TWI641650B - Organic electroluminescent display element sealant - Google Patents

Abstract

An object of the present invention is to provide a post-curing resin composition which is capable of suppressing generation of outgas and having excellent transparency and reliability.

The present invention is a post-curing resin composition comprising a cationically curable resin, a photocationic polymerization initiator, and a compound having an amine group and a cationically polymerizable functional group.

Description

Organic electroluminescent display element sealant

The present invention relates to a post-curing resin composition which is capable of suppressing generation of outgas and having excellent transparency and reliability.

In recent years, research into organic optical devices using organic thin film elements such as organic electroluminescence (organic EL) display elements or organic thin film solar cell elements has been continuously conducted. The organic thin film device can be easily produced by vacuum vapor deposition or solution coating, and is therefore excellent in productivity.

The 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. Self-luminescence is performed by injecting electrons from one electrode into the organic light-emitting material layer and injecting holes from the other electrode to bond electrons and holes in the organic light-emitting material layer. Compared with a liquid crystal display element or the like of a required backlight device, it is excellent in visibility, can be further reduced in thickness, and can be driven by DC low voltage.

However, in such an organic EL display device, when the organic light-emitting material layer or the electrode is exposed to the outside atmosphere, the light-emitting characteristics are rapidly deteriorated and the lifetime is shortened. Therefore, in order to improve the stability and durability of the organic EL display element, it is indispensable for the organic EL display element to seal the organic light-emitting material layer or the electrode with moisture or oxygen in the atmosphere.

Patent Document 1 discloses a method in which a photocurable adhesive is filled between organic EL display element substrates in an upper surface light-emitting type organic EL display device or the like, and light is irradiated and sealed. However, when a photocurable adhesive is used in this manner, There is a problem in that an outgas is generated at the time of light irradiation to fill the inside of the element, thereby promoting deterioration of the element.

Patent Document: Japanese Laid-Open Patent Publication No. 2001-357973

An object of the present invention is to provide a post-curing resin composition which is capable of suppressing generation of outgas and having excellent transparency and reliability.

The present invention is a post-curing resin composition comprising a cationically curable resin, a photocationic polymerization initiator, and a compound having an amine group and a cationically polymerizable functional group.

The invention is described in detail below.

The inventors of the present invention have thought that the reason why the photocurable adhesive is used for the sealing of an organic EL display device or the like is, in particular, that the post-light-curable adhesive is usually formulated with an ether such as a crown ether. A hardening retarder composed of a compound of a bond. In other words, it is considered that the hardening retarder is decomposed by an acid or the like upon light irradiation, thereby generating two as a gassing. Alkane, etc.

Therefore, the present inventors have found that by using a compound having an amine group and a cationically polymerizable functional group instead of such a hardening retarder, the amine group can exert a hardening retarding effect and can be obtained by using a cationically polymerizable functional group. The present invention has been completed by entering a hardened material and suppressing the generation of outgas.

The post-light curable resin composition of the present invention contains a compound having an amine group and a cationically polymerizable functional group. The above compound having an amine group and a cationically polymerizable functional group can exert an effect of hardening retardation on the amine group, and can suppress generation of outgas by taking in a hardened substance by using a cationically polymerizable functional group. Further, the compound having an amine group and a cationically polymerizable functional group has a cationically polymerizable functional group, but has an amine group, so that the cationic polymerizability is extremely low.

Examples of the above amine group include a primary amino group, a secondary amino group, and a tertiary amino group. to In the case where a secondary amino group or a tertiary amino group is used as the above amine group, it is preferred that at least one of the amine nitrogen atoms is bonded to the cationically polymerizable functional group directly or via an alkylene group.

From the viewpoint of exerting an appropriate hardening retardation effect, the above amine group is preferably a tertiary amine group.

Examples of the cationically polymerizable functional group include an epoxy group, an oxetanyl group, a hydroxyl group, a vinyl ether group, an episulfide group, and an ethyleneimine group. Among them, an epoxy group is preferred from the viewpoint of easy entry into a cured product.

Moreover, it is preferable that the compound having an amine group and a cationically polymerizable functional group has two or more of the above cationically polymerizable functional groups in one molecule, from the viewpoint of easy entry into the cured product.

