JP2024019999A - Glass composition, glass paste, sealed package, and organic electroluminescence element - Google Patents

Abstract

To provide a glass composition that is superior in terms of water resistance, has a smaller coefficient of thermal expansion, and has excellent fluidity during melting and width of allowable temperature range during calcination.SOLUTION: Provided is a glass composition that is characterized by containing V2O5 by 25.0 to 40.0%, TeO2 by 25.5 to 30.0%, ZnO by 15.0 to 30.0%, Nb2O5 by 5.5% to 8.0%, Al2O3 by 0 to 5.0%, BaO by 0 to 4.5%, B2O3 by 0 to 6.0%, Bi2O3 by 0 to 0.4%, and ZrO2 by 0 to 4.5% in terms of mol% based on oxides, and being substantially free of alkali metal oxides and PbO.SELECTED DRAWING: None

Description

The present invention relates to a glass composition, a glass paste, a sealed package, and an organic electroluminescent device.

Flat panel display devices (FPD), such as organic electro-luminescence displays (OELDs) and plasma display panels (PDPs), have light-emitting elements sealed in a glass package with a pair of glass substrates sealed together. Has a structure. Furthermore, a liquid crystal display (LCD) has a structure in which liquid crystal is sealed between a pair of glass substrates. Furthermore, solar cells such as organic thin film solar cells and dye-sensitized solar cells have a structure in which a solar cell element (photoelectric conversion element) is sealed between a pair of glass substrates.

Among these, in organic EL displays, the light emitting characteristics of the organic EL elements are significantly deteriorated by contact with moisture, so it is necessary to strictly shield the organic EL elements from the outside air. Furthermore, since organic EL elements are damaged when exposed to high temperatures, the sealing method is extremely important.

Therefore, as a method for sealing organic EL displays, a method of using a glass composition as a sealing material and sealing by local heating is considered to be a promising method. Generally, a glass composition is used after being mixed with an organic vehicle to form a paste. This paste is applied to one glass substrate by screen printing or dispensing, and baked to form a pre-fired layer. Next, the other glass substrate is stacked on top of the other glass substrate, and the glass composition is melted and sealed by locally heating the temporarily fired layer using a laser or the like.

The glass composition used as the sealing material has high water resistance, a coefficient of thermal expansion close to that of the material to be sealed, and a glass composition that is suitable for reducing thermal adverse effects on organic EL elements during laser sealing. It is desirable to have a wide allowable temperature (process margin) when melting materials.

As described above, as a glass composition used as a sealing material, for example, Patent Document 1 describes a TeO ₂ -ZnO-B ₂ O _3- based glass composition used for sealing an organic EL display. There is. Further, Patent Document 2 discloses a V ₂ O ₅ -ZnO-TeO ₂ -based glass composition.

Patent No. 6357937 Patent No. 6022070

In recent years, the screen size of organic EL displays has been increasing. When the screen size becomes large, it is necessary to increase the line width of the sealed portion compared to a case where the screen size is small. If the line width of the sealing part is increased, stress due to the difference in thermal expansion between the material to be sealed and the material to be sealed becomes more likely to be applied during laser sealing, which may cause cracks in the sealing layer and the material to be sealed. be. Therefore, in order to ensure the reliability of the sealed package, the sealing material is required to have a coefficient of thermal expansion closer to that of the material to be sealed.

Furthermore, conventional sealed packages generally had glass substrates sealed together, but in recent years, for example, sealed packages have been developed, for example, by sealing a glass substrate with a substrate with a metal film formed on the surface. Packages are also in demand. Even when sealing a substrate on which a metal film is formed, excellent sealing strength is required. Sealing strength can be improved by increasing the fluidity of the sealing material.

The glass compositions described in Patent Document 1 and Patent Document 2 have room for further improvement in terms of water resistance, coefficient of thermal expansion, fluidity during melting, and wide allowable temperature range during firing. Ta.

In view of the above-mentioned circumstances, the present invention provides a vanadium-based glass composition used for sealing joints between glass members in a flat display such as an organic EL display or a liquid crystal display by a local heating method such as laser heating. It is an object of the present invention to provide a glass composition that is superior in terms of water resistance, has a smaller coefficient of thermal expansion, and has excellent fluidity during melting and a wider allowable temperature range during firing than conventional glass compositions. purpose.
Further, the present invention aims to provide a sealing material and a glass paste containing the glass composition, as well as a sealed package and an organic electroluminescent device having a sealing layer containing the glass composition. .

The present inventors have discovered that the above-mentioned problems can be solved by using a glass composition having a glass composition within a specific range, and have completed the present invention.
The present invention provides a glass composition, a glass paste, a sealed package, and an organic electroluminescent device having the following configurations.
[1] Expressed as mol% based on oxides,
25.0 to 40.0% V ₂ O ₅ ,
25.5-30.0% _TeO2 ,
15.0 to 30.0% ZnO,
5.5 to 8.0% Nb ₂ O ₅ ,
0 to 5.0% Al ₂ O ₃ ,
BaO 0-4.5%,
B ₂ O ₃ from 0 to 6.0%,
Contains 0 to 0.4% Bi ₂ O ₃ and 0 to 4.5% ZrO ₂ ,
A glass composition characterized in that it is substantially free of alkali metal oxides and PbO.
[2] The glass composition according to [1], which contains 1.0 to 5.0% of B ₂ O ₃ in terms of mol% based on oxides.
[3] The glass composition according to [1] or [2], which contains more than 6.2% of Nb ₂ O ₅ in terms of mol% based on oxides.
[4] The total content of V ₂ O ₅ , TeO ₂ and ZnO (V ₂ O ₅ + TeO ₂ + ZnO) is 80 to 91% in terms of mol% based on oxides, [1] to [3] The glass composition according to any one of the above.
[5] Any one of [1] to [4], where the ratio of the content expressed as (V ₂ O ₅ /TeO ₂ ) is 1.0 to 1.6 in mol% based on oxides. 1. The glass composition according to item 1.
[6] The total content of Bi ₂ O ₃ , TeO ₂ and BaO (Bi ₂ O ₃ +TeO ₂ +BaO) is 25.5 to 31.0% in terms of mol% based on oxides, [1] The glass composition according to any one of ~[5].
[7] In [1] to [6], the total content of Al ₂ O ₃ and ZrO ₂ (Al ₂ O ₃ + ZrO ₂ ) is 0 to 7.0% in terms of mol% based on oxides. The glass composition according to any one of the above.
[8] A glass paste containing the glass composition according to any one of [1] to [7] and an organic vehicle.
[9] A first substrate, a second substrate disposed opposite the first substrate, and a second substrate disposed between the first substrate and the second substrate, the first substrate and a sealing layer that adheres the second substrate, the package comprising:
A sealed package in which the sealing layer includes the glass composition according to any one of [1] to [7].
[10] A laminated structure including a substrate, an anode, an organic thin film layer, and a cathode laminated on the substrate, and a glass member placed on the substrate to cover the outer surface side of the laminated structure. , a sealing layer that adheres the substrate and the glass member,
An organic electroluminescent device, wherein the sealing layer contains the glass composition according to any one of [1] to [7].

