)-Fe (II) hexafluoro antimonate, (2,4- cyclopentadiene -1- bases) ((1- Methylethyls) benzene) - Fe (II) tetrafluoroborate, (2,4- cyclopentadiene -1- bases) ((1- Methylethyls) benzene)-Fe (II) four (pentafluorophenyl group) Borate etc..
The light cationic polymerization initiator of acid type is produced as above-mentioned nonionic light, such as nitrobenzyl ester, sulphur can be enumerated Acid derivative, phosphate, sulfophenylate, diazo naphthoquinone, N- hydroxy imide sulphonic acid esters etc..
As product commercially available in above-mentioned light cationic polymerization initiator, can enumerate for example:DTS-200 (MIDORY chemistry Company system);UVI6990, UVI6974 (are Union Carbide Corporation systems);SP-150, SP-170 (are ADEKA company systems);FC-508, FC-512 (are 3M company systems);IRGACURE261 (BASF AG's system);PI2074 (Rhodia company systems) etc..
Relative to the above-mentioned weight portion of cationically polymerizable compound 100, the content of above-mentioned light cationic polymerization initiator Preferred lower limit is 0.1 weight portion, the preferred upper limit is 10 weight portions.By the content for making above-mentioned light cationic polymerization initiator More than 0.1 weight portion, so that the photo-curable of the organic EL display element sealant of gained is more excellent.It is above-mentioned by making The content of light cationic polymerization initiator is below 10 weight portions, from the organic EL display element sealant without making gained Curing reaction is too fast, and makes operability more excellent, can make solidfied material evenly.Above-mentioned light cationic polymerization initiator contains The preferred lower limit of amount is 0.5 weight portion, the preferred upper limit is 5 weight portions.
Organic EL display element sealant of the invention contains the water imbibition filler of alkaline-earth metal system and/or magnesium system.It is logical The water imbibition filler containing above-mentioned alkaline-earth metal system and/or magnesium system is crossed, so that the organic EL display element sealant of gained Solidfied material block it is excellent.
As above-mentioned alkaline-earth metal system and/or the water imbibition filler of magnesium system, such as calcium oxide, magnesia, oxidation can be enumerated Barium, strontium oxide strontia etc..Wherein, from from the viewpoint of water imbibition, calcium oxide and/or magnesia are preferably comprised, as above-mentioned alkaline earth gold Belong to the water imbibition filler of system, further preferably specific surface area is less than 10.0m2The calcium oxide of/g.
In addition, in the case where combination is containing alkaline-earth metal system water imbibition filler and magnesium system water imbibition filler, preferred compositions It is that dolomite is heated and obtained further preferably by by calcium carbonate and the double salt of magnesium carbonate containing calcium oxide and magnesia Light dolomite.
Relative to the above-mentioned weight portion of cationically polymerizable compound 100, the water imbibition of above-mentioned alkaline-earth metal system and/or magnesium system The preferred lower limit of the content of filler is 3.0 weight portions, the preferred upper limit is 100 weight portions.By making above-mentioned alkaline-earth metal system And/or the content of the water imbibition filler of magnesium system is more than 3.0 weight portions, so that the organic EL display element sealant of gained Solidfied material block it is more excellent.By making the content of the water imbibition filler of above-mentioned alkaline-earth metal system and/or magnesium system be 100 weights Below amount part, so that the toughness of the solidfied material of the organic EL display element sealant of gained is improved, and make suppression crackle Generation and panel stripping effect it is more excellent.The content of the water imbibition filler of above-mentioned alkaline-earth metal system and/or magnesium system is more Preferred lower limit is 5.0 weight portions, the preferred upper limit is 80 weight portions.
