KR101668907B1 - Gettering agent and moisture absorbent film using the same - Google Patents

Abstract

The present invention relates to a getter material, a hygroscopic film containing the getter material, and an organic light emitting device. Specifically, the present application relates to a hygroscopic particle having an average particle diameter within a range of 10 nm to 100 nm; And a silane compound surrounding the surface of the particles, and a hygroscopic film comprising the getter material. The getter material is positioned on the front and / or rear surface of the organic light emitting device to effectively absorb and block moisture, And durability can be improved. In addition, the getter material of the present application uses nano-sized hygroscopic particles to ensure the transparency of the hygroscopic film, thereby realizing a top emitting device, and the hygroscopic particles absorb moisture in the air during the manufacturing process The problem that the total amount of moisture absorption is lost can be solved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a getter material and a hygroscopic film containing the same,

The present invention relates to a getter material, a hygroscopic film containing the getter material, and an organic light emitting device.

An organic electronic device (OED) is an element including at least one layer of an organic material capable of conducting electric current. Examples of the organic electronic device include an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC), or an organic transistor.

An organic light emitting device, which is a typical organic electronic device, typically includes a substrate, a first electrode layer, an organic layer, and a second electrode layer sequentially. In a structure referred to as a so-called bottom emitting device, the first electrode layer may be formed of a transparent electrode layer, and the second electrode layer may be formed of a reflective electrode layer. In a structure referred to as a top emitting device, the first electrode layer may be formed as a reflective electrode layer, and the second electrode layer may be formed as a transparent electrode layer. Electrons and holes injected by the electrode layer can be recombined in the light emitting layer existing in the organic layer to generate light. Light can be emitted toward the substrate in the bottom emission type device and toward the second electrode layer side in the top emission type device.

Durability exists as an important problem to be considered in organic electronic devices. The organic layer and the electrode can be easily oxidized to foreign substances such as water and oxygen, and it is important to secure durability against environmental factors. For this purpose, for example, Patent Documents 1 to 4 propose a structure capable of blocking the penetration of foreign substances.

U.S. Patent No. 6,226,890 U.S. Patent No. 6,808,828 Japanese Patent Application Laid-Open No. 2000-145627 Japanese Patent Laid-Open No. 2001-252505

The present application provides a getter material, a hygroscopic film containing the getter material, and an organic light emitting device.

The present application relates to a hygroscopic particle having an average particle diameter within a range of 10 nm to 100 nm; And a silane compound surrounding the surface of the particles.

The present application also provides a hygroscopic film comprising the getter material.

The present application also provides an organic light emitting device comprising the hygroscopic film.

The getter material according to the present application may include a hygroscopic particle surface-treated with a silane compound to suppress rapid moisture absorption during the getter layer production process, and the hygroscopic film containing the getter material may be placed on the front and / Thus, the lifetime and durability of the organic light emitting device can be improved by effectively absorbing and blocking moisture. Further, the hygroscopic film of the present application secures transparency and can be positioned on the side where light is emitted, thereby facilitating the implementation of the top emitting device.

1 is a view showing an exemplary hygroscopic film according to the present application.
Figures 2 and 3 are diagrams illustrating exemplary organic light emitting devices according to the present application.

Exemplary getter materials include hygroscopic particles having an average particle size within the range of 10 nm to 100 nm; And a silane compound surrounding the surface of the particle.

In the above, the silane compound may be a silane compound represented by the following formula (1) or a fluoro polyether-modified silane.

[Chemical Formula 1]

Si (R ₁ ) _m

In formula 1 R ₁ is hydrogen, halogen, an amino group, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an amino group, an aryl group or a hydrolyzable functional group, provided that m is 4, R ₁ are each May be the same or different, and preferably R ₁ may have at least one or more hydrolysable functional groups.

The silane compound of the present application is not particularly limited as long as it is a substance that can be coated on the surface of the hygroscopic particle. The hygroscopic particles are coated with the silane compound to prepare particles having a hydrophobic surface, thereby suppressing rapid moisture absorption during the process and maintaining the total amount of hygroscopic absorption of the hygroscopic particles.

In one example, R ₁ in formula (I) may include one or more hydrolyzable functional groups. The hydrolyzable functional group can be used without limitation as long as it is a functional group capable of undergoing a hydrolysis reaction. For example, R ₁ may be an alkoxy group having 1 to 8 carbon atoms or halogen, and specifically may be methoxy, ethoxy, butoxy, fluorine, chlorine or bromine.

