JP6718220B2 - Sealant for organic electroluminescence display device - Google Patents

Description

The present invention relates to a sealant for organic electroluminescent display elements, which has excellent barrier properties, adhesiveness, and shape retention.

An organic electroluminescence (hereinafter, also referred to as “organic EL”) display element has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. Electrons are injected into this organic light emitting material layer from one electrode and holes are injected from the other electrode, so that electrons and holes are combined in the organic light emitting material layer to perform self-light emission. The organic EL display element has advantages that it has better visibility, can be made thinner, and can be driven at a DC low voltage, as compared with a liquid crystal display element that requires a backlight.

However, such an organic EL display element has a problem that when the organic light emitting material layer and the electrodes are exposed to the outside air, the light emitting characteristics thereof are rapidly deteriorated and the life is shortened. Therefore, for the purpose of improving the stability and durability of the organic EL display element, a sealing technique for shielding the organic light emitting material layer and the electrode from moisture and oxygen in the atmosphere is indispensable.

Patent Document 1 discloses a method of sealing an electrode material or a light emitting device using a composition containing an epoxy compound, a cationic polymerization initiator, and an alkaline earth metal oxide as a hygroscopic agent. ..

JP, 2009-051980, A

When the composition disclosed in Patent Document 1 is used as a sealant for an organic EL display element, if a large amount of alkaline earth metal oxide is blended in order to exert sufficient barrier properties (moisture permeation preventive property). However, there is a problem that the panel peels off easily.
An object of the present invention is to provide a sealant for an organic electroluminescence display element, which has excellent barrier properties, adhesiveness, and shape retention.

The present invention contains an epoxy compound, a thermal anion curing agent, a (meth)acrylic compound, a photoradical polymerization initiator, and an alkaline earth metal oxide, and the epoxy compound and the (meth)acrylic compound described above. The total content of 100 parts by weight of the (meth)acrylic compound is 10 parts by weight or more and 50 parts by weight or less, and the alkaline earth metal oxide has a water absorption rate of 10% by weight or more. It is a sealing agent for elements.
The present invention will be described in detail below.

The present inventor has found that the composition as disclosed in Patent Document 1 is an epoxy cationic curing system comprising an epoxy compound and a cationic polymerization initiator, and therefore inhibits curing when a large amount of alkaline earth metal oxide is blended. It was thought that, as a result, the adhesiveness was lowered and panel peeling was likely to occur. On the other hand, when the amount of the alkaline earth metal oxide compounded was reduced to suppress the inhibition of curing, sufficient barrier properties were not exhibited. Therefore, the present inventor does not cause curing inhibition by using an epoxy anion curing type composition of an epoxy compound and a thermal anion curing agent as an organic EL display element sealing agent instead of the epoxy cation curing type. It was studied to add a large amount of alkaline earth metal oxides to the above to exert sufficient barrier properties while maintaining excellent adhesiveness. However, when such a composition is used, there is a problem that the resin flows during heating and the shape cannot be maintained.
Therefore, as a result of further intensive studies by the present inventor, a composition containing such an epoxy compound, a thermal anion curing agent, and an alkaline earth metal oxide was further provided with a (meth)acrylic compound and a photoradical polymerization initiator. It was found that the compounding agent can provide a sealing agent for organic EL display elements, which has excellent barrier properties, adhesive properties, and shape retention properties, and has completed the present invention.

The organic EL display element sealing agent of the present invention contains an epoxy compound.
As the epoxy compound, at least one epoxy resin selected from the group consisting of an epoxy resin having a bisphenol skeleton, an epoxy resin having a novolac skeleton, an epoxy resin having a naphthalene skeleton, and an epoxy resin having a dicyclopentadiene skeleton. Is more preferable, an epoxy resin having a bisphenol skeleton is more preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are further preferable.
A compound having an epoxy group and a (meth)acryloyl group is treated as a (meth)acrylic compound as described later.

