Composition for sealing organic light-emitting element and organic light-emitting-device display apparatus

Abstract

To provide a composition for sealing an organic light-emitting element with a low dielectric constant and an excellent processability and reliability, the composition suppressing generation of wrinkles when an inorganic layer is formed repeatedly.SOLUTION: The present invention relates to a composition for sealing an organic light-emitting element including a curable component containing a first aliphatic photocurable monomer, a second aliphatic photocurable monomer, and an aromatic photocurable monomer, and a photoinitiator. The present invention also relates to an organic layer formed with the composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] One embodiment of the present invention relates to a composition for sealing an organic light-emitting element and an organic light-emitting element display device. [Background technology]

[0002] Organic light-emitting devices are easily damaged and may lose their functionality and become less reliable when exposed to external moisture, oxygen, etc. Therefore, the organic light-emitting device needs to be sealed with a sealing layer including an organic layer and an inorganic layer formed from a composition for sealing an organic light-emitting device.

[0003] The encapsulating layer may have a structure in which organic layers and inorganic layers are alternately formed. For example, in an organic light-emitting device, organic layers and inorganic layers are alternately formed, such as an organic layer-inorganic layer-organic layer-inorganic layer, to form the encapsulating layer. Unlike the organic layer, the inorganic layer may be formed of an inorganic material. Generally, the inorganic layer may be formed by a plasma process or a vacuum process, such as sputtering, chemical vapor deposition, plasma-enhanced chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma vapor deposition, or a combination thereof.

[0004] The background art of the present invention is described in Korean Patent Publication No. 10-2016-0150255 and the like. [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] One embodiment of the present invention provides a composition for sealing an organic light-emitting device, which forms an organic layer having a low dielectric constant.

[0007] One embodiment of the present invention provides a composition for sealing an organic light-emitting device that forms an organic layer that is excellent in processability and reliability by suppressing the occurrence of wrinkles when inorganic layers are repeatedly formed.

[0008] One embodiment of the present invention provides a composition for sealing an organic light-emitting element, which has excellent inkjetability. [Means for solving the problem]

[0009] One embodiment of the present invention is a composition for sealing an organic light-emitting device.

[0010] The composition for sealing an organic light-emitting device includes a curable component including a first aliphatic photocurable monomer, a second aliphatic photocurable monomer, and an aromatic photocurable monomer, as well as a photoinitiator, and the first aliphatic photocurable monomer is represented by the following general formula 1:

[0011] [ka]

[0012] In general formula 1, L 11 , L 12 , L 13 and L 14 are each independently a substituted or unsubstituted, linear or branched alkylene group having two or more carbon atoms; L 11 , L 12 , L 13 and L 14 The total number of carbon atoms in the main chain is 6 or more, X 1 , X 2 , X 3 and X 4 are each independently hydrogen or represented by the following general formula 2: X 1 , X 2 , X 3 and X 4 At least three of them are represented by the following general formula 2.

[0013] General formula 2 *-OC(=O)-C(=CH2)(X 5 )

[0014] In general formula 2, * is the linking site of the element, X 5 is hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.

[0015] Another embodiment of the present invention is an organic light emitting diode display device.

[0016] The organic light emitting device display device includes an organic layer formed from a composition for sealing an organic light emitting device. [Effects of the Invention]

[0017] It is possible to provide a composition for sealing an organic light-emitting element that forms an organic layer having a low dielectric constant.

[0018] By suppressing the occurrence of wrinkles when inorganic layers are repeatedly formed, it is possible to provide a composition for sealing an organic light-emitting device that forms an organic layer that is excellent in processability and reliability.

[0019] It is possible to provide a composition for sealing an organic light-emitting element that has excellent inkjet jetting properties. [Brief explanation of the drawings]

[0020] [Figure 1] 1 is a cross-sectional view of an organic light emitting display device according to an embodiment of the present invention; [Figure 2] 1 is a cross-sectional view of an organic light-emitting display device according to another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention will be described in detail with reference to the accompanying drawings, by way of embodiments, 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. To clearly explain the present invention in the drawings, parts that are not relevant to the description are omitted, and the same reference numerals are used throughout the specification to refer to the same or similar components. In the drawings, the length and size of each component are for the purpose of explaining the present invention, and the present invention is not limited to the length and size of each component shown in the drawings.

[0022] In this specification, "(meth)acrylic" means acrylic and / or methacrylic.

[0023] In this specification, unless otherwise defined, the term "substituted" means that one or more hydrogen atoms of the functional group of the present invention are substituted with a halogen (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"'), where R', R", and R"' are each independently an alkyl group having 1 to 10 carbon atoms), an amidino group, a hydrazine or hydrazone group, a carboxyl 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.

[0024] In the general formulas described herein, unless otherwise specified, hydrogen can be considered to be bonded in the structure of the general formula.

