TW202408952A - Glass compositions, glass pastes, sealed packages and organic electroluminescent components - Google Patents

Abstract

The present invention relates to a glass composition, a glass paste, a sealing package and an organic electroluminescent element. The glass composition is characterized in that, expressed in mole % on an oxide basis, it contains 25.0-40.0% of _V2O5 , 25.5-30.0 _{% of TeO2, 15.0-30.0% of ZnO, 5.5-8.0% of Nb2O5, 0-5.0% of Al2O3 , 0-4.5 % of BaO} , 0-6.0% of _{B2O3 , 0-0.4% of Bi2O3 and} 0-4.5% of _ZrO2 , and _is substantially free of alkali metal oxides and PbO.

Description

Glass composition, glass paste, sealed package and organic electroluminescent element

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

Flat panel display devices (FPD, Flat Panel Display) such as organic EL display (Organic Electro-Luminescence Display: OELD) and plasma display panel (PDP, Plasma Display Panel) have a structure in which a light-emitting element is sealed by a glass package that seals a pair of glass substrates. In addition, liquid crystal display devices (LCD, Liquid Crystal Display) have 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 them, organic EL displays require strict isolation from the outside air because the EL element's light-emitting properties will deteriorate significantly if it comes into contact with moisture. Also, if the organic EL element is exposed to high temperatures, it will be damaged, so the sealing method is extremely important.

Therefore, as a sealing method for organic EL displays, a method of using a glass composition as a sealing material and sealing by local heating is considered to be effective. Generally, a glass composition is mixed with an organic medium and used as a paste. The paste is applied to a glass substrate by screen printing or dispensing, and then fired to form a pre-calcined layer. Then, another glass substrate is superimposed, and the pre-calcined layer is locally heated by laser or the like to melt the glass composition and seal.

Regarding the glass composition used in the sealing material, in order to make it have high water resistance, have a thermal expansion coefficient close to that of the material to be sealed, and reduce the thermal adverse effects on the organic EL element during laser sealing, it is ideal to melt the glass composition The allowable temperature (process margin) is wider.

As a glass composition used in a sealing material, for example, Patent Document 1 describes a TeO ₂ -ZnO-B ₂ O ₃ glass composition for sealing an organic EL display. Also, Patent Document 2 discloses a V ₂ O ₅ -ZnO-TeO ₂ glass composition. [Prior Art Document] [Patent Document]

[Patent document 1] Japanese Patent No. 6357937 [Patent document 2] Japanese Patent No. 6022070

[The problem the invention is trying to solve]

In recent years, the screen size of organic EL displays has gradually increased. When the screen size increases, the line width of the sealing part needs to be increased compared to a smaller screen size. If the line width of the sealing part is increased, stress caused by the thermal expansion difference between the sealing material and the sealing material will easily occur during laser sealing, and there is a risk of cracks in the sealing layer and the sealing material. Therefore, in order to ensure the reliability of the sealed package, the thermal expansion coefficient of the sealing material is required to be closer to the thermal expansion coefficient of the sealed material.

Furthermore, conventional hermetic packages are generally those in which glass substrates are sealed together. However, in recent years, for example, hermetic packages in which a substrate with a metal film formed on its surface and a glass substrate are sealed are also being sought. Even when sealing a substrate with a metal film formed 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 have room for further improvement in terms of water resistance, thermal expansion coefficient, fluidity during melting, and allowable temperature range during firing.

In view of the above, the purpose of the present invention is to provide a vanadium-based glass composition for sealing the joints between glass components in flat-panel displays such as organic EL displays or liquid crystal displays by local heating such as laser heating, which is superior to previous glass compositions in terms of water resistance, smaller thermal expansion coefficient, and excellent fluidity during melting and allowable temperature range during firing. In addition, the purpose of the present invention is to provide a sealing material and glass paste containing the glass composition, as well as a sealed package and an organic electroluminescent element having a sealing layer containing the glass composition. [Technical means for solving the problem]

The present inventors found that the above-mentioned problems can be solved by 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, sealed package and organic electroluminescent element composed of the following. [1] A glass composition characterized by: containing 25.0 to 40.0% V ₂ O ₅ , 25.5 to 30.0% TeO ₂ , 15.0 to 30.0% ZnO, 5.5 to 8.0% Nb ₂ O ₅ , 0～5.0% Al ₂ O _{3 ,} 0～4.5% BaO, 0～6.0% B ₂ O _{3 ,} 0～0.4% Bi ₂ O _{3 ,} and 0～4.5% ZrO ₂ and does not substantially contain alkali metal oxides and PbO. [2] The glass composition according to [1], which contains 1.0 to 5.0% of B ₂ O ₃ expressed as mol% 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 as mol% on an oxide basis. [4] The glass composition according to any one of [1] to [3], wherein V ₂ O ₅ represented by (V ₂ O ₅ + TeO ₂ + ZnO) expressed in mol% on an oxide basis, The total content of TeO ₂ and ZnO is 80 to 91%. [5] The glass composition according to any one of [1] to [4], wherein the content ratio (V ₂ O ₅ /TeO ₂ ) expressed in mol% on an oxide basis is 1.0 to 1.6. [6] The glass composition according to any one of [1] to [5], wherein Bi ₂ O ₃ represented by (Bi ₂ O ₃ + TeO ₂ + BaO) expressed in mol% on an oxide basis, The total content of TeO ₂ and BaO is 25.5~31.0%. [7] The glass composition according to any one of [1] to [6], wherein Al _{2 O 3 and ZrO are represented by (Al 2 O 3 +} ZrO ₂ ) expressed in mol% on an oxide basis. The total content of ₂ is 0~7.0%. [8] A glass paste containing the glass composition according to any one of [1] to [7], and an organic vehicle. [9] A sealed package having a first substrate, a second substrate disposed opposite to the first substrate, and a sealing package disposed between the first substrate and the second substrate. 2. A sealing layer attached to the substrate; and the sealing layer includes the glass composition as described in any one of [1] to [7]. [10] An organic electroluminescent element, comprising: a substrate; a laminated structure laminated on the substrate and having an anode, an organic thin film layer, and a cathode; and placed on the above-mentioned laminated structure so as to cover the outer surface side thereof. A glass member on a substrate; and a sealing layer connecting the substrate and the glass member; and the sealing layer includes the glass composition according to any one of [1] to [7]. [Effects of the invention]

Compared with the previous glass compositions, the glass composition of the present invention is superior in terms of water resistance, has a smaller thermal expansion coefficient, and has excellent fluidity during melting and a larger allowable temperature range during firing.

