KR101554378B1 - Adhesive Film and Encapsulation Method of Organic Electronic Device Using the Same - Google Patents

Abstract

The present invention relates to an adhesive film, an organic electronic device encapsulation product using the same, and a sealing method of an organic electronic device, and more particularly to an adhesive film for encapsulating an organic electronic device, the adhesive film comprising a curable resin and a moisture adsorbent The present invention provides an adhesive film comprising a curable hot melt adhesive layer and a moisture absorption capacity of 0.5 to 10% and a method of encapsulating an organic electronic device using the adhesive film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an adhesive film and an encapsulating method of an organic electronic device using the same,

The present invention relates to an adhesive film and a sealing method of 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 commercialization of OLEDs and expansion of applications, the main problem 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 penetration of oxygen or moisture from the outside into organic electronic devices such as OLEDs.

Conventionally, a metal can or a glass is processed into a cap shape having grooves, and a moisture-absorbing agent for absorbing moisture is mounted on the grooves in powder form or made into a film form and adhered using a double-sided tape.

Patent Document 1 discloses a laminate having a structure in which an organic light emitting layer made of an organic compound is placed between a pair of electrodes facing each other, an airtight container for blocking the laminate from the outside air and an alkali metal oxide, an alkali metal oxide Discloses an organic EL device having the same drying means. However, due to the shape of the airtight container, the thickness of the entire display device is increased, and the organic EL device is weak against the physical impact due to the internal space, and the heat dissipation property in the enlargement is not good.

Patent Document 2 discloses a drying method of an electronic element employing a hygroscopic layer formed by using a hygroscopic agent and a binder including solid particles having a particle size of 0.1 to 200 탆, but the water adsorption ability thereof is not sufficient. If the moisture permeability of the binder surrounding the moisture adsorbent does not satisfy the moisture permeability of 50 g / m ² · day or less in the cured state, the adsorption rate of moisture is high during the acceleration test, so that the performance is not sufficient.

In order to solve this problem, in Patent Document 3, by including a moisture adsorbent in the epoxy sealant, the moisture entering the organic light emitting device can be chemically adsorbed to slow the penetration of moisture into the organic light emitting device. However, when the moisture adsorbent reacts with moisture When the metal oxide is used as a moisture adsorbent, it may react with water to form a strong basic material and cause chemical damage to the protective layer and the cathode layer.

Therefore, there is a need to develop an encapsulant that can effectively prevent moisture penetration and reduce damage to the organic electronic device and ensure long-term reliability.

1. Japanese Patent Application Laid-Open No. 9-148066 2. U.S. Patent No. 6,226,890 3. Korean Patent Publication No. 2007-0072400

The present invention provides an adhesive film, an organic electronic device encapsulating product using the same, and a sealing method of an organic electronic device.

The present invention relates to an adhesive film for sealing an organic electronic device,

The adhesive film comprises a curable hot melt adhesive layer including a curable resin and a moisture adsorbent, and provides an adhesive film having a moisture absorption capacity of 0.5 to 10%.

The curable hot melt adhesive layer may have a multi-layer structure including a first region contacting the organic electronic device and a second region not contacting the organic electronic device during sealing of the organic electronic device.

In addition, the present invention provides a semiconductor device comprising a substrate; An organic electronic device formed on the substrate; And the adhesive film for sealing the organic electronic device, wherein a first region of the adhesive layer of the adhesive film covers the organic electronic device.

The present invention also provides a method of manufacturing an organic electronic device, the method comprising: applying the adhesive film to a substrate on which an organic electronic device is formed, the first area of the adhesive layer of the adhesive film covering the organic electronic device; And a step of curing the adhesive layer.

The adhesive film of the present invention not only effectively blocks moisture or oxygen from the outside into the organic electronic device by controlling the moisture absorption capacity but also facilitates the manufacturing process in the production of the organic electronic device panel, Can be improved and long-term reliability can be ensured.

1 to 3 are sectional views showing an adhesive film according to one example of the present invention.
4 and 5 are cross-sectional views showing an encapsulation product of an organic electronic device according to one example of the present invention.
Fig. 6 shows FT-IR analysis results of the adhesive film of Example 1. Fig.
Fig. 7 shows FT-IR analysis results of the adhesive film of Comparative Example 2. Fig.

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. It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. And the scope of the present invention is not limited by the thickness, size, ratio or the like shown in the drawings.

