CN1657155A - Film type drier for closed electronic device and its manufacturing method - Google Patents
Film type drier for closed electronic device and its manufacturing method Download PDFInfo
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- CN1657155A CN1657155A CN 200510004838 CN200510004838A CN1657155A CN 1657155 A CN1657155 A CN 1657155A CN 200510004838 CN200510004838 CN 200510004838 CN 200510004838 A CN200510004838 A CN 200510004838A CN 1657155 A CN1657155 A CN 1657155A
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Abstract
To obtain a film-like moisture removal agent for sealed type electronic devices and to provide a production method, both to be used for sealed type electronic devices like OLED or a battery impaired by moisture, easy in use due to its film type form, and with a thin thickness. The film-like moisture removal agent for sealed type electronic devices contains a moisture removal component selected from metals, metal hydrides, metal oxides, organic metal compounds or mixtures thereof; and a polymer binder selected from a thermoplastic resin or a reaction curing resin. After mixing the moisture removal component with the thermoplastic resin, the removal agent is produced by extrusion and/or calendering.
Description
Technical Field
The present invention relates to a thin film type desiccant for a sealed electronic device, which is used for forming a sealed electronic device such as an OLED (organic light emitting display) or a battery to prevent the influence of moisture, and a method for manufacturing the same.
Background
The sealed electronic device is provided with an element in an airtight case and sealed with a polymer having low moisture permeability, but if moisture permeating during the sealing process and use is not eliminated, the performance is gradually degraded, and therefore, it is necessary to use a desiccant for eliminating the moisture.
The performance of a desiccant for a sealed electronic device is determined by the moisture removal rate, the removal amount, and the moisture concentration in an equilibrium state, and the higher the moisture removal rate, the lower the moisture concentration in the equilibrium state, and the better.
The drying substance includes a substance that eliminates moisture by physical adsorption, such as silica gel, and a substance that eliminates moisture by chemical reaction. Since the physical drying substance has a high equilibrium concentration of moisture and a strong temperature dependence, the adsorbed moisture is released again when the temperature is raised at a normal use temperature.
As a desiccant for a sealed electronic device using a physically drying substance, U.S. Pat. No. 5,304,419 describes a desiccant produced using a pressure sensitive adhesive (pressure sensitive adhesive) and a porous desiccant (desiccant); a desiccant made using a polymer and aluminum silicate powder is described in U.S. patent No. 5,401,536; U.S. Pat. No. 5,591,379 describes a desiccant produced by using a moisture-permeable adhesive and a porous desiccant such as a molecular sieve. However, these desiccants have a disadvantage of releasing adsorbed moisture again even at a normal use temperature, and when moisture is adsorbed by the adsorbent, the drying rate is slow because the moisture needs to pass through a polymer layer as a binder.
Therefore, a desiccant that eliminates moisture by using a chemical reaction using compounds including: alkali metal oxides, alkaline earth metal oxides, sulfates, metal halides, perchlorates, phosphorus pentoxide, and the like.
As for the chemical desiccant, japanese laid-open patent publication No. 3-261091 describes a desiccant for containing phosphorus pentoxide powder in a gas-permeable container and being installed inside an OLED, but the handling of the powder is troublesome, and phosphoric acid generated by the reaction of phosphorus pentoxide with water has a melting point as low as 41 to 44 ℃, and therefore, the phosphorus pentoxide powder may flow out of the container even at a normal use temperature, causing a risk of contaminating the elements.
U.S. Pat. No. 5,882,761 describes using a metal oxide, a metal sulfate, a metal halide, a metal perchlorate, and the like in a powder state, or applying the metal oxide, the metal sulfate, the metal halide, the metal perchlorate, and the like inside a sealed case by vacuum deposition, sputtering, or spin coating. However, the use of powder has problems such as contamination, as in japanese laid-open patent publication No. 3-261091, and the method of applying a dry substance to the inside of a sealed case by vacuum deposition, sputtering, or spin coating (spin coating) is difficult to implement and is liable to fall off with time.
Recently, since OLEDs and the like tend to be thinner and thinner, a method of curing after applying a liquid phase desiccant in order to reduce the thickness of the desiccant has been attempted, but the process thereof is complicated.
