CN113105117A

CN113105117A - Glass composition, glass powder, sealing material, glass paste, sealing method, sealed package, and organic electroluminescent element

Info

Publication number: CN113105117A
Application number: CN202110355193.2A
Authority: CN
Inventors: 渡边智之; 川浪壮平
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2018-12-11
Filing date: 2019-12-11
Publication date: 2021-07-13
Also published as: CN111302629B; CN111302629A; KR20200071675A

Abstract

The invention aims to provide a glass composition and a glass powder which have excellent bonding strength and strength when used for a sealing material and can obtain a sealing material with low-temperature sealing property. The glass composition is substantially free of alkali metal oxides and contains 10.0 to 50.0% of V in terms of mole% based on oxides₂O₅14.5 to 45.0 percent of TeO₂5.0 to 45.0 percent of ZnO and 0.5 to 20.0 percent of Bi₂O₃。

Description

Glass composition, glass powder, sealing material, glass paste, sealing method, sealed package, and organic electroluminescent element

The present application is a divisional application of the invention application having application No. 201911265188.1, application date 2019, 12/11/h, and the invention name "glass composition, glass powder, sealing material, glass paste, sealing method, sealed package, and organic electroluminescent element".

Technical Field

The invention relates to a glass composition, a glass powder, a sealing material, a glass paste, a sealing method, a sealed package and an organic electroluminescent element.

Background

Flat panel Display devices (FPDs) such as Organic Electro-Luminescence displays (OELDs) and Plasma Display Panels (PDPs) have a structure in which a light-emitting element is sealed by a glass package in which 1 pair of glass substrates are sealed. In addition, a Liquid Crystal Display (LCD) has a structure in which liquid crystal is sealed between 1 pair of glass substrates. In addition, a solar cell such as an organic thin film solar cell or a dye-sensitized solar cell has a structure in which a solar cell element (photoelectric conversion element) is sealed between 1 pair of glass substrates.

Among them, in the organic EL display, since the light emission characteristics of the organic EL element are significantly deteriorated due to contact with moisture, it is necessary to shield the organic EL element from the outside air tightly. In addition, since the organic EL element is damaged when exposed to high temperature, a sealing method is extremely important.

Therefore, as a sealing method of an organic EL display, a method of using glass powder for a sealing material and sealing by local heating is considered promising. The glass powder is obtained by pulverizing a glass composition, and is usually used by mixing the glass powder with an organic vehicle to prepare a paste. This paste is applied to one glass substrate by screen printing, dispensing, or the like, and fired to form a temporary firing layer. Next, another glass substrate is stacked, and the temporary baked layer is locally heated by a laser or the like to melt the glass powder and seal it.

As described above, patent document 1 describes a glass composition used as a sealing material, for example, TeO applied to sealing of an organic EL display₂－ZnO－B₂O₃A glass composition of the present invention. Patent document 2 discloses V₂O₅－ZnO－TeO₂A glass composition of the present invention.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 6357937

Patent document 2: japanese patent No. 6022070

Disclosure of Invention

In recent years, with diversification of the shape of display panels, the sealed display panels are sometimes subjected to processing such as cutting and polishing at the sealed portion and the periphery thereof. However, when such processing is performed, peeling is likely to occur at the sealed portion, and thus the yield is lowered. In order to solve this problem, it is required to improve the sealing strength.

The sealing strength of the sealing material using the glass powder is mainly controlled by the bonding strength between the sealing material and the glass substrate (hereinafter, also simply referred to as "bonding strength"), the strength of the sealing material itself, and the magnitude of thermal stress (residual stress) accumulated in the sealing material.

In particular, since the adhesion strength is controlled by the reaction between the sealing material and the glass substrate, it is preferable that the sealing material contains a component having high reactivity with the glass substrate in order to increase the adhesion strength.

Further, since thermal stress is accumulated mainly in the process of cooling the heated sealing material from the vicinity of the glass transition point to room temperature, it is preferable to use a sealing material having a low glass transition point and capable of sealing at a low temperature, that is, having low-temperature sealing properties, in order to suppress the thermal stress.

Therefore, a sealing material having reactivity with a substrate, high strength, and low-temperature sealing properties is desired.

However, the glass transition point of the glass composition described in patent document 1 is about 350 ℃ or higher. Therefore, a sealing material containing the glass composition has a large residual stress after sealing, and the sealing strength is not sufficient.

In addition, the glass composition described in patent document 2 has a low glass transition point, but has insufficient reactivity with a substrate and insufficient strength, and therefore, has insufficient sealing strength.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a glass composition and a glass powder which are excellent in adhesion strength and strength when used for a sealing material and which can provide a sealing material having low-temperature sealing properties.

Further, the present invention aims to provide a sealing material and a glass paste containing the glass powder, a sealing method using them, and a sealed package and an organic electroluminescent element having a sealing layer containing the glass composition.

The present inventors have found that the above problems can be solved by a glass composition having a glass composition in a specific range, and have completed the present invention.

The invention provides a glass composition, a glass powder, a sealing material, a glass paste, a sealing method, a sealed package and an organic electroluminescent element.

[1]A glass composition which contains substantially no alkali metal oxide and contains 10.0 to 50.0% of V in terms of mol% based on the oxide₂O₅14.5 to 45.0 percent of TeO₂5.0 to 45.0 percent of ZnO and 0.5 to 20.0 percent of Bi₂O₃。

[2]According to the above [1]The glass composition contains 15.0 to 45.0% of V in terms of mol% based on oxides₂O₅16.0 to 40.0% of TeO₂10.0 to 40.0% of ZnO and 1.0 to 15.0% of Bi₂O₃。

[3]According to the above [1]Or [ 2]]The glass composition contains 20.0 to 40.0% of V in terms of mol% based on oxides₂O₅18.0 to 35.0% of TeO₂15.0 to 35.0% of ZnO and 1.5 to 10.0% of Bi₂O₃。

[4]According to the above [1]～[3]The glass composition according to any of the preceding claims, wherein V is 25.0 to 35.0% in mol% on an oxide basis₂O₅20.0 to 30.0% of TeO₂20.0 to 30.0% of ZnO and 2.0 to 7.0% of Bi₂O₃。

[5]According to the above [1]～[4]The glass composition according to any of the above items, wherein CuO and Fe are further represented by mol% based on oxides₂O₃And the total of MnO content (CuO + Fe)₂O₃+ MnO) is 1.0 to 10.0%, and 0.5 to 10.0% of B₂O₃。

[6]According to the above [1]～[5]The glass composition according to any of the above items, wherein CuO and Fe are further represented by mol% based on oxides₂O₃And the total of MnO content (CuO + Fe)₂O₃+ MnO) is 2.0 to 8.0% and contains 1.0 to 7.5% of B₂O₃。

[7]According to the above [1]～[6]The glass composition according to any of the above items, wherein CuO and Fe are further represented by mol% based on oxides₂O₃And the total of MnO content (CuO + Fe)₂O₃+ MnO) is 4.0 to 7.5% and contains 1.5 to 5.0% of B₂O₃。

[8]According to [ 5] above]～[7]The glass composition of any of the above, wherein CuO is contained in an amount corresponding to the amount of CuO and Fe₂O₃And the total of MnO content (CuO + Fe)₂O₃+ MnO) ratio { CuO/(CuO + Fe)₂O₃+ MnO) } is 30% or more.

