KR20130054194A - Adhesive film and encapsulation method of organic electronic device using the same - Google Patents

Abstract

PURPOSE: An adhesive film is provided to control viscosity at room temperature and use temperature, thereby obtaining excellent room temperature handling and maintaining uniform thickness. CONSTITUTION: An adhesive film comprises an adhesive layer(22) which includes a curable resin and a moisture absorbent. The adhesive layer has a viscosity of 10^1-10^6 Pa·s at 30-130 °C and a viscosity of 10^6 Pa·s at room temperature. A sealing method of an organic electronic device comprises a step of applying the adhesive film to a substrate in which the organic electronic device is formed in the upper part, to cover the front side of the organic electronic device; and a step of curing the adhesive film.

Description

Adhesive film and encapsulation method of organic electronic device using the same

Embodiments of the present invention relate to an adhesive film and a method of encapsulating an organic electronic device using the same.

An organic electronic device (OED) refers to an apparatus that includes an organic material layer that generates holes and electrons to generate an alternating current. Examples thereof include a photovoltaic device, a rectifier, A transmitter and an organic light emitting diode (OLED).

Organic light emitting diodes (OLEDs) among the organic electronic devices have lower power consumption, faster response speed, and are advantageous for thinning display devices or illumination. In addition, OLEDs are expected to be applied in various fields covering various portable devices, monitors, notebooks, and televisions because of their excellent space utilization.

In commercializing OLEDs and expanding their use, the biggest problem that the prior art has attempted to solve is durability. Organic materials and metal electrodes contained in OLEDs are very easily oxidized by external factors such as moisture. Thus, products containing OLEDs are highly sensitive to environmental factors. Accordingly, various methods have been proposed to effectively block the penetration of oxygen or moisture from the outside into organic electronic devices such as OLEDs.

In addition, a fundamental problem prior to the durability problem is to reduce the defect rate caused by the deterioration of the cohesiveness during panel assembly. It is also important that the adhesion between the panels is maintained at a certain level when assembling the panel, and it is also important to maintain a uniform thickness without adhesion with bubbles.

Therefore, in the embodiments of the present invention, it is possible to meet the enlargement and thinness of the organic electronic device, to provide a structural advantage by sealing the organic electronic device with a simpler process, We want to provide ashes.

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

One embodiment of the present invention is an adhesive film for encapsulating an organic electronic device,

Wherein the adhesive film comprises an adhesive layer comprising a curable resin and a moisture adsorbent, wherein the adhesive layer has a viscosity of 10 ¹ to 10 ⁶ Pa · s at 30 to 130 ° C in an uncured state, A viscosity of 10 ⁶ Pa · s or more is provided.

Another embodiment of the present invention includes a substrate; An organic electronic device formed on the substrate; And an adhesive film for sealing the organic electronic device to cover the front surface of the organic electronic device.

According to another embodiment of the present invention, there is also provided a method of manufacturing an organic electronic device, including the steps of: applying the adhesive film to a substrate on which an organic electronic device is formed, the adhesive layer of the adhesive film covering a front surface of the organic electronic device; And it provides a method of encapsulating an organic electronic device comprising the step of curing the adhesive layer.

The adhesive film according to the embodiments of the present invention can control the viscosity of the adhesive layer in the B-stage state at room temperature and in the heating range to a specific range, Not only uniform thickness can be maintained over the entire surface, but also unattached portions are not formed at the time of lamination (heat bonding), so that they can be bonded together without bubbles and the defective rate can be lowered. In addition, the use of a film-type adhesive, which is not a liquid adhesive, can improve the lifetime and durability of the organic electronic device. In addition, the adhesive film provides a structural advantage of supporting and fixing the upper and lower substrates of the organic electronic device, thereby simplifying the organic electronic device sealing method and reducing the cost.

1 to 3 are sectional views showing an adhesive film according to one embodiment of the present invention.
4 is a cross-sectional view illustrating an encapsulation product of an organic electronic device according to an embodiment of the present invention.
5 to 7 are optical microscope photographs showing the degree of residual bubbles after the laminating process when the organic luminescent panel was manufactured using the adhesive films of Example 1, Comparative Example 1 and Comparative Example 2, respectively.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. In the following description of the present invention, a detailed description of known general functions or configurations will be omitted. In addition, the accompanying drawings are schematic for the purpose of better understanding of the present invention, and in order to more clearly describe the present invention, parts irrelevant to the description are omitted. It is shown, and the scope of the present invention is not limited by the thickness, size, ratio and the like shown in the drawings.

The adhesive film according to one embodiment of the present invention is used for encapsulating or encapsulating an organic electronic device. The term " organic electronic device " means an article or apparatus having a structure including an organic material layer that generates alternating electric charges using holes and electrons between a pair of electrodes facing each other, , Rectifiers, transmitters, and organic light emitting diodes (OLEDs), but are not limited thereto. In one example of the present invention, the organic electronic device may be an OLED.

The adhesive film according to the embodiments of the present invention can improve the processability by controlling the viscosity of the adhesive layer in an uncured (B-stage) state at a room temperature and a heating temperature range, and can provide an adhesive Layer.

In one example, the adhesive layer may be formed using a curable hot melt adhesive composition comprising at least one type of curable resin. In the present specification, the term "curable hot melt adhesive composition" refers to a composition that maintains a solid or semi-solid state at room temperature, melts to exhibit adhesiveness upon application of heat, Which may be an adhesive capable of firmly fixing an object.