The glass composition of the present invention is superior to conventional glass compositions in terms of water resistance, has a smaller coefficient of thermal expansion, and has excellent fluidity during melting and a wider allowable temperature range during firing. .

FIG. 1 is a front view showing one embodiment of a sealed package. FIG. 2 is a cross-sectional view taken along line AA of the sealed package shown in FIG. FIG. 3A is a process diagram showing one embodiment of a method for manufacturing a sealed package. FIG. 3B is a process diagram showing one embodiment of a method for manufacturing a sealed package. FIG. 3C is a process diagram showing one embodiment of a method for manufacturing a sealed package. FIG. 3D is a process diagram showing one embodiment of a method for manufacturing a sealed package. FIG. 4 is a plan view of the first substrate used for manufacturing the sealed package shown in FIG. 1. FIG. 5 is a sectional view taken along line BB of the first substrate shown in FIG. FIG. 6 is a plan view of the second substrate used for manufacturing the sealed package shown in FIG. 1. FIG. 7 is a cross-sectional view taken along line CC of the second substrate shown in FIG. FIG. 8 is a conceptual diagram of an organic electroluminescent device that is an example of a sealed package.

Embodiments of the present invention will be described below. Note that the present invention is not limited to the embodiments described below. Furthermore, in the following drawings, members and portions that have the same function may be described with the same reference numerals, and overlapping descriptions may be omitted or simplified. Further, the embodiments illustrated in the drawings are schematically illustrated to clearly explain the present invention, and do not necessarily accurately represent the actual size or scale.

<Glass composition>
The glass composition of the present embodiment contains 25.0 to 40.0% V ₂ O ₅ , 25.5 to 30.0% TeO ₂ , and 15.0 to 15.0% ZnO in terms of mol% based on oxides. 30.0%, Nb ₂ O ₅ 5.5-8.0%, Al ₂ O ₃ 0-5.0%, BaO 0-4.5%, B ₂ O ₃ 0-6.0 %, Bi ₂ O ₃ in an amount of 0 to 0.4%, and ZrO ₂ in an amount of 0 to 4.5%, and is substantially free of alkali metal oxides and PbO.

Next, each component of the glass composition of this embodiment will be explained. In the following description, unless otherwise specified, "%" in the content of each component of the glass composition is expressed on an oxide basis, that is, expressed as mole % in terms of oxide. In this specification, "~" representing a numerical range is used to include the upper and lower limits.

If the glass composition used as a sealing material contains an alkali metal oxide, the alkali component may be released into the material to be sealed such as a glass substrate when the sealing material is exposed to high temperatures during or after sealing. is diffused and the material to be sealed deteriorates. Therefore, the glass composition of this embodiment does not substantially contain an alkali metal oxide. In this specification, "substantially not containing" means that it does not contain anything other than inevitable impurities, that is, it means that it is not intentionally added. Therefore, the glass composition of this embodiment may contain a trace amount of an alkali metal oxide as an unavoidable impurity. The content of the alkali metal oxide in the glass composition of this embodiment is preferably 1000 ppm or less, more preferably 500 ppm or less.
Note that in this specification, the alkali metal oxide means Li ₂ O, Na ₂ O, and K ₂ O. Moreover, ppm means mass ppm.

Moreover, the glass composition of this embodiment does not substantially contain lead, that is, PbO, in order to reduce the load on the environment. Regarding PbO, "substantially not containing" means that the content of PbO in the glass composition is 1000 ppm or less.

V ₂ O ₅ is a glass-forming oxide that forms a glass network and is essential as a low softening component. It is also effective as a laser absorption component. On the other hand, if the content of V ₂ O ₅ is large, water resistance may decrease, and glass stability may decrease during glass production, making the glass more likely to devitrify. Furthermore, if the content of V ₂ O ₅ is too small, the glass transition temperature may rise and low-temperature sealing properties may deteriorate. Therefore, the content of V ₂ O ₅ is set to 25.0 to 40.0%. The content of V ₂ O ₅ is preferably 28.0% or more, more preferably 30.0% or more, even more preferably 32.0% or more, and preferably 39.0% or less, and 38.0% or less. More preferably, it is 37.0% or less.

TeO ₂ is a glass-forming oxide that forms a glass network and is essential as a low softening component. It also has the function of improving the fluidity and water resistance of the glass composition. On the other hand, when the content of TeO ₂ is large, the coefficient of thermal expansion becomes large. On the other hand, if the amount is too small, the glass transition temperature may rise and low-temperature sealing properties may deteriorate, and crystallization may easily occur during sealing firing. Furthermore, the effects of improving fluidity and water resistance cannot be sufficiently obtained. Therefore, the content of TeO ₂ is set to 25.5 to 30.0%. The content of TeO ₂ is preferably 26.0% or more, preferably 29.0% or less, more preferably 28.0% or less, and even more preferably 27.5% or less.

ZnO is essential as a component that lowers the coefficient of thermal expansion. On the other hand, if the content of ZnO is large, the glass stability may be reduced during glass production, and the glass may easily devitrify. On the other hand, if the amount is too small, the coefficient of thermal expansion will increase. Therefore, the ZnO content is 15.0 to 30.0%. The content of ZnO is preferably 17.0% or more, more preferably 18.5% or more, even more preferably 20.0% or more, and preferably 28.0% or less, more preferably 26.5% or less, More preferably, it is 25.0% or less.

