阅读说明：本技术 有机el显示元件用密封剂 (Sealing agent for organic EL display element ) 是由 渡边康雄 于 2019-04-15 设计创作，主要内容包括：本发明的目的在于,提供涂布性、快速固化性、低脱气性及保存稳定性优异、且能够获得显示性能优异的有机EL显示元件的有机EL显示元件用密封剂。本发明为有机EL显示元件用密封剂,其含有固化性树脂和热阳离子聚合引发剂,上述固化性树脂含有脂环式环氧化合物和氧杂环丁烷化合物,关于所述有机EL显示元件用密封剂,在差示扫描量热测定中以40℃/分种的升温速度进行升温,并以100℃进行保持时,从以100℃进行保持开始至发热峰起峰为止的时间为3分钟以下,并且在40℃、22.5％RH的环境下保存4天后的增粘率为20％以下。(The purpose of the present invention is to provide a sealing agent for an organic EL display element, which has excellent coatability, rapid curability, low outgassing properties, and storage stability, and which can provide an organic EL display element having excellent display performance. The present invention is a sealant for an organic EL display element, which contains a curable resin containing an alicyclic epoxy compound and an oxetane compound and a thermal cationic polymerization initiator, wherein the sealant for an organic EL display element has a thickening ratio of 20% or less after being stored for 4 days in an environment of 40 ℃ and 22.5% RH, and the time from the start of the holding at 100 ℃ to the start of the peak of the heat generation is 3 minutes or less when the temperature is raised at a temperature rise rate of 40 ℃/min and the temperature is maintained at 100 ℃ in a differential scanning calorimetry.)

1. A sealing agent for an organic EL display element, characterized by comprising a curable resin and a thermal cationic polymerization initiator,

the curable resin contains an alicyclic epoxy compound and an oxetane compound,

the sealing agent for an organic EL display element has a time from the start of holding at 100 ℃ to the start of the peak of heat generation when the temperature is raised at a temperature rise rate of 40 ℃/min and held at 100 ℃ in a differential scanning calorimetry measurement, and a thickening ratio after being stored for 4 days in an environment of 40 ℃ and 22.5% RH, of 20% or less.

2. The sealant for an organic EL display element according to claim 1, wherein the alicyclic epoxy compound comprises 3, 4-epoxycyclohexylmethyl (meth) acrylate.

3. The sealant for an organic EL display element according to claim 1 or 2, wherein the oxetane compound comprises at least any one of 4, 4' -bis ((3-ethyl-3-oxetanyl) methoxymethyl) biphenyl and 3-ethyl-3- (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane.

4. The sealant for an organic EL display element according to claim 1, 2 or 3, wherein a content ratio of the alicyclic epoxy compound in the total of the alicyclic epoxy compound and the oxetane compound is 20% by weight or more and 80% by weight or less.

5. The sealant for an organic EL display element according to claim 1, 2, 3 or 4, wherein the thermal cationic polymerization initiator is a quaternary ammonium salt whose counter anion is a borate system.

Technical Field

The present invention relates to a sealing agent for an organic EL display element, which has excellent coatability, rapid curability, low outgassing property, and storage stability, and can provide an organic EL display element having excellent display performance.

Background

An organic electroluminescent 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 from one electrode into the organic light emitting material layer, and holes are injected from the other electrode into the organic light emitting material layer, whereby the electrons and the holes are combined in the organic light emitting material layer to emit light. Compared with a liquid crystal display element or the like which requires a backlight, the following advantages are provided: the device has good visibility, can be further thinned, and can be driven by DC low voltage.

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, the light emitting characteristics thereof are rapidly deteriorated and the lifetime thereof is shortened. Therefore, in order to improve the stability and durability of the organic EL display element, a sealing technique for isolating the organic light emitting material layer and the electrode from moisture and oxygen in the atmosphere is indispensable for the organic EL display element.

Patent document 1 discloses: a method for sealing an organic EL display element, comprising a constitution having an organic filling layer containing an in-plane sealing agent for covering and sealing a laminate having an organic light emitting material layer and a moisture absorption sealing layer containing a peripheral sealing agent containing a moisture absorbent and covering the side surface of the organic filling layer.