The following is an explanation of the embodiments of the present invention. Furthermore, the present invention is not limited to the embodiments described below. In the following drawings, the same symbols are sometimes used to describe components and parts that play the same role, and repeated descriptions are omitted or simplified. In addition, the embodiments described in the drawings are schematically illustrated to clearly describe the present invention and may not accurately represent actual sizes or scales.

<Glass composition> The glass composition of this embodiment is characterized by containing 25.0 to 40.0% of V ₂ O ₅ , 25.5 to 30.0% of TeO ₂ , and 15.0 to 30.0% in mol% on an oxide basis. ZnO, 5.5～8.0% Nb ₂ O ₅ , 0～5.0% Al ₂ O ₃ , 0～4.5% BaO, 0～6.0% B ₂ O ₃ , 0～0.4% Bi ₂ O ₃ , and 0~4.5% ZrO ₂ , and essentially does not contain alkali metal oxides and PbO.

Next, each component of the glass composition of this embodiment is demonstrated. In the following description, unless otherwise stated, "%" in the content of each component of the glass composition represents the molar % based on the oxide, that is, in terms of oxide conversion. In this specification, "~" indicating a numerical range is used to include the upper and lower limits.

If the glass composition used in the sealing material contains alkali metal oxides, when the sealing material is exposed to high temperature during or after sealing, the alkali metal components will diffuse into the sealed material such as the glass substrate, causing the sealed material to deteriorate. Therefore, the glass composition of the present embodiment does not substantially contain alkali metal oxides. Furthermore, in this specification, "substantially free of" means that it does not contain anything other than unavoidable impurities, that is, it means that it is not intentionally added. Therefore, the glass composition of the present embodiment may contain a trace amount of alkali metal oxides as unavoidable impurities. The content of alkali metal oxides in the glass composition of the present embodiment is preferably less than 1000 ppm, and more preferably less than 500 ppm. Furthermore, in this specification, alkali metal oxides mean _Li2O , _Na2O and _K2O . In addition, ppm refers to mass ppm.

In addition, in order to reduce the load on the environment, the glass composition of this embodiment does not substantially contain lead, that is, PbO. Furthermore, regarding PbO, "substantially does not contain" 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 absorbing component. On the other hand, if the content of V ₂ O ₅ is too high, there is a risk that the water resistance decreases, or the glass stability decreases during glass manufacturing, and the glass becomes easily devitrified. Moreover, if the content of V ₂ O ₅ is too low, there is a risk that the glass transition temperature increases and the low-temperature sealing property deteriorates. Therefore, the content of V ₂ O ₅ is set to 25.0-40.0%. The content of V ₂ O ₅ is preferably 28.0% or more, more preferably 30.0% or more, and further preferably 32.0% or more, and further preferably 39.0% or less, more preferably 38.0% or less, and further preferably 37.0% or less.

_TeO2 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, if the _TeO2 content is high, the thermal expansion coefficient becomes larger. Moreover, if it is too little, there is a risk that the glass transition temperature will rise, the low-temperature sealing will deteriorate, or it will be easy to crystallize during the sealing firing. Furthermore, the effect of improving fluidity and water resistance cannot be fully obtained. Therefore, the _TeO2 content is set to 25.5-30.0%. The _TeO2 content is preferably 26.0% or more, and preferably 29.0% or less, more preferably 28.0% or less, and further preferably 27.5% or less.

ZnO is necessary as a component to reduce the thermal expansion coefficient. On the other hand, if the content of ZnO is large, the stability of the glass may decrease during glass production and the glass may become easily devitrified. On the other hand, if it is too small, the thermal expansion coefficient will increase. Therefore, the content of ZnO is 15.0~30.0%. The content of ZnO is preferably 17.0% or more, more preferably 18.5% or more, further preferably 20.0% or more, and further preferably 28.0% or less, more preferably 26.5% or less, further preferably 25.0% or less.

Nb ₂ O ₅ is necessary as a component to reduce the thermal expansion coefficient or improve water resistance. On the other hand, if the content of Nb ₂ O ₅ is large, the glass will easily crystallize during laser firing and sealing. If it is too small, the thermal expansion coefficient will become large, and the effect of improving water resistance cannot be fully obtained. Therefore, the content of Nb ₂ O ₅ is set to 5.5 to 8.0%. Generally speaking, if the content of Nb ₂ O ₅ is large (for example, more than 5%), the glass will easily crystallize during laser firing and sealing, so it was previously difficult to add a large amount of Nb ₂ O ₅ . The present inventors discovered that by sufficiently increasing the ratio of amorphous components such as TeO ₂ , even if the glass contains 5.5% or more of Nb ₂ O ₅ , the glass will not crystallize due to firing, and excellent water resistance and excellent water resistance can be obtained. Glass composition with small thermal expansion coefficient. The content of Nb ₂ O ₅ is preferably more than 6.2%, more preferably more than 6.5%. In addition, in order to avoid crystallization of glass during laser firing and 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 further preferably 7.4% or less.

Al ₂ O ₃ is not essential, but it is a component that has the effect of reducing the thermal expansion coefficient and further has the effect of improving water resistance, so it is preferably contained in the glass composition of the present embodiment. In this embodiment, the content of Al ₂ O ₃ 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 within an appropriate range and thereby avoid crystallization of the glass during laser firing and sealing, the content of Al ₂ O ₃ is 5.0% or less, preferably 4.5% or less, and more preferably 4.0% or less. , and more preferably 3.5% or less.

BaO is not essential, but it is an effective component for stabilizing the glass, so it is preferably contained in the glass composition of the present embodiment. In the present embodiment, the content of BaO is 0 to 4.5%. Here, when BaO is contained, the content of BaO is preferably 0.5% or more. In order to keep the glass transition temperature or thermal expansion coefficient within an appropriate range, the content of BaO is 4.5% or less, preferably 3.5% or less, more preferably 2.5% or less, and further preferably 2.0% or less.

