JPWO2020149359A1 - Encapsulant set for organic EL display element and organic EL display element - Google Patents

Abstract

An object of the present invention is to provide a sealant set for an organic EL display element capable of obtaining an organic EL display element having excellent display performance. Another object of the present invention is to provide an organic EL display element having a cured product of the sealant set for the organic EL display element. In the present invention, a peripheral sealant that surrounds and seals the peripheral edge of an organic EL display element and an in-plane seal that coats and seals a laminate having an organic light emitting material layer inside the peripheral sealant. A encapsulant set for an organic EL display element formed by combining an agent, wherein the peripheral encapsulant contains a polyolefin, a curable resin A, a polymerization initiator and / or a thermosetting agent, and is described above. The in-plane encapsulant contains a curable resin B, a cationic polymerization initiator, and a stabilizer, and the curable resin B is an epoxy compound represented by the following formula (1) and the following formula (2). The content of the epoxy compound represented by the following formula (1) in 100 parts by weight of the curable resin B including the oxetane compound represented by the following formula is 10 parts by weight or more and 90 parts by weight or less, and the following formula. The content of the oxetane compound represented by (2) is 10 parts by weight or more and 90 parts by weight or less, and the content of the stabilizer is 0.001 part by weight or more and 5 parts by weight with respect to 100 parts by weight of the curable resin B. It is a sealant set for an organic EL display element which is less than a part. In formula (1), X is a linear or branched hydrocarbon having 1 to 6 carbon atoms which may be interrupted or directly connected at −C (= O) O− or −C (= O) −. Represents a group or a bond. [Chemical 1] [Chemical 2]

Description

The present invention relates to a sealant set for an organic EL display element capable of obtaining an organic EL display element having excellent display performance. The present invention also relates to an organic EL display element having a cured product of the sealant set for the organic EL display element.

The organic electroluminescence display element (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 the 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-luminous emission. Compared to a liquid crystal display element or the like that requires a backlight, it has the advantages of better visibility, thinner size, and low DC voltage drive.

However, such an organic EL display element has a problem that when the organic light emitting material layer or the electrode is exposed to the outside air, its light emitting characteristics are rapidly deteriorated and its life is shortened. Therefore, in order to improve the stability and durability of the organic EL display element, a sealing technique that shields the organic light emitting material layer and the electrode from atmospheric moisture and oxygen is indispensable for the organic EL display element. There is.

Patent Document 1 includes an organic packed layer that covers and seals a laminate having an organic light emitting material layer, and a moisture-absorbing seal layer (sealing wall) that covers the side surface of the organic packed layer. A method of sealing a display element is disclosed. Usually, as a sealing agent for an organic EL display element, an in-plane sealing agent is used for the organic packing layer, and a peripheral sealing agent having a component different from that of the in-plane sealing agent is used for the sealing wall. Has been done. However, when the organic EL display element is sealed by using such an in-plane sealing agent and a peripheral sealing agent, a peripheral sealing agent having excellent moisture permeation prevention property is used as the in-plane sealing agent. Even if those having excellent coatability and low outgassing property are used, there is a problem that their performance may not be sufficiently exhibited and display defects may occur in the organic EL display element.

Japanese Unexamined Patent Publication No. 2014-67598

An object of the present invention is to provide a sealant set for an organic EL display element capable of obtaining an organic EL display element having excellent display performance. Another object of the present invention is to provide an organic EL display element having a cured product of the sealant set for the organic EL display element.

In the present invention, a peripheral sealant that surrounds and seals the peripheral edge of an organic EL display element and an in-plane seal that coats and seals a laminate having an organic light emitting material layer inside the peripheral sealant. A sealant set for an organic EL display element formed by combining an agent, the peripheral sealant contains a polyolefin, a curable resin A, a polymerization initiator and / or a thermosetting agent, and is described above. The in-plane encapsulant contains a curable resin B, a cationic polymerization initiator, and a stabilizer, and the curable resin B is an epoxy compound represented by the following formula (1) and the following formula (2). The content of the epoxy compound represented by the following formula (1) in 100 parts by weight of the curable resin B including the oxetane compound represented by the following formula is 10 parts by weight or more and 90 parts by weight or less, and the following formula. The content of the oxetane compound represented by (2) is 10 parts by weight or more and 90 parts by weight or less, and the content of the stabilizer is 0.001 part by weight or more and 5 parts by weight with respect to 100 parts by weight of the curable resin B. It is a sealant set for an organic EL display element which is less than a part.

In formula (1), X is a linear or branched hydrocarbon having 1 to 6 carbon atoms which may be interrupted or directly connected at −C (= O) O− or −C (= O) −. Represents a group or a bond.

The present invention will be described in detail below.
The present inventors display by using a sealant set for an organic EL display element, which is a combination of a peripheral sealant composed of a specific component and an in-plane sealant composed of a specific component. They have found that an organic EL display element having excellent performance can be obtained, and have completed the present invention.

The sealant set for an organic EL display element of the present invention comprises a peripheral sealant that surrounds and seals the peripheral edge of the organic EL display element, and a laminate having an organic light emitting material layer inside the peripheral sealant. It is made in combination with an in-plane sealant that is coated and sealed.

(Peripheral sealant)
The peripheral sealant contains polyolefin.
By containing the polyolefin, the peripheral sealant makes the cured product excellent in moisture permeation prevention property and difficult to be compatible with the in-plane sealant described later.

From the viewpoint of further improving the moisture permeation prevention property of the cured product, the polyolefin preferably contains at least one selected from the group consisting of polyisobutylene, polybutene, and polybutadiene, and more preferably contains polyisobutylene. preferable.
The above-mentioned polyolefin may be used alone or in combination of two or more.

