JP6487840B2 - Curable resin composition for sealing organic electroluminescence display element, curable resin sheet for sealing organic electroluminescence display element, and organic electroluminescence display element - Google Patents

Description

The present invention relates to a curable resin composition for sealing an organic electroluminescence display element, which is excellent in transparency and barrier properties of a cured product. Moreover, this invention relates to the curable resin sheet for organic electroluminescent display element sealing formed using this curable resin composition for organic electroluminescent display element sealing, and an organic electroluminescent display element.

An organic electroluminescence (hereinafter, also referred to as “organic EL”) display element has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and the organic light emitting material layer is formed from one electrode on the organic light emitting material layer. When electrons are injected and holes are injected from the other electrode, the electrons and holes are combined in the organic light emitting material layer to emit light. Thus, since the organic EL display element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. Has the advantage.

The organic light-emitting material layer and electrodes constituting the organic EL display element have a problem that the characteristics are easily deteriorated by moisture, oxygen, and the like. Therefore, in order to obtain a practical organic EL display element, it is necessary to extend the life by blocking the organic light emitting material layer and the electrode from the atmosphere. As a method for blocking the organic light emitting material layer and the electrode from the atmosphere, an organic EL display element is sealed with a sealant (for example, Patent Document 1). When sealing an organic EL display element with a sealant, an inorganic film called a passivation film is usually provided on a laminate having an organic light emitting material layer in order to sufficiently suppress the transmission of moisture, oxygen, and the like. A method of sealing the top with a sealant is used.

In recent years, instead of a bottom emission type organic EL display element that extracts light emitted from an organic light emitting material layer from the side of the substrate surface on which the light emitting element is formed, a top emission type organic substance that extracts light from the upper surface side of the organic light emitting layer EL display elements have attracted attention. This method has an advantage that it has a high aperture ratio and is driven at a low voltage, which is advantageous for extending the life. In such a top emission type organic EL display element, since the upper surface side of the light emitting layer needs to be transparent, a transparent moisture-proof substrate such as glass is interposed on the upper surface side of the light emitting element via a transparent sealing resin. It seals by laminating | stacking a material (for example, patent document 2).
However, in such a top emission type organic EL display element, there is no space for disposing a desiccant so as not to shield the light extraction direction, and it is difficult to obtain a sufficient moisture-proofing effect and the life is short. There was a problem of becoming.

JP 2007-115692 A JP 2001-357773 A

An object of this invention is to provide the curable resin composition for organic electroluminescent display element sealing which is excellent in transparency and barrier property of hardened | cured material. Moreover, this invention aims at providing the curable resin sheet for organic electroluminescent display element sealing which uses this curable resin composition for sealing an organic electroluminescent display element, and an organic electroluminescent display element. .

The present invention contains a polyfunctional cation polymerizable compound, an organic layered silicate, and a curing agent, and the organic layered silicate is dispersed in the polyfunctional cationic polymerizable compound, It is a curable resin composition for organic electroluminescent display element sealing whose content of a silicate is 20-250 weight part with respect to 100 weight part of said polyfunctional cation polymeric compounds.
The present invention is described in detail below.

In order to improve the barrier property (moisture permeability prevention property) of the curable resin composition for sealing an organic EL display element, the present inventors disperse an inorganic filler such as talc or silica in a polyfunctional cationic polymerizable compound. I tried to make it. However, if such an inorganic filler is to be dispersed in the polyfunctional cationically polymerizable compound, it is difficult to disperse due to thickening, and the aggregate of the inorganic filler is inferior in transparency, or the inorganic filler is Even if it is dispersed to such an extent that transparency can be obtained, there is a problem that the obtained cured product has insufficient barrier properties.
As a result of intensive studies, the present inventors have made it possible to disperse the organically modified layered silicate in the polyfunctional cation polymerizable compound with almost no aggregation up to the nanometer-sized primary particles. It was found that a transparent cured product can be obtained. Therefore, the present inventors have formulated the organic layered silicate so that the content is within a specific range, thereby maintaining an excellent barrier property while maintaining high transparency. It discovered that the curable resin composition for sealing could be obtained, and came to complete this invention.

The curable resin composition for sealing an organic EL display element of the present invention contains a polyfunctional cation polymerizable compound.
The polyfunctional cationically polymerizable compound has two or more cationically polymerizable groups in one molecule, and crosslinks and cures by polymerization to express a strong adhesive force.

Examples of the cationic polymerizable group possessed by the polyfunctional cationic polymerizable compound include an epoxy group, an oxetanyl group, and a vinyl ether group. Of these, an epoxy group is preferable.

The minimum with a preferable cation polymerizable group equivalent of the said polyfunctional cation polymeric compound is 50 g / mol, and a preferable upper limit is 400 g / mol. When the cation polymerizable group equivalent of the polyfunctional cation polymerizable compound is less than 50 g / mol, the cured product of the resulting curable resin composition for sealing an organic EL display element generates cracks by heating or deformation. There is. When the cation polymerizable group equivalent of the polyfunctional cation polymerizable compound exceeds 400 g / mol, the cured product of the resulting curable resin composition for sealing an organic EL display element may be inferior in barrier properties. The more preferable lower limit of the cation polymerizable group equivalent of the polyfunctional cation polymerizable compound is 70 g / mol, and the more preferable upper limit is 300 g / mol.
In addition, the cation polymerizable group equivalent of the polyfunctional cation polymerizable compound is the number of moles (mol) of the cation polymerizable group contained in the polyfunctional cation polymerizable compound by weight (g) of the polyfunctional cation polymerizable compound. The value obtained by dividing.

The minimum with a preferable molecular weight of the said polyfunctional cation polymeric compound is 150, and a preferable upper limit is 1000. When the molecular weight of the polyfunctional cation polymerizable compound is less than 150, outgas may be generated. When the molecular weight of the polyfunctional cation polymerizable compound exceeds 1000, the fluid adhesiveness of the resulting curable resin composition for sealing an organic EL display element may be lowered. The more preferable lower limit of the molecular weight of the polyfunctional cation polymerizable compound is 200, the more preferable upper limit is 700, the still more preferable lower limit is 250, and the still more preferable upper limit is 550.
The molecular weight of the polyfunctional cationically polymerizable compound is the molecular weight obtained from the structural formula for the compound whose molecular structure is specified, but for the compound with a wide distribution of polymerization degree and the compound whose modification site is unspecified. , Sometimes expressed using weight average molecular weight. In the present specification, the above “weight average molecular weight” is a value determined by polystyrene conversion after measurement by gel permeation chromatography (GPC). As a column used when measuring the weight average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko KK) etc. are mentioned, for example.