In the above, the hydrolyzable functional group may mean a group in which a water molecule acts to cause a decomposition reaction. That is, in the silane compound surrounding the hygroscopic particles, the hydrolyzable functional group can be separated from molecules containing the central silicon atom by reacting with moisture. The hydrolyzable functional groups are separated from the rest of the molecules containing the central silicon atoms, and hydroxyl groups can be formed in molecules containing the central silicon atoms.

The hygroscopic particles can be surface-treated with a silane compound containing a hydrolyzable functional group, and hydrolytic functional groups are decomposed during the surface treatment, and as a result, a silane radical having a residual radical can be bonded to the hygroscopic particles by an oxygen-silicon bond .

As used herein, the substituted amino group may mean a functional group in which the hydrogen of the amino group is substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group or silicon, unless otherwise specified.

The term alkyl group as used herein includes, unless otherwise specified, a linear or branched alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms or a linear or branched alkyl group having 3 to 20 carbon atoms, Or a cycloalkyl group having 3 to 16 carbon atoms or 4 to 12 carbon atoms. The alkyl group may be optionally substituted with one or more substituents.

The alkenyl group in the present specification may mean an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms unless otherwise specified. The alkenyl group may be linear, branched or cyclic. In addition, the alkenyl group may be optionally substituted with one or more substituents.

Unless otherwise specified, the alkynyl group in the present specification may mean an alkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms.

As used herein, the term aminoalkyl group refers to a straight or branched chain alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, 20, a cycloalkyl group having 3 to 16 carbon atoms or a cycloalkyl group having 4 to 12 carbon atoms. The aminoalkyl group may be optionally substituted with one or more substituents.

As used herein, the term aryl group may refer to a monovalent residue derived from a compound or derivative thereof including a structure containing benzene or a structure in which two or more benzenes are condensed or bonded, unless otherwise specified. The aryl group may be, for example, an aryl group having 6 to 22 carbon atoms, preferably 6 to 16 carbon atoms, and more preferably 6 to 13 carbon atoms, and examples thereof include a phenyl group, a phenylethyl group, a phenylpropyl group, , A tolyl group, a xylyl group or a naphthyl group.

The term alkoxy group as used herein may mean an alkoxy group having 1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwise specified. The alkoxy group may be linear, branched or cyclic. In addition, the alkoxy group may be optionally substituted with one or more substituents.

In embodiments of the present application, the silane compound may be an aminoalkyltrialkoxysilane, a trialkylhalogen silane, a hexaalkyldisilazane, a fluoropolyether modified silane or an alkyltrialkoxysilane, and in one example, trimethylchlorosilane , Hexamethyldisilazane, 3-aminopropyltriethoxysilane, or methyltrimethoxysilane, but is not limited thereto.

In one example, the average particle size of the hygroscopic particles may be from 10 nm to 100 nm, from 10 nm to 90 nm, from 10 nm to 80 nm, from 10 nm to 70 nm, from 10 nm to 60 nm, from 10 nm to 50 nm, or from 20 to 40 nm. The particle size in the above can be measured, for example, by a scanning electron microscope (SEM) image. When the average particle size of the hygroscopic particles is less than 10 nm, the specific surface area is very large, so that water is absorbed abruptly in the atmosphere, resulting in a disadvantage in terms of processability. When the average particle size exceeds 100 nm, transparency can not be secured when the hygroscopic film is produced. In particular, since the hygroscopic film containing the getter material can ensure transparency due to the hygroscopic particles controlled to a specific size, the structure and manufacturing process of the bottom emission type device that is currently commercialized at the time of sealing the organic light emitting device It is possible to realize a top emission type device without changing the device, which is effective in terms of reduction in device manufacturing cost.

In the embodiments of the present application, the hygroscopic particles are CaO, MgO, CaCl ₂ , CaCO ₃ , CaZrO ₃ , _{CaTiO 3, SiO 2, Ca 2} SiO 4, MgCl 2, P 2 O 5, Li 2 O, Na 2 O, BaO, 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, 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 , but the present invention is not limited thereto.