Nb ₂ O ₅ is essential as a component that lowers the coefficient of thermal expansion and improves water resistance. On the other hand, if the content of Nb ₂ O ₅ is high, the glass tends to crystallize during laser firing sealing, and if it is too low, the coefficient of thermal expansion becomes large, and the effect of improving water resistance cannot be sufficiently obtained. . Therefore, the content of Nb ₂ O ₅ is set to 5.5 to 8.0%.
Generally, if the content of Nb ₂ O ₅ is high (for example, 5% or more), the glass tends to crystallize during laser firing sealing, so it has been difficult to add a large amount of Nb ₂ O ₅ in the past. . The present inventors have found that by sufficiently increasing the proportion of amorphous components such _{as TeO2} , the glass does not crystallize during firing even when containing 5.5% or more of _Nb2O5 , and has excellent water resistance. It has been found that a glass composition with low elasticity and low coefficient of thermal expansion can be obtained.
The content of Nb ₂ O ₅ is preferably more than 6.2%, more preferably 6.5% or more. Further, in order to avoid crystallization of the glass during laser firing sealing, the content of Nb ₂ O ₅ is 8.0% or less, preferably 7.8% or less, more preferably 7.6% or less, More preferably, it is 7.4% or less.

Although Al ₂ O ₃ is not essential, it is a component that has the effect of lowering the coefficient of thermal expansion and further has the effect of improving water resistance, so it is preferably included in the glass composition of this embodiment. In this embodiment, the content of Al ₂ O ₃ is 0 to 5.0%. Here, when containing Al ₂ O ₃ , the content of Al ₂ O ₃ is preferably 0.5% or more, more preferably 1.0% or more, and even more preferably 1.5% or more. In addition, in order to keep the glass transition temperature within an appropriate range and further avoid crystallization of the glass during laser firing sealing, the content of Al ₂ O ₃ is 5.0% or less, and 4.5%. It is preferably at most 4.0%, more preferably at most 3.5%.

Although BaO is not essential, since it is an effective component for stabilizing glass, it is preferable to include it in the glass composition of this embodiment. In this embodiment, the BaO content is 0 to 4.5%. Here, when BaO is contained, the content of BaO is preferably 0.5% or more. In addition, in order to maintain the glass transition temperature and thermal expansion coefficient within appropriate ranges, the BaO content is 4.5% or less, preferably 3.5%, more preferably 2.5% or less, and 2. More preferably, it is 0% or less.

Although B ₂ O ₃ is not essential, it is preferably included in the glass composition of this embodiment because it is a glass-forming oxide and is a component that forms a glass network and improves glass stability. In this embodiment, the content of B ₂ O ₃ is 0 to 6.0%. Here, when B ₂ O ₃ is contained, the content of B ₂ O ₃ is preferably 1.0% or more, more preferably 1.5% or more, and even more preferably 2.0% or more. Moreover, if the content of B ₂ O ₃ is large, the glass becomes unstable and tends to crystallize during laser firing and sealing. Therefore, in order to avoid crystallization of the glass due to excessive B ₂ O ₃ content, the content of B ₂ O ₃ is 6.0% or less, preferably 5.0% or less, and 4. It is more preferably 5% or less, and even more preferably 4.0% or less.

Since Bi ₂ O ₃ is a component that easily reacts with the glass substrate during sealing and improves adhesive strength by forming a reaction layer, it is preferably included in the glass composition of this embodiment. Moreover, if the content of Bi ₂ O ₃ is large, the glass is likely to crystallize during laser firing sealing, and there is a possibility that the coefficient of thermal expansion will further increase. Furthermore, by excessively reacting with the glass substrate and incorporating high melting point components such as SiO ₂ in the glass substrate into the glass composition, the fixing point increases and residual stress in the sealing material after sealing increases. There is a risk. Therefore, the content of Bi ₂ O ₃ is 0 to 0.4%. Here, the content of Bi ₂ O ₃ is preferably 0.3% or less, more preferably 0.2% or less, further preferably 0.15% or less, and particularly preferably 0.1% or less. Moreover, the lower limit of the content of Bi ₂ O ₃ is 0%, that is, the glass composition of this embodiment does not need to contain substantially Bi ₂ O ₃ .

Although ZrO ₂ is not essential, it is preferably included because it is a component that improves chemical stability. In this embodiment, the content of ZrO ₂ is 0 to 4.5%. Here, when containing ZrO ₂ , the content of ZrO ₂ is preferably 0.5% or more, and more preferably 1.0% or more. In addition, in order to keep the glass transition temperature within an appropriate range and further avoid crystallization of the glass during laser firing sealing, the content of ZrO ₂ is 4.5% or less, and 3.5% or less. It is preferably 3.0% or less, more preferably 2.5% or less.

It is preferable that the total content of V ₂ O ₅ , TeO ₂ and ZnO (V ₂ O ₅ +TeO ₂ +ZnO) is 80 to 91% because it is easy to achieve both water resistance and glass stabilization. Further, for the same reason, (V ₂ O ₅ +TeO ₂ +ZnO) is more preferably 82% or more, even more preferably 84% or more, and more preferably 89% or less, even more preferably 88% or less.

When the content ratio of V ₂ O ₅ and TeO ₂ (V ₂ O ₅ /TeO ₂ ) is 1.0 to 1.6, crystallization during sealing and firing can be suppressed and the glass is stabilized. Therefore, it is preferable. Further, for the same reason, (V ₂ O ₅ /TeO ₂ ) is more preferably 1.1 or more, and more preferably 1.5 or less.

It is preferable that the total content of Bi ₂ O ₃ , TeO ₂ and BaO (Bi ₂ O ₃ +TeO ₂ +BaO) is 25.5 to 31.0% because the coefficient of thermal expansion can be kept within an appropriate range. Further, for the same reason, (Bi ₂ O ₃ +TeO ₂ +BaO) is more preferably 26.0% or more, and more preferably 30.0% or less.

When the total content of Al ₂ O ₃ and ZrO ₂ (Al ₂ O ₃ + ZrO ₂ ) is 0 to 7.0%, water resistance is improved while suppressing glass crystallization during laser firing and sealing. It is preferable because it can be done. Furthermore, for the same reason, (Al ₂ O ₃ +ZrO ₂ ) is more preferably 1.5% or more, even more preferably 2.5% or more, and more preferably 6.0% or less, and 5.0% or less. is even more preferable.

