TWI494391B - Adhesive film and method of encapsulating organic electronic device - Google Patents

Description

Method for bonding film and packaging organic electronic device Cross-reference to related applications

The priority and interest of Korean Patent Application No. 2011-0118476, filed on Nov. 14, 2011, and the Korean Patent Application No. 2012-0129018, filed on Nov. 14, 2012, are hereby incorporated by reference. The way it is incorporated in its entirety.

The present invention relates to a bonding film and a method of using the same for packaging an organic electronic device (OED).

An organic electronic device is a device that includes a layer of organic material that utilizes holes and electrons to generate charge exchange, and may include photovoltaic devices, rectifiers, transformers, and organic light emitting diodes (OLEDs).

A representative organic electronic device, which is an organic light emitting diode (OLED), has lower power consumption and higher response speed, and forms a display device or light that is thinner than a conventional light source. In addition, the OLED has excellent space utilization, and thus is expected to be applicable to a variety of different fields, including all types of portable devices, monitors, notebooks, and TVs.

In order to extend the compatibility and use of the OLED, the main problem to be solved in the related art is persistence. The organic materials and metal electrodes included in the OLED are very susceptible to oxidation by external factors such as moisture, and products including OLEDs are very sensitive to environmental factors. So already someone A number of different methods are proposed to effectively prevent oxygen or moisture from penetrating from the external environment into the organic electronic device, such as an OLED.

Furthermore, a more fundamental problem than durability is to reduce failures due to reduced laminate properties during panel assembly. When assembling the panel, it is very important to maintain the bonding strength between the panels to a certain level and stack the panels without bubbles and maintain a uniform thickness.

Accordingly, an exemplary embodiment of the present invention is to provide a relatively large and thin organic electronic device, to provide structural advantages by manufacturing a packaged organic electronic device in a relatively simple manner, and to provide reliability from the operation of the assembled panel. Package.

The present invention is directed to providing a method of bonding a film, using a packaged product of the organic electronic device thereof, and a method of packaging an organic electronic device.

In one aspect, the present invention provides a bonded film for packaging an organic electronic device comprising a bonding layer comprising a curable resin and a moisture adsorbent. When the bonding layer in an uncured state, the bonding layer having between ¹ to 10 10 ⁶ Pa at temperatures of 30 to 130 ℃ of. s viscosity and 10 ⁶ Pa at room temperature. s or greater viscosity.

In another aspect, the present invention provides a packaged product of an organic electronic device, comprising: a substrate; an organic electronic device formed on the substrate; and a bonding film encapsulating the organic electronic device to cover an entire surface of the organic electronic device.

In yet another aspect, the present invention provides a packaged organic electronic device A method comprising applying the bonding film to a substrate, wherein an organic electronic device is formed on the substrate, whereby a bonding layer of the bonding film covers an entire surface of the organic electronic device; and the bonding layer is cured.

A bonding film according to an exemplary embodiment of the present invention is used to encapsulate or encapsulate an organic electronic device. As used herein, the phrase "organic electronic device (OED)" means having a product or device comprising a layer of organic material that utilizes holes and electrons to create a charge exchange between a pair of opposing electrodes. The organic electronic device may include a photovoltaic device, a rectifier, a transformer, and an OLED, but the invention is not limited thereto. In a specific embodiment, the organic electronic device can be an OLED.

A bonding film according to an exemplary embodiment of the present invention includes a bonding layer whose processability is improved by controlling the viscosity at room temperature or increasing the temperature of the bonding layer in an uncured (B-stage) state, and The moisture vapor barrier effect is maximized by including a moisture adsorbent.

In a particular embodiment, the tie layer can be formed using a curable hot melt adhesive composition comprising at least one curable resin. The phrase "curable hot melt adhesive composition" as used herein may be meant to remain solid or semi-solid at room temperature, melted by application of heat to exhibit pressure sensitive adhesive properties, and after the adhesive has cured Only firmly adhere the adhesive of the target material.

The bonding film according to an exemplary embodiment of the present invention may have 10 ⁶ Pa in an uncured state at room temperature. s or greater or 10 ⁷ Pa. s or greater viscosity. The phrase "room temperature" means a temperature that is not raised or lowered in the natural environment. The room temperature can be from about 15 ° C to 35 ° C, specifically from about 20 ° C to 25 ° C, and more specifically about 25 ° C. This viscosity can be measured using a higher rheological expansion system (ARES). When the viscosity of the curable hot-melt adhesive is controlled within the above range, no burrs or cracks are generated during punching, whereby the film is easily handled, and the film has good processability when the organic electronic device is packaged. The flat plate is packaged into a uniform thickness. Further, when the problem of shrinkage and volatile gas generation is naturally reduced when the resin is cured, it (the film) can prevent physical or chemical damage to the organic electronic device. As long as the adhesive is in a solid or semi-solid state, the upper limit of the viscosity is not particularly limited, and for example, when the processability is considered, the viscosity can be controlled to be about 10 ⁶ Pa. s or smaller.

The bonding film according to an exemplary embodiment of the present invention may have a temperature of 10 ¹ to 10 ⁶ Pa when laminated. s or 10 ² to 10 ⁵ Pa. The viscosity of s, that is, in the tempered state in the elevated temperature range before curing. As used herein, the phrase "uncured state" means an intermediate state in which the curing reaction of the curable resin is rarely performed, also referred to as "B-stage." When the bonding layer of the bonding film is laminated in an uncured state, the viscosity in an increasingly higher temperature range of about 30 to 130 ° C, which is in an increasingly higher temperature range before curing, can be controlled. Within the above range, to reduce failures and improve the reliability of panel assembly.