The compound having an amine group and a cationically polymerizable functional group is preferably at least one selected from the group consisting of compounds represented by the following formulas (1) to (7) because of the combination of hardening delay. The effect is particularly excellent in terms of the effect of taking in a hardened substance and suppressing outgassing.

In the formula (1), R ¹ represents an alkylene group having 1 to 3 carbon atoms. Each R ¹ may be the same or different.

In the formula (2), R ² represents an alkylene group having 1 to 3 carbon atoms. Each R ² may be the same or different.

In the formula (3), R ³ represents an alkylene group having 1 to 3 carbon atoms. Each R ³ may be the same or different.

In the formula (4), R ⁴ represents an alkylene group having 1 to 3 carbon atoms. Each R ⁴ may be the same or different. R ⁵ is any one of a methyl group, an ethyl group, an extended ethyl group, and a propyl group.

In the formula (5), R ⁶ represents an alkylene group having 1 to 3 carbon atoms. Each R ⁶ may be the same or different. R ⁷ is any one of a methyl group, an ethyl group, an extended ethyl group, and a propyl group, and each R ⁷ may be the same or different.

In the formula (6), R ⁸ represents an alkylene group having 1 to 3 carbon atoms. Each R ⁸ may be the same or different.

In the formula (7), R ⁹ represents an alkylene group having 1 to 3 carbon atoms. Each R ⁹ may be the same or different.

In the above formula (1), R ^{1 is} preferably a methylene group, and in the above formula (2), R ^{2 is} preferably a methylene group, and in the above formula (3), R ^{3 is} preferably a methylene group. In the above formula (4), R ^{4 is} preferably a methylene group, and R ^{5 is} preferably a propyl group. In the above formula (5), R ^{6 is} preferably a methylene group, and R ^{7 is} preferably a propyl group. In the above formula (6), R ^{8 is} preferably a methylene group, and in the above formula (7), R ^{9 is} preferably a methylene group.

The lower limit of the weight average molecular weight of the compound having an amine group and a cationically polymerizable functional group is preferably 200, and the upper limit is preferably 1,000. When the weight average molecular weight of the compound having an amine group and a cationically polymerizable functional group is less than 200, there is a case where the above compound having an amine group and a cationic polymerizable functional group remains without being taken into a cured product. Become the cause of outgassing. When the weight average molecular weight of the compound having an amine group and a cationically polymerizable functional group exceeds 1,000, the viscosity of the obtained post-light curable resin composition becomes too high, and the coating property or the like may be deteriorated. The lower limit of the weight average molecular weight of the compound having an amine group and a cationically polymerizable functional group is more preferably 300, and the upper limit is more preferably 800.

In the present specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) and is determined by polystyrene conversion. As a column for measuring the weight average molecular weight in terms of polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) or the like can be mentioned.

The commercially available ones of the compounds having an amine group and a cationically polymerizable functional group include, for example, TEPIC (manufactured by Nissan Chemical Co., Ltd.), jER604, and jER630 (all manufactured by Mitsubishi Chemical Corporation).

The content of the compound having an amine group and a cationically polymerizable functional group is preferably 0.01 parts by weight, and the upper limit is preferably 20 parts by weight, based on 100 parts by weight of the cationically curable resin. When the content of the compound having an amine group and a cationically polymerizable functional group is less than 0.01 part by weight, the curing delay effect may not be sufficiently exhibited. If the content of the compound having an amine group and a cationic polymerizable functional group exceeds 20 parts by weight, the obtained light is hard. The chemical resin composition is inferior in hardenability. The lower limit of the content of the compound having an amine group and a cationically polymerizable functional group is more preferably 0.05 part by weight, the upper limit is more preferably 15 parts by weight, the lower limit is more preferably 0.1 part by weight, and the upper limit is more preferably 10 parts by weight.

The post-light curable resin composition of the present invention contains a cationic curable resin. The cation-curable resin is not particularly limited as long as it is a compound having at least one cationically polymerizable functional group in the molecule and rich in cationic polymerizability.

Examples of the cationically polymerizable functional group include an epoxy group, an oxetanyl group, a hydroxyl group, a vinyl ether group, an episulfide group, and an ethyleneimine group. Among them, the cation curable resin preferably contains an epoxy resin in terms of exhibiting high adhesion and durability after curing.

