KR20060041411A - Organic electroluminescence display and manufacturing method thereof - Google Patents

Abstract

The present invention is a substrate; Sealing substrate; An organic electroluminescent part disposed between the substrate and the encapsulation substrate, and located in an inner space provided by the substrate and the encapsulation substrate, i) at least one selected from metal oxides and metal salts having an average particle diameter of 100 nm or less, and ii) a binder. And iii) a transparent hygroscopic film comprising a dispersant. According to the present invention, it is possible to manufacture a top-emitting organic electroluminescent device having excellent hygroscopic characteristics and transparent characteristics compared to the case of using a conventional getter by using a transparent hygroscopic film and ensuring a required lifespan. Thus, the transparent moisture absorption film of this invention is excellent in water and oxygen adsorption characteristic, and lifespan characteristic is improved. And as the front substrate, etched glass or unetched planar glass which requires processing can be used.

Description

Organic electroluminescent device and manufacturing method thereof

1A to 1D are diagrams schematically showing the structure of an organic EL device according to the present invention,

2A is a scanning electron microscope (SEM) photograph showing a cross section of a transparent hygroscopic film obtained according to Example 1 of the present invention,

Figure 2b is an electron scanning micrograph showing the state of the film of the moisture absorption layer according to Example 6 of the present invention,

3 illustrates a transmittance spectrum of an organic EL device manufactured according to Example 1 of the present invention.

4 is a view showing the moisture absorption rate of the transparent moisture absorption film formed according to Example 3 of the present invention,

FIG. 5A illustrates the life characteristics of the organic EL device according to Example 3 and Comparative Example 1-2 of the present invention.

5B is a graph illustrating the lifespan characteristics of the organic EL devices according to Examples 5 and 8 and Comparative Examples 1-2 of the present invention.

6 shows transmittance spectra of organic electroluminescent devices manufactured according to Example 6-7 and Comparative Example 6-7 of the present invention.

<Brief description of the major symbols in the drawings>

10 ... Substrate 11 ... Encapsulant

12 ... organic electroluminescent part 13 ... transparent moisture absorption film

14 ... sealant layer

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device and a method of manufacturing the same, and more particularly, to an organic electroluminescent device employing a transparent hygroscopic film applicable to a top emission type and a method of manufacturing the same.

The organic electroluminescent device has a property that is degraded by the penetration of moisture. Therefore, the encapsulation structure is required to secure their stable operation and lifetime.

Conventionally, a metal can or glass is processed in a cap shape to have a groove, and a drying or drying agent for water absorption is mounted in a powder form or manufactured in a film form to adhere to the double-sided tape.

Japanese Patent Laid-Open No. 9-148066 discloses a laminate having a structure in which an organic light emitting material layer made of an organic compound is disposed between a pair of electrodes facing each other, and an airtight container and an airtight container which block the laminate from outside air. An organic electroluminescent display device having a drying means such as an alkali metal oxide or an alkali metal oxide is disclosed. However, due to the shape of the hermetic container, the organic electroluminescent device has a thick thickness of the entire display device. In addition, even if the drying means retains a solid state after adsorbing moisture, the drying means is not opaque and cannot be applied to front emission.

U. S. Patent No. 6,226, 890 discloses an organic electroluminescent device employing a hygroscopic layer formed using a hygroscopic agent and a binder comprising solid particles having a particle size of 0.1 to 200 mu m.

However, this organic electroluminescent device is not only applicable to the front emission type due to its translucent or opaque transmission characteristics, but also has a lot of room for improvement due to insufficient water adsorption capacity .

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide an organic electroluminescent device having a transparent hygroscopic film that can be applied to a top emission type as well as being improved in moisture absorption ability by solving the above problems and providing a method of manufacturing the same.

In order to achieve the above technical problem, in the present invention; Sealing substrate; An organic electroluminescent part disposed between the substrate and the encapsulation substrate,

Located in the interior space provided by the substrate and the sealing substrate, an organic electroluminescent device comprising a transparent hygroscopic film comprising i) at least one selected from metal oxides and metal salts having an average particle diameter of 100 nm or less and ii) a binder and iii) a dispersant To provide.

Technical problem of the present invention is also a substrate; Sealing substrate; An organic electroluminescent part disposed between the substrate and the encapsulation substrate,

Located in the inner space provided by the substrate and the sealing substrate,

An organic EL device having a transparent moisture absorption film including at least one selected from metal oxides and metal salts having a difference between a particle diameter (D10) corresponding to a weight percentage of 10% and a particle diameter (D90) corresponding to a weight percentage of 90% of 100 nm or less. Is made by.

Technical problem of the present invention is also a substrate; Sealing substrate; An organic electroluminescent part disposed between the substrate and the encapsulation substrate,

Located in the inner space provided by the substrate and the sealing substrate,

An organic electroluminescent device comprising at least one selected from metal oxides and metal salts having a particle average particle diameter of 100 nm or less and a binder, and having a transparent moisture absorption film having a film thickness of 100 to 300 µm and a transmittance of 95% or more.

Another technical problem of the present invention is a first step of preparing a substrate on which an organic electroluminescent part formed by sequentially stacking a first electrode, an organic layer, and a second electrode;

A transparent moisture absorption film is obtained by applying and curing a transparent moisture absorption film-forming composition comprising at least one selected from a metal oxide and a metal salt having a particle average particle diameter of 100 nm or less, a binder, a dispersant, and a solvent in an inner space provided in the substrate and the sealing substrate. Step 2;

A third step of applying a sealant to a portion of the organic electroluminescent portion on at least one side of the substrate and the encapsulation substrate; And

It is made by a method of manufacturing an organic electroluminescent device comprising a fourth step of bonding the substrate and the sealing substrate.

Another technical problem of the present invention is a first step of preparing a substrate on which an organic electroluminescent part formed by sequentially stacking a first electrode, an organic film, and a second electrode;

At least one selected from a metal oxide and a metal salt having a difference between a particle size (D10) corresponding to a weight percentage of 10% and a particle size (D90) corresponding to a weight percentage of 90% in an internal space provided in the substrate and the encapsulation substrate, 100 nm or less, and a solvent A second step of obtaining a transparent moisture absorbing film by applying and curing the composition for forming a transparent moisture absorbing film comprising a;

A third step of applying a sealant to a portion corresponding to an outer portion of the organic electroluminescent portion on at least one side of the substrate and the encapsulation substrate; And

And a fourth step of bonding the substrate and the sealing substrate to each other.

Hereinafter, the present invention will be described in more detail.

The organic electroluminescent element of this invention is equipped with the transparent moisture absorption film suitable for top emission type. The transparent moisture absorption film is obtained by applying and curing a transparent moisture absorption film composition comprising a metal oxide and / or a metal salt, a binder, a dispersant, and a solvent having a particle average diameter of 100 nm or less, and the metal oxide reacts with water to react with metal-oxygen- Metal bonds are broken to form metal hydroxides, and water is removed through this process. In the case of metal salts, water is coordinated to unfilled coordination sites of the central metal to remove water by forming a stable compound.