Generally, in order to assemble a panel, thermal lamination is performed by applying a heat of 50 ° C to 100 ° C under vacuum. However, when there is a bubble remaining or an unstacked portion is generated during the lamination operation, a malfunction may occur. In addition, when sticky When the mixture leaks due to the viscosity of the bonding film below a certain level during thermal lamination, precise assembly boundaries may not be provided, and a uniform thickness may not be maintained in a large product. Conversely, when the viscosity is above a certain desired level, uncomplexed portions may be formed in the bonded film. However, unlike the conventional process, the bonding film according to an exemplary embodiment of the present invention can prevent bubble generation or retention, and control the viscosity gradually increased in the uncured state within a specified range by providing a sticker according to the adhesive panel. At the same time, the panel with no step difference is adhered to the viscous property of the film temperature increment. Further, in the curing operation after the pasting, the fluidity of the bonding film may be improved and the wettability may be improved, thereby achieving better adhesive properties and removing the remaining fine bubbles.

When the panel is assembled, the adhesive flows or leaks at the lamination temperature. When the bonding film is laminated to the adherend at a temperature of 50 to 100 ° C in an uncured state, the adhesive of the bonding layer may leak 1 mm or less from the original position. That is, the adhesive present in any portion of the bonding layer in the uncured state is unlikely to leak more than 1 mm from the original position when laminated. In such an uncured state, since the fluidity of the binder is controlled by controlling the viscosity of the bonding layer in the rising temperature range, reliability can be provided when the binder is applied to the process.

The bonding layer may be formed in a single layer or a multilayer structure including at least two sub-bonding layers. When the bonding film has a multilayer structure including at least two sub-bonding layers, the difference in viscosity between the sub-bonding layers may be less than 30 Pa at a temperature between 30 and 130 ° C in the uncured state. s, 25 Pa. s or smaller or 20 Pa. s or smaller. In the sub-bonding layers, the upper or lower layer The viscosity may be high or low, and the difference in viscosity between the sub-bonding layers may preferably be 0 Pa. s.

In addition, when the uncured state is at a temperature between 30 and 130 ° C, the difference in viscosity between the sub-bonding layers is less than 30 Pa. In the case of s, the fluidity or leakage between the sub-bonding layers may be from 0 μm to 300 μm at the time of lamination. Here, in the general lamination operation, the bonding film may be thermally laminated on the adherend at a temperature of 50 to 100 ° C and a variable pressure range, but the invention is not limited thereto. As a specific example, the laminate can be applied at a pressure of from 0.05 MPa to 5 MPa.

The viscosity of each sub-bonding layer can be controlled by changing the components included in the bonding layer, or changing the content ratio of the components, the content of the additive, the type or diameter of the moisture adsorbent or filler, and the conditions for forming the bonding film. .

When the bonding layer includes at least two sub-bonding layers, the at least one sub-bonding layer may include a curable resin and a moisture adhesive. For example, when the bonding layer is made of two layers, a moisture adsorbent may be included in the upper bonding layer instead of the lower bonding layer. In this case, when the bonding layer is to be used to assemble the panel, the moisture adsorbent may not be contained in the component directly attached to the organic electronic device, and thus damage to the device due to the moisture adsorbent may be prevented.

In the sub-bonding layer constituting the bonding layer, the kind and content of the curable resin, the moisture adsorbent or another additive, and the kind and content of the filler may be the same or different from each other.

The curable resin can have a solid state of 50 g/m ² . Day or less, 30 g/m ² . Day or smaller, 20 g/m ² . Day or smaller or 15 g/m ² . Water vapor transmission rate (WVTR) for days or less. The phrase "cured state of the curable resin" means that when the curable resin is used alone or in combination with other components such as a curing agent and then applied to the package, it is cured or crosslinked by heat or radiation of light. It is converted into a state in which the curable resin has a fixed component of the moisture adsorbent and the filler as a structural binder. The WVTR can be measured after the curable resin is cured and the cured product is formed into a film having a thickness of 80 μm, depending on the thickness direction of the cured product at 38 ° C and at a relative humidity of 100%. In addition, the WVTR can be measured in accordance with ASTM F1249.

Since the WVTR of the curable resin is controlled within the above range, it is possible to effectively suppress the penetration of water, steam or oxygen into the packaged product of the organic electronic device, and it is possible to exhibit the effect of initiating the moisture-reactive adsorbent.

Since the WVTR of the resin in a cured state is lowered, the package structure has better performance. The lower limit of the WVTR is not particularly limited, but is preferably 0 g/m ² . day.

The bonding film may have a glass transition temperature (Tg) in a cured state of 90 ° C or higher.

The curable resin of a specified type which can be used in the exemplary embodiment of the present invention is not particularly limited, and may include, for example, a plurality of different heat-curable, photocurable, and dual-purpose curable resins known in the related art. . The phrase "heat-curable resin" means a resin which can be cured by applying a suitable heat or aging process, and the phrase "photocurable resin" means a resin which can be cured by electromagnetic wave radiation, and the phrase "dual-use curable" "Resin" means a resin which has both the characteristics of a heat curable resin and a photocurable resin and which can be cured by electromagnetic wave radiation and heat application. In addition, the classification of electromagnetic waves Among them, particle beams such as microwaves, IR rays, UV rays, X-rays, and gamma rays, and electron beams such as α-particle beams, photon beams, neutron beams, and electron beams may be included. As a specific example of the photocurable resin, a cationic photocurable resin can be used. The cationic photocurable resin means a resin which can be cured by a cationic curing reaction caused by cationic polymerization or electromagnetic wave radiation.

The curable resin of the specified type which can be used in the exemplary embodiment of the present invention is not particularly limited as long as the curable resin has the above characteristics. For example, the resin capable of curing to exhibit adhesive properties may include at least one thermally curable functional group selected from the group consisting of glycidyl groups, isocyanate groups, hydroxyl groups, carboxyl groups or phosphonium groups, or at least one capable of curing by radiation or electromagnetic waves. a functional group selected from the group consisting of an epoxy group, a cyclic ether group, a thio group, an acetal group or a lactone group. Further, the resin of the specified type may include an acrylic resin, a polyether resin, an isocyanate resin or an epoxy resin, but the invention is not limited thereto.

