Composition for sealing organic light-emitting device and organic light-emitting display device including organic layer produced therefrom

Abstract

To provide a composition for sealing an organic light-emitting element that can form an organic layer with excellent plasma resistance after curing, and an organic light-emitting display device including the organic layer formed therewith.SOLUTION: A composition for sealing an organic light-emitting element includes a cation polymerizable compound with a vinyl group, an allyl group, or a vinyl ether group, and a photoacid generator. The cation polymerizable compound is contained by 95 to 99.9 parts by mass in 100 parts by mass of the composition for sealing the organic light-emitting element on the solid content basis.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition for sealing an organic light-emitting element and an organic light-emitting display device including an organic layer manufactured using the composition. More specifically, the present invention relates to a composition for sealing an organic light-emitting element, which has a reduced plasma etching rate after curing, a reduced dielectric constant (ε), and a high photocuring rate, and an organic light-emitting display device including the organic layer manufactured using the composition. [Background technology]

[0002] When external moisture, oxygen, etc. penetrate into an organic light-emitting element, the organic light-emitting element is easily damaged, and may lose its function and become less reliable. Therefore, the organic light-emitting element needs to be sealed with a sealing layer (a laminate of an organic layer and an inorganic layer) that includes an inorganic layer together with an organic layer formed from a composition for sealing an organic light-emitting element.

[0003] The organic layer is formed by applying a composition for sealing an organic light-emitting device to a predetermined thickness and then curing it. In recent years, inkjet methods have been considered as a method for applying compositions for sealing an organic light-emitting device. In the inkjet method, a composition for sealing an organic light-emitting device is placed in a nozzle and then dropped at a predetermined temperature and dropping speed. To apply the composition to the inkjet method, a method for reducing the viscosity of the composition for sealing an organic light-emitting device can be considered. However, reducing the viscosity does not necessarily result in successful inkjet application.

[0004] In an organic light-emitting display device, in addition to an encapsulation layer, various display elements are stacked on the top and bottom of the organic light-emitting element. However, various types of electricity, static electricity, or electromagnetic waves emitted from the display elements almost always affect the organic light-emitting element. These various types of electricity, static electricity, or electromagnetic waves emitted from the display elements can cause the organic light-emitting element to malfunction or cancel out its function. Therefore, it is necessary to minimize the impact by stacking additional elements on the organic light-emitting element while maintaining the basic function of encapsulating the organic light-emitting element due to its low dielectric constant. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2016-0150255 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a composition for sealing an organic light-emitting element, which is capable of forming an organic layer having excellent plasma resistance after curing.

[0007] Another object of the present invention is to provide a composition for sealing an organic light-emitting element, which is capable of forming an organic layer having a low relative dielectric constant over a wide range of frequencies after curing.

[0008] It is still another object of the present invention to provide a composition for sealing an organic light-emitting element that has a high photocuring rate and is capable of forming an organic layer having high light transmittance after curing.

[0009] A further object of the present invention is to provide a composition for sealing an organic light-emitting element that can be suitably applied by inkjet coating. [Means for solving the problem]

[0010] One aspect of the present invention is a composition for sealing an organic light-emitting device.

[0011] 1. The composition for sealing an organic light-emitting element of the present invention comprises a cationically polymerizable compound having a vinyl group, an allyl group, or a vinyl ether group, and a photoacid generator, and the cationically polymerizable compound is contained in an amount of 95 to 99.9 parts by mass based on the solid content in 100 parts by mass of the composition for sealing an organic light-emitting element.

[0012] 2. In the above item 1, the cationically polymerizable compound may include at least one selected from the group consisting of compounds having an alicyclic group or an aromatic group in the molecular structure and one or more vinyl groups, allyl groups, or vinyl ether groups, and compounds having no alicyclic group or aromatic group in the molecular structure and one or more vinyl groups, allyl groups, or vinyl ether groups.

[0013] 3. In the above items 1 and 2, the cationically polymerizable compound may include at least one selected from the group consisting of divinylbenzene, 1,4-cyclohexanedimethanol divinyl ether, allyl benzyl ether, 5-vinylbicyclo[2.2.1]hept-2-ene, diethylene glycol divinyl ether, 1-tetradecene, triethylene glycol divinyl ether, octadecyl vinyl ether, trimethylolpropane diallyl ether, and 1,4-butanediol divinyl ether.