The preferable lower limit of the weight average molecular weight of the polyolefin is 10,000, and the preferable upper limit is 400,000. When the weight average molecular weight of the polyolefin is in this range, the obtained peripheral encapsulant is excellent in coatability, adhesiveness, and moisture permeation prevention property of the cured product.
In the present specification, the above-mentioned "weight average molecular weight" is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene. Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK) and the like.

The preferable lower limit of the content of the polyolefin in 100 parts by weight of the total of the polyolefin and the curable resin A described later is 10 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the polyolefin is 10 parts by weight or more, the obtained peripheral encapsulant becomes more excellent in the moisture permeation prevention property of the cured product. When the content of the polyolefin is 80 parts by weight or less, the obtained peripheral encapsulant is excellent in coatability and adhesiveness. The more preferable lower limit of the content of the polyolefin is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.

The peripheral sealant contains a curable resin A.
From the viewpoint of curability, the curable resin A preferably contains at least one selected from the group consisting of an epoxy compound, an oxetane compound, a (meth) acrylic compound, and a urethane compound, and preferably contains an epoxy compound and /. Alternatively, it is more preferable to contain a (meth) acrylic compound.
In the present specification, the above-mentioned "(meth) acrylic" means acrylic or methacrylic, and the above-mentioned "(meth) acrylic compound" means a compound having a (meth) acryloyl group, and the above-mentioned "(meth)". "Acryloyl" means acryloyl or methacryloyl.

Examples of the epoxy compound include glycidyl ether compounds and alicyclic epoxy compounds.
Examples of the glycidyl ether compound include diethylene glycol diglycidyl ether and the like.
Examples of the alicyclic epoxy compound include 3,4,3', 4'-diepoxybicyclohexyl, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, and 2,2-bis (2,2-bis). Examples thereof include 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of hydroxymethyl) -1-butanol.
Of these, diethylene glycol diglycidyl ether is preferable from the viewpoint of making it difficult to be compatible with the in-plane encapsulant described later.

Examples of the oxetane compound include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [2- (3-oxetanyl) butyl] ether, and 3-ethyl-3-hydroxy. Methyloxetane and the like can be mentioned.

As the (meth) acrylic compound, a (meth) acrylic acid ester compound is preferably used from the viewpoint of making it difficult to be compatible with the in-plane encapsulant described later.
Examples of the (meth) acrylic acid ester compound include isobornyl (meth) acrylate, (meth) adamantyl acrylate, (meth) methylcyclohexyl acrylate, (meth) norbornylmethyl acrylate, and (meth) acrylate di. Cyclopentanyl, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclodecyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate And so on.
In addition, in this specification, the said "(meth) acrylate" means acrylate or methacrylate.

Examples of the urethane compound include a reaction product of an isocyanate compound and an arbitrary polyol compound.
Examples of the isocyanate compound include toluene diisocyanate compounds and diphenylmethane diisocyanate compounds.
Examples of the toluene diisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate, and a mixture thereof.
Examples of the diphenylmethane diisocyanate compound include 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), and a mixture thereof. ..

The peripheral sealant preferably contains a tackifier resin for the purpose of further improving the adhesiveness.
Examples of the tackifier resin include terpene resin, modified terpene resin, kumaron resin, inden resin, petroleum resin and the like.
Examples of the modified terpene resin include hydrogenated terpene resin, terpene phenol copolymer resin, aromatic modified terpene resin and the like.
Examples of the petroleum resin include aliphatic petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymerized petroleum resins, alicyclic petroleum resins, and dicyclopentadiene petroleum. Examples thereof include resins and hydrides thereof.
Among them, the tackifier resin is a terpene resin, an aromatic-modified terpene resin, a terpene phenol copolymer resin, a hydrocarbon alicyclic petroleum resin, from the viewpoints of adhesiveness, moisture permeability resistance, compatibility, etc. of the resin composition. , Aromatic petroleum resins, aliphatic aromatic copolymerized petroleum resins, alicyclic petroleum resins are preferred, alicyclic petroleum resins are more preferred, alicyclic saturated hydrocarbon resins, alicyclic unsaturated hydrocarbons. Hydrogen resins are more preferred, and cyclohexyl ring-containing saturated hydrocarbon resins and dicyclopentadiene-modified hydrocarbon resins are particularly preferred.
These tackifier resins may be used alone or in combination of two or more.

The content of the tackifier resin is preferably 0.01 parts by weight and a preferable upper limit is 100 parts by weight with respect to 100 parts by weight of the total of the polyolefin and the curable resin A. When the content of the tackifier resin is in this range, the effect of improving the adhesiveness can be further exhibited while maintaining the moisture permeation prevention property. The more preferable lower limit of the content of the tackifier resin is 0.2 parts by weight, and the more preferable upper limit is 20 parts by weight.

The peripheral sealant contains a polymerization initiator and / or a thermosetting agent.
The peripheral sealant preferably contains at least one selected from the group consisting of a radical polymerization initiator, a cationic polymerization initiator, and a thermosetting agent.

Examples of the radical polymerization initiator include a photoradical polymerization initiator and a thermal radical polymerization initiator.

Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds and the like.
Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, and 1,2- (dimethylamino). -2-((4-Methylphenyl) Methyl) -1- (4- (4-morpholinyl) phenyl) -1-butanone, 2,2-dimethoxy-2-phenylacetophenone, bis (2,4,6-trimethyl) Phenyl) Phenylphosphinoxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1-(4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2- Methyl-1-propane-1-one, 1- (4- (phenylthio) phenyl) -1,2-octanedione 2- (O-benzoyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoinmethyl Examples thereof include ether, benzoin ethyl ether, benzoin isopropyl ether and the like.

Examples of the thermal radical polymerization initiator include azo compounds and organic peroxides.
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, peroxydicarbonate and the like.