In addition, the total surface area of the water imbibition filler of above-mentioned alkaline-earth metal system and/or magnesium system is poly- relative to above-mentioned cation Preferred lower limit of the conjunction property compound per 100g is 10m2, the preferred upper limit be 200m2.By make above-mentioned alkaline-earth metal system and/or The total surface area of the water imbibition filler of magnesium system is 10m2More than, so that the solidification of the organic EL display element sealant of gained The block of thing is more excellent.By making the total surface area of the water imbibition filler of above-mentioned alkaline-earth metal system and/or magnesium system be 200m2With Under, so that the toughness of the solidfied material of the organic EL display element sealant of gained is improved, and make the generation of suppression crackle And the effect of the peeling of panel is more excellent.The total surface area of the water imbibition filler of above-mentioned alkaline-earth metal system and/or magnesium system it is preferred Lower limit be 20m2, the preferred upper limit be 150m2
It is explained, the total surface area of the water imbibition filler of above-mentioned alkaline-earth metal system and/or magnesium system is by above-mentioned alkaline-earth metal The content and BET specific surface area of the water imbibition filler of system and/or magnesium system are calculated.Specifically, for example by utilizing specific surface area Determine device (Shimadzu Seisakusho Ltd.'s company system, ASAP-2000) and BET specific surface area obtained from being measured using nitrogen is come Calculated.
For the purposes such as cementability are improved, organic EL display element sealant of the invention can not hinder the present invention Contain other fillers in addition to the water imbibition filler of above-mentioned alkaline-earth metal system and/or magnesium system in the range of purpose.
As above-mentioned other fillers, can enumerate for example:The inorganic fillers such as silica, talcum, aluminum oxide;Polyester micropartical, Organic fillers such as polyurethane particulate, polyvinyl particulate, acrylic polymer particulate etc..Wherein, from making raising moisture-proof Set out in terms of the excellent effect of property, preferably talc.
Relative to the above-mentioned weight portion of cationically polymerizable compound 100, the preferred lower limit of the content of above-mentioned other fillers For 5 weight portions, the preferred upper limit are 100 weight portions.It is the scope by making the content of above-mentioned other fillers, so as to institute will not be made The coating of the organic EL display element sealant for obtaining is deteriorated, and can give full play to raising cementability and other effects.It is above-mentioned other The preferred lower limit of the content of filler is 10 weight portions, the preferred upper limit is 80 weight portions.
Organic EL display element sealant of the invention can contain thermal curing agents.As thermal curing agents, example can be enumerated Such as hydrazide compound, imdazole derivatives, acid anhydrides, dicyandiamide, guanidine derivatives, modified aliphatic polyamine, various amine and epoxy resin Addition compound product etc..
As above-mentioned hydrazide compound, can enumerate such as 1,3- double (diazanyl carbonyl ethyl -5- isopropyls hydantoins), Sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, acid dihydrazide etc..
As above-mentioned imdazole derivatives, such as 1- cyano ethyls -2- phenylimidazoles, N- (2- (2- first can be enumerated Base -1- imidazole radicals) ethyl) urea, 2,4- diaminourea -6- (2 '-methylimidazolyl-(1 '))-ethyl-s-triazine, N, N '-bis- (2- methyl isophthalic acids-imidazolylethyl) urea, N, N '-(2- methyl isophthalic acids-imidazolylethyl)-adipamide, 2- phenyl -4- methyl -5- hydroxymethylimidazoles, 2- phenyl -4,5- bishydroxymethyl imidazoles etc..
As above-mentioned acid anhydrides, such as tetrabydrophthalic anhydride, ethylene glycol double (dehydration trimellitates) etc. can be enumerated.
These thermal curing agents can be used alone, it is also possible to and use two or more.
As product commercially available in above-mentioned thermal curing agents, such as SDH (Japanese FINECHEM company systems), ADH can be enumerated (big Mound chemical company system), AMICURE VDH, AMICURE VDH-J, AMICURE UDH (be Ajinomoto Fine- Techno company systems) etc..
Relative to the above-mentioned weight portion of cationically polymerizable compound 100, the preferred lower limit of the content of above-mentioned thermal curing agents For 0.5 weight portion, the preferred upper limit are 30 weight portions.By making the content of above-mentioned thermal curing agents for more than 0.5 weight portion, so that Make the Thermocurable of the organic EL display element sealant of gained more excellent.By making the content of above-mentioned thermal curing agents be 30 weights Below amount part, so that the storage stability of the organic EL display element sealant of gained is more excellent, and make solidfied material Moisture-proof is more excellent.The preferred lower limit of the content of above-mentioned thermal curing agents is 1 weight portion, the preferred upper limit is 15 weight Part.