Although CuO is not essential, it is a component that has the effect of lowering the thermal expansion coefficient and also has the effect of improving water resistance, so it may be included. Furthermore, it is effective as a laser absorption component. Therefore, by including CuO, it is possible to reduce the amount of pigment added for the purpose of laser absorption when making glass paste, and instead, it is possible to include a large amount of low expansion filler, which makes it possible to make glass with a lower coefficient of thermal expansion. It becomes possible to manufacture paste. On the other hand, when the CuO content is high, crystallization tends to occur during laser sealing and firing. Therefore, the content of CuO is preferably 1.0 to 10.0%. Here, in order to obtain a sufficient laser absorption effect, the content of CuO is preferably 1.0% or more, more preferably 2.0% or more, and even more preferably 3.0% or more. Further, in order to avoid crystallization of the glass, the content of CuO is preferably 10.0% or less, more preferably 8.0% or less, and even more preferably 7.0% or less.

Although Fe ₂ O ₃ is not essential, it may be included since it is also effective as a laser absorption component. By containing Fe ₂ O ₃ , the amount of pigment added for the purpose of laser absorption can be reduced during the production of glass paste, and instead a large amount of low expansion filler can be included, resulting in a lower coefficient of thermal expansion. It becomes possible to create glass paste. On the other hand, if the content of Fe ₂ O ₃ is high, the glass tends to crystallize during laser firing sealing, and furthermore, the softening point of the glass increases, resulting in poor low-temperature sealing properties. Therefore, the content of Fe ₂ O ₃ is preferably 1.0 to 7.0%. Here, the content of Fe ₂ O ₃ is preferably 7.0% or less, more preferably 5.0% or less, and even more preferably 2.0% or less. Further, in order to obtain the effect of laser absorption, the content of Fe ₂ O ₃ is preferably 1.0% or more. However, as long as CuO is contained, the above effects can be obtained even if Fe ₂ O ₃ is not contained.

Although MnO ₂ is not essential, it may be included since it is an effective component as a laser absorption component. By including MnO ₂ , it is possible to reduce the amount of pigments added for laser absorption when making glass paste, and instead include a large amount of low-expansion filler, resulting in a glass paste with a lower coefficient of thermal expansion. It becomes possible to create On the other hand, when the MnO ₂ content is high, the glass tends to crystallize during laser firing and sealing. Therefore, the content of MnO ₂ is preferably 1.0 to 7.0%. Here, the content of MnO ₂ is preferably 7.0% or less, more preferably 5.0% or less, and even more preferably 2.0% or less. Further, in order to obtain the effect of laser absorption, the content of MnO ₂ is preferably 1.0% or more. However, as long as CuO and Fe ₂ O ₃ are contained, the above effects can be obtained even if MnO ₂ is not contained.

The glass composition of the present embodiment may contain components other than the above-mentioned components (hereinafter referred to as "other components") within a range that does not impair the object of the present invention. The total content of other components is preferably 10.0% or less.

The glass composition of this embodiment includes SiO ₂ , MgO, CaO, SrO, P ₂ O ₅ , TiO ₂ , CeO ₂ , La ₂ O ₃ , CoO, MoO ₃ , Sb ₂ O ₃ , WO ₃ as other components. , GeO ₂ , Ta ₂ O ₅ and the like. However, if too much P ₂ O ₅ is contained, the water resistance may decrease. Therefore, although P ₂ O ₅ may be contained, the content is preferably 5% or less, and more preferably substantially not contained. Regarding P ₂ O ₅ , “substantially not containing” means that the content of P ₂ O ₅ in the glass composition is 1000 ppm or less.

(Thermal properties of glass composition)
It is preferable that the glass composition of this embodiment has a glass transition temperature Tg of 340° C. or less because low-temperature sealing properties become good. Tg is more preferably 330°C or lower, even more preferably 320°C or lower. The lower limit of Tg is not particularly limited, but is, for example, 280° C. or higher.

The glass composition of the present embodiment preferably has a fourth inflection point Ts of 400° C. or less when heated using a thermal analyzer (DTA), since this provides good low-temperature sealing properties. Ts is more preferably 390°C or lower, even more preferably 380°C or lower. The lower limit of Ts is not particularly limited, but is, for example, 350° C. or higher.

The glass composition of the present embodiment preferably has a crystallization start temperature Tcs of 470° C. or higher when heated using a thermal analyzer (DTA) because low-temperature sealing properties are improved. Tcs is more preferably 480°C or higher, and even more preferably 490°C or higher. The upper limit of Tcs is not particularly limited.

It is preferable that the glass composition of the present embodiment has a crystallization temperature Tcp of 450° C. or higher when heated using a thermal analyzer (DTA), since this provides good low-temperature sealing properties. Tcp is more preferably 470°C or higher, even more preferably 480°C or higher. The upper limit of Tcp is not particularly limited.

In the glass composition according to the present embodiment, the temperature difference (Tcs-Ts) between the crystallization start temperature and the fourth inflection point is preferably greater than 100°C. When (Tcs-Ts) is larger than 100° C., the process margin during glass melting can be widened, and the thermal influence on the organic EL element during laser firing sealing can be reduced. (Tcs-Ts) is more preferably 110°C or higher, even more preferably 120°C or higher. The upper limit of (Tcs-Ts) is not particularly limited.

The glass transition temperature Tg, the fourth inflection point Ts, the crystallization start temperature Tcs, and the crystallization temperature Tcp are the first inflection point of the DTA chart measured using a differential thermal analysis (DTA) device, and the fourth inflection point Tg. It is determined by setting the curve point as Ts, the starting point of the exothermic peak as Tcs, and the exothermic peak temperature as Tcp.

(Method for manufacturing glass composition)
The method for manufacturing the glass composition of this embodiment is not particularly limited. For example, it can be manufactured by the method shown below.

First, a raw material mixture is prepared. The raw material is not particularly limited as long as it is a raw material used in the manufacture of ordinary oxide-based glasses, and oxides, carbonates, and the like may be used. A raw material mixture is prepared by appropriately adjusting the types and proportions of the raw materials so that the composition of the resulting glass composition falls within the above range.

Next, the raw material mixture is heated by a known method to obtain a melt. The heating melting temperature (melting temperature) is preferably 950 to 1200°C, more preferably 1000°C or higher, and more preferably 1150°C or lower. The heating and melting time is preferably 30 to 90 minutes.