Examples of the polyfunctional cationic polymerizable compound include bisphenol A skeleton, bisphenol F skeleton, hydrogenated bisphenol A skeleton, hydrogenated bisphenol F skeleton, phenol novolac skeleton, biphenyl skeleton, hydrogenated biphenyl skeleton, dicyclopentadiene skeleton, and naphthalene. Examples thereof include monomers or oligomers having a skeleton, a triazine skeleton, and the like. Among them, since moisture absorption and water vapor transmission rate are reduced and deterioration of light emission of the obtained organic EL display element can be further suppressed, hydrogenated bisphenol A skeleton, hydrogenated bisphenol F skeleton, dicyclopentadiene skeleton, etc. A monomer or oligomer having an alicyclic skeleton is preferred. An alicyclic epoxy monomer or oligomer having both an alicyclic skeleton and cationic polymerizability is also preferred. By using a monomer or oligomer having an alicyclic skeleton or an alicyclic epoxy monomer or oligomer as the polyfunctional cation polymerizable compound, the curable resin composition is hardly colored by heat or light, and the curable resin composition absorbs light. It is possible to reduce the loss of EL emission and the change in color tone. These polyfunctional cation polymerizable compounds may be used independently and 2 or more types may be used together.

The curable resin composition for sealing an organic EL display element of the present invention contains an organically modified layered silicate.
By containing the organically modified layered silicate, the curable resin composition for sealing an organic EL display element of the present invention is particularly excellent in barrier properties.

The organically modified layered silicate is obtained by replacing an exchangeable cation existing between the crystal layers of the layered silicate with an organic cation and treating the layered silicate with an organic onium salt (ion exchange). preferable.
Specifically, the organically modified layered silicate is a layered silicic acid in which 50 to 90 milligram equivalents / 100 g of exchangeable cations of a layered silicate having an ion exchange capacity of 50 to 130 milligram equivalents / 100 g are substituted with organic onium ions. A salt is preferred.

Examples of the layered silicate include smectite clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite, nontronite, swelling mica, vermiculite, and halloysite. Especially, it is preferable that the layered silicate used for the said organically modified layered silicate is a smectite clay mineral. From the viewpoint of swelling, at least one selected from the group consisting of montmorillonite, hectorite, saponite, swellable mica, and vermiculite is preferably used.
These layered silicates may be used alone or in combination of two or more.

The preferred lower limit of the ion exchange capacity of the layered silicate is 50 milligram equivalent / 100 g, and the preferred upper limit is 130 milligram equivalent / 100 g. When the ion exchange capacity of the layered silicate is less than 50 milligram equivalent / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate due to cation exchange is reduced, so that there is sufficient space between the crystal layers. May not be organic. When the ion exchange capacity of the layered silicate exceeds 130 milligram equivalent / 100 g, the bonding force between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may be difficult to peel off. A more preferred lower limit of the ion exchange capacity of the layered silicate is 80 milligram equivalent / 100 g, a more preferred upper limit is 120 milligram equivalent / 100 g, a still more preferred lower limit is 100 milligram equivalent / 100 g, and a still more preferred upper limit is 105 milligram equivalent / 100 g. .
The ion exchange capacity of the layered silicate can be measured by the amount of methylene blue adsorbed. The amount of methylene blue adsorbed is determined by weighing the layered silicate before ion exchange and preparing a 1 wt% dispersion, then titrating with methylene blue, and the amount of methylene blue required for titration and the amount of layered silicate used. It can be calculated from the quantity.

Examples of the organic onium salts include quaternary ammonium salts, quaternary phosphonium salts, imidazolium salts, and the like. Among these, a quaternary ammonium salt is preferable from the viewpoint of suppressing coloring as much as possible. The said organic onium salt may be used independently and 2 or more types may be used together.

Examples of the quaternary ammonium salt include trioctylalkylammonium salts such as lauryltrimethylammonium salt and stearyltrimethylammonium salt, trioctylalkylammonium salt, tributylalkylammonium salt, and trioctylmethylammonium salt. Dimethyldialkylammonium salts such as salt, distearyl dimethylammonium salt, di-cured tallow dimethylammonium salt, dibutyldialkylammonium salt, trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt, Dibenzyl dialkyl ammonium salts such as methyl benzyl dialkyl ammonium salt and distearyl dibenzyl ammonium salt, Quaternary ammonium salts having an aromatic ring such as tilphenyl ammonium salt, dialkyl quaternary ammonium salts having two polyethylene glycol chains, dialkyl quaternary ammonium salts having two polypropylene glycol chains, N-polyoxyethylene- Examples thereof include a trialkyl quaternary ammonium salt having one polyethylene glycol chain such as N-lauryl-N, N-dimethylammonium salt, and a trialkyl quaternary ammonium salt having one polypropylene glycol chain. Among these, from the viewpoint of improving dispersibility of the layered silicate, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl-N, N-dimethylammonium salt is more preferred. These quaternary ammonium salts may be used alone or in combination of two or more.

Examples of the quaternary phosphonium salt include dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylphosphonium salt, distearyldimethylphosphonium salt, distearyldibenzylphosphonium salt, and the like. Is mentioned.

Examples of the imidazolium salt include dimethylbutylimidazolium salt, dimethyloctylimidazolium salt, dimethyldecylimidazolium salt, dimethyldodecylimidazolium salt, dimethylhexadecylimidazolium salt, and the like.

The phosphonium salt and the imidazolium salt may be used alone, or only one kind may be used in combination with a quaternary ammonium salt, or two or more kinds may be used in combination with a quaternary ammonium salt. .

