Glass paste

Abstract

To provide a glass paste exhibiting excellent shear strength when being used in a sealing material.SOLUTION: A glass paste contains a glass composition, an inorganic filler, and an organic vehicle, wherein the glass composition has a coefficient of thermal expansion at 50-250°C of 70×10-7 / °C or more and 110×10-7 / °C or less, the inorganic filler contains a negative thermal expansion filler having spectral radiation emissivity at a wavelength of 808 nm of less than 80% and a coefficient of thermal expansion at 30-500°C of -40×10-7 / °C or more and less than 0×10-7 / °C, and a positive thermal expansion filler having a coefficient of thermal expansion at 30-500°C of 60×10-7 / °C or more and 110×10-7 / °C or less, the content of the negative thermal expansion filler in the inorganic filler is 60 vol.% or more and 95 vol.% or less, and the content of the positive thermal expansion filler in the inorganic filler is 5 vol.% or more and 40 vol.% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a glass paste, a glass paste sealing method, a sealed package, and an organic electroluminescence element. [Background technology]

[0002] Flat panel display devices (FPDs) such as organic electroluminescence displays (OLEDs) and plasma display panels (PDPs) have a structure in which light-emitting elements are sealed in a glass package formed by sealing a pair of glass substrates. Liquid crystal display devices (LCDs) 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.

[0003] Among these, organic EL displays require strict isolation from the outside air because the light-emitting properties of the organic EL elements deteriorate significantly when exposed to moisture.In addition, organic EL elements are damaged when exposed to high temperatures, so the sealing method is extremely important.

[0004] Therefore, a promising sealing method for organic EL displays is to use glass powder as a sealing material and seal by localized heating. Glass powder is glass powder obtained by pulverizing a glass composition. Typically, the glass powder is mixed with an inorganic filler, a laser-absorbing substance, and an organic vehicle to form a paste. This paste is applied to one glass substrate by screen printing or dispensing, and baked to form a pre-baked layer. Next, the other glass substrate is placed on top of the display, and the pre-baked layer is locally heated using a laser or the like to melt the glass powder and seal the display.

[0005] As such a sealing material, for example, Patent Document 1 discloses a glass paste obtained by mixing a V2O5-TeO2-ZnO-based glass composition, an inorganic filler, a laser absorbing substance, and an organic vehicle. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6885445 Summary of the Invention [Problem to be solved by the invention]

[0007] With the demand for displays of various shapes, sealed display panels are often subjected to processes such as cutting and polishing at or around the sealed area. In particular, in recent years, there has been a demand for display panels with more complex shapes, such as those with large curves, and polishing processes such as edge polishing are often performed. However, such polishing processes generate shear stress, which can easily cause shear failure (cohesive failure) in the sealing layer. To solve this problem, improvement of shear strength is required.

[0008] The shear strength of a sealing material using glass powder is mainly determined by the adhesive strength between the sealing material and the glass substrate (hereinafter simply referred to as "adhesive strength"), the strength of the sealing material itself, and the magnitude of the thermal stress (residual thermal stress) accumulated within the sealing material.

[0009] In particular, shear fracture due to polishing occurs when the shear stress generated during polishing exceeds the strength of the sealing material itself, and therefore, in order to prevent shear fracture, it is necessary to improve the strength of the sealing material itself. However, although the glass paste described in Patent Document 1 exhibits good adhesive strength and thermal stress when used as a sealing material, there is room for further improvement in the strength of the sealing material itself from the viewpoint of suppressing shear fracture.

[0010] The present invention has been made in view of the above, and aims to provide a glass paste that exhibits excellent shear strength when used in a sealing material. It is also an object of the present invention to provide a sealing material containing the glass paste, a sealing method using the same, a sealed package, and an organic electroluminescence element. [Means for solving the problem]

[0011] The present inventors have found that in a glass paste containing a glass composition, an inorganic filler, and an organic vehicle, by configuring the inorganic filler so as to contain a combination of inorganic fillers having a thermal expansion coefficient within a specific range, the shear strength is improved when the glass paste is used as a sealing material, and have completed the present invention based on this finding.

[0012] That is, the present invention is as follows. [1] A glass paste comprising a glass composition, an inorganic filler, and an organic vehicle, The glass composition has a thermal expansion coefficient of 70×10 at 50 to 250°C. -7 / ℃ or more 110×10 -7 / °C or less, The inorganic filler has a spectral emissivity of less than 80% at a wavelength of 808 nm, and Thermal expansion coefficient between 30 and 500°C is -40×10 -7 / ℃ or more 0×10 -7 a negative thermal expansion filler having a thermal expansion coefficient of less than 1 / °C; Thermal expansion coefficient between 30 and 500°C is 60×10 -7 / ℃ or more 110×10 -7 / °C or less positive thermal expansion filler, The content of the negative thermal expansion filler in the inorganic filler is 60% by volume or more and 95% by volume or less, The glass paste, wherein the content of the positive thermal expansion filler in the inorganic filler is 5% by volume or more and 40% by volume or less. [2] The glass paste according to [1], wherein the glass composition is substantially free of alkali metal oxides and contains, in mole percent on an oxide basis, 15.0 to 45.0% of V2O5, 16.0 to 40.0% of TeO2, and 10.0 to 40.0% of ZnO. [3] The glass paste according to [1] or [2], wherein the negative thermal expansion filler contains a zirconium phosphate compound. [4] The glass paste according to any one of [1] to [3], wherein the positive thermal expansion filler contains at least one of zirconia and alumina. [5] The glass paste according to any one of [1] to [4], wherein the glass composition is a glass powder. [6] The glass paste according to any one of [1] to [5], further comprising a laser absorbing substance. [7] A sealing method for sealing substrates together by using the glass paste according to any one of [1] to [6] and heating the glass paste by irradiating it with laser light. [8] A sealed package having a first substrate, a second substrate disposed opposite to the first substrate, and a sealing layer disposed between the first substrate and the second substrate and bonding the first substrate to the second substrate, The sealing layer is a sealing package comprising the glass composition according to any one of [1] to [5] and the inorganic filler. [9] A device comprising: a substrate; a laminated structure having an anode, an organic thin film layer, and a cathode laminated on the substrate; a glass member placed on the substrate to cover the outer surface side of the laminated structure; and a sealing layer bonding the substrate and the glass member; The sealing layer is an organic electroluminescence element comprising the glass composition according to any one of [1] to [5] and the inorganic filler.

