JP2019029355A - Sealing agent for organic EL display element - Google Patents

Abstract

To provide a sealing agent for an organic EL display element which can be easily applied by an inkjet method, is excellent in low outgassing property, and can obtain an organic EL display element excellent in reliability.SOLUTION: A sealing agent for an organic EL display element containing a polymerizable compound and a polymerization initiator includes a compound having a hydrophilic functional group, the hydrophilic functional group value of the compound having the hydrophilic functional group is 0.003 mol/g or more and 0.02 mol/g or less and the viscosity of the entire sealing agent for the organic EL display element at 25°C is 80 mPa s or less.SELECTED DRAWING: None

Description

The present invention relates to an encapsulant for an organic EL display element that can be easily applied by an ink jet method, can provide an organic EL display element that is excellent in low outgassing properties and excellent in reliability.

An organic electroluminescence (hereinafter, also referred to as “organic EL”) display element has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and the organic light emitting material layer is formed from one electrode on the organic light emitting material layer. When electrons are injected and holes are injected from the other electrode, the electrons and holes are combined in the organic light emitting material layer to emit light. Thus, since the organic EL display element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. Has the advantage.

The organic light-emitting material layer and electrodes constituting the organic EL display element have a problem that the characteristics are easily deteriorated by moisture, oxygen, and the like. Therefore, in order to obtain a practical organic EL display element, it is necessary to extend the life by blocking the organic light emitting material layer and the electrode from the atmosphere. Patent Document 1 discloses a method of sealing an organic light emitting material layer and an electrode of an organic EL display element with a laminated film of a silicon nitride film and a resin film formed by a CVD method. Here, the resin film has a role of preventing pressure on the organic layer and the electrode due to internal stress of the silicon nitride film.

In the method of sealing with a silicon nitride film disclosed in Patent Document 1, organic light emission occurs when a silicon nitride film is formed due to unevenness on the surface of the organic EL display element, adhesion of foreign matters, generation of cracks due to internal stress, or the like. The material layer or electrode may not be completely covered. If the coating with the silicon nitride film is incomplete, moisture will enter the organic light emitting material layer through the silicon nitride film.
As methods for preventing moisture from entering the organic light emitting material layer, Patent Documents 2 to 4 disclose a method of laminating an inorganic material film and a resin film. However, in the methods disclosed in Patent Documents 2 and 3, since the resin film is formed by the vacuum deposition method, there is a problem that a large-scale apparatus is required or foreign matter may be mixed. was there. In addition, the method disclosed in Patent Document 4 is that the resin film is formed by the screen printing method, so that it is difficult to form a thin film, and there is a possibility that foreign matter is mixed by a screen plate or a squeegee. There was a problem.

As another method for forming the resin film, there is a method using an ink jet method. If an ink jet method is used, a resin film can be uniformly formed at high speed. However, when the sealant is made to have a low viscosity in order to be suitable for application by the ink jet method, outgas is generated or cracks are generated in the inorganic material film, resulting in insufficient sealing. There has been a problem that the organic EL display element is inferior in reliability.

JP 2000-223264 A JP 2005-522891 A JP 2001-307873 A JP 2012-190612 A

An object of the present invention is to provide a sealing agent for organic EL display elements that can be easily applied by an ink jet method, can provide an organic EL display element that is excellent in low outgassing properties and excellent in reliability. And

The present invention 1 is an organic EL display element sealing agent containing a polymerizable compound and a polymerization initiator, which contains a compound having a hydrophilic functional group, and the hydrophilicity of the compound having the hydrophilic functional group The sealant for organic EL display elements has a functional group value of 0.003 mol / g or more and 0.02 mol / g or less, and the viscosity of the whole sealant for organic EL display elements at 25 ° C. is 80 mPa · s or less. .
Invention 2 contains a polymerizable compound and a polymerization initiator, and is an organic EL display element sealing agent used for coating by an ink jet method, which contains a compound having a hydrophilic functional group, and is hydrophilic. It is a sealing agent for organic EL display elements in which the hydrophilic functional group value of the compound having a functional group is 0.003 mol / g or more and 0.02 mol / g or less.
The present invention is described in detail below. In addition, about the matter common to the sealing agent for organic EL display elements of this invention 1 and the sealing agent for organic EL display elements of this invention 2, it describes as "the sealing agent for organic EL display elements of this invention". To do.

The present inventors usually use a compound having a hydrophilic functional group that is preferably not used for a sealant for an organic EL display element from the viewpoint of moisture permeation prevention property, thereby easily using an inkjet method. It has been found that an organic EL display element that can be applied, has low outgassing properties, and is excellent in reliability, and has completed the present invention.

The sealing agent for organic EL display elements of this invention contains the compound which has a hydrophilic functional group. By containing the compound having the hydrophilic functional group, the organic EL display element sealing agent of the present invention can be easily applied by an ink jet method, and has excellent low outgassing properties and excellent reliability. An organic EL display element can be obtained.