In the present invention, the particle average particle diameter of the metal oxide or the metal salt is atomized by physical and chemical methods so as to have a range of 100 nm or less. Then, it is blended with a binder and then subjected to a process of applying and curing it.

It is preferable that the average particle diameter of the said metal oxide or metal salt particle is 100 nm or less especially 50-90 nm. If the average particle diameter exceeds 100 nm, the hygroscopic layer made using particles having such a large average particle diameter is undesirable because scattering occurs in the visible light region, causing a haze of the film and a decrease in transmittance.

As the binder, an organic binder, an inorganic binder, an organic / inorganic composite binder or a mixture thereof is used. Herein, the organic binder is a low molecule or a polymer, and should be excellent in compatibility with metal oxide or metal salt particles and excellent in film formation. As an example of the organic binder which satisfy | fills such a characteristic, the at least 1 selected from acrylic resin, methacryl resin, polyisoprene, vinyl resin, epoxy resin, urethane resin, and cellulose resin is used. Examples of the acrylic resins include butyl acrylate, ethylhexyl acrylate, and the like. Examples of the methacryl resins include propylene glycol methacrylate and tetrahydrofurfree methacrylate. Examples thereof include vinyl acetate, N-vinylpyrrolidone, and the like. Examples of the epoxy resins include cycloaliphatic epoxides, and the like. Examples of the urethane resins include urethane acrylates, and the like. Examples include cellulose nitrate and the like.

The inorganic binder is a metal or nonmetallic material such as silicon, aluminum, titanium, zirconium, etc., and has excellent miscibility with metal oxide or metal salt particles and excellent film forming property. As such an example, one or more selected from the group consisting of titania, silicon oxide, zirconia, alumina and their precircers are used.

The organic / inorganic composite binder is a material in which a metal, a non-metal material such as silicon, aluminum, titanium, zirconium, and the like are covalently linked to each other and have excellent miscibility with the above-described metal oxide or metal salt particles and excellent film forming properties. do. As the material satisfying these conditions, at least one selected from the group consisting of epoxy silane or derivatives thereof, vinyl silane or derivatives thereof, amine silane or derivatives thereof, methacrylate silane or a result of partial curing reaction thereof is used. In the case of using the above-mentioned partial curing reaction product, it may be used when controlling physical properties such as the viscosity of the composition.

Specific examples of the epoxy silane or derivatives thereof include 3-glycidoxypropyltrimethoxysilane or a polymer thereof.

Specific examples of the vinyl silane or derivatives thereof include vinyltriethoxysilnae or polymers thereof.

Moreover, 3-aminopropyltriethoxysilnae and its polymer can be mentioned as a specific example of the said aminesilane or its derivative (s).

Specific examples of the methacrylate silane or derivatives thereof include 3-tri (methoxysilyl) propyl acrylate} and polymers thereof.

As the binder used in the present invention, it is particularly preferable to select one having excellent thixotropy and leveling properties which can be printed.

The dispersant used in the present invention serves to improve dispersibility when mixed with the absorbent dispersion and the binder in the transparent moisture absorbent film. Etc. Using a dispersant as described above, metal oxide particles such as CaO present in the transparent moisture absorption film can be present in nano size. If the dispersant is not used, even if the metal oxide particles having a nano size are initially used, it is difficult to exist in nano size in the finally obtained transparent hygroscopic film due to aggregation during the manufacturing process. In order to disperse the fine particles in the solution to uniformly prevent aggregation and precipitation, it can be dispersed in two ways. First, there is a method of dispersing the surface of the particles by giving a positive or negative charge so that they do not aggregate with each other by the electrostatic repulsive force between the particles. The advantage of this is that it is relatively easy to disperse, and in the case of particles requiring electrical properties, it can be used by dispersing without changing the properties. It has the disadvantage of being easily broken. The second dispersion method is to wrap the polymer dispersant on the surface of the particles so that they are not aggregated due to steric hindrance between them. The advantage of this method is that a wide range of solvents can be selected regardless of the polarity of the dispersant and the dispersion stability is excellent. Since the dispersant of the moisture absorbent dispersion used in the present invention was dispersed using a polymer-based dispersant, it is possible to mix well while maintaining dispersibility when it is mixed with a binder.

By using the binder and the dispersing agent described above, it is possible to obtain a transparent moisture absorbing film as a thick film, and to increase the amount of the nano-size moisture absorbent impregnated in the film to improve the moisture absorption amount. And the kind of binder can be selected suitably, and the film | membrane which has a very transparent characteristic even in thickness of 100 micrometers or more can be obtained. And by using a binder, it becomes possible to adjust the viscosity of the composition for transparent moisture absorption film suitably, and to form a transparent moisture absorption film by a printing process.

In the organic electroluminescent device of the present invention, the transparent hygroscopic film may be located in the inner space provided by the substrate and the sealing substrate. In particular, the transparent moisture absorbing film may be formed on the inner surface of the encapsulation substrate as shown in FIGS. 1A and 1D, the side of the sealant layer as illustrated in FIG. 1B, or at least one side of the substrate and the encapsulation substrate (for example, a recess of the substrate as illustrated in FIG. 1C). .

The organic electroluminescent element of this invention is equipped with the transparent moisture absorption film suitable for top emission type. The transparent moisture absorbing film includes at least one selected from metal oxides and metal salts having a difference between a particle diameter (D10) corresponding to a weight percentage of 10% and a particle size (D90) corresponding to a weight percentage of 90% of 100 nm or less, particularly 50 to 80 nm. do. If the difference between D10 and D90 exceeds 100 nm, the transmittance decreases and the haze increases, which is undesirable.

The average particle diameter of at least one particle selected from the metal oxide and the metal salt is 100 nm or less, in particular from 50 to 90 nm, and the minimum particle diameter (Dmin) of the at least one particle selected from the metal oxide and metal salt is at least 30 nm, in particular from 35 to 45 nm, and the maximum particle size ( It is preferable that Dmax) is 120 nm or less, especially 90-100 nm. If the minimum particle size (Dmin) of at least one particle selected from metal oxides and metal salts is less than 30 nm, the thixotropy may increase and the viscosity may increase. I can't.

The transparent moisture absorbing film of the present invention is obtained by applying and curing the transparent moisture absorbing film composition including the metal oxide and / or the metal salt, the binder, and the solvent, and the metal oxide reacts with moisture to break the metal-oxygen-metal bond. Metal hydroxides are formed and water is removed through this process. In the case of metal salts, water is coordinated to unfilled coordination sites of the central metal to remove water through a process of forming a stable compound.

In the present invention, the particle average particle diameter of the metal oxide or metal salt is atomized by physical and chemical methods so as to have a range of 100 nm or less. Then, it is blended with a binder and then subjected to a process of applying and curing it.