As described above, the organically modified layered silicate is preferably one in which 50 to 90 milligram equivalents / 100 g of exchangeable cations in the layered silicate are substituted with organic onium ions. That is, it is preferable that the substitution ratio of the organic onium ion to the exchangeable cation is adjusted to 50 to 90%. When the substitution ratio of the organic onium ion to the exchangeable cation is less than 50%, the dispersibility of the organically modified layered silicate is lowered, and the transparency of the resulting curable resin composition for sealing an organic EL display element is obtained. May get worse. When the substitution ratio of the organic onium ion to the exchangeable cation exceeds 90%, the organic onium ion is thermally decomposed when the curable resin composition for sealing an organic EL display element is heated in a drying step for removing the solvent. May occur and coloring may occur.
In addition, the substitution rate of the organic onium ion with respect to the said exchangeable cation can be adjusted to arbitrary ratios by adjusting the usage-amount of the said organic onium salt.
The substitution rate of organic onium ions in the organically modified layered silicate can be measured using an organic element analyzer. Measurement with the above organic element analyzer detects CO ₂ , H ₂ O, and N ₂ gases generated by burning organic layered silicate in pure oxygen and burning C, H, and N, which are constituent elements of organic matter. It is carried out by a known method for quantification.

Examples of the method for treating (ion exchange) the layered silicate with the organic onium salt include a method of adding the organic onium salt to water in which the layered silicate is dispersed.

The organic layered silicate is preferably treated with a silane coupling agent. By treating the organic layered silicate with a silane coupling agent, compatibility with the polyfunctional cationic polymerizable compound is improved, and even when a large amount of the organic layered silicate is blended, the organic layered silicates are Aggregation can be suppressed. As a result, excellent barrier properties can be imparted to the resulting curable resin composition for sealing an organic EL display element while maintaining good transparency.

Examples of the silane coupling agent include N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3- (2-aminoethyl) aminopropyltrimethoxy. Aminosilanes such as silane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, etc. Methacrylic silane such as vinyl silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethosicilla Mercaptosilane such as 3-mercaptopropylethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl Epoxy silanes such as diethoxysilane, ureido silanes such as 3-ureidopropyltriethoxysilane, isocyanate silanes such as 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxy Silane, trimethylmethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyldimethoxysilane, isobutyltrimethoxysilane, cyclohexylmethyldimethyl Alkylsilane and the like Kishishiran include phenyl trimethoxysilane. Especially, since it is excellent in the effect which improves the compatibility with the said polyfunctional cation polymeric compound, aminosilane is preferable.

Examples of the method for treating the organically modified layered silicate with a silane coupling agent include, for example, a wet method of treating in a solution in which the organically modified layered silicate is dispersed, and the organically modified layered silicate as a powder. Examples thereof include a dry method in which treatment is directly performed, an integral blend method in which treatment is performed in a resin composition in which the organically modified layered silicate is dispersed in a resin, and the like. Among these, from the viewpoint of suppressing the aggregation of the organically modified layered silicate by the silane coupling agent, a wet method that can be processed in a state where the organically modified layered silicate is well dispersed is preferable. In the case of performing the wet method, it is preferable that the organically modified layered silicate is blended in the polyfunctional cation polymerizable compound while being dispersed in the solution after being treated with the silane coupling agent without being isolated from the solution.

As for the usage-amount of the said silane coupling agent, a preferable minimum is 0.5 weight part and a preferable upper limit is 10 weight part with respect to 100 weight part of said organically modified layered silicate. When the amount of the silane coupling agent used is 0.5 parts by weight or more, the compatibility between the organically modified layered silicate and the polyfunctional cation polymerizable compound is improved, and the organicated layered silicate is aggregated. Can be suppressed. When the usage-amount of the said silane coupling agent is 10 weight part or less, the coupling | bonding of the organically modified layered silicate by a silane coupling agent becomes difficult to occur. The minimum with the more preferable usage-amount of the said silane coupling agent is 1 weight part, and a more preferable upper limit is 5 weight part.

The preferable lower limit of the average primary particle diameter of the organically modified layered silicate is 10 nm, and the preferable upper limit is 200 nm. When the average primary particle diameter of the organically modified layered silicate is less than 10 nm, the barrier property may be lowered. When the average primary particle diameter of the organically modified layered silicate exceeds 200 nm, transparency may be impaired. The more preferable lower limit of the average primary particle diameter of the organically modified layered silicate is 20 nm, and the more preferable upper limit is 100 nm.
The average primary particle size of the organically modified layered silicate can be measured using a dynamic light scattering particle size measuring device (“ELSZ-1000S” manufactured by Otsuka Electronics Co., Ltd.).

The lower limit of the content of the organically modified layered silicate is 20 parts by weight and the upper limit is 250 parts by weight with respect to 100 parts by weight of the polyfunctional cation polymerizable compound. When the content of the organically modified layered silicate is less than 20 parts by weight, the cured product of the resulting curable resin composition for sealing an organic EL display element is inferior in barrier properties. When content of the said organic layered silicate exceeds 250 weight part, transparency of the curable resin composition for organic EL display element sealing obtained will deteriorate. A preferred lower limit for the content of the organically modified layered silicate is 30 parts by weight, a preferred upper limit is 200 parts by weight, a more preferred lower limit is 50 parts by weight, and a more preferred upper limit is 150 parts by weight.
In addition, as described above, when the organically modified layered silicate is treated with a silane coupling agent, aggregation of the organically modified layered silicate occurs even when blended in a large amount in the polyfunctional cation polymerizable compound. Since it becomes difficult, it becomes possible to mix | blend more organic layered silicate. In this case, the content of the organically modified layered silicate is preferably 100 parts by weight and preferably 220 parts by weight with respect to 100 parts by weight of the polyfunctional cation polymerizable compound. When the amount of the organically modified layered silicate treated with the silane coupling agent is within this range, the barrier property can be further improved while maintaining good transparency. A more preferable lower limit of the content of the organically modified layered silicate is 130 parts by weight.

As a method for producing the curable resin composition for sealing an organic EL display device of the present invention, a solution containing the polyfunctional cation polymerizable compound, a dispersion liquid in which the organically modified layered silicate is dispersed in a dispersion medium, A method is preferably used in which the organically modified layered silicate is dispersed in the polyfunctional cationically polymerizable compound. Here, from the viewpoints of transparency and barrier properties, the organically modified layered silicate is preferably highly dispersed in the polyfunctional cation polymerizable compound. Here, the term “highly” refers to a state in which there is no aggregation of clay and delamination and dispersion can be confirmed by observation with an electron microscope.

