WO2014021696A1

WO2014021696A1 - Adhesive film and product for encapsulating organic electronic device using same

Info

Publication number: WO2014021696A1
Application number: PCT/KR2013/007053
Authority: WO
Inventors: 이승민; 유현지; 장석기; 심정섭; 조윤경; 배경열
Original assignee: 주식회사 엘지화학
Priority date: 2012-08-03
Filing date: 2013-08-05
Publication date: 2014-02-06

Abstract

The present invention relates to an adhesive film and a product for encapsulating an organic electronic device using the same. The present invention maintains a moisture blocking capability by preventing moisture within a matrix resin from moving, thereby effectively blocking moisture or oxygen flowing to the organic electronic device from the outside and increasing stability over time, lifespan, and durability in the thinning of a panel of the organic electronic device, and thus secures long-term reliability.

Description

Adhesive film and encapsulation product of organic electronic device using same

Embodiments of the present invention relate to an adhesive film and an encapsulation product of an organic electronic device using the same.

An organic electronic device (OED) refers to a device including an organic material layer that generates an exchange of electric charges using holes and electrons, and examples thereof include a photovoltaic device, a rectifier, Transmitters and organic light emitting diodes (OLEDs); and the like.

Among the organic electronic devices, organic light emitting diodes (OLEDs) have low power consumption, fast response speed, and are advantageous for thinning a display device or lighting, as compared with conventional light sources. In addition, OLED has excellent space utilization, and is expected to be applied in various fields including various portable devices, monitors, notebooks, and TVs.

In the commercialization of OLEDs and the expansion of their use, the main problem is durability. Organic materials and metal electrodes included in the OLED are easily oxidized by external factors such as moisture, and products including the OLED are highly sensitive to environmental factors. Accordingly, there is a need for development of an encapsulant that can effectively block the penetration of moisture while reducing damage to organic electronic devices and ensuring long-term reliability.

Embodiments of the present invention provide an adhesive film, and an organic electronic device encapsulation product using the same.

The present invention provides an adhesive film for encapsulating an organic electronic device, wherein the adhesive film includes a curable adhesive layer including a curable resin and a moisture adsorbent, and the content of the hydration reaction product of the moisture adsorbent and the moisture adsorbent is represented by the following general formula (1). It is related with the satisfied adhesive film.

[Formula 1]

X / X ₀ ≥ 90 wt%

In the general formula (1), X is the weight of the water adsorbent, and X ₀ is the weight of the product generated by the water adsorbent hydrating with water.

The invention according to another embodiment of the present invention provides an adhesive film having a change over time of the moisture blocking ability of the adhesive film is less than 1%.

In addition, the invention according to another embodiment of the present invention, the substrate; An organic electronic device formed on the substrate; And the adhesive film encapsulating the organic electronic device, wherein the adhesive film covers the entire organic electronic device.

The adhesive film according to the embodiments of the present invention prevents the movement of moisture in the matrix resin to maintain moisture blocking ability to effectively block moisture or oxygen introduced into the organic electronic device from the outside, and also to thin the organic electronic device panel. Over time stability, life and durability are improved to ensure long-term reliability.

1 is an XRD graph showing the change over time of the water absorbent of the adhesive film according to the Examples and Comparative Examples of the present invention.

Hereinafter, embodiments of the present invention will be described in more detail. In addition, in describing the present invention, detailed descriptions of related well-known general functions or configurations are omitted.

The adhesive film according to one embodiment of the present invention includes a curable adhesive layer including a curable resin and a moisture adsorbent, and the content of the hydration reaction product of the moisture adsorbent and the moisture adsorbent satisfies the following general formula (1).

[Formula 1]

X / X ₀ ≥ 90 wt%

As used herein, the term "organic electronic device" means an article or device having a structure including an organic material layer that generates an exchange of electric charge using holes and electrons between a pair of electrodes facing each other. The photovoltaic device, a rectifier, a transmitter, and an organic light emitting diode (OLED) may be mentioned, but is not limited thereto. In one example of the present invention, the organic electronic device may be an OLED.

The curable adhesive can maintain a solid or semi-solid at room temperature, and when heated, flow can be generated to attach a flat plate without bubbles, and when the curing reaction is finished, the object is hardened with an adhesive. It may be an adhesive in the form of fixing.

The adhesive film is important to ensure long-term reliability when encapsulating the organic electronic device. In the case of conventional adhesive films, in particular adhesive films using latent curing agents, they have generally been stored in a temperature range of around 4 ° C. However, the adhesive film according to embodiments of the present invention is stored at a storage temperature of 0 ° C. or lower, so that moisture that may exist from the time of manufacture of the adhesive film, that is, moisture that the adhesive film is moistened, moves in the matrix during the storage period, thereby adsorbing the moisture adsorbent. By reacting with, it is possible to prevent the moisture barrier ability from being lowered as the storage period becomes longer than the initial moisture barrier ability of the adhesive film. This is one of the factors that inhibits the movement of moisture in the matrix due to the storage temperature below zero.

The storage temperature below 0 ° C may be, for example, -10 ° C to -4 ° C, it is possible to prevent a decrease in the moisture barrier ability when maintaining this storage temperature within the above range. In addition, when stored at too low a temperature, when applied to the encapsulation process of the organic electronic device later, the tack time (aging) to room temperature becomes long (long time), the productivity of the process may be reduced.

In addition, the change over time of the moisture blocking ability of the adhesive film according to embodiments of the present invention may be less than 1%. In the case of controlling the change of the water blocking ability of the adhesive film over the above range, the life of the organic electronic device can be maintained long, and the durability can be improved, and the adhesion strength due to excessive moisture adsorption can be prevented to reduce the The interfacial peeling phenomenon can be prevented.

An adhesive film having a time-dependent change in the moisture barrier ability of the adhesive film of less than 1% satisfies at least one of the following three conditions. a) the change in purity of the moisture adsorbent over time by less than 10% by weight; b) the change over time in weight increase rate under the durability condition of 85 ° C. and 85% relative humidity.