[10] The organic electroluminescence element according to [9], wherein the sealing layer contains a plurality of glasses having different compositions. [Effects of the Invention]

[0013] The glass paste of the present invention contains a glass composition, an inorganic filler configured to contain a combination of a negative thermal expansion filler and a positive thermal expansion filler having different thermal expansion coefficient ranges, and an organic vehicle. In this configuration, by incorporating a negative thermal expansion filler into the inorganic filler, residual thermal stress generated during thermal shrinkage after sealing can be suppressed, thereby increasing shear strength. Furthermore, by incorporating a positive thermal expansion filler into the inorganic filler, shrinkage stress generated between the inorganic filler and the glass composition during shrinkage after a sealing process can be reduced, thereby improving the strength of the sealing material itself and improving shear strength. As a result, when the glass paste of the present invention is used as a sealing material, it can exhibit excellent shear strength and suppress shear fracture. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a front view showing one embodiment of a sealed package. [Figure 2] FIG. 2 is a cross-sectional view of the sealed package shown in FIG. 1 taken along line AA. [Figure 3A] FIG. 3A is a process diagram showing one embodiment of a method for manufacturing a sealed package. [Figure 3B] FIG. 3B is a process diagram showing one embodiment of a method for manufacturing a sealed package. [Figure 3C] FIG. 3C is a process diagram showing one embodiment of a method for manufacturing a sealed package. [Figure 3D] FIG. 3D is a process diagram showing one embodiment of a method for manufacturing a sealed package. [Figure 4] FIG. 4 is a plan view of a first substrate used in manufacturing the sealed package shown in FIG. [Figure 5] FIG. 5 is a cross-sectional view of the first substrate taken along line BB shown in FIG. [Figure 6] FIG. 6 is a plan view of a second substrate used in manufacturing the sealed package shown in FIG. [Figure 7] FIG. 7 is a cross-sectional view of the second substrate shown in FIG. 6 taken along line CC. [Figure 8]FIG. 8 is a conceptual diagram of an organic electroluminescence element, which is an example of a sealed package. [Figure 9] FIG. 9 is a plan view of a glass substrate used in manufacturing a sealed package in an example. [Figure 10] FIG. 10 is a cross-sectional view of the glass substrate shown in FIG. 9 taken along line DD. [Figure 11] FIG. 11 is a cross-sectional view showing a sealed package according to an embodiment. [Figure 12] FIG. 12 is a schematic diagram of a sealed package in which both sides of the sealed package are fixed to jigs. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described below. Furthermore, in the following drawings, components and parts that perform the same function may be described using the same reference numerals, and duplicated descriptions may be omitted or simplified. Furthermore, the embodiments shown in the drawings are schematic in order to clearly explain the present invention, and do not necessarily accurately represent the actual size or scale.

[0016] <Glass paste> The glass paste of the present embodiment is a glass paste containing a glass composition, an inorganic filler, and an organic vehicle, and the glass composition has a thermal expansion coefficient of 70×10 at 50 to 250°C. -7 / ℃ or more 110×10 -7 / °C or less, and the inorganic filler has a spectral emissivity of less than 80% at a wavelength of 808 nm and a thermal expansion coefficient of -40 × 10 at 30 to 500°C. -7 / ℃ or more 0×10 -7 / ℃ and a negative thermal expansion filler with a thermal expansion coefficient of 60×10 -7 / ℃ or more 110×10 -7 / °C or less, and a content of the negative thermal expansion filler in the inorganic filler is 60% by volume or more and 95% by volume or less, and a content of the positive thermal expansion filler in the inorganic filler is 5% by volume or more and 40% by volume or less.

[0017] [Glass composition] The glass composition of the present embodiment has a thermal expansion coefficient of 70×10 -7 / ℃ or more 110×10 -7 / °C or less. -7 / °C or more, the adhesive strength can be improved. -7 / °C or less, the strength of the material is improved by including a filler with a specified thermal expansion coefficient. -7 / ℃ or less, more preferably 90×10 -7 / ° C. or less. The thermal expansion coefficient of the glass composition at 50 to 250° C. is measured by the method described later in the examples.

[0018] From the viewpoint of ensuring sufficient adhesive strength, the content of the glass composition is preferably 85% by volume or less, more preferably 80% by volume or less, and even more preferably 75% by volume or less, based on the total of the glass composition and the inorganic filler, and is preferably 55% by volume or more, more preferably 60% by volume or more, and even more preferably 65% ​​by volume or more.

[0019] The glass composition preferably contains substantially no alkali metal oxides and contains V2O5, TeO2, and ZnO.

[0020] Next, a preferred example of each component of the glass composition in this embodiment will be described. In the following description, unless otherwise specified, the "%" in the content of each component of the glass composition is expressed on an oxide basis, i.e., mole % in terms of oxide. In this specification, the symbol "to" indicating a numerical range is used to mean that the upper and lower limits are included.

[0021] If a glass composition used as a sealing material contains alkali metal oxides, the alkali components will diffuse into the sealed material, such as a glass substrate, during sealing or when the sealing material is exposed to high temperatures after sealing, causing deterioration of the sealed material. Therefore, it is preferable that the glass composition does not substantially contain alkali metal oxides. Note that "substantially not containing" means that it does not contain anything other than unavoidable impurities, i.e., it means that it is not intentionally added. Therefore, the glass composition may contain trace amounts of alkali metal oxides as unavoidable impurities. The content of alkali metal oxides in the glass composition is preferably 1000 ppm or less, more preferably 500 ppm or less.

[0022] In this specification, alkali metal oxides refer to Li2O, Na2O, and K2O. Furthermore, ppm refers to ppm by mass.

[0023] V2O5 is a glass-forming oxide that forms a glass network and is a low-softening component. It is also effective as a laser-absorbing component. On the other hand, if the V2O5 content is high, water resistance may decrease and glass stability may decrease during glass production, making the glass more susceptible to devitrification. Furthermore, if the V2O5 content is too low, the glass transition point may increase and low-temperature sealing properties may deteriorate. Therefore, the V2O5 content is preferably 15.0 to 45.0%. The V2O5 content is more preferably 20.0% or more, even more preferably 25.0% or more, and more preferably 40.0% or less, and even more preferably 35.0% or less.

[0024] TeO2 is a glass oxide that forms a glass network and is a low-softening component. On the other hand, if the TeO2 content is high, the thermal expansion coefficient increases. On the other hand, if the TeO2 content is too low, the glass transition point may increase, which may deteriorate the low-temperature sealing property and may make the glass more susceptible to crystallization during the sealing firing. Therefore, the TeO2 content is preferably 16.0 to 40.0%. The TeO2 content is more preferably 18.0% or more, even more preferably 20.0% or more, and more preferably 35.0% or less, even more preferably 30.0% or less.

