Encapsulation film

Abstract

This application relates to encapsulation films, organic electronic devices including the same, and methods of manufacturing organic electronic devices using the same. This application provides an encapsulation film with excellent reliability, which allows the formation of a structure capable of blocking moisture or oxygen from flowing into the organic electronic device from the outside, absorbing and dispersing stress caused by CTE mismatch as the panel bends, and overcoming performance degradation due to reduced reliability, while preventing bright spots in the organic electronic device.

Description

Technical Field

[0001] This application relates to encapsulation films, organic electronic devices including the same, and methods for manufacturing organic electronic devices. Background Technology

[0002] Organic electronic devices (OEDs) refer to devices comprising layers of organic materials that generate alternating current using holes and electrons, and examples of such devices may include photovoltaic devices, rectifiers, emitters, and organic light-emitting diodes (OLEDs).

[0003] Organic light-emitting diodes (OLEDs) in the above-mentioned organic electronic devices have lower power consumption and faster response times than existing light sources, and are beneficial for making display devices or lighting equipment thinner. Furthermore, OLEDs offer space availability and therefore hold promise for applications in a variety of fields, including various portable devices, monitors, laptops, and TVs.

[0004] In the commercialization and application expansion of OLEDs, the most critical issue is durability. The organic materials and metal electrodes contained in OLEDs are highly susceptible to oxidation by external factors such as moisture. Furthermore, there is the problem of bright spots in OLEDs caused by potential outgassing from within the device. In other words, products including OLEDs are highly sensitive to environmental factors. Additionally, stress arises from bending of the panel at high temperatures, which allows external moisture or oxygen to easily penetrate. Therefore, various methods have been proposed to effectively prevent oxygen or moisture from penetrating into organic electronic devices such as OLEDs while suppressing internally generated outgassing.

[0005] To address these issues, thin-film encapsulation processes are needed to prevent oxygen, moisture, and other contaminants from entering OLEDs. Materials commonly used in conventional thin-film encapsulation processes include glass and Invar (a nickel-iron alloy). However, glass suffers from poor processability, and Invar (a nickel-iron alloy) is expensive and has poor thermal conductivity. Therefore, highly versatile stainless steel (SUS), which can overcome these drawbacks, has attracted attention as a new encapsulating agent.

[0006] However, due to the large difference in thermal expansion coefficients between stainless steel and the substrate, displacement differences may occur between the stainless steel and the substrate under high-temperature conditions during the bonding process or reliability assessment, which may lead to a reduction in the effectiveness of moisture or oxygen barrier. Summary of the Invention

[0007] Technical issues

[0008] This application provides an encapsulation film with excellent reliability, which allows for the formation of a structure that can block moisture or oxygen from flowing into the organic electronic device from the outside, and absorbs and disperses stress caused by panel bending, while preventing bright spots from forming in the organic electronic device.

[0009] Technical solution

[0010] This application relates to encapsulation films. These encapsulation films can be used as encapsulation layers or to encapsulate organic electronic devices such as OLEDs.

[0011] Conventionally, nickel-iron alloys (Invar) are typically used as encapsulation films, but these alloys are expensive, have poor thermal conductivity, and poor cutability. This application provides an encapsulation film with excellent reliability at high temperatures without using nickel-iron alloys. This high-temperature reliable encapsulation film prevents bright spots in organic electronic devices, has excellent heat dissipation characteristics, and absorbs and disperses stress caused by panel bending.

[0012] In this specification, the term "organic electronic device" means an article or device having a structure comprising a layer of organic material that generates an alternating current using holes and electrons between a pair of electrodes facing each other, and examples of such devices may include, but are not limited to, photovoltaic devices, rectifiers, emitters, and organic light-emitting diodes (OLEDs). In one example of this application, the organic electronic device may be an OLED.

[0013] An exemplary organic electronic device encapsulation film may include an encapsulation layer and a metal layer formed on the encapsulation layer. The encapsulation layer may seal the top surface of an organic electronic component formed on a substrate. The encapsulation layer may also contain an encapsulating resin and a desiccant. The content of the desiccant may be in the range of 0.04 to 0.08 in the following general formula 1.

[0014] [General Form 1]

[0015] Desiccant content = Q 最大 ×(H T1 +H T2 ×γ) / H T1

[0016] In the above general formula 1, Q is the solid content relative to 100 parts by weight of the encapsulation layer. 最大 From 60 to 90 parts by weight, H T1 H represents the thickness of the encapsulation layer at 25°C. T2 The length of the outermost part of the bonding substrate and the outermost part of the metal layer of the encapsulation layer at temperature T2, where T1 is 25°C and T2 is 85°C.

[0017] In this specification, the term "thickness" may refer to the average thickness or the average thickness of the side edge portion.

[0018] Although the encapsulation film is used to encapsulate the top surface of organic electronic components formed on a substrate, General Formula 1 and General Formulas 2 and 3, described below, do not necessarily have to be measured on a substrate on which organic electronic components are formed, and the hygroscopic content can be measured with the encapsulation film attached to the substrate. The metal layer can have a CTE range of, for example, 1.5 times or greater, 2 to 5 times, 2.5 to 4 times, or 2.8 to 3.5 times relative to the substrate. After measuring the dimensional change with temperature using a thermomechanical analyzer (expansion mode, force 0.05 N) according to the ASTM E831 method, "CTE (coefficient of thermal expansion)" refers to the value measured by the length change curve of the encapsulation film with respect to temperature (-120°C to 600°C). CTE can also be measured according to ISO 11359-1 or ISO 11359-2.

[0019] In this application, an encapsulation layer for packaging organic electronic components is disposed between a metal layer and a substrate on which the components are formed. However, the substrate and the metal layer are made of different materials and therefore have different thermal expansion characteristics. When the encapsulation film or organic electronic device is exposed to high temperatures for a certain period of time (during the process), dimensional mismatch occurs due to the difference in the degree of expansion between the substrate and the metal layer. This results in some peeling, gaps, or voids appearing in the encapsulation layer between the substrate and the metal layer due to stress, allowing external oxygen or moisture to easily penetrate. By adjusting the desiccant content according to the above general formula 1, the encapsulation layer between the substrate and the metal layer effectively absorbs or disperses stress even at high temperatures to prevent gaps or voids from appearing on the sides of the encapsulation layer. Therefore, this application can effectively prevent foreign matter from penetrating while possessing excellent moisture-blocking properties.

[0020] In one embodiment of this application, the encapsulation layer may satisfy the following general formula 2.

[0021] [General Form 2]

[0022]

[0023] In the general formula 2 above, H T1 and H T2 As defined in general formula 1 above, and ΔL CTE It satisfies the following general formula 3.

[0024] [General Form 3]

[0025] ΔL CTE =(CTE) 金属 -CTE 基底 )×LT1 ×(T2-T1) / 2

[0026] In the general formula 3 above, CTE 金属 CTE is the CTE value of the metal layer. 基底 The CTE value of the base, L T1 Here, T1 is the length of the long side of the encapsulation layer at room temperature, T2 is 85°C, and T1 is 25°C. All general formulas 1 to 3 above can be measured after the encapsulation film is applied to the substrate, and after the long and short sides of the encapsulation film are substantially matched with the long and short sides of the substrate. In this specification, the substantial match can have an error range of ±5μm, ±3μm, or ±1μm. According to general formula 2 above, H... T1 With H T2 The ratio can be in the range of 1 to 9, 2 to 8, or 3 to 7. By adjusting the ratio, this application can simultaneously achieve dimensional reliability at high temperatures, moisture barrier properties, and high-temperature durability reliability.

[0027] As described above, the encapsulation layer may contain an encapsulating resin. The encapsulating resin may be a crosslinkable resin or a curable resin.