Commercially available thermal radical polymerization initiators include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 (all of which are Fujifilm Wako Pure Chemical Industries, Ltd.). Made) and the like.

Examples of the cationic polymerization initiator include a photocationic polymerization initiator and a thermal cationic polymerization initiator.

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

The anionic portion of the ionic photoacid generator type cationic photopolymerization initiator, for _{^{example, BF 4 -, PF 6 -}} , SbF 6 -, or, _(BX 4) ^- (where, X is at least two (Representing a phenyl group substituted with a fluorine or trifluoromethyl group) and the like.
Examples of the ionic photoacid generation type photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, and aromatic ammonium salts, which have the anion moiety. Examples thereof include pentadiene-1-yl) ((1-methylethyl) benzene) -Fe salt and the like.

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 hexa Fluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, triarylsulfonium tetrakis (pentafluorophenyl) borate, bis (4- (di (4- (2-hydroxyethoxy)) phenyl) Sulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluoroantimonate, bis (4- (di (4- (4- (2-hydroxyethoxy))) 2-Hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, tris (4- (4-Acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like can be mentioned.

Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, and bis. (Dodecylphenyl) Iodineium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4-( 1-Methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate and the like can be mentioned.

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

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

Examples of the (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene. ) -Fe (II) hexafluorophosphate, (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimonate, (2,4-cyclopentadiene-1) -Il) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrakis (penta) Fluorophenyl) Borate and the like can be mentioned.

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

Commercially available photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd., a photocationic polymerization initiator manufactured by Union Carbide, and a photocationic polymerization initiator manufactured by DEKA. Examples thereof include a photocationic polymerization initiator manufactured by BASF, a photocationic polymerization initiator manufactured by Rhodia, and the like.
Examples of the photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd. include DTS-200 and the like.
Examples of the photocationic polymerization initiator manufactured by Union Carbide include UVI6990 and UVI6974.
Examples of the photocationic polymerization initiator manufactured by ADEKA include SP-150 and SP-170.
Examples of the photocationic polymerization initiator manufactured by 3M include FC-508 and FC-512.
Examples of the photocationic polymerization initiator manufactured by BASF include IRGACURE261 and IRGACURE290.
Examples of the photocationic polymerization initiator manufactured by Rhodia include PI2074 and the like.

As the thermal cationic polymerization initiator, the anionic portion is _{^{BF 4 -, PF 6 -,}} SbF 6 -, or, _(BX 4) ^- (where, X is substituted by at least two fluorine or trifluoromethyl group Examples thereof include a sulfonium salt, a phosphonium salt, an ammonium salt, etc., which are composed of (representing a phenyl group). Of these, sulfonium salts and ammonium salts are preferable.

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

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

Examples of the ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, and dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl). Borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyl Dibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium hexafluoroantimonate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethyl) Benzyl) 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 can be mentioned.

Examples of commercially available thermal cationic polymerization initiators include thermal cationic polymerization initiators manufactured by Sanshin Chemical Industry Co., Ltd., 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 CXC-1612, CXC-1821 and the like.

The content of the polymerization initiator has a preferable lower limit of 0.05 parts by weight and a preferable upper limit of 10 parts by weight with respect to a total of 100 parts by weight of the polyolefin and the curable resin A. When the content of the polymerization initiator is 0.05 parts by weight or more, the obtained peripheral encapsulant becomes more excellent in curability. When the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the obtained peripheral encapsulant does not become too fast, the workability is improved, and the cured product can be made more uniform. can. The more preferable lower limit of the content of the polymerization initiator is 1 part by weight, and the more preferable upper limit is 3 parts by weight.

Examples of the thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, and addition products of various amines and epoxy resins.

Examples of the hydrazide compound include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydrandin, 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, and 2,4-diamino-6- (2'-methylimidazole-). (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.
Examples of the acid anhydride include tetrahydrophthalic anhydride, ethylene glycol bis (anhydrotrimeritate) and the like.
These thermosetting agents may be used alone or in combination of two or more.

Commercially available thermosetting agents include, for example, SDH (manufactured by Japan Finechem), ADH (manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, and Amicure UDH (all manufactured by Ajinomoto Fine-Techno). ) Etc. can be mentioned.

The content of the thermosetting agent is preferably 0.01 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the total of the polyolefin and the curable resin A. When the content of the thermosetting agent is 0.01 parts by weight or more, the obtained peripheral encapsulant becomes more excellent in thermosetting property. When the content of the thermosetting agent is 10 parts by weight or less, the obtained peripheral encapsulant becomes more excellent in storage stability. The more preferable lower limit of the content of the thermosetting agent is 0.5 parts by weight, the more preferable upper limit is 5 parts by weight, the further preferable lower limit is 1 part by weight, and the further preferable upper limit is 3 parts by weight.

The peripheral sealant preferably contains a water-absorbent filler. By containing the water-absorbent filler, the peripheral sealant becomes more excellent in the moisture permeation prevention property of the cured product.

Examples of the water-absorbent filler include oxides of alkaline earth metals, magnesium oxide, molecular sieves and the like.
Examples of the oxide of the alkaline earth metal include calcium oxide, strontium oxide, barium oxide and the like.
Of these, oxides of alkaline earth metals are preferable, and calcium oxide is more preferable, from the viewpoint of water absorption.
These water-absorbent fillers may be used alone or in combination of two or more.

The content of the water-absorbent filler is preferably 10 parts by weight and a preferable upper limit of 500 parts by weight with respect to 100 parts by weight of the total of the polyolefin and the curable resin A. When the content of the water-absorbent filler is in this range, the obtained peripheral encapsulant suppresses panel peeling, and the cured product has more excellent moisture permeation prevention property. The more preferable lower limit of the content of the water-absorbent filler is 20 parts by weight, and the more preferable upper limit is 150 parts by weight.