B ₂ O ₃ is not essential, but it is a glass-forming oxide and a component that forms a glass network and improves the stability of the glass, so it is preferably contained in the glass composition of this 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. Moreover, if the content of B ₂ O ₃ is high, conversely, the glass becomes unstable and tends to crystallize during laser firing and sealing. Therefore, in order to avoid glass crystallization caused by 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 further preferably 4.0% or less. .

Bi ₂ O ₃ is a component that easily reacts with the glass substrate during sealing to form a reaction layer, thereby improving the bonding strength, so it is preferably contained in the glass composition of this embodiment. In addition, if the content of Bi ₂ O ₃ is high, the glass may easily crystallize during laser firing and sealing, and the thermal expansion coefficient may increase. In addition, it may react excessively with the glass substrate and introduce high melting point components such as SiO ₂ in the glass substrate into the glass composition, which may increase the adhesion point and increase 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, particularly 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 this embodiment may not contain substantially Bi ₂ O ₃ .

ZrO ₂ is not essential, but it is a component that improves chemical stability, so it is preferably contained. 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, more preferably 1.0% or more. In addition, in order to maintain the glass transition temperature within an appropriate range and thereby avoid crystallization of the glass during laser firing and sealing, the content of ZrO ₂ is 4.5% or less, preferably 3.5% or less, more preferably 3.0% or less, and further Preferably it is 2.5% or less.

If the total content of _V2O5 , _TeO2 and ZnO ( _V2O5 + _TeO2 +ZnO) is 80-91%, it is easy to have both _water resistance and glass stability, _so it is more preferred. Moreover, for the same reason _, ( _V2O5 + _TeO2 +ZnO) is more preferably 82% or more, more preferably 84% or more, more preferably 89% or less, and more preferably 88% or less.

The content ratio of _V2O5 to _TeO2 ( _V2O5 / _TeO2 ) is preferably _1.0 to 1.6, since crystallization during _sealing and firing can be suppressed and the glass can be stabilized. For the same reason, ( _V2O5 / _TeO2 ) is more preferably _1.1 or more, and more preferably 1.5 or less.

If 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%, the thermal expansion coefficient can be kept within an appropriate range, so it is preferable. Moreover, 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.

If the total content of Al ₂ O ₃ and ZrO ₂ (Al ₂ O ₃ + ZrO ₂ ) is 0 to 7.0%, it can suppress crystallization of glass during laser firing sealing and improve water resistance, so it is preferable. Moreover, for the same reason, (Al ₂ O ₃ + ZrO ₂ ) is more preferably 1.5% or more, further preferably 2.5% or more, and further preferably 6.0% or less, further preferably 5.0% or less.

CuO is not essential, but it is a component that has the effect of reducing the thermal expansion coefficient and also has the effect of improving water resistance, so it can be contained. Furthermore, it is also effective as a laser absorbing component. Therefore, by containing CuO, when making glass paste, the amount of pigment added for the purpose of laser absorption can be reduced, and a large amount of low expansion filler can be contained instead, thereby making it possible to produce glass paste with a lower thermal expansion coefficient. On the other hand, if the CuO content is high, the laser seal is easily crystallized during firing. Therefore, the CuO content is preferably 1.0-10.0%. Here, in order to fully obtain the laser absorption effect, the CuO content is preferably 1.0% or more, more preferably 2.0% or more, and further preferably 3.0% or more. Furthermore, in order to avoid crystallization of the glass, the CuO content is preferably 10.0% or less, more preferably 8.0% or less, and further preferably 7.0% or less.

Fe ₂ O ₃ is not essential, but it is also effective as a laser absorbing component, so it can be contained. By containing Fe ₂ O ₃ , when making glass paste, the amount of pigment added for the purpose of laser absorption can be reduced, and a large amount of low expansion filler can be contained instead, thereby making it possible to make glass paste with a lower thermal expansion coefficient. On the other hand, if the content of Fe ₂ O ₃ is too high, the glass becomes easy to crystallize during laser firing and sealing, and further, the softening point of the glass rises, and the low-temperature sealing property becomes worse. Therefore, the content of Fe ₂ O ₃ is preferably 1.0-7.0%. Here, the content of Fe ₂ O ₃ is preferably 7.0% or less, more preferably 5.0% or less, and further preferably 2.0% or less. In addition, 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-mentioned effect can be obtained even without containing Fe ₂ O ₃ .

MnO ₂ is not essential, but it is an effective component as a laser absorption component, so it may be included. By containing MnO ₂ , when making glass paste, the amount of pigment added for the purpose of laser absorption can be reduced, and a large amount of low-expansion filler can be included instead, thereby making glass paste with a lower thermal expansion coefficient. On the other hand, if the content of MnO ₂ is high, the glass will easily 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 still more preferably 2.0% or less. In addition, in order to obtain the laser absorption effect, the content of MnO ₂ is preferably 1.0% or more. However, as long as CuO or Fe ₂ O ₃ is contained, the above-mentioned 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 components (hereinafter referred to as "other components") within the scope of not impairing the purpose of the present invention. The total content of the other components is preferably 10.0% or less.

The glass composition of the present embodiment may contain 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 ₂ , Ta ₂ O ₅ and the like as other components. However, if P ₂ O ₅ is contained in excess, there is a concern that water resistance may be reduced. Therefore, although P ₂ O ₅ may be contained, the content is preferably 5% or less, and further preferably substantially free of P 2 O 5 . In addition, regarding P ₂ O ₅ , "substantially free of" means that the content of P ₂ O ₅ in the glass composition is 1000 ppm or less.

(Thermal properties of glass compositions) Regarding the glass composition of this embodiment, it is preferable that the glass transition temperature Tg is 340° C. or lower because the low-temperature sealing property becomes good. Tg is more preferably 330°C or lower, further preferably 320°C or lower. The lower limit of Tg is not particularly limited, but is, for example, 280°C or higher.

Regarding the glass composition of the present embodiment, it is preferred that the fourth inflection point Ts when heated using a thermal analyzer (DTA (Differential Thermal Analysis)) is 400°C or less, because the low-temperature sealing property becomes good. Ts is more preferably 390°C or less, and further preferably 380°C or less. The lower limit of Ts is not particularly limited, and is, for example, 350°C or more.

