KR20240017761A - Glass composition, glass paste, sealing package, and organic electroluminescence element - Google Patents

Abstract

In the present invention, expressed in mole percent based on oxide, V ₂ O ₅ is 25.0 to 40.0%, TeO ₂ is 25.5 to 30.0%, ZnO is 15.0 to 30.0%, Nb ₂ O ₅ is 5.5% to 8.0%, and Al ₂ O Contains 0 to 5.0% of ₃ , 0 to 4.5% of BaO, 0 to 6.0% of B ₂ O ₃ , 0 to 0.4% of Bi ₂ O ₃ , and 0 to 4.5% of ZrO ₂ , and is substantially an alkali metal oxide. and a glass composition, glass paste, sealing package, and organic electroluminescent device characterized by not containing PbO.

Description

Glass composition, glass paste, sealing package, and organic electroluminescence element {GLASS COMPOSITION, GLASS PASTE, SEALING PACKAGE, AND ORGANIC ELECTROLUMINESCENCE ELEMENT}

The present invention relates to glass compositions, glass pastes, sealing packages, and organic electroluminescent devices.

Flat-type display devices (FPDs), such as organic electro-luminescence displays (OELD) and plasma display panels (PDP), have a structure in which the light-emitting element is sealed by a glass package to which a pair of glass substrates are sealed. . Additionally, a liquid crystal display device (LCD) has a structure in which liquid crystal is sealed between a pair of glass substrates. Additionally, 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, organic EL displays require that the organic EL elements be strictly shielded from external air because the luminescence characteristics of the organic EL elements are significantly deteriorated upon contact with moisture. Additionally, since organic EL devices are damaged when exposed to high temperatures, the sealing method is very important.

Therefore, as a method of sealing an organic EL display, a method using a glass composition as a sealing material and sealing by local heating is considered promising. Generally, glass compositions are used by mixing them with an organic vehicle and forming a paste. This paste is applied to one glass substrate by screen printing or dispensing, and baked to form a plastic layer. Next, the other glass substrate is overlapped, and the glass composition is melted and sealed by local heating using a laser or the like on the plastic layer.

The glass composition used for the sealing material must have high water resistance, a coefficient of thermal expansion close to that of the material to be sealed, and an allowable temperature at the time of melting of the glass composition ( It is desirable to have a wide process margin.

In this way, as a glass composition used in 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. Additionally, Patent Document 2 discloses a V ₂ O ₅ -ZnO-TeO ₂ -based glass composition.

Japanese Patent No. 6357937 Publication Japanese Patent No. 6022070 Publication

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

In addition, the conventional sealed package was generally one in which glass substrates were sealed to each other, but in recent years, there has been a demand for a sealed package in which, for example, a substrate with a metal film formed on the surface and a glass substrate are sealed. Even when sealing a substrate with a metal film deposited on its surface, 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 had room for further improvement in terms of water resistance, thermal expansion coefficient, fluidity during melting, and wide allowable temperature range during firing.

In view of the above-mentioned circumstances, the present invention is a vanadium-based glass composition used to seal joints between glass members in a flat display such as an organic EL display or liquid crystal display by a local heating method such as laser heating, comprising: The object is to provide a glass composition that, compared to conventional glass compositions, is superior in terms of water resistance, has a smaller thermal expansion coefficient, and has excellent fluidity when melted and a wide allowable temperature range when fired.

Additionally, the present invention aims to provide a sealing material and glass paste containing the glass composition, and a sealing package and an organic electroluminescent element having a sealing layer containing the glass composition.

The present inventors discovered that the above problem could be solved by using a glass composition having a glass composition within a specific range, and completed the present invention.

The present invention provides a glass composition, glass paste, sealing package, and organic electroluminescent element having the following structures.

[1] Expressed in mole% based on oxide,

V ₂ O ₅ 25.0 to 40.0%,

TeO ₂ from 25.5 to 30.0%,

15.0 to 30.0% ZnO,

Nb ₂ O ₅ 5.5 to 8.0%,

Al ₂ O ₃ 0 to 5.0%,

BaO 0 to 4.5%,

B ₂ O ₃ 0 to 6.0%,

Bi ₂ O ₃ from 0 to 0.4%, and

Contains 0 to 4.5% ZrO ₂ ,

A glass composition characterized by being substantially free of alkali metal oxides and PbO.

[2] The glass composition according to [1], containing 1.0 to 5.0% of B ₂ O ₃ , expressed in mole percent on an oxide basis.

[3] The glass composition according to [1] or [2], which contains more than 6.2% of Nb ₂ O ₅ , expressed in mole percent on an oxide basis.

[4] [1] to [, where the total content of V ₂ O ₅ , TeO ₂ , and ZnO expressed as (V ₂ O ₅ +TeO ₂ +ZnO), expressed in mole percent based on oxide, is 80 to 91%. The glass composition according to any one of [3].

[5] The glass composition according to any one of [1] to [4], wherein the content ratio expressed as (V ₂ O ₅ /TeO ₂ ), expressed in mol% on an oxide basis, is 1.0 to 1.6.