Disclosure of Invention

Problems to be solved by the invention

However, when the organic EL display element is sealed with the sealant for an organic EL display element of patent document 1, there is a problem that a display failure such as dark spots may occur in the obtained organic EL display element.

The purpose of the present invention is to provide a sealing agent for an organic EL display element, which has excellent coatability, rapid curability, low outgassing properties, and storage stability, and which can provide an organic EL display element having excellent display performance.

Means for solving the problems

The present invention is a sealant for an organic EL display element, which contains a curable resin containing an alicyclic epoxy compound and an oxetane compound and a thermal cationic polymerization initiator, wherein the sealant for an organic EL display element has a thickening ratio of 20% or less after being stored for 4 days in an environment of 40 ℃ and 22.5% RH, and the time from the start of holding at 100 ℃ to the start of a heat generation peak is 3 minutes or less when the temperature is raised at a temperature rise rate of 40 ℃/minute in a differential scanning calorimetry measurement and held at 100 ℃.

The present invention will be described in detail below.

The present inventors considered that the cause of display defects such as dark spots in the organic EL display element was the outgas of the sealant used, and studied the sealing of the organic EL display element with a sealant for the organic EL display element containing a material having excellent low outgassing properties. However, even when a sealant having excellent low outgassing property is used, display defects such as dark spots may occur in the obtained organic EL display device. The present inventors considered that, in addition to the occurrence of outgassing, the sealant for an organic EL display element used as an in-plane sealant is lowered in viscosity during heating such as curing and penetrates into a laminate having organic light emitting material layers, which also causes display failure of the organic EL display element. Therefore, the present inventors have studied the use of a curable resin and a thermal polymerization initiator used in a sealing agent which is excellent not only in low outgassing property but also in reactivity, in order to improve the rapid curability of the sealing agent for an organic EL display element and prevent penetration into the laminate. However, the obtained sealant has a problem that it is easily thickened and storage stability is deteriorated. Accordingly, the present inventors studied: the curable resin is obtained by using an alicyclic epoxy compound and an oxetane compound in combination, and adjusting the time until the peak of the exothermic peak is formed when the sealant is subjected to differential scanning calorimetry and the thickening ratio after the sealant is stored for 4 days in an environment of 40 ℃ and 22.5% RH to specific values or less. As a result, the present inventors have found that a sealant for an organic EL display element excellent in all of coatability, rapid curability, low outgassing property, and storage stability can be obtained, and that an organic EL display element excellent in display performance can be obtained by using the sealant for an organic EL display element, and have completed the present invention.

In the case where the temperature is raised at a temperature raising rate of 40 ℃/min in differential scanning calorimetry and the sealant is held at 100 ℃, the time from the start of holding at 100 ℃ to the start of the peak of heat generation (hereinafter also referred to as "curing start time") is 3 minutes or less. When the curing start time is 3 minutes or less, the sealant for an organic EL display element of the present invention has excellent rapid curability, and the resultant organic EL display element has excellent display performance. The curing start time is preferably 2.5 minutes or less, and more preferably 2 minutes or less.

In the differential scanning calorimetry, 10mg of the sealant put in an aluminum pan can be measured under the measurement conditions of a temperature rise rate of 40 ℃/min and a holding temperature of 100 ℃ using a differential scanning calorimeter in an environment of 25 ℃ and 50% RH. Examples of the differential scanning calorimeter include Thermo plusDSC 8230 (manufactured by Rigaku corporation).

The sealing agent for an organic EL display element of the present invention has a thickening ratio of 20% or less after being stored for 4 days at 40 ℃ and 22.5% RH. By setting the thickening ratio to 20% or less, the sealant for an organic EL display element of the present invention can be stably used for a long period of time. The thickening ratio is preferably 15% or less, more preferably 10% or less, and most preferably 0%.

In the present specification, the "thickening ratio" is a value calculated by the following formula when the viscosity immediately after production (before storage) is a and the viscosity after storage for 4 days in an environment at 40 ℃ and 22.5% RH is B.

Thickening ratio (%) ((B-a) ÷ a) × 100

In the present specification, the "viscosity" refers to a value measured by using an E-type viscometer at 25 ℃ and 20 rpm. Examples of the E-type VISCOMETER include a VISCOMETER TV-22 (manufactured by eastern industries), and a cone plate of CP1 can be used.

