WO2018030232A1 - Curable resin composition and sealing agent for organic electroluminescent display elements - Google Patents

Abstract

One purpose of the present invention is to provide a curable resin composition which is capable of suppressing the generation of an outgas, while having excellent coatability. Another purpose of the present invention is to provide a sealing agent for organic electroluminescent display elements, which is composed of this curable resin composition. The present invention is a curable resin composition which contains a cationically polymerizable compound and a cationic polymerization initiator, and wherein the cationically polymerizable compound contains at least one compound selected from the group consisting of compounds represented by formula (1-1), compounds represented by formula (1-2) and compounds represented by formula (1-3). In formula (1-1), R¹ represents a bonding hand, a linear or branched alkylene group having 1-18 carbon atoms or a linear or branched alkenylene group having 2-18 carbon atoms; and each of R² and R³ independently represents a hydrogen atom or a linear or branched alkyl group having 1-18 carbon atoms. In formula (1-2), R⁴ represents a linear or branched alkylene group having 3-18 carbon atoms or a linear or branched alkenylene group having 3-18 carbon atoms; and each of R⁵ and R⁶ independently represents a hydrogen atom or a linear or branched alkyl group having 1-18 carbon atoms. In formula (1-3), each of R⁷ and R⁸ independently represents a linear or branched alkylene group having 1-18 carbon atoms or a linear or branched alkenylene group having 2-18 carbon atoms; and each of R⁹-R¹² independently represents a hydrogen atom or a linear or branched alkyl group having 1-18 carbon atoms.

Description

Curable resin composition and sealant for organic electroluminescence display element

The present invention relates to a curable resin composition that can suppress generation of outgas and is excellent in applicability. Moreover, this invention relates to the sealing agent for organic electroluminescent display elements which consists of this curable resin composition.

In recent years, research on electronic devices using organic thin film elements such as organic electroluminescence display elements (organic EL display elements) and organic thin film solar cell elements has been advanced. The organic thin film element can be easily produced by vacuum deposition, solution coating, or the like, and thus has excellent 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. When electrons are injected from one electrode into the organic light emitting material layer and holes are injected from the other electrode, electrons and holes are combined in the organic light emitting material layer to perform self-light emission. Compared with a liquid crystal display element or the like that requires a backlight, the visibility is better, the thickness can be reduced, and direct current low voltage driving is possible.

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

Patent Document 1 discloses a method of filling a photocurable adhesive between organic EL display element substrates in a top emission organic EL display element or the like, and irradiating light to seal. However, such a conventional photo-curable adhesive has a problem in that an outgas is generated at the time of light irradiation to deteriorate the element, or the coating property is inferior.

JP 2001-357773 A

An object of this invention is to provide the curable resin composition which can suppress generation | occurrence | production of outgas and is excellent in applicability | paintability. Moreover, an object of this invention is to provide the sealing agent for organic electroluminescent display elements which consists of this curable resin composition.

The present invention is a curable resin composition containing a cationically polymerizable compound and a cationic polymerization initiator, wherein the cationically polymerizable compound is a compound represented by the following formula (1-1), -2) and at least one selected from the group consisting of compounds represented by the following formula (1-3).

In formula (1-1), R ¹ represents a bond, a linear or branched alkylene group having 1 to 18 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms. R ² and R ³ are each independently hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms. In Formula (1-2), R ⁴ is a linear or branched alkylene group having 3 to 18 carbon atoms, or a linear or branched alkenylene group having 3 to 18 carbon atoms, R ⁵ and R ⁶ are each independently hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms. In the formula (1-3), R ⁷ and R ⁸ are each independently a linear or branched alkylene group having 1 to 18 carbon atoms, or a linear or branched carbon number 2 to 18 is an alkenylene group, and each of R ⁹ to R ¹² is independently hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms.
The present invention is described in detail below.

The present inventor has found that by using a specific cationically polymerizable compound, generation of outgas can be suppressed and a curable resin composition having excellent coatability can be obtained, and the present invention has been completed. It was.