An adhesive film according to an embodiment of the present invention encapsulates an organic electronic device and includes a curable hot melt adhesive layer including a curable resin and a moisture adsorbent. The adhesive film preferably has a moisture absorption capacity of 0.5 to 10% so as to ensure long-term reliability when sealing the organic electronic device.

As used herein, the term " organic electronic device " refers to 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, But are not limited to, photovoltaic devices, rectifiers, transmitters, and organic light emitting diodes (OLEDs). In one example of the present invention, the organic electronic device may be an OLED.

In the present specification, the term " hot-melt type adhesive " means a solid or semi-solid at room temperature and is flowable when heat is applied to adhere flat plates without bubbles, Means an adhesive in a form capable of firmly fixing an object with an adhesive. The adhesive film of the present invention may have a viscosity at room temperature of 10 ⁶ dyne · sec / cm ² or more, preferably 10 ⁷ dyne · sec / cm ^{2 or} more. The term " ambient temperature " means a natural, unheated or non-warmed temperature, for example, a temperature of about 15 ° C to 35 ° C, more specifically about 20 ° C to 25 ° C, more specifically about 25 ° C It can mean. The viscosity can be measured using an Advanced Rheological Expansion System (ARES). In the present invention, by controlling the viscosity of the hot-melt type adhesive in the above-described range, it is possible to seal the flat plate with a smooth thickness and a uniform thickness in the sealing process of the organic electronic device. In addition, unlike the liquid adhesive, problems such as shrinkage and volatilization gas that may be caused by curing of the resin and the like can be greatly reduced, thereby preventing physical or chemical damage to the organic electronic device. In the present invention, as long as the adhesive is maintained the state of solid or semi-solid at room temperature, the upper limit of the viscosity is not particularly limited, for example, in consideration of the fairness or the like, of from about 10 ⁹ dyne · sec / cm ² or less Range can be controlled.

As used herein, the term " moisture absorption capacity " refers to the ability of the adhesive film to block moisture, and can be measured without limitation by various measurement methods. For example, the moisture absorption capacity can be measured according to the weight increase rate of the adhesive film, which is based on an increase in weight of the moisture adsorbent inside the adhesive film through chemical reaction with moisture penetrated therein. In the present invention, the moisture absorption capacity (weight increase rate) is obtained by curing an adhesive film having a thickness of 200 mu m and then cutting to 5 cm x 5 cm to prepare a specimen. Then, the initial weight of the specimen is recorded, The specimens are allowed to stand for 24 hours under a relative humidity of 85%, and then moisture is removed from the surface, and the weight is measured to determine the increase rate relative to the initial weight.

It is important that the adhesive film secures long-term reliability when encapsulating an organic electronic device. The moisture absorptive capacity of the adhesive film which can maintain the lifetime of the organic electronic device long and improve the durability is preferably 0.5 to 10%, more preferably 1 to 5%. By controlling the hygroscopic capacity within the above range, it is possible to maintain the water shutoff capability for a long period of time, while preventing the adhesive force from falling due to excessive moisture adsorption, thereby preventing interface peeling of the organic electronic device panel.

In addition, since the adhesive film can structurally adhere the substrate and the upper substrate together with the moisture barrier property, it is easy to manufacture the panel of the organic electronic device and the passivation process can be omitted, thereby simplifying the manufacturing process And the thickness of the encapsulation of the organic electronic device can be reduced to contribute to thinning.

The adhesive film may include a multi-layered adhesive layer. Specifically, the adhesive layer of the adhesive film may have a multi-layer structure including a first region contacting the organic electronic device and a second region not contacting the organic electronic device during sealing of the organic electronic device.

In the first region contacting with the organic electronic device at the time of encapsulating the organic electronic device on the basis of the mass of the total moisture adsorbent in the curable hot melt adhesive layer, 0 to 20%, and in a second region not in contact with the organic electronic device And 80 to 100% of the moisture adsorbent. This is because when the content of the moisture adsorbent in the first region close to the organic electronic device is more than 20%, the volume expansion due to the reaction of the moisture adsorbent with the moisture may deviate from the limit that can be controlled by the curable resin, This is to prevent the film from causing cracks. Accordingly, a multi-layered adhesive layer is introduced to control the influence of the moisture adsorbent on the organic electronic device.

By controlling the content of the moisture adsorbent in the multi-layered adhesive layer and the first region and the second region in this way, physical and chemical damage to the organic electronic device due to the moisture adsorbent in the adhesive film used as the sealing material can be prevented And at the same time, by controlling the moisture absorption capacity of the entire adhesive film, the long-term reliability of the adhesive film can be also provided.

