Thermosetting resin composition and encapsulation film using the same

Abstract

The present application relates to a thermosetting resin composition, a packaging film, and an organic electronic device including the packaging film. The packaging film is capable of forming a structure that can block the inflow of moisture or oxygen from the outside into the organic electronic device, and aims to achieve heat resistance and durability of the organic electronic device under harsh conditions such as high temperature.

Description

Technical Field

[0001] The present application relates to a thermosetting resin composition, an encapsulation film using the thermosetting resin composition, an organic electronic device including the encapsulation film, and a method for manufacturing the organic electronic device. Background Art

[0002] An organic electronic device (OED) means a device including an organic material layer that generates an alternating current using holes and electrons, and examples thereof may include a photovoltaic device, a rectifier, a transmitter, and an organic light emitting diode (OLED), etc.

[0003] Among the above organic electronic devices, the organic light emitting diode (OLED) has lower power consumption and faster response speed than existing light sources, and is beneficial for thinning display devices or lighting devices. In addition, the OLED has spatial availability and is thus expected to be applied to various fields, including various portable devices, monitors, laptop computers, and TVs.

[0004] In the commercialization and application expansion of OLEDs, the biggest problem that the prior art attempts to solve is the durability problem. Organic materials and metal electrodes contained in OLEDs are very easily oxidized by external factors such as moisture. Therefore, products containing OLEDs are very sensitive to environmental factors. Therefore, various methods have been proposed to effectively prevent oxygen or moisture from penetrating from the outside into an organic electronic device such as an OLED.

[0005] In particular, Patent Document 1 relates to a composition for encapsulation and an encapsulation device including the composition, which provides such a composition for encapsulation that contains a photocurable mixture and an initiator and is capable of forming a barrier layer having low oxygen, moisture, water vapor, and chemical permeabilities. However, as in Patent Document 1, when a photocurable composition is used as an encapsulation film, it may cause problems such as bending of the panel of the organic electronic device at high temperatures or generation of inclined bubbles. Summary of the Invention

[0006] Technical Problem

[0007] The present application aims to provide an encapsulation film that can form a structure that can block the inflow of moisture or oxygen from the outside into an organic electronic device and achieve heat resistance and durability of the organic electronic device under harsh conditions such as high temperatures.

[0008] In addition, by satisfying the gel fraction of the encapsulation layer within a specific range, the present application can have excellent moisture barrier properties and achieve an appropriate storage elastic modulus at high temperatures, and aims to improve the durability of the organic electronic device by minimizing the concentration of chloride residues to suppress the occurrence of dark spots on the organic electronic component, while achieving excellent reliability under high temperature conditions by controlling the elastic region or gel fraction within a specific range.

[0009] The technical problems of the present invention are not limited to the above technical problems, and those skilled in the art will clearly understand other technical problems not mentioned from the following description.

[0010] Technical solutions

[0011] The terms used in the present application are only for describing specific examples and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, terms such as "including" or "having" are intended to indicate the presence of the features, quantities, steps, operations, components, parts, or combinations thereof described in the specification, but it should be understood that the presence or addition possibility of one or more other features, quantities, steps, operations, components, parts, or combinations thereof is not precluded in advance.

[0012] Unless otherwise defined, all terms (including technical or scientific terms) used herein have the same meanings as those commonly understood by those of ordinary skill in the technical field to which the present invention pertains. Unless clearly defined in the present application, those terms defined, for example, in common dictionaries should be interpreted as having meanings consistent with their meanings in the context of the related art and should not be interpreted as idealized or overly formalized meanings.

[0013] <Encapsulation film>

[0014] According to an example of the present application, an encapsulation film can be provided. As described below, the present application can provide an encapsulation film including an encapsulation layer. The encapsulation layer can seal the top surface of the organic electronic component formed on the substrate, and specifically, can be applied to seal or encapsulate an organic electronic device such as an OLED.

[0015] Herein, the term "organic electronic device" means an article or device having a structure including an organic material layer that generates alternating current by using holes and electrons between a pair of opposing electrodes, and examples thereof may include photovoltaic devices, rectifiers, emitters, and organic light-emitting diodes (OLEDs), etc., but are not limited thereto. In an example of the present application, the organic electronic device can be an OLED.

[0016] The encapsulation film according to the present application can include an encapsulation layer containing an encapsulation resin, wherein the encapsulation resin can contain an olefin-based resin having a thermosetting functional group.

[0017] In the present invention, the encapsulation layer is formed by a thermosetting method rather than a photocuring method, and thus, an encapsulation resin different from the encapsulation resin of the photocuring method can be used. Herein, the photocuring method and the thermosetting method mean methods of crosslinking and polymerizing with each other by light and heat, respectively, to form a cured product.

[0018] Conventionally, an encapsulation layer produced by a photocuring method has been mainly used, and there is a problem in that the panel of the organic electronic device is bent at high temperatures. As a result, inclined bubbles are generated when the encapsulation film and the base layer are laminated and cured, and the reliability of the organic electronic element to which the encapsulation layer according to the photocuring method is applied deteriorates.

[0019] At the same time, in order to suppress the bending phenomenon of the panel during lamination and curing, it is necessary to increase the elastic portion of the encapsulation film at high temperatures. However, according to the photocuring method, there is a limit to increasing the elastic portion (EP) at a high temperature of 85 °C or higher to a certain level or higher, and thus it is difficult to achieve a high elastic portion.

[0020] Therefore, as described below, the present application can provide an encapsulation film having a high elastic portion or gel fraction by thermally curing by introducing an olefin-based resin having a thermosetting functional group into the encapsulation layer, and can provide an organic electronic device having improved heat resistance durability at high temperatures.

[0021] At the same time, the encapsulation layer of the present application may contain a filler as needed, preferably an inorganic filler, so that the movement path of moisture or humidity penetrating into the encapsulation structure can be extended to suppress its penetration, and the barrier properties against moisture and humidity can be maximized by the interaction with the matrix structure of the encapsulation resin and the moisture absorbent, etc. In order to increase the moisture penetration distance, it is necessary to increase the content of the inorganic filler. If the inorganic filler is contained in the photocurable resin composition in a certain amount or more, the curing caused by light is blocked due to the inorganic filler, and thus there is a problem that the photocurable resin is difficult to have a sufficient degree of curing. However, the present application can solve this problem by using an encapsulation resin that can be cured by heat.

[0022] In one embodiment, the concentration of chloride ion residues measured by combustion ion chromatography (IC) of the encapsulation layer according to the present application may be 1,000 ppm or less. Specifically, the concentration of chloride ion residues may be 900 ppm or less, 800 ppm or less, 700 ppm or less, 600 ppm or less, or 500 ppm or less, and the lower limit thereof may be 10 ppm or more.

[0023] The concentration of chloride ion residues can be measured by preparing a 0.1 g specimen of the encapsulation layer through combustion ion chromatography (C-IC). The measurement can be carried out after the equipment is stabilized, and quantitative analysis can be performed by setting standard materials and samples to the following IC conditions. An IC (ICS-5000DP from Dionex) and an AQF (AQF-2100H from Mitsubishi) can be used as the measuring instruments for the measurement.

[0024] - Combustion temperature: inlet temperature 900 °C, outlet temperature 1,000 °C

[0025] - Gas flow rate: Ag gas 200 mL / min, O2 gas 400 mL / min

[0026] - Main column: Dionex IonPac AS18 analytical column (4 mm × 250 mm)

[0027] - Guard column: Dionex IonPac AG18 guard column (4 mm × 50 mm)

[0028] - Eluent: 30.5 mM KOH

[0029] - Eluent flow rate: 1 mL / min

[0030] - Injection volume: 20 μL

[0031] - Detector: suppressed conductivity detector

[0032] - SRS current: 76 mA

[0033] - Isocratic / gradient condition: isocratic

[0034] When chloride ion residues remain in the organic electronic component, they can act as foreign substances in the organic electronic component, causing adverse effects on the component such as the appearance of dark spots on the organic electronic component, thus greatly reducing the quality, and there may be a problem that the durability of the component cannot be fully ensured. Therefore, the present application provides an organic electronic component with excellent reliability by providing a thermosetting resin composition having a significantly reduced concentration of chloride ion residues.