The adhesive film according to the embodiments of the present invention may have a viscosity at room temperature in an uncured state of 10 ⁶ Pa · s or more, or 10 ⁷ Pa · s or more. The term "room temperature" means a natural temperature that is not warmed or reduced, for example, about 15 ° C to 35 ° C, more specifically about 20 ° C to 25 ° C, and more specifically about 25 ° C. Can mean. The viscosity can be measured using an Advanced Rheological Expansion System (ARES). By adjusting the viscosity of the curable hot melt adhesive to the above range, burrs and cracks do not occur during punching, which facilitates handling. In the process of sealing organic electronic devices, the process is smooth and the plate can be sealed with a uniform thickness . In addition, it is possible to greatly reduce problems such as shrinkage and volatile gas, which may occur due to curing of the resin, to prevent physical or chemical damage to the organic electronic device. The upper limit of the viscosity is not particularly limited as long as the adhesive maintains a solid state or a semi-solid state at room temperature, and can be controlled within a range of about 10 ⁹ Pa · s or less in consideration of, for example, .

The adhesive film according to the embodiments of the present invention may have a viscosity of 10 ¹ to 10 ⁶ Pa · s or 10 ² to 10 ⁵ Pa · s at the time of lamination in the uncured state, have. In this specification, the term " uncured state " means an intermediate state in which the curing reaction of the curable resin hardly progresses, and may be referred to as a B-stage state. When the adhesive layer of the adhesive film is laminated in an uncured state, the viscosity of the laminated film in the temperature range from about 30 ° C to 130 ° C, which is the preheating temperature range, can be controlled within the above range, .

Generally, the panel is assembled by heat-bonding at a temperature of 50 to 100 ° C. in a vacuum state during assembly of the panel. However, when the bubble is caught in the cementing step or the non-cemented portion is generated, defects occur. Further, since the viscosity of the adhesive film is lower than a certain level, when the adhesive is leaked at the time of heat bonding, it is impossible to provide an accurate assembly margin, and a uniform thickness can not be maintained in a large area. On the contrary, if the viscosity is higher than a certain level required, there may be a problem that an unadhered portion may occur inside. However, unlike the prior art, the adhesive film according to the embodiments of the present invention controls the viscosity at the time of heating in an uncured state to a specific range to give a tack property to the adhesive film upon heating, Or trapping and to attach the panel without steps. Further, in the curing step after adhering, the flowability of the adhesive film is increased to improve the wettability, so that the adhesive property can be more firmly realized and the remaining fine bubbles can be eliminated.

When the adhesive film is laminated on the adherend in an uncured state at a temperature ranging from 50 to 100 ° C, the adhesiveness of the adhesive layer May be less than 1 mm from the original position. That is, the degree to which the adhesive present in a portion of the adhesive layer in the uncured state flows in the lamination process or the degree of deviation from the original position may not exceed 1 mm. By controlling the viscosity in the heating range of the adhesive layer in the uncured state as described above, the flowability of the adhesive can be controlled to provide reliability in application to the process.

The adhesive layer may be composed of a single layer or may have a multi-layer structure including at least two sub-adhesive layers. When the adhesive film has a multi-layer structure including at least two sub-adhesive layers, the difference in viscosity in the uncured state between the sub-adhesive layers in the temperature range of 30 to 130 占 폚 is less than 30 Pa · s, 25 Pa S or less or 20 Pa s or less. The viscosity of the upper or lower layer in each sub-adhesive layer may be large or small, and ideally the viscosity difference between each sub-adhesive layer may be 0 Pa · s.

When the difference in viscosity between the respective sub-adhesive layers in the uncured state at 30 to 130 ° C is less than 30 Pa · s, May be 0 mu m to 300 mu m. At this time, the general lamination process is to heat-bond the adhesive film to the adherend at a temperature range of 50 ° C to 100 ° C, a variable pressure range, but is not limited thereto. For example, the lamination may be performed at a pressure of 0.05 to 5 MPa.

The viscosity of each sub-adhesive layer can be controlled by varying the constituent components contained in the adhesive layer, by varying the content ratio of the constituent components, the content of the additive, the kind or the particle diameter of the water adsorbent or filler, .

In the case where the adhesive layer includes at least two sub-adhesive layers as described above, at least one sub-adhesive layer may include a curable resin and a moisture adsorbent. For example, when the adhesive layer is composed of two layers, the lower adhesive layer does not include a moisture adsorbent, and only the upper adhesive layer may contain a moisture adsorbent. In this case, if it is used in assembling the panel later, the moisture adsorbent is not included in the portion directly attached to the organic electronic device, and damage to the device by the moisture adsorbent can be prevented.

The type and content of the curing resin, the moisture adsorbent or other additive, the type and content of the filler, etc. may be the same or different in each of the sub-adhesive layers constituting the adhesive layer.

It said curable resin is water vapor transmission rate of at cured state (WVTR; water vapor transmission rate) is 50 g / m ² · day or less, 30 g / m ² · day or less, 20 g / m ² · day or less, or 15 g / m ² · It can be less than day. The term " cured state of the curable resin " means a state in which the curable resin is cured or crosslinked by heat or light irradiation, alone or through reaction with other components such as a curing agent, Or the like, and is converted into a state capable of exhibiting performance as a structural adhesive. The moisture permeability may be the moisture permeability measured in the thickness direction of the cured product at 38 캜 and 100% relative humidity after the curable resin is cured and the cured product is made into a film having a thickness of 80 탆. The moisture permeability can be measured according to ASTM F1249.

By controlling the moisture permeability of the curable resin in the above range, it is possible to effectively inhibit the penetration of moisture, moisture or oxygen into the organic electronic device encapsulation product, and exhibit the effect of introducing a moisture reactive adsorbent.

The lower the lower limit of the moisture permeability, the lower limit of the moisture permeability may ideally be 0 g / m ² · day, while the lower limit of the moisture permeability in the cured state of the resin shows a better performance as the lower the numerical value.