The method of dividing the adhesive layer into the first region and the second region to have a multi-layered structure can be used without limitation as long as it is a method of forming a multi-layered adhesive layer.

The first region and the second region of the adhesive layer may have the same or different structures except for the content of the moisture adsorbent, for example, the curing resin, the moisture adsorbent or other additive, the type and content of the filler, and the like. The following description covers both the first region and the second region of the adhesive layer unless otherwise stated.

The curable resin that can be used in embodiments of the present invention has a water vapor transmission rate (WVTR) in the cured state of less than or equal to 50 g / m ² · day, preferably less than or equal to 30 g / m ² · day, M ² · day or less, and more preferably 15 g / m ² · day or less. The term " cured state of the curable resin " refers to a state in which the curable resin is cured or crosslinked by itself or through reaction with other components such as a curing agent to retain components such as a moisture adsorbent and a filler when applied as an encapsulating material, Quot; refers to a state where the adhesive is converted into a state capable of exhibiting performance as a structural adhesive. In the present invention, the water vapor permeability is a moisture permeability measured with respect to the thickness direction of the cured product at 38 DEG C and 100% relative humidity after the curable resin is cured and the cured product has a film thickness of 80 mu m. The moisture permeability is measured according to ASTM F1249.

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

In the present invention, the lower the numerical value of the moisture permeability in the cured state of the resin, the better the performance of the sealing structure. The lower limit is not particularly limited.

The specific kind of the curable resin that can be used in the present invention is not particularly limited, and for example, various thermosetting or photo-curable resins known in this field can be used. The term " thermosetting resin " means a resin that can be cured through an appropriate heat application or aging process, and the term " photo-curing resin " means a resin that can be cured by irradiation with electromagnetic waves. The category of electromagnetic waves includes microwaves, infrared rays (IR), ultraviolet rays (UV), X-rays and γ-rays, as well as α-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 in the present invention is a cationic photocurable resin. The cationic photocurable resin means a resin which can be cured by cationic polymerization or cationic curing reaction induced by irradiation of an electromagnetic wave. In addition, the curable resin may be a dual curable resin including both of a heat curing property and a light curing property.

The specific kind of the curable resin in the present invention is not particularly limited as long as it has the above-mentioned characteristics. For example, it may include one or more thermosetting functional groups 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.

In the present invention, as the 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, properties such as adhesion performance and glass transition temperature of the cured product can be effectively maintained. 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 the present invention, preferably, an epoxy resin having a cyclic structure in its molecular structure can be used, and more preferably, an epoxy resin containing an aromatic group (e.g., a phenyl group) can 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 that can be used in the present invention include biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, cresol type epoxy resin, A phenol novolac epoxy resin, a triphenol methane type epoxy resin, and an alkyl-modified triphenol methane epoxy resin, and the like, or a mixture of two or more thereof, but is not limited thereto no.

More preferably in the present invention, a silane-modified epoxy resin, preferably a silane-modified epoxy resin having an aromatic group, can be used as the epoxy resin. When an epoxy resin having such a silane-modified structure and having a silane group is used, it is possible to maximize the adhesiveness with the glass substrate or the substrate inorganic material of the organic electronic device, and to improve the moisture barrier property, the durability and the reliability. The specific kind of the above-mentioned epoxy resin which can be used in the present invention is not particularly limited, and such a resin can be easily obtained from, for example, a purchase place such as Kukdo Chemical Co.,

The curable hot melt adhesive layer of the present invention includes a moisture adsorbent in addition to the curable resin. The term " moisture adsorbent " may be used to mean a component capable of adsorbing or removing moisture or moisture introduced from the outside through physical or chemical reaction or the like. Means a water-reactive adsorbent or a physical adsorbent, and mixtures thereof are also usable.

The water-reactive adsorbent chemically reacts with moisture, moisture or oxygen introduced into the adhesive layer to adsorb moisture or moisture. The physical adsorbent can increase permeation of moisture or moisture penetrating into the encapsulation structure to suppress permeation thereof and maximize the barrier property against moisture and moisture through interaction with the matrix structure of the curable resin and the water reactive adsorbent can do.

In one embodiment of the present invention, in order to avoid the risk of damaging the organic electronic device, it is preferable that the moisture adsorbent in the first region of the adhesive layer of the adhesive film contains a small amount of water-reactive adsorbent.