[9]According to [ 5] above]～[8]The glass composition of any of the above, wherein CuO is contained in an amount corresponding to the amount of CuO and Fe₂O₃And the total of the contents of MnO (CuO + F)e₂O₃+ MnO) ratio { CuO/(CuO + Fe)₂O₃+ MnO) } is more than 50%.

[10]According to [ 5] above]～[9]The glass composition of any of the above, wherein CuO is contained in an amount corresponding to the amount of CuO and Fe₂O₃And the total of MnO content (CuO + Fe)₂O₃+ MnO) ratio { CuO/(CuO + Fe)₂O₃+ MnO) } is 70% or more.

[11]According to the above [1]～[10]The glass composition of any of the preceding claims, wherein the glass composition is represented by (V) in mol% on an oxide basis₂O₅/TeO₂) The content ratio is 0.5 to 2.5.

[12]According to the above [1]～[11]The glass composition of any of the preceding claims, wherein the glass composition is represented by (V) in mol% on an oxide basis₂O₅/TeO₂) The content ratio is 1.0 to 2.0.

[13]According to the above [1]～[12]The glass composition of any of the preceding claims, wherein V is expressed in mole percent on an oxide basis₂O₅、TeO₂And the total of ZnO contents (V)₂O₅+TeO₂+ ZnO) of 78.0 to 89.0%, and Al₂O₃And Nb₂O₅Total of contents of (Al)₂O₃+Nb₂O₅) 5.0 to 11.0%.

[14]According to the above [1]～[13]The glass composition of any of the preceding claims, wherein V is expressed in mole percent on an oxide basis₂O₅、TeO₂And the total of ZnO contents (V)₂O₅+TeO₂+ ZnO) of 79.0 to 88.0%, and Al₂O₃And Nb₂O₅Total of contents of (Al)₂O₃+Nb₂O₅) 6.0 to 10.0%.

[15] A glass powder having a volume-based 50% particle diameter in cumulative particle size distribution of 0.1 to 100 μm, which is composed of the glass composition according to any one of the above-mentioned items [1] to [14 ].

[16] A sealing material comprising the glass powder according to [15] above and at least one of a low-expansion filler and a laser absorbing substance.

[17] A glass paste comprising the glass powder according to [15] above and an organic vehicle.

[18] The glass paste according to the above [17], further comprising at least one of a low expansion filler and a laser absorbing substance.

[19] A sealing method comprising using the glass powder according to [15], the sealing material according to [16] or the glass paste according to [17] or [18] and heating the glass powder, the sealing material or the glass paste by laser irradiation to seal substrates to each other.

[20]A sealed package comprising a 1 st substrate, a 2 nd substrate disposed so as to face the 1 st substrate, and a sealing layer disposed between the 1 st substrate and the 2 nd substrate and bonding the 1 st substrate and the 2 nd substrate to each other, wherein the sealing layer comprises a glass composition which does not substantially contain an alkali metal oxide and contains 10.0 to 50.0% of V in terms of mole% based on the oxide₂O₅14.5 to 45.0 percent of TeO₂5.0 to 45.0 percent of ZnO and 0.5 to 20.0 percent of Bi₂O₃。

[21]An organic electroluminescent element includes a substrate, a laminated structure laminated on the substrate and having an anode, an organic thin film layer, and a cathode, a glass member covering an outer surface side of the laminated structure and placed on the substrate, and a sealing layer bonding the substrate and the glass member; the sealing layer contains a glass composition which is substantially free of an alkali metal oxide and contains 10.0 to 50.0% of V in terms of mol% based on the oxide₂O₅14.5 to 45.0 percent of TeO₂5.0 to 45.0 percent of ZnO and 0.5 to 20.0 percent of Bi₂O₃。

[22] The organic electroluminescent element according to [21], wherein the sealing layer contains a plurality of kinds of glasses having different compositions.

The glass composition of the present invention is excellent in adhesion strength and strength when used as a sealing material, and further, a sealing material having low-temperature sealing properties can be obtained.

Drawings

Fig. 1 is a conceptual diagram of a temporary fired layer obtained by temporarily firing a glass powder mixture.

Fig. 2 is a conceptual diagram of a sealing layer obtained by heating a glass powder mixture by laser irradiation or the like.

Fig. 3 is a front view showing one embodiment of the sealing package.

Fig. 4 is a cross-sectional view of the sealed package shown in fig. 3 taken along line a-a.

Fig. 5A is a process diagram showing an embodiment of a method for manufacturing a sealed package.

Fig. 5B is a process diagram showing an embodiment of a method for manufacturing a sealed package.

Fig. 5C is a process diagram showing an embodiment of a method for manufacturing a sealed package.

Fig. 5D is a process diagram showing an embodiment of a method for manufacturing a sealed package.

Fig. 6 is a plan view showing the 1 st substrate used for manufacturing the sealed package shown in fig. 3.

Fig. 7 is a cross-sectional view of the 1 st substrate shown in fig. 6 taken along line B-B.

Fig. 8 is a plan view of the 2 nd substrate used in the manufacture of the sealed package shown in fig. 3.

Fig. 9 is a cross-sectional view of the 2 nd substrate shown in fig. 8 taken along line C-C.

Fig. 10 is a conceptual diagram of an organic electroluminescent element as an example of a sealing package.

Fig. 11 is a plan view of a glass substrate used for producing the test piece for strength evaluation in the example.

Fig. 12 is a cross-sectional view of the glass substrate shown in fig. 11 taken along line D-D.

FIG. 13 is a sectional view showing a test piece for strength evaluation in examples.

Fig. 14 is a plan view of a strength evaluation test piece having support substrates provided on both surfaces thereof.

FIG. 15 is a cross-sectional view taken along line E-E of the strength evaluation test piece provided with the supporting substrate shown in FIG. 14.

Fig. 16 is a diagram showing a method of measuring peel strength.

Fig. 17 is a plan view of a strength evaluation test piece having a supporting substrate provided on one surface thereof.

FIG. 18 is a sectional view taken along line F-F of the strength evaluation test piece provided with the supporting substrate shown in FIG. 17.

Fig. 19 is a diagram showing a method of measuring the falling ball strength.

Description of the symbols

10: sealing package, 11: 1: substrate, 12: 2: substrate, 13: electronic component part, 15: sealing layer, 15a: temporary baking layer, 16: laser, 30: test piece for strength evaluation, 31: glass substrate, 32: glass substrate, 35: sealing layer, 35a: temporary baking layer, 41: support substrate, 42: support substrate, 43: thermosetting adhesive, 46: support substrate, 47: heavy ball, 48: drop height, 100: sealing layer, 100a: temporary baking layer, 101: V: sealing layer₂O₅－TeO₂-ZnO glass, 102: Bi₂O₃－ZnO－B₂O₃Glass series 210, organic electroluminescent element 211, substrate 212, glass member 213, laminated structure 213, anode 213a, organic thin film layer 213b, cathode 213c, sealing layer 215

Detailed Description

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the embodiments described below. In the following drawings, members and portions that exhibit the same function are sometimes described with the same reference numerals, and redundant description may be omitted or simplified. The embodiments shown in the drawings are illustrated for clarity of the description of the present invention, and do not necessarily show actual dimensions or proportions.

< glass composition >

The glass composition of the present embodiment is substantially free of alkali metal oxide, and contains 10.0 to 50.0% of V in mol% based on the oxide₂O₅14.5 to 45.0 percent of TeO₂5.0 to 45.0 percent of ZnO and 0.5 to 20.0 percent of Bi₂O₃。

Next, each component of the glass composition of the present embodiment will be described. In the following description, unless otherwise specified, "%" of the contents of the respective components of the glass composition is expressed on an oxide basis, that is, in terms of oxide in mol%. In the present specification, "to" indicating a numerical range is used in a meaning including upper and lower limits.