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

The specific kind of the curable resin that can be used in the embodiments of the present invention is not particularly limited, and for example, various thermosetting, photo-curing resins or dual curing resins known in the art can be used. The term " thermosetting resin " means a resin that can be cured through an appropriate heat application or aging process, the term " photo-curing resin " means a resin that can be cured by irradiation with electromagnetic waves, Quot; dual curable resin " means a resin that has both the properties of a thermosetting resin and a photo-curable resin and can be cured by irradiation of electromagnetic waves and application of heat. In the above, the category of the electromagnetic wave includes not only microwaves, infrared rays (IR), ultraviolet rays (UV), X-rays and gamma rays but also alpha-particle beams, proton beams, a particle beam such as a neutron beam and an electron beam, and the like. One example of the photocurable resin is a cationic photocurable resin. The cationic photocurable resin means a resin that can be cured by cationic polymerization or cation curing reaction induced by irradiation of electromagnetic waves.

The specific kind of the curable resin that can be used in the embodiments of the present invention is not particularly limited as long as it has the above-mentioned characteristics. For example, it may contain at least one thermosetting functional group such as a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group or an amide group, which may be cured to exhibit an adhesive property, or may contain an epoxide group, a resin containing at least one functional group capable of being cured by irradiation of an electromagnetic wave such as a cyclic ether group, a sulfide group, an acetal group or a lactone group. Specific examples of the resin include acrylic resins, polyester resins, isocyanate resins, epoxy resins, and the like, but the present invention is not limited thereto.

As said curable resin, Aromatic or aliphatic; Or a linear or branched epoxy resin may be used. In one embodiment of the present invention, an epoxy resin having an epoxy equivalent of 180 g / eq to 1,000 g / eq, which contains two or more functional groups, may be used. By using an epoxy resin having an epoxy equivalent in the above range, it is possible to effectively maintain properties such as adhesion performance and glass transition temperature of the cured product. Examples of such an epoxy resin include cresol novolak epoxy resin, bisphenol A epoxy resin, bisphenol A novolac epoxy resin, phenol novolak epoxy resin, tetrafunctional epoxy resin, biphenyl type epoxy resin, An epoxy resin, an alkyl-modified triphenolmethane epoxy resin, a naphthalene-type epoxy resin, a dicyclopentadiene-type epoxy resin, or a dicyclopentadiene-modified phenol-type epoxy resin.

In certain embodiments of the present invention, an epoxy resin containing a cyclic structure in the molecular structure may be used, for example, an epoxy resin containing an aromatic group (e.g., a phenyl group) may be used. When the epoxy resin contains an aromatic group, the cured product has excellent thermal and chemical stability and exhibits a low moisture absorption amount, thereby improving the reliability of the organic electronic device encapsulation structure. Specific examples of the aromatic group-containing epoxy resin include biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, cresol type epoxy resin, bisphenol type epoxy resin, But are not limited to, a mixture of one or more of xylo-based epoxy resin, polyfunctional epoxy resin, phenol novolak epoxy resin, triphenol methane type epoxy resin, and alkyl modified triphenol methane epoxy resin.

The adhesive layer (in the case of a single layer, the adhesive layer, in the case of multiple layers, part or all of the one or more sub-adhesive layers) comprises a moisture adsorbent in addition to the curable resin. The term " moisture adsorbent " can be used to collectively refer to components capable of adsorbing or removing moisture or moisture introduced from the outside through moisture and chemical reaction, and is also referred to as a moisture-reactive adsorbent.

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 that can be used in the embodiments of the present invention is not particularly limited and includes, for example, a metal powder such as alumina, a metal oxide, an organic metal oxide, a metal salt or phosphorus pentoxide (P ₂ O ₅ ) One or a mixture of two or more.

Specific examples of the metal oxide include lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), barium oxide (BaO), calcium oxide (CaO) and magnesium oxide (MgO) Examples 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), sulfate, gallium (Ga ₂ (SO _{4) 3),} titanium sulfate (Ti (SO _{4) 2)} or nickel sulfate (a sulfate such as NiSO _4), calcium chloride (CaCl _2), magnesium chloride (MgCl _2), strontium chloride (SrCl _2), chloride, yttrium (YCl ₃₎ , Cobalt chloride (CuCl ₂ ), cesium fluoride (CsF), tantalum fluoride (TaF ₅ ), niobium fluoride (NbF ₅ ), lithium bromide (LiBr), calcium bromide (CaBr ₂ ), cesium bromide (CeBr ₃ ) (SeBr _4), vanadium bromide (VBr _3), a metal halide such as 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.

In embodiments of the present invention, the moisture adsorbent, such as the metal oxide, etc., may be blended into the composition in a suitably processed state. For example, depending on the type of the organic electronic device to which the adhesive film is to be applied, the adhesive layer may be a thin film having a thickness of 30 μm or less. In this case, a pulverization process of the moisture adsorbent may be required. For pulverizing the moisture adsorbent, a process such as a three-roll mill, a bead mill or a ball mill may be used. In addition, when the adhesive film is used in a top emission type organic electronic device or the like, 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 contain the moisture adsorbent in an amount of 5 parts by weight to 100 parts by weight, or 5 parts by weight to 90 parts by weight, based on 100 parts by weight of the curable resin. By controlling the content of the moisture adsorbent within the above range, it is possible to maximize the moisture barrier property within a range that does not damage the organic electronic device.

In the present specification, unless otherwise specified, the unit " weight part " means a weight ratio between the respective components.

It is preferable that the moisture adsorbent is uniformly dispersed in the adhesive layer of the adhesive film.