The curable resin composition of the present invention contains a cationic polymerizable compound.
The cationic polymerizable compound is a group consisting of a compound represented by the formula (1-1), a compound represented by the formula (1-2), and a compound represented by the formula (1-3). It contains at least one selected from the following (hereinafter also referred to as “the epoxy compound according to the present invention”). By containing the epoxy compound concerning this invention, the curable resin composition of this invention can suppress generation | occurrence | production of outgas and becomes excellent in applicability | paintability. Moreover, by containing the epoxy compound concerning this invention, the obtained curable resin composition is excellent in the softness | flexibility after hardening, and respond | corresponds also to a flexible electronic device.

R ^{1 in} the above formula (1-1), R ⁴ in the above formula (1-2), and R ⁷ and R ⁸ in the above formula (1-3) are compatible with other components. From the viewpoint of the hardness of the cured product, a linear or branched alkylene group having 1 to 18 carbon atoms is preferable, and a linear or branched alkylene group having 3 to 12 carbon atoms is preferable. More preferred.

Examples of the compound represented by the formula (1-1) include 1,3-butadiene diepoxide, 1,5-hexadiene diepoxide, 1,7-octadiene diepoxide, and 1,9-decadiene diepoxide. 1,11-dodecadiene diepoxide and the like.
Examples of the compound represented by the formula (1-2) include 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycycloheptane, 1,2-epoxycyclooctane, 1, Examples include 2-epoxycyclodecane, 1,2-epoxycyclododecane, 1-methyl-1,2-epoxycyclopentane, and 5,6-epoxy-1-cyclooctene.
Examples of the compound represented by the above formula (1-3) include 1,2,5,6-diepoxycyclooctane.
As what is marketed among the epoxy compounds concerning this invention, the reagent etc. by Tokyo Chemical Industry Co., Ltd. are mentioned, for example.
Among these, the cationically polymerizable compound contains the compound represented by the above formula (1-1) because the resulting curable resin composition is particularly excellent in curability and flexibility after curing. Preferably, it contains 1,7-octadiene diepoxide, and more preferably.

The curable resin composition of the present invention may contain other cationically polymerizable compounds as long as the object of the present invention is not impaired.
Examples of the other cationically polymerizable compounds include compounds having two or more cycloalkene oxide groups in one molecule, other epoxy compounds such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, oxetane compounds, Examples include vinyl ether compounds. Especially, since the obtained curable resin composition becomes more excellent in curability, a compound having two or more cycloalkene oxide groups in one molecule is preferable, and two or more cyclohexene oxide groups are contained in one molecule. Compounds are more preferred.

Examples of the compound having two or more cyclohexene oxide groups in one molecule include 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

When the other cationic polymerizable compound is contained, the preferred lower limit of the content of the epoxy compound according to the present invention in 100 parts by weight of the whole cationic polymerizable compound is 10 parts by weight, and the preferred upper limit is 90 parts by weight. When the content of the epoxy compound according to the present invention is within this range, the resulting curable resin composition is more excellent in applicability, the effect of suppressing outgassing, and flexibility. The more preferable lower limit of the content of the epoxy compound according to the present invention is 20 parts by weight, the more preferable upper limit is 80 parts by weight, and the still more preferable upper limit is 50 parts by weight.

The curable resin composition of the present invention contains a cationic polymerization initiator.
Examples of the cationic polymerization initiator include a thermal cationic polymerization initiator that generates a protonic acid or a Lewis acid by heating, and a photocationic polymerization initiator that generates a protonic acid or a Lewis acid by light irradiation. It may be a nonionic acid generation type.

Examples of the thermal cationic polymerization initiator include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , or (BX ₄ ) ⁻ (where X is phenyl substituted with at least two fluorine or trifluoromethyl groups. A sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt, or an iodonium salt, and a sulfonium salt is more preferable.