The curing start time and the thickening ratio can be adjusted to the above ranges by selecting the types and the content ratios of other components such as a curable resin, a thermal cationic polymerization initiator, and a stabilizer, which will be described later.

The sealant for an organic EL display element of the present invention contains a curable resin.

The curable resin contains an alicyclic epoxy compound and an oxetane compound. Even if the sealing agent for an organic EL display element obtained by using the alicyclic epoxy compound and the oxetane compound separately has poor quick curability or the like, the curing start time and the thickening ratio can be easily adjusted to the above ranges by using them in combination.

Examples of the alicyclic epoxy compound include 3, 4-epoxycyclohexylmethyl (meth) acrylate, 1, 2: 8, 9-diepoxy-limonene, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, (3, 4-epoxycyclohexyl) methyl-3, 4-epoxycyclohexyl formate, bis (3, 4-epoxycyclohexylmethyl) ether, 3, 4, 3 ', 4' -diepoxybicyclohexane, bis (3, 4-epoxycyclohexyl) adipate, bis (2, 3-epoxycyclopentyl) ether, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentadiene dioxide and the like. Among them, the alicyclic epoxy compound preferably contains 3, 4-epoxycyclohexylmethyl (meth) acrylate, from the viewpoint of facilitating adjustment of the curing start time and thickening ratio of the organic EL display element sealant obtained by using it in combination with an oxetane compound described later.

In the present specification, the "(meth) acrylate" refers to an acrylate or a methacrylate.

Examples of the oxetane compound include 4, 4' -bis ((3-ethyl-3-oxetanyl) methoxymethyl) biphenyl, 3-ethyl-3- (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane, phenoxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- ((2-ethylhexyloxy) methyl) oxetane, 3-ethyl-3- ((3- (triethoxysilyl) propoxy) methyl) oxetane, oxetanylsilsesquioxane, phenol novolac oxetane, and the like, 1, 4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene, and the like. Among them, the oxetane compound preferably contains at least one of 4, 4' -bis ((3-ethyl-3-oxetanyl) methoxymethyl) biphenyl and 3-ethyl-3- (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane, from the viewpoint of facilitating adjustment of the viscosity, curing start time, and thickening ratio of the sealant for organic EL display elements obtained by using the compound in combination with the alicyclic epoxy compound.

The content of the alicyclic epoxy compound in the total of the alicyclic epoxy compound and the oxetane compound preferably has a lower limit of 20% by weight and an upper limit of 80% by weight. When the content ratio of the alicyclic epoxy compound is in this range, it becomes easier to adjust the viscosity, curing start time, and thickening ratio of the obtained sealant for an organic EL display element. The lower limit of the content of the alicyclic epoxy compound is more preferably 30% by weight, and the upper limit is more preferably 70% by weight.

The curable resin may contain other curable resins for the purpose of adjusting the viscosity and the like, within a range not interfering with the object of the present invention.

Examples of the other curable resin include epoxy compounds other than the alicyclic epoxy compound, and vinyl ether compounds.

Examples of the other epoxy compound include dicyclopentadiene dimethanol diglycidyl ether, bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol a diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether.

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

The sealant for an organic EL display element of the present invention contains a thermal cationic polymerization initiator.

The thermal cationic polymerization initiator may be BF as an anionic moiety (counter anion)₄ ^-、PF₆ ^-、SbF₆ ^-Or (BX)₄)^-(wherein X represents a phenyl group substituted with at least 2 or more fluorine groups or trifluoromethyl groups), sulfonium salts, phosphonium salts, ammonium salts, and the like. Among them, a quaternary ammonium salt having a borate counter anion (hereinafter also referred to as "borate quaternary ammonium salt") is preferable because it is easier to adjust the curing start time and thickening ratio of the obtained sealing agent for an organic EL display element and has excellent low outgassing property. The counter anion of the borate quaternary ammonium salt is preferably BF₄ ^-Or (BX)₄)^-。

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 above ammonium salts include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyldibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium hexafluoroantimonate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3, 4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N-dimethyl-N-benzylammonium hexafluoroantimonate, N-methylbenzyl ammonium hexafluoroantimonate, N-methyl-phenyl salt, N, N-diethyl-N-benzylanilinium tetrafluoroborate, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N-diethyl-N-benzylpyridinium trifluoromethanesulfonate and the like. Among them, dimethyl phenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate is preferable in that the curing start time and thickening ratio of the obtained sealing agent for an organic EL display element can be easily adjusted and that the sealing agent has excellent low outgassing properties.

