WO2019203123A1 - Sealant for organic el display element and top emission type organic el display element - Google Patents

Abstract

The purpose of the present invention is to provide a sealant for an organic EL display element, which has an excellent ink-jet coating property, and with which an organic EL display element with excellent display performance can be obtained even if it is a top emission type. Further, the purpose of the present invention is to provide a top emission type organic EL display element formed using the sealant for the organic EL display element. The present invention is a sealant for an organic EL display element, the sealant containing a polymerizable compound and a polymerization initiator and having a cure shrinkage of less than 11%, and a cured product thereof measured under a thermal deposition condition of 80°C for 30 minutes by a thermal deposition GC-MS method having an outgassing amount of less than 3000 ppm.

Description

Sealant for organic EL display element and top emission type organic EL display element

The present invention relates to an encapsulant for an organic EL display element that can provide an organic EL display element that is excellent in inkjet coating properties and that is excellent in display performance even if it is a top emission type. Moreover, this invention relates to the top emission type organic EL display element which uses this sealing agent for organic EL display elements.

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.

JP 2007-115692 A JP 2009-051980 A

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. As a method for blocking the organic light emitting material layer and the electrode from the atmosphere, an organic EL display element is sealed with a sealant (for example, Patent Document 1). When sealing an organic EL display element with a sealant, an inorganic film called a passivation film is usually provided on a laminate having an organic light emitting material layer in order to sufficiently suppress the transmission of moisture, oxygen, and the like. A method of sealing the top with a sealant is used.
In recent years, instead of a bottom emission type organic EL display element that extracts light emitted from an organic light emitting material layer from the substrate surface side on which the light emitting element is formed, a top emission type organic substance that extracts light from the upper surface side of the organic light emitting layer is used. EL display elements have attracted attention. This method has an advantage that it has a high aperture ratio and is driven at a low voltage, which is advantageous for extending the life. In such a top emission type organic EL display element, since the upper surface side of the light emitting layer needs to be transparent, a transparent moisture-proof group such as glass is provided on the upper surface side of the light emitting element via a transparent sealing layer. It seals by laminating | stacking a material (for example, patent document 2).
As a method of forming the sealing layer, there is a method in which a sealing agent is applied on a substrate using an inkjet method and then the sealing agent is cured. If such a coating method by the ink jet method is used, the sealing layer can be formed at high speed and uniformly. However, when a sealing agent suitable for application by the ink jet method is used in the top emission type organic EL display element, there is a problem that display defects such as dark spots may occur in the obtained organic EL display element. In particular, even a sealant that did not cause display failure in the bottom emission type may cause display failure when used in a top emission type organic EL display element.
An object of this invention is to provide the sealing agent for organic EL display elements which can obtain the organic EL display element which is excellent in inkjet applicability, and is excellent in display performance even if it is a top emission type. Another object of the present invention is to provide a top emission type organic EL display element using the sealing agent for organic EL display elements.

Invention 1 contains a polymerizable compound and a polymerization initiator, has a cure shrinkage of less than 11%, and is measured by a thermal desorption GC-MS method at 80 ° C. for 30 minutes. It is the sealing agent for organic EL display elements whose outgas generation amount of hardened | cured material is less than 3000 ppm.
In addition, the present invention 2 is an organic EL display element sealing agent used for coating by an ink jet method, contains a polymerizable compound and a polymerization initiator, has a curing shrinkage of less than 11%, and This is a sealing agent for organic EL display elements in which the amount of outgas generation of a cured product measured by a thermal desorption GC-MS method at 80 ° C. for 30 minutes is less than 3000 ppm.
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.