Examples of the sulfonium salts include triphenylsulfonium boron tetrafluoride, triphenylsulfonium hexafluoride antimony, triphenylsulfonium hexafluoride arsenic, tri (4-methoxyphenyl) sulfonium hexafluoride arsenic, and diphenyl (4-phenylthiophenyl). ) Sulfonium arsenic hexafluoride and the like.
Examples of the phosphonium salt include ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride.
Examples of the quaternary ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (penta). Fluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate , Methylphenyldibenzylammonium, methylphenyldibenzylammonium hexafluoroantimony Hexafluorophosphate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-N-benzylanilinium hexafluoride antimony, N, N-diethyl-N-benzylanilinium boron tetrafluoride, N, N-dimethyl-N-benzylpyridinium antimony hexafluoride, N, N -Diethyl-N-benzylpyridinium trifluoromethanesulfonic acid and the like.

Commercially available thermal cationic polymerization initiators include, for example, Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, Sun-Aid SI-B4 (all of which are Sanshin Chemical Industry Co., Ltd.). CXC-1612, CXC-1738, CXC-1821 (all manufactured by King Industries), and the like.

Among the above-mentioned photocationic polymerization initiators, ionic photoacid generating types include, for example, that the anion moiety is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , or (BX ₄ ) ⁻ (where X is at least An aromatic sulfonium salt, an aromatic iodonium salt, an aromatic diazonium salt, an aromatic ammonium salt, or (2,4, which represents a phenyl group substituted with two or more fluorine or trifluoromethyl groups) -Cyclopentadien-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 hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis (4- (di ( 4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluoroantimonate, Bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (di ( - (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, and the like.

Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (Dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethyl) Such as phenyl iodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Can be mentioned.

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

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

Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene. ) -Fe (II) hexafluorophosphate, (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimonate, (2,4-cyclopentadiene-1 -Yl) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrakis (penta Fluorophenyl) borate and the like.

Among the above-mentioned photocationic polymerization initiators, nonionic photoacid generators include, for example, nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinone, N-hydroxyimide sulfonates, and the like. Can be mentioned.

Examples of commercially available photocationic polymerization initiators include, for example, DTS-200 (manufactured by Midori Chemical Co., Ltd.), UVI6990, UVI6974 (all manufactured by Union Carbide), SP-150, SP-170 (all ADEKA), FC-508, FC-512 (all from 3M), IRGACURE290 (from BASF), PI 2074 (from Rhodia), and the like.

About what is described in both the said thermal cationic polymerization initiator and the said photocationic polymerization initiator, it can also be used as the said thermal cationic polymerization initiator, and can also be used as the said photocationic polymerization initiator.

The content of the cationic polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound. When the content of the cationic polymerization initiator is 0.01 parts by weight or more, the resulting curable resin composition is more excellent in curability. When the content of the cationic polymerization initiator is 10 parts by weight or less, the curing reaction of the resulting curable resin composition does not become too fast, the workability is improved, and the cured product is made more uniform. be able to. The minimum with more preferable content of the said cationic polymerization initiator is 0.05 weight part, and a more preferable upper limit is 5 weight part.

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

Examples of the sensitizer include anthracene compounds such as 9,10-dibutoxyanthracene, thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1, and the like. -One, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4-benzoyl-4'methyldiphenyl sulfide, and the like.

The content of the sensitizer is preferably 0.05 parts by weight and preferably 3 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound. 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 minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.

The curable resin composition of the present invention may contain a thermosetting agent. Examples of the thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, addition products of various amines and epoxy resins, and the like.

Examples of the hydrazide compound include 1,3-bis (hydrazinocarbonoethyl-5-isopropylhydantoin), sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of the imidazole derivatives include 1-cyanoethyl-2-phenylimidazole, N- (2- (2-methyl-1-imidazolyl) ethyl) urea, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, N, N′-bis (2-methyl-1-imidazolylethyl) urea, N, N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
Examples of the acid anhydride include tetrahydrophthalic anhydride, ethylene glycol bis (anhydrotrimellitate), and the like.
These thermosetting agents may be used independently and 2 or more types may be used together.

Examples of commercially available thermosetting agents include SDH (manufactured by Nippon Finechem Co., Ltd.), ADH (manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.). ) And the like.

The content of the thermosetting agent is preferably 0.5 parts by weight and preferably 30 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound. When the content of the thermosetting agent is 0.5 parts by weight or more, the resulting curable resin composition is more excellent in thermosetting. When the content of the thermosetting agent is 30 parts by weight or less, the obtained curable resin composition is excellent in storage stability, and the cured product is excellent in moisture resistance. The minimum with more preferable content of the said thermosetting agent is 1 weight part, and a more preferable upper limit is 15 weight part.

