KR20040078508A - Flexible film type moisture, oxygen and hydrogen getter body for enclosed electronic devices and production method of the same - Google Patents

Abstract

PURPOSE: Provided are a moisture, oxygen and hydrogen getter for an enclosed electronic device such as organic electroluminescent devices, charge coupled devices and batteries, which are flexible to be conveniently adhered to inside of the electronic device, and a method for preparing thereof. CONSTITUTION: The getter comprises a moisture removing component reacting with moisture to decompose it, an oxygen removing component reacting with oxygen to form a solid state oxide and remove the oxygen, a hydrogenation material reacting with hydrogen to be hydrogenated, a hydrogenation catalyst promoting the hydrogenation and a polymer binder forming and maintaining a flexible film shape. The method comprises steps of (a) mixing the moisture removing component, oxygen removing component, hydrogenation material, hydrogenation catalyst and polymer binder and melting it; and (b) molding the molten mixture by extruding or calendering.

Description

Flexible film type moisture, oxygen and hydrogen getter body for enclosed electronic devices and production method of the same}

In the present invention, since it is impeded by moisture, oxygen, and hydrogen, an electronic device configured in an enclosed type, for example, an organic light emitting device, a polymer light emitting device, a solid state imaging device (CCD) used for information display, or The present invention relates to a moisture, oxygen, hydrogen removing agent for a hermetic electronic device in the form of a flexible film that simultaneously removes water, oxygen, and hydrogen used in a battery and the like, and a manufacturing method thereof.

The hermetic electronic device constitutes an electronic circuit element in an airtight case and is sealed with an adhesive polymer having low moisture permeability. However, if moisture and oxygen that penetrate during the encapsulation process and use and hydrogen generated from electronic circuits due to electrolysis during operation of the device are not removed, side effects such as the function of the electronic device may gradually decrease or the pressure inside the device may increase. Therefore, a dehumidifying agent, an oxygen scavenger, and a hydrogen scavenger are installed inside the airtight case. Particularly, in the case of water, the amount of water adsorbed on the accessory and introduced into the electronic device during the encapsulation process should be removed at an early stage. The performance of dehumidifying agents, oxygen scavengers and hydrogen scavengers used in sealed electronic devices is determined by the removal rate, the removal amount and the equilibrium concentration at equilibrium. The faster the removal rate and the lower the equilibrium concentration, the better the removal agent.

Dehumidifying substances include dehumidifying substances that remove moisture by physical adsorption, such as silica gel, and dehumidifying substances that remove moisture by chemical reaction. Physical adsorbents have high equilibrium moisture concentration and high temperature dependence. There is a disadvantage of re-releasing moisture when higher.

Thus, chemical reactions such as alkali metal oxides, alkaline earth metal oxides, sulfates, metal halides, perchlorates, phosphorus pentoxide, etc. The method of using a dehumidifying material to remove moisture by the water has been studied, but when manufacturing a film, there is a disadvantage in that the dehumidification speed is too slow due to the low moisture permeability of the polymer binder.

Oxygen getters are made by evaporating a metal in a vacuum at high temperature to react with oxygen in a gaseous state to condense metal oxides on the inner wall of the sealed case or to keep the metal powder inside to react slowly with oxygen. Removal has long been used. However, the method of evaporating the metal and condensing it on the inner wall has to be operated at a high temperature, the process is very demanding, and it is limited to a specific use, and the metal powder is difficult to handle, making it difficult to use in a small device.

Hydrogen scavenging materials are oxidized hydrogen with an oxidation catalyst to convert it to water for removal, or a catalyst is used to activate hydrogen to double or 1,4-diphenyl butadiene or polybutadiene. It is known to remove in addition to organics having triple bonds.