In the top emission type organic EL display element, the cathode is thinned from the viewpoint of translucency, and the thinned cathode is influenced by the sealing agent used for the sealing layer formed on the cathode. It becomes easy to receive. In the case of top emission type organic EL display elements, even if the sealing agent did not cause display defects in the bottom emission type due to the influence of the sealing agent on the cathode, the display I thought it was the cause of the failure.
Accordingly, the present inventors set the curing shrinkage rate and the outgas generation amount of the cured product measured under stricter conditions than those of the sealing agent for organic EL display elements excellent in inkjet coating property to less than a specific value, respectively. I examined that. As a result, it has been found that an organic EL display element sealing agent that can provide an organic EL display element that is excellent in ink jet coating property and that is excellent in display performance even in the top emission type can be obtained. It came to complete.

The sealing agent for organic EL display elements of the present invention can be used as an ink jet method for coating by a non-heated ink jet method, or can be used for coating by a heat ink jet method.
In the present specification, the “non-heated ink jet method” is a method of ink jet coating at a coating head temperature of less than 28 ° C., and the “heated ink jet method” is an ink jet at a coating head temperature of 28 ° C. or higher. It is a method of applying.

In the heating ink jet method, an ink jet coating head equipped with a heating mechanism is used. When the inkjet coating head is equipped with a heating mechanism, the viscosity and the surface tension can be lowered when discharging the sealing agent for organic EL display elements.

Examples of the inkjet coating head equipped with the heating mechanism include KM1024 series manufactured by Konica Minolta, SG1024 series manufactured by Fuji Film Dimatix, and the like.

When the sealant for organic EL display elements of the present invention is used for coating by the above-described heating ink jet method, the heating temperature of the coating head is preferably in the range of 28 ° C. to 80 ° C. When the heating temperature of the coating head is within this range, the increase in viscosity with time of the sealant for organic EL display elements is further suppressed, and the ejection stability is improved.

The sealing agent for organic EL display elements of the present invention 1 has a preferable lower limit of viscosity at 25 ° C. of 5 mPa · s, and a preferable upper limit of 50 mPa · s. When the viscosity at 25 ° C. is within this range, it can be suitably applied by an ink jet method.
In the present specification, the “viscosity” means a value measured using an E-type viscometer under the conditions of 25 ° C. and 100 rpm. Examples of the E type viscometer include VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.), and a CP1 type cone plate can be used.

The more preferable minimum of the viscosity in 25 degreeC of the sealing agent for organic EL display elements of this invention in the case of apply | coating by the said non-heating-type inkjet method is 5 mPa * s, and a more preferable upper limit is 20 mPa.s. s. When the viscosity at 25 ° C. is within this range, it can be suitably applied by a non-heating ink jet method. The more preferable lower limit of the viscosity at 25 ° C. of the encapsulant for organic EL display elements of the present invention when applied by the non-heating ink jet method is 8 mPa · s, and the more preferable upper limit is 16 mPa · s. s, a particularly preferred lower limit is 10 mPa · s, and a particularly preferred upper limit is 13 mPa · s. s.

On the other hand, the lower limit of the viscosity at 25 ° C. of the sealing agent for organic EL display elements of the present invention when used for coating by the heating ink jet method is 10 mPa · s, and the more preferable upper limit is 50 mPa · s. s. When the viscosity is within this range, it can be suitably applied by a heating ink jet method. The more preferable lower limit of the viscosity at 25 ° C. of the encapsulant for organic EL display elements of the present invention when used for coating by the heating ink jet method is 20 mPa · s, and the more preferable upper limit is 40 mPa · s. s.

As for the sealing agent for organic EL display elements of this invention 1, the preferable minimum of the surface tension in 25 degreeC is 15 mN / m, and a preferable upper limit is 35 mN / m. When the surface tension at 25 ° C. is within this range, it can be suitably applied by an ink jet method. A more preferable lower limit of the surface tension at 25 ° C. is 20 mN / m, a more preferable upper limit is 30 mN / m, a still more preferable lower limit is 22 mN / m, and a still more preferable upper limit is 28 mN / m.
Moreover, the sealing agent for organic EL display elements of this invention 2 has a preferable lower limit of the surface tension at 25 ° C. of 15 mN / m, and a preferable upper limit of 35 mN / m. When the surface tension at 25 ° C. is within this range, it can be suitably applied by an ink jet method. A more preferable lower limit of the surface tension at 25 ° C. is 20 mN / m, a more preferable upper limit is 30 mN / m, a still more preferable lower limit is 22 mN / m, and a still more preferable upper limit is 28 mN / m.
The surface tension means a value measured by a Wilhelmy method using a dynamic wettability tester. Examples of the dynamic wettability tester include a WET-6100 type (manufactured by Reska).