[0035] That is, as described above, the encapsulation film of the present application can satisfy the elastic part or gel fraction within a specific range, thereby providing an encapsulation layer having excellent reliability while achieving heat resistance equivalent to or better than that of a conventional photocurable composition and minimizing chloride ion residues at the same time.

[0036] In one embodiment of the present application, the encapsulation layer may have an elastic portion of 46% or more calculated by the following General Formula 1.

[0037] [General Formula 1]

[0038] Elastic portion (Ep, unit: %) = 100 × σ2 / σ1

[0039] In the above General Formula 1, σ1 is the stress value at 1 second after applying a strain of 30% to the specimen, where the specimen is prepared by laminating the encapsulation layer onto a film having a size of 20 cm × 30 cm and a thickness of 600 μm, and then loaded by applying a normal force of about 150 gf thereto at 85°C in a stress relaxation mode (stress relaxation test) using parallel plates in the laminated state through ARES (Advanced Rheology Expansion System), and σ2 is the stress value measured after maintaining the state of applying the strain to the specimen for 180 seconds.

[0040] Here, the term "ARES (Advanced Rheology Expansion System)" is a rheological property measuring instrument for evaluating the viscoelastic properties of materials (such as viscosity, shear elastic modulus, loss coefficient, and storage elastic modulus). This instrument is a mechanical measuring device that can apply dynamic and steady states to the specimen and measure the transmitted torque, that is, the degree to which the specimen resists the stress applied in this way.

[0041] As an example, in the encapsulation layer, the lower limit of the elastic portion calculated by the following General Formula 1 may be 47% or more, 48% or more, 49% or more, 50% or more, 51% or more, 52% or more, 53% or more, 54% or more, 55% or more, 56% or more, 57% or more, 58% or more, 59% or more, 60% or more, 61% or more, 62% or more, 63% or more, 64% or more, 65% or more, 70% or more, 75% or more, 80% or more, 82% or more, 85% or more, or 90% or more, and its lower limit is not limited, but may be less than 100%. Since such an elastic portion has a higher value, it is beneficial to increase the amount of fillers such as moisture absorbents. Therefore, even in extreme environments such as high temperature and high humidity, the rate of change with respect to the external environment is small, so that the occurrence of inclined bubbles due to volume expansion can be suppressed.

[0042] In one embodiment of the present application, the cured product of the thermosetting resin composition may have a gel fraction of 70% or more represented by the following General Formula 2.

[0043] [General Formula 2]

[0044] Gel fraction (gel content, unit: %) = (B / A) × 100

[0045] In the above general formula (2), A represents the initial mass of the encapsulation layer sample, and B represents the dry mass of the insoluble content of the encapsulation layer that does not pass through the mesh after immersing the encapsulation layer sample in 70 g of toluene at 60 °C for 3 hours and then filtering through a 200-mesh (pore size 200 μm) screen.

[0046] As an example, the lower limit of the gel fraction represented by the above general formula (2) can be 71% or greater, 73% or greater, 75% or greater, 77% or greater, 79% or greater, 81% or greater, 83% or greater, 85% or greater, 87% or greater, 89% or greater, 90% or greater, 91% or greater, 92% or greater, 94% or greater, 95% or greater, 96% or greater, 97% or greater, or 99% or greater, and its upper limit is not limited and can be less than 100%. When such a gel fraction satisfies the above range, the encapsulation layer has a crosslinked structure and degree of crosslinking within an appropriate range, thereby enabling excellent adhesion and moisture barrier properties.

[0047] In one embodiment of the present application, the encapsulation resin is prepared from a thermosetting resin composition comprising a peroxide (α), an acidic solution (β), and an olefin-based resin (γ), wherein the encapsulation resin may comprise an olefin-based resin having a thermosetting functional group.

[0048] In an example, the weight ratio (α / β) of the peroxide (α) to the acidic solution (β) can satisfy a range of 200 or less. In this specification, the weight of the acidic solution (β) means the weight of the acidic substance (such as HCl, etc.) introduced into the solvent to form the acidic solution, which means that the weight does not include the weight of the solvent. As an example, the upper limit of the weight ratio (α / β) of the peroxide (α) to the acidic solution (β) can be 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 120 or less, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, or 20 or less, and its lower limit is not highly restricted but can be 5 or greater, 10 or greater, or 15 or greater.

[0049] In addition, in one example, relative to 100 parts by weight of the olefin-based resin (γ), the peroxide (α) may be included in an amount of 1.2 parts by weight or more. As an example, relative to 100 parts by weight of the olefin-based resin (γ), the lower limit of the peroxide (α) may be 1.25 parts by weight or more, 1.3 parts by weight or more, 1.35 parts by weight or more, 1.4 parts by weight or more, 1.45 parts by weight or more, or 1.5 parts by weight or more, and the upper limit thereof may be 10 parts by weight or less, 7 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, or 3 parts by weight or less.

[0050] In the present application, the encapsulating resin can be prepared by the reaction of a peroxide (α), an acidic solution (β), and an olefin-based resin (γ), and chloride ion residues derived from the peroxide (α) and the acidic solution (β) by the reaction may be generated. When these chloride ion residues remain in the organic electronic component, they can act as foreign substances on the organic electronic component, causing adverse effects such as the appearance of dark spots on the organic electronic component, thereby greatly reducing the quality, and there may be a problem that the durability of the component cannot be sufficiently ensured. Therefore, the present application can provide an organic electronic component with excellent reliability by providing such an encapsulating layer: in the encapsulating layer, the content of the starting materials required for preparing the encapsulating resin as described above is controlled to reduce the concentration of the chloride ion residues to a certain level or lower.

[0051] Here, the peroxide (α) is an oxide having a peroxy group and -2 valence O2 ([-OO-] 2- ) in the molecule, and there is no limitation as long as it can undergo an epoxy reaction with the olefin-based resin (γ). As an example, it may be meta-chloroperoxybenzoic acid (mCPBA), dimethyldioxirane (DMDO), etc.

[0052] The acidic solution (β) is a solution of an organic acid or an inorganic acid having a pH of 6 or less. As an example, it may be an aqueous solution of hydrochloric acid (HCl), phosphoric acid (H3PO4), nitric acid (HNO3), sulfuric acid (H2SO4), etc.

[0053] The olefin-based resin (γ) may include a polymer derived from an olefin-based monomer. In one example, the polymer derived from the olefin-based monomer may include, for example, an isolefin monomer or a polyolefin monomer, and may be prepared by the polymerization of the monomer.

[0054] The isolefins may be exemplified by, for example, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butene, 2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene or 4-methyl-1-pentene. The polyolefins may be exemplified by, for example, isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethylfulvene, hexadiene, cyclopentadiene or piperylene. Other polymerizable monomers such as styrene and dichlorostyrene may also be homopolymerized or copolymerized. In one example, the olefin-based resin may be a homopolymer or copolymer of an isolefin and / or a polyolefin, which may be exemplified by, for example, polybutadiene, polyisoprene, polyisobutene or butyl rubber.

[0055] In one example of the present application, the olefin-based resin (γ) is a homopolymer of a butene monomer; a copolymer obtained by copolymerizing a butene monomer and 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.