In the present application, a method of surface-treating the hygroscopic particles is as follows. The hygroscopic particle powder is put into an organic solvent and the powder particles which are agglomerated by the ball mill process are dispersed. 0.5 to 3% by weight of the silane compound is added to the slurry thus dispersed, and the mixture is stirred. 0.1 to 0.5% by weight of acetic acid solution is added thereto, and further stirring is performed. Then, the reaction product is separated from the solid component and the solvent through a centrifugal separator, and the solid component powder is dried at 80 ° C in a vacuum dryer to prepare the surface-treated hygroscopic particles. On the other hand, if the silane compound does not have a hydrolyzable functional group, the silane compound may be reacted with the surface of the hygroscopic particle by using a refluxing device after the silane compound is added in the above process.

The present application also relates to hygroscopic films. The hygroscopic film may have a getter layer including the getter material described above. The getter layer may also have a film or sheet shape. This getter layer can be used to encapsulate the organic light emitting device.

The hygroscopic film may further include a substrate film or a release film (hereinafter may be referred to as " first film "), and the getter layer may have a structure formed on the substrate or release film. The structure may further include a substrate or a release film (hereinafter sometimes referred to as " second film ") formed on the getter layer.

1 is a sectional view of an exemplary hygroscopic film.

The hygroscopic film 1 may include a getter layer 11 formed on the base material or the release film 12 as shown in Fig. Although not shown in the drawings, the hygroscopic film has a structure including only the getter material having the getter material without the support material such as the base material or the release film and holding the solid or semi-solid phase at room temperature , A structure in which a getter layer is formed on both sides of one base material or a release film, or a structure in which a base material or a release film is formed on both sides of the getter layer.

The specific kind of the first film is not particularly limited. As the first film, for example, a plastic film can be used. Examples of the first film include a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a vinyl chloride copolymer film, a polyurethane film, an ethylene- -Propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film.

When the first film is a release film, one or both sides of the plastic film may be subjected to appropriate mold release treatment. Examples of the releasing agent used in the releasing treatment include an alkyd releasing agent, a silicone releasing agent, a fluorine releasing agent, an unsaturated ester releasing agent, a polyolefin releasing agent and a wax releasing agent. An alkyd-based releasing agent, a silicone-based releasing agent, a fluorine-containing releasing agent, and the like may be commonly used in view of heat resistance and the like, but the present invention is not limited thereto.

The type of the second film is also not particularly limited. For example, 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.

The thickness of the first or second film is not particularly limited. In one example, the thickness of the first film may be about 50 탆 to 500 탆 or about 100 탆 to 200 탆. In this range, the production process of the getter material or the organic light emitting device can be effectively automated, and it is also advantageous from the viewpoint of economy.

The thickness of the second film is also not particularly limited. For example, the thickness of the second film may be the same as that of the first film, or may be adjusted to a relatively thin or thick thickness as compared with the first film.

The thickness of the getter layer is not particularly limited and may be suitably selected in consideration of the use. For example, the getter layer may have a thickness of about 5 탆 to 200 탆. The thickness of the getter layer can be adjusted, for example, in consideration of the filling property, the processability, and the economical efficiency at the time of use as an encapsulating material for an organic light emitting device.

The hygroscopic film may also have excellent light transmittance in the visible light region. In one example, the present application may exhibit a light transmittance of 90% or greater in the visible light region. In the present application, the hygroscopic film containing the getter material can maintain excellent transparency. For example, the getter material formed by applying and drying the getter material containing the hygroscopic particles controlled to a specific size so as to have a thickness of 50 占 퐉 after drying is 90% or more, 91% or more, 92% or more, 93 Or more, or a light transmittance of 94% or more.

Further, the hygroscopic film can exhibit low haze with excellent light transmittance. In one example, when the hygroscopic particles are combined as described above, the haze can also provide a low hygroscopic film. For example, the getter layer formed in the same manner as the condition for measuring the light transmittance may exhibit a haze of less than 3%, less than 2.9%, or less than 2.8%.

In the embodiments of the present application, the hygroscopic film may further include a curable resin or a binder resin. As the curable resin, thermosetting, active energy ray curable or hybrid curable resins well known in the art can be used. The term " thermosetting resin " is a resin that can be cured through appropriate heat application or aging, and the " active energy ray curable resin " is a resin that can be cured by irradiation of active energy rays, The " hybrid curable resin " may mean a resin in which the curing mechanism of the thermosetting and active energy ray curable resin is cured concurrently or sequentially. The active energy ray may include microwaves, infrared rays, ultraviolet rays, X-rays and gamma rays, alpha-particle beams, proton beams, a particle beam such as a neutron beam or an electron beam can be exemplified.