The lower limit of the hydrophilic functional group value of the compound having a hydrophilic functional group is 0.003 mol / g, and the upper limit is 0.02 mol / g. When the hydrophilic functional group value of the compound having the hydrophilic functional group is 0.003 mol / g or more, the encapsulant for organic EL display elements of the present invention has excellent ink jet coating properties. When the hydrophilic functional group value of the compound having a hydrophilic functional group is 0.02 mol / g or less, the cured product of the organic EL display element sealing agent of the present invention has excellent moisture permeation preventive properties. Become. The preferable lower limit of the hydrophilic functional group value of the compound having the hydrophilic functional group is 0.004 mol / g, the preferable upper limit is 0.015 mol / g, and the more preferable upper limit is 0.012 mol / g.
In the present specification, the hydrophilic functional group value is a value calculated by the following formula.
Hydrophilic functional group value (mol / g) = (Number of hydrophilic functional groups in one molecule having a hydrophilic functional group) / (Molecular weight of a compound having a hydrophilic functional group)
Moreover, the sealing agent for organic EL display elements of the present invention contains a compound having a hydrophilic functional group and having a hydrophilic functional group value of 0.003 mol / g or more and 0.02 mol / g or less. If it does not inhibit the purpose of the present invention, it may contain a compound having a hydrophilic functional group and having a hydrophilic functional group value of less than 0.003 mol / g or more than 0.02 mol / g. . Hereinafter, the description of the compound having a hydrophilic functional group has a hydrophilic functional group and has a hydrophilic functional group value of 0.003 mol / g or more and 0.02 mol unless otherwise specified. It is description about the compound which is below / g.

The compound having a hydrophilic functional group is at least one selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group as the hydrophilic functional group from the viewpoint of the wettability of the obtained sealing agent for organic EL display elements. It preferably has a seed, more preferably has a hydroxyl group and / or a carboxyl group, and most preferably has a hydroxyl group from the viewpoint of storage stability.

The compound having a hydrophilic functional group may be a compound having a polymerizable functional group and included in the polymerizable compound (hereinafter, also referred to as “polymerizable compound having a hydrophilic functional group”) or polymerization. It may be one that does not have a functional functional group and is not included in the polymerizable compound (hereinafter also referred to as “non-polymerizable compound having a hydrophilic functional group”). Especially, it is preferable that it is a polymeric compound which has a hydrophilic functional group from a viewpoint of improving inkjet applicability | paintability and low outgassing property. In particular, an epoxy compound or an oxetane compound having a hydroxyl group as a hydrophilic functional group is preferable.

The polymerizable compound having the hydrophilic functional group will be described later.
Examples of the non-polymerizable compound having a hydrophilic functional group include a non-polymerizable compound having a hydroxyl group, a non-polymerizable compound having a carboxyl group, and a non-polymerizable compound having an amino group.

Examples of the non-polymerizable compound having a hydroxyl group include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, phenyl glycol, and benzyl glycol. Etc.

Examples of the non-polymerizable compound having a carboxyl group include aliphatic carboxylic acids and aromatic carboxylic acids.
Examples of the aliphatic carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethylhexanoic acid, undecylic acid, lauric acid, tridecylic acid, Examples include myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, and melicic acid.
Examples of the aromatic carboxylic acid include benzoic acid and toluic acid.

Examples of the non-polymerizable compound having an amino group include aliphatic amines and aromatic amines.
Examples of the aliphatic amine include ethylene diamine, diethylene triamine, triethylene tetramine, hexamethylene diamine, isophorone diamine, menthane diamine, and 4,4′-diaminodicyclohexyl methane.
Examples of the aromatic amine include m-xylylenediamine, diaminodiphenylmethane, m-phenylenediamine, and the like.

Among these, as the non-polymerizable compound having a hydroxyl group, tripropylene glycol is preferable.

The preferable lower limit of the content of the compound having a hydrophilic functional group in the total of 100 parts by weight of the compound having a hydrophilic functional group and the polymerizable compound is 1 part by weight, and the preferable upper limit is 50 parts by weight. When the content of the compound having a hydrophilic functional group is 1 part by weight or more, the obtained sealing agent for organic EL display elements is more excellent in ink jet coatability. When the content of the compound having a hydrophilic functional group is 50 parts by weight or less, the cured product of the obtained sealing agent for organic EL display elements is superior in moisture permeability prevention. The minimum with more preferable content of the compound which has a hydrophilic functional group in the whole sealing compound for organic EL display elements of this invention is 10 weight part, and a more preferable upper limit is 30 weight part.
The above “total of the compound having a hydrophilic functional group and the polymerizable compound” means the following. That is, when only the polymerizable compound having the hydrophilic functional group is contained as the compound having the hydrophilic functional group, “a polymerizable compound having a hydrophilic functional group and a polymerizable compound having no hydrophilic functional group” And "total". In addition, when only the non-polymerizable compound having the hydrophilic functional group is contained as the compound having the hydrophilic functional group, “non-polymerizable compound having a hydrophilic functional group and polymerization having no hydrophilic functional group” Means "total with other chemical compounds". Furthermore, when the polymerizable compound having the hydrophilic functional group and the non-polymerizable compound having the hydrophilic functional group are contained as the compound having the hydrophilic functional group, the “polymerizable compound having a hydrophilic functional group” “Total of non-polymerizable compound having a hydrophilic functional group and polymerizable compound not having a hydrophilic functional group”.
The “polymerizable compound having no hydrophilic functional group” means a compound having no hydrophilic functional group among the polymerizable compounds described later.