[0014] 4. In the above items 1 to 3, the photoacid generator may contain at least one of N-hydroxynaphthalimide trifluoromethanesulfonate and thio-p-phenylenebis(4,4'-dimethyldiphenylsulfonium)bistetrakis(pentafluorophenyl)borate.

[0015] 5. In the above items 1 to 4, the composition may further contain a (meth)acrylic photocurable monomer and a photoradical initiator.

[0016] 6. In the above items 1 to 5, the composition may have a relative dielectric constant of 2.9 or less after curing.

[0017] 7. In the above 1 to 6, the composition may have an etching rate of an organic layer by plasma calculated by the following formula 1 after curing of 10% or less:

[0018]

number

[0019] In the above formula 1, T1 and T2 are as defined in the detailed description of the invention.

[0020] The organic light-emitting display device of the present invention includes an organic layer formed from the composition for sealing an organic light-emitting element of the present invention. [Effects of the Invention]

[0021] According to the present invention, there is provided a composition for sealing an organic light-emitting element, which is capable of forming an organic layer having excellent plasma resistance after curing.

[0022] Furthermore, the present invention provides a composition for sealing an organic light-emitting element that can form an organic layer having a low relative dielectric constant over a wide range of frequencies after curing.

[0023] According to the present invention, there is provided a composition for sealing an organic light-emitting element that has a high photocuring rate and is capable of forming an organic layer having high light transmittance after curing.

[0024] According to the present invention, there is provided a composition for sealing an organic light-emitting device that can be suitably applied by inkjet coating. [Brief explanation of the drawings]

[0025] [Figure 1] 1 is a schematic cross-sectional view of an organic light emitting display device according to an embodiment of the present invention; [Figure 2] 1 is a schematic cross-sectional view of an organic light emitting display device according to another embodiment of the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0026] The present invention will now be described in detail by way of examples with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may be embodied in various different forms and is not limited to the embodiments described herein. In the drawings, parts that are not relevant to the description are omitted to clearly explain the present invention, and the same reference numerals are used throughout the specification to refer to the same or similar elements. The length and size of each element in the drawings are for the purpose of explaining the present invention, and the present invention is not limited to the length and size of each element depicted in the drawings.

[0027] In this specification, "(meth)acrylic" means acrylic and / or methacrylic.

[0028] In this specification, unless otherwise defined, the term "substituted" may mean that one or more hydrogen atoms in a functional group of the present invention are substituted with a halogen atom (F, Cl, Br, or I), a hydroxy group, a nitro group, a cyano group, an imino group (=NH, =NR, where R is an alkyl group having 1 to 10 carbon atoms), an amino group (-NH, -NH(R'), -N(R")(R'"), R', R", and R'" are each independently an alkyl group having 1 to 10 carbon atoms), an amidino group, a hydrazine group, a hydrazone group, a carboxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, or a heterocycloalkyl group having 2 to 30 carbon atoms.

[0029] In the description of the range of values ​​in this specification, "X to Y" means "at least X and at most Y" (X≦ and ≦Y).

[0030] The present invention provides a composition for sealing organic light-emitting devices (hereinafter also referred to as "composition") that has a high photocuring rate, can be suitably inkjet coated, has excellent plasma resistance after curing, and can form an organic layer that has a low relative dielectric constant (low frequency dependency) over a wide range of frequencies.

[0031] In one embodiment, the composition of the present invention may be cured to form an organic layer having an etching rate of 10% or less, specifically 0 to 8%, when etched by plasma, as calculated by the following equation 1. If the etching rate is within the above range, the organic layer is not damaged when an inorganic layer is formed on the organic layer, thereby extending the life of the organic light-emitting device:

[0032]

number

[0033] In the above formula 1, T1 represents the value obtained by depositing the above composition for sealing an organic light-emitting element on a silicon (Si) wafer and illuminating the resulting material at an illuminance of 100 mW / cm 2 is the initial thickness (unit: μm) of the organic layer obtained by photo-curing the layer by irradiating it with ultraviolet light having a wavelength of 395 nm for 10 seconds. T2 is the thickness (unit: μm) of the organic layer after inductively coupled plasma (ICP) treatment using ICP CVD under the following conditions: ICP power: 2500 W, RE power: 300 W, DC bias: 200 V, Ar flow: 70 sccm, etching time: 1 min, and pressure: 10 mtorr. The thickness (or height) of the organic layer can be measured using an FE-SEM (manufactured by Hitachi High-Tech Corporation), but is not limited thereto.