The change in the purity of the water adsorbent over time can be measured by X-ray diffraction (XRD) analysis. In the case of the metal oxide, there is a peak corresponding to the intrinsic value of each particle. When the water and the metal oxide hydrate by the moisture absorption, the particles are changed and the purity of the metal oxide is reduced. For example, when calcium oxide is used, calcium oxide (CaO) reacted with moisture during storage becomes calcium hydroxide (Ca (OH) ₂ ), in which case the intensity of the peak corresponding to the intrinsic value of calcium oxide (Area value of graph) becomes low. Therefore, when the change in the purity of the water absorbent according to the storage time of the adhesive film is 10% by weight or more, the moisture in the adhesive film is moved during the storage process to react with the water absorbent is to reduce the durability of the adhesive film.

The change in the moisture blocking ability over time can also be measured by the difference in weight increase rate (time change in weight increase rate) after the durability condition of the adhesive film according to the storage time. In the case where the change in the moisture blocking ability of the adhesive film is insignificant, when the adhesive film is left for a certain period of time after storage, the moisture absorption ability is excellent and the weight increase rate of the adhesive film will be increased. On the contrary, in the case where the water blocking ability is lowered, even if the adhesive film after storage is left for a certain time under the durable condition, the weight increase rate of the adhesive film becomes lower than otherwise because of the decrease in the water adsorption capacity. Therefore, when the change over time of the moisture barrier ability is more than a certain level, the difference in weight increase rate after the durability condition of the adhesive film according to the storage time becomes large. The temporal change of the weight increase rate after the endurance condition of 85 ° C. and 85% relative humidity of the adhesive film which can give long-term reliability when encapsulating the organic electronic device may be less than 0.2%. That is, for example, the weight increase rate after the endurance conditions of the adhesive film according to the storage time is only less than 3.7% to 3.5%. Therefore, when the adhesive film having a different storage time is left to the endurance conditions, and then the weight increase rate is measured, when the difference in the weight increase rate is less than 0.2%, the time-dependent change in the moisture barrier ability is less than 1%. In one example, the weight increase rate, after curing the adhesive film of 200㎛ thickness, after cutting to a certain size to prepare a specimen, and record the initial weight of the specimen, the specimen under 85 ℃ and 85% relative humidity After leaving for 24 hours, the surface moisture can be removed, and then the weight can be calculated to calculate the increase in weight relative to the initial weight. Can be.

In addition, the change over time of the moisture barrier ability can also be measured by the difference in moisture penetration rate (change in moisture penetration rate over time) after the durability condition of the adhesive film according to the storage time. This can be measured by the Calcium test. Encapsulate the film with 6mm bezel on the coated Ca and measure the rate of water penetration under 85 ° C. and 85% relative humidity. Changes in moisture penetration rate over time may be less than 10%, and in the case of more than 10%, moisture penetrates quickly, thereby degrading moisture blocking ability and causing OLED panel defects.

The adhesive film may have a viscosity at room temperature of 10 ⁶ dyne / cm ² or more or 10 ⁷ dyne / cm ^{2 or} more. In the above, the term "room temperature" means a natural temperature that is not heated or reduced, for example, about 15 ° C to 35 ° C, more specifically about 20 ° C to 25 ° C, and more specifically about 25 ° C. It can mean the temperature of. The said viscosity can be measured using ARES (Advanced Rheometric Expansion System). By adjusting the viscosity of the curable adhesive to the above range, it is possible to smooth the processability of the organic electronic device encapsulation process, it is possible to seal the plate with a uniform thickness. In addition, unlike liquid adhesives, problems such as shrinkage and volatilization gas, which may occur due to curing of the resin, may be greatly reduced, thereby preventing physical or chemical damage to the organic electronic device. In the present invention, as long as the adhesive maintains a solid or semi-solid state at room temperature, the upper limit of the viscosity is not particularly limited. For example, in consideration of processability, the upper limit of the viscosity is in the range of about 10 ⁹ dyne / cm ² or less. Can be controlled.

In addition, the adhesive film structurally enables the substrate and the upper substrate to be bonded together with the moisture barrier property, thereby facilitating the manufacturing process when manufacturing the panel of the organic electronic device and simplifying the manufacturing process by eliminating a separate passivation process. The thickness of the organic electronic device can be reduced, thereby contributing to thinning.

Curable resins usable in embodiments of the present invention have a water vapor transmission rate (WVTR) in the cured state of 50 g / m ² · day or less, preferably 30 g / m ² · day or less, 20 g / m ² · day or less or 15 g / m ² · day or less. The term “cured state of the curable resin” refers to a curable resin that is cured or crosslinked through its reaction with other components such as alone or with a curing agent or the like, and when used as an encapsulant, retains components such as moisture adsorbents and fillers, It means the state converted to the state which can exhibit the performance as a structural adhesive. The said water vapor transmission rate is the water vapor transmission rate measured with respect to the thickness direction of the said hardened | cured material under 38 degreeC and 100% of relative humidity, after hardening curable resin and making the hardened | cured material into the film form of thickness 80micrometer. In addition, the moisture permeability is measured according to ASTM F1249.

By controlling the moisture permeability within the above range, the penetration of moisture, moisture or oxygen into the organic electronic device encapsulation product can be effectively suppressed, and the introduction effect of the moisture reactive adsorbent can be exerted.

In one embodiment of the present invention, the water vapor transmission rate in the cured state of the resin is that the lower the numerical value shows the excellent performance of the sealing structure, the lower limit is not particularly limited.

The specific kind of curable resin that can be used in the present invention is not particularly limited, and various thermosetting or photocurable resins known in the art may be used. The term "thermosetting resin" means a resin that can be cured through an appropriate heat application or aging process, and the term "photocurable resin" means a resin that can be cured by irradiation of electromagnetic waves. In addition, in the above category of electromagnetic waves, microwaves, infrared (IR), ultraviolet (UV), X-rays and γ-rays, as well as α-particle beam (proton beam), proton beam (neutron) Particle beams such as neutron beams and electron beams may be included. As an example of the said photocurable resin, cationic photocurable resin is mentioned. The cationic photocurable resin means a resin that can be cured by cationic polymerization or cation curing reaction induced by irradiation of electromagnetic waves. In addition, the curable resin may be a dual curable resin including both thermosetting and photocuring properties.