Organic EL display element sealant of the invention can contain sensitizer.Above-mentioned sensitizer has further raising The polymerization initiation efficiency of above-mentioned light cationic polymerization initiator and further promote organic EL display element of the invention to seal The effect of the curing reaction of agent.
As above-mentioned sensitizer, the anthracene based compounds such as such as 9,10- dibutoxy anthracenes, 2,4- diethyl thioxanthenes can be enumerated The thioxanthones such as ketone based compound, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, benzophenone, 2,4- dichloros two Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4,4 '-bis- (dimethylamino) benzophenone, the methyl of 4- benzoyls -4 ' Diphenylsulfide etc..
Relative to the above-mentioned weight portion of cationically polymerizable compound 100, the preferred lower limit of the content of above-mentioned sensitizer is 0.05 weight portion, the preferred upper limit are 3 weight portions.By making the content of above-mentioned sensitizer be more than 0.05 weight portion, so as to enter One step plays sensitization effect.By making the content of above-mentioned sensitizer for below 3 weight portions, so that absorption will not be made excessive, can Light is sent to deep.The preferred lower limit of the content of above-mentioned sensitizer is 0.1 weight portion, the preferred upper limit is 1 weight Part.
For the purposes such as storage stability are improved, organic EL display element sealant of the invention preferably comprises stabilization Agent.
As aforementioned stable agent, such as amine compound, aminobenzene phenol-type epoxy resin etc. can be enumerated.
Relative to the above-mentioned weight portion of cationically polymerizable compound 100, the preferred lower limit of the content of aforementioned stable agent is 0.001 weight portion, the preferred upper limit are 2 weight portions.It is the scope by making the content of aforementioned stable agent, so as to suppress solidification resistance Hinder, and make the storage stability of organic EL display element sealant obtained by raising and other effects more excellent.Aforementioned stable agent Content preferred lower limit for 0.05 weight portion, the preferred upper limit be 1 weight portion.
Organic EL display element sealant of the invention can contain silane coupler.Above-mentioned silane coupler have carry The effect of the cementability of organic EL display element sealant of the invention high and substrate etc..
As above-mentioned silane coupler, such as 3- TSL 8330s, 3- mercaptopropyi front threes can be enumerated TMOS, 3- glycidoxypropyltrime,hoxysilanes, 3- isocyanates propyl trimethoxy silicanes etc..These silane Coupling agent both can be used alone, it is also possible to and with two or more.
Relative to the weight portion of cationically polymerizable compound 100, the preferred lower limit of the content of above-mentioned silane coupler is 0.1 weight portion, the preferred upper limit are 10 weight portions.By making the content of above-mentioned silane coupler for the scope, thus suppress by Oozing out caused by remaining silane coupler, and make the effect of the cementability of organic EL display element sealant obtained by raising Fruit is more excellent.The preferred lower limit of the content of above-mentioned silane coupler is 0.5 weight portion, the preferred upper limit is 5 weight portions.
Organic EL display element sealant of the invention can not hinder to contain surface in the range of the object of the invention Modifying agent.By containing above-mentioned surface modifier, being applied such that it is able to be assigned with sealant to organic EL display element of the invention The flatness of film.
As above-mentioned surface modifier, such as surfactant, levelling agent etc. can be enumerated.
As above-mentioned surfactant, above-mentioned levelling agent, the levelling agent of such as silicon systems, acrylic acid series, fluorine system etc. can be enumerated.
As commercially available product in above-mentioned surfactant, above-mentioned levelling agent, can enumerate for example:BYK-345, BYK- 340 (being BYK-CHEMIEJAPAN company systems), Surflon S-611 (AGC SEMICHEMICAL company systems) etc..
In order to improve the durability of element electrode, organic EL display element sealant of the invention can not hinder this Contain ion exchange resin in the range of goal of the invention.