[0034] In one embodiment, the composition of the present invention may have a dielectric constant of 2.9 or less (e.g., 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, or 2.9) after curing, specifically 1.5 to 2.9 or 2.0 to 2.7. A dielectric constant within the above range may be unaffected by external static or electricity, allowing the organic light emitting device to perform satisfactorily. In particular, the composition of the present invention forms an organic layer that is alternately stacked with an inorganic layer, as described in detail below. In such an alternating laminate structure, in order to form an organic layer that has plasma resistance while maintaining a low relative dielectric constant, it is preferable that the composition of the present invention has a relative dielectric constant of 2.9 or less after curing.

[0035] In one specific example, the photocuring rate of the composition of the present invention can be evaluated by measuring the hardness, for example, pencil hardness, of the composition after curing. For a method of evaluating pencil hardness, see the Examples described in detail below. The composition of the present invention may have a pencil hardness of H or higher after curing. When the pencil hardness is within this range, the photocuring rate of the composition is high, and when used in an organic layer, the device life and reliability can be extended. Preferably, the pencil hardness is H to 3H. Within this range, the photocuring rate of the composition is high, and the device life and reliability can be extended, while the dielectric constant of the organic layer can be reduced.

[0036] The composition of the present invention can maintain the dielectric constant within the above range after curing over a wide range of frequencies. For example, the composition of the present invention can ensure a dielectric constant of 2.9 or less over a frequency range of 200 kHz to 1 GHz, e.g., 200 kHz to 500 kHz, after curing.

[0037] In one embodiment, the composition of the present invention can be suitably inkjet coated. Here, inkjet coating means applying the composition to be coated using an inkjet printer at a drop rate of 2.5 to 3.5 μm / s and a head temperature of the inkjet coating device of 20 to 50° C.

[0038] A composition according to one embodiment of the present invention comprises a cationically polymerizable compound having a vinyl group, an allyl group, or a vinyl ether group (hereinafter also simply referred to as a "cationically polymerizable compound") and a photoacid generator, and the cationically polymerizable compound is contained in an amount of 95 to 99.9 parts by mass (for example, 95.0 parts by mass, 95.1 parts by mass, 95.2 parts by mass, 95.3 parts by mass, 95.4 parts by mass, 95.5 parts by mass, 95.6 parts by mass, 95.7 parts by mass, 95.8 parts by mass, 95.9 parts by mass, 96.0 parts by mass, 96.1 parts by mass, 96.2 parts by mass, 96.3 parts by mass, 96.4 parts by mass, 96.5 parts by mass, 96.6 parts by mass, 96.7 parts by mass, 96.8 parts by mass, 96.9 ...1 parts by mass, 96.2 parts by mass, 96.3 parts by mass, 96.4 parts by mass, 96.5 parts by mass, 96.6 parts by mass, 96.7 parts by mass, 96.8 parts by mass, 96.9 parts by mass, 96.9 parts by mass, 96.1 parts by mass, 96.1 parts by mass, 96.1 parts by mass, 96.1 parts by mass, 96.1 parts by mass, 96.1 parts by mass, 96.1 parts by mass, 9 7 parts by mass, 96.8 parts by mass, 96.9 parts by mass, 97.0 parts by mass, 97.1 parts by mass, 97.2 parts by mass, 97.3 parts by mass, 97.4 parts by mass, 97.5 parts by mass , 97.6 parts by mass, 97.7 parts by mass, 97.8 parts by mass, 97.9 parts by mass, 98.0 parts by mass, 98.1 parts by mass, 98.2 parts by mass, 98.3 parts by mass, 98.4 Parts by mass, 98.5 parts by mass, 98.6 parts by mass, 98.7 parts by mass, 98.8 parts by mass, 98.9 parts by mass, 99.0 parts by mass, 99.1 parts by mass, 99.2 parts by mass, 99.3 parts by mass, 99.4 parts by mass, 99.5 parts by mass, 99.6 parts by mass, 99.7 parts by mass, 99.8 parts by mass, or 99.9 parts by mass). When the content of the cationically polymerizable compound is within this range, an organic layer can be formed that has a high photocuring rate, excellent plasma resistance after curing, and a low dielectric constant over a wide range of frequencies after curing, and inkjet coating can be suitably performed. Preferably, the content of the cationically polymerizable compound is 97 to 99.9 parts by mass based on the solid content in 100 parts by mass of the composition.