[6] [1] to [1], where the total content of Bi ₂ O ₃ , TeO ₂ , and BaO expressed as (Bi ₂ O ₃ +TeO ₂ +BaO) expressed in mole% based on oxide is 25.5 to 31.0%. The glass composition according to any one of [5].

[7] Any of [1] to [6] in which the total content of Al ₂ O ₃ and ZrO ₂ expressed as (Al ₂ O ₃ +ZrO ₂ ), expressed in mole percent based on oxide, is 0 to 7.0%. The glass composition described in one.

[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 to the first substrate, and a sealing layer disposed between the first substrate and the second substrate and adhering the first substrate and the second substrate. It is a sealed package with

A sealing package wherein the sealing layer includes the glass composition according to any one of [1] to [7].

[10] A substrate, a laminated structure having an anode, an organic thin film layer, and a cathode laminated on the substrate, a glass member mounted on the substrate to cover an outer surface side of the laminated structure, and the substrate and the glass member. Provided with a sealing layer that adheres,

The sealing layer is an organic electroluminescent device containing the glass composition according to any one of [1] to [7].

Compared to conventional glass compositions, the glass composition of the present invention is superior in terms of water resistance, has a smaller coefficient of thermal expansion, and is superior in terms of fluidity when melted and a wide allowable temperature range when fired.

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. 1.
3A is a process diagram showing one embodiment of a method for manufacturing a sealed package.
3B is a process diagram showing one embodiment of a method for manufacturing a sealed package.
3C is a process diagram showing one embodiment of a method for manufacturing a sealed package.
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 in manufacturing the sealed package shown in FIG. 1.
FIG. 5 is a cross-sectional view taken along line BB of the first substrate shown in FIG. 4.
FIG. 6 is a plan view of a second substrate used in 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. 6.
Figure 8 is a conceptual diagram of an organic electroluminescence device, which is an example of a sealed package.

Hereinafter, embodiments of the present invention will be described. Additionally, the present invention is not limited to the embodiments described below. In addition, in the drawings below, members and parts that exert the same function may be described with the same reference numerals, and overlapping descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are modeled 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% of V ₂ O ₅ , 25.5 to 30.0% of TeO ₂ , 15.0 to 30.0% of ZnO, and 5.5 to 8.0% of Nb ₂ O ₅ , expressed in mole percent based on oxide. , 0 to 5.0% of Al ₂ O ₃ , 0 to 4.5% of BaO, 0 to 6.0% of B ₂ O ₃ , 0 to 0.4% of Bi ₂ O ₃ , and 0 to 4.5% of ZrO ₂ , and substantially It is characterized by not containing alkali metal oxide and PbO.

Next, each component of the glass composition of this embodiment is explained. In the following description, unless otherwise specified, the expression “%” in the content of each component of the glass composition is on an oxide basis, that is, the mole percentage expressed in oxide conversion. In this specification, “to” indicating a numerical range is used to include upper and lower limits.

If the glass composition used for the sealing material contains an alkali metal oxide, when the sealing material is exposed to high temperature during or after sealing, the alkali component diffuses into the material to be sealed, such as a glass substrate, and the material to be sealed deteriorates. . Accordingly, the glass composition of this embodiment is substantially free of alkali metal oxide. In addition, in this specification, “substantially does not contain” means that it does not contain anything other than inevitable impurities, that is, it means that it is not added intentionally. Therefore, the glass composition of this embodiment may contain a trace amount of 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, and more preferably 500 ppm or less.

In addition, in this specification, alkali metal oxide refers to Li ₂ O, Na ₂ O, and K ₂ O. Also, ppm means mass ppm.

In addition, the glass composition of this embodiment substantially does not contain lead, that is, PbO, in order to reduce the load on the environment. In addition, with respect to PbO, “substantially not contained” means that the content of PbO in the glass composition is 1000 ppm or less.

V ₂ O ₅ is a glass-forming oxide and forms a glass network and is essential as a low softening component. Additionally, it is effective as a laser absorption component. On the other hand, if the content of V ₂ O ₅ is high, water resistance decreases, and there is a risk that glass stability decreases during glass production and the glass becomes prone to devitrification. Additionally, if the content of V ₂ O ₅ is too small, the glass transition temperature may increase 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, further preferably 32.0% or less, further preferably 39.0% or less, more preferably 38.0% or less, and 37.0% or less. It is more desirable.

TeO ₂ is a glass-forming oxide and forms a glass network and is essential as a low softening component. Additionally, it has the function of improving the fluidity and water resistance of the glass composition. On the other hand, as the content of TeO ₂ increases, the thermal expansion coefficient increases. Additionally, if it is too small, the glass transition temperature may increase and the low-temperature sealing properties may deteriorate, and crystallization may easily occur during sealing firing. Additionally, 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, more preferably 29.0% or less, more preferably 28.0% or less, and still more preferably 27.5% or less.