Further, U.S. Pat. No. 6,226,890 describes a method of mixing a metal oxide, a metal sulfate, a metal halide, a metal perchlorate, or the like with a polymer liquid having high moisture permeability, coating the inside of an OLED, and curing, but the process requires a long time. In addition, the patent also describes a method of coating a liquid phase drying agent on one surface of a film and coating an adhesive on the other surface and curing the same, and then mounting the same inside an OLED.
Further, although a method of coating an aluminum thin film is described in U.S. Pat. No. 6,198,217B1, the amount of water to be eliminated is small because aluminum on a plane surface reacts only on the surface.
Japanese laid-open patent publication No. 2003-144830 describes a method of forming a desiccant film by dissolving an organometallic compound in a solvent, applying the solution, and gradually removing the solvent, but the required process time is long, and the resulting desiccant film is not flexible and is liable to crack.
Further, oxygen is also an element for shortening the life of the sealed electronic device, and metal is vacuum-deposited inside the electronic device or metal powder is used as a method for eliminating oxygen, but vacuum deposition of metal requires a high-temperature process and is very troublesome, and therefore, the metal is limited to a special use, and the operation of metal powder is troublesome, and therefore, it is difficult to apply the metal to a small-sized device.
Disclosure of Invention
The invention provides a film type desiccant for a sealed electronic device and a method formanufacturing the same, which is used for eliminating moisture causing the performance degradation of an internal element, and simultaneously eliminating moisture and oxygen as required, and is convenient to use.
In order to achieve the above object, a thin film type desiccant for a sealed electronic device according to the present invention includes: a moisture scavenger component selected from a metal, metal hydride, metal oxide, organometallic compound, or mixture thereof; a polymer binder selected from thermoplastic resins or reaction curable resins.
The metal may be a metal having a greater ionization tendency than hydrogen or a mixture thereof, and moisture is removed by the following reaction formula 1.
[ reaction scheme 1]
The metal hydride is a metal hydride, an alkali metal hydride, an alkaline earth metal hydride, aluminum hydride, or a mixture thereof, and water is removed by the following reaction formula 2.
[ reaction scheme 2]
The metal oxide uses an alkali metal oxide, an alkaline earth metal oxide, alumina, or a mixture thereof, and moisture is removed by the following reaction formula 3.
[ reaction scheme 3]
As the organometallic compound, a compound represented by the following formula [ chemical formula 1]in which a metal is bonded to one or more organic groups is used.
[ chemical formula 1]
Me-RmR’n
In the above formula, Me represents one or two of the same or different metals selected from alkali metals, alkaline earth metals, aluminum, titanium, zirconium, silicon and the like;
r represents a saturated or unsaturated chain hydrocarbon group, a saturated or unsaturated aromatic hydrocarbon group, a saturated or unsaturated chain hydrocarbon oxy group, a saturated or unsaturated aromatic hydrocarbon oxy group;
r' represents hydrogen, saturated or unsaturated chain alkyl, saturated or unsaturated aryl alkyl, saturated or unsaturated chain alkoxy, saturated or unsaturated aryl alkoxy;
m and n are integers of 0 to 4, respectively, and m + n is 1 to 4.
For example, sodium pentoxy and sodium bis (2-methoxyethoxy) aluminum hydride in the organometallic compound undergo the moisture elimination reaction of the following reaction formulas 4 and 5.
[ reaction scheme 4]
[ equation 5]
The oxygen eliminating component uses a metal which eliminates oxygen and reacts with oxygen at room temperature to form an oxide in a solid state. For example, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, zinc, iron, nickel, copper, zirconium, hafnium, antimony, bismuth, and the like.
When the moisture eliminating component is a metal, oxygen is eliminated at the same time as moisture is eliminated, so that it is not necessary to separately use an oxygen eliminating component.
The polymer binder is a thermoplastic resin or a reaction curable resin which can be easily processed into a film, and among them, a resin having good chemical stability is preferably used because a basic compound is generated when an organic metal compound is used as a dry substance.
The thermoplastic resin preferably has a double bond and has good moisture permeability. These resins do not require any other adhesive, can be bonded by heating and pressing, and have strong self-adhesive force.
Examples of the thermoplastic resin include thermoplastic copolymers of polybutadiene and polyisoprene, specifically block copolymers of polybutadiene and polystyrene, and block copolymers of polyisoprene and polystyrene.