The sealing agent for organic EL display elements of the present invention contains a polymerizable compound. As described above, the polymerizable compound preferably contains a polymerizable compound having the hydrophilic functional group.

As the polymerizable compound, a cationic polymerizable compound or a radical polymerizable compound can be used. Of these, cationically polymerizable compounds are preferred.

As said cationically polymerizable compound, an epoxy compound, an oxetane compound, a vinyl ether compound etc. are mentioned, for example. Especially, an epoxy compound or an oxetane compound is preferable, and an epoxy compound having a hydroxyl group as a hydrophilic functional group or an oxetane compound having a hydroxyl group as a hydrophilic functional group is more preferable.

Examples of the epoxy compound include glycidol, epoxy alcohol, 1,5-hexadiene diepoxide, 1,7-octadiene diepoxide, 1,9-decadiene diepoxide, bisphenol A type epoxy compound, and bisphenol E type epoxy compound. Bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol O type epoxy compound, 2,2'-diallylbisphenol A type epoxy compound, cycloalkene oxide type alicyclic epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide Addition bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopen Diene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound, orthocresol novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound, biphenyl novolac type epoxy compound, naphthalene phenol novolac type epoxy compound, glycidylamine type epoxy compound, Examples include alkyl polyol type epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds, and the like. Especially, as an epoxy compound used as the polymeric compound which has the said hydrophilic functional group, glycidol (for example, epiol OH (made by NOF Corporation)), an epoxy alcohol (for example, EOA (made by Kuraray Co., Ltd.)), etc. are preferable. Moreover, as an epoxy compound used as the polymeric compound which does not have the said hydrophilic functional group, 3,4,3 ', 4'-diepoxybicyclohexane, 3', 4'-epoxycyclohexylmethyl-3,4- Cycloalkene oxide type alicyclic epoxy compounds such as epoxycyclohexanecarboxylate, 1,7-octadiene diepoxide and the like are preferable.

Examples of the oxetane compound include phenoxymethyl oxetane, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3- (4-hydroxybutyl) oxymethyl oxetane, 3-ethyl-3-methacryloxymethyl oxetane, 3 -Ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3-((2-ethylhexyloxy) methyl) oxetane, 3-ethyl-3-((3- (triethoxysilyl) propoxy) methyl) oxetane, 3 -Ethyl-3-(((3-ethyloxetane-3-yl) methoxy) methyl) oxetane, oxetanylsilsesquioxane, phenol novolac oxetane, 1,4-bis ((((3-ethyl-3-oxetanyl) methoxy) And methyl) benzene. Especially, as an oxetane compound used as the polymeric compound which has the said hydrophilic functional group, 3-ethyl-3-hydroxymethyl oxetane and 3-ethyl-3- (4-hydroxybutyl) oxymethyl oxetane are preferable. Moreover, as an oxetane compound used as the polymeric compound which does not have the said hydrophilic functional group, 3-ethyl-3-methacryloxymethyl oxetane, 3-ethyl-3-((((3-ethyloxetane-3-yl)) Methoxy) methyl) oxetane is preferred.

Examples of the vinyl ether compound include 2-hydroxyethyl vinyl ether, benzyl vinyl ether, cyclohexane dimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol. Examples include divinyl ether, dipropylene glycol divinyl ether, and tripropylene glycol divinyl ether. Among them, 2-hydroxyethyl vinyl ether is preferable as the vinyl ether compound that becomes the polymerizable compound having the hydrophilic functional group, and cyclohexanedimethanol as the vinyl ether compound that becomes the polymerizable compound not having the hydrophilic functional group. Divinyl ether is preferred.

As the radical polymerizable compound, a (meth) acrylic compound is preferable.
The (meth) acrylic compound may be a monofunctional (meth) acrylic compound or a polyfunctional (meth) acrylic compound. The monofunctional (meth) acrylic compound and the polyfunctional (meth) You may use it in combination with an acrylic compound.
In the present specification, the above “(meth) acryl” means acryl or methacryl, the above “(meth) acryl compound” means a compound having a (meth) acryloyl group, and the above “(meth) “Acryloyl” means acryloyl or methacryloyl.

The monofunctional (meth) acrylic compound preferably has a cationic polymerizable group from the viewpoint of low outgassing property.
Examples of the cationic polymerizable group include a vinyl ether group, an epoxy group, an oxetanyl group, an allyl ether group, a vinyl group, and a hydroxyl group.

Specific examples of the monofunctional (meth) acrylic compound include 2-hydroxyethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, and 4-hydroxybutyl (meth) ) Acrylate glycidyl ether, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 3-ethyl-3- (meth) acryloxymethyloxetane, allyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytri Ethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxytriethylene glycol (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 2- (meta Acryloyloxyethyl succinic acid and the like. Especially, as a monofunctional (meth) acryl compound used as the polymeric compound which has the said hydrophilic functional group, 2-hydroxyethyl (meth) acrylate and 2- (meth) acryloyloxyethyl succinic acid are preferable. Moreover, as a monofunctional (meth) acryl compound used as the polymerizable compound having no hydrophilic functional group, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate is preferable.
In the present specification, the “(meth) acrylate” means acrylate or methacrylate.