ZnO is essential as a component that lowers the thermal expansion coefficient. On the other hand, if the ZnO content is high, there is a risk that the stability of the glass decreases during glass production and the glass becomes prone to devitrification. Also, if it is too small, the thermal expansion coefficient becomes large. Therefore, the ZnO content is 15.0 to 30.0%. The ZnO content is preferably 17.0% or more, more preferably 18.5% or more, still more preferably 20.0% or less, further preferably 28.0% or less, more preferably 26.5% or less, and even more preferably 25.0% or less. .

Nb ₂ O ₅ is an essential component that reduces the thermal expansion coefficient and improves water resistance. On the other hand, if the Nb ₂ O ₅ content is high, the glass is likely to crystallize during laser baking sealing, and if it is too small, the thermal expansion coefficient increases 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%.

In general, if the Nb ₂ O ₅ content is high (for example, 5% or more), the glass becomes prone to crystallization during laser firing sealing, so it has conventionally been difficult to add a large amount of Nb ₂ O ₅ . The present inventors found that by sufficiently increasing the ratio of amorphous components such as TeO ₂ , even if Nb ₂ O ₅ was contained by 5.5% or more, the glass did not crystallize upon firing, and a glass composition with excellent water resistance and a low coefficient of thermal expansion was obtained. did.

The content of Nb ₂ O ₅ is preferably more than 6.2%, and more preferably 6.5% or more. In addition, 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, and even more preferably 7.4% or less. do.

Although Al ₂ O ₃ 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 is preferable to include it in the glass composition of the present embodiment. In this embodiment, the Al ₂ O ₃ content is 0 to 5.0%. Here, when Al ₂ O ₃ is contained, the content of Al ₂ O ₃ is preferably 0.5% or more, more preferably 1.0% or more, and still more preferably 1.5% or more. In addition, in order to maintain the glass transition temperature in an appropriate range and avoid crystallization of the glass during laser firing sealing, the Al ₂ O ₃ content is 5.0% or less, preferably 4.5% or less, and 4.0% or less. It is more preferable, and 3.5% or less is further preferable.

Although BaO is not essential, it is an effective component for stabilizing glass, so 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 included, the BaO content is preferably 0.5% or more. Additionally, in order to maintain the glass transition temperature and thermal expansion coefficient in an appropriate range, the BaO content is 4.5% or less, preferably 3.5% or less, more preferably 2.5% or less, and even more preferably 2.0% or less.

Although B ₂ O ₃ is not essential, it is a glass-forming oxide and is a component that forms a glass network and improves glass stability, so it is preferably contained in the glass composition of the present embodiment. 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 still more preferably 2.0% or more. Additionally, if the content of B ₂ O ₃ is high, the glass becomes unstable and becomes prone to crystallization during laser firing sealing. Therefore, in order to avoid crystallization of 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, more preferably 4.5% or less, and 4.0%. The following is more preferable.

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 preferable to include it in the glass composition of the present embodiment. In addition, if the content of Bi ₂ O ₃ is high, the glass is likely to crystallize during laser firing sealing, and there is a risk that the thermal expansion coefficient will further increase. Furthermore, there is a risk that it reacts excessively with the glass substrate and introduces high-melting point components such as SiO ₂ from the glass substrate into the glass composition, which increases the sticking point and increases the residual stress of the sealing material after sealing. 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 especially preferably 0.1% or less. In addition, the lower limit of the content of Bi ₂ O ₃ is 0%, that is, the glass composition of the present embodiment does not need to contain Bi ₂ O ₃ substantially.

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

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 stabilization of the glass. Also, for the same reason, (V ₂ O ₅ +TeO ₂ +ZnO) is more preferably 82% or more, more preferably 84% or more, more preferably 89% or less, and even more preferably 88% or less. .

The ratio of the content of V ₂ O ₅ to TeO ₂ (V ₂ O ₅ /TeO ₂ ) is preferably 1.0 to 1.6 because crystallization during sealing firing can be suppressed and the glass is stabilized. Also, for the same reason, (V ₂ O ₅ /TeO ₂ ) is more preferably 1.1 or more, and is 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 thermal expansion coefficient can be kept in an appropriate range. Also, 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.

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

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. It is also effective as a laser absorption component. Therefore, by containing CuO, when producing the glass paste, the amount of pigment added for the purpose of laser absorption can be reduced, and instead, a large amount of low-expansion filler can be contained, resulting in a glass paste with a lower thermal expansion coefficient. Manufacturing becomes possible. On the other hand, if the CuO content is high, it becomes easy to crystallize during laser sealing firing. Therefore, the CuO content is preferably 1.0 to 10.0%. Here, in order to sufficiently obtain the effect of laser absorption, the CuO content is preferably 1.0% or more, more preferably 2.0% or more, and still more preferably 3.0% or more. Moreover, in order to avoid crystallization of glass, the CuO content is preferably 10.0% or less, more preferably 8.0% or less, and still more preferably 7.0% or less.