The reaction curable resin is produced by polymerizing a monomer or oligomer having an ethylene group, an propylene group, a methacrylic group, a glycidyl group, or an isocyanate group. The polymerization reaction is carried out by light and heat.
The manufacturing method of the film-type desiccant differs when a thermoplastic resin and a reaction curable resin are used, and when a thermoplastic resin is used as a polymer binder, the manufacturing method includes: a step of mixing a moisture eliminating component and a thermoplastic resin; a step of forming a film shape by extrusion, calendering, or calendering after extrusion. The formed film-like desiccant is bonded using high frequency or heat.
In the case of using a reaction curable resin as the polymer binder, the moisture eliminating component is mixed with a monomer or oligomer of the reaction curable resin, applied, and then polymerized. In this case, the coating is directly coated on the position needing bonding and then is cured.
Drawings
FIG. 1 is a sectional view of a front-emitting or rear-emitting OLED, which is an example of a sealed electronic device incorporating the thin film desiccant of the present invention.
Description of the main part of the figures
10: thin film type desiccants of the present invention, 11, 15: protective layer, 12: gas or solid phase insulating layer, 13: sealant, 14: organic electroluminescent layer
Detailed Description
FIG. 1 is a sectional view of a front-emitting or rear-emitting OLED, which is an example of a sealed electronic device incorporating the thin film desiccant of the present invention.
Reference numeral 10 is a thin film type desiccant of the present invention, 11 and 15 are protective layers of OLEDs, 14 is an organic electroluminescent layer having a plurality of organic layers and electrode layers, 12 is a gas phase or solid phase insulating layer, and 13 is a sealant.
The compositions of the present invention are further illustrated by the following examples.
Examples 1 to 2
The raw materials having the compositions shown in table 1 were mixed, melt-extruded and rolled to produce a moisture and oxygen scavenger in the form of a flexible film, and then the moisture and oxygen scavenging rates were measured.
The water elimination rate is the initial elimination rate measured in air at 25 ℃ and a relative humidity of 50%, and the oxygen elimination rate is measured at 25 ℃ and O2The initial elimination rate in the mixed gas of 5% and 97% Ar is shown in Table 2.
TABLE 1
| Classification | Example 1 | Example 2 | ||
| Name of substance | Milligrams of | Name of substance | Milligrams of | |
| Moisture eliminating component | C4H9OK | 40 | [(CH3OC2H4O)2AlH2]Na | 40 |
| Oxygen scavenging component | Zn | 10 | Cu | 10 |
| Polymer adhesive | Ethylene-propylene-elastomers | 50 | Polybutadiene-polystyrene-interpolymer | 50 |
| Thickness of film | 100 micron | 100 micron | ||
TABLE 2
| Classification | Example 1 | Example 2 |
| Rate of water elimination | 1.4mg/10cm2.hr | 4.6mg/10cm2.hr |
| Rate of oxygen elimination | 0.12mg/10cm224hrs | 0.18mg/10cm224hr |
Examples 3 to 4
The water and oxygen scavengers were prepared in the same manner as in example 1-2 with the compositions shown in Table 3, and the water and oxygen elimination rates were measured in the same manner as in example 1-2. The elimination rates of moisture and oxygen are shown in table 4.
TABLE 3
| Classification | Example 3 | Example 4 | ||
| Name of substance | Milligrams of | Name of substance | Milligrams of | |
| Moisture eliminating component | (C4H9O)3Al | 40 | C5H11ONa | 40 |
| Oxygen scavenging component | Zr | 10 | Ca | 10 |
| Polymer adhesive | Polyisoprene-polystyrene Alkene-interpolymers | 50 | Polytetrafluoroethylene-propylene | 50 |
| Thickness of film | 100 micron | 100 micron | ||
TABLE 4
| Classification | Example 3 | Example 4 |
| Rate of water elimination | 6.4mg/10cm2.hr | 0.7mg/10cm2.hr |
| Rate of oxygen elimination | 0.23mg/10cm224hrs | 0.05mg/10cm224hr |
Examples 5 to 6
After mixing the raw materials in the composition shown in Table 5, a film was produced by extrusion and ultraviolet curing, and then the moisture and oxygen elimination rates were measured in the same manner as in example 1-2. The elimination rates of moisture and oxygen are shown in table 6.