The specific kind of the curable resin is not particularly limited as long as it has the aforementioned characteristics. For example, it may be cured to exhibit adhesive properties, and may include one or more thermosetting functional groups such as glycidyl group, isocyanate group, hydroxy group, carboxyl group or amide group, or may be an epoxide group or a cyclic ether. and resins containing at least one functional group curable by irradiation of electromagnetic waves such as a (cyclic ether) group, a sulfide group, an acetal group, or a lactone group. In addition, specific types of the resin may include an acrylic resin, a polyester resin, an isocyanate resin, an epoxy resin, and the like, but is not limited thereto.

As said curable resin, Aromatic or aliphatic; Or an epoxy resin of linear or branched chain type can be used. In one embodiment of the present invention, as containing two or more functional groups, an epoxy resin having an epoxy equivalent of 180 g / eq to 1,000 g / eq may be used. By using an epoxy resin having an epoxy equivalent in the above range, properties such as adhesion performance and glass transition temperature of the cured product can be effectively maintained. Examples of such epoxy resins include cresol novolac epoxy resins, bisphenol A epoxy resins, bisphenol A novolac epoxy resins, phenol novolac epoxy resins, tetrafunctional epoxy resins, biphenyl epoxy resins, and triphenol methane types. A kind or mixture of an epoxy resin, an alkyl modified triphenol methane epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, or a dicyclopentadiene modified phenol type epoxy resin is mentioned.

In this invention, the epoxy resin which contains a cyclic structure in molecular structure can be used as an example, More specifically, the epoxy resin containing an aromatic group (for example, a phenyl group) can be used. When the epoxy resin contains an aromatic group, the cured product may have excellent thermal and chemical stability while exhibiting low moisture absorption, thereby improving reliability of the organic electronic device encapsulation structure. Specific examples of the aromatic group-containing epoxy resin that can be used in the present invention include biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, cresol type epoxy resin, Bisphenol-based epoxy resins, xylox-based epoxy resins, polyfunctional epoxy resins, phenol novolac epoxy resins, triphenol methane-type epoxy resins and alkyl-modified triphenol methane epoxy resins, such as one or a mixture of two or more, but is not limited thereto. no.

As the epoxy resin, a silane-modified epoxy resin, for example, a silane-modified epoxy resin having an aromatic group can be used.

As the silane-modified epoxy resin, for example, a reactant of at least one of the epoxy resins described above with the silane compound can be used. As the silane compound in the above, for example, the compound represented by the following formula (1) can be exemplified.

[Formula 1]

D _n SiX _(4-n)

In Formula 1, D is a vinyl group, an epoxy group, an amino group, an acryl group, a methacryl group, a mercapto group, an alkoxy group or an isocyanate group, or an alkyl group substituted with any one of the above functional groups, and X is hydrogen or an alkyl group. , Halogen, alkoxy group, aryl group, aryloxy group, acyloxy group, alkylthio group or alkyleneoxythio group, n is a number of 1 to 3.

In the compound of Formula 1, functional group “D” may react with a functional group included in the epoxy resin to form a silane-modified epoxy resin.

For example, if the functional group is an amino group, the silane compound may be introduced into the epoxy group while the amino group reacts with the epoxy group of the epoxy resin to form a "-CH (OH) -CH ₂ -NH-" bond.

In addition, when the functional group "D" is an isocyanate group or an alkoxy group, an epoxy resin containing a hydroxy group (OH), for example, a bisphenol F type epoxy resin, a bisphenol F type novolac epoxy resin, a bisphenol A type epoxy resin or a bisphenol A silane compound may also be introduced by reacting with a bisphenol-type epoxy resin such as an A-type novolac epoxy resin.

As the alkyl group in Chemical Formula 1, an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms may be exemplified. The alkyl group may be a straight chain, branched chain or cyclic alkyl group.

As the halogen atom in Chemical Formula 1, fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) may be exemplified.

In addition, as the alkoxy group in Formula 1, an alkoxy group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms may be exemplified. The alkoxy group may be linear, branched or cyclic.

In addition, the aryl group included in the aryl group or the aryloxy group in the formula (1), as well as the aryl group, so-called aralkyl group (aralkyl group) or arylalkyl group may be included. For example, the aryl group may mean a monovalent moiety derived from a compound or derivative thereof including one or more benzene rings or a structure in which two or more benzene rings are linked or condensed. The aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. As the aryl group, for example, a phenyl group, dichlorophenyl, chlorophenyl, phenylethyl group, phenylpropyl group, benzyl group, tolyl group, xylyl group (xylyl group) or naphthyl group and the like can be exemplified. Phenyl groups can be exemplified.

In addition, as the acyloxy group in Formula 1, an acyloxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, or 1 to 12 carbon atoms may be exemplified.

In addition, as the alkylthio group in Formula 1, an alkylthio group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, or 1 to 8 carbon atoms or 1 to 4 carbon atoms may be exemplified, and an alkyleneoxythio group. Is an alkyleneoxythio group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, or 1 to 8 carbon atoms or 1 to 4 carbon atoms.

The alkyl group, alkoxy group, aryl group, acyloxy group, alkylthio group or alkyleneoxythio group may be optionally substituted with one or more substituents. As the substituent, a hydroxy group, an epoxy group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an acyl group, a thiol group, an acryloyl group, a methacryloyl group, an aryl group or an isocyanate group may be exemplified, but is not limited thereto. It is not.

In Formula 1, the functional group “D” may be, for example, an alkoxy group, an amino group or an isocyanate group.

In addition, at least one, two or more, or three of the functional groups "X" in Formula 1 may be, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, or an alkyleneoxythio group, or the like. Or an alkoxy group.

Examples of the silane-modified epoxy resin include about 0.1 part by weight to about 10 parts by weight, about 0.1 part by weight to about 9 parts by weight, about 0.1 part by weight to about 8 parts by weight, and about 0.1 part by weight based on 100 parts by weight of the epoxy resin. To about 7 parts by weight, about 0.1 to about 6 parts by weight, about 0.1 to about 5 parts by weight, about 0.1 to about 4 parts by weight, about 0.1 to about 3 parts by weight, about 0.3 Epoxy resins in which parts by weight to 2 parts by weight or about 0.5 parts by weight to about 2 parts by weight of the silane compound are introduced may be used. In one example, the epoxy resin into which the silane compound is introduced may be an aromatic epoxy resin. Examples of the aromatic epoxy resins include bisphenol epoxy resins such as bisphenol F epoxy resins, bisphenol F novolac epoxy resins, bisphenol A epoxy resins, and bisphenol A novolac epoxy resins.

