KR102329734B1 - Encapsulation film - Google Patents

Abstract

The present application relates to an encapsulation film, a manufacturing method thereof, an organic electronic device including the same, and a manufacturing method of an organic electronic device using the same, wherein a structure capable of blocking moisture or oxygen flowing into an organic electronic device from the outside is possible , to provide an encapsulation film capable of preventing the occurrence of bright spots in organic electronic devices.

Description

Encapsulation Film {ENCAPSULATION FILM}

The present application relates to an encapsulation film, an organic electronic device including the same, and a method of manufacturing the organic electronic device.

An organic electronic device (OED) refers to a device including an organic material layer that generates an exchange of charges using holes and electrons, and examples thereof include a photovoltaic device, a rectifier, and a transmitter and an organic light emitting diode (OLED).

Among the organic electronic devices, an organic light emitting diode (OLED) consumes less power, has a faster response speed, and is advantageous for thinning a display device or lighting, compared to a conventional light source. In addition, OLED is expected to be applied in various fields including various portable devices, monitors, laptops and TVs because of its excellent space utilization.

In commercialization and expansion of use of OLED, the most major problem is durability. Organic materials and metal electrodes included in OLED are very easily oxidized by external factors such as moisture. In addition, there is also a problem in that the luminescent point of the OLED is generated by the outgas that may be generated inside the OLED device. That is, products including OLEDs are highly sensitive to environmental factors. Accordingly, various methods have been proposed in order to effectively block the penetration of oxygen or moisture from the outside into the organic electronic device such as OLED, and at the same time suppress outgas generated from the inside.

The present application provides an encapsulation film capable of forming a structure capable of blocking moisture or oxygen flowing into an organic electronic device from the outside and preventing the occurrence of bright spots in the organic electronic device.

This application relates to an encapsulation film. The encapsulation film may be applied to, for example, encapsulating or encapsulating an organic electronic device such as an OLED.

As used herein, the term "organic electronic device" refers to an article or device having a structure including an organic material layer that generates an exchange of electric charges between a pair of opposite electrodes by using holes and electrons, for example, may include, but are not limited to, a photovoltaic device, a rectifier, a transmitter, and an organic light emitting diode (OLED). In one example of the present application, the organic electronic device may be an OLED.

An exemplary organic electronic device encapsulation film 20, as shown in Figure 1, the thermal conductivity is in the range of 50 to 800 W / mK of the thermally conductive metal layer 21; an adsorption layer 22 formed on one surface of the thermally conductive metal layer 21 and including a first inorganic component having an adsorption energy for outgas calculated by Density Functional Theory of 0 eV or less; and a nitride layer 23 formed on one surface of the adsorption layer 22 and including a nitride of the first inorganic component. The nitride layer may be formed on a surface opposite to the surface of the adsorption layer on which the thermally conductive metal layer is formed. That is, the encapsulation film may sequentially include a thermally conductive metal layer, an adsorption layer, and a nitride layer. Each of the layers may be directly attached, but is not limited thereto, and another intermediate layer may be present. According to the present application, by using the encapsulation film having the above structure, it is possible to effectively adsorb outgas generated inside the organic electronic device to prevent the occurrence of bright spots, and to provide an organic electronic device having excellent durability and reliability in a harsh environment.

In the embodiment of the present application, the lower limit of the adsorption energy is not particularly limited, but may be -20 eV. The type of the outgas is not particularly limited, but may include H atoms, H ₂ molecules, and/or NH ₃ . The present application provides that the encapsulation film includes an adsorption layer including a first inorganic component having an adsorption energy of 0 eV or less for outgas and a nitride layer including a nitride of the first inorganic component, thereby blocking moisture flowing into the organic electronic device. At the same time, it is possible to prevent a bright spot due to an outgas generated in the organic electronic device.

In the embodiment of the present application, the adsorption energy between the first inorganic component and the atoms or molecules causing the bright spot can be calculated through the electronic structure calculation based on the density functional theory. The calculation may be performed by a method known in the art. For example, the present application makes a two-dimensional slab structure in which the closest packing surface of the first inorganic component having a crystalline structure is exposed as a surface, then proceeds with structural optimization, and a structure in which a molecule causing a bright spot is adsorbed on the surface in a vacuum state After optimizing the structure, the adsorption energy was defined as the difference in the total energy of the two systems minus the total energy of the molecules responsible for the bright spot. To calculate the total energy for each system, the revised-PBE function, a function of the generalized gradient approximation (GGA) series, was used as an exchange-correlation that simulates the electron-electron interaction, and the cutoff of the electron kinetic energy was 500 eV. It was calculated by including only the gamma point corresponding to the origin of the reciprocal space. To optimize the atomic structure of each system, the conjugate gradient method was used, and repeated calculations were performed until the interatomic force was less than 0.01 eV/Å. A series of calculations were performed through the commercial code VASP.

The material of the first inorganic component is not limited as long as the encapsulation film is applied to the organic electronic device and has an effect of preventing bright spots on the panel of the organic electronic device. For example, the first inorganic component is an outgas generated from an inorganic deposition layer of silicon oxide, silicon nitride, or silicon oxynitride deposited on an electrode of an organic electronic device, for example, H ₂ gas, ammonia (NH ₃ ) gas , H ⁺ , NH ²⁺ , NHR ₂ or NH ₂ R may be a material capable of adsorbing. In the above, R may be an organic group, for example, an alkyl group, an alkenyl group, an alkynyl group, etc. may be exemplified, but is not limited thereto.

