KR20210152329A - Encapsulation film - Google Patents

Abstract

The present application relates to an encapsulation film and an organic electronic device including the same, and provides an encapsulation film that can form a structure capable of blocking moisture or oxygen entering an organic electronic device from the outside and can absorb and disperse the stress caused by bending of a panel of the organic electronic device well, thereby having excellent reliability. The encapsulation film of the present invention includes an encapsulation layer containing an encapsulation resin including an olefin-based resin having a thermosetting functional group and a metal layer having a CTE 1.5 or more times the CTE of glass.

Description

Encapsulation Film {ENCAPSULATION FILM}

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

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

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

In the commercialization and expansion of use of OLED, the biggest problem that the prior art tried to solve is the durability problem. Organic materials and metal electrodes included in OLED are very easily oxidized by external factors such as moisture. Therefore, products including OLEDs are highly sensitive to environmental factors. In addition, in general, when heat is applied to the encapsulation film to form the encapsulation layer, the panel of the organic electronic device may warp due to the difference in the coefficient of thermal expansion (CTE) between the substrate of the organic electronic device and the metal layer in the encapsulation film. .

Therefore, it is required to develop an encapsulation film capable of implementing heat resistance and durability at high temperatures while effectively blocking the penetration of oxygen or moisture from the outside into organic electronic devices such as OLEDs.

The purpose of the present application is to provide a highly reliable encapsulation film that can form a structure that can block moisture or oxygen flowing into the organic electronic device from the outside, and absorb and disperse the stress caused by the bending of the panel of the organic electronic device. do.

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

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

The organic electronic device encapsulation film of the present application may include an encapsulation layer and a metal layer. The encapsulation layer may seal the entire surface of the organic electronic device formed on the substrate, and the metal layer has a CTE of 1.5 times or more compared to the CTE of glass.

The encapsulation layer for encapsulating the entire surface of the organic electronic device is disposed between the substrate on which the device is formed and the metal layer. However, the substrate and the metal layer have different materials from each other, and thus also have different thermal expansion characteristics. When the encapsulation film or the organic electronic device is present at a high temperature for a certain time (if present in the process), a dimensional mismatch occurs according to the difference in the degree of expansion between the substrate and the metal layer, and at this time, between the substrate and the metal layer In the encapsulation layer, some peeling, gaps, or voids occur depending on the stress, so that external oxygen or moisture easily penetrates.

The present application includes an encapsulation resin comprising an olefin-based resin having a thermosetting functional group, and an encapsulation layer having an elastic portion (Ep, Elastic Portion) of 40% or more calculated by the following general formula 1, including a substrate and a metal layer at a high temperature The encapsulation layer in between absorbs or disperses the stress well to prevent gaps or voids on the side of the encapsulation layer, thereby effectively preventing foreign substances from penetrating from the outside while having excellent moisture barrier properties.

[General formula 1]

Ep (unit:%) = 100 Х σ2/σ1

In the general formula 1, σ1 is a parallel plate in a stress relaxation test mode with ARES (Advanced Rheometric Expansion System) in a state of lamination with a film having a thickness of 600 μm and is approximately at 85° C. The specimen is loaded by applying a normal force of 150 gf, the stress value 1 second after 30% strain is applied to the film, and σ2 is the state in which the strain is applied to the film is maintained for 180 seconds This is the stress value measured after

In an embodiment of the present application, the olefin-based resin may include a polymer derived from an olefin-based monomer. In one example, the polymer derived from the olefinic monomer may include, for example, an isoolefin monomer or a multiolefin monomer, and may be prepared by polymerization of the monomers.

Isoolefins include, for example, isobutylene, 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 can be exemplified. The multiolefin may be exemplified by, for example, isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-fulvene, 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 the isoolefin and/or multi-olefin, for example, polybutadiene, polyisoprene, polyisobutylene or butyl rubber may be exemplified.