As the curable resin, an aromatic group or an aliphatic group, or a linear or branched epoxy resin can be used. In an exemplary embodiment of the invention, an epoxy resin containing at least two functional groups and an epoxy equivalent weight of from 180 to 1,000 g/eq may be used. When an epoxy resin having the above epoxy equivalent is used, the cured product can have characteristics such as adhesive retention and glass transition temperature which are effectively maintained. Such epoxy resin may be cresol novolac epoxy resin, bisphenol A epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, 4-functional epoxy resin, biphenyl epoxy resin , trisphenol methane epoxy resin, naphthalene epoxy resin, dicyclopentene epoxy resin and A mixture of one or at least two of dicyclopentene-modified phenolic epoxy resins.

In the specified exemplary embodiment of the present invention, an epoxy resin including a ring structure in the molecular structure may be used, and for example, an epoxy resin including an aromatic group (for example, a phenyl group) may be used. When the epoxy resin includes an aromatic group, the cured product can have excellent thermal and chemical stability and low moisture absorption, thereby improving the reliability of the packaged product of the organic electronic device. The aromatic group-containing epoxy resin may be, but not limited to, a biphenyl type epoxy resin, a dicyclopentene type epoxy resin, a naphthalene type epoxy resin, a dicyclopentene modified phenol type epoxy Resin, cresol epoxy resin, bisphenol epoxy resin, aryl phenol ether (xyloc) epoxy resin, polyfunctional epoxy resin, phenol novolac epoxy resin, trisphenol methane epoxy resin and A mixture of one or at least two of an alkyl modified trisphenol methane epoxy resin.

In addition to the curable resin, the bonding layer (the bonding layer in the case of a single layer or part or all of at least one sub-bonding layer in the multilayer case) further includes a moisture adsorbent. The phrase "moisture adsorbent" can be used in response to the chemical reaction with moisture, and is also referred to as a moisture reactive adsorbent, in accordance with the meaning of a component that adsorbs or removes water or vapor entering from the external environment.

The moisture adsorbent adsorbs water or vapor via a chemical reaction with steam, water or oxygen entering the bonding layer. The moisture adsorbent of a specified type which can be used in the exemplary embodiment of the present invention is not particularly limited, and may be, for example, a metal powder such as alumina, metal oxide, organic metal oxide, metal salt, and phosphorus pentoxide. One or a mixture of at least two of (P ₂ O ₅ ).

Specific examples of the metal oxide may be lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), barium oxide (BaO), calcium oxide (CaO) or magnesium oxide (MgO), and the metal salt may be Sulfate such as lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga ₂ (SO _{4 ) 3} ), titanium sulphate (Ti(SO ₄ ) ₂ ) or nickel sulphate (NiSO ₄ ); metal halides such as calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), chlorination Yttrium (YCl ₃ ), copper chloride (CuCl ₂ ), barium fluoride (CsF), barium fluoride (TaF ₅ ), barium fluoride (NbF ₅ ), lithium bromide (LiBr), calcium bromide (CaBr ₂ ), 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 A chlorate such as barium perchlorate (Ba(ClO ₄ ) ₂ ) or magnesium perchlorate (Mg(ClO ₄ ) ₂ ), but the invention is not limited thereto.

In an exemplary embodiment of the invention, the metal oxides may be mixed with the composition in a state where the moisture adsorbent is suitably processed. For example, depending on the kind of the organic electronic device to which the bonding film is applied, the bonding layer may be a film having a thickness of 30 μm or less, and in this case, it may be necessary to perform a grinding process on the moisture adsorbent. In order to grind the moisture adsorbent, processing such as a 3-roll mill, a bead mill or a ball mill can be used. Further, when the bonding film is applied to a top emission type organic electronic device, the transmittance of the bonding layer is very important, and thus the size of the moisture adsorbent must be reduced. Therefore, in order to be applied to this application, the moisture adsorbent must be subjected to a grinding process.

The bonding layer may include 5 to 100 or 5 to 90 parts by weight of a moisture adsorbent with respect to 100 parts by weight of the curable resin. Since the content of the moisture adsorbent is controlled within the above range, the moisture barrier property can be maximized within a range that does not cause damage to the organic electronic device.

Unless specifically defined otherwise, the unit "parts by weight" as used herein refers to the weight ratio between the components.

In the bonding layer of the bonding film, the moisture adsorbent can be uniformly dispersed.

The bonding layer of the bonding film according to an exemplary embodiment of the present invention may include a filler such as an inorganic filler. The filler may extend the passage of water or vapor into the encapsulating structure to inhibit water or vapor infiltration and maximize the resistance to water and vapor due to the matrix structure of the curable resin and through interaction with the moisture adsorbent . The filler of a specified type that can be used in an exemplary embodiment of the invention can be, but is not limited to, clay, talc, cerium oxide, barium sulfate, aluminum hydroxide, calcium carbonate, magnesium carbonate, zeolite, zirconia, oxidation. One or a mixture of at least two of titanium or montmorillonite.

Further, in order to improve the bonding efficiency between the filler and the curable resin, a product treated with an organic material may be used as the filler, or a coupling agent may be additionally added to the filler.

The binder composition may include from 1 to 50 or from 1 to 30 parts by weight of the filler relative to 100 parts by weight of the curable resin. Since the content of the filler is controlled to 1 part by weight or more, a cured product having excellent water or vapor barrier properties and mechanical properties can be provided. Further, since the content of the filler is controlled to 50 parts by weight or less, a film type which can be formed can be provided. And even when formed in a film, a cured product of adhesive properties can be exhibited.