As such, when an epoxy resin modified with silane and structurally having a silane group is used, the adhesion of the organic electronic device to the glass substrate or the substrate inorganic material can be maximized, and the moisture barrier property, durability and reliability can be improved. The specific kind of the epoxy resin is not particularly limited, and such a resin can be easily obtained from a place of purchase such as, for example, Kukdo Chemical.

In the present invention, the curable resin may also include styrene resin, polyolefin resin, thermoplastic elastomer, polyoxyalkylene resin, polyester resin, polyvinyl chloride resin, polycarbonate resin, polyphenylene sulfide resin, and hydrocarbons. A mixture, a polyamide resin, an acrylate resin, an epoxy resin, a silicone resin, a fluorine resin, or a mixture thereof may be exemplified.

In the above, as the styrene resin, for example, styrene-ethylene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), acrylonitrile-butadiene-styrene block copolymer (ABS ), Acrylonitrile-styrene-acrylate block copolymers (ASA), styrene-butadiene-styrene block copolymers (SBS), styrene-based homopolymers or mixtures thereof. As the olefin resin, for example, a high density polyethylene resin, a low density polyethylene resin, a polypropylene resin or a mixture thereof may be exemplified. As the thermoplastic elastomer, for example, an ester thermoplastic elastomer, an olefin thermoplastic elastomer, a mixture thereof, or the like can be used. Among them, polybutadiene resin or polyisobutene resin may be used as the olefinic thermoplastic elastomer. Examples of the polyoxyalkylene resins include polyoxymethylene resins, polyoxyethylene resins, and mixtures thereof. Examples of the polyester resins include polyethylene terephthalate resins, polybutylene terephthalate resins, and mixtures thereof. As the polyvinyl chloride-based resin, for example, polyvinylidene chloride and the like can be exemplified. As the mixture of the hydrocarbons, for example, hexatriacotane or paraffin may be exemplified. As said polyamide resin, nylon etc. can be illustrated, for example. As said acrylate resin, polybutyl (meth) acrylate etc. can be illustrated, for example. As said epoxy resin, For example, Bisphenol-type, such as bisphenol A type, bisphenol F type, bisphenol S type, and these hydrogenated substances; Novolak types such as phenol novolak type and cresol novolak type; Nitrogen-containing cyclic types such as triglycidyl isocyanurate type and hydantoin type; Alicyclic type; Aliphatic type; Aromatic types such as naphthalene type and biphenyl type; Glycidyl types such as glycidyl ether type, glycidyl amine type and glycidyl ester type; Dicyclo types such as dicyclopentadiene type; Ester type; Ether ester type or mixtures thereof and the like can be exemplified. Examples of the silicone resins include polydimethylsiloxane and the like. Moreover, as said fluorine-type resin, polytrifluoroethylene resin, polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyhexafluoropropylene resin, polyvinylidene fluoride, polyvinylidene fluoride, polyfluoro Ethylene propylene propylene or mixtures thereof and the like can be exemplified.

The above-listed resins may be used, for example, by grafting with maleic anhydride, or the like, or may be used after being copolymerized with other listed resins or monomers for preparing the resins, or may be modified with other compounds. Examples of the other compounds include carboxyl-terminated butadiene-acrylonitrile copolymers.

In addition, the resins listed may include one or more functional groups or moieties that can be cured by heat such as glycidyl group, isocyanate group, hydroxy group, carboxyl group or amide group or the like to be cured and exhibit adhesiveness, or one or more functional groups or moieties that can be cured by irradiation of active energy rays such as (epoxide) groups, cyclic ether groups, sulfide groups, acetal groups, or lactone groups. Can be.

In one example, the curable resin may include a polyisobutene resin. Polyisobutene resins may have hydrophobicity and exhibit low water vapor permeability and low surface energy. Specifically as a polyisobutene resin, For example, Homopolymer of an isobutylene monomer; Or the copolymer which copolymerized the isobutylene monomer and the other monomer which can superpose | polymerize can be used. Here, the other monomers polymerizable with the isobutylene monomer may include, for example, 1-butene, 2-butene, isoprene or butadiene.

The curable adhesive layer contains a moisture adsorbent in addition to the curable resin. The term "moisture adsorbent" may be used as a generic term for a moisture reactive adsorbent that is a component capable of adsorbing or removing moisture or moisture introduced from the outside through a chemical reaction or the like.

The moisture adsorbent chemically reacts with moisture, moisture or oxygen introduced into the adhesive layer to adsorb moisture or moisture. The specific kind of the moisture adsorbent is not particularly limited, and examples thereof include a metal powder such as alumina, a metal oxide, a metal salt or a mixture of two or more kinds of phosphorus pentoxide (P ₂ O ₅ ).

Specific examples of the metal oxides include 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). Examples of the metal salts include lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), Sulfates such as gallium sulfate (Ga ₂ (SO ₄ ) ₃ ), titanium sulfate (Ti (SO ₄ ) ₂ ) or nickel sulfate (NiSO ₄ ), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium chloride (YCl ₃ ), copper chloride (CuCl ₂ ), cesium fluoride (CsF), tantalum fluoride (TaF ₅ ), niobium fluoride (NbF ₅ ), lithium bromide (LiBr), calcium bromide (CaBr ₂ ), Metal halides such as cesium bromide (CeBr ₃ ), selenium bromide (SeBr ₄ ), vanadium bromide (VBr ₃ ), magnesium bromide (MgBr ₂ ), barium iodide (BaI ₂ ) or magnesium iodide (MgI ₂ ); Or metal chlorates such as barium perchlorate (Ba (ClO ₄ ) ₂ ) or magnesium perchlorate (Mg (ClO ₄ ) ₂ ), and the like, but is not limited thereto.