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

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

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

The olefin-based resin may have at least one double bond in the main chain of the resin after copolymerization in that the diene compound is copolymerized together. The double bond may be used to introduce a thermosetting functional group to be described later.

In one example, the olefin-based resin may include a thermosetting functional group, and the thermosetting functional group may be derived from an unsaturated group in the olefin-based resin. In the present specification, derived from an unsaturated group may mean that the thermosetting functional group is introduced into an unsaturated group such as a double bond present in the main chain of the olefin-based resin.

As used herein, the thermosetting functional group refers to a functional group capable of cross-linking polymerization with each other by heating at a predetermined temperature or higher to form a cured product. The thermosetting functional group may be at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and an epoxy group. The number of said thermosetting functional groups may be one, and two or more types may be sufficient as them.

The encapsulating resin may have a weight average molecular weight (Mw) to the extent that the encapsulating composition can be molded into a film shape. For example, the resin may have a weight average molecular weight of about 100,000 to 2 million g/mol, 120,000 to 1.5 million g/mol, or 150,000 to 1 million g/mol.

In the above specification, the term "weight average molecular weight" means a value converted to standard polystyrene measured by Gel Permeation Chromatography (GPC), and unless otherwise specified, the unit is g/mol. However, the resin does not necessarily have the above-mentioned weight average molecular weight.

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

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

Such a moisture adsorbent may be controlled to an appropriate size depending on the application. In one example, the average particle diameter of the moisture adsorbent may be controlled to be 100 to 15000 nm, 500 nm to 10000 nm, 800 nm to 8000 nm, 1 μm to 7 μm, 2 μm to 5 μm, or 2.5 μm to 4.5 μm. Moisture adsorbent having a size within the above range is easy to store because the reaction rate with water is not too fast, does not damage the element to be encapsulated, does not interfere with the hydrogen adsorption process in relation to the below-described bright spot inhibitor, and effectively Moisture can be removed. In the present specification, the particle diameter may mean an average particle diameter, and may be measured by a known method with a D50 particle size analyzer.

The content of the moisture adsorbent is not particularly limited and may be appropriately selected in consideration of desired barrier properties. The moisture absorbent may be included in an amount 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 based on 100 parts by weight of the encapsulating resin. have. In addition, as will be described later, the encapsulation layer of the present application may further include a brightening agent, and the weight ratio of the brightening agent 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, a bright spot inhibitor is dispersed in the film to prevent bright spot, but the anti bright spot added to prevent bright spot is the original function of the encapsulation film, which is moisture barrier and device reliability. may be included as a percentage.

The encapsulation layer may further include a bright spot inhibitor. The anti-glare agent may have an adsorption energy for outgas of 0 eV or less, calculated by a density functional theory. The lower limit of the adsorption energy is not particularly limited, but may be -20 eV. The type of the outgas is not particularly limited, but may include H atoms, H ₂ molecules, and/or NH ₃ . Since the encapsulation layer of the present application includes the bright spot prevention agent, it is possible to prevent bright spots due to outgas generated in the organic electronic device. In addition, the encapsulation film of the present application contains a bright spot inhibitor in the second layer located on the opposite side of the device attachment surface of the first layer facing the organic electronic device when encapsulating, so that the organic electronic device according to the stress concentration caused by the bright spot inhibitor. damage can be prevented. In view of the above, the first layer may or may not include a brightening agent in an amount of 15% or less based on the mass of the total brightening agent in the encapsulation film. In addition, the layer that is not in contact with the organic electronic device, except for the first layer, may include 85% or more of the brightening agent based on the mass of the total brightening agent in the encapsulation film. That is, in the present application, compared to the first layer facing the organic electronic device when encapsulating the device, the other encapsulation layer not in contact with the organic electronic device may contain a higher content of the bright spot inhibitor, and through this, the moisture barrier and prevention of the bright spot of the film While realizing the characteristics, it is possible to prevent physical damage to the device.