As the curable resin, for example, a resin that can be cured to exhibit adhesiveness and contains at least one functional group or moiety capable of being cured by heat such as a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group or an amide group, A functional group or moiety capable of being cured by irradiation of an active energy ray such as an epoxide group, a cyclic ether group, a sulfide group, an acetal group or a lactone group, May be used. As the curable resin, an acrylic resin, a polyester resin, an isocyanate resin or an epoxy resin having at least one of the functional groups or sites as described above can be exemplified, but the present invention is not limited thereto.

In one example, as the curable resin, an epoxy resin can be used. The epoxy resin may be an aromatic or aliphatic epoxy resin. As the epoxy resin, an epoxy resin which can be cured by using a thermosetting epoxy resin or by a cationic polymerization reaction by irradiation with an active energy ray curing property, for example, an active energy ray can be used.

One example of an epoxy resin may have an epoxy equivalent of 150 g / eq to 2,000 g / eq. The properties such as the adhesion performance of the cured product and the glass transition temperature can be maintained within an appropriate range in the range of the epoxy equivalent.

The curing agent may be appropriately selected and used depending on the type of the functional group contained in the curable resin or the resin.

In one example, when the curable resin is an epoxy resin, examples of the curing agent that can be used as the curing agent of the epoxy resin known in this field include amine curing agents, imidazole curing agents, phenol curing agents, phosphorus curing agents, and acid anhydride curing agents One or more species may be used, but are not limited thereto.

In one example, as the curing agent, an imidazole compound which is solid at room temperature and has a melting point or a decomposition temperature of 80 ° C or higher can be used. Such compounds include, for example, 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole or 1-cyanoethyl- For example, but not limited to,

The content of the curing agent may be selected depending on the composition of the composition, for example, the type and ratio of the curable resin. For example, the curing agent may be contained in an amount of 1 to 20 parts by weight, 1 to 10 parts by weight, or 1 to 5 parts by weight based on 100 parts by weight of the curable resin. However, the weight ratio can be changed depending on the kind and ratio of the functional groups of the curable resin or the resin, the crosslinking density to be implemented, and the like.

When the curable resin is an epoxy resin that can be cured by irradiation with active energy rays, for example, a cationic photopolymerization initiator may be used as the initiator.

As the cationic photopolymerization initiator, an ionized cationic initiator or an organic silane or latent sulfonic acid series based onium salt or organometallic salt series or a nonionic ionic cationic photopolymerization initiator can be used. As the initiator of the onium salt series, diaryliodonium salt, triarylsulfonium salt or aryldiazonium salt can be exemplified, and the initiation of the organometallic salt series Examples of the initiator of the organosilane series include o-nitrobenzyl triaryl silyl ether, triaryl silyl peroxide, and the like. Or an acyl silane, and examples of the initiator of the latent sulfuric acid series include, but are not limited to,? -Sulfonyloxy ketone or? -Hydroxymethylbenzoin sulfonate, and the like .

In one example, an ionized cationic photopolymerization initiator may be used as the cationic initiator.

The content of the initiator may be varied depending on the kind and ratio of the functional groups of the curable resin or the resin thereof, the crosslinking density to be implemented, and the like, as in the case of the curing agent. For example, the initiator may be blended at a ratio of 0.01 to 10 parts by weight or 0.1 to 3 parts by weight based on 100 parts by weight of the curable resin. If the content of the initiator is too small, there is a fear that sufficient curing will not proceed. If the content of the initiator is excessively large, the content of the ionic substance after curing will increase and the durability of the getter layer will deteriorate. , Which is disadvantageous from the viewpoint of optical durability, and corrosion may occur depending on the base material. Therefore, an appropriate content range can be selected in consideration of this point.

The kind of the binder resin contained in the hygroscopic film is not particularly limited as long as it is compatible with other resins such as a curable resin. As the binder resin, a phenoxy resin, an acrylate resin, or a high molecular weight epoxy resin can be used. The high molecular weight epoxy resin may be, for example, a resin having a weight average molecular weight of about 2,000 to 70,000 or about 4,000 to 6,000. As the high molecular weight epoxy resin, solid bisphenol A type epoxy resin or solid bisphenol F type epoxy resin and the like can be mentioned. As the binder resin, a rubber component such as a rubber containing a high polarity functional group or a reactive rubber containing a high polarity functional group may also be used. In one example, a phenoxy resin may be used as the binder resin.