The adhesive layer of the adhesive film according to embodiments of the present invention may include a filler, for example, an inorganic filler. The filler can suppress the penetration by lengthening the movement path of moisture or moisture that penetrates into the encapsulation structure, and maximize the barrier to moisture and moisture through interaction with the matrix structure of the curable resin and the moisture absorbent. have. Specific examples of the filler that can be used in the embodiments of the present invention are not particularly limited and include clay, talc, silica, barium sulfate, aluminum hydroxide, calcium carbonate, magnesium carbonate, zeolite, zirconia, titania or montmorillonite Or a mixture of two or more of them may be used.

Further, in order to increase the bonding efficiency between the filler and the curable resin, the filler may be a product surface-treated with an organic material, or may further be added with a coupling agent.

The adhesive layer may include 1 to 50 parts by weight, or 1 to 30 parts by weight of a filler based on 100 parts by weight of the curable resin. By controlling the filler content 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. By controlling the content of the filler to 50 parts by weight or less, it is possible to provide a cured product which can be produced in the form of a film and which exhibits adhesive properties even when formed into a thin film.

The adhesive layer of the adhesive film according to the embodiments of the present invention may include a curing agent capable of reacting with the curable resin to form a matrix such as a crosslinked structure or the like and an initiator capable of initiating the curing reaction of the resin such as a cationic photopolymerization initiator And the like.

The specific kind of the curing agent is not particularly limited and may be appropriately selected depending on the type of the functional group contained in the curable resin or resin to be used, and a latent curing agent such as an imidazole-based compound may also be used. For example, when an epoxy resin is used as the curable resin, a general curing agent for epoxy resin known in this field as a curing agent can be used. Specific examples thereof include various amine compounds, imidazole compounds, phenol compounds, A compound or an acid anhydride-based compound, but is not limited thereto.

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

The kind of the initiator, for example, a cationic photopolymerization initiator is not particularly limited, and for example, a known cationic polymerization initiator such as an aromatic diazonium salt, an aromatic iodo aluminum salt, an aromatic sulfonium salt or an iron- Aromatic sulfonium salts can be used, but the present invention is not limited thereto.

In this case, the content of the initiator may be, for example, 0.01 to 10 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the curable resin. If the content of the cationic photopolymerization initiator is too small, there is a fear that sufficient curing will not proceed. If the content is too large, the content of the ionic substance after curing will increase to lower the durability of the adhesive, ) Is formed, which is disadvantageous from the viewpoint of optical durability, and corrosion may occur depending on the base material. Therefore, an appropriate content range can be selected in consideration of this point.

The adhesive layer may further include a high molecular weight resin. The high-molecular-weight resin can play a role of improving moldability, for example, when a composition for forming an adhesive layer is molded into a film or a sheet. In addition, it may serve as a high temperature viscosity regulator to control the flowability during the hot-melting process.

The type of the high molecular weight resin that can be used in the embodiments of the present invention is not particularly limited as long as it is compatible with other components such as the curable resin. Specific examples of the high molecular weight resin that can be used include resins having a weight average molecular weight of 20,000 or more such as phenoxy resin, acrylate resin, high molecular weight epoxy resin, ultra high molecular weight epoxy resin, high polarity functional group- A high polarity functional group-containing reactive rubber, and the like, but is not limited thereto.

When the high molecular weight resin is contained in the adhesive layer, its content is not particularly limited as it can be controlled according to the intended properties. For example, the high molecular weight resin may be contained in an amount of about 10 to 200 parts by weight, 20 to 150 parts by weight or less, or about 20 to 100 parts by weight, based on 100 parts by weight of the curable resin. The content of the binder resin is controlled to 10 to 200 parts by weight or less to effectively maintain compatibility with each component of the resin composition and also to serve as an adhesive. If the binder resin, which is a high molecular weight resin, is too small, the resin may flow out from the resin due to a low viscosity in the adhesion process, or the adhesive force at room temperature may be high, which may make it difficult to control the releasing force. In addition, too much high molecular weight resin may cause poor adhesion. Therefore, by adjusting the content of the high molecular weight resin, it is possible to secure the optimum processability and physical properties by reducing the difference by adjusting the viscosity of each layer.

The adhesive layer of the adhesive film may further contain additives such as a filler for improving the durability of the cured product, a mechanical strength, a coupling agent for improving the adhesion, a plasticizer, a UV stabilizer and an antioxidant to the extent that the effect of the invention is not affected May be included.

The structure of the adhesive film according to the embodiments of the present invention is not particularly limited as long as it includes the above adhesive layer. For example, a substrate film or a release film (hereinafter also referred to as " first film "; And a structure including the adhesive layer formed on the base film or the release film. The adhesive film may further include a base film or release film (hereinafter sometimes referred to as " second film ") formed on the adhesive layer.

1 to 3 are cross-sectional views of an adhesive film according to one example of the present invention. As shown in FIG. 1, the adhesive film according to embodiments of the present invention may include an adhesive 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 adhesive film may include a multi-layered adhesive layer, for example, a film containing no moisture adsorbent formed in sequence on the base film or the release film 21 A first sub-adhesive layer 22a and a second sub-adhesive layer 22b including a moisture adsorbent.

In another aspect of the present invention, an adhesive film may further include a base film or a release film 23 formed on the adhesive layer 22, as shown in Fig. For example, a gas barrier layer for a flexible display implementation may be placed on one side of the substrate film. However, the adhesive film shown in the drawings is only an aspect of the present invention. The adhesive film according to the embodiments of the present invention may have a form including a composition of the present invention without a supporting substrate and an adhesive layer that maintains a solid or semi-solid state at room temperature, In some cases, it may be formed in the form of a double-sided adhesive film.