[0025] ZnO is a component that reduces the thermal expansion coefficient. On the other hand, if the ZnO content is high, the glass stability may decrease during glass production, making the glass more susceptible to devitrification. On the other hand, if the ZnO content is too low, the thermal expansion coefficient increases. Therefore, the ZnO content is preferably 10.0 to 40.0%. The ZnO content is more preferably 15.0% or more, even more preferably 20.0% or more, and more preferably 35.0% or less, even more preferably 30.0% or less.

[0026] Bi2O3 is a component that readily reacts with glass substrates during sealing and improves adhesive strength by forming a reaction layer, and its inclusion is therefore preferred. Inclusion of Bi2O3 improves adhesive strength. On the other hand, a high Bi2O3 content may increase the glass transition temperature, potentially impairing low-temperature sealing. Furthermore, excessive reaction with the glass substrate may result in the incorporation of high-melting-point components in the glass substrate, such as SiO2, into the glass composition, potentially raising the bonding point and increasing the residual thermal stress of the sealing material after sealing. Therefore, the Bi2O3 content is preferably 1.0% or more, more preferably 1.5% or more, and even more preferably 2.0% or more. It is also preferably 15.0% or less, more preferably 10.0% or less, and even more preferably 7.0% or less.

[0027] CuO is a component that reduces the thermal expansion coefficient and improves water resistance, so its inclusion is preferable. It is also effective as a laser-absorbing component. Therefore, by including CuO, the amount of pigment added for the purpose of laser absorption during glass paste preparation can be reduced, and instead, a larger amount of inorganic filler can be added, making it possible to produce a glass paste with a lower thermal expansion coefficient. On the other hand, a high CuO content tends to cause crystallization during sealing and firing. Therefore, to fully achieve the laser absorption effect, the CuO content is preferably 1.0% or more, more preferably 2.0% or more, and even more preferably 3.0% or more. Furthermore, to avoid crystallization of the glass, the CuO content is preferably 10.0% or less, more preferably 9.0% or less, and even more preferably 8.0% or less.

[0028] Fe2O3 is also effective as a laser absorption component and may be included. By including Fe2O3, the amount of pigment added for laser absorption during glass paste preparation can be reduced, allowing for the inclusion of a larger amount of inorganic filler instead, making it possible to produce a glass paste with a lower thermal expansion coefficient. On the other hand, a high Fe2O3 content can lead to glass crystallization during firing and sealing, and can also increase the glass's softening point, resulting in poor low-temperature sealing. Therefore, the Fe2O3 content is preferably 7.0% or less, more preferably 5.0% or less, and even more preferably 2.0% or less. To achieve the laser absorption effect, the Fe2O3 content is preferably 1.0% or more. However, as long as CuO is included, the above effect can be achieved even without Fe2O3.

[0029] MnO is an effective laser-absorbing component, so its inclusion is preferred. By including MnO, the amount of pigment added for laser absorption during glass paste preparation can be reduced, and instead, a larger amount of inorganic filler can be added, making it possible to produce a glass paste with a lower thermal expansion coefficient. On the other hand, a high MnO content makes the glass more likely to crystallize during firing and sealing. Therefore, the MnO content is preferably 7.0% or less, more preferably 5.0% or less, and even more preferably 2.0% or less. Furthermore, to obtain the laser absorption effect, the MnO content is preferably 1.0% or more. However, as long as CuO or Fe2O3 is included, the above effect can be obtained even without MnO.

[0030] To obtain a sufficient laser absorption effect, the total content of CuO, Fe2O3, and MnO (CuO + Fe2O3 + MnO) is preferably 1.0% or more, more preferably 2.0% or more, even more preferably 3.0% or more, and even more preferably 4.0% or more. Furthermore, to avoid crystallization of the glass during laser firing and sealing, the total content of CuO, Fe2O3, and MnO is preferably 10.0% or less, more preferably 9.0% or less, and even more preferably 8.0% or less.

[0031] Although CuO, Fe2O3, and MnO are all effective laser absorbing components, it is preferable to include a large amount of CuO in order to balance the laser absorption effect with preventing crystallization of the glass. Specifically, if the ratio of the CuO content to the total content of CuO, Fe2O3, and MnO (CuO+Fe2O3+MnO) {CuO / (CuO+Fe2O3+MnO)} is 30% or more, the low-temperature sealing properties of the glass are maintained and further, crystallization of the glass can be prevented, so this is preferable, more preferably 50% or more, and even more preferably 70% or more.

[0032] B2O3 is a glass oxide and is a component that forms a glass network and improves glass stability, so its inclusion is preferred. On the other hand, a high B2O3 content can conversely make the glass unstable and prone to crystallization during sealing and firing. Therefore, to stabilize the glass, the B2O3 content is preferably 0.5% or more, more preferably 1.0% or more, and even more preferably 1.5% or more. Furthermore, to avoid glass crystallization due to excessive B2O3 content, the B2O3 content is preferably 10.0% or less, more preferably 7.5% or less, and even more preferably 5.0% or less.

[0033] BaO is an effective component for stabilizing glass and may be contained in the glass composition, and if contained, the content is preferably 1.0% or more. On the other hand, in order to maintain the glass transition temperature and thermal expansion coefficient within appropriate ranges, if BaO is contained in the glass composition, the content is preferably 10.0% or less, and more preferably 8.0% or less.

[0034] Although Al2O3 and Nb2O5 are not essential, they have the effect of lowering the thermal expansion coefficient and improving water resistance, and may be contained in the glass composition. When Al2O3 and / or Nb2O5 are contained in the glass composition, the content of each is preferably 2.0% or more. On the other hand, in order to maintain the glass transition temperature within an appropriate range, when Al2O3 and / or Nb2O5 are contained in the glass composition, the content of each is preferably 10.0% or less, and more preferably 9.0% or less.

[0035] The glass composition may contain components other than the above components (hereinafter referred to as "other components") The total content of the other components is preferably 10.0% or less.

[0036] The glass composition may contain other components such as CaO, TiO2, ZrO2, CeO2, La2O3, CoO, MoO3, Sb2O3, WO3, and GeO2.

[0037] In order to reduce the burden on the environment, the glass composition preferably contains substantially no lead, ie, no PbO.

[0038] The glass composition preferably has a glass transition point (hereinafter referred to as "Tg") of 350°C or less, since this provides good low-temperature sealing properties. Tg is more preferably 330°C or less. The Tg of the glass composition can be measured using a differential thermal analyzer.

[0039] The method for producing the glass composition is not particularly limited, and the glass composition can be produced, for example, by the following method.