Examples of commercially available products among the above thermal cationic polymerization initiators include thermal cationic polymerization initiators manufactured by shin-Etsu chemical Industries, and thermal cationic polymerization initiators manufactured by King Industries.

Examples of the thermal cationic polymerization initiator manufactured by Sanxin chemical industries include San-Aid SI-60, San-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A and San-Aid SI-B4.

Examples of the thermal cationic polymerization initiator manufactured by King Industries include CXC1612 and CXC 1821.

The content of the thermal cationic polymerization initiator is preferably 0.05 parts by weight in the lower limit and 10 parts by weight in the upper limit, based on 100 parts by weight of the curable resin. When the content of the thermal cationic polymerization initiator is in this range, the obtained sealant for organic EL display elements is more excellent in rapid curability and storage stability. The lower limit of the content of the thermal cationic polymerization initiator is more preferably 0.1 part by weight, and the upper limit is more preferably 5 parts by weight.

The sealant for an organic EL display element of the present invention may contain a thermosetting agent within a range not to impair the object of the present invention. Examples of the heat-curing agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamide, guanidine derivatives, modified aliphatic polyamines, and addition products of various amines and epoxy resins.

Examples of the hydrazide compound include 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin, sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, malonic 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 '-bis (2-methyl-1-imidazolylethyl) urea, N' - (2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4, 5-dihydroxymethylimidazole.

Examples of the acid anhydride include tetrahydrophthalic anhydride and ethylene glycol bis (anhydrotrimellitate).

These heat-curing agents may be used alone, or 2 or more of them may be used in combination.

Examples of commercially available products among the above heat-curing agents include a heat-curing agent manufactured by Otsuka chemical Co., Ltd, a heat-curing agent manufactured by Ajinomoto Fine-Technio Co., Inc.

Examples of the heat-curing agent manufactured by Otsuka chemical company include SDH and ADH.

Examples of the thermosetting agent manufactured by Inc. include AMICUROVDH, AMICURE VDH-J, and AMICURE UDH.

The content of the thermosetting agent is preferably 0.5 parts by weight in the lower limit and 30 parts by weight in the upper limit with respect to 100 parts by weight of the curable resin. When the content of the thermosetting agent is in this range, the obtained sealant for a sealant for an organic EL display element has more excellent thermosetting properties while maintaining excellent storage stability. The lower limit of the content of the thermosetting agent is more preferably 1 part by weight, and the upper limit is more preferably 15 parts by weight.

The sealing agent for an organic EL display element of the present invention preferably contains a stabilizer. By containing the stabilizer, the sealing agent for an organic EL display element of the present invention has more excellent storage stability.

Examples of the stabilizer include amine compounds such as benzylamine and the like, and aminophenol type epoxy resins.

The content of the stabilizer is preferably 0.001 parts by weight in the lower limit and 2 parts by weight in the upper limit, based on 100 parts by weight of the curable resin. When the content of the stabilizer is in this range, the obtained sealant for an organic EL display element has more excellent storage stability while maintaining excellent rapid curability. The lower limit of the content of the stabilizer is more preferably 0.005 part by weight, and the upper limit is more preferably 1 part by weight.

The sealing agent for an organic EL display element of the present invention may contain a silane coupling agent. The silane coupling agent has an effect of improving the adhesion of the sealant for an organic EL display element of the present invention to a substrate or the like.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-isocyanatopropyltrimethoxysilane. These silane coupling agents may be used alone, or 2 or more of them may be used in combination.

The content of the silane coupling agent is preferably 0.1 part by weight in the lower limit and 10 parts by weight in the upper limit with respect to 100 parts by weight of the curable resin. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness of the obtained sealant for an organic EL display element while preventing bleeding of the excess silane coupling agent becomes more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.5 part by weight, and the upper limit is more preferably 5 parts by weight.