Specific examples of the moisture adsorbent that can be used in the present invention are not particularly limited. For example, in the case of a water-reactive adsorbent, a metal powder such as alumina, a metal oxide, a metal salt or a phosphorus pentoxide (P ₂ O ₅ ) And mixtures of two or more species. Examples of the physical adsorbent include silica, zeolite, titania, zirconia or montmorillonite.

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 the present invention, a moisture adsorbent such as a metal oxide or the like may be appropriately processed to form a composition. 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 of the present invention 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, a grinding process may be required even in such a use.

The second region of the curable hot melt adhesive layer of the present invention may contain the moisture adsorbent in an amount of 1 part by weight to 100 parts by weight, preferably 5 parts by weight to 50 parts by weight, based on 100 parts by weight of the curable resin . The content of the moisture adsorbent is controlled to 5 parts by weight or more so that the cured product exhibits excellent moisture and moisture barrier properties. Further, the content of the water adsorbent is controlled to be 50 parts by weight or less, so that a moisture-blocking property can be exhibited while forming a thin film sealing structure.

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

Accordingly, the first region of the curable hot melt adhesive layer of the present invention may contain the moisture adsorbent in an amount of 0 to 20 parts by weight based on 100 parts by weight of the curable resin. When the moisture adsorbent is 0 parts by weight, the first region of the curable hot melt adhesive layer does not have a moisture adsorbent, and the moisture adsorbent exists only in the second region. By controlling the content of the moisture adsorbent to 20 parts by weight or less, physical and chemical damage due to the moisture adsorbent to the organic electronic device can be minimized while maximizing the moisture barrier property.

The curable hot melt adhesive of the first and second regions of the present invention may comprise a filler, preferably an inorganic filler. The filler can maximize the barrier property against moisture and moisture through the interaction with the matrix structure of the curable resin and the moisture adsorbent and the like by lengthening the movement path of moisture or moisture penetrating through the bag structure have. The specific kind of the filler that can be used in the present invention is not particularly limited, and for example, clay, talc, needle-like silica or the like may be used.

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

The curable hot melt adhesive layer of the present invention may contain 1 to 50 parts by weight, preferably 1 to 20 parts by weight of filler based on 100 parts by weight of the curable resin. The filler content is controlled to 1 part by weight or more to provide a cured product having excellent moisture or moisture barrier properties and mechanical properties. In addition, by controlling the filler content to 50 parts by weight or less in the present invention, it is possible to provide a cured product which can be produced in the form of a film and exhibits excellent moisture barrier properties even when formed into a thin film.

The curable hot melt adhesive of the first and second regions of the present invention is 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, A cationic photopolymerization initiator, and the like.

The specific kind of the curing agent usable in the present invention is not particularly limited and can be appropriately selected depending on the kind of the curable resin or the functional group contained in the curable resin to be used. For example, when an epoxy resin is used as the curing resin in the present invention, a general curing agent for epoxy resins known in the art can be used as a curing agent. Specific examples thereof include various amine compounds, imidazole compounds, phenol compounds Compounds, phosphorus compounds or acid anhydride compounds, and the like, but not limited thereto.

The curable hot melt adhesive of the first and second regions of the present invention is obtained by mixing the curing agent in an amount of 1 to 20 parts by weight, preferably 1 to 10 parts by weight per 100 parts by weight of the curable resin As shown in FIG. However, the above content is only one example of the present invention. That is, in the present invention, the content of the curing agent can be changed according to the type and content of the curable resin or the functional group, the matrix structure to be implemented, or the crosslinking density.

The kind of the initiator that can be used in the present invention, for example, the cationic photopolymerization initiator is not particularly limited and includes, for example, aromatic diazonium salt, aromatic iodo aluminum salt, aromatic sulfonium salt, A known cationic polymerization initiator can be used. Of these, an aromatic sulfonium salt is preferably 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, preferably 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 in the present invention is too small, there is a fear that the curing will not proceed sufficiently. If the content is too large, the content of the ionic substance after curing will increase and the durability of the adhesive will deteriorate. conjugate acid is formed, which is disadvantageous in terms of optical durability, and corrosion may occur depending on the base material. Therefore, an appropriate content range can be selected in consideration of this.