[0028] In one example, the glass transition temperature of the encapsulating resin can be below 0°C, below -10°C, or below -30°C, below -50°C, or below -60°C. There is no particular limitation on the lower limit, which can be -150°C or higher. Here, the glass transition temperature can be the glass transition temperature after curing, and in one embodiment, it can mean the temperature at which an irradiation level of about 1 J / cm is applied. 2 Or the glass transition temperature after ultraviolet irradiation; or the glass transition temperature after ultraviolet irradiation followed by further thermosetting.

[0029] In one example, the encapsulating resin may include styrene resin or elastomer, polyolefin resin or elastomer, other elastomers, polyoxyethylene resin or elastomer, polyester resin or elastomer, polyvinyl chloride resin or elastomer, polycarbonate resin or elastomer, polyphenylene sulfide resin or elastomer, mixtures of hydrocarbons, polyamide resin or elastomer, acrylate resin or elastomer, epoxy resin or elastomer, silicone resin or elastomer, fluoropolymer resin or elastomer, or mixtures thereof.

[0030] Here, examples of styrene resins or elastomers include, for example, styrene-ethylene-butadiene-styrene block copolymers (SEBS), styrene-isoprene-styrene block copolymers (SIS), acrylonitrile-butadiene-styrene block copolymers (ABS), acrylonitrile-styrene-acrylate block copolymers (ASA), styrene-butadiene-styrene block copolymers (SBS), styrene homopolymers, or mixtures thereof. Examples of olefin resins or elastomers include, for example, high-density polyethylene resins or elastomers, low-density polyethylene resins or elastomers, polypropylene resins or elastomers, or mixtures thereof. Examples of elastomers include, for example, ester thermoplastic elastomers, olefin elastomers, silicone elastomers, acrylic elastomers, or mixtures thereof. In particular, examples of olefin thermoplastic elastomers include polybutadiene resins or elastomers, or polyisobutylene resins or elastomers. Examples of polyoxyethylene resins or elastomers include, for example, polyoxymethylene resins or elastomers, polyoxyethylene resins or elastomers, or mixtures thereof. Examples of polyester resins or elastomers include, for example, polyethylene terephthalate resins or elastomers, polybutylene terephthalate resins or elastomers, or mixtures thereof. Examples of polyvinyl chloride resins or elastomers include, for example, polyvinylidene chloride. Examples of hydrocarbon mixtures include, for example, hexadecane or paraffin. Examples of polyamide resins or elastomers include, for example, nylon. Examples of acrylate resins or elastomers include, for example, poly(meth)acrylate butyl ester. Examples of epoxy resins or elastomers include, for example, bisphenol type, such as bisphenol A, bisphenol F, bisphenol S, and their hydrogenated products; phenolic varnish type, such as phenolic varnish or cresol varnish; nitrogen-containing cyclic type, such as triglycidyl isocyanurate type or hydantoin type; alicyclic type; aliphatic type; aromatic type, such as naphthalene type and biphenyl type; glycidyl group type, such as glycidyl ether type, glycidyl amine type and glycidyl ester type; bicyclic type, such as dicyclopentadiene type; ester type; ether ester type; or mixtures thereof; etc. Examples of silicone resins or elastomers include, for example, polydimethylsiloxane. In addition, examples of fluoropolymers or elastomers include polytrifluoroethylene resins or elastomers, polytetrafluoroethylene resins or elastomers, polychlorotrifluoroethylene resins or elastomers, polyhexafluoropropylene resins or elastomers, polyfluorinated vinylidenes, polyfluorinated vinylides, polyfluorinated ethylene propylene, or mixtures thereof.

[0031] The resins or elastomers listed above can also be used, for example, by grafting with maleic anhydride, by copolymerizing with other resins or elastomers via monomers used to produce the resins or elastomers, and by modification with other compounds. Examples of other compounds mentioned above may include carboxyl-terminated butadiene-acrylonitrile copolymers, etc.

[0032] In one instance, the encapsulation layer may contain, but is not limited to, olefin elastomers, silicone elastomers, or acrylic elastomers as encapsulation resins.

[0033] In one embodiment of the invention, the encapsulating resin may be an olefin-based resin. In one example, the olefin-based resin may be a homopolymer of a butene monomer; a copolymer obtained by copolymerizing a butene monomer with another polymerizable monomer; a reactive oligomer using a butene monomer; or a mixture thereof. The butene monomer may include, for example, 1-butene, 2-butene, or isobutene.

[0034] Other monomers that can be polymerized with butene monomers or derivatives may include, for example, isoprene, styrene, or butadiene. By using copolymers, physical properties such as processability and crosslinking can be maintained, and thus the heat resistance of the adhesive itself can be ensured when applied to organic electronic devices.

[0035] Furthermore, reactive oligomers using butene monomers may include butene polymers having reactive functional groups. The weight-average molecular weight of the oligomers may range from 500 g / mol to 5000 g / mol. Additionally, the butene polymers may be combined with other polymers having reactive functional groups. These other polymers may be, but are not limited to, alkyl (meth)acrylates. The reactive functional groups may be hydroxyl, carboxyl, isocyanate, or nitrogen-containing groups. Furthermore, the reactive oligomers and the other polymers may be crosslinked using a multifunctional crosslinking agent, which may be at least one selected from isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, and metal chelate crosslinking agents.

[0036] In one example, the encapsulating resin of this application may comprise a copolymer of a diene and an alkene compound containing a carbon-carbon double bond. Here, the alkene compound may include butene, etc., and the diene may be a monomer capable of polymerizing with the alkene compound, and may include, for example, isoprene or butadiene. For example, the copolymer of the diene and the alkene compound containing a carbon-carbon double bond may be butyl rubber.

[0037] In the encapsulation layer, the resin or elastomer component may have a weight-average molecular weight (Mw) sufficient to allow the pressure-sensitive adhesive composition to form a film. For example, the weight-average molecular weight of the resin or elastomer may be from about 100,000 g / mol to 2,000,000 g / mol, 120,000 g / mol to 1,500,000 g / mol, or about 150,000 g / mol to 1,000,000 g / mol. In this specification, the term weight-average molecular weight means the value converted to standard polystyrene by GPC (gel permeation chromatography), and unless otherwise stated, the unit is g / mol. However, the resin or elastomer does not necessarily have the above-mentioned weight-average molecular weight. For example, if the molecular weight of the resin or elastomer component is not sufficient to form a film, a separate adhesive resin may be blended into the pressure-sensitive adhesive composition.

[0038] In another embodiment, the encapsulating resin according to this application can be a curable resin. When the encapsulating resin is a curable resin, it can be a resin with a glass transition temperature of 85°C or higher and 200°C or lower after curing. The glass transition temperature can be the glass transition temperature after photocuring or thermal curing of the encapsulating resin. There are no particular limitations on the specific types of curable resins available in this invention; for example, various thermosetting or photocurable resins known in the art can be used. The term "thermosetting resin" means a resin that can be cured by appropriate heat application or an aging process, and the term "photocurable resin" means a resin that can be cured by irradiation with electromagnetic waves. Furthermore, the curable resin can be a dual-curing resin that includes both thermocurable and photocurable properties.

[0039] There is no particular limitation on the specific type of curable resin used in this application, as long as it possesses the aforementioned properties. For example, a resin that can be cured to exhibit adhesive properties may include resins containing one or more thermosetting functional groups (e.g., glycidyl groups, isocyanate groups, hydroxyl groups, carboxyl groups, or amide groups) or containing one or more functional groups that can be cured by electromagnetic irradiation (e.g., epoxide groups, cyclic ether groups, sulfide groups, acetal groups, or lactone groups). Specific examples of such resins may include, but are not limited to, acrylic resins, polyester resins, isocyanate resins, or epoxy resins.