When the polymerizable compound contains the monofunctional (meth) acrylic compound, the preferred lower limit of the content of the monofunctional (meth) acrylic compound in 100 parts by weight of the polymerizable compound is 20 parts by weight, and the preferred upper limit is 80. Parts by weight. When the content of the monofunctional (meth) acrylic compound is within this range, the obtained sealing agent for organic EL display elements is more excellent in low outgassing properties. The minimum with more preferable content of the said monofunctional (meth) acryl compound is 30 weight part, and a more preferable upper limit is 60 weight part.

The polyfunctional (meth) acrylic compound preferably has a polyoxyalkylene skeleton in the main chain from the viewpoint of inkjet coating properties and the like.
The polyoxyalkylene skeleton is preferably a series of 2 to 6 oxyalkylene units.
Examples of oxyalkylene units constituting the polyoxyalkylene skeleton include oxyethylene units and oxypropylene units.

The polyfunctional (meth) acrylic compound preferably has a structure with less carbon chain branching, and more preferably is a straight chain, from the viewpoint of inkjet coating properties and the like.

Specific examples of the polyfunctional (meth) acrylic compound include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate. , Tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate and the like. Especially, as a polyfunctional (meth) acryl compound used as the polymeric compound which has the said hydrophilic functional group, a pentaerythritol triacrylate is preferable. Moreover, as a polyfunctional (meth) acryl compound used as the polymeric compound which does not have the said hydrophilic functional group, tetraethylene glycol di (meth) acrylate and a trimethylol propane tri (meth) acrylate are preferable.

When the polymerizable compound contains the polyfunctional (meth) acrylic compound, the preferred lower limit of the content of the polyfunctional (meth) acrylic compound in 100 parts by weight of the polymerizable compound is 20 parts by weight, and the preferred upper limit is 80. Parts by weight. When the content of the polyfunctional (meth) acrylic compound is within this range, the obtained sealing agent for organic EL display elements is more excellent in ink jet coatability. The minimum with more preferable content of the said polyfunctional (meth) acryl compound is 30 weight part, and a more preferable upper limit is 60 weight part.

When the monofunctional (meth) acrylic compound and the polyfunctional (meth) acrylic compound are used in combination, the content ratio of the monofunctional (meth) acrylic compound and the polyfunctional (meth) acrylic compound is expressed as a weight ratio. Monofunctional (meth) acrylic compound: polyfunctional (meth) acrylic compound = 7: 3 to 3: 7 is preferable. By making the content ratio of the monofunctional (meth) acrylic compound and the polyfunctional (meth) acrylic compound within this range, the obtained sealing agent for organic EL display elements should be excellent in ink jet coating properties. Can do. The content ratio of the monofunctional (meth) acrylic compound and the polyfunctional (meth) acrylic compound is a weight ratio of monofunctional (meth) acrylic compound: polyfunctional (meth) acrylic compound = 6: 4 to 4: 6. It is more preferable that

The sealing agent for organic EL display elements of the present invention contains a polymerization initiator.
As the polymerization initiator, a photocationic polymerization initiator, a thermal cationic polymerization initiator, a photoradical polymerization initiator, or a thermal radical polymerization initiator is suitably used depending on the type of polymerizable compound used.

The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. May be.

Examples of the anion portion of the ionic photoacid-generating photocationic polymerization initiator include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , and (BX ₄ ) ⁻ (wherein X is at least two or more. And a phenyl group substituted with a fluorine or trifluoromethyl group).
Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts having the anion moiety, (2,4-cyclo And pentadien-1-yl) ((1-methylethyl) benzene) -Fe salt.

Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4- ( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) Phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, triarylsulfonium tetrakis (pentafluoro) Phenyl) borate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfo Nio) phenyl) sulfide bishexafluoroantimonate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfo O) phenyl) sulfide bistetrafluoroborate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfidetetrakis (pentafluorophenyl) borate, tris (4- (4-acetylphenyl) ) Thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like.

Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (Dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethyl) Such as phenyl iodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Can be mentioned.

Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.

Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, and 1-benzyl. 2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) Examples include 2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.

Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene. ) -Fe (II) hexafluorophosphate, (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimonate, (2,4-cyclopentadiene-1 -Yl) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrakis (penta Fluorophenyl) borate and the like.

Examples of the nonionic photoacid-generating photocationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate, and the like.

Examples of commercially available photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., a photocationic polymerization initiator manufactured by Union Carbide, a photocationic polymerization initiator manufactured by ADEKA, Examples thereof include a photocationic polymerization initiator manufactured by 3M, a photocationic polymerization initiator manufactured by BASF, and a photocationic polymerization initiator manufactured by Rhodia.
Examples of the photo-cationic polymerization initiator manufactured by Midori Chemical Co., Ltd. include DTS-200.
Examples of the cationic photopolymerization initiator manufactured by Union Carbide include UVI6990, UVI6974, and the like.
Examples of the photocation polymerization initiator manufactured by ADEKA include SP-150 and SP-170.
Examples of the cationic photopolymerization initiator manufactured by 3M include FC-508, FC-512, and the like.
Examples of the cationic photopolymerization initiator manufactured by BASF include IRGACURE261, IRGACURE290, and the like.
Examples of the photocationic polymerization initiator manufactured by Rhodia include PI 2074.