The peripheral encapsulant may contain other fillers in addition to the water-absorbent filler for the purpose of improving adhesiveness and the like, as long as the object of the present invention is not impaired.
As the above-mentioned other filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, and alumina.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like. Of these, talc is preferred.
These other fillers may be used alone or in combination of two or more.

The peripheral sealant 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 peripheral encapsulant.

Examples of the sensitizer include anthracene compounds, thioxanthone compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, and methyl o-benzoylbenzoate. Examples thereof include 4,4'-bis (dimethylamino) benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and the like.
Examples of the anthracene-based compound include 9,10-dibutoxyanthracene and the like.
Examples of the thioxanthone-based compound include 2,4-diethylthioxanthone and the like.
These sensitizers may be used alone or in combination of two or more.

The content of the sensitizer is preferably 0.05 parts by weight and a preferable upper limit is 3 parts by weight with respect to 100 parts by weight of the total of the polyolefin and the curable resin A. When the content of the sensitizer is 0.05 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 more preferable lower limit of the content of the sensitizer is 0.1 parts by weight, and the more preferable upper limit is 1 part by weight.

The peripheral sealant may contain a stabilizer. By containing the stabilizer, the peripheral sealant becomes more excellent in storage stability.

Examples of the stabilizer include aromatic amine compounds, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl and the like.
Examples of the aromatic amine compound include benzylamine and aminophenol type epoxy resins.
Of these, aromatic amine compounds are preferable, and benzylamine is more preferable.
These stabilizers may be used alone or in combination of two or more.

The content of the stabilizer is preferably 0.001 part by weight and a preferable upper limit of 2 parts by weight with respect to 100 parts by weight of the total of the polyolefin and the curable resin A. When the content of the stabilizer is in this range, the obtained peripheral encapsulant becomes more excellent in storage stability while maintaining excellent curability. The more preferable lower limit of the content of the stabilizer is 0.005 parts by weight, and the more preferable upper limit is 1 part by weight.

The peripheral sealant may contain a silane coupling agent. The silane coupling agent has a role of improving the adhesiveness between the peripheral sealant and the substrate or the like.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane and the like.
These silane coupling agents may be used alone or in combination of two or more.

Regarding the content of the silane coupling agent, the preferable lower limit is 0.1 part by weight and the preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the total of the polyolefin and the curable resin A. When the content of the silane coupling agent is in this range, the effect of improving the adhesiveness of the obtained peripheral encapsulant while preventing the bleed-out of the excess silane coupling agent becomes more excellent. 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 is 5 parts by weight.

The peripheral encapsulant may contain a surface modifier as long as the object of the present invention is not impaired. By containing the surface modifier, the flatness of the coating film of the peripheral sealant can be improved.
Examples of the surface modifier include a surfactant, a leveling agent and the like.

Examples of the surface modifier include silicone-based, acrylic-based, and fluorine-based agents.
Among the above surface modifiers, commercially available ones include, for example, a surface modifier manufactured by Big Chemie Japan, a surface modifier manufactured by Kusumoto Kasei Co., Ltd., and a surface modifier manufactured by AGC Seimi Chemical Co., Ltd. Can be mentioned.
Examples of the surface modifier manufactured by Big Chemie Japan Co., Ltd. include BYK-300, BYK-302, BYK-331 and the like.
Examples of the surface modifier manufactured by Kusumoto Kasei Co., Ltd. include UVX-272 and the like.
Examples of the surface modifier manufactured by AGC Seimi Chemical Co., Ltd. include Surflon S-611 and the like.

The peripheral encapsulant may contain a compound that reacts with the acid generated in the peripheral encapsulant and / or an ion exchange resin as long as the object of the present invention is not impaired.

Examples of the compound that reacts with the generated acid include substances that neutralize the acid, such as alkali metal carbonate or hydrogen carbonate, or alkaline earth metal carbonate or hydrogen carbonate. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like are used.

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

The peripheral encapsulant is known as a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber, an antioxidant and the like, as needed, as long as the object of the present invention is not impaired. Various additives may be contained.

The peripheral encapsulant preferably does not contain a solvent from the viewpoint of further suppressing the generation of outgas. The peripheral sealant can be excellent in coatability even if it does not contain a solvent.
In the present specification, "solvent-free" means that the solvent content is less than 1000 ppm.

As a method for producing the peripheral encapsulant, for example, a polyolefin, a curable resin A, a polymerization initiator and / or a thermosetting agent, a water-absorbent filler and, if necessary, are added using a mixer. Examples thereof include a method of mixing with an additive such as a silane coupling agent.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.

(In-plane sealant)
The in-plane encapsulant contains a curable resin B.
The curable resin B contains an epoxy compound represented by the above formula (1) and an oxetane compound represented by the above formula (2). By containing the epoxy compound represented by the above formula (1) and the oxetane compound represented by the above formula (2), the obtained in-plane encapsulant becomes excellent in coatability and low outgassing property.

The lower limit of the content of the epoxy compound represented by the above formula (1) in 100 parts by weight of the curable resin B is 10 parts by weight, and the upper limit is 90 parts by weight. When the content of the epoxy compound represented by the above formula (1) is in this range, the obtained in-plane encapsulant is more excellent in coatability and low outgassing property. The preferable lower limit of the content of the epoxy compound represented by the above formula (1) is 50 parts by weight, the preferable upper limit is 85 parts by weight, the more preferable lower limit is 60 parts by weight, and the more preferable upper limit is 80 parts by weight.