[0040] First, a raw material mixture is prepared. The raw materials are not particularly limited as long as they are raw materials used in the production of ordinary oxide-based glasses, and oxides, carbonates, etc. can be used. The raw material mixture is prepared by appropriately adjusting the types and proportions of the raw materials so that the composition of the resulting glass composition falls within the above-mentioned range.

[0041] 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° C., more preferably 1050° C. or higher, and more preferably 1150° C. or lower. The heating and melting time is preferably 30 to 90 minutes.

[0042] The molten material is then cooled and solidified to obtain a glass composition. The cooling method is not particularly limited. A roll-out machine or a press machine may be used, or rapid cooling by dropping the material into a cooling liquid may also be used. The obtained glass composition is preferably completely amorphous, i.e., has a crystallinity of 0%. However, it may contain crystallized portions as long as the effects of the present invention are not impaired.

[0043] The glass composition thus obtained may be in any form, such as a block, a plate, a thin plate (flake), or a powder.

[0044] When the glass composition is used as a sealing material, the glass composition is preferably in the form of a glass powder. In addition, when evaluating the above properties of the glass composition, the glass powder is also preferred from the viewpoint of performance as a sealing material.

[0045] (glass powder) The glass powder in this embodiment is a glass powder made of the above-mentioned glass composition. Note that glass powder made of a glass composition means that the average composition of the glass powder is the same as the composition of the above-mentioned glass composition. In other words, the glass powder may be made of a single glass powder having the same composition as the glass composition, or may be a glass powder obtained by mixing multiple glass powders with different compositions so that the average composition is the same as the glass composition. Note that, for convenience, a glass powder made of multiple glass powders with different compositions will be referred to as a "glass powder mixture" hereinafter.

[0046] The particle size of the glass powder can be appropriately selected depending on the application. When the application is a sealing material, the particle size of the glass powder is preferably 0.1 to 100 μm. Furthermore, if the particle size of the glass powder of this embodiment is large, it is prone to settling and separation when made into a paste and applied or dried, and there is also the problem that the thickness of the resulting sealing layer increases. Therefore, when the glass powder of this embodiment is made into a paste and used, the particle size of the glass powder is preferably in the range of 0.1 to 5.0 μm, more preferably 0.1 to 2.0 μm.

[0047] In this specification, the term "particle size" refers to the 50% particle size (D 50 ) and specifically refers to the particle size at which the cumulative amount accounts for 50% by volume on the cumulative particle size curve of the particle size distribution measured using a laser diffraction / scattering particle size distribution analyzer.

[0048] Glass powder can be obtained, for example, by pulverizing a glass composition. Therefore, the particle size of the glass powder can be adjusted by the pulverization conditions. Examples of pulverization methods include a rotary ball mill, a vibrating ball mill, a planetary mill, a jet mill, an attritor, a media agitation mill (bead mill), a jaw crusher, and a roll crusher.

[0049] In particular, when obtaining fine particles of 5.0 μm or less, it is best to use wet milling, which involves milling in a solvent such as water or alcohol using alumina or zirconia media or a bead mill.

[0050] In order to adjust the particle size of the glass powder, in addition to pulverizing the glass composition, classification may be carried out using a sieve or the like, if necessary.

[0051] The compositions of the glass powders different in composition that constitute the glass powder mixture are not particularly limited, and the glass powder mixture of this embodiment can be prepared by mixing appropriate types of glass powders so that the average composition is similar to the above-mentioned glass composition. The glass powder mixture may be composed of two types of glass powders different in composition, or may be composed of three or more types of glass powders different in composition. Furthermore, when producing a glass paste containing a glass powder mixture, glass powders may be mixed to form a glass powder mixture and then formed into a paste, or multiple types of pastes containing glass powders with different compositions may be mixed.

[0052] [Inorganic filler] The inorganic filler in this embodiment has a spectral emissivity of less than 80% at a wavelength of 808 nm and a thermal expansion coefficient of −40×10 -7 / ℃ or more 0×10 -7 / ℃ and a negative thermal expansion filler with a thermal expansion coefficient of 60×10 -7 / ℃ or more 110×10 -7 / °C or less, and a positive thermal expansion filler, wherein the content of the negative thermal expansion filler in the inorganic filler is 60% by volume or more and 95% by volume or less, and the content of the positive thermal expansion filler in the inorganic filler is 5% by volume or more and 40% by volume or less.

[0053] The inorganic filler is a substance having a spectral emissivity of less than 80% at a wavelength of 808 nm. In this specification, the spectral emissivity is determined using a spectrophotometer. The spectral emissivity may be determined in accordance with JIS R1801 (2002), or may be determined by measuring the reflectance and transmittance and then using Kirchhoff's law to calculate the spectral emissivity as follows: (spectral emissivity) = 1 - (reflectance) - (transmittance).

[0054] (Negative thermal expansion filler) The inorganic filler in this embodiment has a thermal expansion coefficient of −40×10 at 30 to 500° C. -7 / ℃ or more 0×10 -7 / °C. By including a negative thermal expansion filler having a thermal expansion coefficient in the above range in the inorganic filler, the difference between the thermal expansion coefficients of the glass composition and the inorganic filler and the thermal expansion coefficient of the glass substrate to be sealed can be reduced. This makes it possible to suppress residual thermal stress that occurs during thermal contraction after sealing, and increases shear strength.

[0055] The thermal expansion coefficient of an inorganic filler at 30 to 500°C is generally determined by the TMA method, but is not limited to this method and may also be measured by, for example, optical interferometry. Furthermore, for fillers that are difficult to process into a bulk form, such as powder, the thermal expansion coefficient may be determined by measuring the lattice constant using high-temperature X-ray diffraction measurement.

[0056] If the thermal expansion coefficient of the negative thermal expansion filler is too small, residual thermal stress may occur at the interface between the glass composition and the inorganic filler due to excessive negative expansion. -7 / ℃ or more, -35×10 -7 / ℃ or higher is preferable, and -30×10 -7 / °C or more. From the viewpoint of suppressing residual thermal stress occurring at the interface between the glass composition and the glass substrate, the thermal expansion coefficient of the negative thermal expansion filler is preferably 0×10 -7 / ℃ less than -5 × 10 -7 / ℃ or less is preferable, and -10×10 -7 / °C or less is more preferable.