Fe ₂ O ₃ is not essential, but may be included because it is also effective as a laser absorption component. By containing Fe ₂ O ₃ , when producing the glass paste, the amount of pigment added for the purpose of laser absorption can be reduced, and instead, a large amount of low-expansion filler can be contained, resulting in a glass paste with a lower thermal expansion coefficient. Production becomes possible. On the other hand, if the Fe ₂ O ₃ content is high, the glass becomes prone to crystallization during laser firing sealing, and the softening point of the glass increases and low-temperature sealing properties deteriorate. 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 still more preferably 2.0% or less. Additionally, in order to obtain the effect of laser absorption, the content of Fe ₂ O ₃ is preferably 1.0% or more. However, if CuO is contained, the above effect can be obtained even if Fe ₂ O ₃ is not contained.

Although MnO ₂ is not essential, it may be included because it is an effective laser absorption component. By containing MnO ₂ , when producing a glass paste, the amount of pigment added for the purpose of laser absorption can be reduced, and instead, a large amount of low-expansion filler can be contained, making it possible to produce a glass paste with a lower thermal expansion coefficient. It becomes possible. On the other hand, if the MnO ₂ content is high, the glass becomes prone to crystallization during laser firing 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. Additionally, in order to obtain the effect of laser absorption, the MnO ₂ content is preferably 1.0% or more. However, if CuO or Fe ₂ O ₃ is contained, the above effect can be obtained even if MnO ₂ is not contained.

The glass composition of this embodiment may contain components other than the above components (hereinafter referred to as “other components”) as long as they do not impair the purpose of the present invention. The total content of other components is preferably 10.0% or less.

The glass composition of the present embodiment contains 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 , GeO as other components. ₂ , Ta ₂ O ₅ , etc. may be contained. However, if P ₂ O ₅ is contained excessively, there is a risk that water resistance may decrease. Therefore, although it may contain P ₂ O ₅ , the content is preferably 5% or less, and it is more preferable not to contain it substantially. In addition, with respect to P ₂ O ₅ , “substantially not contained” means that the content of P ₂ O ₅ in the glass composition is 1000 ppm or less.

(Thermal properties of glass compositions)

The glass composition of this embodiment preferably has a glass transition temperature Tg of 340°C or lower because low-temperature sealing properties are good. Tg is more preferably 330°C or lower, and 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 this embodiment preferably has a fourth inflection point Ts of 400°C or lower when heated using a thermal analysis device (DTA) because low-temperature sealing properties are good. Ts is more preferably 390°C or lower, and 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 this embodiment preferably has a crystallization start temperature Tcs of 470°C or higher when heated using a thermal analysis device (DTA) because low-temperature sealing properties are good. 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.

The glass composition of this embodiment preferably has a crystallization temperature Tcp of 450°C or higher when heated using a thermal analysis device (DTA) because low-temperature sealing properties are good. Tcp is more preferably 470°C or higher, and 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 greater than 100°C, the process margin during glass melting can be expanded and the thermal effect on the organic EL element during laser firing sealing can be reduced. (Tcs-Ts) is more preferably 110°C or higher, and 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 measured using a differential thermal analysis (DTA) device. The first inflection point of the DTA chart is Tg, the fourth inflection point is Ts, and the exothermic peak is The starting point is determined as Tcs, and the exothermic peak temperature is determined as Tcp.

(Method for producing glass composition)

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

First, prepare the raw material mixture. The raw material is not particularly limited as long as it is a raw material used in the production of ordinary oxide-based glass, and oxides, carbonates, etc. can be used. The type and ratio of the raw materials are appropriately adjusted so that the composition of the obtained glass composition is within the above range to form a raw material mixture.

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

Thereafter, the melt is cooled and solidified to obtain the glass composition of this embodiment. The cooling method is not particularly limited. A roll-out machine or press machine may be used, or a rapid cooling method such as dropping into a cooling liquid may be used. It is preferred that the resulting glass composition is completely amorphous, i.e., has a degree of crystallinity of 0%. However, it may contain a crystallized portion as long as it does not impair the effect of the present invention.

The glass composition of this embodiment obtained in this way may have any form. For example, it may be block-shaped, plate-shaped, thin plate-shaped (flake-shaped), powder-shaped, etc.

When using the glass composition of this embodiment as a sealing material, it is preferable that the glass composition is glass powder. Also, regarding the form when evaluating the above properties of the glass composition, glass powder is preferable from the viewpoint of performance as a sealing material.

(glass powder)

When the glass composition of this embodiment is made of glass powder, the particle size of the glass powder can be appropriately selected depending on the intended use. For sealing materials for which glass powder is a typical application, the particle size of the glass powder is preferably between 0.1 μm and 100 μm.

In addition, if the particle size of the glass powder is large, it is prone to sedimentation and separation when it is made into a paste and applied or dried, and there is also a problem that the thickness of the resulting sealing layer increases. Therefore, when using glass powder in the form of a paste, the particle size of the glass powder is preferably in the range of 0.1 ㎛ to 5.0 ㎛, more preferably 0.1 ㎛ to 2.5 ㎛.