[0025] When describing a range of values ​​in this specification, "X to Y" means at least X and at most Y.

[0026] A composition for sealing an organic light-emitting device (hereinafter referred to as the composition) according to one embodiment can form an organic layer having a significantly low dielectric constant over a wide frequency range after curing. In one embodiment, the frequency range may be 100 kHz to 1000 kHz. The organic layer may have a dielectric constant of 2.8 or less, for example, 2.0 to 2.8, over a wide frequency range. By satisfying the above range, the organic light-emitting device can effectively exhibit its performance without being affected by external static electricity or electricity.

[0027] The composition can form an organic layer with excellent processability and reliability. In relation to this, the composition can form an organic layer with a modulus of 0.8 GPa or more, for example, 0.8 GPa to 5 GPa, after curing. By satisfying the above range, the strength of the organic layer can be ensured and the occurrence of wrinkles during inorganic vapor deposition can be suppressed.

[0028] The composition has excellent inkjet printability and can form a uniform organic layer. In this regard, the composition may have a viscosity of 40 cps or less, for example, 1 cps to 40 cps, at 25±2°C (23°C to 27°C). By satisfying this range, the inkjetability of the sealing composition can be easily improved.

[0029] A composition of one embodiment includes curable components including a first aliphatic photocurable monomer, a second aliphatic photocurable monomer, and an aromatic photocurable monomer, as well as a photoinitiator, and the first aliphatic photocurable monomer is represented by the following general formula 1. Because the composition includes the second aliphatic photocurable monomer, it is possible to form an organic layer with a low dielectric constant, and because the composition simultaneously includes the first aliphatic photocurable monomer and the aromatic photocurable monomer, it is possible to easily provide an organic layer with excellent processability and reliability, and to exhibit a high photocuring rate.

[0030] Each component in the composition of one embodiment will be described in detail below.

[0031] Curing component The curable components include a first aliphatic photocurable monomer, a second aliphatic photocurable monomer, and an aromatic photocurable monomer. The curable components are photocurable components, meaning components that can be cured by light.

[0032] According to one embodiment, the total amount of the first aliphatic photocurable monomer, the second aliphatic photocurable monomer, and the aromatic photocurable monomer may be 95% by weight or more, for example, 99% to 100% by weight, of the curable components. By satisfying this range, the effects of the composition described above can be fully achieved without containing unnecessary monomers.

[0033] First Aliphatic Photocurable Monomer When the composition contains only the second aliphatic photocurable monomer described below, the first aliphatic photocurable monomer can prevent a decrease in the reliability and processability of the organic layer. In this regard, the first aliphatic photocurable monomer may be included in an amount of 30 to 200 parts by weight, or 30 to 190 parts by weight, for example, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or 200 parts by weight, relative to 100 parts by weight of the second aliphatic photocurable monomer. By satisfying this range, reliability and processability can be easily improved without affecting the decrease in the dielectric constant of the organic layer.

[0034] Furthermore, the first aliphatic photocurable monomer has excellent compatibility with the aromatic monomer described below, and can significantly improve reliability and processability. In this regard, the first aliphatic photocurable monomer may be included in an amount of 100 to 300 parts by weight, or 100 to 250 parts by weight, for example, 100, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, or 300 parts by weight, per 100 parts by weight of the aromatic monomer. By satisfying this range, reliability and processability can be significantly improved.

[0035] The first aliphatic photocurable monomer is represented by the following general formula 1.

[0036] [ka]

[0037] In general formula 1, L 11 , L 12 , L 13 and L 14 are each independently a substituted or unsubstituted, linear or branched alkylene group having two or more carbon atoms; L 11 , L 12 , L 13 and L 14 The total number of carbon atoms in the main chain is 6 or more, X 1 , X 2 , X 3 and X 4 are each independently hydrogen or represented by the following general formula 2: X 1 , X 2 , X 3 and X 4 At least three of these are represented by the following general formula 2.

[0038] General formula 2 *-OC(=O)-C(=CH2)(X 5 ) In general formula 2, * is the linking site of the element, X 5 is hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.

[0039] The "number of carbon atoms" mentioned in General Formula 1 refers only to the number of carbon atoms in the main chain, and does not include the number of carbon atoms in the side chains.

[0040] As shown in general formula 1, the first aliphatic photocurable monomer is a photocurable monomer having three or more functionalities, and L 11 , L 12 , L13 and L 14 The total number of carbon atoms in the main chain is 6 or more, and the long-chain alkylene group is included, which can improve the reliability and processability of the organic layer and also provide the effect of suppressing an increase in the dielectric constant.

[0041] In one embodiment, in general formula 1, L 11 , L 12 , L 13 and L 14 The total number of carbon atoms in the main chain may be 8 or more, 9 or more, 10 or more, for example, 9 or more, 10 or more, for example, 9 to 20.