It is preferable that the average particle diameter of the said metal oxide or metal salt particle is 100 nm or less especially 50-90 nm. If the average particle diameter exceeds 100 nm, the hygroscopic layer made using particles having such a large average particle diameter is undesirable because scattering occurs in the visible light region, causing a haze of the film and a decrease in transmittance.

As the binder, an organic binder, an inorganic binder, an organic / inorganic composite binder or a mixture thereof is used. Herein, the organic binder is a low molecule or a polymer, and should be excellent in compatibility with metal oxide or metal salt particles and excellent in film formation. As an example of the organic binder which satisfies these characteristics, at least one selected from acrylic resin, methacryl resin, polyisoprene, vinyl resin, epoxy resin, urethane resin, and cellulose resin is used. Examples of the acrylic resins include butyl acrylate, ethylhexyl acrylate, and the like. Examples of the methacryl resins include propylene glycol methacrylate and tetrahydrofurfree methacrylate. Examples thereof include vinyl acetate, N-vinylpyrrolidone, and the like, examples of epoxy resins include cycloaliphatic epoxides, examples of urethane resins include urethane acrylates, and examples of cellulose resins. Examples thereof include cellulose nitrate.

The inorganic binder is a metal or nonmetallic material such as silicon, aluminum, titanium, zirconium, etc., and has excellent miscibility with metal oxide or metal salt particles and excellent film forming property. As such an example, one or more selected from the group consisting of titania, silicon oxide, zirconia, alumina and their precircers are used.

The organic / inorganic composite binder is a material in which a metal, a non-metal material such as silicon, aluminum, titanium, zirconium, and the like are covalently linked to each other and have excellent miscibility with the above-described metal oxide or metal salt particles and excellent film forming properties. do. As the material satisfying these conditions, at least one selected from the group consisting of epoxy silane or derivatives thereof, vinyl silane or derivatives thereof, amine silane or derivatives thereof, methacrylate silane or a result of partial curing reaction thereof is used. In the case of using the above-mentioned partial curing reaction product, it may be used when controlling physical properties such as the viscosity of the composition.

Specific examples of the epoxy silane or derivatives thereof include 3-glycidoxypropyltrimethoxysilane or a polymer thereof.

Specific examples of the vinyl silane or derivatives thereof include vinyltriethoxysilnae or polymers thereof.

Moreover, 3-aminopropyltriethoxysilnae and its polymer can be mentioned as a specific example of the said aminesilane or its derivative (s).

Specific examples of the methacrylate silane or derivatives thereof include 3-tri (methoxysilyl) propyl acrylate} and polymers thereof.

As the binder used in the present invention, it is particularly preferable to select one having excellent thixotropy and leveling properties which can be printed.

It is possible to obtain a transparent moisture absorbing film as a thick film by manufacturing a transparent moisture absorbing film using the above-mentioned binder, and to increase the amount of the nano-size moisture absorbing agent impregnated in the film to improve the moisture absorbing amount. And the kind of binder can be selected suitably, and the film | membrane which has a very transparent characteristic even in thickness of 100 micrometers or more can be obtained. And by using a binder, it becomes possible to adjust the viscosity of the composition for transparent moisture absorption film suitably, and to form a transparent moisture absorption film by a printing process.

In the organic electroluminescent device of the present invention, the transparent hygroscopic film may be located in the inner space provided by the substrate and the sealing substrate. In particular, the transparent moisture absorbing film may be formed on the inner surface of the encapsulation substrate as shown in FIGS. 1A and 1D, the side of the sealant layer as illustrated in FIG. 1B, or at least one side of the substrate and the encapsulation substrate (for example, a recess of the substrate as illustrated in FIG. 1C). .

1A shows a schematic structure of an organic electroluminescent device according to an embodiment of the present invention.

Referring to this, the organic electroluminescent device is an organic electroluminescent device in which a substrate 10 made of glass or transparent insulator and one surface of the substrate 10 are formed, and a first electrode, an organic film, and a second electrode are sequentially stacked. In order to block the unit 12, the organic electroluminescent unit 12, and the organic electroluminescent unit 12 from the outside, an interior space in which the organic electroluminescent unit 12 is accommodated is combined with the substrate 10. In order to seal, the substrate 11 includes a transparent moisture absorption film 13 including nano-sized porous oxide particles on the inner surface and nano-sized pores.

The substrate 11 and the encapsulation substrate 10 are joined by a sealant layer 14 coated on the outer side of the organic electroluminescent part 12. Here, the encapsulation substrate 11 may have a function of sealing the substrate together with the organic electroluminescent portion therebetween and may have a form of an encapsulation substrate as illustrated in FIG.

Referring to FIG. 1B, in the organic electroluminescent device of the present invention, a transparent nanoporous oxide film 23 is formed on the side of the sealant layer 24.

Referring to FIG. 1C, in the organic electroluminescent device of the present invention, a recess 35 is formed on one surface of an encapsulation substrate 31 that is sealed with the substrate 30 to form an internal space, and the recess 35 is transparent. The transparent moisture absorption film 33 which is a moisture absorption film is formed.

Referring to FIG. 1D, the organic electroluminescent device of the present invention uses an etching glass as the sealing substrate 41, and a transparent moisture absorption film 43 is formed on the inner surface of the etching glass. Although the etching depth h of the said etching glass is not specifically limited, It is preferable that the etching depth is 100-300 micrometers, and the thickness of the transparent moisture absorption film 43 is 0.1-300 micrometers.

It is preferable to form a transparent nano CaO thick film especially as said transparent moisture absorption film 13, (23), (33), (43).

The organic electroluminescent units 12, 22, 32, and 42 may be formed by evaporation, and include a first electrode, an organic film, and a second electrode, and the first electrode may be a cathode. And the second electrode can be an anode. In addition, the organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and / or an electron transport layer.

The encapsulating substrates 11, 21, 31, and 41 use a glass substrate or a transparent plastic substrate that is an insulator, and when formed of a plastic substrate, the inner surface of the plastic substrate is a protective film for protecting from moisture. This can be formed, and the protective film is to have heat resistance, chemical resistance and moisture permeability. As such, when the encapsulation substrate is made of a transparent material, it may be used for the front light emitting type.

In order to apply to the bottom emission, the first electrode of the organic light emitting unit 12, 22, 32, 42 is transparent and the second electrode can be formed as a reflective electrode, In the case of application, the first electrodes of the organic light emitting units 12, 22, 32, and 42 may be reflective electrodes, and the second electrode may be transparent electrodes. The first electrode is an electrode disposed close to the encapsulation substrates 10, 20, 30, and 40, and the second electrode is close to the substrate 11, 21, 31, and 41. It is an electrode arrange | positioned.

In addition, in order to provide heat resistance, chemical resistance, and moisture permeability on the upper surface of the second electrode, an inorganic material capable of flattening the upper surfaces of the organic electroluminescent parts 12, 22, 32, and 42. A protective film made of may be further formed. The protective film may be formed of a metal oxide or a metal nitride.