Thereafter, the glass composition of this embodiment is obtained by cooling and solidifying the melt. The cooling method is not particularly limited. A rollout machine or a press machine may be used, or a method of quenching by dropping into a cooling liquid or the like may be used. Preferably, the resulting glass composition is completely amorphous, ie, has a crystallinity of 0%. However, it may contain a crystallized portion as long as it does not impair the effects of the present invention.

The glass composition of this embodiment obtained in this way may be in any form. For example, it may be in the form of a block, a plate, a thin plate (flake), a powder, or the like.

When using the glass composition of this embodiment as a sealing material, the glass composition is preferably a glass powder. Regarding the form used to evaluate the above-mentioned properties of the glass composition, glass powder is preferable from the viewpoint of its performance as a sealing material.

(glass powder)
When the glass composition of this embodiment is made into glass powder, the particle size of the glass powder can be appropriately selected depending on the application. In the case of sealing materials, which is a typical use of glass powder, the particle size of the glass powder is preferably 0.1 to 100 μm.

Further, if the particle size of the glass powder is large, there is a problem that when it is made into a paste and applied and dried, it tends to settle and separate, and the thickness of the resulting sealing layer increases. Therefore, when glass powder is used as a paste, the particle size of the glass powder is preferably in the range of 0.1 to 5.0 μm, more preferably 0.1 to 2.5 μm.

In addition, in this specification, "particle size" means the volume-based 50% particle size ( _D50 ) in cumulative particle size distribution, and specifically, it is measured using a laser diffraction/scattering type particle size distribution measuring device. In the cumulative particle size curve of the particle size distribution, it means the particle size when the cumulative amount occupies 50% on a volume basis.

The glass powder made of the glass composition of this embodiment can be obtained, for example, by crushing the glass composition. Therefore, the particle size of the glass powder can be adjusted by adjusting the pulverization conditions. Examples of the crushing method include a rotary ball mill, a vibrating ball mill, a planetary mill, a jet mill, an attritor, a media stirring mill (bead mill), a jaw crusher, and a roll crusher.

In particular, when glass powder is to be made into a fine particle size of 5.0 μm or less, wet pulverization is preferably used. Wet grinding involves grinding in a solvent such as water or alcohol using media made of alumina or zirconia or a bead mill.

In order to adjust the particle size of the glass powder, in addition to pulverizing the glass composition, it may be classified using a sieve or the like, if necessary.

Further, when using the glass powder made of the glass composition of this embodiment as a sealing material, the glass powder may be used as it is, but depending on the sealing method, a low expansion filler and/or a laser may be used. It may also be a sealing material mixed with an absorbent substance. Further, from the viewpoint of improving workability, it is preferable to use the glass composition and the sealing material in the form of a paste.

<Glass paste>
The glass paste of this embodiment contains the glass composition of this embodiment described above and an organic vehicle. The glass paste may also contain low expansion fillers and/or laser absorbing substances depending on the sealing method. The organic vehicle, low expansion filler, and laser absorbing substance will be explained below.

As the organic vehicle, for example, one in which a resin as a binder component is dissolved in a solvent is used.
Specifically, resins such as methylcellulose, ethylcellulose, carboxymethylcellulose, oxyethylcellulose, benzylcellulose, propylcellulose, and nitrocellulose are dissolved in solvents such as terpineol, texanol, butyl carbitol acetate, and ethyl carbitol acetate. Can be used as a vehicle.
In addition, acrylic resins such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate, methyl ethyl ketone, terpineol, texanol, butyl carbitol acetate, ethyl carbitol A solution dissolved in a solvent such as acetate can be used as the organic vehicle. In this specification, (meth)acrylate means at least one of acrylate and methacrylate.
In addition, polyalkylene carbonates such as polyethylene carbonate and polypropylene carbonate, acetyl triethyl citrate, propylene glycol diacetate, diethyl succinate, ethyl carbitol acetate, triacetin, texanol, dimethyl adipate, ethyl benzoate, propylene glycol monophenyl ether A solution in a solvent such as a mixture of and triethylene glycol dimethyl ether can be used as the organic vehicle.

The ratio of resin and solvent in the organic vehicle is not particularly limited, but is selected so that the viscosity of the organic vehicle can adjust the viscosity of the glass paste. Specifically, the ratio of resin to solvent in the organic vehicle is preferably about 3:97 to 30:70 by mass ratio of resin:solvent.

The low expansion filler has a coefficient of thermal expansion lower than that of the glass composition, and generally has a coefficient of thermal expansion of about -15×10 ⁻⁷ to 45×10 ⁻⁷ /°C. The low expansion filler is added for the purpose of lowering the thermal expansion coefficient of the sealing layer.

The low expansion filler is not particularly limited, but preferably at least one selected from silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate compounds, soda lime glass, and borosilicate glass. Examples of zirconium phosphate compounds include (ZrO) ₂ P ₂ O ₇ , NaZr ₂ (PO ₄ ) ₃ , KZr ₂ (PO ₄ ) ₃ , Ca _0.5 Zr ₂ (PO ₄ ) ₃ , NbZr (PO ₄ ) ₃ , _Zr2 ( _WO3 )( _PO4 ) ₂ , composite compounds thereof, and the like.

The particle size of the low expansion filler is preferably 0.1 to 5.0 μm, more preferably 0.1 to 2.0 μm.

The content of the low expansion filler is set so that the coefficient of thermal expansion of the sealing layer approaches the coefficient of thermal expansion of the material to be sealed (for example, a glass substrate). The content of the low expansion filler is 1% by volume or more based on the total volume of the mixture of the glass composition, the low expansion filler, and the laser absorbing substance (hereinafter sometimes referred to as mixed material). It is preferably 5% by volume or more, more preferably 10% by volume or more. On the other hand, if the content of the low expansion filler is too large, the fluidity of the sealing material during melting will be poor, so the content of the low expansion filler should be 50% by volume or less based on the volume of the mixed material. It is preferably 45% by volume or less, more preferably 40% by volume or less.

The laser absorbing substance is not particularly limited, but in addition to Cu, Fe, and Mn constituting CuO, Fe ₂ O ₃ , and MnO ₂ mentioned above, at least one metal selected from Cr, Ni, Co, etc. Examples include compounds such as oxides containing metals (inorganic pigments). Further, the laser absorbing substance may be a pigment other than these.

The particle size of the laser absorbing material is preferably 0.1 to 5.0 μm, more preferably 0.1 to 2.0 μm.