As the thermal cationic polymerization initiator, the anion moiety is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , or (BX ₄ ) ⁻ (where X is substituted with at least two fluorine or trifluoromethyl groups. A sulfonium salt, a phosphonium salt, an ammonium salt, and the like. Of these, sulfonium salts and ammonium salts are preferable.

Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

Examples of the ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, and dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl). Borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyl Dibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium Safluoroantimonate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N , N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-diethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl -N-benzylpyridinium trifluoromethanesulfonic acid etc. are mentioned.

Examples of commercially available thermal cationic polymerization initiators include thermal cationic polymerization initiators manufactured by Sanshin Chemical Industry, thermal cationic polymerization initiators manufactured by King Industries, and the like.
Examples of the thermal cationic polymerization initiator manufactured by Sanshin Chemical Industry Co., Ltd. include Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, and Sun-Aid SI-B4.
Examples of the thermal cationic polymerization initiator manufactured by King Industries include CXC1612 and CXC1821.

Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone compounds, and the like.

As what is marketed among the said radical photopolymerization initiators, the radical photopolymerization initiator by BASF, the radical photopolymerization initiator by Tokyo Chemical Industry, etc. are mentioned, for example.
Examples of the radical photopolymerization initiator manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucyrin TPO.
Examples of the photo radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
Examples of the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile) and azobisisobutyronitrile.
Examples of the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.

Examples of commercially available thermal radical polymerization initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 (all of which are Fuji Film Wako Pure Chemical Industries, Ltd.). Manufactured) and the like.

The content of the polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the polymerization initiator is 0.01 parts by weight or more, the obtained sealing agent for organic EL display elements is more excellent in curability. When the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the obtained sealing agent for organic EL display elements does not become too fast, and the workability is improved, and the cured product is more uniform. It can be. The minimum with more preferable content of the said polymerization initiator is 0.05 weight part, and a more preferable upper limit is 5 weight part.

The sealing agent for organic EL display elements of the present invention may contain a sensitizer. The sensitizer has a role of further improving the polymerization initiation efficiency of the polymerization initiator and further promoting the curing reaction of the sealing agent for organic EL display elements of the present invention.

Examples of the sensitizer include thioxanthone compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4 ′. -Bis (dimethylamino) benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and the like.
Examples of the thioxanthone compound include 2,4-diethylthioxanthone.

The content of the sensitizer is preferably 0.01 parts by weight and preferably 3 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the sensitizer is 0.01 parts by weight or more, the sensitizing effect is more exhibited. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption. The minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.

The sealing agent for organic EL display elements of the present invention may contain a silane coupling agent. The said silane coupling agent has a role which improves the adhesiveness of the sealing agent for organic EL display elements of this invention, a board | substrate, etc.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatopropyltrimethoxysilane. These silane coupling agents may be used independently and 2 or more types may be used together.

The content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness is suppressed while suppressing the excess silane coupling agent from bleeding out. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.

The sealing agent for organic EL display elements of the present invention may further contain a surface modifier as long as the object of the present invention is not impaired. By containing the surface modifier, the flatness of the coating film can be imparted to the organic EL display element sealant of the present invention.
Examples of the surface modifier include surfactants and leveling agents.

Examples of the surface modifier include silicone-based and fluorine-based ones.
Examples of commercially available surface modifiers include BYK-340, BYK-345 (all manufactured by Big Chemie Japan), and Surflon S-611 (manufactured by AGC Seimi Chemical).

The encapsulant for organic EL display elements of the present invention may contain a solvent for the purpose of adjusting the viscosity, but problems such as deterioration of the organic light emitting material layer and generation of outgas due to the remaining solvent. Therefore, it is preferable that the solvent is not contained or the solvent content is 0.05% by weight or less.

Moreover, the sealing agent for organic EL display elements of this invention contains well-known various additives, such as a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, a ultraviolet absorber, antioxidant, as needed. May be.

As a method for producing the sealing agent for organic EL display elements of the present invention, for example, using a mixer, a polymerizable compound having a hydrophilic functional group or a non-polymerizable compound having a hydrophilic functional group, and a hydrophilic property are used. Examples thereof include a method of mixing a polymerizable compound having no functional group, a polymerization initiator, and an additive such as a silane coupling agent added as necessary.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll.

The sealing agent for organic EL display elements of the present invention 1 has an upper limit of viscosity at 25 ° C. of 80 mPa · s. By the said viscosity being 80 mPa * s or less, the sealing agent for organic EL display elements of this invention 1 is excellent in inkjet applicability | paintability. The upper limit with the preferable viscosity of the sealing agent for organic EL display elements of this invention 1 is 60 mPa * s, and a more preferable upper limit is 20 mPa * s.
Moreover, the minimum with a preferable viscosity of the sealing agent for organic EL display elements of this invention 1 is 5 mPa * s, and a more preferable minimum is 8 mPa * s.
In addition, the said viscosity in this specification means the value measured on 25 degreeC and 100 rpm conditions using an E-type viscosity meter.

As for the sealing agent for organic EL display elements of this invention 2, the preferable upper limit of the viscosity in 25 degreeC is 80 mPa * s. By the said viscosity being 80 mPa * s or less, the sealing agent for organic EL display elements of this invention 2 becomes more excellent by inkjet applicability | paintability. The more preferable upper limit of the viscosity of the sealing agent for organic EL display elements of the present invention 2 is 60 mPa · s, and the more preferable upper limit is 20 mPa · s.
Moreover, the minimum with a preferable viscosity of the sealing agent for organic EL display elements of this invention 2 is 5 mPa * s, and a more preferable minimum is 8 mPa * s.