The inner space partitioned by the encapsulation substrates 11, 21, 31, 41 and the substrates 10, 20, 30, 40 of the present invention is maintained in a vacuum state or Filled with inert gas.

The thickness of the transparent hygroscopic membranes 13, 23, 33, and 43 is more advantageous under the condition that transparency is ensured, but is preferably 0.1 to 300 µm. If the thickness of the transparent moisture absorbing film is less than 0.1 μm, it does not have sufficient hygroscopic properties. If the thickness of the transparent moisture absorbing film is larger than 300 μm, the size of the transparent moisture absorbing film is larger than the size of the beads included in the sealant. This is undesirable.

More preferably, when using the glass etched as shown in Figure 1d as the sealing substrate, the thickness of the transparent moisture absorption film 13, (23), (33), (43) is suitable, 0.1-300㎛, If the thickness of the transparent moisture absorption film is less than 0.1 mu m in the case of using the etching glass, the oxide film is in contact with the cathode layer because the thickness of the transparent moisture absorption film does not have sufficient moisture absorption characteristics and is larger than the depth of the etched glass etching surface.

When the flat glass is used as the sealing substrate, the thickness of the transparent moisture absorption films 13, 23, 33, and 43 is preferably 0.1-70 µm.

As the material for forming the transparent moisture absorption film, at least one selected from alkali metal oxides, alkaline earth metal oxides, metal halides, metal sulfates, metal perchlorates, and phosphorus pentoxide (P 2 O 5) having an average particle diameter of 100 nm or less, particularly 20 to 100 nm is used. do.

Examples of the alkali metal oxide include lithium oxide (Li ₂ O), sodium oxide (Na ₂ O) or potassium oxide (K ₂ O). Examples of the alkaline earth metal oxide include barium oxide (BaO) and calcium oxide. (CaO), or magnesium oxide (MgO), and examples of the metal sulfate are lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Nai ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), Cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga ₂ (SO ₄ ) ₃ ), titanium sulfate (Ti (SO ₄ ) ₂ ), or nickel sulfate (NiSO ₄ ). Examples of the metal halide include calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium chloride (YCl ₂ ), copper chloride (CuCl ₂ ), cesium fluoride (CsF), Tantalum fluoride (TaF ₅ ), niobium fluoride (NbF ₅ ), lithium bromide (LiBr), calcium bromide (CaBr ₃ ), cerium bromide (CeBr ₄ ), selenium bromide (SeBr ₂ ), vanadium bromide (VBr ₂ ), magnesium bromide (MgBr ₂ ), barium iodide (BaI ₂ ) or magnesium iodide (MgI ₂ ), and examples of the metal perchlorate include barium perchlorate (Ba (ClO ₄ ) ₂ ) or magnesium perchlorate (Mg (ClO ₄ ) ₂ ). .

Looking at the manufacturing method of the organic EL device having a transparent moisture absorption film as described above.

First, a substrate on which an organic EL is formed by sequentially stacking a first electrode, an organic film, and a second electrode is prepared. Subsequently, at least one particle selected from metal oxides and metal salts is mixed with a solvent, a dispersant, and a binder to obtain a composition for forming a transparent moisture absorption film.

The preparation process of the composition for forming a transparent moisture absorption film is preferably in accordance with the following process.

First, at least one selected from a metal oxide as a moisture absorbent and a metal salt and a dispersant are mixed in a solvent and physically milled to prepare a nano-sized absorbent dispersion, and the dispersion is mixed with a binder to prepare a composition for forming a transparent hygroscopic film.

In the transparent moisture absorption film-forming composition, the solid content is 2 to 25% by weight based on the total weight of the composition. If the solid content in the composition is less than 2% by weight, the water adsorption capacity is not sufficient, and if it exceeds 25% by weight, the transmittance is lowered and the haze is high, which is undesirable because it is opaque or translucent.

The composition is applied to the inner surface of the sealing substrate and dried and cured to obtain a transparent moisture absorption film.

In the coating step, it is carried out in accordance with dip coating, spin coating, spray coating, dispensing, or screen printing, in particular in terms of workability is preferred.

In the case of forming the transparent moisture absorption film according to the printing method, the binder and the solvent in the above-described composition for forming the transparent moisture absorption film serves as a vehicle to maintain the flowability of the printing composition. It is preferable that the viscosity of the transparent moisture absorption film formation composition for printing is 500-20,000 cps. If the viscosity is out of the above range, the print workability is poor and not preferable.

The curing step is made by thermal curing or UV curing, the thermal treatment temperature during thermal curing is preferably 100 to 250 ℃. If the heat treatment temperature exceeds 250 ℃, the hygroscopic property is reduced due to the reduction of the specific surface area by pre-sintering between particles and may cause thermal decomposition of the binder component, which is not preferable, if the solvent is less than 100 ℃ It is not preferable because it is not sufficiently dried or hardened, so it is likely to affect the device after encapsulation.

The content of the binder is 10 to 5000 parts by weight based on 100 parts by weight of one or more selected from metal oxides and metal salts. If the content of the binder is less than 10 parts by weight, it is difficult to obtain a transparent moisture absorption film, and if it exceeds 5000 parts by weight, it is not preferable because it does not exhibit sufficient moisture absorption ability.

The content of the dispersant is 1 to 100 parts by weight based on at least one 100 parts by weight selected from metal oxides and metal salts. If the content of the dispersant is less than 1 part by weight, it is difficult to obtain a transparent moisture absorbing film. If the content of the dispersant is more than 100 parts by weight, a sufficient moisture absorption ability is not exhibited.

The solvent may be used as long as it can disperse the metal oxide or metal salt particles. Specific examples thereof include ethanol, methanol, propanol, butanol, and isopropanol. At least one selected from the group consisting of methyl ethyl ketone, propylene glycol, 1-methoxy 2-propanol (PGM), isopropyl cellulose (IPC), methyl cellosolve (MC), ethyl cellosolve (EC), and The content is 100 to 1900 parts by weight based on 100 parts by weight of the metal oxide or metal salt particles.

The transparent moisture absorption film formed by the manufacturing method of the present invention as described above is a thin film or a thick film having a thickness of 0.1 to 300 µm, has sufficient moisture absorption and oxygen adsorption properties, and is excellent in the function of sealing the organic EL device.

The transparent moisture absorption film of this invention has a transparency of 95 to 98% and a moisture absorption of 30 to 50%.

Moreover, when the thickness of the transparent moisture absorption film of this invention is 100-300 micrometers, it is 95% or more, especially 96-98%, moisture absorption is 30-40%, haze is 1.0 or less, especially 0.2-0.8.