If the glass composition used for the sealing material contains an alkali metal oxide, the alkali component diffuses into the sealed member such as a glass substrate during sealing or when the sealing material is exposed to high temperature after sealing, and the sealed member deteriorates. Therefore, the glass composition of the present embodiment does not substantially contain an alkali metal oxide. It should be noted that the term "substantially free" means that the term does not include such a meaning except for unavoidable impurities, i.e., that the term is not intentionally added. Therefore, the glass composition of the present embodiment may contain an alkali metal oxide in a minute amount as an unavoidable impurity. The content of the alkali metal oxide in the glass composition of the present embodiment is preferably 1000ppm or less, and more preferably 500ppm or less.

In the present specification, the alkali metal oxide means Li₂O、Na₂O and K₂And O. Further, ppm means mass ppm.

V₂O₅It is a glass-forming oxide, forms a network of glass, and is necessary as a low softening component. In addition, the composition is also effective as a laser light absorbing component. On the other hand, if V₂O₅When the content (b) is large, the water resistance is lowered, and the glass stability is lowered during the production of the glass, so that the glass may be easily devitrified. In addition, if V₂O₅If the content of (B) is too small, the glass transition point may be increased to deteriorate the low-temperature sealability. Thus, V₂O₅The content of (A) is 10.0-50.0%. V₂O₅The content of (b) is preferably 15.0% or more, more preferably 20.0% or more, further preferably 25.0% or more, and further preferably 45.0% or lessMore preferably 40.0% or less, and still more preferably 35.0% or less.

TeO₂For glass oxides, a glass network is formed, and is necessary as a low softening component. On the other hand, if TeO₂When the content (B) is large, the thermal expansion coefficient becomes large. If the amount is too small, the glass transition point may be increased to deteriorate the sealing property at low temperature, and the glass may be easily crystallized during sealing and baking. Thus, TeO₂The content of (A) is 14.5-45.0%. TeO₂The content of (b) is preferably 16.0% or more, more preferably 18.0% or more, further preferably 20.0% or more, and further preferably 40.0% or less, more preferably 35.0% or less, further preferably 30.0% or less.

ZnO is necessary as a component for lowering the thermal expansion coefficient. On the other hand, if the content of ZnO is large, the glass stability may be lowered during glass production, and the glass may be easily devitrified. In addition, if too small, the thermal expansion coefficient becomes large. Therefore, the content of ZnO is 5.0 to 45.0%. The content of ZnO is preferably 10.0% or more, more preferably 15.0% or more, further preferably 20.0% or more, and further preferably 40.0% or less, more preferably 35.0% or less, further preferably 30.0% or less.

Bi₂O₃Is a component which is easily reacted with a glass substrate at the time of sealing and improves the adhesive strength by forming a reaction layer. Thus, Bi₂O₃Is an important and essential component for the glass composition of the present embodiment. If Bi is present₂O₃If the content of (b) is small, the effect of improving the adhesive strength cannot be sufficiently obtained. On the other hand, if Bi₂O₃If the content (B) is too large, the glass transition point may be increased to impair the low-temperature sealing properties. Further, there is a possibility that SiO in the glass substrate reacts excessively with the glass substrate₂High melting point components such as these are introduced into the glass composition, so that the fixing point rises and the residual stress of the sealing material after sealing becomes large.

The inventors of the present invention have attempted to Bi₂O₃Relative to V₂O₅－TeO₂The amount of the-ZnO glass added was investigatedIt has been found that Bi can improve the adhesive strength while maintaining the low-temperature sealability₂O₃In a suitable amount. Based on this finding, in the glass composition of the present embodiment, Bi₂O₃The content of (A) is 0.5-20.0%. In addition, Bi₂O₃The content of (b) is preferably 1.0% or more, more preferably 1.5% or more, further preferably 2.0% or more, and further preferably 15.0% or less, more preferably 10.0% or less, further preferably 7.0% or less.

If V₂O₅And TeO₂Content ratio of (V)₂O₅/TeO₂) 0.5 to 2.5, in the presence of Bi₂O₃The glass composition as an essential component is preferably (V) because crystallization at the time of sealing firing can be suppressed and the glass can be stabilized₂O₅/TeO₂) More preferably 1.0 or more, and still more preferably 2.0 or less.

CuO is not necessarily required, but is a component having an effect of lowering the thermal expansion coefficient and an effect of improving the water resistance, and therefore, is preferably contained. In addition, the composition is also effective as a laser light absorbing component. Therefore, by containing CuO, the amount of pigment to be added for the purpose of laser absorption can be reduced and instead a large amount of low expansion filler can be contained in the glass paste, so that a glass paste having a lower thermal expansion coefficient can be produced. On the other hand, if the content of CuO is large, crystallization is likely to occur during seal baking. Therefore, in order to sufficiently obtain the effect of laser absorption, the content of CuO is preferably 1.0% or more, more preferably 2.0% or more, and further preferably 5.0% or more. In order to avoid crystallization of the glass, the content of CuO is preferably 10.0% or less, more preferably 8.0% or less, and still more preferably 7.5% or less.

Fe₂O₃It is not essential, and may be contained because it is effective as a laser light absorbing component. By containing Fe₂O₃When the glass paste is produced, the amount of the pigment to be added for the purpose of laser absorption can be reduced and instead a large amount of the low-expansion filler can be contained, so that the thermal expansion coefficient can be producedLower glass paste. On the other hand, if Fe₂O₃When the content of (A) is large, the glass is likely to be crystallized during firing sealing, and the softening point of the glass is increased, resulting in deterioration of low-temperature sealing properties. Thus, Fe₂O₃The content of (b) is preferably 7.0% or less, more preferably 5.0% or less, and further preferably 2.0% or less. In addition, to obtain the effect of laser absorption, Fe₂O₃The content of (b) is preferably 1.0% or more. However, if CuO is contained, Fe is not contained₂O₃The above effects can be obtained.

MnO is not necessarily required, and may be contained because it is a component effective as a laser light absorption component. By containing MnO, 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 when producing a glass paste, and therefore, a glass paste having a lower thermal expansion coefficient can be produced. On the other hand, if the MnO content is large, the glass is easily crystallized at the time of baking sealing. Therefore, the content of MnO is preferably 7.0% or less, more preferably 5.0% or less, and further preferably 2.0% or less. In order to obtain the effect of laser absorption, the content of MnO is preferably 1.0% or more. However, if CuO or Fe is contained₂O₃The above-described effects can be obtained even if MnO is not included.

CuO and Fe for absorption of laser beam₂O₃And the total of MnO content (CuO + Fe)₂O₃+ MnO) is preferably 1.0% or more, more preferably 2.0% or more, even more preferably 4.0% or more, and even more preferably 5.0% or more. In order to avoid crystallization of the glass during laser firing sealing, the above-mentioned CuO and Fe₂O₃The total content of MnO and MnO is preferably 10.0% or less, more preferably 8.0% or less, and further preferably 7.5% or less.