[0056] Additional monomers that can be polymerized with the butene monomer or derivative may include, for example, isoprene, styrene or butadiene, etc. By using the copolymer, physical properties such as processability and crosslinking degree can be maintained, so that when applied to an organic electronic device, the heat resistance of the pressure-sensitive adhesive itself can be ensured.

[0057] In one example of the present application, the olefin-based resin (γ) may include a copolymer of a diene and an olefin-based compound containing one carbon-carbon double bond. Here, the diene may be a monomer that can be polymerized with the olefin-based compound, and may include, for example, isoprene or butadiene, etc. In addition, the olefin-based compound may include butene, etc. More specifically, the copolymer of a diene and an olefin-based compound containing one carbon-carbon double bond may be butyl rubber.

[0058] Because the diene compounds are copolymerized together, the olefin-based resin (γ) may have one or more double bonds in the main chain of the resin after copolymerization, and such double bonds can be used to introduce the following thermosetting functional groups.

[0059] In one embodiment of the present application, the encapsulation resin prepared by the reaction of a peroxide (α), an acidic solution (β) and an olefin-based resin (γ) may be an olefin-based resin having a thermosetting functional group. That is, the thermosetting resin composition of the present application may include an olefin-based resin having a thermosetting functional group as the encapsulation resin.

[0060] The thermosetting functional group can be derived from the unsaturated group in the olefin-based resin (γ) through the reaction of a peroxide (α), an acidic solution (β), and the olefin-based resin (γ). In this specification, the meaning that the thermosetting functional group is derived from the unsaturated group can mean that the thermosetting functional group is introduced into the unsaturated group such as a double bond existing in the main chain of the olefin-based resin (γ).

[0061] In this application, the thermosetting functional group means a functional group that can crosslink and polymerize with each other by heating at a predetermined temperature or higher to form a cured product. The thermosetting functional group can include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group, and can be one or more functional groups selected from the foregoing, where the thermosetting functional group can be one type or two or more types.

[0062] In one embodiment of this application, the weight-average molecular weight (Mw) of the encapsulating resin can reach a level capable of being formed into a film shape of the encapsulating layer. For example, the weight-average molecular weight of the encapsulating resin can be about 100,000 g / mol to 2,000,000 g / mol, where the lower limit thereof can be 200,000 g / mol or greater, 250,000 g / mol or greater, 300,000 g / mol or greater, 350,000 g / mol or greater, 400,000 g / mol or greater, 450,000 g / mol or greater, 500,000 g / mol or greater, or 550,000 g / mol or greater, and the upper limit thereof can be 1,500,000 g / mol or less, 1,200,000 g / mol or less, 1,000,000 g / mol or less, 800,000 g / mol or less, 70 g / mol or less, or 600,000 g / mol or less. The encapsulating layer according to this application can also contain two types of encapsulating resins having different weight-average molecular weights, but can also contain only one type of encapsulating resin obtained as described above by controlling the content of the starting materials during the preparation of the encapsulating resin. Here, the weight-average molecular weight means the value converted to standard polystyrene measured by GPC (gel permeation chromatography), and the unit is g / mol unless otherwise specified. However, the resin does not necessarily have the above weight-average molecular weight.

[0063] In one example of this application, the encapsulating layer can also contain a curing agent. The curing agent is a compound capable of chemically bonding with the thermosetting functional group introduced into the above-obtained encapsulating resin, and a suitable compound can be selected and used according to the type of the thermosetting functional group.

[0064] The curing agent may include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an aziridine-based crosslinking agent, a metal chelate-based crosslinking agent, an amine-based crosslinking agent, or an amino resin-based crosslinking agent. These curing agents can be used alone and can be used in combinations of two or more.

[0065] For example, when the thermosetting functional group introduced into the encapsulation resin is a hydroxyl group (-OH), an isocyanate-based crosslinking agent in the form of a monomer, dimer, trimer, or polymer containing an isocyanate group (-NCO) can be used, and more specifically, toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), or isophorone diisocyanate (IPDI) can be used, but the present invention is not limited thereto.

[0066] For example, when the thermosetting functional group introduced into the encapsulation resin is an epoxy group, an amine curing agent, an imidazole curing agent, a phenol curing agent, a phosphorus curing agent, an acid anhydride curing agent, etc. can be used, but the present invention is not limited thereto.

[0067] In addition, depending on the type of thermosetting functional group introduced into the encapsulation resin, available curing agents may include zinc octoate, iron acetylacetonate, N,N-dimethylethanolamine, or triethylenediamine, etc., but are not limited thereto.

[0068] The content of the curing agent is not particularly limited, but it can be included in an amount of about 0.1 parts by weight to 10 parts by weight relative to 100 parts by weight of the encapsulation resin to achieve effective thermal curing without impairing the physical properties of the entire encapsulation film. The content of the curing agent as a lower limit can be 0.2 parts by weight or more, 0.3 parts by weight or more, 0.3 parts by weight or more, 0.4 parts by weight or more, 0.5 parts by weight or more, 0.6 parts by weight or more, 0.7 parts by weight or more, or 0.8 parts by weight or more relative to 100 parts by weight of the encapsulation resin, and as an upper limit, it can be 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less relative to 100 parts by weight of the encapsulation resin.

[0069] The thermosetting reaction can be carried out at a temperature of about 40°C to 150°C for about 3 minutes to 180 minutes, but it can be appropriately adjusted according to the purpose and use of the present invention and is not limited thereto.

[0070] In one example of the present application, the thermosetting resin composition may further comprise a curing catalyst to facilitate the thermosetting reaction. The curing catalyst is a catalyst that accelerates the chemical reaction between the curing agent and the thermosetting functional groups in the olefin-based resin, and it may include one selected from tin catalysts, bismuth catalysts, mercury-based catalysts, amine-based catalysts, and combinations thereof. When using the above types of curing catalysts, the crosslinking reaction between the curing agent and the thermosetting functional groups in the olefin-based resin can proceed rapidly, and the curing efficiency of the thermosetting resin composition can be improved. Specifically, one or more selected from dibutyltin dilaurate (DBTDL), zinc octoate, iron acetylacetonate, N,N-dimethylethanolamine, and triethylenediamine can be used. These catalysts can be used alone or as a mixture of two or more different types.

[0071] In one example of the present application, the encapsulation layer may further comprise a curing retarder. The curing retarder can inhibit the reaction in the steps before coating the film after blending the final components of the encapsulation layer, and inhibit the excessive increase in the viscosity of the resin components. The type of the curing retarder is not particularly limited, but for example, β-ketoesters such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, or stearyl acetoacetate; or 2,4-hexanedione; benzoylacetone, etc. can be used, and preferably acetylacetone can be used.

[0072] In one example of the present application, the encapsulation layer may further comprise a moisture absorbent. In this specification, the term "moisture absorbent" may mean, for example, a chemically reactive adsorbent that can remove moisture or humidity by chemically reacting with the moisture or humidity that penetrates into the encapsulation film described below.

[0073] For example, the moisture absorbent can be dispersed in the thermosetting resin composition in the form of particles, and thereafter, it can exist in the encapsulation layer or the encapsulation film in a uniformly dispersed state. Here, the uniformly dispersed state may mean a state in which the moisture absorbent exists uniformly at the same density or substantially at the same density in any part of the encapsulation layer or the encapsulation film. Here, available moisture absorbents can include, for example, metal oxides, sulfates, or organometallic oxides, etc. Specifically, examples of sulfates can include magnesium sulfate, sodium sulfate, or nickel sulfate, etc., and examples of organometallic oxides can include aluminum octoate, etc.