The preferable lower limit of the epoxy equivalent of the epoxy compound is 100 g/eq, and the preferable upper limit thereof is 1000 g/eq. When the epoxy equivalent of the epoxy compound is in the above range, the obtained organic EL display element sealing agent has more excellent adhesiveness. The more preferable lower limit of the epoxy equivalent of the epoxy compound is 150 g/eq, and the more preferable upper limit thereof is 500 g/eq.
In the present specification, the “epoxy equivalent” means (molecular weight of epoxy compound)/(number of epoxy groups in one molecule of epoxy compound).

Examples of commercially available epoxy compounds include, for example, EPICLON EXA-830LVP (manufactured by DIC), D.I. E. N. 431 (manufactured by Dow Chemical Co.) and the like.

The encapsulant for organic EL display elements of the present invention contains a thermal anion curing agent.
By making the curing system of the epoxy compound an anion curing system using the thermal anion curing agent, a large amount of alkaline earth metal oxide described below can be blended without causing curing inhibition, and as a result, excellent It is possible to exert a sufficient barrier property while maintaining the adhesiveness.

Examples of the thermal anion curing agent include hydrazide compounds, imidazole derivatives, dicyandiamide, guanidine derivatives, modified aliphatic polyamines, addition products of various amines with epoxy resins, and the like. Of these, hydrazide compounds and imidazole derivatives are preferable.
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 derivative 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 thereof include phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
These thermal anion curing agents may be used alone or in combination of two or more.

Examples of commercially available thermal anion curing agents include, for example, SDH, ADH (manufactured by Otsuka Chemical Co., Ltd.), MDH (manufactured by Nippon Fine Chem Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all are Ajinomoto Fine Techno Co., Ltd.), 2MAOK, 2MAOK-PW, 2MZA, 2P4MHZ (all manufactured by Shikoku Chemicals Co., Ltd.), Fujicure FXR-1020, Fujicure FXR-1030, and Fujicure 7000 (all manufactured by T&K TOKA).

The content of the thermal anion curing agent is preferably 1 part by weight and 30 parts by weight with respect to 100 parts by weight of the total amount of the epoxy compound and the (meth)acrylic compound. When the content of the thermal anion curing agent is within this range, the resulting organic EL display element encapsulant is more excellent in the effect of satisfying both thermosetting property and storage stability. The more preferable lower limit of the content of the thermal anion curing agent is 5 parts by weight, and the more preferable upper limit thereof is 20 parts by weight.

The encapsulant for organic EL display elements of the present invention contains a (meth)acrylic compound.
Since the encapsulant for organic EL display devices of the present invention contains the above (meth)acrylic compound and a photo radical polymerization initiator described below, it can be temporarily cured by light irradiation before the main curing by heating. In addition, the shape retention property is excellent.
In the present specification, the “(meth)acryl” means acryl or methacryl, the “(meth)acryl compound” means a compound having a (meth)acryloyl group, and the (meth)acryloyl group is , Acryloyl group or methacryloyl group.

As the (meth)acrylic compound, a compound having an epoxy group and a (meth)acryloyl group is preferable.
As the compound having the epoxy group and the (meth)acryloyl group, a part obtained by reacting a part of the epoxy group of the epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid ( (Meth)acrylic modified epoxy resin is preferred.