CuO、Fe₂O₃Both MnO and MnO are effective components as laser light absorbing components, and a large amount of CuO is preferably contained from the balance between the effect of laser light absorption and avoidance of crystallization of glass. Specifically, if the content of CuO is relative to the above-mentioned CuO and Fe₂O₃And the content of MnOMeter (CuO + Fe)₂O₃+ MnO) ratio { CuO/(CuO + Fe)₂O₃+ MnO) } is 30% or more, so that the low-temperature sealing property of the glass can be maintained and crystallization of the glass can be avoided, and is preferably 50% or more, and more preferably 70% or more.

B₂O₃It is not necessarily a glass oxide and is a component for forming a glass network and improving glass stability, and therefore, it is preferably contained. On the other hand, if B₂O₃When the content of (b) is large, the glass becomes unstable and is easily crystallized during sealing firing. Therefore, to stabilize the glass, B₂O₃The content of (b) is preferably 0.5% or more, more preferably 1.0% or more, and further preferably 1.5% or more. In addition, to avoid the excessive inclusion of B₂O₃The resultant crystallization of the glass is preferably 10.0% or less, more preferably 7.5% or less, and further preferably 5.0% or less.

BaO is not essential, and is an effective component for stabilizing the glass, and may be contained in the glass composition of the present embodiment, and the content is preferably 2.0% or more in some cases. On the other hand, in order to keep the glass transition point and the thermal expansion coefficient within appropriate ranges, the content of BaO in the glass composition of the present embodiment is preferably 10.0% or less, and more preferably 8.0% or less.

Al₂O₃And Nb₂O₅It is not essential, but has an effect of lowering the thermal expansion coefficient and an effect of improving the water resistance, and may be contained in the glass composition of the present embodiment. Make Al₂O₃And/or Nb₂O₅The content of each of the glass compositions in the present embodiment is preferably 2.0% or more. On the other hand, in order to maintain the glass transition point in an appropriate range, Al is used₂O₃And/or Nb₂O₅The content of each of the components contained in the glass composition of the present embodiment is preferably 10.0% or less, and more preferably 8.0% or less.

If V₂O₅、TeO₂And the total of ZnO contents (V)₂O₅+TeO₂+ ZnO) of 78.0 to 89.0%, and Al₂O₃And Nb₂O₅Total of contents of (Al)₂O₃+Nb₂O₅) Preferably 5.0 to 11.0%, since both water resistance and glass stabilization are easy to achieve. For the same reason, (V)₂O₅+TeO₂+ ZnO) is more preferably 79.0% or more, and still more preferably 88.0% or less. In addition to (Al)₂O₃+Nb₂O₅) More preferably 6.0% or more, and still more preferably 10.0% or less.

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

The glass composition of the present embodiment may contain CaO or TiO₂、ZrO₂、CeO₂、La₂O₃、CoO、MoO₃、Sb₂O₃、WO₃、GeO₂And the like as other components.

In addition, the glass composition of the present embodiment preferably contains substantially no lead, that is, PbO, in order to reduce the load on the environment.

The glass composition of the present embodiment is preferable because the low-temperature sealability becomes good when the glass transition point (hereinafter, referred to as "Tg") is 350 ℃ or lower. The Tg is more preferably 330 ℃ or lower. The Tg of the glass composition can be measured using a differential thermal analyzer.

The method for producing the glass composition of the present embodiment is not particularly limited. For example, the present invention can be manufactured by the following method.

First, a raw material mixture is prepared. The raw material is not particularly limited as long as it is a raw material used for producing a general oxide-based glass, and an oxide, a carbonate, or the like can be used. The raw material mixture is prepared by appropriately adjusting the kind and the ratio of the raw materials so that the composition of the obtained glass composition falls within the above range.

Next, the raw material mixture is heated by a known method to obtain a melt. The temperature for heating and melting (melting temperature) is preferably 1000 to 1200 ℃, more preferably 1050 ℃ or higher, and further preferably 1150 ℃ or lower. The time for heating and melting is preferably 30 to 90 minutes.

Then, the melt is cooled and solidified, whereby the glass composition of the present embodiment can be obtained. The cooling method is not particularly limited. A roll mill or a press may be used, and a method of quenching by dropping a cooling liquid or the like may be used. The resulting glass composition is preferably completely amorphous, i.e., has a degree of crystallinity of 0%. However, the crystallized portion may be included within a range not to impair the effects of the present invention.

The glass composition of the present embodiment thus obtained may be in any form. For example, the material may be in the form of a block, a plate, a sheet (flake), a powder, or the like.

When the glass composition of the present embodiment is used as a sealing material, the glass composition is preferably a glass powder. In the evaluation of the above properties of the glass composition, the glass powder is preferred from the viewpoint of observing the performance as a sealing material.

< glass powder >

The glass powder of the present embodiment is a glass powder composed of the glass composition of the present embodiment. The glass powder composed of the glass composition of the present embodiment means that the average composition of the glass powder is the same as the composition of the glass composition of the present embodiment. That is, the glass powder of the present embodiment may be composed of glass powders of 1 composition having the same composition as the glass composition of the present embodiment, or may be a glass powder obtained by mixing a plurality of types of glass powders having different compositions so that the average composition is the same composition as the glass composition of the present embodiment. For convenience, a glass powder composed of a plurality of glass powders having different compositions is hereinafter referred to as a "glass powder mixture".

The particle size of the glass powder of the present embodiment can be appropriately selected according to the application. In the case of a sealing material, which is a typical application of the glass powder of the present embodiment, the particle size of the glass powder is preferably 0.1 to 100 μm.

Further, if the particle size of the glass powder of the present embodiment is large, precipitation separation is easy to occur when pasting, coating, and drying are performed, and there is a problem that the thickness of the obtained sealing layer increases. Therefore, when the glass powder of the present embodiment is used by being gelatinized, the particle size of the glass powder is preferably in the range of 0.1 to 5.0. mu.m, and more preferably 0.1 to 2.0. mu.m.

In the present specification, "particle size" means a volume-based 50% particle diameter (D) in a cumulative particle size distribution₅₀) Specifically, the particle diameter refers to the particle diameter at which the cumulative amount of the particle diameter distribution measured by using the laser diffraction/scattering particle size distribution measuring apparatus is 50% on a volume basis in the cumulative particle diameter curve of the particle diameter distribution.

The glass powder is obtained by, for example, pulverizing a glass composition. Therefore, the particle size of the glass powder can be adjusted by the conditions of pulverization. Examples of the method of pulverization include a rotary ball mill, a vibration ball mill, a planetary mill, a jet mill, an attritor, a media-stirring mill (bead mill), a jaw crusher, a roll crusher, and the like.

In particular, when the particle size is as small as 5.0 μm or less, wet grinding can be used. Wet pulverization is carried out in a solvent such as water or alcohol using a medium composed of alumina or zirconia or a bead mill.

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

The respective compositions of the glass powders having different compositions constituting the glass powder mixture are not particularly limited, and the glass powder mixture of the present embodiment can be prepared by mixing an appropriate kind of glass powder so that the average composition is the same as that of the glass composition of the present embodiment described above. The glass powder mixture may be composed of 2 kinds of glass powders having different compositions, or may be composed of 3 or more kinds of glass powders having different compositions.

In the production of a glass paste containing a glass powder mixture, glass powders may be mixed to prepare a glass powder mixture, and then the glass powder mixture may be gelatinized, or a plurality of pastes containing glass powders having different compositions may be mixed.