[0057] The content of the negative thermal expansion filler in the inorganic filler is 60% by volume or more, more preferably 65% ​​by volume or more, even more preferably 70% by volume or more, and particularly preferably 75% by volume or more. The content of the negative thermal expansion filler in the inorganic filler is 95% by volume or less, more preferably 93% by volume or less, even more preferably 91% by volume or less, and particularly preferably 89% by volume or less. By setting the content of the negative thermal expansion filler within the above range, the difference between the thermal expansion coefficient of the glass composition and the inorganic filler as a whole and the thermal expansion coefficient of the glass substrate to be sealed is reduced, thereby sufficiently suppressing residual thermal stress and increasing shear strength.

[0058] As a negative thermal expansion filler, the thermal expansion coefficient at 30 to 500°C is -40 × 10 -7 / ℃ or more 0×10 -7 Although there is no particular limitation as long as it is the following, zirconium phosphate compounds are preferred. In this specification, zirconium phosphate compounds refer to oxides containing phosphorus and zirconium as their composition. For example, (ZrO)2P2O7, NaZr2(PO4)3, KZr2(PO4)3, Ca 0.5 Examples include Zr2(PO4)3, NbZr(PO4)3, Zr2(WO3)(PO4)2, and composite compounds thereof. These may be used alone or in combination of two or more.

[0059] From the viewpoint of reactivity with glass and improvement of material strength, the particle size of the negative thermal expansion filler is preferably 0.1 μm or more, more preferably 0.3 μm or more, and even more preferably 0.5 μm or more. It is also preferably 5.0 μm or less, more preferably 3.0 μm or less, and even more preferably 2.0 μm or less. In this specification, the particle size of the inorganic filler refers to the average particle size (D 50 ) refers to

[0060] The particle size of the negative thermal expansion filler can be adjusted by controlling the dry synthesis, wet synthesis, etc. and / or by atomization by dry pulverization, wet pulverization, etc. The pulverization method is not particularly limited, but examples thereof include a rotary ball mill, a vibrating ball mill, a planetary mill, a jet mill, an attritor, a media stirring mill (bead mill), a jaw crusher, and a roll crusher.

[0061] In particular, when obtaining fine particles of 2.0 μm or less, it is best to use wet milling, which involves milling in a solvent such as water or alcohol using alumina or zirconia media or a bead mill.

[0062] In order to adjust the particle size of the negative thermal expansion filler, in addition to pulverizing the negative thermal expansion filler, the negative thermal expansion filler may be classified using a sieve or the like as needed.

[0063] (positive thermal expansion filler) The inorganic filler in this embodiment has a thermal expansion coefficient of 60×10 at 30 to 500°C. -7 / ℃ or more 110×10 -7 The inorganic filler contains a positive thermal expansion filler having a thermal expansion coefficient of 0.1 / °C or less. The thermal expansion coefficient of such a positive thermal expansion filler is close to that of the glass composition. Therefore, by including a positive thermal expansion filler in the inorganic filler, the shrinkage stress that occurs between the inorganic filler and the glass composition during shrinkage after a sealing treatment can be reduced, improving the strength of the sealing material itself and suppressing shear fracture.

[0064] The thermal expansion coefficient of the positive thermal expansion filler is 60 x 10 -7 / ℃ or more, 65 × 10 -7 / ℃ or more is more preferable, and 70×10 -7 / ℃ or more is more preferable, and 75×10 -7 / °C or more. The thermal expansion coefficient of the positive thermal expansion filler is particularly preferably 110 × 10 -7 / ℃ or less, 105 × 10 -7 / ℃ or less is more preferable, and 100×10 -7 / ℃ or less is more preferable, and 95×10 -7 Within this range, residual thermal stress occurring at the interface between the glass composition and the glass substrate, and residual thermal stress occurring at the interface between the glass composition and the inorganic filler can be suppressed.

[0065] The content of the positive thermal expansion filler in the inorganic filler is 5% by volume or more, more preferably 7% by volume or more, even more preferably 9% by volume or more, and particularly preferably 11% by volume or more. The content of the positive thermal expansion filler in the inorganic filler is 40% by volume or less, more preferably 35% by volume or less, even more preferably 30% by volume or less, and particularly preferably 25% by volume or less. By setting the content of the positive thermal expansion filler within the above range, the generation of residual thermal stress during thermal contraction between the glass composition and the inorganic filler is suppressed, and shear strength is improved.

[0066] Positive thermal expansion filler has a thermal expansion coefficient of 60 x 10 at 30 to 500°C.-7 / ℃ or more 110×10 -7 The material is not particularly limited as long as it has a temperature of 1 / °C or less, but examples thereof include zirconia, alumina, forsterite, etc. Among these, at least one of zirconia and alumina is preferred.

[0067] From the viewpoints of reactivity with glass and improving material strength, the particle size of the positive thermal expansion filler is preferably 0.1 μm or more, more preferably 0.3 μm or more, and even more preferably 0.5 μm or more, and is preferably 5.0 μm or less, more preferably 3.0 μm or less, and even more preferably 2.0 μm or less.

[0068] The particle size of the positive thermal expansion filler can be adjusted by the pulverization conditions. The pulverization method and particle size adjustment are the same as those described above for the negative thermal expansion filler.

[0069] The total content of the positive thermal expansion filler and the negative thermal expansion filler is preferably set so that the thermal expansion coefficient when the glass paste of this embodiment is used as a sealing material approaches the thermal expansion coefficient of the glass substrate that is the material to be sealed. The total content of the positive thermal expansion filler and the negative thermal expansion filler is preferably 15% by volume or more, more preferably 20% by volume or more, and even more preferably 25% by volume or more, based on the total of the glass composition and the inorganic filler. Furthermore, from the viewpoint of suppressing a decrease in the fluidity of the sealing material when melted, the total content of the positive thermal expansion filler and the negative thermal expansion filler is preferably 45% by volume or less, more preferably 40% by volume or less, and even more preferably 35% by volume or less, based on the total of the glass composition and the inorganic filler.

[0070] The glass paste of this embodiment, which combines the negative thermal expansion filler and the positive thermal expansion filler, exhibits excellent shear strength when used as a sealing material. This is because, as described above, the negative thermal expansion filler matches the thermal expansion coefficients of the sealing material and the glass substrate, thereby suppressing residual thermal stress. Furthermore, the positive thermal expansion filler matches the thermal expansion coefficients of the inorganic filler and the glass composition, thereby increasing the strength of the sealing material itself. In particular, increasing the strength of the sealing material itself can suppress shear fracture when used as a sealing layer.

[0071] (Other inorganic fillers) The inorganic filler in this embodiment may contain inorganic fillers other than the above-mentioned positive thermal expansion fillers and negative thermal expansion fillers, such as mullite, cordierite, and amorphous silica.