[0039] Each component of the composition of the present invention will be described in detail below.

[0040] (cationically polymerizable compounds having a vinyl group, an allyl group, or a vinyl ether group) When the cationically polymerizable compound having a vinyl group, an allyl group, or a vinyl ether group is contained within the specific content range specified in the present invention, the photocuring rate of the composition of the present invention can be increased and the dielectric constant of the organic layer after curing can be reduced.

[0041] The cationically polymerizable compound having a vinyl group, an allyl group, or a vinyl ether group can include at least one selected from the group consisting of a compound having an alicyclic or aromatic group in its molecular structure and having one or more, preferably one to two, vinyl groups, allyl groups, or vinyl ether groups, and a compound having no alicyclic or aromatic group in its molecular structure and having one or more, preferably one to two, vinyl groups, allyl groups, or vinyl ether groups. One or more of these cationically polymerizable compounds can be included in the composition.

[0042] In compounds having an alicyclic or aromatic group in their molecular structure and one or more, preferably one to two, vinyl, allyl, or vinyl ether groups, the "alicyclic group" refers to a cyclic functional group consisting of 5 to 10 carbon atoms and hydrogen atoms, excluding those containing oxygen atoms. The compound having a vinyl, allyl, or vinyl ether group may include at least one selected from the group consisting of divinylbenzene, including one or more of 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene, 1,4-cyclohexanedimethanol divinyl ether, allyl benzyl ether, and 5-vinylbicyclo[2.2.1]hept-2-ene.

[0043] The compound having no alicyclic group or aromatic group in its molecular structure and having one or more, preferably one to two, vinyl groups, allyl groups, or vinyl ether groups may include at least one selected from the group consisting of diethylene glycol divinyl ether, 1-tetradecene, triethylene glycol divinyl ether, octadecyl vinyl ether, trimethylolpropane diallyl ether, and 1,4-butanediol divinyl ether.

[0044] In one specific example, the cationically polymerizable compound having a vinyl group, an allyl group, or a vinyl ether group may include at least one selected from the group consisting of divinylbenzene including one or more of 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene, 1-tetradecene, diethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and allyl benzyl ether.

[0045] (Photoacid generator) The photoacid generator can cause a cationic polymerizable compound having a vinyl group, an allyl group, or a vinyl ether group to undergo a photocuring reaction, thereby forming an organic layer.

[0046] A photoacid generator is a compound that generates cationic species when irradiated with light, thereby initiating the curing reaction of a cationically polymerizable compound, and may contain a cationic moiety that absorbs light and an anionic moiety that serves as an acid generation source.

[0047] The photoacid generator may include one or more of sulfonate-based, sulfonium-based, diazonium salt-based, iodonium salt-based, sulfonium salt-based, phosphonium salt-based, selenium salt-based, oxonium salt-based, ammonium salt-based, and bromine salt-based compounds. For example, the photoacid generator may be N-hydroxynaphthalimide trifluoromethanesulfonate, thio-p-phenylenebis(4,4'-dimethyldiphenylsulfonium)bistetrakis(pentafluorophenyl)borate, (4-hydroxyphenyl)methylbenzylsulfonium tetrakis(pentafluorophenyl)borate, 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, 4-(phenylthio)phenyldiphenylsulfonium phenyltris(pentafluorophenyl)borate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium phenyltris(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenylsulfonium]hexafluoroantimonate, diphenyl The compound may include, but is not limited to, at least one selected from the group consisting of [4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfidophenyl tris(pentafluorophenyl)borate, and [4-(2-thioxanthonylthio)phenyl]phenyl-2-thioxanthonylsulfonium phenyl tris(pentafluorophenyl)borate.

[0048] Preferably, the photoacid generator may include at least one selected from the group consisting of N-hydroxynaphthalimide trifluoromethanesulfonate and thio-p-phenylenebis(4,4'-dimethyldiphenylsulfonium)bistetrakis(pentafluorophenyl)borate.

[0049] The photoacid generator may be contained in an amount of preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on the solid content, per 100 parts by mass of the composition. When the content of the photoacid generator is within the above range, the curing rate of the cationically polymerizable compound is high, and it is possible to prevent a decrease in the light transmittance of the organic layer due to the remaining uncured cationically polymerizable compound.