A solvent used in a solution containing the polyfunctional cation polymerizable compound, and a dispersion medium used in a dispersion in which the organically modified layered silicate is dispersed in a dispersion medium (hereinafter, also simply referred to as “solvent”). For example, aromatics such as benzene, toluene, xylene, alcohols such as methanol, ethanol, isopropyl alcohol, NN′-dimethylformamide, NN′-dimethylacetamide, N-methyl-2 Amides such as pyrrolidone, lactones such as γ-butyrolactone, γ-valerolactone and δ-valerolactone, carbonates such as ethylene carbonate and propylene carbonate, glymes such as monoglyme, diglyme and triglyme, dimethyl Examples include aprotic polar solvents such as sulfoxide.
Among these, from the viewpoint of easy removal, a solvent having a relatively low boiling point and high volatility is preferable, aromatics such as benzene, toluene and xylene are more preferable, and toluene is more preferable.

For sealing the organic EL display element of the present invention by mixing the polyfunctional cation polymerizable compound or a solution containing the polyfunctional cation polymerizable compound and a dispersion in which the organically modified layered silicate is dispersed in a dispersion medium. When the curable resin composition is produced, when the organic EL display element is sealed using the obtained curable resin composition for sealing an organic EL display element, it is necessary to remove the solvent by drying or the like. .
As a method of removing the solvent, when a method of directly applying a curable resin composition for sealing an organic EL display element containing the solvent on an organic EL display element and then drying the organic EL display element is used, It may be deteriorated by contact with the heat or heating during drying.
Therefore, as a method for removing the solvent, there is a method in which a curable resin composition for sealing an organic EL display element containing a solvent is applied to a transparent moisture-proof substrate such as glass or a gas barrier film and then dried. Preferably used. After drying and removing the solvent, a substrate on which a laminate having an organic light emitting material layer is formed via an organic EL display element sealing curable resin composition (hereinafter also referred to as “organic EL display element substrate”). ) And a transparent moisture-proof substrate, and the organic EL display element can be sealed by curing the curable resin composition for sealing an organic EL display element.
Moreover, as a method for removing the solvent, a curable resin composition for sealing an organic EL display element containing a solvent is applied on a support such as a PET (polyethylene terephthalate) film subjected to a release treatment. The method of drying from is also preferably used. After removing the solvent by drying, the curable resin composition for sealing an organic EL display element coated on the support and dried is transparent moisture-proof on an organic EL display element substrate or glass or the like. After laminating and transferring on the base material, the organic EL display element substrate and the transparent moisture-proof base material are bonded together via a curable resin composition for sealing an organic EL display element, and the organic EL display element sealing is cured. The organic EL display element can be sealed by curing the conductive resin composition.

Examples of the method for drying the curable resin composition for sealing an organic EL display element containing a solvent include a method of heating and drying with hot air, infrared rays, far infrared rays, radiation, an electric heater, and the like, or drying under reduced pressure. Methods and the like. When drying the curable resin composition for sealing an organic EL display element containing a solvent, drying is preferably performed at 120 ° C. or less, and is performed at 100 ° C. or less from the viewpoint of preventing deterioration of the organic EL display element. It is more preferable.

The curable resin composition for sealing an organic EL display element of the present invention contains a curing agent.
As the curing agent, a thermosetting agent and / or a cationic polymerization initiator can be used.

The thermosetting agent has a function of starting curing of the polyfunctional cation polymerizable compound by heating and promoting curing.

Examples of the thermosetting agent include hydrazide compounds, imidazole derivatives, secondary amine compounds, tertiary amine compounds, acid anhydrides, dicyandiamide, guanidine derivatives, modified aliphatic polyamines, addition products of various amines and epoxy resins, and the like. Is mentioned.
These thermosetting agents may be used alone or in combination of two or more.

Examples of the hydrazide compound include 1,3-bis (hydrazinocarbonoethyl-5-isopropylhydantoin).
Examples of the imidazole derivatives include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2,3-dihydro Imidazole compounds such as 1H-pyrrolo [1,2-a] benzimidazole, imidazolines such as 2-methylimidazoline and 2-phenylimidazoline, 1-cyanoethyl-2-undecylimidazolium trimellitate, epoxy- Imidazo Imidazole derivatives such as adduct thereof.
Examples of the secondary amine compound include piperidine.
Examples of the tertiary amine compound include N, N-dimethylpiperazine, triethylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, and the like. .
Examples of the acid anhydride include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, methylhexahydrophthalic anhydride, hydrogenated methylnadic acid anhydride, ethylene glycol-bis (anhydrotrimethylene). Tate) and the like. Of these, alicyclic acid anhydrides containing no double bond are preferred.

The preferable lower limit of the molecular weight of the thermosetting agent is 80, and the preferable upper limit is 800. If the molecular weight of the thermosetting agent is less than 80, volatility increases and outgassing may occur. When the molecular weight of the thermosetting agent exceeds 800, fluidity when thermocompression bonding the curable resin composition for sealing an organic EL display device to the device is reduced, or diffusibility in the composition is reduced, Sufficient curability may not be obtained. The more preferable lower limit of the molecular weight of the thermosetting agent is 100, the more preferable upper limit is 500, the still more preferable lower limit is 120, and the more preferable upper limit is 250.

As the cationic polymerization initiator, a thermal cationic polymerization initiator that initiates a curing reaction by heat or a photo cationic polymerization initiator that initiates a curing reaction by light can be used.