Examples of the partial (meth)acrylic modified epoxy resin include a partial (meth)acrylic modified bisphenol A type epoxy resin, a partial (meth)acrylic modified bisphenol F type epoxy resin, a partial (meth)acrylic modified bisphenol E type epoxy resin, Partial (meth)acrylic modified bisphenol S type epoxy resin, partial (meth)acrylic modified hydrogenated bisphenol A type epoxy resin, partial (meth)acrylic modified hydrogenated bisphenol F type epoxy resin, partial (meth)acrylic modified resorcinol type epoxy resin , Partial (meth) acrylic modified biphenyl type epoxy resin, partial (meth) acrylic modified sulfide type epoxy resin, partial (meth) acrylic modified diphenyl ether type epoxy resin, partial (meth) acrylic modified dicyclopentadiene type epoxy resin, partial (meth ) Acrylic modified naphthalene type epoxy resin, partial (meth)acrylic modified phenol novolac type epoxy resin, partial (meth)acrylic modified orthocresol novolac type epoxy resin, partial (meth)acrylic modified dicyclopentadiene novolac type epoxy resin, partial (meth) ) Acrylic modified biphenyl novolac type epoxy resin, partial (meth)acrylic modified naphthalene phenol novolac type epoxy resin, partial (meth)acrylic modified glycidyl amine type epoxy resin, partial (meth)acrylic modified alkyl polyol type epoxy resin and the like. Among them, the partial (meth)acrylic modified bisphenol E type epoxy resin is preferable from the viewpoint of suppressing curing shrinkage.

Examples of commercially available partial (meth)acrylic modified epoxy resins include KRM8276, UVACURE1561 (manufactured by Daicel Ornex) and the like.

As the (meth)acrylic compound, other (meth)acrylic compounds having no epoxy group may be used.
Examples of the other (meth)acrylic compound include epoxy (meth)acrylate obtained by reacting (meth)acrylic acid with an epoxy compound, and a compound having a hydroxyl group with (meth)acrylic acid. Examples thereof include a (meth)acrylic acid ester compound obtained and a urethane (meth)acrylate obtained by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group.
In the present specification, the “(meth)acrylate” means an acrylate or a methacrylate, and the “epoxy (meth)acrylate” means that all epoxy groups in an epoxy compound are reacted with (meth)acrylic acid. Means a compound.

The preferable lower limit of the content of the (meth)acrylic compound in the total 100 parts by weight of the epoxy compound and the (meth)acrylic compound is 5 parts by weight, and the preferable upper limit thereof is 50 parts by weight. When the content of the (meth)acrylic compound is within this range, the resulting organic EL display element encapsulant is more excellent in adhesiveness and shape retention. The more preferable lower limit of the content of the (meth)acrylic compound is 10 parts by weight, and the more preferable upper limit thereof is 30 parts by weight.

The encapsulant for organic EL display elements of the present invention contains a photoradical polymerization initiator.
As the photoradical polymerization initiator, for example, a compound having an acylphosphine oxide skeleton, a compound having an α-aminoacetophenone skeleton, a compound having a benzyl ketal skeleton, a compound having an α-hydroxyacetophenone skeleton, a compound having a benzoin skeleton, Examples thereof include compounds having an oxime ester skeleton, compounds having a titanocene skeleton, organic peroxides, azo compounds and oligomer compounds. These photo-radical polymerization initiators may be used alone or in combination of two or more kinds.
Among them, from the viewpoint of photocurability, a compound having an acylphosphine oxide skeleton, a compound having an α-aminoacetophenone skeleton, a compound having a benzyl ketal skeleton, a compound having an α-hydroxyacetophenone skeleton, a compound having a benzoin skeleton, and an oxime. At least one selected from the group consisting of a compound having an ester skeleton, a compound having a titanocene skeleton, and an oligomer compound is preferable.
Here, the compound having an acylphosphine oxide skeleton means a compound in which a part of acylphosphine oxide is substituted with another group. The compound having an α-aminoacetophenone skeleton means a compound in which a part of α-aminoacetophenone is replaced with another group. The compound having a benzyl ketal skeleton means a compound in which a part of α-dihydroxyacetophenone is substituted with another group. The compound having the α-hydroxyacetophenone skeleton means a compound in which a part of the α-monohydroxyacetophenone other than the hydroxyl group is substituted with another group. The compound having a benzoin skeleton means a compound in which a part of benzoin is substituted with another group. The compound having the oxime ester skeleton means a compound in which a part of N-acetyldimethyloxime is substituted with another group. The compound having a titanocene skeleton means a compound in which a part of titanocene is replaced with another group. The organic peroxide means a compound having a peroxy group. The azo compound means a compound having an azo group.