Examples of the epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthalene type epoxy resin, and a combination. An epoxy resin having an aromatic ring such as a benzene type epoxy resin or a resorcinol type epoxy resin; or an epoxy having an aliphatic ring such as a hydrogenated bisphenol A type epoxy resin or a hydrogenated bisphenol F type epoxy resin Resin; or alicyclic epoxy resin. Among them, from the viewpoint of suppressing generation of outgassing, it is preferred to contain an alicyclic epoxy resin. These epoxy resins may be used singly or in combination of two or more.

Examples of the alicyclic epoxy resin include 1,2:8,9-diepoxylimene, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, and methylated ethylene. Cyclohexene dioxide, 3,4-epoxycyclohexylcarboxylic acid (3',4'-epoxycyclohexyl)methyl ester, bis-(3,4-epoxycyclohexyl) adipate, Bis-(3,4-epoxycyclohexylmethylene) adipic acid, bis-(2,3-epoxycyclopentyl)ether, adipic acid (2,3-epoxy-6-methyl Cyclohexylmethyl) ester, and dicyclopentadiene dioxide. Among them, 3,4-epoxycyclohexylcarboxylic acid (3',4'-epoxycyclohexyl)methyl ester is preferred. These alicyclic epoxy resins may be used singly or in combination of two or more.

The post-light curable resin composition of the present invention contains a photocationic polymerization initiator.

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

Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic hydrazine, aromatic hydrazine, aromatic diazonium, aromatic ammonium, or (2,4-cyclopentadiene). -1-yl)((1-methylethyl)benzene)-Fe cation, the anion moiety consists of BF ^4- , PF ^6- , SbF ^6- , or (BX ₄ ) ^- (wherein X represents at least 2 An onium salt or the like which is composed of the above fluorine or a trifluoromethyl-substituted phenyl group.

Examples of the aromatic onium salt include bis(4-(diphenylfluorenyl)phenyl) sulfide bishexafluorophosphate and bis(4-(diphenylfluorenyl)phenyl) sulfide. Hexafluoroantimonate, bis(4-(diphenylfluorenyl)phenyl) sulfide ditetrafluoroborate, bis(4-(diphenylfluorenyl)phenyl) sulfide tetrakis(pentafluorophenyl) Borate, diphenyl-4-(phenylthio)phenylphosphonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylphosphonium hexafluoroantimonate, diphenyl-4-( Phenylthio)phenylhydrazine tetrafluoroborate, diphenyl-4-(phenylthio)phenylphosphonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium Fluoride, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis(4-(di(4-(2-hydroxyethoxy))phenyl) Phenyl) thioether bishexafluorophosphate, bis(4-(di(4-(2-hydroxyethoxy))phenyl) phenyl) thioether bis hexafluoroantimonate, double (4 -(bis(4-(2-hydroxyethoxy))phenylindenyl)phenyl) sulfide ditetrafluoroborate, bis(4-(di(4-(2-hydroxyethoxy))benzene) Phenyl) phenyl) thioether tetrakis(pentafluorophenyl)borate.

Examples of the aromatic onium salt include diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, diphenylphosphonium tetrafluoroborate, and diphenylphosphonium tetrakis(pentafluorophenyl). Borate, bis(dodecylphenyl)phosphonium hexafluorophosphate, bis(dodecylphenyl)phosphonium hexafluoroantimonate, bis(dodecylphenyl)phosphonium tetrafluoroborate, double (dodecylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenylphosphonium hexafluorophosphate, 4-methylphenyl 4-(1-methylethyl)phenylphosphonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenylphosphonium tetrafluoroborate, 4-methylbenzene Base-4-(1- Methyl ethyl) phenyl sulfonium tetrakis(pentafluorophenyl) borate.

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

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

As the above (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt, for example, (2,4-cyclopentadien-1-yl) ( (1-methylethyl)benzene)-Fe(II) hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) Hexafluoroantimonate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) tetrafluoroborate, (2,4-cyclopentadiene -1-yl)((1-methylethyl)benzene)-Fe(II)tetrakis(pentafluorophenyl)borate.

Examples of the nonionic photoacid-producing photocationic polymerization initiator include a nitrobenzyl ester, a sulfonic acid derivative, a phosphate ester, a phenolsulfonate, a diazonaphthoquinone, and an N-hydroxyquinone imine. Sulfonate and the like.