In one example, the material of the first inorganic component is not limited as long as it satisfies the adsorption energy value, and may be a metal or a non-metal. The first inorganic component is, for example, Li, Ni, Ti, Rb, Be, Mg, Ca, Sr, Ba, Al, Zn, In, Pt, Pd, Fe, Cr, Si, Zr, Cu, Nb, It may include Y, V or a combination thereof, and may include an oxide of the above material, and may include an alloy of the above material. In one example, the first inorganic component is nickel, nickel oxide, titanium nitride, a titanium-based alloy of iron-titanium, a manganese-based alloy of iron-manganese, a magnesium-based alloy of magnesium-nickel, a rare earth alloy, a zeolite, silica, It may include carbon nanotubes, graphite, aluminophosphate molecular sieves, or mesosilica. According to the present application, since the adsorption layer includes the first inorganic component, it is possible to efficiently adsorb hydrogen generated in the organic electronic device, while simultaneously implementing the moisture barrier properties and durability reliability of the encapsulation film.

In an embodiment of the present application, as described above, the encapsulation film may further include the thermally conductive metal layer. The thermally conductive metal layer of the present application is 50 W/m·K or more, 60 W/m·K or more, 70 W/m·K or more, 80 W/m·K or more, 90 W/m·K or more, 100 W/m·K or more K or more, 110 W/m·K or more, 120 W/m·K or more, 130 W/m·K or more, 140 W/m·K or more, 150 W/m·K or more, 200 W/m·K or more Alternatively, it may have a thermal conductivity of 210 W/m·K or more. The upper limit of the thermal conductivity is not particularly limited, and may be 800 W/m·K or less. By having such high thermal conductivity, heat generated at the bonding interface during the encapsulation film bonding process can be discharged more quickly. In addition, the high thermal conductivity rapidly dissipates heat accumulated during the operation of the organic electronic device to the outside, and accordingly, the temperature of the organic electronic device itself can be kept lower, and cracks and defects are reduced. The thermal conductivity may be measured at any one of a temperature range of 15 to 30 ℃.

As used herein, the term “thermal conductivity” refers to the degree to which a material can transmit heat by conduction, and the unit can be expressed as W/m·K. The unit indicates the degree of heat transfer of a material at the same temperature and distance, and means a unit of heat (watt) for a unit of distance (meter) and a unit of temperature (Kelvin).

In an embodiment of the present application, the thermally conductive metal layer of the encapsulation film may be transparent or opaque. The thickness of the thermally conductive metal layer may be in the range of 5 μm to 200 μm, 10 μm to 100 μm, 20 μm to 90 μm, 30 μm to 80 μm, or 40 μm to 75 μm. The present application may provide a thin-film encapsulation film while sufficiently implementing a heat dissipation effect by controlling the thickness of the thermally conductive metal layer. The thermally conductive metal layer may have a metal deposited on a thin metal foil or a polymer substrate layer. The thermally conductive metal layer is not particularly limited as long as it satisfies the aforementioned thermal conductivity and includes a metal. The thermally conductive metal layer may include any one of a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, a metal oxyboride, and combinations thereof. For example, the thermally conductive metal layer may include an alloy in which one or more metal elements or non-metal elements are added to one metal, for example, stainless steel (SUS). In addition, in one example, the thermally conductive metal layer is iron, chromium, copper, aluminum nickel, iron oxide, chromium oxide, silicon oxide, aluminum oxide, titanium oxide, indium oxide, tin oxide, indium tin oxide, tantalum oxide, zirconium oxide, oxide niobium, and combinations thereof. The thermally conductive metal layer may be deposited by electrolysis, rolling, thermal evaporation, electron beam evaporation, sputtering, reactive sputtering, chemical vapor deposition, plasma chemical vapor deposition or electron cyclotron resonance source plasma chemical vapor deposition means. In an embodiment of the present application, the thermally conductive metal layer may be deposited by reactive sputtering.

Conventionally, a nickel-iron alloy (Invar) has been commonly used as an encapsulation film, but the nickel-iron alloy has disadvantages in that it is expensive, has poor thermal conductivity, and has poor cutability. The present application provides an encapsulation film having excellent heat dissipation properties and preventing the occurrence of bright spots in an organic electronic device without using the nickel-iron alloy as a thermally conductive metal layer.

In an embodiment of the present application, the encapsulation film may sequentially include a thermally conductive metal layer, an adsorption layer, and a nitride layer, as described above. In the encapsulation film, the adsorption layer may have a thickness of 50 nm to 3 µm, 60 nm to 2.5 µm, 70 nm to 2 µm, 80 nm to 1.5 µm, 90 nm to 1 µm, or 95 nm to 0.5 µm. The adsorption layer may be an inorganic deposition layer formed by being deposited on one surface of the thermally conductive metal layer. In addition, the nitride layer may be an inorganic deposition layer formed by being deposited on one surface of the adsorption layer. The thickness of the nitride layer may range from 5 nm to 2 μm, 8 nm to 1.5 μm, 10 nm to 1 μm, 12 nm to 0.8 μm, 15 nm to 0.5 μm, 16 nm to 0.3 μm, or 17 nm to 93 nm. In one example, the thickness of the nitride layer may be thinner than the thickness of the adsorption layer. In one example, the ratio of the thickness of the nitride layer to the thickness of the adsorption layer may be in the range of 0.01 to 0.8, 0.05 to 0.7, 0.1 to 0.5, or 0.15 to 0.3. Like the adsorption layer, the nitride layer may adsorb outgas that causes luminescent spots, but may also serve as a catalyst to decompose and transmit outgas such as hydrogen and transmit it to the adsorption layer. In addition, the first inorganic component included in the adsorption layer is oxidized, and there is a problem in that oxides are generated on the surface of the adsorption layer. The nitride layer prevents surface oxidation of the adsorption layer to efficiently adsorb outgas do. Considering the above role, the nitride layer may be positioned in a direction in which the device is positioned when the encapsulation film encapsulates the organic electronic device. That is, the nitride layer may be applied closer to the device than the thermally conductive metal layer or the adsorption layer when encapsulating the organic electronic device.