Examples of the compound having an acylphosphine oxide skeleton include 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("LUCILIN TPO" manufactured by BASF), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide ( "IRGACURE 819" manufactured by BASF Corp.) and the like.

Examples of the compound having the α-aminoacetophenone skeleton include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (BASF Corporation, “IRGACURE 907”), 2-benzyl. 2-Dimethylamino-1-(4-morpholinophenyl)butanone (manufactured by BASF, “IRGACURE 369”), 1,2-(dimethylamino)-2-((4-methylphenyl)methyl)-1- (4-(4-morpholinyl)phenyl)-1-butanone (manufactured by BASF, "IRGACURE 379") and the like can be mentioned.

Examples of the compound having a benzyl ketal skeleton include 2,2-dimethoxy-1,2-diphenylethan-1-one (manufactured by BASF, “IRGACURE 651”) and the like.

Examples of the compound having an α-hydroxyacetophenone skeleton include 2-hydroxy-1-(4-(4-(2-hydroxy-2-methyl-propionyl)-benzyl)phenyl)-2-methyl-propane-1. -ON (manufactured by BASF, "IRGACURE 127") and the like.

Examples of the compound having an oxime ester skeleton include 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyloxime) (BASF Corporation, "IRGACURE OXE01"), O- Acetyl-1-(6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl)ethanone oxime (BASF Corporation, "IRGACURE OXE02") and the like can be mentioned.

Examples of the compound having a titanocene skeleton include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium. ("IRGACURE 784" manufactured by BASF) and the like.

The oligomer compound mentioned as the photoradical polymerization initiator preferably has a degree of polymerization of 2 to 10 from the viewpoint of reducing the generation of outgas, and further, because outgas is less likely to be generated, water such as a hydroxyl group or an amino group is used. It is preferable to have an acid-bonding functional group.
Specifically, for example, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propane) (Lamberti, "ESACURE KIP 150"), polyethylene glycol 200-di(β -4(4-(2-Dimethylamino-2-benzyl)butanonylphenyl)piperazine) (manufactured by IGM, "Omnipol 910"), (2-carboxymethoxythioxanthone)-(polytetramethylene glycol 250) diester (IGM Examples thereof include "Omnipol TX"), (carboxymethoxymethoxybenzophenone)-(polyethylene glycol 250) diester (manufactured by IGM, "Omnipol BP"), and the like.

With respect to the content of the photoradical polymerization initiator, a preferable lower limit is 0.1 part by weight and a preferable upper limit is 5 parts by weight with respect to 100 parts by weight as a total of the epoxy compound and the (meth)acrylic compound. When the content of the photoradical polymerization initiator is within this range, the resulting organic EL display element encapsulant is more excellent in the effect of achieving both photocurability and storage stability. The more preferable lower limit of the content of the photoradical polymerization initiator is 0.5 parts by weight, and the more preferable upper limit thereof is 3 parts by weight.

The organic EL display element sealing agent of the present invention contains an alkaline earth metal oxide.
The alkaline earth metal oxide has a role of improving the barrier property of the encapsulant for organic EL display elements of the present invention as a hygroscopic agent.

Examples of the alkaline earth metal oxide include calcium oxide, strontium oxide, barium oxide and the like. Among them, calcium oxide is preferable from the viewpoint of hygroscopicity.
These alkaline earth metal oxides may be used alone or in combination of two or more.