The lower limit of the content of the oxetane compound represented by the above formula (2) in 100 parts by weight of the curable resin B is 10 parts by weight, and the upper limit is 90 parts by weight. When the content of the oxetane compound represented by the above formula (2) is in this range, the obtained in-plane encapsulant is more excellent in coatability and low outgassing property. The preferable lower limit of the content of the oxetane compound represented by the above formula (2) is 15 parts by weight, the preferable upper limit is 50 parts by weight, the more preferable lower limit is 20 parts by weight, and the more preferable upper limit is 40 parts by weight.

The curable resin B may contain other curable resin for the purpose of improving the adhesiveness of the obtained in-plane encapsulant.
Examples of the other curable resin include other epoxy compounds other than the epoxy compound represented by the above formula (1), other oxetane compounds other than the oxetane compound represented by the above formula (2), vinyl ether compounds and the like. Can be mentioned.

Examples of the other epoxy compounds include 3,4-epoxycyclohexylmethyl (meth) acrylate, 1,2: 8,9-diepoxylimonene, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, and methylated vinylcyclohexene. Dioxide, bis (3,4-epoxycyclohexylmethyl) ether, 3,4,3', 4'-diepoxycyclohexyl, bis (3,4-epoxycyclohexyl) adipate, bis (2,3-epoxycyclopentyl) Ether, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentadiendioxide, dicyclopentadiene dimethanol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A di Examples thereof include glycidyl ether and hydrogenated bisphenol F diglycidyl ether.

Examples of the other oxetane compounds include 4,4'-bis ((3-ethyl-3-oxetanyl) methoxymethyl) biphenyl, phenoxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, and 3-ethyl-3. -(Phenoxymethyl) oxetane, 3-ethyl-3-((2-ethylhexyloxy) methyl) oxetane, 3-ethyl-3-((3- (triethoxysilyl) propoxy) methyl) oxetane, oxetanylsilsesquioxane , Phenol novolak oxetane, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene and the like.

Examples of the vinyl ether compound include benzyl vinyl ether, cyclohexanedimethanol monovinyl ether, dicyclopentadienvinyl ether, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and dipropylene glycol. Examples thereof include divinyl ether and tripropylene glycol divinyl ether.

The in-plane encapsulant contains a cationic polymerization initiator.
As the cationic polymerization initiator used in the in-plane encapsulant, the same ones as those mentioned in the peripheral encapsulant can be used.

The content of the cationic polymerization initiator has a preferable lower limit of 0.05 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin B. When the content of the cationic polymerization initiator is in this range, the obtained in-plane encapsulant becomes more excellent in curability and storage stability. The more preferable lower limit of the content of the cationic polymerization initiator is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.

The in-plane encapsulant may contain a sensitizer. The sensitizer has a role of further improving the polymerization initiation efficiency of the photocationic polymerization initiator and further promoting the curing reaction of the in-plane encapsulant.
As the sensitizer used in the in-plane encapsulant, the same sensitizer as those mentioned in the peripheral encapsulant can be used.

The content of the sensitizer is preferably 0.05 parts by weight and a preferable upper limit of 3 parts by weight with respect to 100 parts by weight of the curable resin B. When the content of the sensitizer is 0.05 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 more preferable lower limit of the content of the sensitizer is 0.1 parts by weight, and the more preferable upper limit is 1 part by weight.

The in-plane encapsulant may contain a thermosetting agent.
As the thermosetting agent used for the in-plane encapsulant, the same thermosetting agents as those mentioned in the peripheral encapsulant can be used.

Regarding the content of the thermosetting agent, the preferable lower limit is 0.5 parts by weight and the preferable upper limit is 30 parts by weight with respect to 100 parts by weight of the curable resin B. When the content of the thermosetting agent is 0.5 parts by weight or more, the obtained in-plane encapsulant becomes more excellent in thermosetting property. When the content of the thermosetting agent is 30 parts by weight or less, the obtained in-plane encapsulant becomes more excellent in storage stability. The more preferable lower limit of the content of the thermosetting agent is 1 part by weight, and the more preferable upper limit is 15 parts by weight.

The in-plane encapsulant contains a stabilizer.
Examples of the stabilizer include aromatic amine compounds, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl and the like.
Examples of the aromatic amine compound include benzylamine and aminophenol type epoxy resins.
Of these, aromatic amine compounds are preferable, and benzylamine is more preferable.
These stabilizers may be used alone or in combination of two or more.

The content of the stabilizer is 0.001 part by weight at the lower limit and 5 parts by weight at the upper limit with respect to 100 parts by weight of the curable resin B. When the content of the stabilizer is in this range, the obtained in-plane encapsulant has excellent storage stability while maintaining excellent curability. The preferable lower limit of the content of the stabilizer is 0.01 parts by weight, the preferable upper limit is 3 parts by weight, and the more preferable lower limit is 0.05 parts by weight.

The in-plane encapsulant may contain a filler for the purpose of improving adhesiveness and the like, as long as the object of the present invention is not impaired.
As the filler that may be contained in the in-plane encapsulant, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, and alumina.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like.

Regarding the content of the filler, the preferable lower limit is 10 parts by weight and the preferable upper limit is 100 parts by weight with respect to 100 parts by weight of the curable resin B. When the content of the filler is in this range, the effect of improving the adhesiveness of the obtained in-plane encapsulant while maintaining the excellent coatability becomes more excellent.

The in-plane encapsulant may contain a silane coupling agent. The silane coupling agent has a role of improving the adhesiveness between the in-plane encapsulant and a substrate or the like.
As the silane coupling agent used in the in-plane encapsulant, the same silane coupling agent as those mentioned in the peripheral encapsulant can be used.