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

Regarding the glass composition of the present embodiment, the crystallization temperature Tcp when heated using a thermal analyzer (DTA) is preferably 450°C or higher, because the low-temperature sealing property becomes good. Tcp is more preferably 470°C or higher, and further preferably 480°C or higher. The upper limit of Tcp is not particularly limited.

The temperature difference (Tcs-Ts) between the crystallization start temperature and the fourth inflection point of the glass composition of this embodiment is preferably greater than 100°C. By making (Tcs-Ts) greater than 100°C, the process margin during glass melting can be expanded, and the thermal impact on the organic EL element during laser firing and sealing can be reduced. (Tcs-Ts) is more preferably 110°C or higher, and still 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 based on the first inflection point of the DTA chart measured using a differential thermal analysis (DTA) device as Tg, the fourth inflection point The curve point was determined as Ts, the starting point of the exothermic peak was determined as Tcs, and the exothermic peak temperature was 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 produced by the method shown below.

First, prepare the stock mixture. The raw material is not particularly limited as long as it is a raw material commonly used in the production of oxide-based glass, and oxides, carbonates, etc. can be used. The types and ratios of the raw materials are appropriately adjusted so that the composition of the obtained glass composition falls within the above range, and a raw material mixture is prepared.

Then, the raw material mixture is heated by a known method to obtain a melt. The heating and 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 minutes to 90 minutes.

Thereafter, the glass composition of this embodiment can be obtained by cooling and solidifying the molten material. The cooling method is not particularly limited. A rolling machine or a pressing machine may be used, or a method of quenching by dropping into a cooling liquid or the like may be used. The obtained glass composition is completely amorphous, that is, the crystallinity is preferably 0%. However, a crystallized part may be included in the range which does not impair the effect of the present invention.

The glass composition of the present embodiment obtained in this way can be in any form, such as a block, a plate, a thin plate (sheet), a powder, etc.

When the glass composition of this embodiment is used as a sealing material, the glass composition is preferably glass powder. Furthermore, from the viewpoint of observing the performance of the sealing material, the form when evaluating the above-mentioned characteristics of the glass composition is also preferably glass powder.

(glass powder) When the glass composition of this embodiment is used as glass powder, the particle size of the glass powder can be appropriately selected depending on the intended use. In the case of sealing materials, which are typical uses of glass powder, the particle size of the glass powder is preferably 0.1 μm to 100 μm.

In addition, if the particle size of the glass powder is large, it is easy to precipitate and separate when applied or dried after gelatinization. Furthermore, there is also a problem that the thickness of the resulting sealing layer increases. Therefore, when the glass powder is gelatinized and used, the particle size of the glass powder is preferably in the range of 0.1 μm to 5.0 μm, and more preferably 0.1 μm to 2.5 μm.

Furthermore, in this specification, "particle size" means the volume-based 50% particle size (D ₅₀ ) in the cumulative particle size distribution. Specifically, it means the particle size measured using a laser diffraction/scattering particle size distribution measuring device. In the cumulative particle size curve of the obtained particle size distribution, the particle size when the cumulative amount accounts for 50% on a volume basis.

The glass powder including the glass composition of the present embodiment is obtained by, for example, pulverizing the glass composition. Therefore, the particle size of the glass powder can be adjusted according to the pulverization conditions. Examples of the pulverization method include a rotary ball mill, a vibrating ball mill, a planetary mill, a jet mill, an attritor, a medium stirring mill (bead mill), a jaw crusher, a roller crusher, and the like.

In particular, when it is desired to reduce the glass powder to a fine particle size such as 5.0 μm or less, wet grinding is preferably used. Wet grinding is carried out in a solvent such as water or alcohol using a medium containing alumina or zirconia or a bead mill.

In order to adjust the particle size of the glass powder, in addition to the pulverization of the glass composition, it can also be classified using a sieve or the like as needed.

Moreover, when the glass powder containing the glass composition of this embodiment is used as a sealing material, the glass powder may be used in its original form, or it may be made into a sealing material with a low-expansion filling material and/or a laser according to the sealing method. A sealing material obtained by mixing absorbent substances together. Moreover, from the viewpoint of improving workability, the glass composition and the sealing material are preferably used for gelatinization.

＜Glass paste＞ The glass paste of this embodiment contains the glass composition of this embodiment mentioned above, and an organic medium. In addition, the glass paste may contain a low-expansion filling material and/or a laser-absorbing substance depending on the sealing method. The organic medium, low expansion filler, and laser absorbing material will be described below.

As the organic vehicle, for example, a resin in which a resin as a binder component is dissolved in a solvent can be used. Specifically, resins such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, benzylcellulose, propylcellulose, and nitrocellulose can be dissolved in terpineol, TEXANOL, butyl carbitol acetate, ethyl carbitol acetate and other solvents are used as organic vehicles. In addition, it is possible to use (meth)acrylic monomers including methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-(meth)hydroxyethyl acrylate. Acrylic resins dissolved in solvents such as methyl ethyl ketone, terpineol, TEXANOL, butyl carbitol acetate, and ethyl carbitol acetate are used as organic vehicles. Furthermore, in this specification, (meth)acrylate refers to at least one of acrylate and methacrylate. In addition, polyalkylene carbonates such as polyethylene carbonate and polypropylene carbonate can be dissolved in acetyl triethyl citrate, propylene glycol diacetate, diethyl succinate, and ethyl carbitol ethyl. Those obtained from solvents such as acid ester, glycerol triacetate, TEXANOL, dimethyl adipate, ethyl benzoate, a mixture of propylene glycol monophenyl ether and triethylene glycol dimethyl ether are used as organic vehicles.

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

The low expansion filler material has a lower thermal expansion coefficient than the glass composition, and generally has a thermal expansion coefficient of about -15×10 ^-7 to 45×10 ^-7 /°C. The purpose of adding the low expansion filler material is to reduce the thermal expansion coefficient of the sealing layer.

The low-expansion filling material is not particularly limited, but is preferably at least one selected from the group consisting of 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 , and NbZr(PO ₄ ) ₃ , Zr ₂ (WO ₃ )(PO ₄ ) ₂ , these complex compounds, etc.