U.S. Patent 4,405,487 discloses that water is removed by reaction with aluminum powder or zinc powder, and the generated hydrogen is removed by binding to unsaturated organics such as 1,4-diphenyl butadiyne in the presence of a catalyst. As a dehumidifying agent to disclose a method for producing the pellet (pellet) form by a thermocompression method. However, these dehumidifiers have the disadvantage of being prone to dust generation in the manufacturing process and the disadvantage of being inconvenient to use because they cannot be manufactured in a flexible film form.

Japanese Patent Application Laid-Open No. 3-261091 discloses a dehumidifying agent for organic EL devices in which phosphorus pentoxide powder is placed in a breathable container and mounted inside the organic EL device. Since the powder form is difficult, it is difficult to use and the phosphorus pentoxide powder reacts with water. Since the produced phosphoric acid has a low melting point of about 41 to 44 ° C., there is a possibility that it may flow out of the container and contaminate the electronic circuit element even at normal use temperature.

As a manufacturing method of a dehumidifying agent for a sealed electronic device, US Patent No. 5,304,419 discloses a method of preparing a porous desiccant by combining a pressure sensitive adhesive, and US Patent No. 5,401, 536 contains a polymer and an alumina silicate powder. And a method of preparing a mixture of porous desiccants, such as molecular sieves, with a moisture-permeable binder is disclosed in the US Pat. No. 5,591,379. Moisture must penetrate the molecular layer, so the moisture absorption rate is low and the moisture is re-released even at a normal use temperature.

U.S. Patent No. 5,882,761 discloses a method of removing moisture from an organic EL device by using metal oxide, metal sulfate, metal halide and metal perchlorate in powder form or by vacuum deposition, sputtering or spin coating. A method of coating and using the inside of a case is disclosed.

US Pat. No. 6,226,890 discloses a method of removing moisture from a sealed electronic device by combining a polymer having high moisture vapor transmission rate (MVTR) with a metal oxide, a metal sulfate, a metal halide, or a metal perchlorate. A method of attaching and using a dehumidifying agent to a hermetic electronic device is disclosed.

US Pat. No. 6,063,307 discloses a method for removing hydrogen from an enclosed space by adding hydrogen to polybutadiene using a palladium (Pd) catalyst. US Pat. No. 6,203,869 discloses a method for removing hydrogen from palladium oxide using a palladium oxide. The method of converting to and then removing by adsorbing to a molecular sieve (molecular sieve) has been disclosed, but the molecular sieve, a physical adsorbent, may release the moisture again.

SUMMARY OF THE INVENTION An object of the present invention is to provide a film-type water / oxygen / hydrogen remover and a method for producing the same, which is flexible to conveniently attach and use inside a hermetic electronic device and can simultaneously remove water, oxygen and hydrogen.

1 is a conceptual diagram of a hermetically sealed electronic device to which the present invention is applied.

2 is a schematic view of the microstructure of the water, oxygen, and hydrogen removing agent of the present invention.

* Explanation of Signs of Major Parts of Drawings *

10: sealed electronic device 11: electronic circuit

12: moisture, oxygen, hydrogen remover

20: porous material containing hydrogenation catalyst

21: Hydrogenation reactant and polymer binder 22: Moisture remover and oxygen remover

Moisture, oxygen, hydrogen scavenger having a flexible film form to be easily attached to the inside of the sealed electronic device of the present invention for achieving the above object and a moisture removal component for generating hydrogen by reacting with water; An oxygen removing component that reacts with oxygen to form an oxide in a solid state; A hydrogenation reactant reacting with hydrogen to react with hydrogen; A hydrogenation catalyst material for promoting a hydrogenation reaction; And polymeric binders that form and maintain flexible film forms.

The water removal component uses a metal, a metal hydride, or a mixture thereof as a substance that reacts with water to generate hydrogen.