[0042] In one embodiment, in general formula 1, L 11 , L 12 , L 13 and L 14 may each independently be a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, for example, -CH2CH2-, CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2-, etc.

[0043] For example, the compound of general formula 1 may include one or more of the following general formulas 1-1, 1-2, and 1-3.

[0044] [ka]

[0045] The first aliphatic photocurable monomer may be included in an amount of 10 to 60 parts by weight, or 20 to 50 parts by weight, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 parts by weight per 100 parts by weight of the composition. By satisfying the above range, the decrease in dielectric constant caused by the second aliphatic photocurable monomer is not affected, and reliability and processability can be improved.

[0046] Second Aliphatic Photocurable Monomer The second aliphatic photocurable monomer is different from the first aliphatic photocurable monomer. The second aliphatic photocurable monomer is a monofunctional or difunctional monomer having a long-chain alkylene group, which can promote a reduction in the dielectric constant of the organic layer. The second aliphatic photocurable monomer may be one or more of a difunctional photocurable monomer and a monofunctional photocurable monomer.

[0047] In one embodiment, the second aliphatic photocurable monomer may be free of aromatic groups.

[0048] The second aliphatic photocurable monomer may contain one or more compounds represented by the following general formula 2-1 and general formula 2-2.

[0049] [ka]

[0050] In general formula 2-1, R 1 , R 2 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, L 21 is a substituted or unsubstituted, straight or branched chain alkylene group having 8 to 20 carbon atoms.

[0051] [ka]

[0052] In general formula 2-2, R 3 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, L 22 is a substituted or unsubstituted, straight-chain or branched-chain alkyl group having 8 to 30 carbon atoms.

[0053] In General Formula 2-1 and General Formula 2-2, the "number of carbon atoms" means the number of carbon atoms in the main chain, and does not include the number of carbon atoms in the side chain.

[0054] In one embodiment, in general formula 2-1, L 21 may be a substituted or unsubstituted, linear or branched alkylene group having 10 to 16 or 12 to 14 carbon atoms. For example, L 21 is -(CH2) 10 -, -(CH2) 11 -, -(CH2) 12 -, -(CH2) 13 -, -(CH2) 14 -, -(CH2) 15 -, -(CH2) 16 -, -(CH2) 17 -, -(CH2) 18 -, -(CH2) 19 -, -(CH2) 20 For example, the monomer of general formula 2-1 can include one or more of 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, and 1,14-tetradecanediol di(meth)acrylate.

[0055] In one embodiment, in general formula 2-2, L 22 may be a substituted or unsubstituted, straight-chain or branched-chain alkyl group having 10 to 20 or 10 to 18 carbon atoms. For example, the monomer of general formula 2-2 may include one or more of octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, tetradecyl (meth)acrylate, tetradecyl (meth)acrylate including 2-decyl 1-tetradecanyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, isostearyl (meth)acrylate, and cetyl (meth)acrylate.

[0056] The composition may contain one or more second aliphatic photocurable monomers, or two or more second aliphatic photocurable monomers, such as a compound represented by general formula 2-1 alone, a compound represented by general formula 2-2 alone, or a mixture of compounds represented by general formulas 2-1 and 2-2.

[0057] In one embodiment, the second aliphatic photocurable monomer may include a compound represented by general formula 2-2 alone. Preferably, in general formula 2-2, L 22 may be a substituted or unsubstituted, straight or branched chain alkyl group having 8 to 30 carbon atoms.

[0058] In one embodiment, the second aliphatic photocurable monomer can include a mixture of a compound represented by general formula 2-1 and a compound represented by general formula 2-2. Preferably, in general formula 2-1, L 21 may be a substituted or unsubstituted, linear or branched alkylene group having 12 to 14 carbon atoms. 22 may be a substituted or unsubstituted, straight-chain or branched-chain alkyl group having 10 to 30 carbon atoms. In 100 parts by weight of the mixture, the compound represented by general formula 2-1 may be contained in an amount of 50 to 90 parts by weight, for example, 51 to 80 parts by weight, and the compound represented by general formula 2-2 may be contained in an amount of 10 to 50 parts by weight, for example, 20 to 49 parts by weight.

[0059] The second aliphatic photocurable monomer may be contained in an amount of 20 to 60 parts by weight, or 20 to 50 parts by weight, for example, 20, 25, 30, 35, 40, 45, 50, 55, or 60 parts by weight per 100 parts by weight of the composition. By satisfying this range, the dielectric constant of the organic layer can be reduced, and reliability and processability can be improved.