As above-mentioned ion exchange resin, it is possible to use in cation exchange, anion exchange, two ion-exchange types It is any number of, but particularly preferably it is capable of the cation exchange or two ion-exchange types of adsorbing chlorinated thing ion.
In addition, organic EL display element sealant of the invention can not hinder basis in the range of the object of the invention Need to contain the public affairs such as cure retarder, reinforcing agent, softening agent, plasticizer, viscosity modifier, ultra-violet absorber, antioxidant The various additives known.
Method as organic EL display element sealant of the invention is manufactured, can enumerate for example:Use homogenous disperse The mixers such as machine, homogeneous mixer, universal mixer, planetary-type mixer, kneader, three-roller are by cationically polymerizable chemical combination The water imbibition filler of thing, olefin-based rubber particles, light cationic polymerization initiator, alkaline-earth metal system and/or magnesium system and according to need Method of the additive to be added mixing etc..Above-mentioned olefin-based rubber particles can also in advance be distributed to above-mentioned cationically polymerizable Mix with other compositions again after in compound.
Organic EL display element sealant of the invention uses E type viscosity in the case of for the purpose of face interior sealing The preferred lower limit of the viscosity at 25 DEG C for measuring is 50mPas, the preferred upper limit is 8000mPas.It is above-mentioned by making Viscosity is the scope, so that the coating of the organic EL display element sealant of the invention of gained, solidfied material is transparent Property is more excellent.The preferred lower limit of above-mentioned viscosity is 60mPas, the preferred upper limit is 3000mPas, further preferably Lower limit for 70mPas, the further preferred upper limit be 1000mPas.
It is explained, above-mentioned viscosity can be determined for example, by the following manner:Use VISCOMETER TV-22 (east Machine industry companies system) as E type viscosimeters, using optimal moment of torsion number of the cone-plate of CP1 in each viscosity region come appropriate Select the rotating speed of 1~100rpm.
Organic EL display element sealant of the invention uses E type viscosity in the case of the purpose for edge seal The preferred lower limit for counting the viscosity at 25 DEG C for determining is 100Pas, the preferred upper limit is 500Pas.It is above-mentioned by making Viscosity is the scope, so as to prevent the reduction of contact area when vacuum abutted caused by the insertion produced by pressure differential, And make the shape stability after coating and coating more excellent.The preferred lower limit of above-mentioned viscosity is 200Pas, more excellent The upper limit of choosing is 400Pas, and further preferred lower limit is 250Pas, the further preferred upper limit is 350Pas.
It is explained, above-mentioned viscosity can be determined for example, by the following manner:Use VISCOMETER TV-22 (east Machine industry companies system) as E type viscosimeters, using optimal moment of torsion number of the cone-plate of CP7 in each viscosity region come appropriate Select the rotating speed of 1~100rpm.
As the shape of the sealing formed with sealant by organic EL display element of the invention, as long as can protect The shape that layered product with organic light emitting material influences from ambient atmos, then be not particularly limited, and can be to cover completely Cover the shape of the layered product, it is also possible to be formed in the pattern of the edge part closure of the layered product, be additionally formed in the layered product Edge part be provided with outs open portion shape pattern, but can perform well in seal the layered product edge part.
Invention effect
According to the present invention it is possible to provide the block of solidfied material and the organic electro-luminescent display unit of tenacity excellent with close Envelope agent.
Specific embodiment
Embodiment is exemplified below further to be described in detail the present invention, but the present invention is not limited to these implementations Example.
(there is the making of the olefin-based rubber particles A of core shell structure)
The weight portion of butadiene 100, deionized water 200 are put into fully except deoxidation and in having carried out the reaction vessel that nitrogen is replaced Weight portion, the weight portion of tripotassium phosphate 0.05, the weight portion of potassium dihydrogen phosphate 0.04, the weight portion of disodium ethylene diamine tetraacetate 0.002, sulphur The ferrous weight portion of seven hydrated salt 0.001 of acid and the weight portion of neopelex 1.5, are stirred mixing at 45 DEG C.Connect , input hydrogen peroxide is to the weight portion of terpane 0.015 and the weight portion of sodium sulfoxylate formaldehyde 0.04, initiated polymerization.From Additional hydrogen peroxide is put into behind 5 hours that polymerisation has started to the weight portion of terpane 0.01, disodium ethylene diamine tetraacetate 0.002 weight portion and the weight portion of iron 0.001.Residual monomer is removed behind 10 hours since polymerisation, terminates polymerization, Obtain the latex (X-1) comprising polybutadiene rubber particle.