For example, by adding V as a base component₂O₅－TeO₂Bi is added to-ZnO glass powder₂O₃－ZnO－B₂O₃The glass powder mixture of the present embodiment can be obtained from the glass powder of the present embodiment. The base component is contained in an amount of 50 vol% or more based on the total volume of the glass powder mixture. V relative to the total volume of the glass powder mixture₂O₅－TeO₂The content of the — ZnO-based glass powder is more preferably 70 vol% or more, and still more preferably 99.9 vol% or less.

V as a base component in the above glass powder mixture₂O₅－TeO₂The glass transition point of the-ZnO based glass is generally low. Bi as an additive component in the above glass powder mixture₂O₃－ZnO－B₂O₃Glass of the series generally and V₂O₅－TeO₂Bi having a higher glass transition point than that of ZnO-based glass and having high reactivity with a glass substrate₂O₃. Therefore, the sealing material obtained using the glass powder mixture described above exhibits high sealing strength. The sealing material obtained using the glass powder mixture will be described in detail below.

First, when a sealing material using the glass powder mixture is temporarily fired, it is preferable to use a glass powder mixture having a V ratio as a base component₂O₅－TeO₂The ZnO-based glass is heated at a temperature of about 30 to 60 ℃ of the softening point. If the temporary calcination is carried out at such a temperature, Bi can be obtained as shown in FIG. 1₂O₃－ZnO－B₂O₃The glass 102 is dispersed in the softened V₂O₅－TeO₂In the-ZnO based glass 101The layer 100a is temporarily fired.

Next, when the temporary firing layer 100a is fired by heating by laser irradiation or the like, it is preferable that Bi is added as an additive to the temporary firing layer 100a₂O₃－ZnO－B₂O₃The glass is heated to a temperature at which the glass is sufficiently melted. It is considered that Bi is contained if the firing is carried out at such a temperature₂O₃－ZnO－B₂O₃The entire system glass 102 is melted to obtain V as a base component as shown in FIG. 2₂O₅－TeO₂Part of-ZnO glass 101 and Bi as an additive component₂O₃－ZnO－B₂O₃ A sealing layer 100 in which a portion of the glass 102 is mixed.

The sealing layer 100 is formed of V as a base component₂O₅－TeO₂The residual stress after cooling to room temperature is small because of the low glass transition point of the ZnO glass, and Bi contained in the additive component₂O₃High reactivity and excellent adhesive strength. Therefore, the sealing layer 100 is excellent in sealing strength.

In fig. 2, V is₂O₅－TeO₂Part of-ZnO glass 101 and Bi₂O₃－ZnO－B₂O₃The portions of the glass 102 are clearly separated, but fig. 2 is a schematic view, and the boundaries of these portions in the sealing layer 100 are not necessarily clear. Heating the temporary baked layer 100a by laser irradiation or the like to Bi₂O₃－ZnO－B₂O₃When the glass 102 is melted, Bi is added₂O₃－ZnO－B₂O₃Is glass 102 and V₂O₅－TeO₂These glasses are mixed near the interface of the ZnO glass 101. Thus, in the resulting sealing layer, V₂O₅－TeO₂The part of the-ZnO glass 101 may contain Bi₂O₃－ZnO－B₂O₃Is a glass of Bi₂O₃－ZnO－B₂O₃The portion of the glass 102 may contain V₂O₅－TeO₂-ZnO glass.

< glass paste >

When the glass powder of the present embodiment described above is used as a sealing material, the glass powder may be used in its original form, but a sealing material mixed with a low expansion filler and/or a laser absorbing substance may be used depending on the sealing method. In addition, from the viewpoint of improving workability, the glass powder and the sealing material are preferably used by being gelatinized.

The glass paste of the present embodiment contains the glass powder of the present embodiment or a mixture of the glass powder and a low-expansion filler and/or a laser absorbing substance, and an organic vehicle. The low-expansion filler, the laser absorbing substance, and the organic vehicle will be described below. In this description, "sealing material or mixture" is collectively referred to as "mixture".

The low expansion filler has a thermal expansion coefficient lower than that of the glass composition and approximately has a thermal expansion coefficient of-15 to 45 x 10^－7Coefficient of thermal expansion of the order of/° c. The low thermal expansion filler material is added for the purpose of lowering the thermal expansion coefficient of the sealing layer.

The low-expansion filler is not particularly limited, and is preferably at least 1 selected from the group consisting of silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate compounds, soda lime glass, and borosilicate glass. As the zirconium phosphate-based compound, there may be mentioned (ZrO)₂P₂O₇、NaZr₂(PO₄)₃、KZr₂(PO₄)₃、Ca_0.5Zr₂(PO₄)₃、NbZr(PO₄)₃、Zr₂(WO₃)(PO₄)₂And a complex compound thereof.

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

The content of the low expansion filler is set so that the thermal expansion coefficient of the sealing layer is close to the thermal expansion coefficient of the glass substrate as the sealed object. The content of the low-expansion filler is preferably 1 vol% or more, more preferably 5 vol% or more, and still more preferably 10 vol% or more based on the volume of the mixed material, that is, the total volume of the glass powder, the low-expansion filler, and the laser absorbing substance. On the other hand, if the content of the low expansion filler is too large, the fluidity of the sealing material at the time of melting becomes poor, and therefore, the content of the low expansion filler is preferably 50% by volume or less, more preferably 45% by volume or less, and further preferably 40% by volume or less, relative to the volume of the mixed material.

The laser absorbing material is not particularly limited, and may be CuO or Fe in addition to the above-mentioned constitution₂O₃Examples of the metal other than Cu, Fe, and Mn include at least 1 metal selected from Cr, Ni, and the like, and compounds (inorganic pigments) including oxides of the metals. The laser absorbing material may be a pigment other than these pigments.

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

If the content of the laser absorbing substance is too small, it may be difficult to sufficiently melt the sealing material by laser irradiation. Therefore, the content of the laser absorbing substance is preferably CuO or Fe₂O₃And the content of MnO satisfies the above range. The total content of the laser absorbing substances including other laser absorbing substances is preferably 0.1 vol% or more, more preferably 1 vol% or more, and still more preferably 3 vol% or more, based on the volume of the mixed material. On the other hand, if the content of the laser light absorbing substance is too large, the fluidity of the sealing material at the time of melting becomes poor, and the adhesive strength is thereby reduced. Therefore, the content of the laser light absorbing substance is preferably 20 vol% or less, more preferably 18 vol% or less, and further preferably 15 vol% or less, based on the volume of the mixed material.

As the organic vehicle, for example, a resin as a binder component dissolved in a solvent can be used.

Specifically, a resin such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, benzyl cellulose, propyl cellulose, or nitrocellulose is dissolved in a solvent such as terpineol, a dodecanol ester (Texanol), butyl carbitol acetate, or ethyl carbitol acetate, and can be used as the organic vehicle.

In addition, as the organic vehicle, a material obtained by dissolving an acrylic resin such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, or 2-hydroxyethyl (meth) acrylate in a solvent such as methyl ethyl ketone, terpineol, dodecanol ester, butyl carbitol acetate, or ethyl carbitol acetate can be used. In the present specification, the term (meth) acrylate refers to at least one of an acrylate and a methacrylate.

Further, as the organic vehicle, a solution of polyalkylene carbonate such as polyethylene carbonate or polypropylene carbonate in a solvent such as acetyl triethyl citrate, propylene glycol diacetate, diethyl succinate, ethyl carbitol acetate, triacetin, lauryl alcohol ester, dimethyl adipate, ethyl benzoate, a mixture of propylene glycol monophenyl ether and triethylene glycol dimethyl ether, or the like can be used.