The specific kind of the first film that can be used in the embodiments of the present invention is not particularly limited. As the first film, for example, a general polymer film in this field can be used. Examples of the substrate or release film include a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polyvinyl chloride film, a polyurethane film, Acetate film, an ethylene-propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film. In addition, a suitable mold release treatment may be performed on one or both sides of the base film or the release film. Examples of the releasing agent used in the releasing treatment of the base film include an alkyd type, a silicone type, a fluorine type, an unsaturated ester type, a polyolefin type or a wax type. Among them, an alkyd type, a silicone type or a fluorine type releasing agent can be used from the viewpoint of heat resistance , But is not limited thereto.

Also, the kind of the second film (hereinafter sometimes referred to as " cover film ") that can be used in the embodiments of the present invention is not particularly limited either. For example, as the second film, within the scope exemplified in the first film described above, the same or different kinds of the first film may be used. In addition, the second film may also be subjected to appropriate mold release treatment.

The thickness of the above base film or release film (first film) is not particularly limited and may be suitably selected in accordance with the application to which it is applied. For example, the thickness of the first film may be about 10 탆 to 500 탆, or about 20 탆 to 200 탆. If the thickness is less than 10 mu m, the base film may be easily deformed during the manufacturing process. If the thickness exceeds 500 mu m, the economical efficiency is lowered.

The thickness of the second film is also not particularly limited. For example, the thickness of the second film may be set to be the same as that of the first film. Further, the thickness of the second film may be set to be relatively thin in comparison with the first film in consideration of the processability and the like.

The thickness of the adhesive layer included in the adhesive film according to embodiments of the present invention is not particularly limited and can be appropriately selected in accordance with the following conditions in consideration of the application to which the film is applied. The adhesive layer may be, for example, about 5 탆 to 200 탆, or about 5 탆 to 100 탆.

In the 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 solution containing a composition of an adhesive layer on a base film or a release film; And a second step of drying the coating liquid coated in the first step. In the method for producing an adhesive film as described above, a third step of additionally pressing 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 in a suitable solvent. In this process, the content of the curable resin or the like contained in the coating liquid can be appropriately controlled in accordance with the desired moisture barrier property and film formability.

The kind of the solvent used for preparing the coating liquid is not particularly limited. However, when the drying time of the solvent is excessively long or when drying at a high temperature is required, a problem may arise in terms of workability or durability of the adhesive film, so that a solvent having a volatilization temperature of 100 ° C or lower can be used. In view of film formability and the like, a small amount of a solvent having a volatilization temperature higher than the above range may be mixed and used. Examples of such solvents include methyl ethyl ketone (MEK), acetone, toluene, dimethylformamide (DMF), methylcellosolve (MCS), tetrahydrofuran (THF) And the like, but is not limited thereto.

The method of applying the coating liquid as described above to the base film or the release film in the first step is not particularly limited, and examples thereof include a knife coat, a roll coat, a spray coat, a gravure coat, a curtain coat, a comma coat or a lip coat A known method can be used without limitation.

In the second step, the coating liquid coated in the first step is dried to form an adhesive layer. That is, in the second step, the coating liquid applied to the film is heated to dry and remove the solvent, whereby an adhesive layer can be formed. In this case, the drying conditions are not particularly limited. For example, the drying can be performed at a temperature of 70 to 200 DEG C for 1 to 10 minutes.

The manufacturing method may further include a third step of pressing the additional base film or the release film on the adhesive layer formed on the film, following the second step. Such a third step may be performed by pressing a film of a release film or a base film (a cover film or a second film) on the dried adhesive layer by a roll lamination process after being coated on the film.

4 is a cross-sectional view illustrating an encapsulation product of an organic electronic device according to an exemplary embodiment of the present disclosure. Another embodiment of the present invention includes a substrate 31; An organic electronic device (33) formed on the substrate (31); And an adhesive film (32) as described above for sealing the organic electronic device (33) to cover the front surface of the organic electronic device (33). Here, covering the front surface of the organic electronic device 33 means that the adhesive film 32 is attached to the entire surface of the organic electronic device 33 without any gap (all surfaces not in contact with the substrate such as the top, side, etc.) .

The organic electronic device encapsulation product may further include a second substrate (cover substrate) 34 on the adhesive film 32, wherein the adhesive film 32 is bonded to the second substrate 34 And serves to adhere the substrate 31.

The organic electronic device 33 may be, for example, an organic light emitting diode.

The organic electronic device encapsulation product may further include a protective film (not shown) for protecting the organic electronic device 33 between the adhesive film 32 and the organic electronic device 33.

The organic electronic device encapsulation product according to the embodiments of the present invention has an advantage that it is possible to simplify the manufacturing process and reduce the process cost and can be used irrespective of the designing method of the organic electronic device, Can be given.

In another embodiment of the present invention, there is provided a method of manufacturing an organic electronic device, comprising the steps of: applying an adhesive layer of the above-mentioned adhesive film to a substrate on which an organic electronic device is formed to cover the front surface of the organic electronic device; And a step of curing the adhesive layer.

The step of applying the adhesive film to the organic electronic device may be performed by a hot roll laminate, a hot press, or a vacuum press method of an adhesive film, and is not particularly limited.

The step of applying the adhesive film to the organic electronic device may be performed at a temperature of 50 ° C to 100 ° 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.

It is also possible to add a step of attaching the adhesive film so as to be in contact with glass or metal which is an additional sealing material.