The curable hot melt adhesive layer of the present invention may further comprise a high molecular weight resin. The high-molecular-weight resin can play a role of improving moldability, for example, when the composition of the present invention is molded into a film or a sheet. It can also serve as a high-temperature viscosity modifier that stabilizes flowability during the hot-melt process.

The kind of the high molecular weight resin that can be used in 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 curable hot melt adhesive layer of the present invention, its content is not particularly limited as it is controlled depending on the intended physical properties. For example, in the present invention, the high molecular weight resin may be contained in an amount of about 200 parts by weight or less, preferably about 150 parts by weight or less, more preferably about 100 parts by weight or less, based on 100 parts by weight of the curable resin . In the present invention, the content of the high molecular weight resin is controlled to 200 parts by weight or less, effectively maintaining the compatibility with each component of the resin composition, and also acting as an adhesive.

The adhesive film of the present invention 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 in addition to the effect .

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

1 to 3 are sectional views of an adhesive film according to one example of the present invention.

The adhesive film of the present invention may include an adhesive layer 12 formed on a base film or a release film 11, as shown in Figs. Fig. 1 shows that the moisture adsorbent 13 exists only in the second region 12b of the adhesive layer 12 included in the adhesive film of the present invention. Fig. 2 shows that the first region 12a also contains a small amount of moisture adsorbent (13) are included.

In another aspect of the present invention, as shown in Fig. 3, the adhesive film of the present invention may further include a base film or a release film 14 formed on the adhesive layer 12. Fig. However, the adhesive film shown in the drawings is only an embodiment of the present invention, and the first region and the second region lamination order of the adhesive layer may be changed as required.

The specific kind of the first film that can be used in the present invention is not particularly limited. In the present invention, for example, a general polymer film in this field can be used as the first film. In the present invention, for example, the base material or the release film may be a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polyvinyl chloride film, , An ethylene-vinyl acetate film, an ethylene-propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film. In addition, a suitable mold release treatment may be performed on one or both sides of the base film or release film of the present invention. 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, a wax type and the like. Among them, the use of an alkyd type, a silicone type or a fluorine type releasing agent But is not limited thereto.

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

In the present invention, the thickness of the base film or the release film (first film) as described above is not particularly limited and may be suitably selected in accordance with the application to which it is applied. For example, in the present invention, the thickness of the first film may be about 10 μm to 500 μm, preferably about 20 μm to 200 μm. If the thickness is less than 10 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.

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

The thickness of the adhesive layer included in the adhesive film 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. However, it is preferable that the first region of the adhesive layer has a lower thickness than the second region. In the adhesive layer included in the adhesive film of the present invention, for example, the thickness of the first region of the adhesive layer may be about 1 占 퐉 to 20 占 퐉, preferably about 2 占 퐉 to 15 占 퐉. When the thickness is less than 1 mu m, for example, when the adhesive film of the present invention is used as an encapsulant of an organic electronic device, there is a possibility that the ability to protect from the damage factor of the second region of the adhesive layer may deteriorate. Mu m, the efficiency of the water barrier ability of the second region of the adhesive layer can be lowered. The thickness of the second region of the adhesive layer may be about 5 탆 to 200 탆, preferably about 5 탆 to 100 탆. When the thickness of the second region is less than 5 탆, sufficient moisture barrier ability can not be exhibited. When the thickness exceeds 200 탆, it is difficult to secure the processability. Also, the thickness expansion due to moisture reactivity is large, It is not economical.

In 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 the above-mentioned adhesive layer on a base film or a release film; And a second step of drying the coating liquid coated in the first step, each first region and a second region of the adhesive film can be manufactured.

The method of laminating each of the first region and the second region is also not particularly limited. For example, the first region and the second region formed on a separate release film may be laminated together to form a multi-layered adhesive film, or the second region may be directly formed on the first region, It is possible.

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

The first step of the present invention is a step of preparing a coating liquid by dissolving or dispersing the above-mentioned composition of the adhesive layer in an appropriate solvent. In this process, the content of the epoxy resin or the like contained in the coating liquid can be appropriately controlled in accordance with the desired moisture barrier property and film formability.

In the present invention, the type 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 it is necessary to dry at a high temperature, a problem may arise in terms of workability or durability of the adhesive film, and therefore it is preferable to use a solvent having a volatilization temperature of 100 ° C or lower. In the present invention, a small amount of a solvent having a volatilization temperature higher than the above range may be mixed and used in consideration of film formability and the like. Examples of the solvent usable in the present invention include methyl ethyl ketone (MEK), acetone, toluene, dimethylformamide (DMF), methylcellosolve (MCS), tetrahydrofuran (THF) (NMP), and the like, but is not limited thereto.