[0040] In this application, aromatic or aliphatic epoxy resins, or linear or branched epoxy resins, can be used as curable resins. In one embodiment of the invention, an epoxy resin containing two or more functional groups and having an epoxy equivalent of 180 g / equivalent to 1,000 g / equivalent can be used. By using epoxy resins having epoxy equivalents within the above range, the properties of the cured product, such as adhesive properties and glass transition temperature, can be effectively maintained. Examples of such epoxy resins may include one or a mixture of two or more of the following: cresol phenolic varnish epoxy resin, bisphenol A type epoxy resin, bisphenol A type phenolic varnish epoxy resin, phenolic varnish epoxy resin, tetrafunctional epoxy resin, biphenyl type epoxy resin, pyrogallol methane type epoxy resin, alkyl-modified pyrogallol methane epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, or dicyclopentadiene-modified phenolic type epoxy resin.

[0041] In this application, epoxy resins containing cyclic structures in their molecular structure can be used as curable resins, and epoxy resins containing aromatic groups (e.g., phenyl groups) can also be used. When the epoxy resin contains aromatic groups, the cured product exhibits excellent thermal and chemical stability, while also showing low moisture absorption, thereby improving the reliability of the packaging structure of organic electronic devices. Specific examples of aromatic group-containing epoxy resins that can be used in this invention include one or a mixture of two or more of the following: biphenyl-type epoxy resins, dicyclopentadiene-type epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-modified phenolic epoxy resins, cresol-based epoxy resins, bisphenol-based epoxy resins, xylene-based epoxy resins, multifunctional epoxy resins, phenolic varnish epoxy resins, triphenol-methane-type epoxy resins, and alkyl-modified triphenol-methane epoxy resins, but are not limited thereto.

[0042] In one example, the encapsulating resin may be included in the encapsulation layer in an amount of 40% or more, 45% or more, 48% or more, 50% or more, 53% or more, 55% or more, 58% or more, 60% or more, or 65% or more, with an upper limit of 90% or less, 85% or less, 83% or less, 70% or less, 65% or less, 60% or less, or 55% or less. While the encapsulating resin possesses good moisture-barrier properties, it suffers from reduced heat resistance and durability. Therefore, by adjusting the content of the encapsulating resin, this application can achieve sufficient moisture-barrier properties of the resin itself while maintaining heat resistance and durability under high temperature and high humidity conditions.

[0043] As described above, the encapsulation layer may contain a desiccant. In this specification, the term "desiccant" may mean a chemically reactive adsorbent capable of removing moisture or humidity, for example, by chemical reaction with water or moisture that has penetrated the encapsulation film, as described below.

[0044] For example, the desiccant may exist in the encapsulation layer or encapsulation film in a uniformly dispersed state as particulate matter. Here, uniform dispersion can mean that the desiccant exists at the same or substantially the same density even in any part of the encapsulation layer or encapsulation film. The desiccant that can be used above may include, for example, metal oxides, sulfates, or organometallic oxides. Specifically, examples of sulfates may include magnesium sulfate, sodium sulfate, or nickel sulfate, and examples of organometallic oxides may include aluminum oxide octate, etc. Specific examples of metal oxides may include phosphorus pentoxide (P2O5), lithium oxide (Li2O), sodium oxide (Na2O), barium oxide (BaO), calcium oxide (CaO), or magnesium oxide (MgO), etc., and examples of metal salts may include sulfates such as lithium sulfate (Li2SO4), sodium sulfate (Na2SO4), calcium sulfate (CaSO4), magnesium sulfate (MgSO4), cobalt sulfate (CoSO4), gallium sulfate (Ga2(SO4)3), titanium sulfate (Ti(SO4)2), or nickel sulfate (NiSO4); metal halides, such as calcium chloride (CaCl2). Magnesium chloride (MgCl2), strontium chloride (SrCl2), yttrium chloride (YCl3), copper chloride (CuCl2), cesium fluoride (CsF), tantalum fluoride (TaF5), niobium fluoride (NbF5), lithium bromide (LiBr), calcium bromide (CaBr2), cesium bromide (CeBr3), selenium bromide (SeBr4), vanadium bromide (VBr3), magnesium bromide (MgBr2), barium iodide (BaI2), or magnesium iodide (MgI2); or metal chlorates, such as barium perchlorate (Ba(ClO4)2) or magnesium perchlorate (Mg(ClO4)2); etc., but not limited to these. As a desiccant that can be included in the encapsulation layer, one or more of the above-mentioned components may be used. In one example, when using two or more of them as a desiccant, calcined dolomite, etc., may be used.

[0045] Such hygroscopic agents can be controlled to a suitable size depending on the application. In one example, the average particle size of the hygroscopic agent can be controlled to be 100 nm 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. Hygroscopic agents with sizes within the above ranges are easy to store because their reaction rate with moisture is not too fast, they do not damage the components to be encapsulated, and they can effectively remove moisture without interfering with the hydrogen adsorption process related to the bright spot inhibitors described below. In this specification, unless otherwise stated, particle size may refer to the average particle size and may be the particle size measured by a D50 particle size analyzer using known methods.

[0046] The content of the hygroscopic agent is not particularly limited and can be appropriately selected considering the desired barrier properties. The hygroscopic agent can be included in the range of 20 to 200 parts by weight, 25 to 190 parts by weight, 30 to 180 parts by weight, 35 to 170 parts by weight, 40 to 160 parts by weight, or 45 to 155 parts by weight relative to 100 parts by weight of the encapsulating resin. Furthermore, as will be described below, the encapsulation layer of this application may also contain a bright spot inhibitor, and the weight ratio of the bright spot inhibitor to the hygroscopic agent in the encapsulation film of this application can be in the range of 0.05 to 0.8, or 0.1 to 0.7. In this application, the bright spot inhibitor is dispersed in the film to prevent bright spots, but considering the moisture barrier properties as the initial function of the encapsulation film and the realization of the reliability of the element, the bright spot inhibitor added to prevent bright spots can be included in a specific content ratio with the hygroscopic agent.

[0047] Furthermore, in this application, as a result of particle size analysis of the desiccant in a sample after the encapsulation layer has been dissolved in an organic solvent and filtered through a 300-mesh nylon filter, the ratio of the average particle size according to D50 to the average particle size according to D10 can be in the range of 2.3 to 3.5. The lower limit of this ratio can be, for example, 2.4, 2.5, 2.6, or 2.7, and the upper limit can be, for example, 3.4, 3.3, 3.2, 3.1, 3.0, 2.95, or 2.93. There are no particular limitations on the type of organic solvent, but it can be, for example, toluene, and the sample can be a sample measured for a size cut, for example, 1.5 cm × 1.5 cm. Furthermore, in this specification, the unit "mesh" can be the unit of the American ASTM standard. By controlling the particle size distribution, this application can prevent a decrease in moisture barrier reliability due to reduced dimensional stability at high temperatures, thereby achieving long-term durability and reliability of organic electronic devices. In the cumulative distribution plot representing the weight of each particle size, the average particle sizes of D10 and D50 are approximately 10% and 50% by weight, respectively, corresponding to the maximum value (100% by weight).

[0048] In one example, the encapsulation layer may also include a tackifier. The tackifier may be, for example, a compound with a softening point of 70°C or higher, wherein in one embodiment, the softening point may be 75°C or higher, 78°C or higher, 83°C or higher, 85°C or higher, 90°C or higher, or 95°C or higher, and there is no particular upper limit, but it may be 150°C or lower, 140°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, or 100°C or lower. The tackifier may be a compound having a cyclic structure in its molecular structure, wherein the number of carbon atoms in the cyclic structure may be in the range of 5 to 15. The number of carbon atoms may be, for example, in the range of 6 to 14, 7 to 13, or 8 to 12. The cyclic structure may be a monocyclic compound, but is not limited thereto, and may be a bicyclic or tricyclic compound. The tackifier may also be an olefin-based polymer, wherein the polymer may be a homopolymer or a copolymer. Furthermore, the tackifier of this application may be a hydrogenated compound. The hydrogenated compound can be partially or fully hydrogenated. Such a tackifier, while exhibiting good compatibility with other components in the encapsulation layer, can possess excellent moisture-barrier properties and external stress relaxation characteristics. Specific examples of tackifiers may include hydrogenated terpene-based resins, hydrogenated ester-based resins, or hydrogenated dicyclopentadiene-based resins. The weight-average molecular weight of the tackifier can range from about 200 g / mol to 5,000 g / mol, 300 g / mol to 4,000 g / mol, 400 g / mol to 3,000 g / mol, or 500 g / mol to 2,000 g / mol. The content of the tackifier can be appropriately adjusted as needed. For example, relative to 100 parts by weight of encapsulating resin, the tackifier content can be included in ratios of 15 parts by weight to 200 parts by weight, 20 parts by weight to 190 parts by weight, 25 parts by weight to 180 parts by weight, or 30 parts by weight to 150 parts by weight. This application provides an encapsulation film with excellent moisture barrier properties and external stress relaxation properties by using a specific tackifier.