The bonding layer of the bonding film according to an exemplary embodiment of the present invention may additionally include an initiator capable of starting a curing reaction of the curing agent or a resin capable of forming a matrix such as a crosslinked structure via reaction with a curable resin, for example, a cation Type photopolymerization initiator.

The specified kind of the curing agent is not particularly limited and may be appropriately selected depending on the type of the functional group included in the curable resin or the resin to be used. The curing agent may be a latent curing agent such as an imidazole compound. For example, when the epoxy resin is used as a curable resin, a general curing agent for an epoxy resin known in the related art can be used as the curing agent, which can be, but not limited to, an amine compound, an imidazole system. One of a compound, a phenolic compound, a phosphorus compound, and an acid anhydride compound, or a mixture of at least two.

The bonding layer may include 1 to 20 or 1 to 10 parts by weight of a curing agent with respect to 100 parts by weight of the curable resin. However, this content is only an example of the present invention. That is, the curing agent content may vary depending on the kind and content of the curing agent or functional group, and the matrix structure or crosslinking density to be achieved.

Further, such an initiator, for example, the cationic photopolymerization initiator is not particularly limited, and thus a cationic photopolymerization initiator such as an aromatic diazonium salt, an aromatic iodine aluminum salt, or an aromatic hydrazine is known. A salt or an iron-aromatic complex, and preferably an aromatic phosphonium salt, can be used. However, the invention is not limited thereto.

For example, the starter may comprise a curable relative to 100 parts by weight The resin is 0.01 to 10 or 0.1 to 3 parts by weight. When the content of the cationic photopolymerization initiator is too low, curing may be insufficient, and when the content of the cationic photopolymerization initiator is too high, the content of the ionic material may be increased after curing, thereby lowering the binder. Persistence, or due to the initiator having the properties of forming a conjugate acid, the optical durability of the film may be reduced. Corrosion may occur depending on the base, and when this is considered, an appropriate content range may be selected.

The bonding layer may additionally comprise a high molecular weight resin. The high molecular weight resin can be used to improve formability when the composition for forming the bonding layer is formed into a film or sheet. Further, the high molecular weight resin can be used as a high temperature viscosity control agent for controlling fluidity during hot melt processing.

The kind of the high molecular weight resin which can be used in the exemplary embodiment of the present invention is not particularly limited as long as the resin has compatibility with another component such as the curable resin. The specified type of high molecular weight resin that can be used may be, but not limited to, a resin having a weight average molecular weight of 20,000 or more, which is a phenoxy resin, an acrylate resin, a high molecular weight epoxy resin, an ultra high molecular weight epoxy resin. A mixture of one or at least two of a highly polar functional group-containing rubber and a highly polar functional group-containing reactive rubber, but the invention is not limited thereto.

When the high molecular weight resin is included in the bonding layer, the content is controlled according to the desired physical properties, and is not particularly limited. For example, the high molecular weight resin may include about 10 to 200, 20 to 150, or 20 to 100 parts by weight or less with respect to 100 parts by weight of the curable resin. Since the binder resin content is controlled to 10 to 200 parts by weight or less, it can be effectively protected. The compatibility with the components of the resin composition is maintained, and the adhesive resin can be used as a binder. When the content of the high molecular weight resin, that is, the binder resin is too low, the resin may leak due to low viscosity during the lamination process, thereby improving the room temperature pressure-sensitive bond strength and controlling the release property. The difficulty of the aspect. Further, when the content of the high molecular weight resin is too high, a phenomenon of insufficient lamination property may occur. Therefore, since the viscosity of the adhesive layer is controlled by controlling the content of the high molecular weight resin to lower the viscosity difference, optimum processability and physical properties can be ensured.

The bonding layer of the bonding film may additionally include additives such as other fillers to improve the durability of the cured product, and a coupling agent, a plasticizer, a UV stabilizer, and an antioxidant for improving mechanical strength and bonding strength have no effect on the present invention. influences.

In the case where the film includes the bonding layer, the structure of the bonding film according to an exemplary embodiment of the present invention is not particularly limited. For example, the bonding film may have a structure including a base film or a release film (hereinafter, referred to as "first film"); and a bonding layer formed on the base film or the release film. The bonding film may additionally include another base film or a release film (hereinafter, referred to as "first film"), which is formed on the bonding layer.

1 to 3 are cross-sectional views of a bonding film according to an exemplary embodiment of the present invention. As shown in FIG. 1, a bonding film according to an exemplary embodiment of the present invention may include a bonding layer 22 formed on a base film or a release film 21.

In another aspect of the present invention, as shown in FIG. 2, the bonding film may include a bonding layer having a multilayer structure, for example, the bonding layer includes moisture absorption. The first sub-bonding layer 22a excluding the auxiliary agent and the second bonding layer 22b including the moisture adsorbent are formed on the base film or the release film 21, respectively.

In still another aspect, as shown in FIG. 3, the bonding film may additionally include a base film or a release film 23 formed on the bonding layer 22. In a specific embodiment, to complete the flexible display, a gas barrier layer can be disposed on one surface of the base film. However, the bonded film shown in the drawings is only one aspect of the present invention. A bonding film according to an exemplary embodiment of the present invention may include, for example, a composition of the present invention without a supporting substrate, and may have a single layer bonding layer that maintains a solid phase or a semi-solid phase at room temperature, and in some In the case, the type of double-sided bonding film.

The first type of film of the specified kind which can be used in the exemplary embodiment of the present invention is not particularly limited. As for the first film, for example, a general polymer film in the related art can be used. For example, as for the base film or the release film, a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a vinyl chloride copolymer A 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 can be used. In addition, a suitable release treatment can be applied to one or both of the base film or the release film. As the release agent used in the release treatment of the base film, an alkyd, lanthanide, fluorine-based, unsaturated ester-based, polyolefin-based or paraffin-based release agent can be used, and preferably, with respect to heat resistance. The alcoholic, lanthanide or fluorine-based release agent can be used, but the invention is not limited thereto.