In addition, in this specification, “particle size” means the 50% volume-based particle size (D ₅₀ ) in the cumulative particle size distribution, and specifically, the particle size distribution measured using a laser diffraction/scattering type particle size distribution measuring device. In the cumulative particle size curve, it means the particle size when the accumulated amount accounts for 50% of the volume.

The glass powder consisting of the glass composition of this embodiment is obtained, for example, by pulverizing the glass composition. Therefore, the particle size of the glass powder can be adjusted depending on the grinding conditions. Examples of grinding methods include rotary ball mills, vibrating ball mills, planetary mills, jet mills, attritors, medium stirring mills (bead mills), jaw crushers, and roll crushers.

In particular, when making glass powder with a fine particle size of 5.0 μm or less, it is better to use wet grinding. Wet grinding is grinding using media or bead mills made of alumina or zirconia in a solvent such as water or alcohol.

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

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

<Glass paste>

The glass paste of this embodiment contains the glass composition of this embodiment described above and an organic vehicle. Additionally, the glass paste may contain low-expansion filler and/or laser absorbing material depending on the sealing method. Hereinafter, the organic vehicle, low-expansion filler, and laser absorbing material will be described.

As an organic vehicle, for example, one in which resin, which is a binder component, is dissolved in a solvent is used.

Specifically, resins such as methylcellulose, ethylcellulose, carboxymethylcellulose, oxyethylcellulose, benzylcellulose, propylcellulose, and nitrocellulose, and solvents such as terpineol, texanol, butylcarbitol acetate, and ethylcarbitol acetate. What is dissolved in can be used as an organic vehicle.

In addition, an acrylic resin containing (meth)acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate can be used in methyl ethyl ketone. , terpineol, texanol, butylcarbitol acetate, ethylcarbitol acetate, etc. can be used as an organic vehicle. In addition, in this specification, (meth)acrylate means at least one of acrylate and methacrylate.

In addition, polyalkylene carbonates such as polyethylene carbonate and polypropylene carbonate, triethyl acetylcitrate, propylene glycol diacetate, diethyl succinate, ethylcarbitol acetate, triacetin, texanol, and adipic acid. A solution dissolved in a solvent such as dimethyl, ethyl benzoate, or a mixture of propylene glycol monophenyl ether and triethylene glycol dimethyl ether can be used as an 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 is such that the viscosity of the glass paste can be adjusted. The ratio of the resin to the solvent in the organic vehicle, specifically, the mass ratio expressed as resin:solvent is preferably about 3:97 to 30:70.

The low-expansion filler has a lower coefficient of thermal expansion than the glass composition, and has a coefficient of thermal expansion of approximately -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 at least one selected from silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate-based compounds, soda-lime glass, and borosilicate glass is preferable. As zirconium phosphate-based compounds, (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 , Zr ₂ (WO ₃ )(PO ₄ ) ₂ and complex compounds thereof.

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

The content of the low-expansion filler is set so that the thermal expansion coefficient of the sealing layer is close to that of the material to be sealed (eg, a glass substrate). The content of the low-expansion filler is preferably 1% by volume or more relative to the total volume of the glass composition, the low-expansion filler, and the laser absorbing material mixed (hereinafter sometimes referred to as mixed material), and 5% by volume. % or more is more preferable, and 10 volume% or more is further preferable. On the other hand, if the content of the low-expansion filler is too high, the fluidity of the sealing material when melted becomes poor, so the content of the low-expansion filler is preferably 50 volume% or less, and 45 volume% or less relative to the volume of the mixed material. It is more preferable, and 40 volume% or less is still more preferable.

The laser absorbing material is not particularly limited, but includes at least one metal selected from Cr, Ni, Co, etc., in addition to Cu, Fe, and Mn constituting the above-mentioned CuO, Fe ₂ O ₃ , and MnO ₂ , or containing the metal. Compounds such as oxides (inorganic pigments) can be mentioned. Additionally, the laser absorbing material may be a pigment other than these.

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

If the content of the laser absorbing material is too small, there is a risk that it will be difficult to sufficiently melt the sealing material by laser irradiation. Therefore, the total content of laser absorbing materials, including other laser absorbing materials, is preferably 0.1 volume% or more, more preferably 1 volume% or more, and even more preferably 3 volume% or more relative to the volume of the mixed material. On the other hand, if the content of the laser absorbing material is too high, the fluidity of the sealing material when melted becomes poor, thereby reducing the adhesive strength. Therefore, the content of the laser absorbing material is preferably 20 volume% or less, more preferably 18 volume% or less, and still more preferably 15 volume% or less, relative to the volume of the mixed material.

The ratio of the mixed material and the organic vehicle in the glass paste is appropriately adjusted 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 needed, as long as they do not conflict with the purpose of the present invention.

The glass paste is adjusted by a known method using a rotary mixer equipped with a stirring blade, a roll mill, a ball mill, etc.

<Ending Package>

Next, a sealed package to which the glass composition of this embodiment is applied will be described.