[0049] In the encapsulation film of this application, the encapsulation layer may contain a bright spot inhibitor. The adsorption energy of the bright spot inhibitor for exhaust gas, calculated using an approximate method based on density functional theory, may be 0 eV or less. There is no particular limitation on the lower limit of the adsorption energy, but it may be -20 eV. There is no particular limitation on the type of exhaust gas, but it may contain oxygen, H atoms, H2 molecules, and / or NH3. Because the encapsulation film contains a bright spot inhibitor, this application can prevent bright spots caused by exhaust gas generated in the organic electronic device. Furthermore, the encapsulation layer of this application contains a bright spot inhibitor in a second layer located on the surface opposite to the component attachment surface facing the organic electronic component during encapsulation, thereby preventing damage to the organic electronic component due to stress concentration caused by the bright spot inhibitor. From this perspective, based on the total mass of the bright spot inhibitor in the encapsulation film, the first layer may contain 15% or less of the bright spot inhibitor or may contain no bright spot inhibitor at all. Furthermore, based on the total mass of the bright spot inhibitor in the encapsulation film, the layers other than the first layer that do not contact the organic electronic component may contain 85% or more of the bright spot inhibitor. That is, in this application, compared with the first layer that faces the organic electronic component during component packaging, other packaging layers that do not contact the organic electronic component can contain a larger amount of bright spot inhibitors, thereby preventing physical damage to the component while achieving the moisture barrier and bright spot prevention properties of the film.

[0050] In one embodiment of this application, the adsorption energy between the bright spot inhibitor and the bright spot-causing atom or molecule can be calculated using electronic structure calculations based on density functional theory. This calculation can be performed using methods known in the art. For example, in this application, after fabricating a two-dimensional plate structure in which the closest packing of the bright spot inhibitor with a crystalline structure is exposed on the surface, and then optimizing the structure, and after optimizing the structure of the bright spot-causing molecule adsorbed on the vacuum-state surface, the value obtained by subtracting the total energy of the bright spot-causing molecule from the total energy difference between the two systems is defined as the adsorption energy. For the calculation of the total energy of each system, a modified PBE function, as a function of the GGA (Generalized Gradient Approximation) family, is used as exchange-correlation to simulate the interaction between electrons, with an electron kinetic energy cutoff of 500 eV, and only including the gamma point corresponding to the origin of the reciprocal space. The atomic structure of each system is optimized using the conjugate gradient method, and iterative calculations are performed until the interatomic force is 0.01. Or even smaller. A series of calculations are performed via VASP, which is a commercially available code.

[0051] There are no restrictions on the materials used to suppress bright spots, as long as the material has the effect of preventing bright spots on the panel of the organic electronic device when the encapsulation film is applied. For example, the bright spot suppressant can be a material capable of adsorbing materials such as: oxygen, H2 gas, ammonia (NH3) gas, etc., generated from the exhaust gas produced by an inorganic deposition layer of silicon oxide, silicon nitride, or silicon nitride deposited on the electrodes of the organic electronic component. + NH 2+ , NHR2 or NH2R. Here, R can be an organic group, for example, alkyl, alkenyl, alkynyl, etc., but not limited thereto.

[0052] In one example, the material of the bright spot inhibitor is not limited, as long as it meets the above adsorption energy value, and it can be a metal or a non-metal. The bright spot inhibitor may include, for example, Li, Ni, Ti, Rb, Be, Mg, Ca, Sr, Ba, Al, Zn, In, Pt, Pd, Fe, Cr, Si, or combinations thereof, and may include oxides or nitrides of said materials, and may include alloys of said materials. In one example, the bright spot inhibitor may include nickel particles, nickel oxide particles, titanium nitrides, titanium-based iron-titanium alloy particles, manganese-based iron-manganese alloy particles, magnesium-based magnesium-nickel alloy particles, rare earth-based alloy particles, zeolite particles, silica particles, carbon nanotubes, graphite, aluminum phosphate molecular sieve particles, or mesoporous silica particles. Relative to 100 parts by weight of encapsulating resin, the bright spot inhibitor can be included in amounts ranging from 3 to 150 parts by weight, 6 to 143 parts by weight, 8 to 131 parts by weight, 9 to 123 parts by weight, 10 to 116 parts by weight, 10 to 95 parts by weight, 10 to 50 parts by weight, or 10 to 35 parts by weight. Within the above content range, this application can achieve bright spot prevention in organic electronic devices while improving film adhesion and durability. Furthermore, the particle size of the bright spot inhibitor can be in the ranges of 10 nm to 30 μm, 50 nm to 21 μm, 105 nm to 18 μm, 110 nm to 12 μm, 120 nm to 9 μm, 140 nm to 4 μm, 150 nm to 2 μm, 180 nm to 900 nm, 230 nm to 700 nm, or 270 nm to 400 nm. The particle size can be determined based on D50 particle size analysis. By incorporating a bright spot inhibitor, this application can achieve both moisture barrier properties and durability of the encapsulation film while effectively adsorbing hydrogen generated in organic electronic devices.

[0053] Furthermore, in this application, as a result of particle size analysis of the desiccant in a sample after the encapsulation layer has been dissolved in an organic solvent and filtered through a 300-mesh nylon filter, the ratio of the average particle size according to D50 to the average particle size according to D10 can be in the range of 2.3 to 3.5. The lower limit of this ratio can be, for example, 2.4, 2.5, 2.6, or 2.7, and the upper limit can be, for example, 3.4, 3.3, 3.2, 3.1, 3.0, 2.95, or 2.93. There are no particular limitations on the type of organic solvent, but it can be, for example, toluene, and the sample can be a sample measured for a size cut, for example, 1.5 cm × 1.5 cm. Furthermore, in this specification, the unit "mesh" can be the unit of the American ASTM standard. By controlling the particle size distribution, this application can prevent a decrease in moisture barrier reliability due to reduced dimensional stability at high temperatures, thereby achieving long-term durability and reliability of organic electronic devices.

[0054] In one example, the ratio of the particle size of the bright spot inhibitor to the particle size of the hygroscopic agent can be 2.0 or less. The particle size ratio can be determined based on D50 particle size analysis. The lower limit of the particle size ratio can be 0.3, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1 or greater, and the upper limit can be 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9 or less. The initial purpose of the encapsulation film in this application was to block moisture from the outside. To address another technical problem of hydrogen adsorption, a bright spot inhibitor was newly introduced. However, there is a technical problem that it is not easy to maintain the initial moisture-blocking effect when containing the bright spot inhibitor. This application achieves excellent bright spot prevention performance while maintaining the initial moisture-blocking effect by adjusting the particle size ratio of the hygroscopic agent and the bright spot inhibitor and / or the aforementioned particle size distribution.

[0055] In one example, the encapsulation layer of this application may have a single-layer structure or a multi-layer structure including at least two or more encapsulation layers. When including two or more encapsulation layers, the encapsulation layer may include a first layer facing the organic electronic component when encapsulating the component, and a second layer located on a surface of the first layer opposite to the surface facing the component. In one embodiment, as described above... Figure 2 As shown in (a), the encapsulation film includes at least two or more encapsulation layers, wherein the encapsulation layers may include a first layer 2 facing the organic electronic components during encapsulation and a second layer 4 not facing the organic electronic components.