When the binder resin is included, the ratio is not particularly limited as it is controlled according to the intended physical properties. For example, the binder resin may be included in an amount of about 200 parts by weight or less, about 150 parts by weight or less, or about 100 parts by weight or less, based on 100 parts by weight of the curable resin. When the ratio of the binder resin is 200 parts by weight or less, compatibility with each component of the getter layer can be effectively maintained.

The present application also relates to an organic light emitting device comprising the hygroscopic film. An exemplary organic light emitting device of the present application includes a substrate, a transparent electrode layer present on the substrate, an organic layer present on the transparent electrode layer and including at least a light emitting layer, and a reflective electrode layer present on the organic layer, Or between the substrate and the transparent electrode layer or over the reflective electrode layer. When the transparent electrode layer and the reflective electrode layer are constructed as described above, a bottom emission type device in which light generated in the emission layer of the organic layer is emitted toward the substrate can be realized.

In one embodiment of the present application, the hygroscopic film may exist in both the substrate and the transparent electrode layer and on the reflective electrode layer in the hygroscopic film. By further including the hygroscopic film, the water absorption and blocking effect from the outside is excellent.

In addition, the exemplary organic light emitting device of the present application includes a substrate, a reflective electrode layer present on the substrate, an organic layer present on the reflective electrode layer at least including a light emitting layer, and a transparent electrode layer present on the organic layer, A film may be present on the transparent electrode layer. When the transparent electrode layer and the reflective electrode layer are constructed as described above, it is possible to realize a top emission type device in which light generated in the light emitting layer of the organic layer radiates toward the transparent electrode layer side.

Since light emitted from the light emitting layer of the organic layer is emitted toward the transparent electrode layer, the hygroscopic film must satisfy transparency in the case of the top emission type device. The hygroscopic film according to the present application includes a getter material containing hygroscopic particles of a certain size, so that a top emission type device can be realized.

In one embodiment of the present application, the hygroscopic film may further exist between the reflective electrode layer and the substrate.

In the case of the organic light emitting device of the present application, the organic electronic device may have a structure in which an organic layer including at least a light emitting layer is interposed between the hole injection electrode layer and the electron injection electrode layer. For example, if the electrode layer on the substrate is a hole injection electrode layer, the opposite electrode layer is an electron injection electrode layer, and conversely, if the electrode layer on the substrate is an electron injection electrode layer, the opposite electrode layer may be a hole injecting electrode layer.

The organic layer present between the electron and hole injecting electrode layers may include at least one luminescent layer. The organic layer may include a plurality of light emitting layers of two or more layers. When two or more light emitting layers are included, the light emitting layers may have a structure in which the light emitting layers are divided by an intermediate electrode layer having charge generating characteristics, a charge generating layer (CGL) or the like.

The light-emitting layer can be formed, for example, by using various fluorescent or phosphorescent organic materials known in the art. Examples of the material of the light-emitting layer include tris (4-methyl-8-quinolinolate) aluminum (III) (aluminum (III)) (Alg3), 4-MAlq3 or Gaq3 Alq series materials, C-545T (C ₂₆ H ₂₆ N ₂ O ₂ S), DSA-amine, TBSA, BTP, PAP-NPA, Spiro-FPA, Ph ₃ Si (PhTDAOXD), PPCP , 4,5-pentaphenyl-1,3-cyclopentadiene), cyclopenadiene derivatives such as 4,4'-bis (2,2'-diphenylyinyl) -1,1'-biphenyl, Benzene or a derivative thereof or DCJTB (4- (Dicyanomethylene) -2-tert-butyl-6- (1,1,7,7, -tetramethyljulolidyl-9-enyl) -4H-pyran), DDP, AAAP, NPAMLI; Or Firpic, m-Firpic, N- Firpic, bon 2 Ir (acac), (C 6) 2 Ir (acac), bt 2 Ir (acac), dp 2 Ir (acac), bzq 2 Ir (acac), bo _{2 Ir (acac), F 2} Ir (bpy), F 2 Ir (acac), op 2 Ir (acac), ppy 2 Ir (acac), tpy 2 Ir (acac), FIrppy (fac-tris [2- ( ( ₂ , 4'-difluorophenyl) pyridine-C'2, N] iridium (III) or Btp ₂ Ir (acac) C3 'iridium (acetylacetonate)), etc. However, the present invention is not limited thereto. The light emitting layer contains the above material as a host, and also includes perylene, distyrylbiphenyl A host-dopant system including DPT, quinacridone, rubrene, BTX, ABTX or DCJTB as a dopant.