For example, DTS-200 (manufactured by Midori Kagaku Co., Ltd.), UVI6990, UVI6974 (all manufactured by Union Carbide Co., Ltd.), SP-150, and SP-170 (both are commercially available). ADEKA Co., Ltd., FC-508, FC-512 (all manufactured by 3M Company), Irgacure 261 (manufactured by BASF Japan Co., Ltd.), PI2074 (manufactured by Rhodia Co., Ltd.), and the like.

The content of the photocationic polymerization initiator is preferably 0.1 part by weight, and the upper limit is preferably 10 parts by weight, based on 100 parts by weight of the cationically curable resin. If the content of the photocationic polymerization initiator is less than 0.1 parts by weight, the cationic polymerization is insufficiently performed. The combination or hardening reaction becomes too slow. When the content of the photocationic polymerization initiator is more than 10 parts by weight, the hardening reaction of the obtained post-light curable resin composition becomes too fast, and workability is lowered, or the obtained post-light curable resin composition The hardened matter of the object becomes uneven. The lower limit of the content of the above photocationic polymerization initiator is more preferably 0.5 part by weight, and the upper limit is more preferably 5 parts by weight.

The post-light curable resin composition of the present invention may further contain a sensitizer. The sensitizer has a function of further improving the polymerization initiation efficiency of the cationic polymerization initiator and further promoting the curing reaction of the post-light curing resin composition of the present invention.

As the sensitizer, for example, 2,4-diethyl-9-oxosulfuric acid can be cited. 9-oxosulfur a compound, or 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, phthalic acid Ester, 4,4'-bis(dimethylamino)benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, and the like.

The content of the sensitizer is preferably 0.05 parts by weight, and the upper limit is preferably 3 parts by weight, based on 100 parts by weight of the cationically curable resin. When the content of the sensitizer is less than 0.05 parts by weight, the sensitizing effect may not be sufficiently obtained. When the content of the sensitizer exceeds 3 parts by weight, the absorption may become excessively large and light may not be transmitted to the deep portion. The lower limit of the content of the above sensitizer is more preferably 0.1 part by weight, and the upper limit is more preferably 1 part by weight.

The post-light curable resin composition of the present invention may further contain a decane coupling agent. The decane coupling agent has a function of improving the adhesion of the post-light curable resin composition of the present invention to a substrate or the like.

Examples of the above decane coupling agent include γ-aminopropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, and γ-isocyanatepropyl group. Trimethoxy decane and the like. These decane coupling agents may be used singly or in combination of two or more.

The content of the above decane coupling agent is relative to the above cationically curable resin 100 The lower limit is preferably 0.1 part by weight, and the upper limit is preferably 10 parts by weight. When the content of the above decane coupling agent is less than 0.1 part by weight, the effect of improving the adhesion of the obtained light-curable resin composition after light can not be sufficiently exhibited. When the content of the above decane coupling agent exceeds 10 parts by weight, the remaining decane coupling agent may overflow. The lower limit of the content of the above decane coupling agent is more preferably 0.5 part by weight, and the upper limit is more preferably 5 parts by weight.

The post-light curable resin composition of the present invention may further contain a thermosetting agent in a range that does not hinder the object of the present invention. By including the above-mentioned thermosetting agent, thermosetting property can be imparted to the post-curing resin composition of the present invention.

The above-mentioned thermosetting agent is not particularly limited, and examples thereof include an anthracene compound, an imidazole derivative, an acid anhydride, dicyandiamide, an anthracene derivative, a modified aliphatic polyamine, and an addition product of various amines and an epoxy resin.

Examples of the ruthenium compound include 1,3-bis(decylcarbonylethyl-5-isopropylhydantoin).

Examples of the imidazole derivative include 1-cyanoethyl-2-phenylimidazole, N-(2-(2-methyl-1-imidazolyl)ethyl)urea, and 2,4-diamine. -6-(2'-methylimidazolyl-(1'))-ethyl symmetry III , N,N'-bis(2-methyl-1-imidazolylethyl)urea, N,N'-(2-methyl-1-imidazolylethyl)-hexanediamine, 2-benzene Base-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like.

Examples of the acid anhydride include tetrahydrophthalic anhydride and ethylene glycol-bis(hydrogen trimellitate).

These thermosetting agents may be used singly or in combination of two or more.