The sealing method of the organic electronic device includes forming a transparent electrode on a substrate such as a glass or a polymer film by vacuum deposition or sputtering, and forming an organic material layer on the transparent electrode. The organic material layer may include a hole injecting layer, a hole transporting layer, a light emitting layer, an electron injecting layer, and / or an electron transporting layer. Then, a second electrode is further formed on the organic material layer. The adhesive film described above is then applied to cover all of the organic electronic devices on top of the organic electronic device on the substrate. The method of applying the adhesive film is not particularly limited and may be applied to an organic electronic device formed on a substrate, for example, a cover substrate (e.g., a glass or a polymer Film) can be applied by heating, pressing or the like. In this step, for example, when the adhesive film is transferred onto the cover substrate, the substrate or the release film formed on the film is peeled off by using the above-mentioned adhesive film, and then heat is applied to the vacuum press or vacuum laminate Or the like can be transferred onto the cover substrate. In this process, if the curing reaction of the adhesive film is performed over a certain range, the adhesive strength or adhesion of the adhesive film may decrease, so that the process temperature can be controlled to about 100 占 폚 or less and the process time to be controlled within 5 minutes. Similarly, a vacuum press or a vacuum laminator can be used when the cover substrate onto which the adhesive film is transferred is heated and pressed onto the organic electronic device. The temperature condition at this stage can be set as described above, and the process time can be within 10 minutes.

Further, an additional curing process may be performed on the adhesive film to which the organic electronic device is pressed. This curing process (final curing) may be performed, for example, in a heating chamber or a UV chamber. The conditions for the final curing can be appropriately selected in consideration of the stability of the organic electronic device and the like.

However, the above-described manufacturing process is merely an example for encapsulating the organic electronic device, and the process order, process conditions, and the like can be freely modified. For example, the order of the transferring and pressing processes may be changed to a method of first transferring the above-mentioned adhesive film to the organic electronic device on the substrate, and then pressing the cover substrate. Alternatively, after a protective layer is formed on the organic electronic device, an adhesive film may be applied and the cover substrate may be omitted and cured.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited by the following examples.

Example  One

1. Preparation of first sub-adhesive layer solution

50 g of an epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 50 g of phenoxy resin (YP-50, coagulable) were charged into a reactor and diluted with 100 g of methyl ethyl ketone. To this, 1 g of an imidazole hardening agent (2MA.OK, Shikoku Kasei) was added, and the solution was homogenized.

2. Preparation of the second sub adhesive layer solution

10 g of MgO as a moisture adsorbent was added to methyl ethyl ketone at a concentration of 20 wt% to prepare a water adsorbent solution, and the solution was milled for 24 hours by a ball mill process. Separately, 60 g of an epoxy resin (YD-128, Kuko Chemical Co., Ltd.) and 40 g of phenoxy resin (YP-50, coagulable) were added to the reactor at room temperature and diluted with 100 g of methyl ethyl ketone. Thereafter, 1 g of an imidazole curing agent (2 MA.OK, Shikoku Kasei) was added, and the solution was homogenized. A previously prepared water absorbent solution was added to the homogenized solution and stirred at a high speed for 1 hour to prepare a solution of the second sub-adhesive layer.

3. Preparation of Adhesive Film

The solution of the first sub-adhesive layer prepared above was applied to the releasing surface of the releasing PET using a comma coater and dried in a drier at 130 DEG C for 3 minutes to form a first sub-adhesive layer having a thickness of 15 mu m .

The solution of the second sub-adhesive layer prepared above was applied to the releasing surface of the releasing PET using a comma coater and dried at 130 DEG C for 3 minutes in a drier to form a second sub-adhesive layer having a thickness of 30 mu m .

The first sub-adhesive layer and the second sub-adhesive layer were laminated to produce a multi-layered adhesive film.

Example  2

In Example 1, an adhesive film having a single-layer structure with a thickness of 45 탆 was produced using only the second sub-adhesive layer solution.

Example  3

An adhesive film having a multilayer structure was produced in the same manner as in Example 1, except that the first sub-adhesive layer solution and the second sub-adhesive layer solution were prepared as follows.

1. Preparation of first sub-adhesive layer solution

35 g of epoxy resin (YD-014, Kukdo Chemical) and 40 g of phenoxy resin (YP-50, co-graphitizable) were charged into a reactor and diluted with 100 g of methyl ethyl ketone. To this, 1 g of an imidazole hardener (2MA.OK, Shikoku Kasei) was added to homogenize the liquid.

2. Preparation of the second sub adhesive layer solution

10 g of MgO as a moisture adsorbent was added to methyl ethyl ketone at a concentration of 20 wt% to prepare a water adsorbent solution, and the solution was milled for 24 hours by a ball mill process. Separately, 55 g of an epoxy resin (YD-128, Kuko Chemical) and 45 g of phenoxy resin (YP-50, coagulable) were added to the reactor at room temperature and diluted with 100 g of methyl ethyl ketone. Thereafter, 1 g of an imidazole curing agent (2 MA.OK, Shikoku Chemical Co., Ltd.) was added, and the solution was homogenized. A previously prepared water absorbent solution was added to the homogenized solution and stirred at a high speed for 1 hour to prepare a solution of the second sub-adhesive layer.

Example  4

An adhesive film having a multilayer structure was produced in the same manner as in Example 1, except that the first sub-adhesive layer solution and the second sub-adhesive layer solution were prepared as follows.

1. Preparation of first sub-adhesive layer solution

50 g of an epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 50 g of phenoxy resin (YP-50, coagulable) were charged into a reactor and diluted with 100 g of methyl ethyl ketone. 1 g of an imidazole hardener (2MA.OK, Shikoku Kasei) was added to homogenize the solution, and 3 g of nano silica (Aerosil R972, Ebonic) was uniformly dispersed.

2. Preparation of the second sub adhesive layer solution

10 g of MgO as a moisture adsorbent was added to methyl ethyl ketone at a concentration of 20 wt% to prepare a water adsorbent solution, and the solution was milled for 24 hours by a ball mill process. Separately, 50 g of an epoxy resin (YD-128, Kuko Chemical Co., Ltd.) and 50 g of phenoxy resin (YP-50, coagulable) were added to the reactor at room temperature and diluted with 100 g of methyl ethyl ketone. Thereafter, 1 g of an imidazole curing agent (2MA.OK, Shikoku Kasei) was added and the solution was homogenized. The previously prepared water absorbent solution was added to the homogenized solution and stirred at a high speed for 1 hour to prepare a solution of the second sub-adhesive layer.