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

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

In one example, the material of the anti-glare agent is not limited as long as it satisfies the above adsorption energy value, and may be a metal or a non-metal. The anti-glare agent may include, for example, Li, Ni, Ti, Rb, Be, Mg, Ca, Sr, Ba, Al, Zn, In, Pt, Pd, Fe, Cr, Si or a combination thereof, It may include an oxide or nitride of the material, and may include an alloy of the material. In one example, the anti-glare agent is nickel particles, nickel oxide particles, titanium nitride, iron-titanium alloy particles, iron-manganese alloy particles, magnesium-nickel magnesium alloy particles, rare earth alloy particles, It may include zeolite particles, silica particles, carbon nanotubes, graphite, aluminophosphate molecular sieve particles, or mesosilica particles. The bright spot inhibitor is 5 to 100 parts by weight, 6 to 90 parts by weight, 7 to 80 parts by weight, 8 to 70 parts by weight, 9 to 60 parts by weight, 10 parts by weight to 50 parts by weight, based on 100 parts by weight of the resin component in the encapsulation layer. , 12 parts by weight to 30 parts by weight, or 13 parts by weight to 20 parts by weight may be included. In the present specification, the term resin component may refer to the aforementioned encapsulation resin, and may collectively refer to all other resin components that may be included in the encapsulation layer in addition to the encapsulation resin. For example, the resin component may include a tackifier to be described later. According to the present application, the content of the anti-blinding agent can be increased compared to the prior art through the above-described compositional formulation, and a high curing rate can be realized even when a large amount of the anti-blinding agent is included. can be improved together. In addition, the particle diameter of the bright spot inhibitor is 10nm to 30㎛, 50nm to 21㎛, 105nm to 18㎛, 110nm to 12㎛, 120nm to 9㎛, 140nm to 4㎛, 150nm to 2㎛, 180nm to 900nm, 230nm to 700nm or in the range of 270 nm to 400 nm. The particle size may be according to D50 particle size analysis. The present application can realize the moisture barrier properties and durability reliability of the encapsulation film while efficiently adsorbing hydrogen generated in the organic electronic device by including the above bright spot inhibitor.

In addition, in the present application, for a sample filtered through 300 mesh nylon after dissolving the encapsulation layer in an organic solvent, as a result of the particle size analysis of the anti-brightening agent, the ratio of the average particle diameter according to D50 to the average particle diameter according to D10 is 2.3 to 3.5 can be within the scope of tomorrow. The lower limit of the ratio may be, for example, 2.4, 2.5, 2.6 or 2.7, and the upper limit may be, for example, 3.4, 3.3, 3.2, 3.1, 3.0, 2.95 or 2.93. In addition, in the particle size analysis result of the moisture adsorbent, for a sample filtered through 300 mesh nylon after dissolving the encapsulation layer in an organic solvent, the particle size analysis result of the moisture absorbent according to D50 for the average particle size according to D10 The ratio of the average particle diameter may be in the range of 2.3 to 3.5. The lower limit of the ratio may be, for example, 2.4, 2.5, 2.6 or 2.7, and the upper limit may be, for example, 3.4, 3.3, 3.2, 3.1, 3.0, 2.95 or 2.93. The type of the organic solvent may be, for example, toluene, and the sample may be, for example, measured with respect to a sample cut to 1.5 cm x 1.5 cm in width. Also, in the present specification, the unit mesh may be a unit of American ASTM standards. According to the present application, by controlling the particle size distribution, it is possible to prevent a bright spot through hydrogen adsorption while implementing moisture barrier properties, thereby realizing long-term durability reliability of an organic electronic device.

In one example, the ratio of the particle diameter of the anti-glare agent to the particle diameter of the moisture adsorbent may be 2.0 or less. The ratio of the particle size may be according to the D50 particle size analysis. The lower limit of the particle size ratio may be 0.3, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1 or more, and the upper limit may 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. can The original purpose of the encapsulation film of the present application is to block moisture from the outside. In order to solve another technical problem of hydrogen adsorption, a brightening agent is newly introduced, however, while the brightening prevention agent is included, the original moisture There were technical problems that made it difficult to maintain the blocking effect. The present application implements excellent anti-glare performance while maintaining the original moisture-blocking effect by controlling the particle size ratio and/or the aforementioned particle size distribution of the moisture adsorbent and the anti-blinding agent.