The ratio of the resin and the solvent in the organic vehicle is not particularly limited, and is selected so that the viscosity of the organic vehicle can be adjusted to a viscosity capable of adjusting the viscosity of the glass paste. The ratio of the resin to the solvent in the organic vehicle is preferably about 3:97 to 30:70, in particular, in terms of the mass ratio of the resin to the solvent.

The ratio of the mixed material and the organic vehicle 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 vehicle is preferably about 65:35 to 90: 10. In addition to the mixing material and the organic vehicle, a known additive may be blended as necessary in the glass paste within limits not prejudicial to the object of the present invention.

The glass paste can be adjusted by a known method using a rotary mixer, a roll mill, a ball mill, or the like, which is provided with stirring blades.

< sealing Package >

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

Fig. 3 and 4 are a plan view and a cross-sectional view showing one embodiment of the sealing package. Fig. 5A to 5D are process views showing an embodiment of the method for manufacturing a sealed package shown in fig. 3. Fig. 6 and 7 are a plan view and a cross-sectional view of the 1 st substrate used for manufacturing the sealed package shown in fig. 3 and 4. Fig. 8 and 9 are a plan view and a cross-sectional view of the 2 nd substrate used for manufacturing the sealed package shown in fig. 3 and 4.

The sealing package 10 constitutes an FPD such as an OELD, a PDP, and an LCD, an illumination device (OEL illumination or the like) using a light emitting element such as an Organic Electroluminescent (OEL) element, or a solar cell such as a dye-sensitized solar cell.

That is, the sealing package 10 includes a 1 st substrate 11, a 2 nd substrate 12 disposed to face the 1 st substrate, and a sealing layer 15 disposed between the 1 st substrate and the 2 nd substrate and bonding the 1 st substrate and the 2 nd substrate to each other. The sealing layer 15 contains a glass composition which does not substantially contain an alkali metal oxide and contains 10.0 to 50.0% of V in terms of mol% based on the oxide₂O₅14.5 to 45.0 percent of TeO₂5.0 to 45.0 percent of ZnO and 0.5 to 20.0 percent of Bi₂O₃。

The 1 st substrate 11 is, for example, an element substrate mainly provided with an electronic element section 13. The 2 nd substrate 12 is, for example, a sealing substrate mainly used for sealing. The 1 st substrate 11 is provided with an electronic component section 13. The 1 st substrate 11 and the 2 nd substrate 12 are arranged to face each other, and are bonded to each other by a sealing layer 15 arranged in a frame shape.

The 1 st substrate 11 and the 2 nd substrate 12 may be a soda lime glass substrate, an alkali-free glass substrate, or the like. Examples of the soda-lime glass substrate include AS and PD200 (both manufactured by AGC corporation, trade name), and substrates obtained by chemically strengthening these. Further, the glass substrate was made of an alkali-free glass. Examples thereof include AN100 (trade name, manufactured by AGC corporation), EAGEL2000 (trade name, manufactured by Corning corporation), EAGELGX (trade name, manufactured by Corning corporation), JADE (trade name, manufactured by Corning corporation), #1737 (trade name, manufactured by Corning corporation), OA-10 (trade name, manufactured by Schott corporation), and Tempax (trade name, manufactured by Schott corporation).

The electronic element unit 13 includes an OEL element if OELD or OEL lighting, a plasma light emitting element if PDP, a liquid crystal display element if LCD, and a dye-sensitized solar cell element (dye-sensitized photoelectric conversion unit element) if solar cell, for example. The electronic component unit 13 may have various known configurations, and is not limited to the illustrated configuration.

In the sealed package 10 of fig. 3 and 4, an OEL element, a plasma light emitting element, or the like is provided as the electronic element portion 13 on the 1 st substrate 11. When the electronic element section 13 is a dye-sensitized solar cell element or the like, although not shown, an element film such as a wiring film or an electrode film is provided on the facing surface of each of the 1 st substrate 11 and the 2 nd substrate 12.

When the electronic component section 13 is an OEL element or the like, a part of the space remains between the 1 st substrate 11 and the 2 nd substrate 12. The space may be in an original state, or may be filled with a transparent resin or the like. The transparent resin may be bonded to the 1 st substrate 11 and the 2 nd substrate 12, or may be merely in contact with each other.

When the electronic element section 13 is a dye-sensitized solar cell element or the like, the electronic element section 13 is disposed on the entire region between the 1 st substrate 11 and the 2 nd substrate 12, although not shown. The object to be sealed is not limited to the electronic element portion 13, and may be a photoelectric conversion device or the like. The sealed package 10 may be a building material such as a double-glazing glass having no electronic component part 13.

Hereinafter, an organic electroluminescent element constituting an OELD will be described in detail with reference to fig. 10 as an example of a sealing package.

An organic electroluminescent element 210 obtained using the glass composition of the present embodiment includes a substrate 211, a layered structure 213 having an anode 213a, an organic thin film layer 213b, and a cathode 213c layered on the substrate 211, and a glass member 21 placed on the substrate 211 so as to cover the outer surface of the layered structure 2132, and a sealing layer 215 for bonding the substrate 211 and the glass member 212. In addition, the sealing layer 215 includes a glass composition containing 10.0 to 50.0% of V₂O₅14.5 to 45.0 percent of TeO₂5.0 to 45.0% of ZnO and 0.5 to 20.0% of Bi₂O₃。

< method for producing sealing package >

Next, an embodiment of a method for producing a sealed package using the glass composition of the present embodiment will be described.

The glass paste described above was used for sealing. The glass paste is applied in a frame shape to the 2 nd substrate 12, and then dried to form a coating layer. Examples of the coating method include printing methods such as screen printing and gravure printing, dispensing methods, and the like. Drying for removing the solvent is usually carried out at a temperature of 120 ℃ or higher for 10 minutes or more. If the solvent remains in the coating layer, the binder component may not be sufficiently removed by the subsequent provisional baking.

The coating layer is temporarily baked to form a temporary baked layer 15a (fig. 8 and 9). The temporary baking is performed by heating the coating layer to a temperature equal to or lower than the glass transition point of the glass composition contained in the sealing material to remove the binder component, and then heating the coating layer to a temperature equal to or higher than the softening point of the glass composition contained in the sealing material.

The 1 st substrate 11 is provided with an electronic component part 13 (fig. 6 and 7) according to the specification of the sealing package 10.

Next, the 2 nd substrate 12 provided with the temporary firing layer 15A and the 1 st substrate 11 provided with the electronic element portion 13 are arranged and laminated so as to face the temporary firing layer 15A (fig. 5A and 5B).

Then, the temporary firing layer 15a is irradiated with the laser beam 16 through the 2 nd substrate 12 and fired (fig. 5C). The laser beam 16 is irradiated along the frame-shaped temporary firing layer 15a while scanning. By irradiating the laser beam 16 over the entire periphery of the temporary firing layer 15a, a frame-shaped sealing layer 15 is formed between the 1 st substrate 11 and the 2 nd substrate 12. The laser beam 16 may irradiate the temporary baked layer 15a through the 1 st substrate 11.

The type of laser beam 16 is not particularly limited, and a semiconductor laser, a carbon dioxide laser, an excimer laser, a YAG laser, a HeNe laser, or the like can be used. The irradiation condition of the laser 16 may be selected according to the thickness, line width, cross-sectional area in the thickness direction, and the like of the temporary firing layer 15 a. The output power of the laser 16 is preferably 2 to 150W. If the output power of the laser is less than 2W, the temporary baking layer 15a may not melt. If the output power of the laser beam exceeds 150W, cracks and the like are likely to occur in the 1 st substrate 11 and the 2 nd substrate 12. The output power of the laser beam 16 is more preferably 5 to 120W.