1 and 2 are plan and cross-sectional views showing one embodiment of a sealed package. 3A to 3D are process diagrams showing one embodiment of the method for manufacturing the sealed package shown in FIGS. 1 and 2. Figures 4 and 5 are top and cross-sectional views of the first substrate used in manufacturing the sealed package shown in Figures 1 and 2. Figures 6 and 7 are top and cross-sectional views of the second substrate used in manufacturing the sealed package shown in Figures 1 and 2.

The sealing package 10 is a lighting device (OEL lighting, etc.) using a light-emitting device such as an FPD such as OELD, PDP, or LCD, an organic electroluminescence (OEL) device, or a solar cell such as a dye-sensitized solar cell. Compose.

That is, the sealed package 10 is disposed between a first substrate 11, a second substrate 12 disposed opposite to the first substrate, and the first substrate and the second substrate, and the first substrate 10 is disposed between the first substrate and the second substrate. It has a sealing layer 15 that adheres the substrate and the second substrate. Additionally, the sealing layer 15 contains the glass composition of the present embodiment described above.

The first substrate 11 is, for example, an element substrate on which the electronic element portion 13 is mainly provided. The second substrate 12 is, for example, a sealing substrate mainly used for sealing. An electronic element portion 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.

Examples of the first substrate 11 and the second substrate 12 include a glass substrate and a substrate with a metal film formed on the surface.

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 (all manufactured by AGC, brand names), and those chemically strengthened. In addition, as an alkali-free glass substrate, for example, AN100 (manufactured by AGC, brand name), EAGLE2000 (manufactured by Corning, brand), EAGLE , brand name), OA-10 (manufactured by Nippon Denki Glass, brand name), Tempax (manufactured by Shot Company, brand name), etc.

Examples of the substrate on which a metal film is deposited on the surface include a substrate on which a Ti-containing film is deposited on the surface of a glass substrate. Additionally, the material of the substrate is not particularly limited and may be a known material. Additionally, 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 unit 13 includes, for example, an OEL element if it is an OELD or OEL lighting, a plasma light emitting element if it is a PDP, a liquid crystal display element if it is an LCD, and a dye-sensitized solar cell element (dye-sensitized photoelectric conversion element) if it is a solar cell. have The electronic element portion 13 can be configured with various known structures and is not limited to the structure shown.

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

When the electronic device portion 13 is an OEL device, some space remains between the first substrate 11 and the second substrate 12. This space may be left as is or may be filled with 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 device portion 13 is a dye-sensitized solar cell device or the like, the electronic device portion 13 is disposed entirely between the first substrate 11 and the second substrate 12, although not shown. Additionally, the sealing object is not limited to the electronic element portion 13, and may be a photoelectric conversion device or the like. Additionally, the sealed package 10 may be a building material such as double-layer glass without the electronic element portion 13.

Hereinafter, as an example of a sealed package, the organic electroluminescent element constituting the OELD will be described in detail with reference to FIG. 8.

The organic electroluminescent element 210 obtained using the glass composition of this embodiment includes a substrate 211, an anode 213a, an organic thin film layer 213b, and a cathode 213c stacked on the substrate 211. A laminated structure 213 having a glass member 212 that covers the outer surface side of the laminated structure 213 and is mounted on the substrate 211, and a sealing layer that adheres the substrate 211 and the glass member 212 ( 215). Additionally, the sealing layer 215 contains the glass composition of the present embodiment described above.

(Method of manufacturing 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 described above is used for sealing. The glass paste is applied to the second substrate 12 in a frame shape and then dried to form an application layer. Examples of the application method include printing methods such as screen printing and gravure printing, and dispensing methods. Drying is performed to remove the solvent, and is usually performed at a temperature of 120°C or higher for 10 minutes or more. If the solvent remains in the application layer, there is a risk that the binder component may not be sufficiently removed in the subsequent calcination.

The application layer is subjected to plastic firing to become the plastic layer 15a (FIGS. 6 and 7). Plastic 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.

An electronic element portion 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 plastic layer 15a and the first substrate 11 provided with the electronic element portion 13 are stacked with the plastic layers 15a facing each other (FIG. 3A, FIG. 3b).

Afterwards, the plastic layer 15a is fired by irradiating the laser light 16 through the second substrate 12 (FIG. 3C). The laser light 16 is irradiated while scanning along the frame-shaped plastic layer 15a. By irradiating the laser light 16 over the entire circumference of the plastic layer 15a, a frame-shaped sealing layer 15 is formed between the first substrate 11 and the second substrate 12. Additionally, the laser light 16 may be irradiated to the plastic layer 15a through the first substrate 11.

The type of laser light 16 is not particularly limited, and laser lights such as a semiconductor laser, carbon dioxide gas laser, excimer laser, YAG laser, and HeNe laser are used. The irradiation conditions of the laser light 16 are selected depending on the thickness, line width, cross-sectional area in the thickness direction, etc. of the plastic layer 15a. The output of the laser light 16 is preferably 2W to 150W. If the output of the laser light is less than 2W, there is a risk that the plastic layer 15a may not melt. If the output of the laser light exceeds 150 W, cracks, etc. are likely to occur in the first substrate 11 and the second substrate 12. The output of the laser light 16 is more preferably 5W to 120W.