The content of the above-mentioned thermosetting agent is preferably 0.5 parts by weight, and the upper limit is preferably 30 parts by weight, based on 100 parts by weight of the cationically curable resin. When the content of the above-mentioned thermosetting agent is less than 0.5 part by weight, sufficient thermosetting property may not be imparted to the obtained post-light curable resin composition. When the content of the above-mentioned thermosetting agent exceeds 30 parts by weight, the storage stability of the obtained post-light curable resin composition may be insufficient, or the obtained light may be hard. The moisture resistance of the cured product of the chemical resin composition is deteriorated. The lower limit of the content of the above-mentioned thermosetting agent is more preferably 1 part by weight, and the upper limit is more preferably 15 parts by weight.

The post-light curable resin composition of the present invention may contain a surface modifier in a range that does not impair the object of the present invention. By including the surface modifying agent, the flatness of the coating film can be imparted to the post-curing resin composition of the present invention.

Examples of the surface modifier include a surfactant, a leveling agent, and the like.

Examples of the above-mentioned surfactant or the leveling agent include lanthanide, acrylic, fluorine, and the like.

For example, BYK-345 (manufactured by BYK-Chemie Japan Co., Ltd.), BYK-340 (manufactured by BYK-Chemie Japan Co., Ltd.), and Surflon S-611 are mentioned as a commercial product of the above-mentioned surfactant or the above-mentioned leveling agent. (manufactured by AGC Seimi Chemical Co., Ltd.) and the like.

In order to improve the durability of the element electrode, the post-light-curable resin composition of the present invention may contain a compound or ion which reacts with an acid generated in the post-curing resin composition without impeding the transparency of the cured product. Exchange resin.

Examples of the compound which reacts with the acid to be produced include a substance neutralized with an acid, for example, an alkali metal carbonate or hydrogencarbonate, or an alkaline earth metal carbonate or hydrogencarbonate. Specifically, for example, calcium carbonate, calcium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate or the like can be used.

As the ion exchange resin, any of a cation exchange type, an anion exchange type, and an amphoteric ion exchange type can be used, but a cation exchange type or an amphoteric ion exchange type which can adsorb chloride ions is particularly preferable.

Further, the post-light curable resin composition of the present invention may contain various additives such as a reinforcing agent, a softening agent, a plasticizer, a viscosity adjusting agent, an ultraviolet absorber, and an antioxidant, as needed.

Examples of the method for producing the post-light curable resin composition of the present invention include a homogeneous phase disperser, a homomixer, a universal agitator, a planetary mixer, and a kneader. A mixer such as a three-roll mill is a method in which a cationically curable resin, a photocationic polymerization initiator, a compound having an amine group and a cationically polymerizable functional group, and an additive such as a decane coupling agent to be added as needed are mixed.

According to the present invention, it is possible to provide a post-curing resin composition which is capable of suppressing generation of outgas and having excellent transparency and reliability.

The present invention will now be described in further detail by way of examples, but the invention is not limited to the examples.

(Example 1)

50 parts by weight of a bisphenol F type epoxy resin ("EPICLON EXA-830LVP" manufactured by DIC Corporation) and a hydrogenated bisphenol A type epoxy resin ("JER YL8034" manufactured by Mitsubishi Chemical Corporation) 25 25 parts by weight of a hydrogenated bisphenol F-type epoxy resin ("JER YL6753" manufactured by Mitsubishi Chemical Corporation) and an aromatic sulfonium salt as a photocationic polymerization initiator (manufactured by Midori Kagaku Co., Ltd., "DTS-200") 1.0 parts by weight of 5 parts by weight of triglycidyl isocyanurate ("TEPIC" manufactured by Nissan Chemical Co., Ltd.) as a compound having a tertiary amino group and a cationically polymerizable functional group, and 2, 4 as a sensitizer -diethyl-9-oxosulfur ("TX-403") manufactured by Shin-Etsu Silicones Co., Ltd. 1 part by weight of a fluorine-based leveling agent ("Surflon S-611" manufactured by AGC Seimi Chemical Co., Ltd.) was mixed, and after heating to 80 ° C, a homogenous dispersion type mixer was used (PRIMIX) The phase disperser L type ") was uniformly stirred and mixed at a stirring speed of 3000 rpm to prepare a post-light curable resin composition.

(Examples 2 to 6 and Comparative Examples 1 to 3)

Each of the materials described in Table 1 was stirred and mixed in the same manner as in Example 1 in accordance with the blending ratios shown in Table 1, to prepare a post-curable resin composition.