In this manner, a sealing package 10 in which the electronic element portion 13 is hermetically sealed between the 1 st substrate 11 and the 2 nd substrate 12 by the sealing layer 15 can be manufactured (fig. 5D).

Although the method of firing by irradiation with the laser beam 16 has been described above, the method of firing is not necessarily limited to the method of firing by irradiation with the laser beam 16. The baking method may be other methods depending on the heat resistance of the electronic element portion 13, the structure of the sealing package 10, and the like. For example, when the heat resistance of the electronic element section 13 is high or when the electronic element section 13 is not provided, instead of irradiation with the laser beam 16, the entire assembly as shown in fig. 5B may be placed in a baking furnace such as an electric furnace, and the entire assembly including the provisional baking layer 15a may be heated to form the sealing layer 15.

The embodiments of the sealed package of the present invention have been described above by way of examples, but the sealed package of the present invention is not limited to these. The configuration can be changed as needed without departing from the gist of the present invention.

Examples

The present invention will be described in further detail with reference to examples, but the present invention is not limited to the examples. Examples 1-1 to 1-37 and 3-1 to 3-5 are examples. Examples 2-1 to 2-7 are comparative examples, and examples 2-1 to 2-3 and 2-7 are glass compositions prepared so as to have a target average composition by mixing glass powders. In examples 3-1 to 3-5, glass powder mixtures of the target compositions were obtained by mixing glass powders. Further, the glass compositions of examples 2-1 and 2-4 were evaluated for strength as comparative examples.

Examples 1-1 to 1-37 and 2-1 to 2-7

(production of glass composition (glass powder))

Raw materials were prepared and mixed so as to have a composition shown in mol% in the columns of glass compositions in tables 1 to 3, and the mixture was melted in an electric furnace at 1050 to 1150 ℃ for 1 hour using a platinum crucible to obtain molten glass, and the molten glass was formed into sheet-like glass.

The sheet glass was pulverized by a rotary ball mill and classified by a sieve to obtain glass powders of examples 1-1 to 1-37 and 2-1 to 2-7 having a particle size of 0.5 to 15 μm.

[ examples 3-1 to 3-5 ]

(production of glass powder mixture)

The glass powders of examples 2-1 to 2-3 and 2-7 were mixed in the volume ratio shown in Table 4 to obtain glass powder mixtures of examples 3-1 to 3-5. The average compositions of the glass powder mixtures of examples 3-1 to 3-5 are shown in Table 4. In Table 4, "glass 2-1" means the glass powder of example 2-1, and the same meanings apply to other similar descriptions.

The glass powder (glass powder mixture) of each of the obtained examples was subjected to the following measurement and evaluation.

(Tg、Ts)

The glass transition point (Tg, unit:. degree. C.) and the softening point (Ts, unit:. degree. C.) of the glass powder (glass powder mixture) of each example were measured by a differential thermal analyzer. Note that, the 1 st inflection point is described for the glass powder mixture. The results obtained are shown in tables 1 to 4.

(coefficient of thermal expansion (. alpha.))

After each glass powder was molded into a rectangular parallelepiped shape, the resultant was baked at 370 to 480 ℃ for 10 minutes depending on the softening point of each glass powder to obtain a baked body for measuring thermal expansion. The obtained fired body for measuring thermal expansion was processed into a cylindrical shape having a diameter of 5. + -. 0.5mm and a length of 2. + -. 0.05 cm. Thermal expansion of the workpieceThe calcined material was heated at a temperature rise rate of 10 ℃ per minute using a Thermoplus2 system TMA8310 manufactured by RIGAKU corporation to calculate a thermal expansion coefficient α (unit: 10) of 50 to 250 ℃. (^－7/° c). The results obtained are shown in tables 1 to 4. The glass powders of examples 2 to 5 are not described because it is difficult to process the fired body for thermal expansion measurement.

(evaluation of flowability)

5g of the glass powder was press-molded to prepare a sample (Flow button) having a diameter of 15 mm. The obtained flow button was placed on a glass substrate, and firing was performed at 370 to 480 ℃ for 10 minutes depending on the softening point of each glass powder to obtain a fired body for evaluation of fluidity. Then, the obtained calcined body for evaluation of fluidity was divided into 4 equal parts at an angle of 4 to measure the diameter at 4, and the average of the diameters at 4 was calculated as the FB diameter (unit: mm). The fluidity of each sample obtained by these evaluations was evaluated according to the following criteria. The results obtained are shown in tables 1 to 4.

< evaluation Standard of fluidity >

Good quality, FB with a diameter of 18mm or more and lustrous.

FB diameter of less than 18mm and/or no gloss.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ examples 4-1 to 4-8 ]

(production of glass paste)

The glass powder (glass powder mixture) and the laser absorbing material (Fe) of each example were mixed₂O₃-CuO-MnO) and a low expansion filler (zirconium phosphate) were prepared so as to have the proportions (% by volume) shown in table 5. As described above, it is referred to as a mixed material. Further, ethyl cellulose (resin) and diethylene glycol mono-2-ethylhexyl ether (solvent) were prepared so as to have the proportions (mass%) shown in table 5, and organic vehicles were prepared. Then, the mixed material and the organic vehicle were prepared in the mass ratio shown in table 5, and diluted with diethylene glycol mono-2-ethylhexyl ether so that the viscosity became a viscosity suitable for screen printing, to prepare glass pastes of examples 4-1 to 4-8. The particle size of the laser light absorbing substance was 0.8 μm, and the particle size of the low expansion filler was 0.9 μm.

In Table 5, "glass 1-2" means the glass powder of example 1-2, and the same meanings apply to other similar descriptions.

(preparation of test piece for Strength evaluation)

As shown in fig. 11 and 12, the glass paste was applied in a frame shape using a 400-mesh screen to the surface of a glass substrate 32 made of AN alkali-free glass AN100 (25 mm × 25mm × 0.5mm thick, manufactured by AGC corporation), dried at 120 ℃ for 10 minutes, and then temporarily fired at 420 to 480 ℃ for 10 minutes to form a temporarily fired layer 35 a. The width of the temporary baked layer 35a is about 500 μm and the thickness is about 4 to 8 μm when the sealing layer 35 is formed.

Then, the glass substrate 31 and the glass substrate 32 provided with the temporary firing layer 35a are stacked so that the glass substrate 31 and the temporary firing layer 35a are in contact with each other to form an assembly. The assembly was further irradiated with a laser beam (semiconductor laser) having a wavelength of 940nm and a spot diameter of 1.6mm from the glass substrate 32 side at a scanning speed of 10mm/s, and the temporary firing layer 35a was melted and quenched and solidified. Thus, as shown in fig. 13, a test piece 30 for strength evaluation was produced in which a glass substrate 32 was bonded to a glass substrate 31 via a sealing layer 35.

The output power of the laser is adjusted to 5 to 120W while confirming the sealing degree. Specifically, the condition that the width of the sealing layer 35 is equal to the width of the temporary firing layer 35a is adopted.

(measurement of peeling Strength)

Subsequently, as shown in fig. 14 and 15, the

support substrates

41 and 42 having a thickness of 100mm × 50mm × 3.4mm were fixed to both surfaces of the strength evaluation test piece 30 with the thermosetting adhesive 43. The support substrates 41 and 42 are arranged so that their longitudinal directions are orthogonal to each other.