Such metals include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba), aluminum (Al), zinc (Zn), iron (Fe), nickel (Ni) and the like can be used, and the metal hydride is sodium hydride (NaH), potassium hydride (KH), calcium hydride Lide (CaH ₂ ), strontium hydride (SrH ₂ ), aluminum hydride (AlH ₃ ), lithium aluminum hydride (LiAlH ₄ ), sodium aluminum hydride (NaAlH ₄ ), potassium aluminum hydride (KAlH ₄ ), calcium Aluminum hydride (CaAl ₂ H ₈ ) and the like.

The smaller the metal or metal hydride is, because the larger the particle size, the lower the removal rate of water. The particle size of the metal or metal hydride is to be at most 100 microns, preferably at most 10 microns.

The oxygen removing component may use a metal as a substance which reacts with oxygen to become a solid oxide and may be the same as the metal selected as a moisture removing material.

Such metals include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba), aluminum (Al), zinc (Zn), iron (Fe), nickel (Ni) and copper (Cu) are used.

The larger the metal particles, the lower the oxygen removal rate. The particle size of the metal is to be 100 microns or less, preferably 10 microns or less.

The hydrogenation reactant is a substance capable of addition reaction of hydrogen as a low molecular weight organic substance or polymer having a double bond or a triple bond; Or low molecular weight organics or polymers having nitrile bonds; Or low molecular weight organics or polymers having epoxy bonds; Or low molecular weight organics or polymers having ketone bonds.

Hydrogenation catalyst material is a material that promotes a hydrogenation reaction, a porous material such as activated carbon, activated alumina, silica gel, etc., a hydrogenation catalyst such as palladium (Pd), platinum (Pt), rhodium (Rh) , Coated with a catalytic material such as ruthenium (Ru), nickel (Ni).

As the polymer binder, a thermoplastic resin having good processability is used. In particular, it is preferable to use one having high chemical stability with respect to an alkali compound produced by reaction of metal or metal hydride with water. As the thermoplastic polymer binder having high chemical stability, the following materials may be used, and the same polymer as that used for the hydrogenation reaction material may be used.

As the thermoplastic resin, random copolymers or block copolymers containing polyolefins, unsaturated polyethylenes, substituted polyolefins, substituted unsaturated polyolefins and monomers thereof are used. Polymers, such as polyphenylene oxide, polyphenylene sulfide, and polyether sulfone, can also be used.

Polyolefin, polypropylene, polybutene, poly (4-methylpentene) and the like are used as the polyolefin, and polybutadiene, polyisoprene and the like are used as the unsaturated polyolefin. As the substituted polyolefin, polystyrene, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene and the like are used. Polychloroprene or the like is used.

It is most convenient to prepare the water, oxygen, hydrogen removing agent of the present invention in the form of a film comprising the steps of mixing and melting each component; It is manufactured through a process comprising the step of molding into a film form by extrusion and / or calendering. If necessary, a step of imparting adhesion to either side of the film may be added.

In the present invention, the film type is a generic name for a thin form and includes a smooth surface or a weave. Moreover, a filler, a pigment, etc. can be mix | blended and used for the water, oxygen, and hydrogen removal agent by this invention as needed.

<Example 1-2>

After mixing in the following composition, a melt extrusion and calendering process was performed to prepare a flexible film-type moisture, oxygen, and hydrogen remover, and then the removal rate of water, oxygen, and hydrogen was measured.

Hereinafter, in all examples, the water removal rate was measured at an initial removal rate in air at a relative humidity of 50 ^° C. at 20 ^° C., and the oxygen removal rate was initially removed at 20 ^° C. at 3% O ₂ and 97% Ar mixed gas. The rate of hydrogen removal was measured, and the initial rate of hydrogen removal was measured in a mixed gas of 3% H ₂ and 97% Ar at 20 ^° C.