As mentioned above, after preparing the board | substrate with which the transparent moisture absorption film was formed, the sealing material is apply | coated to this board | substrate and the part corresponding to the outer periphery of the organic electroluminescent part of the at least one side of the said sealing substrate using a screen printing machine or a dispenser. Subsequently, the organic electroluminescent element of the present invention is completed by bonding the sealing substrate and the substrate.

In some embodiments, the sealant may be further cured by using ultraviolet light, visible light, or heat after being bonded to the internal space of the organic electroluminescent device formed according to the above manufacturing process to vacuum or filling with an inert gas.

The transparent moisture absorption film formed by the said method has the characteristic to remain transparent before water absorption or after water absorption.

The organic electroluminescent device of the present invention is applicable to all of the top emission type, bottom emission type or both sides emission type.

The driving method of the organic EL device of the present invention is not particularly limited, and both the passive matrix (PM) driving method and the active matrix (AM) driving method are possible.

Hereinafter, the present invention will be described with reference to the following examples, but the present invention is not limited to the following examples.

Example 1

100 parts by weight of anhydrous calcium oxide (CaO) (average particle size: 30 µm) and 10 parts by weight of an epoxy-inorganic composite siloxane, a dispersant, and 10 parts by weight of epoxycyclohexyltrimethoxysilane were mixed with 400 parts by weight of anhydrous ethanol, followed by milling for 24 hours. After preparing a dispersion having an average particle diameter of 70 nm, 3000 parts by weight of urethane acrylate as an organic binder was mixed to prepare a composition for forming a transparent hygroscopic film.

The transparent hygroscopic film-forming composition was printed on the etched glass and heat-treated at 100 ° C and then UV cured to form a transparent hygroscopic film.

 A sealant epoxy resin was applied to at least one side of the soda glass substrate on which the transparent moisture absorption film was formed and at least one side of the glass substrate on which the first electrode, the organic film, and the second electrode were formed. Subsequently, the two substrates were bonded to each other to complete an organic EL device.

The film state of the moisture absorbing layer according to Example 1 was examined using an electron scanning microscope as shown in FIG. 2.

Referring to FIG. 2, it can be seen that the thickness of the transparent moisture absorption film obtained in Example 1 is about 106 μm, and the leveling state of the surface is excellent, and nano-size metal oxide absorbents or metal salts are uniformly dispersed and do not precipitate. I can see that .

In the transparent moisture absorption film of Example 1, the transmittance spectrum was examined and shown in FIG. 3.

Referring to FIG. 3, although the thickness of the transparent moisture absorbing film was 100 μm or more, it was found that the transparent film had almost no decrease in transmittance in the entire visible light region.

Example 2

An organic electroluminescent device was completed in the same manner as in Example 1, except that 3000 parts by weight of tetraethoxysilane was used instead of 3000 parts by weight of an urethane acrylate as an organic binder.

Example 3

An organic electroluminescent device was completed in the same manner as in Example 1, except that 3000 parts by weight of methacrylate polysiloxane was used instead of urethane acrylate as an organic binder.

Example 4

An organic electroluminescent device was completed in the same manner as in Example 1, except that barium oxide (BaO) was used instead of anhydrous calcium oxide (CaO).

Example 5

An organic electroluminescent device was completed in the same manner as in Example 3, except that phosphorus pentoxide (P ₂ O ₅ ) was used instead of anhydrous calcium oxide (CaO).

Comparative Example 1

An organic electroluminescent device was completed in the same manner as in Example 3, except that no transparent moisture absorption film was formed on the soda organic substrate.

Comparative Example 2

An ordinary getter (HD-204, Japan Dininic Co., Ltd.) is installed on top of a soda glass substrate, and the sealant epoxy is formed on at least one side of the soda glass substrate and at least one side of the glass substrate on which the first electrode, the organic film, and the second electrode are formed. Resin was applied. Subsequently, the two substrates were bonded to each other to complete an organic EL device.

Comparative Example 3

CaO particles (70 nm) having a primary particle size of 0.1 μm or less were mixed and stirred with an organic binder PEMA (polyethyl methacrylate) to prepare a solution, which was then printed on the etched glass, and cured to form a hygroscopic film.

An epoxy resin, which is a sealant, was applied to at least one side of the soda glass substrate on which the moisture absorption film was formed and at least one side of the glass substrate on which the first electrode, the organic film, and the second electrode were formed. Subsequently, the two substrates were bonded to each other to complete an organic EL device.

The organic EL device of Comparative Example 3 had a low transmittance of about 85% and a haze of 28.7, which was opaque or translucent. This is because even though the size of the primary particles is 70 nm, these particles are agglomerated with each other due to electrostatic attraction, so that simply mixing the hygroscopic powder and the binder does not uniformly disperse them in the binder.

The transmittance | permeability of the transparent moisture absorption film obtained by the said Example 1-5 was investigated. The transmittance was also 95% or more and was applicable to the front emission type as a transparent membrane.

The moisture absorption rate of the transparent moisture absorption film obtained in Example 1 and Comparative Example 2 was evaluated, and the results are as shown in FIG.

Referring to FIG. 4, it was found that the transparent hygroscopic film of Example 1 was improved in terms of hygroscopic ability and speed compared with the hygroscopic getter of Comparative Example 2.

As described above, the transparent moisture absorbing films of Examples 2, 3, 4, and 5 also exhibited similar moisture absorbing properties, and captured up to 30 parts by weight of water with respect to 100 parts by weight of the total weight of the initial metal oxide or metal salt in the transparent moisture absorbing film. I could confirm that I had the ability to do it.

While maintaining the organic electroluminescent device manufactured according to Example 1 and Comparative Example 1-2 at 70 ° C, 90% relative humidity, the screen state over time was observed using a microscope, the results are shown in Figure 5 As shown in

The organic electroluminescent device manufactured according to Examples 1-5 and Comparative Examples 1-2 was used at 70 ° C. and 90% relative humidity of the organic electroluminescent device manufactured according to Examples 1-5 and Comparative Examples 1-2. After storage, changes in luminance over time were observed.

As a result, even when 500 hours have elapsed under an acceleration condition of 70 ° C and a relative humidity of 90% (equivalent to 20,000 to 30,000 hours of actual time), 90% of the initial luminance is maintained and a conventional opaque absorbent is installed (compared to Compared with Example 2), the same or better results were obtained.

Example 6

100 parts by weight of anhydrous calcium oxide (CaO) (average particle size: 30 µm) and 10 parts by weight of an organic-inorganic composite siloxane, a dispersant, and 10 parts by weight of epoxycyclohexyltrimethoxysilane (400 parts by weight) of anhydrous ethanol, followed by milling for 24 hours. After preparing a dispersion having an average particle diameter of 70nm and a difference between D10 and D90 of about 80nm, 3000 parts by weight of an organic binder urethane acrylate was mixed to prepare a composition for forming a transparent hygroscopic film.

The transparent hygroscopic film-forming composition was printed on the etched glass and heat-treated at 100 ° C., followed by UV curing to form a transparent hygroscopic film.