From the viewpoint of barrier properties, the alkaline earth metal oxide preferably has a water absorption of 10% by weight or more, more preferably 30% by weight or more.
The above "water absorption" is calculated by the rate of change in weight when left for 24 hours in an atmosphere at a temperature of 85°C and a humidity of 85%. Specifically, when the weight before the high temperature and high humidity test (85° C.-85%, 24 hours) is W ₁ and the weight after the high temperature and high humidity test is W ₂ , it is calculated by the following formula (I).
Water absorption rate (% by weight)=(W ₂ −W ₁ )/W ₁ ×100 (I)

The total surface area of the alkaline earth metal oxide, the epoxy compound and the (meth) preferred lower limit is 10 m 2 per total 100g of acrylic ^compound, the desirable upper limit is 100 m ^2. When the total surface area of the alkaline earth metal oxide is in this range, the resulting organic EL display element sealant is more excellent in barrier properties while preventing panel peeling and cracking. The more preferable lower limit of the total surface area of the alkaline earth metal oxide is 20 m ² , and the more preferable upper limit thereof is 80 m ² .
The total surface area of the alkaline earth metal oxide is calculated from the content of the alkaline earth metal oxide and the BET specific surface area. Specifically, for example, it is calculated from the BET specific surface area measured using nitrogen gas with a specific surface area measuring device (ASAP-2000 manufactured by Shimadzu Corporation).

Regarding the content of the alkaline earth metal oxide, a preferable lower limit is 10 parts by weight and a preferable upper limit is 80 parts by weight with respect to 100 parts by weight as a total of the epoxy compound and the (meth)acrylic compound. When the content of the alkaline earth metal oxide is in this range, the resulting organic EL display element sealant has more excellent barrier properties while preventing panel peeling and cracking. The more preferable lower limit of the content of the alkaline earth metal oxide is 20 parts by weight, and the more preferable upper limit thereof is 60 parts by weight.

The encapsulant for organic EL display elements of the present invention contains a filler in addition to the above alkaline earth metal oxide within the range that does not impair the object of the present invention for the purpose of improving adhesiveness and the like. May be.
Examples of the filler include inorganic fillers such as silica, talc and alumina, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles and acrylic polymer fine particles. Of these, talc is preferred.
These fillers may be used alone or in combination of two or more kinds.

Regarding the content of the filler, a preferable lower limit is 5 parts by weight and a preferable upper limit is 100 parts by weight with respect to a total of 100 parts by weight of the epoxy compound and the (meth)acrylic compound. When the content of the filler is within this range, the effect of improving the adhesiveness and the like can be improved without deteriorating the coating property. The more preferable lower limit of the content of the filler is 10 parts by weight, and the more preferable upper limit thereof is 80 parts by weight.

The encapsulant for organic EL display elements of the present invention may contain a silane coupling agent. The silane coupling agent has a role of improving the adhesiveness between the organic EL display element sealing agent of the present invention and the substrate or the like.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatepropyltrimethoxysilane.
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 part by weight and 10 parts by weight with respect to 100 parts by weight of the epoxy compound and the (meth)acrylic compound. When the content of the silane coupling agent is within this range, the resulting organic EL display element encapsulant is more excellent in adhesiveness while suppressing bleed-out due to excess silane coupling agent. The more preferable lower limit of the content of the silane coupling agent is 0.5 parts by weight, and the more preferable upper limit thereof is 5 parts by weight.

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

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

The encapsulant for organic EL display elements of the present invention may contain an ion exchange resin in order to improve the durability of the element electrode within the range that does not impair the object of the present invention.

As the ion exchange resin, any of a cation exchange type, an anion exchange type, and both ion exchange types can be used, and in particular, a cation exchange type or both ion exchange types capable of adsorbing chloride ions. Is preferred.

The organic EL display element sealing agent of the present invention preferably does not contain a solvent from the viewpoint of suppressing the generation of outgas. The encapsulant for organic EL display elements of the present invention can be excellent in coatability without containing a solvent.

Further, the organic EL display element sealing agent of the present invention is a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity adjusting agent, an ultraviolet absorber, if necessary, within a range that does not impair the object of the present invention. , Known various additives such as antioxidants may be contained.