Example 1 Example 2 Substance mg Substance mg Moisture removal ingredients Sodium Hydride (NaH) 10 Lithium Aluminum Hydride (LiAlH ₄ ) 5 Oxygen removal component Calcium (Ca) 20 Sodium (Na) 20 Hydrogenation Catalyst Palladium (Pd, 5%) + Activated Carbon 7 Platinum (Pt, 5%) + activated carbon 7 Hydrogenation reactants Polyisoprene-Polystyrene-Copolymer 60 1,4-diphenylbutadiene 30 Polymer binder Ethylene-Propylene-Elastomer 20 Polybutadiene-Polystyrene-Copolymer 60 Film thickness 100 μm 100 μm

The removal rate of water, oxygen, and hydrogen of the prepared film-type moisture, oxygen, and hydrogen remover was measured and shown in the following table.

Example 1 Example 2 Moisture removal rate 2.7 mg / 10cm ² · hr 6.4 mg / 10cm ² · hr Oxygen removal rate 0.1 mg / 10cm ² · 24hrs 0.2 mg / 10cm ² · 24hrs Hydrogen removal rate 1.0 mg / 10cm ² · hr 0.7 mg / 10cm ² · hr

<Example 3-4>

After mixing in the following composition, a melt extrusion and calendering process was performed to prepare a flexible film-type moisture, oxygen, and hydrogen remover.

Example 3 Example 4 Substance mg Substance mg Moisture removal ingredients Calcium (Ca) 20 Calcium Hydride (CaH ₂ ) 10 Oxygen removal component Aluminum (Al) 10 Zinc (Zn) 30 Hydrogenation Catalyst Platinum (Pt, 5%) + activated alumina 7 Palladium (Pd, 5%) + Activated Carbon 6 Hydrogenation reactants 1,4-diphenylbutadiyne 20 Polybutadiene-Polystyrene-Copolymer 60 Polymer binder Polyisoprene-Polystyrene-Copolymer 60 Polytetrafluoroethylene-propylene 20 Film thickness 100 μm 100 μm

The removal rate of water, oxygen, and hydrogen of the prepared film-type moisture, oxygen, and hydrogen remover was measured and shown in the following table.

Example 3 Example 4 Moisture removal rate 4.3 mg / 10cm ² · hr 1.8 mg / 10cm ² · hr Oxygen removal rate 0.3 mg / 10cm ² · 24hrs 0.1 mg / 10cm ² · 24hrs Hydrogen removal rate 0.5 mg / 10cm ² · hr 0.6 mg / 10cm ² · hr

<Example 5-6>

After mixing in the following composition, a melt extrusion and calendering process was performed to prepare a flexible film-type moisture, oxygen, and hydrogen remover.

Example 5 Example 6 Substance mg Substance mg Moisture removal ingredients Zinc (Zn) 30 Calcium Hydride (CaH ₂ ) 10 Oxygen removal component Sodium (Na) 10 Aluminum (Al) 10 Hydrogenation Catalyst Palladium (Pd, 5%) + Activated Carbon 6 Palladium (Pd, 3%) + Activated Carbon 7 Hydrogenation reactants Polyisoprene-Polystyrene-Copolymer 60 Polybutadiene-Polystyrene-Copolymer 60 Polymer binder Poly (4-methylpentene) 20 Polystyrene-Polyacrylonitrile 20 Film thickness 100 μm 100 μm

The removal rate of water, oxygen and hydrogen of the prepared film-type moisture, oxygen, and hydrogen removing agent was measured and shown in the following table.

Example 5 Example 6 Moisture removal rate 4.5 mg / 10cm ² · hr 5.2 mg / 10cm ² · hr Oxygen removal rate 0.3 mg / 10cm ² · 24hrs 0.2 mg / 10cm ² · 24hrs Hydrogen removal rate 1.8 mg / 10cm ² · hr 1.5 mg / 10cm ² · hr

<Example 7-8>

After mixing in the following composition, a melt extrusion and calendering process was performed to prepare a flexible film-type moisture, oxygen, and hydrogen remover.