The curable resin composition of the present invention may contain a stabilizer for the purpose of improving storage stability.
Examples of the stabilizer include amine compounds such as benzylamine and aminophenol type epoxy resins.

The content of the stabilizer is preferably 0.001 part by weight and preferably 2 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound. When the content of the stabilizer is within this range, the effect of improving the storage stability of the resulting curable resin composition while suppressing inhibition of curing becomes excellent. The minimum with more preferable content of the said stabilizer is 0.05 weight part, and a more preferable upper limit is 1 weight part.

The curable resin composition of the present invention may contain a silane coupling agent. The said silane coupling agent has a role which improves the adhesiveness of curable resin composition of this invention, a board | substrate, etc.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and the like. These silane coupling agents may be used independently and 2 or more types may be used together.

The content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness of the resulting curable resin composition is suppressed while suppressing bleed-out due to excess silane coupling agent. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.

The curable resin composition of the present invention 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 curable resin composition of the present invention can be improved.
Examples of the surface modifier include surfactants and leveling agents.

Examples of the surface modifier include silicone-based, acrylic-based, and fluorine-based ones.
Examples of commercially available surface modifiers include BYK-300, BYK-302, BYK-331 (all manufactured by Big Chemie Japan), UVX-272 (manufactured by Enomoto Kasei), Surflon. S-611 (manufactured by AGC Seimi Chemical Co., Ltd.) and the like.

The curable resin composition of the present invention is a compound or ion exchange resin that reacts with an acid generated in the curable resin composition in order to improve the durability of the element electrode within a range that does not impair the object of the present invention. You may contain.

Examples of the compound that reacts with the generated acid include substances that neutralize the acid, for example, alkali metal carbonates or bicarbonates, or alkaline earth metal carbonates or bicarbonates. 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 both ion exchange type can be used, and in particular, a cation exchange type or a both ion exchange type capable of adsorbing chloride ions. Is preferred.

The encapsulant for organic EL display elements of the present invention preferably does not contain a solvent because the remaining solvent may cause problems such as deterioration of the organic light emitting material layer or generation of outgas.
In addition, when using a solvent for the purpose of viscosity adjustment etc., it is preferable that content of a solvent is 1 weight% or less, and it is more preferable that it is 0.1 weight% or less.

In addition, the curable resin composition of the present invention is a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber, and an antioxidant as necessary, as long as the object of the present invention is not impaired. You may contain well-known various additives, such as an agent and a desiccant.

Examples of the method for producing the curable resin composition of the present invention include a cationic polymerizable compound and a cation using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll. Examples thereof include a method of mixing a polymerization initiator and an additive such as a silane coupling agent added as necessary.

The curable resin composition of the present invention has an overall viscosity lower limit of 5 mPa · s and an upper limit of 200 mPa · s measured using an E-type viscometer at 25 ° C. and 50 rpm. When the viscosity is within this range, the resulting curable resin composition is more excellent in ink jet coating properties and more suitable as an in-plane sealant for organic EL display elements. A more preferable lower limit of the viscosity is 8 mPa · s, and a more preferable upper limit is 30 mPa · s.

The curable resin composition of the present invention is suitably used for sealing, adhesion, coating and the like of electronic devices, and more suitably used as a sealing agent for electronic devices. Especially, it uses especially suitably as a sealing agent for organic EL display elements.
The sealing agent for organic EL display elements which consists of curable resin composition of this invention is also one of this invention.

According to this invention, generation | occurrence | production of outgas can be suppressed and the curable resin composition excellent in applicability | paintability can be provided. Moreover, according to this invention, the sealing compound for organic electroluminescent display elements which consists of this curable resin composition can be provided.

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

(Examples 1 to 9, Comparative Examples 1 to 5)
According to the blending ratios described in Tables 1 and 2, each material was stirred and mixed uniformly at a stirring speed of 3000 rpm using a homodisper type stirring mixer (Primix Co., Ltd., “Homodisper L type”). Curable resin compositions of Examples 1 to 9 and Comparative Examples 1 to 5 were prepared.