[0074] 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. 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 pentafluoride (TaF5), niobium pentafluoride (NbF5), lithium bromide (LiBr), calcium bromide (CaBr2), cerium 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), but are not limited thereto. As the moisture absorbent that can be included in the encapsulation layer or encapsulation film, one of the above components may also be used, or two or more types may also be used. In one example, when using two or more types of moisture absorbents, calcined dolomite, etc. may be used.

[0075] Such a moisture absorbent can be controlled to a suitable size according to the application. In one example, the average particle diameter of the moisture absorbent 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. The moisture absorbent having a size within the above range can effectively remove moisture, and at the same time is easy to store because the reaction rate with water is not too fast, does not damage the element to be encapsulated, and does not interfere with the hydrogen adsorption process related to the bright point inhibitor described below. In this specification, the particle diameter may mean the average particle diameter, and can be measured by a known method using a D50 particle size analyzer.

[0076] The content of the moisture absorbent is not particularly limited and can be appropriately selected in consideration of the desired barrier properties. With respect to 100 parts by weight of the encapsulation resin, the moisture absorbent can be included in the range of 20 parts by weight to 200 parts by weight, 25 parts by weight to 190 parts by weight, 30 parts by weight to 180 parts by weight, 35 parts by weight to 170 parts by weight, 40 parts by weight to 160 parts by weight, or 45 parts by weight to 155 parts by weight. In order to increase the moisture penetration distance, it is necessary to increase the content of the moisture absorbent. However, when the moisture absorbent is included in the photocurable resin composition in a certain amount or more, the curing caused by light is blocked due to the moisture absorbent, so there may be a problem that it is difficult for the photocurable resin to have an excellent gel fraction and elastic part (EP) value while satisfying a sufficient degree of curing. Therefore, the present application can solve the above problems by using an encapsulation resin that can be cured by heat.

[0077] In addition, as described below, the encapsulation layer of the present application may further include a bright spot inhibitor, and the weight ratio of the bright spot inhibitor to the moisture absorbent may be in the range of 0.05 to 0.8 or 0.1 to 0.7. In the present application, the bright spot inhibitor is dispersed in the film to prevent bright spots. However, in consideration of the moisture barrier property (which is the original function of the encapsulation film) and the reliability of the components, the bright spot inhibitor added to prevent bright spots may be included in a specific content ratio with the moisture absorbent.

[0078] In one embodiment of the present application, the encapsulation layer may further include a bright spot inhibitor. The adsorption energy of the bright spot inhibitor for outgassing calculated by an approximate method of density functional theory may be 0 eV or less. The lower limit of the adsorption energy is not particularly limited, but may be -20 eV. The type of outgassing is not particularly limited, but may include oxygen, H atoms, H2 molecules, and / or NH3. Since the encapsulation layer of the present application includes a bright spot inhibitor, it can prevent bright spots caused by outgassing generated in the organic electronic device. In addition, the encapsulation film of the present application includes a bright spot inhibitor in the second layer on the surface opposite to the element attachment surface facing the organic electronic element when encapsulating in the first layer, so that damage to the organic electronic element due to stress concentration caused by the bright spot inhibitor can be prevented. From this perspective, based on the mass of all the bright spot inhibitors in the encapsulation film, the first layer may include 15% or less of the bright spot inhibitor or may not include the bright spot inhibitor. In addition, based on the mass of all the bright spot inhibitors in the encapsulation film, the layer that does not contact the organic electronic element except the first layer may include 85% or more of the bright spot inhibitor. That is, in the present application, when encapsulating the element, other encapsulation layers that do not contact the organic electronic element may include a relatively large amount of bright spot inhibitor compared to the first layer facing the organic electronic element, so that physical damage to the element can be prevented while realizing the moisture barrier property and bright spot prevention property of the film.

[0079] In one example of the present application, the adsorption energy between the bright point inhibitor and the atom or molecule causing the bright point can be calculated by electronic structure calculations based on density functional theory. The above calculations can be performed by methods known in the art. For example, in the present application, on the two-dimensional flat plate structure where the most closely packed filling surface of the bright point inhibitor with a crystal structure is exposed on the surface, and then structural optimization is performed. After structural optimization of the structure in which the molecule causing the bright point is adsorbed on the surface in the vacuum state, the value obtained by subtracting the total energy of the molecule causing the bright point from the total energy difference between the two systems is defined as the adsorption energy. For the total energy calculation of each system, the modified PBE function, which is a function of the GGA (Generalized Gradient Approximation) series, is used as the exchange-correlation to simulate the interaction between electrons and electrons. The cutoff value of the electron kinetic energy used is 500 eV, and only the gamma point corresponding to the origin of the reciprocal space is included and calculated. The conjugate gradient method is used to optimize the atomic structure of each system and iterative calculations are performed until the interatomic force is or less. A series of calculations are performed by VASP, a commercially available code.

[0080] There is no limitation on the material of the bright point inhibitor as long as the material has the effect of preventing bright points on the panel of the organic electronic device when the encapsulation film is applied to the organic electronic device (which will be described in detail below). For example, the bright point inhibitor can be a material capable of adsorbing materials exemplified as follows: for example, oxygen, H2 gas, ammonia (NH3) gas, H + , NH 2+ , NHR2 or NH2R exhausted by the inorganic deposition layer of silicon oxide, silicon nitride or silicon oxynitride deposited on the electrode of the organic electronic component. Here, R can be an organic group, for example, it can be exemplified as an alkyl group, an alkenyl group, an alkynyl group, etc., but is not limited thereto.

[0081] In one example, there is no limitation on the material of the bright point inhibitor as long as it meets the above adsorption energy value, and it can be a metal or a non-metal. The bright point inhibitor can include, for example, Li, Ni, Ti, Rb, Be, Mg, Ca, Sr, Ba, Al, Zn, In, Pt, Pd, Fe, Cr, Si, or a combination thereof, can include oxides or nitrides of the materials, and can include alloys of the materials. In one example, the bright point inhibitor can include nickel particles, nickel oxide particles, titanium nitride, iron-titanium alloy particles based on titanium, iron-manganese alloy particles based on manganese, magnesium-nickel alloy particles based on magnesium, rare-earth-based alloy particles, zeolite particles, silica particles, carbon nanotubes, graphite, aluminophosphate molecular sieve particles or mesoporous silica particles. Relative to 100 parts by weight of the resin component in the encapsulation layer, the bright point inhibitor can be included in an amount of 5 parts by weight to 100 parts by weight, 6 parts by weight to 90 parts by weight, 7 parts by weight to 80 parts by weight, 8 parts by weight to 70 parts by weight, 9 parts by weight to 60 parts by weight, 10 parts by weight to 50 parts by weight, 12 parts by weight to 30 parts by weight, or 13 parts by weight to 20 parts by weight. In this specification, the term resin component can mean the above encapsulation resin and can generally refer to all other resin components that can be included in the encapsulation layer in addition to the encapsulation resin. For example, the resin component can include a tackifier to be described below. Through the above composition formula, compared with the prior art, the present application can increase the content of the bright point inhibitor and can achieve a high curing rate even when a large amount of the bright point inhibitor is included, thereby improving the adhesion and heat resistance durability of the film while preventing bright points. In addition, the particle diameter of the bright point inhibitor can be in the range 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 analyzed according to the D50 particle size. By including the bright point inhibitor, the present application can effectively adsorb hydrogen generated in the organic electronic device while achieving the moisture barrier property and durability reliability of the encapsulation film at the same time.