The sealing agent for organic EL display elements of the present invention has a curing shrinkage rate of less than 11%. When the curing shrinkage rate is less than 11%, the organic EL display element sealing agent of the present invention can obtain an organic EL display element having excellent display performance even if it is a top emission type. A preferable upper limit of the curing shrinkage is 10%, and a more preferable upper limit is 9%.
Further, there is no particular lower limit for the curing shrinkage, but the substantial lower limit is 1%.
Note that the "cure shrinkage" as used herein, a specific gravity at 25 ° C. of sealant before curing G _A, when the specific gravity at 25 ° C. of a cured product of the sealant was G _B, the following formula This is a calculated value.
Cure shrinkage _{(%) = ((G B} -G A) / G B) × 100
Moreover, if the hardened | cured material used for the said specific gravity measurement is a photocurable sealing agent, it can be obtained by, for example, irradiating the sealing agent with 2000 mJ / cm < ² > of ultraviolet rays with a wavelength of 395 nm with an LED lamp. If it is a thermosetting sealing agent, it can obtain by heating at 80 degreeC for 1 hour, for example.

The encapsulant for organic EL display elements of the present invention has an outgas generation amount of a cured product of less than 3000 ppm as measured by a thermal desorption GC-MS method at 80 ° C. for 30 minutes. Since the outgas generation amount of the cured product measured by the above thermal desorption GC-MS method is less than 3000 ppm, the organic EL display element sealant of the present invention is an organic compound having excellent display performance even if it is a top emission type. An EL display element can be obtained. A preferable upper limit of the outgas generation amount of the cured product measured by the thermal desorption GC-MS method is 2500 ppm, and a more preferable upper limit is 2000 ppm.
The outgas generation amount of the cured product measured by the thermal desorption GC-MS method is most preferably 0 ppm.
In addition, the measurement of the outgas generation amount of the cured product by the above thermal desorption GC-MS method was conducted by heating 1 mg of the cured product using a thermal desorption apparatus and a GC-MS apparatus at 80 ° C. for 30 minutes. This can be done by measuring the amount of gas component generated.
In addition, if the cured product used for the measurement of the outgas generation amount by the thermal desorption GC-MS is a photocurable sealant, for example, UV light having a wavelength of 395 nm is applied to the sealant with an LED lamp at 2000 mJ / cm ^2. If it is a thermosetting sealant, it can be obtained by, for example, heating at 80 ° C. for 1 hour.

The viscosity at 25 ° C., the surface tension at 25 ° C., the curing shrinkage rate, and the outgas generation amount of the cured product measured by the thermal desorption GC-MS method are described below, a polymerizable compound, a polymerization initiator, And about other components, such as a sensitizer, it can be set as the range mentioned above by selection of these kinds, and adjustment of a content rate.
In particular, the curing shrinkage rate and the outgas generation amount of the cured product measured by the thermal desorption GC-MS method should be within the above-described ranges by selecting the type of polymerizable compound and adjusting the content ratio described below. Becomes easy.

The sealing agent for organic EL display elements of the present invention contains a polymerizable compound.
As the polymerizable compound, a cationic polymerizable compound or a radical polymerizable compound can be used. Especially, it is preferable that the said polymeric compound contains a cationically polymerizable compound from a viewpoint of making a cure shrinkage rate lower.

Examples of the cationic polymerizable compound include oxetane compounds, epoxy compounds, vinyl ether compounds, and the like. Among these, the polymerizable compound preferably includes at least one of an oxetane compound and an epoxy compound, more preferably includes an oxetane compound, and further preferably includes a polyfunctional oxetane compound.