The method for producing the encapsulant for organic EL display elements of the present invention includes, for example, an epoxy compound using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls. Examples thereof include a method of mixing a thermal anion curing agent, a (meth)acrylic compound, a photoradical polymerization initiator, an alkaline earth metal oxide, and an additive added as necessary.

The shape of the sealing portion formed by the sealant for an organic EL display element of the present invention is not particularly limited as long as it has a shape capable of protecting the laminate having the organic light emitting material layer from the outside air. The shape may be such that it is completely covered, a closed pattern may be formed in the peripheral portion of the laminate, or a pattern having a shape in which some openings are provided in the peripheral portion of the laminate is formed. However, the encapsulant for organic EL display elements of the present invention can be particularly preferably used as a peripheral encapsulant for encapsulating the peripheral portion of the laminate.

ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for organic electroluminescent display elements which is excellent in barrier property, adhesiveness, and shape retention can be provided.

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

(Example 1)
75 parts by weight of a bisphenol F type epoxy resin (manufactured by DIC, "EPICLON EXA-830LVP") as an epoxy compound, and a partially methacryl-modified bisphenol E type epoxy resin (manufactured by Daicel Ornex, "KRM8276") as a (meth)acrylic compound. 25 parts by weight, 7.5 parts by weight of a modified aliphatic polyamine ("Fujicure FXR-1030" manufactured by T&K TOKA Co., Ltd.) as a thermal anion curing agent, and 2,2-dimethoxy-1,2- as a photoradical polymerization initiator. 1 part by weight of diphenylethan-1-one (manufactured by BASF, "IRGACURE 651") and calcium oxide (manufactured by Yoshizawa Lime Industry Co., Ltd., "quicklime J1P", water absorption rate 30% by weight, specific surface area 2.5 m ² ) as a moisture absorbent. /G) 20 parts by weight, 20 parts by weight of talc (manufactured by Nippon Talc Co., Ltd., "MICRO ACE D-600") and 20 parts by weight of core shell acrylate copolymer fine particles ("F351" manufactured by Zeon Kasei Co., Ltd.) as a filler. , 1 part by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso Co., "Sila Ace S510") as a silane coupling agent, and a stirring speed using a stirring mixer (manufactured by Shinky Co., "AR-250"). By uniformly stirring and mixing at 3000 rpm, a sealant for an organic EL display device was produced.

( Reference Example 2, Examples 3 to 10, Comparative Examples 1 to 3)
The respective materials shown in Tables 1 and 2 were stirred and mixed in the same manner as in Example 1 in accordance with the compounding ratios shown in Tables 1 and 2 to prepare an organic EL display element encapsulant.

<Evaluation>
Examples, reference examples, and, for each of the organic EL display element sealing agents obtained in Comparative Examples were evaluated as follows. The results are shown in Tables 1 and 2.

(1) Barrier properties Example, Reference Examples, and, for encapsulant each organic EL display device obtained in Comparative Examples were subjected to the following Ca-TEST.
First, a 30 mm×30 mm glass substrate was covered with a mask having a 2 mm image opening, and Ca was vapor-deposited by a vacuum vapor deposition machine. The conditions of vapor deposition were such that the pressure inside the vapor deposition apparatus of the vacuum vapor deposition apparatus was reduced to 2×10 ⁻³ Pa and Ca was deposited at a deposition rate of 5.0 Å/s to 2000 Å. This was moved to a dew point in the glove box that is managed (-60 ° C. or higher), carried on the surface Examples, Reference Examples, and glass coated with the organic EL display device sealing agent obtained in Comparative Example The substrates were stuck together. At this time, the glass substrates were bonded so that the distance from the end surface of the glass substrate to the deposited Ca was 2 mm, 4 mm, and 6 mm. This substrate was irradiated with ultraviolet rays (wavelength 365 nm) of 3000 mJ/cm ² and further heated at 100° C. for 60 minutes to cure the sealant, thereby producing a Ca-TEST substrate. The obtained Ca-TEST substrate was exposed to a high temperature and high humidity condition of 85° C. and 85% RH, and the permeation distance of water per hour was observed from the disappearance of Ca. As a result, when the time taken for the water penetration distance to reach 6 mm was 1000 hours or more, it was “◎”, when it was 500 hours or more and less than 1000 hours, it was “◯”, and 100 hours or more and less than 500 hours. The barrier property of the cured product was evaluated as “Δ” for the case and “×” for less than 100 hours.
In addition, when the organic EL display element sealant obtained in Example 5 was used, the barrier property was better than when the organic EL display element sealant obtained in Example 1 was used. ..