In one example, the encapsulation layer may further include a tackifier. The tackifier may be, for example, a compound with a softening point of 70°C or higher, and in embodiments, 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 the The upper limit is not particularly limited, but may be 150°C or less, 140°C or less, 130°C or less, 120°C or less, 110°C or less, or 100°C or less. The tackifier may be a compound having a cyclic structure in the molecular structure, and the cyclic structure may have 5 to 15 carbon atoms. The carbon number 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, and the polymer may be a homopolymer or a copolymer.

In addition, the tackifier of the present application may be a hydrogenated compound. The hydrogenated compound may be a partially or fully hydrogenated compound. Such a tackifier may have good compatibility with other components in the encapsulation layer, excellent moisture barrier properties, and may have external stress relaxation properties. Specific examples of the tackifier include a hydrogenated terpene-based resin, a hydrogenated ester-based resin, or a hydrogenated dicyclopentadiene-based resin. The weight average molecular weight of the tackifier may be in the range of about 200 to 5,000 g/mol, 300 to 4,000 g/mol, 400 to 3,000 g/mol, or 500 to 2,000 g/mol. The content of the tackifier may be appropriately adjusted as necessary. For example, the content of the tackifier may be included in a ratio of 15 parts by weight to 200 parts by weight, 20 to 190 parts by weight, 25 parts by weight to 180 parts by weight, or 30 parts by weight to 150 parts by weight based on 100 parts by weight of the encapsulating resin. . The present application can provide an encapsulation film having excellent moisture barrier properties and external stress relaxation properties by using the specific tackifier.

In one example, the encapsulation layer may further include a curing agent. The curing agent is a compound capable of chemical bonding with the thermosetting functional group of the encapsulating resin of the present invention, and an appropriate compound may be selected and used according to the type of the thermosetting functional group.

In the present invention, 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 hardening|curing agents may be used independently and may be used in combination of 2 or more type.

For example, when the thermosetting functional group 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) may be used, and more specifically, toluene diisocyanate ( TDI, toluene diisocyanate), hexamethylene diisocyanate (HDI, hexamethylene diisocyanate), or isophorone diisocyanate (IPDI, isophorone diisocyanate) may be used, but the present invention is not limited thereto.

For example, when the thermosetting functional group is an epoxy group, an amine curing agent, an imidazole curing agent, a phenol curing agent, a phosphorus curing agent, or an acid anhydride curing agent may be used, but the present invention is not limited thereto.

In addition, a curing agent that can be used according to the type of the thermosetting functional group, zinc octoate, iron acetyl acetonate, N,N-dimethyl ethanolamine (N,N-dimethyl ethanolamine), triethylene and diamine (Triethylene diamine), but is not limited thereto.

The content of the curing agent is not particularly limited, but may be included in an amount of about 0.1 to 10 parts by weight based on 100 parts by weight of the encapsulating resin in order to achieve effective thermal curing without impairing the physical properties of the entire encapsulation film.

The thermosetting reaction may be performed at a temperature of about 40° C. to 150° C. for about 3 minutes to 180 minutes, but may be appropriately adjusted according to the purpose and use of the invention, but is not limited thereto.