[0050] ((Meth)acrylic photocurable monomer) The composition according to the present invention may further contain a (meth)acrylic photocurable monomer.

[0051] The (meth)acrylic photocurable monomer can form an organic layer by undergoing a curing reaction. When the (meth)acrylic photocurable monomer is contained in the composition in a suitable content range, the cationically polymerizable compound having a vinyl group, an allyl group, or a vinyl ether group falls within the scope of the present invention, which helps reduce the relative dielectric constant of the composition of the present invention after curing and enables suitable inkjet coating.

[0052] The (meth)acrylic photocurable monomer may be contained in an amount of 0 to 50 parts by mass, specifically 10 to 28 parts by mass, per 100 parts by mass of the composition on a solids basis. If the content of the (meth)acrylic photocurable monomer is within the above range, the photocuring rate of the composition becomes higher, the hardness of the organic layer becomes higher, the relative dielectric constant of the present invention can be ensured, and inkjet coating can be suitably performed.

[0053] The (meth)acrylic photocurable monomer may include a photocurable monomer having one or more (meth)acryloyloxy groups.

[0054] In one specific example, the (meth)acrylic photocurable monomer may include at least one selected from the group consisting of mono(meth)acrylates having an alkyl group with 1 to 15 carbon atoms and di(meth)acrylates having an alkylene group with 6 to 15 carbon atoms.

[0055] The mono(meth)acrylate having an alkyl group having 1 to 15 carbon atoms can include at least one selected from the group consisting of hexyl(meth)acrylate, heptyl(meth)acrylate, octyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, undecyl(meth)acrylate, and dodecyl(meth)acrylate (lauryl(meth)acrylate).

[0056] The di(meth)acrylate having an alkylene group having 6 to 15 carbon atoms can include a di(meth)acrylate having a substituted or unsubstituted alkylene group having 6 to 15 carbon atoms, preferably an unsubstituted alkylene group having 6 to 12 carbon atoms, between two (meth)acryloyloxy groups. For example, such a di(meth)acrylate can be represented by the following Chemical Formula 1:

[0057] [ka]

[0058] In the above chemical formula 1, R 10 and R 11 are each independently a hydrogen atom or a methyl group, R 12 is a substituted or unsubstituted alkylene group having 6 to 15 carbon atoms.

[0059] For example, in the above formula 1, R 12may be an unsubstituted alkylene group having 6 to 12 carbon atoms. Such di(meth)acrylate may include at least one selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecanediol di(meth)acrylate, and 1,12-dodecanediol di(meth)acrylate.

[0060] (Photoradical initiator) The composition according to the present invention may further comprise a photoradical initiator.

[0061] The photoradical initiator may include, without limitation, a typical photoradical initiator that enables the (meth)acrylic photocurable monomer to undergo a photocuring reaction. For example, the photoradical initiator may include a triazine-based, acetophenone-based, benzophenone-based, thioxanthone-based, benzoin-based, phosphorus-based, oxime-based, or mixtures thereof.

[0062] Examples of phosphorus-based photoradical initiators include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, benzyl(diphenyl)phosphine oxide, or a mixture thereof. For example, when a phosphorus-based initiator is used, the composition of the present invention can exhibit better initiation performance under long-wavelength ultraviolet light (UV light). The photoradical initiators can be used alone or in combination of two or more.

[0063] The photoradical initiator may be contained in an amount of 0.5 to 7 parts by mass, specifically 1 to 5 parts by mass, or 2 to 4 parts by mass, per 100 parts by mass of the composition based on the solid content. If the content of the photoradical initiator is within this range, photopolymerization occurs sufficiently during exposure, and a decrease in transmittance due to unreacted initiator remaining after photopolymerization can be prevented.

[0064] The composition of the present invention can be prepared by mixing the above-mentioned components. The composition of the present invention can be prepared as a solvent-free type composition that does not contain a solvent.

[0065] The composition of the present invention is a photocurable composition, and can be cured by ultraviolet light at an illuminance of 10 mW / cm. 2 ~500mW / cm 2 The sealing layer (organic layer) can be formed by photocuring the composition by irradiating it with ultraviolet light for 1 to 50 seconds within the range of 1 to 50 seconds.