In one example, the encapsulation film of the present application may further include a protective layer formed on the other surface of the thermally conductive metal layer. The protective layer may be formed on a surface opposite to one surface on which the adsorption layer is formed among both surfaces of the thermally conductive metal layer. The protective layer may include a polymer component. The material constituting the protective layer is not particularly limited. In one example, the protective layer may be a moisture barrier capable of blocking moisture permeation. In one example, as a polymer component constituting the protective layer, polyorganosiloxane, polyimide, styrene-based resin or elastomer, polyolefin-based resin or elastomer, polyoxyalkylene-based resin or elastomer, polyester-based resin or elastomer, poly Vinyl chloride resin or elastomer, polycarbonate resin or elastomer, polyphenylene sulfide resin or elastomer, polyamide resin or elastomer, acrylate resin or elastomer, epoxy resin or elastomer, silicone resin or elastomer, and fluorine resin It may include one or more selected from the group consisting of a resin or an elastomer, but is not limited thereto.

In an embodiment of the present application, an adhesive or an adhesive may be further included between the protective layer and the thermally conductive metal layer. The material of the pressure-sensitive adhesive or adhesive is not particularly limited and a known material may be used. In one example, the pressure-sensitive adhesive or adhesive may be an acrylic, epoxy, urethane, silicone, or rubber-based pressure-sensitive adhesive or adhesive. Also, in one embodiment, the material of the pressure-sensitive adhesive or adhesive may be the same as or different from the material of the encapsulation layer to be described later.

In the embodiment of the present application, the encapsulation film 2 is formed on one surface of the nitride layer 23, as shown in FIG. 2, and an encapsulation layer 24 encapsulating the entire surface of the organic electronic device formed on the substrate. ) may be additionally included. When the encapsulation layer is included, the encapsulation film may sequentially include a thermally conductive metal layer, an adsorption layer, a nitride layer, and an encapsulation layer.

In one example, the encapsulation layer may include an encapsulation resin and a moisture absorbent, and the encapsulation layer may be an adhesive layer or an adhesive layer.

In an embodiment of the present invention, the encapsulating resin may have a glass transition temperature of less than 0°C, less than -10°C or less than -30°C, less than -50°C or less than -60°C. In the above, the glass transition temperature may be a glass transition temperature after curing, and in one embodiment, the glass transition temperature after irradiating ultraviolet rays with an irradiation ^{amount of about 1J/cm 2 or more;} Alternatively, it may mean a glass transition temperature after further thermal curing after UV irradiation.

In one example, the encapsulating resin is a styrene-based resin or elastomer, a polyolefin-based resin or elastomer, other elastomers, polyoxyalkylene-based resins or elastomers, polyester-based resins or elastomers, polyvinyl chloride-based resins or elastomers, and polycarbonate-based resins. Resin or elastomer, polyphenylene sulfide-based resin or elastomer, mixture of hydrocarbons, polyamide-based resin or elastomer, acrylate-based resin or elastomer, epoxy-based resin or elastomer, silicone-based resin or elastomer, fluorine-based resin or elastomer or mixtures thereof and the like.

In the above, as the styrene-based resin or elastomer, for example, styrene-ethylene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), acrylonitrile-butadiene-styrene block copolymer (ABS), an acrylonitrile-styrene-acrylate block copolymer (ASA), a styrene-butadiene-styrene block copolymer (SBS), a styrenic homopolymer, or a mixture thereof. As the olefin-based resin or elastomer, for example, a high-density polyethylene-based resin or elastomer, a low-density polyethylene-based resin or elastomer, a polypropylene-based resin or elastomer, or a mixture thereof may be exemplified. As the elastomer, for example, an ester-based thermoplastic elastomer, an olefin-based elastomer, a silicone-based elastomer, an acrylic elastomer, or a mixture thereof may be used. Among them, polybutadiene resin or elastomer or polyisobutylene resin or elastomer may be used as the olefinic thermoplastic elastomer. As the polyoxyalkylene-based resin or elastomer, for example, a polyoxymethylene-based resin or elastomer, a polyoxyethylene-based resin or elastomer, or a mixture thereof may be exemplified. As the polyester-based resin or elastomer, for example, polyethylene terephthalate-based resin or elastomer, polybutylene terephthalate-based resin or elastomer, or a mixture thereof may be exemplified. As the polyvinyl chloride-based resin or elastomer, for example, polyvinylidene chloride may be exemplified. As a mixture of the hydrocarbons, for example, hexatriacotane or paraffin may be exemplified. As the polyamide-based resin or elastomer, for example, nylon may be exemplified. As the acrylate-based resin or elastomer, for example, polybutyl (meth)acrylate may be exemplified. As said epoxy resin or elastomer, For example, Bisphenol types, such as a bisphenol A type, a bisphenol F type, a bisphenol S type, and these hydrogenated substances; novolak types, such as a phenol novolak type and a cresol novolak type; nitrogen-containing cyclic types such as triglycidyl isocyanurate and hydantoin; alicyclic; aliphatic; Aromatic types, such as a naphthalene type and a biphenyl type; Glycidyl types, such as a glycidyl ether type, a glycidylamine type, and a glycidyl ester type; dicyclo types, such as a dicyclopentadiene type; ester type; An ether ester type or a mixture thereof may be exemplified. As the silicone-based resin or elastomer, for example, polydimethylsiloxane may be exemplified. In addition, as the fluorine-based resin or elastomer, polytrifluoroethylene resin or elastomer, polytetrafluoroethylene resin or elastomer, polychlorotrifluoroethylene resin or elastomer, polyhexafluoropropylene resin or elastomer, polyfluorinated vinylidene, polyvinyl fluoride, polyfluoride ethylene propylene, or mixtures thereof may be exemplified.