In the reaction vessel of the weight portion of latex (X-1) 1500 comprising polybutadiene rubber particle of gained is added The input weight portion of deionized water 300, is stirred in nitrogen atmosphere at 50 DEG C.Add disodium ethylene diamine tetraacetate 0.01 After weight portion, the weight portion of iron 0.005 and the weight portion of sodium sulfoxylate formaldehyde 0.24, added as the methyl of grafted monomers with 2 hours The weight portion of methyl acrylate 90 and the weight portion of TBHP 0.08, make it carry out glycerol polymerization.Opened from polymerisation Terminate polymerization behind 2 hours for having begun, obtain the latex containing the olefin-based rubber particles A with core shell structure.
The average grain diameter of the olefin-based rubber particles A with core shell structure of gained is 100nm.
(there is the making of the olefin-based rubber particles B of core shell structure)
Except the replacement weight portion of butadiene 100 to the input weight portion of butadiene 75 and the weight of styrene 25 in reaction vessel Beyond part, being made in the same manner as above-mentioned " (having the making of the olefin-based rubber particles A of core shell structure) ", there is stratum nucleare to include fourth Olefin-based rubber particles B (average grain diameter 100nm) of the core shell structure of butadiene-styrene rubber.
(there is the making of the olefin-based rubber particles C of core shell structure)
The weight portion of methyl methacrylate 80 and isocyanuric acid are used except replacing the weight portion of methyl methacrylate 90 Beyond the mixture of the weight portion of triallyl 10 is as grafted monomers, " (there are the olefin-based rubber particles of core shell structure with above-mentioned The making of A) " similarly make the olefin-based rubber particles C with core shell structure of the stratum nucleare comprising Afpol (average grain diameter 100nm).
(embodiment 1)
In bisphenol f type epoxy resin (DIC company systems, " EPICLON EXA- as cationically polymerizable compound 830LVP ") 80 weight portions and solid-state bisphenol f type epoxy resin (Mitsubishi Chemical Ind's system, " jER 4005P ") 20 weight portions in The made weight portions of olefin-based rubber particles A 50 with core shell structure of addition, are equably stirred mixing.Then, add Plus as aromatic iodonium salts (Rhodia company systems, " PI2074 ") 1.0 weight portions of light cationic polymerization initiator, at 60 DEG C Lower heating for dissolving is added as the weight portion of 9,10- dibutoxies anthracene 0.2 of sensitizer, as silane coupler after 1 hour 3- glycidoxypropyltrime,hoxysilanes (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-403 ") 3.0 weight portions, conduct are inhaled Calcium oxide (Ji Ze lime industrial group system, " quick lime J1P ", the specific surface area 2.5m of aqueous filler2/ g) 40 weight portions and work It is talcum (Japanese talcum company system, " MICRO ACE FG-15 ") 50 weight portions of other fillers, uses stirring mixer (THINKY company systems, " AR-250 "), equably stirring mixing under low whipping speed 3000rpm is fabricated to organic EL displays unit Part sealant.
(embodiment 2~12, comparative example 1~5)
Each material of the match ratio described in table 1 and table 2 is stirred into mixing similarly to Example 1, organic EL is fabricated to Display element sealant.
< evaluates >
Each organic EL display element to gained in embodiment and comparative example carries out following evaluation with sealant.Result is such as Shown in table 1 and table 2.
(1) viscosity
To each organic EL display element sealant of gained in embodiment and comparative example, using E types viscosimeter, (eastern machine is produced Industry company system, " VISCOMETER TV-22 "), determine the viscosity (initial viscosity) at 25 DEG C.
(2) block of solidfied material
To each organic EL display element sealant of gained in embodiment and comparative example, following Ca-TEST is carried out.