[0072] The content of the other inorganic fillers is preferably 15% by volume or less relative to the total volume of the entire inorganic filler. By being within this range, it is possible to obtain suitable material strength without affecting the action of the present invention. Furthermore, 10% by volume or less is more preferable, and 5% by volume or less is even more preferable.

[0073] [Organic vehicle] The organic vehicle in this embodiment may be, for example, a solvent in which a resin serving as a binder component is dissolved. Specific examples of the organic vehicle include those in which a resin such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, or nitrocellulose is dissolved in a solvent such as terpineol, texanol, butyl carbitol acetate, or ethyl carbitol acetate.

[0074] Further examples include those obtained by dissolving acrylic resins such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate in solvents such as methyl ethyl ketone, terpineol, texanol, butyl carbitol acetate, and ethyl carbitol acetate. In this specification, (meth)acrylate means at least one of acrylate and methacrylate.

[0075] Further, for example, polyalkylene carbonates such as polyethylene carbonate and polypropylene carbonate dissolved in solvents such as triethyl acetylcitrate, propylene glycol diacetate, diethyl succinate, ethyl carbitol acetate, triacetin, Texanol, dimethyl adipate, ethyl benzoate, and mixtures of propylene glycol monophenyl ether and triethylene glycol dimethyl ether can be used.

[0076] The ratio of resin to solvent in the organic vehicle is not particularly limited, but is selected so that the viscosity of the organic vehicle can adjust the viscosity of the glass paste. Specifically, the ratio of resin to solvent in the organic vehicle is preferably about 3:97 to 30:70 by mass.

[0077] The ratio of the organic vehicle to the total of the glass composition, inorganic filler, and laser absorbing substance in the glass paste of this embodiment is adjusted appropriately depending on the desired viscosity of the glass paste. Specifically, the ratio (by mass) of the total of the glass composition, inorganic filler, and laser absorbing substance to the organic vehicle is preferably about 60:40 to 80:20. In addition to the glass composition, inorganic filler, and organic vehicle, known additives can be blended into the glass paste as needed, provided that the blending does not violate the object of the present invention.

[0078] The glass paste is prepared by a known method using a rotary mixer equipped with stirring blades, a roll mill, a ball mill, or the like.

[0079] [Laser absorbing material] The glass paste of this embodiment may contain a laser-absorbing substance. In the present invention, the laser-absorbing substance is a substance having a spectral emissivity of 80% or more at a wavelength of 808 nm. The laser-absorbing substance increases the absorption rate of the laser irradiated during sealing, and can promote melting of the glass composition contained in the glass paste.

[0080] The laser absorbing substance is not particularly limited, but examples thereof include Cu, Fe, and Mn constituting the above-mentioned CuO, Fe2O3, and MnO, as well as at least one metal selected from Cr, Ni, etc., or a compound (inorganic pigment) such as an oxide containing the metal. Furthermore, the laser absorbing substance may be a pigment other than these.

[0081] The particle size of the laser-absorbing substance is preferably 0.1 to 5.0 μm, more preferably 0.1 to 2.0 μm. In this specification, the particle size of the laser-absorbing substance is the average particle size (D 50 ) refers to

[0082] The content of the laser-absorbing substance is preferably set so that the contents of CuO, Fe2O3, and MnO satisfy the ranges described above in the section [Glass Composition]. This allows the sealing material to be sufficiently melted by laser irradiation. Furthermore, the total content of the laser-absorbing substance including other laser-absorbing substances is preferably 0.1% by volume or more, more preferably 1% by volume or more, and even more preferably 3% by volume or more, based on the total of the glass composition, inorganic filler, and laser-absorbing substance. On the other hand, in order to ensure the fluidity of the sealing material when melted and to increase the adhesive strength, the total content is preferably 20% by volume or less, more preferably 18% by volume or less, and even more preferably 15% by volume or less.

[0083] <Sealed package> Next, a sealing package to which the glass paste of this embodiment is applied will be described. Figures 1 and 2 are plan views and cross-sectional views showing one embodiment of a sealed package. Figures 3A to 3D are process diagrams showing one embodiment of a method for manufacturing the sealed package shown in Figure 1. Figures 4 and 5 are plan views and cross-sectional views of a first substrate used in manufacturing the sealed package shown in Figures 1 and 2. Figures 6 and 7 are plan views and cross-sectional views of a second substrate used in manufacturing the sealed package shown in Figures 1 and 2.

[0084] The sealed package 10 in this embodiment constitutes an FPD such as an OELD, PDP, or LCD, a lighting device (OEL lighting, etc.) using a light-emitting element such as an organic electroluminescence (OEL) element, or a solar cell such as a dye-sensitized solar cell. That is, the sealed package 10 includes a first substrate 11, a second substrate 12 disposed opposite the first substrate, and a sealing layer 15 disposed between the first substrate and the second substrate to bond the first substrate to the second substrate. The sealing layer 15 contains the glass composition of this embodiment and an inorganic filler.

[0085] The first substrate 11 is, for example, an element substrate on which an electronic element section 13 is mainly provided. The second substrate 12 is, for example, a sealing substrate mainly used for sealing. The first substrate 11 is provided with the electronic element section 13. The first substrate 11 and the second substrate 12 are arranged to face each other and are bonded therebetween by a sealing layer 15 arranged in a frame shape.

[0086] A soda-lime glass substrate, an alkali-free glass substrate, or the like is used for the first substrate 11 and the second substrate 12. Examples of soda-lime glass substrates include AS and PD200 (both trade names manufactured by AGC Corporation), and chemically strengthened versions of these. Examples of alkali-free glass substrates include AN100 (trade name manufactured by AGC Corporation), EAGEL2000 (trade name manufactured by Corning Incorporated), EAGEL GX (trade name manufactured by Corning Incorporated), JADE (trade name manufactured by Corning Incorporated), #1737 (trade name manufactured by Corning Incorporated), OA-10 (trade name manufactured by Nippon Electric Glass Co., Ltd.), and Tempax (trade name manufactured by Schott Corporation).

[0087] The electronic element section 13 has, for example, an OEL element in the case of an OELD or OEL lighting, a plasma light-emitting element in the case of a PDP, a liquid crystal display element in the case of an LCD, or a dye-sensitized solar cell element (dye-sensitized photoelectric conversion element) in the case of a solar cell. The electronic element section 13 can have various known structures and is not limited to the structure shown in the figure.

[0088] 1 and 2, an OEL element, a plasma light-emitting element, or the like is provided on the first substrate 11 as the electronic element section 13. When the electronic element section 13 is a dye-sensitized solar cell element, or the like, element films such as wiring films and electrode films (not shown) are provided on the opposing surfaces of the first substrate 11 and the second substrate 12.