 A sealant epoxy resin was applied to at least one side of the soda glass substrate on which the transparent moisture absorption film was formed and at least one side of the glass substrate on which the first electrode, the organic film, and the second electrode were formed. Subsequently, the two substrates were bonded to each other to complete an organic EL device.

Example 7

An organic electroluminescent device was completed in the same manner as in Example 6 except that the average particle diameter of anhydrous calcium oxide was about 70 nm and the difference between D10 and D90 was about 60 nm in the dispersion after milling.

Example 8

An organic electroluminescent device was completed in the same manner as in Example 5 except that the average particle diameter of anhydrous calcium oxide in the dispersion after milling was about 70 nm, and the difference between D10 and D90 was about 70 nm.

The film state of the moisture absorbing layer according to Example 6 was examined using an electron scanning microscope as shown in FIG. 2B.

Referring to FIG. 2B, it can be seen that the thickness of the transparent moisture absorption film obtained in Example 6 is about 100 μm, and the leveling state of the surface is excellent, and nano-size metal oxide absorbents or metal salts are not uniformly dispersed and precipitated. I can see that .

In addition, in the transparent moisture absorption film of Example 6-7 and Comparative Example 6-7, the transmittance spectrum was investigated and shown in FIG.

Referring to FIG. 6, although the thickness of the transparent moisture absorbing film was 100 μm or more, it was found that the transparent film had almost no decrease in transmittance in the entire visible light region.

Example 9

An organic electroluminescent device was completed in the same manner as in Example 6, except that barium oxide (BaO) was used instead of anhydrous calcium oxide (CaO).

Example 10

An organic electroluminescent device was completed in the same manner as in Example 8 except that phosphorus pentoxide (P ₂ O ₅ ) was used instead of anhydrous calcium oxide (CaO).

Comparative Example 4

The organic electroluminescent device was completed in the same manner as in Example 8 except that the transparent moisture absorption film was not formed on the soda organic substrate.

Comparative Example 5

An ordinary getter (HD-204, Japan Dininic Co., Ltd.) is installed on top of a soda glass substrate, and the sealant epoxy is formed on at least one side of the soda glass substrate and at least one side of the glass substrate on which the first electrode, the organic film, and the second electrode are formed. Resin was applied. Subsequently, the two substrates were bonded to each other to complete an organic EL device.

Comparative Example 6

The organic electroluminescent device was completed in the same manner as in Example 6 except that the average particle diameter of anhydrous calcium oxide (CaO) in the dispersion after milling was about 70 nm and the difference between D10 and D90 was about 150 nm. It was.

Comparative Example 7

An organic electroluminescent device was completed in the same manner as in Example 1, except that the average particle diameter of anhydrous calcium oxide (CaO) in the dispersion after milling was about 70 nm and the difference between D10 and D90 was about 300 nm. .

In the organic electroluminescent device manufactured according to Example 6-8 and Comparative Example 6-7, the transmittance and haze were investigated and shown in Table 1 below.

TABLE 1

division Example 6 Example 7 Example 8 Comparative Example 6 Comparative Example 7 Transmittance (%) 95 96 95 87 78 Haze 0.6 0.3 0.5 2.0 12.5

Referring to Table 1, even if the average particle size is the same, if the difference between D10 and D90 is 100 nm or less, a haze of 1.0 or less can be obtained, but if the difference between D10 and D90 is 150 or more, the haze becomes 1.0 or more and the translucent film is obtained. It could be known.

The transmittance | permeability of the transparent moisture absorption membrane obtained in the said Example 6-9 was investigated. The transmittance was also 95% or more and was applicable to the front emission type as a transparent membrane.

The moisture absorption rate of the transparent moisture absorption film obtained in Example 8 and Comparative Example 5 was evaluated, and the results are shown in FIG. 4.

Referring to FIG. 4, it was found that the transparent hygroscopic film of Example 8 was improved in hygroscopic ability and speed in comparison with the hygroscopic getter of Comparative Example 2.

In addition, as a result of examining the transparent moisture absorbing films of Examples 6, 7 and 9, it showed similar moisture absorbing properties as in Example 8, and up to 30 parts by weight of water was added to 100 parts by weight of the total weight of the initial metal oxide or metal salt in the transparent moisture absorbing film. I could confirm that I have the ability to capture.

While keeping the organic EL device manufactured according to Example 8 and Comparative Example 5 at 70 ° C. and relative humidity of 90%, the screen state over time was observed using a microscope, and the results are shown in FIGS. 5A and 5B. As shown in

After storing the organic EL device manufactured according to Examples 6-9 and Comparative Example 4-5 at 70 ° C. and a relative humidity of 90%, changes in luminance over time were observed.

As a result, even when 500 hours have elapsed under an acceleration condition of 70 ° C and a relative humidity of 90% (equivalent to 20,000 to 30,000 hours of actual time), 90% of the initial luminance is maintained and a conventional opaque absorbent is installed (compared to Compared with Example 5, the same or better results were obtained.

According to the present invention, it is possible to manufacture a top-emitting organic electroluminescent device having excellent hygroscopic properties and transparent properties compared to the case of using a conventional getter by using a transparent hygroscopic film and ensuring a required lifespan. Thus, the transparent moisture absorption film of this invention is excellent in water and oxygen adsorption characteristic, and lifespan characteristic is improved. And as the front substrate, etched glass or unetched planar glass which requires processing can be used. Thus, structural weaknesses (destructive properties) caused by using etched glass can be overcome.

Although described above with reference to the preferred embodiment of the present invention, those skilled in the art will be able to variously modify and change the present invention without departing from the spirit and scope of the invention described in the claims below. It will be appreciated.

Claims (51)