The resins or elastomers listed above may be used by grafting, for example, maleic anhydride, etc., may be used by copolymerization with other listed resins or elastomers or monomers for preparing resins or elastomers, modified by other compounds can also be used. Examples of the other compound include a carboxyl-terminated butadiene-acrylonitrile copolymer.

In one example, the encapsulation layer may include, as an encapsulation resin, an olefin-based elastomer, a silicone-based elastomer, or an acrylic-based elastomer, among the above-mentioned types, but is not limited thereto.

In one embodiment of the present invention, the encapsulating resin may be an olefin-based resin. In one example, the olefin-based resin is a homopolymer of butylene monomer; a copolymer obtained by copolymerizing a butylene monomer and another polymerizable monomer; reactive oligomers using butylene monomers; or a mixture thereof. The butylene monomer may include, for example, 1-butene, 2-butene, or isobutylene.

Other monomers polymerizable with the butylene monomer or derivative may include, for example, isoprene, styrene, or butadiene. By using the copolymer, it is possible to maintain physical properties such as fairness and degree of crosslinking, so that heat resistance of the adhesive itself can be secured when applied to an organic electronic device.

In addition, the reactive oligomer using the butylene monomer may include a butylene polymer having a reactive functional group. The oligomer may have a weight average molecular weight in the range of 500 to 5000. In addition, the butylene polymer may be bonded to another polymer having a reactive functional group. The other polymer may be an alkyl (meth)acrylate, but is not limited thereto. The reactive functional group may be a hydroxyl group, a carboxyl group, an isocyanate group, or a nitrogen-containing group. In addition, the reactive oligomer and the other polymer may be crosslinked by a polyfunctional crosslinking agent, and the polyfunctional crosslinking agent may be at least one selected from the group consisting of an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent.

In one example, the encapsulating resin of the present application may be a copolymer of a diene and an olefin-based compound including one carbon-carbon double bond. Here, the olefin-based compound may include butylene, and the like, and the diene may be a monomer polymerizable with the olefin-based compound, and may include, for example, isoprene or butadiene. For example, the copolymer of the diene and the olefin-based compound containing one carbon-carbon double bond may be butyl rubber.

In the encapsulation layer, the resin or the elastomer component may have a weight average molecular weight (Mw) that allows the pressure-sensitive adhesive composition to be molded into a film shape. For example, the resin or elastomer may have a weight average molecular weight of about 100,000 to 2 million, 150,000 to 1.5 million, or 350,000 to 1 million. In the present specification, the term "weight average molecular weight" refers to a value converted to standard polystyrene measured by gel permeation chromatograph (GPC). However, it is not necessary for the resin or elastomer component to have the above-mentioned weight average molecular weight. For example, when the molecular weight of the resin or elastomer component does not reach a level sufficient to form a film, a separate binder resin may be blended into the pressure-sensitive adhesive composition.

In addition, in one example, the encapsulation layer of the present application may include an active energy ray polymerizable compound having high compatibility with the encapsulation resin and forming a specific cross-linked structure together with the encapsulation resin. In this case, the encapsulating resin may be a cross-linkable resin.

For example, the encapsulation layer of the present application may include a polyfunctional active energy ray polymerizable compound that may be polymerized by irradiation with active energy rays together with the encapsulation resin. The active energy ray-polymerizable compound is, for example, a functional group capable of participating in a polymerization reaction by irradiation of active energy ray, for example, a functional group containing an ethylenically unsaturated double bond such as an acryloyl group or a methacryloyl group. , may mean a compound including two or more functional groups such as an epoxy group or an oxetane group.

As the polyfunctional active energy ray-polymerizable compound, for example, multifunctional acrylate (MFA) may be used.

In addition, the active energy ray polymerizable compound is 3 parts by weight to 30 parts by weight, 5 parts by weight to 25 parts by weight, 8 parts by weight to 20 parts by weight, 10 parts by weight to 18 parts by weight or 12 parts by weight based on 100 parts by weight of the encapsulating resin. It may be included in an amount of from 18 parts by weight to 18 parts by weight. The present application provides an encapsulation film having excellent durability and reliability even under severe conditions such as high temperature and high humidity within the above range.