Then, as shown in fig. 16, both ends of the upper support substrate 42 were supported from below as indicated by arrows 44, and a load was applied to both ends of the lower support substrate 41 from above as indicated by arrows 45, and the load when the 1 pair of glass substrates 31 and 32 of the test piece 30 for strength evaluation was peeled was measured as peel strength. TCM1000CR manufactured by mineba was used for the measurement. The results of the peel strength measurement are shown in table 5.

(measurement of falling ball Strength)

Next, as shown in fig. 17 and 18, a supporting substrate 46 of 100mm × 100mm × 3.4mm in thickness was fixed to one surface of the strength evaluation test piece 30 with a thermosetting adhesive 43.

Then, as shown in fig. 19, the weight ball 47 is dropped from the side of the unbonded strength evaluation test piece 30 to the range where the strength evaluation test piece 30 of the support substrate 46 is bonded. The mass and the falling height 48 of the weight ball 47 were changed, and the falling energy at this time was calculated by the following equation (1). The falling energy was increased, and the maximum falling energy at which 1 pair of glass substrates 31 and 32 of the test piece 30 for strength evaluation did not peel was measured as the falling ball strength. The above-mentioned "no peeling of 1 pair of glass substrates 31 and 32 of the test piece 30 for strength evaluation" means that peeling is not caused 2 or more times when 3 tests are performed. The results of the ball drop strength measurement are shown in table 5.

Drop energy [ mJ]Mass of heavy ball [ g]X falling height [ m]X acceleration of gravity [ m/s²]…(1)

[ Table 5]

As examples, the glass pastes of examples 4-1 to 4-6 obtained by using the glass powders (glass powder mixtures) of examples 1-2, 1-3 and 3-1 to 3-4 exhibited high peel strength and high ball drop strength. On the other hand, the composition of the comparative example used a composition containing no Bi₂O₃The glass pastes of examples 4 to 7 and examples 4 to 8 of the glass compositions of examples 2-1 and 2-4 had lower falling ball strengths than those of the glass pastes of examples 4-1 to 4-6.

Claims

1. A glass composition which contains substantially no alkali metal oxide and contains 10.0 to 50.0% of V in terms of mol% based on the oxide₂O₅14.5 to 45.0 percent of TeO₂5.0 to 45.0 percent of ZnO and 0.5 to 20.0 percent of Bi₂O₃。

2. The glass composition according to claim 1, wherein V is contained in an amount of 15.0 to 45.0% in mol% on an oxide basis₂O₅16.0 to 40.0% of TeO₂10.0 to 40.0% of ZnO and 1.0 to 15.0% of Bi₂O₃。

3. The glass composition according to claim 1 or 2, wherein V is contained in an amount of 20.0 to 40.0% in mol% on an oxide basis₂O₅18.0 to 35.0% of TeO₂15.0 to 35.0% of ZnO and 1.5 to 10.0% of Bi₂O₃。

4. The glass composition according to any one of claims 1 to 3,25.0 to 35.0% of V in mol% based on the oxide₂O₅20.0 to 30.0% of TeO₂20.0 to 30.0% of ZnO and 2.0 to 7.0% of Bi₂O₃。

5. The glass composition according to any one of claims 1 to 4, further comprising CuO and Fe in mol% on an oxide basis₂O₃The sum of the contents of MnO and CuO + Fe₂O₃+ MnO of 1.0 to 10.0% and 0.5 to 10.0% of B₂O₃。

6. The glass composition according to any one of claims 1 to 5, further comprising CuO and Fe in mol% on an oxide basis₂O₃The sum of the contents of MnO and CuO + Fe₂O₃+ MnO 2.0-8.0% and B1.0-7.5%₂O₃。

7. The glass composition according to any one of claims 1 to 6, further comprising CuO and Fe in mol% on an oxide basis₂O₃The sum of the contents of MnO and CuO + Fe₂O₃+ MnO of 4.0 to 7.5% and 1.5 to 5.0% of B₂O₃。

8. The glass composition according to any one of claims 5 to 7, wherein CuO is contained in an amount corresponding to the CuO and Fe₂O₃The sum of the contents of MnO and CuO + Fe₂O₃The + MnO ratio, i.e. CuO/(CuO + Fe)₂O₃+ MnO) is more than 30%.

9. The glass composition according to any one of claims 5 to 8, wherein CuO is contained in an amount corresponding to the amount of CuO or Fe₂O₃The sum of the contents of MnO and CuO + Fe₂O₃The + MnO ratio, i.e. CuO/(CuO + Fe)₂O₃+ MnO) is more than 50%.

10. The glass composition according to any one of claims 5 to 9, wherein a content of CuO is relative to the CuO and Fe₂O₃The sum of the contents of MnO and CuO + Fe₂O₃The + MnO ratio, i.e. CuO/(CuO + Fe)₂O₃+ MnO) is more than 70%.

11. The glass composition of any of claims 1-10, wherein in mole percent on an oxide basis, is represented by V₂O₅/TeO₂The content ratio is 0.5 to 2.5.

12. The glass composition of any of claims 1-11, wherein in mole percent on an oxide basis is represented by V₂O₅/TeO₂The content ratio is 1.0 to 2.0.

13. The glass composition of any of claims 1-12, wherein V is expressed in mole% on an oxide basis₂O₅、TeO₂And the sum of the contents of ZnO, i.e. V₂O₅+TeO₂+ ZnO of 78.0-89.0%, and Al₂O₃And Nb₂O₅Al as a total of the contents of₂O₃+Nb₂O₅5.0 to 11.0%.

14. The glass composition of any of claims 1-13, wherein V is expressed in mole% on an oxide basis₂O₅、TeO₂And the sum of the contents of ZnO, i.e. V₂O₅+TeO₂+ ZnO of 79.0-88.0%, and Al₂O₃And Nb₂O₅Al as a total of the contents of₂O₃+Nb₂O₅6.0 to 10.0%.

15. A glass powder having a cumulative particle size distribution in which a 50% particle diameter on a volume basis is 0.1 to 100 μm, which is composed of the glass composition according to any one of claims 1 to 14.

16. A sealing material comprising the glass powder according to claim 15 and at least one of a low-expansion filler and a laser absorber.

17. A glass paste comprising the glass powder of claim 15 and an organic vehicle.

18. The glass paste according to claim 17, further comprising at least one of a low-expansion filler and a laser absorbing substance.

19. A sealing method of sealing substrates to each other by heating the glass powder according to claim 15, the sealing material according to claim 16, or the glass paste according to claim 17 or 18 by irradiating the glass powder, the sealing material, or the glass paste with laser light.

20. A sealing package includes a 1 st substrate, a 2 nd substrate disposed to face the 1 st substrate, and a sealing layer disposed between the 1 st substrate and the 2 nd substrate and bonding the 1 st substrate and the 2 nd substrate together,

the sealing layer contains a glass composition which is substantially free of an alkali metal oxide and contains 10.0 to 50.0% of V in terms of mol% based on the oxide₂O₅14.5 to 45.0 percent of TeO₂5.0 to 45.0 percent of ZnO and 0.5 to 20.0 percent of Bi₂O₃。

21. 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, a glass member placed on the substrate so as to cover an outer surface of the laminated structure,

22. The organic electroluminescent element according to claim 21, wherein the sealing layer contains a plurality of glasses different in composition.