The metal oxides may be blended into the composition in a state of properly processing the moisture adsorbent. For example, the thickness of the adhesive layer may be a thin film of 30 μm or less according to the type of organic electronic device to which the adhesive film is to be applied, and in this case, a grinding process of the moisture absorbent may be necessary. For grinding of the moisture adsorbent, a process such as a three roll mill, bead mill or ball mill may be used. In addition, when the adhesive film of the present invention is used for organic light emitting devices of the top emission type, the permeability of the adhesive layer itself becomes very important, and therefore, the size of the moisture adsorbent needs to be small. Therefore, the grinding process may be required even in such applications.

The adhesive layer may include 1 part by weight to 100 parts by weight or 5 parts by weight to 50 parts by weight of a moisture adsorbent based on 100 parts by weight of the curable resin. When the moisture adsorbent is included in the above range, the volume expansion caused by the reaction between the moisture adsorbent and the moisture can be prevented from causing a crack in the film in the case where the curable resin is used beyond the limit and the organic electronic device is used. It can prevent chemical damage and provide long-term reliability of the adhesive film.

In this specification, unless otherwise specified, a unit "weight part" means the weight ratio between each component.

In the case where the content range of the moisture adsorbent is controlled as described above, the cured product may exhibit excellent moisture and moisture barrier properties, and may exhibit excellent moisture barrier properties while forming a sealing structure of a thin film.

The curable adhesive layer may further include a filler. A filler is a kind of physical moisture adsorbent that can inhibit the penetration by lengthening the movement path of moisture or moisture that penetrates into the encapsulation structure, and blocks the moisture and moisture through interaction with the matrix structure of the curable resin and the moisture adsorbent. You can maximize your sex. The specific kind of filler that can be used in the present invention is not particularly limited, and for example, a mixture of one or more kinds selected from the group consisting of clay, talc, silica, zeolite, zirconia, titania and montmorillonite may be used.

In addition, in order to increase the coupling efficiency between the filler and the organic binder, a product surface-treated with an organic material may be used as the filler, or a coupling agent may be additionally added.

The curable adhesive layer may include 1 part by weight to 50 parts by weight or 1 part by weight to 20 parts by weight of a filler based on 100 parts by weight of the curable resin. In the case of controlling the content of the filler to 1 part by weight or more, it is possible to provide a cured product having excellent moisture or moisture barrier properties and mechanical properties. In addition, in the case of controlling the filler content to 50 parts by weight or less, it is possible to manufacture a film form, it may provide a cured product exhibiting excellent moisture barrier properties even when formed into a thin film.

The specific kind of hardener which can be used is not specifically limited, It can select suitably according to the kind of curable resin used or the functional group contained in the resin. For example, when using an epoxy resin as curable resin in this invention, the hardening | curing agent for general epoxy resins known in this field can be used as a hardening | curing agent, Specifically, various amine compounds, imidazole compound, phenol type One kind or two or more kinds of compounds, phosphorus compounds or acid anhydride compounds may be used, but is not limited thereto.

The curable adhesive layer may include, for example, 1 part by weight to 20 parts by weight or 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the curable resin. However, the content is only one example of the present invention. That is, in the present invention, the content of the curing agent may be changed according to the type and content of the curable resin or functional group, or the matrix structure or crosslinking density to be implemented.

Moreover, the kind of said initiator which can be used by this invention, for example, a cationic photoinitiator, is not specifically limited, For example, an aromatic diazonium salt, an aromatic iodine aluminum salt, an aromatic sulfonium salt, or an iron-arene complex, etc. A well-known cationic polymerization initiator can be used, It is preferable to use an aromatic sulfonium salt among these, but it is not limited to this.

In this case, the content of the initiator may be, for example, 0.01 part by weight to 10 parts by weight or 0.1 part by weight to 3 parts by weight based on 100 parts by weight of the curable resin. In the present invention, when the content of the cationic photopolymerization initiator is too small, there is a fear that sufficient curing does not proceed, and when too large, the content of the ionic substance after curing increases, resulting in poor durability of the adhesive or in view of the nature of the initiator ( conjugate acid) is formed, which is disadvantageous in terms of optical durability, and corrosion may occur depending on the substrate. Therefore, an appropriate content range may be selected in consideration of this point.

The curable adhesive layer may further include a high molecular weight resin. The high molecular weight resin may serve to improve moldability, for example, when molding the composition of the present invention into a film or sheet shape. It can also serve as a high temperature viscosity modifier to control flow during the process.

The kind of high molecular weight resin which can be used above will not be restrict | limited especially if it is compatible with other components, such as said curable resin. Specific examples of high molecular weight resins that can be used are resins having a weight average molecular weight of 20,000 or more, such as phenoxy resins, acrylate resins, high molecular weight epoxy resins, ultra high molecular weight epoxy resins, high polarity functional group-containing rubbers and high One kind or a mixture of two or more kinds such as a high polarity functional group-containing reactive rubber, but is not limited thereto.

When the high molecular weight resin is included in the curable adhesive layer, the content is not particularly limited to be adjusted according to the desired physical properties. For example, in the present invention, the high molecular weight resin may be included in an amount of about 200 parts by weight or less, 150 parts by weight or less or about 100 parts by weight or less based on 100 parts by weight of the curable resin. In the case where the content of the high molecular weight resin is controlled to 200 parts by weight or less as described above, the compatibility with each component of the resin composition can be effectively maintained, and can also serve as an adhesive.

The adhesive film may further include additives such as additional fillers for improving durability of the cured product, coupling agents for improving mechanical strength, adhesion, plasticizers, UV stabilizers, and antioxidants, without affecting the effects of the invention. Can be.

The curable adhesive layer of the adhesive film may have a single layer structure, or may have a multilayer structure having two or more adhesive layers. When the adhesive film includes a multilayer adhesive layer, the moisture adsorbent may be contained more in the layer disposed away from the organic electronic device.

If the structure of the adhesive film of this invention includes the said adhesive bond layer, if it is a thing in particular, it will not restrict | limit, For example, a base film or a release film (henceforth a "first film" may be called.); And it may have a structure including the adhesive layer formed on the base film or a release film.