[0060] Aromatic photocurable monomers The aromatic photocurable monomer can increase the photocuring rate of the composition, thereby improving the reliability and processability of the organic layer. The first aliphatic photocurable monomer can somewhat improve the reliability and processability of the organic layer, but may decrease the photocuring rate of the composition. The aromatic photocurable monomer can increase the photocuring rate of the composition, thereby improving the reliability and processability of the organic layer. However, it should not affect the reduction in dielectric constant caused by the second aliphatic photocurable monomer. In this regard, the aromatic photocurable monomer can be included in an amount of 30 to 80 parts by weight, for example, 35 to 75 parts by weight, per 100 parts by weight of the second aliphatic photocurable monomer. Meeting this range can increase the photocuring rate of the composition without affecting the reduction in dielectric constant.

[0061] In one embodiment, the aromatic photocurable monomer may be a non-silicon monomer that does not contain silicon. In one embodiment, the aromatic photocurable monomer may be a monofunctional monomer.

[0062] The aromatic photocurable monomer can be represented by the following general formula 3.

[0063] General formula 3 (CH2=)-C(R 4 )-C(=O)-O-(-CH2-)sL 31

[0064] In general formula 3, R 4 is hydrogen or an alkyl group having 1 to 5 carbon atoms, and s is an integer of 0 to 10, L 31 is a substituted or unsubstituted C6 to C50 aryl group or a substituted or unsubstituted C6 to C50 aryloxy group.

[0065] For example, L 31is a phenylphenoxyethyl group, a phenoxyethyl group, a benzyl group, a phenyl group, a phenylphenoxy group, a phenoxy group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a methylphenylethyl group, a propylphenylethyl group, a methoxyphenylethyl group, a cyclohexylphenylethyl group, a chlorophenylethyl group, a bromophenylethyl group, a methylphenyl group, a methylethylphenyl group, a methoxyphenyl group, a propylphenyl group, a cyclohexylphenyl group, a chlorophenyl group, a bromophenyl group, a phenylphenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, l) group, anthracenyl group, naphthalenyl group, triphenylenyl group, methylphenoxy group, ethylphenoxy group, methylethylphenoxy group, methoxyphenyloxy group, propylphenoxy group, cyclohexylphenoxy group, chlorophenoxy group, bromophenoxy group, biphenyloxy group, terphenyloxy group, quaterphenyloxy group, anthracenyloxy group, naphthalenyloxy group, and triphenylenyloxy group.

[0066] Specifically, the aromatic photocurable monomers include 2-phenylphenoxyethyl (meth)acrylate, naphthyl (meth)acrylate, naphthalenylmethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenyl (meth)acrylate, phenoxy (meth)acrylate, 2-ethylphenoxy (meth)acrylate, benzyl (meth)acrylate, 2-phenylethyl (meth)acrylate, 3-phenylpropyl (meth)acrylate, 4-phenylbutyl (meth)acrylate, 2-(2-methylphenyl)ethyl (meth)acrylate, acrylate, 2-(3-methylphenyl)ethyl (meth)acrylate, 2-(4-methylphenyl)ethyl (meth)acrylate, 2-(4-propylphenyl)ethyl (meth)acrylate, 2-(4-(1-methylethyl)phenyl)ethyl (meth)acrylate, 2-(4-methoxyphenyl)ethyl (meth)acrylate, 2-(4-cyclohexylphenyl)ethyl (meth)acrylate, 2-(2-chlorophenyl)ethyl (meth)acrylate, 2-(3-chlorophenyl)ethyl (meth)acrylate, 2-(4-chlorophenyl)ethyl (meth)acrylate, 2-(4-bromophenyl)ethyl (meth)acrylate, 2-(3-phenylphenyl)ethyl (meth)acrylate, 4-(biphenyl-2-yloxy)butyl (meth)acrylate, 3-(biphenyl-2-yloxy)butyl (meth)acrylate, 2-(biphenyl-2-yloxy)butyl (meth)acrylate, 1-(biphenyl-2-yloxy)butyl (meth)acrylate, 4-(biphenyl-2-yloxy)propyl (meth)acrylate, 3-(biphenyl-2-yloxy)propyl (meth)acrylate Acrylate, 2-(biphenyl-2-yloxy)propyl (meth)acrylate, 1-(biphenyl-2-yloxy)propyl (meth)acrylate, 4-(biphenyl-2-yloxy)ethyl (meth)acrylate, 3-(biphenyl-2-yloxy)ethyl (meth)acrylate, 2-(biphenyl-2-yloxy)ethyl (meth)acrylate, 1-(biphenyl-2-yloxy)ethyl (meth)acrylate, 2-(4-benzylphenyl)ethyl (meth)acrylate, 1-(4-benzylphenyl)ethyl (meth)acrylate,Alternatively, the (meth)acrylate may include one or more of these structural isomers, but is not limited thereto. In other words, the (meth)acrylates mentioned in the present invention are merely examples and are not limited thereto, and the present invention also includes all acrylates that are structural isomers. For example, even if only 2-phenylethyl (meth)acrylate is mentioned as an example of the present invention, the present invention also includes all isomers including 3-phenylethyl (meth)acrylate and 4-phenyl (meth)acrylate.