Examples of the thermal cationic polymerization initiator include sulfonium salts, phosphonium salts, quaternary ammonium salts, diazonium salts, iodonium salts, and the like. Of these, sulfonium salts are preferred.
Examples of the counter anion in the thermal cationic polymerization initiator include BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , B (C ₆ F ₅ ) ^{4− and the} like.
Examples of the sulfonium salt include triphenylsulfonium boron tetrafluoride, triphenylsulfonium hexafluoride antimony, triphenylsulfonium hexafluoride arsenic, tri (4-methoxyphenyl) sulfonium hexafluoride arsenic, and diphenyl (4-phenyl). And thiophenyl) sulfonium arsenic hexafluoride.
Examples of the phosphonium salt include ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride.
Examples of the quaternary ammonium salt include N, N-dimethyl-N-benzylanilinium hexafluoride antimony, N, N-diethyl-N-benzylanilinium tetrafluoride, N, N-dimethyl-N—. Benzylpyridinium hexafluoroantimony, N, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimony, N, N-diethyl-N- (4-methoxybenzyl) pyridinium hexafluoride, N, N-diethyl-N- (4-methoxybenzyl) toluidinium hexafluoride, N, N-dimethyl-N- (4-methoxybenzyl) toluidinium hexafluoride Antimony etc. are mentioned.

Examples of commercially available thermal cationic polymerization initiators include, for example, Adeka Opton CP-66, Adeka Opton CP-77 (both manufactured by ADEKA), and thermal cations having not only thermal activity but also photoactivity. Examples of the polymerization initiator include Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-100, Sun-Aid SI-110, and Sun-Aid SI-180 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. There may be.
In particular, the resulting curable resin composition for sealing an organic electroluminescence display element is particularly excellent in adhesiveness to a substrate such as Ni-plated Cu glass or non-alkali glass. A salt having a phosphorous ion or a salt represented by the following formula (1) is preferred.

In formula (1), n represents an integer of 1 to 12, m represents an integer of 1 to 5, and Rf represents a fluoroalkyl group formed by substituting all or part of hydrogen of an alkyl group with fluorine. .

The antimony complex is not particularly limited, but is preferably a sulfonium salt.
Specific examples of the sulfonium salt that is the antimony complex include tetraphenyl (diphenyl sulfide-4,4′-diyl) bissulfonium di (antimony hexafluoride), tetra (4-methoxyphenyl) [diphenyl Sulfide-4,4′-diyl] bissulfonium · di (antimony hexafluoride), diphenyl (4-phenylthiophenyl) sulfonium · antimony hexafluoride, di (4-methoxyphenyl) [4-phenylthiophenyl] sulfonium -Antimony hexafluoride etc. are mentioned.
As what is marketed among the said antimony complexes, Adeka optomer SP170 (made by ADEKA) etc. are mentioned, for example.

Examples of the salt having phosphorous hexafluoride include diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, and the like. Examples of commercially available salts having phosphorus hexafluoride ions include WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.) and CPI-100P (manufactured by San Apro).

Examples of commercially available salts represented by the above formula (1) include CPI-200K and CPI-210S (both manufactured by San Apro).

The content of the curing agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polyfunctional cationically polymerizable compound. If the content of the curing agent is less than 0.1 parts by weight, the resulting curable resin composition for sealing an organic EL display element may not be sufficiently cured. When content of the said hardening | curing agent exceeds 10 weight part, the curable resin composition for organic EL display element sealing obtained may be colored, or it may become inferior to storage stability. The minimum with more preferable content of the said hardening | curing agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.
When the acid anhydride is used as the curing agent, the amount of the acid anhydride is preferably 50 parts by weight with respect to 100 parts by weight of the polyfunctional cation polymerizable compound, and 150 parts by weight with respect to the preferred upper limit. It is.

When the acid anhydride is used as the curing agent, the curable resin composition for sealing an organic EL display element of the present invention may contain a curing accelerator.
Examples of the curing accelerator include quaternary ammonium salts, quaternary sulfonium salts, DBU fatty acid salts, various metal salts, imidazoles, and tertiary amines.
Examples of the quaternary ammonium salt include tetramethylammonium bromide and tetrabutylammonium bromide.
Examples of the quaternary sulfonium salt include tetraphenylphosphonium bromide and tetrabutylphosphonium bromide.
Examples of the DBU fatty acid salt include diazabicycloundecene 2-ethylhexanoate.
Examples of the metal salt include zinc octylate and tin octylate.
Examples of the imidazole include 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, and the like.
Examples of the tertiary amine include tris (dimethylaminomethylphenol, benzyldimethylamine and the like.

The preferable upper limit of the content of the curing accelerator is 10 parts by weight with respect to 100 parts by weight of the polyfunctional cation polymerizable compound. By adding the curing accelerator so as to have a content of 10 parts by weight or less, the curing temperature when the acid anhydride is used as the curing agent can be appropriately adjusted.

Moreover, when using the said photocationic polymerization initiator as said hardening | curing agent, it is preferable to contain the sensitizer which consists of a benzophenone derivative represented by following formula (2). The sensitizer has a role of further improving the polymerization initiation efficiency of the photocationic polymerization initiator and appropriately promoting the curing reaction of the curable resin composition for sealing an organic EL display device of the present invention.

In formula (2), R ¹ and R ² represent hydrogen, a substituent represented by the following formula (3-1), or a substituent represented by the following formula (3-2). R ¹ and R ² may be the same as or different from each other.

In formulas (3-1) and (3-2), R ³ is hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group Represents a carboxyl group or a carboxylic acid alkyl ester group having 1 to 20 carbon atoms.

Specific examples of the benzophenone derivative represented by the above formula (2) include benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4- And benzoyl-4′-methyldiphenyl sulfide.

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 polyfunctional cation polymerizable compound. 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, absorption may be excessively increased and light may not be transmitted to the deep part. 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 for sealing an organic EL display element of the present invention may contain a curing retarder. By containing the said hardening retarder, the pot life of the curable resin composition for organic EL display element sealing obtained can be lengthened.

Examples of the curing retardant include amines such as benzylamine and glycidylamine, polyether compounds, and the like.
Examples of the polyether compound include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and a crown ether compound.

The content of the curing retarder is preferably 0.05 parts by weight and preferably 5.0 parts by weight with respect to 100 parts by weight of the polyfunctional cation polymerizable compound. If the content of the curing retarder is less than 0.05 parts by weight, the resulting curable resin composition for sealing an organic EL display element may not be sufficiently imparted with a retardation effect. If the content of the curing retarder exceeds 5.0 parts by weight, a large amount of outgas may be generated when the resulting curable resin composition for sealing an organic EL display element is cured. The minimum with more preferable content of the said retarder is 0.1 weight part, and a more preferable upper limit is 3.0 weight part.