The adhesive film of the present invention may further include a base film or a release film (hereinafter, sometimes referred to as "second film") formed on the adhesive layer.

The specific kind of the said 1st film which can be used by this invention is not specifically limited. In the present invention, as the first film, for example, a general polymer film of this field can be used. In the present invention, for example, 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, as the base material or the release film. , Ethylene-vinyl acetate film, ethylene-propylene copolymer film, ethylene-ethyl acrylate copolymer film, ethylene-methyl acrylate copolymer film, polyimide film and the like can be used. In addition, an appropriate release treatment may be performed on one side or both sides of the base film or the release film of the present invention. Alkyd-based, silicone-based, fluorine-based, unsaturated ester-based, polyolefin-based, or wax-based may be used as an example of the release agent used in the release treatment of the base film, and among these, it is preferable to use an alkyd-based, silicone-based, or fluorine-based release agent in terms of heat resistance. Preferred, but not limited to.

Moreover, the kind of 2nd film (Hereinafter, a "cover film" may be called.) Which can be used by this invention is not specifically limited, either. For example, in the present invention, as the second film, the same or different kind as the first film can be used within the range exemplified in the above-described first film. In addition, in the present invention, an appropriate release treatment may also be performed on the second film.

The thickness of the base film or the release film (first film) as described above is not particularly limited and may be appropriately selected depending on the application to be applied. For example, in the present invention, the thickness of the first film may be about 10 μm to 500 μm or about 20 μm to 200 μm. In the case of adjusting the thickness of the film in the above range, it is possible to prevent the deformation of the base film and to increase the economics.

In addition, the thickness of the second film is also not particularly limited. In this invention, you may set the thickness of the said 2nd film similarly to a 1st film, for example. In addition, the thickness of the second film may be set relatively thinner than the first film in consideration of processability and the like.

The thickness of the adhesive layer included in the adhesive film is not particularly limited and may be appropriately selected according to the following conditions in consideration of the use to which the film is applied.

In embodiments of the present invention, the method for producing such an adhesive film is not particularly limited. For example, a first step of coating a coating liquid containing the composition of the adhesive layer described above on a base film or a release film; And a second step of drying the coating solution coated in the first step.

In the method for producing an adhesive film of the present invention, a third step of additionally compressing the base film or the release film on the coating liquid dried in the second step may be further performed.

The first step is to prepare a coating solution by dissolving or dispersing the composition of the adhesive layer described above in a suitable solvent. In this process, the content of the epoxy resin and the like contained in the coating liquid may be appropriately controlled according to the desired moisture barrier properties and film formability.

The kind of solvent used for the said coating liquid manufacture is not specifically limited. However, when the drying time of the solvent is too long or when drying at a high temperature is necessary, problems may occur in terms of workability or durability of the adhesive film, and it is preferable to use a solvent having a volatilization temperature of 100 ° C. or less. In addition, in consideration of film formability, a small amount of a solvent having a volatilization temperature of the above range or more can be used. Examples of solvents that may be used in embodiments of the present invention include methyl ethyl ketone (MEK), acetone, toluene, dimethylformamide (DMF), methyl cellosolve (MCS), tetrahydrofuran (THF) or N- One kind or a mixture of two or more kinds such as methylpyrrolidone (NMP), but is not limited thereto.

The method of applying the coating solution to the base film or the release film in the first step is not particularly limited, for example, knife coat, roll coat, spray coat, gravure coat, curtain coat, comma coat or lip coat, etc. The same known method can be used without limitation.

The second step is to dry the coating solution coated in the first step, to form an adhesive layer. In the second step, the adhesive layer may be formed by heating and removing the solvent by heating the coating solution applied to the film. At this time, the drying conditions are not particularly limited, for example, the drying may be performed for 1 to 10 minutes at a temperature of 70 ℃ to 200 ℃.

In the method of manufacturing the adhesive film, a third step of pressing the additional base film or the release film on the adhesive layer formed on the film may be further performed after the second step.

This third step may be carried out by coating an additional release film or base film (cover film or second film) onto the dried adhesive layer by hot roll lamination or press process after it is coated on the film. In this case, the third step may be performed by a hot roll lamination method in view of the possibility and efficiency of the continuous process, wherein the process is about 0.1 kgf / cm ² to 10 kgf / at a temperature of about 10 ° C. to 100 ° C. It can be carried out at a pressure of cm ² .

Another embodiment of the invention is a substrate; An organic electronic device formed on the substrate; And an adhesive film as described above for encapsulating the organic electronic device, wherein the adhesive film covers the entire organic electronic device.

The organic electronic device encapsulation product may further include a protective film protecting the organic electronic device between the adhesive film and the organic electronic device.

The organic electronic device encapsulation product may further include an encapsulation substrate on the adhesive film, wherein the adhesive film serves to adhere the encapsulation substrate and the substrate. In one embodiment of the present invention, the organic electronic device may be an organic light emitting diode.

The organic electronic device encapsulation product has the advantage of simplifying the manufacturing process and reducing the process cost, and can be used regardless of the design method of the organic electronic device, and has the advantage of providing excellent mechanical durability to the organic electronic device. have.

Another embodiment of the present invention comprises the steps of applying the adhesive layer of the above-mentioned adhesive film to the substrate on which the organic electronic device is formed to cover the organic electronic device; And a method for encapsulating the organic electronic device, comprising curing the adhesive layer.

The applying of the adhesive film to the organic electronic device may be performed by hot roll lamination, hot pressing, or vacuum pressing of the adhesive film, and is not particularly limited.

The applying of the adhesive film to the organic electronic device may be performed at a temperature of 50 ° C. to 90 ° C., and the curing step may be performed by heating to a temperature range of 70 ° C. to 110 ° C. or by irradiating UV. have.

In addition, the step of attaching the other side of the adhesive film abuts on glass or metal, which is an additional encapsulation material, may be added.