Comparative example  One

An adhesive film having a multilayer structure was produced in the same manner as in Example 1, except that the content of the phenoxy resin (YP-50, coagulable) used in the first sub-adhesive layer solution was changed to 30 g in Example 1 .

Comparative example  2

Except that the epoxy resin and the phenoxy resin were changed to 20 g of the epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and 80 g of the phenoxy resin (YP-50, coagulable) in the second sub-adhesive layer solution in Example 2 Was carried out in the same manner as in Example 2 to produce an adhesive film having a single-layer structure with a thickness of 45 mu m.

Comparative example  3

Except that the epoxy resin and the phenoxy resin were changed to 80 g of the epoxy resin (YD-128, Kuko Chemical) and 20 g of the phenoxy resin (YP-50, co-solvent) in the second sub-adhesive layer solution in Example 2 Was carried out in the same manner as in Example 2 to prepare an adhesive film having a single-layer structure with a thickness of 45 mu m.

Comparative example  4

An adhesive film having a multilayer structure was produced in the same manner as in Example 1, except that the first sub-adhesive layer solution and the second sub-adhesive layer solution were prepared as follows.

1. Preparation of first sub-adhesive layer solution

50 g of epoxy resin (YD-128, Kuko Chemical Co., Ltd.) and 30 g of phenoxy resin (YP-50, coagulable) were charged into the reactor and diluted with 100 g of methyl ethyl ketone. To this, 1 g of an imidazole hardener (2MA.OK, Shikoku Kasei) was added to homogenize the liquid.

2. Preparation of the second sub adhesive layer solution

10 g of MgO as a moisture adsorbent was added to methyl ethyl ketone at a concentration of 20 wt% to prepare a water adsorbent solution, and the solution was milled for 24 hours by a ball mill process. Separately, 60 g of an epoxy resin (YD-128, Kuko Chemical Co., Ltd.) and 40 g of phenoxy resin (YP-50, coagulable) were added to the reactor at room temperature and diluted with 100 g of methyl ethyl ketone. Thereafter, 1 g of an imidazole curing agent (2MA.OK, Shikoku Kasei) was added and the solution was homogenized. The previously prepared water absorbent solution was added to the homogenized solution and stirred at a high speed for 1 hour to prepare a solution of the second sub-adhesive layer.

Comparative example  5

A multi-layered adhesive film was prepared in the same manner as in Example 1, except that the content of MgO was changed to 70 g in the preparation of the water adsorbent solution to be added to the second sub-adhesive layer solution in Example 1.

Experimental Example  1: Measurement of viscosity

The viscosity of the adhesive layer of each of the adhesive films of Examples 1 to 4 and Comparative Examples 1 to 5 was measured by ARES at room temperature and at 80 ° C as shown in Table 1 below.

Viscosity at room temperature (Pa 占 퐏, 25 占 폚) Viscosity in a warmed state (Pa 占 퐏, 80 占 폚) Example 1 3.8 × 10 ⁶ 2367 Example 2 4.2 × 10 ⁶ 2385 Example 3 6.9 × 10 ⁶ 3250 Example 4 1.1 × 10 ⁷ 6790 Comparative Example 1 1.2 × 10 ⁶ 1825 Comparative Example 2 1.9 × 10 ⁸ 1.2 × 10 ⁶ Comparative Example 3 7.8 × 10 ⁴ 890 Comparative Example 4 9.8 × 10 ⁵ 1439 Comparative Example 5 8.8 × 10 ⁶ 5932

Experimental Example  2: Measurement of the interlayer viscosity difference

The viscosity of the two sub-adhesive layers of the adhesive layers of the adhesive films of Examples 1, 3 to 4 and Comparative Examples 1 and 4 to 5 was measured using ARES, and the viscosity at 80 ° C and the difference therebetween are shown in Table 2 below Respectively.

The viscosity of the first sub-adhesive layer (Pa 占 퐏, 80 占 폚) The viscosity (Pa · s, 80 ° C) of the second sub- Interlayer viscosity difference
(Pa · s, 80 ° C) Example 1 2365 2371 6 Example 3 2386 2381 5 Example 4 3265 3248 17 Comparative Example 1 1642 2371 729 Comparative Example 4 1642 890 752 Comparative Example 5 2365 4009 1644

Experimental Example  3: Cementation ( Lamination ) Measurement of degree of deviation

The degree of detachment of the adhesive layer of Examples 1 to 4 and Comparative Examples 1 to 5 from the initial end of the adhesive film at a bonding temperature of 80 캜 was measured using a microscope and is shown in Table 3 below.

Degree of deviation (탆) Difference in deviation
| AB | The first sub-adhesive layer (A) The second sub-adhesive layer (B) Example 1 510 500 10 Example 2 - 485 - Example 3 480 480 0 Example 4 320 320 0 Comparative Example 1 840 530 310 Comparative Example 2 - 30 - Comparative Example 3 - 1500 - Comparative Example 4 850 1480 630 Comparative Example 5 480 40 440

Experimental Example  4: Confirmation of moisture barrier property

In order to investigate the moisture barrier properties of the adhesive films of Examples 1 to 4 and Comparative Examples 1 to 5, a calcium test was carried out. Specifically, calcium (Ca) was deposited on a glass substrate having a size of 100 mm x 100 mm by 9 spots with a size of 5 mm x 5 mm and a thickness of 100 nm, and the films of Examples 1 to 4 and Comparative Examples 1 to 5 The cover glass onto which the adhesive film was transferred was heat-pressed at 80 DEG C for 1 minute by using a vacuum press on each calcium deposition site. 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. The obtained samples were allowed to stand at 85 ° C and 85% R.H. in a thermo-hygrostat chamber, and the time point at which the calcium began to become transparent due to the oxidation reaction due to moisture penetration was evaluated and shown in Table 4 below.