<evaluation>

Each of the post-light curable resin compositions obtained in the examples and the comparative examples was subjected to the following evaluation. The results are shown in Table 1.

(1) Viscosity

For each of the post-light-curable resin compositions obtained in the examples and the comparative examples, an E-type viscometer ("VISCOMETER TV-22" manufactured by Toki Sangyo Co., Ltd.) was used, and the viscosity at 25 ° C and 100 rpm was measured.

(2) Hardening delay

The test pieces of the respective post-light curable resin compositions obtained in the examples and the comparative examples were irradiated with ultraviolet rays at 1,500 mJ/cm ² using an ultraviolet irradiation apparatus ("JL-4300-3S" manufactured by OAK Co., Ltd.). The hardenability after 10 minutes was confirmed, and then heated in an oven at 100 ° C for 15 minutes to confirm the curability. As a result, after curing by UV irradiation for 10 minutes and curing after heating at 100 ° C, it was set to "○", and after UV irradiation for 10 minutes, the viscosity was increased, and after heating at 100 ° C, the curing was performed as "Δ", and UV irradiation was performed. In the case of hardening within 10 minutes or the case of not curing even after heating at 100 ° C, "X" was set, and the hardening retardation was evaluated.

(3) Transparency of hardened material

Each of the post-light curable resin compositions obtained in the examples and the comparative examples was formed to have a thickness of 10 μm between two sheets of a glass plate of 75 mm × 25 mm × 1 mm, and a high-pressure mercury lamp was used in a vacuum atmosphere so that the irradiation amount became 3000 mJ. The ultraviolet rays having a wavelength of 365 nm were irradiated in a manner of /cm ² to harden them to obtain a cured product. The total light transmittance was measured using a spectrophotometer ("U-2900" manufactured by Hitachi High-Technologies Co., Ltd.) for the obtained cured product. As a result, the case where the transmittance is 95 or more is "○", the case where 90 or more is less than 95 is "△", and the case where the temperature is less than 90 is "x", and the transparency of the cured product is evaluated. Sex.

(4) Anti-gassing

Each of the post-light-curable resin compositions obtained in the examples and the comparative examples was weighed to 300 mg and sealed in a vial, and then an ultraviolet irradiation apparatus ("JL-4300-3S" manufactured by OAK Co., Ltd.) was used at 1500 mJ/cm. ^{2 The} ultraviolet ray was irradiated, and then heated at 100 ° C for 15 minutes to cure the resin. Further, the vial was heated in a constant temperature oven at 85 ° C for 100 hours, and the gasification component in the vial was measured using a gas chromatography mass spectrometer ("JMS-k9" manufactured by JEOL Ltd.).

When the amount of the vaporized component is less than 10 ppm, it is set to "?", and when the amount is 10 ppm or more and less than 50 ppm, it is "○", and when it is 50 ppm or more and less than 100 ppm, it is set to "△", and 100 ppm or more is used. Set to "X" to evaluate the resistance to outgassing.

(5) Reliability of organic EL display elements

(Production of a substrate on which a laminate having a layer of a luminescent material layer is disposed)

A substrate having a ITO electrode formed by a thickness of 1000 Å on a glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm) was used as a substrate. The substrate was ultrasonically washed with acetone, an alkaline aqueous solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, and then washed with boiling isopropyl alcohol for 10 minutes, and further used by UV-Ozone Cleaners (manufactured by Nippon Laser Electron Co., Ltd.). , "NL-UV253") for pretreatment.