Example 7 Example 8 Substance mg Substance mg Moisture removal ingredients Sodium (Na) 10 Sodium Hydride (NaH) 10 Oxygen removal component Calcium (Ca) 20 Sodium (Na) 20 Hydrogenation Catalyst Platinum (Pt, 5%) + activated carbon 7 Platinum (Pt, 5%) + activated carbon 7 Hydrogenation reactants 1,4-diphenylbutadiene 30 1,4-diphenylbutadiyne 20 Polymer binder Polyisoprene-Polystyrene-Copolymer 60 Polybutadiene-Polystyrene-Copolymer 60 Film thickness 100 μm 100 μm

The removal rate of water, oxygen, and hydrogen of the prepared film-type moisture, oxygen, and hydrogen remover was measured and shown in the following table.

Example 7 Example 8 Moisture removal rate 5.5 mg / 10cm ² · hr 8.3 mg / 10cm ² · hr Oxygen removal rate 0.3 mg / 10cm ² · 24hrs 0.3 mg / 10cm ² · 24hrs Hydrogen removal rate 0.7 mg / 10cm ² · hr 0.8 mg / 10cm ² · hr

<Example 9-10>

After mixing in the following composition, a melt extrusion and calendering process was performed to prepare a flexible film-type moisture, oxygen, and hydrogen remover.

Example 9 Example 10 Substance mg Substance mg Moisture removal ingredients Calcium Hydride (CaH ₂ ) 10 Lithium Aluminum Hydride (LiAlH ₄ ) 5 Oxygen removal component Calcium (Ca) 20 Aluminum (Al) 10 Hydrogenation Catalyst Palladium (Pd, 5%) + Activated Carbon 7 Palladium (Pd, 3%) + Activated Carbon 7 Hydrogenation reactants Polybutadiene-Polystyrene-Copolymer 60 Polyisopene-Polystyrene-Copolymer 60 Polymer binder Polypropylene 20 polystyrene 20 Film thickness 100 μm 100 μm

The removal rate of water, oxygen, and hydrogen of the prepared film-type moisture, oxygen, and hydrogen remover was measured and shown in the following table.

Example 9 Example 10 Moisture removal rate 2.2 mg / 10cm ² · hr 7.0 mg / 10cm ² · hr Oxygen removal rate 0.2 mg / 10cm ² · 24hrs 0.1 mg / 10cm ² · 24hrs Hydrogen removal rate 1.2 mg / 10cm ² · hr 1.5 mg / 10cm ² · hr

As shown in Example 1-10 above, it can be seen that the flexible film-type water, oxygen, and hydrogen remover prepared according to the present invention can efficiently remove both water, oxygen, and hydrogen.

According to the present invention, there is provided a moisture, oxygen, and hydrogen removing agent for a hermetic electronic device in the form of a flexible film which can be conveniently attached to an hermetic electronic device such as an organic EL device, a CCD, a battery, or the like, as an adhesive tape, and a manufacturing method thereof.

Claims (22)