The polyfunctional active energy ray-polymerizable compound that can be polymerized by irradiation with the active energy ray may be used without limitation. For example, the compound may be 1,4-butanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8- Octanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentylglycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, cyclo Hexane-1,4-dimethanol di(meth)acrylate, tricyclodecanedimethanol(meth)diacrylate, dimethylol dicyclopentane di(meth)acrylate, neopentylglycol modified trimethylpropane di(meth)acryl lactate, adamantane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, or mixtures thereof.

As the polyfunctional active energy ray-polymerizable compound, for example, a compound having a molecular weight of less than 1,000 and containing two or more functional groups can be used. In this case, the molecular weight may mean a weight average molecular weight or a conventional molecular weight. The ring structure included in the polyfunctional active energy ray-polymerizable compound is a carbocyclic structure or a heterocyclic structure; Or any of monocyclic or polycyclic structure may be sufficient.

In an embodiment of the present application, the encapsulation layer may further include a radical initiator. The radical initiator may be a photoinitiator or a thermal initiator. The specific type of the photoinitiator may be appropriately selected in consideration of the curing rate and the possibility of yellowing. For example, benzoin-based, hydroxy ketone-based, amino ketone-based or phosphine oxide-based photoinitiators can be used, and specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether , benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethyl anino acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2 -Hydroxy-2-methyl-1-phenylpropan-1one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1- One, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4 -Dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylketal, p-dimethylaminobenzoic acid ester, oligo[2-hydroxy-2-methyl-1-[4-(1-methyl) vinyl) phenyl] propanone] and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

The radical initiator may be included in an amount of 0.2 parts by weight to 20 parts by weight, 0.5 to 18 parts by weight, 1 to 15 parts by weight, or 2 parts by weight to 13 parts by weight based on 100 parts by weight of the active energy ray-polymerizable compound. Through this, it is possible to effectively induce a reaction of the active energy ray-polymerizable compound, and also to prevent deterioration of the physical properties of the encapsulation layer composition due to the remaining components after curing.

In one example, the encapsulation layer may further include a tackifier, and the tackifier may preferably be a hydrogenated cyclic olefinic polymer. As a tackifier, the hydrogenated petroleum resin obtained by hydrogenating a petroleum resin can be used, for example. Hydrogenated petroleum resins may be partially or fully hydrogenated, and may be mixtures of such resins. Such tackifiers may be selected from those having good compatibility with the pressure-sensitive adhesive composition, excellent moisture barrier properties, and low organic volatile components. Specific examples of the hydrogenated petroleum resin include a hydrogenated terpene-based resin, a hydrogenated ester-based resin, or a hydrogenated dicyclopentadiene-based resin. The weight average molecular weight of the tackifier may be about 200 to 5,000. The content of the tackifier may be appropriately adjusted as necessary. For example, the amount of the tackifier may be 5 to 100 parts by weight, 8 to 95 parts by weight, 10 to 93 parts by weight, or 15 to 90 parts by weight, based on 100 parts by weight of the resin component, according to one example. may be included as a percentage.

As described above, the encapsulation layer may further include a moisture absorbent. As used herein, the term "moisture absorbent" may refer to, for example, a chemically reactive adsorbent capable of removing the moisture through a chemical reaction with moisture or moisture that has penetrated into the encapsulation film to be described later.

For example, the moisture adsorbent may be present in a uniformly dispersed state in the encapsulation layer or encapsulation film. Here, the evenly dispersed state may mean a state in which the moisture adsorbent is present at the same or substantially the same density in any part of the encapsulation layer or the encapsulation film. As the moisture adsorbent that can be used above, for example, metal oxides, sulfates, or organometallic oxides may be mentioned. Specifically, examples of the sulfate include magnesium sulfate, sodium sulfate or nickel sulfate, and examples of the organometallic oxide include aluminum oxide octylate. Specific examples of the metal oxide in the above, phosphorus pentoxide (P ₂ O ₅ ), lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), barium oxide (BaO), calcium oxide (CaO) or magnesium oxide (MgO) ) and the like, and examples of the metal salt include lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), Sulfates such as gallium sulfate (Ga ₂ (SO ₄ ) ₃ ), titanium sulfate (Ti(SO ₄ ) ₂ ) or nickel sulfate (NiSO ₄ ), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl) ₂ ), yttrium chloride (YCl ₃ ), copper chloride (CuCl ₂ ), cesium fluoride (CsF), tantalum fluoride (TaF ₅ ), niobium fluoride _{(NbF 5} ), lithium bromide (LiBr), calcium bromide (CaBr ₂ ), metal halides such as cesium bromide (CeBr ₃ ), selenium bromide (SeBr ₄ ), vanadium bromide (VBr ₃ ), magnesium bromide (MgBr ₂ ), barium iodide (BaI ₂ ) or magnesium iodide (MgI _{2 );} or metal chlorates such as barium perchlorate (Ba(ClO ₄ ) ₂ ) or magnesium perchlorate (Mg(ClO ₄ ) ₂ ), but is not limited thereto. As a moisture adsorbent that may be included in the encapsulation layer, one of the above-described components may be used, or two or more types may be used. In one example, when two or more types of moisture adsorbents are used, calcined dolomite, etc. may be used.

Such a moisture adsorbent may be controlled to an appropriate size depending on the application. In one example, the average particle diameter of the moisture adsorbent may be controlled to be 100 to 15000 nm, 500 nm to 10000 nm, 800 nm to 8000 nm, 1 µm to 7 µm, 2 µm to 5 µm, or 2.5 µm to 4.5 µm. In the present specification, the particle diameter may mean an average particle diameter, and may be measured by a known method with a D50 particle size analyzer.