[0082] In addition, in the present application, as a result of the particle size analysis of the bright point inhibitor as a sample filtered through 300-mesh nylon after dissolving the encapsulation layer in an organic solvent, the ratio of the average particle diameter according to D50 to the average particle diameter 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. In addition, in the present application, in the particle size analysis result of the moisture absorbent, as the particle size analysis result of the moisture absorbent of the sample filtered through 300-mesh nylon after dissolving the encapsulation layer in an organic solvent, 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. The type of the organic solvent is not particularly limited, but can be, for example, toluene, and the sample can be a sample measured for a sample cut into, for example, 1.5 cm × 1.5 cm. In addition, in the present specification, the unit mesh can be the unit of the US ASTM standard. By controlling the particle size distribution, the present application can prevent the reduction of moisture barrier reliability caused by the reduction of size stability at high temperature, thereby achieving the long-term durability reliability of the organic electronic device.

[0083] In one example, the ratio of the particle diameter of the bright point inhibitor to the particle diameter of the moisture absorbent can be 2.0 or less. The particle diameter ratio can be analyzed according to the D50 particle size. The lower limit of the particle diameter ratio can be 0.3, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1 or more, 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 purpose of the present application is to block moisture from the outside by preparing an encapsulation film from a thermosetting resin composition. In order to solve another technical problem of hydrogen adsorption, a bright point inhibitor is newly introduced, but there is a technical problem that it is not easy to maintain the initial moisture barrier effect when the bright point inhibitor is included. The present application achieves excellent bright point prevention performance while maintaining the initial moisture barrier effect by adjusting the particle diameter ratio of the moisture absorbent and the bright point inhibitor and / or the above-mentioned particle size distribution.

[0084] The encapsulation layer may also contain a tackifier. The tackifier may be a compound having a softening point of 70 °C or higher. 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 limitation on the 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, and 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 it may be a bicyclic or tricyclic compound. The tackifier may also be an olefin-based polymer, and the polymer may be a homopolymer or a copolymer.

[0085] In addition, the tackifier may be a hydrogenated compound. The hydrogenated compound may be a partially or fully hydrogenated compound. Such a tackifier may have excellent moisture barrier properties and external stress relaxation properties, while having good compatibility with other components in the thermosetting resin composition. Specific examples of the tackifier may include hydrogenated terpene-based resins, hydrogenated ester-based resins, or hydrogenated dicyclopentadiene-based resins, etc. The weight-average molecular weight of the tackifier may be in the range of 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 may be appropriately adjusted as needed. For example, relative to 100 parts by weight of the encapsulation resin, the content of the tackifier may be included in a ratio 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. By using a specific tackifier, the present application can provide an encapsulation film having excellent moisture barrier properties and external stress relaxation properties.

[0086] In addition, in one embodiment of the present application, the storage modulus of the encapsulation layer at 85 °C may be 110,000 Pa or greater. As an example, the lower limit of the storage modulus at 85 °C may be 120,000 Pa or greater, 121,000 Pa or greater, 122,000 Pa or greater, 125,000 Pa or greater, or 130,000 Pa or greater, and there is no limitation on the lower limit, but it may be 200,000 Pa or smaller.

[0087] The encapsulation layer of the present application maintains the storage modulus at high temperatures within the above range, so that even when the encapsulation layer is applied to the final product, it has the advantages of small deformation and high dimensional stability, and excellent viscoelasticity and durability can be achieved. When the storage modulus of the encapsulation layer is outside the above range, the encapsulation layer deforms according to the temperature, whereby the reliability of the product may deteriorate and the durability may weaken. In addition, when the encapsulation film is applied to the final product, permanent deformation occurs, making it difficult to achieve flexible physical properties.

[0088] In one embodiment of the present application, the encapsulation film may be formed of a single-layer encapsulation layer or a multi-layer encapsulation layer. The encapsulation film may be applied to, for example, seal or encapsulate an organic electronic device such as an OLED.

[0089] When formed as a multi-layer encapsulation layer, the encapsulation layer may include a first layer facing the component when encapsulating the organic electronic component, and a second layer located on the surface of the first layer opposite to the surface facing the component. In one embodiment, as described above Figure 2 (a) shows that the encapsulation film includes two or more encapsulation layers, where the encapsulation layer may include a first layer 2 facing the organic electronic component during encapsulation and a second layer 4 not facing the organic electronic component.

[0090] As described above, when two or more encapsulation layers are included, the composition of each layer of the encapsulation layer may be the same or different. The encapsulation layer may be a pressure-sensitive adhesive layer or an adhesive layer.

[0091] As Figure 2 (a) shows, the encapsulation layers 2, 4 may include a first layer 2 and a second layer 4, and the second layer 4 of the encapsulation layer may contain a bright point inhibitor 3. In addition, as in Figure 2 (b), the second layer 4 may simultaneously contain a bright point inhibitor 3 and a moisture absorbent 5. However, when the encapsulation film is applied to an organic electronic component, the first layer 2, which is the encapsulation layer facing the organic electronic component, may not contain a bright point inhibitor and a moisture absorbent, or even if it contains a bright point inhibitor and a moisture absorbent, it may only contain a small amount of 15% or less, or 5% or less based on the total weight of the bright point inhibitor and the moisture absorbent.

[0092] In one embodiment of the present application, the encapsulation film may include a metal layer formed on the encapsulation layer. The thermal conductivity of the metal layer of the present application may 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 limitation on the upper limit of the thermal conductivity, which may be 800 W / m·K or less. By having such a high thermal conductivity, the heat generated at the bonding interface during the bonding process of the metal layer can be released more quickly. In addition, the heat accumulated during the operation of the organic electronic device is rapidly released due to the high thermal conductivity, whereby the temperature of the organic electronic device itself can be kept low, and the occurrence of cracks and defects is reduced. The thermal conductivity can be measured at any temperature within the temperature range of 15°C to 30°C.

[0093] Here, the term "thermal conductivity" represents the degree of the ability of a material to transfer heat by conduction, and the unit can be expressed by W / m·K. This unit represents the degree of heat transfer of a material at the same temperature and distance, which means the heat unit (watt) relative to the distance unit (meter) and the temperature unit (kelvin).

[0094] In one example, the metal layer of the encapsulation film can be transparent or opaque. The thickness of the metal layer can be in the range of 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, the present application can provide a thin film encapsulation film while achieving a sufficient heat release effect. The metal layer can be a thin metal foil or a polymer base layer deposited with a metal. The metal layer is not particularly limited as long as it is a material that satisfies the above thermal conductivity and contains a metal. The metal layer can include any one of a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, a metal borate oxide, and combinations thereof. For example, the metal layer can include an alloy in which one or more metal elements or non-metal elements are added to a metal, and can include, for example, stainless steel (SUS). In addition, in one example, the metal layer can include 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 the present application, the metal layer can be deposited by reactive sputtering.

[0095] Conventionally, an invar alloy is usually used as the encapsulation film, but the invar alloy has the disadvantages of high price, low thermal conductivity, and poor cutting characteristics. The present application provides an encapsulation film that prevents bright spots from occurring in an organic electronic device, has excellent heat release characteristics, and achieves processing convenience due to magnetism without using an invar alloy as the metal layer.

[0096] In one example, the encapsulation film of the present application can further include a base film or a release film (hereinafter, may be referred to as the "first film"), which can have a structure in which an encapsulation layer is formed on the base film or the release film. In addition, the structure can further include a base film, a protective film, or a release film (hereinafter, may be referred to as the "second film") formed on the metal layer.

[0097] There is no particular limitation on the specific type of the first film that can be used in the present application. In the present application, for example, a general polymer film in this field can be used as the first film. In the present application, for example, as the base film or the release film, a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polyvinyl chloride 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, etc. can be used. In addition, a suitable release treatment can be performed on one or both sides of the base film or the release film in the present application. As an example of the release agent used in the release treatment of the base film, an alkyd series, a silicone series, a fluorine series, an unsaturated ester series, a polyolefin series, or a wax series, etc. can be used. Among them, in terms of heat resistance, it is preferable to use a release agent of the alkyd series, the silicone series, or the fluorine series, but it is not limited thereto.