[0089] When the electronic element section 13 is an OEL element or the like, a space remains between the first substrate 11 and the second substrate 12. This space may be left as is, or may be filled with a transparent resin or the like. The transparent resin may be bonded to the first substrate 11 and the second substrate 12, or may simply be in contact with them.

[0090] When the electronic element unit 13 is a dye-sensitized solar cell element or the like, the electronic element unit 13 is disposed over the entire space between the first substrate 11 and the second substrate 12, although this is not shown. The object to be sealed is not limited to the electronic element unit 13, but may be a photoelectric conversion device or the like. The sealed package 10 may also be a building material such as double-glazed glass that does not have the electronic element unit 13.

[0091] As an example of a sealed package, an organic electroluminescence element constituting an OELD will be described in detail below with reference to FIG. An organic electroluminescence element 210 obtained using the glass paste of this embodiment includes a substrate 211, a laminated structure 213 having an anode 213a, an organic thin film layer 213b, and a cathode 213c laminated on the substrate 211, a glass member 212 placed on the substrate 211 to cover the outer surface side of the laminated structure 213, and a sealing layer 215 that bonds the substrate 211 and the glass member 212. The sealing layer 215 contains the glass composition of this embodiment and an inorganic filler.

[0092] <Method of manufacturing sealed package> Next, an embodiment of a method for manufacturing a sealed package to which the glass paste of the present embodiment is applied will be described. In this embodiment, the above-described glass paste is used for sealing. The glass paste is applied to the second substrate 12 in a frame shape and then dried to form a coating layer. Examples of application methods include printing methods such as screen printing and gravure printing, and dispensing methods. Drying is performed to remove the solvent, and is usually performed at a temperature of 120°C or higher for 10 minutes or longer. If the solvent remains in the coating layer, there is a risk that the binder component will not be sufficiently removed in the subsequent pre-baking.

[0093] The coating layer is pre-baked to form a pre-baked layer 15a (FIGS. 6 and 7). The pre-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.

[0094] An electronic element section 13 is provided on the first substrate 11 in accordance with the specifications of the sealed package 10 (FIGS. 4 and 5).

[0095] Next, the second substrate 12 provided with the pre-baked layer 15a and the first substrate 11 provided with the electronic element section 13 are laminated together, with the pre-baked layer 15a facing the electronic element section 13 (FIGS. 3A and 3B).

[0096] Thereafter, the pre-baked layer 15a is irradiated with laser light 16 through the second substrate 12 to perform baking (FIG. 3C). The laser light 16 is irradiated while scanning along the frame-shaped pre-baked layer 15a. By irradiating the entire periphery of the pre-baked layer 15a with the laser light 16, a frame-shaped sealing layer 15 is formed between the first substrate 11 and the second substrate 12. The laser light 16 may also be irradiated onto the pre-baked layer 15a through the first substrate 11.

[0097] The type of laser beam 16 is not particularly limited, and laser beams such as semiconductor laser, carbon dioxide laser, excimer laser, YAG laser, and HeNe laser can be used. The irradiation conditions of the laser beam 16 are selected depending on the thickness, line width, cross-sectional area in the thickness direction, etc. of the pre-baked layer 15a. The output of the laser beam 16 is preferably 2 to 150 W. If the output of the laser beam is less than 2 W, the pre-baked layer 15a may not be melted. If the output of the laser beam exceeds 150 W, cracks and the like are likely to occur in the first substrate 11 and the second substrate 12. The output of the laser beam 16 is more preferably 5 to 120 W.

[0098] In this way, a sealed package 10 is manufactured in which the electronic element section 13 is hermetically sealed between the first substrate 11 and the second substrate 12 by the sealing layer 15 (FIG. 3D).

[0099] Although the method of firing by irradiation with laser light 16 has been described above, the firing method is not necessarily limited to the method of firing by irradiation with laser light 16. Other firing methods can be adopted depending on the heat resistance of the electronic element section 13, the configuration of the sealed package 10, etc. For example, if the electronic element section 13 has high heat resistance or if the electronic element section 13 is not included, instead of irradiating with laser light 16, the entire assembly as shown in FIG. 5B may be placed in a firing furnace such as an electric furnace and the entire assembly including the pre-fired layer 15a may be heated to form the sealing layer 15.

[0100] Although the embodiment of the sealed package of the present invention has been described above using examples, the sealed package of the present invention is not limited to these. The configuration can be appropriately changed as needed within the scope of the spirit of the present invention. [Example]

[0101] EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples 1 to 11 are Examples, and Examples 12 to 16 are Comparative Examples.

[0102] (Glass Composition (Production of Glass Powder)) Raw materials were prepared and mixed to obtain the compositions shown in the glass composition column of Table 1, expressed in mole percent, and melted in a platinum crucible in an electric furnace at 1050 to 1150°C for 1 hour to obtain molten glass, which was then formed into a thin glass sheet. This thin glass sheet was pulverized in a rotary ball mill and classified using a sieve to obtain glass powders of glass compositions a to c with particle sizes of 0.5 to 15 μm. The following measurements were performed on each of the obtained glass powders.

[0103] (Thermal expansion coefficient (α) of glass composition) Each glass powder was molded into a rectangular parallelepiped shape and then fired at 370 to 480°C for 10 minutes to obtain a fired body for thermal expansion measurement. The obtained fired body for thermal expansion measurement was processed into a cylindrical shape with a diameter of 5±0.5 mm and a length of 2±0.05 cm. The processed fired body for thermal expansion measurement was heated at a heating rate of 10°C / min using a thermal dilatometer Thermoplus2 system TMA8310 manufactured by RIGAKU Corporation, and the thermal expansion coefficient α (unit: 10) at 50 to 250°C was measured. -7 / °C) was calculated. The results are shown in Table 1.

[0104] [Table 1]

[0105] [Examples 1-16] (Glass paste manufacturing) The glass composition (glass powder) obtained above, a laser absorbing material (Fe2O3-CuO-MnO), a positive thermal expansion filler (alumina or zirconia), and a negative thermal expansion filler (zirconium phosphate compound) were mixed in the proportions (volume %) shown in Table 2. Separately, an organic vehicle was prepared by adding ethyl cellulose (resin) to a solvent consisting of at least one of diethylene glycol mono-2-ethylhexyl ether (solvent), 2,4-diethyl-1,5-pentanediol (solvent), and acetyl tributyl citrate (solvent). The resin and solvent were mixed in a mass ratio of 5:95 to 15:85.