If the content of the laser absorbing substance is too small, it may be difficult to sufficiently melt the sealing material by laser irradiation. Therefore, the total content of laser absorbing substances including other laser absorbing substances is preferably 0.1% by volume or more, more preferably 1% by volume or more, and further preferably 3% by volume or more based on the volume of the mixed material. preferable. On the other hand, if the content of the laser-absorbing substance is too large, the fluidity of the sealing material during melting will be poor, resulting in a reduction in adhesive strength. Therefore, the content of the laser absorbing substance is preferably 20% by volume or less, more preferably 18% by volume or less, and even more preferably 15% by volume or less based on the volume of the mixed material.

The ratio of the mixed material and organic vehicle in the glass paste is adjusted as appropriate depending on the required viscosity of the glass paste. Specifically, the mass ratio of mixed material:organic vehicle is preferably about 60:40 to 90:10. In addition to the mixed material and the organic vehicle, known additives can be added to the glass paste as necessary and within the limits that do not contradict the purpose of the present invention.

The glass paste is prepared by a known method using a rotary mixer equipped with stirring blades, a roll mill, a ball mill, or the like.

<Sealed package>
Next, a sealed package to which the glass composition of this embodiment is applied will be described.
1 and 2 are a plan view and a sectional view showing an embodiment of a sealed package. 3A to 3D are process diagrams showing one embodiment of a method for manufacturing the sealed package shown in FIG. 3. 4 and 5 are a plan view and a sectional view of a first substrate used for manufacturing the sealed package shown in FIGS. 1 and 2. FIG. 6 and 7 are a plan view and a cross-sectional view of the second substrate used for manufacturing the sealed package shown in FIGS. 1 and 2. FIG.

The sealed package 10 is an FPD such as an OELD, PDP, or LCD, a lighting device (OEL lighting, etc.) using a light emitting element such as an organic electroluminescence (OEL) element, or a solar cell such as a dye-sensitized solar cell. etc.
That is, the sealed package 10 includes a first substrate 11, a second substrate 12 arranged opposite to the first substrate, and arranged between the first substrate and the second substrate. and a sealing layer 15 for bonding the first substrate and the second substrate. Further, the sealing layer 15 includes the glass composition of the present embodiment described above.

The first substrate 11 is, for example, an element substrate on which the electronic element section 13 is mainly provided. The second substrate 12 is, for example, a sealing substrate mainly used for sealing. An electronic element section 13 is provided on the first substrate 11 . The first substrate 11 and the second substrate 12 are arranged to face each other and are bonded together by a sealing layer 15 arranged in a frame shape between them.

Examples of the first substrate 11 and the second substrate 12 include a glass substrate, a substrate on which a metal film is formed, and the like.
As the glass substrate, a soda lime glass substrate, an alkali-free glass substrate, etc. are used. Examples of soda lime glass substrates include AS, PD200 (both manufactured by AGC, trade names), and chemically strengthened versions of these. In addition, examples of non-alkali glass substrates include AN100 (manufactured by AGC, trade name), EAGLE2000 (manufactured by Corning, trade name), EAGLE GX (manufactured by Corning, trade name), and JADE (manufactured by Corning, trade name). , #1737 (manufactured by Corning Co., Ltd., trade name), OA-10 (manufactured by Nippon Electric Glass Co., Ltd., trade name), and Tempax (manufactured by Schott Co., Ltd., trade name).
Examples of the substrate on which a metal film is formed include a substrate on which a film containing Ti is formed on a glass substrate. Note that the material of the substrate is not particularly limited, and may be a known material. Note that when the metal film is a multilayer film, it is preferable that the outermost layer contains Ti.
The first substrate 11 and the second substrate 12 may be the same substrate, or may be a combination of different substrates.

The electronic element section 13 is, for example, an OEL element for OELD or OEL lighting, a plasma light emitting element for PDP, a liquid crystal display element for LCD, and a dye-sensitized solar cell element for solar cells. type photoelectric conversion element). The electronic element section 13 can be configured with various known structures, and is not limited to the illustrated structure.

In the sealed package 10 of FIGS. 1 and 2, an OEL element, a plasma light emitting element, etc. are provided on the first substrate 11 as the electronic element section 13. When the electronic element section 13 is a dye-sensitized solar cell element or the like, element films such as wiring films and electrode films are provided on opposing surfaces of the first substrate 11 and the second substrate 12, although not shown.

When the electronic device section 13 is an OEL device or the like, a part of space remains between the first substrate 11 and the second substrate 12. This space may be left as is, or may be filled with a transparent resin or the like. The transparent resin may be adhered to the first substrate 11 and the second substrate 12, or may only be in contact with the first substrate 11 and the second substrate 12.

When the electronic element section 13 is a dye-sensitized solar cell element or the like, the electronic element section 13 is arranged entirely between the first substrate 11 and the second substrate 12, although not shown. Note that the object to be sealed is not limited to the electronic element section 13, but may also be a photoelectric conversion device or the like. Alternatively, the sealed package 10 may be a building material such as double-glazed glass that does not have the electronic element section 13.

Hereinafter, as an example of a sealed package, an organic electroluminescent element constituting an OELD will be described in detail with reference to FIG. 8.
The organic electroluminescent device 210 obtained using the glass composition of this embodiment includes a substrate 211, a laminated structure 213 having an anode 213a, an organic thin film layer 213b, and a cathode 213c laminated on the substrate 211; It includes a glass member 212 placed on the substrate 211 so as to cover the outer surface side of the laminated structure 213, and a sealing layer 215 that adheres the substrate 211 and the glass member 212. Further, the sealing layer 215 includes the glass composition of the present embodiment described above.

(Manufacturing method of sealed package)
Next, an embodiment of a method for manufacturing a sealed package to which the glass composition of the present embodiment described above is applied will be described.
The glass paste mentioned above is used for sealing. The glass paste is applied to the second substrate 12 in a frame shape and then dried to form a coating layer. Examples of the coating method include printing methods such as screen printing and gravure printing, and dispensing methods. Drying is carried out to remove the solvent and is usually carried out at a temperature of 120° C. or higher for 10 minutes or more. If the solvent remains in the coating layer, there is a risk that the binder component will not be sufficiently removed during the subsequent pre-baking.