Regarding the content of the silane coupling agent, the preferable lower limit is 0.1 part by weight and the preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the curable resin B. When the content of the silane coupling agent is in this range, the effect of improving the adhesiveness of the obtained in-plane encapsulant while preventing the bleed-out of the excess silane coupling agent becomes more excellent. 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 is 5 parts by weight.

The in-plane encapsulant may contain a surface modifier as long as the object of the present invention is not impaired. By containing the surface modifier, the flatness of the coating film of the in-plane encapsulant can be improved.
As the surface modifier used in the in-plane encapsulant, the same surface modifiers as those mentioned in the peripheral encapsulant can be used.

The in-plane encapsulant for an organic EL display element of the present invention was generated in the in-plane encapsulant for an organic EL display element in order to improve the durability of the element electrode without impairing the object of the present invention. It may contain a compound that reacts with an acid and / or an ion exchange resin.
As the compound that reacts with the generated acid and the ion exchange resin used in the in-plane encapsulant, the same compounds as those mentioned in the peripheral encapsulant can be used.

Further, the above-mentioned in-plane encapsulant may be a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber, an antioxidant, etc., as necessary, as long as the object of the present invention is not impaired. It may contain various known additives of the above.

The in-plane encapsulant preferably does not contain a solvent from the viewpoint of further suppressing the generation of outgas. The in-plane encapsulant can be excellent in coatability even if it does not contain the solvent.

As a method for producing the in-plane encapsulant, a method of mixing the curable resin B, a cationic polymerization initiator, and an additive such as a silane coupling agent to be added as needed, using a mixer. And so on.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.

The in-plane encapsulant has a preferable lower limit of 50 mPa · s and a preferable upper limit of 150 mPa · s as measured under the conditions of 25 ° C. and 20 rpm using an E-type viscometer. When the viscosity of the in-plane encapsulant is in this range, the applicability is improved. The more preferable lower limit of the viscosity of the in-plane encapsulant is 60 mPa · s, and the more preferable upper limit is 140 mPa · s.
Examples of the E-type viscometer include VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) and the like.

The in-plane encapsulant has a preferable lower limit of surface tension of 15 mN / m and a preferable upper limit of 45 mN / m. When the surface tension of the in-plane sealant is within this range, the coatability is improved. The more preferable lower limit of the surface tension of the in-plane encapsulant is 20 mN / m, and the more preferable upper limit is 35 mN / m.
In the present specification, the surface tension is a value measured by a dynamic wettability tester at 25 ° C.

(Organic EL display element)
An organic EL display element having a cured product of the peripheral sealant and a cured product of the in-plane sealant in the sealant set for an organic EL display element of the present invention is also one of the present inventions.

In the organic EL display element of the present invention, the cured product of the peripheral sealant is used for the sealing wall surrounding the peripheral portion of the organic EL display element.
The thickness of the sealing wall made of the cured product of the peripheral sealing agent is preferably 5 mm or less from the viewpoint of securing a wide display area of the obtained organic EL display element.

The organic EL display element of the present invention preferably has a display area having a diagonal size of 40 inches or more and 60 inches or less.

According to the present invention, it is possible to provide a sealant set for an organic EL display element capable of obtaining an organic EL display element having excellent display performance. Further, according to the present invention, it is possible to provide an organic EL display element having a cured product of the sealant set for the organic EL display element.

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

(Examples 1 to 14, Comparative Examples 1 to 16)
According to the compounding ratios shown in Tables 1 to 4, each material was stirred and mixed at a stirring and mixing machine at a stirring speed of 2000 rpm for 3 minutes, and then kneaded with three rolls to prepare a peripheral encapsulant.
Further, according to the compounding ratios shown in Tables 1 to 4, each material was stirred and mixed for 3 minutes at a stirring speed of 2000 rpm using a stirring mixer to prepare an in-plane encapsulant.
AR-250 (manufactured by Shinky Co., Ltd.) was used as the stirring mixer, and NR-42A (manufactured by Noritake Co., Ltd.) was used as the three rolls.
The calcium oxide used in the above examples was pulverized in a dry batch by a ball mill (“ANZ-53D” manufactured by Nikko Kagaku Co., Ltd.) so that the particle size was 10 μm or less.
The obtained peripheral encapsulants and in-plane encapsulants are combined as shown in Tables 1 to 4, and the encapsulants for organic EL display elements of Examples 1 to 14 and Comparative Examples 1 to 16 are combined. Got a set.

<Evaluation>
The following evaluations were performed on each of the encapsulant sets for organic EL display elements obtained in Examples and Comparative Examples. The results are shown in Tables 1 to 4.

(1) Evaluation of Peripheral Encapsulant (1-1) Adhesiveness To 10 g of each peripheral encapsulant according to Examples and Comparative Examples, 0.03 g of spacer particles having a diameter of 10 μm was added, and a stirring mixer was used. It was evenly dispersed. As the spacer particles, Micropearl SP-210 (manufactured by Sekisui Chemical Co., Ltd.) was used, and as the stirring mixer, AR-250 (manufactured by Shinky Co., Ltd.) was used. After applying the peripheral encapsulant in which the spacer particles were dispersed on the glass substrate A, the glass substrate B was attached and pressed to make the thickness uniform. The glass substrate A has a length of 50 mm, a width of 25 mm, and a thickness of 0.7 mm, and the surface of the glass is washed with acetone and then dried. The glass substrate B has a length of 5 mm, a width of 5 mm, and a thickness. A 0.7 mm glass was dipped in acetone, washed, and then dried. Next, the glass substrate A and the glass substrate B were adhered by curing the peripheral sealant. The peripheral encapsulants according to Examples 1 to 7 and Comparative Examples 1 to 8 were cured by heating at 100 ° C. for 30 minutes. The peripheral encapsulants according to Examples 8 to 14 and Comparative Examples 9 to 16 were cured by irradiating them with ^{ultraviolet rays having a wavelength of 365 nm at 3000 mJ / cm 2 with a UV-LED irradiator.}
The shearing adhesive force between the glass substrate A and the glass substrate B was measured with a die shear tester at 23 ° C. and a shear rate of 200 μm / sec. As the die share tester, a bond tester 4000 (manufactured by Daige Co., Ltd.) was used.
The adhesiveness was evaluated as "◯" when the shear adhesive force was 200 N or more, "Δ" when it was less than 200 N and 100 N or more, and "x" when it was less than 100 N.