The content of the moisture adsorbent is not particularly limited and may be appropriately selected in consideration of desired barrier properties. In one example, the encapsulation film of the present application may be included in an amount of 5 to 100 parts by weight or 10 to 80 parts by weight based on 100 parts by weight of the encapsulating resin.

The encapsulation layer may also include a moisture barrier, if desired. As used herein, the term “moisture blocker” may refer to a material that has no or low reactivity with moisture, but can physically block or impede the movement of moisture or moisture in the film. As the moisture barrier, for example, one or two or more of clay, talc, acicular silica, plate-shaped silica, porous silica, zeolite, titania, or zirconia may be used. In addition, the moisture barrier may be surface-treated by an organic modifier or the like to facilitate penetration of organic matter. Such organic modifiers include, for example, dimethyl benzyl hydrogenatedtallow quaternaty ammonium, dimethyl dihydrogenatedtallow quaternary ammonium, methyl tallow bis-2-hydroxyethyl Quaternary ammonium (methyl tallow bis-2-hydroxyethyl quaternary ammonium), dimethyl hydrogenatedtallow 2-ethylhexyl quaternary ammonium, dimethyl dehydrogenated tallow quaternary ammonium ) or an organic modifier that is a mixture thereof may be used.

The content of the moisture barrier agent is not particularly limited and may be appropriately selected in consideration of desired barrier properties.

In addition to the above-described configuration, the encapsulation layer may include various additives depending on the use and the manufacturing process of the encapsulation film to be described later. For example, the encapsulation layer may include a curable material, a crosslinking agent, or a filler in an appropriate range according to desired physical properties.

When the encapsulation layer is formed of two or more layers, the second layer not in contact with the organic electronic device may include the moisture adsorbent. For example, when formed of two or more layers, the layer in contact with the organic electronic device among the encapsulation layers does not contain a moisture absorbent or contains moisture in a small amount of less than 5 parts by weight or less than 4 parts by weight relative to 100 parts by weight of the encapsulating resin. adsorbents may be included.

Specifically, the content of the moisture adsorbent may be controlled in consideration of damage to the device, etc., considering that the encapsulation film is applied to the encapsulation of the organic electronic device. For example, a small amount of a moisture adsorbent may be included in the first layer in contact with the device, or a moisture adsorbent may not be included. In one example, the first encapsulation layer in contact with the device may contain 0 to 20% of the moisture adsorbent based on the total mass of the moisture adsorbent contained in the encapsulation film. In addition, the encapsulation layer not in contact with the device may contain 80 to 100% of the moisture adsorbent based on the total mass of the moisture adsorbent contained in the encapsulation film.

An exemplary encapsulation film may further include a base film or a release film (hereinafter, may be referred to as a “first film”), and have a structure in which the encapsulation layer is formed on the base material or the release film. have. The structure may further include a substrate or a release film (hereinafter, referred to as a “second film”) formed on the thermally conductive metal layer.

A specific kind of the first film that can be used in the present application is not particularly limited. In the present application, as the first film, for example, a general polymer film in this field may be used. In the present application, for example, as the substrate or release film, a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a vinyl chloride copolymer film, a polyurethane film , an ethylene-vinyl acetate film, an ethylene-propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film. In addition, an appropriate release treatment may be performed on one or both surfaces of the base film or release film of the present application. Examples of the release agent used in the release treatment of the base film include alkyd-based, silicone-based, fluorine-based, unsaturated ester-based, polyolefin-based or wax-based release agents. Preferably, but not limited thereto.

In the present application, the thickness of the base film or the release film (first film) as described above is not particularly limited, and may be appropriately selected depending on the application. For example, in the present application, the thickness of the first film may be about 10 μm to 500 μm, preferably about 20 μm to 200 μm. If the thickness is less than 10 μm, there is a risk that deformation of the base film may easily occur during the manufacturing process, and if it exceeds 500 μm, economic efficiency is deteriorated.

The thickness of the encapsulation layer included in the encapsulation film of the present application is not particularly limited, and may be appropriately selected according to the following conditions in consideration of the application to which the film is applied. The thickness of the encapsulation layer may be about 5 μm to 200 μm, preferably about 5 μm to 100 μm. The thickness of the encapsulation layer may be the thickness of the entire multi-layer encapsulation layer. When the thickness of the encapsulation layer is less than 5 μm, sufficient moisture blocking ability cannot be exhibited, and when it exceeds 200 μm, it is difficult to secure fairness. it falls

The present application also relates to an organic electronic device. The organic electronic device includes, as shown in FIG. 3 , a substrate 31; an organic electronic device 32 formed on the substrate 31; and the aforementioned encapsulation film 20 for encapsulating the organic electronic device 32 . The encapsulation film may encapsulate the entire surface, for example, upper and side surfaces, of the organic electronic device formed on the substrate. The encapsulation film may include an encapsulation layer containing a pressure-sensitive adhesive composition or an adhesive composition in a crosslinked or cured state. In addition, the organic electronic device may be formed by sealing the encapsulation layer to contact the entire surface of the organic electronic device formed on the substrate.