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

The content of the low expansion filler is set in such a way that the thermal expansion coefficient of the sealing layer is close to the thermal expansion coefficient of the sealed material (e.g., glass substrate). The content of the low expansion filler is preferably 1 volume % or more, more preferably 5 volume % or more, and further preferably 10 volume % or more, relative to the total volume of the mixture of the glass composition, the low expansion filler, and the laser absorbing substance (hereinafter, sometimes referred to as the mixed material). On the other hand, if the content of the low expansion filler is too much, the fluidity of the sealing material when it is melted deteriorates. Therefore, the content of the low expansion filler is preferably 50 volume % or less, more preferably 45 volume % or less, and further preferably 40 volume % or less, relative to the volume of the mixed material.

The laser absorbing material is not particularly limited, and may include, in addition to Cu, _Fe , and Mn constituting the above-mentioned CuO, _Fe2O3 , and _MnO2 , at least one metal selected from Cr, Ni, and Co, or a compound (inorganic pigment) containing an oxide of the metal. Furthermore, the laser absorbing material may be a pigment other than these.

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

If the content of the laser absorbing material is too small, it may be difficult to fully melt the sealing material by laser irradiation. Therefore, relative to the volume of the mixed material, 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 still more preferably 3 volume % or more. 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, resulting in a reduction in the bonding strength. Therefore, relative to the volume of the mixed material, 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.

The ratio of the mixed material to the organic medium in the glass paste can be appropriately adjusted according to the desired viscosity of the glass paste. Specifically, the mass ratio of the mixed material to the organic medium is preferably about 60:40 to 90:10. In the glass paste, known additives other than the mixed material and the organic medium can be mixed as needed and within the scope that does not violate the purpose of the present invention.

The glass paste can be adjusted by using known methods such as a rotary mixer equipped with stirring blades, a roller mill, and a ball mill.

<Sealed Package> Next, the sealed package of the glass composition applied to the present embodiment is described. Figures 1 and 2 are a top view and a cross-sectional view showing an embodiment of the sealed package. Figures 3A to 3A are step diagrams showing an embodiment of a method for manufacturing the sealed package shown in Figures 1 and 2. Figures 4 and 5 are a top view and a cross-sectional view of the first substrate used in the manufacture of the sealed package shown in Figures 1 and 2. Figures 6 and 7 are a top view and a cross-sectional view of the second substrate used in the manufacture of the sealed package shown in Figures 1 and 2.

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

The first substrate 11 is, for example, a component substrate mainly provided with an electronic component portion 13. The second substrate 12 is, for example, a sealing substrate mainly used for sealing. The electronic component portion 13 is provided on the first substrate 11. The first substrate 11 and the second substrate 12 are arranged in a manner facing each other and are connected with a sealing layer 15 arranged in a frame shape therebetween.

Examples of the first substrate 11 and the second substrate 12 include a glass substrate, a substrate with a metal film formed on the surface, and the like. As the glass substrate, a soda-lime glass substrate, an alkali-free glass substrate, etc. can be used. Examples of the soda-lime glass substrate include AS, PD200 (both trade names, manufactured by AGC Corporation), and those obtained by chemical strengthening. Examples of the alkali-free glass substrate include AN100 (trade name, manufactured by AGC Corporation), EAGLE2000 (trade name, manufactured by Corning Corporation), EAGLE XG (trade name, manufactured by Corning Corporation), JADE (trade name, manufactured by Corning Corporation), and JADE (trade name, manufactured by Corning Corporation). name), #1737 (manufactured by Corning Corporation, trade name), OA-10 (manufactured by Nippon Electric Glass Co., Ltd., trade name), TEMPAX (manufactured by SCHOTT Corporation, trade name), etc. Examples of the substrate having a metal film formed on its surface include a glass substrate having a Ti-containing film formed on its surface. Furthermore, the material of the substrate is not particularly limited and can be a publicly known material. Furthermore, when the metal film is a multilayer film, it is preferable that the surface 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 component 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 if it is a solar cell. Element (dye-sensitized photoelectric conversion unit element). The electronic component part 13 can be composed of various known structures, and is not limited to the structure shown in the figure.

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

When the electronic component part 13 is an OEL component or the like, a partial space remains between the first substrate 11 and the second substrate 12 . The space can be kept as it is, or filled with transparent resin, etc. The transparent resin may be in contact with the first substrate 11 and the second substrate 12 or may only be in contact with them.

When the electronic component part 13 is a dye-sensitized solar cell element or the like, the electronic component part 13 is disposed entirely between the first substrate 11 and the second substrate 12 although not shown in the figure. Furthermore, the sealing object is not limited to the electronic component part 13, but may also be a photoelectric conversion device or the like. In addition, the sealed package 10 may be a building material such as multi-layer glass without the electronic component part 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; a laminated structure 213 laminated on the substrate 211 and having an anode 213a, an organic thin film layer 213b and a cathode 213c; and covering the laminated structure. The glass member 212 is placed on the substrate 211 so as to form the outer surface side of 213; and the sealing layer 215 connects the substrate 211 and the glass member 212. Moreover, this sealing layer 215 contains the glass composition of this embodiment mentioned above.

(Method of manufacturing sealed package) Next, an embodiment of a method for manufacturing a sealed package using the glass composition of the present embodiment will be described. Use the glass paste mentioned above when sealing. The glass paste is applied in a frame shape on the second substrate 12 and then dried to form a coating layer. Examples of coating methods include printing methods such as screen printing and gravure printing, and dispensing methods. Drying is performed to remove solvent, and is usually carried out at a temperature above 120°C for more than 10 minutes. If the solvent remains in the coating layer, the adhesive component may not be fully removed during subsequent calcination.

The coating layer is calcined to form the pre-calcined layer 15a (Figs. 6 and 7). Calcination 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 adhesive component, and then heating until the glass composition contained in the sealing material softens. temperature above the point.

On the first substrate 11, an electronic component portion 13 is provided according to the specification of the sealed package 10 (FIG. 4, FIG. 5).

Next, the second substrate 12 provided with the pre-baked layer 15 a and the first substrate 11 provided with the electronic component part 13 are arranged to face the pre-baked layer 15 a and are laminated ( FIGS. 3A and 3B ).