The coating layer is pre-baked to form a pre-baked layer 15a (FIGS. 6 and 7). Preliminary firing is performed by heating the coating layer to a temperature below the glass transition temperature of the glass composition contained in the sealing material to remove the binder component, and then heating it to a temperature above the softening point of the glass composition contained in the sealing material. This is done by heating.

An electronic element section 13 is provided on the first substrate 11 according to the specifications of the sealed package 10 (FIGS. 4 and 5).

Next, the second substrate 12 provided with the pre-fired layer 15a and the first substrate 11 provided with the electronic element section 13 are arranged and laminated so that the pre-sintered layer 15a faces each other (see FIG. 3A, Figure 3B).

Thereafter, the temporarily fired layer 15a is irradiated with laser light 16 through the second substrate 12 to perform firing (FIG. 3C). The laser beam 16 is irradiated while scanning along the frame-shaped pre-fired layer 15a. A frame-shaped sealing layer 15 is formed between the first substrate 11 and the second substrate 12 by irradiating the laser beam 16 over the entire circumference of the pre-fired layer 15a. Note that the laser beam 16 may be irradiated to the temporarily fired layer 15a through the first substrate 11.

The type of laser beam 16 is not particularly limited, and laser beams such as a semiconductor laser, a carbon dioxide laser, an excimer laser, a YAG laser, and a HeNe laser are used. Irradiation conditions for the laser beam 16 are selected depending on the thickness, line width, cross-sectional area in the thickness direction, etc. of the temporarily fired layer 15a. The output of the laser beam 16 is preferably 2 to 150W. If the output of the laser beam is less than 2 W, there is a possibility that the temporarily fired layer 15a will not be melted. When the output of the laser beam exceeds 150 W, cracks and the like are likely to occur in the first substrate 11 and the second substrate 12. The output of the laser beam 16 is more preferably 5 to 120W.

In this way, a sealed package 10 is manufactured in which the electronic element section 13 is hermetically sealed between the first substrate 11 and the second substrate 12 by the sealing layer 15 (FIG. 3D).

Although the method of baking by irradiation with laser light 16 has been described above, the method of baking is not necessarily limited to the method of performing baking by irradiation with laser light 16. Other firing methods may be used depending on the heat resistance of the electronic element section 13, the configuration of the sealed package 10, and the like. For example, if the electronic element part 13 has high heat resistance or does not have the electronic element part 13, instead of irradiating the laser beam 16, the entire assembly as shown in FIG. 3B is placed in a firing furnace such as an electric furnace. The entire assembly including the pre-fired layer 15a may be heated to form the sealing layer 15.

Although the embodiments of the sealed package of the present invention have been described above by giving one example, the sealed package of the present invention is not limited to these. The configuration can be changed as appropriate within the scope of the spirit of the present invention and as necessary.

Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to the Examples. Examples 1 to 15 are examples. Examples 16 to 37 are comparative examples.

[Examples 1 to 37]
(Manufacture of glass composition)
Raw materials were prepared and mixed so as to have the composition shown in mol% in the glass composition column of Tables 1 and 2, and melted for 1 hour using a platinum crucible in an electric furnace at 1000 to 1100°C. The obtained melt was formed into a sheet using a water-cooled roller, and then dry-pulverized using a ball mill. This was passed through a 100-mesh sieve to obtain a glass composition.
The _D50 of this glass composition was measured using a Microtrac particle size distribution analyzer (manufactured by Nikkiso Co., Ltd.), and was found to be within the range of 2 to 5 μm.

Next, the following measurements and evaluations were performed on these glass compositions.
In Tables 1 and 2, the "-" in the evaluation column indicates that no crystallization peak was observed by DTA or no vitrification was observed, so no evaluation was made.

(DTA exam)
Thermal analysis of the glass composition was performed using a differential thermal analysis (DTA) device TG-DTA8122 manufactured by Rigaku Corporation at a heating rate of 10°C/min, and from the obtained DTA chart, the glass transition temperature Tg, the fourth inflection Point Ts [°C], crystallization start temperature Tcs [°C], and crystallization temperature Tcp [°C] were determined. In addition, the glass transition temperature Tg, the fourth inflection point Ts, the crystallization start temperature Tcs, and the crystallization temperature Tcp are the first inflection point of the DTA chart, Tg, the fourth inflection point, and the starting point of the exothermic peak. was determined as Tcs, and the exothermic peak temperature was determined as Tcp. In addition, as an evaluation of the allowable temperature during firing, the temperature difference between the crystallization start temperature and the fourth inflection point (Tcs-Ts) was determined, and the obtained results are shown in the table below. Those with a value of (Tcs-Ts) greater than 100°C were considered acceptable.

(Thermal expansion coefficient (α))
Each glass composition was molded into a rectangular parallelepiped shape to obtain a fired body for thermal expansion measurement. The obtained fired body for thermal expansion measurement was processed into a cylindrical shape with a diameter of 5±0.5 mm and a length of 2±0.05 cm. The processed fired body for thermal expansion measurement was heated with a thermal dilatometer Thermoplus EVO2 system TDL8411 manufactured by RIGAKU at a temperature increase rate of 10°C/min, and the thermal expansion coefficient α (unit: 10 ^-7 /°C) at 50 to 250°C was measured. ) was calculated. The results obtained are shown in the table below. Those with a thermal expansion coefficient α of less than 91 were accepted.

(Liquidity evaluation)
A sample (flow button) having a diameter of 15 mm was prepared by press-molding 4 g of the glass composition. The obtained flow button was placed on a glass substrate, and fired at 450 to 460°C for 30 minutes in accordance with the softening point of each glass composition to obtain a fired body for fluidity evaluation. Next, the angle of the obtained fired body for fluidity evaluation was divided into four equal parts, the diameters at four places were measured, and the average value of the diameters at the four places was calculated to be the FB diameter (unit: mm). Each sample was evaluated for fluidity, gloss, and presence or absence of adhesion according to the following criteria. The results obtained are shown in the table below. In the evaluation of fluidity and gloss, those with 〇 were considered to be passed.
<Liquidity>
○: FB diameter is 24 mm or more.
×: FB diameter is less than 24 mm.
<Gloss>
○: The entire surface of the fired body for fluidity evaluation was glossy.
Δ: Part of the surface of the fired body for fluidity evaluation lacked gloss.
×: The entire surface of the fired body for fluidity evaluation had no gloss.