In an embodiment of the present application, the organic electronic device may include a pair of electrodes, an organic layer including at least a light emitting layer, and a passivation film. Specifically, the organic electronic device includes a first electrode layer, an organic layer formed on the first electrode layer and including at least a light emitting layer, and a second electrode layer formed on the organic layer, and an electrode and an organic layer on the second electrode layer. It may include a passivation film to protect. The first electrode layer may be a transparent electrode layer or a reflective electrode layer, and the second electrode layer may also be a transparent electrode layer or a reflective electrode layer. More specifically, the organic electronic device may include a transparent electrode layer formed on a substrate, an organic layer formed on the transparent electrode layer and including at least a light emitting layer, and a reflective electrode layer formed on the organic layer.

In the above, the organic electronic device may be, for example, an organic light emitting device.

The passivation layer may include an inorganic layer and an organic layer. In one embodiment, the inorganic layer may be one or more metal oxides or nitrides selected from the group consisting of Al, Zr, Ti, Hf, Ta, In, Sn, Zn, and Si. The inorganic layer may have a thickness of 0.01 μm to 50 μm, or 0.1 μm to 20 μm, or 1 μm to 10 μm. In one example, the inorganic film of the present application may be an inorganic material that does not contain a dopant or an inorganic material that contains a dopant. The dopant that may be doped is at least one element selected from the group consisting of Ga, Si, Ge, Al, Sn, Ge, B, In, Tl, Sc, V, Cr, Mn, Fe, Co and Ni, or the element It may be an oxide of, but is not limited thereto. The organic layer is distinguished from the organic layer including at least the light emitting layer described above in that it does not include an emission layer, and may be an organic deposition layer including an epoxy compound.

The inorganic layer or the organic layer may be formed by chemical vapor deposition (CVD). For example, the inorganic layer may use silicon nitride (SiNx). In one example, silicon nitride (SiNx) used as the inorganic layer may be deposited to a thickness of 0.01 μm to 50 μm. In one example, the thickness of the organic layer may be in the range of 2 μm to 20 μm, 2.5 μm to 15 μm, and 2.8 μm to 9 μm.

The present application also provides a method of manufacturing an organic electronic device. The manufacturing method may include applying the above-described encapsulation film to a substrate having an organic electronic device formed thereon so as to cover the organic electronic device. In addition, the manufacturing method may include curing the encapsulation film. The curing step of the encapsulation film may mean curing of the encapsulation layer, and may be performed before or after the encapsulation film covers the organic electronic device.

As used herein, the term “curing” may mean that the pressure-sensitive adhesive composition of the present invention forms a cross-linked structure through a heating or UV irradiation process, and thus is manufactured in the form of an adhesive. Alternatively, it may mean that the adhesive composition is solidified and adhered as an adhesive.

Specifically, an electrode is formed on a glass or polymer film used as a substrate by a method such as vacuum deposition or sputtering, and on the electrode, for example, a layer of a light-emitting organic material consisting of a hole transport layer, a light emitting layer, and an electron transport layer, etc. After forming, an electrode layer may be additionally formed thereon to form an organic electronic device. Next, the entire surface of the organic electronic device of the substrate subjected to the above process is positioned so as to cover the encapsulation layer of the encapsulation film.

The encapsulation film of the present application may be applied to encapsulation or encapsulation of organic electronic devices such as OLEDs. The film can form a structure that can block moisture or oxygen flowing into the organic electronic device from the outside, and can prevent the occurrence of bright spots in the organic electronic device.

1 to 2 are cross-sectional views illustrating an encapsulation film according to an example of the present application.
3 is a cross-sectional view illustrating an organic electronic device according to an example of the present application.

Hereinafter, the present invention will be described in more detail through Examples according to the present invention and Comparative Examples not according to the present invention, but the scope of the present invention is not limited by the Examples presented below.

Example One

On a thermally conductive metal layer (aluminum foil, 35 μm thick) on which PET with a thickness of 100 μm was formed on one surface as a protective layer, Ti was deposited as an adsorption layer with a thickness of 100 nm using a magnetron sputtering device. Then, TiN was additionally deposited (nitride layer) to a thickness of 20 nm on the adsorption layer using a magnetron sputtering device to prepare an encapsulation film.

comparative example One

Invar having a thickness of 80 μm was used as the encapsulation film.

comparative example 2

A thermally conductive metal layer (aluminum foil, thickness 35 μm) formed on one surface of PET with a thickness of 100 μm as a protective layer was used as an encapsulation film.

comparative example 3

An encapsulation film was prepared in the same manner as in Example 1, except that TiN was not deposited.

comparative example 4

On a thermally conductive metal layer (aluminum foil, 35 μm thick) on which 100 μm thick PET was formed on one side as a protective layer, TiN was additionally deposited to 20 nm using a magnetron sputtering device (nitride layer) to prepare an encapsulation film.

Experimental example 1 - water permeability

For the encapsulation films prepared in Examples and Comparative Examples, moisture permeability was measured according to ASTM F 1249 measurement standard using MOCON Aquatran 2.

Experimental example 2 - Vth (threshold voltage) Shift

A display panel of an active matrix type organic light emitting diode display includes a plurality of pixels arranged in a matrix form. A current supplied to each of the pixels is a scan thin film transistor (TFT) that supplies a data voltage of a data line in response to a scan signal of a scan line, and an organic light emitting diode (OLED) according to a data voltage supplied to a gate electrode. a driving TFT for controlling the amount of In this case, the drain-source current Ids of the driving TFT supplied to the organic light emitting diode may be expressed as in Equation 1.