Then, the substrate was fixed to a substrate holder of a vacuum evaporation apparatus, and 200 mg of N,N'-bis(1-naphthyl)-N,N'-diphenylbenzidine was added to unglazed crucible. (α-NPD), 200 mg of tris(8-hydroxyquinolinyl)aluminum (Alq ₃ ) was added to another different element, and the vacuum chamber was depressurized to 1 × 10 ^-4 Pa. Thereafter, the crucible to which α-NPD was added was heated, and α-NPD was deposited on the substrate at a deposition rate of 15 Å/s to form a hole transport layer having a film thickness of 600 Å. Then, the crucible to which Alq _{3 was} added was heated, and an organic light-emitting material layer having a film thickness of 600 Å was formed at a deposition rate of 15 Å/s. Thereafter, the substrate on which the hole transport layer and the organic light-emitting material layer are formed is transferred to another vacuum evaporation device, and 200 mg of lithium fluoride is added to the tungsten resistance heating boat in the vacuum evaporation device to another tungsten. The boat was added with 1.0 g of aluminum wire. Thereafter, the pressure in the vapor deposition apparatus of the vacuum vapor deposition apparatus was reduced to 2 × 10 ^-4 Pa, and lithium fluoride was formed into a film of 5 Å at a vapor deposition rate of 0.2 Å / s, and then aluminum was formed at a rate of 20 Å / s. Film 1000Å. The inside of the vapor deposition device was returned to normal pressure by nitrogen, and a substrate on which a laminate having an organic light-emitting material layer of 10 mm × 10 mm was placed was taken out.

(Using the coating of the inorganic material film A)

A mask having an opening of 13 mm × 13 mm was provided so as to cover the entire laminated body of the substrate on which the laminate was obtained, and the inorganic material film A was formed by a plasma CVD method.

In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as raw material gases, and the flow rate of each is set to 10 sccm and 200 sccm, the RF power is set to 10 W (frequency 2.45 GHz), and the chamber temperature is set to 100 ° C. The room pressure was set to 0.9 Torr.

The thickness of the formed inorganic material film A was about 1 μm.

(Formation of resin protective film)

The substrate in which the laminate coated with the inorganic material film A was placed was placed in a vacuum apparatus, and 0.5 g of each of the post-light-curable resin compositions obtained in the examples and the comparative examples was added to the heating boat provided in the vacuum apparatus. The post-light curable resin composition was heated to 200 ° C, and a portion having a square shape of 11 mm × 11 mm including a laminate was vacuum-deposited so as to have a thickness of 0.5 μm. Thereafter, a high-pressure mercury lamp was used in a vacuum atmosphere to irradiate ultraviolet rays having a wavelength of 365 nm so that the irradiation amount was 3,000 mJ/cm ² , and the post-light curable resin composition was cured to form a resin protective film.

(Using the coating of the inorganic material film B)

After the resin protective film was formed, a mask having an opening of 12 mm × 12 mm was provided so as to cover the entire resin protective film, and the inorganic material film B was formed by a plasma CVD method to obtain an organic EL display element.

In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as raw material gases, and the flow rate of each is set to 10 sccm of SiH ₄ gas, 200 sccm of nitrogen gas, RF power is set to 10 W (frequency 2.45 GHz), and the chamber temperature is set to 100. °C, the pressure in the chamber was set to 0.9 Torr.

The thickness of the formed inorganic material film B was about 1 μm.

(Observation of the light-emitting state of the organic EL display element)

The obtained organic EL display element was exposed to an environment of a temperature of 85 ° C and a humidity of 85% for 100 hours, and then a voltage of 3 V was applied to visually observe the light-emitting state of the organic EL display element (with or without dark spots and pixel peripheral extinction). The case where the dark spot or the periphery was dull and the light was uniformly emitted was set to "○", and it was observed that even if a little dark spot or the surrounding extinction was set to "x", the reliability of the organic EL display element was evaluated.

[Industrial availability]

According to the present invention, it is possible to provide a post-curing resin composition which is capable of suppressing generation of outgas and having excellent transparency and reliability.

Claims (5)

An organic electroluminescence display element sealing agent comprising a post-curing resin composition containing a cationic curable resin, a photocationic polymerization initiator, and an amine group and a cationic polymerizable functional group The compound of the group, wherein the content of the compound having an amine group and a cationically polymerizable functional group is 0.01 to 20 parts by weight based on 100 parts by weight of the cationically curable resin; and the weight average of the compound having an amine group and a cationically polymerizable functional group The molecular weight is 200 or more and 1,000 or less. The organic electroluminescence display device encapsulant of claim 1, wherein the amine group is a tertiary amine group. The organic electroluminescence display device encapsulant according to claim 1 or 2, wherein the compound having an amine group and a cationically polymerizable functional group has two or more cationically polymerizable functional groups in one molecule. The organic electroluminescence display device encapsulant according to claim 1 or 2, wherein the cationic curable resin contains an epoxy resin. An organic electroluminescence display element encapsulant according to claim 4, which comprises an alicyclic epoxy resin as an epoxy resin.