In the method of encapsulating the organic electronic device, for example, a transparent electrode is formed on a substrate such as glass or a polymer film by vacuum deposition or sputtering, and an organic material layer is formed on the transparent electrode. The organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer and / or an electron transport layer. Subsequently, a second electrode is further formed on the organic material layer. Then, the above-described adhesive film is applied to cover all of the organic electronic devices on the organic electronic device on the substrate. In this case, the method of applying the adhesive film is not particularly limited, and for example, a cover substrate (ex. Glass or the like), which is previously transferred to the upper part of the organic electronic device formed on the substrate, of the adhesive layer of the adhesive film of the present invention. Polymer film) can be applied by a method such as heating and pressing. In the above step, for example, when transferring the adhesive film on the cover substrate, using the adhesive film of the present invention described above, after peeling off the substrate or the release film formed on the film, applying a heat, vacuum press or A vacuum laminator or the like may be used to transfer onto the cover substrate. In this process, when the curing reaction of the adhesive film is made in a certain range or more, the adhesive force or the adhesive force of the adhesive film may be reduced. Therefore, it is preferable to control the process temperature to about 100 ° C. or less and the process time within 5 minutes. Similarly, a vacuum press or a vacuum laminator may be used even when the cover substrate on which the adhesive film has been transferred is heat-compressed to the organic electronic device. The temperature conditions at this stage can be set as described above, and the process time is preferably within 10 minutes.

In addition, an additional curing process may be performed on the adhesive film obtained by compressing the organic electronic device. The curing process (main curing) may be performed in, for example, a heating chamber or a UV chamber. Conditions in the present curing may be appropriately selected in consideration of the stability of the organic electronic device.

However, the above-described manufacturing process is only one example for encapsulating the organic electronic device of the present invention, and the process sequence or process conditions may be freely modified. For example, in the present invention, the order of the transfer and compression processes may be changed by first transferring the adhesive film of the present invention to the organic electronic device on the substrate and then compressing the cover substrate. In addition, the protective layer may be formed on the organic electronic device, then the adhesive film may be applied, and then the cover substrate may be omitted and cured.

Hereinafter, the present invention will be described in more detail with reference to 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 to the following examples.

실시예 1 내지 3Examples 1 to 3

1. 접착제 용액의 제조1. Preparation of adhesive solution

70 g of CaO (Aldrich) as a water adsorbent was added to methyl ethyl ketone at a concentration of 30 wt% to prepare a water adsorbent solution, and the solution was milled for 24 hours by a ball mill process. In addition, 200g of silane-modified epoxy resin (KSR-177, Kukdo Chemical) and 150g of phenoxy resin (YP-50, Kyodo Chemical) were added to the reactor at room temperature and diluted with methyl ethyl ketone. Thereafter, the inside of the reactor was replaced with nitrogen, and the prepared solution was homogenized. A water adsorbent solution prepared in advance was added to the homogenized solution, 4 g of imidazole (Shikoku Chemical), which is a curing agent, was added thereto, and then stirred at high speed for 1 hour to prepare an adhesive solution.

2. 접착 필름의 제조2. Preparation of Adhesive Film

The adhesive solution prepared above was applied to the release surface of the release PET using a comma coater, dried at 130 ° C. for 3 minutes in a dryer to form an adhesive layer having a thickness of 15 μm, and then the release PET was added on the adhesive layer. Pressed.

3. 접착 필름의 보관3. Storage of adhesive film

The adhesive film prepared above was stored frozen for 2 weeks, 4 weeks and 8 weeks at a temperature of -5 ℃.

비교예 1 내지 3Comparative Examples 1 to 3

An adhesive film was prepared in the same manner as in Examples 1 to 3 except that the storage temperature was refrigerated at a temperature of 4 ° C. in the adhesive film storage process of Example 1.

실험예 1: 수분 차단 특성 확인Experimental Example 1: Checking moisture barrier properties

In order to investigate the moisture barrier properties of the adhesive films of Examples 1 to 3 and Comparative Examples 1 to 3 according to the storage temperature and the storage period, calcium tests were performed. Specifically, 9 spots of calcium (Ca) were deposited on a glass substrate having a size of 100 mm × 100 mm with a size of 5 mm × 5 mm and a thickness of 100 nm, and Examples 1 to 3 and Comparative Examples 1 to 3 were used. The cover glass onto which the adhesive film was transferred was heat-pressed at 80 ° C. for 1 minute using a vacuum press at each calcium vapor deposition point. Then, after curing for 3 hours at 100 ℃ in a high temperature dryer, each of the sealed calcium (Ca) specimens to a size of 11mm x 11mm was cut. After the obtained specimens were left at a temperature of 85 ° C. and an environment of 85% R.H. in a constant temperature and humidity chamber, the time points at which calcium became transparent by the oxidation reaction due to water infiltration were evaluated and shown in Tables 1 and 2 below.

Table 1

division	Example 1	Example 2	Example 3
Invisibility start time (h)	900h	900h	895h
Moisture Penetration Rate (㎛ / hr)	6.66	6.66	6.70
	Comparative Example 1	Comparative Example 2	Comparative Example 3
Invisibility start time (h)	850h	820h	750h
Moisture Penetration Rate (㎛ / hr)	7.05	7.41	8.00

실험예 2: 무게 증가율의 경시 변화 측정Experimental Example 2: Measurement of change over time of weight increase rate

The weight increase rates of the adhesive films of Examples 1 to 3 and Comparative Examples 1 to 3 were investigated. Specifically, the adhesive films of Examples 1 to 3 and Comparative Examples 1 to 3 were prepared in a thickness of 200 μm, then cured at 100 ° C. for 3 hours in a high temperature dryer, and then cut into 5 cm × 5 cm Was prepared. After recording the initial weight of the cured specimen, the specimen was left in a constant temperature and humidity chamber at a temperature of 85 ° C. and an environment of 85% R.H. for 24 hours, after which moisture on the surface was removed and weighed. To calculate the weight increase rate of the specimen as shown in Table 2 below.

% Increase in weight = (B-A) / A × 100

Where B is the weight of the specimen after moisture absorption and A is the initial weight of the specimen.