Invisibility start time (h) Example 1 210 Example 2 210 Example 3 210 Example 4 220 Comparative Example 1 190 Comparative Example 2 Can not be measured due to poor adhesion Comparative Example 3 160 Comparative Example 4 100 Comparative Example 5 It can not be measured in bad condition due to leakage

Experimental Example  5: bubble  Measure

Table 3 shows the degree of the residual bubbles when a 3-inch organic luminescent panel was manufactured using the adhesive films of Examples 1 to 4 and Comparative Examples 1 to 5 by a microscope.

Bubble residue degree Example 1 ◎ Example 2 ○ Example 3 ◎ Example 5 ○ Comparative Example 1 ○ Comparative Example 2 × Comparative Example 3 × Comparative Example 4 × Comparative Example 5 ×

*: No bubbles, o: no more than 100 mu m bubbles present in small amounts, x: no less than 1 mm bubbles present

5 to 7 show optical micrographs showing the degree of residual bubbles after the laminating process in the production of the organic luminescent panel using the adhesive film of Example 1, Comparative Example 1 and Comparative Example 2, respectively. Referring to FIG. 5, it can be confirmed that the adhesive films were bonded without bubbles. However, in Comparative Example 4, many bubbles were trapped and defects were produced. In Comparative Example 2, the defective adhesion was confirmed.

As can be seen from the above, the adhesive films of Examples 1 to 4 according to the embodiments of the present invention can control the viscosity in the uncured state at room temperature and the temperature range and the difference in the interlayer viscosity in the multi- When producing an encapsulated product of an organic battery device, the occurrence of defects can be reduced and the organic electronic device can be effectively sealed from moisture. However, when the viscosity control is not performed properly as in the comparative example, effective encapsulation of the organic electronic device is achieved .

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be appreciated that other embodiments are possible. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

21, 23: base film or release film
22: Adhesive layer
31: substrate
32: Adhesive film
33: organic electronic device
34: second substrate (cover substrate)

Claims (25)

An adhesive film for sealing an organic electronic device,
The adhesive film includes an adhesive layer containing a curable resin and a moisture adsorbent,
The adhesive layer has an viscosity of 10 ¹ to 10 ⁶ Pa · s in a temperature range of 30 ° C. to 130 ° C. in an uncured state, and a viscosity at room temperature of 10 ⁶ Pa · s or more. The adhesive film according to claim 1, wherein, when the adhesive film is laminated on the adhesive agent in an uncured state at a temperature range of 50 to 100 占 폚, the degree to which the adhesive agent detaches from the adhesive agent layer is 1 mm or less at the original position. The adhesive sheet according to claim 1, wherein the adhesive layer is composed of at least two sub-adhesive layers, and the difference in viscosity between the respective sub-adhesive layers in an uncured state at 30 to 130 캜 is less than 30 Pa · s . 4. The method according to claim 3, wherein, when the adhesive film is laminated to the adherend in an uncured state at a temperature range of 50 to 100 占 폚, the difference in the degree of detachment of the adhesive of each of the sub- Adhesive film. The adhesive film according to claim 3, wherein at least one sub-adhesive layer among the sub-adhesive layers comprises a curable resin and a moisture adsorbent. The adhesive film according to claim 1, wherein the curable resin has a moisture permeability of 20 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 or a photocurable resin. The curable resin composition according to claim 1, wherein the curable resin comprises at least one curable functional group selected from a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group, an amide group, an epoxide group, a cyclic ether group, a sulfide group, an acetal group and a lactone Lt; / RTI > The adhesive film according to claim 1, wherein the curable resin is an epoxy resin containing an aromatic group in a molecular structure. The adhesive film according to claim 1, wherein the moisture adsorbent is alumina, a metal oxide, a metal salt or phosphorus pentoxide. According to claim 1, wherein said 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, Wherein the adhesive film is at least one 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 5 parts by weight to 100 parts by weight of the moisture adsorbent per 100 parts by weight of the curable resin. The adhesive film of claim 1, wherein the adhesive layer further comprises a filler. The adhesive film according to claim 13, wherein the filler is at least one selected from the group consisting of clay, talc, silica, barium sulfate, aluminum hydroxide, calcium carbonate, magnesium carbonate, zeolite, zirconia, titania or montmorillonite. The adhesive film according to claim 13, 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 16, 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 16, 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 a high molecular weight resin. Board; An organic electronic device formed on the substrate; And an adhesive film according to any one of claims 1 to 19 sealing the organic electronic device to cover the front surface of the organic electronic device. The organic electronic device encapsulation product of claim 20, further comprising a second substrate on top of the adhesive film, wherein the adhesive film bonds the second substrate and the substrate. Applying the adhesive film according to any one of claims 1 to 19 to the substrate on which the organic electronic device is formed so that the adhesive layer of the adhesive film covers the front surface of the organic electronic device; And curing the adhesive layer. The method of claim 22, wherein applying the adhesive film to the organic electronic device is performed by hot roll lamination, hot pressing, or vacuum pressing of the adhesive film. 23. The method of encapsulating organic electronic devices according to claim 22, wherein the step of applying the adhesive film to the organic electronic device is performed at a temperature of from 50 DEG C to 100 DEG C. 23. The method of encapsulating organic electronic devices according to claim 22, wherein the curing step is carried out by heating to a temperature range of 70 占 폚 to 110 占 폚 or by irradiating UV light.

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