Examples of the oxetane compound include 3-ethyl-3-(((3-ethyloxetane-3-yl) methoxy) methyl) oxetane, 3-ethyl-3-((2-ethylhexyloxy) methyl) oxetane, 3 -Ethyl-3-((3- (triethoxysilyl) propoxy) methyl) oxetane, phenol novolac oxetane, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene and the like. Of these, 3-ethyl-3-(((3-ethyloxetane-3-yl) methoxy) methyl) oxetane is preferable.
These oxetane compounds may be used alone or in combination of two or more.

Examples of the epoxy compound include 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and dipropylene glycol. Examples thereof include diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, phenyl glycidyl ether, and phenylene diglycidyl ether.
These epoxy compounds may be used independently and 2 or more types may be used in combination.

Examples of the vinyl ether compound include benzyl vinyl ether, cyclohexane dimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol. Examples thereof include divinyl ether and tripropylene glycol divinyl ether.
These vinyl ether compounds may be used alone or in combination of two or more.

As the radical polymerizable compound, a (meth) acrylic compound is preferable.
In the present specification, “(meth) acryl” means acryl or methacryl, “(meth) acryl compound” means a compound having a (meth) acryloyl group, and “(meth) acryloyl”. "Means acryloyl or methacryloyl.

Examples of the (meth) acrylic compound include isobornyl (meth) acrylate, glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and dicyclopentenyl. (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polytetramethylene Rikoruji (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, lauryl (meth) acrylate. Of these, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentanyl (meth) acrylate are preferable.
These (meth) acrylic compounds may be used alone or in combination of two or more.
In the present specification, the “(meth) acrylate” means acrylate or methacrylate.

The sealing agent for organic EL display elements of the present invention contains a polymerization initiator.
As the polymerization initiator, a cationic photopolymerization initiator or a radical photopolymerization initiator is suitably used depending on the type of polymerizable compound used. Moreover, you may use a thermal cationic polymerization initiator and a thermal radical polymerization initiator in the range which does not inhibit the objective of this invention.

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 ⁻ , (BX ₄ ) ⁻ (where X is at least two or more fluorine atoms) Or a phenyl group substituted with a trifluoromethyl group). Examples of the anion moiety include PF _m (C _n F _{2n + 1} ) _6-m ⁻ (wherein, m is an integer of 0 or more and 5 or less, and n is an integer of 1 or more and 6 or less). Can be mentioned.
Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts having the above anion moiety, and (2,4-cyclohexane). 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, bis (4- (di ( 4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluoroantimonate, Bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (di ( - (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide tetrakis (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, 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-cyclopentadien-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, a photocationic polymerization initiator manufactured by Rhodia, and a photocationic polymerization initiator manufactured by San Apro.
Examples of the photocationic 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.
Examples of the cationic photopolymerization initiator manufactured by Sun Apro include CPI-100P, CPI-200K, CPI-210S, and the like.

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 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, 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 and the like.

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.

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), azobisisobutyronitrile, and the like.
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, 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 Examples include '-bis (dimethylamino) benzophenone and 4-benzoyl-4'-methyldiphenyl sulfide.
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 this invention may contain a thermosetting agent in the range which does not inhibit the objective of this invention.
Examples of the thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, addition products of various amines and epoxy resins, and the like.
Examples of the hydrazide compound include 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of the imidazole derivatives include 1-cyanoethyl-2-phenylimidazole, N- (2- (2-methyl-1-imidazolyl) ethyl) urea, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, N, N′-bis (2-methyl-1-imidazolylethyl) urea, N, N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
Examples of the acid anhydride include tetrahydrophthalic anhydride, ethylene glycol bis (anhydrotrimellitate), and the like.
These thermosetting agents may be used independently and 2 or more types may be used in combination.