[0067] Preferably, the aromatic photocurable monomer is represented by general formula 3, wherein L 31 may be a phenylphenoxyethyl group or a naphthalenyl group.

[0068] The aromatic photocurable monomer may be contained in an amount of 10 to 50 parts by weight, or 20 to 50 parts by weight, for example, 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts by weight, per 100 parts by weight of the composition. By satisfying this range, the dielectric constant of the organic layer can be reduced, and reliability and processability can be improved.

[0069] In one embodiment, the total of the first aliphatic photocurable monomer and the second aliphatic photocurable monomer: the aromatic photocurable monomer may be contained in an amount of 70 to 99 parts by weight: 1 to 30 parts by weight, for example, 70 to 90 parts by weight: 10 to 30 parts by weight, per 100 parts by weight of the total of the first aliphatic photocurable monomer, the second aliphatic photocurable monomer, and the aromatic photocurable monomer. By satisfying this range, the effects of the present invention described above can be more easily achieved.

[0070] Photoinitiator The photoinitiator may include, without limitation, a conventional photopolymerization initiator capable of causing a photocuring reaction, such as a triazine-based, acetophenone-based, benzophenone-based, thioxanthone-based, benzoin-based, phosphorus-based, or oxime-based initiator, or a mixture thereof.

[0071] Preferably, the photoinitiator may include a phosphorus-based initiator having a maximum absorption wavelength of 360 nm to 400 nm. When a phosphorus-based initiator is used, the composition of the present invention can exhibit more efficient initiation performance in the long-wavelength UV (e.g., 300 nm to 400 nm). Examples of phosphorus-based initiators include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphinate, or mixtures thereof. For example, the initiator may be used alone or in combination with two or more types. The "maximum absorption wavelength" may be measured by a conventional method known to those skilled in the art, or may be a value obtained by referring to a product catalog.

[0072] The photoinitiator can be contained in an amount of 1 to 10 parts by weight, for example 1 to 5 parts by weight, per 100 parts by weight of the composition. By satisfying this range, the photocuring rate of the composition increases and a decrease in light transmittance due to residual initiator can be prevented.

[0073] The composition can be formed by mixing the curable component and the photoinitiator. For example, the composition can be formed as a solvent-free type that does not contain a solvent.

[0074] The composition is a photocurable composition and has a UV wavelength of 10 mW / cm 2 ~500mW / cm 2 The sealing layer can be formed by curing the composition by light irradiation for 1 to 50 seconds.

[0075] The composition may further contain conventional additives known to those skilled in the art, including, but not limited to, heat stabilizers, antioxidants, UV absorbers, etc.

[0076] The curing rate of the composition may be 90% to 100%, preferably 91% to 99%, and more preferably 91% to 93%. By satisfying this range, the curing agent of the composition can function as an organic layer. The photocuring rate can be calculated using the following formula 1.

[0077] The composition can be used to encapsulate an organic light-emitting device. Specifically, the composition can form an organic layer in an encapsulation structure in which an inorganic layer and an organic layer are formed in that order.

[0078] The composition can also be used as a sealant for device components, particularly display device components, that may be decomposed or become defective due to permeation of gases or liquids in the surrounding environment, such as atmospheric oxygen and / or moisture and / or water vapor, and chemicals used in processing electronic products. For example, the device component may be, but is not limited to, a lighting device, a metal sensor pad, a microdisk laser, an electrochromic device, a photochromic device, a microelectromechanical system, a solar cell, an integrated circuit, a charge-coupled device, a light-emitting polymer, etc.

[0079] An organic light emitting device display device may include an organic layer formed using the composition for sealing an organic light emitting device according to an embodiment. Specifically, the organic light emitting device display device includes an organic light emitting device and a barrier stack formed on the organic light emitting device, the barrier stack including an inorganic layer and an organic layer, and the organic layer may be formed using the composition for sealing an organic light emitting device according to an embodiment of the present invention. As a result, the reliability of the organic light emitting device display device may be improved.

[0080] 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 cross-sectional view of an organic light emitting diode display device according to an embodiment of the present invention.

[0081] Referring to FIG. 1, an organic light-emitting device display 100 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, where the inorganic layer 31 is in contact with the organic light-emitting device 20 and the organic layer 32 can be formed using a composition for sealing an organic light-emitting device according to an embodiment of the present invention.

[0082] The substrate 10 is not particularly limited as long as it is a substrate on which an organic light emitting device can be formed, and may be made of materials such as transparent glass, a plastic sheet, silicon, or a metal substrate.