[0098] In the present application, the thickness of the above-mentioned base film or release film (the first film) is not particularly limited, and it can be appropriately selected according to the application to which it is applied. For example, in the present application, the thickness of the first film can be 10 μm to 500 μm, preferably about 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, and if the thickness exceeds 500 μm, the economic efficiency is low.

[0099] <Method for producing an encapsulation film>

[0100] In another example, the present application provides a method for producing an encapsulation film.

[0101] The production method may include a step (S10) of producing an encapsulation resin containing an olefin-based resin having a thermosetting functional group by using a thermosetting resin composition containing a peroxide (α), an acidic solution (β), and an olefin-based resin (γ). At this time, the peroxide (α), the acidic solution (β), and the olefin-based resin (γ) can be introduced and reacted simultaneously, or can be introduced successively.

[0102] In one embodiment of the present application, the thermosetting resin composition may contain a peroxide (α) and an acidic solution (β) at a weight ratio (α / β) that satisfies a range of 200 or less. As an example, the upper limit of the weight ratio (α / β) of the peroxide (α) to the acidic solution (β) may be 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 120 or less, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, or 20 or less, and the lower limit is not particularly limited, but may be 5 or greater, 10 or greater, or 15 or greater.

[0103] Furthermore, the thermosetting resin composition of the present application may contain the peroxide (α) in an amount of 1.2 parts by weight or more relative to 100 parts by weight of the olefin-based resin (γ). As an example, the amount of the peroxide (α) relative to 100 parts by weight of the olefin-based resin (γ) may be 1.25 parts by weight or more, 1.3 parts by weight or more, 1.35 parts by weight or more, 1.4 parts by weight or more, 1.45 parts by weight or more, or 1.5 parts by weight or more, and the lower limit may be 10 parts by weight or less, 7 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, or 3 parts by weight or less.

[0104] In one embodiment, it may include a step (S11) of reacting the olefin-based resin (γ) with the peroxide (α). At this time, the reaction can be carried out by dissolving the olefin-based resin (γ) in a non-polar solvent and then introducing the peroxide (α) therein. The non-polar solvent is not limited as long as it can dissolve the olefin-based resin (γ), but as an example, it may be toluene.

[0105] When introduced, the peroxide (α) may satisfy 1.2 parts by weight or more relative to 100 parts by weight of the olefin-based resin (γ). Specifically, the peroxide (α) may be introduced in an amount of 1.25 parts by weight or more, 1.3 parts by weight or more, 1.35 parts by weight or more, 1.4 parts by weight or more, 1.45 parts by weight or more, or 1.5 parts by weight or more relative to 100 parts by weight of the olefin-based resin (γ), and the lower limit may be 10 parts by weight or less, 7 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, or 3 parts by weight or less.

[0106] In addition, the step of reacting the olefin-based resin (γ) with the peroxide (α) can be carried out at room temperature for 6 to 40 hours, and specifically, the reaction time can be 7 hours or longer, 8 hours or longer, 9 hours or longer, 10 hours or longer, 11 hours or longer, 12 hours or longer, 15 hours or longer, or 20 hours or longer, and can be 35 hours or shorter, 30 hours or shorter, or 25 hours or shorter. Here, room temperature means about 18°C to 35°C, and as an example, it can be 24°C to 33°C.

[0107] Next, it can include the step (S12) of introducing an acidic solution (β) to react the mixture at room temperature into the reaction product of the olefin-based resin (γ) and the peroxide (α). At this time, the peroxide (α) and the acidic solution (β) can be introduced at a weight ratio (α / β) that satisfies a range of 200 or less. As an example, the upper limit of the weight ratio (α / β) of the peroxide (α) to the acidic solution (β) can be 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 120 or less, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, or 20 or less, and its lower limit is not particularly limited, but can be 5 or greater, 10 or greater, or 15 or greater.

[0108] It can include the step (S20) of mixing and reacting the obtained encapsulation resin and the curing agent to form an encapsulation layer. In addition, if necessary, it can also contain a moisture absorbent, a reaction promoter, a curing retarder, an inorganic filler, etc.

[0109] <Organic Electronic Device and Method for Manufacturing the Same>

[0110] In another example, the present application provides an organic electronic device.

[0111] As Figure 3 shown, the organic electronic device can include: a substrate 21; an organic electronic element 22 formed on the substrate 21; and an encapsulation film 10 containing a thermosetting resin composition for encapsulating the organic electronic element 22. Specifically, the encapsulation film including the encapsulation layer that is a cured product of the thermosetting resin composition can encapsulate the organic electronic element 22, and the encapsulation film can encapsulate the top surface of the organic electronic element formed on the substrate, for example, all the upper and side surfaces. In addition, an organic electronic device can be formed by sealing the organic electronic device such that the encapsulation layer or the encapsulation film contacts the top surface of the organic electronic element formed on the substrate.

[0112] In one embodiment of the present 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 and the organic layer on the second electrode 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.

[0113] Here, the organic electronic component may be, for example, an organic light-emitting element.

[0114] The passivation film may include an inorganic film and an organic film. In one embodiment, the inorganic film may be a metal oxide or nitride of one or more selected from Al, Zr, Ti, Hf, Ta, In, Sn, Zn, and Si. The thickness of the inorganic film may 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 the present application may be an inorganic material not containing a dopant, or may be an inorganic material containing a dopant. The dopant that can be doped may 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 these elements, but is not limited thereto. The organic film is different from the organic layer including at least the light-emitting layer in that it does not include a light-emitting layer and may be an organic deposited layer containing an epoxy compound.

[0115] The inorganic film or the organic film may be formed by chemical vapor deposition (CVD). For example, as the inorganic film, silicon nitride (SiNx) may be used. In one example, the silicon nitride (SiNx) used as the inorganic film may be deposited to a thickness of from 0.01 μm to 50 μm. In one example, the thickness of the organic film may be in the range of 2 μm to 20 μm, 2.5 μm to 15 μm, or 2.8 μm to 9 μm.

[0116] In another example, the present application provides a method for manufacturing an organic electronic device. The manufacturing method may include the step of applying an encapsulation film containing a thermosetting resin composition to a substrate on which an organic electronic component is formed to cover the organic electronic component. In addition, the manufacturing method may include the step of curing the encapsulation film. The curing step of the encapsulation film may mean the curing of the encapsulation layer, which may be carried out before or after the encapsulation film covers the organic electronic component.

[0117] Specifically, an organic electronic component can be formed as follows: a transparent electrode is formed on a glass or polymer film used as a substrate by vacuum evaporation or sputtering, a light-emitting organic material layer composed of, for example, a hole transport layer, a light-emitting layer, and an electron transport layer is formed on the transparent electrode, and then an electrode layer is further formed on the light-emitting organic material layer. Subsequently, a packaging layer of a packaging film is placed to cover the top surface of the organic electronic component of the substrate that has undergone the above process.

[0118] Advantageous Effects

[0119] As described above, the packaging layer according to the present application can achieve excellent reliability under high-temperature conditions and can achieve an appropriate storage elastic modulus at high temperature by controlling the elastic part within a specific range, and has excellent moisture barrier properties by satisfying the gel fraction or elastic part within a specific range. At the same time, by minimizing the concentration of chloride residues to inhibit the occurrence of dark spots appearing on the organic electronic component, the durability can be improved.

[0120] Therefore, a structure capable of blocking the inflow of moisture or oxygen from the outside into the organic electronic device can be formed, and a packaging film capable of achieving the heat resistance and durability of the organic electronic device under harsh conditions such as high temperature can be provided.