As what is marketed among the said thermosetting agents, the thermosetting agent by an Otsuka Chemical company, the thermosetting agent by Ajinomoto Fine Techno Co., etc. are mentioned, for example.
Examples of the thermosetting agent manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
Examples of the thermosetting agent manufactured by Ajinomoto Fine Techno Co. include Amicure VDH, Amicure VDH-J, Amicure UDH, and the like.

The content of the thermosetting agent is preferably 0.5 parts by weight and preferably 30 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the thermosetting agent is within this range, the obtained sealing agent for organic EL display elements is more excellent in thermosetting properties while maintaining excellent storage stability. The minimum with more preferable content of the said thermosetting agent is 1 weight part, and a more preferable upper limit is 15 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, 3-isocyanatopropyltrimethoxysilane, and the like. These silane coupling agents may be used alone or in combination of two or more.

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 said surface modifier, the flatness of the coating film of the sealing agent for organic EL display elements of this invention can be improved further.
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 surface modifiers manufactured by Big Chemie Japan, and surface modifiers manufactured by AGC Seimi Chemical.
Examples of the surface modifier made by Big Chemie Japan include BYK-340, BYK-345, and the like.
Examples of the surface modifier made by AGC Seimi Chemical include Surflon S-611.

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.

Examples of the method for producing the sealing agent for organic EL display elements of the present invention include a polymerizable compound using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll. And a method of mixing a polymerization initiator and an additive such as a sensitizer and a surface modifier.

The encapsulant for organic EL display elements of the present invention is also referred to as a curing rate after 30 minutes after irradiation with ultraviolet rays having a wavelength of 395 nm at 2000 mJ / cm ² (hereinafter referred to as “curing rate after 30 minutes after light irradiation”). ) Is preferably 80%. When the curing rate after 30 minutes from the light irradiation is 80% or more, the encapsulant for organic EL display elements of the present invention can reduce the sol component and display defects are further reduced. . A more preferable lower limit of the curing rate 30 minutes after the light irradiation is 90%. The curing rate 30 minutes after the light irradiation is most preferably 100%.
In the present specification, the above-mentioned “curing rate” means the encapsulant before curing, the cured product of the encapsulant 30 minutes after light irradiation, and heating at 80 ° C. for 1 hour after light irradiation. It is a value calculated by the following formula from the area value of the peak derived from the polymerizable functional group in the spectrum obtained by measuring FT-IR for the cured product of the later sealing agent.
Curing rate (%) = ((1-y / x) / (1-z / x)) × 100
In said formula, x is a peak area value derived from the polymerizable functional group in the sealing agent before hardening. In said formula, y is a peak area value derived from this polymerizable functional group in the hardened | cured material of the sealing agent 30 minutes after light irradiation. In the above formula, z is a peak area value derived from the polymerizable functional group in the cured product of the sealant after being irradiated with light and heated at 80 ° C. for 1 hour.
The peak derived from the polymerizable functional group is, for example, the peak derived from the epoxy group (911 cm ⁻¹ ) when the polymerizable compound is an epoxy compound, and the oxetanyl when the polymerizable compound is an oxetane compound. It is a peak derived from a group (978 cm ⁻¹ ).

The preferable minimum of the total light transmittance of the light in the wavelength of 380 nm or more and 800 nm or less of the hardened | cured material of the sealing agent for organic EL display elements of this invention is 80%. When the total light transmittance is 80% or more, the obtained organic EL display element has superior optical characteristics. A more preferable lower limit of the total light transmittance is 85%.
The total light transmittance can be measured using a spectrometer such as AUTOMATIC HAZE METER MODEL TC-III DPK (manufactured by Tokyo Denshoku).
Moreover, if the hardened | cured material used for the measurement of the said total light transmittance is a photocurable sealing agent, for example, it will obtain by irradiating 2000 mJ / cm < ² > of ultraviolet rays with a wavelength of 395 nm with a LED lamp to sealing agent. If it is a thermosetting sealant, it can be obtained by heating at 80 ° C. for 1 hour, for example.