[0056] As described above, encapsulation layer 2 can have a single-layer structure. For example... Figure 1 As shown in (a), the encapsulation layer 4 may contain the bright spot inhibitor 3. Furthermore, as... Figure 1 As shown in (b), the encapsulation layer 4 may also contain a bright spot inhibitor 3 and a moisture absorbent 5.

[0057] As described above, the encapsulation layer can have a multilayer structure with two or more layers. When two or more layers constitute the encapsulation layer, the composition of each layer in the encapsulation layer can be the same or different. In one example, the encapsulation layer may contain an encapsulating resin and / or a moisture absorbent, and the encapsulation layer may be a pressure-sensitive adhesive layer or an adhesive layer.

[0058] like Figure 2 As shown in (a), encapsulation layers 2 and 4 may include a first layer 2 and a second layer 4, and the second layer 4 of the encapsulation layer may include a bright spot inhibitor 3. Furthermore, as in... Figure 2 In (b), the second layer may contain both bright spot inhibitor 3 and hygroscopic agent 5. However, when the encapsulation film is applied to organic electronic components, the first layer 2, which is the encapsulation layer facing the organic electronic components, may not contain bright spot inhibitor and hygroscopic agent, or even if it does contain bright spot inhibitor and hygroscopic agent, it may only contain a small amount of 15% or less, or 5% or less, based on the total weight of the bright spot inhibitor and hygroscopic agent.

[0059] Furthermore, in one instance, the encapsulation layer of this application may contain a compound that is highly compatible with the encapsulation resin and can form a specific cross-linked structure with the encapsulation resin through active energy ray polymerization.

[0060] For example, the encapsulation layer of this application may contain a multifunctional, radio-polymerizable compound that can be polymerized with the encapsulation resin by irradiation with active energy rays. A radio-polymerizable compound may refer to a compound containing two or more functional groups capable of participating in a polymerization reaction by irradiation with active energy rays, such as functional groups containing olefinic unsaturated double bonds (e.g., acryloyl or methacryloyl), or functional groups such as epoxy or oxetane.

[0061] As compounds that can be polymerized by multifunctional active energy rays, for example, multifunctional acrylates (MFA) can be used.

[0062] Furthermore, relative to 100 parts by weight of the encapsulating resin, the active energy-ray polymerizable compound can be included in amounts of 3 to 30 parts by weight, 5 to 25 parts by weight, 8 to 20 parts by weight, 10 to 18 parts by weight, or 12 to 18 parts by weight. Within the above range, this application provides an encapsulating film exhibiting excellent durability and reliability even under harsh conditions such as high temperature and high humidity.

[0063] Multifunctional compounds that can be polymerized by irradiation with active energy rays can be used without any restrictions. For example, the compounds may include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate (HDDA), 1,8-octanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, cyclohexane-1,4-diol di(meth)acrylate, tricyclodecanediethanol(meth)acrylate, dimethyloldicyclopentane di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, adamantane di(meth)acrylate, trimethylolpropane tri(meth)acrylate (TMPTA), or mixtures thereof.

[0064] As compounds for multifunctional energy-active X-ray polymerization, for example, compounds having a molecular weight of 100 g / mol or greater and less than 1,000 g / mol and containing two or more functional groups can be used. The ring structure contained in the multifunctional energy-active X-ray polymerizable compound can be a carbocyclic structure or a heterocyclic structure; or any of a monocyclic structure or a polycyclic structure.

[0065] In one embodiment of this application, the encapsulation layer may further comprise a free radical initiator. The free radical initiator may be a photoinitiator or a thermal initiator. The specific type of photoinitiator can be appropriately selected considering factors such as curing rate and yellowing potential. For example, benzoin-based photoinitiators, hydroxy ketone-based photoinitiators, amino ketone-based photoinitiators, or phosphine oxide-based photoinitiators can be used. Specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylprop-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-prop-1-one, 4-(2-hydroxy) Ethoxyphenyl-2-(hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone] and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, etc.

[0066] The free radical initiator can be included in proportions of 0.2 to 20 parts by weight, 0.5 to 18 parts by weight, 1 to 15 parts by weight, or 2 to 13 parts by weight relative to 100 parts by weight of the compound that can be polymerized by active energy rays. Therefore, the reaction of the compound that can be polymerized by active energy rays can be effectively induced, and the deterioration of the physical properties of the encapsulation composition due to residual components after curing can also be prevented.

[0067] In one embodiment of this application, depending on the type of resin component included, the encapsulation layer of the encapsulation film may also include a curing agent. For example, it may also include a curing agent capable of reacting with the aforementioned encapsulation resin to form a cross-linked structure, etc. In this specification, the terms encapsulation resin and / or adhesive resin may be used with the same meaning as resin components.

[0068] The type of curing agent can be appropriately selected and used according to the type of functional groups or resin components contained in the resin.

[0069] In one example, when the resin component is an epoxy resin, the curing agent is a curing agent for epoxy resins known in the art, such as one or more of the following: amine curing agent, imidazole curing agent, phenol curing agent, phosphorus curing agent, or acid anhydride curing agent, etc., but not limited thereto.

[0070] In one instance, an imidazole compound that is solid at room temperature and has a melting point or decomposition temperature of 80°C or higher can be used as a curing agent. Examples of such compounds include, but are not limited to, 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, or 1-cyanoethyl-2-phenylimidazole.

[0071] The content of the curing agent can be selected based on the composition of the composition (e.g., the type or ratio of the encapsulating resin). For example, the curing agent can be included in an amount of 1 to 20 parts by weight, 1 to 10 parts by weight, or 1 to 5 parts by weight relative to 100 parts by weight of the resin component. However, the weight ratio can be varied depending on the encapsulating resin or the type and ratio of its functional groups, or the desired crosslinking density, etc.

[0072] When the resin component is a resin that can be cured by irradiation with active energy rays, for example, a cationic photopolymerization initiator can be used as the initiator.

[0073] As a cationic photopolymerization initiator, it can be used Ionized cationic initiators of salt and organometallic salt series, or nonionic cationic photopolymerization initiators of organosilane or potential sulfonic acid series. As... Salt-based initiators can be exemplified by diaryl iodine. Salt, triaryl Salts or aryl diazonium salts, etc., can be used as initiators for organometallic salt series, such as iron aromatics, etc.; as initiators for organosilane series, such as o-nitrobenzyltriarylsilyl ether, triarylsilyl peroxide or acylsilane, etc.; and as initiators for potential sulfonic acid series, such as α-sulfonyloxy ketone or α-hydroxymethyl benzoyl sulfonate, etc., but are not limited to these.

[0074] In one instance, an ionized cationic photopolymerization initiator can be used as a cationic initiator.

[0075] If necessary, the encapsulation layer may also include a moisture blocker. In this specification, the term "moisture blocker" may refer to a material that is non-reactive or has low reactivity with water, but can physically block or impede the movement of water or moisture within the membrane. Examples of moisture blockers include, for example, one or more of the following: clay, talc, needle-like silica, sheet-like silica, porous silica, zeolite, titanium dioxide, or zirconium oxide. Furthermore, the moisture blocker may be surface-treated with organic modifiers to promote the penetration of organic substances. Examples of such organic modifiers include, for example, dimethylbenzyl hydrogenated tallow quaternary ammonium, dimethyl hydrogenated tallow quaternary ammonium, methyl tallow bis-2-hydroxyethyl quaternary ammonium, dimethyl hydrogenated tallow 2-ethylhexyl quaternary ammonium, dimethyl dehydrogenated tallow quaternary ammonium, or mixtures thereof.