The curable resin composition for sealing an organic EL display element of the present invention preferably contains a silane coupling agent. The said silane coupling agent has a role which improves the adhesiveness of the curable resin composition for organic EL display element sealing of this invention, and a to-be-adhered body.

The silane coupling agent preferably has a cationic polymerizable group.
Examples of the cationic polymerizable group that the silane coupling agent preferably has include an epoxy group and an oxetanyl group.
Examples of the silane coupling agent having a cationic polymerizable group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , 3-ethyl-[(triethoxysilylpropoxy) methyl] oxetane and the like. Of these, 3-glycidoxypropyltrimethoxysilane is preferred from the viewpoint of compatibility with the polyfunctional cationically polymerizable compound and stability. 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 5 parts by weight with respect to 100 parts by weight of the polyfunctional cation polymerizable compound. When the content of the silane coupling agent is less than 0.1 parts by weight, the effect of improving the adhesiveness of the resulting curable resin composition for sealing an organic EL display element may not be sufficiently exhibited. When the content of the silane coupling agent exceeds 5 parts by weight, the cured product of the resulting curable resin composition for sealing an organic EL display element may be inferior in barrier properties due to a decrease in crosslinking density, or excessively. The silane coupling agent may bleed out. The minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 2 weight part.

The curable resin composition for sealing an organic EL display element of the present invention may contain a surfactant. By containing the surfactant, it is possible to further improve the flatness after application when the curable resin composition for sealing an organic EL display element of the present invention to be described later is formed into a sheet shape.
The surfactant may have a function such as an antifoaming agent.

Examples of the surfactant include fluorine-based, silicone-based, acrylic-based and the like. Of these, fluorine-based surfactants and silicone-based surfactants are preferable, and fluorine-based surfactants are more preferable.

As the fluorosurfactant, a compound having a fluoroalkyl group or a fluoroalkylene group in at least one of the terminal, main chain and side chain can be preferably used. Specifically, for example, 1,1 , 2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol di (1,1,2,2- Tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol Di (1,1,2,2,3,3-hexafluoropentyl) ether, perfluorododecyl sulfonate Lilium, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, fluoroalkyl Sodium phosphonate, sodium fluoroalkylcarboxylate, fluoroalkyl polyoxyethylene ether, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl poly Examples include oxyethanol, perfluoroalkyl alkoxylates, and fluorine alkyl esters.

Examples of commercially available fluorosurfactants include BM-1000, BM-1100 (manufactured by BM HEMIE), MegaFuck F142D, MegaFuck F172, MegaFuck F173, MegaFuck. F183, Megafuck F178, Megafuck F191, Megafuck F471, Megafuck F476 (above, manufactured by DIC), Florard FC170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S -112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC 105, Surflon SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF301, F-top EF303, F-top EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Aftergent FT-100, Aftergent FT-110, Aftergent FT-140A, Aftergent FT-150, Aftergent FT-250, Aftergent FT-251, Aftergent FTX-251, Aftergent FTX-218, Aftergent FT-300, Aftergent FT-310, Aftergent FT- 400S (above, manufactured by Neos) and the like.

Moreover, as said silicone type surfactant, polyether modified polydimethylsiloxane and polyester modified polydimethylsiloxane are preferable, and polyether modified polydimethylsiloxane is more preferable.

Examples of commercially available silicone surfactants include BYK-354, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK- 349, BYK-370, BYK-378, BYK-3455 (all manufactured by Big Chemie Japan Co., Ltd.), Surflon S-611 (manufactured by AGC Seimi Chemical Co., Ltd.), Tore Silicone DC3PA, Tore Silicone DC7PA, Tore Silicone SH11PA, Tore Silicone SH21PA , Torresi Corn SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH-190, Torre Silicone SH-193, Torre Silicone SZ-6032, Torre Silicone SF-8428, Torre Silicone DC-57, Tole Silicone DC-190 (above, Toray Silicone -Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (manufactured by Momentive Performance Materials Japan). .

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, and polyoxyethylene. Polyoxyethylene aryl ethers such as n-nonylphenyl ether and polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate can also be used.

The said surfactant may be used independently and 2 or more types may be used in combination.
The content of the surfactant is preferably 0.01 parts by weight and preferably 5 parts by weight with respect to 100 parts by weight of the polyfunctional cation polymerizable compound. If the content of the surfactant is less than 0.01 parts by weight, the effect of improving the flatness after coating may not be sufficiently exhibited. If the content of the surfactant exceeds 5 parts by weight, the flatness after coating may be adversely affected, or the adhesion between the curable resin composition for sealing an organic EL display element of the present invention and the adherend. May decrease. The content of the surfactant is more preferably 0.02 parts by weight and more preferably 1 part by weight for the fluorine-based surfactant. Moreover, in a silicone type surfactant, a more preferable minimum is 0.1 weight part and a more preferable upper limit is 2 weight part.

In addition, the curable resin composition for sealing an organic EL display element of the present invention is a known variety such as a storage stabilizer, a plasticizer, a viscoelasticity adjusting agent, and the like, as long as the object of the present invention is not impaired. An additive may be contained.

As a method for producing the curable resin composition for sealing an organic EL display device of the present invention, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, Examples thereof include a method of mixing a polyfunctional cation polymerizable compound, an organically modified layered silicate, a curing agent, and an additive added as necessary.

When the curable resin composition for sealing an organic EL display element of the present invention is a cured product having a thickness of 20 μm, the visible light transmittance at a wavelength of 400 to 800 nm is preferably 95% or more. If the visible light transmittance is less than 95%, the transparency may be inferior, and it may not be applicable to a top emission type organic EL display element. A more preferable lower limit of the visible light transmittance is 97%. The visible light transmittance can be measured using a spectrophotometer.

The curable resin sheet for sealing an organic EL display element obtained by molding the curable resin composition for sealing an organic EL display element of the present invention into a sheet shape is also one aspect of the present invention.

As a method for forming the curable resin composition for sealing an organic EL display device of the present invention into a sheet, a solution coating method is preferable because a sheet having a uniform film thickness can be formed at a relatively low temperature. Specifically, for example, a PET (polyethylene terephthalate) film (hereinafter referred to as “release film”) obtained by subjecting the curable resin composition solution for sealing an organic EL display element of the present invention containing a solvent to a release treatment. A method of obtaining a film by applying the film to a predetermined thickness and drying the solvent is preferably used.