TABLE 5
| Classification | Example 5 | Example 6 | ||
| Name of substance | Milligrams of | Name of substance | Milligrams of | |
| Moisture eliminating component | (C4H9O)3Al | 40 | CaO | 40 |
| Oxygen scavenging component | Al | 10 | Fe | 10 |
| Polymer adhesive | Polybutadiene dimethyl propylene Acid esters | 50 | Polybutadiene di (dimethacrylate) | 50 |
| Additive agent | Ultraviolet curing initiator | 4 | Ultraviolet curing initiator | 4 |
| Thickness of film | 100 micron | 100 micron | ||
TABLE 6
| Classification | Example 5 | Example 6 |
| Rate of water elimination | 3.3mg/10cm2.hr | 1.4mg/10cm2.hr |
| Rate of oxygen elimination | 0.36mg/10cm224hrs | 0.27mg/10cm224hr |
As shown in examples 1 to 6, the film-type moisture and oxygen scavengers of the present invention are effective not only in eliminating moisture but also in eliminating oxygen.
Effects of the invention
According to the present invention, a thin-film moisture and oxygen scavenger for sealed electronic devices, which can be used by being easily bonded to a sealed electronic device such as an OLED or a battery, whose performance and life are affected by moisture and oxygen, and a method for producing the same can be provided.
The thin film type desiccant for a sealed electronic device of the present invention does not require any other adhesive agent and can be directly adhered by thermal bonding, so that the thickness of the thin film type desiccant becomes thinner and the sealed electronic device becomes thinner.
Claims (12)
1. A thin film type desiccant for a sealed electronic device, comprising: a moisture scavenger component selected from a metal, metal hydride, metal oxide, organometallic compound, or mixture thereof; a polymer binder selected from thermoplastic resins or reaction curable resins.
2. The thin film desiccant for a sealed electronic device as claimed in claim 1, wherein said metal has a higher ionization tendency than hydrogen.
3. The film-like desiccant for a sealed electronic device as defined in claim 1, wherein said metal hydride is selected from the group consisting of alkali metal hydrides, alkaline earth metal hydrides, and aluminum hydrides.
4. The film type desiccant for a hermetically sealed electronic device as claimed in claim 1, wherein said metal oxide is selected from the group consisting of alkali metal oxides, alkaline earth metal oxides and aluminum oxide.
5. The thin film type desiccant for a sealed electronic device according to claim 1, wherein said organometallic compound is selected from the group consisting of compounds represented by the following chemical formula 1, which are obtained by bonding a metal to one or more organic groups,
[ chemical formula 1]
Me-RmR’n
In the above formula, Me represents one or two of the same or different metals selected from alkali metals, alkaline earth metals, aluminum, titanium, zirconium and silicon;
r represents a saturated or unsaturated chain hydrocarbon group, a saturated or unsaturated aromatic hydrocarbon group, a saturated or unsaturated chain hydrocarbon oxy group, a saturated or unsaturated aromatic hydrocarbon oxy group;
r' represents hydrogen, saturated or unsaturated chain alkyl, saturated or unsaturated aryl alkyl, saturated or unsaturated chain alkoxy, saturated or unsaturated aryl alkoxy;
m and n are integers of 0 to 4, respectively, and m + n is 1 to 4.
6. The thin-film desiccant for a sealed electronic device according to any one of claims 3 to 5, wherein the oxygen-eliminating component contains lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, zinc, iron, nickel, copper, antimony, bismuth, or a mixture thereof.
7. The film-like desiccant for a hermetically sealed electronic device as claimed in claim 1, wherein said thermoplastic resin has a double bond.
8. The film desiccant for a hermetically sealed electronic device as claimed in claim 7, wherein the thermoplastic resin having a double bond is a copolymer comprising polybutadiene or polyisoprene.
9. The film desiccant for a hermetically sealed electronic device as claimed in claim 8, wherein the thermoplastic copolymer containing polybutadiene or polyisoprene is a block copolymer of polybutadiene and polystyrene, a block copolymer of polyisoprene and polystyrene, or a mixture thereof.
10. The film desiccant for a sealed electronic device according to claim 1, wherein the reaction curable resin is obtained by polymerizing a monomer or oligomer having an ethylene group, an propylene group, a methacrylic group, a glycidyl group, or an isocyanate group.