[0106] Then, a mixed material obtained by mixing glass powder, a laser absorbing substance, and an inorganic filler with an organic vehicle was mixed in a mass ratio of 70:30 to 85:15, and diluted with at least one solvent selected from diethylene glycol mono-2-ethylhexyl ether (solvent), 2,4-diethyl-1,5-pentanediol (solvent), and acetyl tributyl citrate (solvent) to obtain a viscosity suitable for screen printing, thereby preparing glass pastes of Examples 1 to 16. After dilution, the mixed material and organic vehicle (solvent and resin) had a mass ratio of 65:35 to 75:25.

[0107] The particle sizes of the negative thermal expansion filler (A), the positive thermal expansion filler (B), the inorganic filler other than (A) and (B) (C), and the laser absorbing substance were as follows: Negative thermal expansion filler (A): 1.2 μm Positive thermal expansion filler (B): Alumina (0.7 μm), Zirconia (0.6 μm) Inorganic filler (C) other than (A) and (B): mullite (0.8 μm), cordierite (0.8 μm), amorphous silica (1.2 μm) Laser absorbing material: 0.6 μm

[0108] The thermal expansion coefficients of the negative thermal expansion filler (A) and the positive thermal expansion filler (B) at 30 to 500° C. were as follows. Negative thermal expansion filler (A): -20 x 10 -7 / ℃ Positive thermal expansion filler (B): Alumina (75 x 10 -7 / ℃), zirconia (100×10 -7 / ℃)

[0109] (Sealed package manufacturing) 9 and 10, the glass pastes of Examples 1 to 16 were applied in a line shape of 20 mm using a 400-mesh screen to the surface of a glass substrate 30 made of alkali-free glass AN100 (manufactured by AGC, 25 mm × 25 mm × 0.5 mm thick). The applied paste was then dried at 120 to 140°C for 20 minutes and pre-baked at 390 to 420°C for 10 minutes to form a pre-baked layer 30a. The pre-baked layer 30a was designed to have a width of approximately 500 μm and a thickness of approximately 4 to 8 μm when used as a sealing layer 30.

[0110] Thereafter, as shown in FIG. 11, a glass substrate 32 (45 mm×45 mm×0.5 mm thick) and the glass substrate 31 provided with the pre-fired layer 30a were stacked together so that the glass substrate 32 and the pre-fired layer 30a were in contact with each other to form an assembly.

[0111] Furthermore, this assembly was irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and a spot diameter of 1.6 mm at a scanning speed of 10 mm / s from the glass substrate 31 side to melt and rapidly solidify the pre-baked layer 30a, thereby producing a sealed package 33 in which the glass substrate 32 was bonded to the glass substrate 31 via the sealing layer 30.

[0112] (Shear strength evaluation method) The shear strength is evaluated using a jig as shown in FIG. Glass substrate 32 was pressed in the direction 35 in Figure 12 at a pressing speed of 1 mm / min. The load when glass substrate 32 peeled off from glass substrate 31 was measured to determine the shear strength. The strength was measured 10 times and the average value excluding the maximum and minimum values ​​was used. The results are shown in Table 2.

[0113] [Table 2]

[0114] As shown in Table 2, the glass pastes of Examples 1 to 11, which are working examples, all exhibited higher shear strength than the comparative examples when used as sealing layers. On the other hand, Examples 12 to 15, which contained only one of the negative thermal expansion filler and the positive thermal expansion filler, exhibited inferior shear strength. Also, Example 16, which contained a high proportion of negative thermal expansion filler and a low proportion of positive thermal expansion filler, exhibited inferior shear strength. [Explanation of symbols]

[0115] 10: sealing package, 11: first substrate, 12: second substrate, 13: electronic element portion, 15: sealing layer, 15a: pre-baked layer, 16: laser light, 31: glass substrate, 32: glass substrate, 30: sealing layer, 30a: pre-baked layer, 33: sealing package, 34: jig, 210: organic electroluminescence element, 211: substrate, 212: glass member, 213: laminated structure, 213a: anode, 213b: organic thin film layer, 213c: cathode, 215: sealing layer

Claims

1. A glass paste comprising a glass composition, an inorganic filler, and an organic vehicle, The glass composition has a thermal expansion coefficient of 70×10 at 50 to 250° C. －７ / ℃ or more 110 x 10 －７ / °C or less, The inorganic filler has a spectral emissivity of less than 80% at a wavelength of 808 nm, and Thermal expansion coefficient between 30 and 500°C is -40 x 10 －７ / ℃ or more 0x10 －７ / ° C. or less negative thermal expansion filler; Thermal expansion coefficient at 30 to 500°C is 60 x 10 －７ / ℃ or more 110 x 10 －７ / °C or less positive thermal expansion filler, The content of the negative thermal expansion filler in the inorganic filler is 60% by volume or more and 95% by volume or less, The glass paste, wherein the content of the positive thermal expansion filler in the inorganic filler is 5% by volume or more and 40% by volume or less.

2. The glass composition is substantially free of alkali metal oxides and contains, in mole percent based on oxides, ２ O ５ 15.0 to 45.0%, TeO ２ 2. The glass paste according to claim 1, wherein the glass paste contains 16.0 to 40.0% of SiO 2 and 10.0 to 40.0% of ZnO.

3. The glass paste according to claim 1 or 2, wherein the negative thermal expansion filler contains a zirconium phosphate compound.

4. 4. The glass paste according to claim 1, wherein the positive thermal expansion filler contains at least one of zirconia and alumina.

5. The glass paste according to any one of claims 1 to 4, wherein the glass composition is a glass powder.

6. The glass paste according to any one of claims 1 to 5, further comprising a laser absorbing substance.

7. A sealing method for sealing substrates together by using the glass paste according to any one of claims 1 to 6 and heating the glass paste by irradiating it with laser light.

8. A sealed package including a first substrate, a second substrate disposed opposite to the first substrate, and a sealing layer disposed between the first substrate and the second substrate and bonding the first substrate to the second substrate, A sealed package, wherein the sealing layer comprises the glass composition according to any one of claims 1 to 5 and the inorganic filler.

9. a substrate; a laminated structure having an anode, an organic thin film layer, and a cathode laminated on the substrate; a glass member placed on the substrate and covering an outer surface of the laminated structure; and a sealing layer bonding the substrate and the glass member together; 6. An organic electroluminescence device, wherein the sealing layer comprises the glass composition according to claim 1 and the inorganic filler.

10. 10. The organic electroluminescence device according to claim 9, wherein the sealing layer contains a plurality of glasses having different compositions.

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