In this way, a sealed package 10 is manufactured in which the electronic device portion 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 performing firing by irradiation of the laser light 16 has been described above, the method of firing is not necessarily limited to the method of performing firing by irradiation of the laser light 16. Different firing methods may be adopted depending on the heat resistance of the electronic element portion 13, the configuration of the sealing package 10, etc. For example, when the heat resistance of the electronic element portion 13 is high or when the electronic element portion 13 is not provided, instead of irradiating the laser light 16, the entire assembly as shown in FIG. 3B is electrically It may be placed in a firing furnace or the like, and the entire assembly including the temporarily fired layer 15a may be heated to form the sealing layer 15.

As mentioned above, embodiments of the sealed package of the present invention have been described using examples, but the sealed package of the present invention is not limited to these. As long as it does not conflict with the spirit of the present invention, the configuration can be appropriately changed as needed.

Example

Hereinafter, the present invention will be described in more 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]

(Preparation of glass composition)

The raw materials were combined and mixed to obtain the composition shown in mole percent 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 sieve with an eye size of 100 mesh to obtain a glass composition.

The D ₅₀ of these glass compositions was measured using a Microtrack particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.), and all were within the range of 2 μm to 5 μm.

Next, the following measurements and evaluations were performed on these glass compositions.

In addition, in Tables 1 and 2, the evaluation column "-" indicates that the product was not evaluated because the crystallization peak by DTA was not observed or vitrification was not performed.

(DTA test)

Temperature increase rate using differential thermal analysis (DTA) device TG-DTA8122 manufactured by Rigaku Corporation; Thermal analysis of the glass composition was performed at 10°C/min, and the glass transition temperature Tg, fourth inflection point Ts [°C], crystallization start temperature Tcs [°C], and crystallization temperature Tcp [°C] were respectively determined from the obtained DTA chart. In addition, the glass transition temperature Tg, the fourth inflection point Ts, the crystallization start temperature Tcs, and the crystallization temperature Tcp are defined as the first inflection point of the DTA chart as Tg, the fourth inflection point as Ts, the start point of the exothermic peak as Tcs, and the exothermic peak temperature as Tcp. Saved. Additionally, as an evaluation of the allowable temperature during firing, the temperature difference (Tcs-Ts) between the crystallization start temperature and the fourth inflection point was determined, and the obtained results are shown in the table below. Tests 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, and a fired body for measuring thermal expansion was obtained. The obtained fired body for measuring thermal expansion was processed into a cylindrical shape with a diameter of 5 ± 0.5 mm and a length of 2 ± 0.05 cm. The processed sintered body for thermal expansion measurement is heated with a thermal expansion meter 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 is obtained. was calculated. The obtained results are shown in the table below. Those with a thermal expansion coefficient α of less than 91 were considered acceptable.

(Liquidity Evaluation)

4 g of the glass composition was press-molded to produce a sample (flow button) with a diameter of 15 mm. 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 obtained fired body for evaluation of fluidity was divided into four angles, the diameters were measured at four locations, and the average value of the four diameters was calculated to be the FB diameter (unit: mm). For each sample, fluidity, gloss, and the presence or absence of adhesion were evaluated according to the following criteria. The obtained results are shown in the table below. In the evaluation of fluidity and gloss, the product marked ○ was judged as passing.

<Liquidity>

○: The 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.

△: A part of the surface of the fired body for fluidity evaluation lacked gloss.

×: The entire surface of the fired body for fluidity evaluation lacked gloss.

(Water resistance evaluation)

Glass flakes of each glass composition were used and left 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 standards. The obtained results are shown in the table below. As a judgment, the case of ○ was judged as passing.

<Evaluation criteria for water resistance>

○: No discolored areas were observed on the entire surface of the fired body for water resistance evaluation.

△: Discolored areas were observed on part of the surface of the fired body for water resistance evaluation.

×: The entire surface of the fired body for water resistance evaluation was discolored.

The glass compositions of Examples 1 to 15, which are examples, exhibited excellent water resistance, had a small coefficient of thermal expansion, and were excellent in fluidity when melted and a wide allowable temperature range when fired.

On the other hand, in Example 16, which is a comparative example, Bi ₂ O ₃ was more than 0.4% and TeO ₂ was less than 25.5%, so the allowable temperature range during firing was narrow and fluidity was poor.

Additionally, in Examples 17 to 19, which are comparative examples, Nb ₂ O ₅ was less than 5.5%, so the thermal expansion coefficient was large and water resistance was poor.

In addition, Example 20, which is a comparative example, had a large thermal expansion coefficient because Bi ₂ O ₃ was greater than 0.4%.

In addition, in Example 21, which is a comparative example, Nb ₂ O ₅ exceeded 8.0%, so the allowable temperature range during firing was narrow, and fluidity and water resistance were poor.