[0083] The organic light emitting element 20 is a type commonly used in organic light emitting element display devices, and although not shown in FIG. 1, it includes a first electrode, a second electrode, and an organic light emitting film formed between the first and second electrodes. The organic light emitting film may be formed by sequentially stacking a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

[0084] The barrier stack 30 includes an organic layer and an inorganic layer, and the organic layer and the inorganic layer have different components constituting each layer, and each layer can perform the function of sealing the organic light emitting device.

[0085] The inorganic layer can complement the effects of the organic layer by having different components. 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. The metal or nonmetal can be, but is not limited to, silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), a transition metal, a lanthanum group metal, etc. Specifically, the inorganic layer may be silicon oxide (SiOx), silicon nitride (SiNx), silicon oxynitride (SiOxNy), ZnSe, ZnO, Sb2O3, AlOx, including Al2O3, In2O3, SnO2.

[0086] The inorganic layer can be formed 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.

[0087] When organic layers are deposited alternately with inorganic layers, they can ensure the smoothing properties of the inorganic layers and prevent defects in the inorganic layers from propagating to other inorganic layers.

[0088] The organic layer can be formed by a combination of coating, vapor deposition, curing, etc. of the composition for sealing an organic light-emitting element according to the embodiment of the present invention. For example, the composition for sealing an organic light-emitting element can be coated to a thickness of 1 μm to 50 μm, and the applied light is irradiated at 10 mW / cm. 2 ~500mW / cm 2 It can be hardened by irradiating it with light for 1 to 50 seconds.

[0089] 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 varied 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 may be 10 or less, for example, 2 to 7 layers, and specifically, 7 layers may be formed in the order inorganic layer / organic layer / inorganic layer / organic layer / inorganic layer / organic layer / inorganic layer.

[0090] In the barrier stack, organic and inorganic layers can be deposited alternately, due to the physical properties of the compositions described above, resulting in organic layers that can complement or enhance the sealing effect of the device.

[0091] Hereinafter, an organic light emitting diode 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 diode display device according to another embodiment of the present invention.

[0092] 2, an organic light emitting device display 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, where the inorganic layer 31 seals an internal space 40 housing the organic light emitting device 20, and the organic layer 32 may be formed using a composition for sealing an organic light emitting device according to an embodiment of the present invention. The organic light emitting device display 200 is substantially the same as the organic light emitting device display of an embodiment of the present invention, except that the inorganic layer does not contact the organic light emitting device. [Example]

[0093] The present invention will be described in more detail with reference to preferred embodiments thereof below, which are merely examples of the present invention and should not be construed as limiting the present invention in any way.

[0094] Synthesis Example 1: Synthesis of 4-(3-hydroxypropyl)1,7-heptanediol trimethacrylate

[0095] [ka]

[0096] 4-(3-hydroxypropyl)1,7-heptanediol trimethacrylate was synthesized using tris(2-cyanoethyl)nitromethane (Sigma-Aldrich) by the above method.

[0097] Synthesis Example 2: Synthesis of 3-(hydroxymethyl)-1,9-nonanediol trimethacrylate

[0098] [ka]

[0099] 3-(hydroxymethyl)-1,9-nonanediol trimethacrylate was synthesized using 6-nitro-1-hexanol (Aurora) by the above method.

[0100] Synthesis Example 3: Preparation of 4,4-bis(3-hydroxypropyl)-1,7-heptanediol tetramethacrylate

[0101] [ka]

[0102] 4,4-bis(3-hydroxypropyl)-1,7-heptanediol tetramethacrylate was synthesized using the above method.

[0103] The specific specifications of the components used in the examples and comparative examples are as follows:

[0104] (A) First Aliphatic Photocurable Monomer (A1) 4-(3-hydroxypropyl)1,7-heptanediol trimethacrylate (Synthesis Example 1)

[0105] [ka]

[0106] (A2) 3-(hydroxymethyl)-1,9-nonanediol trimethacrylate (Synthesis Example 2)

[0107] [ka]

[0108] (A3) 4,4-bis(3-hydroxypropyl)-1,7-heptanediol tetramethacrylate (Synthesis Example 3)

[0109] [ka]

[0110] (A4) Trimethylolpropane triacrylate

[0111] [ka]

[0112] (B) Second Aliphatic Photocurable Monomer (B1) 1,12-dodecanediol dimethacrylate (Aldrich) (B2) 1,14-tetradecanediol dimethacrylate (Aldrich) (B3) Dodecyl methacrylate (Aldrich) (B4) Cetyl methacrylate (Aldrich) (B5) DTD-A (2-decyl-1-tetradecanyl acrylate, Kyoeisha)

[0113] (C) Aromatic photocurable monomer (C1) M1142 (o-phenylphenoxyethyl acrylate, Miwon) (C2) NMT-A (2-propenoic acid, 1-naphthalenylmethyl ester) (C3) Benzyl methacrylate (Aldrich)

[0114] (D) Photoinitiator (TPO-L, IGM)

[0115] Example 1 20 parts by weight of (A1), 30 parts by weight of (B2), 27 parts by weight of (B3), 20 parts by weight of (C1), and 3 parts by weight of (D) were added to a 125 mL brown polypropylene bottle and mixed using a shaker at room temperature for 3 hours to prepare a sealing composition.