[0066] The composition of the present invention may further contain conventional additives known to those skilled in the art, including, but not limited to, heat stabilizers, antioxidants, UV absorbers, etc.

[0067] The composition of the present invention can be used to seal an organic light-emitting device. Specifically, the composition of the present invention can form an organic layer in a sealing structure in which an inorganic layer and an organic layer are formed in this order.

[0068] The composition of the present invention can also be used for sealing device components, particularly display device components, which may decompose or become defective due to permeation of gases or liquids in the surrounding environment, such as atmospheric oxygen, moisture, water vapor, and / or compounds used in processing electronic products, etc. Examples of device components include, but are not limited to, lighting devices, metal sensor pads, microdisk lasers, electrochromic devices, photochromic devices, microelectromechanical systems, solar cells, integrated circuits, charge-coupled devices, light-emitting polymers, etc.

[0069] The organic light-emitting display device according to the present invention may include an organic layer formed from the composition for sealing an organic light-emitting device according to one embodiment of the present invention. That is, the organic light-emitting display device according to the present invention may include an organic layer formed by curing the composition for sealing an organic light-emitting device according to one embodiment of the present invention. Specifically, the organic light-emitting display device includes an organic light-emitting device and a barrier stack formed on the organic light-emitting device and including an inorganic layer and an organic layer, and the organic layer may be formed from the composition for sealing an organic light-emitting device according to one embodiment of the present invention. As a result, the reliability of the organic light-emitting display device may be improved.

[0070] Hereinafter, an organic light emitting diode display device according to an embodiment of the present invention will be described with reference to Fig. 1. Fig. 1 is a schematic cross-sectional view of an organic light emitting diode display device according to an embodiment of the present invention.

[0071] Referring to FIG. 1, an organic light-emitting display device 100 includes a substrate 10, an organic light-emitting element 20 formed on the substrate 10, and a barrier stack 30 formed on the organic light-emitting element 20 and including an inorganic layer 31 and an organic layer 32, wherein the inorganic layer 31 is in contact with the organic light-emitting element 20, and the organic layer 32 may be formed from a composition for sealing an organic light-emitting element according to one embodiment of the present invention.

[0072] The substrate 10 is not particularly limited as long as it is a substrate on which an organic light emitting element can be formed, and may be made of materials such as transparent glass, a plastic sheet, silicon, or a metal substrate.

[0073] The organic light-emitting element 20 is typically used in an organic light-emitting display device, and although not shown in FIG. 1, includes a first electrode, a second electrode, and an organic light-emitting layer formed between the first and second electrodes. The organic light-emitting layer may be, but is not limited to, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer stacked in this order.

[0074] The barrier stack 30 includes organic and inorganic layers, and the organic and inorganic layers have different components, and can perform a sealing function for each organic light emitting element.

[0075] The inorganic layer can complement the effect of the organic layer by having different components from the organic layer. For example, the inorganic layer can be a metal, a nonmetal, an intermetallic compound or alloy, a non-intermetallic compound or alloy, a metal or nonmetal oxide, a metal or nonmetal fluoride, a metal or nonmetal nitride, a metal or nonmetal carbide, a metal or nonmetal oxynitride, a metal or nonmetal boride, a metal or nonmetal oxyboride, a metal or nonmetal silicide, or a mixture thereof. Examples of metals or nonmetals include, but are not limited to, silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transition metals, and lanthanum group metals. Specifically, the material of the inorganic layer can be silicon oxide (SiO x ), silicon nitride (SiN x ), silicon oxynitride (SiO x N y ), ZnSe, ZnO, Sb2O3, Al2O3, etc. x , In2O3, SnO2, etc.

[0076] The inorganic layer can be deposited by plasma processes, vacuum processes such as sputtering, chemical vapor deposition, plasma enhanced chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma vapor deposition, and combinations thereof.

[0077] When organic layers are formed by alternately depositing inorganic layers, the smoothing properties of the inorganic layers can be maintained while preventing the bonds of the inorganic layers from propagating to other inorganic layers.

[0078] The organic layer can be formed by a combination of coating, vapor deposition, curing, etc. of the composition for sealing an organic light-emitting device according to one embodiment of the present invention. For example, the composition for sealing an organic light-emitting device can be coated to a thickness of 1 to 50 μm, and the irradiance can be 10 to 500 mW / cm. 2 It can be cured by irradiating it with ultraviolet light at an intensity of 1 to 50 seconds.