(1-2) Moisture Permeability Prevention The following Ca-TEST was performed on each peripheral encapsulant according to Examples and Comparative Examples.
First, 0.03 g of spacer particles having a diameter of 10 μm was added to 10 g of each peripheral encapsulant obtained in Examples and Comparative Examples, and the particles were uniformly dispersed using a stirring mixer. As the spacer particles, Micropearl SP-210 (manufactured by Sekisui Chemical Co., Ltd.) was used, and as the stirring mixer, AR-250 (manufactured by Shinky Co., Ltd.) was used. Next, a peripheral sealant in which spacer particles were dispersed was applied to the surface of the glass substrate.
Next, another glass substrate having a size of 30 mm × 30 mm was covered with a mask having a plurality of openings of 2 mm × 2 mm, and Ca was vapor-deposited by a vacuum vapor deposition machine. The conditions for vapor deposition were such that the inside of the vapor deposition device of the vacuum vapor deposition apparatus ^{was depressurized to 2 × 10 -3} Pa to form 2000 Å of Ca at a vapor deposition rate of 5.0 Å / s. The glass substrate on which Ca is vapor-deposited is moved into a glove box controlled to a dew point (-60 ° C or higher), and the glass substrate on which the peripheral sealant is applied on the surface and the glass substrate on which Ca is vapor-deposited are peripherally sealed. The agents were bonded so that they were on the Ca vapor deposition pattern. At this time, the vapor-deposited Ca was aligned and bonded at positions 2 mm, 4 mm, and 6 mm from the end face of the glass substrate. After pressurizing to make the thickness of the peripheral encapsulant layer uniform, the peripheral encapsulant was cured to prepare a Ca-TEST substrate. The peripheral encapsulants according to Examples 1 to 7 and Comparative Examples 1 to 8 were cured by heating at 100 ° C. for 30 minutes. The peripheral encapsulants according to Examples 8 to 14 and Comparative Examples 9 to 16 were cured by irradiating them with ^{ultraviolet rays having a wavelength of 365 nm at 3000 mJ / cm 2 with a UV-LED irradiator.}
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 moisture from the end face of the glass substrate into the layer composed of the cured product of the peripheral encapsulant was determined by Ca. Observed from the disappearance of.
As a result, the case where the time required for the water infiltration distance to reach 6 mm was 1000 hours or more was "○", the case where it was 500 hours or more and less than 1000 hours was "△", and the case where it was less than 500 hours. The moisture permeation prevention property was evaluated as "x".

(2) Evaluation of in-plane encapsulant (2-1) Applicability 0.1 mL of each in-plane encapsulant according to Examples and Comparative Examples was applied onto a glass substrate using a pipette and spread after 1 minute. The diameter was measured.
The coatability was evaluated as "◯" when the diameter was 12 mm or more, "Δ" when the diameter was 10 mm or more and less than 12 mm, and "x" when the diameter was less than 10 mm.

(2-2) Storage stability When each in-plane encapsulant according to Examples and Comparative Examples was stored at 25 ° C. at 25 ° C. for the initial viscosity immediately after production and at 25 ° C. for 1 week. Viscosity and was measured. (Viscosity after storage at 25 ° C. for 1 week) / (Initial viscosity) was defined as the viscosity change rate, and when the viscosity change rate was less than 2.0, it was "○", and it was 2.0 or more and less than 4.0. The storage stability was evaluated by setting the case as "Δ" and the case of 4.0 or more as "x".
As the E-type viscometer, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) was used.

(2-3) Low outgassing After weighing and enclosing 300 mg of each in-plane encapsulant according to Examples and Comparative Examples in a vial (22 mL glass vial, manufactured by GL Sciences, “22-CV”). , It was cured by heating at 100 ° C. for 30 minutes. Further, 300 mg was weighed and sealed in this vial, and then cured by heating at 100 ° C. for 30 minutes, and the vaporized components in the vial were measured under the following conditions using a gas chromatograph mass spectrometer.
<GC / MS measurement conditions>
Headspace device: TurboMatrix40 (manufactured by PerkinElmer)
Sample amount: Approximately 300 mg Precision scale Heating conditions: 100 ° C, 30 min
Needle transfer temperature: 180 ° C
Lottery temperature: 250 ° C
GC / MS device: JMS-Q1050GC (manufactured by JEOL Ltd.)
GC column: SLBTM-5ms (slight polarity) 0.25mm x 30m x 0.25μm
Equipment: JMS-Q1500GC (manufactured by JEOL Ltd.)
GC temperature rise: 40 ° C (4 min) → 10 ° C / min → 260 ° C (2 min)
Split: 1:50 (injection 0.05 min)
He flow rate: 1.0 mL / min
MS measurement range: 29 to 600
Ionization voltage: 70eV
MS temperature: Ion source 230 ° C, interface 250 ° C
When the amount of the vaporized component was less than 300 ppm, it was evaluated as “◯”, when it was 300 ppm or more and less than 1000 ppm, it was evaluated as “Δ”, and when it was 1000 ppm or more, it was evaluated as “×”.