Furthermore, a second film that can be used in an exemplary embodiment of the invention (The type of "cover film" hereinafter) is also not particularly limited. For example, the second film can be the same or different than the first film exemplified as the first film. In addition, the second film can also be subjected to a suitable release treatment.

The thickness of the base film or the release film (first type) is not particularly limited and may be appropriately selected depending on the use thereof. For example, the first film may have a thickness of from 10 μm to 500 μm or from 20 μm to 200 μm. When the thickness of the film is less than 10 μm, the transformation of the base film may be easily caused in the forming process, and when the thickness of the film is more than 500 μm, economic feasibility may be lowered.

The thickness of the second film is also not particularly limited. For example, the thickness of the second film can be set to be the same as the first film. Alternatively, considering the workability, the thickness of the second film may be set to be smaller than that of the first film.

The thickness of the bonding layer included in the bonding film according to an exemplary embodiment of the present invention is not particularly limited, and may be appropriately selected depending on the use of the film in consideration of the following conditions. The bonding layer may be, for example, 5 μm to 200 μm or 5 μm to 100 μm.

In an exemplary embodiment of the present invention, the method of forming the bonding film is not particularly limited. For example, the bonding film can be formed into a coating solution (first operation) including a composition for a bonding layer on a base film or a release film by a coating method, and dried in the first operation. Medium coated coating solution (second operation). The method of forming the bonding film may additionally comprise further compressing the base film or the release film onto the coating solution dried in the second pass operation (third operation).

The first operation is to prepare a coating solution by dissolving or dispersing the composition for the bonding layer in a suitable solvent. The coating solution used in this operation includes a curable resin content which can be appropriately controlled depending on the desired moisture barrier property and film formability.

The kind of the solvent used to prepare the coating solution is not particularly limited. However, since the drying time of the solvent is too long, or the solvent must be dried at a high temperature, the film may be problematic in terms of workability or durability. For this reason, a solvent having a volatilization temperature of 100 ° C or lower can be used. Further, in consideration of film formability, a small amount of a solvent having a volatilization temperature in the above range or higher may be mixed. The solvent may be, but not limited to, methyl ethyl ketone (MEK), acetone, toluene, dimethylformamide (DMF), methyl cellulose (MCS), tetrahydrofuran (THF) or N-methylpyrrolidone (NMP). One or a mixture of at least two.

In the first operation, the method of applying the coating solution to the base film or the release film is not particularly limited, and known methods such as knife coating, roll coating, spray coating, gravure coating, enamel A coating method, a comma coating method or a lip coating method can be used without limitation.

This second operation is performed by drying the coating solution applied by the first operation to form a bonding layer. That is, in this second operation, the bonding layer can be formed by drying and removing the solvent by heating the coating solution applied to the film. Here, the drying conditions are not particularly limited, and the drying may be carried out at 70 ° C to 200 ° C for 1 minute to 10 minutes.

In this forming method, after the second operation, another base film or a release film may be further compressed to be combined on the film. The third operation of the layer. In this third operation, the other release film or base film (cover film or second film) can be compressed onto the dry bond layer applied to the film via a roll lamination process.

4 is a cross-sectional view of a packaged product of an organic electronic device in accordance with an exemplary embodiment of the present invention. In another exemplary embodiment of the present invention, the packaged product of the organic electronic device includes a substrate 31, an organic electronic device 33 formed on the substrate 31, and an organic electronic device 33 encapsulating the organic electronic device 33. The above-described bonding film 32 of the entire surface. Here, the coverage of the entire surface of the organic electronic device 33 indicates that the bonding film 32 is adhered to the entire area of the organic electronic device 33 (all surfaces not in contact with the substrate, for example, the upper surface and the side surface) without a gap. .

The packaged product of the organic electronic device may further include a second substrate (covering substrate) 34 on the bonding film 32 for bonding the substrate 31 and the second substrate 34.

The organic electronic device 33 can be, for example, an organic light emitting diode (OLED).

The packaged product of the organic electronic device may include a protective layer (not shown) that protects the organic electronic device 33 between the bonding film 32 and the organic electronic device 33.

The packaged product of the organic electronic device according to the exemplary embodiment of the present invention has the advantages of simple process and reduced manufacturing cost. The packaged product of the organic electronic device can also be used regardless of the method of designing the organic electronic device, and provides excellent mechanical durability to the organic electronic device.

In still another exemplary embodiment of the present invention, a method of packaging an organic electronic device includes applying the bonding film to a substrate, wherein an organic electronic device is formed on the substrate to cover an entire surface of the organic electronic device, and the bonding The layer is cured.

The bonding film is applied to the organic electronic device by lamination, hot pressing or vacuum compression of the bonding film, but the invention is not particularly limited.

The bonding film may be applied to the organic electronic device at 50 ° C to 100 ° C, and the curing operation may be performed by heating at 70 ° C to 110 ° C or by irradiation with UV rays.

Additionally, the method can additionally include adhering the bonding film to another encapsulating material such as glass or metal to face each other.