Thereafter, the precalcined layer 15a is irradiated with laser light 16 through the second substrate 12 to perform firing (FIG. 3C). The laser light 16 is irradiated while scanning along the frame-shaped precalcined layer 15a. By irradiating the precalcined layer 15a with laser light 16 all around, a frame-shaped sealing layer 15 is formed between the first substrate 11 and the second substrate 12. Furthermore, the laser light 16 can be irradiated to the precalcined layer 15a through the first substrate 11.

The type of laser light 16 is not particularly limited, and semiconductor lasers, carbon dioxide gas lasers, excimer lasers, YAG (Yttrium Aluminum Garnet) lasers, HeNe lasers and other lasers can be used. The irradiation conditions of the laser light 16 can be selected according to the thickness, line width, cross-sectional area in the thickness direction, etc. of the pre-calcined layer 15a. The output of the laser light 16 is preferably 2 W to 150 W. If the output of the laser light does not reach 2 W, there is a risk that the pre-calcined layer 15a will not melt. If the output of the laser light exceeds 150 W, cracks are likely to occur in the first substrate 11 and the second substrate 12. The output of the laser light 16 is more preferably 5 W to 120 W.

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

The method of performing the firing by irradiating the laser light 16 has been described above. However, the firing method is not limited to the method of performing the firing by irradiating the laser light 16 . As for the firing method, other methods may be used depending on the heat resistance of the electronic component part 13, the structure of the sealed package 10, and the like. For example, when the heat resistance of the electronic component part 13 is high, or when the electronic component part 13 is not provided, the entire assembly as shown in FIG. 3B is placed in a calcining furnace such as an electric furnace, including pre-calcining. The entire assembly of the layer 15a is heated instead of being irradiated with the laser light 16, thereby forming the sealing layer 15.

As mentioned above, the embodiment of the sealing package of this invention was demonstrated using an example, However, the sealing package of this invention is not limited to these. Within the scope that does not violate the gist of the present invention, the structure may be appropriately changed as necessary. [Example]

Hereinafter, the present invention will be further described in 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] (Manufacturing of glass compositions) The raw materials are prepared and mixed so that the compositions are as indicated in the glass composition columns of Tables 1 to 2 in mole %, and melted in a platinum crucible in an electric furnace at 1000 to 1100°C for 1 hour. The resulting molten liquid is formed into sheets by a water-cooled roller and then dry-ground by a ball mill. The sheets are passed through a sieve with a mesh size of 100, and the ones that pass through the sieve are used as glass compositions. The D ₅₀ of the glass compositions is measured using a Microtrac particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.), and the results are all within the range of 2 μm to 5 μm.

Next, the glass compositions were subjected to the following measurements and evaluations. In addition, in Tables 1 and 2, the "-" in the evaluation column indicates that no evaluation was performed because no crystallization peak was observed by DTA or no vitrification occurred.

(DTA test) The differential thermal analysis (DTA) device TG-DTA8122 manufactured by RIGAKU was used to conduct thermal analysis of the glass composition at a temperature rise rate of 10°C/min. The glass transition temperature Tg and the fourth inflection point were calculated based on the obtained DTA chart. Ts[℃], crystallization start temperature Tcs[℃], crystallization temperature Tcp[℃]. Furthermore, regarding the glass transition temperature Tg, the fourth inflection point Ts, the crystallization start temperature Tcs, and the crystallization temperature Tcp, the first inflection point of the DTA diagram is determined as Tg, the fourth inflection point is Ts, and the heat release The starting point of the peak is designated as Tcs, and the exothermic peak temperature is designated as Tcp. In addition, 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. Those with a value of (Tcs-Ts) greater than 100℃ are considered qualified.

(Thermal expansion coefficient (α)) Each glass composition was formed into a rectangular parallelepiped to obtain a sintered body for thermal expansion measurement. The sintered 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 sintered body for thermal expansion measurement was heated at a heating rate of 10°C/min using a thermal expansion meter ThermoplusEVO2 system TDL8411 manufactured by RIGAKU Corporation to calculate the thermal expansion coefficient α (unit: 10 ^-7 /°C) at 50 to 250°C. The results are shown in the table below. Those with a thermal expansion coefficient α of less than 91 were considered qualified.

(Flowability evaluation) 4 g of the glass composition was press-formed 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 450-460°C for 30 minutes according to the softening point of each glass composition to obtain a fired body for flowability evaluation. Then, for the obtained fired body for flowability evaluation, the angle was evenly divided into 4 parts, the diameters at 4 locations were measured, and the average value of the 4 diameters was calculated as the FB diameter (unit: mm). For each sample, the flowability, gloss, and the presence or absence of adhesion were evaluated according to the following criteria. The results are shown in the following table. Those with ○ in the evaluation of flowability and gloss were considered qualified. <Flowability> ○: FB diameter is 24 mm or more. ×: FB diameter is less than 24 mm. <Gloss> ○: The surface of the sintered body for fluidity evaluation has gloss as a whole. △: A part of the surface of the sintered body for fluidity evaluation has no gloss. ×: The surface of the sintered body for fluidity evaluation has no gloss as a whole.

(Water resistance evaluation) Glass sheets of each glass composition were placed in an environment of 121°C and 100%RH for 48 hours. The water resistance of the calcined bodies for water resistance evaluation after the placement was evaluated according to the following criteria. The results are shown in the table below. As the judgment result, the ○ was set as qualified. <Water resistance evaluation criteria> ○: No discoloration was observed on the entire surface of the calcined body for water resistance evaluation. △: Discoloration was observed on a part of the surface of the calcined body for water resistance evaluation. ×: The entire surface of the calcined body for water resistance evaluation was discolored.