In the sealing agent for organic EL display elements of the present invention, the transmittance at 400 nm after irradiating the cured product with ultraviolet rays for 100 hours is preferably 85% or more at an optical path length of 20 μm. When the transmittance after irradiating the ultraviolet rays for 100 hours is 85% or more, the transparency is high, the loss of light emission is small, and the color reproducibility is excellent. A more preferable lower limit of the transmittance after irradiation with the ultraviolet rays for 100 hours is 90%, and a more preferable lower limit is 95%.
As the light source for irradiating the ultraviolet rays, a conventionally known light source such as a xenon lamp or a carbon arc lamp can be used.
Moreover, if the hardened | cured material used for the measurement of the transmittance | permeability after irradiating the said ultraviolet-ray for 100 hours is a photocurable sealing agent, for example, ultraviolet rays with a wavelength of 395 nm will be 2000 mJ / cm with a LED lamp to a sealing agent. ^If it is a thermosetting sealant, it can be obtained, for example, by heating at 80 ° C. for 1 hour.

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 moisture from reaching the organic light emitting material layer and the generation of dark spots is improved, and the resulting organic EL display element is more reliable. It will be a thing.
Moreover, if the hardened | cured material used for the said moisture permeability measurement is a photocurable sealing agent, it can obtain by irradiating 2000 mJ / cm < ² > of ultraviolet rays with a wavelength of 395 nm with a LED lamp to a sealing agent, for example. If it is a thermosetting sealing agent, it can obtain by heating at 80 degreeC for 1 hour, for example.

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.
Moreover, if the hardened | cured material used for the said moisture content measurement is a photocurable sealing agent, it can obtain by irradiating 2000 mJ / cm < ² > of ultraviolet rays with a wavelength of 395 nm with a LED lamp to a sealing agent, for example. If it is a thermosetting sealing agent, it can obtain by heating at 80 degreeC for 1 hour, for example.

The sealing agent for organic EL display elements of the present invention 1 is suitably used for coating by an ink jet method, and the sealing agent for organic EL display elements of the present invention 2 is used for coating by an ink jet method.
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.

The sealing agent for organic EL display elements of this invention can be used suitably for sealing of a top emission type organic EL display element. The top emission type organic EL display element using the sealing agent for organic EL display elements of the present invention is also one aspect of the present invention.
In addition, even when the sealing agent for organic EL display elements of the present invention is used for sealing a bottom emission type organic EL display element, an organic EL display element having excellent display performance can be obtained.

ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for organic EL display elements which can obtain the organic EL display element which is excellent in inkjet applicability | paintability, and is excellent in display performance even if it is a top emission type can be provided. Moreover, according to this invention, the top emission type organic EL display element formed using this sealing agent for organic EL display elements can be provided.

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 to 4, Comparative Examples 1 to 3)
In accordance with the blending ratio described in Table 1, each material was uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer (“Primix Corporation,“ Homodisper L type ”). To 4 and Comparative Examples 1 to 3 were prepared. The cured product was obtained by irradiating the obtained encapsulant for organic EL display elements with 2000 mJ / cm ² of UV light having a wavelength of 395 nm using an LED lamp.
About each sealing agent for organic EL display elements obtained in the Examples and Comparative Examples, an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-22”) was used, and a CP1-type cone plate was used. The viscosity was measured under the conditions of 100 ° C. and 100 ° C. The results are shown in Table 1.
Further, the surface tension of each of the encapsulants for organic EL display elements obtained in Examples and Comparative Examples was measured at 25 ° C. using a dynamic wettability tester (“WET-6100 type” manufactured by Reska Co.). The results are shown in Table 1.
Furthermore, specific gravity of each sealing agent for organic EL display elements and hardened | cured material obtained by the Example and the comparative example was measured. From each specific gravity obtained, the cure shrinkage rate was calculated by the above-described formula. The results are shown in Table 1.
In addition, about 1 mg of each cured product obtained in the examples and comparative examples, using a thermal desorption apparatus and a GC-MS apparatus, a gas component generated when heated at 80 ° C. under a thermal desorption condition of 30 minutes. The amount was measured as the outgas generation amount. Specific measurement conditions are shown below.
Thermal desorption device: Turbo Matrix 650 (manufactured by PerkinElmer)
Thermal desorption conditions: 80 ° C., 30 minutes Split: Inlet 15 mL / min, outlet 15 mL / min, injection amount 5.2%
GC-MS device: JMS Q1000 (manufactured by JEOL Ltd.)
Separation column: EQUITY-1 (Nonpolar)
0.32mm × 60m × 0.25μm
GC temperature rising rate: 40 ° C. for 4 minutes → 10 ° C./minute→300° C. for 10 minutes Carrier gas (flow rate): He (1.5 mL / minute)
MS measurement range: 29-600 amu (scan 500 ms)
Ionization voltage: 70 eV
MS temperature: ion source 230 ° C, interface 250 ° C
The results are shown in Table 1.