First, covering has the mask of the opening portion of multiple 2mm × 2mm on the glass substrate of 30mm × 30mm, utilizes Vacuum evaporation plating machine is deposited with Ca.The condition of evaporation is:2 × 10 will be decompressed in the evaporator of vacuum deposition apparatus- 3Pa, by Ca withEvaporation rate film formingWill be deposited with have Ca glass substrate be moved to be managed to dew point (- 60 DEG C with On) glove box in, be fitted in surface and be coated with each organic EL display element of gained in embodiment and comparative example with close Seal the glass substrate of agent.Now, according in the side that there is the Ca of evaporation for the position of 2mm, 4mm, 6mm apart from glass substrate end face Formula is fitted.Then, with 3000mJ/cm2The ultraviolet of 365nm is irradiated, then is heated 30 minutes at 80 DEG C, thus make sealant Solidification, is fabricated to Ca-TEST substrates.By the Ca-TEST substrates of gained exposed to 85 DEG C, the hot and humid condition of 85%RH, By the immersion distance of the disappearance observation moisture hourly of Ca.
The result of Ca-TEST:Time untill the immersion distance of moisture is reached into 6mm is the situation of more than 1000 hours " ◎ " is set to, the situation by more than 500 hours and less than 1000 hours is set to "○", by more than 100 hours and less than 500 hours Situation be set to " △ ", the situation less than 100 hours is set to "×", so as to be evaluated the block of solidfied material.
(3) toughness of solidfied material
To in embodiment and comparative example gained each organic EL display element sealant with 3000mJ/cm2Irradiation 365nm Ultraviolet, then with 80 DEG C heat 30 minutes, thus obtain solidfied material.To the solidfied material of gained, according to JIS R1607 (IF Method), try to achieve destruction toughness value KIC.Its result:Will destruction toughness value KICValue be that more than 1.0 situation is set to "○", by 0.8 Situation above and less than 1.0 is set to " △ ", and the situation less than 0.8 is set into "×", so as to the toughness to solidfied material is carried out Evaluate.
(4) adhering state of panel
(being configured with the making of the substrate of the layered product with organic light emitting material)
On glass substrate (length 25mm, width 25mm, thickness 0.7mm) withThickness film forming ITO electrode Afterwards, as substrate.Aforesaid substrate is carried out into 15 minutes ultrasonic waves with acetone, aqueous alkali, ion exchange water, isopropanol respectively clear After washing, cleaned 10 minutes using the isopropanol for boiling, recycling UV- ozone cleaners (Japanese electronic laser company system, " NL-UV253 ") carry out pre-treatment.
Then, the substrate is fixed on the substrate holder of vacuum deposition apparatus, N, N '-two is added in unglazed crucible (1- naphthyls)-N, N '-diphenylbenzidine (α-NPD) 200mg, adds three (8- hydroxyl quinolines in another unglazed crucible Quinoline) aluminium (Alq3) 200mg, 1 × 10 will be depressurized in vacuum chamber- 4Pa.Afterwards, the crucible that will be equipped with α-NPD is heated, Make α-NPD with evaporation rateIt is stacked on substrate, film forming thicknessHole transmission layer.Then, will be equipped with Alq3Earthenware Crucible heated, withEvaporation rate film forming thicknessOrganic light emitting material.Afterwards, by shape In moving into another vacuum deposition apparatus into the substrate for having hole transmission layer and organic light emitting material, in the vacuum deposition apparatus Tungsten resistance-heated boat in add lithium fluoride 200mg, the addition aluminum steel 1.0g in another tungsten boat.Afterwards, by vacuum 2 × 10 are decompressed in the evaporator of evaporation coating device- 4Pa, by lithium fluoride withEvaporation rate film formingAfterwards, by aluminium WithSpeed film formingMake to return to normal pressure in evaporator using nitrogen, taking-up be configured with 10mm × The substrate of the layered product of the organic light emitting material of 10mm.
(using the coated of inorganic material film A)
In the way of the layered product entirety of the substrate for being configured with layered product obtained by covering, setting has 13mm × 13mm Opening portion mask, form inorganic material film A using plasma CVD method.