A water removal component that reacts with water to decompose and remove water; An oxygen removing component for reacting with oxygen to form a solid oxide to remove oxygen; A hydrogenation reactant reacting with hydrogen to react with hydrogen; A hydrogenation catalyst material for promoting a hydrogenation reaction; And a polymer binder for forming and maintaining a flexible film form. The water, oxygen, and hydrogen removing agent for a sealed electronic device according to claim 1, wherein the water removing component is selected from a metal, a metal hydride or a mixture thereof. The method of claim 2, wherein the metal is lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium ( Sr), barium (Ba), aluminum (Al), zinc (Zn), iron (Fe), nickel (Ni) or a mixture thereof. Water, oxygen and hydrogen removing agent for sealed electronic devices. The method of claim 2, wherein the metal hydride material is sodium hydride (NaH), potassium hydride (KH), calcium hydride (CaH ₂ ), strontium hydride (SrH ₂ ), aluminum hydride (AlH ₃ ), lithium Hermetic electronic device, characterized in that it is selected from aluminum hydride (LiAlH ₄ ), sodium aluminum hydride (NaAlH ₄ ), potassium aluminum hydride (KAlH ₄ ), calcium aluminum hydride (CaAl ₂ H ₈ ) or mixtures thereof Water, Oxygen, Hydrogen Remover. The moisture, oxygen, and hydrogen remover for sealed electronic devices according to any one of claims 2 to 4, wherein the metal or metal hydride has a particle size of 100 microns or less. The moisture, oxygen, and hydrogen remover for sealed electronic devices according to any one of claims 2 to 4, wherein the metal and metal hydride have a particle size of 10 microns or less. The moisture, oxygen, and hydrogen remover for a hermetic electronic device according to claim 1, wherein the oxygen removing component is a metal. The method of claim 7, wherein the metal is lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium ( Sr), barium (Ba), aluminum (Al), zinc (Zn), iron (Fe), nickel (Ni) or a mixture thereof. Water, oxygen and hydrogen removing agent for sealed electronic devices. The water, oxygen, and hydrogen removing agent for sealed electronic devices according to claim 7, wherein the metal has a particle size of 100 microns or less. The water, oxygen, and hydrogen remover for sealed electronic devices according to claim 7, wherein the metal has a particle size of 10 microns or less. The method of claim 1, wherein the hydrogenation material is a low molecular weight organic material or polymer having a double bond or triple bond; Or low molecular weight organics or polymers having nitrile bonds; Or low molecular weight organics or polymers having epoxy bonds; Or low molecular weight organic substances or polymers having ketone bonds; Or a mixture thereof, wherein the water, oxygen, and hydrogen remover for the hermetic electronic device is selected. The water, oxygen, and hydrogen removing agent for a sealed electronic device according to claim 1, wherein the hydrogenation catalyst material is a porous material coated with a hydrogenation catalyst. 13. The water, oxygen and hydrogen removing agent for a sealed electronic device according to claim 12, wherein the porous material is selected from activated carbon, activated alumina, silica gel or a mixture thereof. The method of claim 12, wherein the hydrogenation catalyst is selected from palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), nickel (Ni) or a mixture thereof. Oxygen-hydrogen remover. The moisture, oxygen, and hydrogen removing agent for a hermetic electronic device according to claim 1, wherein the polymer binder is a thermoplastic resin. 16. The water, oxygen and hydrogen removing agent for hermetic electronic device according to claim 15, wherein the thermoplastic resin is selected from polyolefins, unsaturated polyethylenes, substituted polyolefins, substituted unsaturated polyolefins, and random copolymers or block copolymers of monomers thereof. . 16. The water, oxygen and hydrogen removing agent for a hermetic electronic device according to claim 15, wherein the thermoplastic resin is selected from polyphenylene oxide, polyphenylene sulfide, polyether sulfone or a mixture thereof. 17. The water, oxygen, and hydrogen remover for sealed electronic devices according to claim 16, wherein the polyolefin is selected from polyethylene, polypropylene, polybutene, poly (4-methylpentene) or a mixture thereof. 17. The water, oxygen and hydrogen removing agent for a hermetic electronic device according to claim 16, wherein the unsaturated polyolefin is selected from polybutadiene, polyisoprene or a mixture thereof. 17. The method of claim 16, wherein the substituted polyolefin is selected from polystyrene, polyvinylchloride, polyvinylfluoride, polyvinylidenechloride, polyvinylidene fluoride or mixtures thereof. Hydrogen scavenger. 17. The water, oxygen, and hydrogen remover for sealed electronic devices according to claim 16, wherein the substituted unsaturated polyolefin is polychloroprene. Mixing and melting the water removal component, the oxygen removal component, the hydrogenation reaction material, the hydrogenation reaction catalyst material, and the polymer binder; A method for producing a film-type moisture, oxygen, and hydrogen remover for a hermetic electronic device, which comprises molding by extrusion or calendering.