[0121] However, the effects of the present invention are not limited to the above effects, and those skilled in the art will clearly understand other effects not mentioned from the following description. Description of the Drawings

[0122] Figure 1 and Figure 2 is a cross-sectional view showing a packaging film according to an example of the present application.

[0123] Figure 3 is a cross-sectional view showing an organic electronic device according to an example of the present application. Detailed Description of the Invention

[0124] Hereinafter, the present invention will be described in more detail by way of 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 following examples.

[0125] <Encapsulation Resin>

[0126] Preparation Example 1

[0127] Isobutene-isoprene rubber (IIR, Cenway IIR-532) with a weight average molecular weight of 570,000 g / mol was prepared and dissolved in toluene at about 20%.

[0128] In a 2 L reactor in which nitrogen is refluxed and a cooling device is installed for easy temperature control, 3 parts by weight of meta-chloroperoxybenzoic acid (mCPBA) is introduced therein with respect to 100 parts by weight of isobutene-isoprene rubber, and then stirred at 30 °C for 8 hours to carry out an epoxidation reaction.

[0129] Subsequently, an aqueous hydrochloric acid solution prepared by dissolving 0.12 parts by weight of hydrochloric acid (HCl) with respect to 100 parts by weight of isobutene-isoprene rubber in 1 part by weight of distilled water is introduced therein, stirred at 30 °C for 1 hour, and then heated to 90 °C and stirred for 1 hour. Thus, isobutene-isoprene rubber with hydroxyl groups introduced (IIR-OH IR) having a solid content of 26% and a weight-average molecular weight (Mw) of 580,000 g / mol as an encapsulating resin was prepared, in which hydroxyl groups (thermosetting functional groups) were grafted to the isoprene units of the main chain.

[0130] Preparation Examples 2 to 12

[0131] Isobutene-isoprene rubber with hydroxyl groups introduced (IIR-OH IR) as an encapsulating resin was prepared in the same manner as in Preparation Example 1, except for the parts by weight of meta-chloroperoxybenzoic acid (mCPBA), the parts by weight of hydrochloric acid (HCl), the epoxidation reaction time, and the weight-average molecular weight shown in Table 1 below.

[0132] Comparative Preparation Examples 1 to 5

[0133] Isobutene-isoprene rubber with hydroxyl groups introduced (IIR-OH IR) as an encapsulating resin was prepared in the same manner as in Preparation Example 1, except for the parts by weight of meta-chloroperoxybenzoic acid (mCPBA), the parts by weight of hydrochloric acid (HCl), the epoxidation reaction time, and the weight-average molecular weight shown in Table 1 below.

[0134] Table 1 below summarizes the contents of each reactant according to the preparation examples and comparative preparation examples, which shows the parts by weight of meta-chloroperoxybenzoic acid (mCPBA) with respect to 100 parts by weight of isobutene-isoprene rubber (IIR) and the parts by weight of hydrochloric acid (HCl) introduced to form an aqueous hydrochloric acid solution, the epoxidation reaction time, and the weight-average molecular weight of the isobutene-isoprene rubber with hydroxyl groups introduced obtained from the preparation examples and comparative preparation examples.

[0135] [Table 1]

[0136]

[0137] <Encapsulation layer>

[0138] Example 1

[0139] With respect to 100 parts by weight of the hydroxyl group-introduced isobutene-isoprene rubber obtained according to Preparation Example 1 of the encapsulating resin, 0.81 part by weight of an isocyanate-based curing agent (Asahi Kasei, Duranate TM TKA-100), 0.7 part by weight of a tin catalyst (DBTDL) as a reaction accelerator, and 3.1 parts by weight of acetylacetone (Sigma-Aldrich) as a curing retarder were introduced, and a calcium oxide (CaO) dispersion was further mixed so that the amount of calcium oxide (CaO) as a moisture absorbent was 110 parts by weight, and the solid content was adjusted to 14% by weight with toluene to prepare a thermosetting resin composition.

[0140] The thermosetting resin composition was applied to the release surface of a release PET and dried in an oven at 130 °C for 3 minutes and 30 seconds to prepare an encapsulating layer with a thickness of 40 μm.

[0141] Examples 2 to 12

[0142] An encapsulating layer was prepared in the same manner as in Example 1, except that the parts by weight of the curing agent shown in Table 2 below for each hydroxyl group-introduced isobutene-isoprene rubber obtained according to Preparation Examples 2 to 12 were used.

[0143] Comparative Examples 1 to 5

[0144] An encapsulating layer was prepared in the same manner as in Example 1, except that the parts by weight of the curing agent shown in Table 2 below for each hydroxyl group-introduced isobutene-isoprene rubber obtained according to Comparative Preparation Examples 1 to 5 were used.

[0145] Table 2 below shows the parts by weight of the curing agent added in Examples 2 to 12 and Comparative Examples 1 to 5 with respect to 100 parts by weight of each hydroxyl group-introduced isobutene-isoprene rubber obtained according to Preparation Examples 1 to 12 and Comparative Preparation Examples 1 to 5.

[0146] [Table 2]

[0147] Curing agent Preparation Example 1 0.81 Preparation Example 2 0.81 Preparation Example 3 2.43 Preparation Example 4 0.81 Preparation Example 5 2.43 Preparation Example 6 0.81 Preparation Example 7 0.81 Preparation Example 8 2.43 Preparation Example 9 0.81 Preparation Example 10 0.81 Preparation Example 11 0.81 Preparation Example 12 2.43 Comparative Preparation Example 1 0.81 Comparative Preparation Example 2 0.81 Comparative Preparation Example 3 0.81 Comparative Preparation Example 4 0.81 Comparative Preparation Example 5 0

[0148] Comparative Example 6

[0149] To butyl rubber (Cenway IIR-532) as an encapsulating resin, hydrocarbon resin (SU-525) as a tackifier is mixed at a weight ratio of 53:47, and 15 parts by weight of a bifunctional acrylate (TCDDA, tricyclodecane dimethanol diacrylate) and 3 parts by weight of a Ni dispersion as a bright point inhibitor are mixed relative to 100 parts by weight of the butyl rubber and the tackifier. 2,2-Dimethoxy-1,2-diphenyleth-1-one (Irgacure 651, Ciba) is introduced therein in an amount of 0.2 parts by weight relative to the bifunctional acrylate, and a calcium oxide (CaO) dispersion is additionally mixed such that based on 100 parts by weight in total of the butyl rubber, the tackifier, the bifunctional acrylate and the radical initiator, the amount of calcium oxide (CaO) as a moisture absorbent is 75 parts by weight, and the mixture is diluted with toluene such that the solid content is 36 wt%, thereby preparing an encapsulating layer solution.

[0150] The encapsulating layer solution is applied to the release surface of the release PET and dried in a dryer at 130 °C for 3 minutes to form an encapsulating layer with a thickness of 40 μm, and then irradiated with light energy of 1.5 J / cm 2 of UV-A to prepare a photocured product.

[0151] Experimental Example 1 - Concentration of chloride ion residues

[0152] 0.1 g of each encapsulating layer prepared in the Examples and Comparative Examples is prepared, and the concentration of chloride ion residues is measured by combustion ion chromatography (C-IC).

[0153] The measurement is carried out after the equipment is stabilized, and the measurement is carried out using IC (ICS-5000DP of Dionex) and AQF (AQF-2100H of Mitsubishi), wherein the standard material and the sample are set to the following IC conditions for quantitative analysis.