The light-emitting layer can also be formed by appropriately employing a kind exhibiting light emission characteristics among an electron-accepting organic compound or an electron-donating organic compound.

The organic layer may be formed with various structures, including various other functional layers known in the art, as long as the layer includes a light emitting layer. Examples of the layer that can be included in the organic layer include an electron injecting layer, a hole blocking layer, an electron transporting layer, a hole transporting layer, and a hole injecting layer.

In this field, various materials for forming a hole or electron injection electrode layer and an organic layer such as a light emitting layer, an electron injection or transport layer, a hole injection or transport layer, and a forming method thereof are known and can be used without limitation.

The organic light emitting element may further include a sealing structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture, oxygen and the like from being introduced into the organic layer of the organic electronic device. The sealing structure may be a can, such as a glass can or a metal can, or may be a film covering the entire surface of the organic layer.

2 shows an example in which the sequentially formed substrate 21, the transparent electrode layer 22, the organic layer 23 formed on the transparent electrode layer, and the reflective electrode layer 24 are formed by a sealing structure 25 of a can structure such as a glass can, And a hygroscopic film 26 is present between the transparent electrode layer 22 and the substrate 21 as an example. The sealing structure 25 may be attached to the substrate by, for example, an adhesive. In this way, the protection effect through the sealing structure can be maximized.

3 is a view showing a state in which the substrate 21, the hygroscopic film 26, the reflective electrode layer 24, the organic layer 23 formed on the reflective electrode layer, the transparent electrode layer 22 and the hygroscopic film 26 are formed in a glass can or metal can, And is protected by the encapsulation structure 25 of the same can structure.

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

Example  One

1. Manufacture of hygroscopic particles

3 g of CaO powder having a particle size of 30 nm was added to 100 ml of anhydrous ethanol and the ball mill process was performed for 24 hours to prepare a CaO slurry. To the CaO slurry, 0.5 ml of 3-aminopropyltriethoxysilane was added, followed by stirring for 3 hours. The reaction product is separated by using a centrifugal separator, and the solid component is dried at 80 ° C in a vacuum dryer.

2. Preparation of getter layer solution

The hygroscopic particles prepared above were dispersed in a solvent so as to be uniformly distributed. Separately, a solution (solid content: 70%) obtained by diluting 100 g of an epoxy resin (YD-128, Kuko Chemical) and 70 g of phenoxy resin (YP-70, coagulable) with methyl ethyl ketone was prepared and the solution was homogenized . 250 g of the hygroscopic particle solution previously prepared was added to the homogenized solution, 5 g of imidazole (Shikoku Kasei) as a curing agent was added, and the mixture was stirred at a high speed for 1 hour to prepare a getter layer solution.

3. Preparation of hygroscopic film

The solution of the getter layer prepared above was applied to the releasing surface of the releasing PET using a comma coater and dried at 130 DEG C for 3 minutes in a dryer to form a hygroscopic film having a thickness of 50 mu m.

Example  2

A hygroscopic film was prepared in the same manner as in Example 1 except that 2 ml of 3-aminopropyltriethoxysilane was added.

Comparative Example  One

A hygroscopic film was prepared in the same manner as in Example 1, except that the CaO powder having a particle diameter of 30 nm was not surface-treated.

Comparative Example  2

A hygroscopic film was prepared in the same manner as in Example 1, except that the CaO powder having a size of 200 nm was not surface-treated.

Comparative Example  3

A hygroscopic film was prepared in the same manner as in Comparative Example 1, except that a CaO powder having a size of 1 mu m was used.

Experimental Example  One

Each 1 g of the hygroscopic particle powders prepared above is placed in a vial bottle and placed in a thermostatic chamber without being capped. The temperature and humidity of the thermo-hygrostat were maintained at 25 ° C and 70% humidity. The mass of the vial containing the sample was measured over time, and the amount of water absorption was measured after an elapsed time of 1 hour and defined as an initial moisture absorption rate. After that, it was confirmed that there was no further increase in mass after more than 72 hours, and the moisture absorption amount was defined as the total amount of moisture absorption.