The method of packaging an organic electronic device includes forming a transparent electrode on a substrate such as a glass or polymer film by vacuum deposition or sputtering, and forming an organic material layer on the transparent electrodes. The organic material layer may include a hole injection layer, a hole transport layer, a radiation layer, an electron injection layer, and/or an electron transfer layer. Subsequently, a second electrode system is further formed on the organic material layer. Thereafter, the bonding film is applied to the top surface of the organic electronic device on the substrate to cover the entire surface of the organic electronic device. Here, the method of applying the bonding film is not particularly limited, but may be heating or compressing a cover substrate (for example, a glass or a polymer film), wherein the bonding layer of the bonding film described above is previously transferred to the bonding substrate The top surface of the organic electronic device on the substrate. In this operation, for example, when the bonding film is transferred onto the cover substrate, the bonding film may be applied by a vacuum press or a vacuum laminator by peeling off the base film or the release film formed on the film. Thermal transfer The cover is on the substrate. In this operation, when the curing reaction of the bonding film is performed in a range or a larger range, the cohesive strength or bonding strength of the bonding film may be lowered, thereby respectively controlling the processing temperature and the processing time at about 100 ° C and About 5 minutes. Similarly, even if the cover substrate to which the bonding film is transferred is heat-pressed to the organic electronic device, a vacuum press or a vacuum laminator can be used. The temperature conditions for this operation can be adjusted as above, and the processing time can be within 10 minutes.

Further, another curing process of the bonded film pressed by the organic electronic device may be performed, and such a curing process (main curing) may be performed, for example, in a heating chamber or an ultraviolet chamber. The curing conditions in this main curing can be appropriately selected in consideration of the stability of the organic electronic device.

However, the above-described formation process is merely an example for packaging the organic electronic device, and thus the order or condition of the process can be arbitrarily changed. For example, the order of the transfer and compression processes can be changed to transfer the bonding film to the organic electronic device on the substrate, and then the cover substrate is compressed. Further, after the protective layer is formed on the organic electronic device, the bonding film is applied and then cured without the need to cover the substrate.

Hereinafter, the present invention will be described in more detail with reference to the embodiments of 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.

Example 1

1. Preparation of a solution for the first sub-bonding layer

Put 50 g of epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 50 g of phenoxy resin (YP-50, Tohto Kasei Co., Ltd.) were placed in a reactor and diluted with 100 g of methyl ethyl ketone. 1 g of an imidazole curing agent (2MA.OK, Shikoku Chemicals Co., Ltd.) was added, and the resulting solution was homogenized.

2. Preparation of a solution for the second sub-bonding layer

The moisture adsorbent solution was ground by ball milling for 10 hours by adding 10 g of MgO at a concentration of 20% by weight as a moisture adsorbent. Further, 60 g of an epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 40 g of a phenoxy resin (YP-50, Tohto Kasei Co., Ltd.) were separately placed in the reactor. It was prepared by diluting with 100 g of methyl ethyl ketone. Thereafter, 1 g of an imidazole curing agent (2MA.OK, Shikoku Chemicals Co., Ltd.) was added, and the resulting solution was homogenized. The previously prepared moisture adsorbent solution was placed in this homogenization solution and stirred at high speed for 1 hour to prepare a solution for the second sub-bonding layer.

3. Combined film formation

The first sub-bonding layer having a thickness of 15 μm is applied to the release surface of the release PET by using a knife coater to apply the solution prepared above for the first sub-bonding layer at 130 ° C in a desiccator The resulting surface was dried for 3 minutes to form.

A second sub-bonding layer having a thickness of 30 μm is applied to the release surface of the off-line PET by using a knife coater to apply the solution prepared above for the second sub-bonding layer at 130 ° C in a desiccator The resulting surface was dried for 3 minutes to form.

The first and second sub-bonding layers are assembled to form a multilayer bonding film.

Example 2

A single layer structural bonding film having a thickness of 45 μm was formed using only the solution for the second sub-bonding layer of Example 1.

Example 3

A multilayer bonding film was formed as described in Example 1, except that the solutions for the first and second sub-bonding layers were prepared in the following manner.

1. Preparation of a solution for the first sub-bonding layer

25 g of epoxy resin (YD-128, Kukdo Chemical Co., Ltd.), 35 g of epoxy resin (YD-014, Kukdo Chemical Co., Ltd.) and 40 g of phenoxy resin (YP- 50, Tohto Kasei Co., Ltd.) was placed in a reactor and prepared by diluting with 100 g of methyl ethyl ketone. 1 g of an imidazole curing agent (2MA.OK, Shikoku Chemicals Co., Ltd.) was added, and the resulting solution was homogenized.

2. Preparation of a solution for the second sub-bonding layer

The moisture adsorbent solution was ground by ball milling for 10 hours by adding 10 g of MgO at a concentration of 20% by weight as a moisture adsorbent. Further, 55 g of epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 45 g of phenoxy resin (YP-50, Tohto Kasei Co., Ltd.) were separately placed in the reactor. It was prepared by diluting with 100 g of methyl ethyl ketone. Thereafter, 1 g of an imidazole curing agent (2MA.OK, Shikoku Chemicals Co., Ltd.) was added, and the resulting solution was homogenized. The previously prepared moisture adsorbent solution is placed in the homogenization solution and stirred at high speed for 1 hour. At this time, a solution for the second sub-bonding layer is prepared.

Example 4

A multilayer bonding film was formed as described in Example 1, except that the solutions for the first and second sub-bonding layers were prepared in the following manner.

1. Preparation of a solution for the first sub-bonding layer

50 g of epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 50 g of phenoxy resin (YP-50, Tohto Kasei Co., Ltd.) were placed in the reactor at 100 g The methyl ethyl ketone was diluted and prepared. 1 g of an imidazole curing agent (2MA.OK, Shikoku Chemicals Co., Ltd.) was added, and the resulting solution was homogenized. Subsequently, 3 g of nano cerium oxide (Aerosil R972, Evonik Degussa) was uniformly dispersed.

2. Preparation of a solution for the second sub-bonding layer

The moisture adsorbent solution was ground by ball milling for 10 hours by adding 10 g of MgO at a concentration of 20% by weight as a moisture adsorbent. Further, 50 g of an epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 50 g of a phenoxy resin (YP-50, Tohto Kasei Co., Ltd.) were separately placed in the reactor. It was prepared by diluting with 100 g of methyl ethyl ketone. Thereafter, 1 g of an imidazole curing agent (2MA.OK, Shikoku Chemicals Co., Ltd.) was added, and the resulting solution was homogenized. The previously prepared moisture adsorbent solution was placed in this homogenization solution and stirred at high speed for 1 hour to prepare a solution for the second sub-bonding layer.