TABLE 2

division	Example 1	Example 2	Example 3
Weight increase (t%)	3.72	3.72	3.71
	Comparative Example 1	Comparative Example 2	Comparative Example 3
Weight increase (t%)	3.65	3.51	3.27

실험예 3: 수분 흡착제의 순도의 경시 변화 측정Experimental Example 3: Determination of change in purity of the moisture adsorbent over time

In order to measure the change in moisture blocking ability before and after storage of the adhesive films of Examples 1 to 3 and Comparative Examples 1 to 3, the change of purity of the moisture absorbent (CaO) inside the adhesive film was analyzed by X-ray diffraction (X-ray Diffraction). , XRD). Specifically, using a XRD instrument (Bruker AXS D4 Endeavor XRD (2)), the wavelength of Cu Kα radiation was 1.5418 으로 with a voltage of 40 kV and a current of 40 mA. In FIG. 1, 175 seconds were measured for each degree. Referring to FIG. 1, Ca (OH) ₂ has a different ratio after CaO and water reaction. After performing Rietveld refinement to measure the change in the purity value of CaO of each adhesive film, the weight ratio (wt%) of CaO and Ca (OH) ₂ was calculated and shown in Table 3 below. .

TABLE 3

division	Example 1	Example 2	Example 3
CaO / Ca (OH) ₂ (wt%)	96.0	96.0	95.7
	Comparative Example 1	Comparative Example 2	Comparative Example 3
CaO / Ca (OH) ₂ (wt%)	87.5	80.1	74.5

As can be seen above, as the adhesive films of Examples 1 to 3 according to embodiments of the present invention are stored at sub-zero storage temperature, the change over time in the purity of the moisture adsorbent is less than 10%, and the weight after the endurance conditions. The change over time of the increase rate is 0.2%, it can be confirmed that the change over time of the moisture blocking ability is less than 1%, it can be confirmed that the organic electronic device can be effectively sealed from the moisture. However, it can be seen that the adhesive film stored at a refrigeration temperature of 4 ° C. as in the conventional adhesive film has a large change in moisture blocking ability as the storage time becomes longer than the initial moisture blocking ability.

Although the present invention has been described in detail with reference to exemplary embodiments of the present invention, these are merely exemplary, and those skilled in the art to which the present invention pertains have various modifications and equivalents therefrom. It will be appreciated that other embodiments are possible. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

Claims

An adhesive film for encapsulating an organic electronic device,

The adhesive film includes a curable adhesive layer containing a curable resin and a moisture adsorbent,

An adhesive film whose content of the water adsorbent and the hydration reaction product of the water adsorbent satisfies the following general formula 1:

[Formula 1]

X / X 0 ≥ 90 wt%

In the general formula (1), X is the weight of the water adsorbent, and X 0 is the weight of the product generated by the water adsorbent hydrating with water.
The adhesive film of claim 1, wherein the change over time of the moisture barrier ability of the adhesive film is less than 1%.
The method of claim 2,

An adhesive film in which the adhesive film satisfies at least one of the following three conditions:

a) the change over time in the purity of the water absorbent is less than 10wt%

b) the change over time of the weight increase rate after durability at 85 ° C. and 85% relative humidity is less than 0.2%.

c) the change over time in the rate of penetration of moisture is less than 10%.
The adhesive film according to claim 1, wherein the curable adhesive layer has a viscosity at room temperature of 10 6 dyne / cm 2 or more.
The adhesive film according to claim 1, wherein the curable resin has a water vapor transmission rate of 50 g / m 2 · day or less in a cured state.
The adhesive film according to claim 1, wherein the curable resin is a thermosetting resin, a photocurable resin, or a dual curable resin.
The curable resin according to claim 1, wherein the curable resin includes at least one curable functional group selected from glycidyl, isocyanate, hydroxy, carboxyl, amide, epoxide, cyclic ether, sulfide, acetal and lactone groups. Adhesive film.
The adhesive film according to claim 1, wherein the curable resin is an epoxy resin containing a cyclic structure in a molecular structure.
The adhesive film according to claim 1, wherein the moisture adsorbent is alumina, metal oxide, metal salt or phosphorus pentoxide.
The method of claim 9, wherein the moisture adsorbent is P 2 O 5 , Li 2 O, Na 2 O, BaO, CaO, MgO, Li 2 SO 4 , Na 2 SO 4 , CaSO 4 , MgSO 4 , CoSO 4 , Ga 2 (SO 4) 3, Ti ( SO 4) 2, NiSO 4, CaCl 2, MgCl 2, SrCl 2, YCl 3, CuCl 2, CsF, TaF 5, NbF 5, LiBr, CaBr 2, CeBr 3, SeBr 4, One or more adhesive films selected from the group consisting of VBr 3 , MgBr 2 , BaI 2 , MgI 2 , Ba (ClO 4 ) 2 and Mg (ClO 4 ) 2 .
The adhesive film according to claim 1, wherein the adhesive layer comprises 1 part by weight to 100 parts by weight of a moisture adsorbent based on 100 parts by weight of the curable resin.
The adhesive film of claim 1, wherein the adhesive layer further comprises a filler.
13. The adhesive film of claim 12 wherein the filler is at least one selected from the group consisting of clay, talc, silica, zeolite, zirconia, titania and montmorillonite.
The adhesive film according to claim 12, wherein the adhesive layer comprises 1 part by weight to 50 parts by weight of a filler with respect to 100 parts by weight of the curable resin.
The adhesive film of claim 1, wherein the adhesive layer further comprises a curing agent.
The adhesive film according to claim 15, wherein the curing agent is an amine compound, an imidazole compound, a phenol compound, a phosphorus compound, or an acid anhydride compound.
The adhesive film according to claim 15, wherein the adhesive layer comprises 1 part by weight to 10 parts by weight of a curing agent based on 100 parts by weight of the curable resin.
The adhesive film of claim 1 wherein the adhesive layer further comprises an initiator.
The adhesive film of claim 1, wherein the adhesive layer further comprises a high molecular weight resin.
The adhesive film according to claim 1, wherein the curable adhesive layer has a single layer structure or a multilayer structure of two or more layers.
Board; An organic electronic device formed on the substrate; And an adhesive film according to any one of claims 1 to 20 for encapsulating the organic electronic device, wherein the adhesive film covers the entire organic electronic device.
22. The organic electronic device encapsulation product of claim 21, wherein the organic electronic device is an organic light emitting diode.