In the first step of the present invention, the method of applying the coating solution to the base film or release film 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, Known methods such as coating and the like can be used without limitation.

The second step of the present invention is a step of drying the coating liquid coated in the first step to form an adhesive layer. That is, in the second step of the present invention, 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, and for example, the drying can be performed at a temperature of 70 to 200 캜 for 1 to 10 minutes.

In the method for producing an adhesive film of the present invention, a third step of further pressing the additional base film or release film on the adhesive layer formed on the film may be further performed subsequent to the second step.

Such a third step of the present invention can be carried out by coating the film and then pressing the additional release film or the base film (cover film or second film) on the dried adhesive layer by a hot roll laminate or a pressing process . At this time, the third step may be performed by hot roll lamination in terms of the possibility and efficiency of the continuous process, wherein the process is performed at a temperature of about 10 캜 to 100 캜 at a pressure of about 0.1 kgf / cm ² to 10 kgf / cm < ² >.

4 is a cross-sectional view showing an encapsulation product of an organic electronic device according to one example of the present invention.

Another embodiment of the present invention includes a substrate 21; An organic electronic device (25) formed on the substrate (21); And an adhesive film (22) as described above for encapsulating the organic electronic device (25), wherein a first region (22a) of the adhesive layer of the adhesive film is bonded to the organic electronic device Bag product.

The organic electronic device encapsulation product may further include a protective film 26 between the adhesive film 22 and the organic electronic device 25 to protect the organic electronic device.

The organic electronic device encapsulation product of the present invention may further comprise a second substrate (cover substrate) 24 on top of the adhesive film 22, wherein the adhesive film 22 is bonded to the second substrate 24 ) And the substrate (21).

In the present invention, the organic electronic device may be an organic light emitting diode.

The organic electronic device encapsulation product according to the present invention is advantageous in that it can simplify the manufacturing process and reduce the process cost and can be used irrespective of the designing method of the organic electronic device and can provide excellent mechanical durability to the organic electronic device There is an advantage.

In another embodiment of the present invention, there is provided a method of manufacturing an organic electronic device, comprising: applying a first region of an adhesive layer of the above-mentioned adhesive film to a substrate on which an organic electronic device is formed to cover 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 90 ° C and the curing step may be performed by heating to a temperature range of 70 ° C to 110 ° C or by irradiating UV have.

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

In the method of encapsulating an organic electronic device according to the present invention, for example, a transparent electrode is formed on a substrate such as a glass or a polymer film by vacuum deposition or sputtering, and an organic material layer is formed on the transparent electrode. The organic material layer may include a hole 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. For example, a method of applying the adhesive film of the present invention onto an organic electronic device formed on a substrate, 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 base film or the release film formed on the film is peeled off using the above-mentioned adhesive film of the present invention, It can be transferred onto a cover substrate using a vacuum laminator or the like. In this process, if the curing reaction of the adhesive film is carried out over a certain range, the adhesion or adhesion of the adhesive film may decrease. Therefore, it is preferable to control the process temperature to about 100 ° C or less and the process time to be 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 is preferably 10 minutes or less. However, the adhesive film is applied to the organic electronic device so that the adhesive layer in the first area is in contact with the organic electronic device (in the case where the organic electronic device has a protective film, contact with the protective film) than the second area of the adhesive film.

Further, in the present invention, 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 in, for example, 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 of the present invention, and the process sequence, process conditions and the like can be freely modified. For example, in the present invention, the order of the transferring and pressing step may be changed by first transferring the adhesive film of the present invention 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. First domain solution preparation

200 g of a silane-modified epoxy resin (KSR-177, Kuko Chemical) and 150 g of phenoxy resin (YP-50, coagulable) were charged into a reactor and diluted with methyl ethyl ketone. Thereafter, the inside of the reactor was replaced with nitrogen, and the prepared solution was homogenized.

2. Manufacturing of second zone solution

70 g of CaO (Aldrich) as a moisture adsorbent was added to methyl ethyl ketone at a concentration of 30 wt% to prepare a water adsorbent solution, and the solution was milled for 24 hours by a ball mill process. Separately, 200 g of silane-modified epoxy resin (KSR-177, Kuko Chemical Co., Ltd.) and 150 g of phenoxy resin (YP-50, coagulable) were added to the reactor at room temperature and diluted with methyl ethyl ketone. Thereafter, the inside of the reactor was replaced with nitrogen, and the prepared solution was homogenized. Then, 4 g of imidazole (Shikoku Kasei) as a curing agent was added thereto, and the mixture was stirred at a high speed for 1 hour to prepare a solution of the second region.