(3) Display performance of organic EL display element (manufacturing of a substrate on which a laminate having an organic light emitting material layer is arranged)
A substrate was formed by forming an ITO electrode on a glass having a length of 45 mm, a width of 45 mm, and a thickness of 0.7 mm so as to have a thickness of 1000 Å. The substrate is ultrasonically washed with acetone, an alkaline aqueous solution, ion-exchanged water, and isopropyl alcohol for 15 minutes each, then washed with boiled isopropyl alcohol for 10 minutes, and then immediately treated with a UV-ozone cleaner. went. As the UV-ozone cleaner, NL-UV253 (manufactured by Nippon Laser Electronics Co., Ltd.) was used.
Next, the substrate after the previous treatment is fixed to the substrate holder of the vacuum vapor deposition apparatus, and 200 mg of N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (α-NPD) is put into the unglazed crucible. , 200 mg of tris (8-quinolinolato) aluminum (Alq ₃ ) was placed in another unglazed crucible, and the pressure inside the vacuum chamber was reduced to ^{1 × 10 -4 Pa.} Then, the crucible containing α-NPD was heated, α-NPD was deposited on the substrate at a vapor deposition rate of 15 Å / s, and a hole transport layer having a film thickness of 600 Å was formed. Next, _{the crucible containing Alq 3} was heated to form an organic light emitting material layer having a film thickness of 600 Å at a vapor deposition rate of 15 Å / s. After that, the substrate on which the hole transport layer and the organic light emitting material layer were formed was transferred to another vacuum vapor deposition apparatus having a tungsten resistance heating boat, and lithium fluoride was transferred to one of the tungsten resistance heating boats in the vacuum vapor deposition apparatus. 200 mg was placed and 1.0 g of aluminum wire was placed in another tungsten resistance heating boat. Then, the inside of the vapor deposition device of the vacuum vapor deposition apparatus is ^{depressurized to 2 × 10 -4} Pa to form 5 Å of lithium fluoride at a vapor deposition rate of 0.2 Å / s, and then 1000 Å of aluminum at a rate of 20 Å / s. bottom. The inside of the vapor deposition apparatus 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.

(Manufacturing of organic EL display element)
Peripheral encapsulant is applied to the peripheral edge of the substrate on which the laminate is placed so that the line width (thickness of the encapsulation wall after curing) is 5 mm, and the in-plane encapsulant is applied to the inside of the laminate. After applying so as to cover the whole, glass having a length of 45 mm, a width of 45 mm, and a thickness of 0.7 mm was laminated. After that, an ultraviolet ray having a wavelength of 365 nm is irradiated at 3000 mJ / cm ² using a UV-LED irradiation device, and further heated at 100 ° C. for 30 minutes to cure the peripheral sealant and the in-plane sealant to cure the organic EL display element. Was produced.

(Light emission state of organic EL display element)
After exposing the obtained organic EL display element to an environment of 85 ° C. and 85% RH for 1000 hours, a voltage of 10 V is applied to check the light emission state (presence / absence of dark spots and pixel peripheral quenching) of the organic EL display element. It was visually observed. Organic EL display as "○" when light is emitted uniformly without dark spots or peripheral quenching, "△" when slight dark spots or peripheral quenching is observed, and "×" when the non-light emitting part is significantly enlarged. The display performance of the element was evaluated.

According to the present invention, it is possible to provide a sealant set for an organic EL display element capable of obtaining an organic EL display element having excellent display performance. Further, according to the present invention, it is possible to provide an organic EL display element having a cured product of the sealant set for the organic EL display element.

Claims (8)

A combination of a peripheral sealant that surrounds and seals the peripheral edge of the organic EL display element and an in-plane sealant that coats and seals a laminate having an organic light emitting material layer inside the peripheral sealant. It is a sealant set for organic EL display elements.
The peripheral sealant contains a polyolefin, a curable resin A, a polymerization initiator and / or a thermosetting agent, and contains the polyolefin.
The in-plane encapsulant contains a curable resin B, a cationic polymerization initiator, and a stabilizer.
The curable resin B contains an epoxy compound represented by the following formula (1) and an oxetane compound represented by the following formula (2).
The content of the epoxy compound represented by the following formula (1) in 100 parts by weight of the curable resin B is 10 parts by weight or more and 90 parts by weight or less, and the oxetane compound represented by the following formula (2). The content is 10 parts by weight or more and 90 parts by weight or less.
A sealant set for an organic EL display element, wherein the content of the stabilizer is 0.001 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the curable resin B.

In formula (1), X is a linear or branched hydrocarbon having 1 to 6 carbon atoms which may be interrupted or directly connected at −C (= O) O− or −C (= O) −. Represents a group or a bond.

The sealant set for an organic EL display element according to claim 1, wherein the polyolefin contains at least one selected from the group consisting of polyisobutylene, polybutene, and polybutadiene. The sealant for an organic EL display element according to claim 1 or 2, wherein the curable resin A contains at least one selected from the group consisting of an epoxy compound, an oxetane compound, a (meth) acrylic compound, and a urethane compound. set. The seal for an organic EL display element according to claim 1, 2 or 3, wherein the peripheral sealant contains at least one selected from the group consisting of a radical polymerization initiator, a cationic polymerization initiator, and a thermosetting agent. Initiator set. The sealant set for an organic EL display element according to claim 1, 2, 3 or 4, wherein the in-plane sealant contains a filler. An organic EL display element having a cured product of the peripheral sealant and a cured product of the in-plane sealant in the sealant set for an organic EL display element according to claim 1, 2, 3, 4 or 5. The organic EL display element according to claim 6, wherein the cured product of the peripheral sealant is used for a sealing wall surrounding the peripheral edge of the organic EL display element, and the sealing wall has a thickness of 5 mm or less. The organic EL display element according to claim 6 or 7, wherein the size of the display area is diagonally 40 inches or more and 60 inches or less.