[Table 1] Table 1 example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Glass composition [mol%] V ₂ O ₅ 36.0 36.0 36.0 37.5 34.5 33.5 29.0 33.5 29.0 36.5 36.0 36.0 36.0 36.0 39.5 34.5 36.0 37.0 40.0 _TeO2 26.0 25.5 26.0 28.0 26.5 27.0 28.0 26.5 29.0 26.5 26.0 26.0 26.0 26.0 27.0 21.5 27.0 28.0 26.0 ZnO 22.5 22.5 25.5 17.0 21.0 23.0 24.5 29.0 25.5 25.5 24.0 23.0 25.3 25.0 22.5 23.0 25.5 26.5 23.5 _{Nb2O5 ​} 5.5 5.5 6.5 6.5 6.5 6.0 6.5 6.0 6.5 7.5 6.5 6.5 6.5 6.3 5.5 6.5 4.5 4.5 5.0 Al ₂ O ₃ 3.5 2.5 3.5 3.0 2.5 2.5 3.0 2.0 3.0 2.5 2.5 2.5 3.3 3.5 2.5 3.5 2.0 2.0 3.5 BaO 0.5 0.5 0.5 2.0 4.0 0.5 1.0 0.5 1.0 0.5 0.5 0.5 0.5 0.5 0.5 0.5 3.0 2.0 2.0 _{B2O3 ​} 1.0 1.0 2.0 1.5 1.0 1.5 2.5 1.0 1.0 1.0 4.5 5.5 2.0 2.2 1.0 2.5 2.0 0.0 0.0 _{Bi2O3 ​} 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.4 0.0 0.0 4.5 0.0 0.0 0.0 ZrO ₂ 0.0 3.0 0.0 1.0 1.0 4.0 0.0 0.0 1.0 0.0 0.0 0,0 0.0 0.5 0.5 0.0 0.0 0.0 0,0 CuO 5.0 3.5 0.0 3.5 3.0 2.0 4.0 1.5 3.0 0.0 0.0 0.0 0.0 0.0 1.0 3.5 0.0 0.0 0.0 _MnO2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 _{Fe2O3 ​} 0.0 0.0 0.0 0.0 0.0 0.0 1.5 0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0,0 SiO ₂ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 MgO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CaO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0,0 0.0 0.0 0.0 SrO 0.0 0.0 0.0 0.0 0.0 0.0 0,0 0.0 0.0 0.0 0.0 0.0 0,0 0.0 0.0 0.0 0.0 0.0 0,0 _{P2O5 ​} 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0,0 0,0 0.0 0.0 0.0 0.0 0.0 SUM 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 V ₂ O ₅ ＋TeO ₂ ＋ZnO 84.5 84.0 87.5 82.5 82.0 83.5 81.5 89.0 83.5 88.5 86.0 85.0 87.3 87.0 89.0 79.0 88.5 91.5 89.5 V ₂ O ₅ /TeO ₂ 1.4 1.4 1.4 1.3 1.3 1.2 1.0 1.3 1.0 1.4 1.4 1.4 1.4 1.4 1.5 1.6 1.3 1.3 1.5 _{Bi2O3 ＋ TeO2} ＋BaO 26.5 26.0 26.5 30.0 30.5 27.5 29.0 27.0 30.0 27.0 26.5 26.5 26.9 26.5 27.5 26.5 30.0 30.0 28.0 Al ₂ O ₃ ＋ZrO ₂ 3.5 5.5 3.5 4.0 3.5 6.5 3.0 2.0 4.0 2.5 2.5 2.5 3.3 4.0 3.0 3.5 2.0 2.0 3.5 Vitrification ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ DTA test [℃] DTA_Tg 317 316 313 311 324 322 340 310 339 309 331 303 311 313 298 326 298 297 298 DTA_Ts 369 372 374 366 381 383 397 373 395 370 393 364 372 372 352 374 358 356 357 DTA_Tcs 483 494 494 484 522 499 509 - 509 475 520 502 499 508 477 467 - - - DTA_Tcp 502 499 506 500 527 513 524 - 524 493 532 509 504 511 484 478 - - - Tcs－Ts 113 122 120 117 141 116 111 ＞600 114 105 127 138 128 137 125 93 ＞600 ＞600 ＞600 TMA test [×10 ^-7 /℃] TMA_α (50℃-250℃) 83 85 86 88 90 85 83 89 87 88 81 88 86 86 90 85 98 95 91 Liquidity Assessment Fluidity(mm) 26.5 25.5 24.8 25.8 25.2 24.1 23.6 27.1 23.5 26.6 25.3 25.5 25.6 25.5 27.9 19.7 28.1 29.7 29.2 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ ○ ○ Gloss ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Water resistance evaluation ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × × ×