[Equation 1]

Ids = k'·(Vgs-Vth) ²

In Equation 1, k' is a proportional coefficient determined by the structure and physical characteristics of the driving TFT, Vgs is the gate-source voltage of the driving TFT, and Vth is the threshold voltage of the driving TFT.

However, due to the shift of the threshold voltage due to deterioration of the driving TFT, the threshold voltage Vth of each of the driving TFTs of the pixels may have different values. In this case, since the drain-source current Ids of the driving TFT depends on the threshold voltage Vth of the driving TFT, even if the same data voltage is supplied to each pixel, the current Ids supplied to the organic light emitting diode varies from pixel to pixel. It changes. Accordingly, even when the same data voltage is supplied to each of the pixels, there is a problem in that the luminance of the light emitted by the organic light emitting diodes of each of the pixels is different.

Accordingly, the threshold voltage (Vth) shift value according to whether the encapsulation film prepared in Examples and Comparative Examples was applied was measured. In the results according to Table 1 below, the smaller the threshold voltage shift value is, the better the effect is.

Experimental example 3 - Hydrogen Quantitation

The encapsulation films prepared in Examples and Comparative Examples were subjected to hydrogen heat treatment in a vacuum drying furnace at 200° C. for 1 hour under a hydrogen atmosphere (H ₂ /Ar 10%, 10 mTorr), and then quantitatively analyzed for hydrogen through TDS analysis.

The TDS analysis is carried out in a load-lock chamber ^{until 1 x 10 -3} Pa is evacuated (10 minutes) and then transferred to a measurement chamber. After evacuating the measurement chamber for 60 minutes, the temperature of the sample is raised to 300° C. at a constant temperature increase rate (0.3° C./s). After reaching the set temperature, while maintaining it at a constant temperature (30 minutes), measure the temperature, pressure, and QMS output over time. The unit of measurement is wt ppm, and 1 wt ppm means that 1 mg of hydrogen is present in 1 kg of sample. The hydrogen quantitative analysis was classified as excellent if it was at least 0.15 wt ppm or more.

water permeability
(g/m ² day) Vth(threshold voltage) shift
(dVth) Hydrogen quantitative analysis
(wt ppm) Example 1 < 5x10 ^-5 0.19 0.17 Comparative Example 1 < 5x10 ^-5 1.19 0.08 Comparative Example 2 < 5x10 ^-5 6.42 0.01 Comparative Example 3 < 5x10 ^-5 0.32 0.12 Comparative Example 4 < 5x10 ^-5 0.25 0.14

20: encapsulation film
21: thermally conductive metal layer
22: adsorption layer
23: nitride layer
24: encapsulation layer
31: substrate
32: organic electronic device

Claims (17)

a thermally conductive metal layer having a thermal conductivity in the range of 50 to 800 W/m·K;
an adsorption layer formed on one surface of the thermally conductive metal layer and including a first inorganic component having an adsorption energy for outgas calculated by a density functional theory of 0 eV or less; and
and a nitride layer formed on one surface of the adsorption layer and including a nitride of the first inorganic component. The encapsulation film according to claim 1, wherein the outgas includes H atoms, H ₂ molecules, or NH _{3 .} The encapsulation film of claim 1, wherein the thermally conductive metal layer comprises any one of a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, a metal oxyboride, and a combination thereof. According to claim 1, wherein the thermally conductive metal layer is iron, chromium, aluminum, copper, nickel, iron oxide, chromium oxide, silicon oxide, aluminum oxide, titanium oxide, indium oxide, tin oxide, indium tin oxide, tantalum oxide, zirconium oxide, An encapsulation film comprising niobium oxide, and any one of a combination thereof. The encapsulation film of claim 1 , wherein the thermally conductive metal layer has a thickness ranging from 5 μm to 200 μm. According to claim 1, wherein the first inorganic component is Li, Ni, Ti, Rb, Be, Mg, Ca, Sr, Ba, Al, Zn, In, Pt, Pd, Fe, Cr, Si, Zr, Cu, Nb , Y, V or a combination thereof. The encapsulation film according to claim 1, wherein the adsorption layer has a thickness ranging from 50 nm to 3 µm. The encapsulation film of claim 1 , wherein the adsorption layer is an inorganic deposition layer formed by depositing on one surface of the thermally conductive metal layer. The encapsulation film of claim 1 , wherein the nitride layer has a thickness ranging from 5 nm to 2 μm. The encapsulation film according to claim 1, wherein the nitride layer is an inorganic deposition layer formed by being deposited on one surface of the adsorption layer. The encapsulation film according to claim 1, further comprising a protective layer formed on the other surface of the thermally conductive metal layer. The encapsulation film according to claim 11, wherein the protective layer comprises a polymer component. The encapsulation film of claim 1 , further comprising an encapsulation layer formed on one surface of the nitride layer and encapsulating the entire surface of the organic electronic device formed on the substrate. The encapsulation film of claim 1 , wherein the encapsulation layer includes an encapsulation resin and a moisture absorbent. Board; an organic electronic device formed on a substrate; and the encapsulation film according to claim 1 which encapsulates the entire surface of the organic electronic device. The organic electronic device of claim 15 , wherein the organic electronic device includes a pair of electrodes, an organic layer including at least a light emitting layer, and a passivation layer. A method of manufacturing an organic electronic device comprising the step of applying the encapsulation film according to claim 1 to a substrate on which the organic electronic device is formed to cover the organic electronic device.

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