The sealing agent for organic EL display elements of the present invention has a preferable lower limit of surface tension of 15 mN / m and a preferable upper limit of 35 mN / m. When the surface tension is within this range, it can be suitably applied by an ink jet method. The more preferable lower limit of the surface tension is 20 mN / m, the more preferable upper limit is 30 mN / m, the still more preferable lower limit is 22 mN / m, and the still more preferable upper limit is 28 mN / m.
The surface tension can be measured with a dynamic wettability tester at 25 ° C.

In the sealant for organic EL display elements of the present invention, the preferable lower limit of the light transmittance of the cured product with respect to light having a wavelength of 420 nm is 90%. When the light transmittance is 90% or more, the obtained organic EL display element has superior optical characteristics. A more preferable lower limit of the light transmittance is 95%.
The light transmittance can be measured using a spectrophotometer (for example, “U-3000” manufactured by Hitachi, Ltd.). Moreover, the hardened | cured material used for the measurement of the said light transmittance and the water vapor transmission rate and moisture content mentioned later can be obtained by irradiating 3000 mJ / cm < ² > of ultraviolet rays with a wavelength of 365 nm using light sources, such as an LED lamp, for example. it can.

The sealant for an organic EL display device of the present invention has a moisture permeability of 100 g / 100 μm when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours in accordance with JIS Z 0208. m is preferably ² or less. When the moisture permeability is 100 g / m ² or less, the effect of preventing deterioration of the organic light-emitting material layer due to moisture in the cured product is excellent, and the obtained organic EL display element is excellent in reliability.

In the encapsulant for organic EL display elements of the present invention, the moisture content of the cured product is preferably less than 0.5% when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours. When the moisture content of the cured product is less than 0.5%, the effect of preventing the deterioration of the organic light emitting material layer due to moisture in the cured product is excellent, and the obtained organic EL display element is excellent in reliability. It becomes. A more preferable upper limit of the moisture content of the cured product is 0.3%.
Examples of the method for measuring the moisture content include a method of obtaining by a Karl Fischer method in accordance with JIS K 7251, and a method of obtaining a weight increment after water absorption in accordance with JIS K 7209-2.

As a method for producing an organic EL display element using the sealing agent for organic EL display elements of the present invention, for example, a step of applying the sealing agent for organic EL display elements of the present invention to a substrate by an inkjet method, And a method of curing the applied sealing agent for organic EL display elements by light irradiation and / or heating.

In the step of applying the organic EL display element sealant of the present invention to the substrate, the organic EL display element sealant of the present invention may be applied to the entire surface of the substrate, or on a part of the substrate. It may be applied. The shape of the sealing portion of the sealing agent for organic EL display elements of the present invention formed by coating is not particularly limited as long as it is a shape that can protect the laminate having the organic light emitting material layer from the outside air. A shape that completely covers the body may be formed, a closed pattern may be formed in the peripheral portion of the laminate, or a pattern having a shape in which a partial opening is provided in the peripheral portion of the laminate. It may be formed.

When curing the organic EL display element sealing agent of the present invention by light irradiation, the organic EL display sealant element of the present invention, 300 nm or more 400nm or less wavelength and 300 mJ / cm ² or more 3000 mJ / cm ² or less of It can be suitably cured by irradiating with an accumulated amount of light.

Examples of the light source used for the light irradiation include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, and a xenon. A lamp, an LED lamp, a fluorescent lamp, sunlight, an electron beam irradiation apparatus, etc. are mentioned. These light sources may be used independently and 2 or more types may be used together.
These light sources are appropriately selected according to the absorption wavelength of the photo radical polymerization initiator or the photo cationic polymerization initiator.

Examples of the light irradiation means to the organic EL display element sealant of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, and the like. Any irradiation means may be used.

The cured product obtained by the step of curing the organic EL display element sealing agent by light irradiation and / or heating may be further coated with an inorganic material film.
As the inorganic material forming the inorganic material layer can be a conventionally known, for example, silicon nitride (SiN _x), silicon oxide (SiO _x), and the like. The inorganic material film may be a single layer or may be a laminate of a plurality of types of layers. Moreover, you may coat | cover the said laminated body by repeating alternately the said inorganic material film | membrane and the resin film which consists of the sealing agent for organic EL display elements of this invention.

The method for producing the organic EL display element comprises a step of bonding a base material (hereinafter also referred to as “one base material”) coated with the organic EL display element sealing agent of the present invention and the other base material. You may have.
The substrate on which the sealing agent for organic EL display elements of the present invention is applied (hereinafter also referred to as “one substrate”) may be a substrate on which a laminate having an organic light emitting material layer is formed. A base material on which the laminate is not formed may be used.
When the one substrate is a substrate on which the laminate is not formed, the present invention is applied to the one substrate so that the laminate can be protected from the outside air when the other substrate is bonded. What is necessary is just to apply | coat the sealing agent for organic EL display elements. That is, apply the entire surface to the location of the laminate when the other substrate is bonded, or the location of the laminate is complete when the other substrate is bonded. The sealing agent portion having a closed pattern may be formed in a shape that fits in the shape.