[Table 2] Table 2 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Glass composition [mol%] V ₂ O ₅ 34.0 35.5 42.3 30.0 32.0 32.5 36.0 36.0 33.5 41.5 24.0 32.5 34.5 47.0 31.0 34.4 33.0 36.0 _TeO2 26.0 26.5 26.1 35.0 25.0 23.0 26.5 26.0 27.0 28.0 26.0 26.5 28.0 26.0 26.5 26.0 28.5 26.0 ZnO 29.0 27.5 19.1 26.0 33.0 32.0 23.0 23.0 26.0 13.0 38.0 30.5 24.0 18.5 28.0 29.0 24.4 22.0 Nb ₂ O ₅ 6.5 8.5 4.0 6.0 6.5 7.0 6.0 5.5 6.5 6.5 6.0 5.5 6.0 6.5 7.0 6.5 6.0 6.5 Al ₂ O ₃ 2.0 1.0 4.1 2.0 2.5 3.5 1.0 0.0 2.0 1.0 3.5 2.0 6.0 1.0 4.0 2.0 3.5 2.5 BO 0.5 0.0 0.0 0.0 0.0 0.0 0.5 0.5 0.5 6.0 0.5 0.5 0.5 0.0 1.0 0.5 2.5 0.5 B ₂ O ₃ 1.0 1.0 0.0 1.0 1.0 2.0 1.0 1.0 0.0 0.0 2.0 1.0 1.0 1.0 0.0 1.0 0.5 6.5 Bi ₂ O ₃ 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 4.5 0.0 0.0 0.0 0.0 0.0 1.5 0.6 0.6 0.0 ZrO ₂ 0.0 0.0 0.0 0.0 0.0 0.0 5.0 7.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 CuO 0.0 0.0 0.0 0.0 0.0 0.0 1.0 1.0 0.0 4.0 0.0 1.5 0.0 0.0 0.0 0.0 0.0 0.0 MnO ₂ 0.0 0.0 2.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Fe ₂ O ₃ 0.0 0.0 1.5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0 SiO ₂ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 MgO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CaO 0.0 0.0 0.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0-0 0.0 0.0 0.0 0.0 sO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 P ₂ O ₅ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 SUM 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 V ₂ O ₅ ＋TeO ₂ ＋ZnO 89.0 89.5 87.5 91.0 90.0 87.5 85.5 85.0 86.5 82.5 88.0 89.5 86.5 91.5 85.5 89.4 85.9 84.0 V ₂ O ₅ /TeO ₂ 1.3 1.3 1.6 0.9 1.3 1.4 1.4 1.4 1.2 1.5 0.9 1.2 1.2 1.8 1.2 1.3 1.2 1.4 Bi ₂ O ₃ +TeO ₂ +BaO 27.5 26.5 26.1 35.0 25.0 23.0 27.0 26.5 32.0 34.0 26.5 27.0 28.5 26.0 29.0 27.1 31.6 26.5 Al ₂ O ₃ +ZrO ₂ 2.0 1.0 4.1 2.0 2.5 3.5 6.0 7.0 2.0 1.0 3.5 2.0 6.0 1.0 5.0 2.0 3.5 2.5 vitrification ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ ○ ○ ○ ○ ○ ○ DTA test[℃] DTA_Tg 312 302 300 315 322 320 309 316 296 295 - 316 312 273 321 313 327 301 DTA_Ts 374 365 360 376 385 383 371 376 355 348 - 375 373 322 384 373 385 362 DTA_Tcs 498 452 - 486 488 476 511 498 - 431 - 505 433 378 444 498 511 501 DTA_Tcp 515 464 - 501 504 491 520 514 - 441 - 520 445 421 457 504 525 508 Tcs-Ts 124 87 >600 110 103 92 141 122 >600 83 - 130 60 56 60 125 126 139 TMA test [×10 ^-7 /℃] TMA_α (50℃-250℃) 91 85 90 91 84 80 83 89 93 99 - 88 90 92 87 87 91 90 Liquidity assessment Liquidity(mm) 25.3 26.5 26.2 24.4 23.1 22.8 24.9 27.9 24.9 15.2 - 25.6 26.3 16.5 24.3 25.3 23.5 26.3 ○ ○ ○ ○ ○ × ○ ○ ○ × - ○ ○ × ○ ○ ○ ○ gloss △ × × ○ ○ ○ ○ ○ ○ ○ - ○ × × ○ ○ ○ ○ Water resistance assessment ○ × × × × × △ × ○ ○ - × ○ × ○ × × ×

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

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

This application is based on Japanese Patent Application 2022-122837 filed on August 1, 2022, and the contents are incorporated herein by reference.

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

Figure 1 shows a front view of one embodiment of the hermetic package. FIG. 2 is a cross-sectional view of the sealed package shown in FIG. 1 along line A-A. FIG. 3A is a step diagram showing one embodiment of a method for manufacturing a sealed package. FIG. 3B is a step diagram showing one embodiment of a method for manufacturing a sealed package. FIG. 3C is a step diagram showing one embodiment of a method for manufacturing a sealed package. FIG. 3D is a step diagram showing an embodiment of a method for manufacturing a sealed package. FIG. 4 is a top view of the first substrate used in manufacturing the sealed package shown in FIG. 1 . FIG. 5 is a cross-sectional view of the first substrate shown in FIG. 4 taken along line B-B. FIG. 6 is a top view of the second substrate used in manufacturing the hermetic package shown in FIG. 1 . FIG. 7 is a cross-sectional view along line C-C of the second substrate shown in FIG. 6 . Figure 8 is a conceptual diagram of an organic electroluminescent device as an example of a sealed package.

10: Sealed packaging

11: 1st substrate

12: 2nd substrate

13: Electronic components department

15: Sealing layer

Claims (10)

A glass composition is characterized by containing, expressed in mole % on an oxide basis, _25.0-40.0 % of _V2O5 , 25.5-30.0% of TeO2, 15.0-30.0% of ZnO, _5.5-8.0 % of _{Nb2O5 , 0-5.0% of Al2O3, 0-4.5% of BaO, 0-6.0% of B2O3 , 0-0.4 %} of _{Bi2O3 ,} and 0-4.5% of _ZrO2 , and substantially containing no alkali metal oxides and _PbO . The glass composition of claim 1, which contains 1.0-5.0% B ₂ O ₃ expressed as mole % on an oxide basis. A glass composition as claimed in claim 1 or 2, containing more than 6.2% Nb ₂ O ₅ expressed as mole % on an oxide basis. A glass composition as claimed in claim 1 or 2, wherein the total content of V ₂ O ₅ , TeO ₂ and ZnO represented by (V ₂ O ₅ +TeO ₂ +ZnO) is 80-91% expressed in mole % on an oxide basis. For example, the glass composition of claim 1 or 2, wherein the content ratio (V ₂ O ₅ /TeO ₂ ) expressed in mol% on an oxide basis is 1.0 to 1.6. For example, the glass composition of claim 1 or 2, in which the total content of Bi ₂ O ₃ , TeO ₂ and BaO expressed as mol% on an oxide basis (Bi ₂ O ₃ + TeO ₂ + BaO) is 25.5 to 31.0 %. A glass composition as claimed in claim 1 or 2, wherein the total content of Al ₂ O ₃ and ZrO ₂ represented by (Al ₂ O ₃ +ZrO ₂ ) is 0 to 7.0% expressed in mole % on an oxide basis. A glass paste containing the glass composition according to any one of claims 1 to 7, and an organic vehicle. A sealed package having a first substrate, a second substrate disposed opposite to the first substrate, and a device disposed between the first substrate and the second substrate and bonded to the first substrate and the second substrate the sealing layer; and The above-mentioned sealing layer includes the glass composition according to any one of claims 1 to 7. An organic electroluminescent element comprising: a substrate; a laminated structure laminated on the substrate and having an anode, an organic thin film layer, and a cathode; and a laminated structure placed on the substrate to cover the outer surface side of the laminated structure. a glass member; and a sealing layer connecting the above-mentioned substrate and the above-mentioned glass member; and The above-mentioned sealing layer includes the glass composition according to any one of claims 1 to 7.