<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 Table 1.
In each evaluation of ink jet discharge property, wettability and dark spot diameter enlargement ratio, IJH-30 (manufactured by IJT) was used as the ink jet coating head, and the ink jet coating was performed without heating ( Head temperature 25 ° C.).

(1) Inkjet applicability (1-1) Inkjet ejection properties Each of the organic EL display element sealants obtained in Examples and Comparative Examples was used with an inkjet ejection device (“NanoPrinter500” manufactured by Microjet Co., Ltd.). It was applied on alkali-cleaned non-alkali glass (“AN100” manufactured by Asahi Glass Co., Ltd.) with a droplet volume of 10 picoliter. The ink jet discharge performance was evaluated by assuming that “◯” indicates that the liquid droplets were normally discharged from the ink jet nozzle and landed on the substrate, and “X” indicates that the liquid droplets were not normally discharged.

(1-2) Wetting and spreading property Each of the encapsulants for organic EL display elements obtained in Examples and Comparative Examples is a 10 picoliter liquid using an inkjet discharge device (“NanoPrinter500” manufactured by Microjet). 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. The diameter of the droplet on the alkali-free glass 10 minutes after the coating was measured. The case where the diameter of the droplet was 150 μm or more was “◯”, and the case where the diameter of the droplet was 50 μm or more and less than 150 μm was “ “Δ”, the case where the diameter of the droplet was less than 50 μm was evaluated as “×”, and the wetting and spreading property was evaluated.

(2) Curing rate About each sealing agent for organic EL display elements obtained in Examples and Comparative Examples, before curing, after 30 minutes from light irradiation, and after light irradiation, heat at 80 ° C. for 1 hour. The FT-IR of the cured product of the sealing agent after the measurement was measured. From area values of peaks obtained from the epoxy group in the spectrum (911 cm ^-1), or oxetanyl group derived peak (978cm ^-1), it was calculated hardening rate by the above-mentioned formula.

(3) Light emission state of organic EL display element A top emission type organic EL display element was obtained by the method shown in (3-1) to (3-4) below. Further, the light emitting state of the organic EL display element was evaluated by the methods shown in the following (3-5) and (3-6).

(3-1) Fabrication of a substrate on which a laminate having an organic light emitting material layer is arranged A glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm) having an ITO electrode formed in a thickness of 1000 mm A substrate was used. The substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, respectively, then washed with boiled isopropyl alcohol for 10 minutes, and a 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 holder of a vacuum deposition apparatus, and 200 mg of N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (α-NPD) is added to 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 ｓ / 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. After that, the inside of the vapor deposition unit of the vacuum vapor deposition apparatus is depressurized to 2 × 10 ⁻⁴ Pa to form a lithium fluoride film with a thickness of 5 mm at a deposition rate of 0.2 kg / s, and then aluminum with a film thickness of 1000 mm 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.

(3-2) Covering with inorganic material film A A mask having an opening of 13 mm × 13 mm is placed on the substrate on which the obtained laminate is disposed, and the inorganic material is covered by the plasma CVD method so as to cover the entire laminate. 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.