The sealant for an organic EL display element of the present invention may contain a surface modifier within a range not to impair the object of the present invention. The inclusion of the surface modifier can improve the flatness of the coating film of the sealant 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, and fluorine-based surface modifiers.

Commercially available products among the above surface modifiers include, for example, BYK-300, BYK-302, BYK-331 (both of BYK-CHEMIE JAPAN), UVX-272 (manufactured by NAKAI CHEMICAL Co., Ltd.), Surflon S-611(AGC SEIMICHEMICAL CO., LTD.).

The sealing agent for an organic EL display element of the present invention may contain a compound or an ion exchange resin that reacts with an acid generated in the sealing agent for an organic EL display element in order to improve the durability of the element electrode within a range that does not interfere with the object of the present invention.

Examples of the compound which reacts with the generated acid include a compound which neutralizes the acid, for example, an alkali metal carbonate or bicarbonate, or an alkaline earth metal carbonate or bicarbonate. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium hydrogen carbonate, or the like can be used.

The ion exchange resin may be any of a cation exchange type, an anion exchange type, and an amphoteric ion exchange type, but a cation exchange type or an amphoteric ion exchange type capable of adsorbing chloride ions is particularly preferable.

The sealant for an organic EL display element of the present invention may contain various known additives such as a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber, and an antioxidant as needed, within a range not to impair the object of the present invention.

The sealing agent for an organic EL display element of the present invention preferably contains no solvent from the viewpoint of suppressing the occurrence of outgassing. The sealant for an organic EL display element of the present invention is easy to have excellent coatability even if it does not contain such a solvent.

Examples of the method for producing the sealant for an organic EL display element of the present invention include a method of mixing a curable resin, a thermal cationic polymerization initiator, and additives such as a stabilizer and a silane coupling agent added as necessary with a mixer such as a homomixer, a universal mixer, a planetary mixer, a kneader, or a 3-roll mill.

The viscosity of the sealant for an organic EL display element of the present invention measured with an E-type viscometer at 25 ℃ and 20rpm preferably has a lower limit of 10mPa · s and an upper limit of 500mPa · s. When the viscosity is within this range, the obtained sealant for an organic EL display element has excellent coatability, and is particularly suitable as an in-plane sealant for an organic EL display element. The viscosity is more preferably 30 mPas at the lower limit and 250 mPas at the upper limit.

The sealing agent for an organic EL display element of the present invention is particularly suitable as an in-plane sealing agent for covering and sealing a laminate having an organic light emitting material layer.

Effects of the invention

The present invention can provide a sealing agent for an organic EL display element, which has excellent coatability, rapid curability, low outgassing property, and storage stability, and can provide an organic EL display element having excellent display performance.

Detailed Description

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

(examples 1 to 8, comparative examples 1 to 9)

The materials were uniformly stirred and mixed at a stirring speed of 3000rpm using a stirring mixer (manufactured by THINKY, "AR-250") in the mixing ratios shown in tables 1 and 2, to prepare sealants for organic EL display elements of examples 1 to 8 and comparative examples 1 to 9.

10mg of the obtained sealing agent for an organic EL display element was placed in an aluminum pan, and differential scanning calorimetry was performed under the measurement conditions of a temperature rise rate of 40 ℃ per minute and a holding temperature of 100 ℃ using a differential scanning calorimeter (manufactured by Rigaku corporation, "Therom plus DSC 8230") in an environment of 25 ℃ and 50% RH. The time from the start of the holding at 100 ℃ to the peak of the heat generation peak (curing start time) is shown in tables 1 and 2.

The obtained sealant for organic EL display elements was measured for viscosity immediately after production (before storage) and viscosity after storage for 4 days in an environment of 40 ℃ and 22.5% RH, and the thickening ratio was calculated from the above formula. The results are shown in tables 1 and 2. The sealant that has gelled is described as "gel" instead of the viscosity. The viscosity was measured using an E-type VISCOMETER (manufactured by Toyobo industries, Ltd. "VISCOMETER TV-22") using a CP1 type conical plate at 25 ℃ and 20 rpm.

< evaluation >

The following evaluations were performed on each of the organic EL display element sealants obtained in examples and comparative examples. The results are shown in tables 1 and 2.