Plasma CVD method is using SiH4Gas and nitrogen are set to SiH as unstrpped gas, respective flow4Gas 10sccm, nitrogen 200sccm, RF power are set to 10W (frequency 2.45GHz), chamber indoor temperature and are set to 100 DEG C, cavity indoor pressure It is set to be carried out under conditions of 0.9Torr.
The thickness of the inorganic material film A for being formed is for about 1 μm.
(formation of resin protection film)
The substrate for being configured with the layered product being coated to by inorganic material film A is set in vacuum plant, vacuum holding is being arranged at Each organic EL display element sealant 0.5g of gained in embodiment and comparative example is added in the heated boat put, is depressurized to 10Pa, to the part of the square of the 11mm × 11mm comprising layered product, is sealed with 200 DEG C of heating organic EL display elements Agent, vacuum evaporation is carried out in the way of thickness is reached 0.5 μm.Afterwards, under vacuum conditions using high-pressure sodium lamp, with exposure Reach 3000mJ/cm2Mode illumination wavelength 365nm ultraviolet, make organic EL display element sealant cures, form tree Fat diaphragm.
(using the coated of inorganic material film B)
After forming resin protection film, opening with 12mm × 12mm is set in the overall mode for covering the resin protection film The mask of oral area, inorganic material film B is formed using plasma CVD method, obtains organic EL display element.
Plasma CVD method is using SiH4Gas and nitrogen are set to SiH as unstrpped gas, respective flow4Gas 10sccm, nitrogen 200sccm, RF power are set to 10W (frequency 2.45GHz), chamber indoor temperature and are set to 100 DEG C, cavity indoor pressure It is set to be carried out under conditions of 0.9Torr.
The thickness of the inorganic material film B for being formed is for about 1 μm.
(observation of the adhering state of panel)
After with visually observation, the organic EL display element of gained is exposed 500 hours in the environment of 85 DEG C, 85%RH The adhering state of panel.Situation about being peeled off without panel is set to "○", will confirm that the situation that a part of panel is peeled off is set to " △ ", will confirm that the situation that most panel is peeled off is set to "×", so that the adhering state of counter plate is evaluated.
(5) reliability of organic EL display element
The organic EL display element that to be obtained in the same manner as above-mentioned " adhering state of (4) panel " is in 85 DEG C, 85%RH After being exposed 500 hours under environment, apply the voltage of 3V, stain (is whether there is with the luminance for visually observing organic EL display element And pixel edge delustring).Situation without stain, edge delustring and uniformly light-emitting is set to "○", even if will confirm that a little black Point, the situation of edge delustring are set to "×", so as to the reliability to organic EL display element is evaluated.
[table 1]
[table 2]
Industrial applicability
According to the present invention it is possible to provide the block of solidfied material and the organic electro-luminescent display unit of tenacity excellent with close Envelope agent.

Claims (5)

1. a kind of organic electro-luminescent display unit sealant, it is characterised in that contain cationically polymerizable compound, alkene It is rubber particles, light cationic polymerization initiator, the water imbibition filler also containing alkaline-earth metal system and/or magnesium system,
The olefin-based rubber particles have core shell structure.
2. organic electro-luminescent display unit sealant according to claim 1, it is characterised in that olefin-based rubber granule Sub to have stratum nucleare and shell, the stratum nucleare includes conjugated diene rubber, and the shell includes to have to come from has polymerism not The resin of the segment of the compound of saturation double bond.
3. organic electro-luminescent display unit sealant according to claim 1 and 2, it is characterised in that olefin-based rubber The content of micelle is 5.0~80 weight portions relative to the weight portion of cationically polymerizable compound 100.
4. the organic electro-luminescent display unit sealant according to claim 1,2 or 3, it is characterised in that containing aerobic Change calcium and/or magnesia as alkaline-earth metal system and/or the water imbibition filler of magnesium system.
5. organic electro-luminescent display unit sealant according to claim 4, it is characterised in that contain specific surface area Less than 10.0m2The calcium oxide of/g as alkaline-earth metal system water imbibition filler.
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