3. Preparation of adhesive film

The solution of the first region 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 dryer to form an adhesive layer having a thickness of 15 mu m.

The solution of the second region prepared above was applied to the releasing surface of the releasing PET using a comma coater and dried at 130 캜 for 3 minutes in a dryer to form an adhesive layer having a thickness of 30 탆.

The adhesive layers of the first region and the second region were laminated to produce a multi-layered adhesive film.

Example  2

An adhesive film having a multilayer structure was prepared in the same manner as in Example 1, except that 62 g of CaO was added to the second region solution in the process of producing the adhesive film of Example 1.

Example  3

An adhesive film having a multilayer structure was prepared in the same manner as in Example 1, except that 56 g of CaO was added to the second region solution in the process of manufacturing the adhesive film of Example 1 above.

Comparative Example  One

An adhesive film having a thickness of 45 탆 and consisting of only the film composition of the first region of Example 1 was prepared in the same manner as in Example 1.

Comparative Example  2

An adhesive film having a thickness of 45 탆 and made up only of the second region film composition of Example 1 was produced in the same manner as in Example 1 above.

Comparative Example  3

A multilayer structure adhesive film was produced in the same manner as in Example 1 except that 28 g of CaO was added to the first region solution and 42 g of CaO was added to the second region solution in the process of producing the adhesive film of Example 1 Respectively.

Comparative Example  4

A multi-layered adhesive film was prepared in the same manner as in Example 1, except that the silane-modified epoxy resin was replaced with an acrylic pressure-sensitive adhesive resin.

Experimental Example  1: Confirmation of moisture barrier property

In order to examine the moisture barrier properties of the adhesive films of Examples 1 to 3 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 depositing 9 spots each having a size of 5 mm x 5 mm and a thickness of 100 nm, 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 at 100 ° C for 3 hours in a high-temperature drier, the calcium (Ca) specimen sealed in a size of 11 mm x 11 mm was individually 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 1 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Transparency start time (h) <240 <220 <210 <40 <230 <250 <24

Experimental Example  2: Absorption  Capacity measurement

The moisture absorption capacities of the adhesive films of Examples 1 to 3 and Comparative Examples 1 to 5 were examined. Specifically, the adhesive films of Examples 1 to 3 and Comparative Examples 1 to 5 were formed into a thickness of 200 μm, cured at 100 ° C. for 3 hours in a high-temperature dryer, cut into 5 cm × 5 cm, . After recording the initial weight of the cured specimen, the specimen was left in an environment of 85 ° C and 85% R.H. for 24 hours in a constant temperature and humidity chamber, and the moisture of the surface was removed and the weight was measured. The weight increase rate of the specimen was calculated as shown in Table 2 below.

Weight increase rate (%) = (B-A) / A x 100

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

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Weight Growth Rate (%) 4.8 3.9 2.8 0.4 10.3 4.9 4.3

Experimental Example  3: Check for physical damage

A 3-inch organic luminescent panel was manufactured using the adhesive films of Examples 1 to 3 and Comparative Examples 1 to 3, and the organic vapor-deposited film was broken in an environment of 85 ° C and 85% RH in a constant temperature and humidity chamber Are shown in Table 3 below.

division Damaged Example 1 No damage Example 2 No damage Example 3 No damage Comparative Example 1 No damage Comparative Example 2 Destruction of Organic Vapor Deposition at the Boundary between Moisture Penetration Part and Non-Penetration Part Comparative Example 3 Adhesive failure occurred

Experimental Example  4: Check for chemical damage

Silicon nitride (SiNx) used as a protective film of an organic electronic device was deposited on the glass to a thickness of 1 mu m. The adhesive films of Examples 1 to 3 and Comparative Examples 1 to 3 were cured by thermocompression on the SiNx vapor deposition film and allowed to stand in an environment of 85 ° C and 85% RH. Then, whether or not a chemical change occurred in the SiNx vapor deposition film was evaluated by FT-IR Respectively. The results are shown in Table 4, and FT-IR analysis results of the adhesive films of Example 1 and Comparative Example 2 are shown in FIGS. 6 and 7. FIG. Unlike FIG. 6, it was analyzed in FIG. 7 that a chemical component variation of the SiNx deposited film occurred. It can be seen that the moisture-reactive adsorbent acts as a strong base due to the hydration reaction and chemical damage to the protective film (SiNx deposited film).