The step of curing the organic EL display element sealant by light irradiation and / or heating may be performed before the step of bonding the one base material and the other base material, You may perform after the process of bonding a base material and said other base material.
When the step of curing the organic EL display element sealant by light irradiation and / or heating is performed before the step of bonding the one base material and the other base material, the organic EL display of the present invention. The device sealant preferably has a pot life of 1 minute or longer after irradiation with light and / or heating until the curing reaction proceeds and adhesion becomes impossible. When the pot life is 1 minute or longer, higher adhesion strength can be obtained without excessive curing before the one base material and the other base material are bonded together.

In the step of bonding the one base material and the other base material, a method of bonding the one base material and the other base material is not particularly limited, but it is preferable to bond them in a reduced-pressure atmosphere.
The preferable lower limit of the degree of vacuum in the reduced-pressure atmosphere is 0.01 kPa, and the preferable upper limit is 10 kPa. When the degree of vacuum in the reduced-pressure atmosphere is within this range, the one base material and the other base material are not spent for a long time to achieve a vacuum state due to the airtightness of the vacuum device and the ability of the vacuum pump. Bubbles in the sealing agent for organic EL display elements of the present invention when the material is bonded can be more efficiently removed.

According to the present invention, there is provided an encapsulant for an organic EL display element that can be easily applied by an ink jet method, can obtain an organic EL display element that is excellent in low outgassing properties and excellent in reliability. Can do.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Examples 1-13, Comparative Examples 1-5)
According to the blending ratios described in Tables 1 to 3, each material was stirred and mixed uniformly at a stirring speed of 3000 rpm using a homodisper type stirring mixer (Primix, “Homodisper L type”). The sealing agent for each organic EL display element of Examples 1-13 and Comparative Examples 1-5 was produced.
About each organic electroluminescent display element sealing agent obtained by the Example and the comparative example, it measured on 25 degreeC and 100 rpm conditions using an E-type viscosity meter (the Toki Sangyo company make, "VISCOMETER TV-22"). The obtained viscosity is shown in Tables 1-3.

<Evaluation>
The following evaluation was performed about each sealing agent for organic EL display elements obtained by the Example and the comparative example. The results are shown in Tables 1-3.

(1) Inkjet applicability (1-1) Inkjet ejection properties Each of the organic EL display element sealants obtained in the Examples and Comparative Examples was used with an inkjet ejection device (“NanoPrinter500” manufactured by Microjet Co., Ltd.). Then, 1000 drops were applied at a speed of 5 m / second at a pitch of 500 μm on alkali-washed non-alkali glass (“AN100” manufactured by Asahi Glass Co., Ltd.) with a drop volume of 30 picoliters.
“◯” when the number of droplets that could not be applied was 0, “Δ” when the number of droplets that could not be applied was 1 or more and less than 20, and droplets that could not be applied The case where the number of the ink was 20 or more was evaluated as “x”, and the ink jet discharge property was evaluated.

(1-2) Wetting and spreading property Each of the sealing agents for organic EL display elements obtained in the examples and comparative examples is a liquid of 30 picoliters using an inkjet discharge device (“NanoPrinter500” manufactured by Microjet Co., Ltd.). With a drop amount, 1000 drops were applied at a speed of 5 m / sec on a non-alkali glass (ASA 100, manufactured by Asahi Glass Co., Ltd.) washed with alkali at a pitch of 500 μm. After coating, the sample was allowed to stand at 25 ° C. for 10 minutes, and the diameter of the droplets on the alkali-free glass was measured.
The case where the diameter of the droplet is 150 μm or more is indicated by “◯”, the case where the diameter of the droplet is 50 μm or more and less than 150 μm is indicated by “Δ”, and the case where the diameter of the droplet is less than 50 μm is indicated by “X”. Wet spreadability was evaluated.

(2) Low outgassing property Outgas generated during heating of the cured product of the sealing agent for organic EL display elements obtained in the examples and comparative examples was measured by a gas chromatograph by the headspace method shown below.
First, 100 mg of each organic EL display element sealant was applied to a thickness of 300 μm with an applicator, and then the UV light with a wavelength of 365 nm was irradiated with 3000 mJ / cm ² with an LED lamp to cure the sealant. Next, the obtained sealant cured product was put in a headspace vial, the vial was sealed, heated at 100 ° C. for 30 minutes, and the generated gas was measured by the headspace method.
The case where the generated gas was less than 300 ppm was evaluated as “◯”, the case where it was 300 ppm or more and less than 500 ppm as “Δ”, and the case where it was 500 ppm or more as “x”, and the low outgassing property was evaluated.

(3) Light transmittance The sealants for organic EL display elements obtained in the examples and comparative examples are sandwiched between PET resin films, and sealed by irradiating UV light with a wavelength of 365 nm at 3000 mJ / cm ² with an LED lamp. The agent was cured to prepare a sample for measuring transmittance having a thickness of 100 μm. About the obtained sample for transmittance | permeability, the light transmittance in wavelength 420nm was measured using the spectrophotometer (the Hitachi Ltd. make, "U-3000").