[0079] The barrier stack includes organic and inorganic layers, but the total number of organic and inorganic layers is not limited. The total number of organic and inorganic layers can be changed depending on the level of permeation resistance to oxygen, moisture, water vapor, and / or chemicals. For example, the total number of organic and inorganic layers can be preferably 10 layers or less, for example, 2 to 7 layers. Specifically, the barrier stack can be formed into a 7-layer structure in the order inorganic layer / organic layer / inorganic layer / organic layer / inorganic layer / organic layer / inorganic layer.

[0080] In the barrier stack, organic and inorganic layers can be deposited alternately due to the effect on the organic layers produced by the physical properties of the compositions described above, which can complement or enhance the sealing effect on the device.

[0081] Hereinafter, an organic light emitting display device according to another embodiment of the present invention will be described with reference to Fig. 2. Fig. 2 is a cross-sectional view of an organic light emitting display device according to another embodiment of the present invention.

[0082] 2, an organic light emitting display device 200 includes a substrate 10, an organic light emitting device 20 formed on the substrate 10, and a barrier stack 30 formed on the organic light emitting device 20 and including an inorganic layer 31 and an organic layer 32. The inorganic layer 31 seals an internal space 40 in which the organic light emitting device 20 is housed, and the organic layer 32 may be formed from a composition for sealing an organic light emitting device according to an embodiment of the present invention. The organic light emitting display device 200 is substantially the same as the organic light emitting display device according to an embodiment of the present invention, except that the inorganic layer does not contact the organic light emitting device. [Example]

[0083] The present invention will be described in more detail with reference to preferred embodiments thereof below, which are merely examples of preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention in any way.

[0084] The specific specifications of the components used in the examples and comparative examples are as follows:

[0085] A: a cationically polymerizable compound having a vinyl group, an allyl group, or a vinyl ether group A1: A mixture of 1,3-divinylbenzene and 1,4-divinylbenzene (manufactured by TCI) A2: 1-tetradecene (Aldrich) A3: Diethylene glycol divinyl ether (manufactured by Aldrich) A4: 1,4-cyclohexanedimethanol divinyl ether (Aldrich) A5: Allyl benzyl ether B: (Meth)acrylic photocurable monomer B1: 1,12-dodecanediol diacrylate (manufactured by Sartomer) C: Photoacid generator C1:TR-PAG-21608 (manufactured by Troonly, Thio-p-phenylenebis(4,4'-dimethyldiphenylsulfonium)bis tetrakis(penta fluorophenyl)borate C2: MIPHOTO NIT (Miwon Shoji, N-hydroxynaphthalimide trifluoromethanesulfonate) D: Photoradical initiator D1: Irgacure (registered trademark) TPO (manufactured by IGM Resins BV, phosphorus-based initiator) Example 1 99.9 parts by mass of (A1) and 0.1 parts by mass of (C1) were placed in a 125 ml brown polypropylene bottle and mixed using a shaker at room temperature for 3 hours to prepare a composition.

[0086] (Examples 2 to 10, Comparative Examples 1 to 5) Compositions were prepared in the same manner as in Example 1, except that the type and / or content of each component in Example 1 was changed as shown in Table 1 below. In Table 1 below, "-" means that the corresponding component was not contained. The content of each component is expressed in parts by mass.

[0087] The detailed compositions of the examples and comparative examples are shown in Table 1 below.

[0088] [Table 1]

[0089] The compositions prepared in the examples and comparative examples were measured for the following physical properties, and the results are shown in Table 2.

[0090] (1) Pencil hardness of organic layer (unit: none): The composition was coated on a glass substrate, and the illuminance was 100 mW / cm 2 The organic layer was cured by irradiating it with ultraviolet light at a wavelength of 395 nm for 10 seconds at 1000 kJ / s, yielding a test piece for the organic layer. The pencil hardness of the test piece for the organic layer was measured. An electric pencil hardness tester (Lab-Q D300A) was used to measure pencil hardness, and the pencils used were 6B to 9H pencils manufactured by Mitsubishi Pencil Co., Ltd. The pencil load on the test piece was 500 g, the pencil scratch angle was 45°, and the pencil scratching speed was 48 mm / min. If a scratch occurred at least once after five evaluations, a pencil of the lower pencil hardness level was used for measurement. Five evaluations were performed, and the hardest pencil hardness value when no scratches occurred in all five evaluations was recorded as the pencil hardness.