Comparative example 1

A multilayer bonding film was formed in the same manner as in Example 1 except that the content of the phenoxy resin (YP-50, Tohto Kasei Co., Ltd.) used in the solution for the first sub-bonding layer in Example 1 was changed to 30 g. .

Comparative example 2

Epoxy and phenoxy resins used in the solution for the second sub-bonding layer in Example 2 were 20 g of epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 80 g of phenoxy resin. A bonding film having a single layer structure having a thickness of 45 μm was formed in the same manner as in Example 2 except that (YP-50, Tohto Kasei Co., Ltd.) was replaced.

Comparative example 3

Epoxy and phenoxy resins used in the solution for the second sub-bonding layer in Example 2 were 80 g of epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 20 g of phenoxy resin. A bonding film having a single layer structure having a thickness of 45 μm was formed in the same manner as in Example 2 except that (YP-50, Tohto Kasei Co., Ltd.) was replaced.

Comparative example 4

A multilayer bonding film was formed as described in Example 1, except that the solutions for the first and second sub-bonding layers were prepared in the following manner.

1. Preparation of a solution for the first sub-bonding layer

50 g of epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 30 g of phenoxy resin (YP-50, Tohto Kasei Co., Ltd.) was placed in a reactor and prepared by diluting with 100 g of methyl ethyl ketone. 1 g of an imidazole curing agent (2MA.OK, Shikoku Chemicals Co., Ltd.) was added, and the resulting solution was homogenized.

2. Preparation of a solution for the second sub-bonding layer

The moisture adsorbent solution was ground by ball milling for 10 hours by adding 10 g of MgO at a concentration of 20% by weight as a moisture adsorbent. Further, 60 g of an epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 40 g of a phenoxy resin (YP-50, Tohto Kasei Co., Ltd.) were separately placed in the reactor. It was prepared by diluting with 100 g of methyl ethyl ketone. Thereafter, 1 g of an imidazole curing agent (2MA.OK, Shikoku Chemicals Co., Ltd.) was added, and the resulting solution was homogenized. The previously prepared moisture adsorbent solution was placed in this homogenization solution and stirred at high speed for 1 hour to prepare a solution for the second sub-bonding layer.

Comparative Example 5

A multilayer bonded film was formed in the same manner as in Example 1 except that the MgO content was changed to 70 g in the preparation of the moisture adsorbent solution applied to the solution for the second sub-bonding layer in Example 1.

Experimental Example 1: Measurement of viscosity

The viscosity of the bonding layers according to the bonding films of Examples 1 to 4 and Comparative Examples 1 to 5 was measured using ARES, and the viscosity at room temperature and 80 ° C is shown in Table 1.

Experimental Example 2: Measurement of difference in adhesion between layers

The viscosity of the two sub-bonding layers of the bonding layers of the bonding films of Examples 1, 3 and 4 and Comparative Examples 1, 4 and 5 was measured using ARES, and the viscosity and viscosity difference at 80 ° C were shown in Table 2 ( Interlayer).

Experimental Example 3: Measurement of the degree of leakage at the time of lamination

The bonding layer of the bonding film was measured using a microscope at a lamination temperature of 80 ° C from the beginning of the bonding film of each of Examples 1 to 4 and Comparative Examples 1 to 5. The degree of leakage, and the results are shown in Table 3.

Experimental Example 4: Confirmation of moisture resistance

A calcium test was performed to study the moisture resistance of the bonding films in each of Examples 1 to 4 and Comparative Examples 1 to 5. In particular, 9-point calcium (Ca) was deposited on a glass substrate having a size of 100 mm × 100 mm to a size of 5 mm × 5 mm and a thickness of 100 nm, and a vacuum press was used at 80 ° C. The cover film transferred from the bonded film of each of 1 to 4 and Comparative Examples 1 to 5 was heat-pressed at a point where each of the deposited calcium was passed for 1 minute. Thereafter, the obtained product was cured in a high-temperature drier at 100 ° C for 3 hours, and the encapsulated calcium test piece was cut into a size of 11 mm × 11 mm. The obtained test piece was placed in an environment including a temperature of 85 ° C and a relative humidity of 85% in a constant temperature and humidity chamber, and the time at which the oxidation reaction of calcium caused by moisture permeation began to turn transparent. The results are shown in Table 4.

Experimental Example 5: Measurement of the degree of foaming

When a 3 Å organic light-emitting panel was formed using the bonding films in each of Examples 1 to 4 and Comparative Examples 1 to 5, the degree of leaving bubbles at the time of lamination was observed with a microscope, and the results are shown in Table 5.

*◎: no bubbles, ○: small bubbles having a diameter of 100 μm or more, and ×: bubbles having a diameter of 1 mm or more

In addition, the use of Example 1 and Comparative Example 1 is shown in FIGS. 5 to 7. And an optical microscopic image of the degree of residual air bubbles observed after lamination when the light-emitting panel is formed by the bonding film in each of the two. Referring to Fig. 5, it was confirmed that there was no bubble after the bonding film was laminated. However, it was confirmed that a large amount of bubbles were attached, and thus the failure of Comparative Example 4 was caused, and the lamination failure of Comparative Example 2 was caused.

As seen from the above, in the bonded films of Examples 1 to 4 according to exemplary embodiments of the present invention, the difference in viscosity at room temperature and rising temperature and the difference in interlayer viscosity of the multilayer structure are controlled in the uncured state. In the range, the incidence of failure is reduced and the organic electronic device is effectively packaged so as not to be affected by moisture when manufacturing the packaged product of the organic electronic device. However, it was confirmed that the organic electronic device was not effectively packaged when the viscosity was not moderately controlled as shown in the comparative example.