Board; Sealing substrate; An organic electroluminescent part disposed between the substrate and the encapsulation substrate, Located in the interior space provided by the substrate and the sealing substrate, an organic electroluminescent device comprising a transparent hygroscopic film comprising i) at least one selected from metal oxides and metal salts having an average particle diameter of 100 nm or less and ii) a binder and iii) a dispersant . The organic electroluminescent device according to claim 1, wherein the transparent moisture absorbing film is formed on an inner surface of the encapsulation substrate, a side surface of the sealant layer joining the substrate and the encapsulation substrate, or at least one side of the substrate and the encapsulation substrate. The organic electroluminescent device according to claim 1, wherein at least one selected from the metal oxide and the metal salt is at least one selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, metal halides, metal sulfates, and metal perchlorates. . The method of claim 3, wherein the alkali metal oxide is lithium oxide (Li ₂ O), sodium oxide (Na ₂ O) or potassium oxide (K ₂ O), The alkaline earth metal oxide is barium oxide (BaO), calcium oxide (CaO), or magnesium oxide (MgO), The metal sulfate is lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga ₂ (SO ₄₎ ) ₃ ), titanium sulfate (Ti (SO ₄ ) ₂ ), or nickel sulfate (NiSO ₄ ), The metal halide is calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium chloride (YCl ₂ ), copper chloride (CuCl ₂ ), cesium fluoride (CsF), tantalum fluoride ( TaF ₅ ), niobium fluoride (NbF ₅ ), lithium bromide (LiBr), calcium bromide (CaBr ₃ ), cerium bromide (CeBr ₄ ), selenium bromide (SeBr ₂ ), vanadium bromide (VBr ₂ ), magnesium bromide (MgBr ₂₎ ), Barium iodide (BaI ₂ ) or magnesium iodide (MgI ₂ ), And the metal perchlorate is barium perchlorate (Ba (ClO ₄ ) ₂ ) or magnesium perchlorate (Mg (ClO ₄ ) ₂ ). The organic electroluminescent device according to claim 1, wherein the metal oxide is anhydrous calcium oxide (CaO). The method of claim 1, wherein the dispersant is at least one selected from a low molecular organic dispersant, a polymer organic dispersant, a polymer organic-inorganic complex dispersant, a low molecular organic-inorganic complex dispersant, and an organic acid, the content is at least one selected from metal oxides and metal salts 100 weight An organic electroluminescent device, characterized in that 1 to 100 parts by weight based on parts. The method of claim 1, wherein the binder is at least one selected from an organic binder, an inorganic binder, and an organic / inorganic composite binder, and the content thereof is 10 to 5000 parts by weight based on 100 parts by weight of at least one selected from metal oxides and metal salts. An organic electroluminescent device characterized by. The organic electroluminescence of claim 7, wherein the organic binder is at least one selected from acrylic resins, methacryl resins, polyisoprene, vinyl resins, epoxy resins, urethane resins, and cellulose resins. device. The organic electroluminescent device according to claim 7, wherein the inorganic binder is at least one selected from the group consisting of titania, silicon oxide, zirconia, alumina and precursors thereof. The method of claim 7, wherein the organic / inorganic composite binder is selected from the group consisting of epoxy silane or derivatives thereof, vinyl silane or derivatives thereof, amine silane or derivatives thereof, methacrylate silane or derivatives thereof, or a result of a partial curing reaction thereof. An organic electroluminescent device, characterized in that at least one selected . The organic electroluminescent device according to claim 1, wherein the transparent moisture absorption film has a thickness of 0.1 to 300 µm. The organic electroluminescent device according to claim 1, wherein the transparent moisture absorption film has a transparency of 95 to 98% and a moisture absorption of 30 to 50%. The organic electroluminescent device according to claim 1, wherein when the transparent moisture absorption film is a thick film having a thickness of 100 to 300 µm, the transmittance is 96 to 98% and the moisture absorption is 30 to 40%. Board; Sealing substrate; An organic electroluminescent part disposed between the substrate and the encapsulation substrate, Located in the inner space provided by the substrate and the sealing substrate, An organic EL device having a transparent moisture absorption film including at least one selected from metal oxides and metal salts having a difference between a particle diameter (D10) corresponding to a weight percentage of 10% and a particle diameter (D90) corresponding to a weight percentage of 90% of 100 nm or less. . The organic electroluminescent device according to claim 14, wherein the at least one particle average particle diameter selected from the metal oxide and the metal salt is 100 nm or less. The organic electroluminescent device according to claim 14, wherein the minimum particle size (Dmin) of at least one particle selected from the metal oxide and the metal salt is 30 nm or more, and the maximum particle size (Dmax) is 120 nm or less. 15. The sealant according to claim 14, wherein the transparent moisture absorbing film is formed on an inner surface of the sealing substrate and a sealant layer. An organic EL device, characterized in that formed on the side or at least one side of the substrate and the sealing substrate. 15. The organic electroluminescent device according to claim 14, wherein at least one selected from the metal oxide and the metal salt is at least one selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, metal halides, metal sulfates and metal perchlorates. . The method of claim 14, wherein the alkali metal oxide is lithium oxide (Li ₂ O), sodium oxide (Na ₂ O) or potassium oxide (K ₂ O), The alkaline earth metal oxide is barium oxide (BaO), calcium oxide (CaO), or magnesium oxide (MgO), The metal sulfate is lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga ₂ (SO ₄₎ ) ₃ ), titanium sulfate (Ti (SO ₄ ) ₂ ), or nickel sulfate (NiSO ₄ ), The metal halide is calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium chloride (YCl ₂ ), copper chloride (CuCl ₂ ), cesium fluoride (CsF), tantalum fluoride ( TaF ₅ ), niobium fluoride (NbF ₅ ), lithium bromide (LiBr), calcium bromide (CaBr ₃ ), cerium bromide (CeBr ₄ ), selenium bromide (SeBr ₂ ), vanadium bromide (VBr ₂ ), magnesium bromide (MgBr ₂₎ ), Barium iodide (BaI ₂ ) or magnesium iodide (MgI ₂ ), And the metal perchlorate is barium perchlorate (Ba (ClO ₄ ) ₂ ) or magnesium perchlorate (Mg (ClO ₄ ) ₂ ). The organic electroluminescent device according to claim 14, wherein the metal oxide is anhydrous calcium oxide (CaO). The organic electroluminescent device according to claim 14, wherein the transparent moisture absorption film further comprises 10 to 5000 parts by weight of the binder based on 100 parts by weight or more selected from the metal oxide and the metal salt. The organic electroluminescent device according to claim 21, wherein the binder is an organic binder, an inorganic binder, an organic / inorganic composite binder, or a mixture thereof. The organic electroluminescent device according to claim 22, wherein the organic binder is at least one selected from acrylic resins, methacryl resins, polyisoprene, vinyl resins, epoxy resins, urethane resins, and cellulose resins. . The organic electroluminescent device according to claim 22, wherein the inorganic binder is at least one selected from the group consisting of titania, silicon oxide, zirconia, and alumina. 