[0076] There are no particular restrictions on the amount of moisture-blocking agent, and it can be appropriately selected by considering the desired blocking properties.

[0077] In addition to the components mentioned above, the encapsulation layer may also contain various additives according to the application and manufacturing process of the encapsulation film described below. For example, depending on the desired physical properties, the encapsulation layer may contain curable materials, crosslinking agents, fillers, etc., in appropriate content ranges.

[0078] When the encapsulation layer is formed of two or more layers, the second layer that does not contact the organic electronic components may contain a desiccant. For example, when the encapsulation layer is formed of two or more layers, the layer in the encapsulation layer that contacts the organic electronic components may not contain a desiccant, or may contain a small amount of a desiccant, less than 5 parts by weight or less than 4 parts by weight relative to 100 parts by weight of the encapsulation resin.

[0079] Specifically, considering the application of encapsulation films to the encapsulation of organic electronic components, the content of desiccant can be controlled by taking into account the potential damage to the component. For example, the first layer facing the component during encapsulation may contain a small amount of desiccant, or may contain no desiccant at all. In one example, the first layer of the encapsulation layer facing the component during encapsulation may contain 0% to 20% desiccant relative to the total mass of desiccant contained in the encapsulation film. Furthermore, the encapsulation layer not in contact with the component may contain 80% to 100% desiccant relative to the total mass of desiccant contained in the encapsulation film.

[0080] In one embodiment of this application, the encapsulation film may further include a metal layer formed on the encapsulation layer. The thermal conductivity of the metal layer in this application can be 20 W / m·K or greater, 50 W / m·K or greater, 60 W / m·K or greater, 70 W / m·K or greater, 80 W / m·K or greater, 90 W / m·K or greater, 100 W / m·K or greater, 110 W / m·K or greater, 120 W / m·K or greater, 130 W / m·K or greater, 140 W / m·K or greater, 150 W / m·K or greater, 200 W / m·K or greater, or 210 W / m·K or greater. There is no particular upper limit to the thermal conductivity; it can be 800 W / m·K or less. By having such high thermal conductivity, the heat generated at the bonding interface during the metal layer bonding process can be released more quickly. Furthermore, the heat accumulated during the operation of organic electronic devices is rapidly released due to their high thermal conductivity, thereby keeping the device's temperature low and reducing the occurrence of cracks and defects. Thermal conductivity can be measured at any temperature within the range of 15°C to 30°C.

[0081] The term "thermal conductivity" in this article refers to the degree to which a material can transfer heat by conduction, and the unit can be expressed as W / m·K. This unit indicates the degree to which a material can transfer heat at the same temperature and distance, and it means the unit of heat (watt) relative to the unit of distance (meter) and the unit of temperature (Kelvin).

[0082] In one embodiment of this application, the metal layer of the encapsulation film can be transparent or opaque. The thickness of the metal layer can range from 3 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. By controlling the thickness of the metal layer, this application can provide a thin-film encapsulation film while achieving sufficient heat release. The metal layer can be a thin metal foil or a polymer base layer with deposited metal. There are no particular limitations on the metal layer, as long as it is a material that meets the above-mentioned thermal conductivity and contains metal. The metal layer can contain any of the following: metal, metal oxide, metal nitride, metal carbide, metal oxynitride, metal boron oxide, and combinations thereof. For example, the metal layer can contain an alloy of one or more metallic or non-metallic elements added to one of the metals, and can contain, for example, stainless steel (SUS). Furthermore, in one example, the metal layer may comprise 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, niobium oxide, and combinations thereof. The metal layer can 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. In one example of this application, the metal layer can be deposited by reactive sputtering.

[0083] Conventionally, nickel-iron alloys (Invar) are typically used as encapsulation films, but these alloys suffer from drawbacks such as high cost, low thermal conductivity, and poor cutting characteristics. This application provides an encapsulation film that prevents bright spots in organic electronic devices, exhibits excellent heat release characteristics, and achieves ease of processing due to magnetism, without using a nickel-iron alloy as the metal layer.

[0084] In one example, the CTE of the metal layer can be in the range of 2 ppm / K to 25 ppm / K, 4 ppm / K to 20 ppm / K, 6 ppm / K to 15 ppm / K, or 9 ppm / K to 12 ppm / K. Furthermore, as described below, in the encapsulation film of this application, the encapsulation layer can encapsulate the top surface of an organic electronic component on a substrate. The CTE of the substrate can be in the range of 1 ppm / K to 6 ppm / K, 2 ppm / K to 5 ppm / K, or 3 ppm / K to 4 ppm / K. When the encapsulation film encapsulates an organic electronic component, the substrate, the organic electronic component, the encapsulation layer for encapsulating the organic electronic component, and the metal layer on the encapsulation layer are laminated in this order. In this case, the thermal expansion characteristics between the substrate and the metal layer may be different. The encapsulation film may also include a base film or release film (hereinafter referred to as the "first film"), which may have a structure in which the encapsulation layer is formed on the base film or release film. Furthermore, the structure may also include a base film, a protective film, or a release film (hereinafter referred to as the "second film") formed on the metal layer.

[0085] There are no particular limitations on the specific type of first film that can be used in this application. For example, a general polymer film from the art can be used as the first film. For example, as a base film or release film, polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polyvinyl chloride film, polyurethane film, ethylene-vinyl acetate film, ethylene-propylene copolymer film, ethylene-ethyl acrylate copolymer film, ethylene-methyl acrylate copolymer film, or polyimide film, etc., can be used. Furthermore, suitable demolding treatment can be performed on one or both sides of the base film or release film of this application. Examples of release agents used in the demolding treatment of the base film include alkyd series, silicone series, fluorinated series, unsaturated ester series, polyolefin series, or wax series, etc., wherein, in terms of heat resistance, alkyd series, silicone series, or fluorinated series release agents are preferred, but not limited to these.

[0086] In this application, the thickness of the base film or release film (first film) is not particularly limited and can be appropriately selected according to the application. For example, in this application, the thickness of the first film can be from 10 μm to 500 μm, preferably around 20 μm to 200 μm. If the thickness is less than 10 μm, deformation of the base film may easily occur during the manufacturing process, while if the thickness exceeds 500 μm, the economic benefits are low.

[0087] The thickness of the encapsulation layer included in the encapsulation film of this application is not particularly limited, and can be appropriately selected based on the following conditions when considering the application of the film: The thickness of the encapsulation layer can be from 5 μm to 200 μm, preferably around 5 μm to 100 μm. The thickness of the encapsulation layer can be the entire thickness of the multilayer encapsulation layer. If the thickness of the encapsulation layer is less than 5 μm, it may not exhibit sufficient moisture barrier capability, while if it exceeds 200 μm, it is difficult to ensure processability, the large thickness expansion caused by moisture reactivity may damage the deposited film of the organic light-emitting element, and the economic benefits are low.

[0088] This application also relates to organic electronic devices. For example... Figure 3 As shown, an organic electronic device may include a substrate 21; an organic electronic element 22 formed on the substrate 21; and the aforementioned encapsulation film 10 for encapsulating the organic electronic element 22. The encapsulation film may encapsulate the top surface (e.g., the entire upper portion) and side surfaces of the organic electronic element formed on the substrate. The encapsulation film may include an encapsulation layer comprising a pressure-sensitive adhesive composition or adhesive composition in a cross-linked or cured state. Furthermore, the organic electronic device can be formed by sealing the encapsulation layer to contact the top surface of the organic electronic element formed on the substrate.

[0089] An encapsulation layer for packaging organic electronic components is disposed between a substrate on which the component is formed and a metal layer of the encapsulation film. However, the substrate and the metal layer are made of different materials and therefore have different thermal expansion characteristics. This can lead to dimensional mismatch when the organic electronic device is exposed to high temperatures for a certain period of time due to the difference in the degree of expansion between the substrate and the metal layer.