In one example, the encapsulation layer may further include a curing catalyst to promote the thermosetting reaction. The curing catalyst is a chemical reaction between the curing agent and the thermosetting functional group in the olefin-based resin to rapidly proceed, from the group consisting of a tin catalyst, a bismuth catalyst, a mercury-based catalyst, an amine-based catalyst and combinations thereof It may include a selected one. When the above type of curing catalyst is used, a crosslinking reaction between the curing agent and the thermosetting functional group in the olefin-based resin may proceed rapidly, and curing efficiency of the encapsulation layer may be improved. Specifically, dibutyltindilaurate (DBTDL, dibutyltindilaurate), zinc octoate (Zinc octoate), iron acetyl acetonate (Iron acetyl acetonate), N,N- dimethyl ethanolamine (N,N-dimethyl ethanolamine) and triethylene At least one selected from the group consisting of diamine (Triethylene diamine) may be used. These catalysts may be used alone or in mixture of two or more different types.

In one example, the encapsulation layer may further include a curing retardant. The curing retardant may suppress the reaction from mixing the final encapsulation layer component to the stage before film coating, and suppress excessive viscosity increase of the resin component. The type of the curing retardant is not particularly limited, but for example, β-keto such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, etc. Ester, 2,4-hexanedione, benzoylacetone, etc. can be used, and acetylacetone can be used preferably.

The encapsulation film of the present application may be formed of a single-layer encapsulation layer or a multi-layer encapsulation layer. The encapsulation film may be applied to, for example, encapsulating or encapsulating an organic electronic device such as an OLED.

When formed as a multi-layer encapsulation layer, the encapsulation layer may include a first layer facing the device when encapsulating an organic electronic device and a second layer positioned on a surface opposite to the side of the first layer facing the device. have. In one embodiment, as in (a) of FIG. 2, the encapsulation film includes two or more encapsulation layers, and the encapsulation layer is the first layer 2 facing the organic electronic device and the organic electronic device when encapsulating. It may include a second layer (4) that does not

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 an adhesive layer or an adhesive layer.

As shown in FIG. 2A , the encapsulation layers 2 and 4 may include a first layer 2 and a second layer 4, and a second layer 2 of the encapsulation layers This bright spot inhibitor (3) may be included. In addition, as shown in (b) of FIG. 2 , the second layer 4 may include a bright spot inhibitor 3 and a moisture absorbent 5 together. However, when the encapsulation film is applied on the organic electronic device, the first layer (2), which is the encapsulation layer facing the organic electronic device, does not include the bright spot inhibitor and the moisture absorbent, or even includes the total bright spot inhibitor and moisture absorbent based on the weight. It may contain a small amount of 15% or less, or 5% or less.

In an embodiment of the present application, the encapsulation film may further include a metal layer formed on the encapsulation layer. The metal layer of the present application is 20 W/mK or more, 50 W/mK or more, 60 W/mK or more, 70 W/mK or more, 80 W/mK or more, 90 W/mK or more, 100 W/mK or more, 110 W It may have a thermal conductivity of /mK or more, 120 W/mK or more, 130 W/mK or more, 140 W/mK or more, 150 W/mK or more, 200 W/mK or more, or 210 W/mK or more. The upper limit of the thermal conductivity is not particularly limited, and may be 800 W/mK or less. By having such high thermal conductivity, heat generated at the bonding interface during the metal layer bonding process can be discharged more quickly. In addition, the high thermal conductivity rapidly dissipates heat accumulated during the operation of the organic electronic device to the outside, and accordingly, the temperature of the organic electronic device itself can be kept lower, and cracks and defects are reduced. The thermal conductivity may be measured at any one of a temperature range of 15 °C to 30 °C.

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

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

Conventionally, a nickel-iron alloy (Invar) has been commonly used as an encapsulation film, but the nickel-iron alloy has disadvantages in that it is expensive, has poor thermal conductivity, and has poor cutability. The present application provides an encapsulation film that prevents the occurrence of bright spots in an organic electronic device, has excellent heat dissipation characteristics, and implements process convenience due to magnetism without using the nickel-iron alloy as a metal layer.

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

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

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

The present application also relates to an organic electronic device. As shown in FIG. 3, the organic electronic device includes: a substrate 21; an organic electronic device 22 formed on the substrate 21; and the aforementioned encapsulation film 10 for encapsulating the organic electronic device 22 . The encapsulation film may encapsulate the entire surface, for example, upper and side surfaces, of the organic electronic device formed on the substrate.