In addition, Example 22, which is a comparative example, had poor fluidity and water resistance because V ₂ O ₅ was greater than 40.0% and Nb ₂ O ₅ was less than 5.5%.

Additionally, in Example 23, which is a comparative example, TeO ₂ was greater than 30.0%, so the thermal expansion coefficient was large and water resistance was poor.

Additionally, in Examples 24 and 25, which are comparative examples, TeO ₂ was less than 25.5% and ZnO was more than 30.0%, so water resistance was poor. In Example 25, the allowable temperature range during firing was narrow and fluidity was also poor.

Additionally, in Examples 26 and 27, which are comparative examples, water resistance was poor because ZrO ₂ was more than 4.5%.

In addition, Example 28, which is a comparative example, had a large thermal expansion coefficient because Bi ₂ O ₃ was more than 0.4%.

Additionally, in Example 29, which is a comparative example, V ₂ O ₅ was more than 40.0%, ZnO was less than 15.0%, and BaO was more than 4.5%, so the allowable temperature range during firing was narrow, the thermal expansion coefficient was large, and fluidity was poor.

In addition, Example 30, which is a comparative example, was not vitrified because V ₂ O ₅ was less than 25.5% and ZnO was more than 30.0%.

Additionally, in Example 31, which is a comparative example, the water resistance evaluation was poor because ZnO contained more than 30.0%.

Additionally, in Example 32, which is a comparative example, Al ₂ O ₃ was more than 5.0%, so the allowable temperature range during firing was narrow and fluidity was poor.

In addition, in Example 33, which is a comparative example, since V ₂ O ₅ exceeded 40.0%, the allowable temperature range during firing was narrow, the thermal expansion coefficient was large, and fluidity and water resistance were poor.

In addition, in Examples 34 to 36, which are comparative examples, Bi ₂ O ₃ is more than 0.4%, so Example 34 has a narrow allowable temperature during firing, Example 35 has poor water resistance, and Example 36 has a large thermal expansion coefficient and poor water resistance. lost.

In addition, Example 37, which is a comparative example, had poor water resistance because B ₂ O ₃ was more than 6.0%.

This application is based on Japanese Patent Application No. 2022-122837, filed on August 1, 2022, the contents of which are incorporated herein by reference.

10: Sewing Package
11: first substrate
12: second substrate
13: Electronic element part
15: Sealing layer
15a: plastic layer
16: Laser light
210: Organic electroluminescence device
211: substrate
212: glass member
213: Laminated structure
213a: anode
213b: Organic thin film layer
213c: cathode
215: Seal layer

Claims (10)

Expressed as mole percent based on oxide,
V ₂ O ₅ 25.0 to 40.0%,
TeO ₂ from 25.5 to 30.0%,
15.0 to 30.0% ZnO,
Nb ₂ O ₅ 5.5 to 8.0%,
Al ₂ O ₃ 0 to 5.0%,
BaO 0 to 4.5%,
B ₂ O ₃ 0 to 6.0%,
Bi ₂ O ₃ from 0 to 0.4%, and
Contains 0 to 4.5% ZrO ₂ ,
A glass composition characterized by being substantially free of alkali metal oxides and PbO. According to paragraph 1,
A glass composition containing from 1.0 to 5.0% B ₂ O ₃ , expressed in mole percent on an oxide basis. According to claim 1 or 2,
A glass composition containing greater than 6.2% Nb ₂ O ₅ , expressed in mole percent on an oxide basis. According to claim 1 or 2,
A glass composition, wherein the total content _of V ₂ O ₅ , TeO 2 , and ZnO expressed as (V ₂ O ₅ +TeO ₂ +ZnO), expressed in mole percent on an oxide basis, is 80 to 91%. According to claim 1 or 2,
A glass composition, wherein the content ratio expressed as (V ₂ O ₅ /TeO ₂ ), expressed in mole percent on an oxide basis, is 1.0 to 1.6. According to claim 1 or 2,
A glass composition, wherein the total content _of Bi ₂ O ₃ , TeO 2 , and BaO expressed as (Bi ₂ O ₃ +TeO ₂ +BaO), expressed in mole percent on an oxide basis, is 25.5 to 31.0%. According to claim 1 or 2,
A glass composition, wherein the total content of Al ₂ O ₃ and ZrO ₂ expressed as (Al ₂ O ₃ +ZrO ₂ ), expressed in mole percent on an oxide basis, is 0 to 7.0%. A glass paste containing the glass composition according to claim 1 or 2 and an organic vehicle. A seal comprising a first substrate, a second substrate disposed opposite the first substrate, and a sealing layer disposed between the first substrate and the second substrate and adhering the first substrate and the second substrate. It is a package,
The sealing layer is a sealing package comprising the glass composition according to claim 1 or 2. A substrate, a laminated structure having an anode, an organic thin film layer, and a cathode laminated on the substrate, a glass member placed on the substrate to cover an outer surface side of the laminated structure, and a seal for bonding the substrate and the glass member. Provided with a layer,
An organic electroluminescent element, wherein the sealing layer contains the glass composition according to claim 1 or 2.

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