(4) Reliability of organic EL display element (4-1) Preparation of a substrate on which a laminate having an organic light emitting material layer is disposed An ITO electrode is placed on a glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm). A substrate having a thickness of 1000 mm was prepared. The substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes each, then washed with boiled isopropyl alcohol for 10 minutes, and further UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd., The last treatment was performed with “NL-UV253”).
Next, this substrate is fixed to a substrate folder of a vacuum evaporation apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is put into another unbaked crucible in the unglazed crucible. 200 mg of tris (8-quinolinolato) aluminum (Alq ₃ ) was put in the crucible, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. Thereafter, the crucible containing α-NPD was heated and α-NPD was deposited on the substrate at a deposition rate of 15 Å / s to form a 600 正 孔 hole transport layer. Next, the crucible containing Alq ₃ was heated to form an organic light emitting material layer having a thickness of 600 で at a deposition rate of 15 Å / s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and an aluminum wire is added to another tungsten boat. 1.0 g was added. Then, after reducing the pressure in the vapor deposition unit of the vacuum vapor deposition apparatus to 2 × 10 ⁻⁴ Pa and depositing 5 μm of lithium fluoride at a deposition rate of 0.2 kg / s, deposit 1000 μm of aluminum at a rate of 20 kg / s. did. The inside of the vapor deposition unit was returned to normal pressure with nitrogen, and the substrate on which the laminate having the organic light emitting material layer of 10 mm × 10 mm was arranged was taken out.

(4-2) Coating with Inorganic Material Film A A mask having an opening of 13 mm × 13 mm is installed so as to cover the entire laminated body of the substrate on which the obtained laminated body is arranged, and inorganic by plasma CVD method. A material film A was formed.
In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as source gases, the flow rates of each are SiH ₄ gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
The formed inorganic material film A had a thickness of about 1 μm.

(4-3) Formation of Resin Protective Film Each of the organic EL display element sealants obtained in Examples and Comparative Examples was applied to the obtained substrate using an inkjet discharge device (“NanoPrinter500” manufactured by Microjet Co., Ltd.). Was used to apply a pattern to the substrate. The sealing agents for organic EL display elements obtained in Comparative Examples 3 and 5 were not ejected normally from the inkjet ejection device, and a coating film could not be obtained. .
Thereafter, an ultraviolet ray having a wavelength of 365 nm was irradiated with 3000 mJ / cm ² using an LED lamp to cure the organic EL display element sealant to form a resin protective film.

(4-4) After forming the coating resin protective film with the inorganic material film B, a mask having an opening of 12 mm × 12 mm is installed so as to cover the entire resin protective film, and the inorganic material is formed by plasma CVD. Film B was formed to obtain an organic EL display element.
The plasma CVD method was performed under the same conditions as in the above “(4-2) Coating with inorganic material film A”.
The formed inorganic material film B had a thickness of about 1 μm.

(4-5) Light-Emitting State of Organic EL Display Element The obtained organic EL display element is exposed for 100 hours in an environment of a temperature of 85 ° C. and a humidity of 85%, and then a voltage of 3 V is applied to the organic EL display element. The light emission state (the presence or absence of dark spots and pixel periphery quenching) was visually observed. “○” when there is no dark spot or peripheral quenching, and “△” when there is no dark spot or peripheral quenching, but “△” when there is a slight decrease in brightness, when dark spot or peripheral quenching is observed The reliability of the organic EL display element was evaluated with “×”.

According to the present invention, there is provided an encapsulant for an organic EL display element that can be easily applied by an ink jet method, can obtain an organic EL display element that is excellent in low outgassing properties and excellent in reliability. Can do.

Claims (8)

An organic EL display element sealing agent containing a polymerizable compound and a polymerization initiator,
Containing a compound having a hydrophilic functional group, the hydrophilic functional group value of the compound having the hydrophilic functional group is from 0.003 mol / g to 0.02 mol / g,
A sealing agent for organic EL display elements, wherein the whole sealing agent for organic EL display elements has a viscosity at 25 ° C. of 80 mPa · s or less. An encapsulant for an organic EL display element, which contains a polymerizable compound and a polymerization initiator and is used for coating by an inkjet method,
An organic EL display device comprising a compound having a hydrophilic functional group, wherein the hydrophilic functional group has a hydrophilic functional group value of 0.003 mol / g or more and 0.02 mol / g or less. Sealant. The organic EL display element sealing according to claim 1 or 2, wherein the compound having a hydrophilic functional group has at least one selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group as the hydrophilic functional group. Agent. The sealing compound for organic EL display elements according to claim 3, wherein the compound having a hydrophilic functional group has a hydroxyl group as the hydrophilic functional group. The encapsulant for an organic EL display element according to claim 1, wherein the compound having a hydrophilic functional group is a polymerizable compound having a hydrophilic functional group. The content of the compound having a hydrophilic functional group in a total of 100 parts by weight of the compound having the hydrophilic functional group and the polymerizable compound is 1 part by weight or more and 50 parts by weight or less. The sealing agent for organic EL display elements of 4 or 5. The encapsulant for organic EL display elements according to claim 1, wherein the polymerizable compound is an epoxy compound or an oxetane compound. The sealing agent for organic EL display elements according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the light transmittance of the cured product with respect to light having a wavelength of 420 nm is 90% or more.