Since the bonding film according to the exemplary embodiment of the present invention controls the viscosity of the bonding layer in the B-stage state at room temperature and the rising temperature within a specified range, excellent room temperature treatment property can be obtained, and it is impossible to assemble the panel. To ensure an accurate assembly boundary, the entire surface of the panel can be maintained at a uniform thickness, and an unlaminated portion (stack of rising temperature) cannot be produced at the time of lamination, and the failure rate can be lowered because no lamination of bubbles can be produced. Furthermore, since a film type adhesive and a non-liquid phase adhesive are used, the life and durability of the organic electronic device can be improved. In addition, the bonding film provides structural advantages of supporting and fixing the upper and lower substrates of the organic electronic device, thereby simplifying the method of packaging the organic electronic device and reducing the cost.

21‧‧‧Dissecting film

22‧‧‧Combination layer

22a‧‧‧ first sub-bonding layer

22b‧‧‧Second bonding layer

31‧‧‧Substrate

32‧‧‧ bonded film

33‧‧‧Organic electronic devices

34‧‧‧second substrate

1 to 3 are cross-sectional views of a bonding film according to an exemplary embodiment of the present invention; and FIG. 4 is a cross-sectional view of a package product of an organic electronic device according to an exemplary embodiment of the present invention; and FIGS. 5 to 7 An optical microscopic image was observed which observed the degree of bubble remaining after lamination when the light-emitting panel was formed using the bonding films according to Example 1 and Comparative Examples 1 and 2.

21‧‧‧Dissecting film

22‧‧‧Combination layer

23‧‧‧Dissecting film

Claims (24)

A bonding film for packaging an organic electronic device, comprising: a bonding layer comprising a curable resin and a moisture adsorbent, wherein the bonding layer is between 30 and 130 ° C when the bonding layer is in an uncured state 10 ¹ to 10 ⁶ Pa at any lamination temperature point. s has a viscosity of 10 ⁶ Pa at any room temperature between 15 and 25 ° C. s or greater viscosity, and wherein the bonding layer is composed of at least two sub-bonding layers, and the viscosity difference between the sub-bonding layers is at any laminating temperature point between 30 and 130 ° C in an uncured state. Less than 30Pa. s. The film of claim 1, wherein when the bonding film is laminated on the adhesive in an uncured state at a temperature of 50 to 100 ° C, the adhesive of the bonding layer leaks from the original position. 1mm or less. The film of claim 1, wherein when the bonding film is laminated to the adhesive at a temperature of 50 to 100 ° C in an uncured state, the difference in the degree of leakage of the adhesive of the sub-bonding layer is 0 to 300 μm. The film of claim 1, wherein the at least one sub-bonding layer of the sub-bonding layer comprises a curable resin and a moisture adsorbent. The film of claim 1, wherein the curable resin has 20 g/m ² in a cured state. Day or smaller water and vapor transfer rate. The film of claim 1, wherein the curable resin A heat curable or photocurable resin. The film of claim 1, wherein the curable resin comprises at least one member selected from the group consisting of glycidyl groups, isocyanate groups, hydroxyl groups, carboxyl groups, decylamino groups, epoxy groups, cyclic ether groups, sulfur groups, and acetal groups. Or a curable functional group of a lactone group. The film of claim 1, wherein the curable resin contains an aromatic epoxy resin in a molecular structure. The film of claim 1, wherein the moisture adsorbent is alumina, metal oxide, metal salt or phosphorus pentoxide. The film of claim 1, wherein the moisture adsorbent is selected from the group consisting of 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, At least one of the group consisting of CaBr ₂ , CeBr ₃ , SeBr ₄ , VBr ₃ , MgBr ₂ , BaI ₂ , MgI ₂ , Ba(ClO ₄ ) _{2 ,} and Mg(ClO ₄ ) ₂ . The film of claim 1, wherein the bonding layer comprises 5 to 100 parts by weight of a moisture adsorbent with respect to 100 parts by weight of the curable resin. The film of claim 1, wherein the bonding layer further comprises a filler. The film of claim 12, wherein the filler comprises a layer selected from the group consisting of clay, talc, cerium oxide, barium sulfate, aluminum hydroxide, calcium carbonate, magnesium carbonate, zeolite, zirconia, titania or montmorillonite. In the group At least one. The film of claim 12, wherein the bonding layer comprises from 1 to 50 parts by weight of the filler relative to 100 parts by weight of the curable resin. The film of claim 1, wherein the bonding layer further comprises a curing agent. The film of 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 film of claim 15 wherein the bonding layer comprises from 1 to 10 parts by weight of the curing agent relative to 100 parts by weight of the curable resin. The film of claim 1, wherein the bonding layer further comprises a high molecular weight resin. A packaged product of an organic electronic device, comprising: a substrate; an organic electronic device formed on the substrate; and a bonding film according to any one of claims 1 to 18, the bonding film encapsulating the organic electronic device Covering the entire surface of the organic electronic device. The packaged product of claim 19, further comprising: a second substrate on the bonding film, wherein the bonding film bonds the substrate to the second substrate. A method of packaging an organic electronic device, comprising: Applying a bonding film according to any one of claims 1 to 18 to a substrate, wherein an organic electronic device is formed on the substrate, whereby an entire surface of the organic electronic device is covered by a bonding layer of the bonding film; and the bonding is performed The layer is cured. The method of claim 21, wherein the bonding film is applied to the organic electronic device by laminating, hot pressing or vacuum-compressing the bonding film by a heat roll. The method of claim 21, wherein the bonding film is applied to the organic electronic device at 50 to 100 °C. The method of claim 21, wherein the curing is performed by heating or irradiating UV rays at 70 to 110 °C.