23. The method of claim 22, wherein the organic / inorganic composite binder is selected from the group consisting of epoxy silanes or derivatives thereof, vinyl silanes or derivatives thereof, aminesilanes or derivatives thereof, methacrylate silanes or derivatives thereof, or the result of partial curing reaction thereof. An organic electroluminescent device, characterized in that at least one selected . The organic electroluminescent device according to claim 14, wherein the transparent moisture absorption film has a thickness of 0.1 to 300 µm. The organic electroluminescent device according to claim 14, wherein the transparent moisture absorption film has a transparency of 95 to 98%, a moisture absorption of 30 to 50%, and a haze of 0.2 to 0.8. Board; Sealing substrate; An organic electroluminescent part disposed between the substrate and the encapsulation substrate, Located in the inner space provided by the substrate and the sealing substrate, An organic electroluminescent device comprising at least one selected from metal oxides and metal salts having a particle average particle diameter of 100 nm or less and a binder, and having a transparent moisture absorption film having a film thickness of 100 to 300 µm and a transmittance of 95% or more. 29. The organic electroluminescent device according to claim 28, wherein the transparent moisture absorption film is formed on an inner surface of the encapsulation substrate, a side of the sealant layer joining the substrate and the encapsulation substrate, or at least one side of the substrate and the encapsulation substrate. The organic electroluminescent device according to claim 28, wherein at least one selected from the metal oxide and the metal salt is at least one selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, metal halides, metal sulfates, and metal perchlorates. . The method of claim 30, wherein the alkali metal oxide is lithium oxide (Li ₂ O), sodium oxide (Na ₂ O) or potassium oxide (K ₂ O), The alkaline earth metal oxide is barium oxide (BaO), calcium oxide (CaO), or magnesium oxide (MgO), The metal sulfate is lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga ₂ (SO ₄₎ ) ₃ ), titanium sulfate (Ti (SO ₄ ) ₂ ), or nickel sulfate (NiSO ₄ ), The metal halide is calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium chloride (YCl ₂ ), copper chloride (CuCl ₂ ), cesium fluoride (CsF), tantalum fluoride ( TaF ₅ ), niobium fluoride (NbF ₅ ), lithium bromide (LiBr), calcium bromide (CaBr ₃ ), cerium bromide (CeBr ₄ ), selenium bromide (SeBr ₂ ), vanadium bromide (VBr ₂ ), magnesium bromide (MgBr ₂₎ ), Barium iodide (BaI ₂ ) or magnesium iodide (MgI ₂ ), And the metal perchlorate is barium perchlorate (Ba (ClO ₄ ) ₂ ) or magnesium perchlorate (Mg (ClO ₄ ) ₂ ). The organic electroluminescent device according to claim 30, wherein the metal oxide is anhydrous calcium oxide (CaO). The organic electroluminescent device according to claim 28, wherein the content of the binder of the transparent moisture absorption film is 10 to 5000 parts by weight based on at least 100 parts by weight selected from metal oxides and metal salts having a particle average particle diameter of 100 nm or less. The organic electroluminescent device according to claim 28, wherein the binder is at least one selected from an organic binder, an inorganic binder, and an organic / inorganic composite binder. 35. The organic electroluminescence of claim 34, wherein the organic binder is at least one selected from acrylic resins, methacryl resins, polyisoprene, vinyl resins, epoxy resins, urethane resins, and cellulose resins. device. The organic electroluminescent device according to claim 34, wherein the inorganic binder is at least one selected from the group consisting of titania, silicon oxide, zirconia, alumina and precursors thereof. 35. The method of claim 34, wherein the organic / inorganic composite binder is selected from the group consisting of epoxy silanes or derivatives thereof, vinyl silanes or derivatives thereof, amine silanes or derivatives thereof, methacrylate silanes or derivatives thereof, or the result of partial curing reaction thereof. An organic electroluminescent device, characterized in that at least one selected . The organic electroluminescent device according to claim 28, wherein the moisture absorption rate of the transparent moisture absorption film is 30 to 50% and the haze is 0.2 to 0.8. A first step of preparing a substrate on which an organic electroluminescent unit formed by sequentially stacking a first electrode, an organic layer, and a second electrode is formed; A transparent moisture absorption film is obtained by applying and curing a transparent moisture absorption film-forming composition comprising at least one selected from a metal oxide and a metal salt having a particle average particle diameter of 100 nm or less, a binder, a dispersant, and a solvent in an inner space provided in the substrate and the sealing substrate. Step 2; A third step of applying a sealant to a portion of the organic electroluminescent portion on at least one side of the substrate and the encapsulation substrate; And The method of manufacturing an organic electroluminescent device comprising the fourth step of bonding the substrate and the sealing substrate. 40. The method according to claim 39, wherein the content of the binder in the transparent moisture absorption film forming composition is 10 to 5000 parts by weight based on 100 parts by weight or more selected from metal oxides and metal salts, the content of the dispersant is one selected from metal oxides and metal salts. Method for producing an organic electroluminescent device, characterized in that 1 to 100 parts by weight based on 100 parts by weight or more. 40. The method of claim 39, wherein the solvent is ethanol, methanol, propanol, butanol, isopropanol. At least one selected from the group consisting of methyl ethyl ketone, pure water, propylene glycol (mono) methyl ether (PGM), isopropyl cellulose (IPC), methyl cellulose (MC), ethyl cellulose (EC), The content of the solvent is a method of manufacturing an organic electroluminescent device, characterized in that 100 to 1900 parts by weight based on at least one 100 parts by weight selected from metal oxides and metal salts. 40. The method of manufacturing an organic electroluminescent device according to claim 39, wherein the coating of the transparent hygroscopic film forming composition is performed by dip coating, spray coating, dispensing or screen printing. 40. The method of claim 39, wherein the curing is performed according to a thermosetting or UV curing method. 40. The method of claim 39, wherein the thermosetting is performed by heat treatment at a temperature in the range of 100 to 250 ° C. A first step of preparing a substrate on which an organic electroluminescent unit formed by sequentially stacking a first electrode, an organic layer, and a second electrode is formed; At least one selected from a metal oxide and a metal salt having a difference between a particle size (D10) corresponding to a weight percentage of 10% and a particle size (D90) corresponding to a weight percentage of 90% in an internal space provided in the substrate and the encapsulation substrate, 100 nm or less, and a solvent A second step of obtaining a transparent moisture absorbing film by applying and curing the composition for forming a transparent moisture absorbing film comprising a; A third step of applying a sealant to a portion of the organic electroluminescent portion on at least one side of the substrate and the encapsulation substrate; And The method of manufacturing an organic electroluminescent device comprising the fourth step of bonding the substrate and the sealing substrate. 46. The method of manufacturing an organic electroluminescent device according to claim 45, further comprising adding a binder to the transparent moisture absorption film-forming composition. The method of claim 46, wherein the content of the binder in the transparent moisture absorption film-forming composition is 10 to 1000 parts by weight based on 100 parts by weight of one or more selected from metal oxides and metal salts. 46. The method of claim 45, wherein the solvent in the transparent moisture absorption film forming composition is ethanol, methanol, propanol, butanol, isopropanol. At least one selected from the group consisting of methyl ethyl ketone, pure water, propylene glycol (mono) methyl ether (PGM), isopropyl cellulose (IPC), methyl cellulose (MC), ethyl cellulose (EC), The content of the solvent is a method of manufacturing an organic electroluminescent device, characterized in that 100 to 1900 parts by weight based on at least one 100 parts by weight selected from metal oxides and metal salts. 46. The method of claim 45, wherein the coating of the transparent hygroscopic film-forming composition is performed by dip coating, spray coating, dispensing or screen printing. 46. The method of claim 45, wherein the curing is performed according to a thermosetting or UV curing method. 51. The method of claim 50, wherein the thermal curing is performed by heat treatment at a temperature in the range of 100 to 250 ° C.

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