(3-3) Formation of Resin Protective Film Each organic EL display element sealant obtained in Examples and Comparative Examples was applied to the obtained substrate using an inkjet discharge device (“NanoPrinter300” manufactured by MicroJet). Was used to apply a pattern to the substrate.
Thereafter, an ultraviolet ray having a wavelength of 395 nm was irradiated with 2000 mJ / cm ² using an LED lamp to cure the organic EL display element sealant, thereby forming a resin protective film.

(3-4) After the coating resin protective film is formed by the inorganic material film B, a mask having an opening of 12 mm × 12 mm is set on the substrate, and the whole of the resin protective film is covered by plasma CVD. The material film B was formed to obtain an organic EL display element.
The plasma CVD method was performed under the same conditions as in “(3-2) Coating with inorganic material film A”.
The formed inorganic material film B had a thickness of about 1 μm.

(3-5) Measurement of initial dark spot diameter With respect to the obtained top emission type organic EL display element, the light emission state was observed with an optical microscope, and the initial dark spot diameter was measured. When there were a plurality of dark spots, one with a diameter of about 20 μm was preferentially observed.

(3-6) Dark spot diameter enlargement ratio The organic EL display element obtained was exposed for 100 hours in an environment of temperature 85 ° C. and humidity 85%, and then a voltage of 3 V was applied to the light emission state of the organic EL display element. Were observed with an optical microscope, and the dark spot diameter after 100 hours was measured at 85 ° C. and 85% in the same manner as in the above “(3-5)”.
When the dark spot diameter enlargement ratio is less than 1.1 times, “「 ”, when it is 1.1 times or more and less than 1.2 times,“ ◯ ”, when it is 1.2 times or more and less than 1.5 times The light emission state of the organic EL display element was evaluated with “Δ” as the case where it was present, 1.5 times or more, or “x” as the case where the non-light emitting portion was significantly enlarged.
The dark spot diameter expansion rate was calculated by the following formula.
Dark spot diameter expansion rate = 85 ° C, 85%, dark spot diameter after 100 hours / initial dark spot diameter

ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for organic EL display elements which can obtain the organic EL display element which is excellent in inkjet applicability | paintability, and is excellent in display performance even if it is a top emission type can be provided. Moreover, according to this invention, the top emission type organic EL display element formed using this sealing agent for organic EL display elements can be provided.

Claims (8)

Containing a polymerizable compound and a polymerization initiator,
Organic having a cure shrinkage of less than 11% and an outgas generation amount of a cured product of less than 3000 ppm measured by a thermal desorption GC-MS method at 80 ° C. for 30 minutes. Sealant for EL display element. An organic EL display element sealing agent used for coating by an inkjet method,
Containing a polymerizable compound and a polymerization initiator,
Organic having a cure shrinkage of less than 11% and an outgas generation amount of a cured product of less than 3000 ppm measured by a thermal desorption GC-MS method at 80 ° C. for 30 minutes. Sealant for EL display element. The sealant for organic EL display elements according to claim 1 or 2, wherein the viscosity at 25 ° C is 5 mPa · s or more and 50 mPa · s or less, and the surface tension at 25 ° C is 15 mN / m or more and 35 mN / m or less. The sealing compound for organic EL display elements according to claim 1, wherein the polymerizable compound includes a cationic polymerizable compound. The sealing agent for organic EL display elements according to claim 4, wherein the polymerizable compound contains a polyfunctional oxetane compound. 6. The encapsulant for an organic EL display device according to claim 5, wherein the polymerizable compound contains 3-ethyl-3-(((3-ethyloxetane-3-yl) methoxy) methyl) oxetane. The encapsulant for organic EL display elements according to claim 1, wherein the curing rate after 30 minutes after irradiation with ultraviolet rays having a wavelength of 395 nm is 2000 mJ / cm ² is 80% or more. A top emission type organic EL display element comprising the organic EL display element sealant according to claim 1, 2, 3, 4, 6, or 7.