[0090] When a CTE mismatch occurs between the metal layer and the substrate in an organic electronic device, such as Figure 4 As shown, a displacement difference exists between the substrate 21 and the metal layer 13 of the organic electronic device, thereby allowing the encapsulation layer 11 laminated between the substrate 21 and the metal layer 13 to be stretched.

[0091] In this application, by adjusting the content of the desiccant contained in the encapsulation layer 11 to a range according to the following general formula 1, the encapsulation layer 11 between the substrate 21 and the metal layer 13 effectively absorbs or disperses stress even at high temperatures. Therefore, gaps or voids on the sides of the encapsulation layer 11 can be prevented, and foreign matter can be effectively prevented from penetrating from the outside while possessing excellent moisture-blocking properties. The content of the desiccant can be in the range of 0.04 to 0.08 in the following general formula 1.

[0092] [General Form 1]

[0093] Desiccant content = Q 最大 ×(H T1 +H T2×γ) / H T1

[0094] In the above general formula 1, Q is the solid content relative to 100 parts by weight of the encapsulation layer. 最大 From 60 to 90 parts by weight, H T1 H represents the thickness of the encapsulation layer at 25°C. T2 The length of the outermost part of the bonding substrate and the outermost part of the metal layer of the encapsulation layer at temperature T2, where T1 is 25°C and T2 is 85°C.

[0095] In one embodiment of this application, the organic electronic component may include a pair of electrodes, an organic layer including at least a light-emitting layer, and a passivation film. Specifically, the organic electronic component may include 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 may include a passivation film for protecting the electrodes on the second electrode layer and the organic layer. 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 component 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.

[0096] Here, organic electronic components can be, for example, organic light-emitting elements.

[0097] The passivation film can include inorganic and organic films. In one embodiment, the inorganic film can be a metal oxide or nitride selected from one or more of Al, Zr, Ti, Hf, Ta, In, Sn, Zn, and Si. The thickness of the inorganic film can be from 0.01 μm to 50 μm, or from 0.1 μm to 20 μm, or from 1 μm to 10 μm. In one example, the inorganic film of this application can be an inorganic material without dopant, or an inorganic material containing dopant. The dopant that can be doped can be one or more elements selected from Ga, Si, Ge, Al, Sn, Ge, B, In, Tl, Sc, V, Cr, Mn, Fe, Co, and Ni, or oxides of said elements, but is not limited thereto. The organic film differs from an organic layer that includes at least a light-emitting layer in that it does not include a light-emitting layer and can be an organic deposition layer containing an epoxy compound.

[0098] Inorganic or organic films can be formed by chemical vapor deposition (CVD). For example, silicon nitride (SiNx) can be used as an inorganic film. In one example, silicon nitride (SiNx) used as an inorganic film can be deposited to a thickness of 0.01 μm to 50 μm. In one example, the thickness of the organic film can be in the range of 2 μm to 20 μm, 2.5 μm to 15 μm, or 2.8 μm to 9 μm.

[0099] This application also provides a method for manufacturing an organic electronic device. The manufacturing method may include the step of applying the aforementioned encapsulation film to a substrate on which organic electronic components are formed to cover the organic electronic components. Furthermore, the manufacturing method may include a step of curing the encapsulation film. The curing step of the encapsulation film may refer to the curing of the encapsulation layer, which may be performed before or after the encapsulation film covers the organic electronic components.

[0100] In this specification, the term "curing" may mean that the pressure-sensitive adhesive composition of the present invention is manufactured into the form of a pressure-sensitive adhesive by forming a cross-linked structure through processes such as heating or UV irradiation. Alternatively, it may mean that the adhesive composition is cured and used as an adhesive for attachment.

[0101] Specifically, organic electronic components can be formed by: forming a transparent electrode on a glass or polymer film used as a substrate using methods such as vacuum evaporation or sputtering; forming a light-emitting organic material layer on the transparent electrode, consisting of, for example, a hole transport layer, a light-emitting layer, and an electron transport layer; and then further forming an electrode layer on the light-emitting organic material layer. Subsequently, an encapsulation layer, in which an encapsulation film is placed, is used to cover the top surface of the organic electronic component on the substrate that has undergone the above process.

[0102] Beneficial effects

[0103] The encapsulation film of this application can be used to seal or encapsulate organic electronic devices such as OLEDs. The film provides an encapsulation film with excellent reliability, allowing the formation of a structure that can block moisture or oxygen from flowing into the organic electronic device from the outside, and absorbs and disperses stress caused by panel bending, while preventing bright spots from forming in the organic electronic device. Attached Figure Description

[0104] Figure 1 and Figure 2 This is a cross-sectional view showing an example of an encapsulation film according to this application.

[0105] Figure 3 This is a cross-sectional view showing an example of an organic electronic device according to this application.

[0106] Figure 4 This occurs when a CTE mismatch occurs between the metal layer and the substrate in an organic electronic device. Figure 3 An enlarged cross-sectional view of part "A". Detailed Implementation

[0107] The invention will be described in more detail below by way of embodiments according to the invention and comparative examples not according to the invention, but the scope of the invention is not limited to the following embodiments.

[0108] Example 1

[0109] Fabrication of encapsulation layer

[0110] To prepare the first layer solution, a solution (33% solids content) was prepared in which butyl rubber resin (BR068, EXXON) and tackifier (hydrogenated dicyclopentadiene resin with 9 carbon atoms, softening point: 90℃, Mw: 570 g / mol) were diluted with toluene in a weight ratio of 50:45 (parts by weight). The solution was then homogenized. Five parts by weight of polyfunctional acrylate (HDDA, Miwon) and one part by weight of photoinitiator (Irgacure 819, BASF) were introduced into the homogenized solution and homogenized. The solution was then stirred at high speed for 1 hour to prepare the first layer solution.

[0111] To prepare the second layer solution, CaO (Sigma-Aldrich, average particle size 1 μm) as a hygroscopic agent was prepared as a solution (50% solids content). Separately, a solution (50% solids content) was prepared in which butyl rubber resin (BR068, EXXON), Ni particles (approximately 300 nm in particle size) as a bright spot inhibitor, and a tackifier (hydrogenated dicyclopentadiene resin with 9 carbon atoms, softening point: 90 °C, Mw: 570 g / mol) were diluted with toluene in a weight ratio of 40:10:55 (butyl rubber:Ni:tackifier). The solutions were then homogenized. Five parts by weight of polyfunctional acrylate (HDDA, Miwon) and one part by weight of photoinitiator (Irgacure 819, BASF) were introduced into a homogenized solution and homogenized. Then, a hygroscopic agent solution was introduced into it such that the amount of hygroscopic agent was 100 parts by weight relative to 100 parts by weight of solids in the second layer solution. The solution was then stirred at high speed for 1 hour to prepare the second layer solution.

[0112] For the first and second layers, the encapsulation layer solutions prepared above were applied to the release surface of the release PET using a comma coating machine, and dried in a desiccator at 130°C for 3 minutes to form an encapsulation layer with a first layer thickness of 10 μm and a second layer thickness of 50 μm. The two layers were then laminated together.

[0113] Production of encapsulation film

[0114] On a pre-prepared metal layer (SUS430, 70 μm thick), a release-treated PET layer attached to the encapsulation layer is peeled off and laminated at 70°C through a roll-to-roll process, thereby producing an encapsulation film such that the second layer is in contact with the metal layer.

[0115] The produced encapsulation film is cut to produce encapsulation films for organic electronic components. Measurements are taken at 2J / cm. 2Physical properties of samples obtained by irradiating membranes produced with ultraviolet light.

[0116] Example 2

[0117] An encapsulation film for organic electronic devices was prepared in the same manner as in Example 1, except that a CaO dispersion containing 110 parts by weight of CaO was introduced therein as a hygroscopic agent.

[0118] Example 3

[0119] An encapsulation film for organic electronic devices was prepared in the same manner as in Example 1, except that a CaO dispersion containing 85 parts by weight of CaO was introduced therein as a hygroscopic agent.