Examples of the method of applying the solvent-containing curable resin composition solution for sealing an organic EL display element on a release film include a roll coat, a slit coat, a comma coat, a gravure coat, a kiss coat, a die coat, Known methods such as lip coating, blade coating, and bar coating can be used.

The organic EL display element manufactured using the curable resin composition for sealing an organic EL display element of the present invention and / or the curable resin sheet for sealing an organic EL display element of the present invention is also one aspect of the present invention. It is.
As a method for producing the organic EL display element of the present invention, for example, the curable resin sheet for sealing an organic EL display element of the present invention formed on a release film is laminated on the organic EL display element substrate by roll bonding. After heat laminating and releasing the release film, an ultra-thin glass or a plastic sheet having gas barrier properties is applied to the organic light emitting material of the organic EL display element substrate through the curable resin sheet for sealing the organic EL display element of the present invention. A method of sealing an organic EL display element by laminating on a laminate having a layer, or a curable resin sheet for sealing an organic EL display element of the present invention formed on a release film by roll bonding After heat laminating on a plastic sheet having gas barrier properties and releasing the release film, the curable resin sheet for sealing an organic EL display device of the present invention is further provided. A method in which by laminating the substrate formed with the laminate having an organic luminescent material layer performs sealing of organic EL display device and the like through.

From the viewpoint of preventing damage and deterioration of the organic EL display element, the organic EL display element of the present invention is preferably produced in a temperature range of about 50 to 100 ° C. Therefore, it is preferable that the curable resin sheet for sealing an organic EL display element of the present invention has a melt viscosity that exhibits fluidity in this temperature range.

The curable resin composition for sealing an organic EL display element of the present invention and the curable resin sheet for sealing an organic EL display element of the present invention include a non-reactive sheet-like pressure-sensitive adhesive, a sheet-like thermoplastic resin, etc. Compared with the conventional sealing material, it is excellent in heat resistance and barrier properties.
Moreover, since the curable resin sheet for sealing an organic EL display element of the present invention is not colored and excellent in transparency, it can be applied to a top emission type organic EL display element excellent in emission extraction efficiency.
Furthermore, the organic EL display element of the present invention has an organic light emitting material layer using the curable resin composition for sealing an organic EL display element and / or the curable resin sheet for sealing an organic EL display element of the present invention. By sealing the gap between the glass or film on which the laminate is formed and the opposing glass or film, it is possible to suppress the generation of dark spots due to the ingress of moisture and the deterioration of display due to the growth of the dark spots. Can be made and has excellent lifetime and reliability.

ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition for organic electroluminescent display element sealing which is excellent in transparency and barrier property of hardened | cured material can be provided. Moreover, according to this invention, the curable resin sheet for organic electroluminescent display element sealing and organic electroluminescent display element which use this curable resin composition for organic electroluminescent display element sealing 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.

Example 1
(1) Preparation of Organized Layered Silicate Dispersion In a 500 mL container, smectite (corp chemical) in which 69 milligram equivalent / 100 g of exchangeable cation was replaced with trioctylmethylammonium ion as an organized layered silicate. "Lucentite STN" (amount of organic substance: 26.1 parts by weight, ion exchange capacity of layered silicate before organicization: 110 mg equivalent / 100 g)) and 400 parts by weight of toluene were added. While irradiating ultrasonic waves at a frequency of 40 KHz with a sonic cleaner, the dispersion was simultaneously stirred for 1 hour at a rotational speed of 2000 rpm by a disper to prepare a toluene dispersion containing 20% by weight of organically modified layered silicate.
Here, the amount of the organic substance indicates the number of parts by weight substituted with organic onium ions when the organic layered silicate is 100 parts by weight.

(2) Preparation of curable resin composition solution for sealing organic EL display element 500 parts by weight of toluene dispersion of organicated layered silicate prepared in “(1) Preparation of organicated layered silicate dispersion” 100 parts by weight of a layered silicate), 100 parts by weight of a bisphenol F-type epoxy monomer (manufactured by DIC, “EPICLON EXA-830LVP”) as a polyfunctional cationic polymerizable compound, and 1,2-dimethylimidazole (Shikoku Kasei Co., Ltd.) as a curing agent Manufactured, "1,2DMZ") 3.0 parts by weight, and 1.0 part by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") as a silane coupling agent , The mixture was stirred and mixed for 2 minutes at a stirring speed of 2000 rpm using a rotation / revolution type stirring mixer ("Shinky Co., Ltd.," Awatori Nertaro ARE-310 type "). To obtain a uniform organic EL display device curable resin composition solution for sealing.

(3) Preparation of curable resin sheet for sealing organic EL display elements “Curable resin for sealing organic EL display elements” obtained in “(2) Preparation of curable resin composition solution for sealing organic EL display elements” The composition solution is applied onto a PET film that has been subjected to a mold release treatment by applying an applicator so that the thickness after drying becomes a desired film thickness, followed by drying in an oven at 80 ° C. for 15 minutes. A curable resin sheet for sealing an organic EL display element laminated on the film was obtained.

(Examples 2 to 11, Comparative Examples 2 and 3)
A curable resin composition solution for sealing an organic EL display element and a curing for sealing an organic EL display element, as in Example 1, except that the materials and blending amounts used are shown in Tables 1 and 2 A functional resin sheet was obtained.
“Lucentite SEN” in Tables 1 and 2 is smectite substituted by dihydroxyethylmethyldodecyl ammonium ion (manufactured by Co-op Chemical Co., Ltd., ion exchange capacity of layered silicate before organicization 110 mg equivalent / 100 g). Yes, “Lucentite SPN” is smectite substituted with polyoxypropylene methyldiethylammonium ion (Coop Chemical Co., Ltd., 62 parts by weight of organic substance, 110 mg equivalent of ion exchange capacity of layered silicate before organicization / 100 g "Lucentite SAN" and "Lucentite SAN316" are smectites substituted with dioctadecyldimethylammonium ions (manufactured by Co-op Chemical Co., Ltd., ion exchange capacity of layered silicate 110 mg equivalent / 100 equivalent) ) It is.