[0116] Examples 2 to 6 and Comparative Examples 1 to 5

[0117] A sealing composition was prepared in the same manner as in Example 1, except that the content of each component in Example 1 was changed as shown in Table 1 below (unit: parts by weight).

[0118] In Table 1 below, "-" means that the corresponding ingredient is not contained.

[0119] The following physical properties were measured for the compositions prepared in the examples and comparative examples, and the results are shown in Table 1.

[0120] (1) Dielectric constant (no unit): The sealing compositions of the examples and comparative examples were applied to a chromium (Cr) plate to a predetermined thickness, and the dielectric constant was 100 mW / cm 2 The coating was then photocured by irradiating it with UV light for 10 seconds at 1000 kJ / s, forming a coating film with a thickness of 8 μm. After depositing aluminum (electrode for measuring the dielectric constant) on the coating film, the dielectric constant was measured using an impedance analyzer (E4990A) at a frequency of 200 kHz and a temperature of 25°C.

[0121] (2) Viscosity (unit: cps): The viscosity of the sealing compositions of the examples and comparative examples was measured at 24.8° C. using a viscosity measuring device LV DV-II Pro (manufactured by Brookfield) with a spindle number of 40.

[0122] (3) Photocuring rate (unit: %): The photocuring rate of the sealing composition was measured using FT-IR (NICOLET 4700, manufactured by Thermo Instruments) at 1635 cm -1 Near (C=C), 1720cm -1 The intensity of the absorption peak near (C=O) was measured. The sealing composition was spray-coated onto a glass substrate, and an intensity of 100 mW / cm 2 The film was cured by irradiating it with UV light for 20 seconds at 1635 cm , and a test piece measuring 20 cm × 20 cm × 3 μm (width × length × thickness) was obtained. The cured film was separated and analyzed using an FT-IR (NICOLET 4700, Thermo). -1 Near (C=C), 1720cm -1 The intensity of the absorption peak near (C=O) was measured. The photocuring rate was calculated according to the following formula 1. Formula 1 Photocuring rate (%)=|1-(A / B)|×100

[0123] In Equation 1, A is the 1720 cm of the cured film. -1 Intensity of the absorption peak near 1635 cm -1 is the ratio of the intensities of the absorption peaks in the vicinity of B is the 1720 cm -1 Intensity of the absorption peak near 1635 cm -1 is the ratio of the intensities of the absorption peaks in the vicinity

[0124] (4) Modulus (unit: GPa): The sealing compositions of the examples and comparative examples were applied to a glass plate in a predetermined thickness, and the modulus was measured at 100 mW / cm 2 An 8 μm-thick organic layer was prepared as a specimen for modulus measurement by photocuring with UV irradiation at 400 K for 10 seconds. The modulus of the specimen was measured using a Nano Indentor G200 (Agilent). The modulus was measured at 25°C under the following conditions: Experimental mode: Indentation Mode (using Berkovitz), Control mode: Force control, Maximum force: 60 μN (0213-TJ: 54 μN with 100 nm displacement control). The specimen was loaded into the nano indenter for 5 seconds, held for 2 seconds, and then unloaded for 5 seconds.

[0125] (5) Inkjet processability: Inkjet processability was evaluated using an Omnijet 300 (Unijet, Konica-Minolta KM1024i head). The sealing compositions of the examples and comparative examples were inkjet-jetted at a drop rate of 2.5 μm / sec and an inkjet head temperature of 25°C to 40°C. When inkjetted, if the droplets were precisely spherical, they were evaluated as OK, and if they were not perfectly spherical, they were evaluated as NG.

[0126] (6) CVD processability: When an inorganic layer was vapor-deposited on an organic layer formed from the composition, it was confirmed whether wrinkles occurred in the organic layer. After coating the sealing composition on a glass substrate to a thickness of 8 μm, CVD processability was confirmed by CVD at 100 mW / cm. 2The sample was cured by UV irradiation for 20 seconds at 80°C to obtain a test specimen. SiNx deposition was performed for 40 minutes at 80°C and 2.2 Å / sec using a PECVD (PLUS200-SP, QUROS Corporation). The organic layer was checked for wrinkles. If no wrinkles were observed, the result was rated as OK; if wrinkles were observed, the result was rated as NG.