11. A method for producing a film type desiccant for a sealed electronic device as claimed in any one of claims 7 to 9, comprising a step of mixing a moisture eliminating component and a thermoplastic resin; and a stepof forming a film shape by extrusion, calendering, or post-extrusion calendering.
12. A method for producing a film type desiccant for a sealed electronic device as claimed in claim 10, wherein the moisture eliminating component is mixed with a monomer or oligomer of the reaction curable resin, applied, and polymerized.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040010289A KR100602517B1 (en) | 2004-02-17 | 2004-02-17 | Film type moisture and oxygen getter body for enclosed electronic devices and production method of the same |
| KR1020040010289 | 2004-02-17 | ||
| KR1020040015669A KR20050090543A (en) | 2004-03-09 | 2004-03-09 | Dehumidifying method for organic electro luminescent devices using film-type desiccant body |
| KR1020040015669 | 2004-03-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1657155A true CN1657155A (en) | 2005-08-24 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510004838 Pending CN1657155A (en) | 2004-02-17 | 2005-02-02 | Film type drier for closed electronic device and its manufacturing method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2005230818A (en) |
| CN (1) | CN1657155A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103153453A (en) * | 2010-10-08 | 2013-06-12 | 工程吸气公司 | Dispensable polymeric precursor composition for transparent composite sorber materials |
| TWI458384B (en) * | 2006-02-10 | 2014-10-21 | Jsr Corp | Scavenger sheet for organic electron device and organic electron device |
| TWI582099B (en) * | 2015-01-28 | 2017-05-11 | Futaba Denshi Kogyo Kk | A compound, a desiccant, a sealing structure, and an organic EL element |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4400371B2 (en) * | 2004-08-17 | 2010-01-20 | Ｊｓｒ株式会社 | Organic EL panel capture agent and organic EL panel |
| JP5596250B2 (en) * | 2005-03-02 | 2014-09-24 | スリーエム イノベイティブ プロパティズ カンパニー | Moisture-reactive composition and organic EL device |
| JP2007214015A (en) * | 2006-02-10 | 2007-08-23 | Kokusai Kiban Zairyo Kenkyusho:Kk | Capture agent of water and oxygen, and organic electronic device |
| JP4876609B2 (en) * | 2006-02-13 | 2012-02-15 | Ｊｓｒ株式会社 | Scavenger for organic electronic device and organic electronic device |
| US8421351B2 (en) * | 2006-04-18 | 2013-04-16 | Komatsu Seiren Co., Ltd. | Hot-melt type member and organic EL display panel |
| JP4819603B2 (en) * | 2006-07-12 | 2011-11-24 | キヤノン株式会社 | ORGANIC LIGHT EMITTING ELEMENT AND MULTICOLOR DISPLAY DEVICE USING THE ORGANIC LIGHT EMITTING ELEMENT |
| JP2011026556A (en) * | 2009-06-25 | 2011-02-10 | Jsr Corp | Composition, cured product, and electronic device |
| TWI503169B (en) * | 2009-08-21 | 2015-10-11 | Kolon Inc | Absorbent and passivation layer for optical element comprising same |
| JP6649243B2 (en) * | 2016-12-27 | 2020-02-19 | 双葉電子工業株式会社 | Desiccant composition, sealing structure, and organic EL device |
-
2005
- 2005-02-02 CN CN 200510004838 patent/CN1657155A/en active Pending
- 2005-02-17 JP JP2005040796A patent/JP2005230818A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI458384B (en) * | 2006-02-10 | 2014-10-21 | Jsr Corp | Scavenger sheet for organic electron device and organic electron device |
| CN103153453A (en) * | 2010-10-08 | 2013-06-12 | 工程吸气公司 | Dispensable polymeric precursor composition for transparent composite sorber materials |
| CN103153453B (en) * | 2010-10-08 | 2016-01-20 | 工程吸气公司 | For the distributed polymeric precursors composition of transparent composite absorption agent material |
| TWI582099B (en) * | 2015-01-28 | 2017-05-11 | Futaba Denshi Kogyo Kk | A compound, a desiccant, a sealing structure, and an organic EL element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005230818A (en) | 2005-09-02 |
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