(1) Coatability

Each of the organic EL display elements obtained in examples and comparative examples was applied with 0.1mL of the sealant using a pipette onto a glass substrate, and the diameter of the sealant spreading after 1 minute was measured. The coatability was evaluated by assuming that the diameter was equal to or larger than 15mm as "o", the diameter was equal to or larger than 10mm and smaller than 15mm as "Δ", and the diameter was smaller than 10mm as "x".

(2) Low degassing property

Each of the organic EL display element sealing agents obtained in examples and comparative examples was weighed at 300mg and sealed in a vial, and then cured by heating at 100 ℃ for 30 minutes. Further, the vial was heated in an oven at a constant temperature of 85 ℃ for 100 hours, and the vaporized component in the vial was measured by a gas chromatography mass spectrometer (JMS-Q1050, manufactured by Nippon electronic Co., Ltd.). The low outgassing property was evaluated by "o" when the amount of gasification components was less than 50ppm, by "Δ" when the amount was less than 100ppm at 50ppm or more, and by "x" when the amount was more than 100 ppm.

(3) Display performance of organic EL display element

(production of a substrate having a laminate comprising organic light-emitting Material layers)

An ITO electrode was formed on a glass substrate (45 mm in length, 45mm in width, 0.7mm in thickness)The thickness of (3) is as follows. The substrate was ultrasonically cleaned with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, then cleaned with boiled isopropyl alcohol for 10 minutes, and further pretreated with a UV-ozone cleaner (NL-UV 253, manufactured by japan laser electronics).

Next, the substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200mg of N, N '-bis (1-naphthyl) -N, N' -diphenylbenzidine (α -NPD) was charged into a bisque-fired crucible, and tris (8-quinolinolato) aluminum (Alq) was charged into a different bisque-fired crucible₃)200mg, the pressure in the vacuum chamber was reduced to 1 × 10^-4Pa, thereafter, the crucible containing α -NPD was heated to α -NPDIs deposited on a substrate at a deposition rate to form a film with a thickness ofThe hole transport layer of (1). Then, will be charged with Alq₃Is heated in a crucible toThe deposition rate of (2) is set to a film thicknessThen, the substrate on which the hole transport layer and the organic light-emitting material layer were formed was transferred to another vacuum deposition apparatus, 200mg of lithium fluoride was charged into a tungsten resistance heating boat in the vacuum deposition apparatus, 1.0g of an aluminum wire was charged into another tungsten boat, and then the pressure in the evaporator of the vacuum deposition apparatus was reduced to 2 × 10^-4Pa, adding lithium fluoride toIs deposited at a deposition rate ofThen, aluminum is addedAt a rate of film formation ofThe inside of the evaporator was returned to normal pressure by nitrogen, and the substrate provided with the laminate having 10mm × 10mm organic light-emitting material layers was taken out.

(production of organic EL display device)

E-W207 (manufactured by waterlogging chemical industries) as a peripheral sealant was applied to the outer periphery of the substrate on which the laminate was disposed so that the line width reached 6mm, and the respective organic EL display element sealants obtained in examples and comparative examples as in-plane sealants were applied to the inner side so as to cover the entire laminate, and then another glass substrate (45 mm in length, 45mm in width, and 0.7mm in thickness) was stacked. Then, 3000mJ/cm of the light was irradiated²Further, the surface sealing agent and the peripheral sealing agent were cured by heating at 100 ℃ for 30 minutes to produce an organic EL display element.

(light-emitting state of organic EL display element)

The organic EL display device thus obtained was exposed to 85 ℃ and 85% RH for 1000 hours, and then a voltage of 10V was applied to visually observe the light emission state (presence or absence of dark spots and extinction around the pixel) of the organic EL display device. The display performance of the organic EL display element was evaluated by assuming that the light was uniformly emitted without dark spots or peripheral extinction as "o", assuming that dark spots or peripheral extinction were slightly observed as "Δ", and assuming that the non-light-emitting portion was significantly enlarged as "x".

[ Table 1]

[ Table 2]

Industrial applicability

The present invention can provide a sealing agent for an organic EL display element, which has excellent coatability, rapid curability, low outgassing property, and storage stability, and can provide an organic EL display element having excellent display performance.