[0127] [Table 1]

[0128] As shown in Table 1, the composition for sealing an organic light-emitting device of the present invention formed an organic layer with a low dielectric constant. When inorganic layers were repeatedly formed, the occurrence of wrinkles was suppressed, and an organic layer with excellent processability and reliability was formed. In addition, the composition for sealing an organic light-emitting device had excellent inkjet jetting properties.

[0129] 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.

Claims

1. a curable component including a first aliphatic photocurable monomer, a second aliphatic photocurable monomer, and an aromatic photocurable monomer, and a photoinitiator; The first aliphatic photocurable monomer is represented by the following general formula 1: 【Chemistry 1】 In the general formula 1, L １１ , L １２ , L １３ and L １４ are each independently a substituted or unsubstituted, linear or branched alkylene group having two or more carbon atoms, L １１ , L １２ , L １３ and L １４ The total number of carbon atoms in the main chain is 6 or more, X １ , X ２ , X ３ and X ４ are each independently hydrogen or represented by the following general formula 2: X １ , X ２ , X ３ and X ４ At least three of them are represented by the following general formula 2: General formula 2 *-O-C(=O)-C(=CH ２ )(X ５ ) In the general formula 2, * is the linking site of the element, X ５ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.

2. In the general formula 1, L １１ , L １２ , L １３ and L １４ The composition for sealing an organic light-emitting element according to claim 1 , wherein the total number of carbon atoms in the main chain of

3. The composition for sealing an organic light-emitting element according to claim 1, wherein the compound of general formula 1 includes at least one compound represented by the following general formula 1-1, general formula 1-2, or general formula 1-3: 【Chemistry 2】

4. The composition for sealing an organic light emitting device according to claim 1, wherein the first aliphatic photocurable monomer is contained in an amount of 30 to 200 parts by weight based on 100 parts by weight of the second aliphatic photocurable monomer.

5. The composition for sealing an organic light emitting device according to claim 1, wherein the first aliphatic photocurable monomer is contained in an amount of 100 to 300 parts by weight based on 100 parts by weight of the aromatic photocurable monomer.

6. The second aliphatic photocurable monomer includes one or more compounds represented by the following general formula 2-1 and one or more compounds represented by the following general formula 2-2: 【Transformation 3】 In the general formula 2-1, R １ , R ２ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, L ２１ is a substituted or unsubstituted, linear or branched alkylene group having 8 to 30 carbon atoms, 【Chemistry 4】 In the general formula 2-2, R ３ is hydrogen or an alkyl group having 1 to 5 carbon atoms, L ２２ 2. The composition for sealing an organic light-emitting element according to claim 1, wherein is a substituted or unsubstituted, linear or branched alkyl group having 8 to 30 carbon atoms.

7. 7. The composition for sealing an organic light-emitting element according to claim 6, wherein the second aliphatic photocurable monomer comprises a mixture of the compound represented by General Formula 2-1 and the compound represented by General Formula 2-2.

8. The composition for sealing an organic light-emitting element according to claim 7, wherein, in 100 parts by weight of the mixture, the compound represented by the general formula 2-1 is contained in an amount of 50 parts by weight to 90 parts by weight, and the compound represented by the general formula 2-2 is contained in an amount of 10 parts by weight to 50 parts by weight.

9. The composition for sealing an organic light emitting device according to claim 1, wherein the aromatic photocurable monomer is contained in an amount of 30 to 80 parts by weight based on 100 parts by weight of the second aliphatic photocurable monomer.

10. The aromatic photocurable monomer is represented by the following general formula 3: General formula 3 (CH ２ =)-C(R ４ )-C(=O)-O-(-CH ２ -)s-L ３１ In the general formula 3, R ４ is hydrogen or an alkyl group having 1 to 5 carbon atoms, s is an integer from 0 to 10; L ３１ 2. The composition for sealing an organic light-emitting element according to claim 1, wherein is a substituted or unsubstituted C6 to C50 aryl group, or a substituted or unsubstituted C6 to C50 aryloxy group.

11. In the general formula 3, L ３１ The composition for sealing an organic light-emitting element according to claim 10 , wherein is a phenylphenoxyethyl group or a naphthalenyl group.

12. 2. The composition for sealing an organic light-emitting element according to claim 1, wherein a total amount of the first aliphatic photocurable monomer, the second aliphatic photocurable monomer, and the aromatic photocurable monomer is 95% by weight or more in the curable component.

13. In 100 parts by weight of the composition for sealing an organic light-emitting element, the first aliphatic photocurable monomer is 10 to 60 parts by weight, the second aliphatic photocurable monomer is 20 to 60 parts by weight, the aromatic photocurable monomer is 10 to 50 parts by weight, The composition for sealing an organic light emitting device according to claim 1, wherein the photoinitiator is contained in an amount of 1 to 10 parts by weight.

14. An organic light-emitting element display device comprising an organic layer formed from the composition for sealing an organic light-emitting element according to claim 1 .

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