<Evaluation>
The following evaluation was performed about each curable resin composition obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(1) Viscosity About each curable resin composition obtained in the Examples and Comparative Examples, using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-22”) under the conditions of 25 ° C. and 50 rpm. The viscosity was measured.

(2) 0.1 mL of each curable resin composition obtained in Examples and Comparative Examples was applied on a glass substrate using a coating pipette, and the diameter that spread after 1 minute was measured. When the diameter is 15 mm or more, “と し て”, when 12 mm or more and less than 15 mm, “◯”, when 10 mm or more and less than 12 mm, “Δ”, and when less than 10 mm, “×”, The applicability was evaluated.

(3) Curability Each curable resin composition obtained in the curable examples and comparative examples was irradiated with 395 nm ultraviolet rays at 1500 mJ / cm ² using an ultraviolet irradiation device (“QEL-15SQ3W” manufactured by Quark Technology Co., Ltd.). And cured. The calorific value before and after curing was measured using a DSC apparatus (Rigaku Corporation, “Thermo Plus2 / DSC8230”), and the reaction rate of the epoxy group was derived from the following formula. The curable resin composition obtained in Example 8 was cured by heating at 100 ° C. for 30 minutes instead of ultraviolet irradiation.
Epoxy group reaction rate (%) = 100 × (heat generation amount before curing−heat generation amount after curing) / heat generation amount before curing “◎”, 90% when the reaction rate of the epoxy group is 95% or more The curability was evaluated as “◯” when it was less than 95%, “Δ” when it was 70% or more and less than 90%, and “x” when it was less than 70%.
The “heat generation amount before curing” means the heat generation amount when the unreacted curable resin composition is reacted by heating at a high temperature and completely cured, and the “heat generation amount after curing” It means the calorific value due to the reaction of the residual functional group of the curable resin composition after it has been made.

(4) Flexibility Each curable resin composition obtained in Examples and Comparative Examples is sandwiched between two PET resins with a thickness of 100 μm, and an ultraviolet irradiation device (manufactured by Quark Technology Co., Ltd.) is applied to the curable resin composition. , “QEL-15SQ3W”) was irradiated with 1,500 mJ / cm ^{2 of} 395 nm ultraviolet rays to be cured, and a test film having a thickness of 100 μm was produced. Note that the curable resin composition obtained in Example 8 was cured by heating at 100 ° C. for 30 minutes instead of ultraviolet irradiation to prepare a test film.
When the obtained test film was bent into a curvature having a diameter of 1 cm, the case where the resin film was not broken was evaluated as “◯”, and the case where the resin film was broken was evaluated as “X”.

(5) 100 mg of each curable resin composition obtained in the low outgassing Examples and Comparative Examples was weighed and sealed in a vial, and an ultraviolet irradiation device (manufactured by Quark Technology Co., Ltd., “ QEL-15SQ3W ") was irradiated with 1,500 mJ / cm ^{2 of} 395 nm ultraviolet light and cured. Furthermore, this vial was heated in a constant temperature oven at 85 ° C. for 100 hours, and the vaporized components in the vial were measured using a gas chromatograph mass spectrometer (“JMS-Q1050” manufactured by JEOL Ltd.). The curable resin composition obtained in Example 8 was cured by heating at 100 ° C. for 30 minutes instead of ultraviolet irradiation.
The low outgassing property was evaluated as “◯” when the vaporized component amount was less than 50 ppm, “Δ” when it was 50 ppm or more and less than 100 ppm, and “X” when it was 100 ppm or more.