The encapsulation film includes an encapsulation layer and a metal layer having a CTE of at least 1.5 times that of glass, and the encapsulation layer includes an encapsulation resin comprising an olefin-based resin having a thermosetting functional group, and is calculated by the following general formula 1 The elastic portion (Ep, Elastic Portion) is more than 40%.

[General formula 1]

Ep (unit:%) = 100 Х σ2/σ1

In the general formula 1, σ1 is a parallel plate in a stress relaxation test mode with ARES (Advanced Rheometric Expansion System) in a state of lamination with a film having a thickness of 600 μm and is approximately at 85° C. The specimen is loaded by applying a normal force of 150 gf, the stress value 1 second after 30% strain is applied to the film, and σ2 is the state in which the strain is applied to the film is maintained for 180 seconds This is the stress value measured after

In addition, the organic electronic device may be formed by sealing the encapsulation layer to contact the entire surface of the organic electronic device formed on the substrate.

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

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

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

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

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

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

The encapsulation film of the present application may be applied to encapsulation or encapsulation of an organic electronic device such as an OLED. The encapsulation film can form a structure capable of blocking moisture or oxygen flowing into the organic electronic device from the outside, and includes an encapsulation layer having a high elasticity at high temperature, thereby improving the lifespan and durability of the organic electronic device.

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

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

production example 1: Preparation of isobutylene-isoprene rubber ( IIR -OH IR 1.78 mol% )

An isobutylene-isoprene rubber, which is a copolymer formed from a monomer mixture containing 1.78 mol% of isoprene and 98.22 mol% of isobutylene, was prepared. In a 630 L reactor in which nitrogen gas was refluxed and a cooling device was installed to facilitate temperature control, 3 parts by weight of peroxide (mCPBA) was added to 100 parts by weight of the isobutylene-isoprene rubber, followed by stirring at 30° C. for 6 hours. .

Then, 3.1 parts by weight of an aqueous hydrochloric acid solution having a 1 N concentration was added based on 100 parts by weight of the rubber, and after stirring at 30° C. for 1 hour, the temperature was raised to 90° C. and stirred for 1 hour. Thereby, a hydroxyl group (thermosetting functional group) was grafted to the isoprene unit of the main chain, the hydroxyl group value was 0.65, and the isobutylene-isoprene rubber (IIR-OH IR) having a weight average molecular weight (Mw) of 500,000 g/mol was prepared. .

Example One

of the encapsulation layer Produce

50:50 parts by weight of a tackifier (Sukorez SU-90, Kolon Industries) was mixed with the isobutylene-isoprene rubber of Preparation Example 1, and isocyanate based on 100 parts by weight of the isobutylene-isoprene rubber and the tackifier 5 parts by weight of a curing agent (Desmodur ^® N3300), 1 part by weight of Tin catalyst (DBTDL) (Sigma-Aldrich) as a curing catalyst, and 5 parts by weight of Acetylacetone (TCI chemicals) as a curing retardant are mixed did In addition, the CaO dispersion was mixed so as to contain 60 parts by weight of CaO as a moisture adsorbent, and the Ni dispersion was mixed so that 10 parts by weight of Ni as an anti-fogging agent, and the toluene solid content was 36% by weight to prepare a sealing composition. The encapsulation composition was applied to the release surface of the release PET and dried in an oven at 130° C. for 3 minutes and 30 seconds to form a second encapsulation layer having a thickness of 40 μm.

After mixing in the same composition except that CaO and Ni dispersion were not added in the second encapsulation layer preparation, an encapsulation composition was prepared so that the toluene solid content was 17 wt%. It was applied to the release surface of the release PET and dried in an oven at 130° C. for 2 minutes and 30 seconds to form a first encapsulation layer with a thickness of 10 μm, and laminated with the second encapsulation layer.

manufacture of encapsulation film

On a previously prepared metal layer (Invar) (CTE 3.4), the release-treated PET attached to the second encapsulation layer is peeled off, and laminated at 70° C. in a roll-to-roll process, and the second layer A sealing film was prepared so as to be in contact with this metal layer.