(Water resistance evaluation)
Glass flakes of each glass composition were used and allowed to stand for 48 hours in an environment with a temperature of 121° C. and a humidity of 100% RH. The water resistance of the fired body for water resistance evaluation after standing was evaluated according to the following criteria. The results obtained are shown in the table below. As for the judgment, those with 〇 were considered to have passed.
<Water resistance evaluation criteria>
○: No discolored areas were observed on the entire surface of the fired body for water resistance evaluation.
Δ: Discoloration was observed on a part of the surface of the fired body for evaluating water resistance.
×: The entire surface of the fired body for water resistance evaluation was discolored.

The glass compositions of Examples 1 to 15 exhibited excellent water resistance, a small coefficient of thermal expansion, excellent fluidity during melting, and a wide allowable temperature range during firing.

On the other hand, in Example 16, which is a comparative example, the Bi ₂ O ₃ content was more than 0.4% and the TeO ₂ content was less than 25.5%, so the allowable temperature range during firing was narrow and the fluidity was poor.
Further, Examples 17 to 19, which are comparative examples, had a large coefficient of thermal expansion and poor water resistance because Nb ₂ O ₅ was less than 5.5%.
Further, in Example 20, which is a comparative example, the Bi ₂ O ₃ content was more than 0.4%, so the thermal expansion coefficient was large.
Further, in Example 21, which is a comparative example, since the Nb ₂ O ₅ content was more than 8.0%, the allowable temperature range during firing was narrow, and the fluidity and water resistance were poor.
Further, in Example 22, which is a comparative example, the V ₂ O ₅ content was more than 40.0% and the Nb ₂ O ₅ content was less than 5.5%, so the fluidity and water resistance were poor.
Further, in Example 23, which is a comparative example, since the TeO ₂ content was more than 30.0%, the coefficient of thermal expansion was large and the water resistance was also poor.
In addition, Examples 24 and 25, which are comparative examples, have less than 25.5% TeO ₂ and more than 30.0% ZnO, so they have poor water resistance, and in Example 25, the allowable temperature range during firing is narrow. Liquidity was also poor.
Moreover, Examples 26 and 27, which are comparative examples, had poor water resistance because the ZrO ₂ content was more than 4.5%.
Further, in Example 28, which is a comparative example, the Bi ₂ O ₃ content was more than 0.4%, so the thermal expansion coefficient was large.
In addition, in Example 29, which is a comparative example, the V ₂ O ₅ content is more than 40.0%, the ZnO content is less than 15.0%, and the BaO content is more than 4.5%, so the allowable temperature range during firing is narrow, and the heat The coefficient of expansion was large and the fluidity was poor.
Further, in Example 30, which is a comparative example, the V ₂ O ₅ content was less than 25.5% and the ZnO content was more than 30.0%, so it was not vitrified.
Furthermore, in Example 31, which is a comparative example, the water resistance evaluation was poor because the ZnO content was more than 30.0%.
Further, in Example 32, which is a comparative example, since the Al ₂ O ₃ content was more than 5.0%, the allowable temperature range during firing was narrow, and the fluidity was also poor.
Further, in Example 33, which is a comparative example, since the V ₂ O ₅ content was more than 40.0%, the allowable temperature range during firing was narrow, the coefficient of thermal expansion was large, and the fluidity and water resistance were poor.
In addition, Examples 34 to 36, which are comparative examples, have a Bi ₂ O ₃ content of more than 0.4%, so Example 34 has a narrow allowable temperature during firing, Example 35 has poor water resistance, and Example 36 has poor thermal expansion. The coefficient was large and the water resistance was poor.
In addition, Example 37, which is a comparative example, had poor water resistance because B ₂ O ₃ was more than 6.0%.

10: Sealed package 11: First substrate 12: Second substrate 13: Electronic element section 15: Sealing layer 15a: Preliminary firing layer 16: Laser light 210: Organic electroluminescent element 211: Substrate 212: Glass member 213: Laminated structure 213a: Anode 213b: Organic thin film layer 213c: Cathode 215: Sealing layer

Claims (10)

Expressed as mol% based on oxides,
25.0 to 40.0% V ₂ O ₅ ,
25.5-30.0% _TeO2 ,
15.0 to 30.0% ZnO,
5.5 to 8.0% Nb ₂ O ₅ ,
0 to 5.0% Al ₂ O ₃ ,
BaO 0-4.5%,
B ₂ O ₃ from 0 to 6.0%,
Contains 0 to 0.4% Bi ₂ O ₃ and 0 to 4.5% ZrO ₂ ,
A glass composition characterized in that it is substantially free of alkali metal oxides and PbO. The glass composition according to claim 1, containing 1.0 to 5.0% of B ₂ O ₃ in mol% based on oxides. The glass composition according to claim 1 or 2, containing more than 6.2% Nb ₂ O ₅ expressed in mol% based on oxides. The glass composition according to claim 1 or 2, wherein the total content of V ₂ O ₅ , TeO ₂ and ZnO (V ₂ O ₅ +TeO ₂ +ZnO) is 80 to 91% in terms of mol% based on oxides. thing. The glass composition according to claim 1 or 2, wherein the content ratio expressed as (V ₂ O ₅ /TeO ₂ ) is 1.0 to 1.6 in terms of mol% based on oxides. Claim 1 or 2, wherein the total content of Bi ₂ O ₃ , TeO ₂ and BaO (Bi ₂ O ₃ + TeO ₂ + BaO) is 25.5 to 31.0% in terms of mol% on an oxide basis. The described glass composition. The glass composition according to claim 1 or 2, wherein the total content of Al ₂ O ₃ and ZrO ₂ (Al ₂ O ₃ + ZrO ₂ ) is 0 to 7.0% in mol% based on oxides. . A glass paste containing the glass composition according to claim 1 or 2 and an organic vehicle. a first substrate, a second substrate disposed opposite to the first substrate, and a second substrate disposed between the first substrate and the second substrate; A sealed package having a sealing layer for bonding a second substrate to the second substrate,
A sealed package, wherein the sealing layer includes the glass composition according to claim 1 or 2. A laminated structure including a substrate, an anode, an organic thin film layer, and a cathode laminated on the substrate, a glass member placed on the substrate so as to cover an outer surface of the laminated structure, and the substrate. and a sealing layer that adheres the glass member and the glass member,
An organic electroluminescent device, wherein the sealing layer contains the glass composition according to claim 1 or 2.

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