Experimental Example  2

The hygroscopic films prepared above were measured for light transmittance at 440 nm using a UV-Vis spectrometer and haze was measured according to the ASTM D 1003 standard test method.

Initial moisture absorption rate (wt% / hr) Total amount of moisture absorption (wt%) Example 1 5.8 42.1 Example 2 6.2 42.5 Comparative Example 1 12.1 43.3

Light transmittance (%) Haze (%) Example 1 95.3 2.5 Example 2 94.5 2.8 Comparative Example 1 94.7 3.1 Comparative Example 2 87.3 6.2 Comparative Example 3 65.4 21.6

As shown in Table 1, the CaO nanoparticles treated with silane have a lower initial moisture absorption rate than the CaO nanoparticles not treated with silane at a rate of absorbing moisture in the air. However, the total amount of moisture absorption was kept almost equal.

1, 26: hygroscopic film
11: getter layer
12: release film
21: substrate
22: transparent electrode layer
23:
24: reflective electrode layer
25: bag structure

Claims (18)

Hygroscopic particles having an average particle diameter within a range of 10 nm to 100 nm; And from 0.5% to 3% by weight, the silane compound surrounding the surface of the particle,
1 g of the hygroscopic particles surrounding the silane compound was placed in a vial bottle, and the vial bottle was maintained for 1 hour in a thermostatic hygrostat at 25 ° C and 70% relative humidity without covering the vial, the initial moisture absorption rate measured was 12.1 wt% Getter material less than% / hr. The getter material according to claim 1, wherein the silane compound is a silane compound or fluorine-polyether-modified silane represented by the following general formula (1)
[Chemical Formula 1]
Si (R ₁ ) _m
In formula 1 R ₁ is hydrogen, a substituted amino group, an alkyl group, an alkenyl group, an alkynyl group, an amino group, an aryl group or a hydrolyzable functional group, provided that m is 4, R ₁ are each May be the same or different. The getter material according to claim 2, wherein R ₁ in formula (1) comprises at least one hydrolyzable functional group. The getter material according to claim 2, wherein at least one of R ₁ in the formula (1) is an alkoxy group having 1 to 8 carbon atoms or a halogen. The getter material according to claim 1, wherein the hygroscopic particles have an average particle diameter within a range of 10 nm to 90 nm. The method according to claim 1, wherein the hygroscopic particles are CaO, MgO, CaCl ₂ , CaCO ₃ , CaZrO ₃ , _{CaTiO 3, SiO 2, Ca 2} SiO 4, MgCl 2, P 2 O 5, Li 2 O, Na 2 O, BaO, 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, 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 getter material according to claim 1, wherein the silane compound represented by the general formula (1) is an aminoalkyltrialkoxysilane, a trialkylhalogen silane, a hexaalkyldisilazane, or an alkyltrialkoxysilane. A hygroscopic film comprising the getter material of claim 1. The hygroscopic film according to claim 8, wherein the hygroscopic film exhibits a light transmittance of 90% or more in the visible light region. The hygroscopic film according to claim 8, having a haze of less than 3%. The hygroscopic film according to claim 8, further comprising a curable resin or a binder resin. The hygroscopic film according to claim 11, wherein the curable resin is an acrylic resin, a polyester resin, an isocyanate resin or an epoxy resin. The hygroscopic film according to claim 11, wherein the binder resin is a phenoxy resin, an acrylate resin, or a high molecular weight epoxy resin. 9. An organic light emitting device comprising the hygroscopic film of claim 8. 15. The organic electroluminescent device according to claim 14, comprising a substrate, a transparent electrode layer present on the substrate, an organic layer present on the transparent electrode layer and including at least a light emitting layer, and a reflective electrode layer present on the organic layer,
Wherein the hygroscopic film is present between the substrate and the transparent electrode layer or over the reflective electrode layer. The organic light-emitting device according to claim 15, wherein the hygroscopic film is present both between the substrate and the transparent electrode layer and over the reflective electrode layer. The organic electroluminescent device according to claim 14, comprising a substrate, a reflective electrode layer present on the substrate, an organic layer present on the reflective electrode layer at least including an emissive layer, and a transparent electrode layer present on the organic layer, And the organic light emitting device. The organic light emitting device according to claim 17, further comprising a hygroscopic film between the reflective electrode layer and the substrate.

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