By cutting the prepared encapsulation film, a film for encapsulating an organic electronic device was prepared.

Example 2

On the previously prepared metal layer (SUS430) (CTE 10.4), the release-treated PET attached to the second encapsulation layer prepared in Example 1 was peeled off, and at 70° C. in a Roll-to-Roll process. By lamination, an encapsulation film was prepared so that the second layer was in contact with the metal layer.

By cutting the prepared encapsulation film, a film for encapsulating an organic electronic device was prepared.

comparative example One

of the encapsulation layer Produce

As an encapsulating resin, a tackifier (Sukorez SU-90, Kolon Industries, Ltd.) was mixed with butyl rubber (BR268, EXXON) in a weight ratio of 50:50, and polyfunctional acrylate (based on 100 parts by weight of butyl rubber and tackifier) HDDA) 5 parts by weight, 60 parts by weight of a CaO dispersion as a moisture adsorbent, and 10 parts by weight of a Ni dispersion as an antifogging agent were mixed. As a radical initiator, Irgacure 819 (BASF) was added in an amount of 1 part by weight relative to the polyfunctional acrylate, and diluted with toluene so as to have a solid content of 36% by weight to prepare a second layer solution.

After mixing in the same composition except that CaO and Ni dispersions were not added in the second encapsulation layer preparation, a first layer solution was prepared so that the toluene solid content was 17 wt%.

The encapsulation layer solution prepared above was applied to the release surface of the release PET separately for the first encapsulation layer and the second encapsulation layer, respectively, and dried at 130° C. in a dryer for 3 minutes, and encapsulation layers having a thickness of 40 μm and 10 μm, respectively. After forming, the two layers were laminated. The first encapsulation layer and the second encapsulation layer were irradiated with light energy ^{of 1 J/cm 2 UV-A.}

manufacture of encapsulation film

On a previously prepared metal layer (Invar) (CTE 3.4), the release-treated PET attached to the second encapsulation layer is peeled off, and laminated at 70° C. in a roll-to-roll process, and the second layer A sealing film was prepared so as to be in contact with this metal layer.

By cutting the prepared encapsulation film, a film for encapsulating an organic electronic device was prepared.

comparative example 2

On the previously prepared metal layer (SUS430) (CTE 10.4), the release-treated PET attached to the second encapsulation layer prepared in Comparative Example 1 was peeled off, and at 70° C. in a Roll-to-Roll process. By lamination, an encapsulation film was prepared so that the second layer was in contact with the metal layer.

By cutting the prepared encapsulation film, a film for encapsulating an organic electronic device was prepared.

Experimental example 1- Elastic Portion

After preparing the film samples of Examples 1 and 2 and Comparative Examples 1 and 2 to a thickness of 600 μm, using ARES (Advanced Rheometric Expansion System, TA ARES-G2), parallel in stress relaxation (relaxation test) mode After applying a normal force of about 150 gf at 85° C. using a parallel plate to apply a strain of 30% to the film sample, the measured maximum stress value σ1 was measured at intervals of 1 second. measured. After maintaining the state in which the deformation was applied to the film sample for 180 seconds, the stress value σ2 measured at 180 seconds was additionally measured and the Elastic Portion (Ep) according to the following general formula 1 was calculated.

[General formula 1]

Ep (unit:%) = 100 Х σ2/σ1

In the above measurement, care should be taken not to have air bubbles when loading the adhesive film between the plates.

Experimental example 2 - heat-resistant, durable

The film samples of Examples 1 and 2 and Comparative Examples 1 and 2 were bonded to a glass substrate (0.5 T, CTE3.7) and stored at 85° C. and 85% relative humidity for 900 hours, and the encapsulation film floated on the substrate. It was evaluated whether or not bubbles were generated (oblique bubble phenomenon). A case in which the film sample floated or no bubble was generated on the substrate was classified as O, and a case in which the film sample was lifted or bubbled was classified as X.