(Comparative Example 1)
100 parts by weight of a bisphenol F type epoxy monomer (manufactured by DIC, “EPICLON EXA-830LVP”) as a polyfunctional cationic polymerizable compound, and 1,2-dimethylimidazole (manufactured by Shikoku Kasei Co., “1,2DMZ”) 3 1.0 part by weight, 1.0 part by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-403”) and 400 parts by weight of toluene are added as a silane coupling agent. A uniform curable resin composition solution for sealing an organic EL display element is prepared by stirring and mixing for 2 minutes at a stirring speed of 2000 rpm with a stirring mixer ("Shinky Co., Ltd.," Awatori Netaro ARE-310 type "). did.
Using the obtained curable resin composition solution for sealing an organic EL display element, the same operation as in “(3) Preparation of curable resin sheet for sealing an organic EL display element” in Example 1 was performed, A curable resin sheet for sealing an EL display element was obtained.

(Comparative Example 4)
It replaced with 100 weight part of organic layered silicate, and carried out similarly to Example 1 except having used 100 weight part of layered silicate (Kunimine Kogyo Co., Ltd., "Smecton SA") which has not been subjected to organic treatment. Then, a curable resin composition solution for sealing an organic EL display element and a curable resin sheet for sealing an organic EL display element were obtained.

<Evaluation>
The following evaluation was performed about each organic EL display element sealing curable resin sheet obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(1) Water vapor transmission rate Each curable resin sheet (thickness: 100 μm) for sealing an organic EL display element obtained in the examples and comparative examples is heat-cured in an oven at 100 ° C. for 1 hour, and a test piece is obtained. Obtained. About the obtained test piece, the moisture permeability measurement by the cup method based on JISZ0208 was performed, and the water-vapor-permeation rate was computed.
Specifically, a curable resin sheet for sealing an organic EL display element is set in a 60 mmφ cup, and a test temperature of 60 ° C. and a test humidity using a constant temperature and humidity chamber (“PL-2KP” manufactured by Tabai Espec). Under the condition of 90%, the amount of change in weight every 24 hours was measured at three points to obtain an average value.

(2) Visible light transmittance and a curable resin sheet for sealing each organic EL display element obtained in Examples and Comparative Examples on a non-alkali glass substrate having a haze width of 25 mm, a length of 50 mm, and a thickness of 0.7 mm ( (20 μm thickness) was roll-laminated and transferred, and then heat-cured in an oven at 100 ° C. for 1 hour to obtain a test piece. About the obtained test piece, the visible light transmittance in the wavelength of 400-800 nm was measured with the spectrophotometer using the glass substrate before transferring the curable resin sheet for organic electroluminescent display element sealing as a reference. Moreover, about the said test piece which measured the visible light transmittance | permeability, the haze (cloudiness value) was measured using the haze meter.

(3) Light-emitting state of organic EL display element A non-alkali glass substrate on which an ITO transparent electrode having a thickness of 1000 mm is formed by sputtering is used as a transparent support substrate, and N, N′-di (1-naphthyl) -N is formed by vacuum deposition. , N′-diphenylbenzidine (α-NPD) was deposited on the substrate at a deposition rate of 15 Å / s to form a 600 Å hole transport layer. Next, tris (8-hydroxyquinola) aluminum (Alq ₃ ) was deposited at a film thickness of 600 mm at a deposition rate of 15 mm / s to form a light emitting layer. After that, this substrate is transferred to another vacuum vapor deposition apparatus, and 5 μm of lithium fluoride is deposited at a deposition rate of 0.2 Å / s, and then 1000 μm of aluminum is deposited at a rate of 20 Å / s. The laminated body which has was obtained.
Each organic EL display element sealing curable resin sheet obtained in Examples and Comparative Examples was roll laminated at 80 ° C. and transferred onto the substrate on which this laminate was formed. Furthermore, the glass substrate was overlaid on the transferred curable resin sheet for sealing an organic EL display element, and heat-pressed at 80 ° C. using a vacuum laminator. Thereafter, heat curing was performed in an oven at 100 ° C. for 1 hour to cure the organic EL display element sealing curable resin sheet, thereby obtaining an organic EL display element.
The obtained organic EL display device was exposed for 100 hours under the conditions of a temperature of 60 ° C. and a humidity of 90%, and then a voltage of 10 V was applied to visually observe the light emitting state of the device (the presence or absence of light emission and dark spots). Evaluation was made with “◯” when there was no dark spot and light was emitted uniformly, “Δ” when light was emitted but there was a dark spot, and “X” when no light was emitted.

ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition for organic electroluminescent display element sealing which is excellent in transparency and barrier property of hardened | cured material can be provided. Moreover, according to this invention, the curable resin sheet for organic electroluminescent display element sealing and organic electroluminescent display element which use this curable resin composition for organic electroluminescent display element sealing can be provided. .

Claims (6)

Containing a polyfunctional cationically polymerizable compound, an organically modified layered silicate, and a curing agent;
The organically modified layered silicate is dispersed in the polyfunctional cation polymerizable compound,
Curable resin composition for sealing an organic electroluminescence display element, wherein the content of the organically modified layered silicate is 20 to 250 parts by weight with respect to 100 parts by weight of the polyfunctional cation polymerizable compound. . 2. The curable resin composition for sealing an organic electroluminescence display element according to claim 1, wherein the molecular weight of the polyfunctional cation polymerizable compound is 150 to 1000. 3. The curable resin composition for sealing an organic electroluminescence display device according to claim 1, wherein the layered silicate used in the organically modified layered silicate is a smectite clay mineral. 4. The curable resin composition for sealing an organic electroluminescence display element according to claim 1, wherein the curable resin composition is used for a top emission type organic EL display element. A curable resin sheet for sealing an organic electroluminescence display element, wherein the curable resin composition for sealing an organic electroluminescence display element according to claim 1 is molded into a sheet shape. It manufactures using the curable resin composition for organic electroluminescent display element sealing of Claim 1, 2, 3, or 4 and / or the curable resin sheet for organic electroluminescent display element sealing of Claim 5. An organic electroluminescence display element characterized by that.