division Damaged Example 1 No damage Example 2 No damage Example 3 No damage Comparative Example 1 No damage Comparative Example 2 Chemical damage of protective film Comparative Example 3 Chemical damage to protective film in extreme exposure

As can be seen from the above, the adhesive films of Examples 1 to 3 according to the embodiments of the present invention can effectively seal the organic electronic device from moisture and ensure long-term reliability. However, It can be confirmed that effective sealing of the organic electronic device is not achieved when the adhesive film or the moisture absorptive capacity range is out of the range.

11: Base film or release film
12: adhesive layer
14: Cover film
21: substrate
22: Adhesive film
12a, 22a: first region 12b, 22b: second region
13, 23: Moisture absorbent
24: Cover substrate
25: organic electronic device
26: Shield

Claims (28)

An adhesive film for sealing an organic electronic device,
Wherein the adhesive film comprises a curable hot melt adhesive layer including a curable resin and a moisture adsorbent,
Wherein the curable hot melt adhesive layer has a viscosity of 10 ⁶ dyne · sec / cm ² or more at room temperature,
Wherein the curable hot melt adhesive layer comprises a first region in contact with the organic electronic device during sealing of the organic electronic device and a second region in contact with the organic electronic device, Wherein the first region contains 0 to 20% and the second region contains 80 to 100% of the moisture adsorbent,
An adhesive film having a moisture absorption capacity of 0.5 to 10%. delete delete delete The adhesive film according to claim 1, wherein the curable resin has a moisture permeability of 50 g / m ² · day or less in a cured state. The adhesive film according to claim 1, wherein the curable resin is a thermosetting resin, a photo-curing resin or a dual curing 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 group Lt; / RTI &gt; The adhesive film according to claim 1, wherein the curable resin is an epoxy resin having an annular structure in a molecular structure. The adhesive film according to claim 1, wherein the curable resin is a silane-modified epoxy resin. The adhesive film according to claim 1, wherein the moisture adsorbent is a water-reactive adsorbent, a physical adsorbent, or a mixture thereof. 11. The adhesive film of claim 10, wherein the water-reactive adsorbent is alumina, a metal oxide, a metal salt or phosphorus pentoxide, and the physical adsorbent is silica, zeolite, zirconia, titania or montmorillonite. 11. The method of claim 10, wherein the moisture reactive 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 , 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 second region of the adhesive layer comprises 1 to 100 parts by weight of the moisture adsorbent per 100 parts by weight of the curable resin. The adhesive film according to claim 1, wherein the first region of the adhesive layer comprises 0 to 20 parts by weight of a 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. 16. The adhesive film according to claim 15, wherein the filler is at least one selected from the group consisting of clay, talc, and acicular silica. 16. The adhesive film according to claim 15, wherein the adhesive layer comprises 1 to 50 parts by weight of a filler based on 100 parts by weight of the curable resin. The adhesive film according to claim 1, wherein the adhesive layer further comprises a curing agent. The adhesive film according to claim 18, 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 18, wherein the adhesive layer comprises 1 to 10 parts by weight of a curing agent based on 100 parts by weight of the curable resin. The adhesive film of claim 1, wherein the adhesive layer further comprises an initiator. The adhesive film according to claim 1, wherein the adhesive layer further comprises a high molecular weight resin having a weight average molecular weight of 20,000 or more. Board; An organic electronic device formed on the substrate; And an adhesive film according to any one of claims 1 to 22 for sealing the organic electronic device. 24. The article of claim 23, wherein the organic electronic device is an organic light emitting diode. Applying an adhesive film according to any one of claims 1 and 5 to 22 to a substrate on which an organic electronic device is formed so that an adhesive layer of the adhesive film covers the organic electronic device; And curing the adhesive layer. 26. The method of claim 25, wherein the step of applying the adhesive film to the organic electronic device is performed by a hot roll laminate, a hot press, or a vacuum press method of an adhesive film. 26. The method of claim 25, wherein applying the adhesive film to the organic electronic device is performed at a temperature of 50 DEG C to 90 DEG C. 26. The method of encapsulating organic electronic devices according to claim 25, 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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