[0154] - Combustion temperature: inlet temperature 900 °C, outlet temperature 1,000 °C

[0155] - Gas flow rate: Ag gas 200 mL / min, O2 gas 400 mL / min

[0156] - Main column: Dionex IonPac AS18 analysis (4 mm × 250 mm)

[0157] - Guard column: Dionex IonPac AG18 guard column (4 mm × 50 mm)

[0158] - Eluent: 30.5 mM KOH

[0159] - Eluent flow rate: 1 mL / min

[0160] - Injection volume: 20 μL

[0161] - Detector: Suppressed conductivity detector

[0162] - SRS current: 76 mA

[0163] - Isocratic / gradient condition: Isocratic

[0164] Experimental Example 2 - Elastic part test

[0165] After synthesizing each encapsulation layer prepared in the examples and comparative examples into a film sample with a size of 20 cm × 30 cm and a thickness of 600 μm, using ARES (Advanced Rheology Expansion System, ARES - G2 of TA), a normal force of about 150 gf was applied at 85 °C in stress relaxation (relaxation test) mode using parallel plates to apply 30% strain to the sample, and then the maximum stress value was measured several times at 1 - second intervals, thereby measuring the average value σ1. In addition, after maintaining the state of applying the strain to the sample for 180 seconds, the stress value σ2 measured at 180 seconds was measured separately, and the elastic part (Ep, unit: %) was calculated according to the following general formula 1.

[0166] [General formula 1]

[0167] Ep (%) = 100 × σ2 / σ1

[0168] In the above measurement, it must be noted that there are no bubbles when loading the pressure - sensitive adhesive film between the plates.

[0169] Experimental Example 3 - Gel fraction test

[0170] For each encapsulation layer of the examples and comparative examples, 0.3 g to 0.4 g of the encapsulation layer (initial weight: A) was collected, and the encapsulation layer was immersed in 70 g of toluene at 60 °C for 3 hours. Thereafter, the gel part was filtered through a 200 - mesh metal screen (weight of the metal screen: M), and then dried in an oven at 125 °C for 1 hour. After measuring the combined weight (G) of the gel and the metal screen, the gel fraction (unit: %) was calculated according to the dry mass (B = G - M) of the insoluble content of the encapsulation layer that did not pass through the screen according to the following general formula 2.

[0171] [General formula 2]

[0172] Gel content (%) = (B / A) × 100

[0173] Experimental Example 4 - Measurement of storage elastic modulus

[0174] For each encapsulation layer of the above Examples and Comparative Examples, the dynamic viscoelasticity was measured according to JIS K7244-4 (frequency 1 Hz, heating rate 2 °C / min), and the storage elastic modulus at 85 °C in the shear mode was calculated (unit: Pa).

[0175] Experimental Example 5 - High-temperature Reliability Evaluation

[0176] For each encapsulation layer prepared in the Examples and Comparative Examples, a metal layer was laminated on top to prepare a film sample. The film samples were bonded together on a glass substrate (0.5T) and stored at 85 °C and 85% relative humidity for 900 hours, and whether the encapsulation film was lifted or whether bubbles were generated (tilted bubble phenomenon) was evaluated based on the panel warpage on the substrate. In the case where there was no lifting of the film sample or appearance of bubbles, it was classified as O, and in the case where there was lifting or appearance of bubbles, it was classified as X.

[0177] Table 3 below summarizes the experimental results of Experimental Examples 1 to 5.

[0178] [Table 3]

[0179]

[0180] Although the present invention has been described with reference to the above Examples, those skilled in the relevant technical field should understand that various modifications and changes can be made to the present invention without departing from the concept and scope of the present invention described in the appended claims.

[0181] Explanation of Reference Numerals:

[0182] 1: Encapsulation film

[0183] 11: Encapsulation layer

[0184] 13: Metal layer

Claims

1. An encapsulation film, comprising an encapsulation layer containing an encapsulation resin, the encapsulation resin comprising an olefin-based resin having a thermosetting functional group, wherein the encapsulation resin is produced from a thermosetting resin composition comprising a peroxide α, an acidic solution β, and an olefin-based resin γ, the encapsulation resin comprising an olefin-based resin having a thermosetting functional group, the weight ratio α / β of the peroxide α to the acidic solution β satisfies a range of 200 or less, the peroxide α is included in an amount of 1.2 parts by weight or more relative to 100 parts by weight of the olefin-based resin γ, the concentration of chloride ion residues measured by combustion ion chromatography IC of the encapsulation layer is 1,000 ppm or less, and the encapsulation layer has an elastic part Ep of 46% or more calculated by the following general formula 1: [General formula 1] Elastic part Ep = 100% × σ2 / σ1 Among them, σ1 is the stress value at 1 second after applying 30% strain to the specimen, wherein the specimen is prepared by laminating the encapsulation layer to a film having a size of 20 cm × 30 cm and a thickness of 600 μm, and then loaded by applying a normal force of 150 gf to the specimen at 85 °C in stress relaxation mode using parallel plates in a laminated state, and σ2 is the stress value measured after maintaining the state of applying the strain to the specimen for 180 seconds, wherein the encapsulation layer further comprises a curing agent.

2. The encapsulation film according to claim 1, wherein the encapsulation layer has a gel fraction of 70% or more represented by the following general formula 2: [General formula 2] Gel fraction = (B / A) × 100% Among them, A represents the initial mass of the encapsulation layer specimen, and B represents the dry mass of the insoluble content of the encapsulation layer that does not pass through the mesh after immersing the encapsulation layer specimen in 70 g of toluene at 60 °C for 3 hours and then filtering through a 200-mesh screen with a pore size of 200 μm.

3. The encapsulation film according to claim 1, wherein the olefin-based resin γ comprises a copolymer of a diene and an olefin-based compound containing one carbon-carbon double bond.

4. The encapsulation film according to claim 1, wherein the thermosetting functional group includes a hydroxyl group, a carboxyl group, an amino group, or an epoxy group.

5. The encapsulation film according to claim 1, wherein the thermosetting functional group is derived from an unsaturated group in the olefin-based resin γ.

6. The encapsulation film according to claim 1, wherein the weight average molecular weight of the encapsulation resin is 100,000 g / mol to 2,000,000 g / mol.

7. The encapsulation film according to claim 1, wherein the curing agent is included in an amount of 0.1 parts by weight to 10 parts by weight relative to 100 parts by weight of the encapsulation resin.

8. The encapsulation film according to claim 1, wherein the curing agent includes an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an aziridine-based crosslinking agent, a metal chelate-based crosslinking agent, an amine-based crosslinking agent, or an amino resin-based crosslinking agent.

9. The encapsulation film according to claim 1, wherein the encapsulation layer further comprises a moisture absorbent.

10. The encapsulation film according to claim 9, wherein the moisture absorbent is a chemically reactive adsorbent.

11. The encapsulation film according to claim 9, wherein the moisture absorbent is included in a range of 20 parts by weight to 200 parts by weight relative to 100 parts by weight of the encapsulation resin.

12. The encapsulation film according to claim 1, comprising a multi-layer encapsulation layer.

13. A method for producing an encapsulation film, comprising the step of manufacturing an encapsulation resin containing an olefin-based resin having a thermosetting functional group using a thermosetting resin composition containing peroxide α, acidic solution β, and olefin-based resin γ, and the step of mixing and reacting the encapsulation resin and a curing agent to form an encapsulation layer, wherein the weight ratio α / β of the peroxide α to the acidic solution β satisfies a range of 200 or less, and the peroxide α is included in an amount of 1.2 parts by weight or more relative to 100 parts by weight of the olefin-based resin γ.

14. The method for producing an encapsulation film according to claim 13, wherein the step of reacting the olefin-based resin γ with the peroxide α is carried out for 6 hours to 40 hours.

15. An organic electronic device, comprising a substrate, an organic electronic element formed on the substrate, and the encapsulation film according to claim 1 for encapsulating the top surface of the organic electronic element.

16. A method for manufacturing an organic electronic device, comprising the step of applying the encapsulation 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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