Elastic area (%) Heat resistance and durability test Example 1 59 O Example 2 59 O Comparative Example 1 16 X Comparative Example 2 16 X

1, 10: encapsulation film
2, 4, 11: Encapsulation layer
13: cover substrate
3: bright spot inhibitor
5: Moisture absorbent
21: substrate
22: organic electronic device

Claims (22)

Containing a metal layer having a CTE of 1.5 times or more compared to the CTE of the encapsulation layer and glass,
The encapsulation layer includes an encapsulation resin comprising an olefin-based resin having a thermosetting functional group, and an encapsulation film having an elastic portion (Ep, Elastic Portion) of 40% or more, calculated by the following general formula 1:
[General formula 1]
Ep (unit:%) = 100 Х σ2/σ1
In the general formula 1, σ1 is a parallel plate in a stress relaxation test mode with ARES (Advanced Rheometric Expansion System) in a laminated state by laminating a film having a thickness of 600 μm at 85° C. The specimen is loaded by applying a normal force of 150 gf, the stress value 1 second after 30% strain is applied to the film, and σ2 is the state in which the strain is applied to the film is maintained for 180 seconds This is the stress value measured after The encapsulation film of claim 1, wherein the thermosetting functional group includes a hydroxyl group, a carboxyl group, an amino group, or an epoxy group. The encapsulation film according to claim 1, wherein the thermosetting functional group is derived from an unsaturated group in the olefin-based resin. The encapsulation film according to claim 1, wherein the olefin-based resin comprises a copolymer of a diene and an olefin-based compound including a single carbon-carbon double bond. The encapsulation film according to claim 1, wherein the encapsulation layer further comprises a moisture absorbent. The encapsulation composition according to claim 5, wherein the moisture adsorbent is a chemically reactive adsorbent. The encapsulation film according to claim 5, wherein the moisture absorbent is included in an amount of 20 to 200 parts by weight based on 100 parts by weight of the encapsulating resin. The encapsulation film according to claim 1, wherein the encapsulation layer further comprises a bright spot inhibitor. The encapsulation film according to claim 8, wherein the antifogging agent has an adsorption energy for outgas of 0 eV or less, calculated by Density Functional Theory. The method according to claim 8, wherein the ratio of the average particle diameter according to D50 to the average particle diameter according to D10 to the average particle diameter according to D10 is in the range of 2.3 to 3.5 as a result of particle size analysis of the anti-glare agent for a sample filtered through 300 mesh nylon after dissolving in an organic solvent encapsulation composition. The encapsulation film of claim 1 , wherein the encapsulation layer further comprises a tackifier. The encapsulation film according to claim 11, wherein the tackifier is a compound including a cyclic structure having 5 to 15 carbon atoms. The encapsulation film according to claim 11, wherein the tackifier is a hydrogenated compound. The encapsulation film according to claim 11, wherein the tackifier is included in an amount of 15 to 200 parts by weight based on 100 parts by weight of the encapsulating resin. The encapsulation film of claim 1 , wherein the encapsulation layer further comprises a curing agent. The encapsulation film according to claim 15, 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. The encapsulation film according to claim 15, wherein the curing agent is included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the encapsulating resin. The encapsulation film of claim 1 , wherein the encapsulation layer further comprises a curing catalyst. The encapsulation film of claim 1 , wherein the encapsulation layer further comprises a curing retardant. The encapsulation film according to claim 1, comprising multiple encapsulation layers. An organic electronic device comprising a substrate, an organic electronic device formed on the substrate, and the encapsulation film according to claim 1 for sealing the entire surface of the organic electronic device. A method of manufacturing an organic electronic device comprising the step of applying the encapsulation film according to claim 1 to a substrate on which the organic electronic device is formed to cover the organic electronic device.

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