(6) Display performance of organic EL display element (production of a substrate on which a laminate having an organic light emitting material layer is disposed)
A glass substrate (length 30 mm, width 30 mm, thickness 0.7 mm) on which an ITO electrode was formed to a thickness of 1000 mm was used as the substrate. The substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, respectively, then washed with boiled isopropyl alcohol for 10 minutes, and a UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd.). The last treatment was performed with “NL-UV253”).
Next, this substrate is fixed to the substrate folder of the vacuum deposition apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is put into an unglazed crucible and other different types. 200 mg of tris (8-quinolinolato) aluminum (Alq ₃ ) was put in an unglazed crucible, and the inside of the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa. Thereafter, the crucible containing α-NPD was heated, and α-NPD was deposited on the substrate at a deposition rate of 15 ｓ / s to form a 600 正 孔 hole transport layer. Next, the crucible containing Alq ₃ was heated to form an organic light emitting material layer having a thickness of 600 で at a deposition rate of 15 Å / s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and aluminum is added to another tungsten boat. 1.0 g of wire was added. After that, the inside of the vapor deposition unit of the vacuum vapor deposition apparatus is depressurized to 2 × 10 ⁻⁴ Pa to form a lithium fluoride film with a thickness of 5 mm at a deposition rate of 0.2 kg / s, and then aluminum with a film thickness of 1000 mm at a rate of 20 kg / s. did. The inside of the vapor deposition unit was returned to normal pressure with nitrogen, and the substrate on which the laminate having the organic light emitting material layer was arranged was taken out.

(Coating with inorganic material film A)
A mask having an opening was placed so as to cover the entire laminated body of the substrate on which the obtained laminated body was arranged, and an 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 source gases, the flow rates of each are SiH ₄ gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
The formed inorganic material film A had a thickness of about 1 μm.

(Formation of resin protective film)
Each curable resin composition obtained in Examples and Comparative Examples was applied to a glass substrate with an ejection amount of 80 pL by an inkjet method using an inkjet ejection device (“Nanoprinter 300” manufactured by Microjet Co., Ltd.). At the time of application, the film thickness was adjusted to 20 μm or less. Next, the curable resin composition was irradiated with 1,500 mJ / cm ^{2 of} 395 nm ultraviolet rays using an ultraviolet irradiation device (“QEL-15SQ3W” manufactured by Quark Technology Co., Ltd.), and then cured by heating at 80 ° C. for 30 minutes to obtain a resin. A protective film was formed. The curable resin composition obtained in Example 8 was cured by heating at 100 ° C. for 30 minutes instead of ultraviolet irradiation.

(Coating with inorganic material film B)
After forming the resin protective film, a mask having an opening was placed so as to cover the entire resin protective film, and an 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 source gases, the flow rates of each are SiH ₄ gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
The formed inorganic material film B had a thickness of about 1 μm.

(Light emission state of organic EL display element)
The obtained organic EL display device was exposed for 100 hours under the conditions of a temperature of 85 ° C. and a humidity of 85%, and then a voltage of 10 V was applied, and the light emission state of the device (the presence or absence of light emission and dark spots) was visually observed. . Evaluation was made as “◯” when there was no dark spot or peripheral quenching, and “◯” when the dark spot or peripheral quenching was observed, and “X” when the non-light emitting part was significantly enlarged.

According to this invention, generation | occurrence | production of outgas can be suppressed and the curable resin composition excellent in applicability | paintability can be provided. Moreover, according to this invention, the sealing compound for organic electroluminescent display elements which consists of this curable resin composition can be provided.

Claims (3)

A curable resin composition containing a cationic polymerizable compound and a cationic polymerization initiator,
The cationic polymerizable compound is a group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3). A curable resin composition containing at least one selected from the group consisting of

In formula (1-1), R ¹ represents a bond, a linear or branched alkylene group having 1 to 18 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms. R ² and R ³ are each independently hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms. In Formula (1-2), R ⁴ is a linear or branched alkylene group having 3 to 18 carbon atoms, or a linear or branched alkenylene group having 3 to 18 carbon atoms, R ⁵ and R ⁶ are each independently hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms. In the formula (1-3), R ⁷ and R ⁸ are each independently a linear or branched alkylene group having 1 to 18 carbon atoms, or a linear or branched carbon number 2 to 18 is an alkenylene group, and each of R ⁹ to R ¹² is independently hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms. The curable resin composition according to claim 1, wherein the cationic polymerizable compound contains a compound represented by the formula (1-1). A sealing agent for organic electroluminescence display elements, comprising the curable resin composition according to claim 1.