(2) adhesive Example, Reference Examples, and each organic EL display device sealing agent obtained in Comparative Example was coated on a non-alkali glass to have a diameter of about 3 to 5 mm, on which Another piece of non-alkali glass was laminated in a cross shape and irradiated with ultraviolet rays (wavelength 365 nm) of 3000 mJ/cm ^{2 from} a high pressure mercury lamp, and then heated at 100° C. for 60 minutes to give an adhesive test piece. It was made. The obtained adhesive test piece was subjected to a peel test using EZ GRAPH (manufactured by Shimadzu Corporation) at a peel speed of 5 mm/min to measure the adhesive force. When the adhesive strength is 30 kgf/cm ² or more, it is “⊚”, when it is 20 kgf/cm ² or more and less than 30 kgf/cm ² , it is “◯”, when it is 10 kgf/cm ² or more and less than 20 kgf/cm ^2. Was evaluated as "x", and the case where it was less than 10 kgf/cm ² was evaluated as "x".

(3) shape retention examples, reference examples, and the respective organic EL display element sealing agent obtained in Comparative Example was filled-deaerated 10cc syringe (manufactured by Musashi Engineering, Inc.), a dispenser (Musashi Engineering "SHOTMASTER300" manufactured by the company) was drawn on the glass substrate so that a square frame was drawn. Then, a small drop of our in-plane filler (Sekisui Chemical Co., Ltd., "E-101") is dropped and applied in the frame of the seal pattern by a dropping device, and another glass is applied using a vacuum bonding device. It was attached to the substrate. After that, irradiation with ultraviolet rays (wavelength 365 nm) of 3000 mJ/cm ^{2 was performed with} a high-pressure mercury lamp, and heating was further performed in an oven at 100° C. for 60 minutes to produce a pseudo panel.
Observing the shape of the peripheral sealing part in the obtained pseudo panel, "○" when no irregularity was confirmed in the shape, "△" when slight irregularity was confirmed in the shape, large disturbance in the shape When the resin flow was confirmed, the shape retention was evaluated as "x".

ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for organic electroluminescent display elements which is excellent in barrier property, adhesiveness, and shape retention can be provided.

Claims (5)

Contains an epoxy compound, a thermal anion curing agent, a (meth)acrylic compound, a photoradical polymerization initiator, and an alkaline earth metal oxide,
The content of the (meth)acrylic compound in the total 100 parts by weight of the epoxy compound and the (meth)acrylic compound is 10 parts by weight or more and 50 parts by weight or less,
The alkaline earth metal oxide has a water absorption rate of 10% by weight or more, which is a sealant for an organic electroluminescence display device. The (meth)acrylic compound is a compound having an epoxy group and a (meth)acryloyl group, and the encapsulant for organic electroluminescent display elements according to claim 1. The compound having an epoxy group and a (meth)acryloyl group is a partial (meth)acryl-modified bisphenol E type epoxy resin, The encapsulant for organic electroluminescent display elements according to claim 2. The encapsulant for organic electroluminescence display elements according to claim 1, 2 or 3 , wherein the alkaline earth metal oxide is calcium oxide. Claim content of alkaline earth metal oxides, per 100 parts by weight of the epoxy compound and the (meth) acrylic compound, characterized in that 10 to 80 parts by weight 1,2,3 Or the sealing agent for organic electroluminescence display elements as described in 4 above.