[0091] (2) Etching rate of organic layer by plasma (unit: %): The sealing composition was deposited on a Si wafer, and the illuminance was 100 mW / cm 2The organic layer was photocured by irradiating it with ultraviolet light at a wavelength of 395 nm for 10 seconds at 1000 W, and then the organic layer was photocured to form an organic layer. The initial thickness (T1, unit: μm) of the photocured organic layer was measured. The organic layer was subjected to inductively coupled plasma treatment using an ICP CVD (manufactured by BMR Technology) at an ICP power of 2500 W, RE power of 300 W, DC bias of 200 V, Ar flow of 70 sccm, etching time of 1 min, and pressure of 10 mtorr, and then the thickness (T2, unit: μm) of the organic layer was measured. The etching rate of the organic layer by plasma was calculated using the following equation (1). The thickness of the organic layer was measured using a field emission scanning electron microscope (FE-SEM) (manufactured by Hitachi High-Tech Corporation).

[0092]

number

[0093] (3) Relative dielectric constant (unit: none): The compositions of the examples and comparative examples were applied to a chromium (Cr) plate to a predetermined thickness, and the illuminance was 100 mW / cm 2 The coating was photocured by irradiating it with ultraviolet light at a wavelength of 395 nm for 10 seconds at 1000 kJ / s, forming a coating film with a thickness of 8 μm. After vapor-depositing an aluminum electrode (electrode for measuring the relative dielectric constant) on the coating film, the relative dielectric constant was measured at 200 kHz and 25°C using an impedance measuring instrument (RDMS-200).

[0094] [Table 2]

[0095] In Table 2 above, "-" means that the hardness, plasma etch rate, and dielectric constant could not be measured because the composition was uncured.

[0096] As shown in Table 2 above, the composition for sealing an organic light-emitting element of the present invention has a high hardness after curing, and therefore a high photocuring rate, and can form an organic layer with high light transmittance after curing, and can form an organic layer with excellent plasma resistance after curing and a low relative dielectric constant after curing.

[0097] On the other hand, Comparative Examples 1 to 3, which did not contain a cationic polymerizable compound having a vinyl group, allyl group, or vinyl ether group or a photoacid generator, and Comparative Examples 4 and 5, which contained a cationic polymerizable compound having a vinyl group, allyl group, or vinyl ether group and a photoacid generator but did not contain a cationic polymerizable compound having a vinyl group, allyl group, or vinyl ether group in an amount of 95 to 99.9 parts by mass per 100 parts by mass of the composition, did not achieve all of the effects of the present invention.

[0098] Simple modifications or alterations of the present invention can be easily implemented by a person having ordinary skill in the art, and all such modifications and alterations can be considered to be included within the scope of the present invention. [Explanation of symbols]

[0099] 10 boards, 20 Organic light-emitting devices, 30 barrier stacks, 31 Inorganic layer, 32 organic layer, 40 interior spaces, 100, 200 Organic light-emitting display device.

Claims

1. A composition for sealing an organic light-emitting device, comprising: a cationically polymerizable compound having a vinyl group, an allyl group, or a vinyl ether group; and a photoacid generator, the cationically polymerizable compound is at least one selected from the group consisting of divinylbenzene including one or more of 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene, 1-tetradecene, diethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and allyl benzyl ether; The composition for sealing an organic light-emitting element contains the cationically polymerizable compound in an amount of 95 to 99.9 parts by mass based on the solid content in 100 parts by mass of the composition for sealing an organic light-emitting element.

2. 2. The composition for sealing an organic light-emitting element according to claim 1, wherein the photoacid generator comprises at least one selected from the group consisting of N-hydroxynaphthalimide trifluoromethanesulfonate and thio-p-phenylenebis(4,4'-dimethyldiphenylsulfonium)bistetrakis(pentafluorophenyl)borate.

3. The composition for sealing an organic light-emitting element according to claim 1 or 2, further comprising a (meth)acrylic photocurable monomer and a photoradical initiator.

4. 4. The composition for sealing an organic light-emitting element according to claim 1, wherein the composition for sealing an organic light-emitting element has a relative dielectric constant of 2.9 or less after curing.

5. An organic light-emitting display device comprising an organic layer formed from the composition for sealing an organic light-emitting element according to any one of claims 1 to 4.

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