[0120] Comparative Example 1

[0121] An encapsulation film for organic electronic devices was prepared in the same manner as in Example 1, except that a CaO dispersion containing 70 parts by weight of CaO was introduced therein as a hygroscopic agent.

[0122] Comparative Example 2

[0123] An encapsulation film for organic electronic devices was prepared in the same manner as in Example 1, except that the CaO dispersion was mixed to contain 130 parts by weight of CaO as a hygroscopic agent.

[0124] Comparative Example 3

[0125] An encapsulation film for organic electronic devices was prepared in the same manner as in Example 1, except that the CaO dispersion was mixed to contain 140 parts by weight of CaO as a hygroscopic agent.

[0126] Experimental Example 1 - Calculation of Desiccant Content

[0127] The encapsulation films prepared in the examples and comparative examples were each laminated onto the CTE. 基底 A frame-shaped sample was prepared on a packaging glass with a concentration of 3.7 ppm / K. In the examples and comparative examples, the CTE of the metal layer laminated on the packaging layer was... 金属 It is 10.4 ppm / K.

[0128] After holding the samples in a constant temperature and humidity chamber at 85°C and 85% for approximately 500 hours, any changes in the frame of the frame-type samples were determined. At room temperature (25°C), the thickness (H) of the encapsulation layer was also assessed. T1 The thickness of the first layer is 10 μm and the thickness of the second layer is 50 μm. The length of the long side of the encapsulation layer (L) is 60 μm. T1 The diameter is 1440mm.

[0129] After 500 hours, the length (H) connecting the outermost edge of the encapsulation glass to the outermost edge of the metal layer is calculated according to the following general formula 2. T2 ).

[0130] [General Form 2]

[0131]

[0132] In the general formula 2 above, ΔL CTE It satisfies the following general formula 3.

[0133] [General Form 3]

[0134] ΔL CTE =(CTE) 金属 -CTE 基底 )×L T1 ×(T2-T1) / 2

[0135] H is calculated using the general formula 2 above. T2 It is 296 μm, and by using H T1 and H T2 The value is substituted into the following general formula 1 to calculate the desiccant content.

[0136] [General Form 1]

[0137] Desiccant content = Q 最大 ×(H T1 +H T2 ×γ) / H T1

[0138] In the above general formula 1, Q is the solid content relative to 100 parts by weight of the encapsulation layer. 最大 The amount is 60 to 90 parts by weight, and the amount of γ is 0.04 to 0.08.

[0139] The solid content relative to the second layer is determined to be 70 to 130 parts by weight, calculated according to the general formula 1 above.

[0140] Experimental Example 2 - Room Temperature Adhesion Test

[0141] Adhesion at room temperature was measured using a texture analyzer based on ASTM 3330. The encapsulation films of Examples 1 to 3 and Comparative Examples 1 to 3 were each set to a width of 1 inch and stored at 25°C and 50% relative humidity for 1 hour, and then the peel force of 1,000 gf / inch or greater relative to the glass substrate (0.5T) was measured (peel rate: 5 mm / s, peel angle: 180°).

[0142] Experiment Example 3 - Reliability Assessment (Moisture Barrier Performance)

[0143] After depositing organic electronic components on a 55-inch glass substrate (0.5T), the encapsulation films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were laminated onto the components using a vacuum bonding machine at 25°C, 50 mTorr vacuum and 0.4 MPa to produce organic electronic panels.

[0144] When the produced panel is kept in a constant temperature and humidity chamber at 85°C and 85% for about 500 hours, observe whether lifting or bubbles occur at the interface between the glass substrate and the encapsulation film layer.

[0145] When observed with the naked eye, any lifting or bubble at the interface between the glass substrate and the encapsulation film is marked as X, and any absence of lifting or bubble is marked as O.

[0146] Experiment Example 4 - Creep Test

[0147] In the case where the encapsulation layers of the examples and comparative examples were laminated to a thickness of 600 μm and prepared, an 8 mm aluminum parallel plate cell was used in creep mode to apply a vertical force of 200 gf to the film at 85 °C, thereby applying a stress of 15,000 Pa to the film and holding it for 60 seconds, and then the strain value was measured.

[0148] [Table 1]

[0149]

[0150] [Explanation of reference numerals in the attached figures]

[0151] 1, 10: Encapsulation film

[0152] 2, 4, 11: Encapsulation layer

[0153] 13: Metal layer

[0154] 3: Bright Spot Inhibitor

[0155] 5: Desiccant

[0156] 21: Base

[0157] 22: Organic electronic components

Claims

1. A packaging film comprising a packaging layer containing a packaging resin and a hygroscopic agent and encapsulating a top surface of an organic electronic element formed on a substrate, and a metal layer formed on the packaging layer, wherein a content of the hygroscopic agent satisfies a range of 0.04 to 0.08 in the following general formula 1: [General Formula 1] moisture content = Q 最大 × (H T1 + H T2 × γ) / H T1 wherein Q is 60 to 90 parts by weight relative to 100 parts by weight of the solid content of the encapsulation layer 最大 H is 60 to 90 parts by weight relative to 100 parts by weight of the solid content of the encapsulation layer T1 H is the thickness of the encapsulation layer at 25 °C T2 H is the length of the encapsulation layer connecting the outermost side of the substrate and the outermost side of the metal layer at a temperature T2, T1 is 25 °C, and T2 is 85 °C.

2. The packaging film according to claim 1, wherein the metal layer has a CTE range of 1.5 times or more with respect to a CTE of the substrate.

3. The packaging film according to claim 1, wherein the hygroscopic agent is a chemically reactive adsorbent.

4. The packaging film according to claim 1, wherein a ratio of an average particle diameter according to D50 to an average particle diameter according to D10 is in a range of 2.5 to 3.5 as a result of a particle size analysis of the hygroscopic agent for a sample filtered through a 300 mesh nylon after the packaging layer is dissolved in an organic solvent.

5. The packaging film according to claim 1, wherein a glass transition temperature of the packaging resin is lower than 0°C.

6. The packaging film according to claim 1, wherein the packaging resin comprises an olefin-based resin.

7. The packaging film according to claim 1, wherein the packaging resin comprises a copolymer of a diene and an olefinic compound containing one carbon-carbon double bond.

8. The packaging film according to claim 1, wherein the packaging resin is contained in the packaging layer in an amount of 40% by weight or more.

9. The packaging film according to claim 1, wherein the packaging layer further contains a tackifier.

10. The packaging film according to claim 9, wherein a softening point of the tackifier is 70°C or more.

11. The packaging film according to claim 9, wherein the tackifier is a compound containing a cyclic structure having 5 to 15 carbon atoms.

12. The packaging film according to claim 9, wherein the tackifier is a hydrogenated compound.

13. The packaging film according to claim 11, wherein the cyclic structure is a bicyclic compound or a tricyclic compound.

14. The packaging film according to claim 9, wherein the tackifier is contained in a range of 15 parts by weight to 200 parts by weight with respect to 100 parts by weight of the packaging resin.

15. The packaging film according to claim 1, wherein the packaging layer further contains a bright spot inhibitor.

16. The packaging film according to claim 15, wherein an adsorption energy of the bright spot inhibitor with respect to air calculated by an approximate method of density functional theory is 0 eV or less.

17. The packaging film according to claim 15, wherein the bright spot inhibitor is contained in an amount of 3 parts by weight to 150 parts by weight with respect to 100 parts by weight of the packaging resin.

18. The packaging film according to claim 1, wherein the packaging layer further contains a compound that is polymerizable by active energy rays.

19. An organic electronic device comprising: a substrate; an organic electronic element formed on the substrate; and the packaging film according to claim 1 for encapsulating the organic electronic element.

20. A method for manufacturing an organic electronic device, comprising the step of applying the encapsulating film according to claim 1 to a substrate on which an organic electronic element is formed to cover the organic electronic element.

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